KR102183289B1 - Novel compound for organic electroluminescent device and organic electroluminescent device comprising the same - Google Patents

Abstract

Disclosed are a compound for an organic electroluminescent device and an organic electroluminescent device including the same. As a result, it has excellent electrical stability and hole transport capability, and can be used as a host and hole transport material that can improve the luminous efficiency of phosphorescent materials due to high triplet state energy and organic electroluminescent devices. Can provide.

Description

A new compound for organic electroluminescent devices and an organic electroluminescent device containing the same TECHNICAL FIELD {NOVEL COMPOUND FOR ORGANIC ELECTROLUMINESCENT DEVICE AND ORGANIC ELECTROLUMINESCENT DEVICE COMPRISING THE SAME}

The present invention relates to a compound for an organic electroluminescent device and an organic electroluminescent device including the same, and more particularly, a compound for an organic electroluminescent device capable of improving the luminous efficiency of the organic electroluminescent device, and an organic electroluminescent device comprising the same It relates to the device.

As the movement toward the information society accelerates, the proportion of flat panel displays is gradually increasing. Among them, LCD (liquid crystal display) is currently the most widely used, but it is a method of creating a screen by applying a voltage to the liquid crystal to pass light from the backlight through a color filter to obtain three primary colors. Organic Light Emitting Diodes (OLED) As a self-luminous device, it has excellent viewing angle and contrast ratio, is lightweight and thin, and can be used on a substrate with a bendable property, enabling transparent and flexible displays, attracting attention as a next-generation display device.

Organic EL is a phenomenon in which electrons and holes injected through the cathode and anode in an organic thin film recombine to form excitons, and light of a specific wavelength is generated from the formed excitons.In 1963, from a single crystal of anthracene It was discovered for the first time, and has been actively studied since the report of stacked organic EL devices (CW Tang, SA Vanslyke, Applied Physics Letters. 51 vol. 913p, 1987) by Eastman Kodak's CW Tang et al.

Organic materials used in organic electroluminescent devices are largely divided into polymer and low molecular types, and low molecules can be divided into pure organic materials and metal complexes that form metals and chelates.

Polymeric materials can create multifunctional materials by combining units of various functions with a polymer chain, but there are difficulties when refining composites or forming devices, and low-molecular materials can synthesize materials of each property, but have multifunctional properties. There is a limit to the synthesis of the substances represented.

The organic electroluminescent device can be formed in a stacked structure. The advantage of the stacked structure is that a material can be selected and used according to each function. In general, the device structure is formed by forming a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer between the anode and the cathode. It is possible to facilitate formation of excitons and increase luminous efficiency.

The luminescent material can be broadly divided into a host material and a luminescent material (dopant) material, and the luminescent material is classified into fluorescence and phosphorescence according to the luminescence mechanism.

The excited state of electrons in the compound is a ratio of 1:3 to triplet, resulting in three times more triplet states. Accordingly, the internal quantum efficiency of the fluorescence falling from the singlet state to the ground state is only 25%, while the internal quantum efficiency of the phosphorescence falling from the triplet state to the ground state is 75%. In addition, when a quarterly transition occurs from a singlet state to a triplet state, the theoretical limit of the internal quantum efficiency reaches 100%. A phosphorescent light emitting material is a light emitting material with improved luminous efficiency using this point.

Due to the nature of organic materials, phosphorescence emission is difficult, and organometallic compounds using transition metals (iridium) are being developed as phosphorescent materials, and organic materials are used as host materials to assist them. The material (host) that assists the phosphorescent material must have a wide band gap and high triplet state energy. Phosphorescent materials with excellent current efficiency and luminous efficiency are in the spotlight, but organic electroluminescent devices with excellent electron transport ability, hole transport ability, thermally and electrically stable host material and holes are maintained until excitons form, and excellent electron transport ability There is a need to develop a solvent compound.

The present invention is a host capable of improving the luminous efficiency of a phosphorescent luminescent material due to excellent electrical stability, electron and hole transport ability, high triplet state energy, and an organic electric field comprising the same. A light emitting device can be provided.

In addition, the present invention can provide a compound for an organic light emitting device that can be used for an electron transport material or a hole transport material of an organic light emitting device, and an organic electroluminescent device including the same.

