KR101996650B1 - New compounds and organic light-emitting diode including the same - Google Patents

Abstract

The present invention relates to a condensed aryl compound and an organic electroluminescent device comprising the same as a light emitting material, and more particularly to a condensed aryl compound represented by the following formula (1) and an organic electroluminescent device including the condensed aryl compound. The organic electroluminescent device comprising the luminescent compound of the following formula (1) according to the present invention has an excellent effect on the luminescent characteristics such as the driving voltage and the current efficiency.
[Chemical Formula 1]

Description

TECHNICAL FIELD The present invention relates to a condensed aryl compound and an organic electroluminescent device including the same,

The present invention relates to a condensed aryl compound and an organic electroluminescent device comprising the same as a light emitting material. More particularly, the present invention relates to a condensed aryl compound and organic electroluminescent Device.

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 and has a wide viewing angle and can be made thinner and thinner 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 required to realize 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 can be used as a 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, the light of the desired wavelength can be obtained according to the type of the 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.

Accordingly, a first object of the present invention is to provide a condensed aryl compound having a low driving voltage and a high luminous efficiency.

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

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

[Chemical Formula 1]

In the above formula (1)

The plurality of R's are the same or different from each other and each independently represents a hydrogen atom, a deuterium atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted alkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted carbon number A substituted or unsubstituted C2 to C30 alkenyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C5 to C30 cycloalkenyl group, a substituted or unsubstituted C1 to C30 alkoxy group, A substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms, a substituted or unsubstituted arylthioxy group having 5 to 30 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms An amino group, a substituted or unsubstituted arylamine group having 5 to 30 carbon atoms, a substituted or unsubstituted aryl group having 5 to 50 carbon atoms, a substituted or unsubstituted heteroatom having O, N or S A substituted or unsubstituted aryl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryl group, A halogen group, an amide group, and an ester group, and the plurality of Rs may form a condensed ring of an aliphatic, aromatic, aliphatic hetero or aromatic hetero with groups adjacent to each other.

According to another aspect of the present invention,

There is provided an organic electroluminescent device comprising an anode, a cathode, and a condensed aryl compound interposed between the anode and the cathode, the condensed aryl compound being represented by Formula 1 below.

According to the present invention, the condensed aryl compound represented by the formula (1) has stable and excellent luminescent characteristics as compared with the existing materials, so that the organic electroluminescent device including the condensed aryl compound can be operated at a low voltage and improve the luminous efficiency.

1 is a schematic view of an organic electroluminescent device according to one embodiment of the present invention.

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

The present invention relates to a condensed aryl compound contained in a light emitting layer of an organic electroluminescent device, which is a compound represented by the following formula (1), wherein the substituent is more specifically described below.

[Chemical Formula 1]

In the above formula (1)

The plurality of R's are the same or different from each other and each independently represents a hydrogen atom, a deuterium atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted alkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted carbon number A substituted or unsubstituted C2 to C30 alkenyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C5 to C30 cycloalkenyl group, a substituted or unsubstituted C1 to C30 alkoxy group, A substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms, a substituted or unsubstituted arylthioxy group having 5 to 30 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms An amino group, a substituted or unsubstituted arylamine group having 5 to 30 carbon atoms, a substituted or unsubstituted aryl group having 5 to 50 carbon atoms, a substituted or unsubstituted heteroatom having O, N or S A substituted or unsubstituted aryl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryl group, A halogen group, an amide group, and an ester group, and the plurality of Rs may form a condensed ring of an aliphatic, aromatic, aliphatic hetero or aromatic hetero with groups adjacent to each other.

The above-mentioned formula (1) may be any one selected from the group consisting of the following formulas (2) to (6).

[Chemical Formula 2] < EMI ID =

[Chemical Formula 4]

[Chemical Formula 6]

In the above formulas 2 to 6,

The plurality of R's are the same as defined in the above formula (1), the plurality of X's are the same or different from each other and each independently represents a substituted or unsubstituted C6-C40 aryl group, a substituted or unsubstituted C2- 40 heteroaryl group is selected from substituted or unsubstituted C 1 -C 20 alkyl group and a substituted or unsubstituted group consisting of cycloalkyl group having 6 to 40 carbon atoms of, wherein Ar ₁ and Ar ₂ are the same or different and are each independently A substituted or unsubstituted aryl group having 6 to 40 carbon atoms, and a substituted or unsubstituted heteroaryl group having 2 to 40 carbon atoms.

In the present invention, the term "substituted or unsubstituted" means a group selected from the group consisting of a cyano group, a halogen group, a hydroxyl group, a nitro group, an alkyl group, an alkoxy group, an alkylamino group, an arylamino group, a heteroarylamino group, an alkylsilyl group, Substituted or unsubstituted with at least one substituent selected from the group consisting of an oxygen atom, an aryl group, a heteroaryl group, germanium, phosphorus, boron, hydrogen and deuterium.

The present invention is not limited by the specific examples of the novel condensed aryl compound according to the above formula (1) having the above-mentioned structure, but specifically, among the compounds represented by the following formulas (8) to It can be either.

&Lt; Formula 8 > < EMI ID = 10.0 >

&Lt; Formula 13 > < EMI ID = 15.0 >

&Lt; Formula 18 > < EMI ID = 19.0 >

&Lt; Formula 23 > < EMI ID = 25.0 >

&Lt; Formula 28 > < EMI ID = 31.0 >

(35), (36), (37), (38), (39)

&Lt; Formula 40 > < EMI ID = 41.0 >

&Lt; Formula 46 > < EMI ID = 48.0 >

(52), (53), (54), (55), (56),

<Formula 58> <Formula 59> <Formula 60> <Formula 61> <Formula 62>

&Lt; Formula 64 > < EMI ID =

<Formula 68> <Formula 69> <Formula 70> <Formula 71>

&Lt; Formula 72 > < EMI ID = 73.1 >

&Lt; Formula 76 > < EMI ID = 77.0 >

<Formula 80> <Formula 81> <Formula 82> <Formula 83>

&Lt; Formula 84 > < EMI ID =

&Lt; Formula 88 > < EMI ID = 89.0 >

&Lt; EMI ID = 93.1 >

&Lt; Formula 97 > < EMI ID = 97.0 >

&Lt; Formula 100 > < EMI ID = 101.0 >

&Lt; EMI ID = 106.1 >

<Formula 108> <Formula 109> Formula 110 <Formula 111>

<Formula 112> <Formula 113> <Formula 114>

&Lt; EMI ID = 116.1 >

&Lt; Formula 120 > < EMI ID =

&Lt; Formula 125 > < EMI ID = 124.1 >

&Lt; EMI ID = 129.1 > < EMI ID =

(133), (134), (135), (136), (137)

&Lt; EMI ID = 141.0 > < EMI ID =

<Formula 143> Formula 144> Formula 145> Formula 146> Formula 147>

<Formula 148> <Formula 149> <Formula 150> <Formula 151> <Formula 152>

<Formula 153> <Formula 154> <Formula 155> <Formula 156>

&Lt; EMI ID = 158.1 >< EMI ID =

Further, the present invention provides an organic electroluminescent device comprising an anode, a cathode, and a condensed aryl compound interposed between the anode and the cathode and represented by the formula (1).

In this case, the layer containing the novel 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 And at least one layer 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 ANGSTROM, and the light emitting layer may further include various phosphorescent host materials.

As a specific example, a hole transport layer (HTL) may be further stacked, and an electron transport layer (ETL) may be further stacked between the cathode and the organic 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 hole injection layer (HIL) may be additionally formed 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-methylphenylphenyl amino) triphenylamine) can be used.

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.

The organic electroluminescent device of the present invention and its manufacturing method will be described with reference to FIG. 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, the present invention will be described in more detail with reference to preferred embodiments. It will be apparent, however, to those skilled in the art that these embodiments are for further explanation of the present invention and that the scope of the present invention is not limited thereby.

<Examples>

Synthesis Example 1. Synthesis of [Formula 8]

1- (1) Synthesis of intermediate 1-a

Intermediate 1-a was synthesized according to Reaction Scheme 1 below.

<Reaction Scheme 1>

Intermediate 1-a

(0.5 g, 1 mmol), Pd (PPh3) 4 (0.5 g, 1 mmol) were added to 50 mL of triethylamine and the mixture was stirred well at room temperature (3.6 mL, 35 mmol) was added slowly. After stirring for about 1 hour at room temperature, 300 mL of hexane was added to terminate the reaction. The whole solution was passed through silica gel to separate the product, and the column was further drained with 500 mL of hexane. The solvent was removed to give a white product (yield: 98%).

MS (MALDI-TOF): m / z 257 [M] ^&lt; ^{+ &}

1- (2): Synthesis of Intermediate 1-b

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

<Reaction Scheme 2>

Intermediate 1-b

Intermediate 1-a (10 g, 55 mmol) was dissolved in 100 mL of THF and n-BuLi (50 mL) was slowly added while cooling to -78 ° C. After the addition, trimethyl borate (6.57 g, 63 mmol) was added at -78 ° C for 1 hour. After stirring at -78 ° C for 1 hour, the mixture was stirred at room temperature for 2 hours, and 2N HCl was added to adjust the acidity. After the extraction with EA, the solvent was removed, diluted with hexane, and solidified by stirring at -78 ° C to obtain a white solid (yield: 70%).

MS (MALDI-TOF): m / z 257 [M] ^&lt; ^{+ &}

1- (3): Synthesis of intermediate 1-c

Intermediate 1-c was synthesized according to Reaction Scheme 3 below.

<Reaction Scheme 3>

Intermediate 1-c

A 500 mL reactor was charged with 20.0 g (0.07 mol) of 1,4-Dibromonaphthalene, 37.3 g (0.16 mol) of Intermediate 1-b, 1.6 g (0.001 mol) of Pd (PPh3) 4, 19.3 g 100 mL of dioxane, 100 mL of toluene and 40 mL of water were added, and the mixture was refluxed for 10 hours. Upon completion of the reaction, the reaction mixture was extracted with water and ethyl acetate. The organic layer was dried under reduced pressure and column separated, and the separated solution was recrystallized with MC / MeOH. (22.6 g, 67.2%).

1- (4): Synthesis of Intermediate 1-d

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

<Reaction Scheme 4>

Intermediate 1-d

20.0 g (0.04 mol) of intermediate 1-c was dissolved in MC in a 250 mL round bottom flask, cooled to -78 ° C, and 99.9 mL of iodine monochloride was slowly dropped. The mixture was stirred at the same temperature for 1 hour, the temperature was raised to room temperature, and the reaction was terminated by adding a saturated sodium bisulfite solution. The reaction mixture was extracted with MC / H2O and the organic layer was concentrated to precipitate crystals. g, 69%)

1- (5): Synthesis of [Formula 8]

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

<Reaction Scheme 5>

8

To a 250 mL round bottom flask was added 10.0 g (0.014 mol) of Intermediate 1-d, 5.5 g (0.033 mol) diphenylamine, 0.12 g (0.001 mol) palladium (II) acetate, 5.2 g (0.055 mol) sodium- And 100 mL of toluene were added and stirred while heating. When the temperature reached 60 ° C., 0.2 mL (0.001 mol) of tri-t-butylphosphine was added and refluxed. After the reaction was completed, the reaction mixture was cooled to room temperature, concentrated, and then subjected to column separation. The separated solution was concentrated, recrystallized from toluene and acetone, and the resulting crystals were dried. (4.2 g, 37.7%).

Synthesis Example 2. Synthesis of [Formula 28]

2- (1): Synthesis of Compound (28)

(28) was synthesized according to Scheme 6 below.

<Reaction Scheme 6>

28

(0.042 mol) of Intermediate 1-c, 4.2 g (0.008 mol) of iron (III) trifluoromethanesulfonate and 300 mL of 1,2-dichloroethane were placed and refluxed for 24 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, concentrated, and then subjected to column separation. The separated solution was concentrated, recrystallized with MeOH, and dried (12.4 g, 62.0%

Synthesis Example 3. Synthesis of [Formula 78]

3- (1): Synthesis of intermediate 3-a

Intermediate 3-a was synthesized according to Scheme 7 below.

<Reaction Scheme 7>

Intermediate 3-a

1 L Reactor 50 g (0.467 mol) of para-toluidine, 87.8 g (0.513 mol) of 4-bromo-toluene, 8.5 g (0.009 mol) of Pd (dba) 3, 5.8 g (0.009 mol) of BINAP, sodium t-butoxide 87.7 g (0.933 mol) was dissolved in 500 mL of toluene and refluxed for 4 hours. The completion of the reaction was confirmed by TLC, and the reaction was terminated by hot filtration. The organic layer was dried and separated by column chromatography, and the separated solution was recrystallized from dichloromethane and hexane to obtain 50.0 g (54%).

3- (2): Synthesis of intermediate 3-b

Intermediate 3-b was synthesized according to Scheme 8 below.

<Reaction Scheme 8>

Intermediate 3-b

10.0 g (0.021 mol) of Formula 28 and 80 mL of chloroform were added to a 500 mL reactor and dissolved. 8.0 g (0.05 mol) of bromine was diluted in 20 mL of chloroform and added dropwise to the reactor at room temperature. The reaction was confirmed by HPLC while continuing the reaction at room temperature. When the reaction was completed, 100 mL of NaHCO3 aqueous solution was slowly added dropwise. After stirring for about 30 minutes, the resulting solid was filtered, and the resulting solid was recrystallized from 1.2-dichlorobenzene to obtain 6.2 g (46.7%) of white solid.

3- (3): Synthesis of 78

78 was synthesized according to Scheme 9 below.

<Reaction Scheme 9>

78

To a 250 mL round bottom flask was added 10.0 g (0.016 mol) of Intermediate 3-b, 7.45 g (0.038 mol) of Intermediate 3-a, 0.14 g (0.001 mol) of palladium (II) acetate, 6.0 g ) And 100 mL of toluene were added and stirred while heating. When the temperature reached 60 ° C, 0.3 mL (0.001 mol) of tri-t-butylphosphine was added and refluxed. After the reaction was completed, the reaction mixture was cooled to room temperature, concentrated, and then subjected to column separation. The separated solution was concentrated, recrystallized from toluene and acetone, and the resulting crystals were dried. (7.2 g, 52.8%).

Synthesis Example 4. Synthesis of [Formula 87]

4- (1): Synthesis of intermediate 4-a

Intermediate 4-a was synthesized according to Reaction Scheme 10 below.

<Reaction formula 10>

Intermediate 4-a

30.0 g (0.163 mol) of dibenzothiophene was dissolved in 240 mL of tetrahydrofuran in a 500 mL reactor. The mixture was cooled to -78 ° C in a nitrogen atmosphere and 122 mL (0.195 mol) of n-butyllithium was slowly added dropwise at the same temperature. After the dropwise addition was completed, the reaction mixture was stirred at the same temperature for 1 hour, the temperature of the reactor was gradually raised to room temperature, and the mixture was stirred for 8 hours. The temperature of the reactor was again cooled to -78 and 53.7 g (0.212 mol) of iodine was added in portions. The temperature of the reactor was slowly raised to room temperature and then stirred for 4 hours. After completion of the reaction, sodium cyan sulfate was added, and the mixture was extracted with ethyl acetate and water. The organic layer was concentrated and recrystallized from acetone to obtain 28 g (52.2%).

4- (2): Synthesis of intermediate 4-b

Intermediate 4-b was synthesized according to Scheme 11 below.

<Reaction Scheme 11>

Intermediate 4-b

250 mL of reactor Aniline 6.0 g (0.064 mol), 22.0 g (0.071 mol) of Intermediate 4-b, 1.2 g (0.001 mol) of Pd (dba) 3, 0.8 g (0.001 mol) of BINAP, 0.129 mol) was dissolved in 160 mL of toluene and refluxed for 4 hours. The completion of the reaction was confirmed by TLC, and the reaction was terminated by hot filtration. The organic layer was dried and separated by column chromatography, and the separated solution was recrystallized from dichloromethane and hexane to obtain 12.0 g (72%).

4- (3): Synthesis of [Formula 87]

87 was synthesized according to Reaction Scheme 12 below.

<Reaction Scheme 12>

Formula 87

87 (9.6 g, yield: 57%) was obtained by using the same method as in Synthesis Example 3- (3), except that Intermediate 4-b was used instead of Intermediate 3-a.

Synthesis Example 5. Synthesis of [Formula 100]

5- (1): Synthesis of intermediate 5-a

Intermediate 5-a was synthesized according to Reaction Scheme 13 below.

<Reaction Scheme 13>

Intermediate 5-a

(0.081 mol) of 4-bromo-t-butylbenzene, 1.4 g (0.001 mol) of Pd (dba) 3, 0.9 g (0.001 mol) of BINAP, mol) and 14.2 g (0.148 mol) of sodium t-butoxide were dissolved in 100 mL of toluene, and the mixture was refluxed for 4 hours. The completion of the reaction was confirmed by TLC, and the reaction was terminated by hot filtration. The organic layer was dried and separated by column chromatography, and the separated liquid was recrystallized from dichloromethane and hexane to obtain 14.2 g (72%).

5- (2): Synthesis of intermediate 5-b

Intermediate 5-b was synthesized according to Scheme 14 below.

<Reaction Scheme 14>

Intermediate 5-b

To a 250 mL reaction were added 14.0 g (0.052 mol) of Intermediate 5-a, 16.3 g (0.058 mol) of 1,4-bromoiodobenzene, 1.0 g (0.001 mol) of Pd (dba) 10.1 g (0.105 mol) of sodium t-butoxide was dissolved in 140 mL of toluene and refluxed for 4 hours. The completion of the reaction was confirmed by TLC, and the reaction was terminated by hot filtration. The organic layer was dried and separated by column chromatography, and the separated solution was recrystallized from dichloromethane and hexane to obtain 15.6 g (71%).

5- (3): Synthesis of intermediate 5-c

Intermediate 5-c was synthesized according to Reaction Scheme 15 below.

<Reaction Scheme 15>

Intermediate 5-c

15.0 g (0.036 mol) of Intermediate 5-b was added to a 250 mL reactor and dissolved in 120 mL of tetrahydrofuran. The mixture was cooled to -78 ° C in a nitrogen atmosphere and 53.3 mL (0.085 mol) of n-butyllithium was slowly added dropwise at the same temperature. When the addition was completed, the mixture was stirred at the same temperature for 1 hour. Trimethylborate was slowly added dropwise at the same temperature, and after completion of dropwise addition, the temperature was slowly raised to room temperature and stirred for 8 hours. When the reaction was completed, 2 N hydrochloric acid was added and acidified and stirred for 1 hour. The mixture was extracted with ethyl acetate and water, and the organic layer was concentrated under reduced pressure and recrystallized from hexane to obtain 24.0 g (70%) of a white solid.

5- (4): Synthesis of 100

(100) was synthesized according to Scheme 16 below.

<Reaction Scheme 16>

100

To a 250 mL reactor were added 10.0 g (0.014 mol) of Intermediate 1-d, 11.6 g (0.030 mol) of Intermediate 5-c, 0.32 g (0.001 mol) of Pd (PPh3) 4, 3.8 g (0.027 mol) , 50 mL of 1,4-dioxane, and 20 mL of water, and the mixture was refluxed for 24 hours. After completion of the reaction, the reaction mixture was extracted with ethyl acetate and water. The organic layer was dried and then subjected to column separation. The separated solution was recrystallized from toluene and acetone to obtain 8.9 g (56%) of the formula

Synthesis Example 6. Synthesis of [Formula 117]

6- (1): Synthesis of intermediate 6-a

According to the following reaction scheme 17, intermediate 6-a was synthesized.

<Reaction Scheme 17>

Intermediate 6-a

A solution of 14.0 g (0.083 mol) of diphenylamine, 26.2 g (0.092 mol) of 1,4-dibromonaphthalene, 1.5 g (0.001 mol) of Pd (dba) 3, 1.0 g (0.002 mol) of BINAP, -2-butoxide (16.0 g, 0.166 mol) was dissolved in 140 mL of toluene, and the mixture was refluxed for 4 hours. The completion of the reaction was confirmed by TLC, and the reaction was terminated by hot filtration. The organic layer was dried and separated by column chromatography, and the separated solution was recrystallized from dichloromethane and hexane to obtain 15.6 g (50.1%).

6- (2): Synthesis of intermediate 6-b

Intermediate 6-b was synthesized according to Scheme 18 below.

<Reaction Scheme 18>

Intermediate 6-b

To a 250 mL reactor was added 15.0 g (0.040 mol) of Intermediate 6-a and dissolved in 120 mL of tetrahydrofuran. The mixture was cooled to -78 ° C in a nitrogen atmosphere and 30.1 mL (0.048 mol) of n-butyllithium was slowly added dropwise at the same temperature. When the addition was completed, the mixture was stirred at the same temperature for 1 hour. At the same temperature, 8.33 g (0.080 mol) of trimethyl borate was slowly added dropwise, then the temperature was slowly raised to room temperature and stirred for 8 hours. When the reaction is completed, 2 N hydrochloric acid is added and acidified and stirred for 1 hour. The mixture was extracted with ethyl acetate and water, and the organic layer was concentrated under reduced pressure and recrystallized with hexane to obtain 10.2 g (75%) of a white solid.

6- (3): Synthesis of Compound (117)

(117) was synthesized according to Scheme 19 below.

<Reaction Scheme 19>

(117)

117 (4.2 g, yield 41%) was obtained using the same method except for using Intermediate 6-b instead of Intermediate 5-c in Synthesis Example 5- (4).

Synthesis Example 7. Synthesis of [Formula 136]

7- (1): Synthesis of Intermediate 7-a

Intermediate 7-a was synthesized according to Scheme 20 below.

<Reaction Scheme 20>

Intermediate 7-a

Intermediate 7-a (18.2 g, yield 82%) was obtained using the same method except that N-phenyl-1-naphthylamine was used in place of Intermediate 5-a in Synthesis Example 7- (2).

7- (2): Synthesis of Intermediate 8-b

Intermediate 8-b was synthesized according to Reaction Scheme 21 below.

<Reaction Scheme 21>

Intermediate 7-b

Intermediate 7-b (14.2 g, yield 67%) was obtained using the same method as Intermediate 7-a instead of Intermediate 6-a in Synthesis Example 6- (2).

7- (3): Synthesis of Compound (136)

136 was synthesized according to Scheme 22 below.

<Reaction Formula 22>

136

To a 250 mL reactor was charged 10.0 g (0.016 mol) of Intermediate 3-b, 11.7 g (0.034 mol) of Intermediate 7-b, 0.36 g (0.001 mol) of Pd (PPh3) 4, 4.3 g (0.031 mol) , 50 mL of 1,4-dioxane, and 20 mL of water, and the mixture was refluxed for 24 hours. After completion of the reaction, the reaction mixture is extracted with ethyl acetate and water. The organic layer is dried and then separated by column. The separated liquid is recrystallized from toluene and acetone. 7.4 g (44.3%) of compound 136 was obtained.

Synthesis Example 8. Synthesis of [Formula 145]

8- (1): Synthesis of Formula 145

According to Reaction Scheme 24, Formula 145 was synthesized.

145

145 (4.7 g, yield 59%) was obtained by using the same method except that Intermediate 6-b was used instead of Intermediate 7-b in Synthesis Example 7- (3).

Examples 1 to 8

The ITO glass was patterned to have a light emitting area of 2 mm x 2 mm and then cleaned. After the ITO glass was mounted in a vacuum chamber, the base pressure was adjusted to 1 × 10 ^-7 torr, and CuPc was deposited on the ITO to form a hole injection layer having a thickness of 800 Å. On the hole injection layer, NPD was deposited to form a 300 Å thick hole transport layer. The compound of the present invention was deposited on the hole transport layer to form a 250 Å thick light emitting layer, and Alq ₃ was deposited on the light emitting layer to form a 350 Å thick electron transport layer. Then, a 5 Å thick LiF electron injection layer and a 500 Å thick Al electrode were sequentially formed to complete an organic light emitting device.

Comparative Example 1

An organic light emitting device was fabricated using the same method as in the above example except that the following compound A was used instead of the compound 1.

<Compound A>

Comparative Example 2

An organic light emitting device was fabricated in the same manner as in Example 1 except that the following compound B was used instead of the compound 1.

<Compound B>

Evaluation example 1

Current, luminance (measured at 0.4 mA), color coordinates and lifetime (T80) were measured with a PR650 Spectroscan Source Measurement Unit (PhotoResearch Co., Ltd.) according to Examples 1 to 8 and Comparative Examples 1 and 2, Product), and the results are shown in Table 1 below. T80 means the time required for the measured luminance to be reduced to 80% of the initial luminance and measured at 3,000 nits.

division Dopant Voltage
(V) Current density
(mA / cm ² ) External quantum
efficiency Luminance
(cd / m ² ) CIEx CIEy T80
(hr) Example 1 One 4.0 10 5.61 471 0.145 0.096 187 Example 2 3 3.6 10 6.83 690 0.142 0.123 379 Example 3 9 3.8 10 6.09 695 0.141 0.148 257 Example 4 10 3.8 10 6.33 624 0.143 0.120 207 Example 5 11 4.0 10 6.71 677 0.142 0.125 180 Example 6 12 3.8 10 6.16 693 0.141 0.145 211 Example 7 28 3.8 10 5.43 480 0.145 0.103 150 Example 8 29 3.9 10 6.46 663 0.141 0.127 194 Comparative Example 1 A 4.3 10 5.06 534 0.133 0.137 45 Comparative Example 2 B 4.3 10 4.59 504 0.134 0.144 35

From Table 1, it can be seen that the organic luminescent devices of Examples 1 to 8 have excellent driving voltage, external quantum efficiency, luminance, color purity and lifetime characteristics as compared with the organic luminescent devices of Comparative Examples 1 and 2, Accordingly, it can be seen that the compound according to the present invention can be usefully used in display devices, display devices, lighting, and the like.

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

Claims (8)

A condensed aryl compound which is any one selected from the group consisting of the following formulas (2) to (6):
[Chemical Formula 2] &lt; EMI ID =

[Chemical Formula 4]

[Chemical Formula 6]

In the above formulas 2 to 6,
The plurality of Rs are the same or different and each is a hydrogen atom, a substituted or unsubstituted aryl group having 5 to 50 carbon atoms, and a substituted or unsubstituted heteroaryl group having 3 to 50 carbon atoms having O, N or S as a hetero atom &Lt; / RTI &gt;
The plurality of X's are the same or different from each other and are independently selected from the group consisting of substituted or unsubstituted aryl groups having 6 to 40 carbon atoms and substituted or unsubstituted heteroaryl groups having 2 to 40 carbon atoms,
Ar ₁ and Ar ₂ are the same or different from each other and each independently selected from the group consisting of a substituted or unsubstituted aryl group having 6 to 40 carbon atoms and a substituted or unsubstituted heteroaryl group having 2 to 40 carbon atoms. delete The method according to claim 1,
The condensed aryl compound represented by any of the above formulas (2) to (6) is any one selected from the group consisting of the following formulas (8) to (162)

&Lt; Formula 8 >< EMI ID = 10.0 >

&Lt; Formula 13 >< EMI ID = 15.0 >

&Lt; Formula 18 >< EMI ID = 19.0 >

&Lt; Formula 23 >< EMI ID = 25.0 >

&Lt; Formula 28 >< EMI ID = 31.0 >

(35), (36), (37), (38), (39)

&Lt; Formula 40 >< EMI ID = 41.0 >

&Lt; Formula 46 >< EMI ID = 48.0 >

(52), (53), (54), (55), (56),

<Formula 58><Formula59><Formula60><Formula61><Formula62>

&Lt; Formula 64 >< EMI ID =

<Formula 68><Formula69><Formula70><Formula71>

&Lt; Formula 72 &gt;&lt; EMI ID = 73.1 &gt;

&Lt; Formula 76 &gt;&lt; EMI ID = 77.0 &gt;

<Formula 80><Formula81><Formula82><Formula83>

&Lt; Formula 84 &gt;&lt; EMI ID =

&Lt; Formula 88 >< EMI ID = 89.0 >

&Lt; EMI ID = 93.1 >

&Lt; Formula 97 >< EMI ID = 97.0 >

&Lt; Formula 100 >< EMI ID = 101.0 >

&Lt; EMI ID = 106.1 >

<Formula 108><Formula109> Formula 110 <Formula 111>

<Formula 112><Formula113><Formula114>

&Lt; EMI ID = 116.1 >

&Lt; Formula 120 >< EMI ID =

&Lt; Formula 125 &gt;&lt; EMI ID = 124.1 &gt;

&Lt; EMI ID = 129.1 &gt;&lt; EMI ID =

(133), (134), (135), (136), (137)

&Lt; EMI ID = 141.0 >< EMI ID =

<Formula 143> Formula 144> Formula 145> Formula 146> Formula 147>

<Formula 148><Formula149><Formula150><Formula151><Formula152>

<Formula 153><Formula154><Formula155><Formula156>

&Lt; EMI ID = 158.1 &gt;&lt; EMI ID = Anode;
Cathode; And
An organic electroluminescent element interposed between the anode and the cathode and comprising the compound according to claim 1. 5. The method of claim 4,
Wherein the compound is contained in the light emitting layer between the anode and the cathode. 6. The method of claim 5,
Wherein 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. 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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