KR101567610B1 - New nitrogen-containing heterocyclic compounds and organic electronic device using the same - Google Patents

Abstract

The present invention provides a novel nitrogen-containing heterocyclic compound and an organic electronic device using the same. The organic electronic device according to the present invention exhibits excellent characteristics in terms of efficiency, driving voltage and lifetime.

Description

TECHNICAL FIELD [0001] The present invention relates to a novel nitrogen-containing heterocyclic compound and an organic electronic device using the same. BACKGROUND ART < RTI ID = 0.0 >

The present invention relates to a novel nitrogen-containing heterocyclic compound and an organic electronic device using the same.

In the present specification, an organic electronic device is an electronic device using an organic semiconductor material, and requires the exchange of holes and / or electrons between the electrode and the organic semiconductor material. The organic electronic device can be roughly classified into two types according to the operating principle as described below. First, an exciton is formed in an organic material layer by a photon introduced into an element from an external light source. The exciton is separated into an electron and a hole, and the electrons and holes are transferred to different electrodes to be used as a current source Type electronic device. The second type is an electronic device that injects holes and / or electrons into an organic semiconductor material layer that interfaces with an electrode by applying a voltage or current to two or more electrodes, and operates by injected electrons and holes.

Examples of the organic electronic device include an organic light emitting device, an organic solar cell, an organic photoconductor (OPC) drum, and an organic transistor. These devices include an electron / hole injecting material, an electron / hole extracting material, Materials or luminescent materials. Hereinafter, the organic light emitting device will be described in detail, but in the organic electronic devices, the electron / hole injecting material, the electron / hole extracting material, the electron / hole transporting material, or the light emitting material all have a similar principle.

In general, organic light emission phenomenon refers to a phenomenon in which an organic material is used to convert electric energy into light energy. An organic light emitting device using an organic light emitting phenomenon generally has a structure including an anode, a cathode, and an organic material layer therebetween. Here, in order to increase the efficiency and stability of the organic light emitting device, the organic material layer may have a multi-layer structure composed of different materials and may include a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer. When a voltage is applied between two electrodes in the structure of such an organic light emitting 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 falling to the ground state, light is emitted. Such an organic light emitting device is known to have characteristics such as self-emission, high luminance, high efficiency, low driving voltage, wide viewing angle, high contrast, and high speed response.

As materials used in organic light emitting devices, pure organic materials or complexes in which an organic material and a metal form a complex are mostly used. Depending on the application, a hole injecting material, a hole transporting material, an electron transporting material, an electron injecting material, . As the hole injecting material and the hole transporting material, an organic material having a p-type property, that is, an organic material that is easily oxidized and electrochemically stable at the time of oxidation is mainly used. On the other hand, as an electron injecting material or an electron transporting material, an organic material having an n-type property, that is, an organic material that is easily reduced and electrochemically stable when being reduced is mainly used. As the luminescent material, a material having both a p-type property and an n-type property, that is, a material having both a stable state in oxidation and in a reduced state is preferable, and a material having high luminescence efficiency, desirable.

In addition to the above, it is preferable that the material used in the organic light emitting device further has the following properties.

In order to obtain a highly efficient organic light emitting device capable of driving at a low voltage, holes or electrons injected into the organic light emitting element must be smoothly transferred to the light emitting layer, and injected holes and electrons should not escape from the light emitting layer. For this purpose, the material used in the organic light emitting device should have an appropriate band gap and a HOMO or LUMO energy level. In the case of Alq ₃ , which is mainly used as an electron transporting layer material, the HOMO energy level is higher than the HOMO energy level of organic materials used as a light emitting layer material, so that it is difficult to manufacture an organic light emitting device having high efficiency and long life characteristics.

In addition, materials used in organic light emitting devices should have excellent chemical stability, charge mobility, and interface characteristics with electrodes or adjacent layers. That is, the material used in the organic light emitting device should have little deformation of the material due to moisture or oxygen. In addition, by having appropriate hole or electron mobility, it is necessary to maximize the formation of excitons by balancing the density of holes and electrons in the light emitting layer of the organic light emitting device. And, for the stability of the device, the interface with the electrode including the metal or the metal oxide should be good.

Therefore, in order for the organic light emitting device to fully exhibit the above-described excellent characteristics, development of organic materials having the above-mentioned requirements is required, and the necessity of developing such materials is the same in other organic electronic devices described above.

Thus, the present inventors have revealed a novel nitrogen-containing heterocyclic compound. In addition, when the organic compound layer of the organic electronic device is formed using the novel nitrogen-containing heterocyclic compound, it has been found that the organic compound layer can exhibit the effects of increasing the efficiency of the device, improving the driving voltage, extending the service life, and increasing the stability.

Accordingly, it is an object of the present invention to provide a novel nitrogen-containing heterocyclic compound and an organic electronic device using the same.

The present invention provides compounds of formula 1:

In Formula 1,

R ₁ and R ₂ are the same or different and each independently hydrogen; heavy hydrogen; A halogen group; A nitrile group; Alkyl substituted or unsubstituted C _{1 -50;} Cycloalkyl substituted or unsubstituted C _{3 -50;} A substituted or unsubstituted C _{2 -50} alkenyl group; A substituted or unsubstituted C _{6 -50} aryl group; And is selected from O, N, S or the hetero group, an aryl substituted or unsubstituted C _{2 -50} with P as hetero atoms,

R ₃ to R ₆ are the same or different from each other, and each independently hydrogen; heavy hydrogen; A halogen group; A nitrile group; Alkyl substituted or unsubstituted C _{1 -50;} Cycloalkyl substituted or unsubstituted C _{3 -50;} Alkoxy group, a substituted or unsubstituted C _{1 -50;} A substituted or unsubstituted C _{1 -50} alkylthio group; A substituted or unsubstituted C _{6 -50} aryloxy group; A substituted or unsubstituted C _{2 -50} alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted fluorenyl group; A substituted or unsubstituted C _6-50 arylamine group; A substituted or unsubstituted C _{6 -50} aryl group; And is selected from cattle heteroatom O, N, S or the hetero group, an aryl substituted or unsubstituted C _{2 -50} with the P,

R ₇ is hydrogen; heavy hydrogen; A halogen group; A nitrile group; Alkyl substituted or unsubstituted C _{1 -50;} Cycloalkyl substituted or unsubstituted C _{3 -50;} A substituted or unsubstituted C _{2 -50} alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted C _{13 -50} fluorenyl group; A substituted or unsubstituted C _{6 -50} arylamine group; A substituted or unsubstituted C _{6 -50} aryl group; And is selected from cattle heteroatom O, N, S or the hetero group, an aryl substituted or unsubstituted C _{2 -50} with the P,

At least one of R ₁ to R ₇ is a group represented by - (L) p- (Y) q, wherein p is an integer of 0 to 10, q is an integer of 1 to 10,

L is a substituted or unsubstituted C _{6 -50} arylene group; Substituted or unsubstituted alkenylene group of _{2 -50} C ring; A substituted or unsubstituted C _{13 -50} fluorenylene group; And is selected from cattle heteroatom O, N, heteroarylene group consisting of substituted or unsubstituted C _{2 -50} having the S or P,

Y is hydrogen; heavy hydrogen; A halogen group; A nitrile group; Alkyl substituted or unsubstituted C _{1 -50;} Cycloalkyl substituted or unsubstituted C _{3 -50;} Alkoxy group, a substituted or unsubstituted C _{1 -50;} A substituted or unsubstituted C _{1 -50} alkylthio group; A substituted or unsubstituted C _{6 -50} aryloxy group; A substituted or unsubstituted C _{2 -50} alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted C _13-50 fluorenyl group; A substituted or unsubstituted C _{6 -50} arylamine group; A substituted or unsubstituted C _{6 -50} aryl group; And is selected from cattle heteroatom O, N, S or the hetero group, an aryl substituted or unsubstituted C _{2 -50} with the P,

When two or more L or Y are present, they are the same or different from each other,

R ₁ and R ₂ , R ₃ and R ₄ , R ₄ and R ₅ and R ₅ and R ₆ may form a fused ring of an aliphatic, aromatic, aliphatic hetero or aromatic hetero or may form a spiro bond.

Also, the present invention provides an organic electronic device comprising a first electrode, a second electrode, and at least one organic compound layer disposed between the first electrode and the second electrode, wherein at least one of the organic compound layers is a compound represented by Formula 1 Wherein the organic electronic device is an organic electronic device.

