KR20230111146A - Novel organic compounds and an organic electroluminescent device comprising the same - Google Patents

Abstract

The present invention relates to an organic electroluminescent device in which an organic thin film layer composed of one or a plurality of layers including at least a light emitting layer is laminated between a cathode and an anode,
The dopant constituting the light emitting layer is composed of a first dopant and a second dopant, the HOMO (based on absolute value) of the first dopant is smaller than the HOMO (based on absolute value) of the second dopant, and the LUMO (based on absolute value) of the first dopant is smaller than the LUMO (based on absolute value) of the second dopant.

Description

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

The present invention relates to the display field, and more particularly, to an organic compound that can be used in manufacturing an organic light emitting device, which is a kind of display, and an organic light emitting device including the organic compound.

Until now, liquid crystal displays have occupied most of the flat panel displays, but efforts to develop new flat panel displays that are more economical and superior in performance and differentiated from liquid crystal displays are being actively conducted worldwide. Recently, an organic light emitting device that has been in the limelight as a next-generation flat panel display has advantages such as a low driving voltage, a fast response speed, and a wide viewing angle compared to a liquid crystal display.

The structure of the organic light emitting device includes 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, a light emitting layer that emits light by combining holes and electrons, 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 It consists of a cathode. In some cases, the light emitting layer may be formed by doping the electron transport layer or the hole transport layer with a small amount of fluorescent or phosphorescent dye without a separate light emitting layer. 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 the organic light emitting device is manufactured in a multi-layered thin film structure is to stabilize the interface between the electrode and the organic material, and in the case of the organic material, since the difference in the movement speed of holes and electrons is large, luminous efficiency can be increased by effectively transferring holes and electrons to the light emitting layer using an appropriate hole transport layer and electron transport layer to balance the density of holes and electrons.

The driving principle of the organic light emitting device is as follows. When a voltage is applied between the anode and the cathode, holes injected from the anode move 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 region to generate excitons. This exciton changes from an excited state to a ground state, and as a result, fluorescent molecules in the light emitting layer emit light, thereby forming an image. At this time, light emission while falling to the ground state through a singlet excited state is called "fluorescence", and light emission while falling to the ground state through a triplet excited state is called "phosphorescence". In the case of fluorescence, the probability of a singlet excited state is 25% (triplet state 75%), and there is a limit in luminous efficiency, whereas when phosphorescence is used, up to 75% of the triplet state and 25% of the singlet excited state can be used for light emission, so theoretically, up to 100% of internal quantum efficiency is possible.

Lifespan and efficiency are the most problematic issues in organic light emitting devices, and as displays become larger, these efficiency and lifespan problems must be solved.

In particular, in the case of blue, materials such as ADN and DPVBi are used as host materials, and materials such as aromatic amine compounds, copper phthalocyanine compounds, carbazole derivatives, perylene derivatives, coumarine derivatives, and pyrene derivatives are used as dopants.

Therefore, development of a deep blue material with a long lifespan and development of other organic materials matching the energy level with the blue material are required to realize a full color display of natural color.

Republic of Korea Patent No. 1008462210000 Republic of Korea Patent No. 1023130450000 Republic of Korea Patent No. 1018256120000 Republic of Korea Patent No. 1012267000000 Republic of Korea Patent No. 1022021710000

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

An object of the present invention is to provide a novel organic compound that is used as a dopant material to improve the luminous efficiency and luminous lifetime of an organic light emitting device.

The dopant is composed of a first dopant and a second dopant, the HOMO (based on absolute value) of the first dopant is smaller than the HOMO (based on absolute value) of the second dopant, and the LUMO (based on absolute value) of the first dopant is smaller than the LUMO (based on absolute value) of the second dopant.

In addition, an object of the present invention is to provide an organic light emitting device with improved driving voltage, luminous efficiency, and luminous lifetime by including the dopant material as described above.

The present invention provides a dopant combination composed of a first dopant and a second dopant, and the first dopant provides an organic compound represented by Formula 1 below.

[Formula 1]

in the above formula

Ar1, Ar2, Ar3 and Ar4 are each independently selected from tritium, deuterium, hydrogen, CN, straight chain or branched chain alkyl having 1 to 40 carbon atoms, alkoxy having 1 to 40 carbon atoms, thioalkyl having 1 to 40 carbon atoms, cycloalkyl having 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, pyrazinyl, pyrimidinyl, and quinolinyl groups, substituted or unsubstituted with one or more selected from the group consisting of aromatic hydrocarbon groups having 6 to 60 carbon atoms,

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

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

n and m are each independently 0 and 1;

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

Tritium, Deuterium, Hydrogen, F, Cl, Br, I, CN, Si(CH₃)₃, B(OH)₂, straight chain or branched chain alkyl having 1 to 40 carbon atoms, alkoxy having 1 to 40 carbon atoms, thioalkyl having 1 to 40 carbon atoms, cycloalkyl having 3 to 40 carbon atoms, phenyl, biphenyl, naphthyl, anthracenyl, anthracenyl substituted with a phenyl group, phenanthrenyl, pyrenyl, 9,9-dimethylfluorenyl, carbazolyl, dibenzofuranyl, pyrrole, triazole, An aromatic hydrocarbon group having 6 to 60 carbon atoms unsubstituted or substituted with one or more selected from the group consisting of pyridinyl, pyrazinyl, pyrimidinyl, and quinolinyl groups;

Tritium, Deuterium, Hydrogen, F, Cl, Br, I, CN, Si(CH₃)₃, B(OH)₂, straight chain or branched chain alkyl having 1 to 40 carbon atoms, alkoxy having 1 to 40 carbon atoms, thioalkyl having 1 to 40 carbon atoms, cycloalkyl having 3 to 40 carbon atoms, phenyl, biphenyl, naphthyl, anthracenyl, anthracenyl substituted with a phenyl group, phenanthrenyl, pyrenyl, 9,9-dimethylfluorenyl, spirobi [fluorene], carbazolyl, dibenzofuranyl , pyrrole, triazole, pyridinyl, pyrazinyl, pyrimidinyl group, and substituted or unsubstituted with one or more selected from the group consisting of quinolinyl group, S, O, N, and Si A heteroaromatic hydrocarbon group having 5 to 70 carbon atoms containing at least one element selected from,

Tritium, Deuterium, Hydrogen, F, Cl, Br, I, CN, Si(CH₃)₃, B(OH)₂, phenyl, biphenyl, naphthyl, anthracenyl, anthracenyl, phenanthrenyl, pyrenyl, 9,9-dimethylfluorenyl, carba unsubstituted or substituted with one or more selected from the group consisting of straight chain or branched chain alkyl having 1 to 40 carbon atoms, alkoxy having 1 to 40 carbon atoms, thioalkyl having 1 to 40 carbon atoms, and cycloalkyl group having 3 to 40 carbon atoms It is an amino group substituted with one or more selected from the group consisting of zolyl, quinolinyl, dibenzofuranyl, pyrrole, triazole, pyridinyl, pyrazinyl, and pyrimidinyl groups.

In addition, the present invention provides a second dopant represented by Chemical Formula 2 below.

[Formula 2]

in the above formula

R1 is tritium, deuterium, halogen, CN, CF₃, straight chain or branched chain alkyl having 1 to 40 carbon atoms, alkoxy having 1 to 40 carbon atoms, thioalkyl having 1 to 40 carbon atoms, cycloalkyl having 3 to 40 carbon atoms, phenyl, biphenyl, naphthyl, phenyl substituted with an anthracenyl group, naphthanyl, biphenyl, anthracenyl, phenanthrenyl, pyrenyl, 9,9-dimethylfluorenyl, carbazolyl, dibenzofuranyl , A pyrrole, triazole, pyridinyl, pyrazinyl, pyrimidinyl, quinolinyl, phenyl pyridinyl, phenyl pyrimidinyl, phenyl imidazole, or an aromatic hydrocarbon group having 6 to 60 carbon atoms unsubstituted or substituted with one or more selected from the group consisting of imidazole or phenyl triazinyl,

Tritium, Deuterium, Halogen, CN, CF₃, straight chain or branched chain alkyl having 1 to 40 carbon atoms, alkoxy having 1 to 40 carbon atoms, thioalkyl having 1 to 40 carbon atoms, cycloalkyl having 3 to 40 carbon atoms, phenyl, biphenyl, naphthyl, anthracenyl substituted with an anthracenyl group, phenanthrenyl, pyrenyl, 9,9-dimethylfluorenyl, spirobifluorenyl, carbazolyl, dibenzofuranyl, pyrrole , triazole, pyridinyl, pyrazinyl, pyrimidinyl, quinolinyl, phenyl pyridinyl, phenyl pyrimidinyl, phenyl imidazole, or phenyl triazinyl group consisting of one or more substituted or unsubstituted, and is a heteroaromatic hydrocarbon group having 5 to 70 carbon atoms containing at least one element selected from the group consisting of S, O, N and Si;

Z1, Z4, and Z5 are each independently a single bond or a C1-C10 straight-chain or branched-chain alkyl, C3-C12 cycloalkyl, C1-C10 alkoxy, halogen, CN, CF ₃ , phenyl, naphthanyl, biphenylamine, phenyl pyridinyl, phenyl pyrimidinyl, phenyl imidazole, and Si(CH ₃ ) ₃ substituted or unsubstituted phenyl an amine;

Z2 and Z3 are each independently a single bond or phenyl unsubstituted or substituted with one or more selected from the group consisting of halogen, CN, CF ₃ , phenyl, naphthanyl, phenyl pyridinyl, phenyl pyrimidinyl, phenyl imidazole and Si(CH ₃ ) ₃ groups;

a, b, c, d, e are each independently 0 or 1;

Z6, Z7, Z8 are each independently a single bond, a C1-C2 alkylenyl, phenyl or biphenyl group;

f, g, h are each independently 0 or 1;

M is boron or carbon or nitrogen;

G1, G2 and G3 are each independently carbon or nitrogen or oxygen or sulfur;

G4, G5 and G6 are each independently carbon or nitrogen;

R2, R3, R4, R5, R6, R7, R8 and R9 are each independently hydrogen, deuterium, tritium, F, Cl, Br, I, CN, Si(CH ₃ ) ₃ , B(OH) ₂ , straight or branched chain alkyl of 1 to 40 carbon atoms, alkoxy of 1 to 40 carbon atoms, thioalkyl of 1 to 40 carbon atoms, or a cycloalkyl group,

Hydrogen, deuterium, tritium, F, Cl, Br, I, CN, Si(CH₃)₃, B(OH)₂, straight chain or branched chain alkyl having 1 to 40 carbon atoms, alkoxy having 1 to 40 carbon atoms, thioalkyl having 1 to 40 carbon atoms, cycloalkyl having 3 to 40 carbon atoms, phenyl, biphenyl, naphthyl, anthracenyl, anthracenyl substituted with a phenyl group, phenanthrenyl, pyrenyl, 9,9-dimethylfluorenyl, carbazolyl, dibenzofuranyl, pyrrole, triazole, An aromatic hydrocarbon group having 6 to 60 carbon atoms unsubstituted or substituted with one or more selected from the group consisting of pyridinyl, pyrazinyl, pyrimidinyl, and quinolinyl groups;

Hydrogen, deuterium, tritium, F, Cl, Br, I, CN, Si(CH₃)₃, B(OH)₂, straight chain or branched chain alkyl having 1 to 40 carbon atoms, alkoxy having 1 to 40 carbon atoms, thioalkyl having 1 to 40 carbon atoms, cycloalkyl having 3 to 40 carbon atoms, phenyl, biphenyl, naphthyl, anthracenyl, anthracenyl substituted with a phenyl group, phenanthrenyl, pyrenyl, 9,9-dimethylfluorenyl, spirobi [fluorene], carbazolyl, dibenzofuranyl , pyrrole, triazole, pyridinyl, pyrazinyl, pyrimidinyl group, and substituted or unsubstituted with one or more selected from the group consisting of quinolinyl group, S, O, N, and Si A heteroaromatic hydrocarbon group having 5 to 70 carbon atoms containing at least one element selected from,

Hydrogen, deuterium, tritium, F, Cl, Br, I, CN, Si(CH₃)₃, B(OH)₂, phenyl, biphenyl, naphthyl, anthracenyl, anthracenyl, phenanthrenyl, pyrenyl, 9,9-dimethylfluorenyl, carba unsubstituted or substituted with one or more selected from the group consisting of straight chain or branched chain alkyl having 1 to 40 carbon atoms, alkoxy having 1 to 40 carbon atoms, thioalkyl having 1 to 40 carbon atoms, and cycloalkyl group having 3 to 40 carbon atoms It is an amino group substituted with one or more selected from the group consisting of zolyl, quinolinyl, dibenzofuranyl, pyrrole, triazole, pyridinyl, pyrazinyl, and pyrimidinyl groups.

The present invention provides a novel organic compound that is used as a dopant material to improve luminous efficiency and luminous lifetime of an organic light emitting device.

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

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

The dopant constituting the light emitting layer is composed of a first dopant and a second dopant, the HOMO (based on absolute value) of the first dopant is smaller than the HOMO (based on absolute value) of the second dopant, and the LUMO (based on absolute value) of the first dopant is smaller than the LUMO (based on absolute value) of the second dopant.

More preferably, the HOMO and LUMO of the first dopant and the second dopant satisfy the following correlation.

0.05 ≤ |HOMO of the second dopant| - |HOMO of the first dopant| ≤ 0.5

0.05 ≤ |LUMO of the second dopant| - |LUMO of the first dopant| ≤ 0.5

The |HOMO| of the first dopant means an absolute value of the HOMO of the first dopant.

In addition, the present invention provides a first dopant represented by Chemical Formula 1 below.

[Formula 1]

in the above formula

Ar1, Ar2, Ar3 and Ar4 are each independently selected from tritium, deuterium, hydrogen, CN, straight chain or branched chain alkyl having 1 to 40 carbon atoms, alkoxy having 1 to 40 carbon atoms, thioalkyl having 1 to 40 carbon atoms, cycloalkyl having 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, pyrazinyl, pyrimidinyl, and quinolinyl groups, substituted or unsubstituted with one or more selected from the group consisting of aromatic hydrocarbon groups having 6 to 60 carbon atoms,

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

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

n and m are each independently 0 and 1;

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

Tritium, Deuterium, Hydrogen, F, Cl, Br, I, CN, Si(CH₃)₃, B(OH)₂, straight chain or branched chain alkyl having 1 to 40 carbon atoms, alkoxy having 1 to 40 carbon atoms, thioalkyl having 1 to 40 carbon atoms, cycloalkyl having 3 to 40 carbon atoms, phenyl, biphenyl, naphthyl, anthracenyl, anthracenyl substituted with a phenyl group, phenanthrenyl, pyrenyl, 9,9-dimethylfluorenyl, carbazolyl, dibenzofuranyl, pyrrole, triazole, An aromatic hydrocarbon group having 6 to 60 carbon atoms unsubstituted or substituted with one or more selected from the group consisting of pyridinyl, pyrazinyl, pyrimidinyl, and quinolinyl groups;

Tritium, Deuterium, Hydrogen, F, Cl, Br, I, CN, Si(CH₃)₃, B(OH)₂, straight chain or branched chain alkyl having 1 to 40 carbon atoms, alkoxy having 1 to 40 carbon atoms, thioalkyl having 1 to 40 carbon atoms, cycloalkyl having 3 to 40 carbon atoms, phenyl, biphenyl, naphthyl, anthracenyl, anthracenyl substituted with a phenyl group, phenanthrenyl, pyrenyl, 9,9-dimethylfluorenyl, spirobi [fluorene], carbazolyl, dibenzofuranyl , pyrrole, triazole, pyridinyl, pyrazinyl, pyrimidinyl group, and substituted or unsubstituted with one or more selected from the group consisting of quinolinyl group, S, O, N, and Si A heteroaromatic hydrocarbon group having 5 to 70 carbon atoms containing at least one element selected from,

Tritium, Deuterium, Hydrogen, F, Cl, Br, I, CN, Si(CH₃)₃, B(OH)₂, C1-C40 straight-chain or branched-chain alkyl, C1-C40 alkoxy, C1-C40 thioalkyl, and C3-C40 cycloalkyl groups unsubstituted or substituted with one or more selected from the group consisting of phenyl, biphenyl, naphthyl, anthracenyl, anthracenyl substituted with a phenyl group, phenanthrenyl, pyrenyl, 9,9-dimethylfluorenyl, carba It is an amino group substituted with one or more selected from the group consisting of zolyl, quinolinyl, dibenzofuranyl, pyrrole, triazole, pyridinyl, pyrazinyl, and pyrimidinyl groups.

Specific examples of the organic compound include any one of the following compounds 1-1 to 1-249.

In addition, the present invention provides a second dopant represented by Chemical Formula 2 below.

