KR101791023B1 - 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 the following general formula (1) and an organic electroluminescent device including the condensed aromatic compound. More particularly, the present invention relates to a condensed aromatic compound having a low driving voltage and excellent luminous efficiency when used in an organic electroluminescent device, And to provide an organic electroluminescent device.
[Chemical Formula 1]

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

Description

FIELD OF THE INVENTION [0001] The present invention relates to a condensed aromatic compound and an organic electroluminescent device including the same.

The present invention relates to a condensed aromatic compound and an organic electroluminescent device including the condensed aromatic compound and, more particularly, to a condensed aromatic compound having a low driving voltage and excellent luminous efficiency when used in an organic electroluminescent device and an organic electroluminescent device including the condensed aromatic compound .

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.

Generally, an organic light emitting phenomenon refers to a phenomenon in which an electric energy is converted into light energy by using an organic material. An organic light emitting device using an organic light emitting phenomenon typically has a structure including an anode, an anode, and an organic layer between the anode and the cathode. 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 a condensed aromatic compound having a low driving voltage and an excellent luminous efficiency when used in an organic electroluminescent device.

A second object of the present invention is to provide an organic electroluminescent device comprising the condensed aromatic compound.

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

[Chemical Formula 1]

In this formula,

R ₁ to R ₉ each independently represent 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, A substituted or unsubstituted heteroaryl group having 3 to 40 carbon atoms, a germanium group, phosphorus, boron,

At least one of R ₇ to R ₉ is a substituted or unsubstituted heteroaryl group having 3 to 40 carbon atoms including nitrogen,

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

l, m and n are integers of 0 or 1, and l + m + n is at least 2 or more.

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

According to another embodiment of the present invention, R ₁ to R _{9 each} represent a hydrogen atom, a deuterium atom, a cyano group, a halogen atom, a hydroxyl group, a nitro group, an alkyl group having 1 to 40 carbon atoms, an alkoxy group having 1 to 40 carbon atoms, An aryloxy group having 6 to 40 carbon atoms, an arylamino group having 6 to 40 carbon atoms, a heteroarylamino group having 3 to 40 carbon atoms, an alkylsilyl group having 1 to 40 carbon atoms, an arylsilyl group having 6 to 40 carbon atoms, an aryl group having 6 to 40 carbon atoms, An aryloxy group having 3 to 40 carbon atoms, a heteroaryl group having 3 to 40 carbon atoms, a germanium group, phosphorus, or boron, and the substituents may be bonded to each other to form a saturated or unsaturated ring And can be attached together or fused by a pendant method.

In order to solve the second technical problem, the present invention provides a semiconductor device comprising: an anode; Cathode; And a layer containing a condensed aromatic compound represented by Formula 1 interposed between the anode and the cathode.

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

The organic electroluminescent device comprising the condensed aromatic compound represented by the formula (1) according to the present invention in the organic material layer can be used for display and illumination because of low driving voltage and excellent luminous efficiency.

1 is a schematic view of an organic electroluminescent device according to one embodiment of the present invention.
2 is a chemical structure showing a representative structure of the condensed aromatic compound according to 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 condensed aromatic compound according to the present invention is characterized by being represented by the following general formula (1).

[Chemical Formula 1]

In this formula,

Each of R 1 to R 9 independently represents 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, An unsubstituted heteroaryl group having 3 to 40 carbon atoms, a germanium group, phosphorus, and boron,

At least one of R 7 to R 9 is a substituted or unsubstituted heteroaryl group having 3 to 40 carbon atoms including nitrogen,

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

l, m and n are integers of 0 or 1, and l + m + n is at least 2 or more.

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

According to another embodiment of the present invention, R 1 to R 9 each independently represent 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, An arylamino group having 6 to 40 carbon atoms, a heteroarylamino group having 3 to 40 carbon atoms, an alkylsilyl group having 1 to 40 carbon atoms, an arylsilyl group having 6 to 40 carbon atoms, an aryl group having 6 to 40 carbon atoms, An aryloxy group having 3 to 40 carbon atoms, a heteroaryl group having 3 to 40 carbon atoms, a germanium group, phosphorus, or boron, and the substituents may be bonded to each other to form a saturated or unsaturated ring And may be attached together or fused by a pendant method.

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

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 " (R '), wherein R, R' and R "are each independently a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms 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, an alkylamino 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, 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 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.

The condensed aromatic compound according to the present invention may be any one of the compounds represented by the following formulas (2) to (79).

[Chemical Formula 2] < EMI ID =

[Chemical Formula 5] < EMI ID =

[Chemical Formula 8]

[Chemical Formula 12] [Chemical Formula 13]

[Chemical Formula 14]

[Chemical Formula 18] [Chemical Formula 19]

[Chemical Formula 20]

[Chemical Formula 23] [Chemical Formula 25]

[Chemical Formula 26]

[Chemical Formula 30] [Chemical Formula 30]

[Chemical Formula 32]

[Chemical Formula 35]

[Chemical Formula 38] [Chemical Formula 39]

[Chemical Formula 41]

[Chemical Formula 45]

[Chemical Formula 48] [Chemical Formula 48]

[Chemical Formula 50] [Chemical Formula 51]

[Chemical Formula 55] [Chemical Formula 55]

[Chemical Formula 57] [Chemical Formula 58]

[Chemical Formula 60] [Chemical Formula 61]

[Chemical Formula 62]

[Chemical Formula 65]

[Chemical Formula 70] [Chemical Formula 70]

[Chemical Formula 71] [Chemical Formula 72]

[Chemical Formula 75] [Chemical Formula 75]

[Formula 77] [Formula 79]

The present invention also relates to a fuel cell comprising an anode; Cathode; And a layer containing a condensed aromatic compound represented by Formula 1 interposed between the anode and the cathode.

The layer containing the condensed aromatic 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, and an electron injecting layer are provided between the anode and the cathode And at least one layer selected from the group consisting of

According to another embodiment of the present invention, the thickness of the light emitting layer is preferably 50 to 2,000 ANGSTROM.

According to another embodiment of the present invention, 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 may further be interposed between the anode and the cathode At this time, any one or more layers selected from the group consisting of a hole injecting layer, a hole transporting layer, a light emitting layer, an electron blocking layer, a hole blocking layer, an electron transporting layer and an electron injecting layer may be prepared by a solution process.

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, according to another embodiment of the present invention, the thickness of the light emitting layer is preferably 50 to 2,000 ANGSTROM, 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 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.

<Examples>

Synthesis Example 1 Synthesis of Compound (10)

1-1. Synthesis of Formula 1-a

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

[Reaction Scheme 1]

                                                           <1-a>

To a 500 ml round bottom flask was added 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, mol) and potassium carbonate (61.00 g, 0.44 mol) were added 240 ml of diphenyl ether, and the mixture was stirred at 190 ° C for 48 hours. When the reaction was completed, the reaction mixture was filtered under reduced pressure, and the residue was purified by column chromatography using hexane and ethyl acetate as eluent. The solids were dried to obtain 37.5 g of <1-a>, 46.6%.

1-2. Synthesis of 1-b

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

[Reaction Scheme 2]

                                                              <1-b>

<1-a> obtained from the above reaction 1-1 was added to a 5000 ml round-bottomed flask, 1200 mL of ethyl ether was added thereto, and the mixture was stirred for 30 minutes under a nitrogen atmosphere. The reaction temperature was lowered to -78 ° C., 592.3 ml (0.948 mol) of lithium are added dropwise for 1 hour. After stirring at the same temperature for 2 hours, 160.56 g (0.940 mol) of 4-bromotoluene dissolved in tetrahydrofuran was added dropwise for 30 minutes, stirred at room temperature for 12 hours, and then a small amount of water was added. After stirring for 30 minutes, the solvent was distilled off under reduced pressure, and the resulting solid was stirred in ethanol, which was then quenched under reduced pressure, washed with water, ethanol and hexane, and dried. To the dried material, 1200 ml of acetic acid was added, and 120 ml of hydrochloric acid was slowly added dropwise thereto. The mixture was refluxed for 3 hours, and cold water was added thereto. After stirring, the resulting solid was filtered under reduced pressure and washed with ethanol and washed with hexane and methylene chloride , And the solid was dried to obtain 64.0 g of <1-b>, 81.7%.

1-3. Synthesis of 1-c

&Lt; 1-c > was synthesized by the following Reaction Scheme 3.

[Reaction Scheme 3]

                                                              <1-c>

In a 2000 ml round-bottomed flask, 30.0 g (0.036 mol) of <1-b> obtained from the above reaction 1-2 was dissolved in 1200 ml of chloroform, 6.5 g (0.036 mol) of N-bromosuccinimide was added slowly and the mixture was stirred at room temperature for 5 hours . After completion of the reaction, the organic layer was separated from the solution at room temperature, and the filtrate was concentrated under reduced pressure. The residue was purified by column chromatography using hexane and methylene chloride as eluent to obtain 31.8 g (92%) of <1-c> .

1-4. Synthesis of 1-d

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

[Reaction Scheme 4]

                                                             <1-d>

31.8 g (0.035 mol) of <1-c>, 13.4 g (0.053 mol) of bis (pinacolato) diboron and 0.865 g (0.001 mol) of PdCl ₂ (dppf) obtained in the above reaction 1-3 were added to a 500- , 8.00 g (0.106 mol) of potassium acetate and 320 ml of toluene, and the mixture is refluxed for 12 hours. When the reaction is completed, the temperature is lowered to room temperature and extracted with toluene and water. The organic layer was concentrated under reduced pressure, and then hexane and methylene chloride were separated by column chromatography. The solids were dried to obtain <1-d> of 17.5 g and 52.3%.

1-5. Synthesis of Compound (10)

(10) was synthesized according to Reaction Scheme 5 below.

[Reaction Scheme 5]

                                                               10

In a 250 ml round-bottomed flask were added 5.3 g (0.006 mol) of <1-d>, 1.2 g (0.005 mol) of bromobipyridine and 0.12 g (0.1 mmol) of tetrakistriphenylphosphine palladium, 60 ml of tetrahydrofuran, 60 ml of toluene and 20 ml of water are added to 1.4 g (0.01 mol) of potassium and the mixture is refluxed for 12 hours. After completion of the reaction, the temperature is lowered to room temperature and extraction is carried out using toluene and water. The organic layer was concentrated under reduced pressure, and the residue was purified by column chromatography using hexane and ethyl acetate as eluent. The solid was dried to obtain 3.2 g (64.1%) of the compound of formula (10).

¹ H NMR (300 MHz, CDCl ₃ ):? 8.70 (m, 2H), 7.60-7.80 (m, 6H), 7.40 ), 2.50 (s, 12H), 2.40 (s, 6H)

MS (MALDI-TOF): m / z 975.5 [M] ^&lt; ⁺ & gt ^;

2. Synthesis Example: Synthesis of Compound (8)

2-1. Synthesis of Formula 8

(8) was synthesized according to Reaction Scheme 6 below.

[Reaction Scheme 6]

                                                               8

5.8 g (0.006 mol) of <1-d>, 1.5 g (0.005 mol) of chlorodiphenyltriazine and 0.13 g (0.1 mmol) of tetrakistriphenylphosphine palladium obtained in Reaction 1-4 were added to a 250 ml round- 60 ml of tetrahydrofuran, 60 ml of toluene and 20 ml of water are added to 1.5 g (0.01 mol) of potassium carbonate, and the mixture is refluxed for 12 hours. After completion of the reaction, the temperature is lowered to room temperature and extraction is carried out 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 obtain 3.3 g of the compound of Formula 10 (60.2%).

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

MS (MALDI-TOF): m / z 1052.5 [M] ^&lt; ⁺ & gt ^;

Synthetic example  3. The compound of formula  Synthesis of compounds

3-1. Synthesis of 3-a

&Lt; 3-a > was synthesized according to the following Reaction Scheme 7 below.

[Reaction Scheme 7]

                                                              <3-a>

To a 500 ml round bottom flask was added 25.00 g (0.165 mol) of methyl-2-aminobenzoate, 52.01 g (0.198 mol) of methyl-2-iodobenzoate, 1.05 g (0.017 mol) ) To 27.43 g (0.198 mol) of potassium carbonate, 200 ml of diphenyl ether was added and the mixture was stirred at 190 ° C for 48 hours. After the completion of the reaction, the reaction mixture was filtered, separated by column chromatography using hexane and ethyl acetate as eluent, and the solid was dried to obtain 28.3 g (60.0%) of <3-a>.

3-2. Synthesis of 3-b

<3-b> was synthesized according to the following Reaction Scheme 8:

[Reaction Scheme 8]

                                                    <3-b>

28.0 g (0.098 mol) of <3-a> obtained in the above reaction 3-1, 27.45 g (0.118 mol) of 4-bromobiphenyl, 0.62 g (0.010 mol) of copper powder and 0.93 g g (0.005 mol) of potassium carbonate, 16.28 g (0.118 mol) of potassium carbonate, and the mixture was stirred at 190 DEG C for 48 hours. After the completion of the reaction, the reaction mixture was filtered, separated by column chromatography using hexane and ethyl acetate as eluent, and the solid was dried to obtain 31.5 g (73.4%) of <3-b>.

3-3. Synthesis of 3-c

<3-c> was synthesized according to the following Reaction Scheme 9.

[Reaction Scheme 9]

                                                           <3-c>

Then, 31.0 g (0.071 mol) of <2-b> obtained from the above reaction 3-2 was added to a 500 ml round-bottomed flask, 1200 mL of ethyl ether was added thereto and stirred for 30 minutes under a nitrogen atmosphere. , And then 310.0 ml (0.496 mol) of 1.6 mol of n-butyllithium was added dropwise for 1 hour. After stirring at the same temperature for 2 hours, 84.83 g (0.496 mol) of 4-bromotoluene dissolved in tetrahydrofuran was added dropwise for 30 minutes, stirred at room temperature for 12 hours, and a small amount of water was added. After stirring for 30 minutes, the solvent was distilled off under reduced pressure, and the resulting solid was stirred in ethanol, which was then quenched under reduced pressure, washed with water, ethanol and hexane, and dried. To the dried material, 1200 ml of acetic acid was added, and 120 ml of hydrochloric acid was slowly added dropwise thereto. The mixture was refluxed for 3 hours, and cold water was added thereto. After stirring, the resulting solid was filtered under reduced pressure and washed with ethanol and washed with hexane and methylene chloride , And the solid was dried to obtain 38.7 g (77.4%) of <3-c>.

3-4. Synthesis of 3-d

&Lt; 3-d > was synthesized according to Reaction Scheme 10 below.

[Reaction Scheme 10]

                                                             <3-d>

In a 2000 ml round-bottomed flask, 38.0 g (0.054 mol) of <2-c> obtained from the above reaction 3-3 was dissolved in 1200 ml of chloroform, 9.58 g (0.054 mol) of N-bromosuccinimide was added slowly and stirred at room temperature for 5 hours . After the reaction was completed, the organic layer was separated from the solution at room temperature, and the residue was purified by column chromatography using hexane and methylene chloride as a developing solvent. The solids were dried to obtain 37.6 g of <3-d> .

3-5. Synthesis of 3-e

<3-e> was synthesized according to the following Reaction Scheme 11.

[Reaction Scheme 11]

                                                           <3-e>

37.0 g (0.047 mol) of <3-d>, 18.0 g (0.071 mol) of bis (pinacolato) diboron and 1.155 g (0.001 mol) of PdCl ₂ (dppf) obtained from the above reaction 3-4 were added to a 500 ml round- , 10.71 g (0.141 mol) of potassium acetate and 370 ml of toluene, and the mixture is refluxed for 12 hours. When the reaction is completed, the temperature is lowered to room temperature and extracted with toluene and water. The organic layer was concentrated under reduced pressure, followed by separation by column chromatography using hexane and methylene chloride as developing solvents, and the solid was dried to obtain 18.2 g (46.4%) of <3-e>.

3-6. Synthesis of compound of formula (73)

(73) was synthesized according to the following Reaction Scheme 12.

[Reaction Scheme 12]

                                                           Formula 73

In a 250 ml round-bottomed flask was added 9.7 g (0.011 mol) of <1-d>, 2.5 g (0.012 mol) of bromobipyridine, 0.94 g (0.021 mmol) of tetrakistriphenylphosphine palladium, 60 ml of tetrahydrofuran, 60 ml of toluene and 20 ml of water are added to 2.9 g (0.01 mol) of potassium and refluxed for 12 hours. After completion of the reaction, the temperature is lowered to room temperature and extraction is carried out using toluene and water. The organic layer was concentrated under reduced pressure, and then separated by column chromatography using hexane and ethyl acetate as eluent. The solid was dried to obtain 4.8 g (52%) of compound (73).

_{^{1 H NMR (300MHz, 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] ^&lt; ^{+ &}

Synthetic example  4. Synthesis of Compound (71)

(71) was synthesized according to the following Reaction Scheme 13

[Reaction Scheme 13]

                                                              71

7.5 g (0.009 mol) of <3-e>, 2.2 g (0.008 mol) of chlorodiphenyltriazine and 0.19 g (0.2 mmol) of tetrakistriphenylphosphine palladium obtained in the above reaction 3-5 were added to a 250 ml round- 60 ml of tetrahydrofuran, 60 ml of toluene and 20 ml of water are added to 2.3 g (0.016 mol) of potassium carbonate, and the mixture is refluxed for 12 hours. After completion of the reaction, the temperature is lowered to room temperature and extraction is carried out 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 obtain the compound of Formula 71 (3.8 g, 49.3%).

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

MS (MALDI-TOF): m / z 936.4 [M] ^&lt; ⁺ & gt ^;

Synthetic example  5. Synthesis of Compound (62)

Compound (62) was synthesized by using 1-chloro-3-diphenylamine-5-phenyltriazine instead of chlorodiphenyltriazine in the above formula (2-1).

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

MS (MALDI-TOF): m / z 1143.5 [M] ^&lt; ^{+ &}

Example: Preparation of organic light emitting diode

The ITO glass was patterned to have a light emitting area of 2 mm x mm and then cleaned. After the substrate was mounted in a vacuum chamber and the base pressure was adjusted to ¹ × 10 ^-6 torr, an organic material was added to the ITO by DNTPD (700 Å), NPD (300 Å), the condensed aromatic compound according to the present invention + Ir ppy) ₃ (10%) (300 Å), Alq ₃ (350 Å), LiF (5 Å) and Al (1,000 Å).

Comparative Example

The organic light emitting diode device for the comparative example was fabricated in the same manner except that CBP was used instead of the compound prepared according to the above embodiment in the device structure of the above embodiment.

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 Compound 8 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 Compound 62 Ir (ppy) 3 10 Alq3 3.52 43.35 0.32 0.61 Example 4 Compound 71 Ir (ppy) 3 10 Alq3 3.51 44.74 0.32 0.61 Example 5 Compound 73 Ir (ppy) 3 10 Alq3 3.33 43.96 0.32 0.61

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

Claims (9)

A condensed aromatic compound represented by the following formula (1)
[Chemical Formula 1]

In this formula,
Each of R 1 to R 6 is independently a substituted or unsubstituted aryl group having 6 to 40 carbon atoms,
R 7 to R 9 are each independently selected from a hydrogen atom, a deuterium atom, a halogen atom, a substituted or unsubstituted aryl group having 6 to 40 carbon atoms, and a substituted or unsubstituted heteroaryl group having 3 to 40 carbon atoms,
At least one of R 7 to R 9 is a substituted or unsubstituted 6-membered heteroaryl group containing nitrogen,
X is C,
l, m and n are integers of 0 or 1, and l + m + n is at least 2 or more. delete The method according to claim 1,
A halogen atom, a cyano group, a halogen atom, a hydroxyl group, a nitro group, an alkyl group having 1 to 40 carbon atoms, or a substituted or unsubstituted alkyl group having 1 to 40 carbon atoms, provided that R 1 to R 9 , An alkoxy group having 1 to 40 carbon atoms, an arylamino group having 6 to 40 carbon atoms, an aryl group having 6 to 40 carbon atoms, and a heteroaryl group having 3 to 40 carbon atoms. Condensed aromatic compound. The method according to claim 1,
A condensed aromatic compound represented by any one of the following formulas (2) to (79):

[Chemical Formula 2] &lt; EMI ID =

[Chemical Formula 5] &lt; EMI ID =

[Chemical Formula 8]

[Chemical Formula 12] [Chemical Formula 13]

[Chemical Formula 14]

[Chemical Formula 18] [Chemical Formula 19]

[Chemical Formula 20]

[Chemical Formula 23] [Chemical Formula 25]

[Chemical Formula 26]

[Chemical Formula 30] [Chemical Formula 30]

[Chemical Formula 32]

[Chemical Formula 35]

[Chemical Formula 38] [Chemical Formula 39]

[Chemical Formula 41]

[Chemical Formula 45]

[Chemical Formula 48] [Chemical Formula 48]

[Chemical Formula 50] [Chemical Formula 51]

[Chemical Formula 55] [Chemical Formula 55]

[Chemical Formula 57] [Chemical Formula 58]

[Chemical Formula 60] [Chemical Formula 61]

[Chemical Formula 62]

[Chemical Formula 65]

[Chemical Formula 70] [Chemical Formula 70]

[Chemical Formula 71] [Chemical Formula 72]

[Chemical Formula 75] [Chemical Formula 75]

[Formula 77] [Formula 79]
Anode; Cathode; And a layer interposed between the anode and the cathode, the layer including the condensed aromatic compound according to claim 1. 6. The method of claim 5,
Wherein the condensed aromatic compound is contained in the light emitting layer between the anode and the cathode. The method according to claim 6,
Wherein the thickness of the light emitting layer is 50 to 2,000 ANGSTROM. The method according to claim 6,
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. 9. The method of claim 8,
Wherein at least one layer selected from the group consisting of the hole injecting layer, the hole transporting layer, the light emitting layer, the electron blocking layer, the hole blocking layer, the electron transporting layer and the electron injecting layer is prepared by a solution process.

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