KR101581948B1 - Fluoranthene derivative 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 a fluoranthene derivative represented by the following formula (1).
[Chemical Formula 1]

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

Description

[0001] Fluoranthene derivatives and organic electroluminescent devices including the same [0002]

The present invention relates to a flooranthene derivative and an organic electroluminescent device including the same, and more particularly, to an organic electroluminescent device having a high luminous efficiency and a novel fluoranthene 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. This is why OLEDs (organic light emitting diodes) are attracting attention as next-generation flat panel displays.

In the case of OLED, since it is a self-luminous type, it can be made much thinner because it does not need a separate light source, and the power consumption is very small, and the natural color is perfectly expressed. Since the light is emitted in all directions, the viewing angle is wide and the response speed of the pixels is also very fast, which is less than microseconds, so that high-quality video can be expressed. 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.

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.

In order for the OLED to emit light properly, electrons in the organic thin film are transported to the organic light emitting layer with the help of the electron transport layer, and in the anode, holes are transported to the light emitting layer with the help of the hole transport layer, Thereby forming an exciton. The generated excitons drop to a low energy state, and energy is emitted and light of a specific wavelength is generated. At this time, the color of the light changes depending on the organic material constituting the light emitting layer, and the organic material of R, G, and B can be used to produce a full color.

This OLED was first attempted in 1963 by Pope et al. To study carrier injection 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, 91 (1987)], OLEDs have a high potential for use in LCD backlighting and lighting 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].

In the case of the blue material in terms of the light emitting material, the blue material system (DPVBi) of Idemitsu-Gosan, the anthracene (9,10-di (2-naphthyl) anthracene of KODAK, tetra (t-butyl) perlyene) system.

In the field of OLEDs, the following compounds as fluoranthene structures are disclosed in the prior art. Specifically, Japanese Patent Application Laid-Open No. 11-149987, Japanese Patent Application Laid-Open No. 2001-307883, International Patent Application Publication No. WO 2005/026088, Japanese Patent Application Laid-Open No. 2005-240008, Open Patent Publication No. 2005-240011 discloses a host material for a blue light emitting device and a fluoranthene structural material as a light emitting material.

As the screen of the display is enlarged in the direction of the enlargement of the display, more delicate and sharper materials are required for the OLED. Among them, the problem to be solved and the material to be solved are blue, and high performance light emitting materials are required in the current sky blue to blue and deep blue directions. In addition, due to problems such as color purity and efficiency of the blue light emitting material, stability of the device, chemical structural thermal stability of the material, etc., a sufficient life can not be secured and the materials used in practical commercial products are very limited. Thus, full color display It is a field that requires a lot of research and development. Furthermore, considering that the blue emission wavelength range required for mid- to large-sized TV applications is shorter than the present wavelength (450 nm or less), it is very urgent to research and develop OLEDs with much improved material life and device life It is true.

Disclosure of the Invention The object of the present invention is to provide a novel fluoranthene derivative which is superior in luminous efficiency and durability to that of a conventional material, and that the fluoranthene derivative is contained in the organic layer to lower the driving voltage of the device and improve the luminous efficiency And to provide an organic electroluminescent device.

According to an aspect of the present invention, there is provided a fluoranthene derivative represented by the following formula (1).

[Chemical Formula 1]

Wherein Ar ₁ and Ar ₂ are each independently a substituted or unsubstituted C ₆ -C ₃₀ aryl or a substituted or unsubstituted C ₅ -C ₃₀ heteroaryl;

p is 0 or 1;

X ₁ , X ₂ , X ₃ , X ₄ , X ₅ and X ₆ are each independently CH or N, provided that at least one of X ₁ to X ₆ is N when p is 1 and X ₃ To X < ₆ > is N;

A is a substituted or unsubstituted C ₆ -C ₃₀ aryl or a substituted or unsubstituted C ₅ -C ₃₀ heteroaryl.]

According to another aspect of the present invention, there is provided an organic electroluminescent device comprising the above-mentioned fluoranthene derivative.

According to another aspect of the present invention, there is provided an organic electroluminescent device including a first electrode, a second electrode, and at least one organic film disposed between the electrodes, wherein the organic film includes an organic electroluminescent device including the fluoranthene derivative / RTI >

The fluoranthene derivative according to an embodiment of the present invention may be included in an organic layer of an organic electroluminescent device to improve the luminous efficiency. In particular, the thermal stability of the compound can improve the lifetime of the device.

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 electrical luminescence characteristics of the organic light emitting device manufactured in Comparative Examples and Test Examples 1 to 4.

As used herein, the term "alkyl" includes straight chain, branched or cyclic hydrocarbon radicals or combinations thereof, optionally including one or more double bonds, triple bonds or combinations thereof in the chain. E., "Alkyl" includes alkenyl or alkynyl.

The term "heteroalkyl ", by itself or in combination with other terms, unless otherwise indicated, includes one or more carbon atoms and one or more heteroatoms selected from the group consisting of O, N, P, Si and S Means a stable straight or branched or cyclic hydrocarbon radical or combination thereof, wherein the nitrogen, phosphorus and sulfur atoms may optionally be oxidized, and the nitrogen heteroatom may optionally be quaternized.

The terms "cycloalkyl" and "heterocycloalkyl ", by themselves or in conjunction with another term, refer to a cyclic version of" alkyl "and" heteroalkyl ", respectively,

The term "aryl" means a polyunsaturated, aromatic, hydrocarbon substituent which may be a single ring or multiple rings (one to three rings) fused or covalently bonded together unless otherwise specified. 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 optionally quaternized. 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, pyreneyl, perylenyl, But is 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, triazinyl, tetrazinyl, Monocyclic heteroaryl such as pyridyl, pyridyl, pyrazinyl, pyridazinyl and the like, benzofuranyl, benzothiophenyl, isobenzofuranyl, benzoimidazolyl, benzothiazolyl , Benzoisothiazolyl, benzoisoxazolyl, benzoxazolyl, isoindolyl, indolyl, indazolyl, benzothiadiazolyl, quinolyl, isoquinolyl, cinnolinyl, quinazolinyl, quinoxalinyl, (Such as pyridyl N-oxide, quinolyl N-oxide), quaternary salts thereof, and the like, but are not limited thereto. But is not limited thereto.

The term "aralkyl" refers to an alkyl group substituted with aryl, wherein the alkyl and aryl moieties are independently optionally substituted.

The term "heteroaralkyl" refers to an alkyl group substituted with heteroaryl, wherein the alkyl and heteroaryl moieties are independently optionally substituted.

"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 with -F, -Cl, -Br, -CN, -NO ₂ or -OH; A C ₆ -C ₃₀ aryl group which is unsubstituted or substituted by a C ₁ -C ₂₀ alkyl group, a C ₁ -C ₂₀ alkoxy group, -F, -Cl, -Br, -CN, -NO ₂ or -OH; A C ₆ -C ₃₀ heteroaryl group which is unsubstituted or substituted by a C ₁ -C ₂₀ alkyl group, a C ₁ -C ₂₀ alkoxy group, -F, -Cl, -Br, -CN, -NO ₂ or -OH; C ₁ -C ₂₀ alkyl, 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, C ₁ -C ₂₀ alkoxy group, -F, -Cl, -Br, -CN , -NO 2 , or substituted by -OH or 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.

The fluoranthene derivative according to one embodiment of the present invention can be represented by the following formula (1).

[Chemical Formula 1]

In Formula 1, Ar ₁ and Ar ₂ are each independently a substituted or unsubstituted C ₆ -C ₃₀ aryl or a substituted or unsubstituted C ₅ -C ₃₀ heteroaryl.

p is 0 or 1;

X ₁ , X ₂ , X ₃ , X ₄ , X ₅ and X ₆ are each independently CH or N, provided that at least one of X ₁ to X ₆ is N when p is 1 and X ₃ To X < ₆ > is N.

A is an aryl or a substituted or unsubstituted C ₆ -C _30, a substituted or unsubstituted C ₅ -C ₃₀ heteroaryl.

Preferably, Ar ₁ and Ar ₂ are substituted or unsubstituted C ₆ -C ₃₀ aryl and specific examples thereof include phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, , 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 9-phenanthryl, 9-phenanthryl, 1-naphthacetyl, Biphenyl, 4-biphenyl, p-terphenyl-4-yl, p-terphenyl- , m-tolyl, p-tolyl, pt-butylphenyl, p- (2- Methyl-1-naphthyl, 4-methyl-1-anthryl, 4'-methylbiphenyl, 4 "-t-butyl- Phenyl-4-yl group, etc. More preferably, Ar ₁ and Ar ₂ are phenyl.

Preferably, A may have any of the structures represented by the following formula (2).

(2)

Wherein R ₁ to R ₅ are each independently selected from the group consisting of hydrogen, halogen, amino, nitro, cyano, hydroxy, substituted or unsubstituted C ₁ -C ₁₀ alkyl, substituted or unsubstituted C ₃ -C ₈ cyclo Alkyl, substituted or unsubstituted C ₆ -C ₃₀ silyl, substituted or unsubstituted C ₁ -C ₂₀ alkoxy, substituted or unsubstituted C ₆ -C ₂₀ aryloxy, substituted or unsubstituted C ₁ -C ₂₀ alkyl Substituted or unsubstituted C ₆ -C ₃₀ aryl, substituted or unsubstituted C ₆ -C ₃₀ aralkyl, substituted or unsubstituted C ₁ -C ₁₀ heteroalkyl, substituted or unsubstituted C ₂ -C ₈ alkyl Substituted or unsubstituted C ₅ -C ₃₀ heteroaryl, substituted or unsubstituted C ₅ -C ₃₀ heteroaryl, substituted or unsubstituted C ₆ -C ₂₀ arylthio, or substituted or unsubstituted C ₆ -C ₄₀ mono or diarylamino. Further, in R ₁ to R ₅ , adjacent substituents may be bonded to each other to form a saturated or unsaturated cyclic structure, and the cyclic structure may be substituted.

Z is O, S or NR '. Wherein R 'is a substituted or unsubstituted C ₆ -C ₃₀ aryl. Preferably, R 'is phenyl.

의 잔기는 하기의 화학식 3으로 표시되는 어느 하나의 잔기인 것이 바람직하다.
On the other hand, when p = 1,

Is preferably any one of the residues represented by the following formula (3).

(3)

의 잔기는 하기의 화학식 4로 표시되는 어느 하나의 잔기인 것이 바람직하다.
Also

Is preferably any one of the residues represented by the following formula (4).

[Chemical Formula 4]

Specific examples of the fluoranthene derivative represented by the formula (1) according to an embodiment of the present invention may be represented by the following formula (5), and examples of various structures other than the fluoranthene derivatives represented by the following formula (5) .

[Chemical Formula 5]

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

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

The fluoranthene derivative of Formula 1 is preferably used as a blue fluorescent dopant material, and may be used as a material for green, red fluorescence, blue, green, or red phosphorescent devices, or as a hole injecting or hole transporting material.

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 includes at least one fluoranthene 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 fluoranthene derivative may be included 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 fluoranthene derivative may be contained in one or more layers 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 fluoranthene derivative may be included in the organic film as a single substance or a combination of different substances. Alternatively, the fluoranthene 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, or 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 material layer 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.

The organic layer may be prepared by a variety of polymer materials, not by vapor deposition, but by a solvent process such as spin coating, dip coating, doctor blading, screen printing, inkjet printing, or thermal transfer.

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]

The structures of the synthesized compounds are as follows.

Intermediate Synthesis Example 1: Synthesis of Intermediate ( 3 ) Synthesis of

 (Synthesis of Intermediate (1)

20.0 g (0.086 mol) of 5-bromoacenaphthylene and 400 mL of dried benzene were added to 2,3-dichloro-5,6-dicyano-1,4-benzoquinone -5,6-dicyano-1,4-benzoquinone, DDQ) was added and the mixture was heated under reflux for 12 hours. To the reaction mixture, 6.0 g (26.4 mmol) of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) ) Was further added, and the mixture was refluxed and stirred for 4 hours. After cooling, the precipitate was separated by filtration and washed with chloroform. The filtrate was collected and washed with 10% NaOH Solution and H ₂ O. After separation, the organic phase was dried over anhydrous MgSO ₄ and the solvent was distilled off. And dried under reduced pressure to obtain 11.0 g (yield: 55%) of a brown solid compound (intermediate (1)).

(Synthesis of Intermediate (2)

A mixture of 11 g (0.048 mol) of Intermediate (1) and 43.6 ml of Toluene in 12.8 g (0.048 mol) of 1,3-diphenylisobenzofuran was stirred at reflux for 16 hours. After distilling off the solvent, 1000 ml of acetic acid was added and the mixture was heated to 80 ° C. To this mixture was added 132 ml of 48% HBr solution, and the mixture was refluxed and stirred at 80 占 폚 for 2 hours. After cooling to room temperature, the precipitate was filtered off and washed with MeOH. The resulting yellow solid was recrystallized from 100 ml of toluene. The crystals were collected by filtration to obtain 17.5 g (yield: 75%) of a brown solid compound (Intermediate (2)).

(Synthesis of Intermediate (3)

A flask was charged with 30 g (0.062 mol) of intermediate (2), 18.9 g (0.074 mol) of PIN ₂ B ₂ , 1.5 g (1.86 mmol) of Pd (dppf) Cl ₂ , 12.2 g (0.124 mol) And the mixture was refluxed under nitrogen at 100-110 ^° C for 2 hours. After the temperature was lowered to room temperature, the solvent was distilled off. Add 600 mL of MC to the mixture, filter the solid with silica gel, and wash with MC. The filtrate was distilled off, and the obtained solid was recrystallized. The crystals were filtered to obtain 26 g (yield: 79%) of a brown solid compound (Intermediate (3)).

Intermediate Synthesis Example 2: Synthesis of Intermediate (4)

In 1 100 mL flask carbazole (Carbazole) 1.0 g (5.98 mmol ), 2,5- dibromo-pyridine (2,5-dibromopyridine) 2.1 g ( 8.97 mmol) and CuI 113 mg (0.598 mmol), CS 2 3.9 g (11.96 mmol) of CO ₃ and 215 mg (1.196 mmol) of 1,10-phenanthroline were dissolved in 30 mL of 1,4-dioxane under a nitrogen atmosphere, and the mixture was refluxed at 100 ° C. After completion of the reaction, the mixture was cooled to room temperature and 20 mL of MC was added to the mixture. The solid was filtered and the filtrate was concentrated under reduced pressure. The obtained solid was purified by silica gel column chromatography to obtain 1.35 g (yield: 70.2%) of a white solid compound (Intermediate (4)).

Intermediate Synthesis Example 3: Synthesis of Intermediate (5)

A 1-necked 100 mL flask was charged with 1.0 g (5.95 mmol) of delta-carboline, 2.5 g of 2,5-dibromopyridine (8.92 mmol) and 566 mg of CuI (2.98 mmol 3.9 g (11.9 mmol) of CS ₂ CO ₃ and 1.07 g (5.95 mmol) of 1,10-phenanthroline were dissolved in 30 mL of 1,4-dioxane under a nitrogen atmosphere, and the mixture was refluxed at 100 ° C. After completion of the reaction, the mixture was cooled to room temperature and 20 mL of MC was added to the mixture. The solid was filtered and the filtrate was concentrated under reduced pressure. The resulting solid was purified by silica gel column chromatography to obtain 1.52 g (yield: 78.8%) of a light yellow solid compound (Intermediate (5)).