[Formula 2]

in the above formula

R1 is tritium, deuterium, halogen, CN, CF₃, straight chain or branched chain alkyl having 1 to 40 carbon atoms, alkoxy having 1 to 40 carbon atoms, thioalkyl having 1 to 40 carbon atoms, cycloalkyl having 3 to 40 carbon atoms, phenyl, biphenyl, naphthyl, phenyl substituted with an anthracenyl group, naphthanyl, biphenyl, anthracenyl, phenanthrenyl, pyrenyl, 9,9-dimethylfluorenyl, carbazolyl, dibenzofuranyl , A pyrrole, triazole, pyridinyl, pyrazinyl, pyrimidinyl, quinolinyl, phenyl pyridinyl, phenyl pyrimidinyl, phenyl imidazole, or an aromatic hydrocarbon group having 6 to 60 carbon atoms unsubstituted or substituted with one or more selected from the group consisting of imidazole or phenyl triazinyl,

Tritium, Deuterium, Halogen, CN, CF₃, straight chain or branched chain alkyl having 1 to 40 carbon atoms, alkoxy having 1 to 40 carbon atoms, thioalkyl having 1 to 40 carbon atoms, cycloalkyl having 3 to 40 carbon atoms, phenyl, biphenyl, naphthyl, anthracenyl substituted with an anthracenyl group, phenanthrenyl, pyrenyl, 9,9-dimethylfluorenyl, spirobifluorenyl, carbazolyl, dibenzofuranyl, pyrrole , triazole, pyridinyl, pyrazinyl, pyrimidinyl, quinolinyl, phenyl pyridinyl, phenyl pyrimidinyl, phenyl imidazole, or phenyl triazinyl group consisting of one or more substituted or unsubstituted, and is a heteroaromatic hydrocarbon group having 5 to 70 carbon atoms containing at least one element selected from the group consisting of S, O, N and Si;

Z1, Z4, and Z5 are each independently a single bond or a C1-C10 straight-chain or branched-chain alkyl, C3-C12 cycloalkyl, C1-C10 alkoxy, halogen, CN, CF ₃ , phenyl, naphthanyl, biphenylamine, phenyl pyridinyl, phenyl pyrimidinyl, phenyl imidazole, and Si(CH ₃ ) ₃ substituted or unsubstituted phenyl an amine;

Z2 and Z3 are each independently a single bond or phenyl unsubstituted or substituted with one or more selected from the group consisting of halogen, CN, CF ₃ , phenyl, naphthanyl, phenyl pyridinyl, phenyl pyrimidinyl, phenyl imidazole and Si(CH ₃ ) ₃ groups;

a, b, c, d, e are each independently 0 or 1;

Z6, Z7, Z8 are each independently a single bond, a C1-C2 alkylenyl, phenyl or biphenyl group;

f, g, h are each independently 0 or 1;

M is boron or carbon or nitrogen;

G1, G2 and G3 are each independently carbon or nitrogen or oxygen or sulfur;

G4, G5 and G6 are each independently carbon or nitrogen;

R2, R3, R4, R5, R6, R7, R8 and R9 are each independently hydrogen, deuterium, tritium, F, Cl, Br, I, CN, Si(CH ₃ ) ₃ , B(OH) ₂ , straight or branched chain alkyl of 1 to 40 carbon atoms, alkoxy of 1 to 40 carbon atoms, thioalkyl of 1 to 40 carbon atoms, or a cycloalkyl group,

Hydrogen, deuterium, tritium, F, Cl, Br, I, CN, Si(CH₃)₃, B(OH)₂, straight chain or branched chain alkyl having 1 to 40 carbon atoms, alkoxy having 1 to 40 carbon atoms, thioalkyl having 1 to 40 carbon atoms, cycloalkyl having 3 to 40 carbon atoms, phenyl, biphenyl, naphthyl, anthracenyl, anthracenyl substituted with a phenyl group, phenanthrenyl, pyrenyl, 9,9-dimethylfluorenyl, carbazolyl, dibenzofuranyl, pyrrole, triazole, An aromatic hydrocarbon group having 6 to 60 carbon atoms unsubstituted or substituted with one or more selected from the group consisting of pyridinyl, pyrazinyl, pyrimidinyl, and quinolinyl groups;

Hydrogen, deuterium, tritium, F, Cl, Br, I, CN, Si(CH₃)₃, B(OH)₂, straight chain or branched chain alkyl having 1 to 40 carbon atoms, alkoxy having 1 to 40 carbon atoms, thioalkyl having 1 to 40 carbon atoms, cycloalkyl having 3 to 40 carbon atoms, phenyl, biphenyl, naphthyl, anthracenyl, anthracenyl substituted with a phenyl group, phenanthrenyl, pyrenyl, 9,9-dimethylfluorenyl, spirobi [fluorene], carbazolyl, dibenzofuranyl , pyrrole, triazole, pyridinyl, pyrazinyl, pyrimidinyl group, and substituted or unsubstituted with one or more selected from the group consisting of quinolinyl group, S, O, N, and Si A heteroaromatic hydrocarbon group having 5 to 70 carbon atoms containing at least one element selected from,

Hydrogen, deuterium, tritium, F, Cl, Br, I, CN, Si(CH₃)₃, B(OH)₂, C1-C40 straight-chain or branched-chain alkyl, C1-C40 alkoxy, C1-C40 thioalkyl, and C3-C40 cycloalkyl groups unsubstituted or substituted with one or more selected from the group consisting of phenyl, biphenyl, naphthyl, anthracenyl, anthracenyl substituted with a phenyl group, phenanthrenyl, pyrenyl, 9,9-dimethylfluorenyl, carba It is an amino group substituted with one or more selected from the group consisting of zolyl, quinolinyl, dibenzofuranyl, pyrrole, triazole, pyridinyl, pyrazinyl, and pyrimidinyl groups.

Specific examples of the organic compound include any one of the following compounds 2-1 to 2-376.

Hereinafter, the organic electroluminescent device of the present invention will be described as an example. However, the content exemplified below does not limit the organic electroluminescent device of the present invention.

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

Next, a hole injection layer (HIL) material is vacuum thermally deposited or spin-coated on the surface of the anode in a conventional manner to form a hole injection layer. Examples of materials for the hole injection layer include copper phthalocyanine (CuPc), 4,4',4"-tris(3-methylphenylamino)triphenylamine (m-MTDATA), 4,4',4"-tris(3-methylphenylamino)phenoxybenzene (m-MTDAPB), 4,4',4"-tri(N-carbazolyl)triphenylamine (TCTA), which is a starburst type amine, Examples include 4',4"-tris(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 in a conventional manner to form a hole transport layer. At this time, examples of the hole transport layer material 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). Compounds of Formula 2 of the invention may be used.

A light-emitting layer (EML) material is vacuum thermally deposited or spin-coated on the surface of the hole transport layer in a conventional manner to form the light-emitting layer. At this time, examples of the light emitting material used include phosphorescent fluorescent materials, optical whitening agents, laser dyes, organic scintillators, and reagents for fluorescence analysis. Specifically, carbazole-based compounds, phosphine oxide-based compounds, carbazole-based phosphine oxide compounds, polyaromatic compounds such as bis((3,5-difluoro-4-cyanophenyl)pyridine) iridium picolinate (FCNIrpic), tris(8-hydroxyquinoline) aluminum (Alq3), anthracene, phenanthrene, pyrene, chrysene, perylene, coronene, rubrene and quinacridone, quinacridone Oligophenylene compounds such as terphenyl, 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, Liquid scintillators such as 3-butadiene, 1,6-diphenyl-1,3,5-hexatriene, 1,1,4,4-tetraphenyl-1,3-butadiene, metal complexes of auxin derivatives, coumarin pigments, dicyanomethylenepyran pigments, dicyanomethylenethiopyran pigments, polymethine pigments, oxobenzanthracene pigments, xanthene pigments, carbostyril pigments, perylene pigments, An oxazine compound, a stilbene derivative, a spiro compound, an oxadiazole compound, etc. are mentioned. In particular, in the case of a blue organic light emitting device, it may be preferable to use the organic compound represented by Chemical Formula 1 of the present invention as a dopant.

Optionally, an electron blocking layer (EBL) may be further 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 in a conventional manner to form an electron transport layer. At this time, the electron transport layer material used is not particularly limited, and preferably, tris(8-hydroxyquinolinolato) aluminum (Alq ₃ ) may be 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 together with the light emitting layer, diffusion of triplet excitons or holes into the electron transport layer can be prevented.

Formation of the hole blocking layer can be carried out by vacuum thermal evaporation and spin coating of the hole blocking layer material in a conventional manner, and the hole blocking layer material is not particularly limited, but preferably (8-hydroxyquinolinolato) lithium (Liq), bis (8-hydroxy-2-methylquinolinolnato) -aluminum biphenoxide (BAlq), bathocuproine (BCP) and Bphen, etc. can be used.

An electron injection layer (EIL) material is vacuum thermally deposited or spin-coated on the surface of the electron transport layer in a conventional manner 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 material for the electron injection layer.

A negative electrode is formed by vacuum thermal evaporation of a negative electrode material on the surface of the electron injection layer in a conventional manner.

At this time, as the negative electrode material used, lithium (Li), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium (Mg), magnesium-indium (Mg-In), magnesium-silver (Mg-Ag), etc. may be used. In addition, in the case of a top emission organic electroluminescent device, a transparent cathode through which light can pass may be formed using indium tin oxide (ITO) or indium zinc oxide (IZO).

A capping layer (CPL) may be formed on the surface of the negative electrode by the composition for forming a capping layer according to the present invention.

The organic electroluminescent device according to the present invention may be manufactured in the order as described above, that is, in the order of anode/hole injection layer/hole transport layer/emission layer/electron transport layer/electron injection layer/cathode, or vice versa.

<Synthesis of Compound of Formula 1>

<Synthesis of Intermediate-1>

Add 1.44g (10mmol) of Naphthalen-2-ol, 98mg (0.50mmol) of Pt/C, 5mL of tritiated water (T ₂ O), 3.0mL of isopropanol, and 60mL of cyclonucleic acid. After stirring at 140 ° C. for 12 hours in a high-pressure reactor, it is cooled to room temperature. After adding dichloromethane, the layers are separated to obtain an organic layer. After drying with MgSO4, filter. After concentrating the filtrate, isopropanol is added. The resulting solid was filtered and columnized to obtain 1.25 g (78%, tritium conversion 79%) of Intermediate-1.

Intermediate-1 MS (FAB): 160 (M ⁺ )

<Synthesis of Intermediate-2>

Put 1.60 g (10 mmol) of intermediate-1, 3.93 g (15 mmol) of triphenylphosphine, 0.96 g (6 mmol) of bromine, and 30 mL of acrylonitrile into a 100 ml three-necked round bottom flask. After stirring at 80°C for 18 hours, cool to room temperature. After adding 250 ml of EA and 250 ml of water, the layers were separated to obtain an organic layer. After distillation and column, 1.90 g (86%) of Intermediate-2 was obtained.

Intermediate-2 MS (FAB): 221 (M ⁺ )

<Synthesis of Intermediate-3>

Add 1.28g (10mmol) of naphthalene, 98mg (0.50mmol) of Pt/C, 3.0mL of isopropanol, and 60mL of cyclohexane. After stirring at 140 ° C. for 24 hours under a T ₂ atmosphere in a high-pressure reactor, it is cooled to room temperature. After filtration under reduced pressure, the organic solvent was concentrated and the resulting compound was columned at Hex: EA = 5: 1 to obtain 1.18 g of Intermediate-3 (91%, 14% tritium conversion).

Intermediate-3 MS (FAB): 130 (M ⁺ )

<Synthesis of Intermediate-4>

After dissolving 1.30 g (10 mmol) of Intermediate-3 in 30 ml of MC in a 100 ml three-necked round bottom flask, 2.14 g (12 mmol) of NBS was slowly added at 0 degrees. After removing the bath, the temperature was raised to room temperature to complete the reaction after 6 hours, and 250 ml of EA and 250 ml of water were added. The organic layer was extracted, distilled, and columnized to obtain 1.74 g (83%) of Intermediate-4.

Intermediate-4 MS (FAB): 209 (M ⁺ )

<Synthesis of Intermediate-5>

After dissolving 100g (480mmol) of 1,2,3,6,7,8-hexahydropyrene in 1L of MC, 48ml of bromine was dissolved in 200ml of MC and added slowly. After 30 minutes, the resulting solid was washed with Ethanol, filtered, and dried to obtain 60 g (33% yield) of Intermediate-5.

Intermediate-5 MS (FAB): 366 (M ⁺ )

<Synthesis of Intermediate-6>

After dissolving 60g (163.9mmol) of Intermediate-5 in 2L of Toluene, 120mg of DDQ was added and refluxed for 4 hours. After completion of the reaction, toluene was distilled and column was performed to obtain 23 g (39% yield) of Intermediate-6.

Intermediate-6 MS (FAB): 360 (M ⁺ )

<Synthesis of Intermediate-7>

After dissolving 23 g (63.88 mmol) of Intermediate-6 in 100 ml of THF, -78 degrees was maintained in an Acetone/dryice bath. After slowly dropping 56ml (140mmol) of 2.5M n-BuLi, the mixture was stirred for 30 minutes. After adding iodomethane 22.7g (160mmol), the temperature was gradually raised to room temperature. The organic layer was extracted by adding 300 ml of EA and 300 ml of H ₂ O, and then distilled. Column was performed to obtain 9.4 g (64% yield) of Intermediate-7.

Intermediate-7 MS (FAB): 230 (M ⁺ )

<Synthesis of Intermediate-8>

After dissolving 9.4g (40.8mmol) of Intermediate-7 in 100ml of MC, 14.35g (89.8mmol) of bromine was slowly added. After 6 hours, the completion of the reaction was confirmed, and MC was distilled and columned. 3.6 g (23% yield) of Intermediate-8 was obtained.

Intermediate-8 MS (FAB): 388 (M ⁺ )

<Synthesis of Intermediate-9>

Intermediate-6 100g (277.7mmol) and phenylboronic acid 74.5g (611.0mmol) were dissolved in Toluene 600ml and Ethanol 60ml. After adding 611 ml of 2M K ₂ CO ₃ and 16.04 g (13.9 mmol) of Pd(PPh ₃ ) ₄ , the mixture was refluxed for 12 hours. After completion of the reaction, the toluene layer was extracted and filtered through silica. Recrystallization from n-hexane/MC yielded 64 g (65% yield) of Intermediate-9.

Intermediate-9 MS (FAB): 354 (M ⁺ )

<Synthesis of Intermediate-10>

After dissolving 64g (180.57mmol) of Intermediate-9 in 1000ml of MC, 63.5g (397.25mmol) of Bromine was slowly added. After 6 hours, the completion of the reaction was confirmed, and MC was distilled and columned. 66.6 g (72% yield) of Intermediate-10 was obtained.

Intermediate-10 MS (FAB): 512 (M ⁺ )

<Synthesis of Intermediate-11>

After dissolving 100g (494.4mmol) of pyrene in 1000ml of MC, 158g (988.8mmol) of bromine was slowly added. After 6 hours, the completion of the reaction was confirmed, and MC was distilled and columned. 71.2 g (40% yield) of Intermediate-11 was obtained.

Intermediate-11 MS (FAB): 360 (M ⁺ )

<Synthesis of Intermediate-12>

After dissolving 100 g (434.2 mmol) of Intermediate-7 in 1000 ml of MC, 138.8 g (868.4 mmol) of Bromine was slowly added. After 6 hours, the completion of the reaction was confirmed, and MC was distilled and columned. 27.0 g (16% yield) of Intermediate-12 was obtained.

Intermediate-12 MS (FAB): 388 (M ⁺ )

<Synthesis of Intermediate-13>

After dissolving 27 g (69.6 mmol) of Intermediate-12 in 100 ml of THF, -78 degrees was maintained in an Acetone/dryice bath. After slowly dropping 61ml (153.1mmol) of 2.5M n-BuLi, the mixture was stirred for 30 minutes. After adding iodomethane 22.7g (160mmol), the temperature was gradually raised to room temperature. The organic layer was extracted by adding 300 ml of EA and 300 ml of H ₂ O, and then distilled. Column was performed to obtain 9.7 g (54% yield) of Intermediate-13.

Intermediate-13 MS (FAB): 258 (M ⁺ )

<Synthesis of Intermediate-14>

After dissolving 9.7g (37.5mmol) of Intermediate-13 in 1000ml of MC, 12.6g (78.8mmol) of Bromine was slowly added. After 6 hours, the completion of the reaction was confirmed, and MC was distilled and columned. 14.7 g (94% yield) of Intermediate-14 was obtained.

Intermediate-14 MS (FAB): 416 (M ⁺ )

<Synthesis of Intermediate-15>

After dissolving 100 g (277.8 mmol) of Intermediate-6 in 1000 ml of THF, -78 degrees was maintained in an Acetone/dryice bath. After slowly dropping 122ml (305.6mmol) of 2.5M n-BuLi, the mixture was stirred for 30 minutes. After adding iodomethane 47.3g (333.4mmol), the temperature was gradually 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, followed by distillation. Column was performed to obtain 55.7 g (68% yield) of Intermediate-15.

Intermediate-15 MS (FAB): 295 (M ⁺ )

<Synthesis of Intermediate-16>

After dissolving 55.7g (188.9mmol) of Intermediate-15 in 500ml of THF, 2.58g (3.8mmol) of NiCl ₂ dppf was added. Cyclohexylmagnesium chloride (1M) 190ml was slowly added at room temperature. After stirring at room temperature for 6 hours and completing the reaction, 500 ml of H2O was slowly added to quench. THF was distilled off and extracted by adding 500 ml of MC. Column was performed to obtain 25.9 g (46% yield) of Intermediate-16.

Intermediate-16 MS (FAB): 298 (M ⁺ )

<Synthesis of Intermediate-17>

After dissolving 25.9g (86.9mmol) of Intermediate-16 in 500ml of MC, 30.6g (191.2mmol) of bromine was slowly added. After 6 hours, the completion of the reaction was confirmed, and MC was distilled and columned. 10.3 g (26% yield) of Intermediate-17 was obtained.

Intermediate-17 MS (FAB): 456 (M ⁺ )

<Synthesis of Intermediate-18>

After dissolving 100g (404.7mmol) of 4-bromodibenzofuran and 54.7g (404.7mmol) of 4-isopropylaniline in 500ml of Toluene, 58.3g (607.1mmol) of sodium tert-butoxide was added. After adding 1.82 g (8.1 mmol) of palladium acetate and 6.55 g (16.2 mmol) of tri-tert-butylphosphine (50% in toluene), it was refluxed for 3 hours. After completion of the reaction, the mixture was cooled to room temperature, and after adding 500 ml of water, the organic layer was extracted. Recrystallization from N-hexane/MC yielded 122 g (63% yield) of Intermediate-18.

