KR20230099655A - Novel organic compounds and an organic electroluminescent device comprising the same - Google Patents

Abstract

In an organic electroluminescent element wherein an organic thin film layer consisting of one layer or a plurality of layers comprising at least a light emitting layer is stacked between a negative pole and a positive pole, provided is the organic electroluminescent element wherein a compound constituting the organic thin film layer is characterized in comprising tritium in a chemical structure. Therefore, the present invention is capable of improving light emitting efficiency and light emitting lifespan.

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 dopant material to improve the luminous efficiency and luminous lifetime of an 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 dopant material as described above.

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 the dopant material and a specific hole transport layer material in combination.

Tritium is a hydrogen that is heavier than normal hydrogen, which is the most abundant in nature, and is denoted by T or 3H. Usually, a hydrogen atom consists of one proton and one electron, but a tritium atom has two more neutrons attached to it. Since the weight of electrons is negligible, it is 'three times as heavy as hydrogen' as the name suggests. In addition to being heavy, tritium has radioactivity that normal hydrogen does not. Tritium gives off an energy of 18.6 keV as it changes to helium 3 (2 protons + 1 neutron), which has one less neutron than normal helium (2 protons + 2 neutrons). Because the energy is not great, it cannot penetrate paper or water, nor can it penetrate human skin. This means that compared to other radioactive substances, tritium is relatively safe. Such tritium can emit beta rays, and the emitted beta rays can stimulate fluorescent materials, so if such tritium is used as an OLED material, the lifetime and efficiency, which are the most problematic issues in organic light emitting devices, will be greatly improved. You will be able to. Since organic molecules or organic/metal molecules that actually emit fluorescence and phosphorescence per unit time when a voltage is applied to the organic light emitting device are only a small portion, such tritium is present in a very small amount in the compound constituting the organic light emitting device. It will be possible to greatly improve the lifetime and efficiency compared to the organic light emitting device.

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;

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, naphthyl , anthracenyl, anthracenyl substituted with a phenyl group, phenanthrenyl, pyrenyl, 9,9-dimethylfluorenyl, spirobi [fluorene], carbazolyl, dibenzofuranyl, pyrrole, triazole, pyridinyl, pyra Hetero having 5 to 70 carbon atoms, substituted or unsubstituted with one or more selected from the group consisting of zinyl, pyrimidinyl, and quinolinyl, and containing one or more elements selected from the group consisting of S, O, N, and Si It is an aromatic hydrocarbon group,

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

n and m are independently 0 and 1, respectively;

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

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, 1 carbon atom thioalkyl of 3 to 40 carbon atoms, cycloalkyl of 3 to 40 carbon atoms, phenyl, biphenyl, naphthyl, anthracenyl, anthracenyl substituted with a phenyl group, phenanthrenyl, pyrenyl, 9,9-dimethylfluorenyl, carba An aromatic hydrocarbon group having 6 to 60 carbon atoms unsubstituted or substituted with one or more selected from the group consisting of zoyl, dibenzofuranyl, pyrrole, triazole, pyridinyl, pyrazinyl, pyrimidinyl, and quinolinyl,

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

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

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 dopant material to improve luminous efficiency and luminous lifetime of an organic light emitting device.

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

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

The present invention provides an organic light emitting device characterized in that a compound constituting the organic light emitting device includes tritium in its chemical structure.

In addition, the present invention relates to a novel 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;

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, naphthyl , anthracenyl, anthracenyl substituted with a phenyl group, phenanthrenyl, pyrenyl, 9,9-dimethylfluorenyl, spirobi [fluorene], carbazolyl, dibenzofuranyl, pyrrole, triazole, pyridinyl, pyra Hetero having 5 to 70 carbon atoms, substituted or unsubstituted with one or more selected from the group consisting of zinyl, pyrimidinyl, and quinolinyl, and containing one or more elements selected from the group consisting of S, O, N, and Si It is an aromatic hydrocarbon group,

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

n and m are independently 0 and 1, respectively;

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

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, 1 carbon atom thioalkyl of 3 to 40 carbon atoms, cycloalkyl of 3 to 40 carbon atoms, phenyl, biphenyl, naphthyl, anthracenyl, anthracenyl substituted with a phenyl group, phenanthrenyl, pyrenyl, 9,9-dimethylfluorenyl, carba An aromatic hydrocarbon group having 6 to 60 carbon atoms unsubstituted or substituted with one or more selected from the group consisting of zoyl, dibenzofuranyl, pyrrole, triazole, pyridinyl, pyrazinyl, pyrimidinyl, and quinolinyl,

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

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

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 and can improve the performance of an organic light emitting device by mixing with other functional layers, its use is not limited.

