KR101840313B1 - Pyridine derivative compound and organic electroluminescent device comprising the same - Google Patents

Abstract

The present invention relates to a pyridine derivative represented by the following formula (1) and an organic electroluminescent device including the same, wherein the pyridine derivative compound according to the present invention is a compound having high triplet energy (T1) and high thermal stability, The organic electroluminescent device including the same is stable and excellent in light emission characteristics such as luminance, color purity and long life.
[Chemical Formula 1]

Description

[0001] The present invention relates to a pyridine derivative compound and an organic electroluminescent device including the same,

The present invention relates to a pyridine compound and an organic electroluminescent device including the same, and more particularly, to a pyridine compound having a low driving voltage and excellent in light emission characteristics such as brightness, color purity and long life, and an organic electroluminescent device including the same .

In recent years, the demand for a flat display device having a small space occupation has been increasing due to the enlargement of a display device. The liquid crystal display, which is a typical flat display device, has an advantage of being lighter than a conventional CRT (cathode ray tube) angle is limited and a back light is necessarily required. On the other hand, an organic light emitting diode (OLED), which is a new flat display device, is a display using a self-luminous phenomenon, has a large viewing angle, is slimmer and smaller than a liquid crystal display, And in recent years, application to a full-color display or illumination is expected.

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 electroluminescent device using an organic light emitting phenomenon usually has a structure including an anode, an anode, and an organic material layer therebetween. Here, in order to enhance the efficiency and stability of the organic electroluminescent 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 the two electrodes in the structure of such an organic electroluminescent device, holes are injected into the anode, electrons are injected into the organic layer from the cathode, excitons are formed when injected holes and electrons meet, When it falls back to the ground state, the light comes out. Such an organic electroluminescent device is known to have properties 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 electroluminescent 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 light emitting material may be classified into a polymer type and a low molecular type depending on the molecular weight and may be classified into a fluorescent material derived from singlet excited state of electrons and a phosphorescent material derived from the triplet excited state of electrons according to an emission mechanism . Further, the light emitting material can be classified into blue, green, and red light emitting materials and yellow and orange light emitting materials required to realize better natural color depending on the luminescent color.

On the other hand, when only one material is used as a light emitting material, there arises a problem that the maximum light emission wavelength shifts to a long wavelength due to intermolecular interaction, the color purity decreases, or the efficiency of the device decreases due to the light emission attenuating effect. A host / dopant system may be used as the light emitting material in order to increase the light emitting efficiency through the light emitting layer. When the dopant having a smaller energy band gap than the host forming the light emitting layer is mixed with a small amount of the light emitting layer, the excitons generated in the light emitting layer 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, light of a desired wavelength can be obtained depending on the type of dopant used.

In order for the organic electroluminescent device to sufficiently exhibit the above-described excellent characteristics, materials 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 are supported by a stable and efficient material However, the development of a stable and efficient organic material layer material for an organic electroluminescence device has not been sufficiently developed yet. Therefore, there is a continuing need in the art for the development of new materials.

Therefore, the first problem to be solved by the present invention is to provide a long-life pyridine derivative compound having excellent luminance and color purity of green phosphorescence.

A second object of the present invention is to provide an organic electroluminescent device comprising the pyridine derivative compound.

In order to achieve the first object of the present invention,

There is provided a pyridine derivative represented by the following formula (1).

[Chemical Formula 1]

In the above formula (1)

R ₁ to R ₅ each independently represent a hydrogen atom, a deuterium atom, a halogen atom, a nitro group, a substituted or unsubstituted aryl group having 6 to 40 carbon atoms, a substituted or unsubstituted heteroaryl group having 2 to 40 carbon atoms, A substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 6 to 40 carbon atoms, a substituted or unsubstituted amino group having 2 to 40 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 40 carbon atoms, A substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C1- A substituted or unsubstituted C6-C40 cycloalkylene group, a substituted or unsubstituted C1-C20 alkyl Group is selected from substituted or unsubstituted germanium group, a substituted or unsubstituted, a substituted or unsubstituted boron,

At least one of R ₁ , R ₂ and R ₃ is A,

o is an integer from 0 to 4,

When o is 2 or more, plural R ₄ and R ₅ may each independently be the same or different.

According to an embodiment of the present invention, each of R ₁ to R ₅ independently represents an aryl group having 6 to 24 carbon atoms, a heteroaryl group having 2 to 24 carbon atoms, an alkyl group having 1 to 24 carbon atoms, a heteroalkyl group having 1 to 24 carbon atoms , An alkoxy group having 1 to 24 carbon atoms, a cyano group, a halogen group, an aryloxy group having 6 to 24 carbon atoms, a silyl group having 1 to 24 carbon atoms, hydrogen, and deuterium.

According to another aspect of the present invention,

Anode; Cathode; And a layer comprising a pyridine derivative compound represented by the formula (1) interposed between the anode and the cathode.

Since the pyridine derivative represented by Formula 1 according to the present invention is a compound having a high triplet energy (T1) and high thermal stability, the organic electroluminescent device including the pyridine derivative compound is excellent in brightness, color purity, And can be usefully used for display and illumination.

1 is a schematic view of an organic electroluminescent device according to one embodiment of the present invention.
2 is a graph showing TGA and DSC according to an embodiment of the present invention.
3 is a graph showing TGA and DSC according to one embodiment of the present invention.
4 is a graph showing TGA and DSC of Formula 181 according to an embodiment of the present invention.
5 is a graph showing EL spectra of Formula 25 and Comparative Example 1 according to an embodiment of the present invention.
6 is a schematic diagram showing the structure of a pyridine derivative compound according to the present invention.

Hereinafter, the present invention will be described in more detail.

The pyridine derivative compound according to the present invention is characterized by having a high triplet energy (T1) and a high thermal stability, which are represented by the above formula (1) and are characterized in that various substituents are bonded to the pyridine derivative compound.

In the pyridine compound according to the present invention, the substituents of the above formula (1) will be more specifically described below.

Wherein R ₁ to R ₅ each independently represent an aryl group having 6 to 24 carbon atoms, a heteroaryl group having 2 to 24 carbon atoms, an alkyl group having 1 to 24 carbon atoms, a heteroalkyl group having 1 to 24 carbon atoms, A cyano group, a halogen group, an aryloxy group having 6 to 24 carbon atoms, a silyl group having 1 to 24 carbon atoms, hydrogen, and deuterium.

Specific examples of the alkyl group as the substituent used in the present invention include a methyl group, an ethyl group, a propyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an isoamyl group, a hexyl group, a heptyl group, A halogen atom, a hydroxyl group, a nitro group, a cyano group, a trifluoromethyl group, a silyl group (in this case, a " alkylsilyl group "hereinafter), a substituted or unsubstituted amino group _{(-NH 2, -NH (R)} , -N (R ') (R"), where R, R' and R "are independently C 1 each A hydrazine group, a hydrazone group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, an alkyl group having 1 to 24 carbon atoms, a halogenated alkyl group having 1 to 24 carbon atoms, an alkylamino group having 1 to 24 carbon atoms, An alkenyl group having 2 to 24 carbon atoms, an alkynyl group having 2 to 24 carbon atoms, An aryl group having from 5 to 24 carbon atoms, an aryl group having from 5 to 24 carbon atoms, an arylalkyl group having from 6 to 24 carbon atoms, a heteroaryl group having from 3 to 24 carbon atoms, or a heteroarylalkyl group having from 3 to 24 carbon atoms.

Specific examples of the alkoxy group used as the substituent in the compound of the present invention include methoxy, ethoxy, propoxy, isobutyloxy, sec-butyloxy, pentyloxy, isoamyloxy, And can be substituted with substituents similar to those in the case of the alkyl group.

Specific examples of the halogen group which is a substituent used in the compound of the present invention include fluorine (F), chlorine (Cl), bromine (Br) and the like.

Specific examples of the aryl group as the substituent group used in the compound of the present invention include a phenyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, a 4-ethylphenyl group, Examples of the aryl group include phenyl group, 4-methylbiphenyl group, 4-ethylbiphenyl group, o-terphenyl group, m-terphenyl group, p-terphenyl group, 1-naphthyl group, , Anthryl group, phenanthryl group, pyrenyl group, fluorenyl group, tetrahydronaphthyl group and the like, which may be substituted with the same substituents as those in the case of the alkyl group.

Specific examples of the heteroaryl group used as the substituent in the compound of the present invention include pyridinyl, pyrimidinyl, triazinyl, indolinyl, quinolinyl, pyrrolidinyl, piperidinyl, An oxazolyl group, an oxadiazolyl group, a benzoxazolyl group, a thiazolyl group, a thiadiazolyl group, a benzothiazolyl group, a triazolyl group, an imidazolyl group, a benzoimidazole group, And at least one of the hydrogen atoms of the heteroaryl group may be substituted with the same substituent as the alkyl group.

In the present invention, the term "substituted or unsubstituted" means a group selected from the group consisting of hydrogen, deuterium, a halogen group, a cyano group, an alkyl group, an alkoxy group, an aryl group, a heteroaryl group, a heteroalkyl group, Substituted or unsubstituted with one or more substituents.

Although the present invention is not limited by the specific examples of the pyridine derivative compounds according to the above formula (1) having the above-mentioned structure, specifically, any one of the compounds represented by formulas (2) to (193) .

[Chemical Formula 2] < EMI ID =

[Chemical Formula 7] [Chemical Formula 8] [Chemical Formula 9]

[Chemical Formula 11] [Chemical Formula 12] [Chemical Formula 13]

[Chemical Formula 14] [Chemical Formula 15]

[Chemical Formula 20] [Chemical Formula 20]

[Chemical Formula 22] [Chemical Formula 23] [Chemical Formula 25]

[Chemical Formula 28] [Chemical Formula 28]

[Chemical Formula 32] [Chemical Formula 32]

[Chemical Formula 35] [Chemical Formula 35]

[Chemical Formula 40] [Chemical Formula 40] [Chemical Formula 40]

[Chemical Formula 43] [Chemical Formula 44] [Chemical Formula 45]

[Chemical Formula 48] [Chemical Formula 48] [Chemical Formula 48]

[Chemical Formula 51] [Chemical Formula 52] [Chemical Formula 53]

[Chemical Formula 55] [Chemical Formula 55] [Chemical Formula 55]

[Chemical Formula 60] [Chemical Formula 61]

[Chemical Formula 62] [Chemical Formula 65] [Chemical Formula 65]

[Chemical Formula 67] [Chemical Formula 68] [Chemical Formula 69]

[Chemical Formula 71] [Chemical Formula 72] [Chemical Formula 73]

[Chemical Formula 75] [Chemical Formula 76] [Chemical Formula 77]

[Formula 79] [Formula 80] [Formula 81]

[Chemical Formula 82]

[Chemical Formula 88] [Chemical Formula 88] [Chemical Formula 89]

[Chemical Formula 91] [Chemical Formula 92] [Chemical Formula 93]

[Chemical Formula 95] [Chemical Formula 96] [Chemical Formula 97]

[Chemical Formula 100] [Chemical Formula 100]

[Formula 103] [Formula 103]

[Chemical Formula 10] [Chemical Formula 10] [Chemical Formula 10] [Chemical Formula 10]

[Formula 110] [Formula 111] [Formula 112] [Formula 113]

[Chemical Formula 115]

[Chemical Formula 120] [Chemical Formula 120] [Chemical Formula 120]

[Formula 124] [Formula 124] [Formula 125]

[Formula 126] < EMI ID = 129.1 >

[Formula 130] < EMI ID = 131.0 >

[Formula 135] [Formula 135] [Formula 137]

[Chemical Formula 140] [Chemical Formula 140] [Chemical Formula 140]

[Chemical Formula 144] [Chemical Formula 144] [Chemical Formula 145]

[Chemical Formula 146] [Chemical Formula 148] [Chemical Formula 149]

[Formula 15] [Formula 15] [Formula 15] [Formula 15]

[Chemical Formula 155] [Chemical Formula 156] [Chemical Formula 157]

[Formula 15] [Formula 15] [Formula 15] [Formula 15] [Formula 15]

[166] [165] [165]

[Formula 166] [Formula 169] [Formula 169]

[173] [173] [173]

[Formula 177] [Formula 177] [Formula 177]

[Formula 181] [Formula 181] [Formula 181] [Formula 181]

[Formula 182] [Formula 184] [Formula 184]

[Formula 188] [Formula 188] [Formula 189]

[Formula 19] [Formula 19] [Formula 193] [Formula 193]

The method for producing the pyridine derivative compound according to the present invention is specifically shown in the following Examples.

The present invention also relates to a fuel cell comprising an anode; Cathode; And a layer comprising a pyridine derivative compound represented by the formula (1) interposed between the anode and the cathode.

In this case, the layer containing the pyridine derivative compound is preferably a light emitting layer between the anode and the cathode, and a hole injecting layer, a hole transporting layer, an electron blocking layer, a hole blocking layer, an electron transporting layer, ≪ RTI ID = 0.0 > and / or < / RTI >

In addition, according to another embodiment of the present invention, the thickness of the light emitting layer is preferably 0.5 nm to 500 nm, and the light emitting layer may further include Ir (ppy) ₃ of the following structural formula.

[Ir (ppy) ₃ ]

As a specific example, a hole transport layer (HTL) may be additionally stacked, and an electron transport layer (ETL) may be further stacked between the cathode and the organic emission layer. An electron donor molecule having a low ionization potential is used as the material of the hole transport layer. A diamine, triamine or tetraamine derivative having a basic skeleton of triphenylamine is used as the material of the hole transport layer. It is widely used.

In the present invention, the material for the hole transport layer is not particularly limited as long as it is commonly used in the art. For example, N, N'-bis (3-methylphenyl) -N, N'- , 1-biphenyl] -4,4'-diamine (TPD) or N, N'-di (naphthalene-1-yl) -N, N'-diphenylbenzidine (a-NPD).

A HIL (Hole Injection Layer) may be additionally deposited on the lower portion of the hole transport layer. The material for the hole injection layer is not particularly limited as long as it is commonly used in the art. For example, (4,4 ', 4 "-tri (N-carbazolyl) triphenylamine), m-MTDATA (4,4', 4" -tris- (3-methylphenylphenylamino) triphenylamine).

In addition, the electron transport layer used in the organic electroluminescent device according to the present invention can transport electrons supplied from the cathode smoothly to the organic luminescent layer and inhibit the movement of holes which are not bonded in the organic luminescent layer, . The material of the electron transport layer is not particularly limited as long as it is commonly used in the art. For example, oxadiazole derivative PBD, BMD, BND or Alq ₃ can be used.

Meanwhile, an electron injection layer (EIL) may be further formed on the electron transport layer to facilitate injection of electrons from the cathode to ultimately improve power efficiency. The electron injection layer material As long as it is commonly used in the art, it can be used without any particular limitation. For example, materials such as LiF, NaCl, CsF, Li ₂ O, and BaO can be used.

The organic electroluminescent device according to the present invention can be used for a display device, a display device, an element for a single color or a white light, and the like.

1 is a cross-sectional view showing the structure of an organic electroluminescent device of the present invention. The organic electroluminescent device according to the present invention includes an anode 20, a hole transport layer 40, an organic emission layer 50, an electron transport layer 60 and a cathode 80, The electron injecting layer 70 may be further formed. In addition, one or two intermediate layers may be further formed, or a hole blocking layer or an electron blocking layer may be further formed.

Referring to FIG. 1, the organic electroluminescent device of the present invention and its manufacturing method will be described as follows. First, an anode electrode material is coated on the substrate 10 to form an anode 20. Here, as the substrate 10, an organic substrate or a transparent plastic substrate which is excellent in transparency, surface smoothness, ease of handling, and waterproofness is used as a substrate used in a conventional organic EL device. As the material for the anode electrode, indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO ₂ ), zinc oxide (ZnO) and the like which are transparent and excellent in conductivity are used.

A hole injection layer 30 is formed on the anode 20 by vacuum thermal deposition or spin coating. Subsequently, a hole transport layer 40 is formed by vacuum thermal deposition or spin coating on the hole transport layer 30 above the hole injection layer 30. A hole blocking layer (not shown) is selectively formed on the organic light emitting layer 50 by a vacuum deposition method or a spin coating method to form a thin film on the organic light emitting layer 50 can do. In the case where holes are injected into the cathode through the organic light-emitting layer, the lifetime and the efficiency of the device are reduced, and thus the hole blocking layer plays a role of preventing such a problem by using a material having a very low HOMO (Highest Occupied Molecular Orbital) level . In this case, the hole blocking material to be used is not particularly limited, but it is required to have an ionization potential higher than that of the light emitting compound while having electron transporting ability. Typically, BAlq, BCP, TPBI and the like can be used.

After the electron transport layer 60 is deposited on the hole blocking layer by a vacuum deposition method or a spin coating method, an electron injection layer 70 is formed, and a cathode forming metal is deposited on the electron injection layer 70 in a vacuum heat- And the cathode 80 is formed by vapor deposition to complete the organic EL device. Here, as the metal for forming the cathode, lithium, magnesium, aluminum, aluminum-lithium, calcium, magnesium-magnesium, Mg-Ag), and a transmissive cathode using ITO or IZO can be used to obtain a top light-emitting device.

According to another embodiment of the present invention, at least one layer selected from the hole injecting layer, the hole transporting layer, the electron blocking layer, the light emitting layer, the hole blocking layer, the electron transporting layer and the electron injecting layer is formed by a single molecular deposition method or a solution process And the organic electroluminescent device according to the present invention can be used for a display device, a display device, and a monochromatic or white illumination device.

Hereinafter, the present invention will be described in more detail with reference to preferred embodiments. It will be apparent, however, to those skilled in the art that these embodiments are for further explanation of the present invention and that the scope of the present invention is not limited thereby.

<Examples>

Synthesis Example 1 Synthesis of Compound Represented by Formula 5

(1) Synthesis of Compound Represented by Formula (1-a)

A compound represented by the formula (1-a) was synthesized by the following reaction scheme (1).

[Reaction Scheme 1]

[Chemical Formula 1-a]

119.5 g (1.052 mol) of trifluoroacetic acid was added to a 5 L round bottom flask, and 250 g (1.594 mol) of 2,2'-bipyridine was slowly added thereto. 275.0 g of hydrogen peroxide was slowly added at room temperature and then stirred for 4 hours. The pH was adjusted to 9-11 with aqueous sodium hydroxide solution and extracted with methylene chloride. The organic layer was separated, the water was removed, and the solvent was removed by distillation under reduced pressure. The precipitated solid was washed with ethanol and filtered to obtain 219.1 g (79.8%) of a compound represented by the formula (1-a).

(2) Synthesis of Compound Represented by Formula (1-b)

[Chemical Formula 1-b] was synthesized by the following Reaction Scheme 2.

[Reaction Scheme 2]

[Chemical Formula 1-b]

219.2 g (1.274 mol) of the [Formula 1-a] obtained from the above Reaction Scheme 1 was placed in a 5 L round bottom flask, and 1705 g of sulfuric acid was added thereto and stirred. 679.5 g (7.983 mol) of potassium nitrate was added slowly, followed by stirring at 90 占 폚 for 23 hours. The temperature was lowered to room temperature, slowly poured into 2.0 L of cold water, and neutralized with aqueous potassium hydroxide solution. After extracting with methylene chloride, the organic layer was separated to remove water, and the solvent was removed by distillation under reduced pressure to obtain 140.0 g (yield 50%) of the compound represented by the formula (1-b).

(3) Synthesis of Compound Represented by Formula (1-c)

The compound represented by the formula (1-c) was synthesized by the following reaction scheme [3].

[Reaction Scheme 3]

[Chemical Formula 1-c]

140.0 g (0.652 mol) of [Formula 1-b] obtained from Reaction Scheme 2 was placed in a 10 L round bottom flask and 1.4 L of acetic acid was added thereto. Then, 2.4 L (19.351 mol) of acetyl bromide was slowly added dropwise at 60 占 폚. The reaction mixture was refluxed at 90 ° C for 9 hours, cooled to room temperature, and then added to 2.7 L of cold water and adjusted to pH 9-10 with aqueous potassium hydroxide solution. The organic layer was separated to remove moisture, and the solvent was removed by distillation under reduced pressure to obtain 107 g (yield: 66%) of a compound represented by the formula (1-c).

(4) Synthesis of a compound represented by the formula (1-d)

[Chemical Formula 1-d] was synthesized by the following Reaction Scheme 4.

[Reaction Scheme 4]

[Chemical formula 1-d]

A 5 L round bottom flask was substituted with nitrogen gas, and 107.0 g (0.431 mol) of the formula 1-c obtained from the scheme 3 was added and dissolved in 2.7 L of chloroform. After 180.3 g (1.922 mol) of tribromophosphine was slowly added dropwise at 0 ° C, the mixture was stirred at 60 ° C for 2 hours. After cooling to room temperature, it was put into 2 L of water and adjusted to pH 11 with aqueous sodium hydroxide solution. After extraction with methylene chloride, the organic layer was separated to remove water, and the solvent was removed by distillation under reduced pressure. The precipitated solid was washed with ethanol and filtered to obtain 100.1 g (yield: 99.0%) of a brown solid compound represented by the formula [1-d].

(5) Synthesis of Compound Represented by Formula (1-e)

[Chemical Formula 1-e] was synthesized by the following Reaction Scheme 5.

[Reaction Scheme 5]

[Formula 1-e]

2L round bottom flask into the bromo-nitrobenzene 100.0g (0.501mol), bis To the solution were dissolved in toluene 1.5L (pinacolato) diboron 150.9g (0.593 mol), Pd ( dppf) Cl 2 12.1 g (0.015 mol) of potassium acetate and 145.8 g (1.493 mol) of potassium acetate were added thereto, followed by refluxing for 10 hours. After the solution was cooled to room temperature, the solvent was distilled off under reduced pressure, and the resulting solid was separated by column chromatography using n-hexane as eluent to obtain 80.2 g (yield: 65.1%) of the compound represented by the formula (1-e) .

(6) Synthesis of a compound represented by the formula (1-f)

[Chemical Formula 1-f] was synthesized by the following Reaction Scheme 6.

[Reaction Scheme 6]

[Chemical Formula 1-f]

100 g (0.432 mol) of [Formula 1-d] obtained from the above-mentioned Reaction Scheme 4, 148.2 g (0.601 mol) of the formula 1-e obtained from the above Reaction Scheme 5 and 117 g (0.851 mol) of potassium carbonate were added to a 1 L round bottom flask ), 24.6 g of tetrakis triphenylpalladium, 200 mL of water, 500 mL of dioxane and 100 mL of tetrahydrofuran were added and refluxed for 24 hours. After the completion of the reaction, the reaction product was separated to remove the aqueous layer, and the organic layer was separated, concentrated under reduced pressure, and then separated by column chromatography using hexane and ethyl acetate as eluent to obtain a solid. f] was obtained (yield: 55%).

(7) Synthesis of Compound Represented by Formula (1-g) and Formula (1-h)

[Chemical Formula 1-g] and [Chemical Formula 1-h] were synthesized by the following Reaction Scheme 7.

[Reaction Scheme 7]

[Chemical Formula 1-g] [Chemical Formula 1-h]

65.7 g (0.243 mol) of [Formula 1-f] and 311.0 g (1.192 mol) of triphenylphosphine obtained in the above Reaction Scheme 6 were dissolved in 800 mL of o-dichlorobenzene and then refluxed for 24 hours in a 1 L round bottom flask. After completion of the reaction, the solution was cooled to room temperature, and the solvent was removed by distillation under reduced pressure. The resulting solid was subjected to column chromatography using hexane and ethyl acetate as eluent to obtain the compound represented by Formula 1-g and Formula 1-h (Yield: 9.8%) and 20.0 g (yield: 34%) of the compound obtained.

(8) Synthesis of a compound represented by the formula (1-i)

The compound represented by the formula (1-i) was synthesized by the following reaction scheme (8).

[Reaction Scheme 8]

[Chemical Formula 1-i]

(0.0620 mol) of 3-bromo-N-phenylcarbazole, 14.9 g (0.0744 mol) of 4-bromo-1-phenylboronic acid and 3.6 g 17.1 g (0.1240 mol) of potassium carbonate, 200 mL of tetrahydrofuran, 200 mL of toluene and 100 mL of water were placed and refluxed for 12 hours. When the reaction was completed, it was cooled to room temperature and extracted with methylene chloride and water. The organic layer was dehydrated with magnesium sulfate and concentrated under reduced pressure to obtain crystals, which were recrystallized from methylene chloride and hexane to obtain 22.0 g (89.1%) of a compound represented by the formula (1-i).

(9) Synthesis of Compound Represented by Formula 5

A compound represented by the following formula (5) was synthesized by the following Reaction Scheme (9).

[Reaction Scheme 9]

[Chemical Formula 5]

5.0 g (0.0204 mol) of the compound represented by the formula (1-g) obtained from the above Reaction Scheme 7 and 12.2 g (0.0306 mol) of the compound represented by the formula 1-i obtained from the above Reaction Scheme 8 were added to a 200 mL round bottom flask. 19.9 g (0.0612 mol) of cesium carbonate, 2.2 g (0.0347 mol) of copper and 120 mL of o-dichlorobenzene were placed and refluxed for 24 hours. After completion of the reaction, dichlorobenzene was removed by distillation, and the organic layer was separated using water and ethyl acetate. The organic layer was concentrated under reduced pressure, and then the residue was separated by column chromatography using ethyl acetate and methylene chloride as eluent to obtain a solid. 7.7 g (67.1%) of the compound to be displayed was obtained.

MS: m / z Calcd 562.22; found 562. Anal. Calcd. for C ₄₀ H ₂₆ N ₄ : C, 85.38; H, 4.66; N, 9.96. Found: C, 84.19; H, 4.47; N, 10.18.

Synthesis Example 2 Synthesis of Compound Represented by Formula 8

(1) Synthesis of Compound Represented by Formula 8

A compound represented by the formula (2-a) was synthesized by the following reaction scheme [Reaction formula 10].

[Reaction Scheme 10]

[Chemical Formula 2-a]

(0.1090 mol) of 2,4,6-trichloropyrimidine, 36.9 g (0.3053 mol) of phenylboronic acid, 5.0 g (0.0044 mol) of tetrakistriphenylphosphine palladium and 30.0 g g (0.2180 mol), tetrahydrofuran (400 mL) and water (200 mL), and the mixture was refluxed for 12 hours. When the reaction was terminated, it was cooled to room temperature and extracted with ethyl acetate and water. The organic layer was dehydrated with magnesium sulfate and concentrated under reduced pressure to obtain crystals, which were recrystallized from methylene chloride and hexane to obtain 22.8 g (78.5%) of the compound represented by the formula (2-a).

(2) Synthesis of a compound represented by the formula (2-b)

[Chemical Formula 2-b] was synthesized by the following Reaction Scheme 11.

[Reaction Scheme 11]

[Formula 2-b]

20.0 g (0.0750 mol) of the compound represented by the formula (2-a), 18.1 g (0.0900 mol) of 3-bromo-1-phenylboronic acid, 1.7 g (0.0015 mol) of phosphine palladium, 20.7 g (0.1500 mol) of potassium carbonate, 400 mL of tetrahydrofuran and 200 mL of water were placed and refluxed for 12 hours. When the reaction was completed, it was cooled to room temperature and extracted with methylene chloride and water. The organic layer was dehydrated with magnesium sulfate and concentrated under reduced pressure to obtain crystals. The crystals were recrystallized from methylene chloride and hexane to obtain 23.2 g (80.2%) of the compound represented by the formula 2-b.

(3) Synthesis of Compound Represented by Formula 8

A compound represented by the formula (8) was synthesized by the following reaction scheme (12).

[Reaction Scheme 12]

[Chemical Formula 8]

5.0 g (0.0204 mol) of the compound represented by the formula (1-g) obtained from the above-mentioned scheme 7 and 11.8 g (0.0306 mol) of the compound represented by the formula 2-b obtained from the above scheme 11 were added to a 200 mL round bottom flask. mol), 5.5 g (48.9%) of the compound represented by the formula (8) was obtained in the same manner as in the reaction scheme [9].

MS: m / z Calcd 551.60; found 552. Anal. Calcd. for C ₃₈ H ₂₅ N ₅ : C, 82.74; H, 4.57; N, 12.70. Found: C, 83, 11; H, 4.73; N, 12.23.

&Lt; Synthesis Example 3 > Preparation of a compound represented by the formula (25)

(1) Synthesis of Compound Represented by Formula 3-a

A compound represented by the general formula [3-a] was synthesized by the following scheme [Scheme 13].

[Reaction Scheme 13]

[Formula 3-a]

39.5 g (1.627 mol) of magnesium, 10.0 g of iodine and 80 mL of tetrahydrofuran were added to a 500 mL round bottom flask, and the mixture was stirred under reflux for 2 hours. After the temperature was lowered to room temperature, 212.8 g (1.356 mol) of bromobenzene was dissolved in 200 mL of tetrahydrofuran and slowly added. The mixture was refluxed with stirring for 2 hours. 100.0 g (0.5423 mol) of 1,3,5-trichlorotriazine was dissolved in 200 mL of tetrahydrofuran in a 2 L round-bottomed flask, the reaction mixture was slowly added and stirred for 1 hour. 300 mL of 4M hydrochloric acid was poured into the mixture, and the organic layer was separated using toluene and water. The organic layer was concentrated under reduced pressure, and the residue was recrystallized with hexane. The resulting solid was dried to obtain 266.8 g (73.5%) of the compound represented by formula 3-a.

(2) Synthesis of Compound Represented by Formula 3-b

[Chemical Formula 3-b] was synthesized by the following Reaction Scheme 14.

[Reaction Scheme 14]

[Formula 3-b]

(0.304 mol) of 2-bromoallyl, 81.0 g (0.253 mol) of 2-iodo-9,9-dimethylfluorene and 6.3 g (0.010 mol) of bisdiphenylphosphinobinaphthalene were added to a 2 L round- 4.6 g (0.0051 mol) of dibenzylidene acetone palladium, 36.5 g (0.379 mol) of sodium tert-butoxide and 810 mL of dioxane were added and stirred under reflux for 12 hours. After the completion of the reaction, the reaction mixture was cooled to room temperature and extracted. The organic layer was concentrated under reduced pressure, and then separated by column chromatography using methylene chloride and hexane to obtain 62.6 g (68%) of a compound represented by the formula 3-b.

(3) Synthesis of Compound Represented by Formula 3-c

[Chemical Formula 3-c] was synthesized by the following Reaction Scheme 15.

[Reaction Scheme 15]

[Chemical Formula 3-c]

59.0 g (0.162 mol) of the compound represented by the formula (3-b), 1.2 g (0.003 mol) of tricyclohexylphosphine tetrafluoroborate and 0.4 g (0.003 mol) of palladium acetate , Potassium carbonate (44.8 g, 0.324 mol) and N, N-dimethylacetamide (700 mL) were added, and the mixture was stirred at 130 ° C for 15 hours. After the temperature was lowered to room temperature and extracted, the organic layer was concentrated under reduced pressure, and then separated by column chromatography using methylene chloride and hexane to obtain 34.0 g (74.1%) of the compound represented by the formula 3-c.

(4) Synthesis of Compound Represented by Formula 3-d

[Chemical formula 3-d] was synthesized by the following reaction scheme [16].

[Reaction Scheme 16]

[Chemical formula 3-d]

46.0 g (0.162 mol) of the compound represented by the above formula [3-c] and 460 mL of N, N-dimethylformamide obtained from the above-mentioned scheme 15 were placed in a 2 L round bottom flask, (0.170 mol) of cinnamide was dissolved in 460 mL of N, N-dimethylformamide and slowly added thereto, followed by stirring at room temperature for 8 hours. The organic layer was separated using ethyl acetate and water, concentrated under reduced pressure, and recrystallized from methylene chloride and hexane. The resulting solid was dried to obtain 50.0 g (85.2%) of the compound represented by the formula 3-d.

(5) Synthesis of Compound Represented by Formula 3-e

[Chemical Formula 3-e] was synthesized by the following Reaction Scheme 17.

[Reaction Scheme 17]

[Formula 3-e]

50.0 g (0.1380 mol) of the compound represented by the formula (3-d) obtained from the above-mentioned reaction formula [16], 38.6 g (0.1518 mol) of bisphenacol diboron, and bisdiphenylphosphinoferrocene dichloropalladium 2.2 g (0.0025 mol) of potassium acetate, 27.0 g (0.5106 mol) of potassium acetate and 1440 mL of toluene, and the mixture was refluxed for 6 hours. When the reaction was complete, it was filtered under hot conditions and extracted with toluene and water. The organic layer was dehydrated with magnesium sulfate, concentrated under reduced pressure, and separated by column chromatography with methylene chloride and hexane to obtain 45.0 g (79.8%) of a compound represented by the formula 3-e.

(6) Synthesis of Compound Represented by Formula 3-f

[Chemical Formula 3-f] was synthesized by the following Reaction Scheme 18.

[Reaction Scheme 18]

[Chemical Formula 3-f]

23.6 g (0.0880 mol) of the compound represented by the formula (3-a) and 43.1 g (0.1056 (g) of the compound represented by the formula (3-e) 24.3 g (0.1760 mol) of potassium carbonate, 5.1 g (0.0044 mol) of tetrakis (triphenylphosphine) palladium, 120 mL of water and 240 mL of tetrahydrofuran were added and stirred at reflux for 24 hours. When the reaction was completed, the reaction solution was cooled to room temperature. The resultant product was separated into layers, and the water layer was removed. The organic layer was separated, concentrated under reduced pressure, and then separated by column chromatography using hexane and ethyl acetate as eluent to obtain a solid. The solid was dried to give the compound represented by Formula 3-f (Yield: 75.6%).

(7) Synthesis of Compound Represented by Formula 3-g

[Chemical Formula 3-g] was synthesized by the following Reaction Scheme (19).

[Reaction Scheme 19]

[Formula 3-g]

(0.0585 mol) of the compound represented by the general formula [3-f] obtained from the above-mentioned Scheme 18, 21.2 g (0.0643 mol) of diiodobenzene, 57.2 g (0.1755 mol) of cesium carbonate, 6.3 g (0.0995 mol), 18-crown-6 (0.312 g, 0.0012 mol) and dichlorobenzene (300 mL) were added and refluxed for 24 hours. After completion of the reaction, the dichlorobenzene was removed by distillation, and the organic layer was separated using water and ethyl acetate. The organic layer was separated and concentrated under reduced pressure. The residue was separated by column chromatography using methylene chloride and hexane as eluent to obtain a solid. (76.3%) was obtained.

(8) Synthesis of Compound Represented by Formula 25

A compound represented by the formula (25) was synthesized by the following reaction scheme (20).

[Reaction Scheme 20]

(25)

(0.0204 mol) of the compound represented by the formula (1-g) obtained from the above-mentioned scheme 7 and 21.9 g (0.0306 mol) of the compound represented by the formula 3-g obtained from the above scheme [19] mol), 10.3 g (60.8%) of a compound represented by the formula (25) was obtained in the same manner as in the reaction scheme [9].

MS: m / z Calcd 833.33; found 833. Anal. Calcd. for C ₅₈ H ₃₉ N ₇ : C, 83.53; H, 4.71; N, 11.76. Found: C, 83, 11; H, 4.63; N, 12.23.

&Lt; Synthesis Example 4 > Preparation of a compound represented by the formula (29)

(1) Synthesis of Compound Represented by Formula 4-a

[Chemical Formula 4-a] and [Chemical Formula 4-b] were synthesized by the following Reaction Formula 21.

[Reaction Scheme 21]

[Formula 4-a] [Formula 4-b]

20.0 g (0.1556 mol) of 4-amino-2-chloropyridine, 27.8 g (0.1711 mol) of iodine chloride, 98.1 g (0.3111 mol) of potassium acetate and 60 mL of acetic acid were placed in a 1 L round bottom flask, Lt; / RTI &gt; The reaction mixture was concentrated under reduced pressure and the residue was recrystallized from methylene chloride and a hexane solvent to obtain 16.0 g (40.4%) of the compound represented by the formula (4-a) and 18 g (45.5% .

(2) Synthesis of Compound Represented by Formula 4-c

[Chemical Formula 4-c] was synthesized by the following Reaction Formula 22.

[Reaction Scheme 22]

[Chemical formula 4-c]

18.0 g (0.0715 mol) of [Formula 4-b], 12.8 g (0.0679 mol) of 4-bromo isocyanol, 0.7 g (0.0036 mol) of copper iodide and 8.9 g (0.1430 mol) of potassium carbonate and 19.8 g (0.1430 mol) of potassium carbonate were added to 180 ml of isopropanol, and the mixture was refluxed for 24 hours. The mixture was cooled to room temperature and then concentrated under reduced pressure. The residue was recrystallized from methylene chloride and a hexane solvent to obtain 4- (68.1%) was obtained.

(3) Synthesis of Compound Represented by Formula 4-d

[Chemical Formula 4-d] was synthesized by the following Reaction Scheme 23.

[Reaction Scheme 23]

[Chemical formula 4-d]

14.6 g (0.0463 mol) of the compound represented by the formula [4-c] obtained from the reaction formula [22] and 600 mL of acetone were added to a 1 L round bottom flask, and 4.8 g (0.0463 mol) of butyl nitrite was slowly added thereto. And stirred for 1 hour. 2.1 g (0.0199 mol) of butyl nitrite was added to the reaction mixture, followed by stirring for 2 hours, and water was added slowly to terminate the reaction. The resulting solid was filtered and recrystallized from methylene chloride to obtain 8.0 g (57.9%) of [Formula 4-d].

(4) Synthesis of Compound Represented by Formula 4-e

[Chemical Formula 4-e] was synthesized by the following Reaction Formula 24.

[Reaction Scheme 24]

[Chemical Formula 4-e]

8.0 g (0.0268 mol) of the compound represented by the formula [4-d] obtained from the above-mentioned reaction formula [23], 16.8 g (0.0616 mol) of triphenyleneboronic acid and 1.5 g of tetrakistriphenylphosphine palladium (0.0536 mol) of potassium carbonate, 50 mL of tetrahydrofuran, 50 mL of dioxane and 20 mL of water were placed and refluxed for 12 hours. When the reaction was completed, it was cooled to room temperature and extracted with ethyl acetate and water. The organic layer was dehydrated with magnesium sulfate and concentrated under reduced pressure to obtain crystals. The crystals were recrystallized from methylene chloride and hexane to obtain 10.3 g (78.4%) of the compound represented by the formula 4-e.

(5) Synthesis of Compound Represented by Formula 4-f

[Chemical Formula 4-f] was synthesized by the following Reaction Scheme 25.

[Reaction Scheme 25]

[Chemical Formula 4-f]

10.0 g (0.0204 mol) of the compound represented by the formula [4-e], 6.9 g (0.0245 mol) of 6-bromopyridine borate, 0.0257 mol of tetrakistriphenylphosphine palladium g (0.0004 mol) of potassium carbonate, 5.6 g (0.0408 mol) of potassium carbonate, 50 mL of tetrahydrofuran, 50 mL of dioxane and 20 mL of water were added and refluxed for 12 hours. When the reaction was completed, it was cooled to room temperature and extracted with ethyl acetate and water. The organic layer was dehydrated with magnesium sulfate and concentrated under reduced pressure to obtain crystals. The crystals were recrystallized from methylene chloride and hexane to obtain 8.9 g (77.1%) of the compound represented by the formula 4-f.

(6) Synthesis of Compound Represented by Formula 29

A compound represented by the formula (29) was synthesized by the following reaction scheme.

[Reaction Scheme 26]

[Chemical Formula 29]

(0.0112 mol) of the compound represented by the formula (1-g) obtained from the above-mentioned scheme 7 and 8.0 g (0.0141 (g) of the compound represented by the formula 4-f obtained from the above scheme [25] mol), and 4.1 g (49.8%) of a compound represented by the formula (25) was obtained in the same manner as in the reaction scheme [9].

MS: m / z Calcd 731.21; found 731. Anal. Calcd. for C ₅₀ H ₂₉ N ₅ S: C, 82.06; H, 3.99; N, 9.57; S, 4.38. Found: C, 82,61; H, 4.15; N, 10.05.

&Lt; Synthesis Example 5 > Preparation of a compound represented by the formula (51)

(1) Synthesis of a compound represented by the formula (5-a)

[Chemical Formula 5-a] was synthesized by the following Reaction Scheme 27.

[Reaction Scheme 27]

[Formula 5-a]

10.0 g (0.0352 mol) of the compound represented by the general formula [3-c] obtained from the above-mentioned Scheme 15, 17.5 g (0.0529 mol) of diiodobenzene, 31.8 g (0.0975 mol) of cesium carbonate, g (0.0553 mol), 18-crown-6 (0.2 g, 0.0007 mol) and o-dichlorobenzene (100 mL) were added and refluxed for 24 hours. After completion of the reaction, dichlorobenzene was removed by distillation, and the organic layer was separated using water and ethyl acetate. The organic layer was concentrated under reduced pressure, and then separated by column chromatography using methylene chloride and hexane as eluent to obtain a solid. (61.9%) was obtained.

(2) Synthesis of Compound Represented by Formula 5-b

[Chemical Formula 5-b] was synthesized by the following Reaction Formula 28.

[Reaction Scheme 28]

[Chemical Formula 5-b]

10.0 g (0.0206 mol) of the compound represented by the formula 5-a, 2.1 g (0.0227 mol) of 3-aminopyridine, 0.1 g (0.0004 mol) of palladium acetate, 0.1 g (0.0004 mol) of tert-butylphosphine, 3.9 g (0.0412 mol) of sodium tert-butoxide, and 100 mL of toluene, and the mixture was refluxed for 12 hours. After the completion of the reaction, the reaction mixture was cooled to room temperature and extracted. The organic layer was concentrated under reduced pressure, and then separated by column chromatography using ethyl acetate and hexane. The solid was dried to obtain 6.5 g (70.1%) of the compound represented by the formula 5-b .

(3) Synthesis of Compound Represented by Formula 5-c

[Chemical Formula 5-c] was synthesized by the following Reaction Scheme 29.

[Reaction Scheme 29]

[Chemical Formula 5-c]

6.0 g (0.0133 mol) of the compound represented by the above formula [5-b], 4.8 g (0.0146 mol) of 1,4-diiodobenzene and 0.06 g (0.0003 mol) of palladium acetate were added to a 100 mL round- 0.05 g (0.0003 mol) of triethylbutylphosphine, 2.6 g (0.0266 mol) of sodium tallow butoxide and 60 mL of toluene were placed and refluxed for 12 hours. After the completion of the reaction, the reaction mixture was cooled to room temperature and extracted with water. The organic layer was concentrated under reduced pressure, and then separated by column chromatography using methylene chloride and hexane. The solid was dried to obtain 7.1 g (81.7%) of a compound represented by the formula 5-c .

(4) Synthesis of Compound Represented by Formula 51

A compound represented by the formula (51) was synthesized by the following scheme (30).

[Reaction Scheme 30]

(51)

(0.0096 mol) of the compound represented by the formula (1-g) obtained from the above-mentioned reaction formula 7 and 7.0 g (0.0107 mol) of the compound represented by the formula 5-c obtained from the above-mentioned reaction formula 29 were added to a 200 mL round bottom flask. mol), and 4.1 g (49.8%) of a compound represented by the formula (25) was obtained in the same manner as in the reaction scheme [9].

MS: m / z Calcd 770.32; found 770. Anal. Calcd. for C ₅₄ H ₃₈ N ₆ : C, 84.13; H, 4.97; N, 10.90. Found: C, 83.89; H, 4.71; N, 11.21.

Synthesis Example 6 Synthesis of Compound Represented by Formula 67

(1) Synthesis of Compound Represented by Formula 6-a

A compound represented by the formula [6-a] was synthesized by the following reaction scheme [31].

[Reaction Scheme 31]

[Chemical Formula 6-a]

200 g of dibenzothiophene and 2 L of chloroform were added to a 5 L round bottom flask and the temperature was lowered to 0 캜 with stirring. 170.8 g of bromine was dissolved in 512 ml of chloroform and then slowly added dropwise. After completion, the mixture was stirred at room temperature for 12 hours. After the reaction was completed, sodium thiosulfate was extracted with the dissolved water, and the organic layer was collected, concentrated, and then solidified with ethanol. The solid was filtered and recrystallized from dichloromethane and ethanol to obtain 140.0 g (50.5%) of the compound represented by the formula 6-a.

(2) Synthesis of Compound Represented by Formula 6-b

[Chemical Formula 6-b] was synthesized by the following Reaction Formula 32.

[Reaction Scheme 32]

[Chemical Formula 6-b]

21.0 g (0.080 mol) of the compound represented by the formula 6-a, 38.4 g (0.191 mol) of 3-bromophenylboronic acid, 22.1 g (0.160 mol) of potassium carbonate, Phenylphosphine palladium (4.6 g), tetrahydrofuran (200 mL) and water (100 mL) were added, and the mixture was refluxed for 24 hours. After completion of the reaction, the reaction product was layered to remove the aqueous layer, and the organic layer was separated, concentrated under reduced pressure, and then separated by column chromatography using hexane and dichloromethane as eluent to obtain a solid. -b] was obtained (yield: 87.7%).

(3) Synthesis of Compound Represented by Formula 6-c

[Chemical Formula 6-c] was synthesized by the following Reaction Formula 33.

[Reaction Scheme 33]

[Chemical formula 6-c]

20.0 g (0.0589 mol) of the compound represented by the formula (6-b) obtained from the above-mentioned reaction formula 32, 18.0 g (0.0707 mol) of bispinacoloboron, 1.0 g of bisdiphenylphosphinoferrocene dichloropalladium 1.0 g (0.00118 mol) of potassium acetate, 9.3 g (0.1767 mol) of potassium acetate and 200 mL of toluene were put and refluxed for 6 hours. When the reaction was complete, it was filtered under hot conditions and extracted with toluene and water. The organic layer was dehydrated with magnesium sulfate, concentrated under reduced pressure, and then subjected to column chromatography using methylene chloride and hexane to obtain 18.2 g (79.8%) of the compound represented by the formula 6-c.

(4) Synthesis of Compound Represented by Formula 6-d

[Chemical formula 6-d] was synthesized by the following reaction scheme.

[Reaction Scheme 34]

[Chemical formula 6-d]

18.0 g (0.0466 mol) of 1,3,6-tribromobenzene represented by the following formula [6-c], 13.2 g (0.0419 mol) of 1,3,5-tribromobenzene and 11.6 g 1.0 g (0.0008 mol) of tetrakistriphenylphosphine palladium, 200 mL of tetrahydrofuran and 100 mL of water were placed, and the mixture was refluxed for 24 hours. After completion of the reaction, the reaction product was separated into layers, and the aqueous layer was separated. The organic layer was separated, concentrated under reduced pressure, and then separated by column chromatography using hexane and dichloromethane as eluent to obtain a solid. d] was obtained (yield: 81.7%).

(5) Synthesis of Compound Represented by Formula 6-e

A compound represented by the formula [6-e] was synthesized by the following reaction scheme [35].

[Reaction Scheme 35]

[Chemical Formula 6-e]

(0.0325 mol), carbazole (5.4 g, 0.0325 mol), potassium carbonate (9.0 g, 0.0650 mol) and copper (1.3 g) were added to a 50 mL round bottom flask, (0.0325 mol) of copper iodide (1.2 g, 0.0065 mol) and 160 mL of o-xylene were added and refluxed for 24 hours. After completion of the reaction, the o-xylene was removed by distillation, and the organic layer was separated using water and ethyl acetate. The organic layer was concentrated under reduced pressure, and then the residue was purified by column chromatography using hexane and methylene chloride as eluting solvents. 13.8 g (73.1%) of a compound represented by the formula [e] was obtained.

(6) Synthesis of Compound Represented by Formula 67

A compound represented by the formula (67) was synthesized by the following scheme (36).

[Reaction Scheme 36]

(67)

(0.0112 mol) of the compound represented by the formula (1-h) obtained from the above-mentioned scheme 7 and 8.1 g (0.0141 mol) of the compound represented by the above formula [6-e] mol), 4.1 g (49.8%) of the compound represented by the formula (68) was obtained in the same manner as in the reaction scheme [9].

MS: m / z Calcd 744.23; found 744. Anal. Calcd. for C ₅₂ H ₃₂ N ₄ S: C, 83.84; H, 4.33; N, 7.52; S, 4.30. Found: C, 83.65; H, 4.22; N, 7.74.

Synthesis Example 7 Synthesis of Compound Represented by Formula 70

(1) Synthesis of Compound Represented by Formula 7-a

A compound represented by the formula [7-a] was synthesized by the following reaction scheme [37].

[Reaction Scheme 37]

[Formula 7-a]

20.0 g (0.0813 mol) of 2-bromocarbazole, 15.4 g (0.0975 mol) of 3-bromopyridine, 22.4 g (0.1626 mol) of potassium carbonate and 0.7 g (0.0813 mol) of copper were mixed in a 50 mL round- 0.0163 mol), and 200 mL of o-xylene was added thereto, followed by refluxing for 24 hours. After completion of the reaction, the o-xylene was removed by distillation, and the organic layer was separated using water and ethyl acetate. The organic layer was concentrated under reduced pressure, and then the residue was purified by column chromatography using hexane and methylene chloride as eluting solvents. to obtain 20.8 g (79.1%) of a compound represented by the formula [e].

(2) Synthesis of Compound Represented by Formula 70

A compound represented by the formula (70) was synthesized by the following scheme [Reaction formula 38].

[Reaction Scheme 38]

(70)

(0.0112 mol) of the compound represented by the formula [1-h] obtained from the above-mentioned scheme [7] and 4.6 g (0.0141 mol) of the compound represented by the above formula [7-a] mol), 3.6 g (65.6%) of the compound represented by the formula (70) was obtained in the same manner as in the reaction scheme [9].

MS: m / z calcd 487.18; found 487. Anal. Calcd. _{for C 33 H 21 N 5:} C, 81.29; H, 4.34; N, 14.36. Found: C, 80.47; H, 4.23; N, 14.92.

Synthesis Example 8 Synthesis of Compound Represented by Formula 94

(1) Synthesis of Compound Represented by Formula (8-a)

A compound represented by the following formula (8-a) was synthesized by the following scheme (Scheme 39).

[Reaction Scheme 39]

[Formula 8-a]

200.0 g (1.270 mol) of 2-bromopyridine and 2.4 L of tetrahydrofuran were placed in a 5 L round bottom flask, and the temperature of the reaction product was lowered to -78 캜 under a nitrogen atmosphere. 422.6 g (1.524 mol) of normal butyl lithium in 2.5 mol- Was added dropwise over 1 hour. After stirring at the same temperature for 1 hour, 392.8 g (1.207 mol) of tributyltin chloride was added and the temperature was raised to room temperature. After stirring for 8 hours, the organic layer was separated by using an aqueous ammonium chloride solution and ethyl ether and concentrated under reduced pressure. To obtain 390.0 g (75.2%) of the compound represented by the formula (8-a).

(2) Synthesis of Compound Represented by Formula (8-b)

A compound represented by the following formula (8-b) was synthesized by the following reaction scheme (40).

[Reaction Scheme 40]

[Formula 8-b]

231.9 g (0.630 mol) of the compound represented by the formula (8-a), 150.0 g (0.633 mol) of the 2,6-dibromopyridine obtained in the reaction scheme 39, 0.6 g of the tetrakistriphenylphosphine palladium , And 1.5 L of toluene were placed, and the mixture was stirred under reflux for 10 hours under a nitrogen atmosphere. The organic layer was concentrated under reduced pressure, and then separated by column chromatography using ethyl acetate and hexane. The solid was dried to obtain 96.0 g (64.5%) of the compound represented by the formula 8-b, ).

(3) Synthesis of Compound Represented by Formula (8-c)

A compound represented by the formula (8-c) was synthesized according to the following scheme (Scheme 41).

[Reaction Scheme 41]

[Formula 8-c]

51.8 g (0.220 mol) of the compound represented by the above formula [10-b], 65.6 g (0.260 mol) of the formula 1-e obtained from the above scheme 5, , 25.4 g (0.020 mol) of tetrakistriphenylphosphine palladium, 500 mL of tetrahydrofuran and 250 mL of water were placed, and the mixture was refluxed with stirring for 16 hours. After the completion of the reaction, the reaction mixture was cooled to room temperature and extracted. The organic layer was concentrated under reduced pressure, and then separated by column chromatography using ethyl acetate and hexane. The solid was dried to obtain 29.0 g (47.5%) of a compound represented by the formula 8-c .

(4) Synthesis of Compound Represented by Formula 8-d

A compound represented by the formula (8-d) was synthesized by the following scheme (42).

[Reaction Scheme 42]

[Chemical formula 8-d]

29.0 g (0.110 mol) of [Formula 8-c] and 192.8 g (0.740 mol) of triphenylphosphine obtained in the above Reaction Scheme 41 were dissolved in 350 mL of o-dichlorobenzene and refluxed for 24 hours in a 500 mL round bottom flask. After the reaction was completed, the solution was cooled to room temperature, and the solvent was removed by distillation under reduced pressure. The resulting solid was separated by column chromatography using methylene chloride and hexane as eluent to obtain 15.0 g of a compound represented by the formula 8-d (Yield: 51.7%).

(5) Synthesis of Compound Represented by Formula 8-e

A compound represented by the following formula [8-e] was synthesized by the following reaction scheme [43].

[Reaction Scheme 43]

[Formula 8-e]

(0.0633 mol) of 3-bromopyridine, 15.3 g (0.0759 mol) of 3-bromo-1-phenylboronic acid, 3.7 g (0.0032 mol) of tetrakistriphenylphosphine palladium, (0.1266 mol), 100 mL of tetrahydrofuran and 50 mL of water, and the mixture was refluxed with stirring for 16 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and extracted. The organic layer was concentrated under reduced pressure, and then the residue was purified by column chromatography using ethyl acetate and hexane. The solid was dried to obtain 9.0 g (60.5%) of a compound represented by the following formula 8-e .

(6) Synthesis of Compound Represented by Formula 8-f

A compound represented by the following formula (8-f) was synthesized according to the following scheme (Scheme 44).

[Reaction Scheme 44]

[Chemical Formula 8-f]

1.1 g (0.0461 mol) of magnesium, 1.0 g of iodine and 20 mL of tetrahydrofuran were added to a 100 mL round bottom flask, and the mixture was refluxed with stirring for 2 hours. After the temperature was lowered to room temperature, 9.0 g (0.0384 mol) of the compound represented by the formula [8-e] obtained from the above-mentioned scheme 43 was dissolved in 20 mL of tetrahydrofuran, and the mixture was slowly added with stirring for 2 hours. 3.5 g (0.0192 mol) of 1,3,5-trichlorotriazine was dissolved in 40 mL of tetrahydrofuran in a 250 mL round-bottomed flask, the reaction mixture was slowly added, and the mixture was stirred for 1 hour. The organic layer was separated using toluene and water, concentrated under reduced pressure, and recrystallized with hexane to obtain a solid. The resulting solid was dried to obtain 5.7 g (70.9%) of a compound represented by the formula 8-f.

(7) Synthesis of Compound Represented by Formula 94

A compound represented by the formula (94) was synthesized according to the following scheme (45).

[Reaction Scheme 45]

&Lt; EMI ID =

0.4 g (0.0097 mol) of sodium hydride and 10 mL of N, N-dimethylformamide were added to a 100 mL round-bottom flask, and the mixture was stirred at 0 ° C. 1.2 g (0.00498 mol) of the compound represented by the formula 8-d obtained from the above-mentioned scheme 42 was dissolved in 10 ml of N, N-dimethylformamide, and the mixture was slowly added dropwise and stirred for 1 hour. 2.5 g (0.0058 mol) of the compound represented by the general formula [8-f] obtained from the above-mentioned Scheme 44 was dissolved in 20 mL of N, N-dimethylformamide, added dropwise to the reaction, and the mixture was stirred for 5 hours. When the reaction was terminated, water was poured to form a solid. The solid was filtered, and ethyl acetate and hexane were separated by column chromatography using a developing solvent and recrystallized from ethyl acetate and hexane to obtain 1.3 g (42.4%) of a compound represented by the formula (94).

MS: m / z Calcd 630.23; found 630. Anal. Calcd. _{for C 41 H 26 N 8:} C, 78.08; H, 4.16; N, 17.77. Found: C, 78.81; H, 4.29; N, 17.21.

Synthesis Example 9 Synthesis of Compound Represented by Formula 123

(1) Synthesis of Compound Represented by Formula 9-a

A compound represented by the following formula (9-a) was synthesized by the following reaction scheme (46).

[Reaction Scheme 46]

[Chemical Formula 9-a]

165 g (1.05 mol) of 2,2'-bipyridine was added to a 5 L round bottom flask, dissolved in 570 mL of chloroform, and then cooled to -78 ° C. 389 g (2.25 mol) of m-chloroperbenzoic acid was added by dissolving in 1.5 L of chloroform. After stirring at room temperature for 12 hours, the solid was filtered. The solid was washed with methanol and filtered. This procedure was repeated twice to obtain 172.3 g (yield: 89.4%) of the compound represented by the general formula [9-a].

(2) Synthesis of Compound Represented by Formula 9-b

[Chemical Formula 9-b] was synthesized by the following Reaction Formula 47.

[Reaction Scheme 47]

[Formula 9-b]

In a 2 L round bottom flask, 199.0 g (1.06 mol) of the compound represented by the formula (9-a) obtained from the scheme [46] was added and 1038 g (10.58 mol) of oleum sulfuric acid was added and stirred. Fuming nitric acid was slowly added dropwise at a low temperature and stirred at 80 占 폚 for 12 hours. The temperature was lowered to room temperature and slowly poured into 4.5 L of cold water. The resulting solid was filtered and sufficiently washed with water to obtain 126.9 g (yield: 43%) of the compound represented by the formula 9-b.

(3) Synthesis of Compound Represented by Formula 9-c

[Chemical Formula 9-c] was synthesized by the following Reaction Scheme 48.

[Reaction Scheme 48]

[Chemical Formula 9-c]

126.0 g (0.456 mol) of the compound represented by the formula 9-b obtained from the reaction scheme 47 was added to a 5-liter round bottom flask, and then 1.9 L of acetic acid was added thereto, and 140 g (1.14 mol) of acetyl bromide was slowly added dropwise at 40 ° C. After 3 hours, the mixture was cooled to room temperature, and the mixture was neutralized with sodium hydroxide in 19 L of cold water. The solid was washed with methanol and then filtered. This process was repeated twice to obtain 116.0 g (yield: 74%) of the compound represented by the formula 9-c.

(4) Synthesis of Compound Represented by Formula 9-d

[Chemical Formula 9-d] was synthesized by the following Reaction Scheme 49.

[Reaction Scheme 49]

[Chemical Formula 9-d]

37 g (0.1 mol) of the compound represented by the formula [9-c] obtained from the reaction formula [48] was placed in a 2 L round bottom flask and dissolved in 950 mL of chloroform. 297 g (1.1 mol) of tribromophosphine was slowly added dropwise at -3 DEG C, followed by stirring at 60 DEG C for two hours. After cooling to room temperature, it was put into 1 L of water and adjusted to pH 11 with caustic soda. After extraction with methylene chloride, the organic layer is separated to remove water, and the solvent is removed by distillation under reduced pressure. The precipitated solid was washed with ethanol and filtered to obtain 26.0 g (yield: 77%) of the compound represented by the formula 9-d.

(5) Synthesis of Compound Represented by Formula 9-e

[Chemical Formula 9-e] was synthesized by the following Reaction Scheme 50.

[Reaction Scheme 50]

[Formula 9-e]

25.0 g (0.0801 mol) of the compound represented by the formula (9-d) obtained from the scheme 49 and 24.0 g (0.0961 mol) of the compound represented by the formula 1-e obtained from the scheme 5 were added to a 500- , Potassium carbonate (22.1 g, 0.160 mol), tetrakis (triphenylphosphine) palladium (1.8 g, 0.0016 mol), water (40 mL), toluene (100 mL) and tetrahydrofuran (100 mL) were added and refluxed for 24 hours. After completion of the reaction, the reaction product was separated into layers, the water layer was removed, and the organic layer was separated, concentrated under reduced pressure, and then separated by column chromatography using hexane and dichloromethane as eluent to obtain a solid. e] was obtained (yield: 87.8%).

(6) Synthesis of a compound represented by the formula 9-f and 9-g

A compound represented by the following formula (9-f) and (9-g) was synthesized by the following reaction scheme.

[Reaction Scheme 51]

[Formula 9-f] [Formula 9-g]

20.0 g (0.0564 mol) of [Formula 9-e] and 73.9 g (0.2823 mol) of triphenylphosphine obtained in Reaction Formula 50 were dissolved in 200 mL of o-dichlorobenzene and refluxed for 24 hours in a 500 mL round bottom flask. When the reaction is completed, the solution is cooled to room temperature, and the solvent is removed by distillation under reduced pressure. The resulting solid is subjected to column chromatography using dichloromethane as a developing solvent to obtain the compound represented by the formula 9-f and the compound represented by the formula 9-g 10.1 g (yield: 55.1%) of the compound and 6.1 g (yield: 33.2%) of the compound were obtained, respectively.

(7) Synthesis of Compound Represented by Formula 9-h

[Chemical Formula 9-h] was synthesized by the following Reaction Formula 52.

[Reaction Scheme 52]

[Chemical Formula 9-h]

200 g (1.085 mol) of dibenzothiophene and 2 L of chloroform were placed in a 5 L round-bottomed flask and cooled to 0 캜 with stirring. 170.8 g (1.0678 mol) of bromine was dissolved in 512 mL of chloroform and then slowly added dropwise. After completion, the mixture was stirred at room temperature for 12 hours. After the reaction was completed, sodium thiosulfate was extracted with the dissolved water, and the organic layer was collected, concentrated, and then solidified with ethanol. The solid was filtered and recrystallized from methylene chloride and ethanol to obtain 142 g (50.5%) of the compound represented by the formula 9-h.

(8) Synthesis of Compound Represented by Formula 9-i

[Chemical Formula 9-i] was synthesized by the following Reaction Formula 53.

[Reaction Scheme 53]

[Chemical Formula 9-i]

(0.544 mol) of the compound represented by the above formula [9-h] obtained from the above Reaction Scheme 52, 152 g (0.598 mol) of bispinacol diboron and 8.8 g of bisdiphenylphosphinoferrocene dichloropalladium 107g (2.02mol) of potassium acetate and 1440mL of toluene were put into the flask and refluxed for 6 hours. When the reaction was complete, it was filtered under hot conditions and extracted with toluene and water. The organic layer was dehydrated with magnesium sulfate, concentrated under reduced pressure, and separated by column chromatography with methylene chloride and hexane to obtain 161 g (95%) of the compound represented by the formula 9-i.

(9) Synthesis of Compound Represented by Formula 9-j

[Chemical Formula 9-j] was synthesized by the following Reaction Formula 54.

[Reaction Scheme 54]

[Chemical formula 9-j]

158.4 g (0.51 mol) of the compound represented by the above formula [9-i], 86 g (0.0426 mol) of bromonitrobenzene, 9.8 g of tetrakis (triphenylphosphine) palladium in a 2 L round- (0.852 mol) of potassium carbonate, 430 mL of tetrahydrofuran, 430 mL of dioxane, and 172 mL of water were added, and the mixture was refluxed for 12 hours. When the reaction was completed, it was cooled to room temperature and extracted with ethyl acetate and water. The organic layer was dehydrated with magnesium sulfate and concentrated under reduced pressure to obtain crystals, which were recrystallized from methylene chloride and hexane to obtain 62 g (93%) of a compound represented by the formula 9-j.

(10) Synthesis of Compound Represented by Formula 9-k

A compound represented by the following formula (9-k) was synthesized by the following reaction scheme (55).

[Reaction Scheme 55]

[Formula 9-k]

200 mL of dichlorobenzene was added to a 500 mL round bottom flask, and after boiling, 20 g (0.0654 mol) of the compound represented by the above formula [9-j] and 42.8 g of triphenylphosphine were added thereto and refluxed for 12 hours. After completion of the reaction, dichlorobenzene was removed by distillation, followed by column chromatography using ethyl acetate and hexane, and the solid was dried to obtain 16.6 g (93.1%) of the compound represented by the formula 9-k.

(11) Synthesis of a compound represented by the general formula [9-1]

A compound represented by the following formula [9-1] was synthesized by the following reaction scheme.

[Reaction Scheme 56]

[Formula 9-1]

6.0 g (0.0185 mol) of the compound represented by the above formula [9-f] and 8.2 g (0.0222 mol) of 9- (4-iodophenyl) -9H- carbazole obtained in the above Reaction Scheme 51 were added to a 100 mL round bottom flask, 18.1 g (0.0555 mol) of cesium carbonate, 2.0 g (0.0315 mol) of copper, 0.1 g (0.0004 mol) of 18-crown-6 and 100 mL of dichlorobenzene were added and refluxed for 24 hours. After completion of the reaction, dichlorobenzene was removed by distillation. The organic layer was separated using water and ethyl acetate, and the filtrate was concentrated under reduced pressure. The residue was separated by column chromatography using ethyl acetate and hexane as eluent to obtain a solid. ] Was obtained in an amount of 7.5 g (71.3%).

(12) Synthesis of Compound Represented by Formula 123

A compound represented by the formula (123) was synthesized by the following scheme (57).

[Reaction Scheme 57]

(123)

7.0 g (0.0124 mol) of the compound represented by the above formula [9-1] and 5.1 g (0.0186 mol) of the compound represented by the above formula [9-k] obtained from the above scheme [55] were added to a 100 mL round bottom flask. mol) to obtain 6.8 g (66.9%) of a compound represented by the formula (123) in the same manner as in the reaction scheme [9].

MS: m / z Calcd 757.23; found 757. Anal. Calcd. for C ₅₂ H ₃₁ N ₅ S: C, 82.41; H, 4.12; N, 9.24; S, 4.23. Found: C, 82.88; H, 4.35; N, 9.01.

Synthesis Example 10 Preparation of a compound represented by the formula (134)

(1) Synthesis of Compound Represented by Formula 10-a

A compound represented by the formula (10-a) was synthesized by the following reaction scheme (58).

[Reaction Scheme 58]

[Chemical Formula 10-a]

10.0 g (0.0308 mol) of the compound represented by the above formula [9-f] obtained in the above Reaction Scheme 51, 4.7 g (0.0277 mol) of diphenylamine, 0.1 g (0.0006 mol) of palladium acetate, 0.1 g (0.0006 mol) of butylphosphine, 5.9 g (0.0616 mol) of sodium tallow butoxide, and 100 mL of toluene were placed and refluxed for 12 hours. After the completion of the reaction, the reaction mixture was cooled to room temperature and extracted. The organic layer was concentrated under reduced pressure, and then separated by column chromatography using ethyl acetate and hexane. The solid was dried to obtain 7.1 g (55.9%) of the compound represented by Formula 10-a .

(2) Synthesis of Compound Represented by Formula 134

A compound represented by the formula (134) was synthesized by the following scheme (59).

[Reaction Scheme 59]

(134)

A solution of 7.0 g (0.0170 mol) of the compound represented by the above formula [10-a] and 10.7 g (0.0221 mol) of the compound represented by the above formula [5-a] mol), 8.1 g (61.9%) of the compound represented by the formula (134) was obtained in the same manner as in the reaction scheme [9].

MS: m / z Calcd 769.32; Found 769. Anal. Calcd. for C ₅₅ H ₃₉ N ₅ : C, 85.80; H, 5.11; N, 9.10. Found: C, 84.99; H, 5.01; N, 9.54.

Synthesis Example 11 Synthesis of a compound represented by the formula (Formula 165)

(1) Synthesis of Compound Represented by Formula (11-a)

A compound represented by the formula (11-a) was synthesized by the following scheme (60).

[Reaction Scheme 60]

[Formula 11-a]

100.0 g (0.422 mol) of 2,6-dibromopyridine and 200 mL of diethyl ether were placed in a 500 mL round-bottomed flask, and the temperature of the reaction mixture was lowered to -78 ° C under a nitrogen atmosphere. Then, 290 mL of normal butyl lithium mol) was added dropwise for 1 hour. After stirring at the same temperature for 2 hours, 16.1 g (0.106 mol) of phosphoryl chloride was added slowly and stirred at the same temperature for 2 hours. The temperature was raised to room temperature, and the organic layer was separated using water and diethyl ether. The organic layer was concentrated under reduced pressure, and then recrystallized from methylene chloride and methanol to obtain 29.0 g (18.9%) of the compound represented by Formula 11-a.

(2) Synthesis of Compound Represented by Formula (11-b)

A compound represented by the formula (11-b) was synthesized by the following scheme (61).

[Reaction Scheme 61]

[Formula 11-b]

29.0 g (0.0923 mol) of the compound represented by the formula (11-a) obtained from the above-mentioned scheme 60, 23.0 g (0.0923 mol) of the formula 1-e obtained from the scheme 5, , 2.1 g (0.0002 mol) of tetrakistriphenylphosphine palladium, 300 mL of tetrahydrofuran and 150 mL of water, and the mixture was stirred under reflux for 16 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and extracted. The organic layer was concentrated under reduced pressure, and then separated by column chromatography using ethyl acetate and hexane. The solid was dried to obtain 16.7 g (50.7%

(3) Synthesis of Compound Represented by Formula 11-c

The compound represented by the formula (11-c) was synthesized by the following scheme (Scheme 62).

[Reaction Scheme 62]

[Chemical Formula 11-c]

16.0 g (0.0493 mol) of [Formula 11-b] and 95.8 g (0.3652 mol) of triphenylphosphine obtained from the above Scheme 61 were dissolved in 160 mL of o-dichlorobenzene and refluxed for 24 hours in a 500 mL round bottom flask. After the reaction was completed, the solution was cooled to room temperature, and the solvent was removed by distillation under reduced pressure. The resulting solid was separated by column chromatography using ethyl acetate and hexane as eluent to obtain 10.8 g of a compound represented by the formula 11-c (Yield: 58.4%).

(4) Synthesis of Compound Represented by Formula (11-d)

A compound represented by the formula (11-d) was synthesized by the following scheme (Scheme 63).

[Reaction Scheme 63]

[Chemical Formula 11-d]

20 g (0.0848 mol) of 1,4-dibromobenzene and 200 mL of tetrahydrofuran were placed in a 500 mL round-bottomed flask, and the temperature of the reaction product was lowered to -78 ° C under a nitrogen atmosphere. 25.8 g (0.0932 mol ) Was added dropwise over 20 minutes. After stirring at the same temperature for 1 hour, 27.4 g (0.0932 mol) of chlorodiphenylsilane was added and the temperature was raised to room temperature. After stirring for 13 hours, the organic layer was separated using ammonium chloride aqueous solution and ethyl ether, Was separated by column chromatography using methylene chloride and a hexane developing solvent, and the solid was dried to obtain 27.0 g (76.8%) of a compound represented by the formula [11-d].

(5) Synthesis of Compound Represented by Formula 11-e

The compound represented by the formula (11-e) was synthesized by the following scheme (64).

[Reaction Scheme 64]

[Formula 11-e]

10.0 g (0.0427 mol) of the compound represented by the formula (8-e), 13.0 g (0.0512 mol) of bisphenacol diboron and 0.8 g of bisdiphenylphosphinoferrocene dichloropalladium 0.8 g (0.0008 mol) of potassium acetate, 4.5 g (0.0854 mol) of potassium acetate and 100 mL of toluene were put and refluxed for 6 hours. When the reaction was complete, it was filtered under hot conditions and extracted with toluene and water. The organic layer was dehydrated with magnesium sulfate, concentrated under reduced pressure, and separated by column chromatography with methylene chloride and hexane to obtain 10.7 g (89.2%) of the compound represented by the formula 11-e.

(6) Synthesis of a compound represented by the formula (11-f)

A compound represented by the formula (11-f) was synthesized according to the following scheme (Scheme 65).

[Reaction Scheme 65]

[Chemical Formula 11-f]

10.0 g (0.0370 mol) of the compound represented by the above formula [11-c], 0.045 g (0.0370 mol) of the compound represented by the above formula [11] 0.7 g (0.0006 mol) of tetrakis (triphenylphosphine) palladium, 100 mL of tetrahydrofuran and 50 mL of water were placed, and the mixture was refluxed with stirring for 16 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and extracted with water. The organic layer was concentrated under reduced pressure, and then separated by column chromatography using ethyl acetate and hexane. The solid was dried to obtain 8.8 g (71.7% .

(7) Synthesis of Compound Represented by Formula 165

A compound represented by the formula (165) was synthesized by the following scheme (Scheme 66).

[Reaction Scheme 66]

(165)

8.0 g (0.0201 mol) of the compound represented by the above formula [11-f] obtained from the above-mentioned scheme 65 and 10.0 g (0.0241 mol) of the compound represented by the formula 11-d obtained from the above scheme [63] were added to a 100 mL round bottom flask. mol), 8.1 g (54.9%) of a compound represented by the formula (165) was obtained in the same manner as in the reaction scheme [9].

MS: m / z Calcd 732.27; found 732. Anal. Calcd. for C ₅₁ H ₃₆ N ₄ Si: C, 83.57; H, 4.95; N, 7.64; Si, 3.83. Found: C, 84.01; H, 5.12; N, 7.29.

Synthesis Example 12 Synthesis of the compound represented by the formula (170)

(1) Synthesis of Compound Represented by Formula 12-a

A compound represented by the formula (12-a) was synthesized by the following scheme (67).

[Reaction Scheme 67]

[Chemical Formula 12-a]

20.0 g (0.0619 mol) of the compound represented by the formula (7-a), 18.8 g (0.0742 mol) of bisphenacol diboron, 0.0742 mol of bisdiphenylphosphinoferrocene dichloropalladium 1.1 g (0.0012 mol), potassium acetate (6,5 g, 0.1238 mol) and toluene (200 mL) were added and refluxed for 6 hours. When the reaction was complete, it was filtered under hot conditions and extracted with toluene and water. The organic layer was dehydrated with magnesium sulfate, concentrated under reduced pressure, and separated by column chromatography with methylene chloride and hexane to obtain 22.9 g (88.5%) of a compound represented by the formula 12-a.

(2) Synthesis of Compound Represented by Formula 12-b

A compound represented by the formula (12-b) was synthesized by the following scheme (68).

[Reaction Scheme 68]

[Chemical Formula 12-b]

10.0 g (0.0308 mol) of the compound represented by the formula (9-g) obtained from the above-mentioned scheme 51 and 13.7 g (0.0370 mol) of the compound represented by the formula 12-a obtained from the above scheme 67 in the 2 L round- 0.7 g (0.0006 mol) of tetrakistriphenylphosphine palladium, 8.5 g (0.0616 mol) of potassium carbonate, 10 mL of tetrahydrofuran, 10 mL of toluene and 10 mL of water were placed and refluxed for 12 hours. When the reaction was completed, it was cooled to room temperature and extracted with ethyl acetate and water. The organic layer was dehydrated with magnesium sulfate and concentrated under reduced pressure to obtain crystals, which were recrystallized from ethyl acetate and hexane to obtain 14.0 g (93.6%) of a compound represented by the formula 12-b.

(3) Synthesis of a compound represented by the formula (170)

A compound represented by the formula (170) was synthesized by the following scheme (69).

[Reaction Scheme 69]

(170)

10.0 g (0.0205 mol) of the compound represented by the formula 12-b] obtained from the above-mentioned scheme 68 and 8.0 g (0.0246 (g) of the compound represented by the formula 7-a obtained from the above scheme 37) mol), 10.4 g (69.9%) of the compound represented by the formula (170) was obtained in the same manner as in the reaction scheme [9].

MS: m / z Calcd 729.26; found 729. Anal. Calcd. for C ₅₀ H ₃₁ N ₇ : C, 82.28; H, 4.28; N, 13.43. Found: C, 83.01; H, 4.87; N, 12.87.

Synthesis Example 13: Preparation of a compound represented by the formula 181

(1) Synthesis of Compound Represented by Formula (13-a)

A compound represented by the formula (13-a) was synthesized by the following reaction scheme (70).

[Reaction Scheme 70]

[Chemical Formula 13-a]

20.0 g (0.0848 mol) of 1,3-dibromophenyl, 20.7 g (0.0763 mol) of triphenyleneboronic acid, 1.9 g (0.0017 mol) of tetrakistriphenylphosphine palladium and 23.4 g 0.1700 mol), tetrahydrofuran (100 mL), toluene (100 mL) and water (100 mL) were added and refluxed for 12 hours. When the reaction was completed, it was cooled to room temperature and extracted with ethyl acetate and water. The organic layer was dehydrated with magnesium sulfate and concentrated under reduced pressure to obtain crystals. The crystals were recrystallized from methylene chloride and hexane to obtain 25.6 g (78.8%) of the compound represented by the formula (13-a).

(2) Synthesis of Compound Represented by Formula (13-b)

The compound represented by the formula (13-b) was synthesized by the following reaction scheme (71).

[Reaction Scheme 71]

[Chemical Formula 13-b]

23.7 g (0.0619 mol) of the compound represented by the above formula (13-a), 18.8 g (0.0742 mol) of bisphenacol diboron and 0.0742 mol of bisdiphenylphosphinoferrocene dichloropalladium 1.1 g (0.0012 mol) of potassium acetate, 6,5 g (0.1238 mol) of potassium acetate and 200 mL of toluene were put and refluxed for 6 hours. When the reaction was complete, it was filtered under hot conditions and extracted with toluene and water. The organic layer was dehydrated with magnesium sulfate, concentrated under reduced pressure, and separated by column chromatography with methylene chloride and hexane to obtain 22.6 g (84.9%) of the compound represented by the formula 13-b.

(3) Synthesis of Compound Represented by Formula 13-c

The compound represented by the formula (13-c) was synthesized by the following reaction scheme (72).

[Reaction Scheme 72]

[Chemical Formula 13-c]

10.0 g (0.0308 mol) of the compound represented by the formula [9-g] obtained from the above-mentioned scheme [51] and 15.9 g (0.0370 mol) of the compound represented by the above formula [ 0.7 g (0.0006 mol) of tetrakistriphenylphosphine palladium, 8.5 g (0.0616 mol) of potassium carbonate, 100 mL of tetrahydrofuran, 100 mL of toluene and 100 mL of water were placed and refluxed for 12 hours. When the reaction was completed, it was cooled to room temperature and extracted with ethyl acetate and water. The organic layer was dehydrated with magnesium sulfate and concentrated under reduced pressure to obtain crystals, which were recrystallized from ethyl acetate and hexane to obtain 13.1 g (77.9%) of a compound represented by the formula 13-c.

(4) Synthesis of Compound Represented by Formula 181

A compound represented by the formula (181) was synthesized by the following scheme (73).

[Reaction Scheme 73]

[181]

11.2 g (0.0205 mol) of the compound represented by the formula 13-c] obtained from the above-mentioned scheme [72] and 9.4 g (0.0246 (g) of the compound represented by the formula 13-a obtained from the above scheme 70] were added to a 100 mL round bottom flask. mol), 10.1 g (57.9%) of the compound represented by the formula (181) was obtained in the same manner as in the reaction scheme [9].

MS: m / z Calcd 849.31; found 849. Anal. Calcd. for C ₆₄ H ₃₉ N ₃ : C, 90.43; H, 4.62; N, 4.94. Found: C, 91.01; H, 4.82; N, 4.64.

&Lt; Examples 1 to 13 > Preparation of Organic Electroluminescent Device

The ITO glass was patterned to have a light emitting area of 2 mm x 2 mm and then cleaned. DNTPD (700Å) of ITO on the organic material so that after a then attached to a vacuum chamber base pressure was 1 × 10 ^-6 torr substrate, NPD (300Å), the compound + Ir (ppy) ₃ prepared according to the present invention ( Alq ₃ (350 Å), LiF (5 Å), and Al (1,000 Å).

[DNTPD]

[NPD]

[Ir (ppy) ₃ ]

[Alq ₃ ]

&Lt; Comparative Example 1 &

The organic electroluminescent device for the comparative example was fabricated in the same manner except that CBP of the following structural formula was used in place of the compound prepared by the invention in the device structures of Examples 1 to 13 above.

[CBP]

The driving voltage, luminance, color coordinates, and lifetime of the organic electroluminescent device manufactured according to Examples 1 to 13 and Comparative Example 1 were measured, and the results are shown in Table 1 below. T50 means the time required for the luminance to be reduced to 50% of the initial luminance.

division Host Dopant Doping concentration (%) ETL V Cd / A CIEx CIEy T50 (Hr) Comparative Example 1 CBP Ir (ppy) ₃ 10 Alq ₃ 8.20 38.81 0.29 0.62 76 Example 1 Formula 5 Ir (ppy) ₃ 10 Alq ₃ 5.73 48.87 0.32 0.62 104 Example 2 8 Ir (ppy) ₃ 10 Alq ₃ 5.94 50.11 0.32 0.63 138 Example 3 25 Ir (ppy) ₃ 10 Alq ₃ 5.19 58.67 0.33 0.64 281 Example 4 Formula 29 Ir (ppy) ₃ 10 Alq ₃ 5.92 55.71 0.31 0.63 185 Example 5 Formula 51 Ir (ppy) ₃ 10 Alq ₃ 5.83 51.66 0.33 0.64 172 Example 6 (67) Ir (ppy) ₃ 10 Alq ₃ 6.39 51.72 0.31 0.63 136 Example 7 70 Ir (ppy) ₃ 10 Alq ₃ 5.88 49.90 0.31 0.63 114 Example 8 94 Ir (ppy) ₃ 10 Alq ₃ 5.59 51.51 0.32 0.64 150 Example 9 127 Ir (ppy) ₃ 10 Alq ₃ 5.51 52.59 0.32 0.64 198 Example 10 (134) Ir (ppy) ₃ 10 Alq ₃ 4.94 55.01 0.31 0.63 205 Example 11 (165) Ir (ppy) ₃ 10 Alq ₃ 5.91 57.88 0.32 0.63 139 Example 12 170 Ir (ppy) ₃ 10 Alq ₃ 5.41 50.96 0.31 0.64 181 Example 13 181 Ir (ppy) ₃ 10 Alq ₃ 5.96 56.81 0.32 0.64 208

(25) according to the present invention. (UV / Vis absorption spectrometer) and a cyclic voltammetry were used to measure the band gaps of [Formula 134] and [Formula 181].

division UVl _max PLl _max HOMO (eV) LUMO (eV) Band gap (eV) 25 328 373 6.01 2.69 3.32 (135) 330 399 5.98 2.72 3.26 183 358 401 6.07 2.86 3.21

Referring to Table 1, it can be seen that the organic electroluminescent device according to Examples 1 to 13 and Comparative Example 1 has superior brightness and long life. Therefore, it is understood that the organic electroluminescent device comprising the compound represented by the formula (1) according to the present invention in the light emitting layer is excellent in luminance, lifetime characteristics, and light emitting efficiency and can be used for display devices, display devices, have.

10: substrate 20: anode
30: Hole injection layer 40: Hole transport layer
50: organic light emitting layer 60: electron transporting layer
70: electron injection layer 80: cathode

Claims (8)

A pyridine derivative compound represented by any one of the following formulas (2) to (193):
[Chemical Formula 2] &lt; EMI ID =

[Chemical Formula 7] [Chemical Formula 8] [Chemical Formula 9]

[Chemical Formula 11] [Chemical Formula 12] [Chemical Formula 13]

[Chemical Formula 14] [Chemical Formula 15]

[Chemical Formula 20] [Chemical Formula 20]

[Chemical Formula 22] [Chemical Formula 23] [Chemical Formula 25]

[Chemical Formula 28] [Chemical Formula 28]

[Chemical Formula 32] [Chemical Formula 32]

[Chemical Formula 35] [Chemical Formula 35]

[Chemical Formula 40] [Chemical Formula 40] [Chemical Formula 40]

[Chemical Formula 43] [Chemical Formula 44] [Chemical Formula 45]

[Chemical Formula 48] [Chemical Formula 48] [Chemical Formula 48]

[Chemical Formula 51] [Chemical Formula 52] [Chemical Formula 53]

[Chemical Formula 55] [Chemical Formula 55] [Chemical Formula 55]

[Chemical Formula 60] [Chemical Formula 61]

[Chemical Formula 62] [Chemical Formula 65] [Chemical Formula 65]

[Chemical Formula 67] [Chemical Formula 68] [Chemical Formula 69]

[Chemical Formula 71] [Chemical Formula 72] [Chemical Formula 73]

[Chemical Formula 75] [Chemical Formula 76] [Chemical Formula 77]

[Formula 79] [Formula 80] [Formula 81]

[Chemical Formula 82]

[Chemical Formula 88] [Chemical Formula 88] [Chemical Formula 89]

[Chemical Formula 91] [Chemical Formula 92] [Chemical Formula 93]

[Chemical Formula 95] [Chemical Formula 96] [Chemical Formula 97]

[Chemical Formula 100] [Chemical Formula 100]

[Formula 103] [Formula 103]

[Chemical Formula 10] [Chemical Formula 10] [Chemical Formula 10] [Chemical Formula 10]

[Formula 110] [Formula 111] [Formula 112] [Formula 113]

[Chemical Formula 115]

[Chemical Formula 120] [Chemical Formula 120] [Chemical Formula 120]

[Formula 124] [Formula 124] [Formula 125]

[Formula 126] &lt; EMI ID = 129.1 &gt;

[Formula 130] &lt; EMI ID = 131.0 &gt;

[Formula 135] [Formula 135] [Formula 137]

[Chemical Formula 140] [Chemical Formula 140] [Chemical Formula 140]

[Chemical Formula 144] [Chemical Formula 144] [Chemical Formula 145]

[Chemical Formula 146] [Chemical Formula 148] [Chemical Formula 149]

[Formula 15] [Formula 15] [Formula 15] [Formula 15]

[Chemical Formula 155] [Chemical Formula 156] [Chemical Formula 157]

[Formula 15] [Formula 15] [Formula 15] [Formula 15] [Formula 15]

[166] [165] [165]

[Formula 166] [Formula 169] [Formula 169]

[173] [173] [173]

[Formula 177] [Formula 177] [Formula 177]

[Formula 181] [Formula 181] [Formula 181] [Formula 181]

[Formula 182] [Formula 184] [Formula 184]

[Formula 188] [Formula 188] [Formula 189]

[Formula 19] [Formula 19] [Formula 193] [Formula 193]

delete delete Anode;
Cathode; And
And a layer comprising the pyridine derivative compound according to claim 1 interposed between the anode and the cathode. 5. The method of claim 4,
Wherein the pyridine derivative compound is contained in the light emitting layer between the anode and the cathode. 6. The method of claim 5,
Wherein at least one layer selected from the group consisting of a hole injecting layer, a hole transporting layer, an electron blocking layer, a hole blocking layer, an electron transporting layer and an electron injecting layer is further interposed between the anode and the cathode. The method according to claim 6,
Wherein at least one layer selected from the group consisting of the hole injection layer, the hole transport layer, the electron blocking layer, the light emitting layer, the hole blocking layer, the electron transport layer and the electron injection layer is formed by a single molecular deposition method or a solution process. 5. The method of claim 4,
Wherein the organic electroluminescent device is used in a display device, a display device, or a device for monochromatic or white illumination.

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