KR101548370B1 - Anthracene derivative and organic electroluminescent device including the same - Google Patents

Abstract

[상기 화학식 1에서, 각 치환기들의 정의는 발명의 상세한 설명에서 정의한 바와 같다.]An anthracene derivative represented by the following formula (1) is provided.
[Chemical Formula 1]

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

Description

TECHNICAL FIELD The present invention relates to an anthracene derivative and an organic electroluminescent device including the same,

The present invention relates to an anthracene 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 anthracene derivative for the same.

In 1987, Tang and Van Slyke reported the characteristics of high efficiency using a multilayer thin film structure of an organic light emitting diode (OLED) [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) perylene) system are known, but they still do not satisfy the high color purity blue, and have a problem of low lifetime and low brightness, so that much research and development is required.

 In addition, it is preferable that the material used in the organic light emitting device is less deformed by moisture or oxygen. In addition, for the stability of the device, it is necessary to improve the interface with the electrode including the metal or the metal oxide. Therefore, research on such organic EL materials is continuously required.

It is an object of the present invention to provide a novel anthracene derivative which is superior in luminous efficiency and durability to that of a conventional material, and that the anthracene derivative is included in the organic material layer to improve the luminous efficiency.

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

[Chemical Formula 1]

[In the formula 1,

R ₁ is hydrogen, halogen, amino, nitro, cyano, hydroxy, substituted or unsubstituted C ₁ -C ₃₀ alkyl, substituted or unsubstituted C ₃ -C ₃₀ cycloalkyl, substituted or unsubstituted C ₆ - C ₃₀ aryl group, a substituted or unsubstituted C ₆ -C ₃₀ aralkyl (aralkyl), substituted or unsubstituted C ₁ -C ₃₀ heteroalkyl, substituted or unsubstituted C ₂ -C ₃₀ heterocycloalkyl, substituted or unsubstituted Substituted C ₅ -C ₃₀ heteroaryl, substituted or unsubstituted C ₅ -C ₃₀ heteroaralkyl,

p is an integer of 1 to 4,

Are two or more substituted in one ring R ₁ are the same or different, and adjacent R ₁ are connected to each other, each substituted or unsubstituted C ₃ -C ₂₀ alkylene or a substituted or unsubstituted C ₃ -C ₂₀ alkenylene To form a fused ring,

L ₁ and L ₂ are each independently a chemical bond, a substituted or unsubstituted C ₆ -C ₃₀ aryl or a substituted or unsubstituted C ₆ -C ₃₀ heteroaryl,

Ar is a substituted or unsubstituted C ₆ -C ₃₀ aryl or a substituted or unsubstituted C ₆ -C ₃₀ heteroaryl group.]

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

An anthracene derivative according to an embodiment of the present invention can improve the organic layer, preferably the luminous efficiency, of the organic electroluminescent device. 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 shows the results of LC-MS analysis of Compound 3-1 (mks-3-8).
3 shows the result of LC-MS analysis of Compound 3-2 (mks-3-20).
4 shows the result of LC-MS analysis of compound 3-3 (mks-3-22).
5 shows the result of LC-MS analysis of compound 3-4 (mks-3-34).
6 shows the results of LC-MS analysis of Compound 3-5 (mks-3-36).
Fig. 7 shows LC-MS analysis results of Compound 3-6 (mks-3-38).
8 shows the results of LC-MS analysis of compound 3-7 (mks-3-40).
Figure 9 shows the results of LC-MS analysis of compound 3-8 (mks-3-46).
10 shows the result of LC-MS analysis of Compound 3-9 (mks-3-48).
11 shows the results of LC-MS analysis of compound 3-10 (mks-4-1).
12 shows the results of LC-MS analysis of the compound 3-11 (mks-4-3).
13 shows the results of LC-MS analysis of Compound 3-12 (mks-4-5).
Fig. 14 shows LC-MS analysis results of compound 3-13 (mks-4-7).
15 shows the results of LC-MS analysis of compound 3-14 (mks-4-11).
16 shows the results of LC-MS analysis of Compound 3-15 (mks-4-15).
17 shows the results of LC-MS analysis of compound 3-16 (mks-4-17).
18 shows the results of LC-MS analysis of Compound 3-17 (mks-4-19).
19 shows the results of LC-MS analysis of compound 3-18 (mks-4-29).
20 shows the results of LC-MS analysis of Compound 3-19 (mks-4-31).
21 shows the results of LC-MS analysis of compound 3-20 (mks-4-33).
22 shows the results of LC-MS analysis of Compound 3-21 (mks-4-35).
23 shows the results of LC-MS analysis of the compound 3-22 (mks-4-37).
24 shows the results of LC-MS analysis of the compound 3-23 (mks-6-5).

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 and aryl, wherein the alkyl and aryl moieties are independently optionally substituted.

The term "heteroaralkyl" refers to an alkyl group substituted with aryl and heteroaryl, respectively, 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.

Among the terms indicating the number of carbon atoms, for example, "C _n -C ₃₀ " may have n to 30 carbon atoms, may have n to 20 carbon atoms, may have n to 10 carbon atoms, And may have 6 carbon atoms. Similarly, "C _n -C ₂₀ " may have n to 20 carbon atoms, may have n to 10 carbon atoms, and may have n to 6 carbon atoms (n is an integer of 1 to 6).

Hereinafter, the present invention will be described in detail.

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

An anthracene derivative represented by the following formula (1) is provided.

[Chemical Formula 1]

In Formula 1,

R ₁ is hydrogen, halogen, amino, nitro, cyano, hydroxy, substituted or unsubstituted C ₁ -C ₃₀ alkyl, substituted or unsubstituted C ₃ -C ₃₀ cycloalkyl, substituted or unsubstituted C ₆ - C ₃₀ aryl group, a substituted or unsubstituted C ₆ -C ₃₀ aralkyl (aralkyl), substituted or unsubstituted C ₁ -C ₃₀ heteroalkyl, substituted or unsubstituted C ₂ -C ₃₀ heterocycloalkyl, substituted or unsubstituted Substituted C ₅ -C ₃₀ heteroaryl, substituted or unsubstituted C ₅ -C ₃₀ heteroaralkyl.

p is an integer of 1 to 4; That is, R ₁ substituted on one ring may be one to four. Two or more R < ₁ > substituted in one ring may be the same or different from each other. Adjacent R ₁ are connected to each other, each substituted or unsubstituted C ₃ -C ₂₀ alkylene or a substituted or unsubstituted C ₃ -C ₂₀ alkenylene may form a fused ring.

