KR20230108713A - 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 consisting of one or multiple layers including at least a light emitting layer is stacked between a cathode and an anode, wherein the compound constituting the organic thin film layer is an organic compound represented by chemical formula 1.

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 is a substrate, an anode, a hole injection layer that accepts holes from the anode, a hole transport layer that transports holes, an electron blocking layer that blocks electrons from entering the hole transport layer from the light emitting layer, and a combination of holes and electrons to emit light. It consists of a light emitting layer that emits light, a hole blocking layer that blocks the entry of holes from the light emitting layer to the electron transport layer, an electron transport layer that accepts electrons from the cathode and transports them to the light emitting layer, an electron injection layer that accepts electrons from the cathode, and a cathode. In some cases, 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. can be performed simultaneously. The organic thin film layers between the two electrodes are formed by methods such as vacuum deposition, spin coating, inkjet printing, or laser thermal transfer. The reason why 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 movement speed between holes and electrons is large, an appropriate hole transport layer and electron transport layer are used to transport holes. This is because luminous efficiency can be increased by effectively transferring electrons and holes to the light emitting layer so that the density of holes and electrons is balanced.

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. Theoretically, up to 100% 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 aromatic amine compounds, copper phthalocyanine compounds, carbazole derivatives, perylene derivatives, and coumarin are used as dopants. Materials such as coumarine-based derivatives and pyrene-based derivatives are used, but there is a problem in that it is difficult to obtain deep blue and the luminous lifetime becomes shorter as the wavelength goes shorter.

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 material of an organic light emitting device and improves the luminous efficiency and lifespan of the organic light emitting device.

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 above materials of the organic light emitting device.

In addition, an object of the present invention is to provide an organic light emitting device with further improved driving voltage, device efficiency and lifespan by including a combination of the material of the organic light emitting device and a specific hole transport layer material.

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 material of an organic light emitting device and improves the luminous efficiency and lifespan of the organic light emitting device.

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 above materials of the organic light emitting device.

In addition, an object of the present invention is to provide an organic light emitting device with further improved driving voltage, device efficiency and lifespan by including a combination of the material of the organic light emitting device and a specific hole transport layer material.

In addition, the present invention 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 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 3 to 40 carbon atoms. of cycloalkyl, phenyl, biphenyl, naphthyl, anthracenyl, anthracenyl substituted with a phenyl group, phenanthrenyl, pyrenyl, 9,9-dimethylfluorenyl, carbazolyl, dibenzofuranyl, pyrrole, tria An aromatic hydrocarbon group having 6 to 60 carbon atoms unsubstituted or substituted with one or more selected from the group consisting of sol, pyridinyl, pyrazinyl, pyrimidinyl, and quinolinyl groups;

independently deuterium, substituted 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, anthra Cenyl, anthracenyl in which all hydrogens are deuterium substituted with a phenyl group, phenanthrenyl in which all hydrogens are deuterium, pyrenyl in which all hydrogens are deuterium, 9,9-dimethylfluorenyl in which all hydrogens are deuterium, and all hydrogens are deuterium carbazolyl, dibenzofuranyl in which all hydrogens are deuterium, pyrrole in which all hydrogens are deuterium, triazoles in which all hydrogens are deuterium, pyridinyl, pyrazinyl in which all hydrogens are deuterium, pyrimidinyl groups in which all hydrogens are deuterium, and An aromatic hydrocarbon group having 6 to 60 carbon atoms unsubstituted or substituted with one or more selected from the group consisting of a quinolinyl group in which all hydrogens are deuterium;

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

independently deuterium, 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 in which all hydrogens are deuterium substituted with a phenyl group, phenanthrenyl in which all hydrogens are deuterium, pyrenyl in which all hydrogens are deuterium, 9,9-dimethylfluorenyl in which all hydrogens are deuterium, spirobi[fluorene], all hydrogens Carbazolyl with all hydrogens deuterium, dibenzofuranyl with all hydrogens deuterium, pyrrole with all deuterium hydrogens, triazole with all deuterium hydrogens, pyridinyl, pyrazinyl with all deuterium hydrogens, pyrimidi with all deuterium hydrogens substituted or unsubstituted with one or more selected from the group consisting of a yl group and a quinolinyl group in which all hydrogens are deuterium, and having 5 to 70 carbon atoms containing at least one element selected from the group consisting of S, O, N and Si A heteroaromatic hydrocarbon group,

X1 and X2 are each independently oxygen or sulfur,

a, b, c are each independently 0 or 1, and when 0, no bond exists,

R1, R2, and R3 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; , an alkoxy group having 1 to 40 carbon atoms, a thioalkyl group having 1 to 40 carbon atoms, or a cycloalkyl group having 3 to 40 carbon atoms,

each independently a straight or branched chain alkyl of 1 to 40 carbon atoms in which all hydrogens are deuterium, alkoxy of 1 to 40 carbon atoms in which all hydrogens are deuterium, thioalkyl of 1 to 40 carbon atoms in which all hydrogens are deuterium, or all hydrogens are deuterium A cycloalkyl group having 3 to 40 carbon atoms;

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 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 group substituted or unsubstituted with one or more aromatic hydrocarbons having 6 to 60 carbon atoms selected from the group consisting of or

independently deuterium, 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 in which all hydrogens are deuterium, phenanthrenyl in which all hydrogens are deuterium, pyrenyl in which all hydrogens are deuterium, 9,9-dimethylfluorenyl in which all hydrogens are deuterium, carbane in which all hydrogens are deuterium. Zolyl, dibenzofuranyl, all hydrogens are deuterium, pyrrole, all hydrogens are deuterium, triazoles, all hydrogens are deuterium, pyridinyl, all hydrogens are deuterium, pyrazinyl, all hydrogens are deuterium, pyrimidi, all hydrogens are deuterium An aromatic hydrocarbon group having 6 to 60 carbon atoms unsubstituted or substituted with one or more selected from the group consisting of a yl group and a quinolinyl group in which all hydrogens are deuterium;

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 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 S , A heteroaromatic hydrocarbon group having 5 to 70 carbon atoms containing at least one element selected from the group consisting of O, N and Si, or

independently deuterium, 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 in which all hydrogens are deuterium substituted with a phenyl group, phenanthrenyl in which all hydrogens are deuterium, pyrenyl in which all hydrogens are deuterium, 9,9-dimethylfluorenyl in which all hydrogens are deuterium, spirobi[fluorene], all hydrogens Carbazolyl with all hydrogens deuterium, dibenzofuranyl with all hydrogens deuterium, pyrrole with all deuterium hydrogens, triazole with all deuterium hydrogens, pyridinyl with all hydrogens deuterium, pyrazinyl with all deuterium hydrogens, all hydrogens substituted or unsubstituted with at least one selected from the group consisting of a pyrimidinyl group in which all hydrogens are deuterium and a quinolinyl group in which all hydrogens are deuterium, and containing at least one element selected from the group consisting of S, O, N and Si A heteroaromatic hydrocarbon group having 5 to 70 carbon atoms;

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 having 1 to 40 carbon atoms, and cycloalkyl groups having 3 to 40 carbon atoms substituted or unsubstituted with at least one selected from the group consisting of phenyl, biphenyl, naphthyl, anthracenyl, anthracenyl substituted with a phenyl group, selected from the group consisting of phenanthrenyl, pyrenyl, 9,9-dimethylfluorenyl, carbazolyl, quinolinyl, dibenzofuranyl, pyrrole, triazole, pyridinyl, pyrazinyl, and pyrimidinyl groups an amino group substituted with one or more

Each independently substituted with one or more selected from the group consisting of heavy hydrogen, 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 groups having 3 to 40 carbon atoms. or unsubstituted phenyl, biphenyl, naphthyl, anthracenyl, anthracenyl in which all hydrogens are deuterium substituted with a phenyl group, phenanthrenyl in which all hydrogens are deuterium, pyrenyl in which all hydrogens are deuterium, 9 in which all hydrogens are deuterium. ,9-dimethylfluorenyl, carbazolyl with all deuterium hydrogens, quinolinyl with all deuterium hydrogens, dibenzofuranyl with all deuterium hydrogens, pyrrole with all deuterium hydrogens, triazoles with all deuterium hydrogens , An amino group substituted with one or more selected from the group consisting of pyridinyl in which all hydrogens are deuterium, pyrazinyl in which all hydrogens are deuterium, and pyrimidinyl group in which all hydrogens are deuterium.

In addition, the present invention is 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,

It provides an organic electroluminescent device characterized in that the light emitting layer contains the organic compound of the present invention alone or in combination of two or more.

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

The hole transport layer may contain an organic compound represented by Formula 2 below, alone or in combination of two or more:

[Formula 2]

In the above formula,

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

Each of R1, R2, R3 and R4 may be independently bonded to the phenyl group of the basic structure to form an aromatic hydrocarbon or a heteroaromatic hydrocarbon.

The present invention provides a novel organic compound that is used as a material for an organic light emitting device and improves the luminous efficiency and lifespan of the organic light emitting device.