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 It is selected from the group consisting of; 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 (78%, tritium conversion 79%) of Intermediate-1.

Intermediate-1 MS (FAB): 160 (M ⁺ )

<Synthesis of Intermediate-2>

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

Intermediate-2 MS (FAB): 221 (M ⁺ )

<Synthesis of Intermediate-3>

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

Intermediate-3 MS (FAB): 130 (M ⁺ )

<Synthesis of Intermediate-4>

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

Intermediate-4 MS (FAB): 209 (M ⁺ )

<Synthesis of Intermediate-5>

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

Intermediate-5 MS (FAB): 366 (M ⁺ )

<Synthesis of Intermediate-6>

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

Intermediate-6 MS (FAB): 360 (M ⁺ )

<Synthesis of Intermediate-7>

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

Intermediate-7 MS (FAB): 230 (M ⁺ )

<Synthesis of Intermediate-8>

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

Intermediate-8 MS (FAB): 388 (M ⁺ )

<Synthesis of Intermediate-9>

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

Intermediate-9 MS (FAB): 354 (M ⁺ )

<Synthesis of Intermediate-10>

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

Intermediate-10 MS (FAB): 512 (M ⁺ )

<Synthesis of Intermediate-11>

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

Intermediate-11 MS (FAB): 360 (M ⁺ )

<Synthesis of Intermediate-12>

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

Intermediate-12 MS (FAB): 388 (M ⁺ )

<Synthesis of Intermediate-13>

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

Intermediate-13 MS (FAB): 258 (M ⁺ )

<Synthesis of Intermediate-14>

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

Intermediate-14 MS (FAB): 416 (M ⁺ )

<Synthesis of Intermediate-15>

After dissolving 100 g (277.8 mmol) of Intermediate-6 in 1000 ml of THF, -78 degrees was maintained in an Acetone/dryice bath. After slowly dropping 122ml (305.6mmol) of 2.5M n-BuLi, the mixture was stirred for 30 minutes. After adding iodomethane 47.3g (333.4mmol), the temperature was gradually raised to room temperature. After THF distillation, 1000 ml of EA and 100 ml of H ₂ O were added to extract the organic layer, followed by distillation. Column was performed to obtain 55.7 g (68% yield) of Intermediate-15.

Intermediate-15 MS (FAB): 295 (M ⁺ )

<Synthesis of Intermediate-16>

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

Intermediate-16 MS (FAB): 298 (M ⁺ )

<Synthesis of Intermediate-17>

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

Intermediate-17 MS (FAB): 456 (M ⁺ )

<Synthesis of Intermediate-18>

After dissolving 100g (404.7mmol) of 4-bromodibenzofuran and 54.7g (404.7mmol) of 4-isopropylaniline in 500ml of Toluene, 58.3g (607.1mmol) of sodium tert-butoxide was added. After adding 1.82 g (8.1 mmol) of palladium acetate and 6.55 g (16.2 mmol) of tri-tert-butylphosphine (50% in toluene), it was refluxed for 3 hours. After completion of the reaction, the mixture was cooled to room temperature, and 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-18.

Intermediate-18 MS (FAB): 301 (M ⁺ )

<Synthesis of Intermediate-19>

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

Intermediate-19 MS (FAB): 169 (M ⁺ )

<Synthesis of Intermediate-20>

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

Intermediate-20 MS (FAB): 335 (M ⁺ )

<Synthesis of Intermediate-21>

After dissolving 59g (175.7mmol) of Intermediate-20 in 600ml of DMA, 33.8g (351.4mmol) of sodium tert-butoxide was added. After adding 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-21.

