KR20170126059A - Organic compound comprising pyrimidine and organic electroluminescent device comprising the same - Google Patents

Abstract

The present invention relates to an organic aromatic organic compound containing pyridine, and an organic electroluminescent device using the same, wherein the compound may be used as thermally activated delayed fluorescent (TADF) material due to having little energy difference between an excited singlet state and an excited triplet state. Further, the compound of the present invention may be used in an organic light-emitting diode to improve efficiency of the organic light-emitting diode and lower driving voltage thereof.

Description

[0001] The present invention relates to organic compounds containing pyrimidines and organic electroluminescent devices comprising the same,

The present invention relates to a novel luminescent material having excellent luminescent efficiency and an organic electroluminescent device exhibiting excellent efficiency characteristics by incorporating it 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 materials are classified into phosphorescent materials, phosphorescent materials, and delayed fluorescence (TADF), which is recently studied mainly in the Adachi group, according to the principle of emitting light. 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, there is a disadvantage in that the color purity and luminous efficiency are inferior when a single material is used as a light emitting material. 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 Thermally Activated Delayed Fluorescence (TADF) It has become an issue by presenting fluorescent materials. 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.

Accordingly, the present inventors have made intensive research to develop a novel TADF luminescent material, and as a result, they have completed the present invention by designing a novel luminescent material containing pyrimidine.

It is an object of the present invention to provide a novel light emitting material which can be expected to improve the efficiency of the organic light emitting diode and reduce the driving voltage, and an organic light emitting device including the organic light emitting diode.

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, -CH ₂ -, S or O, each of R ₂ to R ₃ independently represents hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted group having 6 to 40 A substituted or unsubstituted aryl group having 2 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 60 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 60 carbon atoms, A cycloalkyl group having 3 to 60 carbon atoms, and a substituted or unsubstituted cycloalkenyl group having 5 to 30 carbon atoms,

Optionally, R ₁ to R ₃ are each independently selected from the group consisting of C 6 -C 50 aryl, C 1 -C 50 alkyl, and C 3 -C 50 cycloalkyl substituted or unsubstituted with alkyl having 1 to 6 carbons And may be substituted with any one or more substituents selected.

Preferably, R ₂ and R ₃ are each independently selected from the group consisting of hydrogen, deuterium, carbazole, droacridine, phenothiazine, phenoxazine, dibenzofuran, , Dibenzothiophene, and phenylcarbazole. The compound of formula (I)

R ₁ , R ₂ and R ₃ may combine with each other to form a xanthene,

R ₂ and R ₃ may each combine with adjacent carbons to form benzofuran, hydrobenzothiophene, indene or indoline,

Optionally, R ₁ to R ₃ are each independently selected from the group consisting of C 6 -C 50 aryl, C 1 -C 50 alkyl, and C 3 -C 50 cycloalkyl substituted or unsubstituted with alkyl having 1 to 6 carbons And may be substituted with any one or more substituents selected.

Hereinafter, the present invention will be described in detail.

The compound represented by formula (1) of the present invention is characterized by having a structure of a donor connected to pyrimidine and an aromatic compound having acceptor substituents. The compound of the present invention can exhibit thermally activated delayed fluorescence (TADF) because of a small difference in energy between the lowest excited singlet singlet state (S1) and the lowest triplet state (T1). For example, the compounds of the present invention may have a separation between S ₁ and T ₁ of at most 0.15 eV.

In addition, the pyrimidine molecule of the compound represented by the formula (1) according to the present invention 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.

Representative examples of the compound represented by the formula (1) are as follows.

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 a compound represented by the above formula (1)

[Reaction Scheme 1]

In the above Reaction Scheme 1, the definitions of R ₁ to R ₃ are the same as those described above, and X is halogen.

Preferably, X is chlorine or bromine.

That is, the present invention provides a process for preparing a compound represented by the following formula (1), comprising the step of reacting a compound represented by the following formula (2) with a compound represented by the following formula (3)

[Chemical Formula 1]

(2)

(3)

In the above formula, the definitions of R ₁ to R ₃ are the same as those described above, and X is halogen.

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 step 1), but is not limited thereto.

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

In the present invention, the reaction time of the step 1) is preferably 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.

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

The present invention also provides an organic electroluminescence device comprising a compound represented by the formula (1), preferably one of the compounds (1) to (33) in at least one organic layer. 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) Preferably 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, preferably 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, preferably the compounds (1) to (33) may be used alone or in combination of two or more, or a light emitting host substance or a dopant ) Materials and may be used with other known light emitting dopant materials or host materials. When the compound represented by the formula (1), preferably 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 relative to the light emitting layer. Specific examples of the light emitting material, the host material or the dopant material which can be used in the light emitting layer together with the compound represented by the formula (1), preferably the compound (1) to (33) include anthracene, naphthalene, phenanthrene, But are not limited to, naphthalene, naphthalene, naphthalene, naphthalene, naphthalene, naphthalene, naphthalene, naphthalene, Anthraquinone metal complexes, benzoquinoline metal complexes, imine, diphenylethylene, vinyl anthracene, diaminocarbazole, pyran, thiopyran, polymethine, meloxane, Imidazole chelated oxinoid compounds, quinacridone, rubrene, fluorescent dyes, and mixtures thereof, but are not limited thereto. When a dopant material is selected, it is preferable to select a dopant having 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 thin, pin holes are generated and an electric field is applied A sufficient light emission luminance can not be obtained. A typical film thickness is preferably in the range of 5 nm to 10 mu m, more preferably 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 3- (6-bromopyridin-2-yl) imidazo [1,2-a] pyrimidine, was synthesized by the following synthesis method.

1) Synthesis of intermediate C-1

2-aminopyrimidine (5 g), bromoacetaldehyde diethyl acetal (20.7 g), 48% aqueous solution of bromic acid (5 ml) and ethanol (50 ml) were placed in a 250 ml three-neck round bottom flask, Lt; / RTI > The reaction solution was cooled to room temperature and adsorbed on silica gel. 5 g of the title compound was obtained by column separation using dichloromethane and methanol.

2) Synthesis of intermediate C-2

Compound C-1 (4 g) and sodium acetate (4.3 g) were dissolved in methanol (40 ml) into a 100 ml three-necked round bottom flask and then cooled to -10. Bromine (5.38 g) was slowly added dropwise. 1 M aqueous sodium sulfide solution (40 ml) was added, and the mixture was concentrated under reduced pressure. The by-product was extracted with ethyl acetate and water, and the resulting material was subjected to column separation using dichloromethane and methanol to obtain 3.2 g of the title compound.

3) Synthesis of intermediate C-3

Compound C-2 (4 g) and anhydrous tetrahydrofuran (120 ml) were added to a 250-ml three-neck round bottom flask, stirred under an argon atmosphere and the temperature of the mixture was lowered to -78. 2.9M isopropylmagnesium bromide (7.6 ml) was added slowly and stirred at the same temperature for 1 hour. Tributyltin chloride (7.9 g) was added at the same temperature, the temperature of the mixture was raised to room temperature, and the mixture was stirred for 12 hours. Water was added and the organic layer was separated and concentrated under reduced pressure. The following reaction was carried out without purification for the material produced by concentration.

4) Synthesis of intermediate C-4

Intermediate C-3 (8 g), 2,6-dibromopyridine (5.5 g) and toluene (60 ml) were placed in a 100 ml three-neck round bottom flask and stirred under argon atmosphere. Bis (triphenylphosphine) palladium (II) dichloride (0.66 g) was added to the mixture and the mixture was heated to 80 ° C. Water was added and the reaction mixture 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. Columns separation using dichloromethane on the material produced by concentration yielded 3 g of the title compound.

(2) Synthesis of Compound 1

Intermediate C-4 (3 g), carbazole (2.2 g) and toluene (60 ml) were placed in a 250 ml three-necked round bottom flask and stirred under argon atmosphere. To the mixture was added tris (dibenzylidine) acetone dipalladium (0) (0.2 g), tri-t-butylphosphine (0.2 g) and sodium-t-butoxide (2.3 g) 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-dihydrothiocridine 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

3-Iodocarbazole (10 g) and dimethylformamide (25 ml) were added to a 250 ml three-neck round bottom flask and stirred. The temperature of the mixture is maintained at 0, and sodium hydride (1.22 g) is added. After 10 minutes, toluenesulfonyl chloride (7.1 g) was added thereto, followed by stirring for 4 hours. After addition of water, the solid phase was separated by filtering. Recrystallization from dichloromethane gave 12 g of the title compound.

Synthesis of Intermediate 5-2

Intermediate 5-1 (12 g), carbazole (7 g), cuprous oxide (8.98 g) and dimethylformamide (24 ml) were placed in a 250 ml three-necked round bottom flask and stirred at 100 for 12 hours. After cooling at room temperature, the silica was filtered. 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

Intermediate 5-2 (12 g), potassium hydroxide (1.0 g), tetrahydrofuran (36 ml) and methanol (18 ml) were added to a 100 ml three-necked round bottom flask and stirred at room temperature for 4 hours. After silica gel filtration, the filtrate was concentrated under reduced pressure. The solid phase was washed with water and then recrystallized from dichloroethane to obtain 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-dihydropyridine was used 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

Bromoiodobenzene (20 g) and aniline (6.58 g) were placed in a 250 ml three-necked round bottom flask and stirred. To this mixture was added sodium-t-butoxide (9.51 g), 2 ', 4', 6'-triisopropylbiphenyl-2-dicyclohexylphosphine (0.82 g), trisdibenzylidineacetone dipalladium ) Was added and the temperature was maintained at 80. After 12 hours, the reaction mixture was cooled to 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

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

Synthesis of intermediate 9-3

Compound 9-2 (8 g), chloroform (100 ml) and methanesulfonic acid (6.82 g) extracted into a 250 ml three-necked round bottom flask were added and kept at 60 ° C. Sodium bicarbonate aqueous solution was slowly added and stirred. Chloroform was extracted several times. The solid was filtered off with chloroform and methanol to obtain 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

2-bromocarbazole (10 g) and dimethylformamide (25 ml) were added to a 250 ml three-neck round bottom flask and stirred. The temperature of the mixture was maintained at 0, and sodium hydride (1.22 g) was added. After 10 minutes, toluenesulfonyl chloride (7.1 g) was added thereto, followed by stirring for 4 hours. After adding water, the solid phase was separated by filtering. Recrystallization from dichloromethane gave 12 g of the title compound.

Synthesis of Intermediate 10-2

Compound 10-1 (12 g), carbazole (7 g), cuprous oxide (8.98 g) and dimethylformamide (24 ml) were placed in a 250 ml three-necked round bottom flask and stirred at 100 for 12 hours. After cooling at room temperature, the silica was filtered. The filtered solution was concentrated under reduced pressure and 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 10-3

Compound 10-2 (12 g), potassium hydroxide (1.0 g), tetrahydrofuran (36 ml) and methanol (18 ml) were added to a 100 ml three-necked round bottom flask and stirred at room temperature for 4 hours. The filtrate was concentrated under reduced pressure, and the solid phase was washed with water and then 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 Example 10, except that 9,9-dimethyl-9,10-dihydraacridine 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 Example 10 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 Example 10 except that phenoxazine 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

3-bromocarbazole (10 g), phenylboronic acid (7.4 g), tetrahydrofuran (200 ml), potassium carbonate (16.8 g) and water (60 ml) were added to a 250 ml three-necked round bottom flask and stirred. Tetrakis (triphenylphosphine) palladium (0) (0.95 g) 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. Columns separation using hexane was performed on the material formed by concentration to obtain 7.1 g of the title compound.

Synthesis of Intermediate 14-2

Dimethylformamide (600 ml) was added to a 1000 ml three-neck round bottom flask and stirred at 0 ° C. Sodium hydride (2.6 g) was slowly added, and 2-bromocarbazole (10 g) was 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 filtering, and recrystallized from dichloromethane to obtain 7.6 g of the title compound.

Synthesis of Intermediate 14-3

Compound 14-1 (6.9 g), intermediate 14-2 (7.6 g), cuprous oxide (5.4 g) and dimethylformamide (20 ml) were placed in a 250 ml three-necked round bottom flask and stirred at 100 for 12 hours. After cooling at room temperature, silica gel filtration was performed. 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

Compound 13-3 (5.3 g), potassium hydroxide (0.46 g), tetrahydrofuran (16 ml) and methanol (8 ml) were added to a 100 ml three-necked round bottom flask and stirred at room temperature for 4 hours. After silica filtration, the filtrate 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-bromocarbazole (3 g), dibenzofuran 4-boronic acid (3.1 g), tetrahydrofuran (60 ml), potassium carbonate (8.4 g) and water (60 ml) were added to a 250 ml three- And stirred. Tetrakis (triphenylphosphine) palladium (0) (0.4 g) 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. Column separation was performed on the material produced by concentration 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.

Dibenzofuran 3g 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 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), dibenzofuran 4-boronic acid (3.1 g), tetrahydrofuran (60 ml), potassium carbonate (8.4 g) and water (60 ml) were added to a 250 ml three- And stirred. Tetrakis (triphenylphosphine) palladium (0) (0.4 g) 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. Column separation was performed on the material produced by concentration 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

4-dibenzothiophene-boronic acid (10 g), 1-bromo-2-nitrobenzene (11.8 g), toluene (100 ml) and ethanol (20 ml) were added to a 250 ml three- Potassium carbonate (12.1 g) and water (20 ml) were added and stirred. Tetrakis (triphenylphosphine) palladium (0) (1.5 g) 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. Column separation using a dichloromethane and hexane mixed solvent was performed on the substance produced by concentration to obtain 11.3 g of the title compound.

Synthesis of intermediate 31-2

Compound 31-1 (8 g), triphenylphosphine (20.6 g) and 1,3-dichlorobenzene (56 ml) were placed in a 250 ml three-necked round bottom flask, and the mixture was refluxed and stirred for 12 hours. The solvent was removed by concentration under reduced pressure. Column separation using a dichloromethane and hexane mixed solvent was performed on the substance produced by concentration 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

2-Bromo- (9-phenyl-carbazole) (20 g), 2-chloroaniline (9.5 g) and toluene (400 ml) were placed in a 1 L three-necked round bottom flask and stirred under argon atmosphere. Tris-dibenzylidineacetone dipalladium (0) (0.8 g), tri-t-butylphosphine (0.8 g) and sodium-t-butoxide (8.9 g) were added to the mixed solution, and the mixture was refluxed with stirring for 5 hours. The reaction solution was separated into water and ethyl acetate, and the organic layer was concentrated under reduced pressure. Column separation using a mixed solvent of dichloromethane and hexane was carried out on the substance produced by concentration to obtain 17 g of the title compound.

Synthesis of intermediate 33-2

To a 500 ml 3-necked round bottom flask were added intermediate 33-1 (12.5 g), palladium (.) Acetate (0.38 g), tricyclohexylphosphine tetrafluoroborate (1.25 g), cesium carbonate (33.1 g), dimethylacetamide (180 ml) was added and the mixture was stirred at 190 for 5 hours and then cooled. The reaction solution was separated into water and ethyl acetate, and the organic layer was concentrated under reduced pressure. Columns separation using dichloromethane and hexane mixed solvent was performed on the substance produced by concentration to obtain 5 g of the title compound.

Structural formulas and NMR data of the respective compounds prepared in Examples 1 to 33 are shown in Table 1 below.

compound constitutional formula ^{1 H NMR (500 MHz, CDCl} 3, TMS) δ (PPM) One

(Dd, 1H), 8.94-8.77 (dd, 1H), 8.56-8.53 (dd, 1H), 8.41-8.40 2H), 7.72-7.63 (m, 2H), 7.51-7.49 (m, 2H), 7.33-7.22 (m, 4H) 2

1H), 7.51 (s, 1H), 7.41-7.39 (m, 1H), 7.28-7.26 (dd, 1H), 8.83-8.80 (dd, 1H), 8.78-8.77 ), 7.05-7.02 (m, 4H), 6.73-6.66 (m, 3H), 6.55-6.51 (dd, 2H), 1.72 3

(Dd, 1H), 7.62-7.60 (m, 3H) ), 7.20-7.16 (m, 4H), 6.99-6.96 (dd, 2H), 6.66-6.64 (dd, 4

1H), 7.41-7.39 (m, 1H), 7.28-7.24 (m, 3H), 7.82-7.40 (dd, ), 7.21-7.17 (m, 4H), 6.98-6.96 (dd, 2H), 6.68-6.66 (dd, 5

(Dd, 1H), 8.78-8.76 (dd, 1H), 8.57-8.55 (dd, 2H), 8.43-8.41 2H), 7.33-7.25 (m, 7H), 7.60 (dd, 6

(Dd, 1H), 8.86-8.77 (dd, 1H), 8.55-8.54 (dd, 1H), 8.41-8.39 (dd, 1H), 7.94-7.92 (M, 4H), 7.77-7.73 (m, 4H), 6.55-6.53 (m, 4H) (dd, 2H). 1.73 (s, 6 H) 7

(Dd, 1H), 8.87-8.75 (dd, 1H), 8.55-8.54 (dd, 1H), 8.41-8.39 2H), 6.77-6.75 (m, 4H), 7.25-7.16 (m, 6H), 6.97-6.95 (dd, (dd, 2H) 8

(Dd, 1H), 8.87-8.76 (dd, 1H), 8.55-8.53 (dd, 1H), 8.41-8.39 (dd, 1H), 7.97-7.95 (M, 6H), 6.96-6.94 (dd, 2H), 6.76-6.74 (m, 4H), 7.74-7.72 (dd, 2H) 9

(Dd, IH), 7.64-7.62 (dd, IH), 7.51 (s, IH), 7.42-7.40 (dd, IH), 7.28-7.19 ), 7.05-6.98 (m, 6H), 6.66-6.60 (m, 3H), 6.51-6.49 (dd, 2H) 10

(Dd, 1H), 8.78-8.76 (dd, 1H), 8.55-8.52 (dd, 2H), 8.40-8.38 2H), 7.33-7.25 (m, 7H), 7.72-7.70 (dd, 11

(Dd, 1H), 8.84-8.76 (dd, 1H), 8.55-8.52 (dd, 1H), 8.40-8.38 1H), 7.86-7.84 (dd, 1H), 7.72-7.70 (m, 4H), 6.73-6.67 (m, 4H), 6.65-6.62 (dd, 2H), 1.75 (s, 6H) 12

(Dd, 1H), 8.84-8.76 (dd, 1H), 8.55-8.52 (dd, 1H), 8.40-8.38 1H), 7.86-7.84 (dd, 1H), 7.72-7.70 (m, 4H), 6.73-6.67 (m, 4 H), 6.65 - 6.62 (dd, 2 H) 13

(Dd, 1H), 8.83-8.76 (dd, 1H), 8.83-8.76 (dd, 1H), 8.53-8.51 (D, 1H), 7.86-7.84 (dd, 1H), 7.70-7.68 (dd, IH), 7.49 (s, IH), 7.33-7.24 (m, 3H), 7.05-7.02 (m, 4 H), 6.63 - 6.61 (dd, 2 H) 14

2H), 8.40-8.38 (dd, 1H), 8.12 (dd, 1H), 7.94-7.92 (dd, 2H), 8.82-8.80 (dd, 1H), 8.78-8.76 ), 7.86-7.83 (m, 3H), 7.77-7.69 (m, 3H), 7.51 (s, 1H), 7.48-7. 41 (m, 4H), 7.38-7.25 15

(Dd, 1H), 8.8-8.76 (dd, 1H), 8.55-8.53 (dd, 1H), 8.40-8.38 1H), 7.94-7.83 (m, 5H), 7.77-7.69 (m, 4H), 7.53 16

(Dd, 1H), 8,88-8,76 (dd, 1H), 8.55-8.53 (dd, 1H), 8.41-8.38 1H), 7.94-7.83 (m, 5H), 7.77-7.70 (m, 4H), 7.56 (m, 17

2H), 8.40-8.38 (dd, 1H), 8.12 (dd, 1H), 7.94-7.92 (dd, 2H), 8.82-8.80 (dd, 1H), 8.78-8.76 ), 7.86-7.83 (m, 3H), 7.77-7.69 (m, 3H), 7.51 (s, 1H), 7.48-7.43 (m, 4H), 7.40-7.27 18

(Dd, 1 H), 7.90-7.83 (dd, 1 H), 7.85-8. 2H), 7.51-7.49 (s, IH), 7.36-7. 25 (m, 6H) 19

(Dd, 1H), 8.78-8.76 (dd, 1H), 8.55-8.52 (dd, 1H), 8.40-8.38 (dd, 1H), 7.92-7.90 2H), 7.51-7.49 (s, IH), 7.38-7.26 (m, 6H) 20

(Dd, 1 H), 7.90-7.84 (dd, 1 H), 8.87-8.76 (dd, 2H), 7.51-7.49 (s, IH), 7.36-7.26 (m, 6H), 7.70-7. 21

(Dd, 1H), 8.86-8.76 (dd, 1H), 8.55-8.52 (dd, 1H), 8.41-8.38 2H), 7.51-7.49 (s, IH), 7.36-7. 25 (m, 6H) 22

(Dd, 1 H), 7.90-7.83 (dd, 1 H), 7.85-8. 2H), 7.51-7.49 (s, IH), 7.36-7. 25 (m, 6H) 23

(Dd, 1 H), 7.90-7.84 (dd, 1 H), 8.87-8.76 (dd, 2H), 7.51-7.49 (s, IH), 7.36-7.26 (m, 6H), 7.70-7. 24

(Dd, 1 H), 7.90-7.83 (dd, 1 H), 7.85-8. 2H), 7.51-7.49 (s, IH), 7.36-7. 25 (m, 6H) 25

(Dd, 1H), 8.78-8.76 (dd, 1H), 8.55-8.52 (dd, 1H), 8.40-8.38 (dd, 1H), 7.92-7.90 2H), 7.51-7.49 (s, IH), 7.38-7.26 (m, 6H) 26

(Dd, 1H), 8.78-8.76 (dd, 1H), 8.54-8.52 (dd, 1H), 8.41-8.39 (M, 6H), 7.58-7.51 (m, 9H), 7.45-7.28 (m, 5H) 27

(Dd, 1 H), 7.94-7.92 (dd, 1 H), 8.83-8.81 (dd, , 7.86-7.84 (dd, 1H), 7.79-7.77 (dd, 1H), 7.72-7.70 -7.24 (m, 4 H), 1.72 (s, 6 H) 28

(Dd, 1H), 8.87-8.76 (dd, 1H), 8.57-8.54 (dd, 1H), 8.41-8.39 , 7.86-7.84 (dd, 1H), 7.79-7.77 (dd, 1H), 7.72-7.70 -7.27 (m, 4 H), 1.72 (s, 6 H) 29

(Dd, 1H), 8.78-8.76 (dd, 1H), 8.56-8.54 (dd, 1H), 8.41-8.39 , 7.86-7.84 (dd, 1H), 7.80-7.78 (dd, 1H), 7.73-7.71 -7.26 (m, 4 H), 1.72 (s, 6 H) 30

(Dd, 1H), 8.78-8.76 (dd, 1H), 8.56-8.54 (dd, 1H), 8.40-8.38 (M, 4H), 7.63-7.45 (m, 8H), 7.33-7.25 (m, 4H) 31

2H), 8.05-8.03 (dd, 1H), 7.98-7.86 (m, 2H), 8.82-8.80 (dd, 1H), 7.78-7.76 , 3H), 7.72-7.68 (t, IH), 7.52-7.50 (m, 3H), 7.33-7.25 (m, 4H) 32

(Dd, 1H), 7.87-7.76 (dd, 1H), 8.55-8.53 (dd, 1H), 8.40-8.38 1H), 7.31-7.28 (m, 5H), 7.13-7.12 (d, 1H), 7.72-7.71 33

(Dd, 1H), 8.84-8.76 (dd, 1H), 8.55-8.53 (dd, 1H), 8.40-8.38 , 7.86-7.84 (dd, 1H), 7.72-7.69 (t, 1H), 7.63-7.50 (m, 8H), 7.45-7.29

Experimental Example 1: Production of organic electroluminescence device using Compound 1 of Example 1

An ITO transparent electrode with a thin film thickness of 100 nm was cut to a size of 40 mm × 40 mm × 0.7 m. 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 (naphthalen-1-yl) -N ⁴ , N ^{4 '} -diphenylbiphenyl-Naphthalen-1-yl) which is capable of transporting holes on the layer of the compound represented by Formula 4,4'-diamine) was vacuum-deposited at 20 nm.

[Chemical Formula B]

A compound represented by the following formula (C) (N- (4- (4aH-carbazol-9 (4bH, 8aH, 9aH) - yl) phenyl) -N- (4- (9H-carbazol-9-yl) phenyl) -4- (9H-carbazol-9-yl) benzenamine in vacuum at 10 nm.

≪ RTI ID = 0.0 &

Compound 1 of Example 1 was mixed and vapor-deposited at a concentration of 5 wt% as a dopant together with a compound represented by the following formula (D) as a luminescent host on the layer of the compound represented by the formula (C) to form a 30 nm thick luminescent 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) with a thickness of 0.7 nm and aluminum with a thickness of 120 nm were sequentially deposited on the electron injection and transport layer to form a cathode. A current density of 3.73 mA / cm < 2 > was measured at a voltage of 4 V in the thus fabricated organic electroluminescent device. The luminance was 493 cd / m < 2 > corresponding to x = 0.148 and y = The near - light spectrum was observed and the efficiency was 13.2 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. A current density of 2.7 mA / cm < 2 > was formed on the thus fabricated organic electroluminescent device at a voltage of 4V. The current density was 346 cd / m < 2 > corresponding to x = 0.148 and y = A spectrum close to pure blue was observed and the efficiency was 12.8 cd / A.

Comparative Experimental Example 1

Was prepared in the same manner as in Experimental Example 1, except that Compound (F) below was used instead of Compound (1) as a light emitting dopant substance. 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) Color coordinates Experimental Example 1 (Compound 1) 3.73 493 13.2 0.148, 0.192 Experimental Example 2 (Compound 2) 2.7 346 12.8 0.148, 0.189 Comparative Experimental Example 1 (Formula F) 6.1 329 6.9 0.149, 0.173

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

Claims (7)

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

In this formula,
R ₁ is a single bond, -CH ₂ -, S or O, each of R ₂ to R ₃ independently represents hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted group having 6 to 40 A substituted or unsubstituted aryl group having 2 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 60 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 60 carbon atoms, A cycloalkyl group having 3 to 60 carbon atoms, and a substituted or unsubstituted cycloalkenyl group having 5 to 30 carbon atoms,
Optionally, R ₁ to R ₃ are each independently selected from the group consisting of C 6 -C 50 aryl, C 1 -C 50 alkyl, and C 3 -C 50 cycloalkyl substituted or unsubstituted with alkyl having 1 to 6 carbons And may be substituted with any one or more substituents selected. The method according to claim 1,
Wherein R ₂ and R ₃ are each independently selected from the group consisting of hydrogen, deuterium, carbazole, droacridine, phenothiazine, phenoxazine, dibenzofuran, dibenzothi Dibenzothiophene, and phenylcarbazole. In the present invention,
R ₁ , R ₂ and R ₃ may combine with each other to form a xanthene,
R ₂ and R ₃ may each combine with adjacent carbons to form benzofuran, hydrobenzothiophene, indene or indoline,
Optionally, R ₁ to R ₃ are each independently selected from the group consisting of C 6 -C 50 aryl, C 1 -C 50 alkyl, and C 3 -C 50 cycloalkyl substituted or unsubstituted with alkyl having 1 to 6 carbons And may be substituted with any one or more substituents selected. The compound according to claim 1, wherein the compound is

≪ / RTI > is a compound selected from the group consisting of < RTI ID = 0.0 > 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 5, 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 5, wherein the compound of any one of claims 1 to 3 is used as a light emitting host material or a dopant material.