KR101801047B1 - 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 electroluminescent device including the same, and an organic electroluminescent device including the amine compound according to the present invention has an excellent effect on luminance, color purity and lifetime characteristics.

Description

(AMINE-BASED COMPOUND AND ORGANIC ELECTROLUMINESCENT DEVICES COMPRISING THE SAME)

The present invention relates to an amine compound and an organic electroluminescent device including the same, and more particularly, to an amine compound having excellent luminance, color purity and lifetime, and an organic electroluminescent device including the same.

In recent years, the demand for a flat display device having a small space occupation has been increasing due to the enlargement of a display device. The liquid crystal display, which is a typical flat display device, has an advantage of being lighter than a conventional CRT (cathode ray tube) angle is limited and a back light is necessarily required. On the other hand, an organic light emitting diode (OLED), which is a new flat display device, is a display using a self-luminous phenomenon, has a large viewing angle, is slimmer and smaller than a liquid crystal display, And in recent years, application to a full-color display or illumination 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 electroluminescent device using an organic light emitting phenomenon usually has a structure including an anode, an anode, and an organic material layer therebetween. Here, in order to enhance the efficiency and stability of the organic electroluminescent device, the organic material layer may have a multi-layer structure composed of different materials and may include a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer. When a voltage is applied between the two electrodes in the structure of the organic electroluminescent device, holes are injected into the anode, electrons are injected into the organic layer, and excitons are formed when injected holes and electrons meet. When it falls back to the ground state, the light comes out. Such an organic electroluminescent device is known to have properties such as self-emission, high luminance, high efficiency, low driving voltage, wide viewing angle, high contrast, and high speed response.

A material used as an organic material layer in an organic electroluminescent device can be classified into a light emitting material and a charge transporting material such as a hole injecting material, a hole transporting material, an electron transporting material, and an electron injecting material depending on functions. The light emitting material may be classified into a polymer type and a low molecular type depending on the molecular weight and may be classified into a fluorescent material derived from singlet excited state of electrons and a phosphorescent material derived from the triplet excited state of electrons according to an emission mechanism . Further, the light emitting material can be classified into blue, green, and red light emitting materials and yellow and orange light emitting materials necessary for realizing better natural color depending on the luminescent 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 is shifted to the wavelength band of the dopant, light of a desired wavelength can be obtained depending on the type of dopant used.

In order for the organic electroluminescent device to sufficiently exhibit the above-described excellent characteristics, materials constituting the organic material layer in the device, such as a hole injecting material, a hole transporting material, a light emitting material, an electron transporting material, and an electron injecting material are supported by a stable and efficient material However, the development of a stable and efficient organic material layer material for an organic electroluminescence device has not been sufficiently developed yet. Therefore, there is a continuing need in the art for the development of new materials.

SUMMARY OF THE INVENTION The present invention provides an amine compound having excellent light emission luminance and color purity and long life.

A second object of the present invention is to provide an organic electroluminescent device including the amine compound.

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

[Chemical Formula 1]

In Formula 1,

At least one of R 1 to R 10 is represented by the following formula (1-1), and the remainder each independently represents 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 aryloxy 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, A substituted or unsubstituted alkylamino group having 1 to 20 carbon atoms, a substituted or 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 arylamino group having 6 to 30 carbon atoms An arylsilyl group, a substituted or unsubstituted arylalkylamino group having 1 to 50 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, a substituted or unsubstituted aliphatic hydrocarbon group having 2 to 10 carbon atoms An adjacent group of R 1 to R 10 may be bonded to each other to form a condensed ring of a substituted or unsubstituted aliphatic, aromatic, heteroaliphatic or heteroaromatic ring, ,

[Formula 1-1]

In Formula 1-1,

L is a divalent linking group selected from the group consisting of R11 to R14 and a divalent linking group connected to any one of R1 to R10 of the formula (1), which is a direct bond, a substituted or unsubstituted alkylene group having 1 to 60 carbon atoms, A substituted or unsubstituted C2-C60 alkenylene group, a substituted or unsubstituted C2-C60 alkynylene group, a substituted or unsubstituted C3-C60 cycloalkylene group, a substituted or unsubstituted C2- 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 represents 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, a 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,

R 11 to R 14 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, a substituted or unsubstituted A substituted or unsubstituted C1-C20 alkoxy group, a substituted or unsubstituted C6-C30 aryloxy group, a substituted or unsubstituted C1-C20 alkylamino group, a substituted or unsubstituted C1- Or an unsubstituted or substituted 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 C1- A substituted or unsubstituted alkynyl group having 2 to 10 carbon atoms, a cyano group, a halogen group, a medium-small water group, and hydrogen Is selected from the group,

A and adjacent groups of R1 to R10 may be bonded to each other to form a substituted or unsubstituted aliphatic, aromatic, heteroaliphatic or heteroaromatic condensation ring.

In order to solve the second technical problem, the present invention provides a semiconductor device comprising: an anode; Cathode; And a layer including an amine compound represented by the general formula (1), which is interposed between the anode and the cathode.

The organic electroluminescent device including the amine compound represented by Chemical Formula 1 in the organic material layer according to the present invention is excellent in brightness, color purity, and lifetime characteristics, and thus can be used for display and illumination.

1 is a schematic view of an organic electroluminescent device according to one embodiment of the present invention.
Description of the Related Art
10: substrate 20: anode
30: Hole injection layer 40: Hole transport layer
50: organic light emitting layer 60: electron transporting layer
70: electron injection layer 80: cathode

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

The amine compound according to the present invention is characterized by being represented by the above formula (1).

In the amine compound according to the present invention, the substituents of the above formula (1) will be described in more detail as follows.

delete

Specific examples of the alkyl group as the substituent used in the present invention include a methyl group, an ethyl group, a propyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an isoamyl group, a hexyl group, a heptyl group, A halogen atom, a hydroxyl group, a nitro group, a cyano group, a trifluoromethyl group, a silyl group (in this case, a " alkylsilyl group "hereinafter), a substituted or unsubstituted amino group _{(-NH 2, -NH (R)} , -N (R ') (R''), where R, R' and R" are each independently a carbon number A hydrazine group, a hydrazone group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, an alkyl group having 1 to 24 carbon atoms, a halogenated alkyl group having 1 to 24 carbon atoms (for example, an alkyl group having 1 to 24 carbon atoms , An alkenyl group having 2 to 24 carbon atoms, an alkynyl group having 2 to 24 carbon atoms, An aryl group having from 5 to 24 carbon atoms, an aryl group having from 5 to 24 carbon atoms, an arylalkyl group having from 6 to 24 carbon atoms, a heteroaryl group having from 3 to 24 carbon atoms, or a heteroarylalkyl group having from 3 to 24 carbon atoms.

Specific examples of the cycloalkyl group as the substituent used in the compound of the present invention include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group and an adamantyl group. And can be substituted with the same substituent.

Specific examples of the alkoxy group used as the substituent in the compound of the present invention include methoxy, ethoxy, propoxy, isobutyloxy, sec-butyloxy, pentyloxy, isoamyloxy, And can be substituted with substituents similar to those in the case of the 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 as the substituent group used in the compound of the present invention include a phenyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, a 4-ethylphenyl group, Examples of the aryl group include phenyl group, 4-methylbiphenyl group, 4-ethylbiphenyl group, o-terphenyl group, m-terphenyl group, p-terphenyl group, 1-naphthyl group, , Anthryl group, phenanthryl group, pyrenyl group, fluorenyl group, tetrahydronaphthyl group and the like, which may be substituted with the same substituents as those in the case of the alkyl group.

Specific examples of the heteroaryl group used as the substituent in the compound of the present invention include pyridinyl, pyrimidinyl, triazinyl, indolinyl, quinolinyl, pyrrolidinyl, piperidinyl, An oxazolyl group, an oxadiazolyl group, a benzoxazolyl group, a thiazolyl group, a thiadiazolyl group, a benzothiazolyl group, a triazolyl group, an imidazolyl group, a benzoimidazole group, And at least one of the hydrogen atoms of the heteroaryl group may be substituted with the same substituent as the alkyl group.

In the present invention, the term "substituted or unsubstituted" refers to a group selected from the group consisting of deuterium, halogen, alkyl, alkenyl, alkoxy, aryl, arylalkyl, arylalkenyl, heteroaryl, Substituted or unsubstituted with at least one substituent selected from the group consisting of an acetylene group, 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 Chemical Formulas (2) to (768) shown in Table 1 below.

[Table 1]

The method for producing an amine compound according to the present invention is specifically shown in the following Examples.

The present invention also relates to a fuel cell comprising an anode; Cathode; And a layer including an amine compound represented by the general formula (1), which is interposed between the anode and the cathode.

In this case, the layer containing the amine compound is preferably a light emitting layer between the anode and the cathode, and a hole injecting layer, a hole transporting layer, an electron blocking layer, a hole blocking layer, an electron transporting layer, ≪ RTI ID = 0.0 > and / or < / RTI >

In addition, according to another embodiment of the present invention, the thickness of the light emitting layer is preferably 0.5 nm to 500 nm, and the light emitting layer further includes ADN (9,10-di (2-naphthyl) anthracene) can do.

[ADN (9,10-di (2-naphthyl) anthracene]

As a specific example, a hole transport layer (HTL) may be additionally stacked, and an electron transport layer (ETL) may be further stacked between the cathode and the organic emission layer. An electron donor molecule having a low ionization potential is used as the material of the hole transport layer. A diamine, triamine or tetraamine derivative having a basic skeleton of triphenylamine is used as the hole transport layer. It is widely used.

In the present invention, the material for the hole transport layer is not particularly limited as long as it is commonly used in the art. For example, N, N'-bis (3-methylphenyl) -N, N'- , 1-biphenyl] -4,4'-diamine (TPD) or N, N'-di (naphthalene-1-yl) -N, N'-diphenylbenzidine (a-NPD).

A HIL (Hole Injection Layer) may be additionally deposited on the lower portion of the hole transport layer. The material for the hole injection layer is not particularly limited as long as it is commonly used in the art. For example, (4,4 ', 4 "-tri (N-carbazolyl) triphenylamine), m-MTDATA (4,4', 4" -tris- (3-methylphenylphenylamino) triphenylamine).

In addition, the electron transport layer used in the organic electroluminescent device according to the present invention can transport electrons supplied from the cathode smoothly to the organic luminescent layer and inhibit the movement of holes which are not bonded in the organic luminescent layer, . The material of the electron transport layer is not particularly limited as long as it is commonly used in the art. For example, oxadiazole derivative PBD, BMD, BND or Alq ₃ can be used.

Meanwhile, an electron injection layer (EIL) may be further formed on the electron transport layer to facilitate injection of electrons from the cathode to ultimately improve power efficiency. The electron injection layer material As long as it is commonly used in the art, it can be used without any particular limitation. For example, materials such as LiF, NaCl, CsF, Li ₂ O, and BaO can be used.

The organic electroluminescent device according to the present invention can be used for a display device, a display device, an element for a single color or a white light, and the like.

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

Referring to FIG. 1, the organic electroluminescent device of the present invention and its manufacturing method will be described as follows. First, an anode electrode material is coated on the substrate 10 to form an anode 20. Here, as the substrate 10, an organic substrate or a transparent plastic substrate which is excellent in transparency, surface smoothness, ease of handling, and waterproofness is used as a substrate used in a conventional organic EL device. As the material for the anode 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 are used.

A hole injection layer 30 is formed on the anode 20 by vacuum thermal deposition or spin coating. Subsequently, a hole transport layer 40 is formed by vacuum thermal deposition or spin coating on the hole transport layer 30 above the hole injection layer 30. 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 to form a thin film on the organic light emitting layer 50 can do. In the case where holes are injected into the cathode through the organic light-emitting layer, the lifetime and the efficiency of the device are reduced, and thus the hole blocking layer plays a role of preventing such a problem by using a material having a very low HOMO (Highest Occupied Molecular Orbital) level . In this case, the hole blocking material to be used is not particularly limited, but it is required to have an ionization potential higher than that of the light emitting compound while having electron transporting ability. Typically, BAlq, BCP, TPBI and the like can be used.

After the electron transport layer 60 is deposited on the hole blocking layer by a vacuum deposition method or a spin coating method, an electron injection layer 70 is formed, and a cathode forming metal is deposited on the electron injection layer 70 in a vacuum heat- And the cathode 80 is formed by vapor deposition to complete the organic EL device. Here, as the metal for forming the cathode, lithium, magnesium, aluminum, aluminum-lithium, calcium, magnesium-magnesium, Mg-Ag), and a transmissive cathode using ITO or IZO can be used to obtain a top light-emitting device.

According to another embodiment of the present invention, at least one layer selected from the hole injecting layer, the hole transporting layer, the electron blocking layer, the light emitting layer, the hole blocking layer, the electron transporting layer and the electron injecting layer is formed by a single molecular deposition method or a solution process And the organic electroluminescent device according to the present invention can be used for a display device, a display device, and a monochromatic or white illumination device.

Hereinafter, preferred embodiments of the present invention will be described in order to facilitate understanding of the present invention. However, the following examples are provided only for the purpose of easier understanding of the present invention, and the present invention is not limited thereto.

< Example >

< Synthetic example  1> Preparation of the compound represented by the formula (541)

1) Synthesis of the compound represented by the formula 1-a

The compound represented by the formula (1-a) was synthesized by the following Reaction Scheme 1.

[Reaction Scheme 1]

(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 and 10.74 g 0.060 mol) were refluxed with 370 ml of toluene while stirring. After completion of the reaction, the reaction solution was filtered through celite, and the filtrate was concentrated under reduced pressure. The crystals were precipitated with methanol at -78 ° C and then filtered to obtain 21 g (yield 50%) of the compound represented by the formula 1-a.

2) Synthesis of the compound represented by the formula 1-b

A compound represented by the formula 1-b was synthesized by the following Reaction Scheme 2.

[Reaction Scheme 2]

13.0 g (0.091 mol) of the compound represented by the formula 1-a obtained from the reaction formula 1 was dissolved in 484 ml of dimethylformamide (DMF), and the temperature was lowered to -10 ° C in a 1,000 ml round bottom flask. When the temperature dropped, 32.32 g (0.182 mol) of N-bromosuccinimide (NBS) was added and stirred. After the completion of the reaction, 18.31 g (0.145 mol) of sodium sulfite was dissolved in water, and the reaction solution was added to the reaction solution. The organic layer was separated using methylene chloride, concentrated under reduced pressure, and purified by column chromatography using hexane to obtain Compound 28.5 g (97% yield).

3) Synthesis of the compound represented by the formula 1-c

The compound represented by the formula 1-c was synthesized by the following Reaction Scheme 3.

[Reaction Scheme 3]

28.5 g (0.095 mol) of the compound represented by the formula 1-b obtained from the reaction formula 2, 28.86 g (0.237 mol) of 1-phenylboronic acid, tetrakis triphenylphosphine palladium (Pd [PPh ₃ ] ₄ ), 52.35 g (0.379 mol) of potassium carbonate, 285 ml of toluene, 142 ml of water and 142 ml of ethanol were placed and refluxed. After completion of the reaction, the organic layer was separated using methylene chloride and water and concentrated under reduced pressure. Concentration was followed by column chromatography using methylene chloride and hexane to obtain 14 g (yield: 50%) of the compound represented by the formula (1-c).

4) Synthesis of the compound represented by the formula (1-d)

The compound represented by the formula 1-d was synthesized by the following Reaction Scheme 4.

[Reaction Scheme 4]

10.0 g (0.034 mol) of the compound represented by the formula (1-c) obtained from the reaction formula 3 was dissolved in dimethylformamide in a 250 ml round bottom flask, and the temperature was lowered to -10 ° C. When the temperature dropped, 6 g (0.034 mol) of N-bromosuccinimide (NBS) was added and stirred. After completion of the reaction, 6.8 g (0.05 mol) of sodium sulfite was dissolved in water and the reaction solution was added. The organic layer was separated using methylene chloride, concentrated under reduced pressure, and then purified by column chromatography using methylene chloride and hexane to obtain (Yield: 78.7%) of the title compound.

5) Synthesis of the compound represented by the formula 1-e

The compound represented by the formula 1-e was synthesized according to the following Reaction Scheme 5.

[Reaction Scheme 5]

10 g (0.027 mol) of the compound represented by the formula 1-d, 0.08 mol (0.027 mol) of bis (pinacolato) diboron and 0.65 g (0.001 mol) of PdCl ₂ (dppf) obtained from the reaction formula 4 were added to a 250- , 6.07 g (0.080 mol) of calcium acetate and 80 ml of toluene were added and refluxed for 20 hours. After the completion of the reaction, the reaction solution was filtered through celite. The filtrate was concentrated, and 7 g (yield: 61%) of the compound represented by the formula (1-e) was obtained by column chromatography using methylene chloride and hexane.

6) Synthesis of the compound represented by the formula (541).

A compound represented by the general formula (541) was synthesized by the following Reaction Scheme (6).

[Reaction Scheme 6]

(0.014 mol) of the compound represented by the formula 1-e obtained in the reaction formula 5, 3 g (0.006 mol) of 2,6-dibromo-9,10-phenylanthracene, tetrakistriphenylphosphine palladium _{(Pd [PPh 3] 4)} 0.36g (0.0001mol), potassium carbonate 3.40g (0.025mol), 45ml of toluene, 22ml of ethanol, 22ml of water into the mixture was refluxed for 20 hours. After completion of the reaction, the organic layer was separated using toluene and water, and then concentrated under reduced pressure. The precipitated crystals were separated by filtration to obtain 2g of the compound represented by Chemical Formula 541 (yield: 35.5%).

MS (MALDI-TOF): m / z 916.38 [M] ^&lt; ^{+ &}

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 the formula (431)

1) Synthesis of the compound represented by the formula 2-a

The compound represented by the formula 2-a was synthesized according to the following Reaction Scheme 7.

[Reaction Scheme 7]

Except that 1-bromo-4-cyanobenzene was used instead of the iodobenzene used in the reaction scheme 1 to obtain 23 g (yield: 45.9%) of the compound represented by the formula 2-a.

2) Synthesis of the compound represented by the formula 2-b

The compound represented by the formula (2-b) was synthesized by the following Reaction Scheme 8.

[Reaction Scheme 8]

Except that the compound represented by the formula 2-a synthesized in the reaction scheme 7 was used instead of the compound represented by the formula 1-a used in the scheme 2 to obtain 23 g of the compound represented by the formula 2-b (yield: 91.3%).

3) Synthesis of the compound represented by the formula 2-c

The compound represented by the formula 2-c was synthesized according to the following Reaction Scheme 9.

[Reaction Scheme 9]

Except that 1-phenyl-d5-boronic acid was used in place of 1-phenylboronic acid instead of using the compound represented by the formula 2-b synthesized in the reaction scheme 8 instead of the compound represented by the formula 1-b used in the reaction scheme 3 Synthesis was conducted in the same manner to obtain 14 g (yield 69.1%) of the compound represented by the formula (2-c).

4) Synthesis of the compound represented by the formula 2-d

The compound represented by the formula (2-d) was synthesized by the following Reaction Scheme 10.

[Reaction Scheme 10]

Synthesis was carried out in the same manner except that the compound represented by the formula 2-c synthesized in the reaction scheme 9 was used instead of the compound represented by the formula 1-c used in the scheme 4 to obtain 11.3 g (yield: 70%) of the compound represented by the formula 2-d %).

5) Synthesis of the compound represented by the formula 2-e

The compound represented by the formula 2-e was synthesized by the following Reaction Scheme 11.

[Reaction Scheme 11]

Synthesis was carried out in the same manner except that the compound represented by the formula 2-d synthesized in the reaction scheme 10 was used instead of the compound represented by the formula 1-d used in the scheme 5 to obtain 7.2 g (yield 59%) of the compound represented by the formula 2-e %).

6) Synthesis of compound represented by formula (431)

A compound represented by the formula (431) was synthesized according to the following reaction scheme (12).

[Reaction Scheme 12]

Except that the compound represented by the formula 2-e synthesized in the reaction scheme 11 was used instead of the compound represented by the formula 1-e used in the scheme 6 to obtain 2.7 g (yield: 38.1%) of the compound represented by the formula 431, ) Were synthesized.

MS (MALDI-TOF): m / z 986.5 [M] ^&lt; ^{+ &}

Anal.Calcd for C ₇₄ H ₂₈ D ₂₀ N 4 : 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 the formula 590

1) Synthesis of Compound Represented by Formula 3-a

A compound represented by the formula (3-a) was synthesized by the following Reaction Scheme (13).

[Reaction Scheme 13]

Except that bromobenzene-d5 was used in place of the iodobenzene used in the reaction scheme 1 to synthesize 24 g (yield: 54.3) of the compound represented by the formula 3-a.

2) Synthesis of the compound represented by the formula 3-b

The compound represented by the general formula (3-b) was synthesized by the following Reaction Scheme (14).

[Reaction Scheme 14]

Except that the compound represented by the formula 3-a synthesized in the reaction scheme 13 was used instead of the compound represented by the formula 1-a used in the reaction scheme 2 to obtain 43 g of the compound represented by the formula 3-b (the yield: 86.8 %).

3) Synthesis of the compound represented by the formula 3-c

The compound represented by the formula 3-c was synthesized according to the following Reaction Scheme 15.

[Reaction Scheme 15]

(0.141 mol) of the compound represented by the formula 3-b obtained from the reaction formula 14, 21.41 g (0.169 mol) of 1-phenylboronic acid, tetrakistriphenylphosphine palladium (Pd [PPh ₃ ] ₄ ), 77.68 g (0.562 mol) of potassium carbonate, 215 ml of toluene, 107 ml of water and 107 ml of ethanol were placed and refluxed. After completion of the reaction, the organic layer was separated using methylene chloride and water and concentrated under reduced pressure. Concentrated, and then subjected to column chromatography using methylene chloride and hexane to obtain 20 g (yield: 47%) of the compound represented by the formula (3-c).

4) Synthesis of Compound Represented by Formula 3-d

The compound represented by the formula 3-d was synthesized according to the following Reaction Scheme 16.

[Reaction Scheme 16]

D-d was used instead of the compound represented by the formula 1-d used in the reaction scheme 5 to obtain 12.5 g of the compound represented by the formula 3-d (yield: 54%).

5) Synthesis of compound represented by formula 590

A compound represented by the formula 590 was synthesized by the following Reaction Scheme 17.

[Reaction Scheme 17]

Synthesis was carried out in the same manner except that the compound represented by the formula 3-d synthesized in the reaction scheme 16 was used instead of the compound represented by the formula 1-e used in the scheme 6 to obtain 3.6 g (yield: 32.4%) of the compound represented by the formula 590, ) Were synthesized.

MS (MALDI-TOF): m / z 774.38 [M] ^&lt; ^{+ &}

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 the compound represented by the formula (102)

The compound represented by the general formula (102) was synthesized by the following reaction scheme (18).

[Reaction Scheme 18]

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

MS (MALDI-TOF): m / z 810.38 [M] ^&lt; ^{+ &}

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 the compound represented by the formula 385

The compound represented by the formula (385) was synthesized by the following reaction scheme (19).

[Reaction Scheme 19]

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

MS (MALDI-TOF): m / z 1122.47 [M] ^&lt; ⁺ & gt ^;

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 the compound represented by the formula (431)

A compound represented by the formula 431 was prepared according to the following Reaction Scheme 20.

[Reaction Scheme 20]

Dibromo-9,10-diphenylanthracene was used instead of 2,6-dibromo-9,10-bis (trifluorophenyl) anthracene used in Scheme 19, g (yield: 24.7%).

MS (MALDI-TOF): m / z 986.5 [M] ^&lt; ^{+ &}

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 the formula (390)

1) Synthesis of the compound represented by the formula 7-a

A compound represented by the general formula (7-a) was prepared by the following Reaction Scheme (21).

[Reaction Scheme 21]

Synthesis was conducted in the same manner as in Example 9, except that 3,4,5-trimethylphenylboronic acid was used instead of 1-phenyl-d5-boronic acid used in Reaction Formula 9 to obtain 21 g (yield 67.7%) of a compound represented by the formula 7-c .

2) Synthesis of the compound represented by the formula 7-b

The compound represented by the general formula (7-b) was prepared by the following reaction scheme (22).

[Reaction Scheme 22]

20.0 g (0.049 mol) of the compound represented by the formula (7-a) obtained from the reaction formula 21 was dissolved in dimethylformamide and the temperature was lowered to -10 ° C in a 250 ml round bottom flask. When the temperature dropped, 8.8 g (0.049 mol) of N-bromosuccinimide (NBS) was added and stirred. After the completion of the reaction, 9.97 g (0.079 mol) of sodium sulfite was dissolved in water and the reaction solution was added. The organic layer was separated using methylene chloride, concentrated under reduced pressure, and then purified by column chromatography with methylene chloride and hexane to give 7- (Yield: 75.3%).

3) Synthesis of the compound represented by the formula 7-c

The compound represented by the formula 7-c was prepared according to the following Reaction Scheme 23.

[Reaction Scheme 23]

Synthesis was carried out in the same way except that the compound represented by the formula 7-b was used instead of the compound represented by the formula 1-d used in the reaction formula 5 to obtain 12.0 g of the compound represented by the formula 7-c (yield: 55.8%).

4) Synthesis of Compound Represented by Formula 390

The compound represented by Formula 390 was prepared according to Reaction Scheme 24 below.

[Reaction Scheme 24]

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

MS (MALDI-TOF): m / z 1270.53 [M] ^&lt; ^{+ &}

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 the formula (437) was synthesized according to the following reaction scheme (25).

[Reaction Scheme 25]

The same procedure was followed except that 2,6-dibromo-9,10-diphenyltartracene was used instead of 2,6-dibromo-9,10-bis (4-trifluorophenyl) To obtain 1.7 g (yield: 29.2%) of a compound represented by the formula (437).

MS (MALDI-TOF): m / z 1134.56 [M] ^&lt; ^{+ &}

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> The organic electroluminescent device  Produce

The ITO glass was patterned to have a light emitting area of 2 mm x 2 mm and then cleaned. After the substrate was mounted in a vacuum chamber, the substrate was adjusted to have a pressure of 1 × 10 ^-6 torr, and then an organic material was injected onto the ITO using DNTPD (700 Å), NPD (300 Å), ADN + 300 Å), Alq ₃ (350 Å), LiF (5 Å), and Al (1,000 Å).

[DNTPD]

[NPD]

[ADN]

[Alq ₃ ]

< Comparative Example  1>

The organic electroluminescent device for the comparative example was fabricated in the same manner except that the compound of the present invention was replaced with the compound of the following formula in the device structures of Examples 1 to 11.

[perylene]

[Table 2]

The results of Examples 1 to 8, Comparative Example 1 and Table 2 show that the compound represented by Formula 1 according to the present invention has a lower driving voltage and a better luminous efficiency than Comparative Example 1, Display device, illumination, and the like.

Claims (10)

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

In the above formula (1)
R 1 and R 6 are each independently a substituted or unsubstituted aryl group having 6 to 20 carbon atoms,
At least one of R 2 to R 5 and R 7 to R 10 is represented by the following formula [1-1]
[Formula 1-1]

In the above formula (1-1)
L is a divalent linking group bonded to any one of R &lt; 11 &gt; to R &lt; 14 &gt; and any one of R2 to R5 and R7 to R10 of the formula (1), which may be a direct bond or a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms Or a substituted or unsubstituted arylene group having 6 to 20 carbon atoms,
A and R11 to R14 are each independently selected from hydrogen, a substituted or unsubstituted C6-C20 aryl group and a substituted or unsubstituted C3-C20 heteroaryl group. The method according to claim 1,
Each of R1 to R14, A and L (except when R1 to R14 and A are hydrogen) is independently selected from the group consisting of deuterium, cyano, halogen, alkyl of 1 to 20 carbon atoms, alkoxy of 1 to 20 carbon atoms , An alkylsilyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and a heteroaryl group having 3 to 20 carbon atoms. The method according to claim 1,
Wherein the amine compound is any one of compounds represented by Chemical Formulas (2) to (768) shown in Table 1 below:
[Table 1]

Anode;
Cathode; And
And a layer containing the amine compound of any one of claims 1 to 3 interposed between the anode and the cathode. 5. The method of claim 4,
Wherein the layer containing the amine compound is a light emitting layer between the anode and the cathode. 6. The method of claim 5,
And at least one layer selected from the group consisting of a hole injecting layer, a hole transporting layer, an electron blocking layer, a hole blocking layer, an electron transporting layer and an electron injecting layer is further interposed between the anode and the cathode. 6. The method of claim 5,
Wherein the thickness of the light emitting layer is 0.5 nm to 500 nm. 6. The method of claim 5,
Wherein the light emitting layer further comprises ADN (9,10-di (2-naphthyl) anthracene) of the following structural formula:
[ADN (9,10-di (2-naphthyl) anthracene]

The method according to claim 6,
Wherein at least one layer selected from the group consisting of 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 molecular deposition method or a solution process. 5. The method of claim 4,
Wherein the organic electroluminescent device is used in a display device, a display device, or a device for monochromatic or white illumination.

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