However, the problem to be solved by the present application is not limited to the problems mentioned above, and other problems that are not mentioned will be clearly understood by those skilled in the art from the following description.

According to an aspect of the present invention, a compound for an organic electroluminescent device represented by the following Structural Formula 1 may be provided.

[Structural Formula 1]

In the above structural formula 1,

L is a valent bond, a substituted or unsubstituted C6 to C30 arylene group, or a substituted or unsubstituted C1 to C30 heteroarylene group,

Ar ¹ is a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C12 to C30 arylaryl group, a substituted or unsubstituted C7 to C30 heteroaryl aryl group, a substituted or unsubstituted C1 to C30 heteroaryl group , A substituted or unsubstituted C7 to C30 arylheteroaryl group, or a substituted or unsubstituted C2 to C30 heteroarylheteroaryl group,

R ¹ and R ² may be the same as or different from each other, and R ¹ and R ² are each independently a hydrogen atom, a deuterium atom, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted Or an unsubstituted C1 to C30 heterocycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C1 to C30 heteroaryl group, or at least any one of R ¹ and R ² is any one substituted with a combination of carbon atoms (C _b 1) neighboring carbon atom (C _b 2) and added to the combined carbon atom (C _b 1) and the neighboring carbon atom (C _b 2) coupled to the or Unsubstituted fused C3 to C30 cycloalkyl group, substituted or unsubstituted fused C1 to C30 heterocycloalkyl group, substituted or unsubstituted fused C6 to C30 aryl group, or substituted or unsubstituted fused C1 to C30 hetero Forming an aryl group,

R ³ to R ⁶ may be the same as or different from each other, and R ³ to R ⁶ are each independently a hydrogen atom, a deuterium atom, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted Or an unsubstituted C1 to C30 heterocycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C1 to C30 heteroaryl group.

Specific examples of the alkyl group as a substituent include methyl group, ethyl group, propyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, iso-amyl group, hexyl group, heptyl group, octyl group, stearyl group, trichloro Romethyl group, trifluoromethyl group, and the like. At least one hydrogen atom in the alkyl group is a deuterium atom, a halogen atom, a hydroxy group, a nitro group, a cyano group, a trifluoromethyl group, a silyl group (in this case, a "alkylsilyl group" ), the amino group (-NH2, -NH(R), -N(R')(R''), R'and R" are independently of each other an alkyl group having 1 to 20 carbon atoms, in this case "alkylamino group" ), an amidino group, a hydrazine group, a hydrazone group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, an alkyne having 1 to 20 carbon atoms It may be substituted with a nil group, a C1-C20 heteroalkyl group, a C6-C30 aryl group, a C6-C60 arylalkyl group, a C4-C40 heteroaryl group, or a C4-C40 heteroarylalkyl group.

Specific examples of the cycloalkyl group as a substituent may be a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and an adamantyl group.

Specific examples of the alkoxy group as a substituent may be a methoxy group, an ethoxy group, a propoxy group, an isobutyloxy group, a sec-butyloxy group, a pentyloxy group, an iso-amyloxy group, and a hexyloxy group.

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

Examples of the C6 to C30 aryl group are phenyl group, biphenyl group, terphenyl group, naphthalenyl group, anthracenyl group, phenanthrenyl group, fluorenyl group, spirofluorenyl group, chrysene group, tetracene group, pentacene group, tetrahydro It may be a naphthyl group, a pyrenyl group, or a perylenyl group.

Examples of the C2 to C30 heteroaryl group include a pyridinyl group, a pyrimidinyl group, a triazinyl group, a thiophenyl group, a pyrrolyl group, a benzothiophenyl group, an indolyl group, an imidazo[1,2-a]pyridinyl group, Benziimidazolyl group, indazolyl group, phenothiazinyl group, phenazinyl group, carbazolyl group, dibenzothiophenyl group, imidazolyl group, triazolyl group, tetrazolyl group, oxadiazolyl group, oxatriazolyl Group, thitriazolyl group, benzotriazolyl group, pyrazinyl group, pyridazinyl group, purinyl group, quinolinyl group, isoquinolinyl group, phthalazinyl group, naphpyridinyl group, quinoxalinyl group, quinazoli Nyl group, acridinyl group, or phenanthrolinyl group, preferably pyridinyl group, pyrimidinyl group, triazinyl group, thiophenyl group, pyrrolyl group, benzothiophenyl group, indolyl group, imidazo[1,2-a] It may be a pyridinyl group, a benziimidazolyl group, an indazolyl group, a phenothiazinyl group, a phenazinyl group, a carbazolyl group, or a dibenzothiophenyl group.

