KR20120061056A - New nitrogen-containing heterocyclic compounds and organic electronic device using the same - Google Patents

Abstract

PURPOSE: An organic electronic device using a novel nitrogen-containing heterocyclic compound is provided to enhance efficiency, driving voltage, and lifetime. CONSTITUTION: A novel nitrogen-containing heterocyclic compound is denoted by chemical formula 1. An organic electronic device comprises a first electrode, a second electrode, and one or more organic layers placed between the first and second electrodes. The organic layer contains the heterocyclic compounds. The organic layer comprises a hole injection layer, a hole transport layer, or a layer for simultaneous hole injection and hole transport.

Description

Novel nitrogen-containing heterocyclic compound and organic electronic device using the same {NEW NITROGEN-CONTAINING HETEROCYCLIC COMPOUNDS AND ORGANIC ELECTRONIC DEVICE USING THE SAME}

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 an exchange of holes and / or electrons between an electrode and an organic semiconductor material. The organic electronic device can be divided into two types according to the operating principle. First, an exciton is formed in the organic layer by photons introduced into the device from an external light source, and the exciton is separated into electrons and holes, and these electrons and holes are transferred to different electrodes to be used as current sources (voltage sources). Form of electronic devices. The second type is an electronic device in which holes and / or electrons are injected into the organic semiconductor material layer that interfaces with the electrodes by applying voltage or current to two or more electrodes, and is operated by the injected electrons and holes.

Examples of organic electronic devices include organic light emitting devices, organic solar cells, organic photoconductor (OPC) drums, and organic transistors, all of which are electron / hole injection materials, electron / hole extraction materials, and electron / hole transport materials for driving the devices. Materials or luminescent materials are required. Hereinafter, the organic light emitting device will be described in detail. However, in the organic electronic devices, an electron / hole injection material, an electron / hole extraction material, an electron / hole transport material, or a light emitting material may all operate on a similar principle.

In general, organic light emitting phenomenon refers to a phenomenon of converting electrical energy into light energy using an organic material. An organic light emitting device using an organic light emitting phenomenon usually has a structure including an anode, a cathode, and an organic material layer therebetween. In this case, the organic material layer is often formed of a multilayer structure composed of different materials to increase the efficiency and stability of the organic light emitting device, and may include, for example, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and the like. When the voltage is applied between the two electrodes in the structure of the organic light emitting device, holes are injected into the organic material layer at the anode, electrons are injected into the organic material layer, and excitons are formed when the injected holes and electrons meet. When it falls to the ground, it glows. Such organic light emitting devices are known to have characteristics such as self-luminous, high brightness, high efficiency, low driving voltage, wide viewing angle, high contrast, and high speed response.

Most of the materials used in the organic light emitting device are pure organic materials or complex compounds in which organic materials and metals are complexed, and depending on the purpose, hole injection materials, hole transport materials, electron transport materials, electron injection materials, light emitting materials, etc. It can be divided into. Here, as the hole injection material or the hole transport material, an organic material having a p-type property, that is, an organic material which is easily oxidized and has an electrochemically stable state during oxidation, is mainly used. On the other hand, as the electron injecting material or the electron transporting material, an organic material having an n-type property, that is, an organic material which is easily reduced and has an electrochemically stable state at the time of reduction is mainly used. As the light emitting material, a material having a p-type property and an n-type property at the same time, that is, a material having a stable form in both oxidation and reduction states, and a material having high luminous efficiency for converting it to light when excitons are formed desirable.

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

In order to obtain a high-efficiency organic light emitting device capable of driving a low voltage, holes or electrons injected into the organic light emitting device should be smoothly transferred to the light emitting layer, and the injected holes and electrons should not escape out of the light emitting layer. For this purpose, the material used for the organic light emitting device should have an appropriate band gap and HOMO or LUMO energy level. Alq ₃ , which is mainly used as an electron transport layer material, has a high HOMO energy level compared to the HOMO energy levels of organic materials used as the light emitting layer material, thus making it difficult to manufacture an organic light emitting device having high efficiency and long lifespan.

In addition, the material used in the organic light emitting device should be excellent in chemical stability, charge mobility, interface characteristics between the electrode and the adjacent layer. That is, the material used in the organic light emitting device should be less deformation of the material by moisture or oxygen. In addition, by having an appropriate hole or electron mobility it should be able to maximize the exciton formation by balancing the density of holes and electrons in the light emitting layer of the organic light emitting device. In addition, for the stability of the device should be able to improve the interface with the electrode containing a metal or metal oxide.

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

Accordingly, the inventors have discovered a novel nitrogen-containing heterocyclic compound. In addition, it has been found that when the organic material layer of the organic electronic device is formed by using the novel nitrogen-containing heterocyclic compound, the efficiency of the device, the driving voltage, the lifespan, and the stability may be exhibited.

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

The present invention provides a compound of formula

In Formula 1,

R ₁ and R ₂ are the same as or different from each other, and each independently hydrogen; heavy hydrogen; A halogen group; 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; An aryl group, a substituted or unsubstituted C _{6 -50} ring; 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 as or different from each other, and each independently hydrogen; heavy hydrogen; A halogen group; 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;} Tiok alkyl group a substituted or unsubstituted C _{1 -50;} Aryloxy substituted or unsubstituted C _{6 -50} ring; A substituted or unsubstituted C _{2 -50} alkenyl group; Substituted or unsubstituted silyl group; Substituted or unsubstituted boron group; A substituted or unsubstituted fluorenyl group; A substituted or unsubstituted C _6-50 arylamine group; An aryl group, a substituted or unsubstituted C _{6 -50} ring; 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; 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; Substituted or unsubstituted silyl group; Substituted or unsubstituted boron group; Fluorenyl group a substituted or unsubstituted C _{13 -50} ring; Arylamine group, a substituted or unsubstituted C _{6 -50} ring; An aryl group, a substituted or unsubstituted C _{6 -50} ring; 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, where p is an integer from 0 to 10, q is an integer from 1 to 10,

L is an aryl group a substituted or unsubstituted C _{6 -50} ring; Substituted or unsubstituted alkenylene group of _{2 -50} C ring; Fluorenyl group a substituted or unsubstituted C _{13 -50} ring; 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; 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;} Tiok alkyl group a substituted or unsubstituted C _{1 -50;} Aryloxy substituted or unsubstituted C _{6 -50} ring; A substituted or unsubstituted C _{2 -50} alkenyl group; Substituted or unsubstituted silyl group; Substituted or unsubstituted boron group; A substituted or unsubstituted C _13-50 fluorenyl group; Arylamine group, a substituted or unsubstituted C _{6 -50} ring; An aryl group, a substituted or unsubstituted C _{6 -50} ring; 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 L or Y is present at least 2, they are the same as 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 condensed ring of aliphatic, aromatic, aliphatic hetero or aromatic hetero, or form spiro bonds.

In addition, the present invention is an organic electronic device comprising a first electrode, a second electrode and at least one organic layer disposed between the first electrode and the second electrode, at least one of the organic layer is a compound of Formula 1 It provides an organic electronic device comprising.

The novel nitrogen-containing heterocyclic compound according to the present invention can be used as an organic material layer material for organic electronic devices including organic light emitting devices, and organic electronic devices including organic light emitting devices using the same have increased efficiency, lowered driving voltage, extended life, and stability. Excellent properties.