Intermediate-21 MS (FAB): 299 (M ⁺ )

<Synthesis of Intermediate-22>

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

Intermediate-22 MS (FAB): 198 (M ⁺ )

<Synthesis of Intermediate-23>

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

Intermediate-23 MS (FAB): 356 (M ⁺ )

<Synthesis of Intermediate-24>

After adding 84.1g (236.2mmol) of Intermediate-23 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-24.

Intermediate-24 MS (FAB): 325 (M ⁺ )

<Synthesis of Intermediate-25>

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

Intermediate-25 MS (FAB): 380 (M ⁺ )

<Synthesis of Intermediate-26>

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

Intermediate-26 MS (FAB): 299 (M ⁺ )

<Synthesis of Intermediate-27>

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

Intermediate-27 MS (FAB): 244 (M ⁺ )

<Synthesis of Intermediate-28>

After dissolving 83 g (340 mmol) of Intermediate-27 in 500 ml of THF, -78 degrees was maintained using an acetone/dryice bath.

After slowly adding 150ml (374mmol) of 2.5M n-BuLi, the bath was removed and the temperature was raised to room temperature. After 1 hour, -78 degrees was maintained using an acetone/dryice bath, and 38.9 g (374 mmol) of trimethylborate was added. After removing the bath, the temperature was raised to room temperature to terminate the reaction. After extracting the organic layer by adding 1L of EA and 1L of water, it was distilled and columned to obtain 38.2g (39% yield) of Intermediate-28.

Intermediate-28 MS (FAB): 288 (M ⁺ )

<Synthesis of Intermediate-29>

After dissolving 100 g (739.6 mmol) of 4-isopropylaniline in 1 L of DMF, 131.6 g (739.6 mmol) of NBS was slowly added at 0 degrees. After removing the bath, the temperature was raised to room temperature to complete the reaction, and 2L of EA and 2L of water were added. The organic layer was extracted, distilled, and columnized to obtain 139.4 g (88% yield) of Intermediate-29.

Intermediate-29 MS (FAB): 214 (M ⁺ )

<Synthesis of Intermediate-30>

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

Intermediate-30 MS (FAB): 456 (M ⁺ )

<Synthesis of Intermediate-31>

After dissolving 52g (114mmol) of Intermediate-30 in 500ml of DMA, 21.9g (228mmol) of sodium tert-butoxide was added. After adding 768mg (3.42mmol) of Palladium acetate and 992mg (3.42mmol) of t-Bu ₃ PHBF ₄ , it was refluxed for 6 hours. After completion of the reaction, the mixture was cooled to room temperature, 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-31.

Intermediate-31 MS (FAB): 375 (M ⁺ )

<Synthesis of Intermediate-32>

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

Intermediate-32 MS (FAB): 420 (M ⁺ )

<Synthesis of Intermediate-33>

After dissolving 100g (739.6mmol) of 4-isopropylaniline in 1L of DMF, 166.4g (739.6mmol) of NIS was slowly added at 0°C. After removing the bath, the temperature was raised to room temperature to complete the reaction, and 2L of EA and 2L of water were added. The organic layer was extracted, distilled, and columnized to obtain 166.1 g (86% yield) of Intermediate-33.

Intermediate-33 MS (FAB): 261 (M ⁺ )

<Synthesis of Intermediate-34>

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

Intermediate-34 MS (FAB): 290 (M ⁺ )

<Synthesis of Intermediate-35>

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

Intermediate-35 MS (FAB): 503 (M ⁺ )

<Synthesis of Intermediate-36>

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

Intermediate-36 MS (FAB): 375 (M ⁺ )

<Synthesis of Intermediate-37>

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

Intermediate-37 MS (FAB): 325 (M ⁺ )

<Synthesis of Intermediate-38>

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

Intermediate-38 MS (FAB): 459 (M ⁺ )

<Synthesis of Intermediate-39>

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

Intermediate-39 MS (FAB): 406 (M ⁺ )

<Synthesis of Intermediate-40>

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

Intermediate-40 MS (FAB): 451 (M ⁺ )

<Synthesis of Intermediate-41>

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

Intermediate-41 MS (FAB): 606 (M ⁺ )

<Synthesis of Intermediate-42>

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

Intermediate-42 MS (FAB): 690 (M ⁺ )

<Synthesis of Intermediate-43>

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

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

<Synthesis of Intermediate-44>

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

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

<Synthesis of Intermediate-45>

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

Intermediate-45 MS (FAB): 396 (M ⁺ )

Synthesis of Intermediate-46

After injecting 2.21 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%) of Intermediate-46.

Intermediate-46 MS (FAB): 275 (M ⁺ )

Synthesis of Intermediate-47

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%) of Intermediate-47.

Intermediate-47 MS (FAB): 263 (M ⁺ )

<Synthesis of Compound-1>

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

¹ H NMR (DMSO, 300 Hz): δ (ppm) = 8.32-8.09 (d, 1H), 8.03-7.91 (d, 2H), 7.86-7.73 (m, 2H), 7.69-7.47 (m, 7H), 7.43-7.16(m, 10H), 7.13-6.87(m, 6H), 3.21-2.52(m, 6H), 1.94-1.51(m, 5H), 1.38-1.03(d, 17H)

MS(FAB): 901(M ⁺ )

<Synthesis of Compound-13>

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

¹ H NMR (DMSO, 300 Hz): δ (ppm) = 9.12-8.87 (s, 2H), 8.35-8.09 (m, 2H), 8.03-7.92 (m, 6H), 7.88-7.74 (d, 2H), 7.68-7.47(m, 4H), 7.42-7.16(m, 4H), 7.13-6.92(m, 2H), 3.21-2.52(m, 8H), 1.37-1.03(d, 12H)

MS(FAB): 831(M ⁺ )

<Synthesis of Compound-25>

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

¹ H NMR (DMSO, 300 Hz): δ (ppm) = 8.32-8.02 (m, 4H), 7.98-7.88 (d, 2H), 7.84-7.62 (m, 6H), 7.58-7.45 (m, 4H), 7.37-7.11(m, 6H), 7.13-6.92(d, 2H), 3.21-2.52(m, 8H), 1.37-1.03(d, 12H)

MS(FAB): 833(M ⁺ )

<Synthesis of Compound-37>

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

¹ H NMR (DMSO, 300 Hz): δ (ppm) = 8.25-7.87 (m, 10H), 7.82-7.74 (d, 2H), 7.71-7.65 (d, 2H), 7.61-7.46 (m, 10H), 7.42-7.21(m, 6H), 7.18-6.97(d, 2H), 3.21-2.51(m, 8H), 1.36-1.03(d, 12H)

MS(FAB): 985(M ⁺ )

<Synthesis of Compound-49>

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

NMR (DMSO, 300 Hz): δ (ppm) = 8.21-7.92 (m, 6H), 7.86-7.77 (d, 2H), 7.73-7.66 (d, 2H), 7.63-7.51 (m, 6H), 7.38- 7.22(m, 22H), 7.18-6.96(d, 2H), 3.21-2.52(m, 8H), 1.37-1.03(d, 12H)

MS(FAB): 1137(M ⁺ )

<Synthesis of Compound-61>

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

¹ H NMR (DMSO, 300 Hz): δ (ppm) = 8.34-8.08 (m, 4H), 8.04-7.90 (d, 2H), 7.71-7.59 (m, 6H), 7.56-7.44 (m, 4H), 7.39-7.21(m, 14H), 7.05-6.92(d, 2H), 3.21-2.52(m, 8H), 1.37-1.03(d, 12H)

MS(FAB): 976.40(M ⁺ )

<Synthesis of Compound-73>

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

¹ H NMR (DMSO, 300 Hz): δ (ppm) = 9.11-8.89 (s, 2H), 8.23-8.02 (m, 4H), 7.98-7.88 (m, 6H), 7.84-7.74 (m, 6H), 7.59-7.26(m, 12H), 7.18-7.02(d, 2H), 3.05-2.72(m, 2H), 1.36-1.03(d, 12H)

MS(FAB): 955(M ⁺ )

<Synthesis of Compound-75>

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

¹ H NMR (DMSO, 300 Hz): δ (ppm) = 8.24-7.95 (m, 4H), 7.89-7.81 (d, 1H), 7.75-7.49 (m, 9H), 7.44-7.24 (m, 6H), 7.22-7.13(d, 2H), 7.10-7.01(d, 2H), 6.98-6.91(m, 2H), 3.21-2.52(m, 8H), 1.37-1.03(d, 12H)

MS(FAB): 829(M ⁺ )

<Synthesis of Compound-87>

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

¹ H NMR (DMSO, 300 Hz): δ (ppm) = 9.12-8.88 (s, 2H), 8.62-8.51 (d, 2H), 8.31-8.12 (d, 2H), 8.09-7.81 (m, 10H), 7.78-7.68(s, 4H), 7.62-7.45(m, 6H), 7.42-7.28(m, 6H), 7.26-7.02(m, 6H), 3.05-2.72(m, 2H), 1.37-1.03(d) , 12H)

MS(FAB): 1133(M ⁺ )

<Synthesis of Compound-100>

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

¹ H NMR (DMSO, 300 Hz): δ (ppm) = 8.61-8.51 (d, 2H), 8.27-8.12 (d, 2H), 8.08-7.91 (m, 4H), 7.83-7.53 (m, 14H), 7.48-7.12(m, 16H), 7.10-7.01(m, 4H), 6.98-6.88(d, 2H), 3.05-2.72(m, 2H), 1.37-1.03(d, 12H)

MS(FAB): 1135(M ⁺ )

<Synthesis of Compound-123>

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

¹ H NMR (DMSO, 300 Hz): δ (ppm) = 9.13-8.89 (s, 2H), 8.05-7.95 (m, 4H), 7.91-7.78 (m, 4H), 7.62-7.47 (m, 4H), 7.42-7.27(m, 4H), 7.16-7.04(d, 2H), 3.21-2.52(m, 14H), 1.37-1.03(d, 12H)

MS(FAB): 859(M ⁺ )

<Synthesis of Compound-196>

4.44g (10mmol) of 1,6-dibromo-3,8-diisopropylpyrene and 6.06g (22mmol) of Intermediate-46 were injected under nitrogen and dissolved in 60ml of toluene, followed by 0.05g (0.2mmol) of Pd (OAc) ₂ and 1M t -Bu ₃ P 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 = 3: 1 to obtain 6.2g (74% yield) of Compound 196.

¹ H NMR (DMSO, 300 Hz): δ (ppm) = 8.08-7.75 (m, 8H), 7.71-7.62 (d, 2H), 7.59-7.51 (d, 2H), 7.48-7.41 (m, 6H), 7.38-6.91 (m, 10H), 2.95-2.71 (m, 4H), 1.46-1.31 (d, 12H), 1.31-1.12 (d, 12H)

MS(FAB): 833(M ⁺ )

<Synthesis of Compound-245>

After injecting 4.44g (10mmol) of 1,6-dibromo-3,8-diisopropylpyrene and 5.79g (22mmol) of Intermediate-47 under nitrogen and dissolving them in 60ml of toluene, 0.05g (0.2mmol) of Pd (OAc) ₂ and 1M t -Bu ₃ P 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 = 3: 1 column to obtain 6.2g (76% yield) of compound 245.

¹ H NMR (DMSO, 300 Hz): δ (ppm) = 8.35-8,13 (m, 4H), 8.03-7.79 (d, 2H), 7.76-7.62 (d, 10H), 7.58-7.51 (m, 4H) ), 7.45-7.01 (m, 8H), 2.95-2.72 (m, 4H), 1.46-1.30 (d, 12H), 1.31-1.13 (d, 12H)

MS(FAB): 809(M ⁺ )

<Synthesis of Compound of Formula 2>

<Synthesis of Intermediate-48>

[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-48.

Intermediate-48 MS (FAB): 397 (M ⁺ )

<Synthesis of Intermediate-49>

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-49.

Intermediate-49 MS (FAB): 552 (M ⁺ )

<Synthesis of Intermediate-50>

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-50.