According to another aspect of the present invention, a compound for an organic electroluminescent device, which is any one selected from compounds 1 to 238 represented by the following formula, may be provided.

According to another aspect of the present invention, an organic electroluminescent device including the compound for an organic electroluminescent device may be provided.

According to another aspect of the present invention, in an organic light emitting device comprising a first electrode, a second electrode, and a single or a plurality of organic material layers between the first electrode and the second electrode, At least one organic material layer may be provided with an organic electroluminescent device comprising the compound for an organic electroluminescent device.

The single or plurality of organic material layers may include an emission layer.

The plurality of organic material layers include an emission layer, and the plurality of organic material layers may further include at least one selected from an electron injection layer, an electron transport layer, a hole blocking layer, an electron blocking layer, a hole transport layer, and a hole injection layer.

The emission layer may include a host and a dopant.

The present invention is a host capable of improving the luminous efficiency of a phosphorescent material due to excellent electrical stability and electron and hole transport capability, high triplet state energy, and a compound for an organic electroluminescent device that can be used in the light emitting layer and containing the same. It is possible to provide an organic electroluminescent device.

In addition, the present invention can provide a compound for an organic EL device that can be used for an electron transport material or a hole transport material of an organic EL device, and an organic EL device including the same.

1 is a cross-sectional view of an organic light emitting diode according to an exemplary embodiment of the present invention.
2 is a cross-sectional view of an organic light emitting device according to another embodiment of the present invention.

The present invention is intended to illustrate specific embodiments and to be described in detail in the detailed description, since various transformations may be applied and various embodiments may be provided. However, this is not intended to limit the present invention to a specific embodiment, it is to be understood to include all conversions, equivalents, and substitutes included in the spirit and scope of the present invention. In describing the present invention, when it is determined that a detailed description of a related known technology may obscure the subject matter of the present invention, a detailed description thereof will be omitted.

In addition, terms including ordinal numbers such as first and second to be used hereinafter may be used to describe various elements, but the elements are not limited by the terms. These terms are used only for the purpose of distinguishing one component from another component. For example, without departing from the scope of the present invention, a first element may be referred to as a second element, and similarly, a second element may be referred to as a first element.

In addition, when a component is referred to as being "formed" or "stacked" on another component, it may be formed or stacked by being directly attached to the front surface or one surface on the surface of the other component. It should be understood that there may be more other components in the.

Singular expressions include plural expressions unless the context clearly indicates otherwise. In the present application, terms such as "comprise" or "have" are intended to designate the presence of features, numbers, steps, actions, components, parts, or combinations thereof described in the specification, but one or more other features. It is to be understood that the presence or addition of elements or numbers, steps, actions, components, parts, or combinations thereof, does not preclude in advance.

In the present specification, "atomic bond" means a single bond, a double bond, or a triple bond unless otherwise defined.

In the present specification, unless otherwise defined, the substituent or at least one hydrogen in the compound for an organic electroluminescent device is deuterium, a halogen group, a hydroxy group, an amino group, a C1 to C30 amine group, a nitro group, a silyl group , C1 to C30 alkyl group, C1 to C30 alkylsilyl group, C6 to C30 arylsilyl group, C7 to C30 alkylarylsilyl group, C7 to C30 arylalkylsilyl group, C3 to C30 cycloalkyl group, C1 to C30 heterocycloalkyl group, C6 To C30 aryl group, C1 to C30 hetero aryl group, C1 to C20 alkoxy group, C1 to C10 trifluoroalkyl group or cyano group.

In addition, the substituted halogen group, hydroxy group, amino group, C1 to C30 amine group, silyl group, C1 to C30 alkyl group, C1 to C30 alkylsilyl group, C3 to C30 cycloalkyl group, C6 to C30 aryl group, C1 to C20 alkoxy group, Two adjacent substituents among a C1 to C10 trifluoroalkyl group or a cyano group may be fused to form a fused ring.

In the present specification, unless otherwise defined, "hetero" means that one functional group contains 1 to 4 heteroatoms selected from the group consisting of N, O, S and P, and the rest are carbon.

In the present specification, unless otherwise defined, "a combination thereof" means that two or more substituents are bonded with a linking group or two or more substituents are condensed and bonded.

In the present specification, "hydrogen" refers to singlet hydrogen, dihydrogen, or tritium unless otherwise defined.

In the present specification, "alkyl (alkyl) group" refers to an aliphatic hydrocarbon group unless otherwise defined.

The alkyl group may be a "saturated alkyl group" that does not contain any double bonds or triple bonds.

The alkyl group may be an "unsaturated alkyl group" including at least one double bond or triple bond.

“Alkenylene group” refers to a functional group in which at least two carbon atoms are formed of at least one carbon-carbon double bond, and “alkynylene group” refers to at least two carbon atoms at least one carbon-carbon triple It means a functional group consisting of a bond. Alkyl groups, whether saturated or unsaturated, can be branched, straight-chain or cyclic.

The alkyl group may be a C1 to C30 alkyl group. More specifically, the alkyl group may be a C1 to C30 alkyl group, a C1 to C20 alkyl group, a C1 to C10 alkyl group, or a C1 to C6 alkyl group.

For example, a C1 to C4 alkyl group has 1 to 4 carbon atoms in the alkyl chain, i.e., the alkyl chain is methyl, ethyl, propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl and t-butyl. It indicates that it is selected from the group consisting of.

For specific examples, the alkyl group is a methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, hexyl group, ethenyl group, propenyl group, butenyl group, cyclopropyl group, cyclo It means a butyl group, a cyclopentyl group, a cyclohexyl group, etc.

"Amine group" includes an arylamine group, an alkylamine group, an arylalkylamine group, or an alkylarylamine group.

“Cycloalkyl groups” include monocyclic or fused ring polycyclic (ie, rings that share adjacent pairs of carbon atoms) functional groups.

"Heterocycloalkyl group" means that the cycloalkyl group contains 1 to 4 heteroatoms selected from the group consisting of N, O, S, and P, and the remainder is carbon. When the heterocycloalkyl group is a fused ring, at least one ring among the fused rings may contain 1 to 4 hetero atoms.

"Aromatic group" refers to a functional group in which all elements of a functional group in the form of a ring have a p-orbital, and these p-orbitals form a conjugation. Specific examples include an aryl group and a heteroaryl group.

“Aryl groups” include monocyclic or fused ring polycyclic (ie, rings that share adjacent pairs of carbon atoms) functional groups.

"Heteroaryl group" means that the aryl group contains 1 to 4 heteroatoms selected from the group consisting of N, O, S and P, and the remainder is carbon. When the heteroaryl group is a fused ring, at least one ring among the fused rings may contain 1 to 4 hetero atoms.

In the aryl group and the heteroaryl group, the number of ring atoms is the sum of the number of carbon atoms and the number of non-carbon atoms.

When used in combination such as "alkylaryl group" or "arylalkyl group", the terms of each of the alkyl and aryl mentioned above have the meanings and contents indicated above.

The term "arylalkyl group" refers to an aryl substituted alkyl radical such as benzyl and is included in the alkyl group.

The term "alkylaryl group" refers to an alkyl substituted aryl radical and is included in an aryl group.

Hereinafter, embodiments of the present invention will be described with reference to the accompanying drawings, and in the description with reference to the accompanying drawings, the same or corresponding constituent elements are assigned the same reference numbers, and redundant descriptions thereof will be omitted. .

1 and 2, according to an embodiment of the present invention, an organic electroluminescent device 1 including the compound for an organic electroluminescent device according to the present invention may be provided.

According to another embodiment of the present invention, the organic light emitting device includes a first electrode 110; A second electrode 150; And a single or a plurality of organic material layers 130 between the first electrode and the second electrode, wherein at least one organic material layer selected from the singular or plurality of organic material layers 130 includes the compound for an organic light emitting device according to the present invention. can do.