FIG. 1 shows an example of an organic light emitting device consisting of a substrate 1, an anode 2, a hole injection layer 3, a hole transport layer 4, a light emitting layer 5, an electron transport layer 6 and a cathode 7 It is.
2 shows the mass spectra of compounds 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 in that the compound represented by the formula (1).

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

In Chemical Formulas 2 to 4,

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

R ₈ to R ₁₂ are the same as the definition of 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 Chemical Formula 1.

Hereinafter, the substituents of Chemical Formulas 1 to 4 will be described in detail.

The number of carbon atoms in the alkyl group of Formulas 1 to 4 is preferably 1 to 50, more preferably 1 to 30, specifically, methyl, ethyl, propyl, isopropyl, butyl, t-butyl, pen Although there exist a methyl group, hexyl group, heptyl group, etc., It is not limited to these.

In addition, the cycloalkyl group of Formulas 1 to 4 preferably has 3 to 50 carbon atoms, more preferably 3 to 40 carbon atoms, and specifically, cyclopentyl group or cyclohexyl group, but is not limited thereto.

In addition, it is preferable that carbon number of the alkylthioxy group and the alkoxy group of said Formula (1)-(4) is 1-50, and it is more preferable that it is 1-40.

In addition, the carbon number of the alkenyl group of Formulas 1 to 4 is preferably 2 to 50, more preferably 2 to 40, specifically, an aryl group such as stylbenyl, styrenyl, etc. Substituted alkenyl groups and the like, but are not limited thereto.

In addition, the aryl group of Formula 1 to Formula 4 may be monocyclic or polycyclic, preferably 6 to 50, more preferably 6 to 40 carbon atoms. Specifically, examples of the monocyclic aryl group include a phenyl group, a biphenyl group, and a terphenyl group, and examples of the polycyclic aryl group include naphthyl group, anthryl group, phenanthryl group, pyrenyl group, perrylenyl group, and chrysenyl group. However, the scope of the present invention is not limited only to these examples.

In addition, the number of carbon atoms of the heteroaryl groups of Formulas 1 to 4 is preferably 2 to 50, more preferably 2 to 40, and preferably has O, N, S or P as the hetero atom. Examples of the heteroaryl group include a thiophene group, a furan group, a pyrrole 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 pyrazine group and a quinolinyl group , Isoquinoline group, carbazole group, benzocarbazole group, acridyl group and the like, compounds such as the following structural formulas are preferred, but are not limited thereto.

In addition, examples of the halogen group of Formula 1 to Formula 4 include fluorine, chlorine, bromine or iodine.

In addition, the number of carbon atoms of the arylamine group of Formula 1 to Formula 4 is preferably 6 to 50, more preferably 6 to 40, specifically, a phenylamine group, naphthylamine group, biphenylamine group, anthracenyl Amine group, 3-methyl-phenylamine group, 4-methyl-naphthylamine group, 2-methyl-biphenylamine group, 9-methyl-anthracenylamine group, diphenylamine group, phenylnaphthyl amine group, di Tolylamine group, phenyltolylamine group and triphenylamine group. It is not limited to these.

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

In addition, unless otherwise specified in Formulas 1 to 4, the term "substituted or unsubstituted" is deuterium, halogen, alkyl, alkenyl, alkoxy, silyl, arylalkenyl, aryl, heteroaryl A group, a carbazole group, an arylamine group, a fluorenyl group unsubstituted or substituted with an aryl group, and one or more substituents selected from the group consisting of nitrile groups means no substituents.

In 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, and L is an arylene group and flu. It is preferable that it is an orenylene group, an alkenylene group, or a hetero arylene group, and Y is 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 it is not limited to this.

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

Moreover, it is preferable that carbon number of the fluorenylene group of the said Formula (1)-(4) is 13-50, and it is more preferable that it is 13-40.

In addition, the arylene group of Formula 1 to Formula 4 preferably has 6 to 50 carbon atoms, more preferably 6 to 40, specifically, a phenylene group, biphenylene group, naphthalenyl group, binaphthalene group, anthracenylene group , Crysenylene group, phenanthrenylene and pyrenylene group, but is not limited thereto.

In addition, the number of carbon atoms of the heteroarylene group of Formula 1 to Formula 4 is preferably 2 to 50, more preferably 2 to 40, and preferably has O, N, S or P as the hetero atom, and specifically, Imidazolylene group, oxazolylene group, thiazolylene group, triazylene group, pyridylene group, pyrimidylene group, quinolylene group, carbazolylene group, indolizylene group and thiophenylene group are preferred, but not limited thereto. .

In addition, the compounds represented by Formula 1 to Formula 4 include the following compounds, but are not limited thereto.

The compound of Chemical Formula 1 according to the present invention has an imidazole structure and a pyrazine structure in the compound, and thus may have electron injection and / or electron transport. It also has stability against electrons. This makes it easy to transport electrons in the electron injection layer, the electron transport layer and the light emitting layer.

In addition, when P-type substituents, such as arylamines, are added, it enables hole transport and has stability with respect to an electron, and can also be used for a hole transport layer. Therefore, the compound having such a structure can be applied to the organic electronic device to improve the efficiency, driving voltage, and lifetime of the device.

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

According to an exemplary embodiment of the present invention, the compound represented by Formula 1 is

1) In the presence of a base such as K ₂ CO ₃ or Cs ₂ CO ₃ , a compound 1-A in which a halogen group and NO ₂ are substituted, and an imidazole compound 1-B are reacted, where NO ₂ is substituted. Preparing compound 1-C,

2) reducing the compound 1-C prepared in step 1) using Na ₂ S ₂ O ₄ to prepare NH ₂ substituted compound 1-D,

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

4) The compound 1-E prepared in step 3) may be prepared by a method comprising preparing compound 1-F (compound represented by Formula 1) using POCl ₃ . Such a manufacturing method may be represented by the following Scheme 1, but the method of preparing the compound represented by Chemical Formula 1 is not limited to the following Scheme 1.

Scheme 1

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

The compound represented by Chemical Formula 1 may be prepared by referring to the above general preparation method and the following examples of the present specification.

In addition, the present invention is an organic electric 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 layer is the formulas (1) to (1). It provides an organic electronic device comprising a compound represented by 4.

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

Hereinafter, the organic light emitting device will be exemplified.

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

When the organic light emitting device according to the present invention has a multi-layered organic material layer, the compound of Formula 1 is a light emitting layer, a hole transport layer, a layer for simultaneously transporting holes and light emission, a layer for simultaneously emitting light and electron transport, electron transport layer, electron transport And / or injection layers and the like. In the present invention, the compound represented by Formula 1 to Formula 4 is particularly preferably included in the electron injection and / or transport layer or the light emitting layer.

In particular, when the compound of Formula 1 according to the present invention is included in the 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, and Li, LiQ , LiF and the like are preferable, but the present invention is not limited thereto.

The organic material layer may include a hole injection layer and a hole transport layer, and the hole injection layer and the hole transport layer may include a compound represented by Chemical Formulas 1 to 4.

The organic light emitting device according to the present invention may be manufactured using a conventional method and material for manufacturing an organic light emitting device, except that the compound of Chemical Formulas 1 to 4 is used in at least one layer of the organic material layer of the organic light emitting device. Can be. For example, the organic light emitting device according to the present invention uses a metal vapor deposition (PVD) method such as sputtering or e-beam evaporation, and has a metal oxide or a metal oxide or an alloy thereof on a substrate. It can be prepared by depositing an anode to form an anode, an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer and an electron transport layer thereon, and then depositing a material that can be used as a cathode thereon. In addition to the above method, in order to fabricate an organic light emitting device having a reverse structure as described above, an organic light emitting device may be manufactured by sequentially depositing an anode material, an organic material layer, and an anode material on a substrate.

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

As the anode material, a material having a large work function is usually preferred to facilitate hole injection into the organic material layer. Specific examples of the positive electrode 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), indium zinc oxide (IZO); A combination of a metal and an oxide such as ZnO: Al or SnO ₂ : Sb; Conductive polymers such as poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (PEDOT), polypyrrole and polyaniline, and the like, but are not limited thereto.

It is preferable that the cathode material is 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; Multilayer structure materials such as LiF / Al or LiO ₂ / Al, and the like, but are not limited thereto.

The hole injection material is a material capable of well injecting holes from the anode at a low voltage, and the highest occupied molecular orbital (HOMO) of the hole injection material is preferably between the work function of the anode material and the HOMO of the surrounding organic material layer. Specific examples of the hole injection material include metal porphyrine, oligothiophene, arylamine-based organics, hexanitrile hexaazatriphenylene-based organics, quinacridone-based organics, and perylene-based Organic substances, anthraquinone and polyaniline and polythiophene-based conductive polymers, but are not limited thereto.

As the hole transporting material, a material capable of transporting holes from the anode or the hole injection layer and transferring the holes to the light emitting layer is suitable. Specific examples include arylamine-based compounds; Carbazole-based compounds; Anthracene-based compounds; Pyrene-based compounds; Conductive polymers, and block copolymers having a conjugated portion and a non-conjugated portion, and the like, but are not limited thereto.

The light emitting material is a material capable of emitting light in the visible region by transporting and combining holes and electrons from the hole transporting layer and the electron transporting layer, respectively, and a material having good quantum efficiency with respect to fluorescence or phosphorescence is preferable. Specific examples thereof include 8-hydroxyquinoline aluminum complex (Alq ₃ ); Carbazole series compounds; Dimerized styryl compounds; Bis-methyl-8-hydroxyquinoline paraphenylphenol aluminum complex (bAlq); 10-hydroxybenzoquinoline-metal compound; Benzoxazole, benzthiazole and benzimidazole series compounds; Anthracene-based compounds; Pyrene-based compounds; Poly (p-phenylenevinylene) (PPV) -based polymers; Spiro compounds; Polyfluorene, rubrene and the like, but are not limited thereto.

The electron transporting material is a material capable of injecting electrons well from the cathode and transferring the electrons to the light emitting layer. A material having high mobility to electrons is suitable. Specific examples include Al complexes of 8-hydroxyquinoline; Complexes including Alq ₃ ; Organic radical compounds; Hydroxyflavone-metal complexes; Anthracene-based compounds; Pyrene-based compounds; Benzoxazole, benzthiazole and benzimidazole series compounds; Pyridyl family compounds; Phenanthroline series compounds; Quinoline family compounds; Quinazoline-based compounds and the like, and these compounds may be doped with metals or metal compounds to form an electron transport layer, but are 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 of Chemical Formulas 1 to 4 according to the present invention may also operate on a similar principle to those applied to organic light emitting devices in organic electronic devices including organic solar cells, organic phosphorescent devices, organic photoconductors (OPCs), 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 invention, whereby the scope of the invention is not limited.

< Example >

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

1) Preparation of Compound A-1

2-Fluoronitrobenzene (10g, 70.9mmol), Benzimidazole (9.2g, 77.9mmol) and Cs ₂ CO ₃ (53g, 163mmol) were added to DMF (N, N-dimethylformamide, 150ml). ), And stirred at room temperature for 24 hours. The resulting reaction mixture was filtered, excess Cs ₂ CO _{3 was} removed, the filtrate was concentrated under reduced pressure, and tetrahydrofuran (THF): n-hexane (n-hexane) = 1: 10 was developed as column chromatography. After chromatography (Column chromatography) purification and dried to prepare a compound A-1 (15.3g, 90% yield).

MS: [M + H] ⁺ = 240

2) Preparation of the 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) / water 100 mL was added while stirring at room temperature under a nitrogen atmosphere. Stirring to reflux for 3 hours, lower the temperature to room temperature, and add a solution of K ₂ CO ₃ (23.1 g, 167 mmol) / 40 mL of water. In addition, a solution of 4-bromobenzoyl chloride (4-Bromobenzoyl chloride, 9.2 g, 41.8 mmol) / THF 20 mL was added dropwise, and stirred under reflux 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 filtered. The filtrate was concentrated under reduced pressure and the compound A-2 (11.5g, yield 70%) was prepared by column with THF: n-hexane = 1: 10.

MS: [M + H] ⁺ = 393

3) Preparation of the Compound A-3

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 stirring for 5 hours under reflux, 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 prepare compound A-3 (5.15 g, 72% yield).

MS: [M + H] ⁺ = 375

4) Preparation of the Compound A-4

Compound A-4 (6.3 g, 16.8 mmol), bis (pinacolato) diboron (4.7 g, 18.5 mmol) and potassium acetate (KOAc, 4.96 g, 50.5 mmol) were converted into dioxane (1,4-Dioxane, In suspension (100 mL) and Pd (dba) ₂ (0.29 g, 3 mol%) and PCy ₃ (0.28 g, 6 mol%) were added. 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 × 50 mL). The organic extract was dried over magnesium sulfate free and filtered. The filtrate was concentrated under reduced pressure, and recrystallized with ethyl ether and hexane to prepare the compound A-4 (5.66g, 80%).

MS: [M + H] ⁺ = 422

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

1) Preparation of Compound A-5

In preparing Compound A-2 of Preparation Example 1 2), except that 6-bromonaphthoyl chloride (6-Bromonaphthoyl chloride, 11.3 g, 41.8 mmol) was used instead of 4-bromobenzoyl chloride. Compound A-5 (13.9 g, yield 75%) was prepared by synthesis method.

MS: [M + H] ⁺ = 443

2) Preparation of the Compound A-6

In the preparation of Compound A-3 of Preparation Example 1 3), a compound A-6 (5.27) was synthesized in the same manner except for using Compound A-5 (8.4 g, 19.1 mmol) instead of Compound A-2. g, yield 65%).

MS: [M + H] ⁺ = 425

3) Preparation of the Compound A-7

In the preparation of Compound A-4 of Preparation Example 1 4), except that Compound A-6 (7.12 g, 16.8 mmol) was used instead of Compound A-3, and synthesized in the same manner, Compound A-7 (6.49 g, yield 82%) was prepared.

MS: [M + H] ⁺ = 472

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

1) Preparation of Compound A-8

In the preparation of Compound A-2 of Preparation Example 1 2), except that 6-bromopicolinoyl chloride (6-Bromopicolinoyl chloride, 9.21 g, 41.8 mmol) was used instead of 4-bromobenzoyl chloride. Compound A-8 (11.2 g, yield 68%) was prepared by synthesis method.

MS: [M + H] ⁺ = 394

2) Preparation of the Compound A-9

In the preparation of Compound A-3 of Preparation Example 3, Compound A-9 was synthesized in the same manner except for using Compound A-8 (7.5 g, 19.1 mmol) instead of Compound A-2. 4.44 g, 62% yield).

MS: [M + H] ⁺ = 376

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

1) Preparation of Compound A-10

In the preparation of compound A-1 of 1) of Preparation Example 1, 2,5-dibromonitrobenzene (2,5-Dibromonitrobenzene, 19.9 g, 70.9 mmol) was used instead of 2-fluoronitrobenzene. Compound A-10 (18.7 g, yield 83%) was prepared by the same method as the synthesis method.

MS: [M + H] ⁺ = 319

2) Preparation of Compound A-11

In the preparation of Compound A-2 of Preparation Example 1 2), a compound A-11 was synthesized in the same manner except that benzoyl chloride (Benzoylchloride, 5.87 g, 41.8 mmol) was used instead of 4-bromobenzoyl chloride. (11.6 g, 71% yield) was prepared.

MS: [M + H] ⁺ = 393

3) Preparation of the Compound A-12

In the preparation of compound A-3 of Preparation Example 1 3), a compound A-12 (4.65) was synthesized in the same manner except that Compound A-11 (7.49 g, 19.1 mmol) was used instead of Compound A-2. g, yield 65%).

MS: [M + H] ⁺ = 375

4) Preparation of the Compound A-13

In the preparation of Compound A-4 of Preparation Example 1 4), the compound A-13 (5.66) was synthesized in the same manner except for using the compound A-12 (6.29 g, 16.8 mmol) instead of the compound A-3. g, yield 80%) was prepared.

MS: [M + H] ⁺ = 422

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

1) Preparation of Compound A-14

In the preparation of Compound A-1 of Preparation Example 1, Compound A-14 was synthesized in the same manner except for using Compound C-1 (Benzoylchloride, 17.0 g, 77.9 mmol) instead of benzimidazole. (18.8 g, 78% yield) was prepared.

MS: [M + H] ⁺ = 340

2) Preparation of the Compound A-15

In the preparation of Compound A-2 of Preparation Example 1 2), a compound A-15 (14.4) was synthesized in the same manner except that Compound A-14 (14.2 g, 41.8 mmol) was used instead of Compound A-2. g, yield 70%) was prepared.

MS: [M + H] ⁺ = 493

3) Preparation of the Compound A-16

In the preparation of Compound A-3 of Preparation Example 1 3), a compound A-16 (6.16) was synthesized in the same manner except that Compound A-15 (9.4 g, 19.1 mmol) was used instead of Compound A-2. g, yield 68%).

MS: [M + H] ⁺ = 475

4) Preparation of the Compound A-17

In the preparation of Compound A-4 of Preparation Example 1 4), except that Compound A-16 (7.97 g, 16.8 mmol) was used instead of Compound A-3, Compound A-17 (7.01) was synthesized in the same manner. g, yield 80%) was prepared.

MS: [M + H] ⁺ = 522

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

1) Preparation of Compound A-18

In preparing Compound A-1 of 1) of Preparation Example 1, except that 4,5-diphenylimidazole (4,5-diphenylimidazole, 17.2 g, 77.9 mmol) was used instead of benzimidazole. Compound A-18 (19.6 g, yield 81%) was prepared by synthesis method.

MS: [M + H] ⁺ = 342

2) Preparation of the Compound A-19

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

MS: [M + H] ⁺ = 495

3) Preparation of Compound A-20

In the preparation of Compound A-3 of Preparation Example 3, Compound A-20 (5.91) was synthesized in the same manner except for using Compound A-19 (9.4 g, 19.1 mmol) instead of Compound A-2. g, yield 65%).

MS: [M + H] ⁺ = 477

4) Preparation of the Compound A-21

In the preparation of Compound A-4 of Preparation Example 1 4), except that Compound A-20 (8.00 g, 16.8 mmol) was used instead of Compound A-3, Compound A-21 (7.30) was synthesized in the same manner. g, yield 83%).

MS: [M + H] ⁺ = 524

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

1) Preparation of the Compound A-22

In the preparation of compound A-1 of 1) of Preparation Example 1, the 4,5-di- (2-pyridyl) imidazole (4,5-di- (2-pyridyl) imidazole, instead of benzimidazole, Compound A-22 (18.3 g, yield 75%) was prepared in the same manner except using 17.3 g, 77.9 mmol).

MS: [M + H] ⁺ = 344

2) Preparation of the Compound A-23

In the preparation of Compound A-2 of Preparation Example 1 2), except that Compound A-22 (14.4 g, 41.8 mmol) was used instead of Compound A-2, Compound A-23 (13.5) was synthesized in the same manner. g, yield 65%).

MS: [M + H] ⁺ = 497

3) Preparation of the Compound A-24

In the preparation of Compound A-3 of Preparation Example 1 3), except that Compound A-23 (9.5g, 19.1mmol) was used instead of Compound A-2, Compound A-24 (5.66) was synthesized in the same manner. g, yield 62%).

MS: [M + H] ⁺ = 479

4) Preparation of the Compound A-25

In the preparation of Compound A-4 of Preparation Example 1 4), except that Compound A-24 (8.04 g, 16.8 mmol) was used instead of Compound A-3, Compound A-25 (6.36) was synthesized in the same manner. g, yield 72%).

MS: [M + H] ⁺ = 526

The following preparations are examples of intermediates that were advanced to prepare the compound of Formula 1.

< Manufacturing example  8> Preparation of the following Compounds B-1, B-2, B-3

1) Compound B-1

The 9- (2-naphthyl) -anthracene (9- (2-naphthyl) -anthracene, 7.36 g, 24.2 mmol) was dissolved in chloroform (150 mL), and acetic acid (150 mL) was added. Br ₂ (1.3 mL, 25.4 mmol) was added dropwise. The resulting mixture was raised to room temperature and stirred for 5 hours. After the reaction was completed, the reaction solution was concentrated and recrystallized with ethanol to give compound B-1 (6.49g, 70% yield).

MS: [M] ⁺ = 383

2) Compound B-2

After dissolving Compound B-1 (6.86 g, 17.9 mmol) in tetrahydrofuran (150 mL), the temperature was lowered to -78? And 1.7 M tertiary-butyllithium ( t -BuLi) (10.5 mL, 17.9 mmol) was added. Slowly added. After stirring for one hour at the same temperature, trimethyl borate (B (OCH ₃ ) ₃ , 3.72g, 35.8mmol) was added and stirred for 3 hours while gradually raising the temperature to room temperature. 2N aqueous hydrochloric acid solution (30 mL) was added to the reaction mixture, which was stirred for 1.5 hours at room temperature. The resulting precipitate was filtered off, washed successively with water and ethyl ether, and dried in vacuo. After drying, the mixture was dispersed in ethyl ether, stirred for 2 hours, filtered, and dried to prepare Compound B-2 (4.44 g, 71% yield).

MS: [M + H] ⁺ = 349

3) Compound B-3

Compound B-2 (3.48 g, 10.0 mmol) and 1-bromo-4-iodobenzene (1-bromo-4-iodobenzene, 3.4 g, 12.0 mmol) were dissolved in tetrahydrofuran (100 mL), and then 2M potassium carbonate. An aqueous solution (20 mL) was added thereto, tetrakistriphenylphosphinopalladium (Pd (PPh ₃ ) ₄ , 0.231 g, 2 mol%) was added thereto, and the mixture was refluxed 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 with tetrahydrofuran and ethanol to give compound B-3 (3.30g, 72% yield).

MS: [M + H] ⁺ = 460

< Manufacturing example  9> Preparation of the following Compound B-4

In the preparation of Compound B-1 of Preparation Example 8, 9- (1-naphthyl) -anthracene (9- (1-naphthyl) -anthracene) instead of 9- (2-naphthyl) -anthracene Except for using naphthyl) -anthracene), Compound B-4 (6.49 g, Yield 70%) was prepared by the same method as the method for preparing Compound B-1.

MS: [M] ⁺ = 383

< Manufacturing example  10> Preparation of the following Compounds B-5, B-6

1) Compound B-5

9-bromoanthracene (8.2 g, 31.9 mmol), biphenyl boronic acid (7.6 g, 38.4 mmol), and Pd (PPh ₃ ) ₄ (0.737 g, 2 mol%) were added to 2M K ₂ CO ₃ aqueous solution (300 mL) and tetra It was placed in hydrofuran (300 mL) and stirred at reflux for about 24 hours. After cooling 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 with tetrahydrofuran and ethanol to give compound B-5 (8.5 g, 81% yield).

MS: [M] ⁺ = 330

2) Compound B-6

Compound B-1, except that Compound B-5 was used instead of 9- (2-naphthyl) -anthracene (9- (2-naphthyl) -anthracene) in the preparation of Compound B-1 of Preparation Example 8. Compound B-6 (7.03 g, yield 71%) was prepared in the same manner as the preparation method.

MS: [M] ⁺ = 409

< Manufacturing example  11> Preparation of Compound B-7, B-8

1) Compound B-7

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

MS: [M + H] ⁺ = 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, followed by stirring for 10 minutes. After the temperature was lowered to 0 ?, trifluoromethanesulfonic anhydride ((CF ₃ SO ₂ ) ₂ O) (6.76 mL, 40.2 mmol) was slowly added, and the temperature was raised to room temperature, followed by stirring for 1 hour. After adding an aqueous sodium hydrogen carbonate solution, the water layer was removed and water was removed with anhydrous magnesium sulfate. After filtration and concentration under reduced pressure and recrystallized with hexane to give compound B-8 (8.69g, 81% yield).

MS: [M + H] ⁺ = 403

< Manufacturing example  12> Preparation of the following Compounds B-9 and B-10

1) Compound B-9

1-bromonaphthalene (1-bromo-naphthalene, 34.8g, 168mmol) was dissolved in tetrahydrofuran (170mL), and the temperature was lowered to -78 ° C and 2.5M n-butyllithium (67.3mL, 168mmol) was slowly added. After stirring for 1 hour. 2-bromoanthraquinone (21 g, 73.1 mmol) was added and the temperature was raised to room temperature and stirred for 3 hours. Aqueous solution of saturated ammonium chloride was added thereto, the water layer was removed, dried over anhydrous magnesium sulfate, filtered and dried under reduced pressure. Compound B-9 (32.5 g, yield 82%) was prepared by recrystallization with ethyl ether.

MS: [M + H] ⁺ = 544

2) Compound B-10

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 stirred under reflux for 3 hours. After the temperature was lowered to room temperature, the resulting precipitate was filtered and washed with water and ethanol to prepare compound B-10 (25.4 g, yield 84%).

MS: [M] ⁺ = 509

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

1) Compound B-11

In the preparation of Compound B-9 of Preparation Example 12, except that 2-bromo naphthalene was used instead of 1-bromo naphthalene, Compound B-11 (31.8 g, Yield 80%) was prepared.

MS: [M + H] ⁺ = 544

2) Compound B-12

Compound B-12 (25.4 g, Yield 84) in the same manner as in the preparation of Compound B-10, except that Compound B-11 was used instead of Compound B-9 in the preparation of Compound B-10 of Preparation Example 12. %) Was prepared.

MS: [M] ⁺ = 509

3) Compound B-13

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

MS: [M + H] ⁺ = 557

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

[Compound B-14]

Compound B-14 (4.45g, Yield 76) in the same manner as in the preparation of Compound B-3, except that Compound B-13 was used instead of Compound B-2 in the preparation of Compound B-3 of Preparation Example 8. %) Was prepared.

MS: [M + H] ⁺ = 586

< Manufacturing example  15> Preparation of the following Compound B-15

[Compound B-15]

Carbazole (3.34 g, 20 mmol), 1-bromo-4-iodinebenzene (6.79 g, 24 mmol), K ₂ CO ₃ (5.52 g, 40 mmol), copper iodide (CuI, 0.381 g, 2 mmol) and 1,10 -Phenanththroline (1,10-phenanthroline, 0.360 g, 2 mmol) was suspended in xylene (50 mL) and stirred at reflux 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 ethyl ether and hexane to give compound B-15 (4.83g, yield 75%).

MS: [M + H] ⁺ = 322

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

1-amino-2-naphthalenecarbaldehyde (1-amino-2-naphthalenecarbaldehyde, 0.25 g, 1.45 mmol) and 4-bromoacetophenone (2.88 g, 1.45 mmol) were dispersed in ethanol (15 mL), and KOH in ethanol. 0.5 mL of the dissolved solution was slowly added. The resulting mixture was stirred at reflux 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] ⁺ = 334

< Manufacturing example  17> Preparation of the following Compound B-17

Dissolve 1-bromo-4-iodobenzene (2.82g, 10mmol) and 2-phenyl-5-thiophenboronic acid (2.04g, 10mmol) in THF (30mL), and then 2M K ₂ CO ₃ aqueous solution (20mL) Pd (PPh ₃ ) ₄ (0.231 g, 2 mol%) was added thereto, followed by stirring 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 (2.2g, 70% yield).

MS: [M] ⁺ = 315

< Manufacturing example  18> 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), followed by stirring under reflux for 4 hours. Excess thionylchloride (SOCl ₂ ) was removed by vacuum distillation, and then N-methylpyrrolidine (NMP, 20 mL) and N-phenyl-1,2-diamino benzene (3.7 g, 20 mmol) were added to the reaction mixture. 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. Filtration, washing with water and ethanol and drying yielded Compound B-18 (6.2 g, yield 78%).

MS: [M] ⁺ = 399

< Manufacturing example  19> Preparation of the following Compound B-19

[Compound B-19]

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

MS: [M] ⁺ = 349

< Manufacturing example  20> 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 Example 17, except that 2-naphthaleneboronic acid was used instead of 2-phenyl-5-thiophenboronic acid in Preparation Example 17. .

MS: [M] ⁺ = 283

< Manufacturing example  21> Preparation of the following Compound B-21

[Compound B-21]

Compound B-21 (2.33 g, yield 70%) was prepared in the same manner as in Preparation Example 17, except that 9-phenanthrene boronic acid was used instead of 2-phenyl-5-thiophenboronic acid in Preparation Example 17. It was.

MS: [M] ⁺ = 333

< Manufacturing example  22> 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 Example 17, except that 1-pyreneboronic acid was used instead of 2-phenyl-5-thiophenboronic acid in Preparation Example 17.

MS: [M] ⁺ = 357

< Manufacturing example  23> Preparation of the following Compound B-23

4-bromo-aniline (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 (CuI , 0.381 g, 2 mmol) and 1,10-phenanthroline (1,10-phenanthroline, 0.360 g, 2 mmol) were suspended in xylene (50 mL) and stirred at reflux 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 give compound B-23 (1.43 g, yield 30%).

MS: [M] ⁺ = 476

< Manufacturing example  24> Preparation of the following Compound B-24

[Compound B-24]

Except for using 1-bromo-3,5-diiodinebenzene (1-bromo-3,5-diiodobenzene, 3.68g, 9.0mmol) instead of 1-bromo-4-iodinebenzene in Preparation Example 15 , Compound B-24 (1.75g, yield 40%) was prepared in the same manner as in Preparation Example 15.

MS: [M] ⁺ = 487

In addition, in order to prepare the compound of Formula 1, the reagents and intermediates of Table 1 are required, which are commercially readily available or prepared according to existing known methods.

[Table 1]

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

Compound A-4 (4.21 g, 10.0 mmol) and 4-bromobiphenyl (4-bromobiphenyl, 2.33 g, 10.0 mmol) were dispersed in THF (100 mL), 2M K ₂ CO ₃ Aqueous solution (20 mL) was added and Pd (PPh ₃ ) ₄ (0.231 g, 2 mol%) was added thereto, followed by stirring under reflux for 5 hours. The temperature was lowered to room temperature and the resulting solid was filtered. The filtered solid was recrystallized with chloroform and ethanol, filtered and dried to give compound 1-1 (3.58g, yield 80%).

MS: [M + H] ⁺ = 448

< Example  2> Preparation of the following Compound 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), 2M K ₂ CO ₃ Aqueous solution (20 mL) was added and Pd (PPh ₃ ) ₄ (0.231 g, 2 mol%) was added thereto, followed by stirring under reflux for 5 hours. The temperature was lowered to room temperature and the resulting solid was filtered. The filtered solid was recrystallized with chloroform and ethanol, filtered and dried to give compound 1-3 (4.54g, yield 76%).

MS: [M + H] ⁺ = 598

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

In the preparation of Compound 1-4 of Example 2, except that Compound B-4 (3.83 g, 10.0 mmol) was used instead of Compound B-1, and synthesized in the same manner, Compound 1-4 (4.72 g, yield) 79%) was prepared.

MS: [M + H] ⁺ = 598

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

In the preparation of Compound 1-4 of Example 2, except that Compound B-12 (5.09 g, 10.0 mmol) was used instead of Compound B-1, and synthesized in the same manner as Compound 1-7 (5.93 g, yield 82%) was prepared.

MS: [M + H] ⁺ = 724

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

In the preparation of Compound 1-4 of Example 2, except that Compound B-15 (3.22g, 10.0mmol) was used instead of Compound B-1, and synthesized in the same manner Compound 1-9 (4.07g, yield 76%) was prepared.

MS: [M + H] ⁺ = 537

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

In the preparation of Compound 1-4 of Example 2, except that Compound C-2 (3.88 g, 10.0 mmol) was used instead of Compound B-1, and synthesized in the same manner, Compound 1-11 (4.76 g, yield) 79%) was prepared.

MS: [M + H] ⁺ = 603

< Example  7> Preparation of the following compound 1-14

In the preparation of Compound 1-4 of Example 2, except that Compound B-16 (3.34 g, 10.0 mmol) was used instead of Compound B-1, and synthesized in the same manner, Compound 1-14 (4.11 g, yield) 75%) was prepared.

MS: [M + H] ⁺ = 549

< Example  8> Preparation of the following Compound 1-16

In the preparation of Compound 1-4 of Example 2, except that Compound B-16 (3.57g, 10.0mmol) was used instead of Compound B-1, and synthesized in the same manner Compound 1-16 (4.05g, yield 71%) was prepared.

MS: [M + H] ⁺ = 572

< Example  9> Preparation of the following compound 1-22

In the preparation of Compound 1-4 of Example 2, except that Compound B-16 (3.49 g, 10.0 mmol) was used instead of Compound B-1, and synthesized in the same manner, Compound 1-22 (4.11 g, yield) 73%) was prepared.

MS: [M + H] ⁺ = 564

< Example  10> Preparation of the following compound 1-27

In the preparation of Compound 1-4 of Example 2, except that Compound C-3 (2.59 g, 10.0 mmol) was used instead of Compound B-1, and synthesized in the same manner, Compound 1-27 (3.07 g, yield) 65%) was prepared.

MS: [M + H] ⁺ = 474

< Example  11> Preparation of the following compound 1-28

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

MS: [M + H] ⁺ = 691

< Example  12> Preparation of the following Compound 1-30

In the preparation of Compound 1-4 of Example 2, except that Compound C-4 (4.73g, 10.0mmol) was used instead of Compound B-1, and synthesized in the same manner Compound 1-30 (5.08g, yield 74%) was prepared.

MS: [M + H] ⁺ = 688

< Example  13> Preparation of the following compound 1-32

In the preparation of Compound 1-4 of Example 2, except that Compound C-5 (5.25 g, 10.0 mmol) was used instead of Compound B-1, and synthesized in the same manner, Compound 1-32 (5.84 g, yield) 79%) was prepared.

MS: [M + H] ⁺ = 740

< Example  14> Preparation of the following compound 1-34

In the preparation of Compound 1-4 of Example 2, except that Compound B-24 (4.87 g, 10.0 mmol) was used instead of Compound B-1, and synthesized in the same manner, Compound 1-34 (4.84 g, yield) 69%) was prepared.

MS: [M + H] ⁺ = 702

< Example  15> Preparation of the following compound 1-35

In the preparation of Compound 1-4 of Example 2, Compound A-7 (4.71 g, 10.0 mmol) was used instead of Compound A-4, and Compound C-6 (2.32 g, 10.0 mmol) was used instead of Compound B-1. Except for the synthesis in the same manner to prepare compound 1-35 (3.32g, yield 67%).

MS: [M + H] ⁺ = 497

< Example  16> Preparation of the following compound 1-38

In the preparation of Compound 1-4 of Example 2, Compound A-7 (4.71 g, 10.0 mmol) was used instead of Compound A-4, and Compound C-7 (2.57 g, 10.0 mmol) was used instead of Compound B-1. Except for the synthesis in the same manner to prepare compound 1-38 (3.86g, 74% yield).

MS: [M + H] ⁺ = 522

< Example  17> Preparation of the following Compound 1-40

In preparing Compound 1-4 of Example 2, using Compound A-7 (4.71 g, 10.0 mmol) instead of Compound A-4, and Compound B-8 (4.02 g, 10.0 mmol) instead of Compound B-1 Synthesis was carried out in the same manner, except that compound 1-40 (4.66 g, yield 78%) was prepared. 2 shows the mass spectrum of Compound 1-40.

MS: [M + H] ⁺ = 598

< Example  18> Preparation of the following Compound 1-48

In the preparation of Compound 1-4 of Example 2, except that Compound C-8 (2.38g, 10.0mmol) was used instead of Compound B-1, and synthesized in the same manner Compound 1-48 (3.25g, yield 72%) was prepared.

MS: [M + H] ⁺ = 453

< Example  19> Preparation of the following Compound 1-42

In preparing Compound 1-4 of Example 2, using Compound A-9 (3.75 g, 10.0 mmol) instead of Compound A-4 and Compound B-2 (3.48 g, 10.0 mmol) instead of Compound B-1 Synthesis was carried out in the same manner except that Compound 1-42 (3.71 g, yield 62%) was prepared.

MS: [M + H] ⁺ = 599

< Example  20> 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), 2M K ₂ CO ₃ Aqueous solution (20 mL) was added and Pd (PPh ₃ ) ₄ (0.231 g, 2 mol%) was added thereto, followed by stirring under reflux for 5 hours. The temperature was lowered to room temperature and the resulting solid was filtered. The filtered solid was recrystallized with chloroform and ethanol, filtered and dried to give compound 2-2 (4.61 g, 74% yield).

MS: [M + H] ⁺ = 624

< Example  21> Preparation of the following Compound 2-5

In the preparation of Compound 2-2 of Example 20, except that Compound B-3 (4.59 g, 10.0 mmol) was used instead of Compound B-6, and synthesized in the same manner, Compound 2-5 (4.75 g, yield) 71%) was prepared.

MS: [M + H] ⁺ = 674

< Example  22> Preparation of the following Compound 2-6

In the preparation of Compound 2-2 of Example 20, except that Compound B-10 (5.09 g, 10.0 mmol) was used instead of Compound B-6, and synthesized in the same manner, Compound 2-6 (5.42 g, yield) 75%) was prepared.

MS: [M + H] ⁺ = 724

< Example  23> Preparation of the following Compound 2-11

In the preparation of Compound 2-2 of Example 20, except that Compound C-9 (4.15 g, 10.0 mmol) was used instead of Compound B-6, and synthesized in the same manner, Compound 2-11 (4.21 g, yield) 67%) was prepared.

MS: [M + H] ⁺ = 630

< Example  24> Preparation of the following compound 2-24

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

MS: [M + H] ⁺ = 566

< Example  25> Preparation of the following compound 2-27

In the preparation of Compound 2-2 of Example 20, except that Compound B-24 (4.87 g, 10.0 mmol) was used instead of Compound B-6, and synthesized in the same manner, Compound 2-27 (4.77 g, yield) 68%) was prepared.

MS: [M + H] ⁺ = 702

< Example  26> Preparation of the following compound 2-31

In the preparation of Compound 2-2 of Example 20, except that Compound B-14 (5.85 g, 10.0 mmol) was used instead of Compound B-6, and synthesized in the same manner, Compound 2-31 (6.07 g, Yield) 76%) was prepared.

MS: [M + H] ⁺ = 800

< Example  27> Preparation of the following compound 2-32

In the preparation of Compound 2-2 of Example 20, except that Compound B-17 (3.15 g, 10.0 mmol) was used instead of Compound B-6, and synthesized in the same manner, Compound 2-32 (3.70 g, yield) 70%) was prepared.

MS: [M + H] ⁺ = 530

< Example  28> Preparation of the following compound 2-33

In the preparation of Compound 2-2 of Example 20, except that Compound B-18 (3.99 g, 10.0 mmol) was used instead of Compound B-6, and synthesized in the same manner, Compound 2-33 (4.47 g, yield) 73%) was prepared.

MS: [M + H] ⁺ = 614

< Example  29> 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), 2M K ₂ CO ₃ Aqueous solution (20 mL) was added and Pd (PPh ₃ ) ₄ (0.231 g, 2 mol%) was added thereto, followed by stirring under reflux for 5 hours. The temperature was lowered to room temperature and the resulting solid was filtered. The filtered solid was recrystallized with chloroform and ethanol, filtered and dried to give compound 3-1 (5.11 g, yield 79%).

MS: [M + H] ⁺ = 648

< Example  30> Preparation of the following compound 3-2

In the preparation of Compound 3-1 of Example 29, except that Compound B-20 (2.83 g, 10.0 mmol) was used instead of Compound B-21, and synthesized in the same manner as Compound 3-2 (4.34 g, yield 73%) was prepared.

MS: [M + H] ⁺ = 598

< Example  31> Preparation of the following compound 3-13

In the preparation of Compound 3-1 of Example 29, except that Compound C-11 (3.35g, 10.0mmol) was used instead of Compound B-21 and synthesized in the same manner as Compound 3-13 (4.54g, yield 70%) was prepared.

MS: [M + H] ⁺ = 650

< Example  32> Preparation of the following compound 3-21

In the preparation of Compound 3-1 of Example 29, except that Compound C-12 (4.51 g, 10.0 mmol) was used instead of Compound B-21, and synthesized in the same manner as Compound 3-21 (5.05 g, yield) 66%) was prepared.

MS: [M + H] ⁺ = 766

< Example  33> Preparation of the following compound 3-34

In the preparation of Compound 3-1 of Example 29, except that Compound B-24 (4.87g, 10.0mmol) was used instead of Compound B-21, and synthesized in the same manner as Compound 3-34 (5.69g, yield) 71%) was prepared.

MS: [M + H] ⁺ = 802

< Example  34> Preparation of the following compound 4-3

Compound A-21 (5.23 g, 10.0 mmol) and Compound B-1 (3.83 g, 10.0 mmol) were dispersed in THF (100 mL), 2M K ₂ CO ₃ Aqueous solution (20 mL) was added and Pd (PPh ₃ ) ₄ (0.231 g, 2 mol%) was added thereto, followed by stirring under reflux for 5 hours. The temperature was lowered to room temperature and the resulting solid was filtered. The filtered solid was recrystallized with chloroform and ethanol, filtered and dried to give compound 4-3 (5.24 g, yield 75%).

MS: [M + H] ⁺ = 700

< Example  35> Preparation of the following compound 4-6

In the preparation of Compound 4-3 of Example 34, except that Compound B-12 (5.09 g, 10.0 mmol) was used instead of Compound B-1, and synthesized in the same manner, Compound 4-6 (5.78 g, yield) 70%) was prepared.

MS: [M + H] ⁺ = 827

< Example  36> Preparation of the following Compound 4-9

In the preparation of Compound 4-3 of Example 34, except that Compound C-2 (3.88 g, 10.0 mmol) was used instead of Compound B-1, and synthesized in the same manner, Compound 4-9 (5.07 g, yield) 72%) was prepared.

MS: [M + H] ⁺ = 705

< Example  37> Preparation of the following compound 4-19

In the preparation of Compound 4-3 of Example 34, except that Compound B-24 (4.87 g, 10.0 mmol) was used instead of Compound B-1, and synthesized in the same manner, Compound 4-19 (5.46 g, yield) 68%) was prepared.

MS: [M + H] ⁺ = 804

< Example  38> Preparation of the following compound 4-22

In preparing Compound 4-3 of Example 34, using Compound A-25 (5.25 g 10.0 mmol) instead of Compound A-21 and Compound B-8 (4.02 g, 10.0 mmol) instead of Compound B-1 Except for the synthesis in the same manner to give compound 4-22 (4.62g, 71% yield).

MS: [M + H] ⁺ = 652

< Example  39> Preparation of the following compound 4-25

In the preparation of Compound 4-3 of Example 34, except that Compound A-25 (5.25 g 10.0 mmol) was used instead of Compound A-21, and synthesized in the same manner as Compound 4-25 (4.77 g, Yield 68 %) Was prepared.

MS: [M + H] ⁺ = 702

< Experimental Example  1>

A glass substrate coated with a thin film of ITO (indium tin oxide) at a thickness of 500 kPa was placed in distilled water in which detergent was dissolved and ultrasonically cleaned. At this time, Fischer Co. product was used as a detergent, and distilled water filtered secondly as a filter of Millipore Co. product was used as distilled water. After ITO was washed for 30 minutes, ultrasonic washing was performed twice with distilled water for 10 minutes. After washing the distilled water, ultrasonic washing with a solvent of isopropyl alcohol, acetone, methanol, dried and transported to a plasma cleaner. In addition, the substrate was cleaned for 5 minutes using an oxygen plasma, and then the substrate was transferred to a vacuum evaporator.

The hexanitrile hexaazatriphenylene (HAT) of the following formula was thermally vacuum deposited to a thickness of 100 kPa on the prepared ITO transparent electrode to form a hole injection layer.

4,4'-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (NPB) (1000 kV) of the above formula, which is a material for transporting holes on the hole injection layer, was vacuum deposited to form a hole transport layer. Formed.

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

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

On the electron injection and transport layer, lithium fluoride (LiF) and aluminum were deposited to a thickness of 2,000 kW in order 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 lithium fluoride of the anode was maintained at 0.3 Å / sec, and the aluminum was maintained at a deposition rate of 2 Å / sec. ^An organic light-emitting device was manufactured by maintaining ⁻⁷ to 5 × 10 ⁻⁸ torr.

< Comparative example  1>

In Experimental Example 1, an organic light emitting device was manufactured in the same manner as in Experimental Example 1, except that the compound of Formula ET-A1 was used instead of Compound 1-1.

[ET-A1]

< Experimental Example  2 to 30>

In Experimental Example 1, an organic light emitting device was manufactured in the same manner as in Experimental Example 1, except that each compound shown in Table 2 was used instead of the compound of Formula 1-1.

When current was applied to the organic light emitting diodes manufactured by Experimental Examples 1 to 30 and Comparative Example 1, the results shown in Table 2 were obtained. The values shown in Table 2 below were measured at current densities of 10 mA / cm ² .

TABLE 2

From the results of Table 2, when the organic compound layer of the organic light emitting device is formed using the compound of Formula 1 according to the present invention, it can be seen that the excellent characteristics in the efficiency increase, drive voltage drop, stability increase, and the like.

Claims (14)

Compound represented by the following formula (1):
[Formula 1]

In Chemical Formula 1,
R ₁ and R ₂ are the same as or different from each other, and each independently hydrogen; heavy hydrogen; A halogen group; 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; An aryl group, a substituted or unsubstituted C _{6 -50} ring; 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 ₃ to R ₆ are the same as or different from each other, and each independently hydrogen; heavy hydrogen; A halogen group; 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;} Tiok alkyl group a substituted or unsubstituted C _{1 -50;} Aryloxy substituted or unsubstituted C _{6 -50} ring; A substituted or unsubstituted C _{2 -50} alkenyl group; Substituted or unsubstituted silyl group; Substituted or unsubstituted boron group; A substituted or unsubstituted fluorenyl group; A substituted or unsubstituted C _6-50 arylamine group; An aryl group, a substituted or unsubstituted C _{6 -50} ring; 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; 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; Substituted or unsubstituted silyl group; Substituted or unsubstituted boron group; Fluorenyl group a substituted or unsubstituted C _{13 -50} ring; Arylamine group, a substituted or unsubstituted C _{6 -50} ring; An aryl group, a substituted or unsubstituted C _{6 -50} ring; 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, where p is an integer from 0 to 10, q is an integer from 1 to 10,
L is an aryl group a substituted or unsubstituted C _{6 -50} ring; Substituted or unsubstituted alkenylene group of _{2 -50} C ring; Fluorenyl group a substituted or unsubstituted C _{13 -50} ring; 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; 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;} Tiok alkyl group a substituted or unsubstituted C _{1 -50;} Aryloxy substituted or unsubstituted C _{6 -50} ring; A substituted or unsubstituted C _{2 -50} alkenyl group; Substituted or unsubstituted silyl group; Substituted or unsubstituted boron group; A substituted or unsubstituted C _13-50 fluorenyl group; Arylamine group, a substituted or unsubstituted C _{6 -50} ring; An aryl group, a substituted or unsubstituted C _{6 -50} ring; 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 L or Y is present at least 2, they are the same as 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 condensed ring of aliphatic, aromatic, aliphatic hetero or aromatic hetero, or form spiro bonds. The compound of claim 1, wherein the compound represented by Formula 1 is selected from the group represented by Formula 2 or Formula 4.
(2)

(3)

[Chemical Formula 4]

In Chemical Formulas 2 to 4,
R ₃ to R ₇ are the same as defined in Formula 1,
R ₈ to R ₁₂ are the same as defined in the formula 1 R ₁ and R ₂ ,
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 Chemical Formula 1. The compound of claim 1, wherein the heteroaryl group is selected from the group consisting of

The compound of claim 1, wherein the fluorenyl group is selected from the group consisting of:

The compound of claim 1, wherein the compound represented by Chemical Formula 1 is selected from the group represented by Compound 1-1 to Compound 1-48:

The compound of claim 1, wherein the compound represented by Chemical Formula 1 is selected from the group represented by the following Compounds 2-1 to 2-3-3:

The compound of claim 1, wherein the compound represented by Chemical Formula 1 is selected from the group represented by the following Compounds 3-1 to 3-48:

The compound of claim 1, wherein the compound represented by Chemical Formula 1 is selected from the group represented by Compounds 4-1 to 4-30:

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 any one of claims 1 to 8. An organic electronic device comprising the compound of formula (1) described. The organic electronic device of claim 9, wherein the organic material layer includes at least one layer of an electron injection layer and an electron transport layer, and at least one layer of the electron injection layer and the electron transport layer includes the compound of Formula 1. 11. The organic electronic device of claim 9, wherein the organic material layer includes a light emitting layer, and the light emitting layer includes the compound represented by Chemical Formula 1. 11. The method according to claim 9, wherein the organic layer comprises a hole injection layer, a hole transport layer, and at least one layer of the hole injection and hole transport at the same time, wherein one of the layers comprises the compound of Formula 1 An organic electronic device characterized by the above. The organic electronic device of claim 9, wherein the organic electronic device is selected from the group consisting of an organic light emitting device, an organic phosphorescent device, an organic solar cell, an organic photoconductor (OPC), and an organic transistor. The method according to claim 9, wherein the organic material layer comprises an electron transport layer comprising the compound of Formula 1, the electron transport layer further comprises an alkali metal, alkali metal compound, alkaline earth metal or alkaline earth metal compound, or a combination thereof Organic electronic device.

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