The novel nitrogen-containing heterocyclic compound according to the present invention can be used as an organic material layer of an organic electronic device including an organic light emitting device, and an organic electronic device including the organic light emitting device using the same can be improved in efficiency, driving voltage drop, And the like.

1 shows an example of an organic light emitting element comprising a substrate 1, a cathode 2, a hole injecting layer 3, a hole transporting layer 4, a light emitting layer 5, an electron transporting layer 6 and a cathode 7 It is.
2 shows the mass spectrum of Compound 1-40.

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

The novel nitrogen-containing heterocyclic compound according to the present invention is characterized by being a compound represented by the above formula (1).

The compound represented by Formula 1 according to the present invention is preferably selected from compounds represented by Chemical Formulas 2 to 4, but is not limited thereto.

In the above Chemical Formulas 2 to 4,

R ₃ to R ₇ are the same as defined in Formula 1,

R ₈ to R ₁₂ have the same definitions as R ₁ and R ₂ in Formula 1,

At least one of R ₃ to R ₇ is a group represented by - (L) p- (Y) q, wherein L, Y, p and q are as defined in the above formula (1).

The substituents of the above formulas (1) to (4) will be described in detail.

The number of carbon atoms of the alkyl group represented by any one of Chemical Formulas 1 to 4 is preferably 1 to 50, more preferably 1 to 30, and specifically includes methyl, ethyl, propyl, isopropyl, butyl, A heptyl group, a hexyl group, a heptyl group and the like, but are not limited thereto.

The number of carbon atoms of the cycloalkyl groups represented by the above formulas (1) to (4) is preferably 3 to 50, more preferably 3 to 40, and specifically includes, but is not limited to, cyclopentyl group or cyclohexyl group.

The number of carbon atoms of the alkylthio group and the alkoxy group of the general formulas (1) to (4) is preferably 1 to 50, more preferably 1 to 40.

The alkenyl group of the above general formulas (1) to (4) preferably has 2 to 50 carbon atoms, more preferably 2 to 40 carbon atoms. Specifically, an aryl group such as a stilbenyl group or styrenyl group Substituted alkenyl groups, and the like, but are not limited thereto.

In addition, the aryl group of the above-mentioned general formulas (1) to (4) may be monocyclic or polycyclic, and the number of carbon atoms is preferably 6 to 50, more preferably 6 to 40. Specific examples of the monocyclic aryl group include a phenyl group, a biphenyl group and a terphenyl group. Examples of the polycyclic aryl group include a naphthyl group, an anthryl group, a phenanthryl group, a pyrenyl group, a perylenyl group, However, the scope of the present invention is not limited to these examples.

The heteroaryl group of the above formulas (1) to (4) preferably has 2 to 50 carbon atoms, more preferably 2 to 40 carbon atoms, and O, N, S or P as a heteroatom. Examples of the heteroaryl group include a thiophene group, a furan group, a pyrrolyl group, an imidazole group, a thiazole group, an oxazole group, an oxadiazole group, a triazole group, an oxazole group, a benzoquinoline group, a pyridyl group, a pyrazinyl group, , An isoquinoline group, a carbazole group, a benzocarbazole group, an acridyl group, and the like, but are not limited thereto.

Examples of the halogen group of the above formulas (1) to (4) include fluorine, chlorine, bromine or iodine.

The number of carbon atoms of the arylamine group represented by any one of Chemical Formulas 1 to 4 is preferably 6 to 50, more preferably 6 to 40, and specifically includes a phenylamine group, a naphthylamine group, a biphenylamine group, An amine group, a 3-methylphenylamine group, a 4-methyl-naphthylamine group, a 2-methyl-biphenylamine group, a 9-methyl-anthracenylamine group, a diphenylamine group, a phenylnaphthylamine group, A tolylamine group, a phenyltolylamine group, and a triphenylamine group. But are not limited thereto.

The number of carbon atoms of the fluorenyl group of the above formulas (1) to (4) is preferably from 13 to 50, more preferably from 13 to 40, and is preferably a compound of the following structural formula, but is not limited thereto.

The term "substituted or unsubstituted" refers to a group selected from the group consisting of deuterium, a halogen group, an alkyl group, an alkenyl group, an alkoxy group, a silyl group, an arylalkenyl group, an aryl group, a heteroaryl Means a group substituted with at least one substituent selected from the group consisting of a halogen atom, a hydroxyl group, a carboxyl group, a carbazole group, an arylamine group, a fluorenyl group substituted or unsubstituted with an aryl group, and a nitrile group, or has no substituent.

In the above Chemical Formulas 1 to 4, at least one of R ₁ to R ₇ is a group represented by - (L) p- (Y) q wherein p and q are not 0, L is an arylene group, Y is preferably a deuterium, a fluorine, a nitrile group, an alkyl group, a cycloalkyl group, a silyl group, an aryl group, a fluorenyl group or a heteroaryl group, but is not limited thereto.

The number of carbon atoms of the alkenyl group of the above formulas (1) to (4) is preferably 2 to 50, more preferably 2 to 40.

In addition, the number of carbon atoms of the fluorenylene group represented by any one of formulas (1) to (4) is preferably from 13 to 50, more preferably from 13 to 40.

The number of carbon atoms of the arylene group represented by any one of Chemical Formulas 1 to 4 is preferably 6 to 50, more preferably 6 to 40, and specifically, a phenylene group, a biphenylene group, a naphthalenylene group, a binaphthalene group, , A chlorenylene group, a phenanthrenylene group, and a pyrenylene group are preferable, but not limited thereto.

The number of carbon atoms of the heteroarylene group of the above formulas (1) to (4) is preferably 2 to 50, more preferably 2 to 40, and O, N, S or P as a heteroatom is preferable. An imidazolylene group, an imidazolylene group, an imidazolylene group, an imidazolylene group, an imidazolylene group, an imidazolylene group, an imidazolylene group, an imidazolylene group, an imidazolylene group, a thiazolylene group, .

The compounds represented by Chemical Formulas 1 to 4 include, but are not limited to, the following compounds.

The compound of formula (I) according to the present invention has an imidazole structure and pyrazine structure in the compound, so that it has a characteristic of being capable of electron injection and / or electron transport. It also has stability to electrons. This facilitates electron transport in the electron injection layer, the electron transport layer, and the light emitting layer.

Further, when a P-type substituent such as an arylamine is further added, hole transport can be performed, and further stability against electrons can be obtained, so that the hole transport layer can be used. Accordingly, by applying a compound having such a structure to an organic electronic device, the efficiency, driving voltage, and lifetime of the device can be improved.

Hereinafter, a method for producing the compound of Formula 1 will be described.

According to one embodiment of the present invention, the compound represented by the formula (1)

1) K ₂ CO ₃ or in the presence of a base (base) such as Cs ₂ CO _3, by imidazole reacting the compound 1-B as a halogen group and NO compound 1-A in ₂ is substituted, NO ₂ is substituted Preparing compound 1-C,

2) reduction of compound 1-C prepared in the above step 1 with Na ₂ S ₂ O ₄ to prepare NH ₂ -substituted compound 1-D,

3) reacting the compound 1-D prepared in the above 2) with an acyl chloride compound (R ₇ -COCl) to prepare a compound 1-E containing an amide, and

4) Preparing the compound 1-E prepared in the above step 3) with Compound 1-F (compound represented by the formula 1) using POCl ₃ . Such a preparation method can be represented by the following Reaction Scheme 1, but the production method of the compound represented by Formula 1 is not limited to Reaction Scheme 1 below.

[Reaction Scheme 1]

In the above Reaction Scheme 1, R ₁ to R ₇ are the same as R ₁ to R ₇ defined in the above formula (1).

The compound represented by the formula (1) can be prepared by referring to the general production method described above and the following examples.

The present invention also provides an organic electronic device comprising a first electrode, a second electrode, and at least one organic material layer disposed between the first electrode and the second electrode, 4. ≪ / RTI >

The organic electronic device of the present invention can be manufactured by a conventional method and material for producing an organic electronic device, except that one or more organic compound layers are formed using the above-described compounds.

Hereinafter, the organic light emitting device will be described.