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

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

The present invention relates to a novel 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 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 3 to 40 carbon atoms. of cycloalkyl, phenyl, biphenyl, naphthyl, anthracenyl, anthracenyl substituted with a phenyl group, phenanthrenyl, pyrenyl, 9,9-dimethylfluorenyl, carbazolyl, dibenzofuranyl, pyrrole, tria An aromatic hydrocarbon group having 6 to 60 carbon atoms unsubstituted or substituted with one or more selected from the group consisting of sol, pyridinyl, pyrazinyl, pyrimidinyl, and quinolinyl groups;

independently deuterium, substituted 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, anthra Cenyl, anthracenyl in which all hydrogens are deuterium substituted with a phenyl group, phenanthrenyl in which all hydrogens are deuterium, pyrenyl in which all hydrogens are deuterium, 9,9-dimethylfluorenyl in which all hydrogens are deuterium, and all hydrogens are deuterium carbazolyl, dibenzofuranyl in which all hydrogens are deuterium, pyrrole in which all hydrogens are deuterium, triazoles in which all hydrogens are deuterium, pyridinyl, pyrazinyl in which all hydrogens are deuterium, pyrimidinyl groups in which all hydrogens are deuterium, and An aromatic hydrocarbon group having 6 to 60 carbon atoms unsubstituted or substituted with one or more selected from the group consisting of a quinolinyl group in which all hydrogens are deuterium;

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

independently deuterium, 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 in which all hydrogens are deuterium substituted with a phenyl group, phenanthrenyl in which all hydrogens are deuterium, pyrenyl in which all hydrogens are deuterium, 9,9-dimethylfluorenyl in which all hydrogens are deuterium, spirobi [fluorene], all hydrogens Carbazolyl with all hydrogens deuterium, dibenzofuranyl with all hydrogens deuterium, pyrrole with all deuterium hydrogens, triazole with all deuterium hydrogens, pyridinyl, pyrazinyl with all deuterium hydrogens, pyrimidi with all deuterium hydrogens substituted or unsubstituted with one or more selected from the group consisting of a yl group and a quinolinyl group in which all hydrogens are deuterium, and having 5 to 70 carbon atoms containing at least one element selected from the group consisting of S, O, N and Si A heteroaromatic hydrocarbon group,

X1 and X2 are each independently oxygen or sulfur,

a, b, c are each independently 0 or 1, and when 0, no bond exists,

R1, R2, and R3 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; , an alkoxy group having 1 to 40 carbon atoms, a thioalkyl group having 1 to 40 carbon atoms, or a cycloalkyl group having 3 to 40 carbon atoms,

each independently a straight or branched chain alkyl of 1 to 40 carbon atoms in which all hydrogens are deuterium, alkoxy of 1 to 40 carbon atoms in which all hydrogens are deuterium, thioalkyl of 1 to 40 carbon atoms in which all hydrogens are deuterium, or all hydrogens are deuterium A cycloalkyl group having 3 to 40 carbon atoms;

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 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 group substituted or unsubstituted with one or more aromatic hydrocarbons having 6 to 60 carbon atoms selected from the group consisting of or

independently deuterium, 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 in which all hydrogens are deuterium, phenanthrenyl in which all hydrogens are deuterium, pyrenyl in which all hydrogens are deuterium, 9,9-dimethylfluorenyl in which all hydrogens are deuterium, carbane in which all hydrogens are deuterium. Zolyl, dibenzofuranyl, all hydrogens are deuterium, pyrrole, all hydrogens are deuterium, triazoles, all hydrogens are deuterium, pyridinyl, all hydrogens are deuterium, pyrazinyl, all hydrogens are deuterium, pyrimidi, all hydrogens are deuterium An aromatic hydrocarbon group having 6 to 60 carbon atoms unsubstituted or substituted with one or more selected from the group consisting of a yl group and a quinolinyl group in which all hydrogens are deuterium;

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 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 S , A heteroaromatic hydrocarbon group having 5 to 70 carbon atoms containing at least one element selected from the group consisting of O, N and Si, or

independently deuterium, 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 in which all hydrogens are deuterium substituted with a phenyl group, phenanthrenyl in which all hydrogens are deuterium, pyrenyl in which all hydrogens are deuterium, 9,9-dimethylfluorenyl in which all hydrogens are deuterium, spirobi [fluorene], all hydrogens Carbazolyl with all hydrogens deuterium, dibenzofuranyl with all hydrogens deuterium, pyrrole with all deuterium hydrogens, triazole with all deuterium hydrogens, pyridinyl with all hydrogens deuterium, pyrazinyl with all deuterium hydrogens, all hydrogens substituted or unsubstituted with at least one selected from the group consisting of a pyrimidinyl group in which all hydrogens are deuterium and a quinolinyl group in which all hydrogens are deuterium, and containing at least one element selected from the group consisting of S, O, N and Si A heteroaromatic hydrocarbon group having 5 to 70 carbon atoms;

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 having 1 to 40 carbon atoms, and cycloalkyl groups having 3 to 40 carbon atoms substituted or unsubstituted with at least one selected from the group consisting of phenyl, biphenyl, naphthyl, anthracenyl, anthracenyl substituted with a phenyl group, selected from the group consisting of phenanthrenyl, pyrenyl, 9,9-dimethylfluorenyl, carbazolyl, quinolinyl, dibenzofuranyl, pyrrole, triazole, pyridinyl, pyrazinyl, and pyrimidinyl groups an amino group substituted with one or more

Each independently substituted with one or more selected from the group consisting of heavy hydrogen, 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 groups having 3 to 40 carbon atoms. or unsubstituted phenyl, biphenyl, naphthyl, anthracenyl, anthracenyl in which all hydrogens are deuterium substituted with a phenyl group, phenanthrenyl in which all hydrogens are deuterium, pyrenyl in which all hydrogens are deuterium, 9 in which all hydrogens are deuterium. ,9-dimethylfluorenyl, carbazolyl with all deuterium hydrogens, quinolinyl with all deuterium hydrogens, dibenzofuranyl with all deuterium hydrogens, pyrrole with all deuterium hydrogens, triazoles with all deuterium hydrogens , An amino group substituted with one or more selected from the group consisting of pyridinyl in which all hydrogens are deuterium, pyrazinyl in which all hydrogens are deuterium, and pyrimidinyl group in which all hydrogens are deuterium.

Specific examples of the organic compound include any one of Compounds 1 to 249 below.

Since the organic compound can be used as a material for a blue dopant, can be used as a material for a light emitting layer, can be used as a material for an electron blocking layer, and can improve the performance of an organic light emitting device by mixing with other functional layers, its use do not limit on

The present invention also

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,

It relates to an organic electroluminescent device characterized in that the light emitting layer contains the organic compound alone or in combination of two or more.

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

The hole transport layer may contain an organic compound represented by Formula 2 below, alone or in combination of two or more:

[Formula 2]

In the above formula,

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

Each of R1, R2, R3, and R4 may be independently bonded to a phenyl group of a back bone to form an aromatic hydrocarbon or a heteroaromatic hydrocarbon.

In the above formula, more preferably,

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

The R1, R2, R3, and R4 may each independently bond to a phenyl group of a basic structure to form naphthalene, anthracene, or phenanthrene.

Specific examples of the organic compound include any one of the following compounds 250 to 261.

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 method of manufacturing an 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. Materials for the hole injection layer include copper phthalocyanine (CuPc), 4,4',4"-tris(3-methylphenylamino)triphenylamine (m-MTDATA), and 4,4',4"-tris(3-methylphenyl). Amino) phenoxybenzene (m-MTDAPB), starburst type amines 4,4',4"-tri(N-carbazolyl)triphenylamine (TCTA), 4,4',4"-tris (N-(2-naphthyl)-N-phenylamino)-triphenylamine (2-TNATA) or IDE406 available from Idemitsu is exemplified.

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, the hole transport layer material is bis (N- (1-naphthyl-n-phenyl)) benzidine (α-NPD), N, N'-di (naphthalen-1-yl) -N, N'-biphenyl Examples include -benzidine (NPB) or N,N'-biphenyl-N,N'-bis(3-methylphenyl)-1,1'-biphenyl-4,4'-diamine (TPD); More preferably, the compound of Formula 2 of the present invention 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, bis((3,5-difluoro-4-cyanophenyl)pyridine) iridium picolinate (FCNIrpic), tris( 8-hydroxyquinoline) aluminum (Alq3), polyaromatic compounds such as anthracene, phenanthrene, pyrene, chrysene, perylene, coronene, rubrene and quinacridone, oligophenylene compounds such as quaterphenyl, 1, 4-bis (2-methylstyryl) benzene, 1,4-bis (4-methylstyryl) benzene, 1,4-bis (4-methyl-5-phenyl-2-oxazolyl) benzene, 1,4 -bis(5-phenyl-2-oxazolyl)benzene, 2,5-bis(5-t-butyl-2-benzoxazolyl)thiophene, 1,4-diphenyl-1,3-butadiene, 1, Scintillators for liquid scintillation such as 6-diphenyl-1,3,5-hexatriene and 1,1,4,4-tetraphenyl-1,3-butadiene, metal complexes of auxin derivatives, coumarin pigments, dicyano Methylenepyran pigment, dicyanomethylenethiopyran pigment, polymethine pigment, oxobenzanthracene pigment, xanthene pigment, carbostyril pigment, perylene pigment, oxazine compound, stilbene derivative, spiro compound, oxadiazole compound, etc. can be heard 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 may be carried out by vacuum thermal evaporation and spin coating of the hole blocking layer material in a conventional manner. In the case of the hole blocking layer material, it is not particularly limited, but preferably (8-hydroxyquinolinola To) lithium (Liq), bis(8-hydroxy-2-methylquinolinolnato)-aluminum biphenoxide (BAlq), bathocuproine (BCP), Bphen, and the like 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. In this case, 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, the negative electrode material used is lithium (Li), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium (Mg), magnesium-indium (Mg-In), magnesium-silver (Mg-Ag) and the like 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 described above, that is, in the order of anode/hole injection layer/hole transport layer/light emitting layer/electron transport layer/electron injection layer/cathode, or vice versa, cathode/electron injection layer/ It may be prepared in the order of electron transport layer/light emitting layer/hole transport layer/hole injection layer/anode.

Hereinafter, a method for synthesizing the compound of Formula 1 will be described below as a representative example. However, the synthesis method of the compounds of the present invention is not limited to the methods exemplified below, and the compounds of the present invention may be prepared by methods exemplified below and methods known in the art.

In particular, in the preparation of the following tritium-containing intermediate, this example explains that a new tritium intermediate can be prepared by substituting tritium in an existing intermediate, and the method for preparing the compound of the present invention is illustrated below. method is not limited. In addition, it is obvious that the compound of Formula 1 can also prepare a tritium compound through such a tritium substitution method.

<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 of Intermediate-1 (78% yield, 79% tritium conversion).

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% yield) 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% yield, 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% yield) of Intermediate-4.

Intermediate-4 MS (FAB): 209 (M ⁺ )

<Synthesis of Intermediate-5>

에 서 42시간 동안 교반하였다. 실온까지 냉각시킨 후, 침전물을 여과하고, 아세톤(25 mL), 이어서 탈이온수 50 mL, 이어서 희석 HCl 50 ml(5 v/v%), 이어서 물 50ml, 마지막으로 아세톤25ml으로 세척하였다. 얻어진 고체를 감압 하에서 건조시키고 column하여 중간체-5 3.4g(71% yield)을 얻었다.After adding 2.75g (8.65mmol) of 3,7-dibromonaphthalene-2,6-diol to 250ml of acetone in a 1L 3-necked round bottom flask, 3.45g (17.3mmol) of 2-bromo-1-phenylethan-1-one and K2CO3 4.78 g, 34.6 mmol) was added. 65 mixture

was stirred for 42 hours. After cooling to room temperature, the precipitate was filtered and washed with acetone (25 mL), then 50 mL of deionized water, then 50 ml of dilute HCl (5 v/v%), then 50 ml of water, and finally 25 ml of acetone. The obtained solid was dried under reduced pressure and columned to obtain 3.4 g (71% yield) of Intermediate-5.

Intermediate-5 MS (FAB): 554 (M+)

<Synthesis of Intermediate-6>

에서 12시간 교반한 후，실온으로 냉각한다. 포화 염화암모니아 수용액을 넣고 반응을 종결시키고, 물과 디클로로메탄를 투입한 후，층분리하고 유기층을 얻는다. Na2SO4로 건조한 후 여과한다. 여액을 농축시킨 후，이소프로판올을 투입한다. 생성된 고체를 여과하고 column하여 중간체-6 3.96g (71% yield, 삼중수소 전환 10%)을 얻었다.In a 100ml three-neck round bottom flask, 5.54 g (10 mmol) of intermediate-5, 668 mg (2.4 mmol) of silver carbonate, 1.63 g (6.1 mmol) of cyclohexyldiphenylphosphine, 1.67 g (12 mmol) of potassium carbonate, tritiated water (T2O) ) 5.29 g (0.24 mol) and 10 mL of toluene were added. 120

After stirring 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 Na2SO4, filter. After concentrating the filtrate, isopropanol is added. The resulting solid was filtered and columned to obtain 3.96 g of Intermediate-6 (71% yield, 10% tritium conversion).

Intermediate-6 MS (FAB): 558 (M+)

<Synthesis of Intermediate-7>

에서 가열 환류시켰다. 현탁액은 회백색의 우윳빛이었다. 여기에 메탄 설폰산 2.75g(28.6mmol)을 첨가하였다. 혼합물을 78

에서 16시간동안 교반하였다. 이어서, 실온까지 냉각시켰다. 반응 현탁액을 감압하에서 농축시켰다. 생성물을 column하고, 헥산에서 재결정하여 중간체-7 0.51g(26% yield)을 얻었다.2.08 g (3.72 mmol) of Intermediate-6 was added to a 500 ml 3-necked round bottom flask followed by 150 ml of chloroform. 78 mixture

heated to reflux. The suspension was an off-white milky color. To this was added 2.75 g (28.6 mmol) of methane sulfonic acid. 78 mixture

was stirred for 16 hours. It was then cooled to room temperature. The reaction suspension was concentrated under reduced pressure. The product was columned and recrystallized from hexane to obtain 0.51 g (26% yield) of Intermediate-7.

Intermediate-7 MS (FAB): 522 (M+)

<Synthesis of Intermediate-8>

에 서 42시간 동안 교반하였다. 실온까지 냉각시킨 후, 침전물을 여과하고, 아세톤(25 mL), 이어서 탈이온수 50 mL, 이어서 희석 HCl 50 ml(5 v/v%), 이어서 물 50ml, 마지막으로 아세톤25ml으로 세척하였다. 얻어진 고체를 감압 하에서 건조시키고 column하여 중간체-8 1.56g(74% yield)을 얻었다.1.39g (8.65mmol) of naphthalene-2,6-diol and 250ml of acetone were added to a 1L 3-necked round bottom flask, and then 2.13g (17.3mmol) of 2-bromoacetaldehyde and 4.78g (34.6mmol) of K2CO3 were added. 65 mixture

was stirred for 42 hours. After cooling to room temperature, the precipitate was filtered and washed with acetone (25 mL), then 50 mL of deionized water, then 50 ml of dilute HCl (5 v/v%), then 50 ml of water, and finally 25 ml of acetone. The obtained solid was dried under reduced pressure and columned to obtain 1.56 g (74% yield) of Intermediate-8.

Intermediate-8 MS (FAB): 244 (M+)

<Synthesis of Intermediate-9>

에서 가열 환류시켰다. 현탁액은 회백색의 우윳빛이었다. 여기에 메탄설폰산 2.75g(28.6mmol)을 첨가하였다. 혼합물을 78

에서 16시간동안 교반하였다. 이어서, 실온까지 냉각시켰다. 반응 현탁액을 감압하에서 농축시켰다. 생성물을 column하고, 헥산에서 재결정하여 중간체-9 0.25g(32% yield)을 얻었다.0.91 g (3.72 mmol) of Intermediate-8 was added to a 500 ml three-necked round bottom flask followed by 150 ml of chloroform. 78 mixture

heated to reflux. The suspension was an off-white milky color. 2.75 g (28.6 mmol) of methanesulfonic acid was added thereto. 78 mixture

was stirred for 16 hours. It was then cooled to room temperature. The reaction suspension was concentrated under reduced pressure. The product was columned and recrystallized from hexane to obtain 0.25 g (32% yield) of Intermediate-9.

Intermediate-9 MS (FAB): 208 (M+)

<Synthesis of Intermediate-10>

To a 500 ml three-neck round bottom flask, 3.0 g (14.4 mmol) of Intermediate-9, 100 ml of chloroform and 20 ml of acetic acid were added, and 5.38 g (30.2 mmol) of N-bromosuccinimide was added. The reaction was stirred at reflux for 1 hour. First, a clear solution formed, followed by a pale yellow precipitate. After cooling to room temperature, water was added. The organic phase was separated, washed with water, saturated brine and dried over MgSO4. Thereafter, the solution was columned, and the residue was recrystallized with chloroform/hexane to obtain 3.9 g (74% yield) of Intermediate-10.

Intermediate-10 MS (FAB): 366 (M+)

<Synthesis of Intermediate-11>

에서 12시간 교반한 후，실온으로 냉각한다. 포화 염화암모니아 수용액을 넣고 반응을 종결시키고, 물과 디클로로메탄를 투입한 후，층분리하고 유기층을 얻는다. Na2SO4로 건조한 후 여과한다. 여액을 농축시킨 후，이소프로판올을 투입한다. 생성된 고체를 여과하고 column하여 중간체-11 2.78g (75% yield, 삼중수소 전환 27%)을 얻었다.In a 100ml three-necked round bottom flask, 3.66 g (10 mmol) of intermediate-10, 668 mg (2.4 mmol) of silver carbonate, 1.63 g (6.1 mmol) of cyclohexyldiphenylphosphine, 1.67 g (12 mmol) of potassium carbonate, tritiated water (T2O) ) 5.29 g (0.24 mol) and 10 mL of toluene were added. 120

After stirring 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 Na2SO4, filter. After concentrating the filtrate, isopropanol is added. The resulting solid was filtered and columned to obtain 2.78 g of Intermediate-11 (75% yield, 27% tritium conversion).

