KR102004388B1 - Aromatic compound and organoelectroluminescent device comprising the compound - Google Patents

Abstract

The present invention relates to a novel aromatic compound and an organic electroluminescent device comprising the same, the organic electroluminescent device comprising the aromatic compound according to the present invention has a low driving voltage and excellent luminous efficiency.

Description

Aromatic compound and organoelectroluminescent device comprising the compound

The present invention relates to an aromatic compound and an organic electroluminescent device using the same, wherein the organic electroluminescent device comprising the aromatic compound according to the present invention has a low driving voltage and excellent luminous efficiency.

An organic light emitting display device using an organic light emitting phenomenon usually has a structure including an anode, a cathode, and an organic material layer therebetween. In this case, the organic material layer is often formed of a multi-layered structure composed of different materials in order to increase the efficiency and stability of the organic light emitting device, for example, it may be made of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer. When the voltage is applied between the two electrodes in the structure of the organic light emitting device, holes are injected into the organic material layer at the anode and electrons are injected into the organic material layer, and excitons are formed when the injected holes and electrons meet each other. 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.

The material used as the organic material layer in the organic electroluminescent device may be classified into a light emitting material and a charge transport material such as a hole injection material, a hole transport material, an electron transport material, an electron injection material and the like according to a 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 the light emitting material, the maximum light emission wavelength is shifted to the long wavelength due to the intermolecular interaction, and the color purity decreases or the efficiency of the device decreases due to the light emission attenuation effect. A host-dopant system can be used as the luminescent material to increase the luminous efficiency through.

The principle is that when a small amount of dopant having an energy band gap smaller than that of the host forming the light emitting layer is mixed in the light emitting layer, excitons generated in the light emitting layer are transported to the dopant, thereby producing high efficiency light. 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.

The organic light emitting device is gradually expanding its application field to the display and lighting field of various electronic products, but the efficiency and lifespan characteristics are restricting the expansion of the application field. There is a lot of research going on. In terms of materials, the host-dopant system is mainly adopted as a method for maximizing luminous efficiency, and the dopant as a luminescent material is phosphorescent material, and CBP (4, 4'-N, N'-dicarbazolbiphenyl) and substances in which various substituents are introduced into carbazole are disclosed (Japanese Patent Laid-Open No. 2008-214244, Japanese Patent Laid-Open No. 2003-133075), but further improvement in efficiency and lifespan characteristics is required.

Japanese Patent Publication 2008-214244 Japanese Patent Publication 2003-133075

The first object of the present invention is to provide a novel aromatic compound.

In addition, a second technical problem to be solved by the present invention is to provide an organic light emitting device having a low driving voltage and improved luminous efficiency using the aromatic compound.

In order to achieve the above technical problem, the present invention provides an aromatic compound represented by the following [Formula 1].

 [Formula 1]

In Chemical Formula 1,

X is selected from the group consisting of CR ₇ R ₈ , NR, O, Se, P, S and SiR ₉ R ₁₀ ,

m is an integer from 0 to 4, n is an integer from 3 to 6,

when m is 2 or more, a plurality of Ls may be the same or different, respectively,

L is a single bond or one or more selected from alkylene having 1 to 60 carbon atoms, alkenylene having 2 to 60 carbon atoms, alkynylene having 2 to 60 carbon atoms, cycloalkylene having 3 to 60 carbon atoms, N, O and S; A divalent linking group selected from heterocycloalkylene having 2 to 6 carbon atoms, arylene having 6 to 50 carbon atoms and heteroarylene having 3 to 50 carbon atoms,

R ₁ to R ₁₀ are each independently an alkyl group having 1 to 60 carbon atoms, a cycloalkyl group having 3 to 60 carbon atoms, an aryl group having 6 to 60 carbon atoms, a heteroaryl group having 3 to 60 carbon atoms, an alkoxy group having 1 to 60 carbon atoms, and carbon atoms Aryloxy group having 6 to 30 carbon atoms, alkylamino group having 1 to 20 carbon atoms, arylamino group having 6 to 30 carbon atoms, alkylsilyl group having 1 to 20 carbon atoms, arylsilyl group having 6 to 30 carbon atoms, and arylalkylamino group having 1 to 50 carbon atoms , Alkenyl group having 2 to 60 carbon atoms, alkynyl group having 2 to 60 carbon atoms, hydroxyl group, nitro group, amino group, amidino group, hydrazine, hydrazone, carboxyl group or salt thereof, sulfonic acid group or salt thereof, phosphoric acid or salt thereof, A cycloalkyl group having 3 to 60 carbon atoms, an aryloxy group having 5 to 60 carbon atoms, an arylthio group having 5 to 60 carbon atoms, a cyano group, a halogen group, a small to medium number, hydrogen,

Provided that at least one of R ₁ to R ₆ is a heteroaryl group containing nitrogen,

L and R ₁ to R ₁₀ are each independently a deuterium atom, cyano group, halogen atom, hydroxy group, nitro group, alkyl group of 1 to 40 carbon atoms, alkoxy group of 1 to 40 carbon atoms, alkylamino group of 1 to 40 carbon atoms, carbon number Arylamino group having 6 to 40 carbon atoms, heteroarylamino group having 3 to 40 carbon atoms, alkylsilyl group having 1 to 40 carbon atoms, arylsilyl group having 6 to 40 carbon atoms, aryl group having 6 to 40 carbon atoms, and aryloxy group having 3 to 40 carbon atoms It may be substituted by one or more substituents selected from the group consisting of a heteroaryl group, a germanium group, phosphorus, boron having 3 to 40 carbon atoms, and the substituents of L and R ₁ to R ₁₀ may form a condensed ring with adjacent substituents. Can be.

Meanwhile, the present invention provides an anode; Cathode; And it provides an organic electroluminescent device having a layer comprising an aromatic compound represented by the above [Formula 1] between the anode and the cathode.

According to an embodiment of the present invention, the organic light emitting device is one selected from the group consisting of a hole injection layer, a hole transport layer, a hole blocking layer, a light emitting layer, an electron transport layer, an electron injection layer and an electron blocking layer between the anode and the cathode The above layer may be further included, and the aromatic compound is preferably included in the light emitting layer between the anode and the cathode.

In addition, 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.

When the aromatic compound according to the present invention is used in the organic material layer of the organic light emitting device, the organic light emitting device is driven at a low voltage and the luminance is improved, which is very economic.

1 is a cross-sectional view showing a laminated structure of an organic light emitting display device according to a preferred embodiment of the present invention.

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

The aromatic compound according to the present invention may be represented by the following formula (1).

[Formula 1]

In Chemical Formula 1,

X is selected from the group consisting of CR ₇ R ₈ , NR, O, Se, P, S and SiR ₉ R ₁₀ ,

m is an integer from 0 to 4, n is an integer from 3 to 6,

when m is 2 or more, a plurality of Ls may be the same or different, respectively,

L is a single bond or one or more selected from alkylene having 1 to 60 carbon atoms, alkenylene having 2 to 60 carbon atoms, alkynylene having 2 to 60 carbon atoms, cycloalkylene having 3 to 60 carbon atoms, N, O and S; A divalent linking group selected from heterocycloalkylene having 2 to 6 carbon atoms, arylene having 6 to 50 carbon atoms and heteroarylene having 3 to 50 carbon atoms,

R ₁ to R ₁₀ are each independently an alkyl group having 1 to 60 carbon atoms, a cycloalkyl group having 3 to 60 carbon atoms, an aryl group having 6 to 60 carbon atoms, a heteroaryl group having 3 to 60 carbon atoms, an alkoxy group having 1 to 60 carbon atoms, and carbon atoms Aryloxy group having 6 to 30 carbon atoms, alkylamino group having 1 to 20 carbon atoms, arylamino group having 6 to 30 carbon atoms, alkylsilyl group having 1 to 20 carbon atoms, arylsilyl group having 6 to 30 carbon atoms, and arylalkylamino group having 1 to 50 carbon atoms , Alkenyl group having 2 to 60 carbon atoms, alkynyl group having 2 to 60 carbon atoms, hydroxyl group, nitro group, amino group, amidino group, hydrazine, hydrazone, carboxyl group or salt thereof, sulfonic acid group or salt thereof, phosphoric acid or salt thereof, A cycloalkyl group having 3 to 60 carbon atoms, an aryloxy group having 5 to 60 carbon atoms, an arylthio group having 5 to 60 carbon atoms, a cyano group, a halogen group, a small to medium number, hydrogen,

Provided that at least one of R ₁ to R ₆ is a heteroaryl group containing nitrogen,

L and R ₁ to R ₁₀ are each independently a deuterium atom, cyano group, halogen atom, hydroxy group, nitro group, alkyl group of 1 to 40 carbon atoms, alkoxy group of 1 to 40 carbon atoms, alkylamino group of 1 to 40 carbon atoms, carbon number Arylamino group having 6 to 40 carbon atoms, heteroarylamino group having 3 to 40 carbon atoms, alkylsilyl group having 1 to 40 carbon atoms, arylsilyl group having 6 to 40 carbon atoms, aryl group having 6 to 40 carbon atoms, and aryloxy group having 3 to 40 carbon atoms It may be substituted by one or more substituents selected from the group consisting of a heteroaryl group, a germanium group, phosphorus, boron having 3 to 40 carbon atoms, and the substituents of L and R ₁ to R ₁₀ may form a condensed ring with adjacent substituents. Can be.

Specific examples of the aromatic compound according to the present invention may include any one compound selected from the group consisting of compounds represented by the following [Formula 2] to [Formula 225], but the present invention is not limited thereto.

In another aspect, the present invention provides an organic light emitting device having a layer comprising an aromatic compound represented by the above [Formula 1] between the anode and the cathode.

According to one embodiment of the present invention, the anode and the cathode further comprises one or more layers selected from the group consisting of a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer and an electron injection layer The compound of Formula 1 may be included in the light emitting layer between the anode and the cathode, and the thickness of the light emitting layer is preferably 50 to 2,000 kPa.

In still another embodiment of the present invention, at least one or more of the hole injection layer, the hole transport layer, the hole blocking layer, the light emitting layer, the electron transport layer, the electron injection layer and the electron blocking layer is formed by a solution process. An organic electroluminescent device is provided.

The hole transport layer is laminated in order to easily inject holes from the anode, the material of the hole transport layer is an electron-donating molecule with a small ionization potential, mainly diamine, triamine or tetra based on triphenylamine Many amine derivatives are used.

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. For example, CuPc or Starburst type amines such as TCTA, m-MTDATA, etc., which are listed in the following chemical formulas, may be used.

The light emitting layer is a layer for emitting light by recombination of electrons or holes injected from the electron transporting layer and the hole transporting layer, and the light emitting portion may be in a layer of the light emitting layer or may be an interface between the light emitting layer and an adjacent layer.

According to an embodiment of the present invention, the light emitting layer may further include other host compounds and phosphorescent compounds in addition to the carbazole compound of Formula 1. 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 upper portion of the electron transport layer to facilitate electron injection from the cathode and ultimately improve power efficiency. The electron injection layer material may also be stacked. If it is conventionally used in the art can be used without particular limitation, for example, materials such as LiF, NaCl, CsF, Li ₂ O, BaO and the like can be used.

The organic light emitting display device according to an embodiment of the present invention may 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 diode 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 The 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 method of manufacturing 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. In addition, transparent and conductive indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO 2), and zinc oxide (ZnO) are used as the anode electrode material.

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 serves to prevent such a problem by using a material having a very low 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 used is not particularly limited, but has an ion transporting potential and has a higher ionization potential than the light emitting compound, and BAlq, BCP, TPBI, etc. 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.

Hereinafter, the present invention will be described in more detail with reference to the following examples, which are merely illustrative to aid the understanding of the present invention, and the scope of the present invention is not limited thereto.

Synthesis Example  1.Synthesis of Formula 4

Synthesis Example  1-1. Synthesis of <1-a>

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

Scheme 1

                                          <1-a>

87 g (0.576 mol) of methyl anthranilate, 135.1 g (0.478 mol) of 1-bromo-4-iodobenzene, and palladium acetate (Pd (OAc) ₂ ) 1.3 g (0.006 mol) under nitrogen in a 5000 ml round bottom flask 10 g (0.017 mol) of xantose, 217.5 g (0.668 mol) of cesium carbonate, and 2500 mL of toluene were added and refluxed for 6 hours. When the reaction was completed, the resulting product was separated into layers to remove the aqueous layer, and the organic layer was separated and concentrated under reduced pressure to obtain <1-a> 110 g (75%) through column chromatography.

Synthesis Example  1-2. Synthesis of <1-b>

<1-b> was synthesized by the following Scheme 2.

Scheme 2

                              <1-b>

In a 1000 ml round bottom flask, 27 g (0.088 mol) of a compound represented by Chemical Formula 1-a obtained from Scheme 1 and 400 ml of diisopropyl ether were added to a 1000 ml round bottom flask, and 309 ml of tolyl magnesium bromide was slowly added dropwise thereto. After dropping, the mixture was stirred at 50 degrees. When the reaction was terminated, the resultant of the reaction was separated into layers to remove the aqueous layer, and the organic layer was separated and concentrated under reduced pressure to obtain <1-b> 40g (98%) through column chromatography.

Synthesis Example  1-3. Synthesis of <1-c>

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

Scheme 3

<1-c>

40 g (0.087 mol) of the compound represented by Chemical Formula 1-b obtained from Scheme 2 and 550 ml of phosphoric acid were added to a 1000 ml round bottom flask, followed by stirring at 60 degrees. When the reaction was completed, water was added to the resultant of the reaction and stirred. After stirring, the mixture was filtered and washed with water and methanol. Column chromatography gave 37 g (94%) of <1-c>.

Synthesis Example  1-4. Synthesis of <1-d>

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

Scheme 4

                                   <1-d>

91.0 g (0.529 mol) of 4-bromoaniline, 514.2 ml of water and 1028.3 ml of 12N hydrochloric acid were added to a 5 L round bottom flask, and the internal temperature was lowered to 0 ° C. under a nitrogen atmosphere. After lowering to 0 ° C, 36.5 g (0.529 mol) of sodium nitrile (NaNO2) is dissolved in 365.1 ml of water, and then slowly added dropwise to the reaction solution. After stirring for 30 minutes, 501.6 g of tin chloride (SnCl 2) is dissolved in 350 ml of 12N hydrochloric acid and slowly added dropwise. When the addition was completed, the reaction solution was heated to room temperature, stirred for 3 hours, cooled to 5 ° C. after 3 hours, and filtered to obtain 116.2 g (yield 98.3%) of <1-d>.

Synthesis Example  1-5 Synthesis of <1-e>.

<1-e> was synthesized according to Scheme 5 below.

Scheme 5

                                                        <1-e>

116.2 g (0.520 mol) of <1-d> synthesized in [Scheme 1], 51.0 g (0.520 mol) of cyclohexanone and 1162.0 ml of ethanol were added to a 2 L round bottom flask and refluxed for 10 hours. When the reaction was terminated, the reaction solution was concentrated and then obtained by column chromatography to give <1-e> 128.6g (yield 98.9%).

Synthesis Example  1-6 Synthesis of <1-f>.

<1-f> was synthesized according to Scheme 6 below.

Scheme 6

                                                           <1-f>

60.0 g (0.240 mol) of <1-e> synthesized in Reaction 5 in a 1 L round bottom flask, 73.4 g (0.360 mol) of iobenzene, 2.3 g (0.012 mol) of copper iodide (CuI), tripotassium phosphate 106.96 g (0.504 mol) of (K ₃ PO ₄ ), 54.8 g (0.480 mol) of trans-1,2-cyclohexanediamine, and 300.0 ml of 1,4-dioxane were added and refluxed for 12 hours. After completion of the reaction, the mixture was cooled to room temperature, extracted with 1 L of water, and the organic layer was anhydrous and concentrated under reduced pressure. Then, 72.0 g (yield 92.0%) of <1-f> was obtained by using an adsorption column chromatography.

Synthesis Example  1-7 Synthesis of <1-g>.

<1-g> was synthesized by the following Scheme 7.

Scheme 7

                                      <1-g>

37.0 g (0.113 mol) of <1-f> synthesized in Scheme 6, 43.2 g (0.170 mol) of bispinacol diborone, and 4.6 g (0.006 mol) of bisdiphenylphosphinoferrocene dichloropalladium in a 500 ml round bottom flask 25.8 g (0.340 mol) of potassium acetate and 300 ml of toluene were added and refluxed for 12 hours. After the reaction was completed, the mixture was filtered while hot and extracted using toluene and water. The organic layer was concentrated under reduced pressure after anhydrous treatment, and 36.1 g (yield 85.3%) of <1-g> was obtained by using column chromatography.

Synthesis Example  1-8 Synthesis of <1-h>

<1-h> was synthesized according to Scheme 8 below.

Scheme 8

                                                  <1-h>

In a 500 ml round bottom flask, <1-c> 8 g (0.018 mol) synthesized in [Scheme 3], <1-h> 7.5 g (0.020 mol) synthesized in [Scheme 7], tetrakistriphenylphosphinepalladium ( Pd (PPh ₃ ) ₄ ) 0.63 g (0.001 mol), potassium carbonate 7.53 g (0.054 mol), toluene 40 ml. 40 ml of tetrahydrofuran and 20 ml of water were added and refluxed for 12 hours. After the reaction is completed, the reaction solution is cooled to room temperature, extracted with ethyl acetate and water, the organic layer is anhydrous and the organic layer is concentrated under reduced pressure. After concentration under reduced pressure, 8.9 g (yield 80.7%) of <1-h> was obtained by using column chromatography.

Synthesis Example  1-9 Synthesis of <1-i>.

<1-i> was synthesized by the following Scheme 9.

Scheme 9

                                                          <1-i>

After making a nitrogen atmosphere in a 100ml reactor, add magnesium (3.36g, 0.1384mol), 40ml of dry tetrahydrofuran and a small amount of iodine and stir for 30 minutes. To this mixed pressure solution, 20 ml of a dry tetrahydrofuran solution of bromobenzene (19.2 g, 0.1216 mol) is added dropwise at zero degrees. After dropping, the mixture is heated and stirred at 65 ° C. for 2 hours. 2-diphenylamino-4,6-dichloro-1,3,5-triazine (18 g, 0.0568 mol) is dissolved in 100 ml of dry tetrahydrofuran in a 250 ml reactor, and the mixed solution of the 100 ml reactor is added dropwise at zero degree. After dropping, the mixture is stirred at room temperature for 12 hours. After the reaction is completed, 200 ml of 2N HCl is added, ethyl acetate and water are extracted. After the anhydrous treatment of the organic layer was concentrated under reduced pressure to give 9.8g (yield 64.5%) of <1-f> using column chromatography.

Synthesis Example  1-10 Synthesis of [Formula 4].

[Scheme 4] was synthesized according to Scheme 10 below.

Scheme 10

                                                      [Formula 4]

In a 500 ml round bottom flask, sodium hydride (60% mineral oil) (NaH), 0.8 g (0.022 mol), and 90.0 ml of N, N-dimethylformamide were added to a 500 ml round bottom flask, and the reaction solution was cooled to 0 ° C. A solution of 8.9 g (0.015 mol) of <1-h> synthesized in [Scheme 8] at 0 ° C. in 90.0 ml of N, N-dimethylformamide was slowly added dropwise, followed by stirring for 1 hour while maintaining 0 ° C. . After 1 hour, a solution of 6.5 g (0.018 mol) of <1-i> synthesized in [Scheme 9] in 130 ml of N, N-dimethylformamide was slowly added dropwise. When the addition is completed, the reaction solution is raised to room temperature and stirred. When the reaction is completed, the reaction solution is poured into 1L of water to precipitate a solid and then filtered. The solid was recrystallized with toluene to obtain 7.1 g (yield 57.8%).

MS (MALDI-TOF): m / z 837.38 [M] ⁺

Anal. Calc. for C ₄₅ H ₃₃ N ₅ C, 85.99; H, 5.65; N, 8.36. Found C, 85.94; H, 5.68; N, 8.39.

Synthesis Example  2. Synthesis of Chemical Formula 10

Synthesis Example  2-1. Synthesis of <2-a>

<2-a> was synthesized according to Scheme 11 below.

Scheme 11

                                  <2-a>

108-g (98.2%) of <2-a> were obtained by the same method as the compound synthesis method of Chemical Formula 1-b.

Synthesis Example  2-2. Synthesis of <2-b>

<2-b> was synthesized according to Scheme 12 below.

Scheme 12

<2-b>

75 g (75%) of <2-b> were obtained by the same method as the compound synthesis method of Chemical Formula 1-c.

Synthesis Example  2-3 Synthesis of <2-c>

<2-c> was synthesized by the following Scheme 13.

Scheme 13

                                                    <2-c>

In a 500 ml round bottom flask, <1-c> 8 g (0.018 mol) synthesized in [Scheme 3], <1-h> 7.5 g (0.020 mol) synthesized in [Scheme 7], tetrakistriphenylphosphinepalladium ( Pd (PPh ₃ ) ₄ ) 0.63 g (0.001 mol), potassium carbonate 7.53 g (0.054 mol), toluene 40 ml. 40 ml of tetrahydrofuran and 20 ml of water were added and refluxed for 12 hours. After the reaction is completed, the reaction solution is cooled to room temperature, extracted with ethyl acetate and water, the organic layer is anhydrous and the organic layer is concentrated under reduced pressure. After concentration under reduced pressure, 8.9 g (80.7%) of <1-h> was obtained by using column chromatography.

Synthesis Example  2-4. Synthesis of <2-d>

<2-d> was synthesized by the following Scheme 14.

Scheme 14

                                                           <2-d>

Make a nitrogen atmosphere in a 500 ml round bottom flask, add magnesium (16.9 g, 0.696 mol), 200 ml of dry tetrahydrofuran and a small amount of iodine and stir for 30 minutes. 100 ml of dry tetrahydrofuran solution of bromobenzene (91.1 g, 0.580 mol) was added dropwise to this mixed pressure solution at zero degree. After dropping, the mixture is heated and stirred at 65 ° C. for 2 hours. 2-diphenylamino-4,6-dichloro-1,3,5-triazine (107.0 g, 0.580 mol) was dissolved in 500 ml of dry tetrahydrofuran in a 2 L reactor, and the mixed solution of the 500 ml reactor was added dropwise at zero degree. After dropping, the mixture is stirred at 0 ° C. for 12 hours. After the reaction is completed, 200 ml of 2N HCl is added, ethyl acetate and water are extracted. The organic layer was treated with anhydrous and concentrated under reduced pressure, and then obtained 81.0 g (61.8%) of <2-d> by column chromatography.

Synthesis Example  2-5 Synthesis of <2-e>.

<2-e> was synthesized according to Scheme 15 below.

Scheme 15

                                                     <2-e>

In a 1 L round bottom flask, sodium hydride (60% mineral oil) (NaH), 10.1 g (0.425 mol), and 30.0 ml of N, N-dimethylformamide were added to a 1 L round bottom flask, and the reaction solution was cooled to 0 ° C. A solution of 59.1 g (0.354 mol) of carbazole in 180 ml of N, N-dimethylformamide was slowly added dropwise at 0 ° C., and then stirred for 1 hour while maintaining the temperature at 0 ° C. After 1 hour, a solution of 80.0 g (0.354 mol) of <2-a> synthesized in [Scheme 8] in 160 ml of N, N-dimethylformamide was slowly added dropwise. When the addition is completed, the reaction solution is raised to room temperature and stirred. When the reaction is completed, the reaction solution is poured into 3L of water to precipitate a solid and then filtered. The solid was recrystallized with toluene to give 80.0 g (63.4%) of <2-e>.

Synthesis Example  2-6 Synthesis of Formula 10.

[Scheme 10] was synthesized according to Scheme 16 below.

Scheme 16

                                       [Formula 10]

Synthesis was carried out in the same manner as the compound synthesis method represented by Formula 4, to obtain 6.4 g (37.5%).

MS (MALDI-TOF): m / z 732.30 [M] ⁺

Anal. Calc. for C ₅₄ H ₄₂ N ₆ C, 83.69; H, 5. 46; N, 10.84. Found C, 83.65; H, 5.49; N, 10.85.

Synthesis Example  3. Synthesis of Chemical Formula 37

Synthesis Example  3-1. Synthesis of <3-a>

<3-a> was synthesized according to Scheme 17 below.

Scheme 17

<3-a>

In a 2000 mL round bottom flask, 100 g (0.457 mol) of 2-iodoaniline, 58 g (0.913 mol) of copper, 446.3 g (1.37 mol) of cesium carbonate, 2.4 g (0.009 mol) of 18-crown-6-ether and 500 ml of dichlorobenzene Was added and refluxed for 24 hours. After the completion of the reaction, the mixture was extracted and the organic layer was concentrated under reduced pressure, and then 30g (72.1%) was obtained by column chromatography.

Synthesis Example  3-2 Synthesis of <3-b>.

<3-b> was synthesized according to Scheme 18 below.

Scheme 18

                            <3-b>

To 30 g (0.165 mol) of the compound represented by 3-a obtained in Scheme 16 in a 5 L round bottom flask, 130 ml of N, N-dimethylamide was added, stirred for 30 minutes under nitrogen, and the reaction was cooled to 0 degrees. 29.3 g (0.165 mol) of N-bromosuccinimide was dissolved in 170 ml of N, N-dimethylamide and added dropwise. After dropping, the mixture was stirred at room temperature. When the reaction was completed, the resultant of the reaction was poured into water, stirred, filtered and washed with water and methanol to give 38.5g (89.5%) of the compound represented by the formula 3-b.

Synthesis Example  3-3 Synthesis of <3-c>.

<3-c> was synthesized according to Scheme 19 below.

Scheme 19

                                               <3-c>

43.1 g (86.7%) of <3-c> were obtained by the same method as the compound synthesis method of Chemical Formula 1-f.

Synthesis Example  3-4 Synthesis of <3-d>

<3-d> was synthesized according to Scheme 20 below.

Scheme 20

                                                 <3-d>

51.9 g (80.6%) of <3-d> were obtained by the same method as the compound synthesis method of Chemical Formula 1-h.

Synthesis Example  Synthesis of 3-5 <3-e>.

<3-e> was synthesized according to Scheme 21 below.

Scheme 21

         <3-e>

50 g (0.221 mol), 2-naphthylboronic acid (0.288 mol), potassium carbonate (K ₂ CO ₃ ) 76.42 g (0.55 mol), tetrakistri, synthesized in Scheme 6 in a 250 ml round bottom flask 7.67 g (0.0066 mol) of phenylphosphine palladium (Pd (PPh ₃ ) ₄ ), 100.0 mL of water, 250.0 mL of toluene and 250.0 mL of tetrahydrofuran were added and refluxed for 24 hours. When the reaction was completed, the resultant of the reaction was separated into layers to remove the aqueous layer, and the organic layer was separated and concentrated under reduced pressure to give 57.6g (82%) of <3-e> through column chromatography.

Synthesis Example  3-6 Synthesis of Formula 37.

[Scheme 37] was synthesized according to Scheme 22 below.

Scheme 22

                                           [Formula 37]

Synthesis was carried out in the same manner as in the synthesis of compound represented by Formula 4 to obtain 5.8 g (37.2%).

MS (MALDI-TOF): m / z 784.33 [M] ⁺

Anal. Calc. for C ₅₅ H ₄₀ N ₆ C, 84.16; H, 5. 14; N, 10.71. Found C, 84.18; H, 5.13; N, 10.70.

Synthesis Example  4. Synthesis of Chemical Formula 53

Synthesis Example  4-1. Synthesis of <4-a>

<4-a> was synthesized according to Scheme 23 below.

Scheme 23

                                                      <4-a>

72-g (74.7%) of <4-a> were obtained by the same method as the compound synthesis method of Chemical Formula 2-d.

Synthesis Example  4-2 Synthesis of <4-b>.

<4-b> was synthesized according to Scheme 24 below.

Scheme 24

                                      <4-b>

In a 1 L round bottom flask, 72.0 g (0.223 mol) of <3-a> synthesized in Scheme 11 was dissolved in 576.0 ml of tetrahydrofuran under a nitrogen atmosphere, and then cooled to minus 70 degrees. After cooling, 167.60 ml (0.268 mol) of n-butyllithium (1.6 M hexane solution) was slowly added dropwise. After stirring for 1 hour while maintaining a low temperature, trimethyl borate 75.7g (0.402mol) was added dropwise and stirred at room temperature for 12 hours. After completion of the reaction, 200 ml of 2N HCl solution was added dropwise, followed by extraction with ethyl acetate and water. The organic layer is anhydrous and then depressurized to remove the organic solvent. After concentration under reduced pressure, 500 ml of hexane was added and recrystallized. The resulting solid was filtered to give 48.3 g (75.3%) of <4-b>.

Synthesis Example  4-3 Synthesis of <4-c>.

<4-c> was synthesized by the following Scheme 25.

Scheme 25

                                                      <4-c>

In a 250 ml round bottom flask, <2-d> 12.5 g (0.055 mol) synthesized in Scheme 14, <3-b> 15.9 g (0.055 mol) synthesized in Scheme 12, potassium carbonate (K ₂ CO ₃ ) 30.6gg ( 0.221 mol), tetrakistriphenylphosphinepalladium (Pd (PPh ₃ ) ₄ ) 3.2 g (0.003 mol), 25.0 mL of water, 62.5 mL of toluene and 62.5 mL of tetrahydrofuran were added and refluxed for 24 hours. When the reaction was completed, the resulting product was separated into layers to remove the aqueous layer, and the organic layer was separated and concentrated under reduced pressure to obtain <4-c> 18.7 g (78.1%) through column chromatography.

Synthesis Example  4-4 Synthesis of Formula 53.

[Scheme 53] was synthesized according to Scheme 26 below.

Scheme 26

[화학식 53]

[Formula 53]

7.6 g (42.5%) was obtained by the same method as the compound synthesis method of Chemical Formula 4.

MS (MALDI-TOF): m / z 899.37 [M] ⁺

Anal. Calc. for C ₆₃ H ₄₅ N ₇ C, 84.07; H, 5.04; N, 10.89. Found C, 84.08; H, 5.02; N, 10.90.

Synthesis Example  5. Synthesis of Chemical Formula 71

Synthesis Example  5-1. Synthesis of <5-a>

<5-a> was synthesized according to Scheme 27 below.

Scheme 27

                            <5-a>

In a 1 L round bottom flask, 40.0 g (0.253 mol) of 2-bromopyridine was dissolved in 300.0 ml of tetrahydrofuran under a nitrogen atmosphere, and then cooled to minus 70 degrees. After cooling, 174.05 ml (0.278 mol) of n-butyllithium (1.6 M hexane solution) is slowly added dropwise. After stirring for 1 hour while maintaining a low temperature, 90.6 g (0.178 mol) of tributyltin chloride was added dropwise, followed by stirring at room temperature for 12 hours. After completion of the reaction, 200 ml of 2N NH ₄ Cl solution was added dropwise, followed by extraction with ethyl acetate and water. The organic layer is anhydrous and then depressurized to remove the organic solvent. Concentration under reduced pressure and purification by distillation gave <5-a> 66g (70.8%).

Synthesis Example  5-2 Synthesis of <5-b>.

<5-b> was synthesized according to Scheme 28 below.

Scheme 28

                                                     <5-b>

Synthesis was carried out in the same manner as in the synthesis of the compound represented by formula 4-c to give <5-b> 26g (72.9%).

Synthesis Example  5-3 Synthesis of <5-c>.

<5-c> was synthesized by the following Scheme 29.

Scheme 29

                              <5-c>

61.3 g (87.8%) of <5-c> were obtained by the same method as the compound synthesis method of Chemical Formula 3-b.

Synthesis Example  5-4 Synthesis of <5-d>

<5-d> was synthesized according to Scheme 30 below.

Scheme 30

                                                         <5-d>

74.2 g (75.7%) of <5-d> were obtained by the same method as the compound synthesis method of Chemical Formula 1-h.

Synthesis Example  5-5 Synthesis of Formula 71.

By following Reaction Scheme 31 was synthesized.

Scheme 31

                                                     [Formula 71]

Compound 5.4g (35.5%) was obtained by the same method as the method for synthesizing compound represented by Chemical Formula 4.

MS (MALDI-TOF): m / z 676.24 [M] ⁺

Anal. Calc. for C ₄₄ H ₃₂ N ₆ SC, 78.08; H, 4.77; N, 12.42; S, 4.74. Found C, 78.06; H, 4.76; N, 12.44; S, 4.75.

Synthesis Example  6. Synthesis of Chemical Formula 130

Synthesis Example  6-1 Synthesis of <6-a>.

<6-a> was synthesized by the following Scheme 32.

Scheme 32

                                                      <6-a>

Into a 500 ml round bottom flask was added 25.0 g (0.112 mol) of <1-d> synthesized in [Scheme 4], 9.4 g (0.112 mol) of cyclopentanone and 250.0 ml of ethanol and refluxed for 10 hours. When the reaction was terminated, the reaction solution was concentrated and then column chromatography was used to obtain <6-a> 26.0g (92.9%).

Synthesis Example  6-2 Synthesis of <6-b>.

<6-b> was synthesized by the following Scheme 33.

Scheme 33

                                                     <6-b>

Synthesis was carried out in the same manner as the compound synthesis method represented by Chemical Formula 1-f, to obtain 29.1g (84.6%) of <6-b>.

Synthesis Example  6-3 Synthesis of <6-c>.

<6-c> was synthesized by the following Scheme 34.

Scheme 34

                                                 <6-c>

Synthesis was carried out in the same manner as the compound synthesis method represented by Chemical Formula 1-g, to obtain 24.8 g (74.1%) of <6-c>.

Synthesis Example  6-4 Synthesis of <6-d>

<6-d> was synthesized according to Scheme 35 below.

Scheme 35

                                                  <6-d>

Synthesis was carried out in the same manner as the compound synthesis method represented by Chemical Formula 2-c, to obtain 13.6 g (70.4%) of <6-d>.

Synthesis Example  6-4 Synthesis of Formula 130.

By following Scheme 36 was synthesized.

Scheme 36

                                                     [Formula 130]

Synthesis was carried out in the same manner as in the synthesis of compound represented by Formula 4 to obtain 7.6 g (36.6%).

MS (MALDI-TOF): m / z 671.30 [M] ⁺

Anal. Calc. for C ₄₇ H ₃₇ N ₅ C, 84.02; H, 5.55; N, 10.42. Found C, 84.01; H, 5.55; N, 10.43.

Synthesis Example  7. Synthesis of Chemical Formula 154

Synthesis Example  7-1. Synthesis of <7-a>

<7-a> was synthesized according to Scheme 37 below.

Scheme 37

              <7-a>

36.5 g (62.8%) of <7-a> was obtained by the same method as the compound synthesis method of Chemical Formula 1-i.

Synthesis Example  7-2 Synthesis of Chemical Formula 154

The chemical formula 130 was synthesized according to Scheme 38 below.

Scheme 38

                                                    Formula 154

Synthesis was carried out in the same manner as in the synthesis of compound represented by Formula 4 to obtain 5.9 g (39.2%).

MS (MALDI-TOF): m / z 684.33 [M] ⁺

Anal. Calc. for C ₄₉ H ₄₀ N ₄ C, 85.93; H, 5.89; N, 8.18. Found C, 85.91; H, 5. 90; N, 8.19.

Synthesis Example  8. Synthesis of Chemical Formula 159

Synthesis Example  8-1 Synthesis of Formula 159.

To [Scheme 159] was synthesized by the following Scheme 39.

Scheme 39

                                                      [Formula 159]

6.1g (40.2%) was obtained by the same method as the synthesis method of the compound represented by Formula 4.

MS (MALDI-TOF): m / z 674.25 [M] ⁺

Anal. Calc. for C ₄₆ H ₃₄ N ₄ SC, 81.87; H, 5.08; N, 8.30; S, 4.75. Found C, 81.89; H, 5.07; N, 8. 29; S, 4.75.

Synthesis Example  9. Synthesis of Chemical Formula 171

Synthesis Example  9-1 Synthesis of <9-a>.

<9-a> was synthesized by the following Scheme 40.

Scheme 40

                                                          <9-a>

31.6 g (64.4%) of <9-a> was obtained by the same method as the compound synthesis method of Chemical Formula 2-d.

Synthesis Example  9-2 Synthesis of <9-b>.

<9-b> was synthesized by the following Scheme 41.

Scheme 41

      <9-b>

31.6 g (0.14 mol) of <9-a> synthesized in Scheme 39 in a 500 ml round bottom flask, 35.2 g (0.154 mol) of 2-dibenzothiophenboronic acid, 58.21 g (0.421 mol) of potassium carbonate (K ₂ CO ₃ ) ), Tetrakistriphenylphosphinepalladium (Pd (PPh ₃ ) ₄ ) 4.87 g (0.004 mol), 60.0 mL of water, 150.0 mL of toluene and 150.0 mL of tetrahydrofuran were added and refluxed for 24 hours. When the reaction was completed, the resulting product was separated into layers to remove the aqueous layer, and the organic layer was separated and concentrated under reduced pressure to obtain 37 g (70.7%) through column chromatography.

Synthesis Example  9-3. Synthesis of <9-c>

<9-c> was synthesized by the following Scheme 42.

Scheme 42

                              <9-c>

39.6 g (93.9%) of <9-c> was obtained by the same method as the compound synthesis method of Chemical Formula 1-b.

Synthesis Example  9-4. Synthesis of <9-d>

<9-d> was synthesized according to Scheme 43 below.

Scheme 43

<9-d>

24.3 g (84.5%) of <9-d> was obtained by the same method as the compound synthesis method of Chemical Formula 1-c.

Synthesis Example  9-5 Synthesis of <9-e>

<9-e> was synthesized according to Scheme 44 below.

Scheme 44

                                                   <9-e>

11.9 g (70.6%) of <9-e> was obtained by the same method as the compound synthesis method of Chemical Formula 2-c.

Synthesis Example  9-6 Synthesis of Formula 171.

To [Scheme 171] was synthesized by Reaction Scheme 45.

Scheme 45

                                                      [Formula 171]

7.2 g (38.3%) was obtained by synthesizing according to the same method as the compound synthesis method represented by Chemical Formula 4.

MS (MALDI-TOF): m / z 914.34 [M] ⁺

Anal. Calc. for C ₆₅ H ₄₆ N ₄ SC, 85.31; H, 5.07; N, 6. 12; S, 3.50. Found C, 85.35; H, 5.06; N, 6. 10; S, 3.49.

Synthesis Example  10. Synthesis of Chemical Formula 204

Synthesis Example  10-1 Synthesis of <10-a>.

<10-a> was synthesized by the following Scheme 46.

Scheme 46

                                            <10-a>

60.0 g (0.325 mol) of 1,3,5-trichlorotriazine and 300 ml of acetone are added to a 500 ml round bottom flask, and 61.2 g (0.651 mol) of phenol, 210.0 ml of water, and 26 g of sodium hydroxide are added dropwise to the mixture at 10 degrees. . When the reaction is complete the solid is filtered off. Recrystallization gave 64 g (65.6%) of <10-a>.

Synthesis Example  10-2 Synthesis of Formula 204.

To [Scheme 204] was synthesized by the following Reaction Scheme 47.

Scheme 47

                                                     Formula 204

5.3 g (34.9%) of [Formula 204] was obtained by the same method as the synthesis method of the compound represented by Formula 4.

MS (MALDI-TOF): m / z 869.37 [M] ⁺

Anal. Calc. for C ₆₀ H ₄₇ N ₅ O ₂ C, 82.83; H, 5. 44; N, 8.04; 0, 3.68. Found C, 82.85; H, 5. 45; N, 8.02; 0, 3.67.

EXAMPLE

Fabrication of Organic Light Emitting Diode

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

Comparative example

The organic light emitting diode device for the comparative example was manufactured in the same manner except that CBP, which is generally used as a phosphorescent host material, was used instead of the compound prepared by the invention in the device structure of the above embodiment, and the structure of the CBP is as follows.

<CBP>

As shown in Table 1, the aromatic compound according to the present invention has a low driving voltage and excellent luminous efficiency as compared to CBP which is widely used as a phosphorescent host material.

Claims (6)

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

In Chemical Formula 1,
X is selected from the group consisting of CRR, NR, O, S and SiRR, wherein R is selected from an alkyl group having 1 to 10 carbon atoms and an aryl group having 6 to 20 carbon atoms,
L is a single bond or a divalent linking group selected from an arylene group having 6 to 10 carbon atoms and a heteroarylene group having 3 to 10 carbon atoms, m is an integer of 0 to 1,
R ₁ to R ₆ are each independently hydrogen, deuterium, cyano group, halogen group, alkyl group of 1 to 10 carbon atoms, cycloalkyl group of 3 to 20 carbon atoms, aryl group of 6 to 20 carbon atoms, heteroaryl group of 3 to 20 carbon atoms And it is selected from the group consisting of alkylsilyl group having 1 to 10 carbon atoms,
Provided that at least one of R ₁ to R ₆ is a heteroaryl group containing nitrogen,
L, R and R ₁ to R ₆ are each independently a deuterium atom, cyano group, halogen atom, hydroxy group, nitro group, alkyl group of 1 to 10 carbon atoms, alkoxy group of 1 to 10 carbon atoms, alkylamino group of 1 to 20 carbon atoms , Arylamino group having 6 to 20 carbon atoms, heteroarylamino group having 3 to 20 carbon atoms, alkylsilyl group having 1 to 10 carbon atoms, arylsilyl group having 6 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, aryl having 3 to 20 carbon atoms It may be substituted by one or more substituents selected from the group consisting of oxy group, heteroaryl group having 3 to 20 carbon atoms, germanium group, phosphorus and boron, and substituents of L, R and R ₁ to R ₆ are condensed with each other with adjacent substituents. Can form a ring,
n is an integer of 3-6. The method of claim 1,
An aromatic compound, characterized in that any one selected from the group of compounds represented by the following [Formula 2] to [Formula 225]:

Anode; Cathode; And a layer comprising the aromatic compound according to claim 1 between the anode and the cathode. The organic light emitting device of claim 3, wherein the aromatic compound is included in a light emitting layer between the anode and the cathode. The hole injection layer, the hole transport layer, the electron blocking layer between the anode and the cathode. An organic electroluminescent device further comprising at least one layer selected from the group consisting of a hole blocking layer, an electron transport layer and an electron injection layer. The organic light emitting device of claim 3, wherein the organic light emitting display device is used for a display device, a display device, and a monochrome or white illumination device.

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