Intermediate-18 MS (FAB): 301 (M ⁺ )

<Synthesis of Intermediate-19>

After dissolving 100 g (739.6 mmol) of 4-isopropylaniline in 1 L of DMF, it was maintained at -20 degrees using an ice salt bath. After slowly adding 98.8 g (739.6 mmol) of NCS, the temperature was gradually raised to room temperature. After completion of the reaction, EA layer was extracted by adding 2L of EA and 2L of water, and distilled. column to obtain 41.4 g (33% yield) of Intermediate-19.

Intermediate-19 MS (FAB): 169 (M ⁺ )

<Synthesis of Intermediate-20>

After dissolving 60.3 g (244 mmol) of 4-bromodibenzofuran and 41.4 g (244 mmol) of Intermediate-19 in 600 ml of Toluene, 117.2 g (1220 mmol) of sodium tert-butoxide was added. After adding Palladium acetate 1.64g (7.32mmol) and t-Bu ₃ PHBF ₄ 2.12g (7.32mmol), it was refluxed for 6 hours. After completion of the reaction, the mixture was cooled to room temperature, and an organic layer was extracted by adding 1 L of EA and 1 L of water. After column, it was recrystallized with n-hexane/MC to obtain 59 g (72% yield) of Intermediate-20.

Intermediate-20 MS (FAB): 335 (M ⁺ )

<Synthesis of Intermediate-21>

After dissolving 59g (175.7mmol) of Intermediate-20 in 600ml of DMA, 33.8g (351.4mmol) of sodium tert-butoxide was added. After adding Palladium acetate 1.18g (5.27mmol) and t-Bu ₃ PHBF ₄ 1.53g (5.27mmol), it was refluxed for 6 hours. After completion of the reaction, the mixture was cooled to room temperature, and EA layer was extracted after adding 500ml of EA and 1L of water. After column, it was recrystallized with n-hexane/MC to obtain 30.5 g (58% yield) of Intermediate-21.

Intermediate-21 MS (FAB): 299 (M ⁺ )

<Synthesis of Intermediate-22>

After adding 100 g (306.8 mmol) of 4,6-dibromodibenzofuran to a 2L high-pressure reactor, 1200 ml of PEG 300 and 400 ml of ammonium hydroxide (30% aq) were added. After adding 584 mg (3.07 mmol) of Copper(I) iodide, the mixture was reacted at 130 degrees for 24 hours. After completion of the reaction, the mixture was cooled to room temperature, and an organic layer was extracted by adding 500 ml of EA and 500 ml of water. After silica filter, it was recrystallized with n-hexane/MC to obtain 57.8 g (95% yield) of Intermediate-22.

Intermediate-22 MS (FAB): 198 (M ⁺ )

<Synthesis of Intermediate-23>

After dissolving 57.8 g (291.6 mmol) of Intermediate-22 in 600 ml of DMF, it was maintained at -20 degrees using an ice-salt bath. After slowly adding 103.8 g (583.2 mmol) of NBS, the temperature was gradually raised to room temperature. After completion of the reaction, 1 L of EA and 1 L of water were added, and the organic layer was extracted. After column, it was recrystallized with n-hexane/MC to obtain 84.1 g (81% yield) of Intermediate-23.

Intermediate-23 MS (FAB): 356 (M ⁺ )

<Synthesis of Intermediate-24>

After adding 84.1 g (236.2 mmol) of Intermediate-23 to 1 L of ethanol, 100 ml of H ₂ SO ₄ was slowly added. 48.9 g (708.6 mmol) of NaNO ₂ was added slowly. After 2 hours of reflux, the completion of the reaction was confirmed and cooled to room temperature. After adding 1 L of EA and 2 L of water, the organic layer was extracted. Column with N-hexane to obtain 24.6 g (32% yield) of Intermediate-24.

Intermediate-24 MS (FAB): 325 (M ⁺ )

<Synthesis of Intermediate-25>

After dissolving 24.6g (75.6mmol) of 1,9-dibromodibenzofuran and 10.2g (75.6mmol) of 4-isopropylaniline in 300ml of toluene, 36.3g (378mmol) of sodium tert-butoxide was added. After adding 510 mg (2.27 mmol) of Palladium acetate and 660 mg (2.27 mmol) of t-Bu3PHBF4, it was refluxed for 3 hours. After completion of the reaction, the mixture was cooled to room temperature, and an organic layer was extracted by adding 1 L of EA and 1 L of water. After column, it was recrystallized with n-hexane/MC to obtain 16.1 g (56% yield) of Intermediate-25.

Intermediate-25 MS (FAB): 380 (M ⁺ )

<Synthesis of Intermediate-26>

After dissolving 16.1g (42.3mmol) of Intermediate-25 in 300ml of DMA, 8.1g (84.6mmol) of sodium tert-butoxide was added. After adding 285mg (1.27mmol) of Palladium acetate and 370mg (1.27mmol) of t-Bu3PHBF4, it was refluxed for 6 hours. After completion of the reaction, the mixture was cooled to room temperature, 300 ml of EA and 500 ml of water were added, and the EA layer was extracted. After column, it was recrystallized with n-hexane/MC to obtain 5.45 g (43% yield) of Intermediate-26.

Intermediate-26 MS (FAB): 299 (M ⁺ )

<Synthesis of Intermediate-27>

100g (404.7mmol) of 3-bromodibenzofuran and 74g (607.1mmol) of phenylboronic acid were dissolved in 600ml of Toluene and 60ml of Ethanol. After adding 607 ml of 2M K ₂ CO ₃ and 23.4 g (20.2 mmol) of Pd(PPh ₃ ) ₄ , the mixture was refluxed for 12 hours. After completion of the reaction, the toluene layer was extracted and filtered through silica. Recrystallization from n-hexane/MC yielded 83 g (84% yield) of Intermediate-27.

Intermediate-27 MS (FAB): 244 (M ⁺ )

<Synthesis of Intermediate-28>

After dissolving 83 g (340 mmol) of Intermediate-27 in 500 ml of THF, -78 degrees was maintained 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, -78 degrees was maintained using an acetone/dryice bath, and 38.9 g (374 mmol) of trimethylborate was added. After removing the bath, the temperature was raised to room temperature to terminate the reaction. After extracting the organic layer by adding 1L of EA and 1L of water, it was distilled and columned to obtain 38.2g (39% yield) of Intermediate-28.

Intermediate-28 MS (FAB): 288 (M ⁺ )

<Synthesis of Intermediate-29>

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 columnized to obtain 139.4 g (88% yield) of Intermediate-29.

Intermediate-29 MS (FAB): 214 (M ⁺ )

<Synthesis of Intermediate-30>

After dissolving 38.2g (132.6mmol) of Intermediate-28 and 28.4g (132.6mmol) of Intermediate-29 in 300ml of MC, 482mg (2.65mmol) of Cupper acetate was added and reacted for 24 hours while blowing air. After completion of the reaction, column was performed to obtain 52 g (86% yield) of Intermediate-30.

Intermediate-30 MS (FAB): 456 (M ⁺ )

<Synthesis of Intermediate-31>

After dissolving 52g (114mmol) of Intermediate-30 in 500ml of DMA, 21.9g (228mmol) of sodium tert-butoxide was added. After adding 768mg (3.42mmol) of Palladium acetate and 992mg (3.42mmol) of t-Bu ₃ PHBF ₄ , it was refluxed for 6 hours. After completion of the reaction, the mixture was cooled to room temperature, and 1000 ml of EA and 1000 ml of water were added thereto, and the EA layer was extracted. After column, it was recrystallized with n-hexane/MC to obtain 22.3 g (52% yield) of Intermediate-31.

Intermediate-31 MS (FAB): 375 (M ⁺ )

<Synthesis of Intermediate-32>

After dissolving 100 g (306.8 mmol) of 1,9-dibromodibenzofuran and 233.7 g (920.3 mmol) of B2pin2 in 1 L of 1,4-dioxane, 150.5 g (1534 mmol) of potassium acetate was added. After adding 6.89 g (30.68 mmol) of Palladium acetate and 17 g (30.68 mmol) of dppf, it was refluxed for 12 hours. After completion of the reaction, the solvent was distilled off and column was performed to obtain 56.7 g (44% yield) of Intermediate-32.

Intermediate-32 MS (FAB): 420 (M ⁺ )

<Synthesis of Intermediate-33>

After dissolving 100g (739.6mmol) of 4-isopropylaniline in 1L of DMF, 166.4g (739.6mmol) of NIS was slowly added at 0°C. 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 columnized to obtain 166.1 g (86% yield) of Intermediate-33.

Intermediate-33 MS (FAB): 261 (M ⁺ )

<Synthesis of Intermediate-34>

100g (383mmol) of Intermediate-33 and 76.9g (383mmol) of (2-bromophenyl)boronic acid were dissolved in 600ml of Toluene and 60ml of Ethanol. After adding 383 ml of 2M K2CO3 and 22.1 g (19.15 mmol) of Pd(PPh ₃ ) ₄ , it was refluxed for 12 hours. After completion of the reaction, the toluene layer was extracted and filtered through silica. It was recrystallized from n-hexane/MC to obtain 84.5 g (76% yield) of Intermediate-34.

Intermediate-34 MS (FAB): 290 (M ⁺ )

<Synthesis of Intermediate-35>

56.7g (135mmol) of Intermediate-32 and 39.2g (135mmol) of Intermediate-34 were dissolved in 500ml of Toluene and 50ml of Ethanol. After adding 135 ml of 2M K2CO3 and 7.8 g (6.75 mmol) of Pd(PPh ₃ ) ₄ , it was refluxed for 12 hours. After completion of the reaction, the toluene layer was extracted and columned to obtain 24.5 g (36% yield) of Intermediate-35.

Intermediate-35 MS (FAB): 503 (M ⁺ )

<Synthesis of Intermediate-36>

After dissolving 24.5 g (48.6 mmol) of Intermediate-35 in 300 ml of MC, 177 mg (0.97 mmol) of Cupper acetate was added and reacted for 24 hours while blowing air. After completion of the reaction, column was performed to obtain 15.3 g (84% yield) of Intermediate-36.

Intermediate-36 MS (FAB): 375 (M ⁺ )

<Synthesis of Intermediate-37>

After dissolving 100 g (404.7 mmol) of 3-bromodibenzofuran in 1000 ml of THF, -78 degrees was maintained using an acetone/dryice bath. After slowly adding 445ml (445mmol) of 1.0M LDA, the mixture was stirred for 1 hour. While maintaining -78 degrees, 147.6 g (445.2 mmol) of CBr ₄ was added. The reaction was terminated by removing the bath, raising the temperature to room temperature, and stirring for 1 hour. After extracting the organic layer by adding 1L of EA and 1L of water, it was distilled and columned to obtain 83.1 g (63% yield) of Intermediate-37.

Intermediate-37 MS (FAB): 325 (M ⁺ )

<Synthesis of Intermediate-38>

After dissolving 83.1 g (255 mmol) of Intermediate-37 and 54.6 g (255 mmol) of Intermediate-29 in 300 ml of NMP, 166.2 g (510 mmol) of Cesium carbonate was added. After confirming the completion of the reaction by stirring at 180 degrees for 3 hours, the mixture was cooled to room temperature. The organic layer was extracted by adding 300 ml of EA and 300 ml of water. Column was performed to obtain 69.1 g (59% yield) of Intermediate-38.

Intermediate-38 MS (FAB): 459 (M ⁺ )

<Synthesis of Intermediate-39>

After dissolving 95.7g (306.8mmol) of 2,2'-dibromo-1,1'-biphenyl and 233.7g (920.3mmol) of B2pin2 in 1L of 1,4-dioxane, 150.5g (1534mmol) of potassium acetate was added. After adding 6.89 g (30.68 mmol) of Palladium acetate and 17 g (30.68 mmol) of dppf, it was refluxed for 12 hours. After completion of the reaction, the solvent was distilled off and column was performed to obtain 51.1 g (41% yield) of Intermediate-39.

Intermediate-39 MS (FAB): 406 (M ⁺ )

<Synthesis of Intermediate-40>

69g (150.3mmol) of Intermediate-38 and 61g (150.3mmol) of Intermediate-39 were dissolved in 1000ml of Toluene and 100ml of Ethanol. After adding 300 ml of 2M K ₂ CO ₃ and 17.4 g (15.03 mmol) of Pd(PPh ₃ ) ₄ , the mixture was refluxed for 12 hours. After completion of the reaction, the toluene layer was extracted and columned to obtain 23.8 g (35% yield) of Intermediate-40.

Intermediate-40 MS (FAB): 451 (M ⁺ )

<Synthesis of Intermediate-41>

After dissolving 20 g (51.5 mmol) of Intermediate-8 and 15.4 g (51.5 mmol) of Intermediate-26 in 500 ml of toluene, 19.8 g (206.1 mmol) of sodium tert-butoxide was added. After adding 231 mg (1.03 mmol) of Palladium acetate and 417 mg (2.06 mmol) of Tri-tert-butylphosphine, it was refluxed for 12 hours. After completion of the reaction, the mixture was cooled to room temperature and an organic layer was extracted by adding 500 ml of water. After column, it was recrystallized with n-hexane/MC to obtain 13.4 g (43% yield) of Intermediate-41.

Intermediate-41 MS (FAB): 606 (M ⁺ )

<Synthesis of Intermediate-42>

Dissolve 200g (386.2mmol) of 1,3,6,8-tetrabromopyrene and 129.2g (772.5mmol) of carbazole in 500ml of nitrobenzene. After adding 7.36g (115.9mmol) of copper powder and 160.1g (1158.7mmol) of potassium carbonate, reflux for 6 hours. After completion of the reaction, cool to room temperature and distill nitrobenzene. After washing with MC and column after celite filter, 34.7 g (13% yield) of Intermediate-42 was obtained.

Intermediate-42 MS (FAB): 690 (M ⁺ )

<Synthesis of Intermediate-43>

Add 3.01 g (10 mmol) of Intermediate-18, 114 mg (0.50 mmol) of Pt/C, 2 mL of tritiated water (DTO), 3.0 mL of 2-pentanol, and 60 mL of decahydronaphthalene. After stirring at 140 ° C. for 12 hours in a high-pressure reactor, it is cooled to room temperature. After adding dichloromethane, the layers are separated to obtain an organic layer. After drying with MgSO4, filter. After concentrating the filtrate, isopropanol is added. The resulting solid was filtered and columned to obtain 2.19 g (72%, tritium conversion 5%) of Intermediate-43.

Intermediate-43 MS (FAB): 304 (M+)

<Synthesis of Intermediate-44>

Add 2.99g (10mmol) of Intermediate-21, 114mg (0.50mmol) of Pt/C, 2mL of tritiated water (DTO), 3.0mL of 2-pentanol, and 60mL of decahydronaphthalene. After stirring at 140 ° C. for 12 hours in a high-pressure reactor, it is cooled to room temperature. After adding dichloromethane, the layers are separated to obtain an organic layer. After drying with MgSO4, filter. After concentrating the filtrate, isopropanol is added. The resulting solid was filtered and columned to obtain 2.27 g (75%, tritium conversion 5.8%) of Intermediate-44.

Intermediate-44 MS (FAB): 302 (M+)

<Synthesis of Intermediate-45>

3.88g (10mmol) of intermediate-8, 668mg (2.4mmol) of silver carbonate, 1.63g (6.1mmol) of cyclohexyldiphenylphosphine, 1.67g (12mmol) of potassium carbonate, 5.34g (0.24mol) of tritiated water (T ₂ O) and 10mL of toluene were added to a 100ml three-necked round bottom flask. After stirring at 120°C for 12 hours, cool to room temperature. A saturated aqueous ammonia chloride solution was added to terminate the reaction, and after adding water and dichloromethane, the layers were separated to obtain an organic layer. After drying with Na ₂ SO ₄ , it is filtered. After concentrating the filtrate, isopropanol is added. The resulting solid was filtered and columned to obtain 2.69 g of Intermediate-45 (68%, tritium conversion 33%).

Intermediate-45 MS (FAB): 396 (M ⁺ )

Synthesis of Intermediate-46

After injecting 2.21g (10mmol) of Intermediate-2 and 1.35g (10mmol) of 4-isopropylaniline under nitrogen and dissolving them in 40ml of toluene, 0.05g (0.2mmol) of Pd(OAc) ₂ , 0.4ml (0.4mmol) of 1M t-Bu ₃ P, and 2.88g (30mmol) of t-BuONa were added, respectively. It was then refluxed for 6 hours.

After the reaction was completed, the temperature of the reactant was cooled to room temperature, extracted with 150 ml of toluene and 150 ml of H ₂ O, and a small amount of water in the organic layer was removed with anhydrous MgSO ₄ . After filtration under reduced pressure, the organic solvent was concentrated and the resulting compound was columned with Hex: EA = 5: 1 to obtain 2.45 g (89%) of Intermediate-46.

Intermediate-46 MS (FAB): 275 (M ⁺ )

Synthesis of Intermediate-47

After injecting 2.09g (10mmol) of Intermediate-4 and 1.35g (10mmol) of 4-isopropylaniline under nitrogen and dissolving them in 40ml of toluene, 0.05g (0.2mmol) of Pd(OAc) _2, 0.4ml (0.4mmol) of 1M t-Bu ₃ P, and 2.88g (30mmol) of t-BuONa were added, respectively. It was then refluxed for 6 hours.

After the reaction was completed, the temperature of the reactant was cooled to room temperature, extracted with 150 ml of toluene and 150 ml of H ₂ O, and a small amount of water in the organic layer was removed with anhydrous MgSO ₄ . After filtration under reduced pressure, the organic solvent was concentrated. The resulting compound was columned with Hex: EA = 5: 1 to obtain 2.29 g (87%) of Intermediate-47.

Intermediate-47 MS (FAB): 263 (M ⁺ )

<Synthesis of Intermediate-48>

Add 1.69g (10mmol) of diphenylamine, 98mg (0.50mmol) of Pt/C, 5mL of tritiated water (T ₂ O), 3.0mL of isopropanol, and 60mL of cyclonucleic acid. After stirring at 140 ° C. for 36 hours in a high-pressure reactor, it is cooled to room temperature. After adding dichloromethane, the layers are separated to obtain an organic layer. After drying with MgSO ₄ , it is filtered. After concentrating the filtrate, isopropanol is added. The resulting solid was filtered and columned to obtain 1.43 g of Intermediate-48 (75%, 93% conversion of hydrogen to tritium).

Intermediate-48 MS (FAB): 191 (M ⁺ )

<Synthesis of Intermediate-49>

113.1 g (591 mmol) of intermediate-48, 167.2 g (591 mmol) of 1-bromo-3-iodobenzene, 11.3 g (177 mmol) of Copper, 245.0 g (1.77 mol) of copper, 245.0 g (1.77 mol) of copper, and 1 L of nitrobenzene were added to a 2L three-necked round bottom flask and heated to reflux for 12 hours. After the reaction was completed, washed with EA, filtered with celite, and concentrated. After concentrating the organic solvent, 134.3 g (66%) of Intermediate-49 was obtained by column.

Intermediate-49 MS (FAB): 344 (M ⁺ )

<Synthesis of Intermediate-50>

134.3g (390mmol) of Intermediate-49 and 72.6g (780mmol) of aniline were added to a 3L 3-necked round bottom flask, and then dissolved in 1.5L of Toluene. After adding 112.4 g (1.17 mol) of sodium tert-butoxide, 1.75 g (8 mmol) of palladium acetate, and 6.31 g (16 mmol) of tri-tert-butyl phosphine (50% in toluene), the mixture was heated to reflux. After confirming the completion of the reaction, the mixture was cooled to room temperature, and an organic layer was extracted by adding 1 L of EA and 1 L of water. The organic layer was concentrated and recrystallized after column to obtain 118.2 g (85%) of Intermediate-50.

Intermediate-50 MS (FAB): 336 (M ⁺ )

<Synthesis of Intermediate-51>

120.9g (339mmol) of intermediate-50, 115.1g (407mmol) of 1-bromo-3-iodobenzene, 6.47g (102mmol) of Copper, 140.7g (1.02mol) of potassium carbonate, and 1L of nitrobenzene were added to a 2L three-necked round bottom flask and heated to reflux for 12 hours. After completion of the reaction, washed with EA, filtered with celite, and concentrated. After concentrating the organic solvent, 124.8 g (72%) of Intermediate-51 was obtained by column.

Intermediate-51 MS (FAB): 511 (M ⁺ )

<Synthesis of Intermediate-52>

128.4g (251mmol) of Intermediate-51 and 85.0g (502mmol) of [1,1'-biphenyl] -3-amine were added to a 3L 3-necked round bottom flask and dissolved in 1.2L of THF. After adding 72.4 g (753 mmol) of sodium tert-butoxide, 1.13 g (5 mmol) of palladium acetate, and 4.06 g (10 mmol) of tri-tert-butyl phosphine (50% in toluene), the mixture was heated to reflux. After confirming the completion of the reaction, the mixture was cooled to room temperature, and an organic layer was extracted by adding 1 L of EA and 1 L of water. The organic layer was concentrated and recrystallized after column to obtain 122.0 g (81%) of Intermediate-52.

Intermediate-52 MS (FAB): 599 (M ⁺ )

<Synthesis of Intermediate-53>

100g (591mmol) of [1,1'-biphenyl]-4-amine was added to a 2L 3-necked round bottom flask, dissolved in 1L of DMF, and maintained at 0 degrees by installing an icebath. While maintaining 0 degrees, 133.0 g (591 mmol) of N-iodosuccinimide was slowly added. After completion of the reaction, DMF was concentrated, and an organic layer was extracted by adding 1 L of EA and 1 L of water. After concentrating the organic layer, column and recrystallization were performed to obtain 157.0 g (90%) of Intermediate-53.

Intermediate-53 MS (FAB): 295 (M ⁺ )

<Synthesis of Intermediate-54>

After putting 157.0 g (532 mmol) of Intermediate-53 in a 3 L 3-necked round bottom flask, it was dissolved in 1.5 L of acetonitrile. After adding 142.5g (638mmol) of Copper(II) bromide, slowly add 91.4g (798mmol) of t-Butyl nitrite while heating to 60 degrees. When the reaction was completed after heating under reflux for 1 hour, the mixture was cooled to room temperature and an organic layer was extracted by adding 1 L of EA and 1 L of water. The organic layer was concentrated and then columnarized to obtain 116.5 g (61%) of Intermediate-54.

Intermediate-54 MS (FAB): 359 (M ⁺ )

<Synthesis of Intermediate-55>

120.6g (201mmol) of Intermediate-52 and 86.5g (241mmol) of Intermediate-54 were added to a 3L three-necked round bottom flask, and then dissolved in 1.2L of Toluene. After adding 57.9g (603mmol) of sodium tert-butoxide, 900mg (4mmol) of Palladium acetate, and 3.25g (8mmol) of tri-tert-butyl phosphine (50% in toluene), the mixture was heated to reflux. After confirming the completion of the reaction, the mixture was cooled to room temperature, and an organic layer was extracted by adding 1 L of EA and 1 L of water. The organic layer was concentrated and recrystallized after column to obtain 105.2 g (63%) of Intermediate-55.

Intermediate-55 MS (FAB): 830 (M ⁺ )

<Synthesis of Intermediate-56>

After dissolving 100 g (670 mmol) of 4-(tert-butyl)aniline and 212.6 g (670 mmol) of 4-bromo-1-chloro-2-iodobenzene in 1.5 L of Toluene in a 3L three-necked round bottom flask, 322 g (3.35 mol) of sodium tert-butoxide was added. After adding 3.01 g (13.4 mmol) of Palladium acetate and 7.78 g (26.8 mmol) of Tri-tert-butylphosphonium tetrafluoroborate, the mixture was heated under reflux for 5 hours. After confirming the completion of the reaction, it was cooled to room temperature, 1.5 L of water was added, and the organic layer was extracted. The water layer was further washed with 1 L of EA. After concentrating the organic layer and recrystallizing after column, 145.2 g (64%) of Intermediate-56 was obtained.

Intermediate-56 MS (FAB): 338 (M ⁺ )

<Synthesis of Intermediate-57>

After dissolving 145g (429mmol) of Intermediate-56 in 1.5L of Dimethylacetamide in a 3L three-necked round bottom flask, 419g (1.286mol) of Cesium carbonate was added. After adding 1.93 g (9 mmol) of Palladium acetate and 4.98 g (17 mmol) of Tri-tert-butylphosphonium tetrafluoroborate, the mixture was heated under reflux for 5 hours. After confirming the completion of the reaction, the mixture was cooled to room temperature, and an organic layer was extracted by adding 2 L of EA and 2 L of water. The organic layer was concentrated and recrystallized after column to obtain 72.6 g (56%) of Intermediate-57.

Intermediate-57 MS (FAB): 302 (M ⁺ )

<Synthesis of Intermediate-58>

After adding 72.6 g (240 mmol) of 2L 3-hole round bottom intermediate-57, 700 ml of DMF was added and dissolved. After dissolving 28.8g (720mmol) of NaOH in 100ml of water, it was added and stirred for 30 minutes. 49.3 g (288 mmol) of benzyl bromide was added slowly through a dropping funnel. After 1 hour, when the reaction was complete, 1 L of EA and 1 L of water were added, and the organic layer was extracted. The organic layer was concentrated and then columnarized to obtain 66.8 g (92%) of Intermediate-58.

Intermediate-58 MS (FAB): 392 (M ⁺ )

<Synthesis of Intermediate-59>

66.8g (170mmol) of Intermediate-58 and 58.5g (187mmol) of bis(4-(tert-butyl)phenyl)amine were added to a 2L 3-necked round bottom flask and dissolved in 1L of Toluene. After adding 49.1g (511mmol) of sodium tert-butoxide, 760mg (3mmol) of Palladium acetate, and 2.75g (7mmol) of tri-tert-butyl phosphine (50% in toluene), the mixture was heated to reflux. After confirming the completion of the reaction, the mixture was cooled to room temperature, and an organic layer was extracted by adding 1 L of EA and 1 L of water. The organic layer was concentrated and recrystallized after column to obtain 73.7 g (73%) of Intermediate-59.

Intermediate-59 MS (FAB): 592 (M ⁺ )

<Synthesis of Intermediate-60>

73.7g (124mmol) of Intermediate-59 was added to a 2L 3-necked round bottom flask and dissolved in 700ml of THF. 6.6g (6mmol) of Palladium on activated carbon (10%) was added and stirred while bubbling hydrogen. After confirming the completion of the reaction, it was bubbling with nitrogen for 1 hour and filtered with celite. After concentrating THF, it was recrystallized to obtain 59.3 g (95%) of Intermediate-60.

Intermediate-60 MS (FAB): 502 (M ⁺ )

<Synthesis of Intermediate-61>

A mechanical stirrer was installed in a 2L 3-necked round bottom flask, 100g (438mmol) of 2-bromo-4-(tert-butyl)aniline was added, and 200ml of water and 200ml of conc.HCl were added. It was maintained at minus 5 degrees using an ice-salt bath, and 60.5 g (877 mmol) of sodium nitrite dissolved in 100 ml of water was slowly added. After 30 minutes, 145.5 g (877 mmol) of potassium iodide dissolved in 100 ml of water was slowly added. The bath was removed, and the temperature was slowly raised to room temperature, followed by stirring for 2 hours. After confirming the completion of the reaction, 500 ml of water was added and stirred, followed by filtration. After column recrystallization, 62.4 g (41%) of Intermediate-61 was obtained.

Intermediate-61 MS (FAB): 339 (M ⁺ )

<Synthesis of Intermediate-62>

100ml 3-ball round floor flasks intermediate-61 3.39g (10 mmol), silver carbonate 668 mg (2.4 mmol), cyclohexylphenyl phosph 1.63g (6.1 mmol), potassium carbonate 1.67g (12mmol), triple hydrogen (T ₂ O) 5.29g L) Inject 10 ml of toluene. After stirring at 120°C for 24 hours, cool to room temperature. A saturated aqueous ammonia chloride solution was added to terminate the reaction, and after adding water and dichloromethane, the layers were separated to obtain an organic layer. After drying with Na ₂ SO ₄ , it is filtered. After concentrating the filtrate, isopropanol is added. The resulting solid was filtered and columned to obtain 2.55 g of Intermediate-62 (74%, 19% conversion of hydrogen to tritium).

Intermediate-62 MS (FAB): 345 (M ⁺ )

<Synthesis of Intermediate-63>

59.3g (118mmol) of Intermediate-60 and 49.0g (142mmol) of Intermediate-62 were added to a 1L three-necked round bottom flask, and then 600ml of xylene was added. After adding 4.5g (24mmol) of copper(I) iodide, 2.84g (24mmol) of ethylene diamine, and 32.6g (236mmol) of potassium carbonate, the mixture was heated to reflux. After the reaction was completed, washed with EA, filtered with celite, and concentrated. After column recrystallization, 64.9 g (77%) of Intermediate-63 was obtained.

Intermediate-63 MS (FAB): 719 (M ⁺ )

<Synthesis of Intermediate-64>

After putting 100g (405mmol) of 2-bromodibenzo[b,d]furan, 200ml of ammonia (25-30%), and 400ml of PEG300 into a 1L high-pressure reactor, 7.7g (40mmol) of copper (I) iodide was added and stirred at 180 degrees overnight. After cooling to room temperature, 1 L of EA and 1 L of water were added to the reaction mixture to extract an organic layer. The organic layer was concentrated and recrystallized to obtain 676.5 g of Intermediate-64 in a yield of 91%.

Intermediate-64 MS (FAB): 183 (M ⁺ )

<Synthesis of Intermediate-65>

71.92g (393mmol) of Intermediate-64 was added to a 2L 3-necked round bottom flask, dissolved in 700ml of DMF, and then installed in an icebath to maintain 0 degrees. 88.3g (393mmol) of N-iodosuccinimide was slowly added while maintaining 0 degree. After completion of the reaction, DMF was concentrated, and an organic layer was extracted by adding 500 ml of EA and 500 ml of water. After concentrating the organic layer, column and recrystallization were performed to obtain 51.0 g (42%) of Intermediate-65.

Intermediate-65 MS (FAB): 309 (M ⁺ )

<Synthesis of Intermediate-66>

After adding 51.0 g (165 mmol) of Intermediate-65 to a 1L 3-necked round bottom flask, it was dissolved in 500 ml of acetonitrile. After adding 44.2g (198mmol) of Copper(II) bromide, slowly add 28.3g (247mmol) of t-Butyl nitrite while heating to 60 degrees. When the reaction was completed after heating under reflux for 1 hour, the mixture was cooled to room temperature and an organic layer was extracted by adding 1 L of EA and 1 L of water. The organic layer was concentrated and then columnarized to obtain 44.9 g (73%) of Intermediate-66.

Intermediate-66 MS (FAB): 372 (M ⁺ )

<Synthesis of Intermediate-67>

100ml 3-ball round floor flasks intermediate-66 3.73g (10 mmol), silver carbonate 668 mg (2.4 mmol), cyclohexylphenyl phosph 1.63g (6.1mmol), potassium carbonate 1.67g (12mmol), triple hydrogen (T ₂ O) 5.29g L) Inject 10 ml of toluene. After stirring at 120°C for 24 hours, cool to room temperature. A saturated aqueous ammonia chloride solution was added to terminate the reaction, and after adding water and dichloromethane, the layers were separated to obtain an organic layer. After drying with Na ₂ SO ₄ , it is filtered. After concentrating the filtrate, isopropanol is added. The resulting solid was filtered and columned to obtain 2.75 g of Intermediate-67 (73%, 31% conversion of hydrogen to tritium).

Intermediate-67 MS (FAB): 377 (M ⁺ )

<Synthesis of Intermediate-68>

45.2g (120mmol) of Intermediate-67, 33.8g (120mmol) of bis(4-(tert-butyl)phenyl)amine, 2.3g (36mmol) of Copper, 49.9g (361mmol) of copper, 49.9g (361mmol) of copper, and 500ml of nitrobenzene were added to a 1L three-necked round bottom flask and heated to reflux for 12 hours. After completion of the reaction, washed with EA, filtered with celite, and concentrated. After concentrating the organic solvent, column was performed to obtain 35.7 g (56%) of Intermediate-68.

Intermediate-68 MS (FAB): 530 (M ⁺ )

<Synthesis of Intermediate-69>

72.0 g (393 mmol) of Intermediate-64 was added to a 2L 3-neck round bottom flask, dissolved in 700 ml of DMF, and then installed in an ice bath to maintain 0 degrees. 88.3g (393mmol) of N-iodosuccinimide was slowly added while maintaining 0 degree. After completion of the reaction, DMF was concentrated, and an organic layer was extracted by adding 500 ml of EA and 500 ml of water. After concentrating the organic layer, column and recrystallization were performed to obtain 43.7 g (36%) of Intermediate-69.

Intermediate-69 MS (FAB): 309 (M ⁺ )

<Synthesis of Intermediate-70>

After putting 43.7g (141mmol) of Intermediate-69 in a 1L 3-necked round bottom flask, it was dissolved in 500ml of acetonitrile. After adding 37.9g (170mmol) of Copper(II) bromide, slowly add 24.3g (212mmol) of t-Butyl nitrite while heating to 60 degrees. When the reaction was completed after heating under reflux for 1 hour, the mixture was cooled to room temperature and an organic layer was extracted by adding 1 L of EA and 1 L of water. The organic layer was concentrated and then columnarized to obtain 39.5 g (75%) of Intermediate-70.

Intermediate-70 MS (FAB): 372 (M ⁺ )

<Synthesis of Intermediate-71>

100ml 3-ball round floor flasks intermediate-70 3.72g (10 mmol), silver carbonate 668 mg (2.4 mmol), cyclohexylphenyl phosph 1.63g (6.1 mmol), potassium carbonate 1.67g (12mmol), triple hydrogen (T ₂ O) 5.34g L) Inject 10 ml of toluene. After stirring at 120°C for 24 hours, cool to room temperature. A saturated aqueous ammonia chloride solution was added to terminate the reaction, and after adding water and dichloromethane, the layers were separated to obtain an organic layer. After drying with Na ₂ SO ₄ , it is filtered. After concentrating the filtrate, isopropanol is added. The resulting solid was filtered and columned to obtain 2.68 g of Intermediate-71 (71%, 29% conversion of hydrogen to tritium).

Intermediate-71 MS (FAB): 377 (M ⁺ )

<Synthesis of Intermediate-72>

40.0g (106mmol) of Intermediate-71, 29.8g (106mmol) of bis(4-(tert-butyl)phenyl)amine, 2.0g (32mmol) of Copper, 44.0g (318mmol) of copper, 44.0g (318mmol) of copper, and 500ml of nitrobenzene were added to a 1L three-necked round bottom flask and heated to reflux for 12 hours. After completion of the reaction, washed with EA, filtered with celite, and concentrated. After concentrating the organic solvent, 34.3 g (61%) of Intermediate-72 was obtained by column.

Intermediate-72 MS (FAB): 530 (M ⁺ )

<Synthesis of Intermediate-73>

100g (546mmol) of dibenzo[b,d]furan-4-amine was added to a 2L 3-necked round bottom flask, dissolved in 1L of DMF, and maintained at 0 degrees by installing an icebath. 122.8 g (546 mmol) of N-iodosuccinimide was slowly added while maintaining 0 degree. After completion of the reaction, DMF was concentrated, and an organic layer was extracted by adding 1 L of EA and 1 L of water. After concentrating the organic layer, column and recrystallization were performed to obtain 121.5 g (72%) of Intermediate-73.

Intermediate-73 MS (FAB): 309 (M ⁺ )

<Synthesis of Intermediate-74>

121.5g (393mmol) of Intermediate-73 was added to a 2L 3-necked round bottom flask, dissolved in 1L of DMF, and maintained at 0 degrees by installing an icebath. 69.9 g (393 mmol) of N-Bromosuccinimide was slowly added while maintaining 0 degree. After completion of the reaction, DMF was concentrated, and an organic layer was extracted by adding 1 L of EA and 1 L of water. The organic layer was concentrated and then recrystallized by column to obtain 134.2 g (88%) of Intermediate-74.

Intermediate-74 MS (FAB): 388 (M ⁺ )

<Synthesis of Intermediate-75>

134.2g (346mmol) of Intermediate-74 and 1.3L of ethanol were added to a 3L 3-necked round bottom flask, and 270ml of sulfuric acid was slowly added thereto. While heating under reflux, 123.1 g (692 mmol) of sodium nitrite was added slowly in portions. After completion of the addition, the mixture was heated to reflux for 3 hours and cooled to room temperature when the reaction was completed. 1.5 L of water was added, and the resulting solid was filtered and columned to obtain 80.0 g of Intermediate-75 in a yield of 62%.

Intermediate-75 MS (FAB): 372 (M ⁺ )

<Synthesis of Intermediate-76>

79.8g (214mmol) of intermediate-75, 60.2g (214mmol) of bis(4-(tert-butyl)phenyl)amine, 4.1g (64mmol) of Copper, 88.9g (643mmol) of copper, 88.9g (643mmol) of copper, and 800ml of nitrobenzene were added to a 2L three-necked round bottom flask and heated to reflux for 12 hours. After completion of the reaction, washed with EA, filtered with celite, and concentrated. After concentrating the organic solvent, 72.1 g (64%) of Intermediate-76 was obtained by column.

Intermediate-76 MS (FAB): 526 (M ⁺ )

<Synthesis of Intermediate-77>

72.1g (137mmol) of Intermediate-76, 350ml of DMF, and 58.1g (274mmol) of Copper(I) iodide were added to a 2L 3-necked round bottom flask. 321 g (1.78 mol) of sodium methoxide (30% in MeOH) was slowly added and heated to reflux. After confirming the completion of the reaction, the mixture was cooled to room temperature, and an organic layer was extracted by adding 1 L of EA and 1 L of water. The organic layer was concentrated and then columnarized to obtain 58.2 g (89%) of Intermediate-77.

Intermediate-77 MS (FAB): 477 (M ⁺ )

<Synthesis of Intermediate-78>

61.1g (128mmol) of Intermediate-77 was added to a 2L 3-necked round bottom flask and dissolved in 600ml of THF. A dryice bath was installed to maintain minus 78 degrees, and 88ml (140mmol) of n-Butyllithium (1.6M) was added dropwise. After removing the bath and raising the temperature to room temperature, the mixture was stirred for 30 minutes. A dryice bath was installed to maintain minus 78 degrees, and after adding 21.0 g (153 mmol) of isobutyl bromide dropwise, the bath was removed and the temperature was gradually raised to room temperature. After completion of the reaction, the mixture was concentrated, and an organic layer was extracted by adding 500 ml of EA and 500 ml of water. After concentration, the mixture was columnized to obtain 57.4 g (84%) of Intermediate-78.

Intermediate-78 MS (FAB): 533 (M ⁺ )

<Synthesis of Intermediate-79>

In a 1L three-necked round bottom flask, 57.1 g (107 mmol) of Intermediate-78 was dissolved in 600 ml of MC, and an ice bath was installed to maintain 0 degrees. 29.5 g (118 mmol) of boron tribromide was slowly added dropwise, and after confirming the completion of the reaction, 500 ml of water was added. The organic layer was extracted, concentrated, and recrystallized to obtain 50.1 g (90%) of Intermediate-79.

Intermediate-79 MS (FAB): 519 (M ⁺ )

<Synthesis of Intermediate-80>

49.9g (96mmol) of Intermediate-79, 33.1g (96mmol) of Intermediate-62, and 41.0g (193mmol) of Potassium phosphate tribasic were added to a 1L three-necked round bottom flask, and then 500ml of DMSO was added. After adding 3.7 g (19 mmol) of Copper(I) iodide and 6.8 g (19 mmol) of Iron(III) acetyl acetonate, the mixture was heated to 110 degrees. After completion of the reaction, the mixture was cooled to room temperature, and an organic layer was extracted and concentrated by adding 1 L of EA and 1 L of water. After column, 44.6 g (63%) of Intermediate-80 was obtained.

Intermediate-80 MS (FAB): 736 (M ⁺ )

<Synthesis of Intermediate-81>

Add 1.41g (10mmol) of 1-fluoro-2-nitrobenzene, 98mg (0.50mmol) of Pt/C, 3.0mL of isopropanol, and 60mL of cyclohexane. After stirring at 140 ° C. for 12 hours in a high-pressure reactor under T ₂ atmosphere, it is cooled to room temperature. After filtration under reduced pressure, the organic solvent was concentrated and the resulting compound was columned at Hex: EA = 5: 1 to obtain 1.27 g of Intermediate-81 (89%, 17% conversion of hydrogen to tritium).

Intermediate-81 MS (FAB): 143 (M ⁺ )

<Synthesis of Intermediate-82>

100g (598mmol) of 9H-carbazole, 92.8g (658mmol) of Intermediate-81, 584.5g (1.79mol) of Cesium carbonate, and 1L of DMF were added to a 2L three-necked round bottom flask, followed by heating under reflux. After completion of the reaction, it was cooled to room temperature and concentrated. The organic layer was extracted by adding 1L of EA and 1L of water, and concentrated after silicagel filtering. After recrystallization, 118.1 g (68%) of Intermediate-82 was obtained.

Intermediate-82 MS (FAB): 290 (M ⁺ )

<Synthesis of Intermediate-83>

117.9g (406mmol) of Intermediate-82 and 183.5g (813mmol) of Tin(II) chloride dehydrate were added to a 2L three-necked round bottom flask, and then 1L of Ethanol was added and heated to reflux. After confirming the completion of the reaction, the mixture was cooled to room temperature and concentrated. The organic layer was extracted by adding 1 L of EA and 1 L of water, and concentrated. After column recrystallization, 88.8 g (84%) of Intermediate-83 was obtained.

Intermediate-83 MS (FAB): 260 (M ⁺ )

<Synthesis of Intermediate-84>

89.0 g (342 mmol) of Intermediate-83, 880 ml of acetic acid, and 88 g of sulfuric acid were added to a 3L three-necked round bottom flask. After dissolving 47.1 g (683 mmol) of sodium nitrite in 88 ml of water, it was added dropwise and heated to reflux. After confirming the completion of the reaction, it was cooled to room temperature and acetic acid was distilled off. After extraction by adding 1 L of EA and 1 L of water, the organic layer was concentrated. After column recrystallization, 46.6 g (56%) of Intermediate-84 was obtained.

Intermediate-84 MS (FAB): 243 (M ⁺ )

<Synthesis of Intermediate-85>

46.5g (191mmol) of Intermediate-84 was added to a 1L 3-necked round bottom flask and dissolved in 500ml of MC. After maintaining 0 degree by installing an ice bath, 34.1 g (191 mmol) of N-Bromosuccinimide was slowly added. After confirming the completion of the reaction, 500 ml of water was added, and the organic layer was extracted and concentrated. After column recrystallization, 44.3 g (72%) of Intermediate-85 was obtained.

Intermediate-85 MS (FAB): 322 (M ⁺ )

<Synthesis of Intermediate-86>

100g (379mmol) of 3,5-dibromobenzaldehyde and 1L of Ethanol were added to a 2L 3-neck round bottom flask, and 35.3g (379mmol) of aniline was added while stirring. After heating to reflux and confirming the completion of the reaction, the mixture was cooled to room temperature and filtered. 116.9 g (91%) of Intermediate-86 was obtained.

Intermediate-86 MS (FAB): 339 (M ⁺ )

<Synthesis of Intermediate-87>

161.7g (477mmol) of Intermediate-86 and 74.7g (477mmol) of benzimidamide hydrochloride were added to a 2L 3-necked round bottom flask, and then 1L of EtOH was added and stirred. After slowly adding 57.2g (1.43mol) of sodium hydroxide, it was heated to reflux. After confirming the completion of the reaction, it was cooled to room temperature and recrystallized after filtration. 198.3 g (89%) of Intermediate-87 was obtained.

Intermediate-87 MS (FAB): 467 (M ⁺ )

<Synthesis of Intermediate-88>

198.5g (425mmol) of Intermediate-87 was added to a 3L 3-necked round bottom flask and dissolved in 2L of THF. A dryice bath was installed to maintain minus 78 degrees, and 271ml (433mmol) of n-Butyllithium (1.6M) was added dropwise. After 30 minutes, 48.5 g (467 mmol) of trimethylborate was added. After confirming the completion of the reaction, it was concentrated and extracted after adding 1L of 2N HCl and 1L of EA. After concentrating the organic layer, it was recrystallized to obtain 123.0 g (67%) of Intermediate-88.

Intermediate-88 MS (FAB): 432 (M ⁺ )

<Synthesis of Intermediate-89>

After adding 50g (347mmol) of 1-phenyl-1H-imidazole to a 1L 3-necked round bottom flask, it was dissolved in 500ml of THF. A dryice bath was installed to maintain minus 78 degrees, and 221ml (354mmol) of n-Butyllithium (1.6M) was added dropwise. After 30 minutes, 96.8 g (381 mmol) of iodine was added and the temperature was raised to room temperature. After confirming the completion of the reaction, the mixture was concentrated, and an organic layer was extracted after adding 500 ml of EA and 500 ml of water. Recrystallization gave 78.7 g (84%) of Intermediate-89.

Intermediate-89 MS (FAB): 270 (M ⁺ )

<Synthesis of Intermediate-90>

99.8g (231mmol) of Intermediate-88, 75.1g (278mmol) of Intermediate-89, 13.4g (12mmol) of Pd(PPh3)4, 347ml (694mmol) of 2M K2CO3, and 1L of THF were added to a 3L 3-necked round bottom flask and heated to reflux. After confirming the completion of the reaction, the mixture was cooled to room temperature and concentrated. After adding 500 ml of MC and 500 ml of water, the organic layer was extracted and concentrated. After column recrystallization, 71.1 g (58%) of Intermediate-90 was obtained.

Intermediate-90 MS (FAB): 530 (M ⁺ )

<Synthesis of Intermediate-91>

67.4g (127mmol) of Intermediate-90 was added to a 2L 3-necked round bottom flask and dissolved in 700ml of THF. A dryice bath was installed to maintain minus 78 degrees, and 81ml (130mmol) of n-Butyllithium (1.6M) was added dropwise. After 30 minutes, 14.6 g (140 mmol) of trimethylborate was added. After confirming the completion of the reaction, it was concentrated and extracted after adding 500ml of 2N HCl and 500ml of EA. After concentrating the organic layer, it was recrystallized to obtain 37.1 g (59%) of Intermediate-91.

Intermediate-91 MS (FAB): 495 (M ⁺ )

<Synthesis of Intermediate-92>

In a 100ml three-neck round bottom flask, 2.70 g (10 mmol) of 1,3-dibromo-2-chlorobenzene, 668 mg (2.4 mmol) of silver carbonate, 1.63 g (6.1 mmol) of cyclohexyldiphenylphosphine, 1.67 g (12 mmol) of potassium carbonate, 5.29 g (0.24 mol) of tritiated water (T ₂ O) and toluene Add 10 mL of N. After stirring at 120°C for 24 hours, cool to room temperature. A saturated aqueous ammonia chloride solution was added to terminate the reaction, and after adding water and dichloromethane, the layers were separated to obtain an organic layer. After drying with Na ₂ SO ₄ , it is filtered. After concentrating the filtrate, isopropanol is added. The resulting solid was filtered and columned to obtain 1.96 g of Intermediate-92 (71%, 87% conversion of hydrogen to tritium).

Intermediate-92 MS (FAB): 276 (M ⁺ )

<Synthesis of Intermediate-93>

Inject bis(4-(tert-butyl)phenyl)amine 2.81g (10mmol) and Intermediate-92 2.76g (10mmol) and dissolve in 40ml toluene, Pd(OAc)2 0.05g (0.2mmol), 1M t-Bu3P 0.4ml (0.4mmol), t-BuONa 2.88g (30mm) ol), respectively, and then refluxed for 6 hours.

After the reaction was completed, the temperature of the reactant was cooled to room temperature, extracted with 150 ml of toluene and 150 ml of H2O, and then a small amount of water in the organic layer was removed with anhydrous MgSO4, filtered under reduced pressure, and the organic solvent was concentrated. The resulting compound was columned with Hex: EA = 5: 1 to obtain 5.69 g (84%) of Intermediate-93.

Intermediate-93 MS (FAB): 677 (M ⁺ )

<Synthesis of Intermediate-94>

After injecting bis(4-(tert-butyl)phenyl)amine 2.81g (10mmol) and 3-bromophenol 1.73g (10mmol) and dissolving in 40ml toluene, Pd(OAc)2 0.05g (0.2mmol), 1M t-Bu3P 0.4ml (0.4mmol), t-BuONa 2.88g (30 mmol), respectively, and then refluxed for 6 hours.

After the reaction was completed, the temperature of the reactant was cooled to room temperature, extracted with 150 ml of toluene and 150 ml of H2O, and then a small amount of water in the organic layer was removed with anhydrous MgSO4, filtered under reduced pressure, and the organic solvent was concentrated. The resulting compound was columned with Hex: EA = 5: 1 to obtain 3.14 g (84%) of Intermediate-94.

Intermediate-94 MS (FAB): 373 (M ⁺ )

<Synthesis of Intermediate-95>

In a 100ml three-neck round bottom flask, 2.72 g (10 mmol) of 1,5-dibromo-2,4-difluorobenzene, 668 mg (2.4 mmol) of silver carbonate, 1.63 g (6.1 mmol) of cyclohexyldiphenylphosphine, 1.67 g (12 mmol) of potassium carbonate, 5.29 g (0.24 mol) of tritiated water (T ₂ O) and Add 10 mL of toluene. After stirring at 120°C for 22 hours, cool to room temperature. A saturated aqueous ammonia chloride solution was added to terminate the reaction, and after adding water and dichloromethane, the layers were separated to obtain an organic layer. After drying with Na ₂ SO ₄ , it is filtered. After concentrating the filtrate, isopropanol is added. The resulting solid was filtered and columned to obtain 2.37 g of Intermediate-95 (86%, 89% conversion of hydrogen to tritium).

Intermediate-95 MS (FAB): 275 (M ⁺ )

<Synthesis of Intermediate-96>

After injecting 1.22g (10mmol) of phenylboronic acid and 2.76g (10mmol) of Intermediate-95 under nitrogen and dissolving them in 40ml of toluene, 0.05g (0.2mmol) of Pd(OAc)2, 0.4ml (0.4mmol) of 1M t-Bu3P, and 2.88g (30mmol) of t-BuONa were added thereto, respectively, followed by 6 hours. refluxed during

After the reaction was completed, the temperature of the reactant was cooled to room temperature, extracted with 150 ml of toluene and 150 ml of H2O, and then a small amount of water in the organic layer was removed with anhydrous MgSO4, filtered under reduced pressure, and the organic solvent was concentrated. The resulting compound was columned with Hex: EA = 5: 1 to obtain 2.35 g (87%) of Intermediate-96.

Intermediate-96 MS (FAB): 270 (M ⁺ )

<Synthesis of Intermediate-97>

35.9g (96mmol) of Intermediate-94, 25.9g (96mmol) of Intermediate-96, and 41.0g (193mmol) of Potassium phosphate tribasic were added to a 1L three-necked round bottom flask, and then 500ml of DMSO was added. After adding 3.7 g (19 mmol) of Copper(I) iodide and 6.8 g (19 mmol) of Iron(III) acetyl acetonate, the mixture was heated to 110 degrees. After completion of the reaction, the mixture was cooled to room temperature, and an organic layer was extracted and concentrated by adding 1 L of EA and 1 L of water. After column, 62.9 g (67%) of Intermediate-97 was obtained.

Intermediate-97 MS (FAB): 977 (M ⁺ )

<Synthesis of Compound 1-1>

After dissolving 20g (43.8mmol) of Intermediate-17 and 29.3g (96.4mmol) of Intermediate-43 in 500ml of toluene, 21g (219mmol) of sodium tert-butoxide was added. After adding Palladium acetate 197mg (0.88mmol) and Tri-tert-butylphosphine 709mg (1.75mmol), it was refluxed for 12 hours. After completion of the reaction, the mixture was cooled to room temperature and an organic layer was extracted by adding 500 ml of water. After column, it was recrystallized with n-hexane/MC to obtain 21.7 g (55% yield) of Compound 1-1.

¹ H NMR (DMSO, 300 Hz): δ (ppm) = 8.32-8.09 (d, 1H), 8.03-7.91 (d, 2H), 7.86-7.73 (m, 2H), 7.69-7.47 (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): 901(M ⁺ )

<Synthesis of Compound 1-13>

After dissolving 20 g (51.5 mmol) of Intermediate-8 and 32.7 g (108.2 mmol) of Intermediate-44 in 500 ml of toluene, 19.8 g (206.1 mmol) of sodium tert-butoxide was added. After adding 231 mg (1.03 mmol) of Palladium acetate and 417 mg (2.06 mmol) of Tri-tert-butylphosphine, it was refluxed for 12 hours. After completion of the reaction, the mixture was cooled to room temperature and an organic layer was extracted by adding 500 ml of water. After column, it was recrystallized with n-hexane/MC to obtain 22.7 g (53% yield) of compound 1-13.

¹ H NMR (DMSO, 300 Hz): 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), 7.68-7.47 (m, 4H), 7.42-7.1 6(m, 4H), 7.13-6.92(m, 2H), 3.21-2.52(m, 8H), 1.37-1.03(d, 12H)

MS(FAB): 831(M ⁺ )

<Synthesis of Compound 1-25>

After dissolving 20.4g (51.5mmol) of Intermediate-45 and 32.4g (108.2mmol) of Intermediate-26 in 500ml of toluene, 19.8g (206.1mmol) of sodium tert-butoxide was added. After adding 231 mg (1.03 mmol) of Palladium acetate and 417 mg (2.06 mmol) of Tri-tert-butylphosphine, it was refluxed for 12 hours. After completion of the reaction, the mixture was cooled to room temperature and an organic layer was extracted by adding 500 ml of water. After column, it was recrystallized with n-hexane/MC to obtain 17.6 g (41% yield) of Compound 1-25.

¹ H NMR (DMSO, 300 Hz): δ (ppm) = 8.32-8.02 (m, 4H), 7.98-7.88 (d, 2H), 7.84-7.62 (m, 6H), 7.58-7.45 (m, 4H), 7.37-7.11 (m, 6H), 7.13-6.9 2(d, 2H), 3.21-2.52(m, 8H), 1.37-1.03(d, 12H)

MS(FAB): 833(M ⁺ )

<Synthesis of Compound 1-37>

After dissolving 20.4g (51.5mmol) of Intermediate-45 and 40.6g (108.2mmol) of Intermediate-31 in 500ml of toluene, 19.8g (206.1mmol) of sodium tert-butoxide was added. After adding 231 mg (1.03 mmol) of Palladium acetate and 417 mg (2.06 mmol) of Tri-tert-butylphosphine, it was refluxed for 12 hours. After completion of the reaction, the mixture was cooled to room temperature and an organic layer was extracted by adding 500 ml of water. After column, it was recrystallized with n-hexane/MC to obtain 20.3 g (40% yield) of compound 1-37.

¹ H NMR (DMSO, 300 Hz): δ (ppm) = 8.25-7.87 (m, 10H), 7.82-7.74 (d, 2H), 7.71-7.65 (d, 2H), 7.61-7.46 (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): 985(M ⁺ )

<Synthesis of Compound 1-49>

After dissolving 20.4g (51.5mmol) of Intermediate-45 and 48.9g (108.2mmol) of Intermediate-40 in 500ml of toluene, 19.8g (206.1mmol) of sodium tert-butoxide was added. After adding 231 mg (1.03 mmol) of Palladium acetate and 417 mg (2.06 mmol) of Tri-tert-butylphosphine, it was refluxed for 12 hours. After completion of the reaction, the mixture was cooled to room temperature and an organic layer was extracted by adding 500 ml of water. After column, it was recrystallized with n-hexane/MC to obtain 15.8 g (27% yield) of Compound 1-49.

NMR (DMSO, 300 Hz): δ (ppm) = 8.21-7.92 (m, 6H), 7.86-7.77 (d, 2H), 7.73-7.66 (d, 2H), 7.63-7.51 (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): 1137(M ⁺ )

<Synthesis of Compound 1-61>

After dissolving 20.4g (51.5mmol) of Intermediate-45 and 40.6g (108.2mmol) of Intermediate-36 in 500ml of toluene, 19.8g (206.1mmol) of sodium tert-butoxide was added. After adding 231 mg (1.03 mmol) of Palladium acetate and 417 mg (2.06 mmol) of Tri-tert-butylphosphine, it was refluxed for 12 hours. After completion of the reaction, the mixture was cooled to room temperature and an organic layer was extracted by adding 500 ml of water. After column, it was recrystallized with n-hexane/MC to obtain 22.8 g (45% yield) of compound 1-61.

¹ H NMR (DMSO, 300 Hz): δ (ppm) = 8.34-8.08 (m, 4H), 8.04-7.90 (d, 2H), 7.71-7.59 (m, 6H), 7.56-7.44 (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 1-73>

After dissolving 20g (39mmol) of Intermediate-10 and 24.8g (82mmol) of Intermediate-44 in 500ml of toluene, 15g (156.2mmol) of sodium tert-butoxide was added. After adding 175 mg (0.78 mmol) of Palladium acetate and 316 mg (1.56 mmol) of Tri-tert-butylphosphine, it was refluxed for 12 hours. After completion of the reaction, the mixture was cooled to room temperature and an organic layer was extracted by adding 500 ml of water. After column, it was recrystallized with n-hexane/MC to obtain 21.6 g (58% yield) of Compound 1-73.

¹ H NMR (DMSO, 300 Hz): 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), 7.59-7.26 (m, 12H), 7.18-7. 02(d, 2H), 3.05-2.72(m, 2H), 1.36-1.03(d, 12H)

MS(FAB): 955(M ⁺ )

<Synthesis of Compound 1-75>

After dissolving 13.4g (22.1mmol) of Intermediate-41 and 7.4g (24.3mmol) of Intermediate-43 in 200ml of toluene, 8.5g (88.4mmol) of sodium tert-butoxide was added. After adding 100 mg (0.44 mmol) of Palladium acetate and 179 mg (0.88 mmol) of Tri-tert-butylphosphine, it was refluxed for 12 hours. After completion of the reaction, the mixture was cooled to room temperature and an organic layer was extracted by adding 500 ml of water. After column, it was recrystallized with n-hexane/MC to obtain 11.2 g (61% yield) of compound 1-75.

¹ H NMR (DMSO, 300 Hz): δ (ppm) = 8.24-7.95 (m, 4H), 7.89-7.81 (d, 1H), 7.75-7.49 (m, 9H), 7.44-7.24 (m, 6H), 7.22-7.13 (d, 2H), 7.10-7.0 1(d, 2H), 6.98-6.91(m, 2H), 3.21-2.52(m, 8H), 1.37-1.03(d, 12H)

MS(FAB): 829(M ⁺ )

<Synthesis of Compound 1-87>

After dissolving 15 g (21.7 mmol) of Intermediate-42 and 14.5 g (47.8 mmol) of Intermediate-44 in 300 ml of toluene, 8.4 g (86.9 mmol) of sodium tert-butoxide was added. After adding Palladium acetate 98mg (0.43mmol) and Tri-tert-butylphosphine 176mg (0.87mmol), it was refluxed for 12 hours. After completion of the reaction, the mixture was cooled to room temperature and an organic layer was extracted by adding 500 ml of water. After column, it was recrystallized with n-hexane/MC to obtain 7.6 g (31% yield) of Compound 1-87.

¹ H NMR (DMSO, 300 Hz): 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. 45(m, 6H), 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): 1133(M ⁺ )

<Synthesis of Compound 1-100>

After dissolving 15 g (21.7 mmol) of Intermediate-42 and 14.6 g (47.8 mmol) of Intermediate-43 in 300 ml of toluene, 8.4 g (86.9 mmol) of sodium tert-butoxide was added. After adding Palladium acetate 98mg (0.43mmol) and Tri-tert-butylphosphine 176mg (0.87mmol), it was refluxed for 12 hours. After completion of the reaction, the mixture was cooled to room temperature and an organic layer was extracted by adding 500 ml of water. After column, it was recrystallized with n-hexane/MC to obtain 10.1 g (41% yield) of compound 1-100.

¹ H NMR (DMSO, 300 Hz): δ (ppm) = 8.61-8.51 (d, 2H), 8.27-8.12 (d, 2H), 8.08-7.91 (m, 4H), 7.83-7.53 (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): 1135(M ⁺ )

<Synthesis of Compound 1-123>

After dissolving 20 g (48.1 mmol) of Intermediate-14 and 30.5 g (100.9 mmol) of Intermediate-44 in 500 ml of toluene, 18.5 g (192.2 mmol) of sodium tert-butoxide was added. After adding Palladium acetate 216mg (0.96mmol) and Tri-tert-butylphosphine 389mg (1.92mmol), it was refluxed for 12 hours. After completion of the reaction, the mixture was cooled to room temperature and an organic layer was extracted by adding 500 ml of water. After column, it was recrystallized with n-hexane/MC to obtain 21.5 g (52% yield) of Compound 1-123.

¹ H NMR (DMSO, 300 Hz): δ (ppm) = 9.13-8.89 (s, 2H), 8.05-7.95 (m, 4H), 7.91-7.78 (m, 4H), 7.62-7.47 (m, 4H), 7.42-7.27 (m, 4H), 7.16-7.0 4(d, 2H), 3.21-2.52(m, 14H), 1.37-1.03(d, 12H)

MS(FAB): 859(M ⁺ )

<Synthesis of Compound 1-196>

After injecting 4.44g (10mmol) of 1,6-dibromo-3,8-diisopropylpyrene and 6.06g (22mmol) of Intermediate-46 under nitrogen and dissolving in 60ml of toluene, Pd (OAc) ₂ 0.05g (0.2mmol), 1M t-Bu _3P 0.4ml (0.4mmol), t-BuONa 2.8 8g (30mmol) was added to each and then refluxed for 8 hours.

After the reaction was completed, the temperature of the reactant was cooled to room temperature, extracted using 200 ml of toluene and 200 ml of H ₂ O, and a small amount of water in the organic layer was removed with anhydrous MgSO ₄ . After filtration under reduced pressure, the organic solvent was concentrated. The resulting compound was columned with Hex: EA = 3: 1 to obtain 6.2 g (74% yield) of compound 1-196.

¹ H NMR (DMSO, 300 Hz): δ (ppm) = 8.08-7.75 (m, 8H), 7.71-7.62 (d, 2H), 7.59-7.51 (d, 2H), 7.48-7.41 (m, 6H), 7.38-6.91 (m, 10H), 2.95-2. 71(m, 4H), 1.46-1.31(d, 12H), 1.31-1.12(d, 12H)

MS(FAB): 833(M ⁺ )

<Synthesis of Compound 1-245>

After injecting 4.44g (10mmol) of 1,6-dibromo-3,8-diisopropylpyrene and 5.79g (22mmol) of Intermediate-47 under nitrogen and dissolving in 60ml of toluene, 0.05g (0.2mmol) of Pd (OAc) _2, 0.4ml (0.4mmol) of 1M t-Bu _3P , t-BuONa 2.8 8g (30mmol) was added to each and then refluxed for 8 hours.

After the reaction was completed, the temperature of the reactant was cooled to room temperature, extracted with 200 ml of toluene and 200 ml of H ₂ O, and then a small amount of water in the organic layer was removed with anhydrous MgSO ₄ , filtered under reduced pressure, and the organic solvent was concentrated. The resulting compound was columned with Hex: EA = 3: 1 to obtain 6.2 g (76% yield) of Compound 1-245.

¹ H NMR (DMSO, 300 Hz): δ (ppm) = 8.35-8,13 (m, 4H), 8.03-7.79 (d, 2H), 7.76-7.62 (d, 10H), 7.58-7.51 (m, 4H), 7.45-7.01 (m, 8H), 2.95-2. 72(m, 4H), 1.46-1.30(d, 12H), 1.31-1.13(d, 12H)

MS(FAB): 809(M ⁺ )

<Synthesis of Compound 2-1>

108.9g (131mmol) of Intermediate-55 and 500ml of THF were added to a 3L 3-neck round bottom flask, and after filling with nitrogen, it was maintained at minus 78 degrees using a Dryice bath. After adding 261ml (418mmol) of 1.6M n-Butyllithium dropwise, the dryice bath was removed and stirred at room temperature. After 1 hour, a dryice bath was installed to maintain minus 78 degrees, and then 32.7 g (131 mmol) of boron tribromide was slowly added. After removing the bath, the temperature was slowly raised to room temperature and heated by adding 1L of o-xylene. THF was removed by distillation so that the internal thermometer reached 140 degrees, and when only o-xylene remained, a condenser was installed and heated under reflux for 3 days. After completion of the reaction, the mixture was cooled to room temperature and concentrated. After column recrystallization, 26.9 g (27%) of Compound 2-1 was obtained.

^1H NMR (DMSO, 300Hz): δ(ppm)= 8.85~8.96(t, 1H), 7.81~8.28(m, 3H), 7.56~7.73(m, 2H), 7.37~7.48(m, 7H), 7.17~7.34(m, 11H), 7.01~7. 11(m, 7H), 6.74~6.96(m, 5H), 5.69~5.91(d, 2H)

MS(FAB): 759(M ⁺ )

<Synthesis of Compound 2-45>

65.5g (91mmol) of Intermediate-63 and 300ml of THF were added to a 1L 3-necked round bottom flask, and after filling with nitrogen, it was maintained at minus 78 degrees using a Dryice bath. After adding 187ml (300mmol) of 1.6M n-Butyllithium dropwise, the dryice bath was removed and stirred at room temperature. After 1 hour, a dryice bath was installed to maintain minus 78 degrees, and then 22.8 g (91 mmol) of boron tribromide was slowly added. After removing the bath, the temperature was slowly raised to room temperature and heated by adding 500ml of xylene. THF was removed by distillation so that the internal thermometer reached 140 degrees, and when only o-xylene remained, a condenser was installed and heated under reflux for 3 days. After completion of the reaction, the mixture was cooled to room temperature and concentrated. After column recrystallization, 21.8 g (37%) of compound 2-45 was obtained.

^1H NMR (DMSO, 300Hz): δ(ppm)= 8.90~8.98(s, 1H), 8.21~8.29(d, 1H), 7.82~7.89(m, 1H), 7.62~7.68(m, 1H), 7.41~7.53(m, 4H), 7.25~7.3 5(m, 2H), 7.01~7.15(m, 7H), 5.62~5.78(s, 2H), 1.43~1.52(s, 18H), 1.28~1.39(s, 18H)

MS(FAB): 648(M ⁺ )

<Synthesis of Compound 2-107>

35.5g (67mmol) of Intermediate-68 was added to a 1L 3-necked round bottom flask and dissolved in 400ml of THF. A dryice bath was installed to maintain minus 78 degrees, and 177ml (283mmol) of 1.6M n-Butyllithium was added dropwise. After removing the bath and slowly raising the temperature to room temperature, the mixture was stirred for 1 hour. A dryice bath was installed to maintain minus 78 degrees, and 16.9 g (67 mmol) of boron tribromide was slowly added. After 1 hour, 23ml (67mmol) of Phenylmagnesium (3M) was additionally added, the bath was removed, the temperature was slowly raised to room temperature, and 500ml of o-xylene was added and heated. THF was removed by distillation so that the internal thermometer reached 140 degrees, and when only o-xylene remained, a condenser was installed and heated under reflux for 3 days. After completion of the reaction, the mixture was cooled to room temperature and concentrated. After column recrystallization, 12.6 g (35%) of Compound 2-107 was obtained.

^1H NMR (DMSO, 300Hz): δ(ppm)= 7.81~8.29(m, 2H), 7.52~7.73(m, 5H), 7.31-7.46(m, 6H), 7.13~7.25(m, 4H), 6.94-7.09(d, 1H), 1.43~1.5 3(s, 9H), 1.28~1.39(s, 9H),

MS(FAB): 537(M ⁺ )

<Synthesis of Compound 2-165>

34.5g (65mmol) of Intermediate-72 was added to a 1L 3-necked round bottom flask and dissolved in 400ml of THF. A dryice bath was installed to maintain minus 78 degrees, and 170ml (272mmol) of 1.6M n-Butyllithium was added dropwise. After removing the bath and slowly raising the temperature to room temperature, the mixture was stirred for 1 hour. A dryice bath was installed to maintain minus 78 degrees, and 16.2 g (65 mmol) of boron tribromide was slowly added. After 1 hour, 22ml (65mmol) of phenylmagnesium (3M) was additionally added, the bath was removed, the temperature was slowly raised to room temperature, and 500ml of xylene was added and heated. THF was removed by distillation so that the internal thermometer reached 140 degrees, and when only o-xylene remained, a condenser was installed and heated under reflux for 3 days. After completion of the reaction, the mixture was cooled to room temperature and concentrated. After column recrystallization, 13.3 g (38%) of compound 2-165 was obtained.

^1H NMR (DMSO, 300Hz): δ(ppm)= 7.72~8.28(m, 3H), 7.57~7.69(m, 2H), 7.31-7.48(m, 8H), 7.14~7.25(m, 4H), 6.94-7.09(d, 1H), 1.43~1.5 2(s, 9H), 1.29~1.39(s, 9H).

MS(FAB): 537(M ⁺ )

<Synthesis of Compound 2-201>

50.8g (69mmol) of Intermediate-80 was added to a 1L 3-necked round bottom flask and dissolved in 400ml of THF. A dryice bath was installed to maintain minus 78 degrees, and 139ml (222mmol) of 1.6M n-Butyllithium was added dropwise. After removing the bath and slowly raising the temperature to room temperature, the mixture was stirred for 1 hour. A dryice bath was installed to maintain minus 78 degrees, and 17.4 g (69 mmol) of boron tribromide was slowly added. The bath was removed, the temperature was slowly raised to room temperature, and 500ml of o-xylene was added and heated. THF was removed by distillation so that the internal thermometer reached 140 degrees, and when only o-xylene remained, a condenser was installed and heated under reflux for 3 days. After completion of the reaction, the mixture was cooled to room temperature and concentrated. After column recrystallization, 14.7 g (32%) of compound 2-201 was obtained.

^1H NMR (DMSO, 300Hz): δ(ppm)= 7.91~8.05(d, 1H), 7.56~7.69(m, 2H), 7.29-7.48(m, 4H), 7.02~7.21(m, 6H), 6.84-6.98(d, 1H), 2.47~2.5 4(d, 2H), 1.91~1.99(m, 1H), 1.42~1.53(s, 18H), 1.28~1.39(s, 9H), 0.91~0.99(d, 6H)

MS(FAB): 665(M ⁺ )

<Synthesis of Compound-249>

37.2g (75mmol) of Intermediate-91, 24.2g (75mmol) of Intermediate-85, 4.3g (4mmol) of Pd(PPh3)4, 113ml (225mmol) of 2M K ₂ CO ₃ , and 400ml of THF were added to a 1L three-necked round bottom flask and heated to reflux. After confirming the completion of the reaction, the mixture was cooled to room temperature and concentrated. After adding 500 ml of MC and 500 ml of water, the organic layer was extracted and concentrated. After column recrystallization, 35.8 g (69%) of compound 2-249 was obtained.

¹ H NMR (DMSO, 300 Hz): δ (ppm) = 8.30-8.45 (m, 4H), 8.15-8.26 (d, 2H), 7.95-8.11 (m, 3H), 7.64-7.84 (m, 2H), 7.46-7.61 (m, 14H), 7.32-7. 41(m, 2H), 7.11~7.20(m, 3H)

MS(FAB): 692(M ⁺ )

<Synthesis of Compound 2-356>

까지 냉각하고 N,N-디이소프로필에틸아민(30ml)을 가하고, o-xylene 400ml를 첨가하여 가열하였다. 내부 온도계가 140도가 되도록 THF를 증류하여 제거하고 o-xylene만 남았을 때 condenser를 설치하여 3일 동안 가열 환류였다. 반응 완결 후 상온으로 식히고 농축하였다. 컬럼 후 재결정하여 화합물2-356 13.9g(31%)을 얻었다.46.7g (69mmol) of Intermediate-93 was added to a 1L 3-necked round bottom flask and dissolved in 300ml of THF. A dryice bath was installed to maintain minus 78 degrees, and 139ml (222mmol) of 1.6M t-Butyllithium was added dropwise. After removing the bath and slowly raising the temperature to room temperature, the mixture was stirred for 1 hour. A dryice bath was installed to maintain minus 78 degrees, and 17.4 g (69 mmol) of boron tribromide was slowly added. The bath was removed, the temperature was slowly raised to room temperature, and the mixture was stirred for 1 hour. After that, back to 0

After cooling, N,N-diisopropylethylamine (30ml) was added, and 400ml of o-xylene was added and heated. THF was removed by distillation so that the internal thermometer reached 140 degrees, and when only o-xylene remained, a condenser was installed and heated under reflux for 3 days. After completion of the reaction, the mixture was cooled to room temperature and concentrated. After column recrystallization, 13.9 g (31%) of compound 2-356 was obtained.

^1H NMR (DMSO, 300Hz): δ(ppm)= 8.89~9.02(d, 2H), 7.68~7.89(m, 4H), 7.56~7.65(m, 2H), 7.41~7.48(m, 2H), 7.32~7.39(m, 3H), 7.23~7.2 8(m, 1H), 6.73~6.83(d, 1H), 6.13~6.21(d, 2H), 1.33~1.48(d, 36H).

MS(FAB): 650(M ⁺ )

<Synthesis of Compound 2-372>

까지 냉각하고 N,N-디이소프로필에틸아민(30ml)을 가하고, o-xylene 500ml를 첨가하여 가열하였다. 내부 온도계가 140도가 되도록 THF를 증류하여 제거하고 o-xylene만 남았을 때 condenser를 설치하여 3일 동안 가열 환류였다. 반응 완결 후 상온으로 식히고 농축하였다. 컬럼 후 재결정하여 화합물2-372 19.7g(29%)을 얻었다.67.4g (69mmol) of Intermediate-97 was added to a 2L 3-necked round bottom flask and dissolved in 400ml of THF. A dryice bath was installed to maintain minus 78 degrees, and 139ml (222mmol) of 1.6M t-Butyllithium was added dropwise. After removing the bath and slowly raising the temperature to room temperature, the mixture was stirred for 1 hour. A dryice bath was installed to maintain minus 78 degrees, and 17.4 g (69 mmol) of boron tribromide was slowly added. The bath was removed, the temperature was slowly raised to room temperature, and the mixture was stirred for 1 hour. After that, back to 0

After cooling, N,N-diisopropylethylamine (30ml) was added, and 500ml of o-xylene was added and heated. THF was removed by distillation so that the internal thermometer reached 140 degrees, and when only o-xylene remained, a condenser was installed and heated under reflux for 3 days. After completion of the reaction, the mixture was cooled to room temperature and concentrated. After column recrystallization, 19.7 g (29%) of compound 2-372 was obtained.

^1H NMR (DMSO, 300Hz): δ(ppm)= 8.26~8.37(d, 2H), 7.74~7.81(s, 1H), 7.66~7.72(d, 4H), 7.39~7.47(t, 4H), 7.21~7.36(t, 2H), 7.05-7.1 9(m, 16H), 6.87~6.95(m, 4H), 1.33~1.48(d, 36H)

MS(FAB): 983(M ⁺ )

<Manufacture of organic light emitting device>

Example 1

An anode was formed with ITO on the substrate on which the reflective layer was formed, and the surface was treated with N ₂ plasma or UV-Ozone. HAT-CN was deposited thereon to a thickness of 10 nm as a hole injection layer (HIL). Subsequently, NPD was deposited to a thickness of 120 nm as a hole transport layer (HTL). While depositing 5 nm of 9,10-bis(2-naphthyl)anthracene (ADN) as the first light emitting layer (EML1) on the hole transport layer, Compound 2-45 as the compound of Formula 2 of the present invention was doped by about 8% as a second dopant. While depositing 20 nm of 9,10-bis(2-naphthyl)anthracene (ADN) as the second light-emitting layer (EML2) on the first light-emitting layer (EML1), Compound 1-1 as the compound of Formula 1 of the present invention was doped by about 4%. ET254 and LiQ were mixed 1:1 thereon to deposit an electron transport layer (ETL) to a thickness of 30 nm, and LiQ was deposited thereon to a thickness of 10 nm as an electron injection layer (EIL). Then, a mixture of magnesium and silver (Ag) in a ratio of 9:1 was deposited to a thickness of 15 nm as a cathode, and N4,N4′-bis[4-[bis(3-methylphenyl)amino]phenyl]-N4,N4′-diphenyl-[1,1′-biphenyl]-4,4′-diamine (DNTPD) was deposited to a thickness of 65 nm on the cathode as a capping layer. An organic light emitting device was manufactured by bonding a seal cap containing a moisture absorbent with a UV curable adhesive thereon to protect the organic light emitting device from O ₂ or moisture in the air.

Examples 2 to 10

Instead of Compound 1-1 of Formula 1 of the present invention as the second light emitting layer (EML2) in Example 1. Organic electroluminescent devices of Examples 2 to 10 were prepared in the same manner as in Example 1, except that Chemicals 1-8, 1-11, 1-13, 1-25, 1-37, 1-49, 1-54, 1-61 and 1-73 of Chemical Formula 1 were used, respectively.

Example 11

An anode was formed with ITO on the substrate on which the reflective layer was formed, and the surface was treated with N ₂ plasma or UV-Ozone. HAT-CN was deposited thereon to a thickness of 10 nm as a hole injection layer (HIL). Subsequently, NPD was deposited to a thickness of 120 nm as a hole transport layer (HTL). While depositing 5 nm of 9,10-bis(2-naphthyl)anthracene (ADN) as the first light emitting layer (EML1) on the hole transport layer, compound 2-249 as the compound of Formula 2 of the present invention was doped by about 8% as a second dopant. While depositing 20 nm of 9,10-bis(2-naphthyl)anthracene (ADN) as the second light-emitting layer (EML2) on the first light-emitting layer (EML1), Compound 1-75 as the compound of Formula 1 of the present invention was doped by about 4%. ET254 and LiQ were mixed 1:1 thereon to deposit an electron transport layer (ETL) to a thickness of 30 nm, and LiQ was deposited thereon to a thickness of 10 nm as an electron injection layer (EIL). Then, a mixture of magnesium and silver (Ag) in a ratio of 9:1 was deposited to a thickness of 15 nm as a cathode, and N4,N4′-bis[4-[bis(3-methylphenyl)amino]phenyl]-N4,N4′-diphenyl-[1,1′-biphenyl]-4,4′-diamine (DNTPD) was deposited to a thickness of 65 nm on the cathode as a capping layer. An organic light emitting device was manufactured by bonding a seal cap containing a moisture absorbent with a UV curable adhesive thereon to protect the organic light emitting device from O ₂ or moisture in the air.

Examples 12 to 20

In Example 1, the compound 1-75 of Chemical Formula 1 of the present invention was used as the second light emitting layer (EML2). Organic electroluminescent devices of Examples 12 to 20 were prepared in the same manner as in Example 11, except that Chemicals 1-87, 1-100, 1-114, 1-123, 1-166, 1-183, 1-196, 1-245 and 1-249 of Chemical Formula 1 were used, respectively.

Example 21

An anode was formed with ITO on the substrate on which the reflective layer was formed, and the surface was treated with N ₂ plasma or UV-Ozone. HAT-CN was deposited thereon to a thickness of 10 nm as a hole injection layer (HIL). Subsequently, NPD was deposited to a thickness of 120 nm as a hole transport layer (HTL). While depositing 20 nm of 9,10-bis(2-naphthyl)anthracene (ADN) as the first light emitting layer (EML1) on the hole transport layer, Compound 1-196 as the compound of Formula 1 of the present invention was doped by about 4% as the first dopant. While depositing 5 nm of 9,10-bis(2-naphthyl)anthracene (ADN) as the second light-emitting layer (EML2) on the first light-emitting layer (EML1), compound 2-1 as the compound of Formula 2 of the present invention was doped by about 8%. ET254 and LiQ were mixed 1:1 thereon to deposit an electron transport layer (ETL) to a thickness of 30 nm, and LiQ was deposited thereon to a thickness of 10 nm as an electron injection layer (EIL). Then, a mixture of magnesium and silver (Ag) in a ratio of 9:1 was deposited to a thickness of 15 nm as a cathode, and N4,N4′-bis[4-[bis(3-methylphenyl)amino]phenyl]-N4,N4′-diphenyl-[1,1′-biphenyl]-4,4′-diamine (DNTPD) was deposited to a thickness of 65 nm on the cathode as a capping layer. An organic light emitting device was manufactured by bonding a seal cap containing a moisture absorbent with a UV curable adhesive thereon to protect the organic light emitting device from O ₂ or moisture in the air.

Examples 22 to 40

Instead of Compound 2-1 of Chemical Formula 2 of the present invention as the second light emitting layer (EML2) in Example 1. Chemical Formula 2 2-24, 2-45, 2-56, 2-88, 2-107, 2-140, 2-151, 2-165, 2-201, 2-224, 2-236, 2-249, 2-265, 2-301, 2-337, 2-344, 2-350, Organic electroluminescent devices of Examples 22 to 40 were prepared in the same manner as in Example 21, except that 2-356 and 2-372 were used.

Example 41

An anode was formed with ITO on the substrate on which the reflective layer was formed, and the surface was treated with N ₂ plasma or UV-Ozone. HAT-CN was deposited thereon to a thickness of 10 nm as a hole injection layer (HIL). Subsequently, NPD was deposited to a thickness of 120 nm as a hole transport layer (HTL). While depositing 25 nm of 9,10-bis(2-naphthyl)anthracene (ADN) as the light emitting layer (EML1) on the hole transport layer, Compound 1-196 as the compound of Formula 1 of the present invention was doped by about 3.2% as the first dopant, and Compound 2-249 as the compound of Formula 2 of the present invention was doped by about 1.6% as the second dopant. ET254 and LiQ were mixed 1:1 thereon to deposit an electron transport layer (ETL) to a thickness of 30 nm, and LiQ was deposited thereon to a thickness of 10 nm as an electron injection layer (EIL). Then, a mixture of magnesium and silver (Ag) in a ratio of 9:1 was deposited to a thickness of 15 nm as a cathode, and N4,N4′-bis[4-[bis(3-methylphenyl)amino]phenyl]-N4,N4′-diphenyl-[1,1′-biphenyl]-4,4′-diamine (DNTPD) was deposited to a thickness of 65 nm on the cathode as a capping layer. An organic light emitting device was manufactured by bonding a seal cap containing a moisture absorbent with a UV curable adhesive thereon to protect the organic light emitting device from O ₂ or moisture in the air.

Example 42

An anode was formed with ITO on the substrate on which the reflective layer was formed, and the surface was treated with N ₂ plasma or UV-Ozone. HAT-CN was deposited thereon to a thickness of 10 nm as a hole injection layer (HIL). Subsequently, NPD was deposited to a thickness of 120 nm as a hole transport layer (HTL). 25 nm of 9,10-bis(2-naphthyl)anthracene (ADN) was deposited on the hole transport layer as the light emitting layer (EML1) while doping the premix dopant by about 4.8%. The premix dopant is a mixture of a first dopant, Compound 1-196 of Formula 1, and a second dopant, Compound 2-249 of Formula 2, in a ratio of 2:1. ET254 and LiQ were mixed 1:1 thereon to deposit an electron transport layer (ETL) to a thickness of 30 nm, and LiQ was deposited thereon to a thickness of 10 nm as an electron injection layer (EIL). Then, a mixture of magnesium and silver (Ag) in a ratio of 9:1 was deposited to a thickness of 15 nm as a cathode, and N4,N4′-bis[4-[bis(3-methylphenyl)amino]phenyl]-N4,N4′-diphenyl-[1,1′-biphenyl]-4,4′-diamine (DNTPD) was deposited to a thickness of 65 nm on the cathode as a capping layer. An organic light emitting device was manufactured by bonding a seal cap containing a moisture absorbent with a UV curable adhesive thereon to protect the organic light emitting device from O ₂ or moisture in the air.

Comparative Example 1

An anode was formed with ITO on the substrate on which the reflective layer was formed, and the surface was treated with N ₂ plasma or UV-Ozone. HAT-CN was deposited thereon to a thickness of 10 nm as a hole injection layer (HIL). Subsequently, NPD was deposited to a thickness of 120 nm as a hole transport layer (HTL). While depositing 25 nm of 9,10-bis(2-naphthyl)anthracene (ADN) as a light emitting layer (EML) on the hole transport layer, Compound 1-1 as the compound of Formula 1 of the present invention was doped by about 4.8% as a dopant. ET254 and LiQ were mixed 1:1 thereon to deposit an electron transport layer (ETL) to a thickness of 30 nm, and LiQ was deposited thereon to a thickness of 10 nm as an electron injection layer (EIL). Then, a mixture of magnesium and silver (Ag) in a ratio of 9:1 was deposited to a thickness of 15 nm as a cathode, and N4,N4′-bis[4-[bis(3-methylphenyl)amino]phenyl]-N4,N4′-diphenyl-[1,1′-biphenyl]-4,4′-diamine (DNTPD) was deposited to a thickness of 65 nm on the cathode as a capping layer. An organic light emitting device was manufactured by bonding a seal cap containing a moisture absorbent with a UV curable adhesive thereon to protect the organic light emitting device from O ₂ or moisture in the air.

Comparative Example 2

An anode was formed with ITO on the substrate on which the reflective layer was formed, and the surface was treated with N ₂ plasma or UV-Ozone. HAT-CN was deposited thereon to a thickness of 10 nm as a hole injection layer (HIL). Subsequently, NPD was deposited to a thickness of 120 nm as a hole transport layer (HTL). While depositing 25 nm of 9,10-bis(2-naphthyl)anthracene (ADN) as a light emitting layer (EML) on the hole transport layer, compound 1-196 as a compound of Formula 1 of the present invention was doped by about 4.8% as a dopant. ET254 and LiQ were mixed 1:1 thereon to deposit an electron transport layer (ETL) to a thickness of 30 nm, and LiQ was deposited thereon to a thickness of 10 nm as an electron injection layer (EIL). Then, a mixture of magnesium and silver (Ag) in a ratio of 9:1 was deposited to a thickness of 15 nm as a cathode, and N4,N4′-bis[4-[bis(3-methylphenyl)amino]phenyl]-N4,N4′-diphenyl-[1,1′-biphenyl]-4,4′-diamine (DNTPD) was deposited to a thickness of 65 nm on the cathode as a capping layer. An organic light emitting device was manufactured by bonding a seal cap containing a moisture absorbent with a UV curable adhesive thereon to protect the organic light emitting device from O ₂ or moisture in the air.

The compounds used in Examples 1 to 40, 41 and 42 and Comparative Examples 1 and 2 are shown below.

Test Example: Characteristic evaluation of organic light emitting device

1. Evaluation of characteristics of organic light emitting devices of Examples 1 to 20 and Comparative Example 1

The characteristics of the organic light emitting devices prepared in Examples 1 to 20 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) EQE
(%) CIE_x CIE_y T ₉₅ (hours) Example 1 3.7 10.8 0.137 0.056 332 Example 2 3.4 10.3 0.136 0.058 355 Example 3 3.6 11.0 0.139 0.054 349 Example 4 3.5 10.2 0.138 0.055 368 Example 5 3.6 10.3 0.138 0.057 353 Example 6 3.5 10.7 0.136 0.058 389 Example 7 3.8 11.0 0.137 0.055 340 Example 8 3.9 11.2 0.137 0.056 355 Example 9 3.7 10.7 0.137 0.056 342 Example 10 3.5 10.3 0.137 0.057 378 Example 11 3.5 10.1 0.137 0.057 381 Example 12 3.4 10.4 0.136 0.056 392 Example 13 3.5 10.3 0.136 0.057 385 Example 14 3.6 10.4 0.136 0.057 374 Example 15 3.3 10.3 0.137 0.056 400 Example 16 3.5 11.1 0.136 0.057 433 Example 17 3.6 11.4 0.137 0.056 420 Example 18 3.7 11.6 0.135 0.059 422 Example 19 3.6 10.8 0.136 0.060 462 Example 20 3.4 11.3 0.138 0.055 451 Comparative Example 1 3.8 9.3 0.136 0.058 309

As a result of the experiment, the organic light emitting devices of Examples 1 to 20 using the compounds of Formulas 1 and 2 of the present invention together as the first dopant and the second dopant have improved efficiency and voltage characteristics compared to the conventional organic light emitting device using a single dopant of Comparative Example 1.

In addition, as a result of measuring the afterimage lifespan (T ₉₅ ), the organic light emitting device of Comparative Example 1 had a lifespan of 310 hours or less, whereas Examples 1 to 20 had a long lifespan of 330 hours or more.

Accordingly, it can be seen that the organic light emitting device using the compounds of Formulas 1 and 2 of the present invention together as the first dopant and the second dopant has excellent efficiency, voltage, and lifetime characteristics.

2. Evaluation of characteristics of organic light emitting devices of Examples 21 to 40 and Comparative Example 2

The characteristics of the organic light emitting devices prepared in Examples 21 to 40 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) EQE
(%) CIE_x CIE_y T ₉₅ (hours) Example 21 3.6 10.6 0.136 0.057 435 Example 22 3.7 11.1 0.137 0.057 432 Example 23 3.7 11.4 0.139 0.054 432 Example 24 3.5 11.3 0.139 0.054 429 Example 25 3.5 11.7 0.144 0.052 430 Example 26 3.8 10.6 0.134 0.060 409 Example 27 3.7 11.5 0.141 0.052 421 Example 28 3.6 11.4 0.140 0.054 431 Example 29 3.7 10.8 0.135 0.058 420 Example 30 3.5 11.3 0.138 0.056 447 Example 31 3.6 11.5 0.138 0.056 429 Example 32 3.6 11.3 0.136 0.056 431 Example 33 3.6 11.8 0.135 0.058 435 Example 34 3.5 11.3 0.137 0.056 423 Example 35 3.6 11.4 0.135 0.058 433 Example 36 3.6 11.8 0.139 0.054 432 Example 37 3.5 11.5 0.138 0.055 434 Example 38 3.7 12.2 0.136 0.057 423 Example 39 3.6 11.6 0.136 0.060 438 Example 40 3.6 12.0 0.142 0.051 429 Comparative Example 2 3.8 9.8 0.134 0.061 359

As a result of the experiment, the organic light emitting devices of Examples 21 to 40 using the compounds of Formulas 1 and 2 of the present invention together as the first dopant and the second dopant showed significantly improved efficiency and voltage characteristics compared to the conventional organic light emitting device of Comparative Example 2 using a single dopant. In particular, the organic light emitting devices of Examples 24, 25, 30, 34, 37 and 38 exhibited remarkably improved characteristics in voltage characteristics and luminous efficiency.

In addition, as a result of measuring the afterimage lifespan (T ₉₅ ), the organic light emitting device of Comparative Example 2 had a lifespan of 360 hours or less, whereas Examples 21 to 40 had a long lifespan of 400 hours or more. In particular, the organic light emitting device of Example 30 was confirmed to have a long lifespan of 440 hours or more.

Therefore, it can be seen that the organic light emitting device using the compounds of Formulas 1 and 2 of the present invention together as the first dopant and the second dopant has significantly better efficiency, voltage, and lifespan compared to conventional technologies.

3. Evaluation of characteristics of organic light emitting devices of Examples 18, 33, 41, 42 and Comparative Example 2

The characteristics of the organic light emitting devices prepared in Examples 18, 33, 41, 42 and Comparative Example 2 were measured at a current density of 10 mA/cm ² , and the results are shown in Table 3 below.

Voltage
(V) EQE
(%) CIE_x CIE_y T ₉₅ (hours) Example 18 3.7 11.6 0.135 0.059 422 Example 33 3.6 11.8 0.135 0.058 435 Example 41 3.8 11.8 0.136 0.059 413 Example 42 3.7 11.9 0.136 0.058 439 Comparative Example 2 3.8 9.8 0.134 0.061 359

As a result of the experiment, the organic light emitting devices of Examples 18, 21, 41, and 42 using the compounds of Formulas 1 and 2 of the present invention together as the first dopant and the second dopant exhibited remarkably superior voltage characteristics, luminous efficiency and lifetime characteristics compared to Comparative Example 2. The organic light emitting devices of Examples 18, 21, 41, and 42 used Compound 1-196 of Formula 1 of the present invention in the same manner as in Comparative Example 2, but exhibited superior voltage characteristics, luminous efficiency and lifetime characteristics compared to Comparative Example 2. As the compounds of Formulas 1 and 2 were used together as the first dopant and the second dopant, the balance between HOMO and LUMO in the light emitting layer was achieved, resulting in improved voltage characteristics and charge balance of the device. At the same time, the movement of excitons to the interface of the light emitting layer is reduced, which seems to improve the efficiency of the organic light emitting device. In addition, since the HOMO and LUMO in the light emitting layer are well balanced, the diffusion of excitons to other layers (hole transport layer or electron blocking layer) is reduced, thereby preventing overall deterioration and increasing the lifespan of the organic light emitting device.

Claims (7)

In the organic electroluminescent device in which an organic thin film layer composed of one or a plurality of layers including at least a light emitting layer is laminated between a cathode and an anode,
The dopant constituting the light emitting layer is composed of a first dopant and a second dopant, the HOMO (based on absolute value) of the first dopant is smaller than the HOMO (based on absolute value) of the second dopant, and the LUMO (based on absolute value) of the first dopant is smaller than the LUMO (based on absolute value) of the second dopant. The organic light emitting device according to claim 1, characterized in that the HOMO and LUMO of the first dopant and the second dopant satisfy the following correlation,
0.05 ≤ |HOMO of the second dopant| - |HOMO of the first dopant| ≤ 0.5
0.05 ≤ |LUMO of the second dopant| - |LUMO of the first dopant| ≤ 0.5 The organic electroluminescent device according to claim 1, wherein the first dopant comprises an organic compound represented by Chemical Formula 1 below.
[Formula 1]

in the above formula
Ar1, Ar2, Ar3 and Ar4 are each independently selected from tritium, deuterium, hydrogen, CN, straight chain or branched chain alkyl having 1 to 40 carbon atoms, alkoxy having 1 to 40 carbon atoms, thioalkyl having 1 to 40 carbon atoms, cycloalkyl having 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, pyrazinyl, pyrimidinyl, and quinolinyl groups, substituted or unsubstituted with one or more selected from the group consisting of aromatic hydrocarbon groups having 6 to 60 carbon atoms,
tritium, deuterium, hydrogen, CN, straight chain or branched chain alkyl of 1 to 40 carbon atoms, alkoxy of 1 to 40 carbon atoms, thioalkyl of 1 to 40 carbon atoms, cycloalkyl of 3 to 40 carbon atoms, phenyl, biphenyl, naphthyl, anthracenyl, anthracenyl substituted with a phenyl group, phenanthrenyl, pyrenyl, 9,9-dimethylfluorenyl, spirobi[fluorene ], carbazolyl, dibenzofuranyl, pyrrole, triazole, pyridinyl, pyrazinyl, pyrimidinyl, and quinolinyl substituted or unsubstituted with one or more selected from the group consisting of S, O, N, and Si It is a heteroaromatic hydrocarbon group having 5 to 70 carbon atoms and containing at least one element selected from the group consisting of;
B1 and B2 are each independently selected from straight or branched chain alkyl having 1 to 40 carbon atoms, alkoxy having 1 to 40 carbon atoms, thioalkyl having 1 to 40 carbon atoms, cycloalkyl having 3 to 40 carbon atoms, phenyl, biphenyl, naphthyl, anthracenyl, anthracenyl substituted with a phenyl group, phenanthrenyl, pyrenyl, 9,9-dimethylfluorenyl, carbazolyl, dibenzofuranyl, An aromatic hydrocarbon group having 6 to 60 carbon atoms unsubstituted or substituted with one or more selected from the group consisting of pyrrole, triazole, pyridinyl, pyrazinyl, pyrimidinyl, and quinolinyl;
n and m are each independently 0 and 1;
R1, R2, R3, R4, R5, R6, R7 and R8 are each independently tritium, deuterium, hydrogen, F, Cl, Br, I, CN, Si(CH ₃ ) ₃ , B(OH) ₂ , straight or branched chain alkyl of 1 to 40 carbon atoms, alkoxy of 1 to 40 carbon atoms, thioalkyl of 1 to 40 carbon atoms, or a cycloalkyl group,
삼중수소, 중수소, 수소, F, Cl, Br, I, CN, Si(CH ₃ ) ₃ , B(OH) ₂ , 탄소수 1 내지 40의 직쇄 또는 분지쇄 알킬, 탄소수 1 내지 40의 알콕시, 탄소수 1 내지 40의 티오알킬, 탄소수 3 내지 40의 시클로 알킬, 페닐, 바이페닐, 나프틸, 안트라세닐, 페닐기로 치환된 안트라세닐, 페난트렌일, 파이레닐, 9,9-디메틸플루오레닐, 카르바졸일, 디벤조퓨란일, 피롤, 트리아졸, 피리딘일, 피라지닐, 피리미디닐기, 및 퀴놀리닐기로 이루어진 군으로부터 선택되는 하나 이상으로 치환 또는 비치환된 탄소수 6~60의 방향족 탄화수소기이거나,
삼중수소, 중수소, 수소, F, Cl, Br, I, CN, Si(CH ₃ ) ₃ , B(OH) ₂ , 탄소수 1 내지 40의 직쇄 또는 분지쇄 알킬, 탄소수 1 내지 40의 알콕시, 탄소수 1 내지 40의 티오알킬, 탄소수 3 내지 40의 시클로 알킬, 페닐, 바이페닐, 나프틸, 안트라세닐, 페닐기로 치환된 안트라세닐, 페난트렌일, 파이레닐, 9,9-디메틸플루오레닐, spirobi[fluorene], 카르바졸일, 디벤조퓨란일, 피롤, 트리아졸, 피리딘일, 피라지닐, 피리미디닐기, 및 퀴놀리닐기로 이루어진 군으로부터 선택되는 하나 이상으로 치환 또는 비치환되고, S, O, N 및 Si로 이루어진 군으로부터 선택되는 하나 이상의 원소를 포함하는 탄소수 5 내지 70의 헤테로 방향족 탄화수소기이거나,
삼중수소, 중수소, 수소, F, Cl, Br, I, CN, Si(CH ₃ ) ₃ , B(OH) ₂ , 탄소수 1 내지 40의 직쇄 또는 분지쇄 알킬, 탄소수 1 내지 40의 알콕시, 탄소수 1 내지 40의 티오알킬, 및 탄소수 3 내지 40의 시클로 알킬기로 이루어진 군으로부터 선택되는 1종 이상으로 치환 또는 비치환된 페닐, 바이페닐, 나프틸, 안트라세닐, 페닐기로 치환된 안트라세닐, 페난트렌일, 파이레닐, 9,9-디메틸플루오레닐, 카르바졸일, 퀴놀리닐, 디벤조퓨란일, 피롤, 트리아졸, 피리딘일, 피라지닐, 및 피리미디닐기로 이루어진 군으로부터 선택되는 1종 이상으로 치환된 아미노기이다. The method of claim 3,
The organic compound is characterized in that any one of the following compounds 1-1 to 1-249.
The organic electroluminescent device according to claim 1, wherein the second dopant comprises an organic compound represented by Chemical Formula 2 below.
[Formula 2]


in the above formula
R1은 삼중수소, 중수소, 할로겐, CN, CF ₃ , 탄소수 1 내지 40의 직쇄 또는 분지쇄 알킬, 탄소수 1 내지 40의 알콕시, 탄소수 1 내지 40의 티오알킬, 탄소수 3 내지 40의 시클로 알킬, 페닐, 바이페닐, 나프틸, 안트라세닐기로 치환된 페닐, 나프타닐, 바이페닐, 안트라세닐, 페난트렌일, 파이레닐, 9,9-디메틸플루오레닐, 카르바졸일, 디벤조퓨란일, 피롤, 트리아졸, 피리딘일, 피라지닐, 피리미디닐, 퀴놀리닐, 페닐 피리디닐, 페닐 피리미디닐, 페닐 이미다졸 또는 페닐 트리아지닐기로 이루어진 군으로부터 선택되는 하나 이상으로 치환 또는 비치환된 탄소수 6~60의 방향족 탄화수소기이거나,
삼중수소, 중수소, 할로겐, CN, CF ₃ , 탄소수 1 내지 40의 직쇄 또는 분지쇄 알킬, 탄소수 1 내지 40의 알콕시, 탄소수 1 내지 40의 티오알킬, 탄소수 3 내지 40의 시클로 알킬, 페닐, 바이페닐, 나프틸, 안트라세닐기로 치환된 안트라세닐, 페난트렌일, 파이레닐, 9,9-디메틸플루오레닐, 스파이로바이플루오레닐, 카르바졸일, 디벤조퓨란일, 피롤, 트리아졸, 피리딘일, 피라지닐, 피리미디닐, 퀴놀리닐, 페닐 피리디닐, 페닐 피리미디닐, 페닐 이미다졸 또는 페닐 트리아지닐기로 이루어진 군으로부터 선택되는 하나 이상으로 치환 또는 비치환되고, S, O, N 및 Si로 이루어진 군으로부터 선택되는 하나 이상의 원소를 포함하는 탄소수 5 내지 70의 헤테로 방향족 탄화수소기이며;
Z1, Z4, and Z5 are each independently a single bond or a C1-C10 straight-chain or branched-chain alkyl, C3-C12 cycloalkyl, C1-C10 alkoxy, halogen, CN, CF ₃ , phenyl, naphthanyl, biphenylamine, phenyl pyridinyl, phenyl pyrimidinyl, phenyl imidazole, and Si(CH ₃ ) ₃ substituted or unsubstituted phenyl an amine;
Z2 and Z3 are each independently a single bond or phenyl unsubstituted or substituted with one or more selected from the group consisting of halogen, CN, CF ₃ , phenyl, naphthanyl, phenyl pyridinyl, phenyl pyrimidinyl, phenyl imidazole and Si(CH ₃ ) ₃ groups;
a, b, c, d, e are each independently 0 or 1;
Z6, Z7, Z8 are each independently a single bond, a C1-C2 alkylenyl, phenyl or biphenyl group;
f, g, h are each independently 0 or 1;
M is boron or carbon or nitrogen;
G1, G2 and G3 are each independently carbon or nitrogen or oxygen or sulfur;
G4, G5 and G6 are each independently carbon or nitrogen;
R2, R3, R4, R5, R6, R7, R8 and R9 are each independently hydrogen, deuterium, tritium, F, Cl, Br, I, CN, Si(CH ₃ ) ₃ , B(OH) ₂ , straight or branched chain alkyl of 1 to 40 carbon atoms, alkoxy of 1 to 40 carbon atoms, thioalkyl of 1 to 40 carbon atoms, or a cycloalkyl group,
수소, 중수소, 삼중수소, F, Cl, Br, I, CN, Si(CH ₃ ) ₃ , B(OH) ₂ , 탄소수 1 내지 40의 직쇄 또는 분지쇄 알킬, 탄소수 1 내지 40의 알콕시, 탄소수 1 내지 40의 티오알킬, 탄소수 3 내지 40의 시클로 알킬, 페닐, 바이페닐, 나프틸, 안트라세닐, 페닐기로 치환된 안트라세닐, 페난트렌일, 파이레닐, 9,9-디메틸플루오레닐, 카르바졸일, 디벤조퓨란일, 피롤, 트리아졸, 피리딘일, 피라지닐, 피리미디닐기, 및 퀴놀리닐기로 이루어진 군으로부터 선택되는 하나 이상으로 치환 또는 비치환된 탄소수 6~60의 방향족 탄화수소기이거나,
수소, 중수소, 삼중수소, F, Cl, Br, I, CN, Si(CH ₃ ) ₃ , B(OH) ₂ , 탄소수 1 내지 40의 직쇄 또는 분지쇄 알킬, 탄소수 1 내지 40의 알콕시, 탄소수 1 내지 40의 티오알킬, 탄소수 3 내지 40의 시클로 알킬, 페닐, 바이페닐, 나프틸, 안트라세닐, 페닐기로 치환된 안트라세닐, 페난트렌일, 파이레닐, 9,9-디메틸플루오레닐, spirobi[fluorene], 카르바졸일, 디벤조퓨란일, 피롤, 트리아졸, 피리딘일, 피라지닐, 피리미디닐기, 및 퀴놀리닐기로 이루어진 군으로부터 선택되는 하나 이상으로 치환 또는 비치환되고, S, O, N 및 Si로 이루어진 군으로부터 선택되는 하나 이상의 원소를 포함하는 탄소수 5 내지 70의 헤테로 방향족 탄화수소기이거나,
수소, 중수소, 삼중수소, F, Cl, Br, I, CN, Si(CH ₃ ) ₃ , B(OH) ₂ , 탄소수 1 내지 40의 직쇄 또는 분지쇄 알킬, 탄소수 1 내지 40의 알콕시, 탄소수 1 내지 40의 티오알킬, 및 탄소수 3 내지 40의 시클로 알킬기로 이루어진 군으로부터 선택되는 1종 이상으로 치환 또는 비치환된 페닐, 바이페닐, 나프틸, 안트라세닐, 페닐기로 치환된 안트라세닐, 페난트렌일, 파이레닐, 9,9-디메틸플루오레닐, 카르바졸일, 퀴놀리닐, 디벤조퓨란일, 피롤, 트리아졸, 피리딘일, 피라지닐, 및 피리미디닐기로 이루어진 군으로부터 선택되는 1종 이상으로 치환된 아미노기이다. The method of claim 5,
The organic compound is characterized in that the organic compound is any one of the following compounds 2-1 to 2-376.
The organic electroluminescent device according to claim 1, characterized in that the content of the dopant combination composed of the first dopant and the second dopant is 40% or less compared to the host constituting the light emitting layer,