Intermediate-11 MS (FAB): 370 (M+)

<Synthesis of Intermediate-12>

4.46 g (20 mmol) of 7-bromonaphthalen-2-ol was dissolved in 100 mL toluene in a 500 ml three-necked round bottom flask, and 8.34 g (30 mmol) of 2-bromo-1-(4-bromophenyl)ethan-1-one was added thereto. was added. 13 g of basic alumina was added, and the mixture was stirred at reflux for 16 hours under atmospheric conditions. After filtering the reaction solution, the slightly orange clear solution was recrystallized and columned to obtain 5.71 g (71% yield) of Intermediate-12.

Intermediate-12 MS (FAB): 402 (M+)

<Synthesis of Intermediate-13>

에서 24시간 교반한 후，실온으로 냉각한다. 감압 여과 후, 유기용매를 농축하여 생성된 화합물을 Hex : EA = 5 : 1로 column하여 중간체-13 3.27g (81% yield, 삼중수소 전환 8%)을 얻었다.Put 4.02g (10mmol) of Intermediate-12, 98mg (0.50mmol) of Pt/C, 3.0mL of isopropanol, and 60mL of cyclonucleic acid in a 250ml 3-necked round bottom flask. 140 under T2 atmosphere in high-pressure reactor

After stirring for 24 hours, cool 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 3.27 g of Intermediate-13 (81% yield, 8% tritium conversion).

Intermediate-13 MS (FAB): 404 (M+)

<Synthesis of Intermediate-14>

에서 12시간동안 교반하였다. 반응혼합물을 클로로포름 250 ml으로 2번 희석시켰다. 생성된 현탁액을 물 300ml와 HCl 10mL(1N)로 세척하였다. 유기층을 층분리해 회전증발 하에서 농축시켜 슬러지를 얻었다. 슬러지를 DCM 200ml에 용해시키고 물 300ml로 세척하였다. 유기층을 Na2SO4로 건조시키고, 여과한 후 회전증발기에서 농축시키고 column하여 중간체-14 1.49g(58% yield)을 얻었다.Pd(PPh3)2Cl2 (0.350 g, 0.497 mmol), IPr2NH 50mL, and DMAc 50ml were added to a 250ml 3-necked round bottom flask under a nitrogen atmosphere, followed by CuI 0.190g (1.00mmol), 3,7-dibromonaphthalene-2,6- 2.01 g (5 mmol) of diyl diacetate and 1.38 g (10.10 mmol) of 1-chloro-4-ethynylbenzene were added. Reaction mixture to 60

was stirred for 12 hours. The reaction mixture was diluted twice with 250 ml of chloroform. The resulting suspension was washed with 300 ml of water and 10 ml of HCl (1N). The organic layer was layer-separated and concentrated under rotary evaporation to obtain a sludge. The sludge was dissolved in 200 ml of DCM and washed with 300 ml of water. The organic layer was dried over Na 2 SO 4 , filtered, concentrated on a rotary evaporator, and columned to obtain 1.49 g (58% yield) of Intermediate-14.

Intermediate-14 MS (FAB): 513 (M+)

<Synthesis of Intermediate-15>

에서 밤새 교반하였다. 실온까지 냉각시킨 후, 탈이온수 40ml를 첨가하였다. 침전물을 여과하고 탈이온수 20ml, 메탄올 20ml 및 클로로포름 20ml으로 세척하였다. 침전물을 감압하에서 건조시켜 중간체-15 0.47g(89% yield)을 얻었다.To a 250 mL 3-neck round bottom flask was added 0.63 g (1.23 mmol) of Intermediate-14, followed by 20 ml of DMAc and 4.00 g (12.3 mmol) of cesium carbonate and 4 ml of deionized water. 80 to the mixture

was stirred overnight. After cooling to room temperature, 40 ml of deionized water was added. The precipitate was filtered and washed with 20 ml of deionized water, 20 ml of methanol and 20 ml of chloroform. The precipitate was dried under reduced pressure to obtain 0.47 g (89% yield) of Intermediate-15.

Intermediate-15 MS (FAB): 513 (M+)

<Synthesis of Intermediate-16>

에서 24시간 교반한 후，실온으로 냉각한다. 감압 여과 후, 유기용매를 농축하여 생성된 화합물을 Hex : EA = 5 : 1로 column하여 중간체-16 3.68g (85% yield, 삼중수소 전환 10%)을 얻었다.4.29g (10mmol) of Intermediate-15, 98mg (0.50mmol) of Pt/C, 3.0mL of isopropanol, and 60mL of cyclonucleic acid were put in a 250ml 3-necked round bottom flask. 140 under T2 atmosphere in high-pressure reactor

After stirring for 24 hours, cool 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 3.68 g of Intermediate-16 (85% yield, 10% tritium conversion).

Intermediate-16 MS (FAB): 433 (M+)

<Synthesis of Intermediate-17>

에서 18시간동안 교반하였다. 반응혼합물을 실온까지 냉각시키고, 물200ml로 ??칭시켰다. ??칭된 혼합물을 에틸아세테이트 100ml로 5회 추출하고, MgSO4로 건조시키고, 감압 하에서 농축하여 생성된 화합물을 Hex : EA = 5 : 1로 column하여 중간체-17 2.39g (71% yield)을 얻었다.1.61 g (10.0 mmol) of naphthalene-2,7-diol was dissolved in N,N-dimethylformamide (33.3 mL) in a 250 ml three-necked round bottom flask under a nitrogen atmosphere. To this solution, 0.48 g (20 mmol) of sodium hydride was added little by little. The reaction mixture was stirred for 30 minutes. 3.72 g (22 mmol) of 2-bromo-1,1-dimethoxyethane was added dropwise. After completion of the addition, the reaction mixture was heated to 130

was stirred for 18 hours. The reaction mixture was cooled to room temperature and quenched with 200 ml of water. The quenched mixture was extracted 5 times with 100 ml of ethyl acetate, dried with MgSO4, and concentrated under reduced pressure. The resulting compound was columned at Hex:EA = 5:1 to obtain 2.39 g (71% yield) of Intermediate-17.

Intermediate-17 MS (FAB): 336 (M+)

<Synthesis of Intermediate-18>

1.01 g (3.00 mmol) of Intermediate-17 and 30 ml of chlorobenzene were added to a 250 ml three-necked round bottom flask. 10.0 g of polyphosphoric acid was added, and the reaction mixture was stirred at reflux for 19 hours. After completion of the reaction, it was cooled to room temperature and filtered. The filtered grayish solid was washed 5 times with 100 ml hot toluene, added with 200 ml water, extracted with 50 ml toluene, washed 5 times with 50 ml brine, dried over magnesium sulfate and concentrated under reduced pressure. The obtained product was columned in dichloromethane: hexane = 1: 9 to obtain 0.22 g (35% yield) of Intermediate-18.

Intermediate-18 MS (FAB): 208 (M+)

<Synthesis of Intermediate-19>

3.0 g (14.4 mmol) of Intermediate-18, 100 ml of chloroform and 20 ml of acetic acid were added to a 500 ml three-necked round bottom flask, and 5.38 g (30.2 mmol) of N-bromosuccinimide was added. The reaction was stirred at reflux for 1 hour. First, a clear solution formed, followed by a pale yellow precipitate. After cooling to room temperature, water was added. The organic phase was separated, washed with water, saturated brine and dried over MgSO4. Thereafter, the solution was columned, and the residue was recrystallized from chloroform/hexane to obtain 4.16 g (79% yield) of Intermediate-19.

Intermediate-19 MS (FAB): 366 (M+)

<Synthesis of Intermediate-20>

에서 24시간 교반한 후，실온으로 냉각한다. 감압 여과 후, 유기용매를 농축하여 생성된 화합물을 Hex : EA = 5 : 1로 column하여 중간체-20 3.22g (87% yield, 삼중수소 전환 30%)을 얻었다.Put 3.66 g (10 mmol) of Intermediate-19, 98 mg (0.50 mmol) of Pt/C, 3.0 mL of isopropanol, and 60 mL of cyclonucleic acid in a 250 ml 3-necked round bottom flask. 140 under T2 atmosphere in high-pressure reactor

After stirring for 24 hours, cool 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 3.22 g of Intermediate-20 (87% yield, 30% tritium conversion).