L ₁ and L ₂ are each independently a chemical bond, a substituted or unsubstituted C ₆ -C ₃₀ aryl, or a substituted or unsubstituted C ₆ -C ₃₀ heteroaryl. For example, L ₁ and L ₂ are each phenyl or anthracenyl.

Ar is a substituted or unsubstituted C ₆ -C ₃₀ aryl or a substituted or unsubstituted C ₆ -C ₃₀ heteroaryl group.

,

,

,

,

,

,

,

또는

일 수 있다.In one embodiment, Ar is < RTI ID = 0.0 >

,

,

,

,

,

,

,

or

Lt; / RTI >

R ₂ , R ₃ , R ₄ and R ₅ are each independently the same as defined for R ₁ above.

And q, r, s and t are each independently selected from the integers of 1 to 5, and the maximum value is 3, 4 or 5 days depending on the type of ring to which R ₂ , R ₃ , R ₄ or R ₅ groups are attached have.

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

(2)

In Formula 2, R ₁ , p and Ar are the same as defined in Formula 1.

In some embodiments of Formula 1 or Formula 2, R ₁ , R ₂ , R ₃ , R _4, and R ₅ may be hydrogen.

More specifically, the compound represented by Formula 1 may be selected from among the compounds represented by Formula 3, but is not limited thereto.

(3)

The anthracene derivative represented by the above formula (1) can be synthesized using a known organic synthesis method. The method for synthesizing the anthracene 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 an anthracene derivative represented by the above formula (1).

The anthracene derivative of Formula 1 is preferably used as a blue fluorescent dopant and a host material of a light emitting layer.

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 layer includes at least one anthracene derivative represented by the general 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.

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 intended to illustrate the present invention and the scope of the present invention is not limited thereto.

Synthesis Example 1: Synthesis of Compound 3-1 (mks-3-8)

The synthesis route of mks-3-8 is shown below.

(Synthesis of Intermediate (1 )

50 mL of toluene and 20 mL of ethanol, 0.73 g (0.63 mmol) of tetrakis triphenylphosphine palladium and 2 M aqueous potassium carbonate solution (20 mL) were added to 5.14 g (20.0 mmol) of 9- bromoanthracene and 2.56 g mL, and the mixture was refluxed for 12 hours. The reaction solution was cooled to room temperature, 150 mL of toluene was added, and the organic layer was washed with 200 mL of water and 100 mL of saturated brine, dried over anhydrous magnesium sulfate, and filtered. After the filtrate was concentrated under reduced pressure, 50 mL of ethyl acetate was added to the concentrated residue, and the mixture was heated to 70 DEG C and dissolved. The resulting solution was slowly cooled to room temperature and stirred for 2 hours. The resulting solid was filtered under reduced pressure and dried to obtain 4.10 g (yield: 81%) of intermediate (1) .

(Synthesis of Intermediate (2 )

4.1 g (16.1 mmol) of the compound (1) and 3.16 g (17.7 mmol) of NBS were added to 150 mL of chloroform and the mixture was refluxed for 3 hours. The reaction solution was cooled to room temperature, washed with 200 mL of water, dried over anhydrous magnesium sulfate, and filtered. The filtrate was concentrated under reduced pressure, and the residue was dissolved in dichloromethane. The residue was recrystallized from methanol, filtered and dried to obtain 4.71 g (yield: 88%) of Compound (2) .

(Synthesis of final compound)

A solution of 0.50 g (1.50 mmol) of the compound (2) and 3- (5H-pyrido [3,2- b] indol-5-yl) phenylboronic acid pinacol ester b] indol-5-yl) phenylboronic acid pinacol ester (0.61 g, 1.65 mmol) was dissolved in 5 mL of toluene and 2 mL of ethanol, 0.052 g (0.045 mmol) of tetrakistriphenylphosphine palladium and 2 mL of a 2M aqueous potassium carbonate solution And the mixture was refluxed for 12 hours. After the reaction mixture was cooled to room temperature, 50 mL of toluene was added thereto, and the organic layer was washed with water and concentrated under reduced pressure. The concentrated residue was dissolved in dichloromethane, recrystallized from n-hexane, filtered, and dried to obtain 0.35 g (yield 47%) of the compound (3-1, mks-3-8) .

LC-MS: [M + H] < ⁺ > = 497.42 (see Fig. 2).

Synthesis Example 2: Synthesis of Compound 3-2 (msk-3-20)

The synthesis route of msk-3-20 is shown below.

(Synthesis of Intermediate (3 )

To 14.24 g (55.4 mmol) of 9-bromoanthracene and 10.48 g (60.9 mmol) of naphthalene-1-boronic acid were added 150 mL of toluene and 40 mL of ethanol, 1.92 g (1.66 mmol) of tetrakis triphenylphosphine palladium and 2M potassium carbonate 80 mL of an aqueous solution was added, and the mixture was refluxed and stirred for 24 hours. The reaction solution was cooled to room temperature, 500 mL of toluene was added, and the organic layer was washed with 200 mL of water, dried over anhydrous magnesium sulfate, and filtered. After the filtrate was concentrated under reduced pressure, 140 mL of ethyl acetate and 140 mL of isopropyl alcohol were added to the concentrated residue, and the mixture was heated to 75 DEG C to dissolve. This solution was slowly cooled to room temperature and allowed to stand overnight. The resulting solid was filtered under reduced pressure and dried to obtain 9.70 g (yield: 56%) of the compound (3) .

(Synthesis of Intermediate (4 )

9.70 g (31.9 mmol) of the compound (3) and 6.25 g (35.1 mmol) of NBS were added to 300 mL of chloroform and the mixture was stirred under reflux for 3 hours. The reaction solution was cooled to room temperature, washed with 300 mL of water, dried over anhydrous magnesium sulfate, and filtered. The filtrate was concentrated under reduced pressure. The residue was dissolved in dichloromethane, recrystallized from methanol, filtered, and dried to obtain 10.66 g (yield: 87%) of compound (4) .

(Synthesis of intermediate 5 )

5.0 g (13.0 mmol) of the compound (4) was dissolved in 200 mL of anhydrous tetrahydrofuran and cooled to -78 ° C. 9.8 mL (15.7 mmol) of n-butyllithium (1.6 M normal hexane solution) was slowly added thereto, and the mixture was stirred for 30 minutes. Then, 2.66 g (18.2 mmol) of triethylborate was added and stirred overnight. 20 mL of a 2N hydrochloric acid solution was added and the mixture was stirred for 1 hour, and then the organic layer was separated. The organic layer was diluted with ethyl acetate (800 mL), washed with water, dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The concentrated residue was dissolved in dichloromethane, recrystallized from n-hexane, filtered and dried to obtain 2.08 g (yield 46%) of compound (5) .

