KR20150112880A - Organic compounds for an organic electroluminescent device and an organic electroluminescent device comprising the same - Google Patents

Abstract

The present invention provides an organic compound for a novel organic electroluminescent element selected from the group consisting of chemical formula 1 and an organic electroluminescent element comprising the organic compound.

Description

TECHNICAL FIELD The present invention relates to an organic compound for 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 same, and more particularly to a novel organic compound which can be used as a hole transporting layer (HTL) or an electron blocking layer (EBL) And an organic electroluminescent device including the same.

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.

A more detailed 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 electrons from entering from the light emitting layer to 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.

In an organic electroluminescent device, an electron blocking layer (EBL) is formed between the light emitting layer and the hole transporting layer to prevent electrons from being injected into the hole transporting layer without bonding in the light emitting layer and to improve the probability of recombination of electrons and holes by enclosing electrons in the light emitting layer. ) Can be installed.

When the hole transport layer transmits holes well and the electron blocking layer (EBL) performs the functions as described above, the driving voltage of the device can be lowered, the luminous efficiency and brightness can be increased, and the luminous efficiency of the organic electroluminescent device The life span can be extended.

However, development of a stable and efficient compound as a material capable of forming a hole transport layer (HTL) or an electron blocking layer (EBL) has not been sufficiently developed so far.

Korean Patent Application No. 10-2010-0103837

The present invention can be applied to organic electroluminescent devices as a hole transporting layer or an electron blocking layer material. When applied to an organic electroluminescent device, the present invention can lower a driving voltage and improve luminous efficiency, brightness, thermal stability, And to provide a novel organic compound having such a structure.

It is still another object of the present invention to provide a hole transport layer or a material for forming an electron blocking 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

R1, R2, R3 and R4 are each, independently,

Hydrogen, linear or branched C1 ~ C10 alkyl, alkoxy, halogen of C1 ~ C10, CN, CF _3, or Si (CH _{3) 3,} or;

A C1 ~ C10 linear or branched alkyl, alkoxy of C1 ~ C10, _{halogen, CN, CF 3, Si (} CH 3) 3, pyridyl, phenyl, naphthyl group substituted phenyl, a biphenyl, a naphthyl group, a dibenzo Thiophene, and thianthrenyl, which is unsubstituted or substituted with one or more substituents selected from the group consisting of phenyl, naphthyl, phenanthrenyl, fluorenyl, pyrrole, pyrazole, imidazole, triazole, oxazole , Oxadiazole, thiophenyl, thiazole, thiadiazole, pyrazinyl, pyridazinyl, pyridinyl, pyrimidinyl, triazinyl, dibenzofuranyl, dibenzothiophene, carbazole, or thianthrenyl group thianthrenyl group;

Together with the attached phenyl group, may form a dibenzothiophene group;

However, the R1, R2, two or more of R3 and R4 from hydrogen, the group consisting of C1 ~ C10 linear or branched alkyl, alkoxy of C1 ~ C10, halogen, CN, CF _3, and Si (CH _{3) 3} Lt; / RTI >

In addition,

There is provided a hole transporting layer or an electron blocking layer-forming material containing an 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 compound according to the present invention can be applied to an organic light emitting device as a hole transporting layer or an electron blocking layer material. When applied to an organic light emitting device, the driving voltage is lowered and luminous efficiency, brightness, thermal stability, and device lifetime are improved.

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

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

[ Formula 1 ]

In the above formula

R1, R2, R3 and R4 are each, independently,

Hydrogen, linear or branched C1 ~ C10 alkyl, alkoxy, halogen of C1 ~ C10, CN, CF _3, or Si (CH _{3) 3,} or;

A C1 ~ C10 linear or branched alkyl, alkoxy of C1 ~ C10, _{halogen, CN, CF 3, Si (} CH 3) 3, pyridyl, phenyl, naphthyl group substituted phenyl, a biphenyl, a naphthyl group, a dibenzo Thiophene, and thianthrenyl, which is unsubstituted or substituted with one or more substituents selected from the group consisting of phenyl, naphthyl, phenanthrenyl, fluorenyl, pyrrole, pyrazole, imidazole, triazole, oxazole , Oxadiazole, thiophenyl, thiazole, thiadiazole, pyrazinyl, pyridazinyl, pyridinyl, pyrimidinyl, triazinyl, dibenzofuranyl, dibenzothiophene, carbazole, or thianthrenyl group thianthrenyl group;

Together with the attached phenyl group, may form a dibenzothiophene group;

However, the R1, R2, two or more of R3 and R4 from hydrogen, the group consisting of C1 ~ C10 linear or branched alkyl, alkoxy of C1 ~ C10, halogen, CN, CF _3, and Si (CH _{3) 3} Lt; / RTI >

More preferably, R 1, R 2, R 3 and R 4 in the above formula (1)

Hydrogen, linear or branched C1 ~ C10 alkyl, alkoxy, halogen of C1 ~ C10, CN, CF _3, or Si (CH _{3) 3,} or;

Lt; / RTI >

Together with the attached phenyl group, may form a dibenzothiophene group;

However, the R1, R2, two or more of R3 and R4 from hydrogen, the group consisting of C1 ~ C10 linear or branched alkyl, alkoxy of C1 ~ C10, halogen, CN, CF _3, and Si (CH _{3) 3} Lt; / RTI >

More preferably, R 1, R 2, R 3 and R 4 are each, independently,

Hydrogen or a C1 to C10 linear or branched alkyl group;

Phenyl, naphthyl, phenanthrenyl, dibenzofuranyl, dibenzothiophene, carbazole, dibenzothiophene, dibenzothiophene, and thianthrenyl. Or a thianthrenyl group;

Together with the attached phenyl group, may form a dibenzothiophene group;

Provided that at least two of R 1, R 2, R 3 and R 4 are not substituents selected from the group consisting of hydrogen and C 1 -C 10 linear or branched alkyl groups.

Representative examples of the organic compound include the following compounds 1 to 42:

The organic compounds of the present invention can be used as a hole transporting layer material or an electron blocking layer material in organic electroluminescence device materials, and can be preferably used as an electron blocking layer material in particular.

In addition,

A hole transport layer containing the organic compound or a material for forming an electron blocking layer.

The hole transport layer or the material for forming an electron blocking layer may further include a material conventionally added when preparing the organic compound in a form necessary for forming a hole transporting layer or an electron blocking 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 an organic compound represented by the above formula (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 transporting layer material and an electron blocking layer material.

The organic thin film layer may include a hole injecting layer, a hole transporting layer, a light emitting layer, an electron transporting layer, and an electron injecting layer in this order. If necessary, an electron blocking layer may be further included between the hole transporting layer and the light emitting layer. And may further include a hole blocking layer between the light emitting layer and the electron transporting layer.

The organic electroluminescent device may have a structure in which an anode, a hole injecting layer, a hole transporting layer, a light emitting layer, an electron transporting layer, an electron injecting layer, and a cathode are stacked in this order, and an electron blocking layer, Can be further stacked.

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 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. 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 this case, tris (8-hydroxyquinolinolato) aluminum (Alq ₃ ) may be used as the sole luminescent material or the luminescent host material among the luminescent layer materials used. In case of blue, Balq (8-hydroxyquinoline Beryllium salts), DPVBi (4,4'-bis (2,2-biphenylethenyl) -1,1'-biphenyl) series, Spiro material, Spiro- DPVBi (2-benzooxazolyl) -phenol lithium salt), bis (biphenylvinyl) benzene, aluminum < RTI ID = 0.0 & -Quinoline metal complex, metal complexes of imidazole, thiazole and oxazole, and the like can be used.

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 further formed between the hole transporting layer and the light emitting layer, and the organic compound of the present invention may be preferably used as the electron blocking layer material.

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), and LiF may be used as the lithium salt.

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.

Hereinafter, a method of synthesizing the above compounds will be described as a representative example. 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.

Manufacturing example  1: Synthesis of Compound

Synthesis of intermediate A

[Reaction Scheme 1]

(10 mmol) of 9H-carbazole and 3.40 g (12 mmol) of 1-bromo-4-iodobenzene were dissolved in 25 ml of nitrobenzene under nitrogen, and then 0.19 g ( ₃ mmol) of Cu and 4.15 g of K ₂ CO ₃ were added And refluxed for 16 hours.

After the reaction was completed, the temperature of the reaction mixture was cooled to room temperature, 75 ml of MeOH was added, and the mixture was filtered to obtain a solid, which was then dissolved in 100 ml of MC and filtered.

The MC layer was distilled under reduced pressure and then subjected to column chromatography with Hex: MC = 5: 1 to obtain 2.09 g (65%) of Intermediate A.

Intermediate A MS (FAB): 322 (M ^< ^{+ &} gt ^; ) [

Synthesis of intermediate B

[Reaction Scheme 2]

After 4-bromo-2-iodo-1-nitrobenzene in a nitrogen is also injected into 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 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 to extract the MC layer. The organic layer was distilled under reduced pressure and then 1.97 g (71% ).

Intermediate B MS (FAB): 278 (M ^< ^{+ &} gt ^; ).

Synthesis of intermediate C

[Reaction Scheme 3]

2.78 g (10 mmol) of Intermediate B was dissolved in 20 ml of o-dichlorobenzene under nitrogen, 6.56 g (25 mmol) of triphenylphosphine was added and the mixture was 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 with anhydrous MgSO ₄ and concentrated. Hex: MC = 5: 1 column to obtain 1.94 g (79%) of intermediate C.

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

Synthesis of intermediate D

[Reaction Scheme 4]

Under nitrogen, 2.46 g (10 mmol) of intermediate C and 3.06 g (15 mmol) of iodobenzene were dissolved in 25 ml of nitrobenzene, and then 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, and 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 product was then subjected to column chromatography with Hex: MC = 5: (81%).

Intermediate D MS (FAB): 322 (M <^+> ) <

Synthesis of intermediate E

[Reaction Scheme 5]

Under nitrogen, 2.46 g (10 mmol) of Intermediate D were dissolved in 15 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.

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 recrystallized with Hex / MC to obtain 2.15 g (75%) of intermediate E.

Intermediate E MS (FAB): 287 (M <^+> ) <

Synthesis of intermediate F

[Reaction Scheme 6]

After injection of intermediate E 2.87g (10mmol) and 1-bromo-4-iodo-benzene 2.83g (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, and the mixture was dried over anhydrous MgSO ₄ and concentrated. The product was then fractionated by Hex: MC = 5: (74%).

Intermediate F MS (FAB): 398 (M <^+> ) <

Synthesis of intermediate G

[Reaction Scheme 7]

Under nitrogen m, m'- di-tolyl amine 1.97g (10mmol) and 1-fluoro-4-nitrobenzene 24 hours, was dissolved 1.41g (10mmol) in 15ml DMF was added K ₂ CO ₃ 0.83g (6mmol) Lt; / RTI &gt;

After completion of the reaction, the reaction mixture was cooled to room temperature, and 50 ml of H ₂ O was added thereto. The resulting solid was filtered and dried. The dried product was subjected to column chromatography with Hex: MC = 2: 1 to obtain 1.94 g (61%) of Intermediate Compound G.

Intermediate G MS (FAB): 318 (M ^&lt; ^{+ &} gt ^; ) [

Synthesis of Intermediate H

[Reaction Scheme 8]

Under argon, 3.18 g (10 mmol) of Intermediate G are dissolved in THF-tOH (50 mL / 15 mL). To this solution is added palladium on carbon (10%, 0.4 g) dissolved in 1 ml of EtOH. After 30 minutes, 2.4 bar of H ₂ was added to the mixed solution, and the mixture was refluxed for 16 hours.

After the completion of the reaction, the reaction mixture was filtered through celite and extracted. The organic layer was distilled under reduced pressure to obtain 2.82 g (98%) of Intermediate H.

Intermediate H MS (FAB): 288 (M <^+> )

Synthesis of Intermediate I

[Reaction Scheme 9]

(0.2 mmol) of Pd ₂ dba ₃ , 0.4 ml (0.4 mmol) of 1 M t-Bu ₃ P, and 0.28 g (0.1 mmol) of t-BuONa And then refluxed for 6 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 to extract the MC layer. The organic layer was distilled under reduced pressure and then 3.23 g (61% ).

Intermediate I MS (FAB): 529 (M ^&lt; ^{+ &} gt ^; ) [

Synthesis of intermediate J

[Reaction Scheme 10]

After a nitrogen dissolved -N- phenyl-4-bromo-aniline 2.4g (10mmol), thianthrene-1-Daily acid (thianthren-1-ylboronic acid) 2.6g (10mmol) in toluene 50ml Pd (PPh _{3) 4} 0.5 g (0.5 mmol), 2M K ₂ CO ₃ 15 ml (30 mmol) was added and the mixture was refluxed for 15 hours.

When the reaction is completed, the temperature of the reaction product is cooled to room temperature, 200 ml of H ₂ O 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 subjected to column chromatography with Hex: MC = 5: 1 to obtain 2.60 g (68%) of Intermediate J.

Intermediate J MS (FAB): 383 (M <^+> ) <

Synthesis of Intermediate K

[Reaction Scheme 11]

After a nitrogen dissolved 4-bromoaniline 1.7g (10mmol), thianthrene-1-Daily acid (thianthren-1-ylboronic acid0 2.6g (10mmol) in toluene _{30ml Pd (PPh 3) 4 0.5g} (0.5mmol) , 2M K ₂ CO ₃ 25 ml (50 mmol) was added and the mixture was refluxed for 15 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 to extract the MC layer. The organic layer was distilled under reduced pressure and then 2.34 g (78% ).

Intermediate K MS (FAB): 307 (M <^+> )

Synthesis of Intermediate L

[Reaction Scheme 12]

3.0 g (10 mmol) of Intermediate K and 2.6 g (10 mmol) of 4-bromodibenzo [b, d] thiophene were dissolved in 30 ml of toluene under nitrogen, and Pd ₂ dba ₃ 0.2 g (1 mmol) of t-Bu ₃ P and 2.8 g (30 mmol) of t-BuONa were added, and the mixture was refluxed for 6 hours.

After the reaction was completed, the reaction mixture was cooled to room temperature, and then 200 ml of MC and 200 ml of H ₂ O were added to extract the MC layer. The organic layer was distilled under reduced pressure and then 3.97 g (81% ).

Intermediate L MS (FAB): 489 (M <^+> )

Synthesis of compound [5]

[ Scheme 13 ]

(OAC) ₂ , 1.25 g ( ₂ mmol) of BINAP and 2.88 g (30 mmol) of t-BuONa were dissolved in 50 ml of toluene after 5.30 g (10 mmole) of Intermediate I and 3.98 g And the mixture was refluxed for 6 hours.

After the reaction was completed, the reaction mixture was cooled to room temperature, and 300 ml of MC and 300 ml of H ₂ O were added thereto to extract the MC layer. The organic layer was distilled under reduced pressure, and 6.35 g (75% ).

^{1 H NMR (DMSO-d,} 300Hz): δ (ppm) = 7.7-7.3 (m, 14H), 7.25-6.3 (m, 26H), 2.35 (s, 6H)

MS (FAB): 847 (M ^&lt; ^{+ &} gt ^; ).

Synthesis of Compound [31]

[ Scheme 14 ]

After a nitrogen dissolved Intermediate J 8.44g (22mmol), 1,4- DI Goto benzene 3.30g (10mmol) in toluene _{60ml Pd (OAc) 2 0.10g (} 0.4mmol), t-Bu 3 P 0.32g (1.6mmol ), t-BuONa (5.76 g, 60 mmol) was added, and the mixture was refluxed for 6 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 = 2: 1 to obtain 6.56 g (78%) of Compound 31.

^{1 H NMR (CDCl3, 300Hz)} : δ (ppm) = 7.55-7.47 (m, 4H), 7.46-7.41 (d, 2H), 7.37-7.13 (m, 28H), 7.11-7.04 (m, 2H)

MS (FAB): 841 (M ^&lt; ^{+ &} gt ^; ).

Synthesis of Compound [35]

[Reaction Scheme 15]

After a nitrogen dissolved Intermediate L 8.6g (20mmol), 1,4- DI Goto benzene 3.30g (10mmol) in toluene _{50ml Pd (OAc) 2 0.10g (} 0.4mmol), t-Bu 3 P 0.32g (1.6mmol ), t-BuONa (5.76 g, 60 mmol) was added, and the mixture was refluxed for 6 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 column was subjected to Hex: MC = 2: 1 to obtain 7.48 g (71%) of Compound 35.

^{1 H NMR (CDCl3, 300Hz)} : δ (ppm) = 8.21-8.14 (m, 2 H), 8.07-8.00 (m, 2 H), 7.82-7.74 (m, 2 H), 7.55-7.35 (m, 14H), 7.32-7. 10 (m, 20H)

MS (FAB): 1053 (M ^&lt; ^{+ &} gt ^; ).

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 to 12: 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, NPD 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 on the hole transport layer by vacuum evaporation of the compounds of the present invention as shown in Table 1 below. Blue EML was formed on the electron blocking layer (EBL) 2,5,8,11-tetrabutyl-perylene was doped with about 5% by doping with 9,10-bis (2-naphthyl) anthracene (ADN) 250 &lt; / RTI &gt; 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, magnesium (Mg) and silver (Ag) were deposited as a negative electrode at a ratio of 9: 1 at a thickness of 150 ANGSTROM. (4-bis (3-methylphenyl) amino] phenyl] -N4, N4'-diphenyl- [1,1'-biphenyl] -4,4'- diamine was deposited to a thickness of 65 nm. A seal cap containing a moisture absorbent with a UV curable adhesive was attached to the capping layer (CPL) 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 TCTA was used instead of the organic compound of the present invention as the electron blocking layer material in Example 1.

Test Example . The organic electroluminescent device  Character rating

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

EBL Current Density
(mA / cm ² ) Voltage
(V) Efficiency
(Cd / A) CIE (X Y) Comparative Example TCTA 10 3.6 6.5 (0.150 0.090) Example 1 Compound 2 10 3.9 10.0 (0.150 0.091) Example 2 Compound 3 10 3.9 9.8 (0.150 0.088) Example 3 Compound 5 10 4.0 10.0 (0.151 0.089) Example 4 Compound 7 10 4.0 9.9 (0.151 0.090) Example 5 Compound 10 10 3.9 10.1 (0.152 0.092) Example 6 Compound 14 10 4.1 10.1 (0.151 0.091) Example 7 Compound 17 10 3.9 9.8 (0.152 0.090) Example 8 Compound 22 10 4.0 9.6 (0.151 0.089) Example 9 Compound 27 10 3.9 9.9 (0.152 0.091) Example 10 Compound 29 10 3.85 10.0 (0.150 0.093) Example 11 Compound 31 10 3.91 10.5 (0.150 0.093) Example 12 Compound 35 10 3.95 10.9 (0.150 0.093)

Claims (10)

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

In the above formula
R1, R2, R3 and R4 are each, independently,
Hydrogen, linear or branched C1 ~ C10 alkyl, alkoxy, halogen of C1 ~ C10, CN, CF _3, or Si (CH _{3) 3,} or;
A C1 ~ C10 linear or branched alkyl, alkoxy of C1 ~ C10, _{halogen, CN, CF 3, Si (} CH 3) 3, pyridyl, phenyl, naphthyl group substituted phenyl, a biphenyl, a naphthyl group, a dibenzo Thiophene, and thianthrenyl, which is unsubstituted or substituted with one or more substituents selected from the group consisting of phenyl, naphthyl, phenanthrenyl, fluorenyl, pyrrole, pyrazole, imidazole, triazole, oxazole , Oxadiazole, thiophenyl, thiazole, thiadiazole, pyrazinyl, pyridazinyl, pyridinyl, pyrimidinyl, triazinyl, dibenzofuranyl, dibenzothiophene, carbazole, or thianthrenyl group thianthrenyl group;
Together with the attached phenyl group, may form a dibenzothiophene group;
However, the R1, R2, two or more of R3 and R4 from hydrogen, the group consisting of C1 ~ C10 linear or branched alkyl, alkoxy of C1 ~ C10, halogen, CN, CF _3, and Si (CH _{3) 3} Lt; / RTI &gt; The method according to claim 1,
R1, R2, R3 and R4 are each, independently,
Hydrogen, linear or branched C1 ~ C10 alkyl, alkoxy, halogen of C1 ~ C10, CN, CF _3, or Si (CH _{3) 3,} or;
Lt; / RTI &gt;

Together with the attached phenyl group, may form a dibenzothiophene group;
However, the R1, R2, two or more of R3 and R4 from hydrogen, the group consisting of C1 ~ C10 linear or branched alkyl, alkoxy of C1 ~ C10, halogen, CN, CF _3, and Si (CH _{3) 3} Lt; / RTI &gt; is not a selected substituent. The method according to claim 1,
R1, R2, R3 and R4 are each, independently,
Hydrogen or a C1 to C10 linear or branched alkyl group;
Phenyl, naphthyl, phenanthrenyl, dibenzofuranyl, dibenzothiophene, carbazole, dibenzothiophene, dibenzothiophene, and thianthrenyl. Or a thianthrenyl group;
Together with the attached phenyl group, may form a dibenzothiophene group;
Provided that at least two of said R1, R2, R3 and R4 are not substituents selected from the group consisting of hydrogen and C1-C10 straight-chain and branched-chain alkyl groups. The method of claim 3,
Wherein the organic compound is any one of the following compounds 1 to 42:

The method according to claim 1,
Wherein the organic compound is used as an electron transporting layer or an electron blocking layer material in an organic electroluminescence device. A hole transporting layer-forming material comprising the compound of claim 1. An electron blocking layer-forming material comprising 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 as a hole transporting layer or an electron blocking layer material. The method according to any one of claims 8 and 9,
Wherein the organic electroluminescent device has a structure in which an anode, a hole injecting layer, a hole transporting layer, an electron blocking layer, a light emitting layer, an electron transporting layer, an electron injecting layer, and a cathode are stacked in this order.