KR20150102734A - Organic compounds for an organic electroluminescent device and an organic electroluminescent device comprising the same - Google Patents

Abstract

Provided are novel organic compounds for an organic electroluminescent device and an organic electroluminescent device comprising the same wherein the compounds are selected from a group of chemical formula 1.

Description

TECHNICAL FIELD The present invention relates to an organic electroluminescent device and an organic electroluminescent device including the organic compound,

The present invention relates to a novel organic compound used in an organic electroluminescent device and an organic electroluminescent device comprising 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.

In general, the simplest structure of an organic electroluminescent device is composed of a light emitting layer and a pair of opposite electrodes sandwiching the layer. That is, in the organic electroluminescent device, when an electric field is applied between the electrodes, electrons are injected from the cathode, holes are injected from the anode, and they are recombined in the light emitting layer to emit light.

More specifically, 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 injection 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. At this time, it is called? 奐 ?, that the excited state is emitted when the excited state falls to the ground state through the singlet excited state, and it is said that it emits light while falling to the ground state through the triplet excitation state. In the case of fluorescence, the probability of singlet excitation is 25% (triplet state 75%), and there is a limit to the luminous efficiency. However, when phosphorescence is used, 75% of the triplet state and 25% 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. An organic light emitting compound having an excellent hole injection and transport ability in an organic electroluminescent device improves the light emission lifetime of the electric device by lowering the driving voltage of the device and increasing the luminous efficiency and brightness.

An aromatic amine compound, a copper phthalocyanine compound, a hexaazatriphenylene derivative, and a carbazole derivative have been used for an organic electroluminescent device, but a stable and efficient organic luminescent compound for an organic electroluminescent device has not yet been sufficiently developed , The development of new materials is continuously required.

Korean Patent Publication No. 10-2006-0059068

The present invention can be applied to an organic electroluminescent device as a hole injecting layer material, a hole transporting layer material, an electron blocking layer material or a light emitting layer material drawn to solve the problems of the related art as described above, It is an object of the present invention to provide a novel organic compound capable of lowering the driving voltage and improving the luminous efficiency, luminance, thermal stability, color purity, and device life.

It is another object of the present invention to provide a hole injecting layer, a hole transporting layer, an electron blocking layer or a material for forming a light emitting layer containing the organic compound.

It is another object of the present invention to provide an organic electroluminescence device using the organic compound.

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

[ Formula 1 ]

In the above formula

X is a carbon, nitrogen, oxygen, sulfur or silicon atom;

R1 and R2 are each independently selected from the group consisting of hydrogen; A linear or branched alkyl group of C1 to C10; A C3 to C12 cycloalkyl group; An alkoxy group of C1 ~ C10 linear or branched alkyl group, C1 ~ C10 of halogen, CN, CF ₃ and Si (CH ₃₎ substituted with one or more selected from the group consisting of ₃ groups or unsubstituted aromatic ring, and C1 ~ selected from straight or branched chain alkyl, alkoxy, halogen, CN, CF ₃ and Si (CH ₃₎ group consisting of a substituted or unsubstituted aromatic heterocycle with one or more selected from the group consisting of ₃ groups of C1 ~ C10 for C10 Aromatic hydrocarbons having 4 to 60 carbon atoms and at least one compound selected from the group consisting of:

를 형성할 수 있으며;R3 and R4 are each independently selected from the group consisting of hydrogen; A linear or branched alkyl group of C1 to C10; Halogen, _{nitrile, CF 3, -Si (CH 3} ) 3, C1 ~ C10 linear or branched alkyl, optionally substituted with the same or different groups linear or branched alkoxy of C1 ~ C10 unsubstituted phenyl, pyridinyl, triazinyl, naphthyl Dibenzofuranyl, dibenzothiophene, carbazole or thianthrenyl group, and R 3 and R 4 are combined to form a

Lt; / RTI >

Y is a substituted or unsubstituted aromatic with one or more selected from the group consisting of a straight or branched chain alkyl group of C1 ~ C10, an alkoxy group of C1 ~ C10, halogen, CN, CF ₃ and Si (CH _{3) 3} ring, and straight or branched chain alkyl group of C1 ~ C10, an alkoxy group of C1 ~ C10, halogen, CN, CF ₃ and Si (CH ₃₎ into one or more selected from the group consisting of _3-group the group consisting of a substituted or unsubstituted aromatic heterocyclic ring And an aromatic hydrocarbon having 4 to 60 carbon atoms.

In addition,

A hole injection layer, a hole transport layer, an electron blocking layer or a material for forming a light emitting layer containing the organic compound represented by the above formula (1).

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 sandwiched between a cathode and an anode,

Wherein at least one of the organic thin film layers contains the organic compound represented by the formula (1) alone or in combination of two or more.

The organic light emitting compound according to the present invention can be applied to organic light emitting devices such as a hole injecting layer material, a hole transporting layer material, an electron blocking layer material, or a phosphorescent green or red host material. Lowers the voltage, and improves the luminous efficiency, luminance, thermal stability, color purity, and device life.

In addition, the organic electroluminescent device manufactured using the organic electroluminescent compound of the present invention has high efficiency and long life.

The present invention relates to novel organic compounds represented by the general formula

 [ Formula 1 ]

In the above formula

X is a carbon, nitrogen, oxygen, sulfur or silicon atom;

R1 and R2 are each independently selected from the group consisting of hydrogen; A linear or branched alkyl group of C1 to C10; A C3 to C12 cycloalkyl group; An alkoxy group of C1 ~ C10 linear or branched alkyl group, C1 ~ C10 of halogen, CN, CF ₃ and Si (CH ₃₎ substituted with one or more selected from the group consisting of ₃ groups or unsubstituted aromatic ring, and C1 ~ selected from straight or branched chain alkyl, alkoxy, halogen, CN, CF ₃ and Si (CH ₃₎ group consisting of a substituted or unsubstituted aromatic heterocycle with one or more selected from the group consisting of ₃ groups of C1 ~ C10 for C10 Aromatic hydrocarbons having 4 to 60 carbon atoms and at least one compound selected from the group consisting of:

를 형성할 수 있으며;R3 and R4 are each independently selected from the group consisting of hydrogen; A linear or branched alkyl group of C1 to C10; Halogen, _{nitrile, CF 3, -Si (CH 3} ) 3, C1 ~ C10 linear or branched alkyl, optionally substituted with the same or different groups linear or branched alkoxy of C1 ~ C10 unsubstituted phenyl, pyridinyl, triazinyl, naphthyl Dibenzofuranyl, dibenzothiophene, carbazole, or thianthrenyl group, and R 3 and R 4 are combined to form a

Lt; / RTI >

Y is a substituted or unsubstituted aromatic with one or more selected from the group consisting of a straight or branched chain alkyl group of C1 ~ C10, an alkoxy group of C1 ~ C10, halogen, CN, CF ₃ and Si (CH _{3) 3} ring, and straight or branched chain alkyl group of C1 ~ C10, an alkoxy group of C1 ~ C10, halogen, CN, CF ₃ and Si (CH ₃₎ into one or more selected from the group consisting of _3-group the group consisting of a substituted or unsubstituted aromatic heterocyclic ring And an aromatic hydrocarbon having 4 to 60 carbon atoms.

In the organic compound, preferably,

또는 R5이며, Y is

Or R5,

R 1 and R 2 and R 5 may each independently be selected from the following chemical structural formulas,

In the above formula, B is each independently hydrogen, a straight-chain or branched alkyl group having 1 to 10 carbon atoms, or a cycloalkyl group having 3 to 12 carbon atoms;

Further, R1 and R2 may be, independently of each other, hydrogen, a C1-C10 linear or branched alkyl group, or a C3-C12 cycloalkyl group.

More preferably, in the organic compound,

R2 is hydrogen, a C1 to C10 linear or branched alkyl group, a phenyl group, a naphthyl group, or a dibenzothiophenyl group;

를 형성할 수 있다.
R3 and R4 each independently may be hydrogen, a C1-C10 linear or branched alkyl group, a phenyl group substituted or unsubstituted with a C1-C10 linear or branched alkyl group, or a thianthrenyl group, R3 and R4 are combined to form

Can be formed.

In the organic compound, preferably,

At least one of B contained in the organic compound may be a C1-C10 linear or branched alkyl group or a C3-C12 cycloalkyl group.

When at least one of the B groups is a straight-chain or branched alkyl group having from 1 to 10 carbon atoms or a cycloalkyl group having from 3 to 12 carbon atoms, the condition for easily melting and depositing can be easily formed when the material is used in a vacuum linear source.

The B may more preferably be a C1 to C6 linear or branched alkyl group.

Specifically, the organic compound may be any one of the following compounds 1 to 150:

The organic compounds of the present invention can be used as a hole injecting layer material, a hole transporting layer material, an electron blocking layer material, or a light emitting layer material in an organic electroluminescent device material. The light emitting layer material may be, for example, a phosphorescent green or red host material.

In addition,

A hole transporting layer, an electron blocking layer or a material for forming a light emitting layer.

The material for forming the hole injection layer, the hole transporting layer, the electron blocking layer or the light emitting layer may be a material which is conventionally added when preparing the organic compound in a form necessary for forming the thin film of the capping layer, such as a solvent .

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 sandwiched between a cathode and an anode,

Wherein at least one of the organic thin film layers contains the organic compound of claim 1 singly or in combination of two or more kinds.

In the organic electroluminescent device, the organic compound may be contained in at least one of a hole injecting layer material, a hole transporting layer material, an electron blocking layer material, or a light emitting layer material.

The organic electroluminescent device

A hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and a cathode may be stacked in this order. Further, an electron blocking layer, a hole blocking layer, and the like may be further stacked .

In the organic electroluminescent device of the present invention, the organic thin film layer may include a hole injecting layer, a hole transporting layer, an electron blocking layer, a light emitting layer, an electron transporting layer, and an electron injecting layer.

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.

The organic electroluminescent device of the present invention may have a structure in which a cathode (a hole injection electrode), a hole injection layer (HIL) and / or a hole transport layer (HTL), a light emitting layer (EML) Preferably, an electron blocking layer (EBL) may be interposed between the anode and the light emitting layer, and an electron transport layer (ETL) and an electron injection layer (EIL) may be interposed between the cathode and the light emitting layer. Further, a hole blocking layer (HBL) may be further included between the cathode and the light emitting layer.

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 the hole injection layer material include the organic compound of the present invention, copper phthalocyanine (CuPc), 4,4 ', 4 "-tris (3-methylphenylamino) triphenylamine (m-MTDATA) 4,4'-tri (N-carbazolyl) triphenylamine (TCTA), which is a starburst type amine, Triphenylamine (2-TNATA) or 4'-tris (N- (2-naphthyl) -N-phenylamino) or IDE406 available from Idemitsu.

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. As the hole transport layer material, organic compound of the present invention, bis (N- (1-naphthyl-n-phenyl)) benzidine (? -NPD), N, N'- (NPB) or N, N'-biphenyl-N, N'-bis (3-methylphenyl) -1,1'-biphenyl-4,4'-diamine (TPD) For example.

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. In the case of green, the organic compound of the present invention, tris (8-hydroxyquinolinolato) aluminum (Alq ₃ ) and the like may be used as the single luminescent material or the luminescent host material, (8-hydroxyquinoline beryllium salt), DPVBi (4,4'-bis (2,2-biphenylethenyl) -1,1'-biphenyl) series, Spiro material, spiro-DPVBi (2,2-biphenylethenyl) -1,1'-biphenyl), LiPBO (2- (2-benzoxazolyl) -phenol lithium salt), bis Phenylvinyl) benzene, aluminum-quinoline metal complexes, metal complexes of imidazole, thiazole and oxazole, and the like. The organic compound of the present invention may be used as a phosphorescent red host material.

Among the light emitting layer materials, IDE102 and IDE105 available from Idemitsu as phosphorescent dopants and tris (2-phenylpyridine) iridium (III) (Ir (ppy ) ₃ ), iridium (III) bis [(4,6-difluorophenyl) pyridinate-N, C-2 '] picolinate (FIrpic) (Chihaya Adachi et al., Appl. Phys Platy (II) octaethylporphyrin (PtOEP), TBE002 (Cobion), etc. may be used.

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 evaporation and spin coating using a hole blocking layer material in a conventional manner. The hole blocking layer material is not particularly limited, Hydroxyquinolinolato) lithium (Liq), bis (8-hydroxy-2-methylquinolinonato) -aluminum biphenoxide (BAlq), bathocuproine (BCP) Can be used.

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 a composition for forming a capping layer.

Hereinafter, a method of synthesizing the above compounds will be described with reference to representative 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 intermediate A

[Reaction Scheme 1]

After injecting a phenylboronic acid 1.22g (10mmol) and 4-bromoaniline 1.72g (10mmol) under nitrogen and dissolved in _{THF 20ml, Pd (PPh 3)} 4 0.58g (0.5mmol), 2M K 2 CO 3 15 ml (30 mmol) was added and the mixture was refluxed for 24 hours.

After 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 thereto to extract the MC layer. The organic layer was distilled under reduced pressure and then 1.20 g (71% ).

Intermediate A MS (FAB): 169 (M <^+> ) <

Synthesis of intermediate B

[Reaction Scheme 2]

After injection the o- tolyl Daily acid 1.36g (10mmol) and 4-bromoaniline 1.72g (10mmol) under nitrogen and dissolved in _{THF 20ml, Pd (PPh 3)} 4 0.58g (0.5mmol), 2M K 2 CO 3 15 ml (30 mmol) was added and the mixture was refluxed for 24 hours.

After the reaction was completed, the reaction mixture was cooled to room temperature, and 200 ml of MC and 200 ml of H ₂ O were added thereto to extract the MC layer. The organic layer was distilled under reduced pressure and then 1.28 g (70% ).

Intermediate B MS (FAB): 183 (M <^+> ),

Synthesis of Intermediates C and D

[Reaction Scheme 3]

2.Og (10mmol) of 2-iodobiphenyl was dissolved in 15ml of THF, then cooled to -78 ° C, and 4ml of 2.5M n-BuLi was added dropwise. After stirring at -78 ° C for 1 hour, 2.59 g (10 mmol) of 2-bromo-9H-fluoren-9-one dissolved in 30 ml of THF was slowly added dropwise and the temperature was raised to room temperature to complete the reaction. MC and 2N HCl The organic layer was extracted.

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: EA = 5: 1 to obtain 3.27 g (79%) of intermediate C.

The intermediate C was dissolved in acetic acid, concentrated hydrochloric acid was added, and the mixture was refluxed for 1 hour to complete the reaction. After extracting with ether and water, the organic layer was separated by Sat? And washed with NaHCO ₃ . The organic layer was dried over MgSO ₄ and then recrystallized and columned with Hex: EA = 5: 1 to obtain 3.20 g (81%) of Intermediate D.

Intermediate C MS (FAB): 413 (M ^&lt; ^{+ &} gt ^; ) [

Intermediate D MS (FAB): 395 (M <^+> )

Synthesis of intermediate E

[Reaction Scheme 4]

After a nitrogen iodo 4-nitrobenzene-1-FIG injecting 3.28g (10mmol) and phenylboronic acid 1.22g (10mmol) is dissolved in _{THF 25ml, Pd (PPh 3)} 4 0.58g (0.5mmol ), 2M K ₂ CO ₃ 15 ml (30 mmol) was added and the mixture was refluxed for 24 hours.

After the completion of the reaction, 200 ml of MC and 200 ml of H ₂ O were added to extract the MC layer, followed by drying with anhydrous MgSO ₄ , followed by concentration with Hex: EA = 5: 1 to obtain 1.97 g (71%) of Intermediate E.

Intermediate E MS (FAB): 278 (M ^&lt; ^{+ &} gt ^; ) [

Synthesis of intermediate F

[Reaction Scheme 5]

Under nitrogen, 2.78 g (10 mmol) of Intermediate E was dissolved in 40 ml of o-dichlorobenzene, and then 6.56 g (25 mmol) of triphenylphosphine was added and refluxed.

After completion of the reaction, 200 ml of MC and 200 ml of H ₂ O were added to extract the MC layer, and the mixture was dried over anhydrous MgSO ₄ and concentrated. The product was then fractionated by Hex: EA = 5: 1 to obtain 1.94 g (79%) of Intermediate F.

Intermediate F MS (FAB): 246 (M ^&lt; ^{+ &} gt ^; ).

Synthesis of intermediate G

[Reaction Scheme 6]

Intermediate F 2.46g (10mmol) under nitrogen and 1-iodo-3-methylbenzene was dissolved 3.27g (15mmol) in nitrobenzene 30ml, K ₂ CO ₃ 4.15 g (30 mmol) of Cu and 0.19 g (3 mmol) of Cu were added and refluxed for 16 hours.

After the completion of the reaction, the nitrobenzene was removed by distillation, 200 ml of MC and 200 ml of H ₂ O were added to extract the MC layer, followed by drying with anhydrous MgSO ₄ and concentration. The resulting product was subjected to column chromatography with Hex: EA = 5: (78%).

Intermediate G MS (FAB): 336 (M ^&lt; ^{+ &} gt ^; ) [

Synthesis of Intermediate H

[Reaction Scheme 7]

Under nitrogen, 2.46 g (10 mmol) of Intermediate G 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, and then 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: EA = 5: 1 to obtain 2.23 g (74%) of Intermediate H.

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

Synthesis of Intermediate I

[Reaction Scheme 8]

After the intermediate H 3.01g (10mmol) under nitrogen and 1-bromo-4-iodo benzene injection 2.83g (10mmol) is dissolved in _{THF 30ml, Pd (PPh 3)} 4 0.58g (0.5mmol) and 2M K ₂ CO ₃ (30 mmol) 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, and 200 ml of MC and 200 ml of H ₂ O were added to extract the MC layer. The product was dried over anhydrous MgSO ₄ and concentrated. Hex: EA = 5: (73%).

Intermediate I MS (FAB): 412 (M <^+> ) <

Synthesis of intermediate J

[Reaction Scheme 9]

After injecting the Intermediate A 1.69g (10mmol) and Intermediate I 4.12g (10mmol) under nitrogen and dissolved in toluene _{30ml, 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 refluxed for 5 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 3.55 g (71%) of intermediate J.

Intermediate J MS (FAB): 500 (M <^+> )

Synthesis of Intermediate K

[Reaction Scheme 10]

After injecting bromo-modify-benzo [b, d] thiophene 2.63g (10mmol) and Intermediate B 1.83g (10mmol) under nitrogen and dissolved in toluene _{30ml, Pd 2 dba 3 0.18g (} 0.2mmol), 1M t-Bu 3 0.4 mmol (0.4 mmol) of P, and 2.88 g (30 mmol) of t-BuONa, respectively, and refluxed for 5 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 2.63 g (72%) of Intermediate K.

Intermediate K MS (FAB): 365 (M <^+> )

Synthesis of Intermediate L

[Reaction Scheme 11]

(10 mmol) of thianthrene, 2.67 g (15 mmol) of NBS (N-bromosuccinimide) and 0.12 g (0.5 mmol) of BPO (benzoyl peroxide) were dissolved in CH ₂ Cl ₂ under nitrogen at room temperature for 5 hours Lt; / RTI &gt;

When the reaction is over, Sat? NaHCO ₃ was added thereto, stirred for 30 minutes, and then extracted with MC. The water in the reaction mixture was removed with anhydrous MgSO ₄ , filtered under reduced pressure, and the organic solvent was concentrated. The resulting product was recrystallized and columned at Hex: EA = 5: 1 to obtain 2.27 g (77%) of Intermediate L.

Intermediate L MS (FAB): 295 (M <^+> )

Synthesis of intermediate M

[Reaction Scheme 12]

After injecting 4-chlorophenylboronic acid 1.56g (10mmol) and Intermediate L 2.95g (10mmol) under nitrogen and dissolved in _{THF 30ml, Pd (PPh 3)} 4 0.58g (0.5mmol) and 2M K ₂ CO ₃ (30 mmol) 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, dried over anhydrous MgSO ₄ and concentrated. The product was then subjected to column chromatography with Hex: EA = (72%).

Intermediate M MS (FAB): 326 (M <^+> ) <

Synthesis of Intermediate N

[Reaction Scheme 13]

After injecting the Intermediate B 1.83g (10mmol) and Intermediate D 3.95g (10mmol) under nitrogen and dissolved in toluene _{30ml, 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 then refluxed for 6 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 3.53 g (71%) of Intermediate N. [

Intermediate N MS (FAB): 497 (M <^+> )

Synthesis of Compound [62]

[Reaction Scheme 14]

Under nitrogen, 3.95 g (10 mmol) of Intermediate D and 5.01 g (10 mmol) of Intermediate J were dissolved in 50 ml of toluene, and Pd ₂ dba ₃ 0.4 mmol (0.4 mmol) of t-Bu ₃ P and 2.88 g (30 mmol) of t-BuONa were added and refluxed for 12 hours.

After the completion of the reaction, 300 ml of MC and 300 ml of H ₂ O were added to extract the MC layer. The organic layer was distilled under reduced pressure and then subjected to column chromatography with Hex: MC = 3: 1 to obtain 6.28 g (77%) of Compound 62.

¹ H NMR (DMSO, 300 Hz):? (Ppm) = 7.88-7.59 (m, 7H), 7.48-7.10 (m, 26H), 6.75-6.52

MS (FAB): 815 (M ^&lt; ^{+ &} gt ^; ).

Synthesis of Compound [139]

[Reaction Scheme 15]

Under nitrogen, 2.95 g (10 mmol) of Intermediate L and 3.65 g (10 mmol) of Intermediate K were dissolved in 35 ml of toluene, and Pd ₂ dba ₃ 0.4 mmol (0.4 mmol) of t-Bu ₃ P and 2.88 g (30 mmol) of t-BuONa were added and refluxed for 12 hours.

After completion of the reaction, 300 ml of MC and 300 ml of H ₂ O were added to extract the MC layer. The organic layer was distilled under reduced pressure and then subjected to column chromatography with Hex: MC = 3: 1 to obtain 4.70 g (81%) of compound 139.

^{1 H NMR (CDCl3, 300Hz)} : δ (ppm) = 8.20-8.13 (d, 1H), 8.07-8.01 (d, 1H), 7.78-7.70 (d, 1H), 7.53-7.38 (m, 5H), 2H), 7.35-7.30 (m, 2H), 7.29-7.15 (m, 9H), 7.13-7.07

MS (FAB): 579 (M ^&lt; ^{+ &} gt ^; ).

Synthesis of Compound [148]

[Reaction Scheme 16]

Under nitrogen, 3.27 g (10 mmol) of Intermediate M and 4.98 g (10 mmol) of Intermediate N were dissolved in 50 ml of toluene, and Pd ₂ dba ₃ 0.4 mmol (0.4 mmol) of t-Bu ₃ P and 2.88 g (30 mmol) of t-BuONa were added and refluxed for 12 hours.

After the completion of the reaction, 300 ml of MC and 300 ml of H ₂ O were added to extract the MC layer. The organic layer was distilled under reduced pressure and then subjected to column chromatography with Hex: MC = 2: 1 to obtain 6.23 g (79%) of compound 148.

^{1 H NMR (CDCl3, 300Hz)} : δ (ppm) = 7.80-7.72 (t, 3H), 7.65-7.60 (m, 1H), 7.53-7.46 (m, 3H), 7.40-6.97 (m, 23H), 2H), 6.72-6.65 (d, 1H), 6.62-6.58 (s, 1H), 2.30-2.18 (s, 3H)

MS (FAB): 788 (M ^&lt; ^{+ &} gt ^; ).

Compounds 1 to 150 of the general formula (1) were prepared by referring to the reaction schemes 1 to 16, and the results are shown below.

Hereinafter, the present invention will be described in more detail by way of examples. However, the following examples are intended to further illustrate the present invention, and the scope of the present invention is not limited by the following examples. The following examples can be appropriately modified and changed by those skilled in the art within the scope of the present invention.

Example 1 ~ 29: The organic electroluminescent device  Produce

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 100 ANGSTROM. Subsequently, the organic compound of the present invention was vacuum deposited on the hole injection layer to form a hole transport layer having a thickness of 800 Å. The electron blocking layer (EBL) was formed to a thickness of 150 Å by vacuum deposition of TCTA on the hole transporting layer, and 9,10-Bis 2-naphthyl anthracene (ADN) doped with 2,5,8,11-tetra-butyl-perylene (D-Bu-Perylene) An electron transport layer (ETL) was deposited to a thickness of 300 Å by mixing an anthracene derivative and LiQ at a weight ratio of 1: 1, and LiQ was deposited thereon as an electron injection layer (EIL) to a thickness of 100 Å. Thereafter, silver (Ag) was deposited to a thickness of 150 A as a cathode. 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: The organic electroluminescent device  Produce

An organic electroluminescent device was prepared in the same manner as in Example 1 except that? -NPD was used instead of the organic compound of the present invention as the hole transport layer material in Example 1

Test Example . The organic electroluminescent device  Character rating

The characteristics of the organic electroluminescent devices manufactured in the organic electroluminescent devices 1 to 29 and the organic electroluminescent devices prepared in the comparative example 1 were measured at a current density of 10 mA / cm ² , and the results are shown in Table 1 below.

Material Name Current Density
(mA / cm 2) Voltage
(V) Efficiency
(Cd / A) CIE (X Y) Comparative Example 1 NPD 10 4.1 9.2 (0.150 0.090) Example 1 Compound 1 10 3.9 10.1 (0.150 0.090) Example 2 Compound 4 10 3.8 10.3 (0.150 0.089) Example 3 Compound 8 10 3.9 10.4 (0.151 0.090) Example 4 Compound 11 10 3.7 10.2 (0.152 0.090) Example 5 Compound 13 10 4.0 10.5 (0.151 0.090) Example 6 Compound 15 10 3.7 10.3 (0.152 0.089) Example 7 Compound 17 10 3.9 10.4 (0.151 0.090) Example 8 Compound 19 10 4.0 10.1 (0.152 0.090) Example 9 Compound 23 10 4.1 10.1 (0.150 0.089) Example 10 Compound 27 10 3.9 10.4 (0.151 0.089) Example 11 Compound 29 10 3.8 10.5 (0.151 0.090) Example 12 Compound 37 10 3.6 10.1 (0.152 0.090) Example 13 Compound 39 10 3.9 10.2 (0.150 0.090) Example 14 Compound 51 10 3.9 10.3 (0.151 0.089) Example 15 Compound 62 10 3.8 10.4 (0.152 0.090) Example 16 Compound 70 10 3.9 10.2 (0.151 0.090) Example 17 Compound 82 10 3.8 10.3 (0.151 0.089) Example 18 Compound 83 10 4.2 11.0 (0.152 0.091) Example 19 Compound 88 10 4.1 10.8 (0.152 0.088) Example 20 Compound 91 10 4.0 10.7 (0.152 0.091) Example 21 Compound 97 10 4.1 10.7 (0.152 0.091) Example 22 Compound 104 10 4.0 10.3 (0.151 0.090) Example 23 Compound 107 10 4.1 10.7 (0.151 0.090) Example 24 Compound 113 10 4.2 10.7 (0.150 0.090) Example 25 Compound 128 10 3.9 10.0 (0.152 0.091) Example 26 Compound 135 10 4.0 10.3 (0.151 0.091) Example 27 Compound 139 10 3.8 10.9 (0.151 0.090) Example 28 Compound 141 10 4.0 10.1 (0.152 0.092) Example 29 Compound 148 10 3.9 10.5 (0.151 0.089)

Claims (10)

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

In the above formula
X is a carbon, nitrogen, oxygen, sulfur or silicon atom;
R1 and R2 are each independently selected from the group consisting of hydrogen; A linear or branched alkyl group of C1 to C10; A C3 to C12 cycloalkyl group; An alkoxy group of C1 ~ C10 linear or branched alkyl group, C1 ~ C10 of halogen, CN, CF ₃ and Si (CH ₃₎ substituted with one or more selected from the group consisting of ₃ groups or unsubstituted aromatic ring, and C1 ~ selected from straight or branched chain alkyl, alkoxy, halogen, CN, CF ₃ and Si (CH ₃₎ group consisting of a substituted or unsubstituted aromatic heterocycle with one or more selected from the group consisting of ₃ groups of C1 ~ C10 for C10 Aromatic hydrocarbons having 4 to 60 carbon atoms and at least one compound selected from the group consisting of:
R3 and R4 are each independently selected from the group consisting of hydrogen; A linear or branched alkyl group of C1 to C10; Halogen, _{nitrile, CF 3, -Si (CH 3} ) 3, C1 ~ C10 linear or branched alkyl, optionally substituted with the same or different groups linear or branched alkoxy of C1 ~ C10 unsubstituted phenyl, pyridinyl, triazinyl, naphthyl Dibenzofuranyl, dibenzothiophene, carbazole, or thianthrenyl group, and R 3 and R 4 are combined to form a

Lt; / RTI &gt;
Y is a substituted or unsubstituted aromatic with one or more selected from the group consisting of a straight or branched chain alkyl group of C1 ~ C10, an alkoxy group of C1 ~ C10, halogen, CN, CF ₃ and Si (CH _{3) 3} ring, and straight or branched chain alkyl group of C1 ~ C10, an alkoxy group of C1 ~ C10, halogen, CN, CF ₃ and Si (CH ₃₎ into one or more selected from the group consisting of _3-group the group consisting of a substituted or unsubstituted aromatic heterocyclic ring And an aromatic hydrocarbon having 4 to 60 carbon atoms. Claim 1
Y is

Or R5,
R 1 and R 2 and R 5 may each independently be selected from the following chemical structural formulas,

In the above formula, B is each independently hydrogen, a straight-chain or branched alkyl group having 1 to 10 carbon atoms, or a cycloalkyl group having 3 to 12 carbon atoms;
Further, R1 and R2 may be, independently of each other, hydrogen, a C1-C10 linear or branched alkyl group, or a C3-C12 cycloalkyl group.
In the above formula, B is each independently hydrogen, a straight-chain or branched alkyl group having 1 to 10 carbon atoms, or a cycloalkyl group having 3 to 12 carbon atoms;
Further, R1 and R2 may be, independently of each other, hydrogen, a C1-C10 linear or branched alkyl group, or a C3-C12 cycloalkyl group. The method of claim 2,
R2 is hydrogen, a C1 to C10 linear or branched alkyl group, a phenyl group, a naphthyl group, or a dibenzothiophenyl group;
R3 and R4 each independently may be hydrogen, a C1-C10 linear or branched alkyl group, a phenyl group substituted or unsubstituted with a C1-C10 linear or branched alkyl group, or a thianthrenyl group, R3 and R4 are combined to form

Lt; RTI ID = 0.0 &gt; 1, &lt; / RTI &gt; The method of claim 3,
Wherein at least one of B in the organic compound is a straight-chain or branched alkyl group having from 1 to 10 carbon atoms or a cycloalkyl group having from 3 to 12 carbon atoms. The method of claim 3,
Wherein the organic compound is any one of the following compounds 1 to 150:

The method according to claim 1,
Wherein the organic compound is used as a hole injecting layer material, a hole transporting layer material, an electron blocking layer material or a light emitting layer material in a material for an organic EL device. A material for forming a hole injection layer, a hole transporting layer, an electron blocking layer or a light emitting layer containing the compound of claim 1. 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 sandwiched between a cathode and an anode,
Wherein at least one of the organic thin film layers contains the organic compound of claim 1 singly or in combination of two or more kinds. The method of claim 8,
Wherein the organic compound of claim 1 is contained in at least one of a hole injecting layer material, a hole transporting layer material, an electron blocking layer material or a light emitting layer material. The method according to any one of claims 8 and 9,
The organic electroluminescent device
Wherein the anode, the hole injecting layer, the hole transporting layer, the light emitting layer, the electron transporting layer, the electron injecting layer, and the cathode are stacked in this order.