KR20110115891A - Amine-based compound and organic electroluminescent devices comprising the same - Google Patents

Abstract

The present invention relates to a novel amine compound and an organic light emitting device comprising the same, the organic light emitting device comprising the amine compound according to the present invention has an excellent effect of brightness, color purity and life characteristics.

Description

Amine-based compound and organic electroluminescent device including the same {AMINE-BASED COMPOUND AND ORGANIC ELECTROLUMINESCENT DEVICES COMPRISING THE SAME}

The present invention relates to an amine compound and an organic light emitting device including the same, and more particularly, to an amine compound having excellent brightness, color purity and life characteristics, and an organic light emitting device comprising the same.

Recently, as the size of the display device increases, the demand for a flat display device having a small space is increasing. A liquid crystal display, which is a typical flat display device, has a merit of being lighter than a conventional cathode ray tube (CRT). The disadvantage is that the angle is limited and the back light is necessary. In contrast, the organic light emitting diode (OLED), a new flat panel display device, is a display using a self-luminous phenomenon, and has a large viewing angle, can be thinner and shorter than a liquid crystal display, and has a fast response speed. In recent years, the application to full-color display or lighting is expected.

In general, organic light emission phenomenon refers to a phenomenon in which an organic material is used to convert electric energy into light energy.

An organic light emitting display device using an organic light emitting phenomenon usually has a structure including an anode, a cathode, and an organic material layer therebetween. In this case, the organic material layer is often formed of a multi-layered structure composed of different materials in order to increase the efficiency and stability of the organic light emitting device, for example, it may be made of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer. When the voltage is applied between the two electrodes in the structure of the organic light emitting device, holes are injected into the organic material layer at the anode and electrons are injected into the organic material layer, and excitons are formed when the injected holes and electrons meet. When it falls back to the ground, it glows. Such organic light emitting diodes are known to have characteristics such as self-luminous, high brightness, high efficiency, low driving voltage, wide viewing angle, high contrast, and high speed response.

Materials used as the organic material layer in the organic light emitting device may be classified into light emitting materials and charge transport materials such as hole injection materials, hole transport materials, electron transport materials, electron injection materials and the like depending on their function. The light emitting material may be classified into a polymer type and a low molecular type according to molecular weight, and may be classified into a fluorescent material derived from a singlet excited state of electrons and a phosphorescent material derived from a triplet excited state of electrons according to a light emitting mechanism. . In addition, the light emitting material may be classified into blue, green, and red light emitting materials and yellow and orange light emitting materials required to achieve a better natural color according to the light emitting color.

On the other hand, when only one material is used as a light emitting material, there arises a problem that the maximum light emission wavelength shifts to a long wavelength due to intermolecular interaction, the color purity decreases, or the efficiency of the device decreases due to the light emission attenuating effect. A host / dopant system may be used as the light emitting material in order to increase the light emitting efficiency through the light emitting layer. When the dopant having a smaller energy band gap than the host forming the light emitting layer is mixed with a small amount of the light emitting layer, the excitons generated in the light emitting layer are transported to the dopant to emit light with high efficiency. At this time, since the wavelength of the host shifts to the wavelength of the dopant, light having a desired wavelength can be obtained according to the type of dopant to be used.

In order for the organic electroluminescent device to fully exhibit the above-mentioned excellent features, the organic layer in the device, such as a hole injection material, a hole transport material, a light emitting material, an electron transport material, an electron injection material, etc. is supported by a stable and efficient material Although this should be preceded, the development of a stable and efficient organic material layer for an organic light emitting device has not been made yet. Therefore, the development of new materials in the art continues to be required.

The technical problem to be achieved by the present invention is to provide an amine compound having excellent emission luminance and color purity and a long lifespan.

The second technical problem to be achieved by the present invention is to provide an organic electroluminescent device comprising the amine compound.

In order to achieve the first technical problem, the present invention provides an amine compound represented by the following formula (1).

[Formula 1]

In Chemical Formula 1,

At least one of R 1 to R 10 is represented by the following Chemical Formula 1-1, and the remaining ones are each independently a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, substituted or unsubstituted An aryl group having 6 to 50 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 50 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, Substituted or unsubstituted C1-C20 alkylamino group, substituted or unsubstituted C6-C30 arylamino group, substituted or unsubstituted C1-C20 alkylsilyl group, substituted or unsubstituted C6-C30 Arylsilyl group, substituted or unsubstituted arylalkylamino group having 1 to 50 carbon atoms, substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, substituted or unsubstituted C2-10 egg Selected from the group consisting of a silyl group, a cyano group, a halogen group, a small to medium number and hydrogen, and adjacent groups of R1 to R10 may combine with each other to form a substituted or unsubstituted aliphatic, aromatic, heteroaliphatic or heteroaromatic condensed ring; ,

[Formula 1-1]

In Chemical Formula 1-1,

L is a divalent linking group connecting a bonding site selected from R11 to R14 with any one of R1 to R10 of Formula 1, and a direct bond, a substituted or unsubstituted alkylene group having 1 to 60 carbon atoms, a substituted or unsubstituted carbon number. 2 to 60 carbon atoms containing at least one selected from alkenylene group, substituted or unsubstituted alkynylene group having 2 to 60 carbon atoms, substituted or unsubstituted cycloalkylene group having 3 to 60 carbon atoms, N, O and S A heterocycloalkylene group of 6 to 6, a substituted or unsubstituted arylene group having 6 to 50 carbon atoms, and a substituted or unsubstituted heteroarylene group having 3 to 50 carbon atoms,

A is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 50 carbon atoms, substituted Or an unsubstituted alkoxy group having 1 to 20 carbon atoms, and a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms,

R11 to R14 each independently represent a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, and a substituted or unsubstituted group Heteroaryl group having 3 to 50 carbon atoms, substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, substituted or unsubstituted alkylamino group having 1 to 20 carbon atoms, substituted Or an unsubstituted arylamino group having 6 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 1 to 20 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms, a substituted or unsubstituted carbon atom having 1 to 50 carbon atoms An arylalkylamino group, a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 10 carbon atoms, a cyano group, a halogen group, a small to medium number and hydrogen Is selected from the group,

Adjacent groups of A and R1 to R10 may combine with each other to form a substituted or unsubstituted aliphatic, aromatic, heteroaliphatic or heteroaromatic condensed ring.

In order to solve the second technical problem, the present invention is an anode; Cathode; And it is interposed between the anode and the cathode, and provides an organic light emitting device having a layer comprising an amine compound represented by the formula (1).

The organic light emitting device including the amine compound represented by Chemical Formula 1 according to the present invention in an organic material layer may be usefully used for display and lighting because of its excellent brightness, color purity, and lifetime characteristics.

1 is a schematic diagram of an organic light emitting display device according to an embodiment of the present invention.
<Description of the symbols for the main parts of the drawings>
10: substrate 20: anode
30: hole injection layer 40: hole transport layer
50: organic light emitting layer 60: electron transport layer
70: electron injection layer 80: cathode

Hereinafter, the present invention will be described in more detail.

Amine compound according to the invention is characterized in that represented by the formula (1).

In the amine compound according to the present invention, the substituents of Formula 1 will be described in more detail.

In Formula 1, the substituents are each independently a deuterium atom, a cyano group, a halogen atom, a hydroxy group, a nitro group, an alkyl group having 1 to 40 carbon atoms, an alkoxy group having 1 to 40 carbon atoms, an alkylamino group having 1 to 40 carbon atoms, and 6 to 40 carbon atoms. Arylamino group, C3-C40 heteroarylamino group, C1-C40 alkylsilyl group, C6-C40 arylsilyl group, C6-C40 aryl group, C3-C40 aryloxy group, C3 It may be substituted by one or more substituents selected from the group consisting of heteroaryl group, germanium group, phosphorus and boron of to 40, it may be further substituted by the substituent. The substituents may be bonded to each other to form a condensed ring of aliphatic, aromatic, heteroaliphatic or heteroaromatic.

Specific examples of the alkyl group which is a substituent used in the present invention include methyl, ethyl, propyl, isobutyl, sec-butyl, tert-butyl, pentyl, iso-amyl, hexyl, heptyl, octyl, A stearyl group, a trichloromethyl group, a trifluoromethyl group, and the like, and at least one hydrogen atom of the alkyl group may be a deuterium atom, a halogen atom, a hydroxy group, a nitro group, a cyano group, a trifluoromethyl group, or a silyl group (in this case, Alkylsilyl groups ", substituted or unsubstituted amino groups (-NH ₂ , -NH (R), -N (R ') (R''), wherein R, R' and R" are each independently carbon atoms An alkyl group of 1 to 24 (in this case referred to as an "alkylamino group"), an amidino group, a hydrazine group, a hydrazone group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, an alkyl group of 1 to 24 carbon atoms, a halogenated alkyl group of 1 to 24 carbon atoms , Alkenyl group having 2 to 24 carbon atoms, alkynyl group having 2 to 24 carbon atoms, 1 carbon atom It may be substituted with a heteroalkyl group of 24 to 24, an aryl group of 5 to 24 carbon atoms, an arylalkyl group of 6 to 24 carbon atoms, a heteroaryl group of 3 to 24 carbon atoms or a heteroarylalkyl group of 3 to 24 carbon atoms.

Specific examples of the cycloalkyl group which is a substituent used in the compound of the present invention include cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, adamantyl group, and the like. It can be substituted by the same substituent.

Specific examples of the alkoxy group which is a substituent used in the compound of the present invention include methoxy group, ethoxy group, propoxy group, isobutyloxy group, sec-butyloxy group, pentyloxy group, iso-amyloxy group, hexyloxy group and the like. These can be mentioned and can substitute by the same substituent as the case of the said alkyl group.

Specific examples of the halogen group which is a substituent used in the compound of the present invention include fluorine (F), chlorine (Cl), bromine (Br) and the like.

Specific examples of the aryl group which is a substituent used in the compound of the present invention are phenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 4-ethylphenyl group, o-biphenyl group, m-biphenyl group, p-ratio Phenyl group, 4-methylbiphenyl group, 4-ethylbiphenyl group, o-terphenyl group, m-terphenyl group, p-terphenyl group, 1-naphthyl group, 2-naphthyl group, 1-methylnaphthyl group, 2-methylnaphthyl group And an aromatic group such as an anthryl group, a phenanthryl group, a pyrenyl group, a fluorenyl group, a tetrahydronaphthyl group, and the like, and may be substituted with the same substituent as in the alkyl group.

Specific examples of the heteroaryl group which is a substituent used in the compound of the present invention include pyridinyl group, pyrimidinyl group, triazinyl group, indolinyl group, quinolinyl group, pyrrolidinyl group, piperidinyl group, morpholidinyl group, pipepe Radiinyl, carbazolyl, oxazolyl, oxdiazolyl, benzooxazolyl, chiazolyl, thiadiazolyl, benzothiazolyl, triazolyl, imidazolyl and benzoimidazole At least one hydrogen atom of the heteroaryl group may be substituted with the same substituent as in the alkyl group.

In the present invention, the term "substituted or unsubstituted" is deuterium, halogen, alkyl, alkenyl, alkoxy, aryl, arylalkyl, arylalkenyl, heteroaryl, carbazolyl, fluorenyl, Substituted or unsubstituted with one or more substituents selected from the group consisting of a nitrile group and an acetylene group.

Specifically, the amine compound according to the present invention may be any one of the compounds represented by Formula 2 to Formula 768 shown in Table 1 below.

TABLE 1

The preparation method of the amine compound according to the present invention is shown in detail in Examples described later.

In addition, the present invention is an anode; Cathode; And it is interposed between the anode and the cathode, and provides an organic light emitting device having a layer comprising an amine compound represented by the formula (1).

At this time, the layer containing the amine-based compound is preferably a light emitting layer between the anode and the cathode, the hole injection layer, the hole transport layer, the electron blocking layer, the hole blocking layer, the electron transport layer and the electron injection layer between the anode and the cathode It may further include one or more layers selected from the group consisting of.

In addition, according to another embodiment of the present invention, the thickness of the light emitting layer is preferably 0.5nm to 500nm, the light emitting layer may further include ADN of the following structural formula.

[ADN]

As a specific example, a hole transport layer (HTL) may be further stacked, and an electron transport layer (ETL) may be further stacked between the cathode and the organic light emitting layer. The silver is stacked to facilitate the injection of holes from the anode, and the electron transport molecule having a small ionization potential is used as the material of the hole transport layer. A diamine, triamine or tetraamine derivative mainly based on triphenylamine is used. It is used a lot.

The present invention is not particularly limited as long as it is commonly used in the art as a material of the hole transport layer. For example, N, N'-bis (3-methylphenyl) -N, N'-diphenyl- [1 , 1-biphenyl] -4,4'-diamine (TPD) or N, N'-di (naphthalen-1-yl) -N, N'-diphenyl benzidine (a-NPD) and the like can be used.

A hole injection layer (HIL) may be further stacked on the lower portion of the hole transport layer. The hole injection layer material may also be used without particular limitation as long as it is commonly used in the art. TCP (4,4 ', 4 "-tri (N-carbazolyl) triphenyl-amine), for example, copper phthalocyanine (CuPc) or starburst amines, m-MTDATA (4,4', 4" -tris- (3-methylphenylphenylamino) triphenylamine) etc. can be used.

In addition, the electron transport layer used in the organic electroluminescent device according to the present invention has the opportunity to recombine in the light emitting layer by smoothly transporting the electrons supplied from the cathode to the organic light emitting layer and suppressing the movement of holes not bonded in the organic light emitting layer. Serves to increase. The electron transport layer material may be used without particular limitation as long as it is commonly used in the art, and for example, oxadiazole derivatives such as PBD, BMD, BND or Alq ₃ may be used.

Meanwhile, an electron injection layer (EIL) may be further stacked on the electron transport layer to facilitate electron injection from the cathode and ultimately improve power efficiency. Also commonly used in the art may be used without particular limitation, for example, it may be used a material such as LiF, NaCl, CsF, Li ₂ O, BaO.

The organic light emitting display device according to the present invention can be used for a display device, a display device and a monochrome or white lighting device.

1 is a cross-sectional view showing the structure of an organic light emitting display device according to the present invention. The organic light emitting device according to the present invention includes an anode 20, a hole transport layer 40, an organic light emitting layer 50, an electron transport layer 60 and a cathode 80, and if necessary, the hole injection layer 30 and The electron injection layer 70 may be further included. In addition, an intermediate layer of one or two layers may be further formed, and a hole blocking layer or an electron blocking layer may be further formed.

Referring to Figure 1 with respect to the organic light emitting device and a manufacturing method of the present invention, as follows. First, the anode 20 is formed by coating an anode electrode material on the substrate 10. As the substrate 10, a substrate used in a conventional organic EL device is used. An organic substrate or a transparent plastic substrate excellent in transparency, surface smoothness, ease of handling, and waterproofness is preferable. As the anode electrode material, indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO ₂ ), zinc oxide (ZnO), and the like, which are transparent and have excellent conductivity, are used.

The hole injection layer 30 is formed by vacuum-heat deposition or spin coating of the hole injection layer material on the anode 20 electrode. Next, the hole transport layer 40 is formed by vacuum thermal evaporation or spin coating of the hole transport layer material on the hole injection layer 30. Subsequently, the organic light emitting layer 50 is stacked on the hole transport layer 40, and a hole blocking layer (not shown) is selectively formed on the organic light emitting layer 50 by a vacuum deposition method or a spin coating method. can do. The hole blocking layer prevents such a problem by using a material having a very low highest Occupied Molecular Orbital (HOMO) level because when the hole is introduced into the cathode through the organic light emitting layer is reduced the lifetime and efficiency of the device. . In this case, the hole blocking material to be used is not particularly limited, but should have an ionization potential higher than the light emitting compound while having an electron transport ability, and typically BAlq, BCP, TPBI, and the like may be used.

After the electron transport layer 60 is deposited on the hole blocking layer through a vacuum deposition method or a spin coating method, an electron injection layer 70 is formed and a cathode forming metal is vacuum-heated on the electron injection layer 70. The organic EL device is completed by vapor deposition to form a cathode 80 electrode. The metal for forming the cathode may be lithium (Li), magnesium (Mg), aluminum (Al), aluminum-lidium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), magnesium-silver ( Mg-Ag), and the like, and a transmissive cathode using ITO and IZO can be used to obtain a front light emitting device.

According to another embodiment of the present invention, at least one layer selected from the hole injection layer, the hole transport layer, the electron blocking layer, the light emitting layer, the hole blocking layer, the electron transport layer and the electron injection layer is a single molecule deposition method or a solution process The organic light emitting display device according to the present invention may be used in display devices, display devices, and monochrome or white lighting devices.

Hereinafter, preferred embodiments of the present invention will be described in order to facilitate understanding of the present invention. However, the following examples are merely provided to more easily understand the present invention, and the contents of the present invention are not limited thereto.

< Example >

< Synthetic example  1> Preparation of the compound represented by Chemical Formula 541

1) Synthesis of Compound Represented by Chemical Formula 1-a

A compound represented by Chemical Formula 1-a was synthesized according to Scheme 1 below.

Scheme 1

In a 500 ml round-bottom flask, 20.00 g (0.298 mol) of pyrrole, 72.98 g (0.358 mol) of iodobenzene, 5.68 g (0.030 mol) of CuI, 82.4 g (0.596 mol) of potassium carbonate, 10.74 g of 1,10-phenanthroline 0.060 mol) was refluxed with stirring in 370 ml of toluene. After completion of the reaction, the reaction solution was filtered through Celite, the filtrate was concentrated under reduced pressure, crystals were precipitated with methanol at -78 ° C, and filtered to obtain 21 g of a compound represented by Chemical Formula 1-a (yield 50%).

2) Synthesis of Compound Represented by Chemical Formula 1-b

The compound represented by Chemical Formula 1-b was synthesized by Reaction Scheme 2 below.

Scheme 2

In a 1,000 ml round bottom flask, 13.0 g (0.091 mol) of the compound represented by Chemical Formula 1-a obtained in Scheme 1 was dissolved in 484 ml of dimethylformamide (DMF), and the temperature was decreased to -10 ° C. When the temperature was lowered, 32.32 g (0.182 mol) of N-bromosuccinimide (NBS) was added thereto, followed by stirring. After completion of the reaction, 18.31 g (0.145 mol) of sodium sulfite was dissolved in water, and then added to the reaction solution. The organic layer was separated using methylene chloride, concentrated under reduced pressure, and then reduced to hexane. g (yield 97%) was obtained.

3) Synthesis of Compound Represented by Chemical Formula 1-c

The compound represented by Chemical Formula 1-c was synthesized by Reaction Scheme 3 below.

Scheme 3

In a 1,000 ml round bottom flask, 28.5 g (0.095 mol) of compound represented by the formula 1-b obtained from Scheme 2, 28.86 g (0.237 mol) of 1-phenylboronic acid, tetrakistriphenylphosphinepalladium (Pd [PPh ₃ ] ₄ ) 5.48 g (0.005 mol), 52.35 g (0.379 mol) of potassium carbonate, 285 ml of toluene, 142 ml of water and 142 ml of ethanol were added and refluxed. After completion of the reaction, the organic layer was separated using methylene chloride and water and concentrated under reduced pressure. After concentration, 14 g (yield: 50%) of compound represented by Chemical Formula 1-c was obtained by column chromatography using methylene chloride and hexane.

4) Synthesis of Compound Represented by Chemical Formula 1-d

The compound represented by Chemical Formula 1-d was synthesized by Reaction Scheme 4 below.

Scheme 4

In a 250 ml round bottom flask, 10.0 g (0.034 mol) of the compound represented by Chemical Formula 1-c obtained in Scheme 3 was dissolved in dimethylformamide, and then cooled to -10 ° C. When the temperature was lowered, 6 g (0.034 mol) of N-bromosuccinimide (NBS) was added thereto, followed by stirring. After completion of the reaction, 6.8 g (0.05 mol) of sodium sulfite was dissolved in water, and then added to the reaction solution. The organic layer was separated using methylene chloride, concentrated under reduced pressure, and then represented by Chemical Formula 1-d using column chromatography with methylene chloride and hexane. Obtained compound 10g (yield 78.7%).

5) Synthesis of Compound Represented by Chemical Formula 1-e

A compound represented by Chemical Formula 1-e was synthesized by Reaction Scheme 5 below.

Scheme 5

In a 250 ml round bottom flask, 10 g (0.027 mol) of compound 1-d obtained from Scheme 4, 6.8 g (0.027 mol) of bis (pinacoraito) diboron, 0.65 g (0.001 mol) of PdCl ₂ (dppf) 6.07 g (0.080 mol) of calcium acetate and 80 ml of toluene were added and refluxed for 20 hours. After completion of the reaction, the filtrate was concentrated after filtration of Celite, and 7 g of a compound represented by Chemical Formula 1-e (yield: 61%) was obtained by using column chromatography with methylene chloride and hexane.

6) Synthesis of Compound Represented by Formula 541.

The compound represented by Chemical Formula 541 was synthesized according to Scheme 6 below.

Scheme 6

5.7 g (0.014 mol) of the compound represented by the formula (I-e) obtained in Scheme 5 in a 250 ml round bottom flask, 3 g (0.006 mol) of 2,6-dibromo-9,10-phenylanthracene, tetrakistriphenylphosphinepalladium (Pd [PPh ₃ ] ₄ ) 0.36 g (0.0001 mol), potassium carbonate 3.40 g (0.025 mol), 45 ml of toluene, 22 ml of ethanol, 22 ml of water were added and refluxed for 20 hours. After completion of the reaction, the organic layer was separated using toluene and water, concentrated under reduced pressure, precipitated with crystals of methanol, and filtered to obtain 2 g of a compound represented by Chemical Formula 541 (yield: 35.5%).

MS (MALDI-TOF): m / z 916.38 [M] ⁺

Anal.Calcd for C ₇₀ H ₄₈ N ₂ : C, 91.67; H, 5. 28; N, 3.05. Found: C, 91.45; H, 5.52; N, 3.03.

< Synthetic example  2> Preparation of the compound represented by Chemical Formula 431

1) Synthesis of Compound Represented by Chemical Formula 2-a

The compound represented by Chemical Formula 2-a was synthesized by Reaction Scheme 7 below.

Scheme 7

Except for using 1-bromo-4-cyanobenzene in place of the iodobenzene used in Scheme 1, it was synthesized in the same manner to obtain a compound 23g (Yield: 45.9%) represented by the formula 2-a.

2) Synthesis of Compound Represented by Formula 2-b

The compound represented by Chemical Formula 2-b was synthesized according to Scheme 8 below.

Scheme 8

23 g of a compound represented by Chemical Formula 2-b by using the same compound as in Chemical Formula 7 except that the compound represented by Chemical Formula 7 was synthesized in Scheme 7 instead of the compound represented by Chemical Formula 1-a (yield: 91.3%).

3) Synthesis of Compound Represented by Chemical Formula 2-c

The compound represented by Chemical Formula 2-c was synthesized by Reaction Scheme 9 below.

Scheme 9

Except for using the compound represented by the formula 2-b synthesized in Scheme 8 instead of the compound represented by the formula 1-b used in Scheme 3, and using 1-phenyl-d5-boronic acid instead of 1-phenylboronic acid Synthesis was carried out in the same manner to obtain 14 g of a compound represented by Chemical Formula 2-c (yield 69.1%).

4) Synthesis of Compound Represented by Chemical Formula 2-d

The compound represented by Chemical Formula 2-d was synthesized by Reaction Scheme 10 below.

Scheme 10

11.3 g of a compound represented by Chemical Formula 2-d (yield 70) except that the compound represented by Chemical Formula 9 was synthesized in Scheme 9 instead of the compound represented by Chemical Formula 1-c. %) Was obtained.

5) Synthesis of Compound Represented by Formula 2-e

The compound represented by Chemical Formula 2-e was synthesized according to Scheme 11 below.

Scheme 11

A compound represented by Chemical Formula 2-e 7.2 g (yield 59) was synthesized in the same manner except for using the compound represented by Chemical Formula 2-d synthesized in Scheme 10 instead of the compound represented by Chemical Formula 1-d used in Scheme 5. %) Was obtained.

6) Synthesis of Compound Represented by Chemical Formula 431

A compound represented by Chemical Formula 431 was synthesized according to Scheme 12 below.

[Reaction Scheme 12]

2.7 g of a compound represented by Chemical Formula 431 (yield: 38.1%) synthesized in the same manner except for using the compound represented by Chemical Formula 2-e synthesized in Scheme 11 instead of the compound represented by Chemical Formula 1-e used in Scheme 6 ) Was synthesized.

MS (MALDI-TOF): m / z 986.5 [M] ⁺

Anal.Calcd for C ₇₄ H ₂₈ D ₂₀ N4 : C, 87.59; H, 6.73; N, 5.67. Found: C, 87.63; H, 6.70; N, 5.66.

< Synthetic example  3> Preparation of the compound represented by Chemical Formula 590

1) Synthesis of Compound Represented by Formula 3-a

The compound represented by Chemical Formula 3-a was synthesized according to Reaction Scheme 13 below.

Scheme 13

Except for using bromobenzene-d5 in place of the iodobenzene used in Scheme 1, the compound was synthesized in the same manner to synthesize 24 g (yield: 54.3) represented by the formula 3-a.

2) Synthesis of Compound Represented by Formula 3-b

The compound represented by Chemical Formula 3-b was synthesized by Reaction Scheme 14 below.

[Reaction Scheme 14]

43 g of a compound represented by Chemical Formula 3-b (yield: 86.8) except that the compound represented by Chemical Formula 13a synthesized in Scheme 13 was used instead of the compound represented by Chemical Formula 1-a used in Scheme 2. %) Was obtained.

3) Synthesis of Compound Represented by Chemical Formula 3-c

The compound represented by Chemical Formula 3-c was synthesized by Reaction Scheme 15 below.

[Reaction Scheme 15]

43 g (0.141 mol) of compound represented by the formula (3-b) obtained from Scheme 14, 21.41 g (0.169 mol) of 1-phenylboronic acid, tetrakistriphenylphosphinepalladium (Pd [PPh ₃ ] ₄ ) in a 1,000 ml round bottom flask. ) 8.13 g (0.007 mol), 77.68 g (0.562 mol) of potassium carbonate, 215 ml of toluene, 107 ml of water, and 107 ml of ethanol were added and refluxed. After completion of the reaction, the organic layer was separated using methylene chloride and water and concentrated under reduced pressure. After concentration, 20 g of a compound represented by Chemical Formula 3-c (yield: 47%) was obtained by using column chromatography with methylene chloride and hexane.

4) Synthesis of Compound Represented by Chemical Formula 3-d

The compound represented by Chemical Formula 3-d was synthesized by Reaction Scheme 16 below.

[Reaction Scheme 16]

12.5 g of a compound represented by Chemical Formula 3-d, except that the compound represented by Chemical Formula 3-c synthesized in Scheme 15 was used instead of the compound represented by Chemical Formula 1-d used in Scheme 5 (yield: 54%).

5) Synthesis of Compound Represented by Chemical Formula 590

The compound represented by Chemical Formula 590 was synthesized by Reaction Scheme 17 below.

[Reaction Scheme 17]

3.6 g of a compound represented by the formula (590) by the same method except for using the compound represented by the formula (3-d) synthesized in Scheme 16 instead of the compound represented by the formula (1-e) used in Scheme 6 (yield: 32.4% ) Was synthesized.

MS (MALDI-TOF): m / z 774.38 [M] ⁺

Anal.Calcd for C ₅₈ H ₃₀ D ₁₀ N ₂ : C, 89.88; H, 6. 50; N, 3.61. Found: C, 89.85; H, 6.52; N, 3.62.

< Synthetic example  4> Preparation of a compound represented by Formula 102

The compound represented by Chemical Formula 102 was synthesized according to Scheme 18 below.

[Reaction Scheme 18]

4.9g (0.11mol), 2-bromo-9,10-bis (4-phenylphenyl) anthracene 5g (0.009mol), tetrakistriphenylphosphinepalladium represented by the formula 2-e synthesized in Scheme 11 (Pd [PPh ₃ ] ₄ ) 0.51 g (0.0001 mol), potassium carbonate 4.92 g (0.036 mol), 40 ml of toluene, 20 ml of ethanol and 20 ml of water were added and refluxed for 20 hours. After completion of the reaction, the organic layer was separated using toluene and water, concentrated under reduced pressure, precipitated crystals with methanol, and filtered to obtain 2.1 g of a compound represented by the formula (102) (yield: 29.1%).

MS (MALDI-TOF): m / z 810.38 [M] ⁺

Anal.Calcd for C ₆₁ H ₃₀ D ₁₀ N ₂ : C, 90.33; H, 6. 21; N, 3.45. Found: C, 90.36; H, 6.19; N, 3.44

< Synthetic example  5> Preparation of a compound represented by Chemical Formula 385

The compound represented by Chemical Formula 385 was synthesized by Reaction Scheme 19 below.

Scheme 19

3.22 g (0.007 mol), 2,6-dibromo-9,10-bis (4-trifluorophenyl) anthracene 2.00 g (0.003 mol), tetrakis, represented by Formula 2-e synthesized in Scheme 11 0.19 g (0.0001 mol) of triphenylphosphine palladium (Pd [PPh ₃ ] ₄ ), 1.77 g (0.013 mol) of potassium carbonate, 32 ml of toluene, 16 ml of ethanol and 16 ml of water were added and refluxed for 20 hours. After completion of the reaction, the organic layer was separated with toluene and water, concentrated under reduced pressure, precipitated with crystals of methanol, and filtered to obtain 1.2 g (yield 33.3%) of the compound represented by Chemical Formula 385.

MS (MALDI-TOF): m / z 1122.47 [M] ⁺

Anal.Calcd for C ₇₄ H ₂₄ D ₂₀ F ₆ N ₄ : C, 79.12; H, 5. 74; F, 10.15; N, 4.99. Found: C, 79.10; H, 5.73; F, 10.17; N, 5.00.

< Synthetic example  6> Preparation of a compound represented by Chemical Formula 431

The compound represented by Chemical Formula 431 was prepared by Reaction Scheme 20 below.

[Reaction Scheme 20]

Synthesis was carried out in the same manner, except that 2,6-dibromo-9,10-diphenylanthracene was used instead of 2,6-dibromo-9,10-bis (trifluorophenyl) anthracene used in Scheme 19 and 1.00. g (yield 24.7%) was obtained.

MS (MALDI-TOF): m / z 986.5 [M] ⁺

Anal.Calcd for C ₇₄ H ₂₆ D ₂₀ N ₄ : C, 87.59; H, 6.73; N, 5.67. Found: C, 87.62; H, 6. 70; N, 5.67.

< Synthetic example  7> Preparation of the compound represented by Chemical Formula 390

1) Synthesis of Compound Represented by Chemical Formula 7-a

The compound represented by Chemical Formula 7-a was prepared by Reaction Scheme 21 below.

Scheme 21

Except for using 3,4,5-trimethylphenyl boronic acid instead of 1-phenyl-d5-boronic acid used in Scheme 9 to give a compound 21g (yield 67.7%) represented by the formula 7-c .

2) Synthesis of Compound Represented by Chemical Formula 7-b

The compound represented by Chemical Formula 7-b was prepared by Reaction Scheme 22 below.

[Reaction Scheme 22]

In a 250 ml round bottom flask, 20.0 g (0.049 mol) of the compound represented by Chemical Formula 7-a obtained in Scheme 21 was dissolved in dimethylformamide, and then cooled to -10 ° C. When the temperature was lowered, 8.8 g (0.049 mol) of N-bromosuccinimide (NBS) was added thereto, followed by stirring. After completion of the reaction, 9.97 g (0.079 mol) of sodium sulfite was dissolved in water, and then added to the reaction solution. The organic layer was separated using methylene chloride, concentrated under reduced pressure, and then represented by Chemical Formula 7-b using column chromatography with methylene chloride and hexane. Obtained compound 18g (yield 75.3%).

3) Synthesis of Compound Represented by Chemical Formula 7-c

The compound represented by Chemical Formula 7-c was prepared by Reaction Scheme 23.

[Reaction Scheme 23]

12.0 g of a compound represented by Chemical Formula 7-c, except that the compound represented by Chemical Formula 7-b synthesized in Scheme 22 was used instead of the compound represented by Chemical Formula 1-d, used in Scheme 5 (yield: 55.8%).

4) Synthesis of Compound Represented by Chemical Formula 390

The compound represented by Chemical Formula 390 was prepared by the following Scheme 24.

Scheme 24

4.67 g (0.009 mol) of the compound represented by Chemical Formula 7-c synthesized in Scheme 23, 2,6-dibromo-9,10-bis (4-trifluorophenyl) anthracene 2.50 g (0.004 mol), tetrakis 0.23 g (0.0001 mol) of triphenylphosphine palladium (Pd [PPh ₃ ] ₄ ), 2.21 g (0.016 mol) of potassium carbonate, 46 ml of toluene, 23 ml of ethanol and 23 ml of water were added and refluxed for 20 hours. After completion of the reaction, the organic layer was separated with toluene and water, concentrated under reduced pressure, precipitated with crystals of methanol, and filtered to obtain 1.2 g (yield 33.3%) of the compound represented by Chemical Formula 390.

MS (MALDI-TOF): m / z 1270.53 [M] ⁺

Anal.Calcd for C ₈₆ H ₆₈ F ₆ N ₄ : C, 81.24; H, 5.39; F, 8.97; N, 4.40. Found: C, 81.21; H, 5. 38; F, 8.98; N, 4.43.

< Synthetic example  8> Synthesis of Compound Represented by Chemical Formula 437

The compound represented by Chemical Formula 437 was synthesized by Reaction Scheme 25 below.

Scheme 25

In the same manner, except that 2,6-dibromo-9,10-diphenylatracene was used instead of 2,6-dibromo-9,10-bis (4-trifluorophenyl) anthracene used in Scheme 24 By synthesis, 1.7g (yield 29.2%) of the compound represented by Chemical Formula 437 was synthesized.

MS (MALDI-TOF): m / z 1134.56 [M] ⁺

Anal.Calcd for C ₈₄ H ₇₀ N ₄ : C, 88.85; H, 6. 21; N, 4.93. Found: C, 88.83; H, 6. 22; N, 4.94.

< Example  1 to 8 Of organic light emitting device  Produce

The light emitting area of the ITO glass was patterned to have a size of 2 mm x 2 mm and then washed. After mounting the substrate in a vacuum chamber, the base pressure is 1 × 10 ^-6 torr and the organic material is placed on the ITO DNTPD (700 kPa), NPD (300 kPa), ADN + compound (2%) prepared by the present invention ( 300 Å), Alq ₃ (350 Å), LiF (5 Å), and Al (1,000 Å) were formed in this order, and measured at 0.4 mA.

[DNTPD]

[NPD]

[ADN]

[Alq ₃ ]

< Comparative example  1>

The organic light emitting display device for the Comparative Example was manufactured in the same manner except for using Perylene of the following structural formula instead of the compound prepared by the present invention in the device structure of Examples 1 to 11.

[perylene]

TABLE 2

From the results of Examples 1 to 8, Comparative Example 1 and Table 2, the compound represented by the formula (1) according to the present invention has a lower driving voltage and excellent luminous efficiency than the comparative example 1, the display device, It can be seen that it can be usefully used for display elements and lighting.

Claims (10)

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

In Chemical Formula 1,
At least one of R 1 to R 10 is represented by the following Chemical Formula 1-1, and the remaining ones are each independently a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, substituted or unsubstituted An aryl group having 6 to 50 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 50 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, Substituted or unsubstituted C1-C20 alkylamino group, substituted or unsubstituted C6-C30 arylamino group, substituted or unsubstituted C1-C20 alkylsilyl group, substituted or unsubstituted C6-C30 Arylsilyl group, substituted or unsubstituted arylalkylamino group having 1 to 50 carbon atoms, substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, substituted or unsubstituted C2-10 egg Selected from the group consisting of a silyl group, a cyano group, a halogen group, a small to medium number and hydrogen, and adjacent groups of R1 to R10 may combine with each other to form a substituted or unsubstituted aliphatic, aromatic, heteroaliphatic or heteroaromatic condensed ring; ,
[Formula 1-1]

In Chemical Formula 1-1,
L is a divalent linking group connecting a bonding site selected from R11 to R14 with any one of R1 to R10 of Formula 1, and a direct bond, a substituted or unsubstituted alkylene group having 1 to 60 carbon atoms, a substituted or unsubstituted carbon number. 2 to 60 carbon atoms containing at least one selected from alkenylene group, substituted or unsubstituted alkynylene group having 2 to 60 carbon atoms, substituted or unsubstituted cycloalkylene group having 3 to 60 carbon atoms, N, O and S A heterocycloalkylene group of 6 to 6, a substituted or unsubstituted arylene group having 6 to 50 carbon atoms, and a substituted or unsubstituted heteroarylene group having 3 to 50 carbon atoms,
A is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 50 carbon atoms, substituted Or an unsubstituted alkoxy group having 1 to 20 carbon atoms, and a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms,
R11 to R14 each independently represent a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, and a substituted or unsubstituted group Heteroaryl group having 3 to 50 carbon atoms, substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, substituted or unsubstituted alkylamino group having 1 to 20 carbon atoms, substituted Or an unsubstituted arylamino group having 6 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 1 to 20 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms, a substituted or unsubstituted carbon atom having 1 to 50 carbon atoms An arylalkylamino group, a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 10 carbon atoms, a cyano group, a halogen group, a small to medium number and hydrogen Is selected from the group,
Adjacent groups of A and R1 to R10 may combine with each other to form a substituted or unsubstituted aliphatic, aromatic, heteroaliphatic or heteroaromatic condensed ring. The method of claim 1,
R1 to R10 of Formula 1, and L, A and R11 to R14 of Formula 1-1 are each independently a deuterium atom, a cyano group, a halogen atom, a hydroxy group, a nitro group, an alkyl group having 1 to 40 carbon atoms, and 1 to 40 carbon atoms. Alkoxy group, alkylamino group of 1 to 40 carbon atoms, arylamino group of 6 to 40 carbon atoms, heteroarylamino group of 3 to 40 carbon atoms, alkylsilyl group of 1 to 40 carbon atoms, arylsilyl group of 6 to 40 carbon atoms, An amine compound characterized by being substituted by at least one member selected from the group consisting of an aryl group having 40, an aryloxy group having 3 to 40 carbon atoms, a heteroaryl group having 3 to 40 carbon atoms, a germanium group, phosphorus and boron. The method of claim 1,
The amine compound is an amine compound, characterized in that any one of the compounds represented by Formula 2 to Formula 768 of Table 1 below:
TABLE 1

Anode;
Cathode; And
An organic electroluminescent device having a layer interposed between the anode and the cathode, the layer including the amine compound of any one of claims 1 to 3. The method of claim 4, wherein
The layer containing the amine compound is an organic light emitting device, characterized in that the light emitting layer between the anode and the cathode. The method of claim 5,
An organic electroluminescent device further comprising at least one layer selected from the group consisting of a hole injection layer, a hole transport layer, an electron blocking layer, a hole blocking layer, an electron transport layer and an electron injection layer between the anode and the cathode. The method of claim 5,
The thickness of the light emitting layer is an organic light emitting device, characterized in that 0.5nm to 500nm. The method of claim 5,
The organic light emitting device is characterized in that the light emitting layer further comprises ADN of the following structural formula:
[ADN]

The method of claim 6,
At least one layer selected from the hole injection layer, the hole transport layer, the electron blocking layer, the light emitting layer, the hole blocking layer, the electron transport layer and the electron injection layer is formed by a single molecule deposition method or a solution process. The method of claim 4, wherein
The organic electroluminescent device is an organic electroluminescent device, characterized in that used for a display device, a display device, or a device for monochrome or white illumination.

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