Intermediate-50 MS (FAB): 321 (M ⁺ )

<Synthesis of Intermediate-51>

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-51 MS (FAB): 245 (M ⁺ )

<Synthesis of Intermediate-52>

After injecting 2.45 g (10 mmol) of Intermediate-51 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-52 MS (FAB): 476 (M ⁺ )

<Synthesis of Compound-250>

After injecting 5.53 g (10 mmol) of Intermediate-49 and 3.98 g (10 mmol) of Intermediate-48 under nitrogen and dissolving them in 80 ml of toluene, Pd ₂ dba ₃ 0.18 g (0.2 mmol), 1M t-Bu ₃ P 0.4 ml (0.4 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 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-49 and 3.21g (10mmol) of Intermediate-50 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 4.76g (10mmol) of Intermediate-52 and 3.21g (10mmol) of Intermediate-50 under nitrogen and dissolving them in 60ml 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 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 3.9 6.5 0.136 0.058 158 Example 2 3.5 6.2 0.135 0.060 169 Example 3 3.7 6.6 0.138 0.056 166 Example 4 3.6 6.1 0.137 0.057 175 Example 5 3.7 6.2 0.137 0.059 168 Example 6 3.6 6.4 0.135 0.060 185 Example 7 4.0 6.6 0.136 0.057 162 Example 8 4.1 6.7 0.136 0.058 169 Example 9 3.9 6.4 0.136 0.058 163 Example 10 3.6 6.2 0.136 0.059 180 Example 11 3.7 5.8 0.136 0.059 173 Example 12 3.6 6.2 0.135 0.058 178 Example 13 3.7 6.1 0.135 0.059 175 Example 14 3.8 6.2 0.135 0.059 170 Example 15 3.5 6.1 0.136 0.058 182 Example 16 3.7 6.6 0.135 0.059 197 Example 17 3.8 6.8 0.136 0.058 191 Example 18 3.9 6.9 0.134 0.061 192 Example 19 3.8 6.4 0.135 0.062 210 Example 20 3.6 6.7 0.137 0.057 205 Comparative Example 1 4.6 4.4 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 150 hours or more, In particular, the organic light emitting devices of Examples 19 and 20 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 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 3.8 6.8 0.136 0.057 173 Example 22 3.4 6.4 0.135 0.059 184 Example 23 3.6 6.9 0.138 0.055 181 Example 24 3.5 6.3 0.138 0.056 191 Example 25 3.6 6.4 0.137 0.058 193 Example 26 3.5 6.7 0.136 0.059 215 Example 27 3.9 6.9 0.137 0.056 186 Example 28 4.0 7.0 0.136 0.057 184 Example 29 3.8 6.7 0.135 0.057 207 Example 30 3.5 6.4 0.136 0.058 196 Example 31 3.6 6.0 0.136 0.058 188 Example 32 3.5 6.4 0.136 0.057 194 Example 33 3.6 6.3 0.135 0.058 191 Example 34 3.7 6.4 0.135 0.058 186 Example 35 3.4 6.3 0.137 0.057 199 Example 36 3.6 6.9 0.136 0.058 215 Example 37 3.7 7.1 0.137 0.058 198 Example 38 3.8 7.2 0.135 0.060 209 Example 39 3.7 6.7 0.135 0.061 229 Example 40 3.5 7.0 0.137 0.056 223 Comparative Example 2 4.6 4.6 0.135 0.063 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, 35, 37 and 38 exhibited remarkably improved characteristics in voltage characteristics and luminous efficiency.

In addition, as a result of measuring the afterimage lifespan (T ₉₅ ), the organic 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 26, 29, 36, 38, 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 3.9 6.5 0.136 0.058 158 Example 21 3.8 6.8 0.136 0.057 173 Example 41 3.7 7.0 0.135 0.058 204 Example 42 3.8 6.8 0.136 0.056 187 Comparative Example 1 4.6 4.4 0.135 0.062 95 Comparative Example 2 4.6 4.6 0.135 0.063 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 the organic compounds of Formula 1 of the present invention as well as Comparative Examples 1 and 2. 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 electroluminescent 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 lifetime 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 diffuse 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 move to the interface of the light emitting layer at the same time, so the efficiency of the organic light emitting device seems to be improved. In addition, 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 (7)