Intermediate Synthesis Example 4: Synthesis of Intermediate (6)

Intermediate 1 to obtain 100 mL flask (3) 2.0 g (3.77 mmol ), 2,6- dibromo-pyridine (2,6-dibromopyridine) 2.68 g ( 11.3 mmol) and _{Pd (PPh 3) 4 217 mg} (0.189 mmol ) Was dissolved in 25 mL of toluene and 12.5 mL of EtOH under a nitrogen atmosphere, 4.7 mL of 2M Na ₂ CO ₃ solution was added, and the mixture was stirred under reflux. After the reaction was completed, it was cooled to room temperature and 10 mL of H ₂ O was added. The mixture was extracted twice with 50 mL of MC, the extract was dried with Na ₂ SO ₄ , filtered, and the filtrate was concentrated under reduced pressure. The obtained solid was purified by silica gel column chromatography to obtain 1.0 g (yield: 46.3%) of a yellow solid compound (Intermediate (6)).

Intermediate Synthesis Example 5: Synthesis of Intermediate (7)

Phenyl-1H-benzo [d] imidazol-2-yl) -5H-pyrido [3,2- b] indole (7- (1-phenyl- (500 mg, 1.39 mmol) and 2,5-dibromopyridine (493 mg, 2.08 mmol) in tetrahydrofuran (5 ml) And 120 mg (2.78 mmol) of CS ₂ CO ₃ and 250 mg (1.39 mmol) of 1,10-phenanthroline were dissolved in 10 mL of 1,4-dioxane under nitrogen atmosphere, and the mixture was stirred at 100 ° C. And the mixture was refluxed and stirred. After the reaction was completed, the reaction mixture was cooled to room temperature, and 20 mL of MC was added to the mixture. The solid was filtered and the filtrate was concentrated under reduced pressure. The resulting compound was purified by silica gel column chromatography to obtain 571 mg (yield: 79.6%) of a pale yellow solid (intermediate (7)).

Intermediate Synthesis Example 6: Synthesis of Intermediate (8)

A 1-necked 100 mL flask was charged with 1.0 g (5.95 mmol) of delta-carboline, 2.5 g (8.92 mmol) of 1-bromo-4-iodobenzene and CuI 566 3.9 g (11.9 mmol) of CS ₂ CO ₃ and 1.07 g (5.95 mmol) of 1,10-phenanthroline were dissolved in 30 mL of 1,4-dioxane under a nitrogen atmosphere, and the mixture was stirred under reflux at 100 ° C. . After completion of the reaction, the mixture was cooled to room temperature, and 50 mL of MC was added to the mixture. The solid was filtered and the filtrate was concentrated under reduced pressure. The obtained compound was purified by silica gel column chromatography to obtain 1.65 g (yield: 85.9%) of a white solid compound (intermediate (8)).

Intermediate Synthesis Example 7: Synthesis of Intermediate (9)

1.10 mL (8.92 mmol) of 1-bromo-3-iodobenzene and 1.25 mL 3.9 g (11.9 mmol) of CS ₂ CO ₃ and 1.07 g (5.95 mmol) of 1,10-phenanthroline were dissolved in 30 mL of 1,4-dioxane under a nitrogen atmosphere, and the mixture was stirred under reflux at 100 ° C. . After the reaction was completed, the mixture was cooled to room temperature, and 50 mL of MC was added to the mixture. The solid was filtered and the filtrate was concentrated under reduced pressure. The obtained compound was purified by silica gel column chromatography to obtain 1.35 g (yield: 70.3%) of a white solid compound (Intermediate (9)).

Intermediate Synthesis Example 8: Synthesis of Intermediate (10)

A 100 mL flask was charged with 500 mg (2.29 mmol) of 7H-benzo [e] pyrido [3,2- b] indole (7H-benzo [e] pyrido [ 814 mg (3.44 mmol) of dibromopyridine, 218 mg (1.15 mmol) of CuI and 1.5 g (4.58 mmol) of CS ₂ CO ₃ and 413 mg (2.29 mmol) of 1,10-phenanthroline Dissolved in 10 mL of 1,4-dioxane under a nitrogen atmosphere, and the mixture was stirred under reflux at 100 ° C. After the reaction was completed, the reaction mixture was cooled to room temperature, and 20 mL of MC was added to the mixture. The solid was filtered and the filtrate was concentrated under reduced pressure. The obtained compound was purified by silica gel column chromatography to obtain 421 mg (yield: 49.1%) of a pale yellow solid (intermediate (10)).

Intermediate Synthesis Example 9: Synthesis of Intermediate (11)

A 100 mL flask was charged with 500 mg (2.29 mmol) of 11H-benzo [g] pyrido [3,2- b] indole (11H- 814 mg (3.44 mmol) of dibromopyridine, 218 mg (1.15 mmol) of CuI and 1.5 g (4.58 mmol) of CS ₂ CO ₃ and 413 mg (2.29 mmol) of 1,10-phenanthroline Dissolved in 10 mL of 1,4-dioxane under a nitrogen atmosphere, and the mixture was stirred under reflux at 100 ° C. After the reaction was completed, the reaction mixture was cooled to room temperature, and 20 mL of MC was added to the mixture. The solid was filtered and the filtrate was concentrated under reduced pressure. The resulting compound was purified by silica gel column chromatography to obtain 590 mg (yield: 68.9%) of a pale yellow solid (intermediate (11)).

Intermediate Synthesis Example 10: Synthesis of Intermediate (12)

5-pyrido [3,2-b] indol-7-amine (N, N-diphenyl-5H- amine) 500 mg (1.5 mmol) , 2,5- dibromo-pyridine (2,5-dibromopyridine) 529 mg ( 2.24 mmol) and CuI 143 mg (0.75 mmol), CS 2 CO 3 977 mg (3.0 mmol) and 1,10-phenanthroline (270 mg, 1.5 mmol) was dissolved in 8 mL of 1,4-dioxane under a nitrogen atmosphere, and the mixture was stirred under reflux at 100 ° C. After the reaction was completed, the reaction mixture was cooled to room temperature, and 20 mL of MC was added to the mixture. The solid was filtered and the filtrate was concentrated under reduced pressure. The resulting compound was purified by silica gel column chromatography to obtain 455 mg (yield: 61.7%) of a pale yellow solid (intermediate (12)).

Intermediate Synthesis Example 11: Synthesis of Intermediate (13)

Benzo [4,5] thieno [2,3-e] pyrido [3,2-b] indole (5H- ] pyrido [3,2-b] indole), 1.3 g (5.47 mmol) of 2,5-dibromopyridine and 400 mg (1.83 mmol) of CuI, CS ₂ CO _{3 (} 2.4 g, 7.3 mmol) and 1,10-phenanthroline (658 mg, 3.65 mmol) were dissolved in dimethylformamide (18 mL) under nitrogen atmosphere, followed by reflux stirring at 100 ° C. After the reaction was completed, the reaction mixture was cooled to room temperature, and 20 mL of MC was added to the mixture. The solid was filtered and the filtrate was concentrated under reduced pressure. The obtained compound was purified by silica gel column chromatography to obtain 219 mg (yield: 13.9%) of a pale yellow solid (intermediate (13)).

Intermediate Synthesis Example 12: Synthesis of Intermediate (14)

500 mg (2.97 mmol) of β-caboline, 1.06 g (4.46 mmol) of 2,5-dibromopyridine and 283 mg of CuI (1.49 mmol 1.39 g (5.940 mmol) of CS ₂ CO ₃ and 535 mg (2.975 mmol) of 1,10-phenanthroline were dissolved in 15 mL of 1,4-dioxane under a nitrogen atmosphere, and the mixture was refluxed at 100 ° C. After completion of the reaction, the mixture was cooled to room temperature and 20 mL of MC was added to the mixture. The solid was filtered and the filtrate was concentrated under reduced pressure. The resulting compound was purified by silica gel column chromatography to obtain 537 mg (yield: 55.7%) of a pale yellow solid (intermediate (14)).

Intermediate Synthesis Example 13: Synthesis of Intermediate (15)

In a one-necked 100 mL flask, 1.0 g (5.95 mmol) of delta-carboline, 2.82 g (11.89 mmol) of 2,6-dibromopyridine and 566 mg (2.98 mmol ), 4.85 g (14.9 mmol) of CS ₂ CO ₃ and 1.07 g (5.95 mmol) of 1,10-phenanthroline were dissolved in 60 mL of 1,4-dioxane under a nitrogen atmosphere and the mixture was stirred under reflux at 100 ° C. After completion of the reaction, the mixture was cooled to room temperature, and 40 mL of MC was added to the mixture. The solid was filtered and the filtrate was concentrated under reduced pressure. The obtained compound was purified by silica gel column chromatography to obtain 1.09 g (yield: 57%) of a light yellow solid compound (Intermediate (15)).

Example 1: Synthesis of Compound 5-1 (HSB-04-031)

The synthesis route of HSB-04-031 is shown below.

1 intermediate necked 100 mL flask, (2) 1 g (2.06 mmol ), delta-carbamic Boleyn (δ-carboline) 0.521 g ( 309 mmol) and Cu 13 mg (0.206 mmol), K 2 CO 3 0.285 g (2.06 mmol ) And 0.29 g (2.06 mmol) of Na ₂ SO ₄ were dissolved in 21 mL of Nitrobenzene under a nitrogen atmosphere, followed by reflux stirring at 190 ° C. After the reaction was completed, the mixture was cooled to room temperature and the mixture was purified by silica gel column chromatography (Chloroform to n-Hexane: EtOAc = 9: 1) to obtain 0.6 g of a white solid compound (5-1, HSB-04-031) : 51%).

The obtained compounds were analyzed by LC-MS using a Waters Acquity UPLC H-Class / SQD2 system. The results of LC-MS analysis are as follows.

MS / FAB Calcd.: 569.69

LC-MS / FAB Found: 571.21 [M + 1] < + >

Example 2: Synthesis of Compound 5-2 (KJ-04-31)

The synthesis route of KJ-04-31 is shown below.

1 25 mL flask, to put the intermediate (4) 150 mg (0.464 mmol ), intermediate (3) 271 mg (0.51 mmol ) and _{Pd (PPh 3) 4 27 mg} (0.023 mmol) under a nitrogen atmosphere Toluene 3 mL and MeOH And the mixture was refluxed with 0.7 mL of 2M Na ₂ CO ₃ solution. After the reaction was completed, it was cooled to room temperature and 5 mL of H ₂ O was added. After the mixture was extracted twice with 20 mL of MC, the extract was dried with Na ₂ SO ₄ , filtered, and the filtrate was concentrated under reduced pressure. The obtained compound was purified by silica gel column chromatography to obtain 119 mg (yield: 39%) of a yellow solid compound (5-2, KJ-04-31).

The obtained compounds were analyzed by LC-MS using a Waters Acquity UPLC H-Class / SQD2 system. The results of LC-MS analysis are as follows.

MS / FAB Calcd.: 646.24

LC-MS / FAB Found: 647.45 [M + 1] < + >

Example 3: Synthesis of Compound 5-3 (KJ-04-26)

The synthesis route of KJ-04-26 is shown below.

1 25 mL flask, to put the intermediate (5) 400 mg (1.23 mmol ), intermediate (3) 785 mg (1.48 mmol ) and _{Pd (PPh 3) 4 71 mg} (0.062 mmol) under a nitrogen atmosphere Toluene 4 mL with EtOH 2 mL of Na ₂ CO ₃ solution, and the mixture was refluxed with stirring. After the reaction was completed, it was cooled to room temperature and 5 mL of H ₂ O was added. The mixture was extracted twice with 20 mL of MC, the extract was dried over Na ₂ SO ₄ , filtered, and the filtrate was concentrated under reduced pressure. The resulting compound was purified by silica gel column chromatography to obtain 525 mg (yield: 65.9%) of a green solid (5-3, KJ-04-26).

The obtained compounds were analyzed by LC-MS using a Waters Acquity UPLC H-Class / SQD2 system. The results of LC-MS analysis are as follows.

MS / FAB Calcd.: 647.24

LC-MS / FAB Found: 648.38 [M + 1] < + >

Example 4: Synthesis of Compound 5-4 (KJ-04-29)

The synthesis route of KJ-04-29 is shown below.

In 1 25 mL flask carbazole (Cabazole) 100 mg (0.598 mmol ), intermediate (6) 335 mg (0.598 mmol ) and CuI 57 mg (0.299 mmol), CS 2 CO 3 390 mg (1.19 mmol) and 1, 10-phenanthroline (108 mg, 0.598 mmol) was dissolved in 6 mL of 1,4-dioxane under a nitrogen atmosphere and reacted at 100 ° C. After the reaction was completed, the reaction mixture was cooled to room temperature, and 20 mL of MC was added to the mixture. The solid was filtered and the filtrate was concentrated under reduced pressure. The obtained compound was purified by silica gel column chromatography to obtain 233 mg (yield: 60.4%) of a compound (5-4, KJ-04-29) as a fluorescent solid.

The obtained compounds were analyzed by LC-MS using a Waters Acquity UPLC H-Class / SQD2 system. The results of LC-MS analysis are as follows.

MS / FAB Calcd.: 646.24

LC-MS / FAB Found: 647.52 [M + 1] < + >

Example 5: Synthesis of Compound 5-5 (KJ-04-30))

The synthesis route of KJ-04-30 is shown below.

Phenyl-1H-benzo [d] imidazol-2-yl) -5H-pyrido- [3,2- b] indole 7- (1-phenyl- 256 mg (0.46 mmol) of Intermediate 6 and 40 mg (0.21 mmol) of CuI, 150 mg (0.42 mmol) of benzo [d] imidazol-2-yl) -5H pyrido [ 274 mg (0.84 mmol) of _2- CO ₃ and 76 mg (0.42 mmol) of 1,10-phenanthroline are dissolved in 5 mL of 1,4-dioxane under a nitrogen atmosphere and reacted at 100 ° C. After the reaction was completed, the reaction mixture was cooled to room temperature, and 20 mL of MC was added to the mixture. The solid was filtered and the filtrate was concentrated under reduced pressure. The obtained compound was purified by silica gel column chromatography (n-Hexane: EtOAc = 1: 1 to 1: 2) to obtain 302 mg (yield: 85.6%) of a yellow solid (5-5, KJ- .

The obtained compounds were analyzed by LC-MS using a Waters Acquity UPLC H-Class / SQD2 system. The results of LC-MS analysis are as follows.

MS / FAB Calcd .: 839.30

LC-MS / FAB Found: 840.57 [M + 1] < + >

Example 6: Synthesis of compound 5-6 (HSB-04-037)

The synthesis route of HSB-04-037 is shown below.

1 intermediate necked 100 mL flask, (2) 0.5 g (1.03 mmol ), beta-carbamic Boleyn (β-caboline) 0.26 g ( 1.55 mmol) and CuI 80 mg (0.52 mmol), CS 2 CO 3 0.67 g (2.06 mmol ) And 1,10-phenanthroline (0.186 g, 1.03 mmol) were dissolved in 5 mL of dimethylformamide under a nitrogen atmosphere, and the mixture was refluxed at 140 ° C. After completion of the reaction, the mixture was cooled to room temperature and 20 mL of MC was added to the mixture. The solid was filtered and the filtrate was concentrated under reduced pressure. The obtained compound was purified by silica gel column chromatography to obtain 0.11 g (yield: 19%) of a white solid compound (5-6, HSB-04-037).

The obtained compounds were analyzed by LC-MS using a Waters Acquity UPLC H-Class / SQD2 system. The results of LC-MS analysis are as follows.

MS / FAB Calcd .: 570.68

LC-MS / FAB Found: 571.41 [M + 1] < + >

Example 7: Synthesis of Compound 5-7 (HSB-04-038)

The synthesis route of HSB-04-038 is shown below.

Benzo [e] pyrido [3,2-b] indole in a 1-necked 100 mL flask was charged with 0.5 g (1.03 mmol) of Intermediate (2) , 7H-benzo [e] pyrido [ 0.27 g (1.24 mmol) of CuI, 0.67 g (2.06 mmol) of CS ₂ CO ₃ and 0.186 g (1.03 mmol) of 1,10-phenanthroline were dissolved in 5 mL of dimethylformamide under nitrogen atmosphere, Lt; 0 > C. After completion of the reaction, the mixture was cooled to room temperature and 20 mL of MC was added to the mixture. The solid was filtered and the filtrate was concentrated under reduced pressure. The resulting compound was purified by silica gel column chromatography to obtain 0.06 g (yield: 9%) of a white solid compound 5-7 (HSB-04-038).

The obtained compounds were analyzed by LC-MS using a Waters Acquity UPLC H-Class / SQD2 system. The results of LC-MS analysis are as follows.

MS / FAB Calcd.: 620.74

LC-MS / FAB Found: 622.30 [M + 1] < + >

Example 8: Synthesis of Compound 5-8 (HSB-04-041)

The synthesis route of HSB-04-041 is shown below.

A 1-necked 100 mL flask was charged with 0.5 g (1.03 mmol) of Intermediate (2) , 5H-benzofuro [2,3-e] pyrido [3,2- b] indole (0.13 mmol) of K ₂ CO ₃ and 0.146 g (1.03 mmol) of Na ₂ SO ₄ were placed in a 250 ml _three- necked flask equipped with a stirrer, After the reaction was completed, the reaction mixture was cooled to room temperature and 20 mL of MC was added to the mixture. The solid was filtered and the filtrate was concentrated under reduced pressure. The obtained compound was purified by silica gel column chromatography 0.08 g (Yield: 12%) of a white solid compound 5-8, HSB-04-041 was obtained.

The obtained compounds were analyzed by LC-MS using a Waters Acquity UPLC H-Class / SQD2 system. The results of LC-MS analysis are as follows.

MS / FAB Calcd.: 660.76

LC-MS / FAB Found: 661.42 [M + 1] < + >

Example 9: Synthesis of Compound 5-9 (HSB-04-042)

The synthesis route of HSB-04-042 is shown below.

A 1-necked 100-mL flask was charged with 0.5 g (1.03 mmol) of intermediate (2) , N, N-diphenyl-5H-pyrido [3,2-b] indol- (0.13 mmol) of K ₂ CO ₃ and 0.146 g (1.03 mmol) of Na ₂ SO _{4 were added to a solution of} 0.52 g (1.55 mmol) of [3,2-b] indol- , Dissolved in 5 mL of Nitrobenzene under a nitrogen atmosphere, and stirred at 180 ° C under reflux. After completion of the reaction, the mixture was cooled to room temperature and 20 mL of MC was added to the mixture. The solid was filtered and the filtrate was concentrated under reduced pressure. The obtained compound was purified by silica gel column chromatography to obtain 0.1 g (yield: 13%) of a white solid compound (5-9, HSB-04-042).

The obtained compounds were analyzed by LC-MS using a Waters Acquity UPLC H-Class / SQD2 system. The results of LC-MS analysis are as follows.

MS / FAB Calcd.: 737.89

LC-MS / FAB Found: 738.52 [M + 1] < + >

Example 10: Synthesis of Compound 5-10 (HSB-04-043)

The synthesis route of HSB-04-043 is shown below.

In 1 100 mL flask, intermediate (2) 0.5 g (1.03 mmol ), 7- ( Tet-butyl) -5H- pyrido [3,2-b] indole (7- (tert-butyl) -5H -pyrido [ under 3,2-b] indole) 0.346 g (1.55 mmol) and Cu 7 mg (0.103 mmol), K 2 CO 3 0.142 g (1.03 mmol) and Na ₂ SO ₄ into a 0.146 g (1.03 mmol) of nitrogen atmosphere Nitrobenzene 5 mL, and the mixture was stirred at 180 ° C under reflux. After completion of the reaction, the mixture was cooled to room temperature and 20 mL of MC was added to the mixture. The solid was filtered and the filtrate was concentrated under reduced pressure. The resulting compound was purified by silica gel column chromatography to obtain 0.065 g (yield: 10%) of a white solid compound (5-10, HSB-04-043).

The obtained compounds were analyzed by LC-MS using a Waters Acquity UPLC H-Class / SQD2 system. The results of LC-MS analysis are as follows.

MS / FAB Calcd.: 626.79

LC-MS / FAB Found: 627.29 [M + 1] < + >

Example 11: Synthesis of Compound 5-11 (HSB-04-046)

The synthesis route of HSB-04-046 is shown below.

To a 100 mL 1-necked flask was added 0.5 g (1.03 mmol) of Intermediate (2) , 7- (1-phenyl-1H-benzo [d] imidazol-2-yl) -5H-pyrido [ (7- (1-phenyl-1H -benzo [d] imidazol-2-yl) -5H-pyrido [3,2-b] indole) 0.56 g (1.55 mmol) and Cu 7 mg (0.103 mmol), K 2 0.142 g (1.03 mmol) of CO ₃ and 0.146 g (1.03 mmol) of Na ₂ SO ₄ were added and dissolved in 5 mL of Nitrobenzene under a nitrogen atmosphere, followed by reflux stirring at 180 ° C. After the reaction was completed, the reaction mixture was cooled to room temperature, and 20 mL of MC was added to the mixture. The solid was filtered and the filtrate was concentrated under reduced pressure. The obtained compound was purified by silica gel column chromatography to obtain 0.07 g (yield: 9%) of a white solid compound (5-11, HSB-04-046).

The obtained compounds were analyzed by LC-MS using a Waters Acquity UPLC H-Class / SQD2 system. The results of LC-MS analysis are as follows.

MS / FAB Calcd.: 762.90

LC-MS / FAB Found: 763.47 [M + 1] < + >

Example 12: Synthesis of Compound 5-12 (KJ-04-33)

The synthesis route of KJ-04-33 is shown below.

To a 25 mL 1-necked flask was added 9- (5-bromopyridin-2-yl) -2- (1-phenyl-1H- benzo [d] imidazol- , 200 mg (0.39 mmol) of Intermediate (3), 226 mg (0.43 mmol) of Intermediate (3 ) and 10 mg 23 mg (0.019 mmol) of Pd (PPh ₃ ) ₄ was dissolved in 4 mL of toluene and 2 mL of EtOH under a nitrogen atmosphere. Then, 0.59 mL of 2M Na ₂ CO ₃ solution was added and the mixture was stirred under reflux. After the reaction was completed, it was cooled to room temperature and 5 mL of H ₂ O was added. The mixture was extracted twice with 20 mL of MC, and the extract was washed with Na ₂ SO ₄ Dried, filtered, and the filtrate was concentrated under reduced pressure. The obtained compound was purified by silica gel column chromatography to obtain 69.2 mg (yield: 21.1%) of a yellow solid compound (5-12, KJ-04-33).

The obtained compounds were analyzed by LC-MS using a Waters Acquity UPLC H-Class / SQD2 system. The results of LC-MS analysis are as follows.

MS / FAB Calcd .: 839.30

LC-MS / FAB Found: 840.57 [M + 1] < + >

Example 13: Synthesis of Compound 5-13 (KJ-04-35)

The synthesis route of KJ-04-35 is shown below.

(5-bromopyridin-2-yl) -5H-benzofuro [2,3-e] pyrido [3,2- b] 2-yl) -5H-benzofuro [ 2,3-e] pyrido [3,2-b] indole) 200 mg (0.48 mmol), intermediate (3) 282 mg (0.53 mmol ) and Pd (PPh _{3) 4} 28 (0.024 mmol) were dissolved in 4 mL of toluene and 2 mL of EtOH under a nitrogen atmosphere, followed by addition of 0.72 mL of 2M Na ₂ CO ₃ solution, and the mixture was stirred under reflux. After the reaction was completed, it was cooled to room temperature and 5 mL of H ₂ O was added. The mixture was extracted twice with 20 mL of MC, and the extract was washed with Na ₂ SO ₄ Dried, filtered, and the filtrate was concentrated under reduced pressure. The obtained compound was purified by silica gel column chromatography to obtain 213 mg (yield: 60.4%) of a green solid compound (5-13, KJ-04-35).

The obtained compounds were analyzed by LC-MS using a Waters Acquity UPLC H-Class / SQD2 system. The results of LC-MS analysis are as follows.

MS / FAB Calcd.: 737.25

LC-MS / FAB Found: 738.52 [M + 1] < + >

Example 14: Synthesis of Compound 5-14 (KJ-04-40)

The synthesis route of KJ-04-40 is shown below.

36 mg (0.031 mmol) of Pd (PPh ₃ ) ₄ was added to a 25 mL flask with a stirrer and a stirrer. Thereto was added 200 mg (0.62 mmol) of Intermediate 8, 394 mg 2 mL of a 2 M Na ₂ CO ₃ solution was added, and the mixture was stirred under reflux. After the reaction was completed, it was cooled to room temperature and 5 mL of H ₂ O was added. After the mixture was extracted twice with 20 mL of MC, the extract was dried with Na ₂ SO ₄ , filtered, and the filtrate was concentrated under reduced pressure. The obtained compound was purified by silica gel column chromatography to obtain 212 mg (yield: 52.9%) of a green solid compound (5-14, KJ-04-40).

The obtained compounds were analyzed by LC-MS using a Waters Acquity UPLC H-Class / SQD2 system. The results of LC-MS analysis are as follows.

MS / FAB Calcd.: 646.24

LC-MS / FAB Found: 647.38 [M + 1] < + >

Example 15: Synthesis of Compound 5-15 (KJ-04-43)

The synthesis route of KJ-04-43 is shown below.

1 25 mL flask, to put the intermediate (9) 200 mg (0.62 mmol ), intermediate (3) 492 mg (0.93 mmol ) and _{Pd (PPh 3) 4 36 mg} (0.031 mmol) under a nitrogen atmosphere Toluene 4 mL with EtOH 2 mL of 2M Na ₂ CO ₃ solution was added, and the mixture was stirred under reflux. After the reaction was completed, it was cooled to room temperature and 5 mL of H ₂ O was added. After the mixture was extracted twice with 20 mL of MC, the extract was dried with Na ₂ SO ₄ , filtered, and the filtrate was concentrated under reduced pressure. The obtained compound was purified by silica gel column chromatography to obtain 359 mg (Yield: 89.6%) of a yellow solid (5-15, KJ-04-43).

The obtained compounds were analyzed by LC-MS using a Waters Acquity UPLC H-Class / SQD2 system. The results of LC-MS analysis are as follows.

MS / FAB Calcd.: 646.24

LC-MS / FAB Found: 647.52 [M + 1] < + >

Example 16: Synthesis of Compound 5-16 (KJ-05-04)

The synthesis route of KJ-05-04 is shown below.

1 25 Intermediate 10 in-mL flask was charged with 200 mg (0.53 mmol), intermediate (3) 425 mg (0.80 mmol) and Pd (PPh _{3) 4} 31 placed mg (0.027 mmol) Toluene 4 mL and EtOH under a nitrogen atmosphere 2 ml of Na ₂ CO ₃ solution was added thereto, followed by stirring under reflux. After the reaction was completed, it was cooled to room temperature and 5 mL of H ₂ O was added. After the mixture was extracted twice with 20 mL of MC, the extract was dried with Na ₂ SO ₄ , filtered, and the filtrate was concentrated under reduced pressure. The obtained compound was purified by silica gel column chromatography to obtain 337 mg (yield: 91.1%) of a green solid compound (5-16, KJ-05-04).

The obtained compounds were analyzed by LC-MS using a Waters Acquity UPLC H-Class / SQD2 system. The results of LC-MS analysis are as follows.

MS / FAB Calcd.: 697.25

LC-MS / FAB Found: 699.47 [M + 1] < + >

Example 17: Synthesis of Compound 5-17 (KJ-04-45)

The synthesis route of KJ-04-45 is shown below.

1 25 Intermediate 11 in-mL flask was charged with 150 mg (0.40 mmol), intermediate (3) 318 mg (0.60 mmol) and Pd (PPh _{3) 4} 23 placed mg (0.02 mmol) Toluene 3 mL and EtOH under a nitrogen atmosphere 1.5 mL, and then 0.6 mL of 2M Na ₂ CO ₃ solution was added thereto, followed by stirring under reflux. After the reaction was completed, it was cooled to room temperature and 5 mL of H ₂ O was added. After the mixture was extracted twice with 20 mL of MC, the extract was dried with Na ₂ SO ₄ , filtered, and the filtrate was concentrated under reduced pressure. The obtained compound was purified by silica gel column chromatography to obtain 201 mg (yield: 72.0%) of a green solid compound (5-17, KJ-04-45).

The obtained compounds were analyzed by LC-MS using a Waters Acquity UPLC H-Class / SQD2 system. The results of LC-MS analysis are as follows.

MS / FAB Calcd.: 697.25

LC-MS / FAB Found: 699.47 [M + 1] < + >

Example 18: Synthesis of Compound 5-18 (KJ-04-46)

The synthesis route of KJ-04-46 is shown below.

1 25 mL of intermediate (12) in the flask 150 mg (0.31 mmol), intermediate (3) 243 mg (0.45 mmol) and Pd (PPh _{3) 4} 18 placed mg (0.016 mmol) Toluene 3 mL and EtOH under a nitrogen atmosphere 1.5 mL, and then 0.5 mL of 2M Na ₂ CO ₃ solution was added thereto, followed by stirring under reflux. After the reaction was completed, it was cooled to room temperature and 5 mL of H ₂ O was added. After the mixture was extracted twice with 20 mL of MC, the extract was dried with Na ₂ SO ₄ , filtered, and the filtrate was concentrated under reduced pressure. The obtained compound was purified by silica gel column chromatography to obtain 34 mg (yield: 13.5%) of a yellowish green solid (5-18, KJ-04-46).

The obtained compounds were analyzed by LC-MS using a Waters Acquity UPLC H-Class / SQD2 system. The results of LC-MS analysis are as follows.

MS / FAB Calcd.: 814.31

LC-MS / FAB Found: 815.56 [M + 1] < + >

Example 19: Synthesis of Compound 5-19 (KJ-05-13)

The synthesis route of KJ-05-13 is shown below.

Under one Intermediate 13 in 25 mL flask was charged 170 mg (0.40 mmol), intermediate (3) 314 mg (0.59 mmol) and Pd (PPh _{3) 4} placed 23 mg (0.02 mmol) of nitrogen atmosphere Toluene 4 mL with EtOH , 0.6 mL of 2M Na ₂ CO ₃ solution was added, and the mixture was stirred under reflux. After the reaction was completed, it was cooled to room temperature and 5 mL of H ₂ O was added. After the mixture was extracted twice with 20 mL of MC, the extract was dried with Na ₂ SO ₄ , filtered, and the filtrate was concentrated under reduced pressure. The resulting compound was purified by silica gel column chromatography to obtain 131 mg (yield: 43.7%) of a yellowish green solid (5-19, KJ-05-13).

The obtained compounds were analyzed by LC-MS using a Waters Acquity UPLC H-Class / SQD2 system. The results of LC-MS analysis are as follows.

MS / FAB Calcd.: 753.22

LC-MS / FAB Found: 754.49 [M + 1] < + >

Example 20: Synthesis of Compound 5-20 (KJ-05-14)

The synthesis route of KJ-05-14 is shown below.

1 25 mL flask, to put the intermediate (14) 200 mg (0.62 mmol ), intermediate (3) 491 mg (0.93 mmol ) and _{Pd (PPh 3) 4 36 mg} (0.031 mmol) under a nitrogen atmosphere Toluene 4 mL with EtOH 2 mL of a 2 M Na ₂ CO ₃ solution was added, and the mixture was stirred under reflux. After the reaction was completed, it was cooled to room temperature and 5 mL of H ₂ O was added. After the mixture was extracted twice with 20 mL of MC, the extract was dried with Na ₂ SO ₄ , filtered, and the filtrate was concentrated under reduced pressure. The obtained compound was purified by silica gel column chromatography to obtain 181 mg (yield: 45.1%) of a pale yellow solid (5-20, KJ-05-14).

The obtained compounds were analyzed by LC-MS using a Waters Acquity UPLC H-Class / SQD2 system. The results of LC-MS analysis are as follows.

MS / FAB Calcd.: 647.24

LC-MS / FAB Found: 648.32 [M + 1] < + >

Example 21: Synthesis of Compound 5-21 (KJ-04-47)

The synthesis route of KJ-04-47 is shown below.

5- (5-bromopyridin-2-yl) -7- (tert -butyl) -5H-pyrido [3,2- b] indole _{4 31 mg yl) -7- (tert} -butyl) -5H-pyrido [3,2-b] indole) 200 mg (0.53 mmol), intermediate (3) 418 mg (0.79 mmol ) and Pd (PPh ₃₎ ( 0.027 mmol) were dissolved in 4 mL of toluene and 2 mL of EtOH under a nitrogen atmosphere, followed by the addition of 0.8 mL of 2M Na ₂ CO ₃ solution, followed by stirring under reflux. After the reaction was completed, it was cooled to room temperature and 5 mL of H ₂ O was added. After the mixture was extracted twice with 20 mL of MC, the extract was dried with Na ₂ SO ₄ , filtered, and the filtrate was concentrated under reduced pressure. The obtained compound was purified by silica gel column chromatography to obtain 275 mg (yield: 73.7%) of a yellow solid compound (5-21, KJ-05-47).

The obtained compounds were analyzed by LC-MS using a Waters Acquity UPLC H-Class / SQD2 system. The results of LC-MS analysis are as follows.

MS / FAB Calcd .: 703.30

LC-MS / FAB Found: 704.60 [M + 1] < + >

Example 22: Synthesis of Compound 5-22 (KJ-04-44)

The synthesis route of KJ-04-44 is shown below.

1 25 mL flask, to put the intermediate (15) 200 mg (0.62 mmol ), intermediate (3) 491 mg (0.93 mmol ) and _{Pd (PPh 3) 4 36 mg} (0.031 mmol) under a nitrogen atmosphere Toluene 4 mL with EtOH 2 mL of a 2 M Na ₂ CO ₃ solution was added, and the mixture was stirred under reflux. After the reaction was completed, it was cooled to room temperature and 5 mL of H ₂ O was added. After the mixture was extracted twice with 20 mL of MC, the extract was dried with Na ₂ SO ₄ , filtered, and the filtrate was concentrated under reduced pressure. The obtained compound was purified by silica gel column chromatography to obtain 364 mg (yield: 90.9%) of a yellow solid compound (5-22, KJ-04-44).

The obtained compounds were analyzed by LC-MS using a Waters Acquity UPLC H-Class / SQD2 system. The results of LC-MS analysis are as follows.

MS / FAB Calcd.: 647.24

LC-MS / FAB Found: 648.32 [M + 1] < + >

Example 23: Synthesis of Compound 5-23 (KJ-05-06)

The synthesis route of KJ-05-06 is shown below.

100 mg (0.46 mmol) of 7H-benzo [e] pyrido [3,2-b] indole (7H-benzo [e] pyrido [3,2- b] indole ) (4-dioxane, 5 mL) was added to a solution of 282 mg (0.5 mmol) of CuI and 44 mg (0.23 mmol) of CuI and 300 mg (0.92 mmol) of CS ₂ CO ₃ and 83 mg And the mixture was refluxed and stirred at 100 ° C. After completion of the reaction, the mixture was cooled to room temperature and 20 mL of MC was added to the mixture. The solid was filtered and the filtrate was concentrated under reduced pressure. The obtained compound was purified by silica gel column chromatography to obtain 206 mg (yield: 64.2%) of a yellow solid compound (5-23, KJ-05-06).

The obtained compounds were analyzed by LC-MS using a Waters Acquity UPLC H-Class / SQD2 system. The results of LC-MS analysis are as follows.

MS / FAB Calcd.: 697.25

LC-MS / FAB Found: 698.34 [M + 1] < + >

Example 24: Synthesis of Compound 5-24 (KJ-05-09)

The synthesis route of KJ-05-09 is shown below.

Benzo [g] pyrido [3,2-b] indole (11H-benzo [g] pyrido [3,2- b] indole) 150 mg (0.69 mmol ) 500 mg (0.89 mmol) CuI, 500 mg (1.38 mmol) of CS ₂ CO ₃ and 124 mg (0.69 mmol) 1,10-phenanthroline were placed in 7 mL of 1,4- dioxane under nitrogen atmosphere. And the mixture was refluxed and stirred at 100 ° C. After completion of the reaction, the mixture was cooled to room temperature and 20 mL of MC was added to the mixture. The solid was filtered and the filtrate was concentrated under reduced pressure. The resulting compound was purified by silica gel column chromatography to obtain 283 mg (yield: 58.9%) of a yellow solid compound (5-24, KJ-05-09).

The obtained compounds were analyzed by LC-MS using a Waters Acquity UPLC H-Class / SQD2 system. The results of LC-MS analysis are as follows.

MS / FAB Calcd.: 697.25

LC-MS / FAB Found: 698.48 [M + 1] < + >

Example 25: Synthesis of Compound 5-25 (KJ-05-12)

The synthesis route of KJ-05-12 is shown below.

Benzo [4,5] thieno [2,3-f] thieno [2,3- f] pyrido [3,2- b] indole (5H- ] pyrido [3,2-b] indole ) 150 mg (0.55 mmol), intermediate (6) 368 mg (0.66 mmol ) and CuI 52 mg (0.28 mmol), CS 2 CO 3 358 mg (1.1 mmol) and 1, 10-phenanthroline (99 mg, 0.55 mmol) was dissolved in 5.5 mL of 1,4-dioxane under a nitrogen atmosphere, and the mixture was refluxed at 100 ° C. After completion of the reaction, the mixture was cooled to room temperature and 20 mL of MC was added to the mixture. The solid was filtered and the filtrate was concentrated under reduced pressure. The obtained compound was purified by silica gel column chromatography to obtain 84.8 mg (yield: 20.5%) of a yellow solid compound (5-25, KJ-05-12).

The obtained compounds were analyzed by LC-MS using a Waters Acquity UPLC H-Class / SQD2 system. The results of LC-MS analysis are as follows.

MS / FAB Calcd.: 753.22

LC-MS / FAB Found: 754.49 [M + 1] < + >

Example 26: Synthesis of Compound 5-26 (KJ-05-11)

The synthesis route of KJ-05-11 is shown below.

2,3-f] pyrido [3,2-b] indole) (100 mg) was added to a 25 mL 1-necked flask. 260 mg (0.46 mmol) of intermediate (6 ), 37 mg (0.20 mmol) of CuI and 254 mg (0.78 mmol) of CS ₂ CO ₃ and 70.3 mg (0.39 mmol) of 1,10- And dissolved in 4 mL of 1,4-dioxane, followed by stirring under reflux at 100 ° C. After completion of the reaction, the mixture was cooled to room temperature and 20 mL of MC was added to the mixture. The solid was filtered and the filtrate was concentrated under reduced pressure. The obtained compound was purified by silica gel column chromatography to obtain 115 mg (yield: 15.7%) of a yellow solid compound (5-26, KJ-05-11).

The obtained compounds were analyzed by LC-MS using a Waters Acquity UPLC H-Class / SQD2 system. The results of LC-MS analysis are as follows.

MS / FAB Calcd.: 737.25

LC-MS / FAB Found: 738.39 [M + 1] < + >

Example 27: Synthesis of Compound 5-27 (KJ-05-10)

The synthesis route of KJ-05-10 is shown below.

1 beta in 25 mL flask -carbamic Boleyn (β-caboline) 150 mg ( 0.89 mmol), intermediate (6) 650 mg (1.16 mmol ) and CuI 85 mg (0.45 mmol), CS 2 CO 3 580 mg (1.78 mmol ) And 1,10-phenanthroline (160 mg, 0.89 mmol) were dissolved in 9 mL of 1,4-dioxane under a nitrogen atmosphere, and the mixture was refluxed at 100 ° C. After completion of the reaction, the mixture was cooled to room temperature and 20 mL of MC was added to the mixture. The solid was filtered and the filtrate was concentrated under reduced pressure. The resulting compound was purified by silica gel column chromatography to obtain 291 mg (yield: 50.5%) of a yellow solid compound (5-27, KJ-05-10).

The obtained compounds were analyzed by LC-MS using a Waters Acquity UPLC H-Class / SQD2 system. The results of LC-MS analysis are as follows.

MS / FAB Calcd.: 647.24

LC-MS / FAB Found: 648.32 [M + 1] < + >

Example 28: Synthesis of Compound 5-28 (KJ-05-15)

The synthesis route of KJ-05-15 is shown below.

5-pyrido [3,2-b] indole) was added to a 25-mL 1-necked flask. 450 mg (0.8 mmol) of Intermediate 6 and 64 mg (0.335 mmol) of CuI and 437 mg (1.34 mmol) of CS ₂ CO ₃ and 121 mg (0.67 mmol) of 1,10-phenanthroline were placed under nitrogen atmosphere 1,4-dioxane (7 mL), and the mixture was stirred at 100 ° C under reflux. After the reaction was completed, the reaction mixture was cooled to room temperature, and 20 mL of MC was added to the mixture. The solid was filtered and the filtrate was concentrated under reduced pressure. The resulting compound was purified by silica gel column chromatography to obtain 67.5 mg (yield: 14.3%) of a yellow solid compound (5-28, KJ-05-15).

The obtained compounds were analyzed by LC-MS using a Waters Acquity UPLC H-Class / SQD2 system. The results of LC-MS analysis are as follows.

MS / FAB Calcd .: 703.30

LC-MS / FAB Found: 704.40 [M + 1] < + >

Example 29: Synthesis of Compound 5-29 (KJ-05-08)

The synthesis route of KJ-05-08 is shown below.

5-pyrido [3,2-b] indol-7-amine (N, N-diphenyl-5H-pyrido [ amine, 100 mg (0.30 mmol) of Intermediate 6, 217 mg (0.39 mmol) of Intermediate 6 and 29 mg (0.15 mmol) of CuI and 196 mg (0.6 mmol) of CS ₂ CO ₃ and 54 mg (0.30 mmol) Was dissolved in 3 mL of 1,4-dioxane under a nitrogen atmosphere, and the mixture was stirred under reflux at 100 ° C. After completion of the reaction, the mixture was cooled to room temperature and 20 mL of MC was added to the mixture. The solid was filtered and the filtrate was concentrated under reduced pressure. The obtained compound was purified by silica gel column chromatography to obtain 96.4 mg (yield: 39.4%) of a yellow solid compound (5-29, KJ-05-08).

The obtained compounds were analyzed by LC-MS using a Waters Acquity UPLC H-Class / SQD2 system. The results of LC-MS analysis are as follows.

MS / FAB Calcd.: 814.31

LC-MS / FAB Found: 815.56 [M + 1] < + >

Test Example

The UV / VIS spectra of the OLED 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.

[Table 1] UV / VIS and PL results of the compounds

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 Test Example: ITO / 2-TNATA / NPB / αβ-ADN, Pyrene-CN / Bphen / Liq / Al

The blue fluorescent organic light-emitting device is composed of ITO (180 nm) / 2-TNATA (60 nm) / NPB (20 nm) / αβ-ADN: blue fluorescent dopant 10% (30 nm) / Bphen nm) / Al (100 nm) in this order. Before deposition of the organic material, the ITO electrode was subjected to oxygen plasma treatment at 125 W for 2 minutes at 2 × 10 ^-2 Torr. Organic matters 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 Pyrene-CN, 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, HSB-04-031 (2)  / Bphen / Liq / Al

In the above comparative test example, a device was fabricated in the same manner as in the comparative test except that Pyrene-CN was used instead of 5-1 (HSB-04-031) compound prepared in Example 1 as a light emitting layer .

Test Example 2: ITO / 2-TNATA / NPB /? Beta-ADN, KJ-04-31 (7)  / Bphen / Liq / Al

In the above Comparative Test Example, an element was fabricated in the same manner as in the Comparative Test Example except that Pyrene-CN was used instead of 5-2 (KJ-04-31) compound prepared in Example 2 as a light emitting layer .

Test Example 3: ITO / 2-TNATA / NPB /? Beta-ADN, KJ-04-26 (8)  / Bphen / Liq / Al

In the comparative test example, a device was fabricated in the same manner as in the comparative test except that Pyrene-CN was used instead of 5-3 (KJ-04-26) compound prepared in Example 3 as a light emitting layer .

Test Example 4: ITO / 2-TNATA / NPB / αβ-ADN, KJ-04-35 (22)  / Bphen / Liq / Al

In the comparative test example, a device was fabricated in the same manner as in the comparative test except that Pyrene-CN was used instead of 5-13 (KJ-04-35) compound prepared in Example 13 as a light emitting layer .

Table 2 shows the electroluminescent characteristics of the organic luminescent devices prepared in the Comparative Test Examples and Test Examples 1 to 4.

 [Table 2]

(result)

As can be seen from Table 2 and FIG. 2, the device fabricated using the compounds of the present invention as a light emitting layer emits light in the blue wavelength range, and the devices of Test Examples 1 to 4 are superior in color purity and luminous efficiency characteristics Can be improved. It is also confirmed that the external quantum efficiency is improved in Test Examples 2 and 3 as compared with the Comparative Examples.

Claims (13)

A fluoranthene derivative represented by the following formula (1).
[Chemical Formula 1]

Wherein Ar ₁ and Ar ₂ are each independently C ₆ -C ₃₀ aryl or C ₅ -C ₃₀ heteroaryl;
p is 1;
X _1, X ₂ , X ₃ , X ₄ , X ₅ and X ₆ are each independently CH or N, provided that at least one of X ₁ and X ₂ is N;
A has any one of the structures represented by the following formula (2)
(2)

[In the formula 2, R ₁ to R ₅ are each independently hydrogen, C ₁ -C ₁₀ alkyl, C ₃ -C ₈ cycloalkyl, C ₁ -C ₂₀ alkoxy, C ₆ -C ₂₀ aryloxy, C ₁ - C ₂₀ alkylthio, C ₆ -C ₃₀ aryl, C ₆ -C ₃₀ aralkyl, C ₁ -C ₁₀ heteroalkyl, C ₂ -C ₈ heterocycloalkyl, C ₅ -C ₃₀ heteroaryl, C ₅ -C ₃₀ Heteroaralkyl, C ₆ -C ₂₀ arylthio, or C ₆ -C ₄₀ mono or diarylamino, and in R ₁ to R ₅ , adjacent substituents are bonded to each other to form a saturated or unsaturated cyclic structure And Z is O, S or NR 'where R' is C ₆ -C ₃₀ aryl) The method according to claim 1,
Ar ₁ and Ar ₂ are phenyl. delete delete The method according to claim 1,

Is any one residue represented by the following formula (4).
[Chemical Formula 4]

6. An organic electroluminescent device comprising a fluoranthene derivative according to any one of claims 1, 2 and 5. The method according to claim 6,
Wherein the fluoranthene derivative is used as a light emitting layer material. 8. The method of claim 7,
Wherein the light emitting layer material is a blue fluorescent dopant material. The method according to claim 6,
Wherein the fluoranthene derivative is used as a dopant material for blue, green, red fluorescence and phosphorescent devices. A first electrode, a second electrode, and at least one organic film disposed between the electrodes,
Wherein the organic film comprises the fluoranthene derivative of any one of claims 1, 2, and 5. 11. The method of claim 10,
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. 11. The method of claim 10,
Wherein the fluoranthene derivative is 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. 11. The method of claim 10,
Wherein the fluoranthene derivative is 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.

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