KR101714509B1 - Dibenzo-benzimidazol derivatives and organic electroluminescent device including the same - Google Patents

Abstract

[상기 화학식 1에서 각 치환기들의 정의는 발명의 상세한 설명에서 정의한 바와 같다.]There is provided an imidazole derivative substituted with an amine compound represented by the following formula (1).
[Chemical Formula 1]

[Wherein the definition of each substituent in Formula 1 is as defined in the description of the invention]

Description

[0001] The present invention relates to a dibenzo-benzimidazole derivative and an organic electroluminescent device including the same,

The present invention relates to a dibenzo-benzimidazole derivative and an organic electroluminescent device including the same, and more particularly, to an organic electroluminescent device having high luminous efficiency and a novel dibenzo-benzimidazole derivative therefor.

In the 21st century information society, it is required to display more, more accurate, and clearer information. From the CRT (Cathode Ray Tube), which was the main market of the early display industry, to the LCD (Liquid Crystal Display) which is the most used now, the display industry has developed remarkably over the past few decades. The LCD, which occupies the whole of our lives, is not self-luminous and requires a separate light source. Other displays have various problems such as power consumption. For this reason, OLEDs (Organic Light Emitting Diodes) are attracting attention as next-generation flat panel displays.

OLEDs can be made much thinner because they do not require a separate light source and can be formed on a flexible transparent substrate such as a plastic as well as on a plasma display panel or an inorganic electroluminescence It can be driven at a voltage as low as 10V or less, completely expresses natural colors with very low power consumption, emits light in all directions, has wide viewing angle, and the response speed of pixels is also very fast, Can be displayed. In addition, it has a merit that manufacturing process is simple compared with other displays and its production cost is low, and thus it is attracting attention as the most promising next generation flat panel display.

This OLED was first attempted in 1963 by Pope et al. To study the carrier injection type electroluminescence (EL) using an anthracene aromatic hydrocarbon single crystal. From these studies, it was found that charge injection, recombination, exciton generation, And the basic mechanism of electroluminescence and electroluminescence characteristics.

In addition, after Tang and Van Slyke in 1987 reported the characteristics of high efficiency using a multilayer thin film structure of organic electroluminescent devices [Tang, C. W., Van Slyke, S. A. Appl. Phys. Lett. 51, 913 (1987)], OLEDs have a high potential for use in LCD backlighting and illumination as well as excellent characteristics as a next generation display, and many studies have been conducted under the spotlight [Kido, J., Kimura, M., and Nagai, K., Science 267,1332 (1995)]. Especially, in order to increase the luminous efficiency, various approaches such as structural change and material development have been performed [Sun, S., Forrest, S. R., Appl. Phys. Lett. 91, 263503 (2007) / Ken-Tsung Wong, Org. Lett., 7, 2005, 5361-5364].

The basic structure of an OLED display generally includes an anode, a hole injection layer (HIL), a hole transporting layer (HTL), an emission layer (EML), an electron transporting layer (ETL) ), And a cathode (cathode), and the electron-emitting organic multi-layer film has a sandwich structure formed between both electrodes. When a voltage is applied between both electrodes in this structure, holes are injected into the anode and electrons from the cathode are injected into the organic layer. When excited holes and electrons meet, an excition is formed. And emits light of a color corresponding to the energy band gap of the light emitting layer in the course of conversion into light energy. At this time. The color of the light varies depending on the organic material constituting the light emitting layer. In the case where only the light emitting material is used, there is a problem that the color purity and the light emitting efficiency are deteriorated due to intermolecular interaction. Therefore, the host / dopant ) Structure.

As for the blue color of the three primary colors of the luminescent material, 4,4'-bis (2,2-diphenylvinyl) -1,1'-biphenyl (DPVBi) and TBSA series materials have been developed. Particularly, in the case of idemitsu- Distyryl compounds are known to exhibit good performance.

However, the blue light emitting material can not secure a sufficient lifetime due to problems such as color purity and efficiency, long-term thermal stability, and the materials used in practical commercial products are extremely limited, so development of materials is continuously required.

Korea Patent Publication No. 2014-0009095

The object of the present invention is to provide a novel imidazole derivative which is superior in luminous efficiency and durability to that of a conventional material, and that the imidazole derivative is contained in an organic film and has high luminous efficiency and long lifetime And to provide an organic electroluminescent device.

According to an aspect of the present invention, there is provided an imidazole derivative substituted with an amine compound represented by the following formula (1).

[Chemical Formula 1]

[In Formula 1 A is aryl substituted or unsubstituted C ₆ ~ C _30, substituted or non-substituted or heteroaryl-substituted C ₅ ~ C _30, or a substituted or unsubstituted alkyl of the unsubstituted C ₁ ~ C _30, A substituted or unsubstituted C ₃ to C ₃₀ cycloalkyl, a substituted or unsubstituted C ₁ to C ₁₀ alkoxy,

R ₁ , R ₂ and R ₃ are each independently a substituted or unsubstituted C ₁ -C ₆ alkyl or a substituted or unsubstituted C ₆ -C ₃₀ aryl,

L is a single bond,

q is 0 or 1.]

According to another aspect of the present invention, there is provided an organic electroluminescent device including the substituted imidazole derivative.

According to another aspect of the present invention, there is provided an organic electroluminescent device comprising a first electrode, a second electrode, and at least one organic film disposed between the electrodes, wherein the organic film comprises an organic field including an imidazole derivative substituted with the amine compound A light emitting element is provided.

According to still another aspect of the present invention, there is provided an organic EL device comprising: an electron blocking layer, an electron transport layer, an electron injection layer, a functional layer having both an electron transport function and an electron injection function, and a light emitting layer And the organic electroluminescent device is included in any one selected from the group consisting of organic electroluminescent devices.

An imidazole derivative according to an embodiment of the present invention is included in an organic layer of an organic electroluminescent device, thereby lowering the driving voltage of the device, improving the luminous efficiency and extending the lifetime.

1 is a schematic cross-sectional view of an organic electroluminescent device according to an embodiment of the present invention.
2 is a graph showing the EL peaks of the organic EL device manufactured in the comparative test example and the test example 1. Fig.

Unless otherwise specified herein, the term "aryl" refers to a polyunsaturated aromatic hydrocarbon substituent which may be a single ring or a multiple ring (one to three rings) fused or covalently bonded.

The term "heteroaryl" means an aryl group (or a ring) comprising one to four heteroatoms selected from N, O and S (in each case on a separate ring in the case of multiple rings) Optionally oxidized, and the nitrogen atom (s) are quaternized, as the case may be. Heteroaryl groups can be attached to the remainder of the molecule through carbon or heteroatoms.

The aryl includes a single or fused ring system, suitably containing from 4 to 7, preferably 5 or 6, ring atoms in each ring. Also included are structures in which one or more aryls are attached through a chemical bond. Specific examples of the aryl include phenyl, naphthyl, biphenyl, anthryl, indenyl, fluorenyl, phenanthryl, triphenylenyl, pyrenyl, perylenyl, But are not limited thereto.

The heteroaryl includes 5- to 6-membered monocyclic heteroaryl and polycyclic heteroaryl fused with one or more benzene rings, and may be partially saturated. Also included are structures in which one or more heteroaryls are attached via a chemical bond. The heteroaryl groups include divalent aryl groups in which the heteroatoms in the ring are oxidized or trisubstituted to form, for example, an N-oxide or a quaternary salt.

Specific examples of the heteroaryl include furyl, thiophenyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, imidazolyl, tetrazinyl , Monocyclic heteroaryl such as triazolyl, tetrazolyl, furazanyl, pyridyl, pyrazinyl, pyrimidinyl and pyridazinyl, benzofuranyl, benzothiophenyl, isobenzofuranyl, benzoimidazolyl, benzothiazole Benzoimidazolyl, quinazolinyl, quinoxalinyl, quinazolinyl, quinoxalinyl, quinoxalinyl, quinoxalinyl, quinoxalinyl, quinoxalinyl, quinoxalinyl, quinoxalinyl, (Such as pyridyl N-oxide, quinolyl N-oxide), quaternary salts thereof, and the like, and the like, as well as the polycarboxylic heteroaryl such as phenanthryl, , But is not limited thereto.

"Substituted" in the expression " substituted or unsubstituted ", as used herein, means that at least one hydrogen atom in the hydrocarbon is each independently replaced with the same or different substituents. Useful substituents include, but are not limited to:

Such substituents include, but are not limited to, -F; -Cl; -Br; -CN; -NO ₂ ; -OH; A C ₁ -C ₂₀ alkyl group which is unsubstituted or substituted by -F, -Cl, -Br, -CN, -NO ₂ or -OH; A C ₁ -C ₂₀ alkoxy group unsubstituted or substituted by -F, -Cl, -Br, -CN, -NO ₂ or -OH; C ₁ ~ C ₂₀ alkyl group, C ₁ ~ C ₂₀ alkoxy group, -F, -Cl, -Br, -CN , -NO _2, or substituted by -OH or unsubstituted C ₆ ~ C ₃₀ aryl group; C ₁ ~ C ₂₀ alkyl group, C ₁ ~ C ₂₀ alkoxy group, -F, -Cl, -Br, -CN , -NO 2 or -OH-substituted or unsubstituted C ₆ ~ C ₃₀ heteroaryl group, a; C ₁ ~ C ₂₀ alkyl group, C ₁ ~ C ₂₀ alkoxy group, -F, -Cl, -Br, -CN , -NO 2 , or substituted by -OH or unsubstituted C ₅ ~ C ₂₀ cycloalkyl group; C ₁ ~ C ₂₀ alkyl group, C ₁ ~ C ₂₀ alkoxy group, -F, -Cl, -Br, -CN , -NO 2 , or substituted or unsubstituted by -OH unsubstituted C ₅ ~ C ₃₀ heterocycloalkyl group; And a group represented by -N (G ₁ ) (G ₂ ). Wherein G ₁ and G ₂ are each independently selected from the group consisting of hydrogen; A C ₁ -C ₁₀ alkyl group; Or a C ₆ -C ₃₀ aryl group substituted or unsubstituted with a C ₁ -C ₁₀ alkyl group.

Hereinafter, the present invention will be described in detail.

An imidazole derivative according to an embodiment of the present invention may be represented by the following formula (1).

[Chemical Formula 1]

Wherein A is substituted or unsubstituted C ₆ -C ₃₀ aryl, substituted or unsubstituted C ₅ -C ₃₀ heteroaryl, substituted or unsubstituted C ₁ -C ₃₀ alkyl, or substituted Or unsubstituted C ₃ -C ₃₀ cycloalkyl, substituted or unsubstituted C ₁ -C ₁₀ alkoxy,

R ₁ , R ₂ and R ₃ are each independently a substituted or unsubstituted C ₁ -C ₆ alkyl or a substituted or unsubstituted C ₆ -C ₃₀ aryl,

L is a single bond,

q is 0 or 1;

The compound represented by Formula 1 may be selected from among the structures represented by Formula 2 below.

(2)

Wherein A is substituted or unsubstituted C ₆ -C ₃₀ aryl, substituted or unsubstituted C ₅ -C ₃₀ heteroaryl, substituted or unsubstituted C ₁ -C ₃₀ alkyl, or substituted Or unsubstituted C ₃ -C ₃₀ cycloalkyl, or substituted or unsubstituted C ₁ -C ₁₀ alkoxy.

In formula (1) or (2), A may be specifically selected from the structures represented by the following formula (3).

(3)

Specific examples of the compound represented by the formula (1) of the present invention include a compound represented by the following formula (4). However, the compounds represented by Formula 1 of the present invention are not limited to these compounds.

[Chemical Formula 4]

The imidazole derivative represented by the above formula (1) can be synthesized using a known organic synthesis method. The method for synthesizing the imidazole derivative can be easily recognized by those skilled in the art with reference to the following examples.

Also, according to the present invention, there is provided an organic electroluminescent device comprising an imidazole derivative represented by the above formula (1).

The imidazole derivative of Formula 1 is useful as a light emitting layer material, and can be used as a material for various layers of organic electroluminescent devices.

The organic electroluminescent device according to the present invention includes a first electrode, a second electrode, and at least one organic film disposed between the electrodes. The organic film contains at least one imidazole derivative represented by the above formula (1).

The organic layer includes a hole injecting layer, a hole transporting layer, a functional layer having both a hole injecting function and a hole transporting function, a buffer layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transporting layer, And at least one layer selected from the group consisting of functional layers having at the same time.

For example, the imidazole derivative may be contained in at least one selected from the group consisting of a light emitting layer, an organic layer disposed between the anode and the light emitting layer, and an organic layer disposed between the light emitting layer and the cathode. Preferably, the imidazole derivative may be contained in at least one layer selected from the group consisting of a light emitting layer, a hole injecting layer, a hole transporting layer, and a functional layer having both a hole injecting function and a hole transporting function. The imidazole derivative may be included in the organic film as a single substance or a combination of different substances. Alternatively, the imidazole derivative may be used in combination with a conventionally known compound such as a light emitting layer, a hole transporting layer, and a hole injecting layer.

The organic electroluminescent device according to the present invention can be applied to an organic electroluminescent device including a positive electrode / a light emitting layer / a cathode, a positive electrode / a hole injecting layer / a light emitting layer / a negative electrode, an anode / a hole injecting layer / a hole transporting layer / a light emitting layer / an electron transporting layer / / Light emitting layer / electron transporting layer / electron injecting layer / cathode structure. Alternatively, the organic electroluminescent device may include a functional layer / a light emitting layer / an electron transporting layer / a cathode having both an anode / hole injecting function and a hole transporting function, a functional layer / a light emitting layer / an electron transporting layer / Electron injecting layer / cathode structure, but the present invention is not limited thereto.

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

The organic electroluminescent device may be manufactured using a physical vapor deposition (PVD) method such as sputtering or e-beam evaporation. For example, an anode is formed by depositing a metal or a metal oxide having conductivity or an alloy thereof on a substrate, and an organic film including a hole injecting layer, a hole transporting layer, a light emitting layer, an electron transporting layer, and an electron injecting layer is formed thereon And then depositing a material which can be used as a cathode thereon. In addition to such a method, an organic electroluminescent device may be formed by sequentially depositing a cathode material, an organic film, and a cathode material on a substrate.

Meanwhile, the organic layer may be prepared by a wet process such as spin coating, dip coating, doctor blading, screen printing, inkjet printing, or thermal transfer by using various polymer materials instead of a vapor deposition method.

The organic electroluminescent device according to the present invention may be a front emission type, a back emission type, or a both-sided emission type, depending on the material used.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the following examples are for illustrative purposes only and are not intended to limit the scope of the present invention.

[Example]

Intermediate Synthesis Example 1: Synthesis of Intermediate (1)

16.8 g (81 mmol) of 9,10-phenanthrenequinone, 15.0 g (81 mmol) of 6-bromonicotinaldehyde, 9.0 g (97 mmol) of aniline, 74.6 g (968 mmol) of ammonia acetate was dissolved in 400 mL of acetic acid, and the mixture was stirred under reflux for 18 hours. After cooling to room temperature, 1 L of water was poured into the reaction solution, and the resulting solid was washed with methanol and hexane to obtain a yellow solid. This was purified by silica gel column chromatography to obtain 27.1 g (yield: 74%) of a colorless solid compound (intermediate (1)).

Intermediate Synthesis Example 2: Synthesis of Intermediate (2)

6.15 g (29.5 mmol) of 9,10-phenanthrenequinone, 3.3 g (35.4 mmol) of aniline, 5.5 g of 6-bromopicolin-aldehyde (29.5 mmol) and ammonium acetate (27.7 g, 359 mmol) were added to acetic acid (300 ml), and the mixture was stirred under reflux for 12 hours. After cooling, H ₂ O was poured off, the precipitate was separated by filtration, washed with a large amount of H ₂ O, The residue was purified by silica gel column chromatography to obtain 9.8 g (yield: 74%) of a solid compound (intermediate (2)).

Intermediate Synthesis Example 3: Synthesis of Intermediate (3)

To a 500 ml two-neck flask was added 5.0 g (0.024 mol) of benzyl, 7.4 g (0.096 mol) of ammonium acetate, and 4.8 g of 6-bromopicolinaldehyde 0.026 mol) and acetic acid (350 mL) were added, and 6.5 mL (0.072 mol) of aniline was added thereto while stirring. The mixture was stirred for 12 hours under reflux. After completion of the reaction, the reaction mixture was cooled to room temperature, water was added, and the mixture was extracted with methylene chloride. The organic phase was dried over anhydrous MgSO ₄ and the solvent was distilled off. The residue was purified by silica gel column chromatography to obtain 6.4 g (yield: 60%) of a white solid compound (Intermediate (3)).

Intermediate Synthesis Example 4: Synthesis of Intermediate (4)

5.0 g (0.024 mol) of benzyl, 7.4 g (0.096 mol) of ammonium acetate and 4.8 g of 6-bromonicotinaldehyde were added to a 500 ml two-neck flask 0.026 mol) and acetic acid (350 mL) were added, and 6.5 mL (0.072 mol) of aniline was added thereto while stirring. The mixture was stirred for 12 hours under reflux. After completion of the reaction, the reaction mixture was cooled to room temperature, water was added, and the mixture was extracted with methylene chloride. The organic phase was dried over anhydrous MgSO ₄ and the solvent was distilled off. The residue was purified by silica gel column chromatography to obtain 6.4 g (yield: 60%) of a white solid compound (intermediate (4)).

Example 1: Synthesis of compound (4-1)

The synthesis route of the compound (4-1) is shown below.

Intermediate (1) 1 g (2.22 mmol ), 9H- carbazole 408 mg (2.44 mmol), Pd (dba) 2 64 mg (0.111 mmol), sodium ethoxide teosyeo reviews ^{(NaO t Bu) 427 mg,} (4.44 mmol ) And 90 mg (0.22 mmol) of triphenylsuccinimide t- phosphine ( t- Bu) ₃ P were stirred in 15 mL of toluene under reflux for 24 hours. After cooling, the precipitate was filtered off from the celite pad and washed with CH ₂ Cl ₂ . The filtrate was dried under reduced pressure and then purified by silica gel column chromatography to obtain 547 mg (yield: 45%) of a white solid compound (4-1).

Example 2: Synthesis of compound (4-2)

The synthesis route of the compound (4-2) is shown below.

Intermediate (1) 1 g (2.22 mmol ), delta car Boleyn 411 mg (2.44 mmol), palladium DB A _{(Pd (dba) 2) 64} mg (0.111 mmol), sodium teosyeo review ethoxide (NaO ^t Bu) 427 mg ( T- Bu) ₃ P) (90 mg, 0.22 mmol) were stirred in toluene (15 mL) under reflux for 24 hours. After cooling, the precipitate was filtered off from the celite pad and washed with CH ₂ Cl ₂ . The filtrate was dried under reduced pressure and then purified by silica gel column chromatography to obtain 160 mg (yield: 13%) of a white solid compound (4-2).

Example 3: Synthesis of compound (4-3)

The synthesis route of the compound (4-3) is shown below.

Intermediate (1) 1 g (2.22 mmol ), diphenyl-amine 413 mg (2.44 mmol), palladium DB A _{(Pd (dba) 2) 64} mg (0.111 mmol), sodium teosyeo review ethoxide (NaO ^t Bu) 427 mg ( T- Bu) ₃ P) (90 mg, 0.22 mmol) were stirred in toluene (15 mL) under reflux for 24 hours. After cooling, the precipitate was filtered off from the celite pad and washed with CH ₂ Cl ₂ . The filtrate was dried under reduced pressure and then purified by silica gel column chromatography to obtain 150 mg (yield: 12%) of a white solid compound (4-3).

Example 4: Synthesis of compound (4-4)

The synthesis route of the compound (4-4) is shown below.

Intermediate (1) 1 g (2.22 mmol ), 4- phenylamino bentonite reel 474 mg (2.44 mmol), palladium DB A _{(Pd (dba) 2) 64} mg (0.111 mmol), sodium ethoxide teosyeo reviews (NaO ^t Bu ( T- Bu) ₃ P) (42 mg, 4.44 mmol) and triphenylsulfonium t- phosphine ( t- Bu) 3P were stirred in 15 mL of toluene under reflux for 24 hours. After cooling, the precipitate was filtered off from the celite pad and washed with CH ₂ Cl ₂ . The filtrate was dried under reduced pressure and then purified by silica gel column chromatography to obtain 430 mg (yield: 34%) of a white solid compound (4-4).

Example 5: Synthesis of compound (4-5)

The synthesis route of the compound (4-5) is shown below.

500 mg (1.11 mmol) of Intermediate 1, 1-phenyl-2- (4- (4,4,5,5-tetramethyl-1,3,2-dioxaballolan- 38 mg (2.78 mmol) of tetrakis (triphenylphosphine) palladium and 384 mg (2.78 mmol) of potassium carbonate were dissolved in 5 mL of toluene, 2.5 mL of ethanol and 2.5 mL of water Under reflux for 15 hours. After cooling, the precipitate was filtered off from the celite pad and washed with CH ₂ Cl ₂ . The filtrate was dried under reduced pressure and then purified by silica gel column chromatography to obtain 350 mg (yield: 49%) of a white solid compound (4-5).

Example 6: Synthesis of compound (4-6)

The synthesis route of the compound (4-6) is shown below

A mixture of 500 mg (1.11 mmol) of Intermediate (1), 453 mg of N, N-diphenyl-4- (4,4,5,5-tetramethyl-1,3,2-dioxaballolan- 38 mg (2.78 mmol) of tetrakis (triphenylphosphine) palladium and 384 mg (2.78 mmol) of tetrakis (triphenylphosphine) palladium were stirred under reflux in 5 mL of toluene, 2.5 mL of ethanol and 2.5 mL of water for 15 hours. After cooling, the precipitate was filtered off from the celite pad and washed with CH ₂ Cl ₂ . The filtrate was dried under reduced pressure and then purified by silica gel column chromatography to obtain 134 mg (yield: 19%) of a white solid compound (4-6).

Example 7: Synthesis of compound (4-7)

The synthesis route of the compound (4-7) is shown below.

A mixture of 1 g (2.22 mmol) of Intermediate 1, 6H-benzo [4,5] thieno [2,3-f] pyrido [3,2- b] indole 670 mg (2.44 mmol) 90 mg (0.22 mmol) of 64 mg (0.111 mmol) of Pd (dba) 2), 427 mg (4.44 mmol) of sodium tachyarnitoxide (NaOtBu) and tritiated heptylphosphine And the mixture was stirred under reflux in 15 mL of toluene for 24 hours. After cooling, the precipitate was filtered off from the celite pad and washed with CH ₂ Cl ₂ . The filtrate was dried under reduced pressure and then purified by silica gel column chromatography to obtain 152 mg (yield: 10%) of a white solid compound (4-7).

Example 8: Synthesis of compound (4-8)

The synthesis route of the compound (4-8) is shown below.

Intermediate (1) 1 g (2.22 mmol ), in 5H- benzo Pew [2,3-f] pyrido [3,2-b] indole 631 mg (2.44 mmol), palladium DB A (Pd (dba) ₂₎ 64 mg (0.111 mmol), sodium ethoxide teosyeo reviews ^{(NaO t Bu) 427 mg,} (4.44 mmol), bit lighter Yorkshire review butyl phosphine _{(t -bu) 3 P) 90} mg (0.22 mmol) toluene 15 mL Under reflux for 24 hours. After cooling, the precipitate was filtered off from the celite pad and washed with CH ₂ Cl ₂ . The filtrate was dried under reduced pressure and then purified by silica gel column chromatography to obtain 210 mg (yield: 15%) of a white solid compound (4-8).

Example 9: Synthesis of compound (4-9)

The synthesis route of the compound (4-9) is shown below.

Intermediate (1) 1 g (2.22 mmol ), 7- teosyeo review butyl carbazole 498 mg (2.44 mmol), palladium DB A _{(Pd (dba) 2) 64} mg (0.111 mmol), sodium ethoxide teosyeo reviews (NaO ^t 907 mg (0.22 mmol) of 427 mg (4.44 mmol) of triphenylsuccinic anhydride ( t- Bu) ₃ P) was stirred under reflux in 15 mL of toluene for 24 hours. After cooling, the precipitate was filtered off from the celite pad and washed with CH ₂ Cl ₂ . The filtrate was dried under reduced pressure and then purified by silica gel column chromatography to obtain 142 mg (yield: 10%) of a white solid compound (4-9).

Example 10: Synthesis of compound (4-10)

The synthesis route of the compound (4-10) is shown below.

Intermediate (1) 1 g (2.22 mmol ), N, N- diphenyl -5H- pyrido [3,2-b] indole-7-amine 819 mg (2.44 mmol), palladium DB A (Pd (dba) ₂ ) 64 mg (0.111 mmol), sodium ethoxide teosyeo reviews ^{(NaO t Bu) 427 mg,} (4.44 mmol), bit lighter Yorkshire review butyl phosphine (t -bu) ₃ P) toluene 15 to 90 mg (0.22 mmol) mL < / RTI > under reflux for 24 hours. After cooling, the precipitate was filtered off from the celite pad and washed with CH ₂ Cl ₂ . The filtrate was dried under reduced pressure and then purified by silica gel column chromatography to obtain 210 mg (yield: 13%) of a white solid compound (4-10).

Example 11: Synthesis of compound (4-11)

The synthesis route of the compound (4-11) is shown below.

Benzo [g] pyrido [3,2-b] indole 534 mg (2.44 mmol), Pd (dba) ₂ 64 mg (0.111 mmol), sodium t- (NaO ^t Bu) (427 mg, 4.44 mmol) and triphenylsulfonium t- phosphine ( t- Bu) ₃ P (90 mg, 0.22 mmol) were stirred in 15 mL of toluene under reflux for 24 hours. After cooling, the precipitate was filtered off from the celite pad and washed with CH ₂ Cl ₂ . The filtrate was dried under reduced pressure and then purified by silica gel column chromatography to obtain 175 mg (yield: 13%) of a white solid compound (4-11).

Example 12: Synthesis of compound (4-12)

The synthesis route of the compound (4-12) is shown below.

A solution of 1 g (2.22 mmol) of Intermediate (1), 814 mg (2.44 mmol) of 11-phenyl-5,11-dihydropyrido [2 ', 3': 4,5] pyrrolo [3,2- _{mmol), Pd (dba) 2} 64 mg (0.111 mmol), sodium ethoxide teosyeo reviews ^{(NaO t Bu) 427 mg,} (4.44 mmol), bit lighter Yorkshire review butyl phosphine _{(t -bu) 3 P) 90} mg (0.22 mmol) were stirred in toluene (15 mL) under reflux for 24 hours. After cooling, the precipitate was filtered off from the celite pad and washed with CH ₂ Cl ₂ . The filtrate was dried under reduced pressure and then purified by silica gel column chromatography to obtain 225 mg (yield: 14%) of a white solid compound (4-12).

Example 13: Synthesis of compound (4-13)

The synthesis route of the compound (4-13) is shown below.

In a two-necked 100 mL flask, 161 mg (0.96 mmol) of Pd (5-pyrido [3,2-b] (dba) ₂ , 253 mg (2.63 mmol) of t-BuONa, 0.04 ml (0.088 mmol) of P (t-Bu) ₃ and 30 ml of xylene, Stir for 20 hours. After the reaction was completed, the reaction mixture was cooled to room temperature and purified by silica gel column chromatography to obtain 62 mg (yield: 13%) of a beige solid compound (4-13).

Example 14: Synthesis of compound (4-14)

The synthesis route of the compound (4-14) is shown below.

In a two-necked 100 mL flask, 188 mg (0.96 mmol) of 4- (phenylamino) benzonitrile and 25 mg (0.043 mmol) of Pd (dba) ₂ were added to a mixture of 0.4 g (0.88 mmol) ), 253 mg (2.63 mmol) of t-BuONa, 0.04 ml (0.088 mmol) of P (t-Bu) ₃ and 30 ml of xylene and the mixture was stirred at 140 ° C for 20 hours. After the reaction was completed, the reaction mixture was cooled to room temperature and purified by silica gel column chromatography to obtain 75 mg (yield: 15%) of a pale beige solid compound (4-14).

Example 15: Synthesis of compound (4-15)

The synthesis route of the compound (4-15) is shown below.

To a 2-necked 100 mL flask was added 0.3 g (0.66 mmol) of intermediate (2), N, N-diphenyl-4- (4,4,5,5-tetramethyl-1,3,2-dioxaborane- 270 mg (0.72 mmol) of Pd (PPh ₃ ) ₄ (4,4,5,5-tetramethyl-1,3,2-dioxaborolan- 210 mg (1.98 mmol) of Na ₂ CO ₃ and 30 mL of toluene: EtOH: water = 2: 1: 1, and then stirred at 110 ° C for 20 hours. After the reaction was completed, the reaction mixture was cooled to room temperature and purified by silica gel column chromatography to obtain 360 mg of a white solid (4-15) (yield: 88%).

Example 16: Synthesis of compound (4-16)

The synthesis route of the compound (4-16) is shown below.

In two 100 mL flask, intermediate (2) 0.3 g (0.66 mmol ), imidazole borate (imidazole borate) 287 mg (0.72 mmol), Pd (PPh 3) 4 23 mg (0.0021 mmol), Na 2 CO 3 210 mg (1.98 mmol), and 30 mL of toluene: EtOH: water = 2: 1: 1, followed by stirring at 110 DEG C for 20 hours. After the reaction was completed, the reaction mixture was cooled to room temperature and purified by silica gel column chromatography to obtain 330 mg (yield: 78%) of a white solid compound (4-16).

Example 17: Synthesis of compound (4-17)

The synthesis route of the compound (4-17) is shown below.

1 intermediate (4) 0.5 g (1.108 mmol ), imidazole borate (imidazole borate) 0.5 g (1.219 mmol), Pd (PPh 3) 4 38 mg (0.033 mmol), toluene (toluene) to obtain 100 mL flask, 40 mL 20 mL of ethanol (EtOH), 0.2 g (1.662 mmol) of K ₂ CO ₃ and 20 mL of H ₂ O were added to the solution while stirring, and the mixture was stirred under reflux for 6 hours. After the reaction was completed, water was added, and the mixture was extracted with methylene chloride. The organic phase was dried over anhydrous MgSO ₄ and purified by silica gel column chromatography to obtain 0.5 g (yield: 65%) of a white solid compound (4-17) ≪ / RTI >

Example 18: Synthesis of compound (4-18)

The synthesis route of the compound (4-18) is shown below.

Intermediate 1 (3) 0.5 g (1.108 mmol ), triphenyl borate-4-amine (triphenylamine 4-borate) 0.5 g (1.219 mmol), Pd (PPh 3) 4 38 mg (0.033 mmol) to obtain 100 mL flask, 20 mL of ethanol (EtOH), 0.2 g (1.662 mmol) of K ₂ CO ₃ and 20 mL of H ₂ O were added to the solution while stirring with 40 mL of toluene, and the mixture was stirred under reflux for 6 hours. After the reaction was completed, water was added and the mixture was extracted with methylene chloride. The organic phase was dried over anhydrous MgSO ₄ and purified by silica gel column chromatography to obtain 0.4 g (yield: 60%) of a white solid compound (4-18) ≪ / RTI >

The UV / VIS spectra of the compounds of the present invention were measured using a Jasco V-630 instrument and PL (photoluminescence) spectra were measured using a Jasco FP-8500 instrument.

UV / VIS and PL results of compounds Classification (compound) UV (nm) * 1 PL (nm, room temperature) * 2 Example 1 (Compound 4-1) 239, 255, 346, 361 395.5, 4123.5 Example 2 (Compound 4-2) 259, 299, 345 394.5, 411.5 Example 3 (Compound 4-3) 261, 353 427 Example 4 (Compound 4-4) 262, 311, 368 408.5, 426.5 Example 5 (Compound 4-5) 260, 310, 351, 367 449 Example 6 (Compound 4-6) 258, 381 465 Example 7 (Compound 4-7) 248, 313, 323, 351, 367 397.5, 417 Example 8 (Compound 4-8) 263, 296, 365 398, 417 Example 9 (Compound 4-9) 256, 303, 344 394.5, 412.5 Example 10 (Compound 4-10) 262, 365 436 Example 11 (Compound 4-11) 255, 309, 318, 346, 365 399, 415.5 Example 12 (Compound 4-12) 262, 290, 336, 360 414 Example 13 (Compound 4-13) 245, 295, 344, 367 406 Example 14 (Compound 4-14) 253, 322, 365 413.5 Example 15 (Compound 4-15) 262, 294, 309, 368 432.5 Example 16 (Compound 4-16) 263, 334, 348, 368 402.5 Example 17 (Compound 4-17) 296, 348 446 Example 18 (Compound 4-18) 301, 354 430 * 1: 1.0 x 10 ^-5 M in methylene chloride
* 2: 5.0 x 10 ^-6 M in methylene chloride

The compounds of the present invention were analyzed by LC-MS using a Waters Acquity UPLC H-Class / SQD2 system instrument and the results are shown in Table 2 below.

LC / MS results of the compounds Classification (compound)  MS Calcd. LC-MS Found [M + 1] < + > Example 1 (Compound 4-1) 536.20 537.41 Example 2 (Compound 4-2) 537.20 538.21 Example 3 (Compound 4-3) 538.22 539.34 Example 4 (Compound 4-4) 563.21 564.15 Example 5 (Compound 4-5) 639.24 541.33 Example 6 (Compound 4-6) 614.25 614.98 Example 7 (Compound 4-7) 643.18 644.39 Example 8 (Compound 4-8) 627.21 628.22 Example 9 (Compound 4-9) 593.26 594.21 Example 10 (Compound 4-10) 704.27 705.53 Example 11 (Compound 4-11) 589.23 590.11 Example 12 (Compound 4-12) 702.25 703.60 Example 13 (Compound 4-13) 537.61 538.41 Example 14 (Compound 4-14) 563.65 564.42 Example 15 (Compound 4-15) 614.74 615.25 Example 16 (Compound 4-16) 639.75 640.47 Example 17 (Compound 4-17) 641.76 642.79 Example 18 (Compound 4-18) 616.75 617.71

Device fabrication test example

2-TNATA is a hole injection layer, NPB is a hole transport layer, αβ-ADN is a host of a light emitting layer, Bphen is an electron transport layer, Liq is an electron injection layer, Al is a cathode, Respectively. The structures of these compounds are shown below.

Comparative Example: ITO / 2-TNATA / NPB / αβ-ADN, 9,9-diethyl-2,7-bis ((E) -4-tritylstyryl) -9H-fluorene / Bphen / Liq / Al

A blue fluorescent organic light-emitting device was prepared in the same manner as in Example 1 except that ITO (180 nm) / 2-TNATA (60 nm) / NPB (20 nm) / αβ-ADN: 9,9-diethyl- -9H-fluorene was deposited in the order of 10% (30 nm) / Bphen (40 nm) / Liq (2 nm) / Al (100 nm). Before depositing the organic material, the ITO electrode was subjected to oxygen plasma treatment at 2 10 ^-2 Torr to 125 W for 2 minutes. The organic materials were deposited at a vacuum of 9 10 ^-7 Torr. The blue fluorescent dopant was simultaneously deposited at 0.02 Å / sec on the basis of Liq and 0.18 Å / sec for αβ-ADN, sec. < / RTI > The blue fluorescent dopant used in the experiment was 9,9-diethyl-2,7-bis ((E) -4-tritylstyryl) -9H-fluorene and the concentration of the dopant was fixed at 10%. After fabricating the device, it was sealed in a glove box filled with nitrogen gas to prevent air and moisture contact of the device. Barium oxide (Barium Oxide), which is a hygroscopic agent capable of removing moisture and so on, was put into a glass plate after 3M's adhesive tape was formed.

Test Example 1: ITO / 2-TNATA / NPB /? Beta-ADN, compound (4-2) of Example 2 / Bphen / Liq / Al

A device was prepared in the same manner as in the comparative test except that the compound prepared in Example 2 was used as a light emitting layer instead of the blue fluorescent dopant used in the above Comparative Test Example.

Classification (compound) The color coordinates (x, y) EL peak (nm) The luminous efficiency (cd / A)
@ 20 mA / cm 2 External quantum efficiency (%)
@ 20 mA / cm 2 Comparative test example (0.17, 0.19) 456 1.89 1.20 Test Example 1 (0.16, 0.19) 473 3.15 2.42

As can be seen from Table 3 and FIG. 2, the device manufactured using the compounds of the present invention as a light emitting layer emits light in the blue wavelength region, and the device of Test Example 1 has a higher luminous efficiency and external quantum efficiency It can be confirmed that the characteristics are improved. The improvement of the luminous efficiency and the external quantum efficiency characteristic can provide an organic electroluminescent device with improved driving voltage and luminous efficiency.

Claims (9)

A dibenzo-benzimidazole derivative represented by the following formula (1).
[Chemical Formula 1]

[In the formula (1), A is any one selected from the following formula (3)
(3)

delete delete The method according to claim 1,
The dibenzo-benzimidazole derivative according to claim 1, wherein the compound represented by the formula (1) is selected from the following formula (4).
[Chemical Formula 4]

An organic electroluminescent device comprising the dibenzo-benzimidazole derivative of claim 1 or 4. 6. The method of claim 5,
Wherein the dibenzo-benzimidazole derivative is used in the light emitting layer. A first electrode, a second electrode, and at least one organic film disposed between the electrodes,
Wherein the organic layer comprises the dibenzo-benzimidazole derivative of claim 1 or claim 4. 8. The method of claim 7,
The organic layer includes a hole injecting layer, a hole transporting layer, a functional layer having both a hole injecting function and a hole transporting function, a buffer layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transporting layer, And at least one functional layer having at least one functional group at the same time. 8. The method of claim 7,
The dibenzo-benzimidazole derivative is contained in any one selected from the group consisting of an electron blocking layer, an electron transporting layer, an electron injecting layer, a functional layer having both an electron transporting function and an electron injecting function, and a light emitting layer constituting the organic film Wherein the organic electroluminescent element is an organic electroluminescent element.

Images