KR20170090139A

KR20170090139A - Triazine derivatives linked with fused cyclic phenanthridinyl group, and organic electroluminescent device including the same

Info

Publication number: KR20170090139A
Application number: KR1020160010634A
Authority: KR
Inventors: 김규리; 석문기; 고병수; 김혜정; 구자룡; 김규식; 한갑종; 오유진
Original assignee: 주식회사 랩토
Priority date: 2016-01-28
Filing date: 2016-01-28
Publication date: 2017-08-07

Abstract

Provided are a triazine derivative bound with a fused cyclic phenanthridine group by a linker, represented by chemical formula 1, and an organic electroluminescent device comprising the same. In the chemical formula 1, Ar_1 and Ar_2 are each independently phenyl, naphthyl, or biphenyl; X_1 is O or S; p is an integer of 1 to 2; and R is hydrogen or any one selected from the group consisting of phenyl, biphenyl, pyridyl, quinolyl, isoquinolyl, naphthyl, and phenanthryl, which can be substituted or fused with one to two functional groups selected from halogen, cyano, methoxy, methyl, ethyl, t-butyl, pyridyl, and phenyl.

Description

(Triazine derivatives linked with fused cyclic phenanthridinyl group, and organic electroluminescent device including the same) containing a condensed cyclic phenanthridine group via a linker,

The present invention relates to a triazine derivative in which a condensed-ring-linked phenanthridine group is bonded through a specific linker and an organic electroluminescent device including the triazine derivative and a condenser ring And a triazin derivative to which a phenanthridine group is bonded.

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.

Nevertheless, the demand for a flat display device having a small space occupancy has been increased due to the recent enlargement of display devices. However, LCD has a disadvantage of requiring a separate light source because its viewing angle is limited and is not a self-luminous type. For this reason, OLEDs (Organic Light Emitting Diodes) have attracted attention as displays using self-emission phenomenon.

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

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

The basic structure of an OLED display generally includes an anode, a hole injection layer (HIL), a hole transporting layer (HTL), an emission layer (EML), an electron transporting layer (ETL) ), And a cathode (cathode), and the electron-emitting organic multi-layer film has a sandwich structure formed between both electrodes.

In general, organic light emission phenomenon refers to a phenomenon of converting electric energy into light energy by using an organic material. An organic light emitting device using an organic light emitting phenomenon usually has a structure including an anode and a cathode and an organic layer between them. Here, in order to increase the efficiency and stability of the organic light emitting device, the organic material layer may have a multi-layer structure composed of different materials and may include a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer. When a voltage is applied between two electrodes in the structure of the organic light emitting device, holes are injected into the anode, electrons are injected into the organic layer, electrons are injected into the organic layer, excitons are formed when injected holes and electrons meet, When it falls to a state, it becomes a light. Such an organic light emitting device is known to have characteristics such as self-emission, high luminance, high efficiency, low driving voltage, wide viewing angle, high contrast, and high speed response.

A material used as an organic material layer in an organic light emitting device can be classified into a light emitting material and a charge transporting material such as a hole injecting material, a hole transporting material, an electron transporting material, and an electron injecting material depending on functions. The luminescent material has blue, green, and red luminescent materials and yellow and orange luminescent materials necessary for realizing a better natural color depending on the luminescent color. Further, in order to increase the color purity and increase the luminous efficiency through energy transfer, a host / dopant system can be used as a light emitting material. The principle is that when a small amount of dopant having a smaller energy band gap and a higher luminous efficiency than a host mainly constituting the light emitting layer is mixed with the light emitting layer in a small amount, the excitons generated in the host are transported to the dopant to emit light with high efficiency. At this time, since the wavelength of the host moves to the wavelength of the dopant, light of the desired wavelength can be obtained according to the type of the dopant used.

In order to sufficiently exhibit the excellent characteristics of the organic light emitting device, a material constituting the organic material layer in the device such as a hole injecting material, a hole transporting material, a light emitting material, an electron transporting material, and an electron injecting material is supported by a stable and efficient material However, the development of a stable and efficient organic material layer material for an organic light emitting device has not yet been sufficiently achieved, and therefore, the development of new materials has been continuously required.

Korean Patent Publication No. 10-2012-0046778 Korean Patent Publication No. 10-2014-0091049 Korean Patent Publication No. 10-2013-0135178 Korean Patent Publication No. 10-2015-0077382 Korean Patent Registration No. 10-1558495

As a result of intensive studies, the inventors of the present invention have found that a triazine derivative compound in which a condensed-ring-linked phenanthridine group is bonded through a specific linker, and when it is used as a material for forming an organic material layer of an organic electronic device, Rise in driving voltage, increase in stability, and the like can be exhibited.

The present invention aims to provide a triazine derivative compound having a condensed-ring-linked phenanthridine group bonded through the above linker, and an organic electronic device using the same.

According to one aspect of the present invention, there is provided a triazine derivative represented by the following formula (1) wherein a condensed cyclic phenanthridine group is bonded through a specific linker.

[Chemical Formula 1]

[In the formula 1, Ar ₁ And Ar < ₂ _> are each independently phenyl, naphthyl or biphenyl,

X < ₁ > is O or S,

p is an integer of 1 to 2,

R is hydrogen, or halogen, cyano, methoxy, methyl, ethyl, t- butyl, even if the functional group is selected from pyridyl and phenyl are one to two substituted or fused good phenyl, biphenyl, pyridyl, Quinolyl, isoquinolyl, naphthyl and phenanthryl.]

According to another aspect of the present invention, there is provided an organic electroluminescent device comprising a triazine derivative in which a condensed cyclic phenanthridine group is bonded through the specific linker.

According to another aspect of the present invention, there is provided a plasma display panel comprising a first electrode, a second electrode, and at least one organic film disposed between the electrodes, wherein the organic film is formed by coupling a condensed cyclized phenanthridine group through the specific linker An organic electroluminescent device comprising a triazine derivative represented by the general formula

According to another aspect of the present invention, a triazine derivative having a condensed-ring-linked phenanthridine group bound thereto through the specific linker functions as an electron blocking layer, an electron transport layer, an electron injection layer, A light-emitting layer, a light-emitting layer, and a light-emitting layer.

The triazine derivative compound to which the condensed cyclic phenanthridine group is bonded through the specific linker according to the present invention may be prepared by introducing a specific aryl group or heteroaryl group into the phenyl group of the linker to form an organic electronic device Can be used as an organic material layer material. The organic electronic device including the organic light emitting device using the compound represented by the formula (1) according to the present invention as the material of the organic material layer exhibits excellent characteristics in terms of efficiency, driving voltage and lifetime.

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

As used herein, 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 stated.

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

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

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

Specific examples of the heteroaryl include furyl, thiophenyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, 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.

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

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

Hereinafter, the present invention will be described in detail.

A triazine derivative having a condensed cyclic phenanthridine group bonded through a specific linker according to an embodiment of the present invention may be represented by the following formula (1).

[Chemical Formula 1]

X < ₁ > is O or S,

p is an integer of 1 to 2,

The compound represented by the formula (1) is selected from the group consisting of compounds represented by the following formulas (1a) to (1l).

[Chemical Formula 1a] [Chemical Formula 1b] [Chemical Formula 1c]

[Formula 1d] [Formula 1e]

[Formula 1f] [Formula 1g]

[Chemical Formula 1h] [Chemical Formula 1i]

[Chemical formula 1j] [Chemical formula 1k]

In the above general formulas (1a) to (11)

R ₁ or R ₂ is hydrogen or phenyl which may be substituted or fused with 1 to 2 functional groups independently selected from the group consisting of hydrogen, halogen, cyano, methoxy, methyl, ethyl, t- butyl, , Biphenyl, pyridyl, quinolyl, isoquinolyl, naphthyl and phenanthryl,

X ₁ and Ar ₁ to Ar ₂ are as defined above.

Each of R ₁ to R ₂ has a structure selected from the group consisting of the following formula (2).

(2)

Specific examples of the compound represented by the formula (1) of the present invention include those represented by the following formula (4). However, the compound represented by the formula (1) of the present invention is not limited to the compounds of the following formula (4).

[Chemical Formula 4]

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

Further, according to the present invention, There is provided an organic electroluminescent device comprising a derivative thereof.

The triazine derivative of Formula 1 is useful as an electron transport layer material and can be used as a material for other layers of organic electroluminescent devices.

In addition, 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 triazine derivative represented by the general formula (1) wherein the condensed cyclic phenanthridine group is bonded through a linker.

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

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

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

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]

Intermediate Synthetic example 1: Synthesis of intermediate (4)

(Synthesis of Intermediate (1)

In one 2L flask, 2-bromo-aniline (2-bromoaniline) 30.0 g ( 0.174 mol), dibenzofuran-4-Daily acid (dibenzofuran-4-ylboronic acid) 38.8 g (0.183 mol), Pd (PPh 3) ₄ 6.0 g (5.232 mmol) and 600 mL of toluene, and 300 mL of ethanol and 300 mL of K ₂ CO ₃ (0.349 mol) / H ₂ O were added while stirring, followed by stirring under reflux for 5 hours. After the reaction was completed, the reaction mixture was cooled to room temperature. Water was added thereto and the mixture was extracted with DCM. The organic phase was dried over anhydrous MgSO ₄ and purified by silica gel column chromatography to obtain 29.4 g (yield: 65%) of a white solid compound (Intermediate (1) &Lt; / RTI >

(Synthesis of Intermediate (2)

78.3 g (177 mmol) of Intermediate (1) and 28.6 g (182 mmol) of benzamidine hydrochloride were added to 890 mL of ethanol and stirred. 14.2 g (354 mmol) of sodium hydroxide are added in small portions at room temperature. Thereafter, the reaction solution was refluxed with stirring. After cooling the reaction mixture to room temperature, the precipitate was filtered, washed with water and methanol and purified to obtain 58.7 g (yield: 61.1%) of a solid compound (intermediate (2)).

(Synthesis of Intermediate (3)

42.1 g (0.095 mol) of intermediate (2), 26.6 mL (0.286 mol) of phosphorous oxychloride and 250 mL of nitrobenzene were refluxed for 6 hours at 150 to 160 ° C under nitrogen. After the reaction was completed, the reaction mixture was cooled to room temperature, treated with 500 mL of water, filtered, and washed with 300 mL of water. The obtained solid was adjusted to pH 8 or more with 6N NaOH, extracted with DCM, ₄ , and purified by silica gel column chromatography to obtain 31.1 g (yield: 77%) of a white solid compound (intermediate (3)).

(Synthesis of Intermediate (4)

In 1 500 mL flask, intermediate (3) (10.0 g, 0.024 mol), bis (pinacolato) diboron (bis (pinacolato) diboron) 6.6 g (0.026 mol), Pd (dppf) Cl 2 0.8 g (0.943 mmol), 4.6 g (0.047 mol) of KOAc and 700 mL of dioxane were added thereto, and the mixture was refluxed at 80 to 100 DEG C under nitrogen for 24 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and purified by silica gel column chromatography to obtain 6.9 g (yield: 62%) of white solid compound (intermediate (4)).

Intermediate Synthetic example 2: Synthesis of intermediate (7)

(Synthesis of intermediate 5)

In a 2-necked 2.0 L flask, add 40.6 g (156.5 mmol) of intermediate (1) and dissolve in 420 mL of DCM under a nitrogen atmosphere. 40.0 mL (313.2 mmol) of TEA is added, and the temperature is lowered to 0 占 폚. 34.4 g (156.6 mmol) of 3-bromobenzoylchloride are diluted in 100 mL of DCM and slowly added dropwise to the above reaction at 0 < 0 > C. After stirring at 0 ° C for 2 hours, a saturated aqueous solution of Na ₂ CO ₃ is added, and the solid compound is filtered, washed with water and methanol, and then dried. The obtained reaction mixture was purified to obtain 69.0 g (yield: 99.6%) of a solid compound (intermediate (5)).

(Synthesis of Intermediate (6)

The mixture was dissolved in 69.0 g (156.0 mmol) of intermediate (5) and 312 mL of nitrobenzene in a 1.0 L flask, and 72.5 mL (780.0 mmol) of POCl ₃ was added thereto, followed by stirring at 150 ° C for 12 hours. After cooling to 0 ° C, methanol and water are added slowly and stirred. The solid compound was filtered, washed with water, methanol and ethyl acetate, and then purified to obtain 53.8 g (yield: 81.3%) of a solid compound (Intermediate (6)).

(Synthesis of intermediate 7)

A 1 L 2 L flask was charged with 30.0 g (70.7 mmol) of Intermediate 6, 26.9 g (106.1 mmol) bis (pinacolato diboron), Pd (dppf) Cl ₂ .CH ₂ Cl ₂ 1.15 g (1.41 mmol) of KOAc and 20.8 g (212.1 mmol) of KOAc were mixed with 700 mL of dioxane, and the mixture was refluxed and stirred at 90 占 폚 for 12 hours. After the temperature was lowered to room temperature, the solvent was distilled off under reduced pressure. The resulting compound was purified by silica gel column chromatography to obtain 26.1 g (yield: 78.3%) of a white solid compound (intermediate (7)).

Intermediate Synthetic example 3: Synthesis of intermediate (9)

(Synthesis of Intermediate (8)

42.4 g (0.130 mol) of 3-bromo-5-iodobenzoic acid and 0.85 mL (0.011 mol) of N, N-dimethylformamide were dissolved in 300 mL of DCM, Gt; 5 C. < / RTI > 18.5 g (0.156 mol) of SOCl ₂ was added thereto, and the mixture was refluxed for 12 hours to obtain a solution of 3-bromo-5-iodobenzoyl chloride.

28.0 g (0.108 mol) of intermediate (1) and 45 mL (0.324 mol) of triethylamine were dissolved in 200 mL of DCM and cooled to 0 to 5 째 C. 3-bromo-5-iodobenzoyl chloride solution was added dropwise thereto for 30 minutes, and the mixture was stirred at room temperature for 2 hours. The reaction mixture was diluted with 3000 mL of DCM, washed with 1N hydrochloric acid and water, and then the organic layer was separated, dried over anhydrous magnesium sulfate, and filtered. The organic layer was concentrated under reduced pressure to leave about 500 mL, and the resulting precipitate was filtered and dried to obtain 38.8 g (yield: 63%) of a solid compound (Intermediate (8)).

(Synthesis of intermediate 9)

38.7 g (68.1 mmol) of Intermediate 8 and 11.0 g (71.5 mmol) of POCl ₃ were dissolved in 150 mL of nitrobenzene, and the mixture was heated to 150 to 160 캜 and stirred for 6 hours. The reaction mixture was cooled to room temperature, 450 mL of DCM and 300 mL of water were added, and the mixture was basified with 6N sodium hydroxide solution and stirred for 2 hours. The precipitate was filtered off under reduced pressure, washed with water and methanol, and dried to obtain 30.3 g (yield: 81%) of a solid compound (Intermediate (9)).

Intermediate Synthetic example 4: Synthesis of intermediate (13)

(Synthesis of intermediate 10)

15.0 g (0.087 mol) of 2-bromoaniline and 29.8 g (0.131 mol) of dibenzo [b, d] thiophen-4-ylboronic acid ), and _{Pd (PPh 3) 4 5.04 g} (4.36 mmol), 2.5MK 3 PO 4 220 mL (0.218 mol) and put into a 430 mL dioxane to reflux. After the reaction is completed, the solvent is distilled off under reduced pressure, and then the residue is extracted with EA to remove moisture. 18.8 g (yield: 78.3%) of a solid compound (intermediate (10)) was obtained by column chromatography (EA: HEX).

(Synthesis of intermediate 11)

19.0 mL (0.136 mol) of triethylamine was added slowly while stirring 18.8 g (0.068 mol) of Intermediate 10 and 220 mL of DCM, and the mixture was stirred for 30 minutes. Add 15.0 g (0.068 mol) of 4-bromobenzoyl chloride and 50 mL of DCM slowly dropwise at 0 ° C using a dropping funnel. 0 < [deg.] &Gt; C for one day. After the reaction is complete, slowly add an aqueous solution of sodium carbonate at room temperature. Extract with DCM and wash well with aqueous ammonium chloride solution and water. After removing the water and the solvent, the product was solidified with EA and MeOH to obtain 25.9 g (yield: 82.7%) of a white solid compound (Intermediate (11)).

(Synthesis of intermediate 12)

25.9 g (0.056 mol) of intermediate (11), 26.2 mL (0.282 mol) of phosphoryl chloride and 110 mL of nitrobenzene are added and refluxed at 150 ° C for 8 hours. After the reaction is completed, the reaction mixture is cooled to room temperature, and methanol is slowly added to solidify the reaction mixture. Wash the filtered solid sufficiently with water, then wash it again with methanol. The mixture was solidified with EA and then filtered to obtain 22.8 g (yield: 91.7%) of a white solid compound (Intermediate (12)).

(Synthesis of intermediate 13)

A 1.0 L flask was charged with 15.0 g (34.1 mmol) of Intermediate 12, 10.4 g (40.9 mmol) bis (pinacolato diboron), Pd (dppf) Cl ₂ .CH ₂ Cl ₂ 1.39 g (1.70 mmol) of KOAc, 6.48 g (68.1 mmol) of KOAc and 680 mL of dioxane, and reflux for two days. After the reaction is completed, the reaction mixture is cooled to room temperature, and the solvent is removed by distillation under reduced pressure. Purification is carried out by silica gel column chromatography (EA: HEX). Solidified with MeOH, and then filtered to obtain 10.3 g (yield: 61.9%) of a white solid compound (Intermediate (13)).

Intermediate Synthetic example 5: Synthesis of intermediate (16)

(Synthesis of intermediate 14)

42.8 g (155.4 mmol) of Intermediate (10) is added to a 2-necked 2.0 L flask and dissolved in 518 mL of DCM under a nitrogen atmosphere. 43.7 mL (310.8 mmol) of TEA is added, and the temperature is lowered to 0 占 폚. 34.1 g (155.4 mmol) of 3-bromobenzoylchloride is diluted in 100 mL of DCM and slowly added to the above reaction at 0 < 0 > C. After stirring at 0 ° C for 2 hours, Na ₂ CO ₃ aqueous solution was added and the solid compound was filtered, washed with water and methanol, and then dried. The obtained reaction mixture was purified to obtain 66.9 g (yield: 93.9%) of a solid compound (intermediate (14)).

(Synthesis of intermediate 15)

A 1.0 L flask was charged with 66.9 g (145.9 mmol) of intermediate (14) and 291 mL of nitrobenzene. 68.0 mL (729.8 mmol) of POCl ₃ was added thereto, followed by stirring at 150 ° C for 12 hours. After cooling to 0 ° C, methanol and water are added slowly and stirred. The solid compound was filtered, washed with water, methanol and ethyl acetate, and then purified to obtain 63.2 g (yield: 98.3%) of a solid compound (Intermediate (15)).

(Synthesis of intermediate 16)

A 500 mL flask was charged with intermediate (15) 15.4 g (35.0 mmol), bis (pinacolato) diboron 13.3 g (52.5 mmol), Pd (dppf) Cl ₂ .CH ₂ Cl ₂ 573 mg (0.699 mmol), potassium acetate (KOAc) 10.3 g (104.9 mmol) and dioxane (350 mL) were added together and the mixture was refluxed at 90 ° C for 12 hours. After the temperature was lowered to room temperature, the solvent was distilled off under reduced pressure. The obtained compound was purified by silica gel column chromatography to obtain 17.0 g (yield: 99.7%) of a white solid compound (Intermediate (16)).

Intermediate Synthetic example 6: Synthesis of intermediate (18)

(Synthesis of Intermediate (17)

45.0 g (163.4 mmol) of Intermediate (10) is added to a 2-necked 2.0 L flask and dissolved in 650 mL of DCM under a nitrogen atmosphere. 46 mL (326.8 mmol) of TEA is added, and the temperature is lowered to 0 占 폚. 62.0 g (179.8 mmol) of 3-bromo-5-iodobenzoylchloride are diluted in 150 mL of DCM and slowly added to the above reaction at 0 ° C. After stirring at 0 ° C for 2 hours, Na ₂ CO ₃ aqueous solution was added and the solid compound was filtered, washed with water and methanol, and then dried. The obtained reaction mixture was purified to obtain 67.5 g (yield: 70.7%) of a solid compound (Intermediate (17)).

(Synthesis of intermediate 18)

A 1 liter 1.0 L flask was charged with 67.5 g (115.5 mmol) of Intermediate (17) and 231 mL of nitrobenzene. 53.7 mL (577.6 mmol) of POCl ₃ was added thereto, followed by stirring at 150 ° C for 12 hours. After cooling to 0 ° C, methanol and water are added slowly and stirred. The solid compound was filtered, washed with water, methanol and ethyl acetate, and then purified to obtain 59.5 g (yield: 90.9%) of a solid compound (Intermediate (18)).

Intermediate Synthetic example 7: Synthesis of intermediate (20)

(Synthesis of intermediate 19)

Intermediate (9) 2.0 g (3.6 mmol ), phenylboronic acid (phenylboronic acid) 0.44 g (3.6 mmol), Pd (PPh 3) 4 0.12 g (0.11 mmol), 2M K 2 CO 3 4 mL (8 mmol), 20 mL of toluene and 8 mL of ethanol 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 by heating in 900 mL of chloroform. The insoluble precipitate was removed by filtration, and the filtrate was concentrated under reduced pressure until about 100 mL of chloroform remained. The resulting precipitate was filtered under reduced pressure and dried to obtain the solid compound (Intermediate 19) 1.64 g (Yield: 63%).

(Synthesis of intermediate 20)

2.1 g (8.3 mmol) of bis (pinacolato diboron), 0.25 g (0.30 mmol) of Pd (dppf) Cl _{2 and} 1.5 g (15.0 mmol) and 1, 4-dioxane (100 mL) was stirred at 95 to 100 DEG C for 12 hours. The reaction mixture was concentrated under reduced pressure, then dissolved with 200 mL of DCM and washed with water. The organic layer was separated, dried over anhydrous magnesium sulfate, filtered and concentrated under reduced pressure. The residue was purified by column chromatography to obtain 2.4 g (yield: 54%) of a solid compound (Intermediate (20)).

Intermediate Synthesis Example 8: Synthesis of Intermediate (22)

(Synthesis of intermediate 21)

Intermediate (9) 2.0 g (3.6 mmol ), pyridine-3 Daily acid (pyridin-3-ylboronic acid) 0.44 g (3.6 mmol), Pd (PPh 3) 4 0.12 g (0.11 mmol), 2M K 2 CO 3 4 mL (8 mmol), 20 mL of toluene and 8 mL of ethanol was refluxed with stirring 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 by heating in 1500 mL of chloroform. The insoluble precipitate was removed by filtration, and the filtrate was concentrated under reduced pressure until about 100 mL of chloroform remained. The resulting precipitate was filtered under reduced pressure and dried to obtain the solid compound (21) 1.33 g (Yield: 51%).

(Synthesis of intermediate 22)

2.1 g (8.3 mmol) of bis (pinacolato diboron), 0.25 g (0.30 mmol) of Pd (dppf) Cl _{2 and} 1.5 g (15.0 mmol) and 1, 4-dioxane (100 mL) was stirred at 95 to 100 DEG C for 12 hours. The reaction mixture was concentrated under reduced pressure, then dissolved with 200 mL of DCM and washed with water. The organic layer was separated, dried over anhydrous magnesium sulfate, filtered, concentrated under reduced pressure, and then purified by column chromatography to obtain 2.4 g (yield: 54%) of a solid compound (Intermediate (22)).

Intermediate Synthetic example 9: Synthesis of intermediate (24)

(Synthesis of intermediate 23)

Intermediate (9) 5.0 g (9.1 mmol ), naphthalene-2-Daily acid (naphthalen-2-ylboronic acid) 1.72 g (10.0 mmol), Pd (PPh 3) 4 0.32 g (0.27 mmol), 2M K 2 CO 3 10 mL (20 mmol), 75 mL of toluene and 30 mL of ethanol was refluxed with stirring 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 by heating and the insoluble precipitate was removed by filtration. The filtrate was concentrated under reduced pressure to obtain 4.1 g (yield: 83%) of a solid compound (Intermediate (23)).

(Synthesis of intermediate 24)

2.1 g (8.3 mmol) of bis (pinacolato) diboron, 0.25 g (0.30 mmol) of Pd (dppf) Cl _{2 and} 1.5 g (15.0 mmol) and 1, 4-dioxane (100 mL) was stirred at 95 to 100 DEG C for 12 hours. The reaction mixture was concentrated under reduced pressure, then dissolved with 200 mL of DCM and washed with water. The organic layer was separated, dried over anhydrous magnesium sulfate, filtered, concentrated under reduced pressure, and then purified by column chromatography to obtain a solid compound (Intermediate 24) (2.4 g, yield: 54%).

Intermediate Synthetic example 10: Synthesis of intermediate (26)

(Synthesis of intermediate 25)

In a 250 mL flask, intermediate (18) 5.0 g (8.83 mmol ) and o- tolyl rilbo Nick Acid (o-tolylboronic acid) 1.32 g (9.71 mmol) was dissolved in 30 mL of toluene and ethanol to 15 mL Pd (PPh ₃₎ ₄ 510 mg (441 μmol) and 13.2 mL (26.5 mmol) of 2 M potassium carbonate aqueous solution were added thereto, followed by stirring at 80 ° C. for 12 hours. After the reaction is completed, the reaction mixture is cooled to room temperature, and the solid is filtered, washed with MeOH, and then dried. The obtained reaction mixture was purified to obtain 3.5 g (yield: 74.7%) of a solid compound (Intermediate (25)).

(Synthesis of intermediate 26)

Intermediate to the flask (25) 3.5 g (6.6 mmol ), bis (pinacolato) diboron (bis (pinacolato) diboron) 2.51 g (9.9 mmol), Pd (dppf) Cl 2 · CH 2 Cl 2 108 mg (132 , 1.94 g (19.8 mmol) of potassium acetate (KOAc) and 33 mL of dioxane were added thereto, and the mixture was refluxed and stirred at 90 占 폚 for 12 hours. After the temperature was lowered to room temperature, the solvent was distilled off under reduced pressure. The resulting compound was purified by silica gel column chromatography to obtain 3.5 g (yield: 91.8%) of a white solid compound (intermediate (26)).

Intermediate Synthetic example 11: Synthesis of intermediate (28)

(Synthesis of intermediate 27)

A 250 mL flask was charged intermediate (18) 5.0 g (8.83 mmol ) and t- butyl-phenylboronic acid (4- (tert-butyl) phenyl ) boronic acid) 1.89 g (10.6 mmol) was dissolved in 30 mL toluene and 15 mL ethanol 510 mg (441 μmol) of Pd (PPh ₃ ) ₄ and 13.2 mL (26.5 mmol) of 2M potassium carbonate aqueous solution were added thereto, followed by stirring at 80 ° C. for 12 hours. After the reaction is completed, the reaction mixture is cooled to room temperature, and the solid is filtered, washed with MeOH, and then dried. The obtained reaction mixture was purified to obtain 4.8 g (yield: 94.9%) of a solid compound (Intermediate (27)).

(Synthesis of intermediate 28)

Intermediate (27) was charged to the flask 4.8 g (8.38 mmol), bis (pinacolato) diboron (bis (pinacolato) diboron) 3.2 g (12.6 mmol), Pd (dppf) Cl 2 · CH 2 Cl 2 140 mg (168 2.5 g (25.2 mmol) of potassium acetate (KOAc) and 85 mL of dioxane were added thereto, and the mixture was refluxed and stirred at 90 占 폚 for 12 hours. After the temperature was lowered to room temperature, the solvent was distilled off under reduced pressure. The obtained compound was purified by silica gel column chromatography to obtain 3.7 g (yield: 71.2%) of a white solid compound (Intermediate (28)).

Intermediate Synthetic example 12: Synthesis of intermediate (30)

(Synthesis of intermediate 29)

6.0 g (10.6 mmol) of intermediate (18) and 1.56 g (12.7 mmol) of pyridin-3-ylboronic acid were dissolved in 40 mL of toluene and 20 mL of ethanol, and Pd (PPh ₃ ) ₄ 612 mg (530 μmol) and 16 mL (31.8 mmol) of 2 M potassium carbonate aqueous solution were added thereto, followed by stirring at 80 ° C. for 12 hours. After the reaction is completed, the reaction mixture is cooled to room temperature, and the solid is filtered, washed with MeOH, and then dried. The resulting reaction mixture was purified to obtain 5.23 g (yield: 95.4%) of a solid compound (intermediate (29)).

(Synthesis of intermediate 30)

Intermediate (29) in a flask 5.23 g (10.1 mmol), bis (pinacolato) diboron (bis (pinacolato) diboron) 3.85 g (15.2 mmol), Pd (dppf) Cl 2 · CH 2 Cl 2 165 mg (202 , 2.98 g (30.3 mmol) of potassium acetate (KOAc) and 100 mL of dioxane were added thereto, and the mixture was refluxed and stirred at 90 占 폚 for 12 hours. After the temperature was lowered to room temperature, the solvent was distilled off under reduced pressure. The obtained compound was purified by silica gel column chromatography to obtain 4.0 g (yield: 70.1%) of a white solid compound (Intermediate (30)).

Intermediate Synthetic example 13: Synthesis of intermediate (32)

(Synthesis of intermediate 31)

6.0 g (10.6 mmol) of intermediate (18) and 1.69 g (13.8 mmol) of pyridin-4-ylboronic acid were dissolved in 40 mL of toluene and 20 mL of ethanol, and Pd (PPh ₃ ) ₄ 612 mg (530 μmol) and 16 mL (31.8 mmol) of 2 M potassium carbonate aqueous solution were added thereto, followed by stirring at 80 ° C. for 12 hours. After the reaction is completed, the reaction mixture is cooled to room temperature, and the solid is filtered, washed with MeOH, and then dried. The obtained reaction mixture was purified to obtain 4.2 g (yield: 76.6%) of a solid compound (Intermediate (31)).

(Synthesis of intermediate 32)

Intermediate (31) was charged to the flask 4.2 g (8.1 mmol), bis (pinacolato) diboron (bis (pinacolato) diboron) 3.09 g (12.2 mmol), Pd (dppf) Cl 2 · CH 2 Cl 2 132 mg (162 , 2.39 g (24.4 mmol) of potassium acetate (KOAc) and 80 mL of dioxane were added thereto, followed by reflux stirring at 90 占 폚 for 12 hours. After the temperature was lowered to room temperature, the solvent was distilled off under reduced pressure. The resulting compound was purified by silica gel column chromatography to obtain 4.0 g (yield: 87.3%) of a white solid compound (Intermediate (32)).

Intermediate Synthetic example 14: Synthesis of intermediate (34)

(Synthesis of intermediate 33)

To a 250 mL flask was dissolved 6.0 g (10.6 mmol) of Intermediate 18 and 2.95 g (12.7 mmol) of 2,4-dimethylphenyl boronic acid in 40 mL of toluene and 20 mL of ethanol, and Pd _{PPh 3) 4 612 mg (530} μmol) and 2M aqueous potassium carbonate solution into such a 16 mL (31.8 mmol) was stirred at 80 ℃ for 12 hours. After the reaction is completed, the reaction mixture is cooled to room temperature, and the solid is filtered, washed with MeOH, and then dried. The obtained reaction mixture was purified to obtain 3.0 g (yield: 53.2%) of a solid compound (Intermediate (33)).

(Synthesis of intermediate 34)

To a 250 mL one-necked flask was added 3.0 g (5.6 mmol) of intermediate (33), 2.2 g (8.5 mmol) bis (pinacolato diboron), Pd (dppf) Cl ₂ .CH ₂ Cl ₂ 92 mg (113 μmol), potassium acetate (KOAc) (1.66 g, 16.9 mmol) and dioxane (56 mL) were mixed together and the mixture was refluxed and stirred at 90 ° C. for 12 hours. After the temperature was lowered to room temperature, the solvent was distilled off under reduced pressure. The resulting compound was purified by silica gel column chromatography to obtain 3.0 g (yield: 89.9) of a white solid compound (intermediate (34)).

Intermediate Synthetic example 15: Synthesis of intermediate (36)

(Synthesis of intermediate 35)

6.0 g (10.6 mmol) of intermediate (18) and 2.96 g (12.7 mmol) of 2,6-dimethylpyridyl-3-boronic acid were added to a 250 mL flask in 40 mL of toluene and 20 mL dissolved in _{Pd (PPh 3) 4 612 mg} (530 μmol) and 2M aqueous potassium carbonate solution into such a 16 mL (31.8 mmol) was stirred at 80 ℃ for 12 hours. After the reaction is completed, the reaction mixture is cooled to room temperature, and the solid is filtered, washed with MeOH, and then dried. The obtained reaction mixture was purified to obtain 4.0 g (yield: 70.1%) of a solid compound (Intermediate (35)).

(Synthesis of intermediate 36)

The flask intermediate (35) 4.0 g (7.4 mmol ), bis (pinacolato) diboron (bis (pinacolato) diboron) 2.8 g (11.1 mmol), Pd (dppf) Cl 2 · CH 2 Cl 2 121 mg (148 , 2.19 g (22.3 mmol) of potassium acetate (KOAc) and 74 mL of dioxane were added thereto, and the mixture was refluxed and stirred at 90 DEG C for 12 hours. After the temperature was lowered to room temperature, the solvent was distilled off under reduced pressure. The obtained compound was purified by silica gel column chromatography to obtain 4.0 g (yield: 90.9%) of a white solid compound (intermediate (36)).

Intermediate Synthetic example 16: Synthesis of intermediate (38)

(Synthesis of intermediate 37)

Intermediate (18) 15.0 g (26.5 mmol ), phenylboronic acid (phenylboronic acid) 3.23 g (26.5 mmol), Pd (PPh 3) 4 0.92 g (0.80 mmol), 2M K 2 CO 3 27 mL (54 mmol), 130 mL of toluene and 54 mL of ethanol 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 dissolved in 100 mL of chloroform by heating, and insoluble precipitate was removed by filtration. The filtrate was concentrated under reduced pressure to obtain 9.44 g (yield: 69%) of a solid compound (intermediate (37)).

(Synthesis of intermediate 38)

1.3 g (5.1 mmol) of bis (pinacolato) diboron, 0.15 g (0.18 mmol) of Pd (dppf) Cl ₂ , 0.9 g (9.2 mmol) and 1,4-dioxane (40 mL) was stirred at 100 ° C for 12 hours. The reaction mixture was concentrated under reduced pressure and then dissolved with 100 mL of DCM and washed with water. The organic layer was separated, dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. Ethanol (80 mL) was added to the concentrated residue, and the mixture was stirred overnight. The precipitate was filtered off under reduced pressure and dried to obtain 1.93 g (yield: 75%) of a solid compound (Intermediate (38)).

Intermediate Synthetic example 17: Synthesis of intermediate (40)

(Synthesis of intermediate 39)

Intermediate (18) 6.0 g (10.6 mmol ), naphthalene-2-Daily acid (naphthalen-2-ylboronic acid) 2.0 g (11.7 mmol), Pd (PPh 3) 4 0.37 g (0.32 mmol), 2M K 2 CO 3 A mixture of 11 mL (22 mmol), 60 mL of toluene, 90 mL of THF and 49 mL of water 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 900 mL of chloroform by heating, and the insoluble precipitate was removed by filtration. The filtrate was concentrated under reduced pressure to obtain 5.33 g (yield: 89%) of a solid compound (Intermediate 39).

(Synthesis of intermediate 40)

2.6 g (10.3 mmol) of bis (pinacolato) diboron, 0.31 g (0.38 mmol) of Pd (dppf) Cl ₂ , 1.9 g (19.0 mmol) and 1,4-dioxane (100 mL) was stirred at 95 to 100 DEG C for 12 hours. The reaction mixture was concentrated under reduced pressure and then dissolved with 100 mL of DCM and washed with water. The organic layer was separated, dried over anhydrous magnesium sulfate, filtered, concentrated under reduced pressure, and then purified by column chromatography to obtain 4.4 g (yield: 77%) of a solid compound (Intermediate (40)).

Intermediate Synthesis Example 18: Synthesis of Intermediate (41)

(Synthesis of intermediate 41)

52.0 g (150.6 mmol) of 3-bromo-5-iodobenzoyl chloride is added to a 2.0 L round flask and dissolved in 382 mL of chloroform under a nitrogen atmosphere. Add 31.1 mL (301.1 mmol) of benzonitrile, reduce the temperature to 0 ° C, and add 19.1 mL (150.6 mmol) of antimony pentachloride (SbCl ₅ ). The temperature is slowly raised and refluxed for 12 hours. The temperature was lowered to room temperature and then filtered to obtain a yellow solid compound.

Add 2.3 L of 28% ammonia water to a 3.0 L flask, cool to 0 ° C, and slowly add the yellow solid compound obtained above. The temperature is slowly raised to room temperature and then stirred for 5 hours. The white solid compound is filtered off, washed with water and methanol, and dried. Add a solid compound in chloroform, boil it and dissolve it. The solvent was concentrated under reduced pressure and then rinsed with methanol to obtain 42.8 g (yield: 54.4%) of a white solid compound (Intermediate (41)).

Intermediate Synthetic example 19: Synthesis of Intermediate (43)

(Synthesis of intermediate 42)

Intermediate (41) 35.0 g (68.1 mmol ) and phenylboronic acid (phenylboronic acid) 10.0 g (81.7 mmol) was dissolved in toluene, 500 mL ethanol and _{200 mL Pd (PPh 3) 4} 1.57 g (1.36 mmol) and 1M potassium carbonate 204.2 mL (204.2 mmol) of the aqueous solution was added thereto, followed by stirring at 80 DEG C for 12 hours. After separating by adding 1 L of dichloromethane and 500 mL of water, the organic layer was washed with water and concentrated under reduced pressure. The obtained reaction mixture was purified to obtain 23.0 g (yield: 72.6%) of a solid compound (Intermediate (42)).

(Synthesis of intermediate 43)

A 250 mL flask was charged with intermediate (42) 3.0 g (6.45 mmol), bis (pinacolato) diboron, 2.46 g (9.67 mmol), Pd (dppf) Cl ₂ .CH ₂ Cl ₂ 250 mg (0.129 mmol), potassium acetate (KOAc) (1.90 g, 19.3 mmol) and dioxane (153 mL) were added and the mixture was refluxed and stirred at 90 ° C for 12 hours. After the temperature was lowered to room temperature, the solvent was distilled off under reduced pressure. The obtained compound was purified by silica gel column chromatography to obtain 2.61 g (yield: 79.0%) of a white solid compound (Intermediate (43)).

Intermediate Synthetic example 20: Synthesis of intermediate (45)

(Synthesis of intermediate 44)

Intermediate (41) 35.0 g (68.1 mmol ) and phenyl 3-pyridineboronic acid (pyridin-3-ylboronic acid) 10.0 g Pd (PPh 3) (81.7 mmol) was dissolved in 500 mL of toluene and ethanol to 200 mL ₄ 1.57 g ( 1.36 mmol) and 1M potassium carbonate aqueous solution (204.2 mL, 204.2 mmol) were added thereto, followed by stirring at 80 ° C for 12 hours. After separating by adding 1 L of dichloromethane and 500 mL of water, the organic layer was washed with water and concentrated under reduced pressure. The obtained reaction mixture was purified to obtain 23.0 g (yield: 72.6%) of a solid compound (intermediate (44)).

(Synthesis of intermediate 45)

In a 250 mL flask, add intermediate (44) 3.0 g (6.45 mmol), bis (pinacolato) diboron, 2.46 g (9.67 mmol), Pd (dppf) Cl ₂ .CH ₂ Cl ₂ 250 mg (0.129 mmol), potassium acetate (KOAc) (1.90 g, 19.3 mmol) and dioxane (153 mL) were added and the mixture was refluxed and stirred at 90 ° C for 12 hours. After the temperature was lowered to room temperature, the solvent was distilled off under reduced pressure. The obtained compound was purified by silica gel column chromatography to obtain 2.61 g (yield: 79.0%) of a white solid compound (Intermediate (45)).

Intermediate Synthetic example 21: Synthesis of intermediate (47)

(Synthesis of intermediate 46)

Intermediate (41) 10.0 g (19.5 mmol ) and 2-naphthalene boronic acid (naphthalen-2-ylboronic acid) 3.35 g (19.5 mmol) was dissolved in 150 mL of toluene and ethanol to _{50 mL Pd (PPh 3) 4} 1.12 g (972 and 29.2 mL (58.4 mmol) of 2M potassium carbonate aqueous solution were added thereto, followed by stirring at 80 DEG C for 12 hours. After separating by adding 300 mL of DCM and 100 mL of water, the organic layer was washed with water and concentrated under reduced pressure. The obtained reaction mixture was purified to obtain 9.8 g (yield: 97.9%) of a solid compound (Intermediate (46)).

(Synthesis of intermediate 47)

A 250 mL flask was charged with intermediate (46) 10.0 g (19.4 mmol), bis (pinacolato) diboron 7.40 g (29.2 mmol), Pd (dppf) Cl ₂ .CH ₂ Cl ₂ 317 mg (0.389 mmol) of potassium acetate (KOAc), 5.72 g (58.3 mmol) of dioxane and 195 mL of dioxane were added thereto, followed by reflux stirring at 90 ° C for 12 hours. After the temperature was lowered to room temperature, the solvent was distilled off under reduced pressure. The obtained compound was purified by silica gel column chromatography to obtain 10.0 g (yield: 91.6%) of a white solid compound (Intermediate (47))

Intermediate Synthetic example 22: Synthesis of intermediate (48)

(Synthesis of intermediate 48)

A 1-necked 1000-mL round-bottomed flask was charged with 2- (3-bromophenyl) -4,6-diphenyl-1,3 , 7.2 g (0.028 mol) of bis (pinacolato diboron), 10 g (0.026 mol) of 5-triazine, Pd (dppf) Cl ₂ 5.1 g (0.052 mol) of potassium acetate (KOAc) and 700 mL of dioxane were added thereto, and the mixture was refluxed at 80 to 100 ° C under nitrogen for 24 hours. After the reaction was completed, the reaction mixture was cooled to room temperature and purified by silica gel column chromatography to obtain 8.0 g (yield: 71%) of a white solid compound (Intermediate (48)).

Intermediate Synthetic example 23: Synthesis of Intermediate (52)

(Synthesis of intermediate 51)

A 250 mL flask was charged intermediate (9) 4.86 g (8.83 mmol ) and t- butyl-phenylboronic acid (4- (tert-butyl) phenyl ) boronic acid) 1.89 g (10.6 mmol) was dissolved in 30 mL toluene and 15 mL ethanol 510 mg (441 μmol) of Pd (PPh ₃ ) ₄ and 13.2 mL (26.5 mmol) of 2M potassium carbonate aqueous solution were added thereto, followed by stirring at 80 ° C. for 12 hours. After the reaction is completed, the reaction mixture is cooled to room temperature, and the solid is filtered, washed with MeOH, and then dried. The obtained reaction mixture was purified to obtain 4.8 g (yield: 97.6%) of a solid compound (Intermediate (51)).

(Synthesis of intermediate 52)

Intermediate (51) in a flask 4.66 g (8.38 mmol), bis (pinacolato) diboron (bis (pinacolato) diboron) 3.2 g (12.6 mmol), Pd (dppf) Cl 2 · CH 2 Cl 2 140 mg (168 2.5 g (25.2 mmol) of potassium acetate (KOAc) and 85 mL of dioxane were added thereto, and the mixture was refluxed and stirred at 90 占 폚 for 12 hours. After the temperature was lowered to room temperature, the solvent was distilled off under reduced pressure. The obtained compound was purified by silica gel column chromatography to obtain 3.7 g (yield: 73.5%) of a white solid compound (Intermediate (52)).

Intermediate Synthetic example 24: Synthesis of Intermediate (54)

(Synthesis of intermediate 53)

5.93 g (10.6 mmol) of intermediate (9) and 2.96 g (12.7 mmol) of 2,6-dimethylpyridyl-3-boronic acid were dissolved in a 250 mL flask with 40 mL of toluene and 20 mL of ethanol dissolved in _{Pd (PPh 3) 4 612 mg} (530 μmol) and 2M aqueous potassium carbonate solution into such a 16 mL (31.8 mmol) was stirred at 80 ℃ for 12 hours. After the reaction is completed, the reaction mixture is cooled to room temperature, and the solid is filtered, washed with MeOH, and then dried. The obtained reaction mixture was purified to obtain 4.0 g (yield: 71.2%) of a solid compound (Intermediate (53)).

(Synthesis of intermediate 54)

The flask intermediate (53) 3.9 g (7.4 mmol ), bis (pinacolato) diboron (bis (pinacolato) diboron) 2.8 g (11.1 mmol), Pd (dppf) Cl 2 · CH 2 Cl 2 121 mg (148 , 2.19 g (22.3 mmol) of potassium acetate (KOAc) and 74 mL of dioxane were added thereto, and the mixture was refluxed and stirred at 90 DEG C for 12 hours. After the temperature was lowered to room temperature, the solvent was distilled off under reduced pressure. The resulting compound was purified by silica gel column chromatography to obtain 4.0 g (yield: 93.7%) of a white solid compound (Intermediate (54)).

Intermediate Synthetic example 25: Synthesis of intermediate (56)

(Synthesis of intermediate 55)

Intermediate (18) 15.0 g (26.5 mmol ), 4- cyano-phenyl boronic acid (4-cyanophenylboronic acid) 3.9 g (26.5 mmol), Pd (PPh 3) 4 0.92 g (0.80 mmol), 2M K 2 CO 3 27 mL (54 mmol), 130 mL of toluene and 54 mL of ethanol 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 dissolved in 100 mL of chloroform by heating, and insoluble precipitate was removed by filtration. The filtrate was concentrated under reduced pressure to obtain 9.44 g (yield: 65.8%) of a solid compound (Intermediate (55)).

(Synthesis of intermediate 56)

1.3 g (5.1 mmol) of bis (pinacolato) diboron, 0.15 g (0.18 mmol) of Pd (dppf) Cl _{2 and} 0.9 g (9.2 mmol) and 1,4-dioxane (40 mL) was stirred at 100 ° C for 12 hours. The reaction mixture was concentrated under reduced pressure and then dissolved with 100 mL of DCM and washed with water. The organic layer was separated, dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. Ethanol (80 mL) was added to the concentrated residue, and the mixture was stirred overnight. The precipitate was filtered off under reduced pressure and dried to obtain 1.93 g (yield: 71.3%) of a solid compound (Intermediate (56)).

Intermediate Synthetic example 26: Synthesis of Intermediate (58)

(Synthesis of intermediate 57)

A 250 mL flask was charged intermediate (18) 5.0 g (8.83 mmol ) and p - Toll rilbo Nick Acid (p -tolylboronic acid) 1.32 g ( 9.71 mmol) was dissolved in 30 mL of toluene and ethanol to 15 mL Pd (PPh ₃₎ ₄ 510 mg (441 μmol) and 13.2 mL (26.5 mmol) of 2 M potassium carbonate aqueous solution were added thereto, followed by stirring at 80 ° C. for 12 hours. After the reaction is completed, the reaction mixture is cooled to room temperature, and the solid is filtered, washed with MeOH, and then dried. The obtained reaction mixture was purified to obtain 3.5 g (yield: 74.7%) of a solid compound (intermediate (57)).

(Synthesis of intermediate 58)

To the flask was added 2.5 g (9.9 mmol) of Intermediate 57 (3.5 g, 6.6 mmol), bis (pinacolato diboron), 108 mg of Pd (dppf) Cl ₂ .CH ₂ Cl ₂ , 1.94 g (19.8 mmol) of potassium acetate (KOAc) and 33 mL of dioxane were added thereto, and the mixture was refluxed and stirred at 90 占 폚 for 12 hours. After the temperature was lowered to room temperature, the solvent was distilled off under reduced pressure. The obtained compound was purified by silica gel column chromatography to obtain 3.5 g (yield: 91.8%) of a white solid compound (intermediate (58)).

Intermediate Synthetic example 27: Synthesis of intermediate (60)

(Synthesis of intermediate 59)

Intermediate (18) 5.0 g (8.83 mmol ) and m to 250 mL flask to toll rilbo Nick Acid (m -tolylboronic acid) 1.32 g ( 9.71 mmol) of Pd (PPh ₃₎ was dissolved in 30 mL toluene and 15 mL ethanol ₄ 510 mg (441 μmol) and 13.2 mL (26.5 mmol) of 2 M potassium carbonate aqueous solution were added thereto, followed by stirring at 80 ° C. for 12 hours. After the reaction is completed, the reaction mixture is cooled to room temperature, and the solid is filtered, washed with MeOH, and then dried. The obtained reaction mixture was purified to obtain 3.5 g (yield: 74.7%) of a solid compound (intermediate (59)).

(Synthesis of intermediate 60)

To the flask was added 2.5 g (9.9 mmol) of Intermediate 59 (3.5 g, 6.6 mmol), bis (pinacolato diboron), 108 mg of Pd (dppf) Cl ₂ .CH ₂ Cl ₂ , 1.94 g (19.8 mmol) of potassium acetate (KOAc) and 33 mL of dioxane were added thereto, and the mixture was refluxed and stirred at 90 占 폚 for 12 hours. After the temperature was lowered to room temperature, the solvent was distilled off under reduced pressure. The resulting compound was purified by silica gel column chromatography to obtain 3.5 g (yield: 91.8%) of a white solid compound (intermediate (60)).

Intermediate Synthetic example 28: Synthesis of intermediate (62)

(Synthesis of intermediate 61)

Intermediate (18) 6.0 g (10.6 mmol ), naphthalene-1-Daily acid (naphthalen-1-ylboronic acid) 2.0 g (11.7 mmol), Pd (PPh 3) 4 0.37 g (0.32 mmol), 2M K 2 CO 3 A mixture of 11 mL (22 mmol), 60 mL of toluene, 90 mL of THF and 49 mL of water 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 900 mL of chloroform by heating, and the insoluble precipitate was removed by filtration. The filtrate was concentrated under reduced pressure to obtain 5.33 g (yield: 89%) of a solid compound (Intermediate (61)).

(Synthesis of intermediate 62)

2.6 g (10.3 mmol) of bis (pinacolato) diboron, 0.31 g (0.38 mmol) of Pd (dppf) Cl ₂ , 1.9 g (19.0 mmol) and 1,4-dioxane (100 mL) was stirred at 95 to 100 DEG C for 12 hours. The reaction mixture was concentrated under reduced pressure and then dissolved with 100 mL of DCM and washed with water. The organic layer was separated, dried over anhydrous magnesium sulfate, filtered, concentrated under reduced pressure, and then purified by column chromatography to obtain 4.4 g (yield: 77%) of a solid compound (intermediate (62)).

Intermediate Synthetic example 29: Synthesis of intermediate (64)

(Synthesis of intermediate 63)

Intermediate (18) 15.0 g (26.5 mmol ), 3- biphenyl boronic acid (3-biphenylboronic acid) 5.24g ( 26.5 mmol), Pd (PPh 3) 4 0.92 g (0.80 mmol), 2M K 2 CO 3 27 mL (54 mmol), 130 mL of toluene and 54 mL of ethanol 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 dissolved in 100 mL of chloroform by heating, and insoluble precipitate was removed by filtration. The filtrate was concentrated under reduced pressure to obtain 9.44 g (yield: 60.1%) of a solid compound (Intermediate (63)).

(Synthesis of intermediate 64)

1.3 g (5.1 mmol) of bis (pinacolato diboron), 0.15 g (0.18 mmol) of Pd (dppf) Cl ₂ , 0.9 g of potassium acetate (9.2 mmol) and 1,4-dioxane (40 mL) was stirred at 100 ° C for 12 hours. The reaction mixture was concentrated under reduced pressure and then dissolved with 100 mL of DCM and washed with water. The organic layer was separated, dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. Ethanol (80 mL) was added to the concentrated residue, and the mixture was stirred overnight. The precipitate was filtered off under reduced pressure and dried to obtain 1.93 g (yield: 65.6%) of a solid compound (Intermediate (64)).

Various triazine derivative compounds were synthesized as follows using the synthesized intermediate compound.

Example 1: Synthesis of compound 4-1 (WS15-30-089)

2.2 g (8.218 mmol) of 2-chloro-4,6-diphenyl-1,3,5-triazine was added to a 500 mL round- ), intermediate (4) 3.9 g (8.218 mmol ), Pd (PPh 3) 4 0.3 g (0.247 mmol), while stirring, such as 150 mL of toluene was stirred for 7 hours under ethanol _{100 mL, K 2 CO 3 1.7} g (0.012 mol) / H 2 O was added to 100 mL, and heated to reflux. After the reaction was completed, the reaction mixture was cooled to room temperature, water was added thereto, and the mixture was extracted with DCM. The organic phase was dried over anhydrous MgSO ₄ , concentrated and purified by silica gel column chromatography to obtain 1.9 g of a white solid compound 4-1 (WS15-30-089) (Yield: 40%).

Example 2: Synthesis of Compound 4-2 (WS15-30-188)

A 500 mL flask was charged with 2-chloro-4,6-di (naphthalen-2-yl) -1 , 3,5-triazine) 2.6 g ( 7.068 mmol), intermediate (4) 3.3 g (7.068 mmol ), Pd (PPh 3) 4 0.2 g (0.212 mmol), while stirring, such as 150 mL of toluene was stirred for 6 hours in ethanol _{100 mL, K 2 CO 3 1.5} g (0.011 mol) / H 2 O was added to 100 mL, and heated to reflux. After the reaction was completed, the reaction mixture was cooled to room temperature, water was added thereto, and the mixture was extracted with DCM. The organic phase was dried over anhydrous MgSO ₄ , concentrated and purified by silica gel column chromatography to obtain 2.6 g of a white solid compound 4-2 (WS15-30-188) (Yield: 55%).

Example 3: Synthesis of compound 4-4 (WS15-30-093)

In 1 500 mL flask, intermediate (3) 3.0 g (7.071 mmol ), Intermediate (48) 3.1 g, (7.071 mmol), Pd (PPh 3) 4 0.2 g (0.212 mmol), while stirring, such as toluene, 150 mL ethanol _{100 mL, K 2 CO 3 1.5} g was added to _{(0.011 mol) / H 2 O} 100 mL , and the mixture was stirred for 6 hours under reflux. After the reaction was completed, the reaction mixture was cooled to room temperature, water was added thereto, and the mixture was extracted with DCM. The organic phase was dried over anhydrous MgSO ₄ , concentrated and purified by silica gel column chromatography to obtain 3.2 g of a white solid compound 4-4 (WS15-30-093) (Yield: 70%).

Example 4: Synthesis of Compound 4-25 (WS15-30-216)

In 1 500 mL flask, intermediate (46) 3.2 g (6.221 mmol ), Intermediate (4) 2.9 g (6.22 mmol ), Pd (PPh 3) 4 0.2 g (0.187 mmol), toluene while stirring, such as 150 mL of ethanol was added to _{100 mL, K 2 CO 3 1.3} g (0.009 mol) / H 2 O 100 mL , and the mixture was stirred for 6 hours under reflux. Upon completion of the reaction, the reaction mixture was cooled to room temperature, water was added thereto, and the mixture was extracted with DCM. The organic phase was dried over anhydrous MgSO ₄ and purified by silica gel column chromatography to obtain 2.8 g of a white solid compound 4-25 (WS15-30-216) : 58%).

Example 5: Synthesis of Compound 4-29 (WS15-30-072)

To a 250 ml one-necked flask was added 3.0 g (6.36 mmol) of intermediate (7), 2-chloro-4,6-diphenyl-1,3 (PPh ₃ ) ₄ (367 mg, 318 μmol) and K ₂ CO ₃ (4.05 g, 19.1 mmol) were dissolved in 40 mL of toluene, 10 mL of ethanol and 10 mL of water. Lt; RTI ID = 0.0 > 85 C < / RTI > for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, solidified with MeOH, and filtered. The obtained compound was purified by silica gel column chromatography to obtain 3.17 g (yield: 86.4%) of a white solid compound 4-29 (WS15-30-072).

Example 6: Synthesis of compound 4-32 (WS15-30-074)

Intermediate (6) 3.0 g (7.07 mmol ) and intermediate (48) 3.08 g (7.07 mmol ) was dissolved in toluene, 40 mL ethanol and 15 mL, 15 mL water, _{Pd (PPh 3) 4 408 mg} (353 μmol) and K ₃ 4.50 g (21.2 mmol) of PO ₄ were added thereto, followed by stirring at 85 ° C for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, solidified with MeOH, and filtered. The obtained compound was purified by silica gel column chromatography to obtain 4.25 g (yield: 92.1%) of a white solid compound 4-32 (WS15-30-074).

Example 7: Synthesis of compound 4-38 (WS15-35-13)

A 1-necked 100 mL flask was charged with 1.86 g (3.4 mmol) of intermediate (20), 2-chloro-4,6-diphenyl-1,3 , 5-triazine) 0.92 g ( 3.4 mmol), Pd (PPh 3) 4 0.12 g (0.10 mmol), 2M K 2 CO 3 4 mL (8 mmol), toluene 30 mL and for a mixture of ethanol, 12 mL 12 sigan And the mixture was refluxed and stirred. 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 500 mL of chloroform. The insoluble precipitate was removed by filtration, and the filtrate was concentrated under reduced pressure until about 30 mL of chloroform remained. The resulting precipitate was filtered under reduced pressure and dried to obtain the solid compound 4-38 (WS15-35-13) 1.59 g (yield: 71.6%) was obtained.

Example 8: Synthesis of Compound 4-42 (WS15-35-14)

To a 250 ml one-necked flask was added 3.6 g (5.97 mmol) of intermediate (52) and 2-chloro-4,6-diphenyl-1,3 , 5-triazine) were dissolved in 30 mL of toluene, 15 mL of ethanol and 10 mL of water, and 345 mg (299 μmol) of Pd (PPh ₃ ) ₄ and 3.8 g of potassium tertiary phosphate (K ₃ PO ₄ ) 17.9 mmol) were added thereto, followed by stirring at 80 ° C for 12 hours. After the reaction is completed, the reaction mixture is cooled to room temperature, and the solid is filtered, washed with MeOH, and then dried. The obtained reaction mixture was purified to obtain 2.29 g (yield: 54.1%) of a solid compound 4-42 (WS15-35-14).

Example 9: Synthesis of Compound 4-45 (WS15-35-15)

To a 250 ml one-necked flask was added 3.86 g (6.7 mmol) of Intermediate (54) and 2-chloro-4,6-diphenyl-1,3 , 5-triazine) was dissolved in 30 mL of toluene, 15 mL of ethanol and 15 mL of water, and 390 mg (337 μmol) of Pd (PPh ₃ ) ₄ and 4.3 g of potassium tertiary phosphate (K ₃ PO ₄ ) 20.3 mmol) were added thereto, followed by stirring at 80 ° C for 12 hours. After the reaction is completed, the reaction mixture is cooled to room temperature, and the solid is filtered, washed with MeOH, and then dried. The obtained reaction mixture was purified to obtain 1.74 g (yield: 38.1%) of a solid compound 4-45 (WS15-35-15).

Example 10: Synthesis of compound 4-47 (WS15-30-212)

2.0 g (3.4 mmol) of intermediate (24), 2-chloro-4,6-diphenyl-1,3 , 5-triazine) 0.94 g ( 3.5 mmol), Pd (PPh 3) 4 0.12 g (0.10 mmol), 2M K 2 CO 3 3.5 mL (7 mmol), toluene 9 mL, and while the mixture of ethanol, 3.5 mL 6 sigan And the mixture was refluxed and stirred. 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 dried under reduced pressure, and then extracted with 500 mL of chloroform using a soxlet extractor, followed by filtration and drying to obtain 1.4 g (yield: 60%) of a solid compound 4-47 (WS15-30-212).

Example 11: Synthesis of compound 4-71 (WS15-30-227)

Intermediate (46) 3.27 g (6.36 mmol ) and intermediate (7) 3.00 g (6.36 mmol ) Toluene 40 mL ethanol and 15 mL, dissolved in 15 mL water, _{Pd (PPh 3) 4 367 mg} (318 μmol) and K ₃ 4.05 g (19.1 mmol) of PO ₄ were added thereto, followed by stirring at 85 ° C for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, solidified with MeOH, and filtered. The obtained compound was purified by silica gel column chromatography to obtain 3.65 g (yield: 73.6%) of a white solid compound 4-71 (WS15-30-227).

Example 12: Synthesis of compound 4-74 (WS15-30-222)

Intermediate (9) 2.0 g (3.6 mmol ), phenylboronic acid (phenylboronic acid) 0.44 g (3.6 mmol), Pd (PPh 3) 4 0.12 g (0.11 mmol), 2M K 2 CO 3 4 mL (8 mmol), 20 mL of toluene and 8 mL of ethanol was refluxed with stirring for 12 hours. 1.57 g (3.6 mmol) of Intermediate (48) and 4 mL (8 mmol) of 2M K ₂ CO ₃ were added and the mixture was further 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 by heating in 900 mL of chloroform. The insoluble precipitate was removed by filtration, and the filtrate was concentrated under reduced pressure until about 100 mL of chloroform remained. The resulting precipitate was filtered under reduced pressure and dried to obtain the solid compound 4-74 (WS15-30-222) 1.64 g (Yield: 63%).

Example 13: Synthesis of compound 4-77 (WS15-30-202)

Intermediate (9) 2.0 g (3.6 mmol ), pyridine-3 Daily acid (pyridin-3-ylboronic acid) 0.44 g (3.6 mmol), Pd (PPh 3) 4 0.12 g (0.11 mmol), 2M K 2 CO 3 4 mL (8 mmol), 20 mL of toluene and 8 mL of ethanol was refluxed with stirring for 12 hours. 1.57 g (3.6 mmol) of Intermediate (48) and 4 mL (8 mmol) of 2M K ₂ CO ₃ were added and the mixture was further 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 by heating in 1500 mL of chloroform. The insoluble precipitate was removed by filtration, and the filtrate was concentrated under reduced pressure until about 100 mL of chloroform remained. The resulting precipitate was filtered under reduced pressure and dried to obtain the solid compound 4-77 (WS15-30-202) 1.33 g (Yield: 51%).

Example 14: Synthesis of Compound 4-97 (WS15-30-090)

2.0 g (7.47 mmol) of 2-chloro-4,6-diphenyl-1,3,5-triazine was added to a 250 mL round- ), intermediate (13) 3.71 g (7.62 mmol ), Pd (PPh 3) 4 0.43 g ( mixed with 0.37 mmol), toluene, 74 mL, EtOH 37 mL and _{2M K 2 CO 3 7 mL (} 14.9 mmol) and then, Lt; / RTI > After the reaction was completed, the reaction mixture was cooled to room temperature and the solid was filtered off with toluene. The solid was boiled in chloroform and completely dissolved, dried over MgSO ₄ , filtered through celite, and then the solvent was removed. And solidified in chloroform, followed by filtration to obtain 1.56 g of a white solid compound 4-97 (WS15-30-090) (yield: 35.2%).

Example 15: Synthesis of compound 4-98 (WS15-30-201)

2-chloro-4,6-di (naphthalen-2-yl) - 1,3,5-triazine was added to a 250- 1,3,5-triazine) 1.5 g (4.11 mmol), intermediate (13) 2.10 g (4.32 mmol ), Pd (PPh 3) 4 0.24 g (0.21 mmol), toluene, 41 mL, 20 mL EtOH and 2M K ₂ Was mixed with 4 mL (8.22 mmol) of CO ₃ and then refluxed. After the reaction was completed, the reaction mixture was cooled to room temperature and the solid was filtered off with toluene. The solid was boiled in chloroform and completely dissolved, dried over MgSO ₄ , filtered through celite, and then the solvent was removed. And solidified in chloroform, followed by filtration to obtain 1.75 g of a white solid compound 4-98 (WS15-30-201) (yield: 61.4%).

Example 16: Synthesis of Compound 4-100 (WS15-30-094)

One intermediate (12) 2.0 g in 250 mL flask (4.54 mmol), intermediate (48) 2.0 g (4.59 mmol ), Pd (PPh 3) 4 0.26 g (0.227 mmol), toluene 22 mL, ethanol 11 mL and 2M Was mixed with 5 mL (9.08 mmol) of K ₂ CO ₃ and then refluxed. After the reaction was completed, the reaction mixture was cooled to room temperature and the solid was filtered off with toluene. The solid was boiled in chloroform and completely dissolved, dried over MgSO ₄ , filtered through celite, and then the solvent was removed. The mixture was solidified with chloroform and then filtered under a hot condition to obtain 2.08 g (yield: 30.6%) of Compound 4-100 (WS15-30-094) as a white solid.

Example 17: Synthesis of Compound 4-124 (WS15-30-073)

To a 250 ml one-necked flask was added 3.0 g (6.15 mmol) of intermediate (16), 2-chloro-4,6-diphenyl-1,3 , 5-triazine) was dissolved in 40 mL of toluene, 10 mL of ethanol and 10 mL of water. To the mixture was added 355 mg (307.7 μmol) of Pd (PPh ₃ ) ₄ and 2.55 g (18.5 mmol) of K ₂ CO ₃ Lt; RTI ID = 0.0 > 85 C < / RTI > for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, solidified with MeOH, and filtered. The obtained compound was purified by silica gel column chromatography to obtain 1.42 g of a white solid compound 4-124 (WS15-30-073) (yield: 38.9%).

Example 18: Synthesis of Compound 4-127 (WS15-30-075)

Intermediate (15) 3.0 g (6.81 mmol ) and intermediate (48) 2.97 g (6.81 mmol ) Toluene 40 mL ethanol and 15 mL, dissolved in 15 mL water, _{Pd (PPh 3) 4 393 mg} (340.7 μmol) and tertiary phosphate Potassium (K ₃ PO ₄ ) (4.34 g, 20.4 mmol) was added thereto, followed by stirring at 85 ° C for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, solidified with MeOH, and filtered. The obtained compound was purified by silica gel column chromatography to obtain 3.87 g (Yield: 84.9%) of a white solid compound 4-127 (WS15-30-075).

Example 19: Synthesis of Compound 4-133 (WS15-30-285)

A 1-necked 100 mL flask was charged with 1.9 g (3.4 mmol) of intermediate (38), 2-chloro-4,6-diphenyl-1,3 , 5-triazine) 0.92 g ( 3.4 mmol), Pd (PPh 3) 4 0.12 g (0.10 mmol), 2M K 2 CO 3 4 mL (8 mmol), toluene 30 mL and for a mixture of ethanol, 12 mL 12 sigan And the mixture was refluxed and stirred. 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 500 mL of chloroform. The insoluble precipitate was removed by filtration, and the filtrate was concentrated under reduced pressure until about 30 mL of chloroform remained. The resulting precipitate was filtered under reduced pressure and dried to obtain the solid compound 4-133 (WS15-30-285) 1.59 g (yield 70%) was obtained.

Example 20: Synthesis of Compound 4-134 (WS15-30-293)

A 1-necked 100 mL flask was charged with 3.5 g (6.06 mmol) of intermediate (26) and 2-chloro-4,6-diphenyl-1,3 , 5-triazine) 1.62 g ( 6.06 mmol) was dissolved in toluene, 30 mL ethanol and 15 mL, water _{10 mL Pd (PPh 3) 4} 350 mg (303 μmol) and tertiary potassium phosphate _{(K 3 PO 4) 3.86 g} ( 18.2 mmol) were added thereto, followed by stirring at 80 ° C for 12 hours. After the reaction is completed, the reaction mixture is cooled to room temperature, and the solid is filtered, washed with MeOH, and then dried. The obtained reaction mixture was purified to obtain 1.64 g (yield: 39.6%) of solid compound 4-134 (WS15-30-293).

Example 21: Synthesis of Compound 4-135 (WS15-30-323)

A 1-necked 100 mL flask was charged with 3.0 g (5.07 mmol) of intermediate (34) and 2-chloro-4,6-diphenyl-1,3 , 5-triazine (1.09 g, 4.06 mmol) were dissolved in 30 mL of toluene, 10 mL of ethanol and 10 mL of water, and 293 mg (254 μmol) of Pd (PPh ₃ ) ₄ and 3.23 g of potassium tertiary phosphate (K ₃ PO ₄ ) 15.2 mmol) were added thereto, followed by stirring at 80 ° C for 12 hours. After the reaction is completed, the reaction mixture is cooled to room temperature, and the solid is filtered, washed with MeOH, and then dried. The obtained reaction mixture was purified to obtain 1.61 g (yield: 45.6%) of solid compound 4-135 (WS15-30-323).

Example 22: Synthesis of Compound 4-136 (WS15-35-18)

2.0 g (3.4 mmol) of intermediate (56) and 2-chloro-4,6-diphenyl-1,3 , 5-triazine) 0.92 g ( 3.4 mmol), Pd (PPh 3) 4 0.12 g (0.10 mmol), 2M K 2 CO 3 4 mL (8 mmol), toluene 30 mL and for a mixture of ethanol, 12 mL 12 sigan And the mixture was refluxed and stirred. 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 500 mL of chloroform. The insoluble precipitate was removed by filtration, and the filtrate was concentrated under reduced pressure until about 30 mL of chloroform remained. The resulting precipitate was filtered under reduced pressure and dried to give the solid compound 4-136 (WS15-35-18) 1.59 g (yield 67.4%) was obtained.

Example 23: Synthesis of Compound 4-137 (WS15-30-316)

To a 250 ml one-necked flask was added 3.7 g (5.97 mmol) of intermediate (28) and 2-chloro-4,6-diphenyl-1,3 , 5-triazine) were dissolved in 30 mL of toluene, 15 mL of ethanol and 10 mL of water, and 345 mg (299 μmol) of Pd (PPh ₃ ) ₄ and 3.8 g of potassium tertiary phosphate (K ₃ PO ₄ ) 17.9 mmol) were added thereto, followed by stirring at 80 ° C for 12 hours. After the reaction is completed, the reaction mixture is cooled to room temperature, and the solid is filtered, washed with MeOH, and then dried. The obtained reaction mixture was purified to obtain 2.29 g (yield: 52.9%) of solid compound 4-137 (WS15-30-316).

Example 24: Synthesis of Compound 4-138 (WS15-30-315)

To a 250 ml one-necked flask was added 4.0 g (7.09 mmol) of intermediate (30) and 2-chloro-4,6-diphenyl-1,3 , 5-triazine) was dissolved in 30 mL of toluene, 15 mL of ethanol and 10 mL of water. To the solution was added 409 mg (354 μmol) of Pd (PPh ₃ ) ₄ and 4.51 g of potassium tertiary phosphate (K ₃ PO ₄ ) 21.3 mmol) were added thereto, followed by stirring at 80 占 폚 for 12 hours. After the reaction is completed, the reaction mixture is cooled to room temperature, and the solid is filtered, washed with MeOH, and then dried. The resulting reaction mixture was purified to obtain 2.58 g (yield: 54.4%) of a solid compound 4-138 (WS15-30-315).

Example 25: Synthesis of Compound 4-139 (WS15-30-319)

To a 250 ml one-necked flask was added 4.0 g (7.09 mmol) of intermediate (32) and 2-chloro-4,6-diphenyl-1,3 , 5-triazine (1.33 g, 4.96 mmol) were dissolved in 30 mL of toluene, 15 mL of ethanol and 10 mL of water. Pyridine (PPh ₃ ) ₄ 409 mg (354 μg and potassium tertiary phosphate (K ₃ PO ₄ ) 4.51 g After the reaction was completed, the reaction mixture was cooled to room temperature, the solid was filtered, washed with MeOH, and then dried. The obtained reaction mixture was purified to obtain solid compound 4-139 ( WS15-30-319) (yield: 32.8%).

Example 26: Synthesis of Compound 4-140 (WS15-30-320)

To a 250 ml one-necked flask was added 4.0 g (6.7 mmol) of intermediate (36) and 2-chloro-4,6-diphenyl-1,3 , 5-triazine) was dissolved in 30 mL of toluene, 15 mL of ethanol and 15 mL of water, and 390 mg (337 μmol) of Pd (PPh ₃ ) ₄ and 4.3 g of potassium tertiary phosphate (K ₃ PO ₄ ) 20.3 mmol) were added thereto, followed by stirring at 80 ° C for 12 hours. After the reaction is completed, the reaction mixture is cooled to room temperature, and the solid is filtered, washed with MeOH, and then dried. The obtained reaction mixture was purified to obtain 1.74 g (yield: 36.9%) of solid compound 4-140 (WS15-30-320).

Example 27: Synthesis of Compound 4-141 (WS15-35-19)

2.0 g (3.2 mmol) of Intermediate (62), 2-chloro-4,6-diphenyl-1,3 , 5-triazine) 0.86 g ( 3.2 mmol), Pd (PPh 3) 4 0.11 g (0.096 mmol), 2M K 2 CO 3 4 mL (8 mmol), toluene, 10 mL of ethanol while the mixture of 4 mL 12 sigan And the mixture was refluxed and stirred. 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 500 mL of chloroform. The insoluble precipitate was removed by filtration, and the filtrate was concentrated under reduced pressure until about 50 mL of chloroform remained. The resulting precipitate was filtered under reduced pressure and dried to give the solid compound 4-141 (WS15-35-19) 1.5 g (Yield: 65.2%) was obtained.

Example 28: Synthesis of Compound 4-142 (WS15-30-284)

2.0 g (3.2 mmol) of Intermediate (40), 2-chloro-4,6-diphenyl-1,3 , 5-triazine) 0.86 g ( 3.2 mmol), Pd (PPh 3) 4 0.11 g (0.096 mmol), 2M K 2 CO 3 4 mL (8 mmol), toluene, 10 mL of ethanol while the mixture of 4 mL 12 sigan And the mixture was refluxed and stirred. 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 500 mL of chloroform. The insoluble precipitate was removed by filtration, and the filtrate was concentrated under reduced pressure until about 50 mL of chloroform remained. The resulting precipitate was filtered under reduced pressure and dried to give the solid compound 4-142 (WS15-30-284) 1.32 g (Yield: 57%) was obtained.

Example 29: Synthesis of Compound 4-147 (WS15-35-20)

A 1-necked 100 mL flask was charged with 2.17 g (3.4 mmol) of intermediate (64), 2-chloro-4,6-diphenyl-1,3 , 5-triazine) 0.92 g ( 3.4 mmol), Pd (PPh 3) 4 0.12 g (0.10 mmol), 2M K 2 CO 3 4 mL (8 mmol), toluene 30 mL and for a mixture of ethanol, 12 mL 12 sigan And the mixture was refluxed and stirred. 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 500 mL of chloroform. The insoluble precipitate was removed by filtration, and the filtrate was concentrated under reduced pressure until about 30 mL of chloroform remained. The resulting precipitate was filtered under reduced pressure and dried to obtain the solid compound 4-147 (WS15-35-20) 1.59 g (Yield: 62.8%) was obtained.

Example 30: Synthesis of Compound 4-166 (WS15-30-226)

Intermediate (46) 3.17 g (6.15 mmol ) and intermediate (16) 3.00 g (6.15 mmol ) Toluene 40 mL ethanol and 15 mL, dissolved in 15 mL water, _{Pd (PPh 3) 4 355 mg} (307.74 μmol) and tertiary phosphate Insert as potassium _{(K 3 PO 4) 3.92 g} (18.46 mmol) was stirred at 85 ℃ for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, solidified with MeOH, and filtered. The obtained compound was purified by silica gel column chromatography to obtain 2.20 g (yield: 44.9%) of a white solid compound 4-166 (WS15-30-226).

Example 31: Synthesis of Compound 4-169 (WS15-30-223)

Intermediate (18) 2.0 g (3.5 mmol ), phenylboronic acid (phenylboronic acid) 0.43 g (3.5 mmol), Pd (PPh 3) 4 0.12 g (0.11 mmol), 2M K 2 CO 3 4 mL (8 mmol), A mixture of 30 mL of toluene and 12 mL of ethanol was refluxed with stirring for 6 hours. 1.52 g (3.5 mmol) of Intermediate (48) and 4 mL (8 mmol) of 2M K ₂ CO ₃ were 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 700 mL of chloroform. The insoluble precipitate was removed by filtration, and the filtrate was concentrated under reduced pressure until about 100 mL of chloroform remained. The resulting precipitate was filtered under reduced pressure and dried to give the solid compound 4-169 (WS15-30-223) 1.37 g (Yield: 53%).

Example 32: Synthesis of Compound 4-172 (WS15-30-203)

Intermediate (18) 2.0 g (3.6 mmol ), pyridine-3 Daily acid (pyridin-3-ylboronic acid) 0.43 g (3.6 mmol), Pd (PPh 3) 4 0.12 g (0.11 mmol), 2M K 2 CO 3 4 mL (8 mmol), 30 mL of toluene and 12 mL of ethanol was refluxed with stirring for 12 hours. To this was added 1.52 g (3.6 mmol) of Intermediate (48) and 4 mL (8 mmol) of 2M K ₂ CO ₃ and the mixture was further 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 dried under reduced pressure, and then extracted with 500 mL of chloroform using a soxet extractor, followed by filtration and drying to obtain 1.69 g (yield: 65%) of solid compound 4-172 (WS15-30-203).

Example 33: Synthesis of Compound 4-181 (WS15-30-215)

Intermediate (37) 2.0 g (3.9 mmol ), intermediate (43) 2.2 g (4.2 mmol ), Pd (PPh 3) 4 0.14 g (0.12 mmol), 2M K 2 CO 3 4 mL (8 mmol), toluene 30 mL And ethanol (12 mL) was stirred at 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 400 mL of chloroform, and the insoluble precipitate was removed by filtration, and the filtrate was concentrated under reduced pressure until about 50 mL of chloroform remained. The resulting precipitate was filtered under reduced pressure and dried to give the solid compound 4-181 (WS15-30-215) 1.50 g (yield: 47%) was obtained.

Example 34: Synthesis of Compound 4-190 (WS15-35-16)

A 1-necked 100 mL flask was charged with 3.5 g (6.06 mmol) of intermediate (58) and 2-chloro-4,6-diphenyl-1,3 , 5-triazine) 1.62 g ( 6.06 mmol) was dissolved in toluene, 30 mL ethanol and 15 mL, water _{10 mL Pd (PPh 3) 4} 350 mg (303 μmol) and tertiary potassium phosphate _{(K 3 PO 4) 3.86 g} ( 18.2 mmol) were added thereto, followed by stirring at 80 ° C for 12 hours. After the reaction is completed, the reaction mixture is cooled to room temperature, and the solid is filtered, washed with MeOH, and then dried. The obtained reaction mixture was purified to obtain 1.64 g of a solid compound 4-190 (WS15-35-16) (yield: 39.6%).

Example 35: Synthesis of Compound 4-191 (WS15-35-17)

A 1-necked 250 mL flask was charged with 4.1 g (7.09 mmol) of Intermediate (60) and 2-chloro-4,6-diphenyl-1,3 , 5-triazine) was dissolved in 30 mL of toluene, 15 mL of ethanol and 10 mL of water. To the solution was added 409 mg (354 μmol) of Pd (PPh ₃ ) ₄ and 4.51 g of potassium tertiary phosphate (K ₃ PO ₄ ) 21.3 mmol) were added thereto, followed by stirring at 80 占 폚 for 12 hours. After the reaction is completed, the reaction mixture is cooled to room temperature, and the solid is filtered, washed with MeOH, and then dried. The obtained reaction mixture was purified to obtain 1.56 g (yield: 32.2%) of solid compound 4-191 (WS15-35-17).

&Lt; Test Example 1 >

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

UV / VIS and PL results division compound UV (nm) * 1 PL (nm, room temperature) * 2 Example 1 4-1
(WS15-30-089) 278, 378 391.5 Example 2 4-2
(WS15-30-188) 242, 331 413 Example 3 4-4
(WS15-30-093) 269, 349, 367 377, 395, 430 Example 4 4-25
(WS15-30-216) 266, 348, 367 378.5, 394.5 Example 5 4-29
(WS15-30-072) 278, 378 407 Example 6 4-32
(WS15-30-074) 360, 378 391.5, 407 Example 7 4-38
(WS15-35-13) 269, 349, 367 407 Example 8 4-42
(WS15-35-14) 254, 275, 360, 378 389, 405 Example 9 4-45
(WS15-35-15) 276, 360, 378 389, 405 Example 10 4-47
(WS15-30-212) 360, 378 405 Example 11 4-71
(WS15-30-227) 264, 348, 366 374.5, 393, 408 Example 12 4-74
(WS15-30-222) 267, 349, 367 373.5, 391.5 Example 13 4-77
(WS15-30-202) 268 413 Example 14 4-97
(WS15-30-090) 276, 360, 378 390, 405 Example 15 4-98
(WS15-30-201) 270, 299, 358, 378 413 Example 16 4-100
(WS15-30-094) 278, 360, 378 391.5, 407 Example 17 4-124
(WS15-30-073) 254, 360, 378 389 Example 18 4-127
(WS15-30-075) 269, 349, 367 374.5, 408 Example 19 4-133
(WS15-30-285) 254, 275, 360, 378 389, 405 Example 20 4-134
(WS15-30-293) 276, 360, 378 389, 405 Example 21 4-135
(WS15-30-323) 275, 360, 377 389, 404.5 Example 22 4-136
(WS15-35-18) 374.5, 393, 408 378.5, 394.5 Example 23 4-137
(WS15-30-316) 275, 359, 377 388.5, 405 Example 24 4-138
(WS15-30-315) 276, 360, 378 390, 405 Example 25 4-139
(WS15-30-319) 275, 360, 378 390, 405 Example 26 4-140
(WS15-30-320) 276, 360, 378 389.5, 404.5 Example 27 4-141
(WS15-35-19) 276, 360, 378 389, 405 Example 28 4-142
(WS15-30-284) 255, 275, 359, 378 389, 405 Example 29 4-147
(WS15-35-20) 266, 348, 367 378.5, 394.5 Example 30 4-166
(WS15-30-226) 264, 359, 377 405.5 Example 31 4-169
(WS15-30-223) 275, 360, 378 389, 405 Example 32 4-172
(WS15-30-203) 266, 348, 367 389.5, 404.5 Example 33 4-181
(WS15-30-215) 273, 360, 378 389, 405.5 Example 34 4-190
(WS15-35-16) 276, 360, 378 390, 405 Example 35 4-191
(WS15-35-17) 266, 348, 367 378.5, 394.5 * 1: 1.0 x 10 ^-5 M in Methylene Chloride
* 2: 5.0 x 10 ^-6 M in Methylene Chloride

Device fabrication Test Example

2-TNATA is a hole injecting layer, NPB is a hole transporting layer, αβ-ADN is a host of a light emitting layer, Pyene-CN is a blue fluorescent dopant, Liq is an electron injecting layer , And Al was used as a cathode. The structures of these compounds are shown below.

(60 nm) / NPB (20 nm) /?,? -ADN: Pyrene-CN 10% (30 nm) / electron transport layer (30 nm) / Liq (2 nm) / Al (100 nm) in this order.

Before depositing the organic substance is applied to the ITO electrodes 2 × 10 ^- was for 2 minutes in the oxygen plasma treatment ² Torr to 125 W. Organics are 9 × 10 ^- were deposited at a vacuum degree of ⁷ Torr Liq was 0.1 Å / sec, α, β -ADN was co-deposited with Pyrene-CN is 0.02 Å / sec on the basis of 0.18 Å / sec, the remaining organic substances are all 1 Å / sec. The electron transport layer material used in the experiment was Alq ₃ . 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.

&Lt; Test Examples 1 to 30 &

In the comparative test examples, elements were prepared in the same manner as in the comparative test except that each compound shown in Table 2 below was used instead of Alq ₃ .

Table 2 shows the electroluminescent characteristics of the organic luminescent devices prepared in the Comparative Test Examples and Test Examples 1 to 30.

The organic light emitting device manufactured by the above Comparative Test Example and Test Examples 1 to 30 was subjected to a forward electric field while increasing the voltage by 0.2 V, and the results shown in Table 2 were obtained. In Table 2, the efficiency was measured for the applied current, and the lifetime was expressed as a percentage of the luminance value after 10 hours with respect to the initial specific luminance value.

division compound Driving voltage
(V) efficiency
(cd / A) Lifetime [for 10H]
(%) Comparative test example Alq ₃ 6.60 5.10 91.78 Test Example 1 WS15-30-089 4.93 7.11 97.49 Test Example 2 WS15-30-093 4.62 8.56 96.25 Test Example 3 WS15-30-216 4.23 8.27 97.13 Test Example 4 WS15-30-072 3.97 8.31 97.69 Test Example 5 WS15-30-074 4.25 7.73 98.17 Test Example 6 WS15-35-13 4.10 7.62 97.12 Test Example 7 WS15-35-14 4.05 7.77 98.21 Test Example 8 WS15-35-15 4.51 5.54 96.12 Test Example 9 WS15-30-212 4.17 7.86 97.27 Test Example 10 WS15-30-227 4.47 7.67 97.64 Test Example 11 WS15-30-222 4.47 7.75 96.99 Test Example 12 WS15-30-202 4.29 7.16 97.38 Test Example 13 WS15-30-090 4.10 7.17 98.87 Test Example 14 WS15-30-094 3.87 8.82 97.63 Test Example 15 WS15-30-073 3.77 8.27 98.02 Test Example 16 WS15-30-075 4.01 8.86 97.81 Test Example 17 WS15-30-285 3.86 8.62 97.76 Test Example 18 WS15-35-18 3.95 7.52 97.63 Test Example 19 WS15-30-316 3.96 8.52 97.51 Test Example 20 WS15-30-315 3.94 7.16 97.98 Test Example 21 WS15-30-319 4.24 5.76 97.22 Test Example 22 WS15-30-320 3.65 7.32 98.24 Test Example 23 WS15-35-19 3.77 5.44 91.77 Test Example 24 WS15-30-284 4.19 7.99 97.30 Test Example 25 WS15-35-20 3.60 5.84 98.83 Test Example 26 WS15-30-226 4.11 8.51 97.70 Test Example 27 WS15-30-223 4.13 8.66 97.23 Test Example 28 WS15-30-215 4.31 8.29 97.46 Test Example 29 WS15-35-16 4.11 8.26 97.66 Test Example 30 WS15-35-17 4.29 7.16 97.38

From the results shown in the above Table 2, it can be seen that the triazine derivative compound having a condensed cyclic phenanthridine group bonded through a linker according to the present invention can be used as a material of an organic material layer of an organic electronic device including an organic light emitting device, It can be seen that organic electronic devices including devices exhibit excellent characteristics in terms of efficiency, driving voltage, and stability. In particular, the compounds according to the present invention exhibited high efficiency characteristics because of their excellent electron hole balancing ability and electron transporting ability.

Claims

A triazine derivative represented by the following formula (1) wherein a condensed cyclic phenanthridine group is bonded through a linker.
[Chemical Formula 1]

[In the formula 1, Ar ₁ And Ar < ₂ _> are each independently phenyl, naphthyl or biphenyl,
X < ₁ > is O or S,
p is an integer of 1 to 2,
R is hydrogen, or halogen, cyano, methoxy, methyl, ethyl, t- butyl, even if the functional group is selected from pyridyl and phenyl are one to two substituted or fused good phenyl, biphenyl, pyridyl, Quinolyl, isoquinolyl, naphthyl and phenanthryl.]

The method according to claim 1,
Wherein the compound represented by the formula (1) is selected from the group consisting of compounds represented by the following formulas (1a) to (1l), a triazine derivative in which a condensed cyclic phenanthridine group is bonded via a linker
[Chemical Formula 1a] [Chemical Formula 1b] [Chemical Formula 1c]

[Formula 1d] [Formula 1e]

[Formula 1f] [Formula 1g]

[Chemical Formula 1h] [Chemical Formula 1i]

[Chemical formula 1j] [Chemical formula 1k]

[In the above general formulas (1a) to (11)
R ₁ or R ₂ is hydrogen or phenyl which may be substituted or fused with 1 to 2 functional groups independently selected from the group consisting of hydrogen, halogen, cyano, methoxy, methyl, ethyl, t- butyl, , Biphenyl, pyridyl, quinolyl, isoquinolyl, naphthyl and phenanthryl,
X ₁ and Ar ₁ to Ar ₂ have the same meanings as defined in claim 1,

3. The method of claim 2,
Wherein R ₁ to R ₂ in the general formulas (1a) to (1l) are any one selected from the group consisting of a group represented by the following general formula (2), and a condensed cyclic phenanthridine group is bonded through a linker.
(2)

The method according to claim 1,
The triazine derivative of formula (1) is selected from the group consisting of the following formula (4), wherein the condensed cyclized phenanthridine group is bonded through a linker.
[Chemical Formula 4]

An organic electroluminescent device comprising a triazine derivative having a condensed cyclic phenanthridine group bound thereto through a linker, according to any one of claims 1 to 4.

6. The method of claim 5,
Wherein a triazine derivative in which a condensed cyclic phenanthridine group is bonded through the linker is used as an electron transport layer material.

A first electrode, a second electrode, and at least one organic film disposed between the electrodes,
Wherein the organic film comprises a triazine derivative in which a condensed cyclic phenanthridine group is bonded through the linker of any one of claims 1 to 4.

8. The method of claim 7,
The organic layer includes a hole injecting layer, a hole transporting layer, a functional layer having both a hole injecting function and a hole transporting function, a buffer layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transporting layer, And at least one functional layer having at least one functional group at the same time.

8. The method of claim 7,
A triazine derivative in which a condensed cyclic phenanthridine group is bonded through the linker is composed of an electron blocking layer, an electron transport layer, an electron injection layer, a functional layer having both an electron transport function and an electron injection function and a light emitting layer The organic electroluminescent device comprising: a substrate;