KR101825612B1 - Blue fluorescent dopant materials, and organic thin film and organic light emitting devices comprising the same - Google Patents

Abstract

[화학식 2]

The organic electroluminescent device includes an organic thin film layer sandwiched between a cathode and an anode and including one or more organic layers including a light emitting layer, wherein the organic thin film layer includes a light emitting layer represented by the following formula (1) A hole transporting material, and an organic electroluminescent device. The organic electroluminescent device of the present invention exhibits characteristics of high efficiency and long life.
[Chemical Formula 1]

(2)

Description

TECHNICAL FIELD [0001] The present invention relates to a blue fluorescent dopant material, an organic thin film containing the same, and an organic electroluminescent device,

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a display field, and more particularly, to an organic compound that can be used in manufacturing an organic electroluminescent device, which is a type of display, and an organic electroluminescent device including the organic compound.

Although liquid crystal displays occupy the majority of flat panel displays to date, efforts to develop new flat panel displays that are more economical and superior in performance and differentiated from liquid crystal displays have been actively conducted worldwide. Organic electroluminescent devices, which are currently attracting attention as next generation flat panel displays, have advantages such as lower driving voltage, faster response speed and wide viewing angle as compared with liquid crystal displays.

The structure of the organic electroluminescent device includes a substrate, an anode, a hole injecting layer for receiving holes in the anode, a hole transporting layer for transporting holes, an electron blocking layer for blocking the entry of electrons from the light emitting layer into the hole transporting layer, A hole blocking layer for blocking the entrance of holes from the light emitting layer into the electron transporting layer, an electron transporting layer for receiving electrons from the cathode to transport electrons to the light emitting layer, an electron injecting layer for receiving electrons from the cathode, and a cathode. In some cases, a light emitting layer may be formed by doping a small amount of a fluorescent or phosphorescent dye to an electron transporting layer or a hole transporting layer without a separate light emitting layer. When a polymer is used, generally one polymer acts as a hole transporting layer, a light emitting layer and an electron transporting layer Can be performed simultaneously. The organic thin film layers between the two electrodes are formed by a vacuum deposition method, a spin coating method, an inkjet printing method, a laser thermal transfer method, or the like. The reason for fabricating the organic electroluminescent device as a multilayer thin film structure is to stabilize the interface between the electrode and the organic material, and in the case of the organic material, the difference in the movement speed of holes and electrons is large. Therefore, by using a proper hole transporting layer and an electron transporting layer, And electrons are effectively transferred to the light-emitting layer so that the densities of the holes and electrons are balanced, thereby improving the luminous efficiency.

The driving principle of the organic electroluminescent device is as follows. When a voltage is applied between the anode and the cathode, the holes injected from the anode are transferred to the light emitting layer via the hole injecting layer and the hole transporting layer. On the other hand, electrons are injected from the cathode to the light emitting layer via the electron injection layer and the electron transport layer, and carriers are recombined in the light emitting layer region to generate an exiton. This exciton is changed from the excited state to the ground state, whereby the fluorescent molecules of the light emitting layer emit light, whereby an image is formed. In this case, the excitation state is referred to as " fluorescence " when the excited state falls to the ground state through the singlet excitation state, and the phosphorescence is emitted while falling to the ground state through the triplet excitation state. In the case of fluorescence, the probability of singlet excited state is 25% (triplet state 75%) and there is a limit of luminous efficiency. However, when phosphorescence is used, 75% of triplet state and 25% of singlet excitation state are used for light emission Theoretically, the internal quantum efficiency can be up to 100%.

The most problematic of such an organic electroluminescent device is its lifetime and efficiency. However, as the display becomes larger, efficiency and life time problems must be solved.

Particularly, in the case of blue, materials such as ADN and DPVBi are used as a host material, and as the dopant, an aromatic amine compound, a copper phthalocyanine compound, a carbazole derivative, a perylene derivative, a coumarine ) Based derivatives and pyrene-based derivatives are used. However, it is difficult to obtain deep blue, and there is a problem that the emission life becomes shorter as the wavelength becomes shorter.

Therefore, the development of deep blue materials with a long lifetime and the development of other organic materials that meet these blue materials and energy levels are required to realize a full color display of natural color.

Korean Patent No. 10-0846221

SUMMARY OF THE INVENTION The present invention has been made in order to solve the above problems of the prior art,

And to provide a novel organic compound which is used as a blue dopant material to improve the luminous efficiency and the luminescence lifetime of an organic electroluminescent device.

Another object of the present invention is to provide an organic electroluminescent device including the blue dopant material and having improved driving voltage, luminescent efficiency and luminescent lifetime.

It is another object of the present invention to provide an organic electroluminescent device in which driving voltage, efficiency and lifetime of the device are further improved by combining the blue dopant material and a specific hole transporting layer material.

The present invention provides an organic compound represented by the following Formula 1:

[Chemical Formula 1]

In this formula,

Ar1, Ar2, Ar3, and Ar4 are each independently a C1 ~ C10 linear or branched alkyl, alkoxy of C3 ~ C12 cycloalkyl, C1 ~ C10, _{halogen, CN, CF 3, Si (} CH 3) 3, phenyl Substituted or unsubstituted at least one group selected from the group consisting of an alkyl group, a cycloalkyl group, a cycloalkyl group, a cycloalkyl group, a cycloalkyl group, a cycloalkyl group, a cycloalkenyl group, a cycloalkenyl group, An aromatic hydrocarbon group having 6 to 60 carbon atoms,

Straight-chain or branched-chain alkyl of C1 ~ C10, an alkoxy of C3 ~ C12 cycloalkyl, C1 ~ C10, _{halogen, CN, CF 3, Si (} CH 3) 3, phenyl, naphthyl, 9,9-dimethyl fluorenyl A group consisting of S, O, N, and Si, which is unsubstituted or substituted with at least one member selected from the group consisting of halogen, cyano, carbazolyl, dibenzofuranyl, pyrenyl, anthracenyl, and perylenyl groups A heteroaromatic hydrocarbon group having 5 to 60 carbon atoms containing at least one element selected from the group consisting of

R1, R2, R3 and R4 are each independently hydrogen, C1 ~ C10 straight or branched chain alkyl, C3 ~ C12 cycloalkyl, C1 ~ C10 alkoxy, halogen, CN a, CF _3, or Si (CH _{3) 3} Lt; / RTI >

Straight-chain or branched-chain alkyl of C1 ~ C10, an alkoxy of C3 ~ C12 cycloalkyl, C1 ~ C10, _{halogen, CN, CF 3, Si (} CH 3) 3, phenyl, naphthyl, 9,9-dimethyl fluorenyl , An aromatic hydrocarbon group having 6 to 60 carbon atoms which is substituted or unsubstituted with at least one member selected from the group consisting of carbazolyl, dibenzofuranyl, pyrenyl, anthracene, and perylenyl groups,

Straight-chain or branched-chain alkyl of C1 ~ C10, an alkoxy of C3 ~ C12 cycloalkyl, C1 ~ C10, _{halogen, CN, CF 3, Si (} CH 3) 3, phenyl, naphthyl, 9,9-dimethyl fluorenyl Wherein R is selected from the group consisting of S, O, N, and Si, wherein the substituent is selected from the group consisting of a hydrogen atom, an alkyl group, an alkoxy group, an aryloxy group, a carbazolyl group, a dibenzofuranyl group, a pyrenyl group, an anthracene group, and a perylenyl group, A heteroaromatic hydrocarbon group having 5 to 60 carbon atoms containing at least one element selected,

Provided that R1, R2, R3 and R4 may not all be hydrogen, R1 and R2, and R3 and R4 may combine with each other to form a saturated or unsaturated ring.