(Synthesis of final compound)

(3-bromophenyl) -5H-pyrido [3,2-b] indole was obtained by reacting 0.50 g (1.44 mmol) of the compound (6) b] indole (0.39 g, 1.20 mmol) was dissolved in 5 mL of toluene and 2 mL of ethanol, 0.042 g (0.036 mmol) of tetrakistriphenylphosphine palladium and 2 mL of 2M potassium carbonate aqueous solution were added thereto and the mixture was refluxed with stirring for 18 hours. After the reaction mixture was cooled to room temperature, 50 mL of dichloromethane was added thereto, and the organic layer was washed with water and concentrated under reduced pressure. To the concentrated residue was added 10 mL of toluene and stirred for 1 hour to form a precipitate, which was then filtered under reduced pressure. The precipitate obtained by filtration was dissolved in dichloromethane, recrystallized with n-hexane, filtered and dried to obtain 0.24 g (yield 37%) of the compound ( 3-2, mks-3-20) .

LC-MS: [M + H] < ⁺ > = 547.45 (see Fig. 3).

Synthesis Example 3: Synthesis of Compound 3-3 (msk-3-22)

msk-3-22의 합성 경로를 이하에 나타낸다.

The synthesis route of msk-3-22 is shown below.

(Synthesis of Intermediate (6 )

To 14.24 g (55.4 mmol) of 9-bromoanthracene and 10.48 g (60.9 mmol) of naphthalene-2-boronic acid were added 150 mL of toluene and 40 mL of ethanol, 1.92 g (1.66 mmol) of tetrakis triphenylphosphine palladium and 2M potassium carbonate 80 mL of an aqueous solution was added, and the mixture was refluxed and stirred for 12 hours. The reaction mixture was cooled to room temperature and the resulting precipitate was filtered under reduced pressure and washed with toluene, water, and methanol. The filtered precipitate was dissolved in dichloromethane, recrystallized from methanol, filtered and dried to obtain 13.15 g (yield 78%) of the compound (6) .

(Synthesis of intermediate 7 )

13.15 g (43.2 mmol) of the compound (6) and 8.48 g (47.5 mmol) of NBS were added to 400 mL of chloroform and the mixture was refluxed with stirring for 6 hours. The reaction solution was cooled to room temperature, washed with 400 mL of water, dried over anhydrous magnesium sulfate, and filtered. After the filtrate was concentrated under reduced pressure, the residue was dissolved in chloroform, and the residue was recrystallized from methanol, followed by filtration and drying to obtain 15.42 g (yield 93%) of compound (7) .

(Synthesis of final compound)

A solution of 0.50 g (1.30 mmol) of the compound (7) and 3- (5H-pyrido [3,2- b] indol-5-yl) phenylboronic acid pinacol ester b] indol-5-yl) phenylboronic acid pinacol ester (0.53 g, 1.43 mmol) was dissolved in 5 mL of toluene and 2 mL of ethanol, and 0.045 g (0.039 mmol) of tetrakistriphenylphosphine palladium and 2 mL of a 2M aqueous potassium carbonate solution And the mixture was refluxed for 12 hours. The reaction mixture was cooled to room temperature and the resulting precipitate was filtered under reduced pressure and washed with toluene, water, and methanol. The filtered precipitate was dissolved in chloroform and the solution was gradually concentrated under reduced pressure until about 10 mL of chloroform remained. The resulting precipitate was filtered under reduced pressure and dried to obtain 0.37 g (yield: 52%) of the compound ( 3-3, mks-3-22 ).

LC-MS: [M + H] < ⁺ > = 547.45 (see Fig. 4).

Synthesis Example 4: Synthesis of compound 3-4 (msk-3-34)

The synthesis route of msk-3-34 is shown below.

(Synthesis of final compound)

A solution of 0.47 g (1.23 mmol) of the compound (4) and 4- (5H-pyrido [3,2- b] indol-5-yl) phenylboronic acid pinacol ester b] indol-5-yl) phenylboronic acid pinacol ester (0.50 g, 1.35 mmol) was dissolved in 5 mL of toluene and 2 mL of ethanol, and 0.043 g (0.037 mmol) of tetrakistriphenylphosphine palladium and 2 mL of a 2M aqueous potassium carbonate solution And the mixture was refluxed for 12 hours. After the reaction mixture was cooled to room temperature, 50 mL of dichloromethane was added thereto, and the organic layer was washed with water and concentrated under reduced pressure. The concentrated residue was dissolved in chloroform, recrystallized from methanol, filtered and dried to obtain 0.31 g (yield 46%) of the compound ( 3-4, mks-3-34 ).

LC-MS: [M + H] < ⁺ > = 547.45 (see Fig. 5).

Synthesis Example 5: Synthesis of Compound 3-5 (msk-3-36)

The synthesis route of msk-3-36 is shown below.

(Synthesis of final compound)

A solution of 0.47 g (1.23 mmol) of compound (7) and 4- (5H-pyrido [3,2- b] indol-5-yl) phenylboronic acid pinacol ester b] indol-5-yl) phenylboronic acid pinacol ester (0.50 g, 1.35 mmol) was dissolved in 5 mL of toluene and 2 mL of ethanol, and 0.043 g (0.037 mmol) of tetrakistriphenylphosphine palladium and 2 mL of a 2M aqueous potassium carbonate solution And the mixture was refluxed for 12 hours. After the reaction mixture was cooled to room temperature, 50 mL of dichloromethane was added thereto, and the organic layer was washed with water and concentrated under reduced pressure. The concentrated residue was dissolved in chloroform and recrystallized from methanol, followed by filtration and drying to obtain 0.32 g (yield: 48%) of the compound ( 3-5, mks-3-36 ).

LC-MS: [M + H] < ⁺ > = 547.45 (see Fig. 6).

Synthesis Example 6: Synthesis of Compound 3-6 (msk-3-38)

msk-3-38의 합성 경로를 이하에 나타낸다.

The synthesis route of msk-3-38 is shown below.

(Synthesis of final compound)

A solution of 0.41 g (1.23 mmol) of the compound (2) and 4- (5H-pyrido [3,2- b] indol-5-yl) phenylboronic acid pinacol ester b] indol-5-yl) phenylboronic acid pinacol ester (0.50 g, 1.35 mmol) was dissolved in 5 mL of toluene and 2 mL of ethanol, and 0.043 g (0.037 mmol) of tetrakistriphenylphosphine palladium and 2 mL of a 2M aqueous potassium carbonate solution And the mixture was refluxed for 12 hours. The reaction mixture was cooled to room temperature and the resulting precipitate was filtered under reduced pressure and washed with toluene, water, and methanol. The filtered precipitate was dissolved in chloroform, recrystallized from methanol, filtered and dried to obtain 0.41 g (yield 67%) of the compound ( 3-6, mks-3-38 ).

LC-MS: [M + H] < ⁺ > = 497.42 (see Fig. 7).

Synthesis Example 7: Synthesis of Compound 3-7 (msk-3-40)

The synthesis route of msk-3-40 is shown below.

(Synthesis of Intermediate (8 )

A solution of 3.86 g (15.0 mmol) of 9-bromoanthracene and 4- (4,5-diphenyl-4H-1,2,4-triazol-3-yl) phenylboronic acid pinacol ester (4- To 7.0 g (16.5 mmol) of toluene were added 37 mL of toluene, 0.52 g (0.45 mmol) of tetrakis (triphenylphosphine) palladium and 2M carbonic acid Potassium aqueous solution (15 mL) was added and the mixture was refluxed and stirred for 12 hours. The reaction mixture was cooled to room temperature and the resulting precipitate was filtered under reduced pressure and washed with toluene, water, and methanol. 210 mL of chloroform and 2.80 g (15.7 mmol) of NBS were added to the filtered precipitate, and the mixture was refluxed for 6 hours. The reaction solution was cooled to room temperature, washed with 200 mL of water, dried over anhydrous magnesium sulfate, and filtered. The filtrate was concentrated under reduced pressure, and the residue was dissolved in chloroform. The residue was recrystallized from ethanol, filtered and dried to obtain 5.75 g (yield 69%) of Compound (8) .

(Synthesis of final compound)

A mixture of 0.50 g (0.91 mmol) of the compound (8) and 4- (5H-pyrido [3,2- b] indol-5-yl) phenylboronic acid pinacol ester (4- b] indol-5-yl) phenylboronic acid pinacol ester (0.37 g, 1.00 mmol) was dissolved in 5 mL of toluene and 2 mL of ethanol, 0.031 g (0.027 mmol) of tetrakistriphenylphosphine palladium and 1 mL of a 2M aqueous potassium carbonate solution And the mixture was refluxed for 12 hours. The reaction mixture was cooled to room temperature and the resulting precipitate was filtered under reduced pressure and washed with toluene, water, and methanol. The filtered precipitate was dissolved in chloroform, recrystallized with n-hexane, filtered, and then the main product was separated by column chromatography (ethyl acetate / normal hexane 1: 1) to obtain 0.24 g of a compound ( 3-7, mks- 3-40 ) 37%).

LC-MS: [M + H] < ⁺ > = 716.57 (see Fig. 8).

Synthesis Example 8: Synthesis of Compound 3-8 (msk-3-46)

The synthesis route of msk-3-46 is shown below.

(Synthesis of intermediate 9 )

To a mixture of 5.28 g (23.9 mmol) of anthracene-9-boronic acid and 7.0 g (21.7 mmol) of 9- (4-bromophenyl) carbazole were added 50 mL of toluene and 25 mL of ethanol, 0.75 g of tetrakis triphenylphosphine palladium mmol) and 25 mL of a 2M aqueous potassium carbonate solution were added, and the mixture was refluxed with stirring for 12 hours. The reaction solution was cooled to room temperature, and 450 mL of toluene was added thereto. The organic layer was washed with 150 mL of water, dried over anhydrous magnesium sulfate, and filtered. The mixture was gradually concentrated under reduced pressure until 30 mL of toluene remained, and then stirred at room temperature for 1 hour. The resulting precipitate was filtered under reduced pressure, and the wet cake was dissolved in chloroform, and the precipitate was recrystallized from methanol, followed by filtration and drying to obtain 6.45 g (yield: 71%) of Compound (9) .

(Synthesis of intermediate 10 )

6.45 g (15.3 mmol) of the compound (9) and 2.99 g (16.8 mmol) of NBS were added to 200 mL of chloroform and the mixture was refluxed for 12 hours. The reaction solution was cooled to room temperature, washed with 200 mL of water, dried over anhydrous magnesium sulfate, and filtered. The filtrate was concentrated under reduced pressure, and the residue was dissolved in chloroform, and the residue was recrystallized from methanol, followed by filtration and drying to obtain 6.27 g (yield: 82%) of Compound (10) .

(Synthesis of final compound)

Compound (10) 0.50 g (1.00 mmol ) and 4- (9H- carbazole-9-yl) phenyl view it in acid pinacol ester (4- (9H-carbazol-9 -yl) phenylboronic acid pinacol ester) 0.44 g ( 1.10 mmol) was dissolved in toluene (5 mL) and ethanol (2 mL), and 0.035 g (0.030 mmol) of tetrakistriphenylphosphine palladium and 1.5 mL of 2M potassium carbonate aqueous solution were added thereto and stirred under reflux for 12 hours. The reaction mixture was cooled to room temperature and the resulting precipitate was filtered under reduced pressure and washed with toluene, water, and methanol. The filtered precipitate was dissolved in chloroform and recrystallized from methanol, followed by filtration and drying to obtain 0.47 g (yield: 71%) of the compound ( 3-8, mks-3-46 ).

LC-MS: [M + H] < ⁺ > = 662.55 (see Fig. 9).

Synthesis Example 9: Synthesis of Compound 3-9 (msk-3-48)

The synthesis route of msk-3-48 is shown below.

(Synthesis of final compound)

0.44 g (1.00 mmol) of compound (10) and 0.50 g (1.00 mmol) of 3- (9H-carbazol-9-yl) phenylboronic acid pinacol ester 1.10 mmol) was dissolved in toluene (5 mL) and ethanol (2 mL), and 0.035 g (0.030 mmol) of tetrakistriphenylphosphine palladium and 1.5 mL of 2M potassium carbonate aqueous solution were added thereto and stirred under reflux for 12 hours. After the reaction mixture was cooled to room temperature, 70 mL of dichloromethane was added, and the organic layer was washed with water and concentrated under reduced pressure. The concentrated residue was dissolved in dichloromethane, recrystallized from methanol, filtered and dried to obtain 0.32 g (yield: 48%) of the compound ( 3-9, mks-3-48 ).

LC-MS: [M + H] < ⁺ > = 662.55 (see Fig. 10).

Synthesis Example 10: Synthesis of Compound 3-10 (msk-4-1)

The synthesis route of msk-4-1 is shown below.

(Synthesis of final compound)

A solution of 0.50 g (1.00 mmol) of the compound (10) and 4- (5H-pyrido [3,2- b] indol- b] indol-5-yl) phenylboronic acid pinacol ester (0.41 g, 1.10 mmol) was dissolved in 5 mL of toluene and 2 mL of ethanol, 0.035 g (0.030 mmol) of tetrakistriphenylphosphine palladium and 1.5 mL of a 2M potassium carbonate aqueous solution And the mixture was refluxed for 12 hours. The reaction mixture was cooled to room temperature and the resulting precipitate was filtered under reduced pressure and washed with toluene, water, and methanol. The filtered precipitate was dissolved in 200 mL of chloroform and the solution was gradually concentrated under reduced pressure until about 20 mL of chloroform remained. The resulting precipitate was filtered under reduced pressure and dried to obtain 0.34 g (yield: 51%) of the compound ( 3-10, mks-4-1 ).

LC-MS: [M + H] < ⁺ > = 663.55 (see Fig. 11).

Synthesis Example 11: Synthesis of Compound 3-11 (msk-4-3)

The synthesis route of msk-4-3 is shown below.

A solution of 0.50 g (1.00 mmol) of the compound (10) and 3- (5H-pyrido [3,2- b] indol-5-yl) phenylboronic acid pinacol ester b] indol-5-yl) phenylboronic acid pinacol ester (0.41 g, 1.10 mmol) was dissolved in 5 mL of toluene and 2 mL of ethanol, 0.035 g (0.030 mmol) of tetrakistriphenylphosphine palladium and 1.5 mL of a 2M potassium carbonate aqueous solution And the mixture was refluxed for 12 hours. After the reaction mixture was cooled to room temperature, 50 mL of dichloromethane was added thereto, and the organic layer was washed with water and concentrated under reduced pressure. The concentrated residue was dissolved in dichloromethane, recrystallized from methanol, filtered and dried to obtain 0.44 g (yield 66%) of the compound (3-11, mks-4-3) .

LC-MS: [M + H] < ⁺ > = 663.55 (synthesis of final compound) (see Fig. 12).

Synthesis Example 12: Synthesis of Compound 3-12 (msk-4-5)

The synthesis route of msk-4-5 is shown below.

(Synthesis of final compound)

0.50 g (1.00 mmol) of the compound (10) and 4- (1-phenyl-1H-benzimidazol-2-yl) phenylboronic acid pinacol ester ) phenylboronic acid pinacol ester (0.44 g, 1.10 mmol) was dissolved in 5 mL of toluene and 2 mL of ethanol, 0.035 g (0.030 mmol) of tetrakistriphenylphosphine palladium and 1.5 mL of 2M potassium carbonate aqueous solution were added thereto and the mixture was refluxed for 12 hours . The reaction mixture was cooled to room temperature and the resulting precipitate was filtered under reduced pressure and washed with toluene, water, and methanol. The filtered precipitate was dissolved in chloroform, recrystallized from n-hexane, filtered, and dried to obtain 0.57 g (yield 83%) of the compound ( 3-12, mks-4-5 ).

LC-MS: [M + H] < ⁺ > = 689.63 (see Fig. 13).

Synthesis Example 13: Synthesis of Compound 3-13 (msk-4-7)

The synthesis route of msk-4-7 is shown below.

(Synthesis of final compound)

Compound (10) 0.50 g (1.00 mmol ) and (9-phenyl -9H- carbazole-3-yl) Boro acid ((9-phenyl-9H- carbazol-3-yl) boronic acid) 0.32 g (1.10 mmol) Was dissolved in 5 mL of toluene and 2 mL of ethanol, 0.035 g (0.030 mmol) of tetrakis (triphenylphosphine) palladium and 1.5 mL of 2M potassium carbonate aqueous solution were added, and the mixture was refluxed with stirring for 12 hours. The reaction mixture was cooled to room temperature, and 50 mL of dichloromethane was added thereto. The organic layer was washed with water, concentrated under reduced pressure until about 3 mL of toluene remained, and then stirred at room temperature for 1 hour. The resultant precipitate was filtered under reduced pressure, and the obtained product was separated by column chromatography (ethyl acetate / n-hexane 1: 3 → 1: 2) to obtain 0.30 g of a compound ( 3-13, mks-4-7 ) %).

LC-MS: [M + H] < ⁺ > = 662.55 (see Fig. 14).

Synthesis Example 14: Synthesis of Compound 3-14 (msk-4-11)

The synthesis route of msk-4-11 is shown below.

(Synthesis of final compound)

5 -yl) -5H-pyrido [3,2-b] indole (5- (4'-bromobiphenyl-4-yl) ) 5H-pyrido [3,2-b] indole) was dissolved in 5 mL of toluene and 2 mL of ethanol and 0.042 g (0.036 mmol) of tetrakistriphenylphosphine palladium and 2 mL of a 2M aqueous potassium carbonate solution And the mixture was refluxed for 12 hours. The reaction mixture was cooled to room temperature and the resulting precipitate was filtered under reduced pressure and washed with toluene, water, and methanol. The filtered precipitate was dissolved in 300 mL of chloroform and the solution was gradually concentrated under reduced pressure until about 10 mL of chloroform remained. The resulting precipitate was filtered under reduced pressure and dried to obtain 0.63 g (yield: 84%) of the compound ( 3-14, mks-4-11 ).

LC-MS: [M + H] < ⁺ > = 623.50 (see Fig. 15).

Synthesis Example 15: Synthesis of Compound 3-15 (msk-4-15)

The synthesis route of msk-4-15 is shown below.

(Synthesis of final compound)

Compound (10) 0.50 g (1.00 mmol ) and 4 '- (5H- pyrido [3,2-b] indol-5-yl) biphenyl-4-Daily acid pinacol ester (4' - (5H-pyrido 0.54 g (1.10 mmol) of [3,2-b] indol-5-yl) biphenyl-4-ylboronic acid pinacol ester was dissolved in 5 mL of toluene and 2 mL of ethanol and 0.035 g of tetrakistriphenylphosphine palladium ) And 1.5 mL of 2M potassium carbonate aqueous solution were added thereto, and the mixture was refluxed and stirred for 4 hours. The reaction mixture was cooled to room temperature and the resulting precipitate was filtered under reduced pressure and washed with toluene, water, and methanol. The filtered precipitate was dissolved in 1100 mL of chloroform and the solution was gradually concentrated under reduced pressure until about 50 mL of chloroform remained. The resulting precipitate was filtered under reduced pressure and dried to obtain 0.63 g (yield: 85%) of the compound ( 3-15, mks-4-15 ).

LC-MS: [M + H] < ⁺ > = 739.66 (see Fig. 16).

Synthesis Example 16: Synthesis of Compound 3-16 (msk-4-17)

The synthesis route of msk-4-17 is shown below.

(Synthesis of final compound)

A mixture of 0.50 g (1.30 mmol) of the compound (7) and 4'- (5H-pyrido [3,2- b] indol-5-yl) biphenyl 4-ylboronic acid pinacol ester 0.71 g (1.43 mmol) of [3,2-b] indol-5-yl) biphenyl-4-ylboronic acid pinacol ester was dissolved in 5 mL of toluene and 2 mL of ethanol and 0.045 g of tetrakistriphenylphosphine palladium ) And 2 mL of a 2M aqueous potassium carbonate solution were added, and the mixture was refluxed and stirred for 4 hours. The reaction mixture was cooled to room temperature and the resulting precipitate was filtered under reduced pressure and washed with toluene, water, and methanol. The filtered precipitate was dissolved in 300 mL of chloroform and the solution was gradually concentrated under reduced pressure until about 20 mL of chloroform remained. The resulting precipitate was filtered under reduced pressure and dried to obtain 0.56 g (yield 69%) of the compound ( 3-16, mks-4-17 ).

LC-MS: [M + H] < ⁺ > = 623.50 (see Fig.

Synthesis Example 17: Synthesis of Compound 3-17 (msk-4-19)

The synthesis route of msk-4-19 is shown below.

(Synthesis of final compound)

Compound (2) 0.40 g (1.20 mmol ) and 4 '- (5H- pyrido [3,2-b] indol-5-yl) biphenyl-4-Daily acid pinacol ester (4' - (5H-pyrido 0.64 g (1.44 mmol) of [3,2-b] indol-5-yl) biphenyl-4-ylboronic acid pinacol ester was dissolved in 5 mL of toluene and 2 mL of ethanol and 0.042 g of tetrakis triphenylphosphine palladium ) And 2 mL of a 2M aqueous potassium carbonate solution were added, and the mixture was stirred under reflux for 18 hours. The reaction mixture was cooled to room temperature and the resulting precipitate was filtered under reduced pressure and washed with toluene, water, and methanol. The filtered precipitate was dissolved in 250 mL of chloroform, and then the solution was gradually concentrated under reduced pressure until about 20 mL of chloroform remained. The resulting precipitate was filtered under reduced pressure and dried to obtain 0.45 g (yield 66%) of the compound ( 3-17, mks-4-19 ).

LC-MS: [M + H] < ⁺ > = 573.47 (see Fig. 18).

Synthesis Example 18: Synthesis of Compound 3-18 (msk-4-29)

The synthesis route of msk-4-29 is shown below.

(Synthesis of intermediate 11 )

6.27 g (12.6 mmol) of compound (10) was dissolved in 140 mL of anhydrous tetrahydrofuran and cooled to -78 째 C. 9.5 mL (15.1 mmol) of n-butyllithium (1.6 M normal hexane solution) was slowly added thereto, followed by stirring for 30 minutes. Trimethylborate (1.83 g, 17.6 mmol) was added thereto and stirred overnight. 16 mL of 2N hydrochloric acid solution was added and stirred for 2 hours, and the resulting precipitate was filtered under reduced pressure. The filtered precipitate was suspended in 30 mL of water, 60 mL of tetrahydrofuran was added, and the mixture was slurried for 30 minutes. The precipitate was filtered under reduced pressure and dried to obtain 3.20 g (yield: 55%) of the compound (11) .

(Synthesis of final compound)

0.23 g (0.83 mmol) of 2-bromo-9,9-dimethyl-9H-fluorene and 0.50 g (1.08 mmol) of the compound (11) mL and ethanol 2 mL, 0.029 g (0.025 mmol) of tetrakistriphenylphosphine palladium and 1 mL of 2M potassium carbonate aqueous solution were added, and the mixture was refluxed with stirring for 12 hours. After the reaction mixture was cooled to room temperature, 50 mL of toluene was added thereto, and the organic layer was washed with water and concentrated under reduced pressure. The concentrate residue was dissolved in dichloromethane and recrystallized from methanol. After filtration, the main product was separated by column chromatography (ethyl acetate / normal hexane 1: 3) to obtain 0.28 g of the compound ( 3-18, mks-4-29 ) 55%).

LC-MS: [M + H] < ⁺ > = 613.45 (see Fig. 19).

Synthesis Example 19: Synthesis of Compound 3-19 (msk-4-3)

The synthesis route of msk-4-3 is shown below.

(Synthesis of final compound)

0.33 g (0.83 mmol) of the compound (11) ( 0.50 g, 1.08 mmol) and 2-bromo-9,9'-spirobi [fluorene] And 0.029 g (0.025 mmol) of tetrakistriphenylphosphine palladium and 1 mL of a 2M aqueous solution of potassium carbonate were added thereto, followed by stirring under reflux for 12 hours. The reaction mixture was cooled to room temperature and the resulting precipitate was filtered under reduced pressure and washed with toluene, water, and methanol. The filtered precipitate was dissolved in dichloromethane, recrystallized from methanol, filtered, and then the main product was separated by column chromatography (ethyl acetate / normal hexane 1: 3) to obtain 0.30 g of compound ( 3-19, mks-4-31 ) 49%).

LC-MS: [M + H] < ⁺ > = 735.60 (see Fig.

Synthesis Example 20: Synthesis of Compound 3-20 (msk-4-33)

The synthesis route of msk-4-33 is shown below.

(Synthesis of final compound)

0.35 g (0.98 mmol) of compound (11) ( 0.50 g, 1.08 mmol) and 4-bromo-9,9'-spirobi [fluorene] And 0.033 g (0.029 mmol) of tetrakistriphenylphosphine palladium and 1.5 mL of a 2M aqueous potassium carbonate solution were added to the solution, followed by stirring under reflux for 6 hours. The reaction mixture was cooled to room temperature and the resulting precipitate was filtered under reduced pressure and washed with toluene, water, and methanol. The filtered precipitate was dissolved in chloroform and recrystallized from methanol. The obtained product was filtered, and the main product was separated by column chromatography (ethyl acetate / normal hexane 1: 3) to obtain 0.26 g of the compound ( 3-20, mks-4-33 ) %).

LC-MS: [M + H] < ⁺ > = 735.60 (see FIG.

Synthesis Example 21: Synthesis of Compound 3-21 (msk-4-35)

The synthesis route of msk-4-35 is shown below.

(Synthesis of final compound)

A solution of 0.50 g (1.08 mmol) of the compound (11) and 2'-bromospiro [benzo [c] fluorene-7,9'- fluorene]) was dissolved in 5 mL of toluene and 2 mL of ethanol, 0.033 g (0.029 mmol) of tetrakistriphenylphosphine palladium and 1.5 mL of 2M potassium carbonate aqueous solution were added thereto, and the mixture was refluxed with stirring for 6 hours. The reaction mixture was cooled to room temperature, toluene was added to 50 mL, and the organic layer was washed with water and then concentrated under reduced pressure which was purified by column chromatography (ethyl acetate / n-hexane 1: 3) to remove the major product of the compound (3-21, mks- 4-35 ) (0.30 g, yield 39%).

LC-MS: [M + H] < ⁺ > = 785.69 (see Fig. 22).

Synthesis Example 22: Synthesis of Compound 3-22 (msk-4-37)

The synthesis route of msk-4-37 is shown below.

(Synthesis of final compound)

A solution of 0.50 g (1.08 mmol) of the compound (11) and 5-bromospiro [benzo [c] fluorene-7,9'-fluorene] ) Was dissolved in 5 mL of toluene and 2 mL of ethanol, 0.033 g (0.029 mmol) of tetrakistriphenylphosphine palladium and 1.5 mL of 2 M potassium carbonate aqueous solution were added thereto, and the mixture was refluxed with stirring for 18 hours. The reaction mixture was cooled to room temperature and the resulting precipitate was filtered under reduced pressure and washed with toluene, water, and methanol. The filtered precipitate was separated and concentrated by column chromatography (ethyl acetate / n-hexane 1: 5 → 1: 3), and the concentrated residue was dissolved in dichloromethane, recrystallized from methanol, filtered and dried to obtain 3- 22, mks-4-37 ) (yield 35%).

LC-MS: [M + H] < ⁺ > = 785.76 (see Fig. 23).

Synthesis Example 23: Compound 3-23 ( msk-5-6 ) Synthesis of

The synthesis route of msk-5-6 is shown below.

(Synthesis of final compound)

0.50 g (1.08 mmol) of the compound (11) and 0.32 g (0.98 mmol) of 4-bromo-N, N-diphenyl aniline were dissolved in 5 mL of toluene and 2 mL of ethanol, 0.033 g of tetrakistriphenylphosphine palladium mmol) and 1.5 mL of a 2M aqueous potassium carbonate solution were added, and the mixture was refluxed with stirring for 6 hours. The reaction mixture was cooled to room temperature and the resulting precipitate was filtered under reduced pressure and washed with toluene, water, and methanol. The filtered precipitate was separated and concentrated by column chromatography (ethyl acetate / n-hexane 1: 5 → 1: 3), and the concentrated residue was dissolved in dichloromethane, recrystallized from methanol, filtered and dried to obtain 3- 23, mks-6-5 ) (yield: 55%).

LC-MS: [M + H] < ⁺ > = 664.55 (see Fig.

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.

UV / VIS and PL results of compounds No. UV (nm) PL (nm, room temperature) Compound 3-1
(mks-3-8) 260, 301, 340, 355, 375, 395
(1.0 x 10 ^-5 M in Methylene Chloride) 412.5, 431.5
(5.0 x ^10-6 M in Methylene Chloride) Compound 3-2
(mks-3-20) 261, 340, 356, 375, 396
(1.0 x 10 ^-5 M in Methylene Chloride) 410, 430.5
(5.0 x ^10-6 M in Methylene Chloride) Compound 3-3
(mks-3-22) 228, 259, 356, 376, 396
(1.0 x 10 ^-5 M in Methylene Chloride) 421, 435
(5.0 x ^10-6 M in Methylene Chloride) Compound 3-4
(mks-3-34) 262, 340, 356, 376, 396
(1.0 x 10 ^-5 M in Methylene Chloride) 418.5 431.5
(5.0 x ^10-6 M in Methylene Chloride) Compound 3-5
(mks-3-36) 260, 357, 377, 397,
(1.0 x 10 ^-5 M in Methylene Chloride) 426.5
(5.0 x ^10-6 M in Methylene Chloride) Compound 3-6
(mks-3-38) 261, 301, 356, 376, 396
(1.0 x 10 ^-5 M in Methylene Chloride) 419, 431
(5.0 x ^10-6 M in Methylene Chloride) Compound 3-7
(mks-3-40) 261, 357, 376, 397
(1.0 x 10 ^-5 M in Methylene Chloride) 429
(5.0 x ^10-6 M in Methylene Chloride) Compound 3-8
(mks-3-46) 244, 261, 293, 341, 356, 376, 396
(1.0 x 10 ^-5 M in Methylene Chloride) 428.5
(5.0 x ^10-6 M in Methylene Chloride) Compound 3-9
(mks-3-48) 244, 260, 292, 341, 356, 376, 396
(1.0 x 10 ^-5 M in Methylene Chloride) 421
(5.0 x ^10-6 M in Methylene Chloride) Compound 3-10
(mks-4-1) 261, 301, 355, 376, 396
(1.0 x 10 ^-5 M in Methylene Chloride) 426
(5.0 x ^10-6 M in Methylene Chloride) Compound 3-11
(mks-4-3) 260, 301, 340, 354, 376, 396
(1.0 x 10 ^-5 M in Methylene Chloride) 421.5
(5.0 x ^10-6 M in Methylene Chloride) Compounds 3-12
(mks-4-5) 262, 301, 357, 377, 397
(1.0 x 10 ^-5 M in Methylene Chloride) 432.5
(5.0 x ^10-6 M in Methylene Chloride) Compound 3-13
(mks-4-7) 251, 259, 290, 350, 378, 397
(1.0 x 10 ^-5 M in Methylene Chloride) 442.5
(5.0 x ^10-6 M in Methylene Chloride) Compound 3-14
(mks-4-11) 262, 301, 340, 357, 376, 397
(1.0 x 10 ^-5 M in Methylene Chloride) 420.5
(5.0 x ^10-6 M in Methylene Chloride) Compound 3-15
(mks-4-15) 261, 302, 339, 355, 377, 397
(1.0 x 10 ^-5 M in Methylene Chloride) 428.5
(5.0 x ^10-6 M in Methylene Chloride) Compound 3-16
(mks-4-17) 261, 302, 341, 357, 377, 397
(1.0 x 10 ^-5 M in Methylene Chloride) 428
(5.0 x ^10-6 M in Methylene Chloride) Compound 3-17
(mks-4-19) 262, 301, 340, 356, 376, 396
(1.0 x 10 ^-5 M in Methylene Chloride) 422
(5.0 x ^10-6 M in Methylene Chloride) Compound 3-18
(mks-4-29) 262, 303, 358, 377, 397
(1.0 x 10 ^-5 M in Methylene Chloride) 431
(5.0 x ^10-6 M in Methylene Chloride) Compound 3-19
(mks-4-31) 260, 300, 358, 378, 398
(1.0 x 10 ^-5 M in Methylene Chloride) 431
(5.0 x ^10-6 M in Methylene Chloride) Compound 3-20
(mks-4-33) 259, 298, 357, 377, 397
(1.0 x 10 ^-5 M in Methylene Chloride) 422
(5.0 x ^10-6 M in Methylene Chloride) Compound 3-21
(mks-4-35) 241, 254, 301, 343, 357, 378, 398
(1.0 x 10 ^-5 M in Methylene Chloride) 432.5
(5.0 x ^10-6 M in Methylene Chloride) Compound 3-22
(mks-4-37) 256, 301, 324, 355, 378, 398
(1.0 x 10 ^-5 M in Methylene Chloride) 434
(5.0 x ^10-6 M in Methylene Chloride) Compound 3-23
(mks-6-5) 260, 302, 356, 378, 397
(1.0 x 10 ^-5 M in Methylene Chloride) 503
(5.0 x ^10-6 M in Methylene Chloride)

Example of fabricating device

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.

ITO as a transparent electrode was used as an anode layer, 2-TNATA used as a hole injecting layer, NPB used as a hole transporting layer, αβ-ADN used as a host of a light emitting layer, Bphen used an electron transporting layer, Liq used an electron injecting layer and Al used a negative electrode.

COMPARATIVE EXAMPLE 1 ITO / 2-TNATA / NPB / αβ-AND, mks-2-45 / 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 2 × 10 ^-2 Torr and 125 W for 2 minutes. 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 material used in the experiment was mks-2-45 represented by the following formula, and the concentration of the dopant was fixed at 10%. After fabricating the device, it was encapsulated in a glove box filled with nitrogen gas to prevent air and moisture contact of the device. After forming barrier ribs with 3M's adhesive tape, Barium Oxide, which is a moisture absorber capable of removing water and so on, was put and a glass plate was attached.

Table 2 shows the electroluminescent characteristics of the organic light-emitting device prepared above.

Example 1: ITO / 2-TNATA / NPB / αβ-AND, 3-2 / Bphen / Liq / Al

In the same manner as in Comparative Example 1 except that mks-2-45 was used in the above Comparative Example 1, the 3-2 (mks-3-20) compound prepared in the above Synthesis Example 2 was used as the light emitting layer. Respectively.

Table 2 shows the electroluminescent characteristics of the organic light-emitting device prepared above.

Example 2: ITO / 2-TNATA / NPB / αβ-AND, 3-4 / Bphen / Liq / Al

In the same manner as in Comparative Example 1, except that the compound of 3-4 (mks-3-34) prepared in Synthesis Example 2 was used instead of mks-2-45 in Comparative Example 1, Respectively.

Table 2 shows the electroluminescent characteristics of the organic light-emitting device prepared above.

Example 3: ITO / 2-TNATA / NPB / αβ-AND, 3-6 / Bphen / Liq / Al

In the same manner as in Comparative Example 1, except that mks-2-45 was used in the above Comparative Example 1, and the 3-6 (mks-3-38) compound prepared in the above Synthesis Example 2 was used as the light emitting layer, Respectively.

Table 2 shows the electroluminescent characteristics of the organic light-emitting device prepared above.

Color coordinates
(x, y) efficiency
(cd / A) Comparative Example 1 (0.17, 0.20) 3.11 Example 1 (0.16, 0.19) 3.54 Example 2 (0.15, 0.18) 3.79 Example 3 (0.16, 0.18) 3.51

result

As can be seen from the above Table 2 and FIG. 25, when the device is used as a light emitting layer, the device emits light in the blue wavelength region, and it can be confirmed that the color purity and the light emitting efficiency characteristics are improved when the comparative example and Examples 1 to 3 are compared.

Claims (12)

An anthracene derivative represented by the following formula (1).
[Chemical Formula 1]

[In the formula 1,
R ₁ is hydrogen, C ₁ -C ₃₀ alkyl, C ₃ -C ₃₀ cycloalkyl, C ₆ -C ₃₀ aryl, C ₆ -C ₃₀ aralkyl (aralkyl), C ₁ -C ₃₀ heteroalkyl, C ₂ -C ₃₀ heterocycloalkyl, C ₅ -C ₃₀ heteroaryl and C ₅ -C ₃₀ heteroaralkyl is selected from alkyl, substituted with more than one R ₁ in one of the rings is the same or different, and adjacent R ₁ are each C ₃ -C ₂₀ alkylene or C ₃ -C ₂₀ alkenylene to form a fused ring,
p is an integer of 1 to 4,
L ₁ is independently a chemical bond, C ₆ -C ₃₀ aryl or C ₆ -C ₃₀ heteroaryl,
L ₂ is phenylene,
Ar

,

,

Or -N (Z ₁ ) (Z ₂ ), wherein R ₂ and R ₃ are each independently the same as defined for R ₁ , q and r are each independently selected from integers from 1 to 4, and Z ₁ and Z ₂ are both phenyl.] delete delete delete The method according to claim 1,
The compound represented by Formula 1 is an anthracene derivative selected from the structures listed in Formula 3 below.
(3)

An organic electroluminescent device comprising the anthracene derivative according to any one of claims 1 to 5. The method according to claim 6,
Wherein the anthracene derivative is used as a hole injecting material or a hole transporting material. The method according to claim 6,
Wherein the anthracene derivative is used as a host material of 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 layer comprises the anthracene derivative of any one of claims 1 to 5. 10. The method of claim 9,
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. 10. The method of claim 9,
Wherein the anthracene 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. 10. The method of claim 9,
Wherein the anthracene derivative is contained in at least one layer selected from the group consisting of 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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