KR101788793B1 - Pyridine derivative compound and organic electroluminescent devices comprising the same - Google Patents

Abstract

[화학식 3]

The present invention relates to a pyridine derivative compound and an organic electroluminescent device including the same, and more particularly, to a pyridine derivative compound represented by the following formulas (1) to (3) and an organic electroluminescent device including the same, Color purity and lifetime characteristics.
[Chemical Formula 1] < EMI ID =

(3)

Description

(Pyridine Derivative Compound and Organic Electroluminescent Device Containing the Same)

The present invention relates to a pyridine derivative compound and an organic electroluminescent device including the same, and more particularly, to a pyridine derivative compound having excellent driving voltage, luminance, color purity, and lifetime characteristics, 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 the organic electroluminescent device, holes are injected into the anode, electrons are injected into the organic layer, and 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 necessary for realizing 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 pyridine derivative compound having a low driving voltage of green phosphorescence, excellent luminance and color purity, and long life.

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 formulas (1) to (3).

[Chemical Formula 1] < EMI ID =

(3)

In the above Chemical Formulas 1 to 3,

R ₁ to R ₉ 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,

m is an integer of 1 to 6,

n and o are each independently an integer of 0 to 4,

When m and o are 2 or more, the plurality of R ₁ to R ₉ may independently be the same or different.

According to one embodiment of the present invention, each of R ₁ to R ₉ (except when R ₁ to R ₉ are each a hydrogen atom, a deuterium atom, a halogen atom or a nitro group) is independently a group having 6 to 24 carbon atoms An aryl group, a heteroaryl group having 2 to 24 carbon atoms, and an alkyl group having 1 to 24 carbon atoms.

According to another aspect of the present invention,

Anode; Cathode; And a layer containing a pyridine derivative compound represented by the above Chemical Formulas 1 to 3 interposed between the anode and the cathode.

Since the pyridine derivative compounds represented by the formulas (1) to (3) according to the present invention are compounds having a high triplet energy (T1) and high thermal stability, the organic electroluminescent device comprising the derivative compound has excellent brightness, And lifetime characteristics, and thus 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.
FIG. 2 is a graph showing TGA and DSC according to an embodiment of the present invention. FIG.
3 is a graph showing EL spectra of [Formula 84] and Comparative Example 1 according to an embodiment of the present invention.
4 is a representative view showing the structure of a pyridine derivative represented by the general formulas (1) to (3) 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 represented by the above Chemical Formulas 1 to 3 and has high triplet energies (T1) and high thermal stability. It is also known that a compound having various substituents bonded to a pyridine derivative compound .

In the pyridine derivative compounds according to the present invention, the substituents of the above formulas (1) to (3) will be described in more detail as follows.

In the above Chemical Formulas 1 to 3, R ₁ to R ₉ each independently represent a hydrogen atom, a deuterium atom, a halogen atom, a nitro group, a substituted or unsubstituted C6 to C40 aryl group, a substituted or unsubstituted C2- A substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C6-C40 cycloalkyl group, a substituted or unsubstituted C2-C40 amino group, a substituted or unsubstituted C1- A substituted or unsubstituted C1-C20 alkyloxy group, a substituted or unsubstituted C6-C30 aryloxy group, a substituted or unsubstituted C1-C20 alkylamino group, a substituted or unsubstituted C1-C20 alkylsilyl group, a substituted or unsubstituted C6- A substituted or unsubstituted arylalkylamino group having 1 to 50 carbon atoms, a substituted or unsubstituted cycloalkylene group having 6 to 40 carbon atoms, a substituted or unsubstituted Unsubstituted alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted germanium group, a substituted or unsubstituted phosphorus, or substituted can be selected from the unsubstituted boron.

In addition, Formula (1) to (the end, R ₁ to R ₉ each except hydrogen atom, a heavy hydrogen atom, a halogen atom or a nitro group) [Formula 3] R ₁ to R ₉ in the carbon number of 6 to each independently An aryl group having 1 to 24 carbon atoms, a heteroaryl group having 2 to 24 carbon atoms, and an alkyl group having 1 to 24 carbon atoms.

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 each independently a carbon number 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 (for example, an alkyl 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" refers to a group selected from the group consisting of aryl, heteroaryl, alkyl, heteroalkyl, alkoxy, cyano, halogen, aryloxy, Quot; means substituted or unsubstituted with one or more substituents selected.

The present invention is not limited by the specific examples of the pyridine derivative compounds according to the above-mentioned formulas (1) to (3) having the above-described structure, but specifically, the compounds represented by the following formulas (4) to Lt; / RTI >

[Chemical Formula 4] [Chemical Formula 5] Chemical Formula 7 [Chemical Formula 7]

[Formula 11] < EMI ID =

[Chemical Formula 13] [Chemical Formula 14] [Chemical Formula 15]

[Chemical Formula 18] [Chemical Formula 18] [Chemical Formula 19]

[Chemical Formula 21] [Chemical Formula 22] [Chemical Formula 23]

[Chemical Formula 25] [Chemical Formula 26] [Chemical Formula 27]

[Chemical Formula 30] [Chemical Formula 30]

[Chemical Formula 32] [Chemical Formula 32]

[Chemical Formula 37] [Chemical Formula 38] [Chemical Formula 39]

[Chemical Formula 40] [Chemical Formula 41]

[Chemical Formula 45] [Chemical Formula 46] [Chemical Formula 47]

[Chemical Formula 49] [Chemical Formula 50] [Chemical Formula 51]

[Chemical Formula 55] [Chemical Formula 55]

[Chemical Formula 57] [Chemical Formula 58] [Chemical Formula 59]

[Chemical Formula 60] [Chemical Formula 62] [Chemical Formula 63]

[Chemical Formula 65] [Chemical Formula 66] [Chemical Formula 67]

[Chemical Formula 70] [Chemical Formula 70] [Chemical Formula 70]

[Formula 75] [Formula 75] [Formula 75]

[Chemical Formula 77] [Chemical Formula 78] [Chemical Formula 79]

[Chemical Formula 81] [Chemical Formula 82] [Chemical Formula 83]

[Chemical Formula 85]

[Chemical Formula 90] [Chemical Formula 90] [Chemical Formula 90]

[Chemical Formula 93] [Chemical Formula 95] [Chemical Formula 95]

[Chemical Formula 98] [Chemical Formula 98]

[Chemical Formula 100] [Chemical Formula 101] [Chemical Formula 102] [Chemical Formula 103]

[Chemical Formula 106] [Chemical Formula 106]

[Formula 110] [Formula 110] [Formula 111]

[Formula 113] < EMI ID = 113.1 >

(119) < EMI ID = 116.1 >

[Formula 120] < EMI ID =

[Formula 124] [Formula 125] [Formula 126] [Formula 127]

[Formula 131] [Formula 130] [Formula 131]

[Formula 135] [Formula 135]

[Chemical Formula 138] [Chemical Formula 138] [Chemical Formula 138]

[Formula 140] < EMI ID = 141.0 >

[Chemical Formula 144] [Chemical Formula 145] [Chemical Formula 146]

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 containing a pyridine derivative compound represented by the above Chemical Formulas 1 to 3 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 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) triphenyl-amine) or m-MTDATA (4,4', 4 '' - triphenylamine), which is a copper phthalocyanine (CuPc) or starburst type amine, 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 7

(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 to remove water and the solvent was distilled off under reduced pressure. The precipitated solid was washed with ethanol and then filtered to obtain 219 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 [Formula 1-a] obtained from [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, and the mixture was stirred at 90 占 폚 for 23 hours. The temperature was lowered to room temperature, poured slowly 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 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 to 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 replaced 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 two hours. After cooling to room temperature, the mixture was added to 2 L of water and adjusted to pH ~11 with an aqueous solution of sodium hydroxide. 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 g (yield: 99%) 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 100g (0.501mol), bis To the solution were dissolved in toluene 1.5L (pinacolato) diboron 150.9g (0.593 mol), Pd ( dppf) Cl 2 12.1g (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. The solution was cooled to room temperature, and the solvent was distilled off under reduced pressure. The resulting solid was separated by column chromatography using n-hexane as eluent to obtain 80 g (yield 65%) of a 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 Reaction Scheme 4, 148.2 g (0.601 mol) of Formula 1-e obtained from Reaction Scheme 5, 117 g (0.851 mol) 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 Reaction Scheme 6 were dissolved in 800 mL of o-dichlorobenzene and 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 Compound Represented by Formula 7

[Chemical Formula 7] was synthesized by the following Reaction Scheme 8.

[Reaction Scheme 8]

(7)

(0.0269 mol) of the formula 1-g obtained from the above scheme 7, 3.7 g (0.0112 mol) of bromoiodobenzene, 25.9 g (0.0795 mol) of cesium carbonate, 2.85 g mol) and dichloromethane (70 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 ethyl acetate and methanol as eluent to obtain a solid. (47.4%) of the title compound.

MS: m / z calcd 564.21; found 564. Anal. Calcd. for C ₃₈ H ₂₄ N ₆ : C, 80.83; H, 4.28; N, 14.88. Found: C, 80.76; H, 3.93; N, 14.01.

Synthesis Example 2 Synthesis of Compound Represented by Formula 11

(1) Synthesis of Compound Represented by Formula 11

A compound represented by the formula (11) was synthesized by the following reaction scheme (9).

[Reaction Scheme 9]

(11)

6.6 g (0.0269 mol) of [Formula 1-g] obtained from the above Reaction Scheme 7 and 5.0 g (0.0112 mol) of 2,7-diiodo-9,9-dimethylpolrene were added to a 100 mL round bottom flask 8], 3.9 g (52%) of the compound represented by the formula (11) was obtained.

MS: m / z Calcd 680.27; found 680. Anal. Calcd. for C ₄₇ H ₃₂ N ₆ : C, 82.92; H, 4.74; N, 12.34. Found: C, 82.77; H, 3.98; N, 12.11.

&Lt; Synthesis Example 3 > Preparation of a compound represented by the formula (15)

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

A compound represented by the formula (3-a) or (3-b) was synthesized by the following reaction scheme.

[Reaction Scheme 10]

[Formula 3-a] [Formula 3-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 then recrystallized from methylene chloride and a hexane solvent to obtain 16.0 g (40.4%) of the compound represented by the formula (3-a) and 18 g (45.5%) of the compound represented by the formula .

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

[Chemical Formula 3-c] was synthesized by the following Reaction Scheme 11.

[Reaction Scheme 11]

[Chemical Formula 3-c]

16.0 g (0.0645 mol) of [Formula 3-a], 11.6 g (0.0612 mol) of 4-bromosuophenol, 0.6 g (0.0032 mol) of copper iodide and 8.0 g (0.1289 mol) of potassium carbonate and 17.8 g (0.1289 mol) of isopropanol were added to 160 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 3- (65.7%) was obtained.

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

A compound represented by the formula (3-d) was synthesized by the following reaction scheme (12).

[Reaction Scheme 12]

[Chemical formula 3-d]

12.7 g (0.0402 mol) of the compound represented by the general formula [3-c] obtained from the reaction scheme 11 and 600 mL of acetone were added to a 1 L round bottom flask and stirred. 4.1 g (0.0402 mol) of butyl nitrite was slowly added thereto, And stirred for 1 hour. 1.8 g (0.0173 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 6.8 g (56.6%) of [Formula 3-d].

(4) Synthesis of Compound Represented by Formula 15

A compound represented by the formula (15) was synthesized by the following reaction scheme (13).

[Reaction Scheme 13]

[Chemical Formula 15]

6.6 g (0.0269 mol) of the compound represented by the formula (1-g) obtained from the above Reaction Scheme 7 and 3.3 g (0.0112 mol) of the Formula 3-d obtained from the scheme 12 were added to a 100 mL round- 4.4 g (58.3%) of the compound represented by the formula (15) was obtained in the same manner as in the reaction scheme 8].

MS: m / z Calcd 671.19; found 671. Anal. Calcd. for C ₄₃ H ₂₅ N ₇ S: C, 76.88; H, 3.75; N, 14.60; S, 4.77. Found: C, 76.11; H, 3.54; N, 14.83.

&Lt; Synthesis Example 4 > Preparation of a compound represented by the formula (21)

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

A compound represented by the following formula (4-a) was synthesized by the following reaction scheme (14).

[Reaction Scheme 14]

[Chemical Formula 4-a]

18.0 g (0.0715 mol) of [Formula 3-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 (68.1%) was obtained.

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

[Chemical Formula 4-b] was synthesized by the following Reaction Scheme 15.

[Reaction Scheme 15]

[Formula 4-b]

14.6 g (0.0463 mol) of the compound represented by the formula [4-a] obtained from the reaction scheme 14 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 a compound represented by the formula [3-d].

(3) Synthesis of Compound Represented by Formula 21

A compound represented by the formula (21) was synthesized by the following scheme (16).

[Reaction Scheme 16]

[Chemical Formula 21]

6.6 g (0.0269 mol) of the compound represented by the formula (1-g) obtained from the above-mentioned scheme 7 and 3.3 g (0.0112 mol) of the formula 4-b obtained from the scheme 15 were added to a 100 mL round- 4.4 g (58.3%) of the compound represented by the formula (21) was obtained in the same manner as in the reaction scheme 8].

MS: m / z Calcd 671.19; found 671. Anal. Calcd. for C ₄₃ H ₂₅ N ₇ S: C, 76.88; H, 3.75; N, 14.60; S, 4.77. Found: C, 76.46; H, 3.58; N, 14.87.

&Lt; Synthesis Example 5 > Preparation of a compound represented by the formula (26)

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

A compound represented by the following formula (5-a) was synthesized by the following scheme (17).

[Reaction Scheme 17]

[Formula 5-a]

200 g (1.085 mol) of dibenzothiophene and 2 L of chloroform were added to 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 5-a.

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

[Chemical Formula 5-b] was synthesized by the following Reaction Scheme 18.

[Reaction Scheme 18]

[Chemical Formula 5-b]

143 g (0.544 mol) of the compound represented by the general formula [5-a] obtained from the above-mentioned Reaction Scheme 17, 152 g (0.598 mol) of bispinacoloboron, 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 a 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 (19).

[Reaction Scheme 19]

[Chemical Formula 5-c]

158.4 g (0.51 mol) of the compound represented by the general formula [5-b], 86 g (0.0426 mol) of bromonitrobenzene, 9.8 g of tetrakistriphenylphosphine palladium in a 2 L round bottom flask (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 5-c.

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

[Chemical Formula 5-d] was synthesized by the following Reaction Formula (20).

[Reaction Scheme 20]

[Chemical formula 5-d]

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 [5-c] obtained from the above Scheme 19 and 42.8 g of triphenylphosphine were added and refluxed for 12 hours. After completion of the reaction, dichlorobenzene was removed by distillation, followed by column chromatography using ethyl acetate and hexane. The solid was dried to obtain 16.6 g (93.1%) of a compound represented by the formula 5-d.

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

[Chemical Formula 5-e] was synthesized by the following Reaction Scheme (21).

[Reaction Scheme 21]

[Chemical Formula 5-e]

16.0 g (0.0585 mol) of the compound represented by the formula 5-d] obtained from the above-mentioned Reaction formula 20, 16.6 g (0.0526 mol) of 1,3,5-tribromobenzene, 57.2 g (0.1755 mol) of copper, 6.7 g (0.1053 mol) of copper and 200 mL of dichlorobenzene 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 separated by column chromatography using methylene chloride and hexane as developing solvents, and the resulting solid was dried to obtain 5- Was obtained in an amount of 10.9 g (40.1%).

(6) Synthesis of Compound Represented by Formula 26

A compound represented by the formula (26) was synthesized by the following reaction scheme (22).

[Reaction Scheme 22]

(26)

6.6 g (0.0269 mol) of the compound represented by the formula (1-g) obtained from the above-mentioned scheme 7 and 5.7 g (0.0112 mol) of the formula 5-e obtained from the above scheme were added to a 100 mL round- 4.8 g (51.3%) of the compound represented by the formula (26) was obtained in the same manner as in the reaction scheme 8].

MS: m / z Calcd 835.25; found 835. Anal. Calcd. for C ₅₆ H ₃₃ N ₇ S: C, 80.46; H, 3.98; N, 11.73; S, 3.84. Found: C, 79.98; H, 3.45; N, 12.09.

Synthesis Example 6 Synthesis of Compound Represented by Formula 44

(1) Synthesis of Compound Represented by Formula 44

A compound represented by the formula (44) was synthesized by the following Reaction Scheme (23).

[Reaction Scheme 23]

(44)

6.6 g (0.0269 mol) of the compound represented by the formula (1-g) obtained from the above-mentioned scheme 7 and 4.5 g (0.0112 mol) of dibromotriphenylamine were added to a 100 mL round bottom flask, To obtain 5.0 g (61.5%) of a compound represented by the formula (44).

MS: m / z Calcd 731.28; found 731. Anal. Calcd. for C ₅₀ H ₃₃ N ₇ : C, 82.06; H, 4.54; N, 13.40. Found: C, 81.88; H, 4.35; N, 13.18.

Synthesis Example 7 Synthesis of Compound Represented by Formula 65

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

[Chemical Formula 7-a] was synthesized by the following Reaction Formula 24.

[Reaction Scheme 24]

[Formula 7-a]

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, dichlorodiphenylsilane (0.0932 mol) was added, and the temperature was raised to room temperature. After stirring for 13 hours, an ammonium chloride aqueous solution and ethyl ether were used to separate the organic layer. The mixture was separated by column chromatography using methylene chloride and a developing solvent of hexane, and the solid was dried to obtain 31.5 g (75.2%) of the compound represented by the formula 7-a.

(2) Synthesis of Compound Represented by Formula 65

A compound represented by the formula (65) was synthesized by the following scheme (25).

[Reaction Scheme 25]

(65)

6.6 g (0.0269 mol) of the compound represented by the formula (1-g) obtained from the above Reaction Scheme 7 and 5.5 g (0.0112 mol) of the compound represented by the formula 7-a obtained from the Reaction Formula 24 were added to a 100 mL round bottom flask, (58.2%) was obtained in the same manner as in [Reaction Scheme 8].

MS: m / z Calcd 822.29; found 822. Anal. Calcd. for C ₅₆ H ₃₈ N ₆ Si: C, 81.72; H, 4.65; N, 10.21; Si, 3.41. Found: C, 81.79; H, 4.73; N, 10.03.

Synthesis Example 8 Synthesis of Compound Represented by Formula 84

(1) Synthesis of Compound Represented by Formula (84)

A compound represented by the formula [Formula 84] was synthesized by the following Reaction Formula 26.

[Reaction Scheme 26]

(84)

6.6 g (0.0269 mol) of the compound represented by the formula (1-g) obtained in the above Reaction Scheme 7 and 3.7 g (0.0112 mol) of diiodobenzene were introduced into a 100 mL round bottom flask, (39.7%) was obtained.

MS: m / z calcd 564.21; found 564. Anal. Calcd. for C ₃₈ H ₂₄ N ₆ : C, 80.83; H, 4.28; N, 14.88. Found: C, 80.11; H, 3.99; N, 14.61.

Synthesis Example 9 Synthesis of Compound Represented by Formula (98)

(1) Synthesis of Compound Represented by Formula 98

A compound represented by the formula (98) was synthesized by the following scheme (27).

[Reaction Scheme 27]

(98)

6.6 g (0.0269 mol) of the compound represented by the general formula [1-g] obtained from the above-mentioned Reaction Scheme 7 and 5.3 g (0.0112 mol) of dibromosulfur biplyrolene were placed in a 100 mL round bottom flask, 3.5 g (38.5%) of the compound represented by the formula (98) was obtained.

MS: m / z calcd 802.28; found 802. Anal. Calcd. for C ₅₇ H ₃₄ N ₆ : C, 85.27; H, 4.27; N, 10.47. Found: C, 85.39; H, 4.41; N, 10.07.

Synthesis Example 10: Preparation of a compound represented by the formula (119)

(1) Synthesis of Compound Represented by Formula (119)

[Chemical Formula 10-a] was synthesized by the following Reaction Formula 28.

[Reaction Scheme 28]

[Chemical Formula 10-a]

200 g (1.270 mol) of 2-bromopyridine and 2.4 L of tetrahydrofuran were placed in a 5 L round-bottomed 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- Lt; / RTI &gt; for 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 general formula [10-a].

(2) Synthesis of Compound Represented by Formula 10-b

[Chemical Formula 10-b] was synthesized by the following Reaction Scheme 29.

[Reaction Scheme 29]

[Chemical Formula 10-b]

In a 2 L round bottom flask, 231.9 g (0.630 mol) of the compound represented by the formula 10-a, 150.0 g (0.633 mol) of 2,6-dibromopyridine, , 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 10-b, ).

(3) Synthesis of Compound Represented by Formula 10-c

[Chemical Formula 10-c] was synthesized according to Reaction Scheme 30 below.

[Reaction Scheme 30]

[Chemical Formula 10-c]

51.8 g (0.220 mol) of the compound represented by the above formula [10-b] obtained from the above-mentioned Reaction Formula 29, 65.6 g (0.260 mol) of the Formula 1-e obtained from the Reaction 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 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 29.0 g (47.5%) of a compound represented by the formula 10-c .

(4) Synthesis of Compound Represented by Formula 10-d

[Chemical Formula 10-d] was synthesized by the following Reaction Formula 31.

[Reaction Scheme 31]

[Chemical Formula 10-d]

29.0 g (0.110 mol) of [Formula 10-c] and 192.8 g (0.740 mol) of triphenylphosphine obtained in the above Reaction Scheme 30 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 10-d (Yield: 51.7%).

(5) Synthesis of Compound Represented by Formula 10-e

[Chemical Formula 10-e] was synthesized by the following Reaction Formula 32.

[Reaction Scheme 32]

[Formula 10-e]

10 g (0.0422 mol) of 2,6-dibromopyridine, 7.6 g (0.0380 mol) of 3-bromo-1-phenylboronic acid and 2.4 g (0.0021 mol) of tetrakistriphenylphosphine palladium were added to a 250 mL round bottom flask, 17.5 g (0.1266 mol) of potassium carbonate, 100 mL of tetrahydrofuran and 50 mL of water were added, 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 8.0 g (60.5%) of the compound represented by Formula 10-e .

(6) Synthesis of a compound represented by the formula (119)

A compound represented by the formula (119) was synthesized by the following reaction scheme (33).

[Reaction Scheme 33]

(119)

6.6 g (0.0269 mol) of the compound represented by the formula (1-g) obtained from the above Reaction Scheme 7 and 3.5 g (0.0112 mol) of the Formula 10-e obtained from the above scheme were added to a 100 mL round- (58.6%) of the compound represented by the formula [119] was obtained in the same manner as in the reaction scheme [8].

MS: m / z Calcd 641.23; found 641. Anal. Calcd. _{for C 43 H 27 N 7:} C, 80.48; H, 4.24; N, 15.28. Found: C, 80.77; H, 4.39; N, 14.98.

Synthesis Example 11 Synthesis of Compound Represented by Formula 131

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

A compound represented by the formula (11-a) was synthesized according to the following scheme (Scheme 34).

[Reaction Scheme 34]

[Formula 11-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 to dissolve 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 formula (11-a).

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

[Chemical Formula 11-b] was synthesized by the following Reaction Scheme 35.

[Reaction Scheme 35]

[Formula 11-b]

199 g (1.057 mol) of [Formula 11-a] obtained from the above Reaction Scheme [34] was added to a 2 L round bottom flask and 1038 g (10.581 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 (11-b).

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

A compound represented by the formula [11-c] was synthesized by the following scheme [Reaction formula 36].

[Reaction Scheme 36]

                  [Chemical Formula 11-c]

126 g (0.456 mol) of [Formula 11-b] obtained from the above-mentioned Scheme 34 was added to a 5 L round bottom flask and 1.9 L of acetic acid was added thereto. Then, 140 g (1.141 mol) of acetyl bromide was slowly added dropwise at 40 占 폚. 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 procedure was repeated twice to obtain 116 g (yield 74%) of a compound represented by the formula [11-c].

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

A compound represented by the formula [11-d] was synthesized by the following scheme [Reaction formula 36].

[Reaction Scheme 36]

                [Chemical Formula 11-d]

37 g (0.107 mol) of [Formula 11-c] obtained from the above Reaction Formula [35] was placed in a 2 L round bottom flask and dissolved with 950 mL of chloroform. 297 g (1.132 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 was separated to remove water, and the solvent was removed by distillation under reduced pressure. The precipitated solid was washed with ethanol and then filtered to obtain 26 g (yield: 77%) of a compound represented by the formula (11-d).

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

[Chemical Formula 11-e] was synthesized by the following Reaction Scheme 37.

[Reaction Scheme 37]

[Formula 11-e]

25.0 g (0.0796 mol) of [Formula 11-d] obtained from the above-mentioned Reaction Formula 36, 17.8 g (0.0716 mol) of the Formula 1-e obtained from the Reaction Formula 5, 21.9 g 1.8 g (0.0016 mol) of tetrakistriphenylphosphine palladium, 40 mL of water, 100 mL of toluene and 100 mL of tetrahydrofuran were placed and refluxed for 24 hours. After completion of the reaction, the reaction product was separated to remove the water layer. The organic layer was separated, concentrated under reduced pressure, and then separated by column chromatography using ethyl acetate and hexane as eluent to obtain a solid. to obtain 15.3 g (yield: 54.1%) of a compound represented by the formula [e].

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

A compound represented by the formula [11-f] was synthesized by the following scheme [Scheme 38].

[Reaction Scheme 38]

[Chemical Formula 11-f]

13.0 g (0.033 mol) of [Formula 11-e] and 42.7 g (0.163 mol) of triphenylphosphine obtained in the above Reaction Scheme 37 were dissolved in 200 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 dichloromethane as a developing solvent to obtain 5.8 g (yield: 54% %).

(7) Synthesis of a compound represented by the formula (11-g)

A compound represented by the formula (11-g) was synthesized by the following scheme (Scheme 39).

[Reaction Scheme 39]

[Formula 11-g]

5.0 g (0.0154 mol) of the compound represented by the above formula [11-f], 2.3 g (0.0185 mol) of 3-pyridine boronic acid and 4.2 g (0.0308 mol) of potassium carbonate were added to a 100 mL round bottom flask, 0.4 g (0.00031 mol) of tetrakistriphenylphosphine palladium, 50 mL of tetrahydrofuran and 25 mL of water were added, and the mixture was refluxed for 24 hours. After the reaction was completed, the reaction mixture was separated to remove the aqueous layer, and the organic layer was separated, concentrated under reduced pressure, and then separated by column chromatography using ethyl acetate and hexane as eluent to obtain a solid. (Yield: 78.3%).

(8) Synthesis of a compound represented by the formula (131)

A compound represented by the formula (131) was synthesized by the following reaction scheme (40).

[Reaction Scheme 40]

[Formula 131]

2.9 g (0.0089 mol) of the compound represented by the formula (11-g) and 1.2 g (0.0037 mol) of the 1,4-diiodobenzene obtained from the above scheme [Reaction formula 39] were added to a 100 mL round bottom flask 1.6 g (60.5%) of a compound represented by the formula (131) was obtained.

MS: m / z Calcd 718.26; found 718. Anal. Calcd. for C ₄₈ H ₃₀ N ₈ : C, 80.20; H, 4.21; N, 15.59. Found: C, 79.88; H, 3.95; N, 16.01.

&Lt; Examples 1 to 11 > 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 present invention in the device structures of Examples 1 to 11 above.

[CBP]

&Lt; Test Example 1 >

The organic electroluminescent devices manufactured according to Examples 1 to 11 and Comparative Example 1 were measured for voltage, luminance, color cast and lifetime, and the results are shown in Table 1 below. T80 means the time required for the luminance to be reduced to 80% of the initial luminance.

division Host Dopant Doping concentration ETL V Cd / A CIEx CIEy T ₈₀ (hr) Comparative Example 1 CBP Ir (ppy) ₃ 10 Alq ₃ 8.20 38.81 0.29 0.62 76 Example 1 Compound 7 Ir (ppy) ₃ 10 Alq ₃ 6.18 47.25 0.31 0.62 114 Example 2 Compound 11 Ir (ppy) ₃ 10 Alq ₃ 5.34 51.29 0.29 0.64 101 Example 3 Compound 15 Ir (ppy) ₃ 10 Alq ₃ 5.19 52.67 0.32 0.63 96 Example 4 Compound 21 Ir (ppy) ₃ 10 Alq ₃ 4.48 59.32 0.31 0.64 260 Example 5 Compound 26 Ir (ppy) ₃ 10 Alq ₃ 5.11 48.71 0.33 0.63 92 Example 6 Compound 44 Ir (ppy) ₃ 10 Alq ₃ 5.39 49.72 0.30 0.63 194 Example 7 Compound 65 Ir (ppy) ₃ 10 Alq ₃ 5.27 55.90 0.31 0.63 175 Example 8 Compound 84 Ir (ppy) ₃ 10 Alq ₃ 5.09 51.81 0.32 0.64 288 Example 9 Compound 98 Ir (ppy) ₃ 10 Alq ₃ 6.01 49.55 0.32 0.64 168 Example 10 Compound 119 Ir (ppy) ₃ 10 Alq ₃ 4.62 50.01 0.31 0.63 139 Example 11 Compound 134 Ir (ppy) ₃ 10 Alq ₃ 5.21 53.17 0.33 0.64 171

&Lt; Test Example 2 &

In order to measure the band gaps of [Formula 21] and [Formula 84] according to the present invention, the measurement was performed using an absorption spectrophotometer (UV / Vis absorption spectrometer) and a cyclic voltammetry.

division UVl _max PLl _max HOMO (eV) LUMO (eV) Band gap (eV) Formula 21 328 373 6.01 2.68 3.33 84 358 399 6.06 2.91 3.15

FIG. 2 shows TGA and DSC of Formula 84 according to an embodiment of the present invention.

3 shows EL spectra of [Formula 84] and [Comparative Example 1] according to an embodiment of the present invention.

The results of Examples 1 to 11, Comparative Example 1 and Test Examples 1 and 2 show that the compounds represented by Formulas 1 to 3 according to the present invention are useful as phosphorescent light emitting materials It can be seen that it is useful for display devices, display devices, lighting, and the like because it exhibits excellent thermal characteristics and luminous efficiency as compared with CBP.

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 represented by the following Chemical Formulas 1 to 3:
[Chemical Formula 1] &lt; EMI ID =

(3)

In the above Chemical Formulas 1 to 3,
R ₁ to R ₉ 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,
m is an integer of 1 to 6,
n and o are each independently an integer of 0 to 4,
When n and o are 2 or more, a plurality of R ₁ to R ₉ may independently be the same or different. The method according to claim 1,
Each of R ₁ to R ₉ (except when R ₁ to R ₉ are each a hydrogen atom, a deuterium atom, a halogen atom or a nitro group) is independently an aryl group having 6 to 24 carbon atoms, a heteroaromatic group having 2 to 24 carbon atoms An aryl group and an alkyl group having 1 to 24 carbon atoms. The method according to claim 1,
Wherein the above-mentioned formulas (1) to (3) are any one selected from the following formulas:

[Chemical Formula 4] [Chemical Formula 5] Chemical Formula 7 [Chemical Formula 7]

[Chemical Formula 8] &lt; EMI ID =

[Chemical Formula 22]

[Chemical Formula 25]

[Chemical Formula 30] [Chemical Formula 30]

[Chemical Formula 32] [Chemical Formula 32]

[Chemical Formula 45] [Chemical Formula 62] [Chemical Formula 63]

&Lt; EMI ID = 66.1 &gt;

(82)

[Chemical Formula 85]

(90)

[Chemical Formula 93]

[Chemical Formula 100]

[Chemical Formula 105]

(123)

[Formula 124] [Formula 125] [Formula 126] [Formula 127]

[Formula 131] [Formula 130] [Formula 131]

[Formula 132] [Formula 133] [Formula 134]

[Chemical Formula 140]

[Chemical Formula 144] [Chemical Formula 145] Anode;
Cathode; And
And a layer containing a pyridine derivative according to claim 1 interposed between the anode and the cathode. 5. The method of claim 4,
Wherein the pyridine derivative is contained in the light emitting layer between the anode and the cathode. 6. The method of claim 5,
And 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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