Further, the present invention is an organic electroluminescent device in which one or more organic thin film layers including at least a light emitting layer are laminated between a cathode and an anode,

Wherein the light emitting layer contains the organic compound singly 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 one or more organic compounds represented by the following formula (2)

(2)

In this formula,

R1, R2, R3 and R4 are each independently hydrogen; A linear or branched alkyl group having 1 to 20 carbon atoms; Alkoxy of C1 ~ C10 linear or branched alkyl, C1 ~ C10 of halogen, CN, CF ₃ and Si (CH ₃₎ into one or more selected from the group consisting of _3-group substituted or unsubstituted aromatic hydrocarbon of a carbon number of 6 to 60 ring group; Or C1 ~ C10 linear or branched alkyl, C1 ~ C10 alkoxy, halogen, CN of a, CF _3, and Si (CH ₃₎ substituted with one or more selected from the group consisting of ₃ groups or is unsubstituted, S, O, N And Si; and a heteroaromatic hydrocarbon group having 5 to 60 carbon atoms and containing at least one element selected from the group consisting of Si,

Each of R 1, R 2, R 3 and R 4 may be independently bonded to a phenyl group of a back bone to form an aromatic hydrocarbon or a heteroaromatic hydrocarbon.

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

Further, the present invention provides an organic electroluminescent device including the blue dopant material and having improved driving voltage, luminescent efficiency, and luminescent lifetime.

Also, the present invention provides an organic electroluminescent device in which driving voltage, efficiency and lifetime of the device are further improved by incorporating the blue dopant material and a specific hole transporting layer material in combination.

The present invention provides novel organic compounds represented by the following general formula

[Chemical Formula 1]

In this formula,

Ar1, Ar2, Ar3, and Ar4 are each independently a C1 ~ C10 linear or branched alkyl, alkoxy of C3 ~ C12 cycloalkyl, C1 ~ C10, _{halogen, CN, CF 3, Si (} CH 3) 3, phenyl Substituted or unsubstituted at least one group selected from the group consisting of an alkyl group, a cycloalkyl group, a cycloalkyl group, a cycloalkyl group, a cycloalkyl group, a cycloalkyl group, a cycloalkenyl group, a cycloalkenyl group, An aromatic hydrocarbon group having 6 to 60 carbon atoms,

Straight-chain or branched-chain alkyl of C1 ~ C10, an alkoxy of C3 ~ C12 cycloalkyl, C1 ~ C10, _{halogen, CN, CF 3, Si (} CH 3) 3, phenyl, naphthyl, 9,9-dimethyl fluorenyl A group consisting of S, O, N, and Si, which is unsubstituted or substituted with at least one member selected from the group consisting of halogen, cyano, carbazolyl, dibenzofuranyl, pyrenyl, anthracenyl, and perylenyl groups A heteroaromatic hydrocarbon group having 5 to 60 carbon atoms containing at least one element selected from the group consisting of

R1, R2, R3 and R4 are each independently hydrogen, C1 ~ C10 straight or branched chain alkyl, C3 ~ C12 cycloalkyl, C1 ~ C10 alkoxy, halogen, CN a, CF _3, or Si (CH _{3) 3} Lt; / RTI >

Straight-chain or branched-chain alkyl of C1 ~ C10, an alkoxy of C3 ~ C12 cycloalkyl, C1 ~ C10, _{halogen, CN, CF 3, Si (} CH 3) 3, phenyl, naphthyl, 9,9-dimethyl fluorenyl , An aromatic hydrocarbon group having 6 to 60 carbon atoms which is substituted or unsubstituted with at least one member selected from the group consisting of carbazolyl, dibenzofuranyl, pyrenyl, anthracene, and perylenyl groups,

Straight-chain or branched-chain alkyl of C1 ~ C10, an alkoxy of C3 ~ C12 cycloalkyl, C1 ~ C10, _{halogen, CN, CF 3, Si (} CH 3) 3, phenyl, naphthyl, 9,9-dimethyl fluorenyl Wherein R is selected from the group consisting of S, O, N, and Si, wherein the substituent is selected from the group consisting of a hydrogen atom, an alkyl group, an alkoxy group, an aryloxy group, a carbazolyl group, a dibenzofuranyl group, a pyrenyl group, an anthracene group, and a perylenyl group, A heteroaromatic hydrocarbon group having 5 to 60 carbon atoms containing at least one element selected,

Provided that R1, R2, R3 and R4 may not all be hydrogen, R1 and R2, and R3 and R4 may combine with each other to form a saturated or unsaturated ring.

More preferably, in the above formula,

Ar 1, Ar 2, Ar 3 and Ar 4 are each independently phenyl, naphthyl, substituted or unsubstituted phenyl, naphthyl, 9,9-dimethylfluorenyl, and phenanthrenyl groups, Yl, fluorenyl, carbazolyl, or dibenzofuranyl group;

R1, R2, R3 and R4 are each independently hydrogen or a C1 to C10 alkyl group,

R 1, R 2, R 3 and R 4 may not all be hydrogen. In the formula (I), R 1, R 2, R 3 and R 4 may be the same or different from each other.

Further, it is more preferable that R1 and R3 are not all hydrogen.

Specific examples of the organic compound include any of the following compounds 1 to 45:

The organic compound may be used as a material for a blue dopant.

In addition,

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

Wherein the light emitting layer contains the organic compound singly or in combination of two or more kinds.

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

The hole transport layer may contain one or more organic compounds represented by the following formula (2)

(2)

In this formula,

R1, R2, R3 and R4 are each independently hydrogen; A linear or branched alkyl group having 1 to 20 carbon atoms; Alkoxy of C1 ~ C10 linear or branched alkyl, C1 ~ C10 of halogen, CN, CF ₃ and Si (CH ₃₎ into one or more selected from the group consisting of _3-group substituted or unsubstituted aromatic hydrocarbon of a carbon number of 6 to 60 ring group; Or C1 ~ C10 linear or branched alkyl, C1 ~ C10 alkoxy, halogen, CN of a, CF _3, and Si (CH ₃₎ substituted with one or more selected from the group consisting of ₃ groups or is unsubstituted, S, O, N And Si; and a heteroaromatic hydrocarbon group having 5 to 60 carbon atoms and containing at least one element selected from the group consisting of Si,

Each of R 1, R 2, R 3 and R 4 may be independently bonded to a phenyl group of a back bone to form an aromatic hydrocarbon or a heteroaromatic hydrocarbon.

More preferably, in the above formula,

R 1, R 2, R 3 and R 4 are each independently phenyl, biphenyl, naphthyl, anthracenyl, phenanthrenyl, fluorenylcarbazole or pyrenyl,

Each of R 1, R 2, R 3 and R 4 may independently be bonded to a phenyl group having a basic structure to form naphthalene, anthracene, or phenanthrene.

Specific examples of the organic compound include any one of the following compounds 101 to 112.

Hereinafter, the organic electroluminescent device of the present invention will be described by way of example. However, the following examples do not limit the organic electroluminescent device of the present invention.

In the method of manufacturing an organic electroluminescent device according to the present invention, a cathode material is coated on the surface of a substrate by a conventional method to form a cathode. At this time, the substrate to be used is preferably a glass substrate or a transparent plastic substrate having excellent transparency, surface smoothness, ease of handling, and waterproofness. As the material for the positive electrode, indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO ₂ ), zinc oxide (ZnO) and the like which are transparent and excellent in conductivity may be used.

Next, a hole injection layer (HIL) material is formed on the surface of the anode by vacuum thermal deposition or spin coating using a conventional method. Examples of such hole injection layer materials include copper phthalocyanine (CuPc), 4,4 ', 4 "-tris (3-methylphenylamino) triphenylamine (m-MTDATA), 4,4' Amino) phenoxybenzene (m-MTDAPB), starburst type amines such as 4,4 ', 4 "-tri (N-carbazolyl) triphenylamine (TCTA), 4,4' Triphenylamine (2-TNATA) or IDE406 available from Idemitsu, for example.

A hole transport layer (HTL) material is vacuum-deposited or spin coated on the surface of the hole injection layer by a conventional method to form a hole transport layer. In this case, the hole transport layer material may be at least one selected from the group consisting of bis (N- (1-naphthyl-n-phenyl)) benzidine (? -NPD), N, (NPB) or N, N'-biphenyl-N, N'-bis (3-methylphenyl) -1,1'-biphenyl-4,4'-diamine (TPD) More preferably, the compound of formula (2) of the present invention can be used.

A light emitting layer (EML) material is formed on the surface of the hole transport layer by vacuum thermal deposition or spin coating using a conventional method. Examples of the light-emitting material to be used herein include a phosphorescent fluorescent material, a fluorescent whitening agent, a laser dye, an organic scintillator, and a reagent for fluorescence analysis. Specifically, there may be mentioned a carbazole-based compound, a phosphine oxide-based compound, a carbazole-based phosphine oxide compound, bis ((3,5-difluoro-4-cyanophenyl) pyridine) iridium picolinate (FCNIrpic) 8-hydroxyquinoline) Polyaromatic compounds such as aluminum (Alq3), anthracene, phenanthrene, pyrene, chrysene, perylene, coronene, rubrene and quinacridone, oligophenylene compounds such as quaterphenyl, Benzene, 1,4-bis (4-methylstyryl) benzene, 1,4-bis (4-methylstyryl) Bis (5-t-butyl-2-benzoxazolyl) thiophene, 1,4-diphenyl-1,3-butadiene, Liquid scintillation scintillators such as 6-diphenyl-1,3,5-hexatriene and 1,1,4,4-tetraphenyl-1,3-butadiene, metal complexes of oxine derivatives, coumarin dyes, Methylene pyran pigment, dicyanomethylene cyopyran pigment, polymer A tin dye, an oxobenzanthracene dye, a xanthene dye, a carbostyryl dye, a perylene dye, an oxazine compound, a stilbene derivative, a spiro compound, and an oxadiazole compound. In particular, in the case of a blue organic electroluminescent device, it may be preferable to use the organic compound of the formula 1 of the present invention as a dopant.

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

An electron transport layer (ETL) material is formed on the surface of the light emitting layer by vacuum thermal deposition or spin coating using a conventional method. In this case, the electron transporting material to be used is not particularly limited, and tris (8-hydroxyquinolinolato) aluminum (Alq ₃ ) can be preferably used.

Alternatively, by further forming a hole blocking layer (HBL) between the light emitting layer and the electron transporting layer and using a phosphorescent dopant together with the light emitting layer, it is possible to prevent the phenomenon that the triplet excitons or holes are diffused into the electron transporting layer.

The hole blocking layer can be formed by vacuum thermal deposition and spin coating using a hole blocking layer material in a conventional manner. In the case of the hole blocking layer material, there is no particular limitation, but (8-hydroxyquinolinolato Lithium biphenoxide (BAlq), bathocuproine (BCP), LiF, etc. may be used as the lithium salt (Li), bis (8-hydroxy-2-methylquinolinonato)

An electron injection layer (EIL) material is formed on the surface of the electron transport layer by vacuum thermal deposition or spin coating using a conventional method. At this time, as the electron injection layer material to be used may be a material such as LiF, Liq, Li ₂ O, BaO, NaCl, CsF.

A negative electrode is formed on the surface of the electron injecting layer by vacuum thermal deposition using a conventional method.

At this time, as the negative electrode material to be used, lithium, aluminum, aluminum-lithium, calcium, magnesium, (Mg-Ag) or the like may be used. In the case of a top emission organic electroluminescent device, indium tin oxide (ITO) or indium zinc oxide (IZO) may be used to form a transparent cathode which can transmit light.

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

The organic electroluminescent device according to the present invention may be manufactured in the order as described above, that is, in the order of anode / hole injecting layer / hole transporting layer / light emitting layer / electron transporting layer / electron injecting layer / cathode, Electron transporting layer / light emitting layer / hole transporting layer / hole injecting layer / anode.

Hereinafter, a method of synthesizing the compounds of the above formulas (1) and (2) will be described with reference to typical examples. However, the method of synthesizing the compounds of the present invention is not limited to the following exemplified methods, and the compounds of the present invention can be produced by the methods exemplified below and by methods known in the art.

<Synthesis of Compound of Chemical Formula 1>

Synthesis of intermediate-1

[Reaction Scheme 1]

(10 mmol) of 1,6-dibromopyrene, 0.37 g (0.5 mmol) of Pd (dppf) Cl ₂ and 1.36 g (10 mmol) of ZnCl ₂ were dissolved in 40 ml of anhydrous THF and cooled to -25 ° C under nitrogen. 10 ml of 2.0 M isopropylmagnesium chloride was slowly added dropwise to the flask, and the resulting solution was stirred for 4 hours at a temperature of 80 캜 under heating. After completion of the reaction, 100 ml of dilute hydrochloric acid was added to the reaction solution, and the organic layer was separated, washed with sodium bicarbonate solution and sodium chloride solution, water in the organic layer was removed with anhydrous MgSO ₄ , , The organic solvent was concentrated, and the resulting product was subjected to column chromatography with Hex: MC = 9: 1 to obtain Intermediate-1 1.826 (65%).

Intermediate-1 &^lt; / RTI ^& gt ^; MS (FAB): 286 (M ⁺ )

Synthesis of intermediate-2

[Reaction Scheme 2]

2.86 g (10 mmol) of Intermediate-1 in a three-neck round bottom flask is dissolved in 40 mL of CCl ₄ . 4.00 g (25 mol) of Br ₂ and 30 mL of CCl ₄ are added to a dropping funnel installed in a round bottom flask and slowly dropped over 4 hours in a round bottom flask. N ₂ is injected to remove the generated HBr. After the dropping was completed, the mixture was stirred for 1 hour under a stream of N _{2. When} the reaction was completed, the resulting precipitate was filtered as it was, and the precipitate was recrystallized using toluene to obtain 2.58 g (58%) of Intermediate- .

Intermediate-2 &^lt; / RTI &gt; MS (FAB): 444 (M ⁺ )

Synthesis of intermediate-3

[Reaction Scheme 3]

After the injection of 4-bromo-modify-benzo [b, d] furan 2.47g (10mmol) of 4-isopropyl aniline 1.35g (10mmol) under nitrogen and dissolved in toluene _{30ml, Pd (OAc) 2 0.05g} (0.2mmol), 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 the mixture was refluxed for 5 hours.

After the reaction was completed, the reaction mixture was cooled to room temperature, and then extracted with 150 ml of toluene and 150 ml of H ₂ O. A small amount of water in the organic layer was removed with anhydrous MgSO ₄ , filtered, and the organic solvent was concentrated to obtain Hex : EA = 5: 1 to obtain 2.60 g (86%) of Intermediate-3.

Intermediate 3 MS (FAB): 301 (M <^+>

Synthesis of intermediate-4

[Reaction Scheme 4]

After injection the naphthalene-2-boronic acid 1.72g (10mmol) and 1,2-dibromo-naphthalene 2.86g (10mmol) under nitrogen and dissolved in toluene _{40ml, Pd (PPh 3) 4} 0.58g (0.5mmol) and ₁₅ ml (30 mmol) of 2M K ₂ CO ₃ were added, respectively, and the mixture was refluxed for 24 hours.

After the completion of the reaction, the reaction mixture was cooled to room temperature, 150 ml of MC and 150 ml of H ₂ O were added to extract the MC layer. The mixture was dried with anhydrous MgSO ₄ and concentrated. The product thus obtained was analyzed by Hex: MC = 4: g (65%).

Intermediate 19 MS (FAB): 333 (M ⁺ )

Synthesis of intermediate-5

[Reaction Scheme 5]

After implanting diisopropylaniline 1.35g (10mmol) and Intermediate -4 3.33g (10mmol) under nitrogen and dissolved in toluene _{40ml, Pd (OAc) 2 0.05g} (0.2mmol), 1M t-Bu 3 P 0.4ml (0.4 mmol) and 2.88 g (30 mmol) of t-BuONa, respectively, and the mixture was refluxed for 5 hours.

After the reaction was completed, the reaction mixture was cooled to room temperature, and then extracted with 150 ml of toluene and 150 ml of H ₂ O. A small amount of water in the organic layer was removed with anhydrous MgSO ₄ , filtered, and the organic solvent was concentrated to obtain Hex : EA = 5: 1 to obtain 2.60 g (86%) of Intermediate-5.