In the organic electroluminescent device in which an organic thin film layer composed of one or a plurality of layers including at least a light emitting layer is laminated between a cathode and an anode,
An organic electroluminescent device, characterized in that the compound constituting the organic thin film layer contains tritium in its chemical structure, 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;
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, naphthyl , anthracenyl, anthracenyl substituted with a phenyl group, phenanthrenyl, pyrenyl, 9,9-dimethylfluorenyl, spirobi [fluorene], carbazolyl, dibenzofuranyl, pyrrole, triazole, pyridinyl, pyra Hetero having 5 to 70 carbon atoms, substituted or unsubstituted with one or more selected from the group consisting of zinyl, pyrimidinyl, and quinolinyl, and containing one or more elements selected from the group consisting of S, O, N, and Si It is an aromatic hydrocarbon group,
B1 and B2 are each independently selected from straight or branched chain alkyl having 1 to 40 carbon atoms, alkoxy having 1 to 40 carbon atoms, thioalkyl having 1 to 40 carbon atoms, cycloalkyl having 3 to 40 carbon atoms, phenyl, biphenyl, naphthyl, anthra Anthracenyl, phenanthrenyl, pyrenyl, 9,9-dimethylfluorenyl, carbazolyl, dibenzofuranyl, pyrrole, triazole, pyridinyl, pyrazinyl, pyrimidinyl, and It is an aromatic hydrocarbon group having 6 to 60 carbon atoms substituted or unsubstituted with one or more selected from the group consisting of quinolinyl groups,
n and m are independently 0 and 1, respectively;
R1, R2, R3, R4, R5, R6, R7 and R8 are each independently tritium, deuterium, hydrogen, F, Cl, Br, I, CN, Si(CH ₃ ) ₃ , B(OH) ₂ , carbon atoms a straight-chain or branched-chain alkyl group of 1 to 40 carbon atoms, an alkoxy group of 1 to 40 carbon atoms, a thioalkyl group of 1 to 40 carbon atoms, or a cycloalkyl group of 3 to 40 carbon atoms;
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, 1 carbon atom thioalkyl of 3 to 40 carbon atoms, cycloalkyl of 3 to 40 carbon atoms, phenyl, biphenyl, naphthyl, anthracenyl, anthracenyl substituted with a phenyl group, phenanthrenyl, pyrenyl, 9,9-dimethylfluorenyl, carba An aromatic hydrocarbon group having 6 to 60 carbon atoms unsubstituted or substituted with one or more selected from the group consisting of zoyl, dibenzofuranyl, pyrrole, triazole, pyridinyl, pyrazinyl, pyrimidinyl, and quinolinyl,
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, 1 carbon atom thioalkyl of 3 to 40 carbon atoms, cycloalkyl of 3 to 40 carbon atoms, phenyl, biphenyl, naphthyl, anthracenyl, anthracenyl substituted with a phenyl group, phenanthrenyl, pyrenyl, 9,9-dimethylfluorenyl, spirobi[ fluorene], carbazolyl, dibenzofuranyl, pyrrole, triazole, pyridinyl, pyrazinyl, pyrimidinyl group, and substituted or unsubstituted with one or more selected from the group consisting of S, O, A heteroaromatic hydrocarbon group having 5 to 70 carbon atoms containing at least one element selected from the group consisting of N and Si;
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, 1 carbon atom substituted or unsubstituted phenyl, biphenyl, naphthyl, anthracenyl, anthracenyl, phenanthrenyl substituted with one or more selected from the group consisting of thioalkyl groups having 3 to 40 carbon atoms and cycloalkyl groups having 3 to 40 carbon atoms. At least one selected from the group consisting of pyrenyl, 9,9-dimethylfluorenyl, carbazolyl, quinolinyl, dibenzofuranyl, pyrrole, triazole, pyridinyl, pyrazinyl, and pyrimidinyl groups is an amino group substituted with The method of claim 2,
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 4,
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 5,
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 5,
An organic compound, characterized in that the organic compound is any one of the following compounds 250 to 261: