KR101842503B1 - Fused phenanthridine derivatives substituted with aryl or heteroaryl, and organic electroluminescent device including the same - Google Patents

Abstract

[상기 화학식 1에 있어서, Ar₁는 페닐 또는 피리딜이고, Z₁은 O 또는 S이고, L은 페닐 또는 피리딜이고, Ar₂는 하기 화학식 3으로 표시되는 군중에서 선택되는 어느 하나임]
[화학식 3]

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There is provided an aryl group or heteroaryl group-substituted polycyclic phenanthridine derivative represented by the following formula (1).
[Chemical Formula 1]

Wherein Ar ₁ is phenyl or pyridyl, Z ₁ is O or S, L is phenyl or pyridyl, and Ar ₂ is any one selected from the group consisting of the following formula (3)
(3)

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Description

[0001] The present invention relates to a phenanthridine derivative, an aryl group or a heteroaryl group-substituted polycyclic phenanthridine derivative, an organic electroluminescent device including the same,

The present invention relates to a specific aryl or heteroaryl group-substituted polycyclic phenanthridine derivative and an organic electroluminescent device including the same, and more particularly to an organic electroluminescent device having a high luminous efficiency and a specific aryl or heteroaryl group Substituted phenanthridine derivatives.

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 the display device. However, the LCD has a disadvantage of requiring a separate light source because its viewing angle is limited and it 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 and others. From these studies, it was found that charge injection, recombination, exciton generation, The basic mechanism and the electroluminescence characteristics of the device have been studied and studied.

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 been widely studied for their excellent potential as a next generation display, as well as for their potential to be used for LCD backlighting and illumination [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 in which an organic material is used to convert electric energy into light energy. 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. A host / dopant system may be used as the light emitting material in order to increase the color purity and increase the light emission efficiency through energy transfer. 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 is shifted to the wavelength band of the dopant, the desired wavelength light can be obtained depending on 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. 10-1558495 (entitled: polycyclic compound and organic light emitting device using the same) Korean Patent Publication No. 10-2013-0135178 (entitled "Novel heterocyclic compound and organic electronic device using the same) Korean Patent Publication No. 10-2015-0077382 (entitled Heterocyclic Compound and Organic Light Emitting Device Using the Same) Korean Patent Publication No. 10-2016-0007438 (entitled Heterocyclic Compound and Organic Light Emitting Device Using the Same)

As a result of intensive studies, the inventors of the present invention have found that when a specific aryl group or heteroaryl group substituted polycyclic phenanthridine derivative compound is found and used as a material for forming an organic material layer of an organic electronic device, A driving voltage drop and an increase in stability can be exhibited.

The present invention provides a specific aryl group or heteroaryl group substituted polycyclic phenanthridine derivative compound and an organic electronic device using the same.

According to an aspect of the present invention, there is provided an aryl group or heteroaryl group-substituted polycyclic phenanthridine derivative represented by the following general formula (1).

[Chemical Formula 1]

[Wherein Ar ₁ is phenyl, naphthyl or pyridyl,

L is C ₆ -C ₂₄ aryl or C ₃ -C ₂₄ heteroaryl,

n is an integer of 0 or 1,

Ar ₂ is C ₆ to C ₃₀ aryl or C ₃ to C ₃₀ heteroaryl,

Z ₁ is O or S.]

According to another aspect of the present invention, there is provided an organic electroluminescent device comprising the specific aryl group or the heteroaryl group-substituted polycyclic phenanthridine derivative.

According to another aspect of the present invention, there is provided an organic light emitting display comprising a first electrode, a second electrode, and at least one organic film disposed between the electrodes, wherein the organic film is formed of the specific aryl group or the heteroaryl group- An organic electroluminescent device including a triazine derivative is provided.

According to another aspect of the present invention, the aryl group or the heteroaryl group-substituted polycyclic phenanthridine derivative is used as the electron blocking layer, the electron transporting layer, the electron injecting layer, the electron transporting function, A light emitting layer, a light emitting layer, a light emitting layer, and a light emitting layer.

The specific aryl group or heteroaryl group substituted polycyclic phenanthridine derivative compound according to the present invention can be prepared by introducing a specific aryl group or heteroaryl group into the polycyclic phenanthridine to form an organic electroluminescent 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 via chemical bonds. 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.

The aryl group or the heteroaryl group-substituted polycyclic phenanthridine derivative according to an embodiment of the present invention may be represented by the following formula (1).

[Chemical Formula 1]

In Formula 1, Ar ₁ is phenyl, naphthyl or pyridyl,

L is C ₆ -C ₂₄ aryl or C ₃ -C ₂₄ heteroaryl,

n is an integer of 0 or 1,

Ar ₂ is C ₆ to C ₃₀ aryl or C ₃ to C ₃₀ heteroaryl,

Z ₁ is O or S.

Wherein L in the above formula (1) is any one selected from the group consisting of the following formula (2): wherein R is a substituted or unsubstituted aryl group or a heteroaryl group-substituted polycyclic phenanthridine derivative.

(2)

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The aryl group or heteroaryl group-substituted polycyclic phenanthridine derivative is characterized in that Ar ₂ in the formula (1) is any one selected from the group consisting of the following formula (3).

(3)

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In Formula 3,

Z ₂ is O or S,

R ₁ and R ₂ are each independently hydrogen or methyl,

Ar ₃ And Ar < ₄ > are each independently hydrogen, phenyl, naphthyl or biphenyl,

X ₁ to X ₅ are each independently CH or N;

Specific examples of the compound represented by the formula (1) of the present invention include an aryl group or a heteroaryl group-substituted polycyclic phenanthridine derivative selected from the group 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 phenanthridine derivative represented by the above formula (1) can be synthesized by using a known organic synthesis method. The phenanthridine The method of synthesizing the derivatives can be easily recognized by those skilled in the art with reference to the following production examples.

Further, according to the present invention, the phenanthridine represented by the above formula (1) There is provided an organic electroluminescent device comprising a derivative thereof.

The phenanthridine derivative of Formula 1 is useful as an electron transport layer material and can be used as a material for various 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 layer includes at least one aryl group or heteroaryl group-substituted polycyclic phenanthridine derivative represented by the general formula (1).

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

For example, the phenanthridine 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 phenanthridine 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 phenanthridine derivative may be included in the organic film as a single substance or a combination of different substances. Alternatively, the phenanthridine derivative may be used in combination with a conventionally known compound such as a light emitting layer, a hole transporting layer, and a hole injecting layer.

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

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

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

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

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

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the following examples are intended to illustrate the present invention and the scope of the present invention is not limited thereto.

[Example]

Intermediate Synthetic example  1: Synthesis of intermediate (5)

(Synthesis of Intermediate (1)

A 1 L, 2 L flask was charged with 30.0 g (0.107 mol) of 1,4-dibromo-2-nitrobenzene, dibenzofuran-4-ylboronic acid ) 21.2 g (0.128 mol), Pd (PPh 3) 4 3.7 g (3.20 mmol), were placed 300 mL of toluene as added while stirring the ethanol _{110 mL, Cs 2 CO 3 104} g (0.320 mol) / H 2 O 110 mL , and stirred for one hour 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 dichloromethane (DCM). The organic phase was dried over anhydrous MgSO ₄ and purified by silica gel column chromatography to obtain 25.8 g of a white solid compound (Intermediate (1) : 65.6%).

(Synthesis of Intermediate (2)

25.8 g (70.0 mmol) of Intermediate (1) and 18.4 g (0.329 mol) of iron are added to a 2 L flask with a stirrer and then 88 mL of saturated NH ₄ Cl solution is added and heated to reflux And the mixture was stirred for 4 hours. After the reaction was completed, the reaction mixture was cooled to room temperature and filtered through celite filter. The organic phase was distilled off under reduced pressure. The obtained reaction mixture was purified to obtain 22.6 g (yield: 95.4%) of a white solid compound (intermediate (2)).

(Synthesis of Intermediate (3)

22.6 g (66.8 mmol) of Intermediate (2) (334 mL) was added to a one liter 1 L flask, and 9.58 g (68.2 mmol) of benzoyl chloride was slowly added The mixture is stirred at room temperature for 24 hours. Water was added to the reaction mixture, followed by stirring. The precipitate was filtered, washed with water and purified to obtain 29.0 g (yield: 98.1%) of a solid compound (intermediate (3)).

(Synthesis of Intermediate (4)

29.0 g (65.6 mmol) of intermediate (3), 30.5 mL (0.328 mmol) of phosphorus oxychloride and 130 mL of Nitrobezene were refluxed at 150-160 ° C for 6 hours. And then after the completion of the reaction, the reaction cooled to room temperature and treated with water 500mL filtered and the organic layer was adjusted to obtain a solid with pH 8 or more to 6N NaOH and addition of water, and then separated and extracted with dichloromethane (DCM) with anhydrous MgSO ₄ Dried and purified by silica gel column chromatography to obtain 21.8 g (yield: 78.4%) of a white solid compound (intermediate (4)).

(Synthesis of intermediate 5)

* 1 Intermediate 1 (4) 18.7 g (44.1 mmol ) of L flask, bis (pinacolato) diboron (Bis (pinacolato) diboron) 16.8 g (66.1 mmol), Pd (dppf) Cl ₂ 13 g (0.132 mol) of potassium acetate (KOAc) and 440 mL of dioxane were added thereto, and the mixture was refluxed at 80 to 100 ° 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 18.8 g of a white solid compound (intermediate (5)) (yield: 90.5%).

Intermediate Synthetic example  2: Synthesis of intermediate (8)

(Synthesis of Intermediate (6)

13.2 g (0.037 mol) of Intermediate (2), 5.5 ml (0.039 mol) of triethylamine and 200 ml of dichloromethane (DCM) were added to a 500 ml one-necked flask and stirred for 30 minutes. 3-nicotinoyl chloride 5.5 g (0.039 mol) of 3-nicotinoyl chloride was dissolved in 100 ml of dichloromethane (DCM), and the mixture was slowly added dropwise at 0 ° C for 30 minutes, and the mixture was stirred at room temperature for 4 hours. After confirming the termination of the reaction, water was added, followed by extraction with dichloromethane (DCM). The organic phase was dried over anhydrous MgSO ₄ and then purified by silica gel column chromatography to obtain 13.7 g of a transparent liquid compound (Intermediate (14) %).

(Synthesis of intermediate 7)

13.7 g (0.030 mol) of intermediate (6), 8.4 ml (0.090 mol) of phosphoroxychloride and 200 ml of nitrobezene were refluxed under nitrogen at 150 to 160 ° C for 8 to 10 hours . After confirming the completion of the reaction, the reaction mixture was cooled to room temperature, and the reaction product was slowly added dropwise to 500 mL of water. The precipitate formed was filtered and washed with 300 mL of water to obtain a solid. The solid thus obtained was adjusted to pH 8 or higher with 6N NaOH solution and extracted with dichloromethane (DCM). The organic phase was dried over anhydrous MgSO ₄ and purified by silica gel column chromatography to obtain 9.5 g (yield: 72.2%) of a white solid compound (Intermediate (7)).

(Synthesis of Intermediate (8)

A 1-necked 1000 mL flask was charged with intermediate (7) 10.0 g (0.023 mol), bis (pinacolato) diboron (Bis (pinacolato) diboron) 6.3 g (0.025 mmol), Pd (dppf) Cl 2 4.5 g (0.045 mmol) of potassium acetate (KOAc) and 700 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 8.3 g (yield: 75.3%) of a white solid compound (Intermediate (8)).

Intermediate Synthetic example  3: Synthesis of intermediate (13)

(Synthesis of intermediate 9)

A 1 L 2 L flask was charged with 29.6 g (0.105 mol) of 1,4-dibromo-2-nitrobenzene, dibenzofuran-4-ylboronic acid ) 20.0 g (0.088 mol), Pd (PPh 3) 4 3.0 g (2.631 mmol), insert such as toluene, 600 mL ethanol while stirring was added _{300 mL, Cs 2 CO 3 57.1} g (0.175 mol) / H 2 O 300 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 dichloromethane (DCM). The organic phase was dried over anhydrous MgSO ₄ and purified by silica gel column chromatography to obtain 17.5 g of a yellow liquid compound (Intermediate (9) : 52.0%).

(Synthesis of intermediate 10)

A 1 L flask is charged with 17.5 g (0.046 mol) of intermediate (9) in 300 ml of THF and 300 ml of sodium hydrosulfite / water is slowly added dropwise. After 30 minutes, 50 ml of MeOH was added and the mixture was stirred at room temperature for 8 to 10 hours. After the completion of the reaction, the solvent was removed, and water was added thereto. The mixture was extracted with dichloromethane (DCM). The organic phase was dried over anhydrous MgSO ₄ and then purified by silica gel column chromatography to obtain 13.2 g (Yield: 82.1%).

(Synthesis of intermediate 11)

13.2 g (0.037 mol) of Intermediate (10), 5.5 ml (0.039 mol) of triethylamine and 200 ml of dichloromethane (DCM) were added to a 500 ml 1-necked flask and stirred for 30 minutes. Then, benzoyl chloride 5.5 g (0.039 mol) was diluted with 100 ml of dichloromethane (DCM), and the mixture was slowly added dropwise at 0 占 폚 for 30 minutes, followed by stirring at room temperature for 4 hours. After confirming the termination of the reaction, water was added, followed by extraction with dichloromethane (DCM). The organic phase was dried over anhydrous MgSO ₄ and then purified by silica gel column chromatography to obtain 13.7 g of a transparent liquid compound (Intermediate (11) %).

(Synthesis of intermediate 12)

13.7 g (0.030 mol) of intermediate (11), 8.4 ml (0.090 mol) of phosphorus oxychloride and 200 ml of nitrobezene were refluxed under nitrogen at 150 to 160 ° C for 8 to 10 hours . After confirming the completion of the reaction, the reaction mixture was cooled to room temperature, and the reaction product was slowly added dropwise to 500 mL of water. The precipitate formed was filtered and washed with 300 mL of water to obtain a solid. The solid thus obtained was adjusted to pH 8 or higher with 6N NaOH solution and extracted with dichloromethane (DCM). The organic phase was dried over anhydrous MgSO ₄ and purified by silica gel column chromatography to obtain 9.5 g (yield: 72.2%) of a white solid compound (Intermediate (12)).

(Synthesis of intermediate 13)

A 1-necked 1000 mL flask was charged with intermediate (12) 10.0 g (0.023 mol), bis (pinacolato) diboron (Bis (pinacolato) diboron) 6.3 g (0.025 mmol), Pd (dppf) Cl 2 4.5 g (0.045 mmol) of potassium acetate (KOAc) and 700 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 8.3 g (yield: 75.3%) of a white solid compound (intermediate (13)).

Intermediate Synthetic example  4: Synthesis of intermediate (16)

(Synthesis of intermediate 14)

13.2 g (0.037 mol) of intermediate (10), 5.5 ml (0.039 mol) of triethylamine and 200 ml of dichloromethane (DCM) were added to a 500 ml one-necked flask and stirred for 30 minutes. 3-nicotinoyl chloride 5.5 g (0.039 mol) of 3-nicotinoyl chloride was dissolved in 100 ml of dichloromethane (DCM), and the mixture was slowly added dropwise at 0 ° C for 30 minutes, followed by stirring at room temperature for 4 hours. After confirming the termination of the reaction, water was added, followed by extraction with dichloromethane (DCM). The organic phase was dried over anhydrous MgSO ₄ and then purified by silica gel column chromatography to obtain 13.7 g of a transparent liquid compound (Intermediate (14) %).

(Synthesis of intermediate 15)

13.7 g (0.030 mol) of intermediate (14), 8.4 ml (0.090 mol) of phosphoroxychloride and 200 ml of nitrobezene were refluxed under nitrogen at 150 to 160 ° C for 8 to 10 hours . After confirming the completion of the reaction, the reaction mixture was cooled to room temperature, and the reaction product was slowly added dropwise to 500 mL of water. The precipitate formed was filtered and washed with 300 mL of water to obtain a solid. The solid thus obtained was adjusted to pH 8 or higher with 6N NaOH solution and extracted with dichloromethane (DCM). The organic phase was dried over anhydrous MgSO ₄ and purified by silica gel column chromatography to obtain 9.5 g (yield: 72.2%) of a white solid compound (Intermediate (15)).

(Synthesis of intermediate 16)

A 1-neck 1000 mL flask was charged with intermediate (15) 10.0 g (0.023 mol), bis (pinacolato) diboron (Bis (pinacolato) diboron) 6.3 g (0.025 mmol), Pd (dppf) Cl 2 4.5 g (0.045 mmol) of potassium acetate (KOAc) and 700 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 8.3 g (yield: 75.3%) of a white solid compound (Intermediate (16)).

Intermediate Synthetic example  5: Synthesis of intermediate (21)

(Synthesis of Intermediate (17)

A 1 L 2 L flask was charged with 30.0 g (0.107 mol) of 1,5-dibromo-2-nitrobenzene, dibenzofuran-4-ylboronic acid ) 21.2 g (0.128 mol), Pd (PPh 3) 4 3.7 g (3.20 mmol) were dissolved in toluene as in 300 mL of ethanol was added while stirring _{110 mL, Cs 2 CO 3 104} g (0.320 mol) / H 2 O 110 mL , and the mixture was stirred for one hour under reflux. After the reaction was completed, the mixture was cooled to room temperature, water was added thereto, and the mixture was extracted with dichloromethane (DCM). The organic phase was dried over anhydrous MgSO ₄ and purified by silica gel column chromatography to obtain 25.8 g of a white solid compound (Intermediate (17) : 65.6%).

(Synthesis of intermediate 18)

25.8 g (70.0 mmol) of Intermediate (17) and 18.4 g (0.329 mol) of Fe are added to a 1 L 2L flask and stirred with 438 mL of ethanol. Then, 88 mL of saturated NH ₄ Cl solution is added, And the mixture was stirred for 4 hours. After the reaction was completed, the reaction mixture was cooled to room temperature and filtered through celite filter. The organic phase was distilled off under reduced pressure. The obtained reaction mixture was purified to obtain 22.6 g (yield: 95.4%) of a white solid compound (Intermediate (18)).

(Synthesis of intermediate 19)

22.6 g (66.8 mmol) of Intermediate 18 (184 g) was added to a one liter 1 L flask with 334 mL of N-methylpyrrolidone and stirred. 9.58 g (68.2 mmol) of benzoyl chloride was slowly added Stir at room temperature for 24 hours. Water was added to the reaction mixture, followed by stirring. The precipitate was filtered, washed with water and purified to obtain 29.0 g (yield: 98.1%) of a solid compound (Intermediate (19)).

(Synthesis of intermediate 20)

29.0 g (65.6 mmol) of intermediate (19), 30.5 mL (0.328 mmol) of phosphoroxychloride and 130 mL of Nitrobezene were refluxed at 150 to 160 ° C for 6 hours. The reaction is one of terminated and then cooled to room temperature and then treated with water 500mL adjust the solid obtained by filtration with pH 8 or more to 6N NaOH and addition of water, and then separated and extracted with dichloromethane (DCM) the organic layer with anhydrous MgSO ₄ Dried and purified by silica gel column chromatography to obtain 21.8 g (yield: 78.4%) of a white solid compound (Intermediate (20)).

(Synthesis of intermediate 21)

A 1 L flask was charged with 18.7 g (44.1 mmol) of Intermediate 20, 16.8 g (66.1 mmol) bis (pinacolato diboron), Pd (dppf) Cl ₂ 13 g (0.132 mol) of potassium acetate (KOAc) and 440 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 18.8 g of a white solid compound (Intermediate (21)) (yield: 90.5%).

Intermediate Synthetic example  6: Synthesis of intermediate (26)

(Synthesis of intermediate 22)

A 1 L 2 L flask was charged with 29.6 g (0.105 mol) of 1,5-dibromo-2-nitrobenzene, dibenzofuran-4-ylboronic acid ) 20.0 g (0.088 mol), Pd (PPh 3) 4 3.0 g (2.631 mmol) were dissolved in toluene as in 600 mL of ethanol was added while stirring _{300 mL, Cs 2 CO 3 57.1} g (0.175 mol) / H 2 O 300 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, followed by extraction with dichloromethane (DCM). The organic phase was dried over anhydrous MgSO ₄ and purified by silica gel column chromatography to obtain 17.5 g of a yellow liquid compound (Intermediate 22) : 52.0%).

(Synthesis of intermediate 23)

A 1 L flask is charged with 17.5 g (0.046 mol) of intermediate (22) in 300 ml of THF and 300 ml of sodium hydrosulfite / water is slowly added dropwise. After 30 minutes, 50 ml of MeOH was added and the mixture was stirred at room temperature for 8 to 10 hours. After the completion of the reaction was confirmed, the solvent was removed, water was added, and the mixture was extracted with dichloromethane (DCM). The organic phase was dried over anhydrous MgSO ₄ and then purified by silica gel column chromatography to obtain 13.2 g of a yellow liquid compound (Yield: 82.1%).

(Synthesis of intermediate 24)

13.2 g (0.037 mol) of Intermediate (23), 5.5 ml (0.039 mol) of triethylamine and 200 ml of dichloromethane (DCM) were added to a 500 ml one-necked flask and stirred for 30 minutes. Then, benzoyl chloride 5.5 g (0.039 mol) of 100 ml of dichloromethane (DCM) was added dropwise at 0 ° C for 30 minutes, and the mixture was stirred at room temperature for 4 hours. After confirming the termination of the reaction, water was added, followed by extraction with dichloromethane (DCM). The organic phase was dried over anhydrous MgSO ₄ and then purified by silica gel column chromatography to obtain 13.7 g of a transparent liquid compound (Intermediate (24) %).

(Synthesis of intermediate 25)

13.7 g (0.030 mol) of intermediate (24), 8.4 ml (0.090 mol) of phosphoroxychloride and 200 ml of nitrobezene were refluxed under nitrogen at 150 to 160 ° C for 8 to 10 hours . After confirming the completion of the reaction, the reaction mixture was cooled to room temperature, and the reaction product was slowly added dropwise to 500 mL of water. The precipitate formed was filtered and washed with 300 mL of water to obtain a solid. The solid thus obtained was adjusted to pH 8 or higher with 6N NaOH solution and extracted with dichloromethane (DCM). The organic phase was dried over anhydrous MgSO ₄ and purified by silica gel column chromatography to obtain 9.5 g (yield: 72.2%) of a white solid compound (Intermediate (25)).

(Synthesis of intermediate 26)

To a 1000 mL flask was added an intermediate (25) 10.0 g (0.023 mol), bis (pinacolato) diboron (Bis (pinacolato) diboron) 6.3 g (0.025 mmol), Pd (dppf) Cl 2 4.5 g (0.045 mmol) of potassium acetate (KOAc) and 700 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 8.3 g (yield: 75.3%) of a white solid compound (intermediate (26)).

Intermediate Synthetic example  7: Synthesis of intermediate (28)

(Synthesis of intermediate 27)

30.0 g (0.016 mol) of 4-bromobenzaldehyde and 31.8 g (0.016 mol) of 4-acetylbiphenyl and 1,080 mL of ethanol were added and stirred. 60 mL (0.30 mol) of 5M NaOH was slowly added dropwise, and the mixture was stirred at room temperature all day. After the reaction is complete, wash the solid thoroughly with water and ethanol. And dried under reduced pressure to obtain 48.6 g (yield: 83%) of a white solid compound (Intermediate (27)).

(Synthesis of intermediate 28)

305 mL of ethanol is added to 20.0 g (0.055 mol) of intermediate (27) and 8.88 g (0.057 mol) of benzamine hydrochloride, and the mixture is stirred. 4.40 g (0.110 mol) of NaOH are slowly added and refluxed all day. After the reaction is complete, wash the solid thoroughly with water and ethanol. And dried under reduced pressure to obtain 16.5 g (yield: 65%) of a white solid compound (Intermediate (28))

Intermediate Synthetic example  8: Synthesis of intermediate (30)

(Synthesis of intermediate 29)

30.0 g (162 mmol) of 3-bromobenzaldehyde and 31.8 g (162 mmol) of 4-acetylbiphenyl are placed in 1.0 L of ethanol and stirred at room temperature. 60 mL (300 mmol) of a 5 M sodium hydroxide aqueous solution is slowly added dropwise to the above reaction solution. After stirring overnight at room temperature, the precipitate was filtered and washed with water and ethanol to obtain 57.5 g of a solid compound (intermediate (29)) (yield: 97.6%).

(Synthesis of intermediate 30)

57.5 g (158 mmol) of Intermediate (29) and 25.5 g (163 mmol) of benzamidine hydrochloride were added to 790 mL of ethanol and stirred. Add 12.7 g (318 mmol) of sodium hydroxide in small portions at room temperature. Thereafter, the reaction solution was refluxed overnight. After the reaction mixture was cooled to room temperature, the precipitate was filtered and washed with water and methanol to obtain 52.6 g (yield: 71.7%) of a solid compound (Intermediate (30)).

Intermediate Synthetic example  9: Synthesis of intermediate (32)

(Synthesis of intermediate 31)

10.0 g (0.054 mol) of 2-bromo-4-pyridylcarboxaldehyde, 10.5 g (0.054 mol) of 4-acetylbiphenyl and 300 mL of EtOH were added thereto, After 30 minutes, add a solution of 4.0 g (0.100 mol) of NaOH in 20 mL of H ₂ O slowly. After the dropwise addition, the mixture was stirred for 7 hours or more. After the reaction was completed, the precipitate was filtered, and the solid was dispersed in 200 mL of water, followed by further filtration, washing with 200 mL of EtOH and drying to obtain 16.6 g (yield: 85%) of white solid compound (Intermediate (31)).

(Synthesis of intermediate 32)

15.0 g (0.041 mol) of Intermediate (31), 6.6 g (0.042 mol) of benzamidine hydrochloride, and 300 mL of EtOH were added to a 1-liter L flask and stirred for 30 minutes. After 30 minutes, 3.3 g 0.082 mol) is slowly added dropwise. After the dropwise addition, reflux is carried out at 80 to 100 DEG C for 8 hours or more in a nitrogen atmosphere. After the reaction was completed, the reaction mixture was cooled to room temperature and the precipitate was filtered. The resulting solid was dispersed in 200 mL of water, filtered, washed with 200 mL of EtOH and dried to obtain 4.8 g (yield: 25%) of white solid compound .

Intermediate Synthetic example  10: Synthesis of intermediate (34)

(Synthesis of intermediate 33)

26.2 g (0.24 mol) of 2-aminophenol and 300 mL of methanol were placed in a 500 mL flask and 44.6 g (0.24 mol) of 4-bromobenzaldehyde was slowly added thereto at room temperature . After completion of the reaction for 1 hour, the reaction was confirmed to be complete and the filtrate was concentrated under reduced pressure to obtain 66.4 g (yield: 100%) of a viscous liquid compound (Intermediate (33)).

(Synthesis of intermediate 34)

66.4 g (0.24 mol) of Intermediate (33) and 1.19 L of dichloromethane (DCM) were placed in a 1 L two-necked flask and 2,3-dichloro-5-, 6-dicyanobenzoquinone 59.6 g (0.26 mol) of 5,6-Dicyanobenzoquinone (DDQ) was slowly added portionwise and stirred for 1 hour. After confirming the termination of the reaction, the reaction solution was filtered through a silica plug, and the filtrate was concentrated under reduced pressure. The concentrate was purified in EtOA / methanol to obtain 29.7 g (yield: 45.2%) of a white solid compound (Intermediate (34)).

Intermediate Synthetic example  11: Synthesis of intermediate (35)

(Synthesis of intermediate 35)

36.9 g (0.200 mol) of 4-bromobenzaldehyde was slowly added to 25.0 g (0.200 mol) of 2-aminobenzenethiol at room temperature and refluxed at 125 to 130 ° C. After confirming the reaction, ethanol was slowly added to solidify it, followed by filtration. The solid compound thus obtained was further refined with EA / MeOH to obtain 22.19 g (yield: 38.3%) of a white solid compound (Intermediate (35)).

Intermediate Synthetic example  12: Synthesis of intermediate (39)

(Synthesis of intermediate 36)

The 1L flask 1 1-iodine-2-nitrobenzene (1-iodo-2-nitrobenzene ) 50.0 g (0.201 mol), 3- aminopyridine (3-aminopyridine) 18.9 g ( 0.201 mol), Pd (OAc) 2 After adding 1.8 g (8.0 mmol) of K ₂ CO _3, 55.6 g (0.402 mol) of K ₂ CO ₃ and 600 mL of toluene, the mixture was heated to 90 ° C., 7.5 g (0.012 mol) of BINAP was added and the mixture was refluxed for 12 hours. After confirming the termination of the reaction, the reaction product was cooled to room temperature, 500 mL of toluene and 1000 mL of water were added, and the organic layer was separated. 500 mL of 1N HCl solution was added to the separated organic layer, and the mixture was stirred at room temperature for 30 minutes. The aqueous layer was separated and adjusted to pH 8-9 with 250 mL of saturated Na ₂ CO ₃ solution. The precipitate thus formed was filtered under reduced pressure, washed with 500 mL of water and dried under reduced pressure to obtain 38.9 g (yield: 90.0%) of a solid compound (intermediate (36)).

(Synthesis of intermediate 37)

A solution of 64.0 g (0.25 mol) of Intermediate (36) in 756 mL of tetrahydrofuran and 227 g (1.31 mol) of Na ₂ S ₂ O ₄ in 756 mL of water was slowly added to a ₂ L flask for 1 hour, followed by the addition of 38 mL Respectively. The reaction was stirred at room temperature for 6 hours, then 756 mL of EtOAc was added and the pH was adjusted to 7-8 with saturated Na ₂ CO ₃ solution. The separated organic layer was dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure to obtain 32.07 g (yield: 69.0%) of a compound (intermediate (37)).

(Synthesis of intermediate 38)

32.07 g (0.173 mol) of Intermediate 37 was dissolved in 300 mL of N- methylpyrrolidone and then 45.6 g (0.208 mol) of 4-bromobenzoyl chloride was dissolved in NMP ( n- methylpyrrolidone) 50 mL of the solution is slowly added dropwise using a dropping funnel and stirred for one day. After the reaction is complete, add 1500 mL of water slowly at room temperature. The resulting precipitate was filtered under reduced pressure and washed with 500 mL of water to obtain 56.68 g (yield: 89.0%) of a solid compound (Intermediate (38)). The filtrate was concentrated under reduced pressure and the pH was adjusted to 8 to 9 with saturated sodium carbonate solution. %).

(Synthesis of intermediate 39)

56.0 g (0.15 mol) of intermediate (38), 2.89 g (0.015 mol) of p- toluene sulfonic acid hydrate and 560 mL of xylene were placed in a one liter 1 L flask and dean-stacked After refluxing and stirring for 12 hours, the mixture was cooled to room temperature and concentrated under reduced pressure. 500 mL of dichloromethane (DCM) was added to the concentrate to dissolve it. The saturated solution was washed with 300 mL of sodium carbonate and 500 mL of water. The separated organic layer was dried over anhydrous MgSO ₄ , filtered under reduced pressure, and concentrated under reduced pressure. 900 mL of ethanol was added to the concentrate, followed by heating and dissolution, followed by slow cooling to room temperature to effect crystallization. The formed crystals were filtered under reduced pressure to obtain 38.5 g (yield: 72.0%) of a white solid compound (Intermediate (39)).

Intermediate Synthetic example  13: Synthesis of intermediate (44)

(Synthesis of intermediate 40)

52.3 g (0.555 mol) of 2-aminopyridine and 500 mL of acetonitrile were placed in a 1 L flask and 103.9 g (0.584 mol) of NBS (N-bromosuccinimide) The temperature was then gradually raised to room temperature and stirred for 24 hours. After confirming the completion of the reaction, the reaction solution was concentrated under reduced pressure, 1000 mL of water and 1000 mL of dichloromethane (DCM) were added, and the mixture was stirred for 2 hours. The separated organic layer was washed with 500 mL of brine, dried over anhydrous Na ₂ SO ₄ and concentrated. The concentrate was recrystallized under dichloromethane (DCM) / hexane conditions to obtain 81.5 g (yield: 84.8%) of a white solid compound (Intermediate 40).

(Synthesis of intermediate 41)

A 3L flask 1 1-iodine-2-nitrobenzene (1-iodo-2-nitrobenzene ) 105.8 g (0.405 mol), intermediate (40) 50 g (0.404 mol ), Pd (OAc) 2 3.6 g (16.18 mmol ), 15.2 g (24.28 mol) of BINAP, 167.8 g (1.21 mol) of K ₂ CO ₃ and 1500 mL of toluene were charged and refluxed for 16 hours. After confirming the termination of the reaction, the reaction product was cooled to room temperature, 500 mL of toluene and 1000 mL of water were added, and the organic layer was separated. 500 mL of 1N HCl solution was added to the separated organic layer, and the mixture was stirred at room temperature for 30 minutes. The aqueous layer was separated and adjusted to pH 8-9 with 250 mL of saturated Na ₂ CO ₃ solution. The precipitate thus formed was filtered under reduced pressure, washed with 500 mL of water and dried under reduced pressure to obtain 63.7 g (yield: 53.6%) of a solid compound (Intermediate (41)).

(Synthesis of intermediate 42)

63.0 g (0.214 mol) of intermediate (41) was dissolved in 800 mL of tetrahydrofuran, and a solution prepared by dissolving 227 g (1.31 mol) of Na ₂ S ₂ O ₄ in 756 mL of water was slowly added to a ₂ L flask for 1 hour. Then, 40 mL Respectively. The reaction was stirred at room temperature for 6 hours, then 756 mL of EtOAc was added and the pH was adjusted to 7-8 with saturated Na ₂ CO ₃ solution. The separated organic layer was dried over anhydrous magnesium sulfate, filtered and concentrated under reduced pressure to obtain 48.68 g (yield: 86.1%) of a compound (Intermediate (42)).

(Synthesis of intermediate 43)

A solution obtained by dissolving 49.2 g (0.186 mol) of Intermediate 42 in 550 mL of N- methylpyrrolidone and then dissolving 39.2 g (0.279 mol) of benzoyl chloride in 250 mL of NMP ( n- methylpyrrolidone) The mixture is slowly added dropwise using a pouring funnel and stirred for a day. After the reaction is complete, add 1500 mL of water slowly at room temperature. The resulting precipitate was filtered under reduced pressure and washed with 500 mL of water to obtain 45.9 g (yield: 76.9%) of a solid compound (Intermediate (43)). The precipitate was filtered off under reduced pressure and the filtrate was adjusted to pH 8-9 with saturated sodium carbonate solution. %).

* (Synthesis of intermediate 44)

A 1 L flask was charged with 40.9 g (0.111 mol) of Intermediate (43), 2.1 g (0.011 mol) of p- toluene sulfonic acid hydrate and 330 mL of xylene, and the mixture was dean- After refluxing and stirring for 12 hours, the mixture was cooled to room temperature and concentrated under reduced pressure. 500 mL of dichloromethane (DCM) was added to the concentrate to dissolve it. The saturated solution was washed with 300 mL of sodium carbonate and 500 mL of water. The separated organic layer was dried over anhydrous MgSO ₄ , filtered under reduced pressure, and concentrated under reduced pressure. 900 mL of ethanol was added to the concentrate, followed by heating and dissolution, followed by slow cooling to room temperature to effect crystallization. The formed crystals were filtrated under reduced pressure to obtain 36.8 g (yield: 94.6%) of a white solid compound (Intermediate 44).

Intermediate Synthetic example  14: Synthesis of intermediate (46)

(Synthesis of intermediate 45)

30.0 g (0.24 mol) of 2-aminobenzenethiol and 300 mL of methanol were placed in a 500 mL flask and a solution of 6-bromo pyridine-3-carboaldehyde 44.6 g (0.24 mol) was slowly added in portions. After completion of the reaction for one hour, the reaction was terminated and the filtrate was concentrated under reduced pressure to obtain 70.01 g (yield: 100%) of a viscous liquid compound (Intermediate (45)).

(Synthesis of intermediate 46)

70.0 g (0.24 mol) of Intermediate (45) and 1.19 L of dichloromethane (DCM) were placed in a 1 L two-necked flask and 2,3-dichloro-5-, 6-dicyanobenzoquinone 59.6 g (0.26 mol) of 5,6-Dicyanobenzoquinone (DDQ) was added slowly and stirred for 1 hour. After confirming the termination of the reaction, the reaction solution was filtered through a silica plug, and the filtrate was concentrated under reduced pressure. The concentrate was purified in EtOAc / methanol to obtain 31.4 g (yield: 45.2%) of a white solid compound (Intermediate (46)).

Various phenanthridine derivative compounds were synthesized as follows using the synthesized intermediate compounds.

Example  1: Synthesis of Compound 4-12 (WS16-30-086)

1.41 g (5.30 mmol) of 2-chloro-4,6-diphenylpyrimidine, 2.50 g (5.30 mmol) of intermediate (5), Pd ₃ ) ₄ 0.31 g (0.27 mmol), 40 mL of toluene, 10 mL of EtOH, 10 mL of H ₂ O and 3.38 g (15.9 mmol) of K ₃ PO ₄ were mixed and then refluxed. After the reaction was completed, the reaction mixture was cooled at room temperature and the resulting solid was filtered with EtOH. And purified by silica gel column chromatography (CHCl ₃₎ dissolving the solid in chloroform. Solidification with dichloromethane (DCM) and filtration afforded 2.3 g (yield: 74.7%) of compound 4-12 (WS16-30-086) as a white solid.

Example  2: Synthesis of Compound 4-13 (WS16-30-168)

1.41 g (5.30 mmol) of 4-chloro-2,6-diphenylpyrimidine, 2.50 g (5.30 mmol) of intermediate (5), Pd ₃ ) ₄ 0.31 g (0.27 mmol), 40 mL of toluene, 10 mL of EtOH, 10 mL of H ₂ O and 3.38 g (15.9 mmol) of K ₃ PO ₄ were mixed and then refluxed. After the reaction was completed, the reaction mixture was cooled at room temperature and the resulting solid was filtered with EtOH. The filtrate was purified by silica gel column chromatography (CHCl ₃₎ dissolving the solid in chloroform. Solidification with dichloromethane (DCM) / EA and filtration gave 2.3 g (yield: 75.3%) of compound 4-13 (WS16-30-168) as a white solid.

Example  3: Synthesis of compound 4-14 (WS16-30-087)

1.53 g (5.73 mmol) of 2-chloro-4,6-diphenyl-1,3,5-triazine was added to one 250 mL flask. , 0.70 g (0.29 mmol) of Pd (PPh ₃ ) ₄ , 40 mL of toluene, 10 mL of EtOH, 10 mL of H ₂ O and 3.65 g (17.2 mmol) of K ₃ PO ₄ , Mixed and refluxed. After the reaction was completed, the reaction mixture was cooled at room temperature and the resulting solid was filtered with EtOH. The filtrate was purified by silica gel column chromatography (CHCl ₃₎ dissolving the solid in chloroform. Solidification with dichloromethane (DCM) and filtration afforded 2.7 g (yield: 82.0%) of compound 4-14 (WS16-30-087) as a white solid.

Example  4: Synthesis of compound 4-36 (WS16-30-180)

In 1 250 mL flask Int.10 2.50 g (7.48 mmol), intermediate (5) 3.70 g (7.85 mmol ), Pd (PPh 3) 4 0.43 g (0.37 mmol), toluene, 30 mL, 15 mL EtOH and 2M K ₂ CO ₃ 11 mL (22.4 mmol) and then refluxed. After the reaction was completed, the reaction mixture was cooled at room temperature and the resulting solid was filtered with MeOH. The solid was boiled in chloroform and completely dissolved, then purified by silica gel column chromatography (CHCl ₃ : EA). Solidified with ethyl acetate (EA), boiled, cooled and filtered to obtain 3.1 g (yield: 70.6%) of pale yellow solid Compound 4-36 (WS16-30-180).

Example  5: Synthesis of compound 4-37 (WS16-30-179)

In 1 250 mL flask Int.11 2.50 g (7.48 mmol), intermediate (5) 3.70 g (7.85 mmol ), Pd (PPh 3) 4 0.43 g (0.37 mmol), toluene, 30 mL, 15 mL EtOH and 2M K ₂ CO ₃ 11 mL (22.4 mmol) and then refluxed. After the reaction was completed, the reaction mixture was cooled at room temperature and the resulting solid was filtered with MeOH. The solid was boiled in chloroform and completely dissolved, then purified by silica gel column chromatography (CHCl ₃ : EA). Ethyl acetate (EA) was solidified, boiled, cooled and filtered to obtain 3.2 g (yield: 71.0%) of compound 4-37 (WS16-30-179) as a white solid.

*

Example  6: Synthesis of Compound 4-40 (WS16-30-156)

Intermediate 34 to 1 250 mL flask, 1.45 g (5.30 mmol), intermediate (5) 2.50 g (5.30 mmol ), Pd (PPh 3) 4 0.31 g (0.27 mmol), toluene, 40 mL, EtOH 10 mL, H 10 mL of ₂ O and 3.38 g (15.9 mmol) of K ₃ PO ₄ were mixed and then refluxed. After the reaction was completed, the reaction mixture was cooled at room temperature and the resulting solid was filtered with EtOH. The filtrate was purified by silica gel column chromatography (CHCl ₃₎ dissolving the solid in chloroform. Solidification with dichloromethane (DCM) and filtration gave 2.2 g (yield: 75.6%) of compound 4-40 (WS16-30-156) as a white solid.

Example  7: Synthesis of compound 4-41 (WS16-30-173)

In 1 250 mL flask Int.2 1.74 g (6.36 mmol), intermediate (5) 3.00 g (6.36 mmol ), Pd (PPh 3) 4 0.37 g (0.32 mmol), toluene, 40 mL, EtOH 10 mL, H 2 O 10 mL, and K ₃ PO ₄ were mixed with 4.05 g (19.1 mmol), followed by reflux. After the reaction was completed, the reaction mixture was cooled at room temperature and the resulting solid was filtered with EtOH. The filtrate was purified by silica gel column chromatography (CHCl ₃₎ dissolving the solid in chloroform. Solidification with dichloromethane (DCM) and filtration gave 2.2 g (yield: 63.6%) of compound 4-41 (WS16-30-173) as a white solid.

Example  8: Synthesis of Compound 4-42 (WS16-30-174)

Intermediate 35 to 1 250 mL flask, 1.85 g (6.36 mmol), intermediate (5) 3.00 g (6.36 mmol ), Pd (PPh 3) 4 0.37 g (0.32 mmol), toluene, 40 mL, EtOH 10 mL, H 10 mL of ₂ O and 4.05 g (19.1 mmol) of K ₃ PO ₄ were mixed and then refluxed. After the reaction was completed, the reaction mixture was cooled at room temperature and the resulting solid was filtered with EtOH. The filtrate was purified by silica gel column chromatography (CHCl ₃₎ dissolving the solid in chloroform. Solidification with dichloromethane (DCM) and filtration gave 2.8 g (yield: 77.9%) of compound 4-42 (WS16-30-174) as a white solid.

Example  9: Synthesis of compound 4-43 (WS16-30-185)

In 1 250 mL flask Int.3 1.85 g (6.36 mmol), intermediate (5) 3.00 g (6.36 mmol ), Pd (PPh 3) 4 0.37 g (0.32 mmol), toluene, 40 mL, EtOH 10 mL, H 2 O 10 mL, and K ₃ PO ₄ were mixed with 4.05 g (19.1 mmol), followed by reflux. After the reaction was completed, the reaction mixture was cooled at room temperature and the resulting solid was filtered with EtOH. The filtrate was purified by silica gel column chromatography (CHCl ₃₎ dissolving the solid in chloroform. Solidified with dichloromethane (DCM) and filtered to obtain 1.7 g of a white solid compound 4-43 (WS16-30-185) (yield: 47.6%).

Example  10: Synthesis of compound 4-44 (WS16-30-181)

In 1 250 mL flask Int.4 1.85 g (5.30 mmol), intermediate (5) 2.50 g (5.30 mmol ), Pd (PPh 3) 4 0.31 g (0.27 mmol), toluene, 40 mL, EtOH 10 mL, H 2 O and 3.38 g (15.9 mmol) of K ₃ PO ₄ were mixed and then refluxed. After the reaction was completed, the reaction mixture was cooled at room temperature and the resulting solid was filtered with EtOH. The filtrate was purified by silica gel column chromatography (CHCl ₃₎ dissolving the solid in chloroform. Solidified with dichloromethane (DCM) / ethyl acetate (EA) and filtered to give 586 mg (yield: 18.0%) of compound 4-44 (WS16-30-181) as a white solid.

Example  11: Synthesis of Compound 4-45 (WS16-30-172)

In 1 250 mL flask Int.5 2.22 g (6.36 mmol), intermediate (5) 3.00 g (6.36 mmol ), Pd (PPh 3) 4 0.37 g (0.32 mmol), toluene, 40 mL, EtOH 10 mL, H 2 O 10 mL, and K ₃ PO ₄ were mixed with 4.05 g (19.1 mmol), followed by reflux. After the reaction was completed, the reaction mixture was cooled at room temperature and the resulting solid was filtered with EtOH. The filtrate was purified by silica gel column chromatography (CHCl ₃₎ dissolving the solid in chloroform. Solidified with dichloromethane (DCM) / ethyl acetate (EA) and filtered to obtain 2.3 g (yield: 59.4%) of compound 4-45 (WS16-30-172) as a white solid.

Example  12: Synthesis of compound 4-52 (WS16-30-089)

Intermediate 28 to 1 250 mL flask, 1.74 g (3.76 mmol), intermediate (5) 1.77 g (3.76 mmol ), Pd (PPh 3) 4 0.22 g (0.19 mmol), toluene, 40 mL, EtOH 10 mL, H ₂ O and 2.39 g (11.3 mmol) of K ₃ PO ₄ were mixed and then refluxed. After the reaction was completed, the reaction mixture was cooled at room temperature and the resulting solid was filtered with EtOH. The filtrate was purified by silica gel column chromatography (CHCl ₃₎ dissolving the solid in chloroform. Solidification with dichloromethane (DCM) and filtration gave 1.3 g (yield: 47.9%) of compound 4-52 (WS16-30-089) as a white solid.

Example  13: Synthesis of compound 4-53 (WS16-30-084)

In 1 250 mL flask Int.1 2.46 g (5.30 mmol), intermediate (5) 2.50 g (5.30 mmol ), Pd (PPh 3) 4 0.31 g (0.27 mmol), toluene, 40 mL, EtOH 10 mL, H 2 O and 3.38 g (15.9 mmol) of K ₃ PO ₄ were mixed and then refluxed. After the reaction was completed, the reaction mixture was cooled at room temperature and the resulting solid was filtered with EtOH. The filtrate was purified by silica gel column chromatography (CHCl ₃₎ dissolving the solid in chloroform. Solidification with dichloromethane (DCM) and filtration gave 1.9 g (yield: 48.2%) of compound 4-53 (WS16-30-084) as a white solid.

Example  14: Synthesis of compound 4-55 (WS16-30-085)

Intermediate 30 to 1 250 mL flask, 2.46 g (5.30 mmol), intermediate (5) 2.50 g (5.30 mmol ), Pd (PPh 3) 4 0.31 g (0.27 mmol), toluene, 40 mL, EtOH 10 mL, H 10 mL of ₂ O and 3.38 g (15.9 mmol) of K ₃ PO ₄ were mixed and then refluxed. After the reaction was completed, the reaction mixture was cooled at room temperature and the resulting solid was filtered with EtOH. The filtrate was purified by silica gel column chromatography (CHCl ₃₎ dissolving the solid in chloroform. Solidification with dichloromethane (DCM) and filtration gave 1.9 g (yield: 48.2%) of compound 4-55 (WS16-30-085) as a white solid.

Example  15: Synthesis of compound 4-68 (WS16-30-182)

In 1 250 mL flask Int.6 2.13 g (6.36 mmol), intermediate (5) 3.00 g (6.36 mmol ), Pd (PPh 3) 4 0.37 g (0.32 mmol), toluene, 40 mL, EtOH 10 mL, H 2 O 10 mL, and K ₃ PO ₄ were mixed with 4.05 g (19.1 mmol), followed by reflux. After the reaction was completed, the reaction mixture was cooled at room temperature and the resulting solid was filtered with EtOH. The filtrate was purified by silica gel column chromatography (CHCl ₃₎ dissolving the solid in chloroform. Solidification with dichloromethane (DCM) and filtration gave 2.8 g (yield: 72.9%) of compound 4-68 (WS16-30-182) as a white solid.

*

Example  16: Synthesis of compound 4-84 (WS16-30-088)

One intermediate in 250mL flask (32) 2.46 g (5.30mmol) , Intermediate (5) 2.50 g (5.30mmol) , Pd (PPh 3) 4 0.31 g (0.27mmol), toluene 40mL, 10mL EtOH, H ₂ O 10mL And 3.38 g (15.9 mmol) of K ₃ PO ₄ were mixed and then refluxed. After the reaction was completed, the reaction mixture was cooled at room temperature and the resulting solid was filtered with EtOH. The filtrate was purified by silica gel column chromatography (CHCl ₃₎ dissolving the solid in chloroform. Solidification with dichloromethane (DCM) and filtration gave 2.9 g of a white solid compound 4-84 (WS16-30-088) (yield: 74.5%).

Example  17: Synthesis of compound 4-90 (WS16-30-186)

In one 250mL flask Int.7 1.89 g (6.36mmol), Intermediate (5) 3.00 g (6.36mmol) , Pd (PPh 3) 4 0.37 g (0.32mmol), toluene 40mL, 10mL EtOH, H ₂ O and 10mL 4.05 g (19.1 mmol) of K ₃ PO ₄ were mixed and then refluxed. After the reaction was completed, the reaction mixture was cooled at room temperature and the resulting solid was filtered with EtOH. The filtrate was purified by silica gel column chromatography (CHCl ₃₎ dissolving the solid in chloroform. Solidification with dichloromethane (DCM) and filtration gave 2.5 g of yellow solid compound 4-90 (WS16-30-186) (yield: 68.9%).

Example  18: Synthesis of compound 4-91 (WS16-30-184)

1 Int.8 necked 250mL flask, 1.78 g (6.36mmol), Intermediate (5) 3.00 g (6.36mmol) , Pd (PPh 3) 4 0.37 g (0.32mmol), toluene 40mL, 10mL EtOH, H ₂ O and 10mL 4.05 g (19.1 mmol) of K ₃ PO ₄ were mixed and then refluxed. After the reaction was completed, the reaction mixture was cooled at room temperature and the resulting solid was filtered with EtOH. The filtrate was purified by silica gel column chromatography (CHCl ₃₎ dissolving the solid in chloroform. Solidification with dichloromethane (DCM) and filtration gave 2.5 g (yield: 73.2%) of compound 4-91 (WS16-30-184) as a yellow solid.

Example  19: Synthesis of compound 4-92 (WS16-30-178)

1 Int.9 necked 250mL flask, 2.26 g (6.36mmol), Intermediate (5) 3.00 g (6.36mmol) , Pd (PPh 3) 4 0.37 g (0.32mmol), toluene 40mL, 10mL EtOH, H ₂ O and 10mL 4.05 g (19.1 mmol) of K ₃ PO ₄ were mixed and then refluxed. After the reaction was completed, the reaction mixture was cooled at room temperature and the resulting solid was filtered with EtOH. The filtrate was purified by silica gel column chromatography (CHCl ₃₎ dissolving the solid in chloroform. Solidification with dichloromethane (DCM) and filtration gave 3.3 g (yield: 84.9%) of compound 4-92 (WS16-30-178) as a white solid.

Example  20: Synthesis of Compound 4-105 (WS16-35-001)

In one 250mL flask, 2-chloro-4,6-diphenyl-pyrimidine (2-chloro-4,6-diphenylpyrimidine ) 1.41 g (5.30mmol), Intermediate (21) 2.50 g (5.30mmol) , Pd (PPh 3 ) ₄ , 0.40 g (0.27 mmol) of toluene, 10 mL of EtOH, 10 mL of H ₂ O and 3.38 g (15.9 mmol) of K ₃ PO ₄ were mixed and then refluxed. After the reaction was completed, the reaction mixture was cooled at room temperature and the resulting solid was filtered with EtOH. The filtrate was purified by silica gel column chromatography (CHCl ₃₎ dissolving the solid in chloroform. Solidification with dichloromethane (DCM) and filtration afforded 2.3 g (yield: 74.7%) of compound 4-105 (WS16-35-001) as a white solid.

Example  21: Synthesis of Compound 4-107 (WS16-35-003)

1.53 g (5.73 mmol) of 2-chloro-4,6-diphenyl-, 1,3,5-triazine was added to one 250 mL flask, , a mixture of intermediate (21) 2.70 g (5.73mmol) , Pd (PPh 3) 4 0.33 g (0.29mmol), toluene 40mL, 10mL EtOH, H ₂ O and 10mL _{K 3 PO 4 3.65 g (17.2mmol} ) and then , And refluxed. After the reaction was completed, the reaction mixture was cooled at room temperature and the resulting solid was filtered with EtOH. The filtrate was purified by silica gel column chromatography (CHCl ₃₎ dissolving the solid in chloroform. Solidified by dichloromethane (DCM) and filtered to obtain 2.7 g (yield: 82.0%) of Compound 4-107 (WS16-35-003) as a white solid.

Example  22: Synthesis of Compound 4-129 (WS16-35-007)

In one 250mL flask Int.10 2.50 g (7.48mmol), Intermediate (21) 3.70 g (7.85mmol) , Pd (PPh 3) 4 0.43 g (0.37mmol), toluene 30mL, 15mL EtOH and 2M K ₂ CO ₃ Was mixed with 11 mL (22.4 mmol) and then refluxed. After the reaction was completed, the reaction mixture was cooled at room temperature and the resulting solid was filtered with MeOH. The solid was boiled in chloroform and completely dissolved, then purified by silica gel column chromatography (CHCl ₃ : EA). Ethyl acetate (EA) was solidified, boiled, cooled and filtered to obtain 3.1 g (yield: 70.6%) of pale yellow solid compound 4-129 (WS16-35-007).

Example  23: Synthesis of Compound 4-133 (WS16-35-005)

One intermediate in 250mL flask (34) 1.45 g (5.30mmol) , Intermediate (21) 2.50 g (5.30mmol) , Pd (PPh 3) 4 0.31 g (0.27mmol), toluene 40mL, 10mL EtOH, H ₂ O 10mL And 3.38 g (15.9 mmol) of K ₃ PO ₄ were mixed and then refluxed. After the reaction was completed, the reaction mixture was cooled at room temperature and the resulting solid was filtered with EtOH. The filtrate was purified by silica gel column chromatography (CHCl ₃₎ dissolving the solid in chloroform. Solidification with dichloromethane (DCM) and filtration gave 2.2 g (yield: 75.6%) of compound 4-133 (WS16-35-005) as a white solid.

Example  24: Synthesis of Compound 4-148 (WS16-35-006)

(0.25 mmol) of Pd (PPh ₃ ) ₄ , 40 mL of toluene, 10 mL of EtOH, 10 mL of H ₂ O And 3.38 g (15.9 mmol) of K ₃ PO ₄ were mixed and then refluxed. After the reaction was completed, the reaction mixture was cooled at room temperature and the resulting solid was filtered with EtOH. The filtrate was purified by silica gel column chromatography (CHCl ₃₎ dissolving the solid in chloroform. Solidification with dichloromethane (DCM) and filtration gave 1.9 g (yield: 48.2%) of compound 4-148 (WS16-35-006) as a white solid.

Example  25: Synthesis of Compound 4-198 (WS16-35-002)

In one 250mL flask, 2-chloro-4,6-diphenyl-pyrimidine (2-chloro-4,6-diphenylpyrimidine ) 1.41 g (5.30mmol), Intermediate (8) 2.50 g (5.30mmol) , Pd (PPh 3 ) ₄ , 0.40 g (0.27 mmol) of toluene, 10 mL of EtOH, 10 mL of H ₂ O and 3.38 g (15.9 mmol) of K ₃ PO ₄ were mixed and then refluxed. After the reaction was completed, the reaction mixture was cooled at room temperature and the resulting solid was filtered with EtOH. The filtrate was purified by silica gel column chromatography (CHCl ₃₎ dissolving the solid in chloroform. Solidification with dichloromethane (DCM) and filtration afforded 2.3 g (yield: 74.7%) of compound 4-198 (WS16-35-002) as a white solid.

Example  26: Synthesis of Compound 4-200 (WS16-35-004)

1.53 g (5.73 mmol) of 2-chloro-4,6-diphenyl-, 1,3,5-triazine was added to one 250 mL flask, intermediate Compound (8) 2.70 g (5.73mmol) , Pd (PPh 3) 4 0.33 g (0.29mmol), toluene 40mL, 10mL EtOH, H ₂ O and 10mL K ₃ PO ₄ were mixed with 3.65 g (17.2mmol) and then , And refluxed. After the reaction was completed, the reaction mixture was cooled at room temperature and the resulting solid was filtered with EtOH. The filtrate was purified by silica gel column chromatography (CHCl ₃₎ dissolving the solid in chloroform. Solidification with dichloromethane (DCM) and filtration afforded 2.7 g (yield: 82.0%) of Compound 4-200 (WS16-35-004) as a white solid.

Example  27: Synthesis of Compound 4-222 (WS16-35-008)

In one 250mL flask Int.10 2.50 g (7.48mmol), Intermediate (8) 3.70 g (7.85mmol) , Pd (PPh 3) 4 0.43 g (0.37mmol), toluene 30mL, 15mL EtOH and 2M K ₂ CO ₃ 11 mL (22.4 mmol) were mixed and then refluxed. After the reaction was completed, the reaction mixture was cooled at room temperature and the resulting solid was filtered with MeOH. The solid was boiled in chloroform and completely dissolved, then purified by silica gel column chromatography (CHCl ₃ : EA). Ethyl acetate (EA) was solidified, boiled, cooled and filtered to obtain 3.2 g (yield: 71.0%) of compound 4-222 (WS16-35-008) as a white solid.

Example  28: Synthesis of Compound 4-227 (WS16-35-009)

1 Int.2 necked 250mL flask, 1.45 g (5.30mmol), Intermediate (8) 2.50 g (5.30mmol) , Pd (PPh 3) 4 0.31 g (0.27mmol), toluene 40mL, 10mL EtOH, H ₂ O and 10mL 3.38 g (15.9 mmol) of K ₃ PO ₄ were mixed and then refluxed. After the reaction was completed, the reaction mixture was cooled at room temperature and the resulting solid was filtered with EtOH. The filtrate was purified by silica gel column chromatography (CHCl ₃₎ dissolving the solid in chloroform. Solidification with dichloromethane (DCM) and filtration gave 2.2 g (yield: 75.6%) of compound 4-227 (WS16-35-009) as a white solid.

Example  29: Synthesis of Compound 4-241 (WS16-35-010)

One intermediate in 250mL flask (30) 2.46 g (5.30mmol) , Intermediate (8) 2.50 g (5.30mmol) , Pd (PPh 3) 4 0.31 g (0.27mmol), toluene 40mL, 10mL EtOH, H ₂ O 10mL And 3.38 g (15.9 mmol) of K ₃ PO ₄ were mixed and then refluxed. After the reaction was completed, the reaction mixture was cooled at room temperature and the resulting solid was filtered with EtOH. The filtrate was purified by silica gel column chromatography (CHCl ₃₎ dissolving the solid in chloroform. Solidification with dichloromethane (DCM) and filtration gave 1.9 g (yield: 48.2%) of Compound 4-241 (WS16-35-010) as a white solid.

Example  30: Synthesis of compound 4-384 (WS16-30-060)

2.3 g (8.62 mmol) of 2-chloro-4,6-diphenylpyrimidine, 4.2 g (8.62 mmol) of intermediate (13), Pd (PPh ₃ ) ₄ 0.3 g (0.26 mmol) of toluene and 150 mL of toluene, and 100 mL of ethanol and 100 mL of K ₂ CO ₃ (0.013 mol) / H ₂ O were added while stirring. After the reaction was completed, the reaction mixture was cooled to room temperature, water was added thereto, followed by extraction with dichloromethane (DCM). The organic phase was dried over anhydrous MgSO ₄ and purified by silica gel column chromatography to obtain a white solid compound 4-384 (WS16-30-060) 1.1 g (Yield: 21.6%) was obtained.

Example  31: Synthesis of compound 4-385 (WS16-30-144)

2.3 g (8.62 mmol) of 4-chloro-2,6-diphenylpyrimidine, 4.2 g (8.62 mmol) of intermediate (13) and Pd (PPh ₃ ) ₄ 0.3 g (0.259mmol), insert such as toluene while stirring 150mL of ethanol was added to _{100mL, K 2 CO 3 1.8 g} (0.013mol) / H 2 O 100mL , and stirred for 6 hours under reflux. After the reaction was completed, the reaction mixture was cooled to room temperature, water was added thereto, followed by extraction with dichloromethane (DCM). The organic phase was dried over anhydrous MgSO ₄ and purified by silica gel column chromatography to obtain a white solid compound 4-385 (WS16-30-144) 2.6 g (Yield: 51.1%) was obtained.

Example  32: Synthesis of compound 4-386 (WS16-30-051)

2.3 g (8.59 mmol) of 2-chloro-4,6-diphenyl-1,3,5-triazine was added to a 500 ml one-necked flask, intermediate (13) 4.2 g (8.591mmol) , Pd (PPh 3) 4 0.3 g (0.258mmol), into such a 150mL toluene while stirring the ethanol, _{100mL, K 2 CO 3 1.8 g} (0.013mol) / H 2 O 100mL And the mixture was stirred under reflux for 6 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, water was added thereto, dichloromethane (DCM) extraction was performed, and the organic phase was dried over anhydrous MgSO ₄ and purified by silica gel column chromatography to obtain a white solid compound 4-386 (WS16-30-051) 1.1 g (yield: 21.5%).

Example  33: Synthesis of compound 4-391 (WS16-30-097)

1 Int.12 2.4 g (5.00mmol), Intermediate (13) 2.3 g (5.50mmol) , Pd (PPh 3) 4 0.06 g (0.50mmol) in 250mL flasks, K ₂ CO ₃ 1.7 g (12.5 mmol) of triethylamine, 50 mL of toluene, 25 mL of EtOH and 25 mL of H ₂ O and then refluxed. After the reaction is complete, cool to room temperature and add 200 mL of H ₂ O. The mixture was extracted twice with 300 mL of dichloromethane (DCM), the extract was dried with Na ₂ SO ₄ , filtered and the filtrate was concentrated under reduced pressure. The solid was dissolved in chloroform and purified by silica gel column chromatography (n-hex: EA = 4: 1). Solidification with dichloromethane (DCM) / n-hex and filtration gave 2.1 g (yield: 59.4%) of compound 4-391 (WS16-30-097) as a beige solid.

Example  34: Synthesis of compound 4-394 (WS16-30-120)

The two 250mL flask Int.13 3.0 g (6.15mmol), Intermediate (13) 2.86 g (6.75mmol) , Pd (PPh 3) 4 0.35 g (0.31mmol), toluene 100mL, 50mL EtOH and 2M K ₂ CO ₃ 6.15 mL (12.3 mmol) were mixed and then refluxed. After the reaction was completed, the reaction mixture was cooled at room temperature and the resulting solid was filtered with EtOH. Silica gel by dissolving the solid in chloroform and purified by column chromatography: to give the (CHCl ₃ Hex). Solidified with ethyl acetate (EA) and filtered to obtain 2.9 g (yield: 68.2%) of compound 4-394 (WS16-30-120) as a beige solid.

Example  35: Synthesis of Compound 4-400 (WS16-30-132)

The two 250mL flask Int.14 3.0 g (6.15mmol), Intermediate (13) 1.92 g (6.75mmol) , Pd (PPh 3) 4 0.35 g (0.31mmol), toluene 100mL, 50mL EtOH and 2M K ₂ CO ₃ 6.15 mL (12.3 mmol) were mixed and then refluxed. After the reaction was completed, the reaction mixture was cooled at room temperature and the resulting solid was filtered with EtOH. Silica gel by dissolving the solid in chloroform and purified by column chromatography: to give the (CHCl ₃ Hex). And solidified with ethyl acetate (EA) and filtered to obtain 1.6 g (yield: 47.1%) of a beige solid compound 4-400 (WS16-30-132).

Example  36: Synthesis of Compound 4-408 (WS16-30-100)

The two 250mL flask Int.10 3.0 g (6.15mmol), Intermediate (13) 2.26 g (6.75mmol) , Pd (PPh 3) 4 0.35 g (0.31mmol), toluene 100mL, 50mL EtOH and 2M K ₂ CO ₃ 6.15 mL (12.3 mmol) were mixed and then refluxed. After the reaction was completed, the reaction mixture was cooled at room temperature and the resulting solid was filtered with EtOH. Silica gel by dissolving the solid in chloroform and purified by column chromatography: to give the (CHCl ₃ Hex). Solidified with ethyl acetate (EA) and filtered to obtain 1.5 g (yield: 40.7%) of compound 4-408 (WS16-30-100) as a beige solid.

Example  37: Synthesis of Compound 4-409 (WS16-30-210)

The two 250mL flask Int.11 3.0 g (6.15mmol), Intermediate (13) 2.26 g (6.75mmol) , Pd (PPh 3) 4 0.35 g (0.31mmol), toluene 100mL, 50mL EtOH and 2M K ₂ CO ₃ 6.15 mL (12.3 mmol) were mixed and then refluxed. After the reaction was completed, the reaction mixture was cooled at room temperature and the resulting solid was filtered with EtOH. Silica gel by dissolving the solid in chloroform and purified by column chromatography: to give the (CHCl ₃ Hex). Solidified with ethyl acetate (EA) and filtered to obtain 1.5 g (yield: 40.7%) of compound 4-409 (WS16-30-210) as a beige solid.

Example  38: Synthesis of Compound 4-410 (WS16-30-093)

1 Int.15 3.0 g in 250mL flask (6.1mmol), Intermediate (13) 2.4 g (6.7mmol) , Pd (PPh 3) 4 0.07 g (0.61mmol), K 2 CO 3 2.1 g (15.3mmol), 50 mL of toluene, 25 mL of EtOH and 25 mL of H ₂ O were mixed and then refluxed. After the reaction is complete, cool to room temperature and add 200 mL of H ₂ O. The mixture was extracted twice with 300 mL of dichloromethane (DCM), the extract was dried with Na ₂ SO ₄ , filtered and the filtrate was concentrated under reduced pressure. The solid was dissolved in chloroform and purified by silica gel column chromatography (dichloromethane (DCM): EA = 2: 1). Solidification with dichloromethane (DCM) / n-hex and filtration afforded 2.3 g (yield: 58.2%) of compound 4-410 (WS16-30-093) as a white solid.

Example  39: Synthesis of Compound 4-412 (WS16-30-108)

1 250mL intermediate (34) 3.0 g (6.1mmol) in a flask, intermediate (13) 1.8 g (6.7mmol) , Pd (PPh 3) 4 0.07 g (0.61mmol), K 2 CO 3 2.1 g (15.3 mmol) of toluene, 50 mL of toluene, 25 mL of EtOH and 25 mL of H ₂ O were mixed and then refluxed. After the reaction was completed, the reaction mixture was cooled to room temperature and concentrated under reduced pressure. The solid was dissolved in monochlorobenzene, filtered through silica gel in a hot state, and then concentrated under reduced pressure. Solidification with dichloromethane (DCM) / MeOH and filtration gave 2.6 g of yellow solid compound 4-412 (WS16-30-108) (yield: 76.4%).

Example  40: Synthesis of Compound 4-413 (WS16-30-212)

The two 250mL flask Int.2 2.5g (5.12mmol), Intermediate (13) 1.54 g (5.63mmol) , Pd (PPh 3) 4 0.29 g (0.25mmol), toluene 100mL, 50mL EtOH and 2M K ₂ CO ₃ 5.12 mL (10.2 mmol) were mixed and then refluxed. After the reaction was completed, the reaction mixture was cooled at room temperature and the resulting solid was filtered with EtOH. Silica gel by dissolving the solid in chloroform and purified by column chromatography: to give the (CHCl ₃ HEX). Ethyl acetate (EA) was solidified and filtered to obtain 1.10 g (yield: 38.8%) of a beige solid compound 4-413 (WS16-30-212).

Example  41: Synthesis of Compound 4-415 (WS16-30-211)

The two 250mL flask Int.3 2.5g (5.12mmol), Intermediate (13) 1.63 g (5.63mmol) , Pd (PPh 3) 4 0.29 g (0.25mmol), toluene 100mL, 50mL EtOH and 2M K ₂ CO ₃ 5.12 mL (10.2 mmol) were mixed and then refluxed. After the reaction was completed, the reaction mixture was cooled at room temperature and the resulting solid was filtered with EtOH. Silica gel by dissolving the solid in chloroform and purified by column chromatography: to give the (CHCl ₃ HEX). Solidified with ethyl acetate (EA) and filtered to obtain 1.62 g (yield: 55.7%) of compound 4-415 (WS16-30-211) as a beige solid.

Example  42: Synthesis of Compound 4-416 (WS16-30-095)

The two 250mL flask Int.4 3.0 g (6.15mmol), Intermediate (13) 2.36 g (6.75mmol) , Pd (PPh 3) 4 0.35 g (0.31mmol), toluene 100mL, 50mL EtOH and 2M K ₂ CO ₃ 6.15 mL (12.3 mmol) were mixed and then refluxed. After the reaction was completed, the reaction mixture was cooled at room temperature and the resulting solid was filtered with EtOH. Silica gel by dissolving the solid in chloroform and purified by column chromatography: to give the (CHCl ₃ Hex). Ethyl acetate (EA) was solidified and filtered to obtain 1.2 g (yield: 32.0%) of compound 4-416 (WS16-30-095) as a beige solid.

Example  43: Synthesis of Compound 4-417 (WS16-30-188)

The two 250mL flask Int.5 2.5g (5.12mmol), Intermediate (13) 1.96 g (5.63mmol) , Pd (PPh 3) 4 0.29 g (0.25mmol), toluene 100mL, 50mL EtOH and 2M K ₂ CO ₃ 5.12 mL (10.2 mmol) were mixed and then refluxed. After the reaction was completed, the reaction mixture was cooled at room temperature and the resulting solid was filtered with EtOH. Silica gel by dissolving the solid in chloroform and purified by column chromatography: to give the (CHCl ₃ HEX). Ethyl acetate (EA) was solidified and filtered to obtain 1.42 g (yield: 43.6%) of compound 4-417 (WS16-30-188) as a beige solid.

Example  44: Synthesis of compound 4-418 (WS16-30-067)

1 Int.16 2.4 g (5.00mmol), Intermediate (13) 1.9 g (5.50mmol) , Pd (PPh 3) 4 0.06 g (0.50mmol) in 250mL flasks, K ₂ CO ₃ 1.7 g (12.5 mmol) of triethylamine, 50 mL of toluene, 25 mL of EtOH and 25 mL of H ₂ O were mixed and then refluxed. After the reaction is complete, cool to room temperature and add 200 mL of H ₂ O. The mixture was extracted twice with 300 mL of dichloromethane (DCM), the extract was dried with Na ₂ SO ₄ , filtered and the filtrate was concentrated under reduced pressure. The solid was dissolved in chloroform and purified by silica gel column chromatography (dichloromethane (DCM) / ethyl acetate (EA)). Solidification with dichloromethane (DCM) / n -hex and filtration gave 1.3 g (yield: 43.3%) of compound 4-418 (WS16-30-067) as a beige solid.

Example  45: Synthesis of compound 4-424 (WS16-30-054)

Intermediate 1 (28) 3.0 g (6.47mmol) , Intermediate (13) 3.2 g (6.47mmol) , Pd (PPh 3) to obtain 500mL flask ₄ 0.2 g (0.194 mmol) of triethylamine and 150 mL of toluene. The mixture was stirred, and 100 mL of ethanol and 1.3 g (0.010 mol) of K ₂ CO ₃ / H ₂ O were added and stirred for 7 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 dichloromethane (DCM). The organic phase was dried over anhydrous MgSO ₄ and purified by silica gel column chromatography to obtain a white solid compound 4-424 (WS16-30-054) 1.1 g (Yield: 22.7%) was obtained.

Example  46: Synthesis of Compound 4-425 (WS16-30-046)

1

One

1 Int.1 3.0 g (7.73mmol) in 500mL flask, place the intermediate (13) 3.8 g (7.73mmol) , Pd (PPh 3) 4 0.3 g (0.232mmol), toluene 150mL like while stirring the ethanol, 100mL, was added _{K 2 CO 3 1.6 g (0.012mol} ) / H 2 O 100mL , and stirred for 7 hours under reflux. After the reaction was completed, the reaction mixture was cooled to room temperature, water was added thereto, followed by extraction with dichloromethane (DCM). The organic phase was dried over anhydrous MgSO ₄ and purified by silica gel column chromatography to obtain a white solid compound 4-425 (WS16-30-046) 1.2 g (Yield: 23.5%) was obtained.

Example  47: Synthesis of compound 4-427 (WS16-30-061)

Intermediate 1 (30) 3.0 g (6.47mmol) , Intermediate (13) 3.2 g (6.474mmol) , Pd (PPh 3) to obtain 500mL flask ₄ 0.2 g (0.194 mmol) of toluene and 150 mL of toluene were added together and 100 mL of ethanol and 100 mL of K ₂ CO ₃ (0.010 mol) / H ₂ O were added while stirring, followed by stirring under reflux for 6 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, water was added thereto, and the mixture was extracted with dichloromethane (DCM). The organic phase was dried over anhydrous MgSO ₄ and purified by silica gel column chromatography to obtain a white solid compound 4-427 (WS16-30-061) 1.3 g (Yield: 26.3%).

Example  48: Synthesis of Compound 4-440 (WS16-30-101)

1 Int.6 3.0 g in 250mL flask (6.1mmol), Intermediate (13) 2.3 g (6.7mmol) , Pd (PPh 3) 4 0.07 g (0.6mmol), K 2 CO 3 2.1 g (15.3mmol), 50 mL of toluene, 25 mL of EtOH and 25 mL of H ₂ O were mixed and then refluxed. After the reaction is complete, cool to room temperature and add 200 mL of H ₂ O. The mixture was extracted twice with 300 mL of dichloromethane (DCM), the extract was dried with Na ₂ SO ₄ , filtered and the filtrate was concentrated under reduced pressure. The solid was dissolved in chloroform and purified by silica gel column chromatography (dichloromethane (DCM): ethyl acetate (EA)). Solidification with dichloromethane (DCM) / n- Hex followed by filtration afforded 1.6 g (yield: 42.0%) of 4-440 (WS16-30-101) as a white solid.

Example  49: Synthesis of Compound 4-456 (WS16-30-055)

Intermediate 1 (32) 3.0 g (6.461mmol) , intermediate (13) 3.2 g (6.461mmol) , Pd (PPh 3) to obtain 500mL flask ₄ 0.2 g (0.194 mmol) of toluene and 150 mL of toluene were put together and stirred, and 100 mL of ethanol and 1.3 g (9.691 mmol) of K ₂ CO ₃ / H ₂ O were added and stirred for 7 hours under reflux. After the reaction was completed, the reaction mixture was cooled to room temperature, water was added thereto, followed by extraction with dichloromethane (DCM). The organic phase was dried over anhydrous MgSO ₄ and purified by silica gel column chromatography to obtain a white solid compound 4-456 (WS16-30-055) 1.0 g (Yield: 20.4%).

Example  50: Synthesis of compound 4-462 (WS16-30-215)

In one 250mL flask Int.7 1.89 g (6.36mmol), Intermediate (13) 3.00 g (6.36mmol) , Pd (PPh 3) 4 0.37 g (0.32mmol), toluene 40mL, 10mL EtOH, H ₂ O and 10mL 4.05 g (19.1 mmol) of K ₃ PO ₄ were mixed and then refluxed. After the reaction was completed, the reaction mixture was cooled at room temperature and the resulting solid was filtered with EtOH. The filtrate was purified by silica gel column chromatography (CHCl ₃₎ dissolving the solid in chloroform. Solidified by dichloromethane (DCM) and filtered to obtain 2.5 g (yield: 68.9%) of compound 4-462 (WS16-30-215) as a yellow solid.

Example  51: Synthesis of Compound 4-463 (WS16-30-199)

1 Int.8 necked 250mL flask, 1.78 g (6.36mmol), Intermediate (13) 3.00 g (6.36mmol) , Pd (PPh 3) 4 0.37 g (0.32mmol), toluene 40mL, 10mL EtOH, H ₂ O and 10mL 4.05 g (19.1 mmol) of K ₃ PO ₄ were mixed and then refluxed. After the reaction was completed, the reaction mixture was cooled at room temperature and the resulting solid was filtered with EtOH. The filtrate was purified by silica gel column chromatography (CHCl ₃₎ dissolving the solid in chloroform. Solidification with dichloromethane (DCM) and filtration gave 2.5 g (yield: 73.2%) of compound 4-463 (WS16-30-199) as a yellow solid.

Example  52: Synthesis of compound 4-464 (WS16-30-208)

The two 250mL flask Int.9 2.5g (5.12mmol), Intermediate (13) 2.00 g (5.63mmol) , Pd (PPh 3) 4 0.29 g (0.25mmol), toluene 100mL, 50mL EtOH and 2M K ₂ CO ₃ 5.12 mL (10.2 mmol) were mixed and then refluxed. After the reaction was completed, the reaction mixture was cooled at room temperature and the resulting solid was filtered with EtOH. Silica gel by dissolving the solid in chloroform and purified by column chromatography: to give the (CHCl ₃ HEX). Ethyl acetate (EA) was solidified and filtered to obtain 0.92 g (yield: 28.3%) of compound 4-464 (WS16-30-208) as a beige solid.

Example  53: Synthesis of compound 4-477 (WS16-35-011)

2.3 g (8.62 mmol) of 4-chloro-2,6-diphenylpyrimidine, 4.2 g (8.62 mmol) of intermediate 26 and 8.8 mmol of Pd (PPh ₃₎ ) ₄ 0.3 g (0.259mmol), into such a 150mL toluene was added while stirring the ethanol, _{100mL, K 2 CO 3 1.8 g} (0.013mol) / H 2 O 100mL , and stirred for 6 hours under reflux. After the reaction was completed, the reaction mixture was cooled to room temperature, water was added thereto, followed by extraction with dichloromethane (DCM). The organic phase was dried over anhydrous MgSO ₄ and purified by silica gel column chromatography to obtain a white solid compound 4-477 (WS16-35-011) 2.6 g (Yield: 51.1%) was obtained.

Example  54: Synthesis of compound 4-478 (WS16-35-012)

2.3 g (8.62 mmol) of 2-chloro-4,6-diphenylpyrimidine, 4.2 g (8.62 mmol) of intermediate 26 and 8.8 mmol of Pd (PPh ₃₎ ) ₄ 0.3 g (0.26mmol), insert such a 150mL toluene was added while stirring the ethanol, _{100mL, K 2 CO 3 1.8 g} (0.013mol) / H 2 O 100mL , and stirred for 6 hours under reflux. After the reaction was completed, the reaction mixture was cooled to room temperature, water was added thereto, followed by extraction with dichloromethane (DCM). The organic phase was dried over anhydrous MgSO ₄ and purified by silica gel column chromatography to obtain a white solid compound 4-478 (WS16-35-012) 1.1 g (Yield: 21.6%) was obtained.

Example  55: Synthesis of compound 4-479 (WS16-35-013)

2.3 g (8.59 mmol) of 2-chloro-4,6-diphenyl-1,3,5-triazine was added to a 500 ml one-necked flask, intermediate (26) 4.2 g (8.591mmol) , Pd (PPh 3) 4 0.3 g (0.258mmol), into such a 150mL toluene while stirring the ethanol, _{100mL, K 2 CO 3 1.8 g} (0.013mol) / H 2 O 100mL And the mixture was stirred under reflux for 6 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, water was added thereto, dichloromethane (DCM) extraction was performed, and the organic phase was dried over anhydrous MgSO ₄ and purified by silica gel column chromatography to obtain a white solid compound 4-479 (WS16-35-013) 1.1 g (yield: 21.5%).

Example  56: Synthesis of Compound 4-501 (WS16-35-014)

1 Int.10 3.0 g in 250mL flask (6.1mmol), Intermediate (26) 2.3 g (6.7mmol) , Pd (PPh 3) 4 0.07 g (0.6mmol), K 2 CO 3 2.1 g (15.3mmol), 50 mL of toluene, 25 mL of EtOH and 25 mL of H ₂ O were mixed and then refluxed. After the reaction is complete, cool to room temperature and add 200 mL of H ₂ O. The mixture was extracted twice with 300 mL of dichloromethane (DCM), the extract was dried with Na ₂ SO ₄ , filtered and the filtrate was concentrated under reduced pressure. The solid was dissolved in chloroform and purified by silica gel column chromatography (dichloromethane (DCM): ethyl acetate (EA)). Solidification with dichloromethane (DCM) / n- Hex and filtration gave 1.6 g (yield: 42.0%) of compound 4-501 as a white solid (WS16-35-014).

Example  57: Synthesis of compound 4-505 (WS16-35-015)

2 intermediate to 250mL flask (34) 2.5g (5.12mmol), Intermediate (26) 1.54 g (5.63mmol) , Pd (PPh 3) 4 0.29 g (0.25mmol), toluene 100mL, 50mL EtOH and 2M K ₂ CO ₃ (5.12 mL, 10.2 mmol) were mixed and then refluxed. After the reaction was completed, the reaction mixture was cooled at room temperature and the resulting solid was filtered with EtOH. Silica gel by dissolving the solid in chloroform and purified by column chromatography: to give the (CHCl ₃ HEX). Solidified with ethyl acetate (EA) and filtered to obtain 1.10 g (yield: 38.8%) of compound 4-505 (WS16-35-015) as a beige solid.

Example  58: Synthesis of Compound 4-520 (WS16-35-016)

Intermediate 1 (30) 3.0 g (6.47mmol) , Intermediate (26) 3.2 g (6.47mmol) , Pd (PPh 3) to obtain 500mL flask ₄ 0.2 g (0.194 mmol) of toluene and 150 mL of toluene were added together and 100 mL of ethanol and 100 mL of K ₂ CO ₃ (0.010 mol) / H ₂ O were added while stirring, and the mixture was stirred under reflux for 7 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, water was added thereto, followed by extraction with dichloromethane (DCM). The organic phase was dried over anhydrous MgSO ₄ and purified by silica gel column chromatography to obtain a white solid compound 4-520 (WS16-35-016) 1.1 g (Yield: 22.7%) was obtained.

Example  59: Synthesis of compound 4-569 (WS16-35-017)

2.3 g (8.62 mmol) of 2-chloro-4,6-diphenylpyrimidine, 4.2 g (8.62 mmol) of intermediate (16) and Pd (PPh ₃ ) ₄ 0.3 g (0.26mmol), insert such a 150mL toluene was added while stirring the ethanol, _{100mL, K 2 CO 3 1.8 g} (0.013mol) / H 2 O 100mL , and stirred for 6 hours under reflux. After the reaction was completed, the reaction mixture was cooled to room temperature, water was added thereto, followed by extraction with dichloromethane (DCM). The organic phase was dried over anhydrous MgSO ₄ and purified by silica gel column chromatography to obtain a white solid compound 4-569 (WS16-35-017) 1.1 g (Yield: 21.6%) was obtained.

Example  60: Synthesis of compound 4-593 (WS16-35-018)

The two 250mL flask Int.10 3.0 g (6.15mmol), Intermediate (16) 2.26 g (6.75mmol) , Pd (PPh 3) 4 0.35 g (0.31mmol), toluene 100mL, 50mL EtOH and 2M K ₂ CO ₃ 6.15 mL (12.3 mmol) were mixed and then refluxed. After the reaction was completed, the reaction mixture was cooled at room temperature and the resulting solid was filtered with EtOH. Silica gel by dissolving the solid in chloroform and purified by column chromatography: to give the (CHCl ₃ Hex). Solidified with ethyl acetate (EA) and filtered to obtain 1.5 g (yield: 40.7%) of compound 4-593 (WS16-35-018) as a beige solid.

Example  61: Synthesis of compound 4-612 (WS16-35-019)

Intermediate 1 (30) 3.0 g (6.47mmol) , Intermediate (16) 3.2 g (6.47mmol) , Pd (PPh 3) to obtain 500mL flask ₄ 0.2 g (0.194 mmol) of toluene and 150 mL of toluene were added together and 100 mL of ethanol and 100 mL of K ₂ CO ₃ (0.010 mol) / H ₂ O were added while stirring, and the mixture was stirred under reflux for 7 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, water was added thereto, followed by extraction with dichloromethane (DCM). The organic phase was dried over anhydrous MgSO ₄ and purified by silica gel column chromatography to obtain a white solid compound 4-612 (WS16-35-019) 1.1 g (Yield: 22.7%) was obtained.

≪ 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 and are shown in Tables 1 and 2 below.

UV / VIS  And PL  result division compound UV (nm) * 1 PL (nm, room temperature) * 2 One 4-12 (WS16-30-086) 259, 292, 304, 362, 380 387.5, 407.5, 728.5 2 4-13 (WS16-30-168) 260, 279, 362, 381 390.5, 410.5 3 4-14 (WS16-30-087) 280, 308, 365, 383 396, 414 4 4-36 (WS16-30-180) 253, 299, 358, 379 392, 411, 470.5, 504.5 5 4-37 (WS16-30-179) 258, 293, 358, 377 389.5, 408.5 6 4-40 (WS16-30-156) 322, 330, 381 393.5, 414 7 4-41 (WS16-30-173) 295, 359, 377 388, 407.5 8 4-42 (WS16-30-174) 333, 381 395, 416 9 4-43 (WS16-30-185) 295, 359, 377 388.5, 407.5 10 4-44 (WS16-30-181) 319, 360, 380 394.5, 414.5 11 4-45 (WS16-30-172) 295, 359, 377 389, 408 12 4-52 (WS16-30-089) 304, 333, 380 393.5, 414 13 4-53 (WS16-30-084) 279, 359, 377 389, 408 14 4-55 (WS16-30-085) 283, 358, 377 389, 408 15 4-68 (WS16-30-182) 254, 291, 315, 359, 378 392, 410.5 16 4-84 (WS16-30-088) 273, 316, 332, 384 395, 415 17 4-90 (WS16-30-186) 262, 298, 322, 335, 373, 385 425.5, 450 18 4-91 (WS16-30-184) 259, 296, 336, 364, 399 415, 439 19 4-92 (WS16-30-178) 295, 323, 336, 366 425, 447 20 4-105 (WS16-35-001) 298, 324, 337, 376, 407 426.5, 451.5 21 4-107 (WS15-35-003) 297, 337, 369, 403 417.5, 441.5 22 4-129 (WS16-35-007) 277, 298, 324, 338, 370, 404 427, 448.5 23 4-133 (WS16-35-005) 253, 299, 358, 379 392, 411, 470.5, 504.5 24 4-148 (WS16-35-006) 258, 293, 358, 377 389.5, 408.5 25 4-198 (WS16-35-002) 322, 330, 381 393.5, 414 26 4-200 (WS16-35-004) 295, 359, 377 388, 407.5 27 4-222 (WS16-35-008) 333, 381 395, 416 28 4-227 (WS16-35-009) 295, 359, 377 388.5, 407.5 29 4-241 (WS16-35-010) 319, 360, 380 394.5, 414.5 30 4-384 (WS16-30-060) 253, 301, 369, 388 302, 397 31 4-385 (WS16-30-144) 272, 296, 316, 370, 389 399.5, 419.5 32 4-386 (WS16-30-051) 243, 276, 301, 372, 391 405, 422 33 4-391 (WS16-30-097) 261, 362, 380, 397 439 34 4-394 (WS16-30-120) 260, 283, 360, 380, 397 430.5 35 4-400 (WS16-30-132) 233, 302, 370, 388 402.5, 420 36 4-408 (WS16-30-100) 244, 301, 368, 388 400, 419 37 4-409 (WS16-30-210) 254, 298, 368, 386 398.5, 417 38 4-410 (WS16-30-093) 300, 368, 387 398, 417.5 * 1: 1.0 x 10 ^-5 M in Methylene Chloride
* 2: 5.0 x 10 ^-6 M in Methylene Chloride

UV / VIS  And PL  result division compound UV (nm) * 1 PL (nm, room temperature) * 2 39 4-412 (WS16-30-108) 321, 332, 369, 389 401.5, 421.5 40 4-413 (WS16-30-212) 233, 298, 368, 386 397.5, 416.5 41 4-415 (WS16-30-211) 298, 368, 386 398, 416.5 42 4-416 (WS16-30-095) 319, 369, 389 402, 421 43 4-417 (WS16-30-188) 236, 298, 368, 386 398, 417 44 4-418 (WS16-30-067) 299, 369, 387 399, 417.5 45 4-424 (WS16-30-054) 304, 334, 389 401.5, 421 46 4-425 (WS16-30-046) 281, 367, 386 398.5, 417 47 4-427 (WS16-30-061) 237, 294, 368, 386 388, 417 48 4-440 (WS16-30-101) 251, 299, 316, 368, 387 400, 418.5 49 4-456 (WS16-30-055) 279, 309, 334, 391 403, 422.5 50 4-462 (WS16-30-215) 298, 324, 337, 376, 407 426.5, 451.5 51 4-463 (WS16-30-199) 297, 337, 369, 403 417.5, 441.5 52 4-464 (WS16-30-208) 277, 298, 324, 338, 370, 404 427, 448.5 53 4-477 (WS16-35-011) 253, 299, 358, 379 392, 411, 470.5, 504.5 54 4-478 (WS16-35-012) 258, 293, 358, 377 389.5, 408.5 55 4-479 (WS16-35-013) 322, 330, 381 393.5, 414 56 4-501 (WS16-35-014) 295, 359, 377 388, 407.5 57 4-505 (WS16-35-015) 333, 381 395, 416 58 4-520 (WS16-35-016) 295, 359, 377 388.5, 407.5 59 4-569 (WS16-35-017) 319, 360, 380 394.5, 414.5 60 4-593 (WS16-35-018) 295, 359, 377 389, 408 61 4-612 (WS16-35-019) 304, 333, 380 393.5, 414 * 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.

Comparative Example : ITO / 2- TNATA ( 60 nm ) / NPB ( 20 nm ) / αβ - ADN: 10% Pyrene - CN (30 nm) / Alq 3 (30 nm) / Liq (2 nm) / Al (100 nm)

The blue fluorescent organic light-emitting device was prepared in the same manner as in Example 1 except that ITO (180 nm) / 2-TNATA (60 nm) / NPB (20 nm) / αβ-ADN: Pyrene-CN 10% (30 nm) / electron transport layer nm) / Al (100 nm) in this order. Before depositing the organic material, the ITO electrode was subjected to oxygen plasma treatment at 125 W for 2 minutes at 2 × 10 ^-2 Torr. Organics are 9 × 10 ^- were deposited at a vacuum degree of ⁷ Torr Liq was 0.1 Å / sec, αβ-ADN was co-deposited with Pyrene-CN is 0.02 Å / sec on the basis of 0.18 Å / sec, the remaining organic matter are both 1 Å / sec. < / RTI > 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.

< Test Example  1 to 61>

In the above comparative test examples, devices were prepared in the same manner as in the comparative test except that each compound shown in Tables 3 and 4 was used instead of Alq ₃ .

Table 3 and Table 4 show the electroluminescent characteristics of the organic luminescent devices prepared in the above Comparative Test Examples and Test Examples 1 to 61.

division compound Driving voltage
[V] efficiency
[cd / A] life span
(%) Comparative Example Alq ₃ 6.60 5.10 91.78 Test Example 1 4-12 (WS16-30-086) 3.42 9.12 98.64 Test Example 2 4-13 (WS16-30-168) 3.51 8.16 96.61 Test Example 3 4-14 (WS16-30-087) 4.12 7.24 98.31 Test Example 4 4-36 (WS16-30-180) 3.51 7.95 96.79 Test Example 5 4-37 (WS16-30-179) 4.30 7.58 95.69 Test Example 6 4-40 (WS16-30-156) 3.32 8.32 97.58 Test Example 7 4-41 (WS16-30-173) 3.72 8.87 95.68 Test Example 8 4-42 (WS16-30-174) 3.46 7.96 97.67 Test Example 9 4-43 (WS16-30-185) 3.67 8.51 94.89 Test Example 10 4-44 (WS16-30-181) 3.73 7.86 97.21 Test Example 11 4-45 (WS16-30-172) 4.32 7.33 97.15 Test Example 12 4-52 (WS16-30-089) 3.49 6.76 98.29 Test Example 13 4-53 (WS16-30-084) 3.51 7.95 96.79 Test Example 14 4-55 (WS16-30-085) 3.28 8.81 98.58 Test Example 15 4-68 (WS16-30-182) 3.56 8.43 97.29 Test Example 16 4-84 (WS16-30-088) 3.97 5.76 98.64 Test Example 17 4-90 (WS16-30-186) 4.00 5.82 98.61 Test Example 18 4-91 (WS16-30-184) 3.73 6.67 97.52 Test Example 19 4-92 (WS16-30-178) 3.43 7.89 97.65 Test Example 20 4-105 (WS16-35-001) 4.15 6.68 98.47 Test Example 21 4-107 (WS16-35-003) 3.40 7.28 95.95 Test Example 22 4-129 (WS16-35-007) 3.33 7.74 99.77 Test Example 23 4-133 (WS16-35-005) 3.50 8.30 99.06 Test Example 24 4-148 (WS16-35-006) 3.70 8.90 95.61 Test Example 25 4-198 (WS16-35-002) 4.03 8.31 95.98 Test Example 26 4-200 (WS16-35-004) 3.93 7.57 98.64 Test Example 27 4-222 (WS16-35-008) 3.30 8.54 98.19 Test Example 28 4-227 (WS16-35-009) 3.70 8.82 97.49 Test Example 29 4-241 (WS16-35-010) 3.51 8.78 96.99 Test Example 30 4-384 (WS16-30-060) 3.37 9.21 97.72 Test Example 31 4-385 (WS16-30-144) 3.53 7.30 97.92 Test Example 32 4-386 (WS16-30-051) 4.15 6.68 98.47 Test Example 33 4-391 (WS16-30-097) 3.40 7.28 95.95 Test Example 34 4-394 (WS16-30-120) 3.33 7.74 99.77 Test Example 35 4-400 (WS16-30-132) 3.50 8.30 99.06 Test Example 36 4-408 (WS16-30-100) 3.70 8.90 95.61 Test Example 37 4-409 (WS16-30-210) 4.03 8.31 95.98 Test Example 38 4-410 (WS16-30-093) 3.93 7.57 98.64

division compound Driving voltage
[V] efficiency
[cd / A] life span
(%) Test Example 39 4-412 (WS16-30-108) 3.30 8.54 98.19 Test Example 40 4-413 (WS16-30-212) 3.70 8.82 97.49 Test Example 41 4-415 (WS16-30-211) 3.51 8.78 96.99 Test Example 42 4-416 (WS16-30-095) 3.60 8.68 96.10 Test Example 43 4-417 (WS16-30-188) 4.06 7.95 97.54 Test Example 44 4-418 (WS16-30-067) 4.05 8.19 98.40 Test Example 45 4-424 (WS16-30-054) 3.32 8.04 98.56 Test Example 46 4-425 (WS16-30-046) 3.85 7.27 100.62 Test Example 47 4-427 (WS16-30-061) 3.39 8.75 98.85 Test Example 48 4-440 (WS16-30-101) 3.43 8.81 97.79 Test Example 49 4-456 (WS16-30-055) 4.13 6.17 98.56 Test Example 50 4-462 (WS16-30-215) 3.96 5.79 98.74 Test Example 51 4-463 (WS16-30-199) 3.77 6.62 97.99 Test Example 52 4-464 (WS16-30-208) 3.45 7.93 97.55 Test Example 53 4-477 (WS16-35-011) 3.51 7.95 96.79 Test Example 54 4-478 (WS16-35-012) 4.30 7.58 95.69 Test Example 55 4-479 (WS16-35-013) 3.32 8.32 97.58 Test Example 56 4-501 (WS16-35-014) 3.72 8.87 95.68 Test Example 57 4-505 (WS16-35-015) 3.46 7.96 97.67 Test Example 58 4-520 (WS16-35-016) 3.67 8.51 94.89 Test Example 59 4-569 (WS16-35-017) 3.73 7.86 97.21 Test Example 60 4-593 (WS16-35-018) 4.32 7.33 97.15 Test Example 61 4-612 (WS16-35-019) 3.49 6.76 98.29

From the results of Tables 3 and 4, the specific aryl group or heteroaryl group-substituted phenanthridine derivative compound 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 (7)

An aryl group or a heteroaryl group-substituted polycyclic phenanthridine derivative represented by the following formula (1).
[Chemical Formula 1]

[In the formula 1,
Ar &lt; ₁ &gt; is phenyl or pyridyl,
Z ₁ is O or S,
L is phenyl or pyridyl,
Ar &lt; ₂ &gt; is any one selected from the group consisting of the following formula (3)
(3)
,

,

,

,

[Formula 3]
Z ₂ is O or S,
Ar ₃ and Ar ₄ are each independently hydrogen, phenyl, naphthyl or biphenyl,
X ₁ to X ₃ are each independently CH or N.] The method according to claim 1,
The phenanthridine derivative of Formula 1 is an aryl or heteroaryl group-substituted phenanthridine derivative selected from the group consisting of the following Formula 4.
[Chemical Formula 4]

An organic electroluminescent device comprising the aryl group or the heteroaryl group-substituted polycyclic phenanthridine derivative of claim 1 or 2. The method of claim 3,
Wherein the aryl group or the heteroaryl group-substituted polycyclic phenanthridine derivative 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 layer comprises the aryl group or the heteroaryl group substituted polycyclic phenanthridine derivative of claim 1 or 2. 6. The method of claim 5,
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. 6. The method of claim 5,
The aryl group or the heteroaryl group substituted polycyclic phenanthridine derivative is preferably selected from the group consisting of an electron blocking layer, an electron transporting layer, an electron injecting layer, a functional layer having both an electron transporting function and an electron injecting function, The organic electroluminescent device is included in any one selected layer.

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