In one embodiment of the present invention, the organic light emitting device may have a structure including a first electrode, a second electrode, and one or more organic layers disposed between the first electrode and the second electrode. In the organic light emitting device of the present invention, the organic layer may have a single layer structure or a multi-layer structure in which two or more organic layers are stacked. When the organic material layer of the organic light emitting diode of the present invention has a multilayer structure, it may have a structure in which, for example, a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer are stacked. However, the structure of the organic light emitting device is not limited thereto, and may include a smaller number of organic layers. For example, the structure of the organic light emitting device of the present invention may have a structure as shown in FIG. 1, but the present invention is not limited thereto. 1, reference numeral 1 denotes a substrate, 2 denotes an anode, 3 denotes a hole injecting layer, 4 denotes a hole transporting layer, 5 denotes an organic light emitting layer, 6 denotes an electron transporting layer and 7 denotes a cathode. The organic light emitting device having the structure as shown in FIG. 1 is generally referred to as an organic light emitting device having a normal structure. However, the present invention is not limited to this and includes an organic light emitting device having a reverse structure. That is, the organic light emitting device of the present invention may have a structure in which a substrate, a cathode, an electron transport layer, an organic light emitting layer, a hole transport layer, a hole injection layer, and an anode are sequentially stacked.

In the case where the organic light emitting device according to the present invention has an organic layer having a multilayer structure, the compound of the general formula (1) includes a light emitting layer, a hole transporting layer, a layer simultaneously transporting and emitting light, a layer simultaneously emitting light and electron transporting, And / or an injection layer. In the present invention, the compounds represented by Chemical Formulas 1 to 4 are preferably included in the electron injecting and / or transporting layer or the light emitting layer.

In particular, when the compound of Formula 1 according to the present invention is contained in an electron transport layer, the electron transport layer may include an alkali metal, an alkali metal compound, an alkaline earth metal, an alkaline earth metal compound, or a combination thereof. , LiF, and the like, but it is not limited thereto.

The organic material layer may include a hole injecting layer and a hole transporting layer, and the hole injecting layer and the hole transporting layer may include the compounds represented by the above Chemical Formulas 1 to 4.

The organic electroluminescent device according to the present invention can be manufactured using conventional organic electroluminescent device manufacturing methods and materials, except that the above-described compounds of the formulas (1) to (4) are used for one or more layers of the organic electroluminescent device organic layers . For example, the organic light emitting device according to the present invention may be formed by using a PVD (physical vapor deposition) method such as sputtering or e-beam evaporation to form a metal oxide or a metal oxide having conductivity on the substrate, To form an anode, an organic material layer including a hole injection layer, a hole transporting layer, a light emitting layer, and an electron transporting layer is formed on the anode, and a material which can be used as a cathode is deposited thereon. In addition to such a method, an organic light emitting device may be fabricated by sequentially depositing a cathode material, an organic material layer, and a cathode material on a substrate in order to fabricate an organic light emitting device having a reverse structure as described above.

The compounds of Chemical Formulas 1 to 4 may be formed into an organic material layer by a solution coating method as well as a vacuum evaporation method in the production of an organic light emitting device. Here, the solution coating method refers to spin coating, dip coating, inkjet printing, screen printing, spraying, roll coating, and the like, but is not limited thereto.

As the anode material, a material having a large work function is preferably used so that hole injection can be smoothly conducted into the organic material layer. Specific examples of the cathode material that can be used in the present invention include metals such as vanadium, chromium, copper, zinc, and gold, or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); ZnO: Al or SnO _2: a combination of a metal and an oxide such as Sb; Conductive polymers such as poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (PEDOT), polypyrrole and polyaniline.

The negative electrode material is preferably a material having a small work function to facilitate electron injection into the organic material layer. Specific examples of the negative electrode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin and lead or alloys thereof; Layer structure materials such as LiF / Al or LiO ₂ / Al, but are not limited thereto.

As the hole injecting material, it is preferable that the highest occupied molecular orbital (HOMO) of the hole injecting material is between the work function of the anode material and the HOMO of the surrounding organic layer. Specific examples of the hole injecting material include metal porphyrine, oligothiophene, arylamine-based organic materials, hexanitrile hexaazatriphenylene-based organic materials, quinacridone-based organic materials, perylene , Anthraquinone, polyaniline and polythiophene-based conductive polymers, but the present invention is not limited thereto.

As the hole transporting material, a material capable of transporting holes from the anode or the hole injecting layer to the light emitting layer and having high mobility to holes is suitable. Specific examples thereof include arylamine-based compounds; Carbazole-based compounds; Anthracene-based compounds; Pyrene-based compounds; A conductive polymer, and a block copolymer having a conjugated portion and a non-conjugated portion together, but the present invention is not limited thereto.

The light emitting material is preferably a material capable of emitting light in the visible light region by transporting and receiving holes and electrons from the hole transporting layer and the electron transporting layer, respectively, and having good quantum efficiency for fluorescence or phosphorescence. Specific examples include 8-hydroxy-quinoline aluminum complex (Alq ₃ ); Carbazole-based compounds; Dimerized styryl compounds; Bis-methyl-8-hydroxyquinoline paraphenyl phenol aluminum complex (bAlq); 10-hydroxybenzoquinoline-metal compounds; Compounds of the benzoxazole, benzothiazole and benzimidazole series; Anthracene-based compounds; Pyrene-based compounds; Polymers of poly (p-phenylenevinylene) (PPV) series; Spiro compounds; Polyfluorene, rubrene, and the like, but are not limited thereto.

As the electron transporting material, a material capable of transferring electrons from the cathode well into the light emitting layer, which is suitable for electrons, is suitable. Specific examples include an Al complex of 8-hydroxyquinoline; Complexes containing Alq ₃ ; Organic radical compounds; Hydroxyflavone-metal complexes; Anthracene-based compounds; Pyrene-based compounds; Compounds of the benzoxazole, benzothiazole and benzimidazole series; Pyridyl-based compounds; Phenanthroline compounds; Quinoline series compounds; Quinazoline-based compounds, and the like, and these compounds may be doped with a metal or a metal compound to form an electron transporting layer, but the present invention is not limited thereto.

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

The compounds represented by Chemical Formulas 1 to 4 according to the present invention may act on a principle similar to that applied to organic light emitting devices in organic electronic devices including organic solar cells, organic phosphorescent devices, organic photoconductors (OPC), organic transistors and the like.

Hereinafter, preferred embodiments of the present invention will be described in order to facilitate understanding of the present invention. However, the following examples are intended to illustrate the present invention and do not limit the scope of the present invention.

< Example >

< Manufacturing example  1> Preparation of the following compound A-4

1) Preparation of the compound A-1

2-Fluoronitrobenzene (10 g, 70.9 mmol), benzimidazole (9.2 g, 77.9 mmol) and Cs ₂ CO ₃ (53 g, 163 mmol) were dissolved in DMF (N, ), And the mixture was stirred at room temperature for 24 hours. The resulting reaction mixture was filtered to remove excess Cs ₂ CO ₃ and the filtrate was concentrated under reduced pressure and purified by column chromatography using tetrahydrofuran (THF): n-hexane = 1: 10 as a developing solvent After purification by column chromatography, it was dried to obtain Compound A-1 (15.3 g, yield 90%).

MS: [M + H] &lt; ⁺ &gt; = 240

2) Preparation of compound A-2

The compound A-1 (10 g, 41.8 mmol) was dissolved in THF (70 mL) and a solution of Na ₂ S ₂ O ₄ (29.1 g, 167 mmol) in 100 mL of water was added while stirring at room temperature under a nitrogen atmosphere. The mixture was refluxed for 3 hours, cooled to room temperature and a solution of K ₂ CO ₃ (23.1 g, 167 mmol) in 40 mL of water was added. Further, a solution of 4-bromobenzoyl chloride (9.2 g, 41.8 mmol) in THF (20 mL) was added dropwise, and the mixture was refluxed with stirring for 8 hours. The temperature was lowered to room temperature, the water layer was removed, and the organic layer was dried over anhydrous magnesium sulfate (MgSO ₄ ) and then filtered. The filtrate was concentrated under reduced pressure, and the residue was subjected to column chromatography with THF: n-hexane = 1: 10 to prepare Compound A-2 (11.5 g, yield 70%).

MS: [M + H] &lt; ⁺ &gt; = 393

3) Preparation of Compound A-3

The compound A-2 (7.5 g, 19.1 mmol) was dispersed in pyridine (40 mL), and POCl ₃ (2.7 mL, 29 mmol) was slowly added dropwise while stirring at 0 ° C under a nitrogen atmosphere. After refluxing for 5 hours, the temperature was lowered to room temperature. The resulting reaction mixture was poured into excess ice water. The resulting solid was filtered, dissolved in chloroform, washed sequentially with 1M K ₂ CO ₃ aqueous solution and saturated brine, and then dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure to give the above compound A-3 (5.15 g, yield 72%).

MS: [M + H] &lt; ⁺ &gt; = 375

4) Preparation of compound A-4

(4.3 g, 16.8 mmol), bis (pinacolato) diboron (4.7 g, 18.5 mmol) and potassium acetate (KOAc, 4.96 g, 50.5 mmol) were dissolved in dioxane 100 ml), and Pd (dba) ₂ (0.29 g, 3 mol%) and PCy ₃ (0.28 g, 6 mol%) were added thereto. The mixture was stirred at reflux for 8 hours and the temperature was lowered to room temperature. The mixture was diluted with water (100 mL) and extracted with dichloromethane (CH ₂ Cl ₂ , 3 x 50 mL). The organic extract was dried over anhydrous magnesium sulfate and filtered. The filtrate was concentrated under reduced pressure and recrystallized from ethyl ether and hexane to obtain Compound A-4 (5.66 g, 80%).

MS: [M + H] &lt; ⁺ &gt; = 422

< Manufacturing example  2> Preparation of the following compound A-7

1) Preparation of compound A-5

Except that 6-bromonaphthoyl chloride (11.3 g, 41.8 mmol) was used instead of 4-bromobenzoyl chloride in the preparation of compound A-2 of 2) in Preparation Example 1 To obtain Compound A-5 (13.9 g, yield 75%).

MS: [M + H] &lt; ⁺ &gt; = 443

2) Preparation of the compound A-6

Except that Compound A-5 (8.4 g, 19.1 mmol) was used in place of Compound A-2 in the preparation of Compound A-3 of Production Example 3, 3) g, yield 65%).

MS: [M + H] &lt; ⁺ &gt; = 425

3) Preparation of the compound A-7

Compound A-7 (6.49 g, 16.8 mmol) was synthesized except that Compound A-6 (7.12 g, 16.8 mmol) was used instead of Compound A-3 in the preparation of Compound A- g, yield: 82%).

MS: [M + H] &lt; ⁺ &gt; = 472

< Manufacturing example  3> Preparation of the following compound A-9

1) Preparation of compound A-8

Except that 6-bromopicolinoyl chloride (9.21 g, 41.8 mmol) was used instead of 4-bromobenzoyl chloride in the preparation of compound A-2 of 2) in Preparation Example 1 To obtain Compound A-8 (11.2 g, yield 68%).

MS: [M + H] &lt; ⁺ &gt; = 394

2) Preparation of compound A-9

Compound A-9 was synthesized in the same manner as Compound A-3 of Production Example 1 except that Compound A-8 (7.5 g, 19.1 mmol) was used instead of Compound A-2 in the preparation of Compound A- 4.44 g, yield 62%).

MS: [M + H] &lt; ⁺ &gt; = 376

< Manufacturing example  4> Preparation of the following compound A-13

1) Preparation of compound A-10

(2,5-Dibromonitrobenzene, 19.9 g, 70.9 mmol) was used instead of 2-fluoronitrobenzene in the preparation of the compound A-1 of 1) in Production Example 1 , The compound A-10 (18.7 g, yield 83%) was prepared.

MS: [M + H] &lt; ⁺ &gt; = 319

2) Preparation of the compound A-11

Compound A-11 was synthesized in the same manner as Compound A-2 of Production Example 2, 2) except that benzoylchloride (Benzoylchloride, 5.87 g, 41.8 mmol) was used instead of 4-bromobenzoyl chloride. (11.6 g, yield 71%).

MS: [M + H] &lt; ⁺ &gt; = 393

3) Preparation of the above compound A-12

Except that Compound A-11 (7.49 g, 19.1 mmol) was used instead of Compound A-2 in the preparation of Compound A-3 of Production Example 3, 3) g, yield 65%).

MS: [M + H] &lt; ⁺ &gt; = 375

4) Preparation of Compound A-13

Compound A-13 (5.66 g, 16.8 mmol) was synthesized except that Compound A-12 (6.29 g, 16.8 mmol) was used instead of Compound A-3 in the preparation of Compound A- g, yield 80%).

MS: [M + H] &lt; ⁺ &gt; = 422

< Manufacturing example  5> Preparation of the following compound A-17

1) Preparation of the compound A-14

Compound A-14 was synthesized in the same manner as Compound A-1 of Production Example 1 except that benzoylchloride (17.0 g, 77.9 mmol) was used instead of benzimidazole in the preparation of Compound A-1 in Production Example 1 (18.8 g, yield 78%).

MS: [M + H] &lt; ⁺ &gt; = 340

2) Preparation of compound A-15

Compound A-15 (14.4 g, 41.8 mmol) was synthesized in the same manner as Compound A-2 of Production Example 1 except that Compound A-14 (14.2 g, 41.8 mmol) g, 70% yield).

MS: [M + H] &lt; ⁺ &gt; = 493

3) Preparation of compound A-16

Except that Compound A-15 (9.4 g, 19.1 mmol) was used instead of Compound A-2 in the preparation of Compound A-3 of Production Example 3, 3) g, yield 68%).

MS: [M + H] &lt; ⁺ &gt; = 475

4) Preparation of compound A-17

Except that Compound A-16 (7.97 g, 16.8 mmol) was used instead of Compound A-3 in the preparation of Compound A-4 in Production Example 4-1) g, yield 80%).

MS: [M + H] &lt; ⁺ &gt; = 522

< Manufacturing example  6> Preparation of the following compound A-21

1) Preparation of compound A-18

Except that 4,5-diphenylimidazole (17.2 g, 77.9 mmol) was used instead of benzimidazole in the preparation of Compound A-1 of 1) of Preparation Example 1, To obtain Compound A-18 (19.6 g, yield 81%).

MS: [M + H] &lt; ⁺ &gt; = 342

2) Preparation of compound A-19

Compound A-19 (14.9 g, 41.8 mmol) was synthesized in the same manner as Compound A-2 of Preparation Example 1 except that Compound A-18 (14.3 g, 41.8 mmol) g, yield 72%).

MS: [M + H] &lt; ⁺ &gt; = 495

3) Preparation of Compound A-20

Except that Compound A-19 (9.4 g, 19.1 mmol) was used instead of Compound A-2 in the preparation of Compound A-3 of Production Example 3 (3) g, yield 65%).

MS: [M + H] &lt; ⁺ &gt; = 477

4) Preparation of the above compound A-21

Except that Compound A-20 (8.00 g, 16.8 mmol) was used instead of Compound A-3 in the preparation of Compound A-4 in Production Example 4-1) g, yield: 83%).

MS: [M + H] &lt; ⁺ &gt; = 524

< Manufacturing example  7> Preparation of the following compound A-25

1) Preparation of compound A-22

(2-pyridyl) imidazole was used instead of benzimidazole in the preparation of Compound A-1 of 1) of Preparation Example 1, 17.3 g, 77.9 mmol) was used in place of the compound A-22 (18.3 g, yield 75%).

MS: [M + H] &lt; ⁺ &gt; = 344

2) Preparation of compound A-23

Except that Compound A-22 (14.4 g, 41.8 mmol) was used instead of Compound A-2 in the preparation of Compound A-2 of Production Example 2-1) g, yield 65%).

MS: [M + H] &lt; ⁺ &gt; = 497

3) Preparation of compound A-24

Except that Compound A-23 (9.5 g, 19.1 mmol) was used instead of Compound A-2 in the preparation of Compound A-3 in Production Example 3 (3) g, yield: 62%).

MS: [M + H] &lt; ⁺ &gt; = 479

4) Preparation of compound A-25

Except that Compound A-24 (8.04 g, 16.8 mmol) was used in place of Compound A-3 in the preparation of Compound A-4 of Production Example 4, 4) g, yield 72%).

MS: [M + H] &lt; ⁺ &gt; = 526

The following preparations are examples of intermediates which have been run to prepare the compounds of formula (1).

< Manufacturing example  Preparation of the following compounds B-1, B-2 and B-3

1) Compound B-1

After dissolving the above 9- (2-naphthyl) -anthracene (7.36 g, 24.2 mmol) in chloroform (150 mL), acetic acid (150 mL) , Br ₂ (1.3 mL, 25.4 mmol) was added dropwise. The resulting mixture was warmed to room temperature and stirred for 5 hours. After completion of the reaction, the reaction solution was concentrated and recrystallized from ethanol to obtain Compound B-1 (6.49 g, yield 70%).

MS: [M] ^&lt; ⁺ & gt ^; = 383

2) Compound B-2

The compound B-1 (6.86 g, 17.9 mmol) was dissolved in tetrahydrofuran (150 mL), the temperature was lowered to -78 ° C and 1.7 M tert-butyllithium ( t- BuLi) (10.5 mL, 17.9 mmol) I went slowly. After stirring at the same temperature for one hour, trimethyl borate (B (OCH ₃ ) ₃ , 3.72 g, 35.8 mmol) was added and stirred for 3 hours while slowly raising the temperature to room temperature. To the reaction mixture was added a 2N aqueous hydrochloric acid solution (30 mL) and the mixture was stirred at room temperature for 1.5 hours. The resulting precipitate was filtered, washed sequentially with water and ethyl ether, and vacuum dried. Dried, dispersed in ethyl ether, stirred for 2 hours, filtered and dried to give Compound B-2 (4.44 g, yield 71%).

MS: [M + H] &lt; ⁺ &gt; = 349

3) Compound B-3

The compound B-2 (3.48 g, 10.0 mmol) and 1-bromo-4-iodobenzene (3.4 g, 12.0 mmol) were dissolved in tetrahydrofuran (100 mL) after adding an aqueous solution (20mL) and placed tetrakis triphenyl phosphino palladium _{(Pd (PPh 3) 4,} 0.231g, 2mol%) it was stirred under reflux for 5 hours. The temperature was lowered to room temperature and the resulting solid was filtered. The filtered solid was dissolved in chloroform, dried over anhydrous magnesium sulfate and filtered. The filtrate was concentrated under reduced pressure, and recrystallized from tetrahydrofuran and ethanol to obtain Compound B-3 (3.30 g, yield 72%).

MS: [M + H] &lt; ⁺ &gt; = 460

< Manufacturing example  Preparation of the following compound B-4

9- (1-naphthyl) -anthracene was used in place of 9- (2-naphthyl) -anthracene in the preparation of the compound B-1 of Production Example 8, Compound (B-4) (6.49 g, yield 70%) was prepared in the same manner as the compound B-1, except that naphthylamine was replaced by naphthylamine.

MS: [M] ^&lt; ⁺ & gt ^; = 383

< Manufacturing example  Preparation of the following compounds B-5 and B-6

1) Compound B-5

9-bromo-anthracene (8.2g, 31.9mmol), biphenyl boronic acid (7.6g, 38.4mmol) and _{Pd (PPh 3) 4 (0.737g} , 2mol%) the aqueous 2M K ₂ CO ₃ (300mL) and tetra (300 mL), and the mixture was stirred under reflux for about 24 hours. The mixture was cooled to room temperature, the organic layer was separated from the reaction mixture, and the organic layer was dried over anhydrous magnesium sulfate and filtered. The filtrate was concentrated under reduced pressure and recrystallized from tetrahydrofuran and ethanol to give Compound B-5 (8.5 g, yield 81%).

MS: [M] ^&lt; ⁺ & gt ^; = 330

2) Compound B-6

Except that Compound B-5 was used in place of 9- (2-naphthyl) -anthracene in the preparation of Compound B-1 of Preparation Example 8, the compound B-1 (7.03 g, yield 71%) was prepared in a similar manner to the preparation of Compound B-6.

MS: [M] ^&lt; ⁺ & gt ^; = 409

< Manufacturing example  11> Preparation of compounds B-7 and B-8

1) Compound B-7

2-naphthalene boronic acid (10 g, 58.1 mmol) and 2-bromo-6-naphthol (10.8 g, 48.4 mmol) were completely dissolved in tetrahydrofuran After dissolving, 2M aqueous K ₂ CO ₃ solution (100 mL) was added, Pd (PPh ₃ ) ₄ (1.12 g, 2 mol%) was added, and the mixture was refluxed for 5 hours. The temperature was lowered to room temperature, the water layer was removed, dried with anhydrous magnesium sulfate and filtered. The filtrate was concentrated under reduced pressure and recrystallized with hexane to obtain Compound B-7 (8.5 g, yield 65%).

MS: [M + H] &lt; ⁺ &gt; = 271

2) Compound B-8

Compound B-7 (7.2 g, 26.7 mmol) was dissolved in dichloromethane, triethylamine (7.47 mL, 53.6 mmol) was added, and the mixture was stirred for 10 minutes. After the temperature was lowered to 0 ° C, trifluoromethanesulfonic anhydride ((CF ₃ SO ₂ ) ₂ O) (6.76 mL, 40.2 mmol) was added slowly and the temperature was raised to room temperature and stirred for 1 hour. The aqueous sodium bicarbonate solution was added, the water layer was removed, and water was removed with anhydrous magnesium sulfate. Filtered, concentrated under reduced pressure and recrystallized with hexane to obtain Compound B-8 (8.69 g, yield 81%).

MS: [M + H] &lt; ⁺ &gt; = 403

< Manufacturing example  Preparation of the following compounds B-9 and B-10

1) Compound B-9

After dissolving 1-bromo-naphthalene (34.8 g, 168 mmol) in tetrahydrofuran (170 mL), the temperature was lowered to -78 ° C and 2.5M n-butyl lithium (67.3 mL, 168 mmol) was added slowly Followed by stirring for 1 hour. 2-Bromoanthraquinone (21 g, 73.1 mmol) was added, the temperature was raised to room temperature and stirred for 3 hours. Saturated aqueous ammonium chloride solution was added to remove water layer, dried with anhydrous magnesium sulfate, filtered and dried under reduced pressure. Recrystallization from ethyl ether gave 32.5 g (yield 82%) of compound B-9.

MS: [M + H] &lt; ⁺ &gt; = 544

2) Compound B-10

The compound B-9 (32.3 g, 59.5 mmol), potassium iodide (29.6 g, 178.4 mmol) and sodium hypophosphite (38 g, 256.8 mmol) were added to acetic acid (100 mL) and the mixture was refluxed for 3 hours. After the temperature was lowered to room temperature, the resulting precipitate was filtered and washed with water and ethanol to obtain Compound B-10 (25.4 g, yield 84%).

MS: [M] ^&lt; ⁺ & gt ^; = 509

< Manufacturing example  Preparation of the following compounds B-11, B-12 and B-13

1) Compound B-11

11 was prepared in the same manner as the compound B-9 except that 2-bromonaphthalene was used in place of 1-bromonaphthalene in the preparation of the compound B-9 of the above Production Example 12. The compound B-11 (31.8 g, Yield: 80%).

MS: [M + H] &lt; ⁺ &gt; = 544

2) Compound B-12

Compound B-12 (25.4 g, yield 84%) was obtained in the same manner as in the production of Compound B-10, except that Compound B-11 was used in place of Compound B-9 in the preparation of Compound B- %).

MS: [M] ^&lt; ⁺ & gt ^; = 509

3) Compound B-13

Compound B-13 (8.6 g, yield 92%) was prepared in the same manner as in Production Example 4, except that Compound B-12 was used instead of Compound A-4 in Production Example 4.

MS: [M + H] &lt; ⁺ &gt; = 557

< Manufacturing example  14> Preparation of the following compound B-14

[Compound B-14]

Compound B-14 (4.45 g, Yield: 76%) was obtained in the same manner as the compound B-3, except that Compound B-13 was used in place of Compound B- %).

MS: [M + H] &lt; ⁺ &gt; = 586

< Manufacturing example  Preparation of the following compound B-15

[Compound B-15]

Carbazole (3.34g, 20mmol), 1- bromo-4-iodobenzene _{(6.79g, 24mmol), K 2} CO 3 (5.52g, 40mmol), copper iodide (CuI, 0.381g, 2mmol), and 1, 10 -Phenanthroline (0.360 g, 2 mmol) was suspended in xylene (50 mL) and refluxed with stirring for 24 hours. After cooling to room temperature, the mixture was diluted with water (100 mL) and extracted with ethyl acetate. The organic extract was dried over anhydrous magnesium sulfate and filtered. The filtrate was concentrated under reduced pressure and recrystallized from ethyl ether and hexane to obtain Compound B-15 (4.83 g, yield 75%).

MS: [M + H] &lt; ⁺ &gt; = 322

< Manufacturing example  16> Preparation of the following compound B-16

To a solution of 1-amino-2-naphthalenecarbaldehyde (0.25 g, 1.45 mmol) and 4-bromoacetophenone (2.88 g, 1.45 mmol) in ethanol (15 mL) And 0.5 mL of the dissolved solution is added slowly. The resulting mixture was refluxed with stirring for 15 hours. After cooling to room temperature, the resulting solid was filtered, washed with ethanol, and dried in vacuo to give Compound B-16 (0.290 g, yield 60%).

MS: [M] ^&lt; ⁺ & gt ^; = 334

< Manufacturing example  Preparation of the following compound B-17

(2.82 g, 10 mmol) and 2-phenyl-5-thiopheneboronic acid (2.04 g, 10 mmol) were dissolved in THF (30 mL) and 2M aqueous K ₂ CO ₃ solution (20 mL) after the addition, insert a _{Pd (PPh 3) 4 (0.231g} , 2mol%) was stirred under reflux for 5 hours. The temperature was lowered to room temperature, the water layer was removed, and the organic layer was dried over anhydrous magnesium sulfate and filtered. The filtrate was concentrated under reduced pressure and recrystallized with ethyl ether to give Compound B-17 (2.2 g, yield 70%).

MS: [M] ^&lt; ⁺ & gt ^; = 315

< Manufacturing example  Preparation of the following compound B-18

[Compound B-18]

Thionyl chloride (SOCl ₂ , 20 mL) and dimethylformamide (DMF, 1 mL) were added to 6-bromo-2-naphthoic acid (5.0 g, 20 mmol) and the mixture was stirred and refluxed for 4 hours. After excess thionyl chloride (SOCl ₂ ) was removed by vacuum distillation, N-methylpyrrolidine (NMP, 20 mL) and N-phenyl-1,2-diaminobenzene (3.7 g, 20 mmol) And the mixture was stirred at 160? For 12 hours. The temperature was lowered to room temperature, and excess water was added to form a solid. Filtered, washed with water and ethanol, and dried to give Compound B-18 (6.2 g, yield 78%).

MS: [M] ^&lt; ⁺ & gt ^; = 399

< Manufacturing example  Preparation of the following compound B-19

[Compound B-19]

Compound B-19 (4.54 g, yield 65%) was prepared in the same manner as in PREPARATION 18, except that 4-bromobenzoic acid was used in Preparation 18 instead of 6-bromo-2-naphthoic acid.

MS: [M] ^&lt; ⁺ & gt ^; = 349

< Manufacturing example  Preparation of the following compound B-20

[Compound B-20]

Compound B-20 (2.12 g, yield 75%) was prepared in the same manner as in PREPARATION 17, except that 2-naphthaleneboronic acid was used instead of 2-phenyl-5-thiopheneboronic acid in PREPARATION 17 .

MS: [M] ^&lt; ⁺ & gt ^; = 283

< Manufacturing example  Preparation of the following compound B-21

[Compound B-21]

(2.33 g, yield 70%) was prepared in the same manner as in PREPARATION 17, except that 9-phenanthreneboronic acid was used instead of 2-phenyl-5-thiopheneboronic acid in PREPARATION 17 Respectively.

MS: [M] ^&lt; ⁺ & gt ^; = 333

< Manufacturing example  Preparation of the following compound B-22

[Compound B-22]

Compound B-22 (2.14 g, 60%) was prepared in the same manner as in PREPARATION 17, except that 1-pyreneboronic acid was used instead of 2-phenyl-5-thiopheneboronic acid in PREPARATION 17.

MS: [M] ^&lt; ⁺ & gt ^; = 357

< Manufacturing example  Preparation of the following compound B-23

4-bromo-aniline (1.72 g, 10 mmol), 4-iodobiphenyl (6.72 g, 24 mmol), K ₂ CO ₃ (5.52 g, 40 mmol), copper iodide , 1,10-phenanthroline (0.360 g, 2 mmol) were suspended in xylene (50 mL), and the mixture was refluxed with stirring for 24 hours. After cooling to room temperature, the mixture was diluted with water (100 mL) and extracted with ethyl acetate. The organic extract was dried over anhydrous magnesium sulfate and filtered. The filtrate was concentrated under reduced pressure and recrystallized with hexane to obtain Compound B-23 (1.43 g, yield 30%).

MS: [M] ^&lt; ⁺ & gt ^; = 476

< Manufacturing example  Preparation of the following compound B-24

[Compound B-24]

Except that 1-bromo-3,5-diiodobenzene (3.68 g, 9.0 mmol) was used instead of 1-bromo-4-iodobenzene in the above Production Example 15 , Compound B-24 (1.75 g, yield 40%) was prepared in the same manner as in Production Example 15.

MS: [M] ^&lt; ⁺ & gt ^; = 487

In order to prepare the compound of Formula 1, the reagents and intermediates shown in Table 1 below are required, and they are commercially available or prepared according to known methods.

[Table 1]

< Example  1> Preparation of the following compound 1-1

Compound A-4 (4.21g, 10.0mmol) and 4-bromo-phenyl mobayi (4-bromobiphenyl, 2.33g, 10.0mmol ) of was dispersed in _{THF (100mL), 2M K 2} CO 3 After adding an aqueous solution (20mL) and insert the _{Pd (PPh 3) 4 (0.231g} , 2mol%) it was stirred under reflux for 5 hours. The temperature was lowered to room temperature and the resulting solid was filtered. The filtered solid was recrystallized from chloroform and ethanol, filtered and dried to give Compound 1-1 (3.58 g, yield 80%).

MS: [M + H] &lt; ⁺ &gt; = 448

< Example  2> Preparation of the following compounds 1-3

Compound A-4 (4.21 g, 10.0 mmol) and compound B-1 (3.83 g, 10.0 mmol) were dispersed in THF (100 mL) and 2M K ₂ CO ₃ After adding an aqueous solution (20mL) and insert the _{Pd (PPh 3) 4 (0.231g} , 2mol%) it was stirred under reflux for 5 hours. The temperature was lowered to room temperature and the resulting solid was filtered. The filtered solid was recrystallized from chloroform and ethanol, filtered and dried to give Compound 1-3 (4.54 g, yield 76%).

MS: [M + H] &lt; ⁺ &gt; = 598

< Example  3> Preparation of the following compounds 1-4

The compound 1-4 was synthesized in the same manner as in the preparation of the compound 1-4 of Example 2, except that the compound B-4 (3.83 g, 10.0 mmol) was used instead of the compound B-1 to obtain the compound 1-4 (4.72 g, 79%).

MS: [M + H] &lt; ⁺ &gt; = 598

< Example  4> Preparation of the following compounds 1-7

The compound 1-4 was synthesized by the same method except that the compound B-12 (5.09 g, 10.0 mmol) was used in place of the compound B-1 in the preparation of the compound 1-4 in Example 2 to obtain Compound 1-7 (5.93 g, yield 82%).

MS: [M + H] &lt; ⁺ &gt; = 724

< Example  5> Preparation of the following compounds 1-9

The compound 1-4 was synthesized in the same manner as in the preparation of the compound 1-4 of Example 2 except that the compound B-15 (3.22 g, 10.0 mmol) was used in place of the compound B-1 to obtain Compound 1-9 (4.07 g, yield 76%).

MS: [M + H] &lt; ⁺ &gt; = 537

< Example  6> Preparation of the following compound 1-11

Except that Compound C-2 (3.88 g, 10.0 mmol) was used in place of Compound B-1 in the preparation of Compound 1-4 in Example 2 to obtain Compound 1-11 (4.76 g, yield: 79%).

MS: [M + H] &lt; ⁺ &gt; = 603

< Example  Preparation of the following compounds 1-14

The compound 1-4 was synthesized in the same manner as in the preparation of the compound 1-4 of Example 2 except that the compound B-16 (3.34 g, 10.0 mmol) was used in place of the compound B-1 to obtain the compound 1-14 (4.11 g, 75%).

MS: [M + H] &lt; ⁺ &gt; = 549

< Example  Preparation of the following compounds 1-16

The compound 1-4 was synthesized in the same manner as in the preparation of the compound 1-4 of Example 2 except that the compound B-16 (3.57 g, 10.0 mmol) was used in place of the compound B-1 to obtain a compound 1-16 (4.05 g, yield 71%).

MS: [M + H] &lt; ⁺ &gt; = 572

< Example  Preparation of the following compounds 1-22

The compound 1-4 was synthesized by the same method except that the compound B-16 (3.49 g, 10.0 mmol) was used in place of the compound B-1 in the production of the compound 1-4 in Example 2 to obtain the compound 1-22 (4.11 g, yield 73%).

MS: [M + H] &lt; ⁺ &gt; = 564

< Example  Preparation of the following compounds 1-27

Compound 1-2 was synthesized by the same method as Compound C-3 (2.59 g, 10.0 mmol) instead of Compound B-1 in the preparation of Compound 1-4 of Example 2 to give Compound 1-27 (3.07 g, yield 65%).

MS: [M + H] &lt; ⁺ &gt; = 474

< Example  Preparation of the following compound 1-28

Compound 1-2 was synthesized by the same method except that Compound B-23 (4.76 g, 10.0 mmol) was used instead of Compound B-1 in the preparation of Compound 1-4 of Example 2 to obtain Compound 1-28 (5.31 g, yield 77%).

MS: [M + H] &lt; ⁺ &gt; = 691

< Example  Preparation of the following compound 1-30

Except that Compound C-4 (4.73 g, 10.0 mmol) was used instead of Compound B-1 in the preparation of Compound 1-4 of Example 2 to obtain Compound 1-30 (5.08 g, yield: 74%).

MS: [M + H] &lt; ⁺ &gt; = 688

< Example  Preparation of the following compound 1-32

Except that Compound C-5 (5.25 g, 10.0 mmol) was used in place of Compound B-1 in the preparation of Compound 1-4 in Example 2 to obtain Compound 1-32 (5.84 g, yield: 79%).

MS: [M + H] &lt; ⁺ &gt; = 740

< Example  Preparation of the following compound 1-34

The compound 1-4 was synthesized by the same method except that the compound B-24 (4.87 g, 10.0 mmol) was used in place of the compound B-1 in the production of the compound 1-4 in Example 2 to obtain the compound 1-34 (4.84 g, yield 69%).

MS: [M + H] &lt; ⁺ &gt; = 702

< Example  Preparation of the following compound 1-35

Compound A-7 (4.71 g, 10.0 mmol) was used in place of Compound A-4 and compound C-6 (2.32 g, 10.0 mmol) was used in place of Compound B- , The compound 1-35 (3.32 g, yield 67%) was prepared.

MS: [M + H] &lt; ⁺ &gt; = 497

< Example  Preparation of the following compounds 1-38

Compound A-7 (4.71 g, 10.0 mmol) was used in place of Compound A-4 and Compound C-7 (2.57 g, 10.0 mmol) was used in place of Compound B- , The compound 1-38 (3.86 g, yield 74%) was prepared.

MS: [M + H] &lt; ⁺ &gt; = 522

< Example  Preparation of the following compound 1-40

Compound A-7 (4.71 g, 10.0 mmol) was used in place of Compound A-4 and compound B-8 (4.02 g, 10.0 mmol) was used in place of Compound B- , The compound 1-40 (4.66 g, yield 78%) was prepared. FIG. 2 shows the mass spectrum of Compound 1-40.

MS: [M + H] &lt; ⁺ &gt; = 598

< Example  Preparation of the following compounds 1-48

The compound 1-4 was synthesized by the same method except that the compound C-8 (2.38 g, 10.0 mmol) was used instead of the compound B-1 in the preparation of the compound 1-4 in Example 2 to obtain Compound 1-48 (3.25 g, yield 72%).

MS: [M + H] &lt; ⁺ &gt; = 453

< Example  Preparation of the following compounds 1-42

Compound A-9 (3.75 g, 10.0 mmol) was used in place of Compound A-4 and compound B-2 (3.48 g, 10.0 mmol) was used in place of Compound B- , The compound 1-42 (3.71 g, yield 62%) was prepared.

MS: [M + H] &lt; ⁺ &gt; = 599

< Example  Preparation of the following compound 2-2

Compound A-13 (4.21 g, 10.0 mmol) and compound B-6 (3.83 g, 10.0 mmol) were dispersed in THF (100 mL) and 2M K ₂ CO ₃ After adding an aqueous solution (20mL) and insert the _{Pd (PPh 3) 4 (0.231g} , 2mol%) it was stirred under reflux for 5 hours. The temperature was lowered to room temperature and the resulting solid was filtered. The filtered solid was recrystallized from chloroform and ethanol, filtered and dried to give Compound 2-2 (4.61 g, yield 74%).

MS: [M + H] &lt; ⁺ &gt; = 624

< Example  Preparation of the following compound 2-5

The compound 2-5 (4.75 g, yield: 82%) was synthesized in the same manner as in the preparation of the compound 2-2 of Example 20, except that the compound B-3 (4.59 g, 10.0 mmol) 71%).

MS: [M + H] &lt; ⁺ &gt; = 674

< Example  Preparation of the following compounds 2-6

The compound 2-6 (5.42 g, yield: 82%) was synthesized in the same manner as the compound of Example 20, except that Compound B-10 (5.09 g, 10.0 mmol) 75%).

MS: [M + H] &lt; ⁺ &gt; = 724

< Example  Preparation of the following compounds 2-11

Compound 2-11 (4.21 g, yield: 82%) was synthesized by the same method as Compound C-9 (4.15 g, 10.0 mmol) instead of Compound B-6 67%).

MS: [M + H] &lt; ⁺ &gt; = 630

< Example  Preparation of the following compound 2-24

Compound 2-2-2 was synthesized in the same manner as in Example 20, except that Compound C-10 (4.15 g, 10.0 mmol) was used instead of Compound B-6 to obtain Compound 2-24 (4.01 g, yield 71%).

MS: [M + H] &lt; ⁺ &gt; = 566

< Example  Preparation of the following compound 2-27

The compound 2-2-2 of Example 20 was synthesized in the same manner except that Compound B-24 (4.87 g, 10.0 mmol) was used in place of Compound B-6 to obtain Compound 2-27 (4.77 g, yield 68%).

MS: [M + H] &lt; ⁺ &gt; = 702

< Example  Preparation of the following compound 2-31

The compound 2-2 was synthesized in the same manner as in the preparation of the compound of Example 20, except that Compound B-14 (5.85 g, 10.0 mmol) was used instead of Compound B-6 to obtain Compound 2-31 (6.07 g, yield 76%).

MS: [M + H] &lt; ⁺ &gt; = 800

< Example  Preparation of the following compound 2-32

Except that Compound B-17 (3.15 g, 10.0 mmol) was used in place of Compound B-6 in the preparation of Compound 2-2 of Example 20 to obtain Compound 2-32 (3.70 g, yield 70%).

MS: [M + H] &lt; ⁺ &gt; = 530

< Example  Preparation of the following compound 2-33

Compound 2-33 (4.47 g, yield: 97%) was synthesized in the same manner except that Compound B-18 (3.99 g, 10.0 mmol) was used in place of Compound B- 73%).

MS: [M + H] &lt; ⁺ &gt; = 614

< Example  Preparation of the following compound 3-1

Compound A-17 (5.21 g, 10.0 mmol) and compound B-21 (3.33 g, 10.0 mmol) were dispersed in THF (100 mL) and 2M K ₂ CO ₃ After adding an aqueous solution (20mL) and insert the _{Pd (PPh 3) 4 (0.231g} , 2mol%) it was stirred under reflux for 5 hours. The temperature was lowered to room temperature and the resulting solid was filtered. The filtered solid was recrystallized from chloroform and ethanol, filtered and dried to give Compound 3-1 (5.11 g, yield 79%).

MS: [M + H] &lt; ⁺ &gt; = 648

< Example  Preparation of the following compound 3-2

Compound 3-2 was synthesized in the same manner as Compound 29-1 except that Compound B-20 (2.83 g, 10.0 mmol) was used instead of Compound B-21, 73%).

MS: [M + H] &lt; ⁺ &gt; = 598

< Example  Preparation of the following compounds 3-13

Compound 3-1 (Example 4.5) was synthesized in the same manner as in the preparation of the compound of Example 29 except for using Compound C-11 (3.35 g, 10.0 mmol) instead of Compound B-21 to obtain Compound 3-13 70%).

MS: [M + H] &lt; ⁺ &gt; = 650

< Example  Preparation of the following compound 3-21

Compound 3-1 (Example 5) was synthesized in the same manner as in Example 29, except that Compound C-12 (4.51 g, 10.0 mmol) was used instead of Compound B-21 to give Compound 3-21 66%).

MS: [M + H] &lt; ⁺ &gt; = 766

< Example  Preparation of the following compound 3-34

Compound 3-3 (5.69 g, yield: 97%) was synthesized by the same method except that Compound B-24 (4.87 g, 10.0 mmol) was used instead of Compound B-21 in the preparation of Compound 3-1 of Example 29. 71%).

MS: [M + H] &lt; ⁺ &gt; = 802

< Example  Preparation of the following compound 4-3

The compound A-21 (5.23g, 10.0mmol) and the compound B-1 (3.83g, 10.0mmol) was dispersed in _{THF (100mL), 2M K 2} CO 3 After adding an aqueous solution (20mL) and insert the _{Pd (PPh 3) 4 (0.231g} , 2mol%) it was stirred under reflux for 5 hours. The temperature was lowered to room temperature and the resulting solid was filtered. The filtered solid was recrystallized from chloroform and ethanol, filtered and dried to give compound 4-3 (5.24 g, yield 75%).

MS: [M + H] &lt; ⁺ &gt; = 700

< Example  Preparation of the following compounds 4-6

Synthesis was conducted in the same manner as in the preparation of Compound 4-3 of Example 34 except that Compound B-12 (5.09 g, 10.0 mmol) was used in place of Compound B-1 to obtain Compound 4-6 (5.78 g, yield 70%).

MS: [M + H] &lt; ⁺ &gt; = 827

< Example  Preparation of the following compounds 4-9

The compound 4-9 (5.07 g, yield: 82%) was synthesized in the same manner as in the preparation of the compound 4-3 of Example 34 except that the compound C-2 (3.88 g, 10.0 mmol) was used in place of the compound B- 72%).

MS: [M + H] &lt; ⁺ &gt; = 705

< Example  Preparation of the following compound 4-19

Compound 4-1 was synthesized in the same manner as Compound 34 of Example 34 except for using Compound B-24 (4.87 g, 10.0 mmol) instead of Compound B-1 to obtain Compound 4-19 (5.46 g, yield 68%).

MS: [M + H] &lt; ⁺ &gt; = 804

< Example  Preparation of the following compound 4-22

Compound A-25 (5.25 g, 10.0 mmol) was used in place of Compound A-21 and compound B-8 (4.02 g, 10.0 mmol) was used in place of Compound B-1 in the preparation of Compound 4- , The compound 4-22 (4.62 g, yield 71%) was prepared.

MS: [M + H] &lt; ⁺ &gt; = 652

< Example  Preparation of the following compound 4-25

Example 4 was repeated except that Compound A-25 (5.25 g, 10.0 mmol) was used in place of Compound A-21 in the preparation of Compound 4-3 to give Compound 4-25 (4.77 g, yield 68 %).

MS: [M + H] &lt; ⁺ &gt; = 702

< Experimental Example  1>

A glass substrate coated with ITO (indium tin oxide) having a thickness of 500 Å was immersed in distilled water containing detergent and washed with ultrasonic waves. At this time, Fischer Co. product was used as a detergent, and distilled water filtered by a filter of Millipore Co. was used as distilled water. The ITO was washed for 30 minutes and then washed twice with distilled water and ultrasonically cleaned for 10 minutes. After the distilled water was washed, it was ultrasonically washed with a solvent of isopropyl alcohol, acetone, and methanol, dried, and then transported to a plasma cleaner. Further, the substrate was cleaned using oxygen plasma for 5 minutes, and then the substrate was transported by a vacuum evaporator.

On this ITO transparent electrode, hexanitrile hexaazatriphenylene (HAT) of the following chemical formula was thermally vacuum deposited to a thickness of 100 Å to form a hole injection layer.

(1, naphthyl) -N-phenylamino] biphenyl (NPB) (1000 Å) of the above formula, which is a hole transporting material, was vacuum deposited on the hole injection layer to form a hole transport layer .

Subsequently, the following GH and GD were vacuum deposited on the hole transport layer at a weight ratio of 20: 1 at a thickness of 300 ANGSTROM to form a light emitting layer.

Compound 1-1 prepared in Example 1 was vacuum deposited on the light emitting layer to a thickness of 200 Å to form an electron injection and transport layer.

Lithium fluoride (LiF) and aluminum were deposited to a thickness of 12 Å on the electron injection and transport layer sequentially to form a cathode.

In the above process, the deposition rate of the organic material was maintained at 0.4 to 0.7 Å / sec, the deposition rate of lithium fluoride at the cathode was 0.3 Å / sec and the deposition rate of aluminum was maintained at 2 Å / sec. by keeping the ^-7 to 5 × 10 ^-8 torr, an organic light emitting device was produced.

< Comparative Example  1>

An organic light emitting device was fabricated in the same manner as in Experimental Example 1, except that the compound of the following formula (ET-A1) was used instead of the compound 1-1.

[ET-A1]

< Experimental Example  2 to 30>

An organic light emitting device was fabricated in the same manner as in Experimental Example 1, except that the compounds shown in Table 2 were used instead of the compounds of Formula 1-1.

The results shown in the following Table 2 were obtained when current was applied to the organic light emitting device manufactured by Experimental Examples 1 to 30 and Comparative Example 1. [ The values shown in Table 2 below are values measured at a current density of 10 mA / cm &lt; ² &gt;.

[Table 2]

From the results of Table 2, it was found that when the organic compound layer of the organic light emitting diode is formed using the compound of Formula 1 according to the present invention, the organic EL device exhibits excellent characteristics in terms of efficiency, driving voltage drop and stability.

Claims (14)

delete Is selected from the group consisting of the following formulas (2) to (4):
(2)

(3)

[Chemical Formula 4]

In the above Chemical Formulas 2 to 4,
At least one of R3 to R7 is a group represented by - (L) p- (Y) q and the remainder is hydrogen or deuterium, wherein p is an integer of 0 to 10, q is an integer of 1 to 10,
L is a C _6-50 arylene group; A fluorenylene group of C _13-50 ; Or a C _2-50 heteroarylene group having heteroatoms O, N or S,
Y is hydrogen; Hydrogen; heavy hydrogen; A nitrile group; A silyl group substituted or unsubstituted with an aryl group of C _6-50 ; A C _13-50 fluorenyl group substituted or unsubstituted with a C _1-50 alkyl group or a C _6-50 aryl group; A C _2-50 alkenyl group substituted or unsubstituted with a C _6-50 aryl group; A C _6-50 aryl group substituted or unsubstituted with a C _2-50 heteroaryl group having O, N or S as an arylamine group or hetero atom of C _6-50 ; A C _6-50 arylamine group substituted or unsubstituted with an aryl group of C _6-50 ; Or a C _2-50 heteroaryl group substituted or unsubstituted with an aryl group having O, N or S as a hetero atom,
When two or more L or Y are present, they are the same or different from each other,
R8 to R11 are hydrogen or deuterium. 3. The compound of claim 2, wherein said heteroaryl group is selected from the group consisting of:

3. The compound of claim 2, wherein the fluorenyl group is selected from the group consisting of:

The compound according to claim 2, wherein the compound represented by any one of formulas (2) to (4) is selected from the group consisting of the following compounds 1-1 to 1-48:

The compound according to claim 2, wherein the compound represented by any one of formulas (2) to (4) is selected from the group consisting of the following compounds 2-1 to 2-33:

The compound according to claim 2, wherein the compound represented by any one of Chemical Formulas 2 to 4 is selected from the group consisting of the following compounds 3-1 to 3-48:

The compound according to claim 2, wherein the compound represented by any one of Chemical Formulas 2 to 4 is selected from the group consisting of the following compounds 4-1 to 4-30:

1. An organic electronic device comprising a first electrode, a second electrode, and at least one organic material layer disposed between the first electrode and the second electrode, wherein at least one of the organic material layers is provided in any one of claims 2 to 8 And the compound represented by any one of formulas (2) to (4) described above. [12] The organic electroluminescent device according to claim 9, wherein the organic layer includes at least one of an electron injection layer and an electron transport layer, and at least one of the electron injection layer and the electron transport layer includes a compound represented by any one of Chemical Formulas 2 to 4 . [Claim 11] The organic electronic device according to claim 9, wherein the organic layer includes a light emitting layer, and the light emitting layer comprises a compound represented by any one of Chemical Formulas 2 to 4. [ 10. The organic electroluminescent device according to claim 9, wherein the organic material layer comprises at least one of a hole injecting layer, a hole transporting layer, and a layer simultaneously injecting holes and transporting holes, wherein one of the layers is represented by any one of Formulas 2 to 4 Lt; RTI ID = 0.0 &gt; 1, &lt; / RTI &gt; The organic electronic device according to claim 9, wherein the organic electronic device is selected from the group consisting of an organic light emitting device, an organic phosphor device, an organic solar cell, an organic photoconductor (OPC), and an organic transistor. The organic electroluminescent device according to claim 9, wherein the organic material layer comprises an electron transporting layer containing a compound represented by any one of Chemical Formulas 2 to 4, and the electron transporting layer is an alkali metal, an alkali metal compound, an alkaline earth metal or an alkaline earth metal compound, Lt; RTI ID = 0.0 &gt; water. &Lt; / RTI &gt;

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