Intermediate-5 &^lt; / RTI ^& gt ^; MS (FAB): 283 (M ⁺ )

Synthesis of intermediate-6

[Reaction Scheme 6]

Under nitrogen, 2.57 g (10 mmol) of 2-bromophenanthrene was dissolved in 40 ml of anhydrous THF, the temperature of the reaction was lowered to -78 ° C and 4 ml of 2.5 M n-BuLi was slowly added dropwise, &Lt; / RTI &gt; Then, the temperature of the reactant was lowered to -78 ° C, 12.47 g (12 mmol) of trimethylborate was added dropwise, and the mixture was stirred at room temperature for 12 hours. When the reaction was completed, 2N-HCl aqueous solution was added, stirred for 30 minutes, and extracted with ether.

Water in the organic layer was removed with anhydrous MgSO ₄ , and the organic solvent was concentrated under reduced pressure. The resulting compound was subjected to column chromatography with Hex: MC = 4: 1 to obtain 1.95 g (88%) of Intermediate-6.

Intermediate-6 &^lt; / RTI ^& gt ^; MS (FAB): 222 (M ⁺ )

Synthesis of intermediate-7

[Reaction Scheme 7]

After injecting the Intermediate -6 2.22g (10mmol) and 1-bromo-4-iodobenzene 2.83g (10mmol) under nitrogen and dissolved in toluene _{40ml, Pd (PPh 3) 4} 0.58g (0.5mmol) and 2M K ₂ CO ₃ (30 mmol), respectively, and the mixture was refluxed for 24 hours.

After the completion of the reaction, the reaction mixture was cooled to room temperature, and 200 ml of MC and 200 ml of H ₂ O were added to extract the MC layer. The mixture was dried over anhydrous MgSO ₄ and concentrated. The product thus obtained was analyzed by Hex: EA = 4: g (79%).

Intermediate 7 MS (FAB): 333 (M ^&lt; ^{+ &} gt ^; ).

Synthesis of intermediate-8

[Reaction Scheme 8]

After the injection of 4-isopropyl aniline 1.35g (10mmol) and Intermediate -7 3.33g (10mmol) under nitrogen and dissolved in toluene _{40ml, Pd (OAc) 2 0.05g} (0.2mmol), 1M t-Bu 3 P 0.4ml (0.4 mmol) of t-BuONa and 2.88 g (30 mmol) of t-BuONa, respectively, and refluxed for 6 hours.

After the reaction was completed, the reaction mixture was cooled to room temperature, and then extracted with 150 ml of toluene and 150 ml of H ₂ O. A small amount of water in the organic layer was removed with anhydrous MgSO ₄ , filtered, and the organic solvent was concentrated to obtain Hex : EA = 4: 1 to obtain 3.14 g (81%) of intermediate-8.

Intermediate 8 MS (FAB): 387 (M ^&lt; ^{+ &} gt ^; ) [

Synthesis of intermediate-9

[Reaction Scheme 9]

After injecting the Intermediate -8 3.88g (10mmol) and Intermediate -2 4.44g (10mmol) under nitrogen and dissolved in toluene _{50ml, Pd (OAc) 2 0.05g} (0.2mmol), 1M t-Bu 3 P 0.4ml (0.4 mmol) and 2.88 g (30 mmol) of t-BuONa, respectively, and refluxed for 8 hours.

After the reaction was completed, the reaction mixture was cooled to room temperature, and extracted with 200 ml of toluene and 200 ml of H ₂ O. A small amount of water in the organic layer was removed with anhydrous MgSO ₄ , filtered, and the organic solvent was concentrated. : EA = 4: 1 to obtain 5.86 g (78%) of Intermediate-9.

Intermediate-9 MS (FAB): 750 (M <^+> ).

Synthesis of intermediate-10

[Reaction Scheme 10]

2.86 g (10 mmol) of Intermediate-1 in a three-neck round bottom flask is dissolved in 40 mL of CCl ₄ . 5.59 g (35 mol) of Br ₂ and 40 mL of CCl ₄ are added to a dropping funnel installed in a round bottom flask, and slowly dropped into a round bottom flask over 6 hours. N ₂ is injected to remove HBr generated. After dropping, the mixture was stirred for 1 hour under a stream of N _{2. When} the reaction was completed, the resulting precipitate was filtered as it was, and then the precipitate was recrystallized using toluene and columned with Hex: MC = 5: -10, 2.17 g (36%).

Intermediate 10 MS (FAB): 601 (M ⁺ )

Synthesis of intermediate-11

[Reaction Scheme 11]

After injection bromobenzene 1.57g (10mmol) of 4-isopropyl aniline 1.35g (10mmol) under nitrogen and dissolved in toluene _{40ml, Pd (OAc) 2 0.05g} (0.2mmol), 1M t-Bu 3 P 0.4ml (0.4 mmol) of t-BuONa and 2.88 g (30 mmol) of t-BuONa, respectively, and refluxed for 6 hours.

After the reaction was completed, the reaction mixture was cooled to room temperature, and then extracted with 150 ml of toluene and 150 ml of H ₂ O. A small amount of water in the organic layer was removed with anhydrous MgSO ₄ , filtered, and the organic solvent was concentrated to obtain Hex : EA = 5: 1 to obtain 1.88 g (89%) of Intermediate-11.

Intermediate 11 MS (FAB): 211 (M ⁺ )

Synthesis of intermediate-12

[Reaction Scheme 12]

Under nitrogen, 2.33 g (10 mmol) of 4-bromo-1,1'-biphenyl was dissolved in 40 ml of anhydrous THF, the temperature of the reaction was lowered to -78 ° C, 4 ml of 2.5 M n-BuLi was slowly added dropwise, Was stirred at 0 &lt; 0 &gt; C for 1 hour. Then, the temperature of the reactant was lowered to -78 ° C, 12.47 g (12 mmol) of trimethylborate was added dropwise, and the mixture was stirred at room temperature for 12 hours. When the reaction was completed, 2N-HCl aqueous solution was added, stirred for 30 minutes, and extracted with ether.

Water in the organic layer was removed with anhydrous MgSO ₄ , filtered under reduced pressure, and the organic solvent was concentrated. The resulting compound was subjected to column chromatography with Hex: MC = 6: 1 to obtain 1.82 g (92%) of Intermediate-12.

Intermediate 12 MS (FAB): 198 (M ⁺ )

Synthesis of intermediate-13

[Reaction Scheme 13]

After injecting the Intermediate -11 2.11g (10mmol) and Intermediate -10 6.02g (10mmol) under nitrogen and dissolved in toluene _{50ml, Pd (OAc) 2 0.05g} (0.2mmol), 1M t-Bu 3 P 0.4ml (0.4 mmol) and 2.88 g (30 mmol) of t-BuONa, respectively, and refluxed for 8 hours.

After the reaction was completed, the reaction mixture was cooled to room temperature, and extracted with 200 ml of toluene and 200 ml of H ₂ O. A small amount of water in the organic layer was removed with anhydrous MgSO ₄ , filtered, and the organic solvent was concentrated. : EA = 3: 1 to obtain 4.57 g (53%) of intermediate-13.

Intermediate 13 MS (FAB): 862 (M ^&lt; ^{+ &} gt ^; ) [

Intermediate 13 MS (FAB): 862 (M ^&lt; ^{+ &} gt ^; ) [

Synthesis of intermediate-14

[Reaction Scheme 14]

After 2-yl boronic acid 1.72g (10mmol) and 1-bromo-4-iodo benzene injection 2.83g (10mmol) under nitrogen and dissolved in toluene _{40ml, Pd (PPh 3) 4} 0.58g (0.5mmol ) And ₁₅ ml (30 mmol) of 2M K ₂ CO ₃ , respectively, and refluxed for 24 hours.

After the completion of the reaction, the reaction mixture was cooled to room temperature, 200 ml of MC and 200 ml of H ₂ O were added to extract the MC layer, dried over anhydrous MgSO ₄ and concentrated. The product was then subjected to column chromatography with Hex: MC = (84%).