Intermediate-20 MS (FAB): 370 (M+)

<Synthesis of Intermediate-21>

에서 고온 여과하여 알루미나를 제거하고, 농축하고 결정화시켰다. 생성된 고체를 여과하고 메탄올로 세척한후 중간체-21 4.82g (31% yield)을 얻었다.18.34g (66mmol) of 2-bromo-1-(4-bromophenyl)ethan-1-one, 4.81g (30mmol) of naphthalene-2,3-diol, and 150ml of toluene were added to a 250ml 3-necked round bottom flask. 50 g of basic alumina was added and the slurry was stirred under reflux for 16 hours. Reaction mixture to 70

The alumina was removed by hot filtration, concentrated and crystallized. The resulting solid was filtered and washed with methanol to obtain 4.82 g (31% yield) of Intermediate-21.

Intermediate-21 MS (FAB): 518 (M+)

<Synthesis of Intermediate-22>

에서 24시간 교반한 후，실온으로 냉각한다. 감압 여과 후, 유기용매를 농축하여 생성된 화합물을 Hex : EA = 5 : 1로 column하여 중간체-22 4.20g (81% yield, 삼중수소 전환 12%)을 얻었다.Put 3.66 g (10 mmol) of Intermediate-21, 98 mg (0.50 mmol) of Pt/C, 3.0 mL of isopropanol, and 60 mL of cyclonucleic acid in a 250 ml three-necked round bottom flask. 140 under T2 atmosphere in high-pressure reactor

After stirring for 24 hours, cool 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 4.20 g of Intermediate-22 (81% yield, 12% tritium conversion).

Intermediate-22 MS (FAB): 522 (M+)

<Synthesis of Intermediate-23>

3-bromobenzo[b]benzo[4,5]thieno[2,3-f]benzofuran 3.53g (10mmol) and Pt/C 114mg (0.50mmol), tritiated water (DTO) 2mL, 2-pentanol 3.0mL , Add 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 columnized to obtain 2.17 g of Intermediate-23 (61% yield, 7% tritium conversion).

Intermediate-23 MS (FAB): 356 (M+)

<Synthesis of Intermediate-24>

5-bromobenzo[4,5]thieno[2,3-f]naphtho[2,1-b]benzofuran 4.03g (10mmol) and Pt/C 114mg (0.50mmol), tritiated water (DTO) 2mL, 2- Add 3.0 mL of 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 2.36 g of Intermediate-24 (58% yield, 6% tritium conversion).

Intermediate-24 MS (FAB): 406 (M+)

<Synthesis of Intermediate-25>

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 500 ml of water was added thereto, and the organic layer was extracted. Recrystallization from N-hexane/MC yielded 122 g (63% yield) of Intermediate-25.

Intermediate-25 MS (FAB): 301 (M ⁺ )

<Synthesis of Intermediate-26>

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-26.

Intermediate-26 MS (FAB): 169 (M ⁺ )

<Synthesis of Intermediate-27>

60.3g (244mmol) of 4-bromodibenzofuran and 41.4g (244mmol) of Intermediate-26 were dissolved in 600ml of Toluene, and then 117.2g (1220mmol) 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-27.

Intermediate-27 MS (FAB): 335 (M ⁺ )

<Synthesis of Intermediate-28>

After dissolving 59g (175.7mmol) of Intermediate-27 in 600ml of DMA, 33.8g (351.4mmol) of sodium tert-butoxide was added. After adding 1.18g (5.27mmol) of Palladium acetate and 1.53g (5.27mmol) of t-Bu ₃ PHBF _4, it was refluxed for 6 hours. After completion of the reaction, the mixture was cooled to room temperature, 500ml of EA and 1L of water were added thereto, and the EA layer was extracted. After column, it was recrystallized with n-hexane/MC to obtain 30.5 g (58% yield) of Intermediate-28.

Intermediate-28 MS (FAB): 299 (M ⁺ )

<Synthesis of Intermediate-29>

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-29.

Intermediate-29 MS (FAB): 198 (M ⁺ )

<Synthesis of Intermediate-30>

After dissolving 57.8 g (291.6 mmol) of Intermediate-29 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-30.

Intermediate-30 MS (FAB): 356 (M ⁺ )

<Synthesis of Intermediate-31>

After adding 84.1g (236.2mmol) of Intermediate-30 to 1L of ethanol, 100ml of H ₂ SO ₄ was slowly added. 48.9 g (708.6 mmol) of NaNO ₂ was added slowly. After refluxing for 2 hours, 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-31.

Intermediate-31 MS (FAB): 325 (M ⁺ )

<Synthesis of Intermediate-32>

After dissolving 24.6g (75.6mmol) of Intermediate-31 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-32.

Intermediate-32 MS (FAB): 380 (M ⁺ )

<Synthesis of Intermediate-33>

After dissolving 16.1g (42.3mmol) of Intermediate-32 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-33.

Intermediate-33 MS (FAB): 299 (M ⁺ )

<Synthesis of Intermediate-34>

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. It was recrystallized from n-hexane/MC to obtain 83 g (84% yield) of Intermediate-34.

Intermediate-34 MS (FAB): 244 (M ⁺ )

<Synthesis of Intermediate-35>

After dissolving 83 g (340 mmol) of Intermediate-34 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 EA 1L and water 1L, distillation and column to obtain 38.2g (39% yield) of Intermediate-35.

Intermediate-35 MS (FAB): 288 (M ⁺ )

<Synthesis of Intermediate-36>

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-36.

Intermediate-36 MS (FAB): 214 (M ⁺ )

<Synthesis of Intermediate-37>

After dissolving 38.2 g (132.6 mmol) of Intermediate-33 and 28.4 g (132.6 mmol) of Intermediate-34 in 300 ml of MC, 482 mg (2.65 mmol) of Cupper acetate was added and reacted for 24 hours while blowing air. After completion of the reaction, column was performed to obtain 52 g (86% yield) of Intermediate-37.

Intermediate-37 MS (FAB): 456 (M ⁺ )

<Synthesis of Intermediate-38>

After dissolving 52g (114mmol) of Intermediate-35 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, 1000 ml of EA and 1000 ml of water were added, and the EA layer was extracted. After column, it was recrystallized with n-hexane/MC to obtain 22.3 g (52% yield) of Intermediate-38.

Intermediate-38 MS (FAB): 375 (M ⁺ )

<Synthesis of Intermediate-39>

After dissolving 100 g (306.8 mmol) of Intermediate-31 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-39.

Intermediate-39 MS (FAB): 420 (M ⁺ )

<Synthesis of Intermediate-40>

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-40.

Intermediate-40 MS (FAB): 261 (M ⁺ )

<Synthesis of Intermediate-41>

100g (383mmol) of Intermediate-38 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. Recrystallization from n-hexane/MC yielded 84.5 g (76% yield) of Intermediate-41.

Intermediate-41 MS (FAB): 290 (M ⁺ )

<Synthesis of Intermediate-42>

56.7g (135mmol) of Intermediate-39 and 39.2g (135mmol) of Intermediate-41 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-42.

Intermediate-42 MS (FAB): 503 (M ⁺ )

<Synthesis of Intermediate-43>

After dissolving 24.5 g (48.6 mmol) of Intermediate-42 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 obtained to obtain 15.3 g (84% yield) of Intermediate-43.

Intermediate-43 MS (FAB): 375 (M ⁺ )

<Synthesis of Intermediate-44>

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, distillation and column to obtain 83.1g (63% yield) of Intermediate-44.

Intermediate-44 MS (FAB): 325 (M ⁺ )

<Synthesis of Intermediate-45>

After dissolving 83.1 g (255 mmol) of Intermediate-44 and 54.6 g (255 mmol) of Intermediate-34 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-45.

Intermediate-45 MS (FAB): 459 (M ⁺ )

<Synthesis of Intermediate-46>

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-46 39.

Intermediate-46 MS (FAB): 406 (M ⁺ )

<Synthesis of Intermediate-47>

69g (150.3mmol) of Intermediate-45 and 61g (150.3mmol) of Intermediate-46 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-47.

Intermediate-47 MS (FAB): 451 (M ⁺ )

<Synthesis of Intermediate-48>

Add 3.01 g (10 mmol) of Intermediate-25, 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 columnized to obtain 2.19 g of Intermediate-48 (72% yield, 5% tritium conversion).

Intermediate-48 MS (FAB): 304 (M+)

<Synthesis of Intermediate-49>

Add 2.99 g (10 mmol) of Intermediate-28, 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 columnized to obtain 2.27 g of Intermediate-49 (75% yield, 5.8% tritium conversion).

Intermediate-49 MS (FAB): 302 (M+)

Synthesis of Intermediate-50

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

After the reaction was completed, the temperature of the reactant was cooled to room temperature, extracted using 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 Hex : EA = 5: 1 to obtain 2.45 g (89% yield) of Intermediate-50.

Intermediate-50 MS (FAB): 275 (M ⁺ )

Synthesis of Intermediate-51

After injecting 2.09 g (10 mmol) of Intermediate-4 and 1.35 g (10 mmol) of 4-isopropylaniline under nitrogen and dissolving them in 40 ml of toluene, 0.05 g (0.2 mmol) of Pd (OAc) ₂ and 0.4 ml of 1M t-Bu ₃ P (0.4 mmol) and 2.88 g (30 mmol) of t-BuONa, respectively, and then refluxed for 6 hours.

After the reaction was completed, the temperature of the reactant was cooled to room temperature, extracted using 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 Hex : EA = 5: 1 to obtain 2.29 g (87% yield) of Intermediate-51.

Intermediate-51 MS (FAB): 263 (M ⁺ )

<Synthesis of Compound-1>

After dissolving 22.9g (43.8mmol) of Intermediate-7 and 29.3g (96.4mmol) of Intermediate-48 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 24.1 g (57% yield) of Compound-1.

MS(FAB): 967(M ⁺ )

<Synthesis of Compound-13>

After dissolving 19.1g (51.5mmol) of Intermediate-11 and 32.7g (108.2mmol) of Intermediate-49 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 26.0 g (62% yield) of Compound-13.

MS(FAB): 812(M ⁺ )

<Synthesis of Compound-25>

After dissolving 20.8g (51.5mmol) of Intermediate-13 and 32.4g (108.2mmol) of Intermediate-33 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 28.2 g (65% yield) of Compound-25.

MS(FAB): 841(M ⁺ )

<Synthesis of Compound-37>

After dissolving 22.3g (51.5mmol) of Intermediate-16 and 40.6g (108.2mmol) of Intermediate-38 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 30.3 g (53% yield) of Compound-37.

MS(FAB): 985(M ⁺ )

<Synthesis of Compound-49>

After dissolving 26.9g (51.5mmol) of Intermediate-7 and 48.9g (108.2mmol) of Intermediate-47 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 37.7 g (58% yield) of Compound-49.

MS(FAB): 1263(M ⁺ )

<Synthesis of Compound-61>

After dissolving 19.1g (51.5mmol) of Intermediate-20 and 40.6g (108.2mmol) of Intermediate-43 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 24.2 g (49% yield) of Compound-61.

MS(FAB): 959(M ⁺ )

<Synthesis of Compound-73>

After dissolving 20.4g (39mmol) of Intermediate-22 and 24.8g (82mmol) of Intermediate-28 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 26.7 g (71% yield) of Compound-73.

MS(FAB): 965(M ⁺ )

<Synthesis of Compound-75>

After dissolving 7.9g (22.1mmol) of Intermediate-23 and 7.4g (24.3mmol) of Intermediate-48 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 9.7 g (76% yield) of Compound-75.

MS(FAB): 578(M ⁺ )

<Synthesis of Compound-87>

After dissolving 8.5 g (21 mmol) of Intermediate-24 and 7.0 g (23 mmol) of Intermediate-49 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-87.

MS(FAB): 627(M ⁺ )

<Synthesis of Compound-100>

After dissolving 11.3g (21.7mmol) of Intermediate-22 and 14.6g (47.8mmol) of Intermediate-48 in 300ml of toluene, 8.4g (86.9mmol) 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 16.2 g (77% yield) of Compound-100.

MS(FAB): 967(M ⁺ )

<Synthesis of Compound-123>

After dissolving 25.1 g (48.1 mmol) of Intermediate-22 and 30.5 g (100.9 mmol) of Intermediate-49 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 34.4 g (74% yield) of Compound-123.

MS(FAB): 965(M ⁺ )

<Synthesis of Compound-196>

After injecting 3.7g (10mmol) of Intermediate-20 and 6.6g (22mmol) of Intermediate-28 under nitrogen and dissolving them in 60ml of toluene, 0.05g (0.2mmol) of Pd(OAc) _{2 and} 0.4ml (0.4ml) of 1M t-Bu _3P 3P mmol) and 2.88 g (30 mmol) of t-BuONa, respectively, 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 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 Hex : EA = 3: 1 to obtain 6.3 g (79% yield) of Compound-196.

MS(FAB): 802(M ⁺ )

<Synthesis of Compound-245>

After injecting 5.2g (10mmol) of Intermediate-7 and 5.8g (22mmol) of Intermediate-51 under nitrogen and dissolving in 60ml of toluene, 0.05g (0.2mmol) of Pd(OAc) _{2 and} 0.4ml (0.4ml) of 1M t-Bu ₃ P mmol) and 2.88 g (30 mmol) of t-BuONa, respectively, 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 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 Hex : EA = 3: 1 to obtain 5.2g (59% yield) of Compound-245.

MS(FAB): 887(M ⁺ )

<Synthesis of Compound of Formula 2>

<Synthesis of Intermediate-52>

[1,1'-biphenyl] -4-amine 1.69g (10mmol) and 4-iodo-1,1':4',1''-terphenyl 3.56g (10mmol) were injected under nitrogen, and toluene 50ml After dissolving in, Pd ₂ dba ₃ 0.18g (0.2mmol), 1M t-Bu _3P 0.4ml (0.4mmol), and t-BuONa 2.88g (30mmol) were added, respectively, 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 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 Hex : EA = 4: 1 to obtain 3.02 g (76% yield) of Intermediate-52.

Intermediate-52 MS (FAB): 397 (M ⁺ )

<Synthesis of Intermediate-53>

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

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 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 Hex : EA = 3: 1 to obtain 3.98 g (72% yield) of Intermediate-53.

Intermediate-53 MS (FAB): 552 (M ⁺ )

<Synthesis of Intermediate-54>

After injecting 0.93g (10mmol) of aniline and 3.56g (10mmol) of 4-iodo-1,1':4',1''-terphenyl under nitrogen and dissolving in 50ml of toluene, Pd ₂ dba ₃ 0.18g (0.2 mmol), 0.4 ml (0.4 mmol) of 1M t-Bu ₃ P, and 2.88 g (30 mmol) of t-BuONa, respectively, 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 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 Hex : EA = 5: 1 to obtain 2.38 g (74% yield) of Intermediate-54.

Intermediate-54 MS (FAB): 321 (M ⁺ )

<Synthesis of Intermediate-55>

After injecting 0.93g (10mmol) of aniline and 2.80g (10mmol) of 4-iodo-1,1'-biphenyl under nitrogen and dissolving them in 50ml of toluene, Pd ₂ dba ₃ 0.18g (0.2mmol), 1M t-Bu 0.4ml (0.4mmol) of _3P and 2.88g (30mmol) of t-BuONa were added, respectively, 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 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 Hex : EA = 5: 1 to obtain 1.99g (81% yield) of Intermediate-51.

Intermediate-55 MS (FAB): 245 (M ⁺ )

<Synthesis of Intermediate-56>

After injecting 2.45 g (10 mmol) of Intermediate-55 and 3.59 g (10 mmol) of 4-bromo-4'-iodo-1,1'-biphenyl under nitrogen and dissolving in 60 ml of toluene, Pd ₂ dba ₃ 0.18 g ( 0.2 mmol), 0.4 ml (0.4 mmol) of 1M t-Bu ₃ P, and 2.88 g (30 mmol) of t-BuONa, respectively, 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 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 Hex : EA = 4: 1 to obtain 3.57 g (75% yield) of Intermediate-52.

Intermediate-56 MS (FAB): 476 (M ⁺ )

<Synthesis of Compound-250>

After injecting 5.53g (10mmol) of Intermediate-53 and 3.98g (10mmol) of Intermediate-52 under nitrogen and dissolving them in 80ml of toluene, 0.18g (0.2mmol) of Pd ₂ dba ₃ and 0.4ml (0.4mmol) of 1M t-Bu ₃ P ) and 2.88 g (30 mmol) of t-BuONa, respectively, and then refluxed for 8 hours.

After the reaction was completed, the temperature of the reactant was cooled to room temperature, extracted using 250 ml of toluene and 250 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 Hex : EA = 3: 1 to obtain 6.69 g (77% yield) of Compound-250.

Compound-250 MS (FAB): 869 (M ⁺ )

<Synthesis of Compound-252>

After injecting 5.53g (10mmol) of Intermediate-53 and 3.21g (10mmol) of Intermediate-54 under nitrogen and dissolving them in 70ml of toluene, 0.18g (0.2mmol) of Pd ₂ dba ₃ and 0.4ml (0.4mmol) of 1M t-Bu ₃ P ) and 2.88 g (30 mmol) of t-BuONa, respectively, and then refluxed for 8 hours.

After the reaction was completed, the temperature of the reactant was cooled to room temperature, extracted using 250 ml of toluene and 250 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 Hex : EA = 3: 1 to obtain 5.95 g (75% yield) of Compound-252.

Compound-252 MS (FAB): 793 (M ⁺ )

<Synthesis of Compound-261>

After injecting 4.76 g (10 mmol) of Intermediate-56 and 3.21 g (10 mmol) of Intermediate-54 under nitrogen and dissolving in 60 ml of toluene, 0.18 g (0.2 mmol) of Pd ₂ dba ₃ and 0.4 ml (0.4 mmol) of 1M t-Bu ₃ P ) and 2.88 g (30 mmol) of t-BuONa, respectively, 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 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 Hex : EA = 4: 1 to obtain 5.59 g (78% yield) of Compound-261.

Compound-261 MS (FAB): 716 (M ⁺ )

The compounds of Formula 2 are known compounds, and methods disclosed in known literature may be used for their synthesis.

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

<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 25 nm of 9,10-bis(2-naphthyl)anthracene (ADN) capable of forming blue EML as the light emitting layer (EML) on the hole transport layer, compound 1 as the compound of Formula 1 of the present invention as a dopant was added to about 5 % doped. Anthracene derivative 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). Thereafter, 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. 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 20

In Example 1, instead of Compound 1 of Formula 1 as a dopant of blue EML, Formulas 8, 11, 13, 25, 37, 49, 54, 61, 73, 75, 87, 100, 114, 123, Except for using the compounds 166, 183, 196, 245 and 249, organic light emitting devices of Examples 2 to 20 were prepared in the same manner as in Example 1.

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, as a hole transport layer (HTL), compound 250 as a compound of Formula 2 was deposited to a thickness of 120 nm. While depositing 25 nm of 9,10-bis(2-naphthyl)anthracene (ADN) capable of forming blue EML as the light emitting layer (EML) on the hole transport layer, compound 1 as the compound of Formula 1 of the present invention as a dopant was added to about 5 % doped. Anthracene derivative 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). Thereafter, 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. 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

In Example 8, instead of Compound 1 of Formula 1 as a dopant of blue EML, Formulas 8, 11, 13, 25, 37, 49, 54, 61, 73, 75, 87, 100, 114, 123, Organic light emitting devices of Examples 22 to 40 were prepared in the same manner as in Example 21, except for using the compounds 166, 183, 196, 245 and 249.

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, as a hole transport layer (HTL), compound 252 as a compound of Formula 2 was deposited to a thickness of 120 nm. While depositing 25 nm of 9,10-bis(2-naphthyl)anthracene (ADN) capable of forming blue EML as the light emitting layer (EML) on the hole transport layer, compound 1 as the compound of Formula 1 of the present invention as a dopant was added to about 5 % doped. Anthracene derivative 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). Thereafter, 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. 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, as a hole transport layer (HTL), compound 261 as a compound of Formula 2 was deposited to a thickness of 120 nm. While depositing 25 nm of 9,10-bis(2-naphthyl)anthracene (ADN) capable of forming blue EML as the light emitting layer (EML) on the hole transport layer, compound 1 as the compound of Formula 1 of the present invention as a dopant was added to about 5 % doped. Anthracene derivative 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). Thereafter, 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. 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 organic light emitting device was manufactured in the same manner as in Example 1, except that 2,5,8,11-Tetra-butyl-Perylene (t-Bu-Perylene) was used as the blue EML dopant for the light emitting layer (EML). manufactured.

Comparative Example 2

An organic light emitting device was manufactured in the same manner as in Example 21, except that 2,5,8,11-Tetra-butyl-Perylene (t-Bu-Perylene) was used as the blue EML dopant for the light emitting layer (EML). manufactured.

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) Efficiency
(Cd/A) CIE_x CIE_y T ₉₅ (hours) Example 1 3.6 6.5 0.136 0.057 187 Example 2 3.5 5.7 0.135 0.060 169 Example 3 3.7 5.9 0.138 0.056 166 Example 4 3.6 6.1 0.137 0.057 195 Example 5 3.7 5.9 0.137 0.059 168 Example 6 3.6 6.6 0.136 0.059 175 Example 7 3.8 6.7 0.137 0.058 171 Example 8 3.5 5.8 0.136 0.058 169 Example 9 3.7 6.5 0.136 0.058 175 Example 10 3.6 6.3 0.136 0.059 184 Example 11 3.5 5.8 0.136 0.059 178 Example 12 3.6 6.1 0.137 0.056 196 Example 13 3.7 6.4 0.135 0.059 181 Example 14 3.5 6.1 0.137 0.056 170 Example 15 3.6 6.4 0.136 0.058 202 Example 16 3.7 6.6 0.135 0.059 197 Example 17 3.6 6.5 0.136 0.057 191 Example 18 3.7 6.7 0.134 0.061 184 Example 19 3.7 6.5 0.135 0.060 207 Example 20 3.6 6.7 0.137 0.058 198 Comparative Example 1 4.6 4.7 0.135 0.062 95

As a result of the experiment, the organic light emitting devices of Examples 1 to 20 including the organic compound of Formula 1 as a dopant in the light emitting layer of the present invention have improved efficiency and voltage characteristics compared to the conventional organic light emitting device of Comparative Example 1. seemed

In addition, as a result of measuring the afterimage lifespan (T ₉₅ ), the organic electroluminescent device of Comparative Example 1 had a lifespan of 100 hours or less, whereas Examples 1 to 20 had a long lifespan of 160 hours or more, In particular, it was confirmed that the organic light emitting devices of Examples 15 and 19 had a long lifespan of 200 hours or more.

Therefore, it can be seen that the organic light emitting device including the organic compound of Chemical Formula 1 as a dopant in the light emitting layer of the present invention 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) Efficiency
(Cd/A) CIE_x CIE_y T ₉₅ (hours) Example 21 3.6 6.6 0.137 0.056 195 Example 22 3.5 5.8 0.135 0.060 175 Example 23 3.6 5.9 0.138 0.056 174 Example 24 3.6 6.2 0.137 0.057 203 Example 25 3.7 6.0 0.137 0.058 178 Example 26 3.5 6.6 0.136 0.058 182 Example 27 3.8 6.8 0.137 0.057 180 Example 28 3.5 5.9 0.136 0.057 178 Example 29 3.6 6.6 0.136 0.058 183 Example 30 3.6 6.4 0.136 0.059 194 Example 31 3.5 5.9 0.136 0.058 181 Example 32 3.6 6.1 0.138 0.055 208 Example 33 3.7 6.5 0.135 0.058 192 Example 34 3.5 6.1 0.138 0.055 181 Example 35 3.6 6.5 0.136 0.058 210 Example 36 3.7 6.7 0.135 0.059 203 Example 37 3.6 6.6 0.136 0.057 199 Example 38 3.7 6.8 0.134 0.061 191 Example 39 3.6 6.6 0.135 0.060 226 Example 40 3.6 6.8 0.137 0.058 204 Comparative Example 2 4.5 4.9 0.135 0.062 98

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 in the light emitting layer and the hole transport layer were compared with the conventional organic light emitting device of Comparative Example 2 in efficiency and voltage characteristics. showed markedly improved results. In particular, the organic light emitting devices of Examples 22, 26, 27, 28, 31, 34, 38 and 40 exhibited significantly improved voltage characteristics and luminous efficiency.

In addition, as a result of measuring the afterimage lifespan (T ₉₅ ), the organic electroluminescent device of Comparative Example 2 had a lifespan of 100 hours or less, whereas Examples 21 to 40 had a long lifespan of 170 hours or more. In particular, the organic light emitting devices of Examples 24, 32, 35, 36, 39 and 40 were confirmed to have a long lifespan of 200 hours or more.

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

3. Evaluation of characteristics of organic light emitting devices of Examples 1, 21, 41, 42 and Comparative Examples 1 and 2

The characteristics of the organic light emitting devices prepared in Examples 1, 21, 41, and 42 and Comparative Examples 1 and 2 were measured at a current density of 10 mA/cm ² , and the results are shown in Table 3 below.

Voltage
(V) Efficiency
(Cd/A) CIE_x CIE_y T ₉₅ (hours) Example 1 3.6 6.5 0.136 0.057 187 Example 21 3.6 6.6 0.137 0.056 195 Example 41 3.5 6.8 0.137 0.057 212 Example 42 3.5 6.7 0.138 0.056 204 Comparative Example 1 4.6 4.7 0.135 0.062 95 Comparative Example 2 4.5 4.9 0.135 0.062 98

As a result of the above experiment, the organic electroluminescent devices of Examples 21, 41, and 42 using the compounds of Formulas 1 and 2 of the present invention in the light emitting layer and the hole transport layer were similar to those of Comparative Examples 1 and 2, as well as the organic compounds of Formula 1 of the present invention. As a dopant in the light emitting layer, compared to Example 1, significantly superior voltage characteristics, luminous efficiency, and lifetime characteristics were exhibited. These results are clearly confirmed through comparisons of Example 2 and Example 22, Example 3 and Example 23, Example 4 and Example 24, Example 5 and Example 25, and the like.

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

It can be seen that the above results were obtained by using the compound of Formula 2, which corresponds well to the dopant structure of the compound of Formula 1, as a hole transport material.

In the case of a general organic light emitting device, as degradation progresses at the interface between the hole transport layer and the light emitting layer, electrons are diffused into the hole transport layer through the interface, thereby accelerating the degradation and reducing the lifetime of the organic light emitting device.

However, in the present invention, as the compound of Formula 2 is used as a hole transport material, the charge balance of the device is achieved and excitons cannot migrate to the interface of the light emitting layer, so the efficiency of the organic light emitting device seems to be improved. In addition, it seems that the compound of Chemical Formula 2 prevents excitons from diffusing into the hole transport layer, thereby preventing overall deterioration, thereby increasing the lifetime of the organic light emitting device.

Claims (6)

The organic electroluminescent device according to claim 1, characterized in that it comprises an organic compound represented by the following formula (1)
[Formula 1]

in the above formula
Ar1, Ar2, Ar3 and Ar4 are each independently selected from tritium, deuterium, hydrogen, CN, 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, and 3 to 40 carbon atoms. of cycloalkyl, phenyl, biphenyl, naphthyl, anthracenyl, anthracenyl substituted with a phenyl group, phenanthrenyl, pyrenyl, 9,9-dimethylfluorenyl, carbazolyl, dibenzofuranyl, pyrrole, tria An aromatic hydrocarbon group having 6 to 60 carbon atoms unsubstituted or substituted with one or more selected from the group consisting of sol, pyridinyl, pyrazinyl, pyrimidinyl, and quinolinyl groups;
independently deuterium, substituted 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, anthra Cenyl, anthracenyl in which all hydrogens are deuterium substituted with a phenyl group, phenanthrenyl in which all hydrogens are deuterium, pyrenyl in which all hydrogens are deuterium, 9,9-dimethylfluorenyl in which all hydrogens are deuterium, and all hydrogens are deuterium carbazolyl, dibenzofuranyl in which all hydrogens are deuterium, pyrrole in which all hydrogens are deuterium, triazoles in which all hydrogens are deuterium, pyridinyl, pyrazinyl in which all hydrogens are deuterium, pyrimidinyl groups in which all hydrogens are deuterium, and An aromatic hydrocarbon group having 6 to 60 carbon atoms unsubstituted or substituted with one or more selected from the group consisting of a quinolinyl group in which all hydrogens are deuterium;
tritium, deuterium, hydrogen, CN, 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, cycloalkyl of 3 to 40 carbon atoms, phenyl, biphenyl, each independently , naphthyl, anthracenyl, anthracenyl substituted with a phenyl group, phenanthrenyl, pyrenyl, 9,9-dimethylfluorenyl, spirobi[fluorene], carbazolyl, dibenzofuranyl, pyrrole, triazole, pyridine Substituted or unsubstituted with one or more selected from the group consisting of one, pyrazinyl, pyrimidinyl group, and quinolinyl group, and having 5 to 5 carbon atoms containing at least one element selected from the group consisting of S, O, N and Si 70 heteroaromatic hydrocarbon group;
independently deuterium, 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 in which all hydrogens are deuterium substituted with a phenyl group, phenanthrenyl in which all hydrogens are deuterium, pyrenyl in which all hydrogens are deuterium, 9,9-dimethylfluorenyl in which all hydrogens are deuterium, spirobi[fluorene], all hydrogens Carbazolyl with all hydrogens deuterium, dibenzofuranyl with all hydrogens deuterium, pyrrole with all deuterium hydrogens, triazole with all deuterium hydrogens, pyridinyl, pyrazinyl with all deuterium hydrogens, pyrimidi with all deuterium hydrogens substituted or unsubstituted with one or more selected from the group consisting of a yl group and a quinolinyl group in which all hydrogens are deuterium, and having 5 to 70 carbon atoms containing at least one element selected from the group consisting of S, O, N and Si A heteroaromatic hydrocarbon group,
x1 and x2 are each independently oxygen or sulfur,
a, b, c are each independently 0 or 1, and when 0, no bond exists,
R1, R2, and R3 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; , an alkoxy group having 1 to 40 carbon atoms, a thioalkyl group having 1 to 40 carbon atoms, or a cycloalkyl group having 3 to 40 carbon atoms,
each independently a straight or branched chain alkyl of 1 to 40 carbon atoms in which all hydrogens are deuterium, alkoxy of 1 to 40 carbon atoms in which all hydrogens are deuterium, thioalkyl of 1 to 40 carbon atoms in which all hydrogens are deuterium, or all hydrogens are deuterium A cycloalkyl group having 3 to 40 carbon atoms;
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 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 group substituted or unsubstituted with one or more aromatic hydrocarbons having 6 to 60 carbon atoms selected from the group consisting of or
independently deuterium, 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 in which all hydrogens are deuterium, phenanthrenyl in which all hydrogens are deuterium, pyrenyl in which all hydrogens are deuterium, 9,9-dimethylfluorenyl in which all hydrogens are deuterium, carbane in which all hydrogens are deuterium. Zolyl, dibenzofuranyl, all hydrogens are deuterium, pyrrole, all hydrogens are deuterium, triazoles, all hydrogens are deuterium, pyridinyl, all hydrogens are deuterium, pyrazinyl, all hydrogens are deuterium, pyrimidi, all hydrogens are deuterium An aromatic hydrocarbon group having 6 to 60 carbon atoms unsubstituted or substituted with one or more selected from the group consisting of a yl group and a quinolinyl group in which all hydrogens are deuterium;
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 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 S , A heteroaromatic hydrocarbon group having 5 to 70 carbon atoms containing at least one element selected from the group consisting of O, N and Si, or
independently deuterium, 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 in which all hydrogens are deuterium substituted with a phenyl group, phenanthrenyl in which all hydrogens are deuterium, pyrenyl in which all hydrogens are deuterium, 9,9-dimethylfluorenyl in which all hydrogens are deuterium, spirobi[fluorene], all hydrogens Carbazolyl with all hydrogens deuterium, dibenzofuranyl with all hydrogens deuterium, pyrrole with all deuterium hydrogens, triazole with all deuterium hydrogens, pyridinyl with all hydrogens deuterium, pyrazinyl with all deuterium hydrogens, all hydrogens substituted or unsubstituted with at least one selected from the group consisting of a pyrimidinyl group in which all hydrogens are deuterium and a quinolinyl group in which all hydrogens are deuterium, and containing at least one element selected from the group consisting of S, O, N and Si A heteroaromatic hydrocarbon group having 5 to 70 carbon atoms;
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 having 1 to 40 carbon atoms, and cycloalkyl groups having 3 to 40 carbon atoms substituted or unsubstituted with at least one selected from the group consisting of phenyl, biphenyl, naphthyl, anthracenyl, anthracenyl substituted with a phenyl group, selected from the group consisting of phenanthrenyl, pyrenyl, 9,9-dimethylfluorenyl, carbazolyl, quinolinyl, dibenzofuranyl, pyrrole, triazole, pyridinyl, pyrazinyl, and pyrimidinyl groups an amino group substituted with one or more
Each independently substituted with one or more selected from the group consisting of heavy hydrogen, 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 groups having 3 to 40 carbon atoms. or unsubstituted phenyl, biphenyl, naphthyl, anthracenyl, anthracenyl in which all hydrogens are deuterium substituted with a phenyl group, phenanthrenyl in which all hydrogens are deuterium, pyrenyl in which all hydrogens are deuterium, 9 in which all hydrogens are deuterium. ,9-dimethylfluorenyl, carbazolyl with all deuterium hydrogens, quinolinyl with all deuterium hydrogens, dibenzofuranyl with all deuterium hydrogens, pyrrole with all deuterium hydrogens, triazoles with all deuterium hydrogens , An amino group substituted with one or more selected from the group consisting of pyridinyl in which all hydrogens are deuterium, pyrazinyl in which all hydrogens are deuterium, and pyrimidinyl group in which all hydrogens are deuterium. The method of claim 1,
The organic compound is characterized in that any one of the following compounds 1 to 249.
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,
An organic electroluminescent device characterized in that the light emitting layer contains the organic compound of claim 1 alone or in combination of two or more. The method of claim 3,
The organic thin film layer includes a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer,
The organic electroluminescent device, characterized in that the hole transport layer contains an organic compound represented by the following formula (2) alone or in combination of two or more:
[Formula 2]

In the above formula,
R1, R2, R3 and R4 are each independently hydrogen; a straight-chain or branched-chain alkyl group having 1 to 20 carbon atoms; Aromatic hydrocarbon having 6 to 60 carbon atoms unsubstituted or substituted with one or more selected from the group consisting of C1~C10 straight chain or branched chain alkyl, C1~C10 alkoxy, halogen, CN, CF ₃ and Si(CH ₃ ) ₃ group energy; or C1~C10 straight-chain or branched-chain alkyl, C1~C10 alkoxy, halogen, CN, CF ₃ and Si(CH ₃ ) ₃ groups, substituted or unsubstituted with one or more selected from the group consisting of S, O, N and a heteroaromatic hydrocarbon group having 5 to 60 carbon atoms containing at least one element selected from the group consisting of Si;
Each of R1, R2, R3 and R4 may be independently bonded to the phenyl group of the basic structure to form an aromatic hydrocarbon or a heteroaromatic hydrocarbon. The method of claim 4,
Wherein R1, R2, R3 and R4 are each independently a phenyl, biphenyl, naphthyl, anthracenyl, phenanthrenyl, fluorenyl carbazole or pyrenyl group;
Wherein R1, R2, R3 and R4 are each independently bonded to the phenyl group of the basic structure to form naphthalene, anthracene, or phenanthrene. The method of claim 4,
An organic compound, characterized in that the organic compound is any one of the following compounds 250 to 261: