KR20110111094A - Fused aromatic compound and organic electroluminescent devices comprising the same - Google Patents

Abstract

상기 식에서, 상기 R₁ 내지 R₉는 발명의 상세한 설명에 기재된 바와 같다.The present invention relates to a condensed aromatic compound represented by Chemical Formula 1 and an organic light emitting device including the same, and more particularly, when used in an organic light emitting diode, a condensed aromatic compound having a low driving voltage and excellent luminous efficiency, and including the same. An organic electroluminescent device is provided.
[Formula 1]

Wherein R ₁ to R ₉ are as described in the detailed description of the invention.

Description

A condensed aromatic compound and an organic electroluminescent device including the same {FUSED AROMATIC COMPOUND AND ORGANIC ELECTROLUMINESCENT DEVICES COMPRISING THE SAME}

The present invention relates to a condensed aromatic compound and an organic light emitting device including the same, and more particularly, to provide a condensed aromatic compound having a low driving voltage and excellent luminous efficiency when used in an organic light emitting device and an organic light emitting device comprising the same. It is.

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 emitting phenomenon refers to a phenomenon of converting electrical energy into light energy using an organic material. An organic light emitting diode using organic light emitting phenomenon generally 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.

An object of the present invention is to provide a condensed aromatic compound having a low driving voltage and excellent luminous efficiency when used in an organic light emitting device.

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

In order to achieve the first technical problem, the present invention provides a condensed aromatic compound represented by the following formula (1):

[Formula 1]

Where

R ₁ to R ₉ are each independently a hydrogen atom, a deuterium atom, a halogen atom, a substituted or unsubstituted arylamino group, a substituted or unsubstituted aryloxy group having 3 to 40 carbon atoms, a substituted or unsubstituted aryl group having 6 to 40 carbon atoms, Substituted or unsubstituted heteroaryl group having 3 to 40 carbon atoms, germanium group, phosphorus, is selected from the group consisting of boron,

In this case, at least one or more of R ₇ to R ₉ is a substituted or unsubstituted hetero aryl group having 3 to 40 carbon atoms containing nitrogen,

Each X is independently C or S, which may be the same as or different from each other,

l, m and n are integers of 0 or 1, and l + m + n is at least two.

According to one embodiment of the present invention, condensed aromatic compounds are characterized in that adjacent functional groups combine with each other to form a ring having a saturated or unsaturated ring or a hetero atom.

According to another embodiment of the present invention, R ₁ to R ₉ are a hydrogen atom, 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, and a carbon number An alkylamino group of 1-40, an arylamino group of 6-40 carbon atoms, a heteroarylamino group of 3-40 carbon atoms, an alkylsilyl group of 1-40 carbon atoms, an arylsilyl group of 6-40 carbon atoms, an aryl group of 6-40 carbon atoms, It may be substituted by one or more substituents selected from the group consisting of an aryloxy group having 3 to 40 carbon atoms, a heteroaryl group having 3 to 40 carbon atoms, a germanium group, phosphorus, boron, the substituents are bonded to each other to form a saturated or unsaturated ring Can be formed and attached or fused together in a pendant manner.

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 electroluminescent device having a layer comprising a condensed aromatic compound represented by the formula (1).

According to one embodiment of the invention, the condensed aromatic compound is preferably included in the light emitting layer.

The organic light emitting device including the condensed aromatic compound represented by Chemical Formula 1 in the organic material layer according to the present invention may be usefully used for display and lighting because of low driving voltage and excellent luminous efficiency.

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.

Condensed aromatic compounds according to the invention is characterized in that represented by the formula (1).

[Formula 1]

Where

R1 to R9 are each independently a hydrogen atom, a deuterium atom, a halogen atom, a substituted or unsubstituted arylamino group, a substituted or unsubstituted aryloxy group having 3 to 40 carbon atoms, a substituted or unsubstituted aryl group having 6 to 40 carbon atoms, substituted or It is selected from the group consisting of an unsubstituted heteroaryl group having 3 to 40 carbon atoms, germanium group, phosphorus, boron,

In this case, at least one or more of R7 to R9 is a substituted or unsubstituted heteroaryl group having 3 to 40 carbon atoms containing nitrogen,

Each X is independently C or S, which may be the same as or different from each other,

l, m and n are integers of 0 or 1, and l + m + n is at least two.

According to one embodiment of the present invention, adjacent functional groups in the above formula may combine with each other to form a ring having a saturated or unsaturated ring or a hetero atom.

According to another embodiment of the present invention, R1 to R9 are a hydrogen atom, 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, and 1 carbon atom. An alkylamino group of 40, an arylamino group of 6 to 40 carbon atoms, a heteroarylamino group of 3 to 40 carbon atoms, an alkylsilyl group of 1 to 40 carbon atoms, an arylsilyl group of 6 to 40 carbon atoms, an aryl group of 6 to 40 carbon atoms It may be substituted by one or more substituents selected from the group consisting of a 3 to 40 aryloxy group, a heteroaryl group having 3 to 40 carbon atoms, a germanium group, phosphorus, boron, the substituents are bonded to each other to form a saturated or unsaturated ring May be attached or fused together in a pendant manner.

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

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 (-NH2, -NH (R), -N (R ') (R"), where R, R' and R "are each independently To an alkyl group (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 having 1 to 24 carbon atoms, a halogenated alkyl group having 1 to 24 carbon atoms, Alkenyl group having 2 to 24 carbon atoms, Alkynyl group having 2 to 24 carbon atoms, 1 carbon atom By more than 24 heteroaryl group, a heteroarylalkyl group having a carbon number of 5 to 24 aryl group, C 6 -C 24 aryl group, a C 3 -C 24 heteroaryl group, or having from 3 to 24 of which may be substituted.

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.

The condensed aromatic compound according to the present invention may be any one of compounds represented by the following [Formula 2] to [Formula 79].

[Formula 2] [Formula 3] [Formula 4]

[Formula 5] [Formula 6] [Formula 7]

[Formula 8] [Formula 9] [Formula 10]

[Formula 11] [Formula 12] [Formula 13]

[Formula 14] [Formula 15] [Formula 16]

[Formula 17] [Formula 18] [Formula 19]

[Formula 20] [Formula 21] [Formula 22]

[Formula 23] [Formula 24] [Formula 25]

[Formula 26] [Formula 27] [Formula 28]

[Formula 29] [Formula 30] [Formula 31]

[Formula 32] [Formula 33] [Formula 34]

[Formula 35] [Formula 36] [Formula 37]

[Formula 38] [Formula 39] [Formula 40]

[Formula 41] [Formula 42] [Formula 43]

[Formula 44] [Formula 45] [Formula 46]

[Formula 47] [Formula 48] [Formula 49]

[Formula 50] [Formula 51] [Formula 52]

[Formula 53] [Formula 54] [Formula 55]

[Formula 56] [Formula 57] [Formula 58]

[Formula 59] [Formula 60] [Formula 61]

[Formula 62] [Formula 63] [Formula 64]

[Formula 65] [Formula 66] [Formula 67]

[Formula 68] [Formula 69] [Formula 70]

[Formula 71] [Formula 72] [Formula 73]

[Formula 74] [Formula 75] [Formula 76]

[Formula 77] [Formula 78] [Formula 79]

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

At this time, the layer containing the condensed aromatic compound is preferably a light emitting layer between the anode and the cathode, and between the anode and the cathode as 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 It may further comprise 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 50 to 2,000 kPa.

In addition, according to another embodiment of the present invention, the anode and the cathode may further include one or more layers 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 In this case, at least one layer selected from the group consisting of a hole injection layer, a hole transport layer, a light emitting layer, an electron blocking layer, a hole blocking layer, an electron transport layer and an electron injection layer may be prepared by a solution process.

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, according to another embodiment of the present invention, the thickness of the light emitting layer is preferably 50 to 2,000 kPa, and the light emitting layer may further include Ir (ppy) ₃ of the following structural formula.

[Ir (ppy) ₃ ]

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 this problem by using a material having a very low highest Occupied Molecular Orbital (HOMO) level when the hole is introduced into the cathode through the organic light emitting layer to reduce 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.

<Examples>

Synthesis Example 1 Synthesis of Compound of Formula 10

1-1. Synthesis of Formula 1-a

<1-a> was synthesized according to Scheme 1 below.

Scheme 1

                                                           <1-a>

29.0 g (0.192 mol) of methyl-2-aminobenzoate, 130.71 g (0.499 mol) of methyl-2-iodobenzoate, 2.44 g (0.038 mol) of copper powder, 3.65 g (0.019) of iodo copper in a 500 ml round bottom flask mol) and 240 ml of diphenyl ether were added to 61.00 g (0.44 mol) of potassium carbonate, followed by stirring at 190 degrees for 48 hours. When the reaction was completed, the mixture was filtered under reduced pressure, separated by column chromatography using hexane and ethyl acetate as a developing solvent, and the solid was dried to give 37.5 g, 46.6% of <1-a>.

1-2. Synthesis of 1-b

<1-b> was synthesized according to Scheme 2 below.

Scheme 2

                                                              <1-b>

Into a 5000 ml round bottom flask, <1-a> obtained from the above reaction 1-1 was added, 1200 mL of ethyl ether was added thereto, stirred for 30 minutes under nitrogen, and the temperature of the reactant was lowered to -78 degrees. 592.3 ml (0.948 mol) of lithium are added dropwise over 1 hour. After stirring for 2 hours at the same temperature, 160.56 g (0.940 mol) of 4-bromo toluene dissolved in tetrahydrofuran was added dropwise for 30 minutes, followed by stirring for 12 hours at room temperature, followed by a small amount of water. After stirring for 30 minutes, the solvent was distilled off under reduced pressure, the resulting solid was stirred in ethanol to remove the solid, filtered under reduced pressure, washed with water, ethanol and hexane and dried. 1200 ml of acetic acid was added to the dried material, and the mixture was slowly added dropwise to 120 ml of hydrochloric acid. The mixture was refluxed for 3 hours, cooled, filtered and the resulting solid was filtered under reduced pressure, washed with ethanol, and hexane and methylene chloride were used as a developing solvent. Column chromatography was used to dry the solid to give <1-b> 64.0 g, 81.7%.

1-3. Synthesis of 1-c

<1-C> was synthesized by the following Scheme 3.

Scheme 3

                                                              <1-c>

<1-b> 30.0 g (0.036 mol) obtained from the above reaction 1-2 was dissolved in 1200 ml of chloroform in a 2000 ml round bottom flask, and 6.5 g (0.036 mol) of N-bromosuciimide was slowly added thereto, followed by stirring at room temperature for 5 hours. Let's do it. After the reaction was completed, the organic layer was separated and concentrated under reduced pressure at room temperature, and then separated by column chromatography using hexane and methylene chloride as a developing solvent and dried to obtain <1-c> 31.8 g, 92% .

1-4. Synthesis of 1-d

<1-d> was synthesized according to Scheme 4 below.

Scheme 4

                                                             <1-d>

<1-c> 31.8 g (0.035 mol), bis (pinacorato) diboron 13.4 g (0.053 mol), PdCl ₂ (dppf) 0.865 g (0.001 mol) from reaction 1-3 in 500 ml round bottom flask Add 8.00 g (0.106 mol) of potassium acetate and 320 ml of toluene and reflux for 12 hours. When the reaction is completed, the temperature is lowered to room temperature and extraction is performed using toluene and water. The organic layer was concentrated under reduced pressure, and then separated by column chromatography using hexane and methylene chloride as a developing solvent, and the solid was dried to give 17.5 g and 52.3% of <1-d>.

1-5. Synthesis of Compound of Formula 10

Formula 10 was synthesized according to Scheme 5 below.

Scheme 5

                                                               Formula 10

In a 250 ml round bottom flask, <1-d> 5.3 g (0.006 mol) obtained from the above reactions 1-4, 1.2 g (0.005 mol) bromo bipyridine, 0.12 g (0.1 mmol) tetrakistriphenylphosphine palladium and carbonic acid To 1.4 g (0.01 mol) of potassium, add 60 ml of tetrahydrofuran, 60 ml of toluene and 20 ml of water and reflux for 12 hours. After the reaction is completed, the temperature is reduced to room temperature, and extraction is performed using toluene and water. The organic layer was concentrated under reduced pressure, hexane and ethyl acetate were used as a developing solvent, and the residue was separated by column chromatography, and the solid was dried to obtain 3.2 g of Chemical Formula 10, 64.1%.

¹ H NMR (300 MHz, CDCl ₃ ): σ 8.70 (d, 2H), 7.60-7.80 (m, 6H), 7.40 (d, 1H), 6.90-7.10 (m, 18H), 6.60-6.80 (m, 12H ), 2.50 (s, 12H), 2.40 (s, 6H)

MS (MALDI-TOF): m / z 975.5 [M] ⁺

2. Synthesis Example: Synthesis of Compound of Formula 8

2-1. Synthesis of Formula 8

Formula 8 was synthesized according to Scheme 6 below.

Scheme 6

                                                               Formula 8

In a 250 ml round bottom flask, <1-d> 5.8 g (0.006 mol) obtained from the above reactions 1-4, 1.5 g (0.005 mol) of chlorodiphenyltriazine, 0.13 g (0.1 mmol) of tetrakistriphenylphosphine palladium and To 1.5 g (0.01 mol) of potassium carbonate, add 60 ml of tetrahydrofuran, 60 ml of toluene and 20 ml of water and reflux for 12 hours. After the reaction is completed, the temperature is reduced to room temperature, and extraction is performed using toluene and water. The organic layer was concentrated under reduced pressure, separated by column chromatography using methylene chloride and acetone, and dried to obtain 3.3 g of 60.2% of a solid.

¹ H NMR (300MHz, CDCl ₃ ): σ 8.50 (d, 4H), 8.2 (s, 2H), 7.45-7.60 (m, 6H), 7.05-7.15 (m, 4H), 6.85-7.00 (m, 14H ), 6.60-6.80 (m, 12H), 2.40 (s, 12H), 2.30 (s, 6H)

MS (MALDI-TOF): m / z 1052.5 [M] ⁺

Synthetic example  3. Formula 73  Synthesis of Compound

3-1. Synthesis of 3-a

<3-a> was synthesized according to the following Scheme 7.

Scheme 7

                                                              <3-a>

25.00 g (0.165 mol) methyl-2-aminobenzoate, 52.01 g (0.198 mol) methyl-2-iodobenzoate, 1.05 g (0.017 mol) copper, 1.57 g (0.008 mol) iodo copper in a 500 ml round bottom flask ) 200 ml of diphenyl ether was added to 27.43 g (0.198 mol) of potassium carbonate, followed by stirring at 190 degrees for 48 hours. When the reaction was completed, the resultant was filtered and separated by column chromatography using hexane and ethyl acetate as the developing solvent and dried to give 28.3 g, 60.0% of <3-a>.

3-2. Synthesis of 3-b

<3-b> was synthesized according to Scheme 8 below.

Scheme 8

                                                    <3-b>

In a 500 ml round bottom flask, <3-a> 28.0 g (0.098 mol) obtained from Reaction 3-1, 27.45 g (0.118 mol) 4-bromobiphenyl, 0.62 g (0.010 mol) copper powder, 0.93 copper iodide 200 ml of diphenyl ether was added to g (0.005 mol) and 16.28 g (0.118 mol) of potassium carbonate, followed by stirring at 190 degrees for 48 hours. When the reaction was completed, the mixture was filtered and separated by column chromatography using hexane and ethyl acetate as the developing solvent and dried to give 31.5 g, 73.4% of <3-b>.

3-3. Synthesis of 3-c

<3-c> was synthesized by the following Scheme 9.

Scheme 9

                                                           <3-c>

<2b> 31.0 g (0.071 mol) obtained from Reaction 3-2 was added to a 5000 ml round bottom flask, 1200 mL of ethyl ether was added thereto, stirred for 30 minutes under nitrogen, and the temperature of the reaction was -78 degrees. After falling down, 310.0 ml (0.496 mol) of 1.6 mol normal butyllithium was added dropwise for 1 hour. After stirring for 2 hours at the same temperature, 84.83 g (0.496 mol) of 4-bromo toluene dissolved in tetrahydrofuran was added dropwise for 30 minutes, followed by stirring at room temperature for 12 hours, and a small amount of water was added thereto. After stirring for 30 minutes, the solvent was distilled off under reduced pressure, the resulting solid was stirred in ethanol to remove the solid, filtered under reduced pressure, washed with water, ethanol and hexane and dried. 1200 ml of acetic acid was added to the dried material, and the mixture was slowly added dropwise to 120 ml of hydrochloric acid. The mixture was refluxed for 3 hours. The mixture was stirred under cold water, filtered and washed under reduced pressure. Column chromatography was used to dry the solid to give <3-c> to 38.7 g, 77.4%.

3-4. Synthesis of 3-d

<3-d> was synthesized according to Scheme 10 below.

Scheme 10

                                                             <3-d>

Dissolve 38.0 g (0.054 mol) of <2-c> obtained in the above reaction 3-3 in 1200 ml of chloroform and slowly add 9.58 g (0.054 mol) of N-bromosuciimide to a 2000 ml round bottom flask, and stir at room temperature for 5 hours. Let's do it. After the reaction was completed, the solution was concentrated under reduced pressure by separating the organic layer at room temperature, and then separated by column chromatography using hexane and methylene chloride as a developing solvent, and dried to give 37.6 g (89%) of <3-d>. Got it.

3-5. Synthesis of 3-e

<3-e> was synthesized according to Scheme 11 below.

Scheme 11

                                                           <3-e>

In a 500 ml round bottom flask, <3-d> 37.0 g (0.047 mol) obtained from the above reaction 3-4, 18.0 g (0.071 mol) of bis (pinacorato) diboron, 1.155 g (0.001 mol) PdCl ₂ (dppf) Add 10.71 g (0.141 mol) of potassium acetate and 370 ml of toluene and reflux for 12 hours. When the reaction is completed, the temperature is lowered to room temperature and extraction is performed using toluene and water. The organic layer was concentrated under reduced pressure, hexane and methylene chloride were used as a developing solvent, and the residue was separated by column chromatography, and the solid was dried to give 18.2 g and 46.4% of <3-e>.

3-6. Synthesis of Compound of Formula 73

Formula 73 was synthesized according to Scheme 12 below.

Scheme 12

                                                           Formula 73

In a 250 ml round bottom flask, <1-d> 9.7 g (0.011 mol) obtained from reaction 3-5, bromo bipyridine 2.5 g (0.012 mol), tetrakistriphenylphosphine palladium 0.94 g (0.021 mmol) and carbonic acid To 2.9 g (0.01 mol) of potassium, add 60 ml of tetrahydrofuran, 60 ml of toluene and 20 ml of water and reflux for 12 hours. After the reaction is completed, the temperature is reduced to room temperature, and extraction is performed using toluene and water. The organic layer was concentrated under reduced pressure, hexane and ethyl acetate were used as a developing solvent, and the residue was separated by column chromatography, and the solid was dried to yield 4.8 g (52.5%) of Chemical Formula 73.

¹ H NMR (300 MHz, CDCl ₃ ): σ 8.70 (d, 2H), 8.50 (d, 2H), 7.90-8.00 (m, 2H), 7.40-7.50 (m, 8H), 7.00-7.20 (m, 18H ), 6.60-6.80 (m, 5H), 2.50 (s, 12H)

MS (MALDI-TOF): m / z 859.4 [M] ⁺

Synthetic example  4. Synthesis of Compound of Formula 71

Formula 71 was synthesized according to Scheme 13 below.

Scheme 13

                                                              Formula 71

In a 250 ml round bottom flask, <3-e> 7.5 g (0.009 mol) obtained from reaction 3-5, 2.2 g (0.008 mol) of chlorodiphenyltriazine, 0.19 g (0.2 mmol) of tetrakistriphenylphosphine palladium and To 2.3 g (0.016 mol) of potassium carbonate, add 60 ml of tetrahydrofuran, 60 ml of toluene and 20 ml of water and reflux for 12 hours. After the reaction is completed, the temperature is reduced to room temperature, and extraction is performed using toluene and water. The organic layer was concentrated under reduced pressure, and then separated by column chromatography using methylene chloride and acetone. The solid was dried to give 3.8 g (49.3%) of Chemical Formula 71.

¹ H NMR (300 MHz, CDCl ₃ ): σ 8.40 (d, 4H), 8.2 (s, 1H), 7.40-7.65 (m, 9H), 7.15-7.30 (m, 5H), 6.80-6.95 (m, 16H ), 6.60-6.75 (m, 5H), 2.40 (s, 12H)

MS (MALDI-TOF): m / z 936.4 [M] ⁺

Synthetic example  5. Synthesis of Compound of Formula 62

Compound 62 of compound 62 was synthesized using 1-chloro-3-diphenylamine-5-phenyl triazine in place of chlorodiphenyltriazine in Formula (2-1).

¹ H NMR (300 MHz, CDCl ₃ ): σ 8.45 (d, 2H), 8.1 (d, 2H), 7.40-7.50 (m, 3H), 7.10-7.20 (m, 4H), 6.85-7.00 (m, 24H ), 6.60-6.80 (m, 12H), 2.40 (s, 12H), 2.30 (s, 6H)

MS (MALDI-TOF): m / z 1143.5 [M] ⁺

Example Preparation of Organic Light Emitting Diode

The light emitting area of the ITO glass was patterned to have a size of 2 mm x mm and then washed. After mounting the substrate in a vacuum chamber, the base pressure is 1x10 ^-6 torr, and then the organic material is placed on the ITO, DNTPD (700 kPa), NPD (300 kPa), the condensed aromatic compound + Ir ( ppy) ₃ (10%) (300 Å), Alq ₃ (350 Å), LiF (5 Å), Al (1,000 Å) was formed in the order of, was measured at 0.4mA.

Comparative example

The organic light emitting diode device for the Comparative Example was manufactured in the same manner except that CBP was used instead of the compound prepared according to the Example in the device structure of the Example.

division Host Dopant Doping concentration% ETL V Cd / A CIEx CIEy Comparative Example 1 CBP Ir (ppy) 3 10 Alq3 7.2 36.24 0.29 0.62 Example 1 Compound8 Ir (ppy) 3 10 Alq3 3.45 41.61 0.32 0.61 Example 2 Compound 10 Ir (ppy) 3 10 Alq3 3.59 41.88 0.32 0.62 Example 3 Compound62 Ir (ppy) 3 10 Alq3 3.52 43.35 0.32 0.61 Example 4 Compound71 Ir (ppy) 3 10 Alq3 3.51 44.74 0.32 0.61 Example 5 Compound73 Ir (ppy) 3 10 Alq3 3.33 43.96 0.32 0.61

As shown in the above table, the organic compound secured by the present invention has a low driving voltage and excellent luminous efficiency as compared to CBP which is widely used as a phosphorescent material.

Claims (9)

Condensed aromatic compound represented by the following formula (1):
[Formula 1]

Where
R1 to R9 are each independently a hydrogen atom, a deuterium atom, a halogen atom, a substituted or unsubstituted arylamino group, a substituted or unsubstituted aryloxy group having 3 to 40 carbon atoms, a substituted or unsubstituted aryl group having 6 to 40 carbon atoms, substituted or It is selected from the group consisting of an unsubstituted heteroaryl group having 3 to 40 carbon atoms, germanium group, phosphorus, boron,
In this case, at least one or more of R7 to R9 is a substituted or unsubstituted heteroaryl group having 3 to 40 carbon atoms containing nitrogen,
Each X is independently C or S, which may be the same as or different from each other,
l, m and n are integers of 0 or 1, and l + m + n is at least two. The method of claim 1,
Wherein the adjacent functional groups combine with each other to form a saturated or unsaturated ring or a ring having a hetero atom. The method of claim 1,
R1 to R9 are hydrogen atom, deuterium atom, cyano group, halogen atom, hydroxy group, nitro group, C1-40 alkyl group, C1-40 alkoxy group, C1-40 alkylamino group, C6-40 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 40 heteroaryl group, germanium group, phosphorus, boron, the substituents may be bonded to each other to form a saturated or unsaturated ring, attached together by a pendant method or A condensed aromatic compound, characterized in that it can be fused. The method of claim 1,
A condensed aromatic compound, characterized in that any one compound selected from the group represented by the formula (2) to (79):

[Formula 2] [Formula 3] [Formula 4]

[Formula 5] [Formula 6] [Formula 7]

[Formula 8] [Formula 9] [Formula 10]

[Formula 11] [Formula 12] [Formula 13]

[Formula 14] [Formula 15] [Formula 16]

[Formula 17] [Formula 18] [Formula 19]

[Formula 20] [Formula 21] [Formula 22]

[Formula 23] [Formula 24] [Formula 25]

[Formula 26] [Formula 27] [Formula 28]

[Formula 29] [Formula 30] [Formula 31]

[Formula 32] [Formula 33] [Formula 34]

[Formula 35] [Formula 36] [Formula 37]

[Formula 38] [Formula 39] [Formula 40]

[Formula 41] [Formula 42] [Formula 43]

[Formula 44] [Formula 45] [Formula 46]

[Formula 47] [Formula 48] [Formula 49]

[Formula 50] [Formula 51] [Formula 52]

[Formula 53] [Formula 54] [Formula 55]

[Formula 56] [Formula 57] [Formula 58]

[Formula 59] [Formula 60] [Formula 61]

[Formula 62] [Formula 63] [Formula 64]

[Formula 65] [Formula 66] [Formula 67]

[Formula 68] [Formula 69] [Formula 70]

[Formula 71] [Formula 72] [Formula 73]

[Formula 74] [Formula 75] [Formula 76]

[Formula 77] [Formula 78] [Formula 79]
Anode; Cathode; And an layer interposed between the anode and the cathode, the layer comprising a condensed aromatic compound according to any one of claims 1 to 4. The method of claim 5,
The condensed aromatic compound is an organic light emitting device, characterized in that contained in the light emitting layer between the anode and the cathode. The method of claim 6,
The thickness of the light emitting layer is an organic light emitting device, characterized in that 50 to 2,000 kPa. The method of claim 6,
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 8,
At least one layer selected from the group consisting of the hole injection layer, the hole transport layer, the light emitting layer, the electron blocking layer, the hole blocking layer, the electron transport layer, and the electron injection layer is produced by a solution process.

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