Intermediate 14 MS (FAB): 283 (M ^&lt; ^{+ &} gt ^; ) [

Synthesis of intermediate-15

[Reaction Scheme 15]

Under nitrogen, 2.84 g (10 mmol) of Intermediate-14 was dissolved in 40 ml of anhydrous THF, the temperature of the reaction was lowered to -78 ° C, 4 ml of 2.5M n-BuLi was slowly added dropwise and the reaction was stirred at 0 ° C for 1 hour . Then, the temperature of the reactant was lowered to -78 ° C, 12.47 g (12 mmol) of trimethylborate was added dropwise, and the mixture was stirred at room temperature for 12 hours. When the reaction was completed, 2N-HCl aqueous solution was added, stirred for 30 minutes, and extracted with ether.

Water in the organic layer was removed with anhydrous MgSO ₄ , and the organic solvent was concentrated under reduced pressure. The resulting compound was subjected to column chromatography with Hex: MC = 6: 1 to obtain 2.56 g (91%) of Intermediate-15.

Intermediate 15 MS (FAB): 248 (M <^+> ),

Synthesis of intermediate-16

[Reaction Scheme 16]

After injecting the Intermediate -15 2.48g (10mmol) and 1,6-dibromo pyrene 3.60g (10mmol) under nitrogen and dissolved in toluene _{45ml, Pd (PPh 3) 4} 0.58g (0.5mmol) and 2M K _{2 15} ml (30 mmol) of CO ₃ were added, respectively, and the mixture was refluxed for 24 hours.

After the completion of the reaction, the reaction mixture was cooled to room temperature, 200 ml of MC and 200 ml of H ₂ O were added to extract the MC layer. The mixture was dried over anhydrous MgSO ₄ and concentrated. The product was then fractionated by Hex: MC = 5: (74%).

Intermediate 16 MS (FAB): 606 (M ^&lt; ^{+ &} gt ^; ) [

Synthesis of intermediate-17

[Reaction Scheme 17]

In a three-neck round bottom flask, dissolve 6.07 g (10 mmol) of Intermediate-16 in 50 mL of CCl ₄ . 4.00 g (25 mol) of Br ₂ and 40 mL of CCl ₄ are added to a dropping funnel installed in a round bottom flask, and slowly dropped into a round bottom flask over 6 hours. N ₂ is injected to remove HBr generated. After dropping, the mixture was stirred for 1 hour under a stream of N _{2. When} the reaction was completed, the resulting precipitate was filtered as it was, and the precipitate was recrystallized using toluene. The product was subjected to column chromatography with Hex: MC = 4: -17 (23%).

Intermediate -17 MS (FAB): 764 (M ⁺ )

Synthesis of intermediate-18

[Reaction Scheme 18]

After injection of 1,4-dibromo-naphthalene 2.86g (10mmol) and 1-yl boronic acid 1.72g (10mmol) under nitrogen and dissolved in toluene _{40ml, Pd (PPh 3) 4} 0.58g (0.5mmol) and ₁₅ ml (30 mmol) of 2M K ₂ CO ₃ were added, respectively, and the mixture was refluxed for 24 hours.

After completion of the reaction, the reaction mixture was cooled to room temperature, 150 ml of MC and 150 ml of H ₂ O were added thereto. The MC layer was extracted, dried over anhydrous MgSO ₄ and concentrated. The product thus obtained was analyzed by Hex: EA = 4: (58%).

Intermediate 18 MS (FAB): 333 (M ^&lt; ^{+ &} gt ^; ) [

Synthesis of intermediate-19

[Reaction Scheme 19]

Under nitrogen, 3.33 g (10 mmol) of intermediate-18 was dissolved in 40 ml of anhydrous THF, the temperature of the reaction was lowered to -78 ° C, 4 ml of 2.5 M n-BuLi was slowly added dropwise and the reaction was stirred at 0 ° C for 1 hour . Then, the temperature of the reactant was lowered to -78 ° C, 12.47 g (12 mmol) of trimethylborate was added dropwise, and the mixture was stirred at room temperature for 12 hours. When the reaction was completed, 2N-HCl aqueous solution was added, stirred for 30 minutes, and extracted with ether.

Water in the organic layer was removed with anhydrous MgSO ₄ , filtered under reduced pressure, and the organic solvent was concentrated. The resulting compound was subjected to column chromatography with Hex: MC = 5: 1 to obtain 2.47 g (83%) of Intermediate-19.

Intermediate 19 MS (FAB): 333 (M ⁺ )

Synthesis of intermediate-20

[Reaction Scheme 20]

After injecting the Intermediate -19 3.33g (10mmol) and 1,6-dibromo pyrene 3.60g (10mmol) under nitrogen and dissolved in toluene _{50ml, Pd (PPh 3) 4} 0.58g (0.5mmol) and 2M K _{2 15} ml (30 mmol) of CO ₃ were added, respectively, and the mixture was refluxed for 24 hours.

After completion of the reaction, the reaction mixture was cooled to room temperature, 150 ml of MC and 150 ml of H ₂ O were added thereto. The MC layer was extracted, dried over anhydrous MgSO ₄ and concentrated. The product was then fractionated by Hex: EA = 3: g (72%).

Intermediate 20 MS (FAB): 706 (M ^&lt; ^{+ &} gt ^; ) [

Synthesis of intermediate-21

[Reaction Scheme 21]

In a three-neck round bottom flask, 7.07 g (10 mmol) of Intermediate-20 is dissolved in 50 mL of CCl ₄ . 4.00 g (25 mol) of Br ₂ and 40 mL of CCl ₄ are added to a dropping funnel installed in a round bottom flask, and slowly dropped into a round bottom flask over 6 hours. N ₂ is injected to remove HBr generated. After dropping, the mixture was stirred for 1 hour under a stream of N _{2. When} the reaction was completed, the resulting precipitate was filtered as it was, and the precipitate was recrystallized using toluene. The product was subjected to column chromatography with Hex: MC = 4: -21, 1.82 g (21%).

Intermediate 21 MS (FAB): 864 (M ^&lt; ^{+ &} gt ^; ),

The compound [ 6]  synthesis

[Reaction Scheme 22]

After injecting the Intermediate -2 4.44g (10mmol) and Intermediate -3 3.01g (10mmol) under nitrogen and dissolved in toluene _{60ml, Pd (OAc) 2 0.05g} (0.2mmol), 1M t-Bu 3 P 0.4ml (0.4 mmol) and 2.88 g (30 mmol) of t-BuONa, respectively, and refluxed for 8 hours.

After the reaction was completed, the reaction mixture was cooled to room temperature, and extracted with 200 ml of toluene and 200 ml of H ₂ O. A small amount of water in the organic layer was removed with anhydrous MgSO ₄ , filtered, and the organic solvent was concentrated. : EA = 3: 1 to obtain 6.46 g (73%) of Compound 6. [

^{1 H NMR (DMSO, 300Hz)} : δ (ppm) = 8.20-7.59 (m, 6H), 7.39-6.71 (m, 22H), 3.00-2.52 (q, 4H), 1.36-1.04 (d, 24H)

MS (FAB): 885 (M ^&lt; ^{+ &} gt ^; ).

The compound [ 15] of  synthesis

[Reaction Scheme 23]

After injecting the Intermediate -5 3.88g (10mmol) and Intermediate -9 7.51g (10mmol) under nitrogen and dissolved in toluene _{70ml, Pd (OAc) 2 0.05g} (0.2mmol), 1M t-Bu 3 P 0.4ml (0.4 mmol) and 2.88 g (30 mmol) of t-BuONa, respectively, and refluxed for 8 hours.

After the reaction was completed, the reaction mixture was cooled to room temperature, and extracted with 250 ml of toluene and 250 ml of H ₂ O. A small amount of water in the organic layer was removed with anhydrous MgSO ₄ , filtered under reduced pressure, and then the organic solvent was concentrated. : EA = 3: 1 to obtain 9.31 g (88%) of Compound 15. [

^{1 H NMR (DMSO, 300Hz)} : δ (ppm) = 8.25-7.61 (m, 8H), 7.45-6.61 (m, 32H), 3.01-2.52 (q, 4H), 1.38-1.03 (d, 24H)

MS (FAB): 1057 (M ^&lt; ^{+ &} gt ^; ).

The compound [ 19]  synthesis

[Reaction Scheme 24]

(10 mmol) of Intermediate-12 and 8.63 g (10 mmol) of Intermediate-13 were dissolved under nitrogen in 70 ml of toluene, and then 0.58 g (0.5 mmol) of Pd (PPh ₃ ) ₄ and ₁₅ ml (30 mmol) of 2M K ₂ CO ₃ Respectively, and refluxed for 24 hours.

After the completion of the reaction, the reaction mixture was cooled to room temperature, and 200 ml of MC and 200 ml of H ₂ O were added to extract the MC layer, which was then dried over anhydrous MgSO ₄ , concentrated and then subjected to column chromatography with Hex: EA = 3: (80%).

^{1 H NMR (DMSO, 300Hz)} : δ (ppm) = 8.22-7.60 (m, 8H), 7.45-6.65 (m, 32H), 3.01-2.52 (q, 4H), 1.38-1.04 (d, 24H)

MS (FAB): 1009 (M ^&lt; ^{+ &} gt ^; ).

The compound [ 33]  synthesis

[Reaction Scheme 25]

After injecting the Intermediate -3 3.01g (10mmol) and Intermediate -17 7.65g (10mmol) under nitrogen and dissolved in toluene _{70ml, Pd (OAc) 2 0.05g} (0.2mmol), 1M t-Bu 3 P 0.4ml (0.4 mmol) and 2.88 g (30 mmol) of t-BuONa, respectively, and refluxed for 8 hours.

After the reaction was completed, the reaction mixture was cooled to room temperature, and extracted with 250 ml of toluene and 250 ml of H ₂ O. A small amount of water in the organic layer was removed with anhydrous MgSO ₄ , filtered under reduced pressure, and then the organic solvent was concentrated. : EA = 3: 1 to obtain 8.32 g (69%) of Compound 33.

^{1 H NMR (DMSO, 300Hz)} : δ (ppm) = 8.22-7.61 (m, 8H), 7.50-6.59 (m, 42H), 3.01-2.52 (q, 2H), 1.38-1.03 (d, 12H)

MS (FAB): 1205 (M ^&lt; ^{+ &} gt ^; ).

The compound [ 43]  synthesis

[Reaction Scheme 26]

After injecting the Intermediate -5 3.88g (10mmol) and Intermediate -21 8.65g (10mmol) under nitrogen and dissolved in toluene _{50ml, Pd (OAc) 2 0.05g} (0.2mmol), 1M t-Bu 3 P 0.4ml (0.4 mmol) and 2.88 g (30 mmol) of t-BuONa, respectively, and refluxed for 8 hours.

After the reaction was completed, the reaction mixture was cooled to room temperature, and extracted with 250 ml of toluene and 250 ml of H ₂ O. A small amount of water in the organic layer was removed with anhydrous MgSO ₄ , filtered under reduced pressure, and then the organic solvent was concentrated. : EA = 3: 1 to obtain 9.16 g (62%) of Compound 43.

¹ H NMR (DMSO, 300 Hz):? (Ppm) = 8.25-7.61 (m, 16H), 7.55-6.51 (m, 50H), 3.01-2.52

MS (FAB): 1477 (M ^&lt; ^{+ &} gt ^; ).

&Lt; Synthesis of Compound of Chemical Formula 2 &

Synthesis of intermediate-22

[Reaction Scheme 27]

(10 mmol) of [1,1'-biphenyl] -4-amine and 3.56 g (10 mmol) of 4-iodo-1,1 ': 4' , 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 to the reaction mixture and refluxed for 8 hours.

After the reaction was completed, the reaction mixture was cooled to room temperature, and extracted with 200 ml of toluene and 200 ml of H ₂ O. A small amount of water in the organic layer was removed with anhydrous MgSO ₄ , filtered, and the organic solvent was concentrated. : EA = 4: 1 to obtain 3.02 g (76%) of Intermediate-22.

Intermediate 22 MS (FAB): 397 (M ^&lt; ^{+ &} gt ^; ) [

Synthesis of intermediate-23

[Reaction Scheme 28]

(10 mmol) of di ([1,1'-biphenyl] -4-yl) amine and 3.59 g (10 mmol) of 4-bromo-4'-iodo-1,1'- And 0.18 g (0.2 mmol) of Pd ₂ dba ₃ , 0.4 ml (0.4 mmol) of 1 M t-Bu ₃ P and 2.88 g (30 mmol) of t-BuONa were placed in the flask and refluxed for 8 hours.

After the reaction was completed, the reaction mixture was cooled to room temperature, and extracted with 200 ml of toluene and 200 ml of H ₂ O. A small amount of water in the organic layer was removed with anhydrous MgSO ₄ , filtered, and the organic solvent was concentrated. : EA = 3: 1 to obtain 3.98 g (72%) of Intermediate-23.

Intermediate 23 MS (FAB): 552 (M ⁺ )

Synthesis of intermediate-24

[Reaction Scheme 29]

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

After the reaction was completed, the reaction mixture was cooled to room temperature, and extracted with 200 ml of toluene and 200 ml of H ₂ O. A small amount of water in the organic layer was removed with anhydrous MgSO ₄ , filtered, and the organic solvent was concentrated. : EA = 5: 1 to obtain 2.38 g (74%) of Intermediate-24.

Intermediate 24 MS (FAB): 321 (M <^+>

Synthesis of intermediate-25

[Reaction Scheme 30]

(10 mmol) of aniline and 2.80 g (10 mmol) of 4-iodo-1,1'-biphenyl were dissolved in 50 ml of toluene, and then 0.18 g (0.2 mmol) of Pd ₂ dba ₃ and 1 M t-Bu 0.4 P (0.4 mmol) of ₃ P and 2.88 g (30 mmol) of t-BuONa were added, respectively, and the mixture was refluxed for 8 hours.

After the reaction was completed, the reaction mixture was cooled to room temperature, and extracted with 200 ml of toluene and 200 ml of H ₂ O. A small amount of water in the organic layer was removed with anhydrous MgSO ₄ , filtered, and the organic solvent was concentrated. : EA = 5: 1 to obtain 1.99 g (81%) of Intermediate-25.

Intermediate 25 MS (FAB): 245 (M <^+>

Synthesis of intermediate-26

[Reaction Scheme 31]

(10 mmol) of Intermediate-25 and 3.59 g (10 mmol) of 4-bromo-4'-iodo-1,1'-biphenyl were dissolved in 60 ml of toluene under nitrogen and then 0.18 g of Pd ₂ dba ₃ 0.2 mmol), 0.4 ml (0.4 mmol) of 1M t-Bu ₃ P and 2.88 g (30 mmol) of t-BuONa were added, respectively, and refluxed for 8 hours.

After the reaction was completed, the reaction mixture was cooled to room temperature, and extracted with 200 ml of toluene and 200 ml of H ₂ O. A small amount of water in the organic layer was removed with anhydrous MgSO ₄ , filtered, and the organic solvent was concentrated. : EA = 4: 1 to obtain 3.57 g (75%) of Intermediate-26.

Intermediate 26 MS (FAB): 476 (M ⁺ )

Synthesis of Compound 101

[Reaction Scheme 32]

After injecting the Intermediate -22 5.53g (10mmol) and Intermediate -23 3.98g (10mmol) under nitrogen and dissolved in toluene _{80ml, Pd 2 dba 3 0.18g (} 0.2mmol), 1M t-Bu 3 P 0.4ml (0.4mmol ) and 2.88 g (30 mmol) of t-BuONa, respectively, and the mixture was refluxed for 8 hours.

After the reaction was completed, the reaction mixture was cooled to room temperature, and extracted with 250 ml of toluene and 250 ml of H ₂ O. A small amount of water in the organic layer was removed with anhydrous MgSO ₄ , filtered under reduced pressure, and then the organic solvent was concentrated. : EA = 3: 1 to obtain 6.69 g (77%) of Compound 101.

Compound 101 MS (FAB): 869 (M <^+> ) <

Synthesis of Compound 103

[Reaction Scheme 33]

After injecting the Intermediate -23 5.53g (10mmol) and Intermediate -24 3.21g (10mmol) under nitrogen and dissolved in toluene _{70ml, Pd 2 dba 3 0.18g (} 0.2mmol), 1M t-Bu 3 P 0.4ml (0.4mmol ) and 2.88 g (30 mmol) of t-BuONa, respectively, and the mixture was refluxed for 8 hours.

After the reaction was completed, the reaction mixture was cooled to room temperature, and extracted with 250 ml of toluene and 250 ml of H ₂ O. A small amount of water in the organic layer was removed with anhydrous MgSO ₄ , filtered under reduced pressure, and then the organic solvent was concentrated. : EA = 3: 1 to obtain 5.95 g (75%) of Compound 103.

Compound 103 MS (FAB): 793 (M <^+> ) <

Synthesis of Compound 112

[Reaction Scheme 34]

After injecting the Intermediate -26 4.76g (10mmol) and Intermediate -24 3.21g (10mmol) under nitrogen and dissolved in toluene _{60ml, Pd 2 dba 3 0.18g (} 0.2mmol), 1M t-Bu 3 P 0.4ml (0.4mmol ) and 2.88 g (30 mmol) of t-BuONa, respectively, and the mixture was refluxed for 8 hours.

After the reaction was completed, the reaction mixture was cooled to room temperature, and extracted with 200 ml of toluene and 200 ml of H ₂ O. A small amount of water in the organic layer was removed with anhydrous MgSO ₄ , filtered, and the organic solvent was concentrated. : EA = 4: 1 to obtain 5.59 g (78%) of Compound 112. [

Compound 112 MS (FAB): 716 (M ^&lt; ^{+ &} gt ^; ).

The compound of formula (2) is a known compound, and its synthesis method may be a method disclosed in known literature.

Hereinafter, the present invention will be described in more detail with reference to examples and experimental examples of an organic electroluminescent device. These embodiments and examples are only for illustrating the present invention, and the scope of the present invention is not limited to these examples and experimental examples.

< Organic electroluminescent device  Manufacturing>

Example  One

An anode was formed of ITO on the substrate on which the reflective layer was formed, and was surface-treated with N ₂ plasma or UV-Ozone. HAT-CN was deposited thereon with a hole injection layer (HIL) to a thickness of 10 nm. Next, NPD was deposited to a thickness of 120 nm with a hole transporting layer (HTL). (2-naphthyl) anthracene (ADN) capable of forming blue EML as an emission layer (EML) was deposited on the hole transport layer to a thickness of 25 nm. As a dopant, Compound 2 %. An electron transport layer (ETL) was deposited to a thickness of 30 nm by mixing an anthracene derivative and LiQ at a ratio of 1: 1, and LiQ was deposited thereon as an electron injection layer (EIL) to a thickness of 10 nm. Thereafter, a mixture of magnesium and silver (Ag) in a ratio of 9: 1 was deposited as a cathode to a thickness of 15 nm, 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. And a seal cap containing a moisture absorbent with a UV curable adhesive was adhered thereon to protect the organic electroluminescent device from O ₂ or moisture in the air, thereby manufacturing an organic electroluminescent device.

Example  2 to 7

The procedure of Example 1 was repeated, except that the compounds of formulas (6), (15), (19), (27), (33) and (43) were used instead of compound (2) as a dopant of blue EML in Example 1 The organic electroluminescent devices of Examples 2 to 7 were produced.

Example  8

An anode was formed of ITO on the substrate on which the reflective layer was formed, and was surface-treated with N ₂ plasma or UV-Ozone. HAT-CN was deposited thereon with a hole injection layer (HIL) to a thickness of 10 nm. Compound 101 as a compound of Formula 2 was then deposited as a hole transport layer (HTL) to a thickness of 120 nm. (2-naphthyl) anthracene (ADN) capable of forming blue EML as an emission layer (EML) was deposited on the hole transport layer to a thickness of 25 nm. As a dopant, Compound 2 %. An electron transport layer (ETL) was deposited to a thickness of 30 nm by mixing an anthracene derivative and LiQ at a ratio of 1: 1, and LiQ was deposited thereon as an electron injection layer (EIL) to a thickness of 10 nm. Thereafter, a mixture of magnesium and silver (Ag) in a ratio of 9: 1 was deposited as a cathode to a thickness of 15 nm, 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. And a seal cap containing a moisture absorbent with a UV curable adhesive was adhered thereon to protect the organic electroluminescent device from O ₂ or moisture in the air, thereby manufacturing an organic electroluminescent device.

Example  9-14

The procedure of Example 8 was repeated, except that the compounds of Formulas 6, 15, 19, 27, 33 and 43 of Formula 1 were used instead of Compound 2 of Formula 1 as the dopant of blue EML in Example 8 The organic electroluminescent devices of Examples 9 to 14 were manufactured.

Example  15

An anode was formed of ITO on the substrate on which the reflective layer was formed, and was surface-treated with N ₂ plasma or UV-Ozone. HAT-CN was deposited thereon with a hole injection layer (HIL) to a thickness of 10 nm. Compound 103 was then deposited as a hole transporting layer (HTL) as a compound of Formula 2 to a thickness of 120 nm. (2-naphthyl) anthracene (ADN) capable of forming blue EML as an emission layer (EML) was deposited on the hole transport layer to a thickness of 25 nm. As a dopant, Compound 2 %. An electron transport layer (ETL) was deposited to a thickness of 30 nm by mixing an anthracene derivative and LiQ at a ratio of 1: 1, and LiQ was deposited thereon as an electron injection layer (EIL) to a thickness of 10 nm. Thereafter, a mixture of magnesium and silver (Ag) in a ratio of 9: 1 was deposited as a cathode to a thickness of 15 nm, 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. And a seal cap containing a moisture absorbent with a UV curable adhesive was adhered thereon to protect the organic electroluminescent device from O ₂ or moisture in the air, thereby manufacturing an organic electroluminescent device.

Example  16

An anode was formed of ITO on the substrate on which the reflective layer was formed, and was surface-treated with N ₂ plasma or UV-Ozone. HAT-CN was deposited thereon with a hole injection layer (HIL) to a thickness of 10 nm. Compound 112 as a compound of Formula 2 was then deposited as a hole transport layer (HTL) to a thickness of 120 nm. (2-naphthyl) anthracene (ADN) capable of forming blue EML as an emission layer (EML) was deposited on the hole transport layer to a thickness of 25 nm. As a dopant, Compound 2 %. An electron transport layer (ETL) was deposited to a thickness of 30 nm by mixing an anthracene derivative and LiQ at a ratio of 1: 1, and LiQ was deposited thereon as an electron injection layer (EIL) to a thickness of 10 nm. Thereafter, a mixture of magnesium and silver (Ag) in a ratio of 9: 1 was deposited as a cathode to a thickness of 15 nm, 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. And a seal cap containing a moisture absorbent with a UV curable adhesive was adhered thereon to protect the organic electroluminescent device from O ₂ or moisture in the air, thereby manufacturing an organic electroluminescent device.

Comparative Example  One

Except that 2,5,8,11-tetra-butyl-perylene (t-Bu-Perylene) was used as a dopant of blue EML as the light emitting layer (EML) .

Comparative Example  2

An organic electroluminescent device was fabricated in the same manner as in Example 8, except that 9,10-Bis (2-naphthyl) anthracene (ADN) was used as a blue EML dopant as the light emitting layer (EML).

The compounds used in Examples 1 to 16 and Comparative Examples 1 and 2 are shown below.

Test Example : The organic electroluminescent device  Character rating

One. Example  1 to 7 and Comparative Example  1 of The organic electroluminescent device  Character rating

The characteristics of the organic electroluminescent device manufactured in Examples 1 to 7 and Comparative Example 1 were measured at a current density of 10 mA / cm ² , and the results are shown in Table 1 below.

Voltage
(V) Efficiency
(Cd / A) CIE_x CIE_y T ₉₅ (hr) Example 1 4.4 5.7 0.136 0.059 129 Example 2 4.3 6.3 0.135 0.058 157 Example 3 4.7 5.9 0.134 0.058 151 Example 4 4.8 5.7 0.136 0.056 150 Example 5 4.6 5.2 0.134 0.061 121 Example 6 4.2 6.4 0.135 0.058 162 Example 7 4.9 5.3 0.137 0.057 119 Comparative Example 1 5.3 4.1 0.135 0.058 94

As a result of the experiment, it was found that the organic electroluminescent devices of Examples 1 to 7 including the organic compound of Formula 1 as a dopant in the light emitting layer have improved efficiency and voltage characteristics compared to the conventional organic electroluminescent device of Comparative Example 1 It looked.

In addition, as a result of measuring the after-image lifetime (T ₉₅ ), it was confirmed that the organic electroluminescent device of Comparative Example 1 has a lifetime of 100 hours or less, whereas Examples 1 to 7 have a lifetime of 120 hours or more, In particular, it was confirmed that the organic electroluminescent devices of Examples 2, 3, 4, and 6 had a long life time of 150 hours or more.

Therefore, it can be seen that the organic electroluminescent device including the organic compound of formula (1) of the present invention as a host in the light emitting layer is excellent in efficiency, voltage and lifetime characteristics.

2. Example  8 to 14 and Comparative Example  2 of The organic electroluminescent device  Character rating

The characteristics of the organic EL device manufactured in Examples 8 to 14 and Comparative Example ² were measured at a current density of 10 mA / cm ² , and the results are shown in Table 2 below.

Voltage
(V) Efficiency
(Cd / A) CIE_x CIE_y T ₉₅ (hr) Example 8 4.1 6.0 0.137 0.059 145 Example 9 4.0 6.5 0.135 0.059 172 Example 10 4.4 6.1 0.134 0.058 165 Example 11 4.6 5.9 0.136 0.057 162 Example 12 4.4 5.6 0.134 0.060 141 Example 13 4.0 6.7 0.136 0.058 181 Example 14 4.5 5.6 0.137 0.058 138 Comparative Example 2 5.1 4.3 0.136 0.058 99

As a result of the above experiment, the organic electroluminescent devices of Examples 8 to 14 using the compounds of Formula 1 and Formula 2 of the present invention as the light emitting layer and the hole transporting layer, compared with the conventional organic electroluminescent device of Comparative Example 2, And showed remarkably improved results. In particular, the organic electroluminescent device of Example 13 exhibited remarkably improved characteristics in terms of voltage characteristics and luminous efficiency.

In addition, as a result of measuring the after-image lifetime (T ₉₅ ), it was confirmed that the organic electroluminescent device of Comparative Example 2 had a lifetime of 100 hours or less, whereas Examples 8 to 14 had a lifetime of 138 hours or more, In particular, it was confirmed that the organic electroluminescent devices of Examples 9 and 13 had a long life time of 170 hours or more.

Therefore, it is understood that the organic electroluminescent device including the organic compound of Formula 1 of the present invention in the luminescent layer as a host and the compound of Formula 2 in the hole transport layer is remarkably superior in the efficiency, voltage, have.

3. Example  1, 8, 15, 16, and Comparative Example  1, 2 The organic electroluminescent device  Character rating

The characteristics of the organic electroluminescent device fabricated in Examples 1, 8, 15, 16 and Comparative Examples 1 and ² were measured at a current density of 10 mA / cm ² , and the results are shown in Table 3 below.

Voltage
(V) Efficiency
(Cd / A) CIE_x CIE_y T ₉₅ (hr) Example 1 4.4 5.7 0.136 0.059 129 Example 8 4.1 6.0 0.137 0.059 145 Example 15 4.0 6.4 0.135 0.059 171 Example 16 3,9 6.1 0.136 0.059 177 Comparative Example 1 5.3 4.1 0.135 0.058 94 Comparative Example 2 5.1 4.3 0.136 0.058 99

As a result of the above experiment, the organic electroluminescent devices of Examples 8, 15, and 16 using the compounds of Formula 1 and Formula 2 of the present invention as the light emitting layer and the hole transporting layer, as well as Comparative Examples 1 and 2, Emitting efficiency and lifetime characteristics, as compared with Example 1, which contained the light-emitting layer as a dopant in the light-emitting layer. These results are the same as those of Examples 2 and 9, Examples 3 and 10, Examples 4 and 11, Examples 5 and 12, Examples 6 and 13, and Examples 7 and 14 It is also evident through comparison.

The above results are obtained by using the compound of formula (2) as a hole transport material, which corresponds well to the dopant structure of the compound of formula (1).

In the case of a general organic electroluminescent device, deterioration at the interface between the hole transporting layer and the light emitting layer progresses and electrons are diffused to the hole transporting layer through the interface to accelerate the deterioration, and the lifetime of the organic electroluminescent device is reduced.

However, according to the present invention, the use of the compound of Formula 2 as the hole transport material improves the efficiency of the organic electroluminescent device because the charge balance of the device is achieved and the exciton can not move within the light emitting layer. In addition, the compound of formula (2) prevents the exciton from diffusing into the hole transport layer, thereby preventing the deterioration of the whole, thereby increasing the lifetime of the organic electroluminescent device.

Claims (8)

An organic compound represented by the following formula (1):
[Chemical Formula 1]

In this formula,
R2 and R4 are each independently a phenyl group substituted or unsubstituted with a C1-C10 alkyl group or a phenyl group,
R1 and R3 are each independently a C1 to C10 alkyl group,
Ar 1, Ar 2, Ar 3 and Ar 4 are each independently phenyl, naphthyl, substituted or unsubstituted with at least one member selected from the group consisting of C 1 -C 10 alkyl, phenyl, naphthyl, 9,9-dimethylfluorenyl, Yl, fluorenyl, carbazolyl, or dibenzofuranyl group. delete The method according to claim 1,
Wherein the organic compound is any one of the following compounds 19 to 27:

The method according to claim 1,
Wherein the organic compound is a blue dopant. An organic electroluminescent device in which an organic thin film layer composed of one layer or a plurality of layers including at least a light emitting layer is laminated between a cathode and an anode,
Wherein the light emitting layer contains the organic compound of claim 1 singly or in combination of two or more kinds. The method of claim 5,
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,
Wherein the hole transport layer contains one or more organic compounds represented by the following formula (2)
(2)

In this formula,
R1, R2, R3 and R4 are each independently hydrogen; A linear or branched alkyl group having 1 to 20 carbon atoms; Alkoxy of C1 ~ C10 linear or branched alkyl, C1 ~ C10 of halogen, CN, CF ₃ and Si (CH ₃₎ into one or more selected from the group consisting of _3-group substituted or unsubstituted aromatic hydrocarbon of a carbon number of 6 to 60 ring group; Or C1 ~ C10 linear or branched alkyl, C1 ~ C10 alkoxy, halogen, CN of a, CF _3, and Si (CH ₃₎ substituted with one or more selected from the group consisting of ₃ groups or is unsubstituted, S, O, N And Si; and a heteroaromatic hydrocarbon group having 5 to 60 carbon atoms and containing at least one element selected from the group consisting of Si,
Each of R 1, R 2, R 3 and R 4 may independently be bonded to a phenyl group of a basic structure to form an aromatic hydrocarbon or a heteroaromatic hydrocarbon. The method of claim 6,
Each of R1, R2, R3 and R4 is independently phenyl, biphenyl, naphthyl, anthracenyl, phenanthrenyl, fluorenylcarbazole or pyrenyl group,
Wherein each of R 1, R 2, R 3 and R 4 independently represents a phenyl group of a basic structure to form naphthalene, anthracene, or phenanthrene. The method of claim 6,
Wherein the organic compound of Formula 2 is any one selected from the following compounds 101 to 112: