KR20180131662A - Novel pyridinyl triazolopyridine derivatives and use thereof - Google Patents

Abstract

The present invention relates to novel pyridinyl-triazolopyridine derivatives and uses thereof, and more specifically, to an aromatic organic material including pyrimidine and an organic electroluminescent device using the same. According to an embodiment of the present invention, the organic electroluminescent device using the aromatic organic material including the pyrimidine can obtain light at a short wavelength in a highly efficient manner while lowering the driving voltage.

Description

Novel pyridinyl triazolopyridine derivatives and use thereof <br> <br> <br> Patents - stay tuned to the technology Novel pyridinyl triazolopyridine derivatives &

The present invention relates to a novel compound as a light emitting material having an excellent light emitting efficiency, and an organic electroluminescent device exhibiting excellent efficiency characteristics by incorporating the novel compound into one or more organic layers.

Organic semiconductors are being developed for many types of electronic equipment applications. The organic electroluminescent device has a simple structure compared to other flat panel display devices such as a liquid crystal display (LCD), a plasma display panel (PDP), and a field emission display (FED) And has a high response speed and a low driving voltage, so that it is being actively developed to be used as a light source for a flat panel display such as a wall-mounted TV or a backlight of a display, a lighting, and a billboard.

In the organic electroluminescent device, when a direct current voltage is applied, holes injected from the anode recombine with electrons injected from the cathode to form an exciton, which is an electron-hole pair, and the energy of the exciton is transferred to the light emitting material .

In general, an organic electroluminescent device has a structure including a cathode (electron injection electrode), an anode (hole injection electrode), and at least one organic layer between the two electrodes. In this case, the organic electroluminescent device may include, as an organic layer, a hole injection layer (HIL), a hole transport layer (HTL), an electron transport layer (ETL), or an electron transport layer And may further include an electron injection layer (EIL), and may further include an electron blocking layer (EBL) or a hole blocking layer (HBL) on the light emitting property of the light emitting layer. The organic electroluminescent device including all of these organic layers has a stacked structure in the order of anode / hole injecting layer / hole transporting layer / electron blocking layer / light emitting layer / hole blocking layer / electron transporting layer / electron injecting layer / cathode.

When an electric field is applied to the organic electroluminescent device having such a structure, the holes injected from the anode and the electrons injected from the cathode are recombined to form an electron-hole pair exciton, Light is emitted as it is transmitted.

The luminescent material is divided into a fluorescent light emitting material and a phosphorescent light emitting material according to the principle of emitting light, and a thermally activated delayed fluorescent light which is recently studied mainly in the Adachi group. Generally, a light emitting material can emit almost all the colors that we desire with only the three primary colors of light: red, green, and blue. However, when mixing light, . In addition, when only one material is used as a light emitting material, there is a drawback that the color purity and luminous efficiency are inferior. Therefore, the host / dopant system in which the emission spectrum of the host and the absorption spectrum of the dopant are coincident, There are host materials and dopant materials to increase.

Particularly, in order to commercialize amorphous high-efficiency amorphous, the problem of efficiency must be solved, and in particular, the efficiency of blue and green light emitting materials needs to be improved. However, in the case of a blue light emitting material, it has been difficult to exceed 5% due to a structural problem when a fluorescent material is used, and it is inevitable to expect efficiency improvement through the use of a phosphorescent material. Nevertheless, it is difficult to develop a phosphorescent material because the cost of the metal complex (Ir, Pt, etc.) required to realize phosphorescence is too high and the life is very short, which is a problem in commercialization. However, recently, the paper published in Nature (2012, 492: 234) and JACS (2012, 134, 14706) introduces the concept of TADF to introduce a high-efficiency green fluorescent material with high external quantum efficiency, . The TADF concept refers to the phenomenon that the inverse energy transfer from the excitation triplet state to the excited singlet state is caused by thermal activation resulting in fluorescence emission. Since triplet light oil emits light, it is generally called delayed fluorescent light in that long-lived light emission occurs. A material suitable for the high-efficiency TADF concept through molecular design that reduces the energy difference between singlet and triplet excited states by combining electron donor and acceptor electron acceptor molecule Can be developed. The advantage of TADF is that it can use both fluorescent and phosphorescent luminescence, and it has been attracting much attention as a third-generation material with fluorescence and phosphorescence in that it can solve the problems of external quantum efficiency of existing fluorescent materials .

The TADF concept has been shown to be able to control the excited state of electrons in a relatively simple molecular structure while taking advantage of the freedom of molecular design of organic compounds. As a result, the width of the structural design design in the organic light emitting material is widening, and it is expected that practical use of the organic light emitting device, provision of high-efficiency RGB light emitting material, and high durability are realized.

The present inventors have made intensive research to develop a novel TADF luminescent material, and as a result, they have synthesized a series of compounds containing a pyridinyltriazolopyridine moiety and confirmed that these compounds exhibit excellent properties as an organic luminescent material, .

It is an object of the present invention to provide a novel luminescent material that can improve the efficiency of an organic light emitting diode and reduce a driving voltage, a method for producing the same, and an organic light emitting device including the organic luminescent element.

It is an object of the present invention to provide a compound which can be used as a TADF light emitting material, and an organic light emitting element containing the same in an organic layer.

In order to solve the above-mentioned problems, the present invention provides a compound represented by the following formula (1):

[Chemical Formula 1]

In this formula,

R ₁ is a single bond, -CR ₆ R ₇ -, S or O,

Each of R ₂ to R ₅ is independently hydrogen, a substituted or substituted C _6-40 aryl group, a substituted or unsubstituted 5-to 20-membered heteroaryl group, a substituted or unsubstituted C _3-60 cycloalkyl group, A substituted or unsubstituted 5- to 30-membered heterocyclic group,

R ₂ and R ₃ and R ₄ and R ₅ are each independently located on adjacent carbons and are linked together to form a fused ring structure with the carbon to which they are attached,

R &lt; ₆ &gt; and R &lt; ₇ &gt; are each independently hydrogen or _C1-6alkyl or are linked to each other to form a ring structure together with the carbon to which they are bonded,

Optionally wherein the aryl, heteroaryl, cycloalkyl, a heterocyclic group, and the ring structure are each independently unsubstituted or substituted with C _1-6 alkyl, C _6-50 aryl, C _1-50 alkyl, C _3-50 cycloalkyl Alkyl, and 5-to 30-membered heterocycle.

Specifically, in Formula 1,

R ₂ to R ₅ are each independently selected from the group consisting of hydrogen, carbazole, acridine, phenothiazine, phenoxazine, dibenzofuran, dibenzothiophene ), Phenylcarbazole, or spiro [xanthene-9,9'-acridine]

R ₂ and R ₃ and R ₄ and R ₅ are each located on adjacent carbon and are linked together to form a benzofuran, benzene, indene or indoline ),

R ₆ and R ₇ are both methyl or linked together to form a xanthene,

Optionally, each of the ring structures of R ₂ to R ₇ may be independently substituted with any one or more substituents selected from methyl or phenyl.

Among the compounds represented by Formula 1 according to the present invention, the pyrimidine molecule can improve the electron transferring ability and can realize the dark blue color because of the high energy of the triplet state (T1) Can be expected.

Non-limiting examples of the compound represented by Formula 1 include the following.

The compound represented by Formula 1 may be applied to not only the light emitting layer but also the hole injecting layer, the hole transporting layer, the electron transporting layer, and the electron injecting layer depending on the type of the substituent to be introduced. A number of compounds which can act as a buffer between a hole injection, a hole transport, a hole blocking, a luminescence, an electron transport, an electron injection, and an anode and a hole injection layer are well known and are generally substituted or unsubstituted aromatic or hetero And an aromatic group.

Also, as an example of the present invention, there is provided a process for producing the compound represented by the above formula (1).

Specifically, the compound represented by formula (1) according to the present invention can be prepared by reacting a compound represented by formula (2) and a compound represented by formula (3) (step 1).

(2)

(3)

In the above formula (2), X is halogen, specifically, chlorine or bromine,

In Formula 3, R ₁ to R ₅ are as defined above.

Step 1 is a step of reacting a compound represented by formula (2) with a compound represented by formula (3) to prepare a compound represented by formula (1).

In the present invention, toluene can be used as the reaction solvent in the above step 1, but the present invention is not limited thereto.

In the present invention, the reaction temperature of step 1 may range from 100 to 130 ° C. If the reaction temperature is lower than 100 ° C., the reaction rate becomes slow and the reaction time becomes longer. On the other hand, when the reaction temperature is higher than 130 ° C., impurities are formed and the yield is lowered.

In the present invention, the reaction time of step 1 may be 12 to 20 hours. If the reaction time is shorter than 12 hours, the reaction is not completed and the starting material remains. In general, the reaction time is completed within 20 hours, so that a reaction time of more than 20 hours is not required.

Specifically, the above Step 1 may be represented by the following Reaction Scheme 1, but is not limited thereto.

[Reaction Scheme 1]

In the present invention, the step 1 further comprises a step of preparing a compound represented by the formula (2) by reacting a compound represented by the following formula (2-2) with 2,6-dihalopyridine can do.

[Formula 2-2]

In the above formula (2-2), X is halogen, specifically, chlorine or bromine.

In the present invention, step 1 is a step of reacting a compound represented by the following formula (2-1) with dimethylformamide dimethyl acetal and then reacting with a hydroxylamine hydrochloride ;

And a second step of carrying out a cyclization reaction by reacting the compound obtained in the first step with trifluoroacetic anhydride, to prepare a compound represented by the formula (2-2) can do.

[Formula 2-1]

In the above formula (2-1), X is halogen, specifically, chlorine or bromine.

In the present invention, the step 1 is a step of carrying out an amine group-protecting reaction from a compound represented by the following general formula (3-1);

A second step of reacting the compound in which the amine group obtained from the first step is protected with R-H to replace X with R;

And a third step of removing the amine protecting group of the compound obtained from the second step.

[Formula 3-1]

Wherein R ₁ is as defined above, X is halogen, specifically chlorine or bromine,

R is at least one selected from R ₂ to R ₅ , and R ₂ to R ₅ are as defined above.

The compounds used in the production method of the present invention may be purchased commercially or synthesized by methods known in the art.

The present invention also provides a luminescent host or dopant-containing composition for an organic electroluminescence device containing a compound represented by the formula (1), specifically, any one of the above-mentioned compounds (1) to (33).

The present invention also provides an organic electroluminescent device comprising a compound represented by the formula (1), specifically, a compound of any of the above-mentioned compounds (1) to (33) in one or more organic layers. At this time, the organic layer essentially includes a light emitting layer and may include a hole injecting layer, a hole transporting layer, an electron injecting layer, an electron transporting layer, or a laminate thereof in addition to the light emitting layer.

The organic electroluminescent device of the present invention comprises a single layer or a multilayer organic layer containing a positive electrode, a negative electrode and at least one light emitting layer between the two electrodes, wherein at least one layer of the organic layer is a compound represented by the general formula (1) And specifically includes any one or more of the compounds of the above-mentioned compounds 1 to 33. For example, a multilayer organic electroluminescent device is laminated from the bottom in a multilayer structure of a substrate, an anode, a hole injecting layer, a hole transporting layer, a light emitting layer, an electron transporting layer, an electron injecting layer and a cathode.

The substrate, the anode, and the cathode of the organic electroluminescent device according to the present invention are made of a material used in a conventional organic electroluminescent device, and any one of the hole injecting layer, the hole transporting layer, the light emitting layer, the electron transporting layer, 1, specifically, any one or more of the above-mentioned compounds 1 to 33, or a mixture thereof.

Particularly, in the case of the light emitting layer, the compound represented by the formula (1) of the present invention, specifically, the compound (1) to (33) may be used alone or in combination of two or more, or a light emitting host material or a dopant, Can be used in conjunction with other known luminescent dopant materials or host materials for use as materials. When the compound represented by the formula (1), specifically the compound (1) to (33), is used as a single luminescent material or a host material, it may be added in an amount of 100 to 80% by weight relative to the light emitting layer. May be added in an amount of 0.01 to 20% by weight. Specific examples of the luminescent material, the host material or the dopant material which can be used in the luminescent layer together with the compound represented by the formula (1), specifically the compounds (1) to (33) include anthracene, naphthalene, phenanthrene, pyrene, tetracene, Naphthalene, naphthalene, naphthalene, naphthalene, naphthalene, naphthalene, naphthalene, naphthalene, naphthalene, naphthalene, Aminophenol metal complexes, benzoquinoline metal complexes, imine, diphenylethylene, vinyl anthracene, diaminocarbazole, pyran, thiopyran, polymethine, meloxicam But are not limited to, imidazole chelated oxinoid compounds, quinacridones, rubrene, fluorescent dyes, and mixtures thereof. When a dopant material is selected, it can be selected to have a bandgap equal to or less than the bandgap of the host material while having high efficiency of fluorescence or phosphorescence.

Each of the layers constituting the organic electroluminescent device may be formed by any of a conventional film forming method such as vacuum deposition, sputtering, plasma or ion plating, or a wet film forming method such as spin coating, immersion coating, . If the film thickness is too large, a high applied voltage is required to obtain a constant light output, which leads to deterioration of efficiency. When the film thickness is too small, a pin hole or the like is generated and an electric field is applied A sufficient light emission luminance can not be obtained. Specifically, the film thickness may be in the range of 5 nm to 10 탆, and more specifically in the range of 50 nm to 400 nm.

When the novel compound of the present invention is used in an organic light emitting diode, the efficiency of the organic light emitting diode can be improved and the driving voltage can be lowered.

The novel compounds of the present invention exhibit a small energy difference between the excited state of the triplet and the excited state of the triplet by combining donor and donor electron acceptor molecules so that TADF Retarded fluorescence) luminescent material.

Hereinafter, the present invention will be described in more detail with reference to Examples. These embodiments are only for describing the present invention more specifically, and the scope of the present invention is not limited by these examples.

Example  1: Preparation of compound 1

Compound 1 was prepared by the following reaction formula.

(1) Synthesis of intermediate C-4

The core intermediate C-4 of the present invention, namely, 6- (6-bromopyridin-2-yl) - [1,2,4] triazolo [1,5- a] pyridine was synthesized by the following synthesis method.

1) Synthesis of intermediate C-1

50 g of 2-amino-5-bromopyridine and 100 mL of isopropanol are placed in a 500 mL three-neck round bottom flask, and 50 mL of dimethylformamide-dimethylacetal is slowly added dropwise. After refluxing for 3 hours, the mixture was cooled to 50 DEG C and 30.3 g of hydroxylamine hydrochloride was added. After the reaction at 50 DEG C for 12 hours, the reaction mixture was cooled to room temperature and concentrated under reduced pressure, followed by column separation using ethyl acetate and hexane to obtain 41 g of the title compound.

2) Synthesis of intermediate C-2

In a 1 L three-necked round bottom flask, 41 g of the compound C-1 was dissolved in 400 mL of anhydrous tetrahydrofuran and cooled to 0 占 폚. 80 mL of trifluoroacetic anhydride is added dropwise over 10 minutes. After slowly raising the temperature to room temperature and stirring for 5 hours, add 1 L of 5% aqueous sodium hydrogencarbonate solution and extract three times with t -butyl ether. The organic layer was separated, water was removed, and the filtrate was concentrated under reduced pressure to obtain 23.6 g of the title compound.

3) Synthesis of intermediate C-3

23.6 g of the compound C-2 was placed in a 1 L three-necked round bottom flask, 450 mL of anhydrous tetrahydrofuran was added, and the mixture was stirred under an argon atmosphere and the temperature of the mixture was lowered to -78 ° C. After 2.5 M n -butyl lithium (47.7 mL) was slowly added dropwise and stirred at the same temperature for 1 hour, 20 mL of triethyl borate was added, and the mixture was slowly warmed to room temperature and stirred for 8 hours. Water was added, and the mixture was extracted with ethyl acetate. The organic layer was separated and concentrated under reduced pressure. The material formed by concentration was dissolved in dichloromethane and precipitated with hexane to give 14.5 g of the title compound.

4) Synthesis of intermediate C-4

14.5 g of Intermediate C-4, 21 g of 2,6-dibromopyridine, 600 mL of toluene and 200 mL of ethanol were placed in a 2 L three-necked round bottom flask and stirred under argon atmosphere. To this mixture was added 2.1 g of tetrakis (triphenylphosphine) palladium (0) and 24.6 g of potassium carbonate, and the mixture was stirred at 80 ° C. After stirring for 6 hours, water was added and the reaction solution was separated into layers. The organic layer was dehydrated and concentrated under reduced pressure to remove the solvent. The material formed by concentration was subjected to column separation using ethyl acetate and hexane to obtain 15 g of the title compound.

(2) Synthesis of Compound 1

3 g of Intermediate C-4, 2.2 g of carbazole and 60 mL of toluene were placed in a 250 mL three-neck round bottom flask, and the mixture was stirred under an argon atmosphere. To the mixture, 0.2 g of tris (dibenzylidine) acetone dipalladium (0), 0.2 g of tri-t-butylphosphine and 2.3 g of sodium-t-butoxide were added and the mixture was stirred and refluxed for 18 hours. After the reaction was completed, the reaction mixture was concentrated under reduced pressure, and the resulting material was subjected to column separation using dichloromethane to obtain 2.5 g of the title compound.

Example  2: Preparation of compound 2

Compound 2 was synthesized by the following synthesis method.

Compound 2 was obtained in the same manner as in the synthesis of Compound 1 except that 9,9-dimethyl-9,10-dihydroacridine was added instead of carbazole.

Example  3: Preparation of compound 3

Compound 3 was synthesized by the following synthesis method.

Compound 3 was obtained in the same manner as in the synthesis of Compound 1 except that phenothiazine was added instead of carbazole.

Example  4: Synthesis of compound 4

Compound 4 was synthesized by the following synthesis method.

Compound 4 was obtained in the same manner as in the synthesis of Compound 1, except that phenoxazine was added instead of carbazole.

Example  5: Preparation of compound 5

Compound 5 was obtained in the same manner as in the synthesis of Compound 1 except that Intermediate 5-3 was used instead of Intermediate 1-3. Intermediate 5-3 was synthesized by the following synthesis method.

Synthesis of Intermediate 5-1

10 g of 3-iodocarbazole and 25 mL of dimethylformamide were added to a 250 mL three-neck round bottom flask and stirred. The temperature of the mixture was maintained at 0 캜, and 1.22 g of sodium hydride was added thereto. After 10 minutes, 7.1 g of p-toluenesulfonyl chloride was added and the mixture was stirred for 4 hours. After the addition of water, the solid phase was separated by filtration. 12 g of the title compound was obtained by recrystallization from dichloromethane.

Synthesis of Intermediate 5-2

12 g of Intermediate 5-1, 7 g of carbazole, 8.98 g of cuprous oxide and 24 mL of dimethylformamide were added to a 250 mL three-necked round bottom flask, and the mixture was stirred at 100 ° C for 12 hours. After cooling at room temperature, a silica filter was applied. The filtered solution was concentrated under reduced pressure, and then washed with water and methanol. After the removal of water, the resulting material was subjected to column separation using hexane to obtain 12 g of the title compound.

Synthesis of Intermediate 5-3

12 g of Intermediate 5-2, 1.0 g of sodium hydride, 36 mL of tetrahydrofuran and 18 mL of methanol were added to a 100 mL three-neck round bottom flask, and the mixture was stirred at room temperature for 4 hours. After silica gel filtration, the filtrate was concentrated under reduced pressure. The solid was washed with water and recrystallized from dichloroethane to give 3 g of the title compound.

Example  6: Preparation of Compound 6

3.7 g of the compound of Intermediate 6-3 was obtained in the same manner as in Example 5, except that 9,9-dimethyl-9,10-dihydroacridine was added instead of carbazole.

Compound 6 was obtained in the same manner as in the synthesis of Compound 1, except that Intermediate 6-3 was used instead of Intermediate 1 -3.

Example  7: Preparation of Compound 7

4 g of a compound of Intermediate 7-3 was obtained in the same manner as in Example 5, except that phenothiazine was added instead of carbazole.

Compound 7 was obtained in the same manner as in the synthesis of Compound 1, except that Intermediate 7-3 was used instead of Intermediate 1 -3.

Example  8: Preparation of compound 8

3.5 g of the compound of Intermediate 8-3 was obtained in the same manner as in Example 5, except that phenoxazine was used instead of carbazole.

Compound 8 was obtained in the same manner as in the synthesis of Compound 1, except that Intermediate 8-3 was used instead of Intermediate 1-3.

Example 9: Preparation of Compound 9

Compound 9 was obtained in the same manner as in the synthesis of Compound 1 except that Intermediate 9-3 was used instead of Intermediate 1 -3. Intermediate 9-3 was synthesized by the following synthesis method.

Synthesis of intermediate 9-1

20 g of bromoiodobenzene and 6.58 g of aniline were added to a 250 mL three-neck round bottom flask and stirred. 9.51 g of sodium t -butoxide, 0.82 g of 2,4 ', 6'-triisopropyl biphenyl-2-dicyclohexylphosphine and tris dibenzylidine acetone dipalladium (0) were placed in the mixture, 80 &lt; 0 &gt; C. After 12 hours, the reaction mixture was cooled at room temperature, filtered through silica gel with dichloromethane, and concentrated under reduced pressure to obtain 16 g of the title compound.

Synthesis of intermediate 9-2

In a vacuum-dried 250 mL three-neck round bottom flask, 120 mL of anhydrous tetrahydrofuran was added to 16 g of Compound 9-1, stirred under argon atmosphere, and the temperature of the mixture was lowered to -78 ° C. 56.75 mL of butyllithium was added slowly and stirred at the same temperature for 1 hour. 15.18 g of thionate was added at the same temperature and stirred for 12 hours. After concentration under reduced pressure, the mixture was extracted with chloroform (320 mL) to obtain 8 g of the title compound.

Synthesis of intermediate 9-3

In a 250 ml three-necked round bottom flask, 8.2 g of the compound 9-2, which had been extracted, was added with 6.82 g of methanesulfonic acid to 100 mL of chloroform, and the mixture was maintained at 60 ° C. Sodium bicarbonate aqueous solution was slowly added and stirred. Chloroform is extracted several times. The solids were filtered through chloroform and methanol to give 3.1 g of the title compound.

Example  10: Preparation of compound 10

Compound 10 was obtained in the same manner as in the synthesis of Compound 1, except that Intermediate 10-3 was used instead of Intermediate 1 -3. Intermediate 10-3 was synthesized by the following synthesis method.

Synthesis of Intermediate 10-1

10 g of 2-bromocarbazole and 25 mL of dimethylformamide were added to a 250 mL three-neck round bottom flask and stirred. The temperature of the mixture is maintained at 0 캜, and 1.22 g of sodium hydride is added. After 10 minutes, 7.1 g of p-toluenesulfonyl chloride was added and stirred for 4 hours. After adding water, the solid phase was separated by filtration. 12 g of the title compound was obtained by recrystallization from dichloromethane.

Intermediate 10 Synthesis of -2

12 g of Compound 10-1, 7 g of carbazole, 8.98 g of cuprous oxide and 24 mL of dimethylformamide were placed in a 250 mL three-necked round bottom flask and stirred at 100 ° C for 12 hours. After cooling at room temperature, a silica filter is applied. The filtered solution is concentrated under reduced pressure, then washed with water and methanol. After the removal of water, the resulting material was subjected to column separation using hexane to obtain 12 g of the title compound.

Intermediate 10 Synthesis of -3

12 g of Compound 10-2, 1.0 g of potassium hydroxide, 36 mL of tetrahydrofuran, and 18 mL of methanol were added to a 100 mL three-neck round bottom flask, and the mixture was stirred at room temperature for 4 hours. After silica gel filtration, the filtrate was concentrated under reduced pressure. The solid was washed with water and recrystallized from dichloromethane to obtain 3.6 g of the title compound.

Example  11: Preparation of compound 11

3.6 g of the compound of Intermediate 11-3 was obtained in the same manner as in the synthesis of Intermediate 5-3 except that 9,9-dimethyl-9,10-dihydroacridine was added instead of carbazole.

Compound 11 was obtained in the same manner as in the synthesis of Compound 1, except that Intermediate 11-3 was used instead of Intermediate 1-3.

Example  12: Preparation of compound 12

3.5 g of the compound of Intermediate 12-3 was obtained in the same manner as in the synthesis of Intermediate 5-3 except that phenothiazine was added instead of carbazole.

Compound 12 was obtained in the same manner as in the synthesis of Compound 1, except that Intermediate 12-3 was used instead of Intermediate 1 -3.

Example  13: Preparation of compound 13

3.2 g of the compound of Intermediate 13-3 was obtained in the same manner as in the synthesis of Intermediate 5-3 except that phenoxystane was added instead of carbazole.

Compound 13 was obtained in the same manner as in the synthesis of Compound 1, except that Intermediate 13-3 was used instead of Intermediate 1-3.

Example  14: Preparation of compound 14

Compound 14 was obtained in the same manner as in the synthesis of Compound 1 except that Intermediate 14-4 was used instead of Intermediate 1 -3. Intermediate 14-4 was synthesized by the following synthesis method.

Synthesis of Intermediate 14-1

10 g of 3-bromocarbazole, 7.4 g of phenylboronic acid, 200 mL of tetrahydrofuran, 16.8 g of potassium carbonate and 60 mL of water were added to a 250 mL three-neck round bottom flask and stirred. 0.95 g of tetrakis (triphenylphosphine) palladium (0) was added to the mixture, and the mixture was heated to 80 ° C. The reaction solution was layered to remove water, and the organic layer was washed twice with water. The organic layer was dried over magnesium sulfate and concentrated under reduced pressure to remove the solvent. The material formed by concentration was subjected to column separation using hexane to obtain 7.1 g of the title compound.

Synthesis of Intermediate 14-2

600 mL of dimethylformamide was added to a 1000 mL three-neck round bottom flask, and the mixture was stirred at 0 ° C. 2.6 g of sodium hydride is slowly added, and 10 g of 2-bromocarbazole is slowly added dropwise. After the mixture was stirred for 5 minutes, toluene-sulfonyl para-chloride was slowly added dropwise, followed by stirring for 4 hours. After addition of water, the solid was separated by filtration, and recrystallized from dichloromethane to obtain 7.6 g of the title compound.

Synthesis of Intermediate 14-3

6.9 g of Compound 14-1, 7.6 g of Intermediate 14-2, 5.4 g of cuprous oxide and 20 mL of dimethylformamide were placed in a 250 mL three-neck round bottom flask, and stirred at 100 占 폚 for 12 hours. After cooling at room temperature, a silica gel filter was applied. The filtered solution was concentrated under reduced pressure, and then washed with water and methanol. After the removal of water, the resulting material was subjected to column separation using hexane to obtain 5.3 g of the title compound.

Synthesis of Intermediate 14-4

5.3 g of Compound 14-3, 0.46 g of potassium hydroxide, 16 mL of tetrahydrofuran and 8 mL of methanol were added to a 100 mL three-necked round bottom flask, and the mixture was stirred at room temperature for 4 hours. After the silica filter was concentrated under reduced pressure, the solid was washed with water and recrystallized from dichloromethane to obtain 3 g of the title compound.

Example  15: Preparation of compound 15

5 g of the compound of Intermediate 15-4 was obtained in the same manner as in the synthesis of Intermediate 14-4 except that 3,6-dibromocarbazole was added instead of 3-bromocarbazole.

Compound 15 was obtained in the same manner as in the synthesis of Compound 1, except that Intermediate 15-4 was used instead of Intermediate 1-3.

Example  16: Preparation of compound 18

Compound 18 was obtained in the same manner as in the synthesis of Compound 1, except that Intermediate 18-1 was used instead of Intermediate 1-3. Intermediate 18-1 was synthesized by the following synthesis method.

3 g of 3-bromocarbazole, 3.1 g of dibenzofuran-4-boronic acid, 60 mL of tetrahydrofuran, 8.4 g of potassium carbonate and 60 mL of water were added to a 250 mL three-neck round bottom flask and stirred. 0.4 g of tetrakis (triphenylphosphine) palladium (0) was added to the mixture, and the mixture was heated to 80 ° C. The reaction solution was layered to remove water, and the organic layer was concentrated under reduced pressure to remove the solvent. The material produced by concentration was subjected to column separation to obtain 3 g of the title compound.

Example 17: Preparation of compound 20

Compound 20 was obtained in the same manner as in the synthesis of Compound 1, except that Intermediate 20-1 was used instead of Intermediate 1-3. Intermediate 20-1 was synthesized by the following synthesis method.

3 g of the title compound was obtained in the same manner as in the synthesis of Intermediate 18-1, except that dibenzothiophene-2-boronic acid was added instead of dibenzofuran-4-boronic acid.

Example  18: Preparation of compound 22

Compound 22 was obtained in the same manner as in the synthesis of Compound 1, except that Intermediate 22-1 was used instead of Intermediate 1-3. Intermediate 22-1 was synthesized by the following synthesis method.

3 g of 2-bromocarbazole, 3.1 g of dibenzofuran-4-boronic acid, 60 mL of tetrahydrofuran, 8.4 g of potassium carbonate and 60 mL of water were added to a 250 mL three-necked round bottom flask and stirred. 0.4 g of tetrakis (triphenylphosphine) palladium (0) was added to the mixture, and the mixture was heated to 80 ° C. The reaction solution was layered to remove water, and the organic layer was concentrated under reduced pressure to remove the solvent. The material produced by concentration was subjected to column separation to obtain 3 g of the title compound.

Example  19: Preparation of Compound 24

Compound 24 was obtained in the same manner as in the synthesis of Compound 1, except that Intermediate 24-1 was used instead of Intermediate 1-3. Intermediate 24-1 was synthesized by the following synthesis method.

3 g of the title compound was obtained in the same manner as in the synthesis of Intermediate 22-1, except that dibenzofuran-2-boronic acid was added instead of dibenzofuran-4-boronic acid.

Example  20: Preparation of Compound 31

Compound 31 was obtained in the same manner as in the synthesis of Compound 1 except that Intermediate 31-2 was used instead of Intermediate 1 -3. Intermediate 31-2 was synthesized by the following synthesis method.

Synthesis of Intermediate 31-1

10 g of 4-dibenzothiophene-boronic acid, 11.8 g of 1-bromo-2-nitrobenzene, 100 L of toluene, 20 mL of ethanol, 12.1 g of potassium carbonate and 20 mL of water were added to a 250 mL three-necked round bottom flask and stirred. To this mixture was added tetrakis (triphenylphosphine) palladium (0) 1.5 and the mixture was heated to 80 ° C. The reaction solution was layered to remove water, and the organic layer was washed twice with water. The organic layer was dried over magnesium sulfate and concentrated under reduced pressure to remove the solvent. The material formed by concentration was subjected to column separation using a mixed solvent of dichloromethane and hexane to obtain 11.3 g of the title compound.

Synthesis of intermediate 31-2

Compound 31-1 8g, triphenylphosphine 20.6g and 1,3-dichlorobenzene 56ml were placed in a 250ml three-necked round bottom flask, and the mixture was refluxed and stirred for 12 hours. The solvent was removed by concentration under reduced pressure. The material formed by concentration was subjected to column separation using a mixed solvent of dichloromethane and hexane to obtain 6 g of the title compound.

Example  21: Preparation of compound 33

Compound 33 was obtained in the same manner as in the synthesis of Compound 1, except that Intermediate 33-2 was used instead of Intermediate 1 -3. Intermediate 33-2 was synthesized by the following synthesis method.

Synthesis of Intermediate 33-1

20 g of 2-bromo- (9-phenyl-carbazole), 9.5 g of 2-chloroaniline and 400 mL of toluene were placed in a 1 L three-necked round bottom flask and stirred under argon atmosphere. 0.8 g of tris (dibenzylidine) acetone dipalladium (0), 0.8 g of tri-t-butylphosphine and 8.9 g of sodium-t-butoxide were added to the mixture, and the mixture was refluxed with stirring for 5 hours. The organic layer was concentrated under reduced pressure, and the resulting material was subjected to column separation using a mixed solvent of dichloromethane and hexane to obtain 17 g of the title compound.

Synthesis of intermediate 33-2

To a 500 mL three-neck round bottom flask was added 12.5 g of intermediate 33-1, 0.38 g of palladium (II) acetate, 1.25 g of tricyclohexylphosphine tetrafluoroborate, 33.1 g of cesium carbonate and 180 mL of dimethylacetamide, Stir for 5 hours and then cool. The reaction solution was separated into water and ethyl acetate, and the organic layer was concentrated under reduced pressure. The resulting material was subjected to column separation using a mixed solvent of dichloromethane and hexane to obtain 5 g of the title compound.

Structural formulas and NMR data of the respective compounds prepared in Examples 1 to 21 are shown in Table 1 below.

compound constitutional formula  NMR (500 MHz, CDCl3, TMS) delta (PPM) One

(M, 2H), 7.94 (d, 1H), 7.86 (d, 1H), 7.72-7.63 m, 2 H), 7.51 (t, 1 H), 7.33-7.21 (m, 4 H) 2

(T, 1H), 7.07-7.02 (t, 4H), 6.73-6.66 (m, 1H) 3H), 6.57 - 6.54 (m, 3H), 1.65 (s, 6H) 3

1H), 7.41 (t, 1H), 7.21-7.16 (m, 6H), 6.97 (m, 2H) , 6.60 (d, 1 H), 6.54 (d, 1 H) 4

(M, 2H), 6.77 (m, 2H), 7.42 (d, IH) , 6.67 - 6.51 (m, 4H) 5

2H), 7.98-7.86 (m, 4H), 7.72-7.63 (m, 3H), 8.17-8.12 (m, 2H) 7.50 (t, 1 H), 7.33-7.25 (m, 7 H) 6

1H), 7.70 (d, IH), 7.70 (d, IH), 8.54-8.52 (m, 2H), 8.17 , 7.35-7.25 (m, 4H), 7.05-6.90 (m, 4H), 6.77-6.63 (m, 4H) 7

(S, 1H), 7.99 (d, IH), 7.80 (d, IH), 8.57 (t, 1H), 7.38-7.16 (m, 10H), 6.97 (m, 2H), 6.77-6.75 8

2H), 7.93 (s, 1H), 7.73 (t, 1H), 7.38-7.19 (m, m, 4H), 6.92 - 6.89 (m, 4H),
6.76-6.69 (m, 4H), 6.59 (d, 2H) 9

2H), 7.74-7.86 (m, 2H), 7.74 (t, 1H), 7.33-7.19 (m, m, 10H), 7.05-6.98 (m, 6H), 6.77-6.69 (m, 4H), 6.51 10

(M, 2H), 7.72-7.63 (m, 2H), 8.17-8.12 (m, 3H), 7.29-7.83 7.50 (t, 1 H), 7.33 - 7.23 (m, 7 H) 11

(M, 2H), 8.17 (s, 1H), 8.00 (d, 1H), 7.94 (d, , 7.69 (t, 1 H), 7.29-7.25 (m, 3H), 7.05-7.02 (m, 4H), 6.73-6.67 12

1H), 7.84 (d, IH), 8.92 (d, IH), 8.62-8.52 , 7.74 (t, IH), 7.33-7.16 (m, 9H), 6.97 (m, 2H), 6.69-6.62 13

(M, 2H), 7.72 (t, 1H), 8.93 (d, 1H), 7.30-7.25 (m, 3H), 6.92-6.85 (m, 4H), 6.77-6.59 (m, 6H) 14

(M, 2H), 7.94-7.69 (m, 8H), 7.51-7.25 (m, 11H) 15

2H), 8.18-8.12 (m, 3H), 8.00-7.83 (m, 5H), 7.77-7.68 (m, 4H) 7.52-7.23 (m, 14H) 16

2H), 8.15-8.17 (d, 2H), 8.00-7.86 (m, 5H), 7.76-7.63 (m, 5H) 7.52-7.25 (m, 14H) 17

1H), 7.72-7.63 (m, 4H), 7.52-7.86 (m, 3H) 7.25 (m, 11 H) 18

2H), 8.13 (s, 1H), 7.94-7.66 (m, 10H), 7.38-7.25 (m, 6H) 19

2H), 7.98-7.69 (m, 7H), 7.58-7.50 (m, 3H), 8.59-8. 7.32-7.21 (m, 3H) 20

2H), 7.33-7.25 (m, 3H), 8.17-7.72 (m, 11H), 7.52-7.44 (dd, 21

2H), 8.16 (s, 1H), 7.95-7.66 (m, 11H), 7.38-7.25 (m, 5H) 22

(D, 2H), 7.94-7.62 (m, 9H), 7.38-7.24 (m, 6H) 23

4H), 8.21-8.16 (m, 3H), 7.98-7.72 (m, 5H), 7.62-7.47 (m, 4H) 7.33-7.25 (m, 3H) 24

2H), 7.94-7.66 (m, 10H), 7.38-7.25 (m, 5H), 8.38 (d, 25

2H), 8.00-7.72 (m, 8H), 7.62 (s, 1H), 7.52-8.09 (d, 7.50 (m, 2H), 7.33 - 7.24 (m, 3H) 26

2H), 8.19-8.14 (d, 2H), 8.00-7.86 (m, 5H), 7.76-7.69 (m, 6H), 8.31 (s, 7.58-7.24 (m, 13H) 27

1H), 7.92-7.72 (m, 2H), 8.17 (s, 1H), 8.09 (d, 3H), 7.61 (d, 1H), 7.51-7.44 (m, 2H), 7.33-7.24 28

(S, 1H), 7.94 (d, 1H), 7.86 (d, 1H) , 7.72-7.69 (m, 2H), 7.61 (d, 1H), 7.44 (t, 29

(M, 2H), 7.94 (d, 1H), 7.86 (d, 1H) 1H), 7.72 (t, 1H), 7.61 (d, 1H), 7.54 (s, 30

1H), 7.93-7.69 (m, 10H), 7.58-7.45 (m, 5H), 7.33-8. 7.21 (m, 5 H) 31

1H), 7.72 (t, 1H), 7.52-7.50 (m, 2H) m, 2H), 7.33-7.25 (m, 4H) 32

(M, 2H), 7.38-7.30 (m, 4H), 7.72-7.66 (m, 2H) 7.25 (m, 5 H), 7.13 (d, 1 H) 33

2H), 7.94-7.86 (m, 2H), 7.63-7.23 (m, 14H), 8.17-8.12 (m,

Experimental Example  One: Example  Preparation of organic electroluminescent device using compound 1

The ITO transparent electrode having a thin film thickness of 100 nm was cut into a size of 40 mm x 40 mm x 0.7 m, and the substrate was ultrasonically cleaned in distilled water for 10 minutes and washed twice in distilled water for 10 minutes. After the distilled water was washed, solvents such as isopropyl alcohol, acetone and methanol were sequentially ultrasonically washed and dried. After the wet refining, the substrate was dry-cleaned using oxygen / argon plasma, and then a glass substrate having a transparent electrode line was mounted on a substrate holder of a vacuum evaporation apparatus. On the surface of the ITO side on which the transparent electrode line was formed, Hexanitrile hexaazatriphenylene represented by the following formula was thermally vacuum deposited to a thickness of 60 nm to form a hole injection layer.

(A)

(N ⁴ , N ^{4 '} -di (naphthalene-1-yl) -N ⁴ , N ^4' -diphenyl, which is capable of transporting holes on the layer of the compound represented by the above formula Biphenyl-4,4'-diamine) was vacuum-deposited to a thickness of 20 nm.

[Chemical Formula B]

(4- (4aH-carbazole-9 (4bH, 8aH, 9aH) -quinolinone represented by the following formula (C) capable of preventing electrons from easily flowing into the hole transport layer on the layer of the compound represented by the above formula (9H-carbazol-9-yl) benzenamine) in the form of TCTA was vacuum deposited to a thickness of 10 nm .

&Lt; RTI ID = 0.0 &

Compound 1 of Example 1 was mixed and deposited at a concentration of 5% by weight as a dopant together with a compound represented by the following formula (D) as a light emitting host on a layer of the compound represented by the above formula (C) to form a 30 nm thick light emitting layer.

[Chemical Formula D]

A compound of the following formula (E) serving as an electron injecting and transporting layer was vacuum deposited on the light emitting layer to a thickness of 30 nm.

(E)

Lithium fluoride (LiF) having a thickness of 0.7 nm and aluminum having a thickness of 120 nm were sequentially deposited on the electron injection and transport layer to form a cathode. The resultant organic electroluminescent device was measured at a voltage of 4V. As a result, a current density of 3.73 mA / cm 2 was formed. At this time, a brightness of 472 cd / m 2 corresponding to x = 0.149 and y = 0.182 The near - light spectrum was observed and the efficiency was 12.6 cd / A.

Experimental Example  2: Preparation of Organic Electroluminescent Device Using Compound 2

An organic electroluminescent device was prepared in the same manner as in Experimental Example 1 except that Compound 2 was used as a luminescent dopant material in place of Compound 1 as a luminescent dopant material. The organic EL device thus fabricated had a current density of 3.12 mA / cm 2 and a luminance of 359 cd / m 2 corresponding to x = 0.149 and y = 0.183 on the basis of 1931 CIE color coordinates. A spectrum close to pure blue was observed and the efficiency was 11.5 cd / A.

compare Experimental Example  One

The organic electroluminescent device was fabricated in the same manner as in Experimental Example 1, except that Compound F, which is a dopant material, was used as a luminescent dopant material in the same manner as in Experimental Example 1. [ The organic EL device thus fabricated had a current density of 6.1 mA / cm 2 and a luminance of 329 cd / m 2 corresponding to x = 0.149 and y = 0.173 on the basis of 1931 CIE color coordinates. A spectrum close to pure blue was observed and the efficiency was 6.9 cd / A.

[Chemical Formula F]

Current density
(mA / cm 2) brightness
(cd / m 2) efficiency
(cd / A) The color coordinates (x, y) Experimental Example 1 (Compound 1) 3.73 472 12.6 0.149, 0.182 Experimental Example 2 (Compound 2) 3.12 359 11.5 0.149, 0.183 Comparative Experimental Example 1 (Formula F) 6.1 329 6.9 0.149, 0.173

As shown in Table 2, the organic electroluminescent device using the compound of the present invention had higher brightness and efficiency and lower current density than the organic electroluminescent device of Comparative Experimental Example 1. [

Claims (11)

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

In this formula,
R ₁ is a single bond, -CR ₆ R ₇ -, S or O,
Each of R ₂ to R ₅ is independently hydrogen, a substituted or substituted C _6-40 aryl group, a substituted or unsubstituted 5-to 20-membered heteroaryl group, a substituted or unsubstituted C _3-60 cycloalkyl group, A substituted or unsubstituted 5- to 30-membered heterocyclic group,
R ₂ and R ₃ and R ₄ and R ₅ are each independently located on adjacent carbon atoms and are connected to each other to form a fused ring structure with the carbon to which they are bonded,
R &lt; ₆ &gt; and R &lt; ₇ &gt; are each independently hydrogen or _C1-6alkyl or are linked to each other to form a ring structure together with the carbon to which they are bonded,
Optionally wherein the aryl, heteroaryl, cycloalkyl, a heterocyclic group, and the ring structure are each independently unsubstituted or substituted with C _1-6 alkyl, C _6-50 aryl, C _1-50 alkyl, C _3-50 cycloalkyl Alkyl, and 5-to 30-membered heterocycle.
The method according to claim 1,
Wherein R ₂ to R ₅ are each independently selected from the group consisting of hydrogen, carbazole, acridine, phenothiazine, phenoxazine, dibenzofuran, dibenzothiophene dibenzothiophene, phenylcarbazole, or spiro [xanthene-9,9'-acridine]
R ₂ and R ₃ and R ₄ and R ₅ are each located on adjacent carbon and are linked together to form a benzofuran, benzene, indene or indoline ),
R ₆ and R ₇ are both methyl or linked together to form a xanthene,
Wherein the ring structures of R ₂ to R ₇ are each independently substituted with any one or more substituents selected from methyl or phenyl.
The compound according to claim 1, wherein the compound is

&Lt; / RTI &gt; is a compound selected from the group consisting of:
Reacting a compound represented by the following formula (2) with a compound represented by the following formula (3): &lt; EMI ID =
(2)

(3)

In Formula 2, X is halogen,
Wherein R ₁ to R ₅ are the same as defined in claim 1.
5. The method according to claim 4, further comprising the step of reacting a compound represented by the following formula (2-2) with 2,6-dihalopyridine to prepare a compound represented by the formula (2) , A process for producing a compound represented by the formula (1)
[Formula 2-2]

In Formula 2-2, X is halogen.
6. The method according to claim 5, wherein the compound of formula (2-1) is reacted with dimethylformamide dimethyl acetal and then hydroxylamine hydrochloride.
And a second step of carrying out a cyclization reaction by reacting the compound obtained in the first step with trifluoroacetic anhydride, to prepare a compound represented by the formula (2-2) Wherein R &lt; 1 &gt; and R &lt; 2 &gt;
[Formula 2-1]

In Formula 2-1, X is halogen.
5. The method of claim 4,
A first step of protecting an amine group from a compound represented by the following formula (3-1);
A second step of reacting the compound in which the amine group obtained from the first step is protected with RH to replace X with R;
And a third step of removing the amine protecting group of the compound obtained from the second step. The method for producing the compound represented by the general formula (1), further comprising the step of:
[Formula 3-1]

Wherein R ₁ is as defined in claim 1, X is halogen,
Wherein R is at least one selected from R ₂ to R ₅ , and R ₂ to R ₅ are as defined in claim 1.
A light emitting host or a dopant-containing composition for an organic electroluminescence device containing the compound of any one of claims 1 to 3.
An organic electroluminescent device comprising an anode, a cathode, and an organic layer containing a compound of any one of claims 1 to 3 between the two electrodes.
The organic electroluminescent device according to claim 9, wherein the organic layer is a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, or a laminate thereof.
The organic electroluminescent device according to claim 9, wherein the compound of any one of claims 1 to 3 is used as a light emitting host material or a dopant material.