Here, the single or plurality of organic material layers 130 may include an emission layer 134.

In addition, the plurality of organic material layers 130 include an emission layer 134, and the plurality of organic material layers include an electron injection layer 131, an electron transport layer 132, a hole blocking layer 133, an electron blocking layer 135, and a hole. At least one selected from the transport layer 136 and the hole injection layer 137 may be additionally included.

The emission layer 134 may include a host and a dopant.

The organic electroluminescent device is preferably supported by a transparent substrate. The material of the transparent substrate is not particularly limited as long as it has good mechanical strength, thermal stability and transparency. For a specific example, glass, a transparent plastic film, etc. can be used.

As the anode material of the organic electroluminescent device of the present invention, a metal, an alloy, an electrically conductive compound or a mixture thereof having a work function of 4 eV or more can be used. Specifically, a transparent conductive material such as Au or CuI as a metal, ITO (indium tin oxide), SnO ₂ and ZnO may be mentioned. The thickness of the positive electrode film is preferably 10 to 200 nm.

As the cathode material of the organic electroluminescent device of the present invention, a metal, an alloy, an electrically conductive compound, or a mixture thereof having a work function of less than 4 eV may be used. Specifically, Na, Na-K alloy, calcium, magnesium, lithium, lithium alloy, indium, aluminum, magnesium alloy, and aluminum alloy are mentioned. In addition, aluminum/AlO ₂ , aluminum/lithium, magnesium/silver or magnesium/indium may also be used. The thickness of the negative electrode film is preferably 10 to 200 nm.

In order to increase the luminous efficiency of the organic EL device, it is preferable that at least one electrode has a light transmittance of preferably 10% or more. The sheet resistance of the electrode is preferably several hundred Ω/mm or less. The thickness of the electrode is 10 nm to 1 μm, more preferably 10 to 400 nm. Such an electrode may be manufactured by forming the electrode material into a thin film through a vapor deposition method such as chemical vapor deposition (CVD), physical vapor deposition (PVD), or sputtering.

In addition, when the compound for an organic electroluminescent device of the present invention is used suitably for the purpose of the present invention, a known hole transport material, a hole injection material, a light emitting layer material, a host material of the light emitting layer, an electron transport material, and an electron injection material are each of the above. It may be used alone in the organic material layer of, or may be used selectively in combination with the compound for an organic electroluminescent device of the present invention.

As a hole transport material, N,N-dicarbazolyl-3,5-benzene(mCP), poly(3,4-ethylenedioxythiophene):polystyrenesulfonate (PEDOT:PSS), N, N'-di(1-naphthyl)-N,N '-diphenylbenzidine (NPD), N,N'-diphenyl-N,N'-di(3-methylphenyl)-4,4'-diaminobiphenyl (TPD), N,N'-diphenyl-N, N'-dinaphthyl-4,4'-diaminobiphenyl, N,N,N'N'-tetra-p-tolyl-4,4'-diaminobiphenyl, N,N,N'N' -Porphyrin compound derivatives such as tetraphenyl-4,4'-diaminobiphenyl, copper(II)1,10,15,20-tetraphenyl-21H,23H-porphyrin, aromatic tertiary in the main chain or side chain Polymer with amine, 1,1-bis(4-di-p-tolylaminophenyl)cyclohexane, N,N,N-tri(p-tolyl)amine, 4, 4', 4'-tris[N- Triarylamine derivatives such as (3-methylphenyl)-N-phenylamino]triphenylamine, carbazole derivatives such as N-phenylcarbazole and polyvinylcarbazole, metal-free phthalocyanine, phthalocyanine derivatives such as copper phthalocyanine, Starburst Amine derivatives, enaminestilbene derivatives, derivatives of aromatic tertiary amines and styrylamine compounds, and polysilanes.

As electron transport materials, diphenylphosphine oxide-4-(triphenylsilyl)phenyl (TSPO1), Alq ₃ , 2,5-diaryl silol derivatives (PyPySPyPy), perfluorinated compounds (PF-6P), and Octasubstituted cyclooctatetraene compounds (COTs) were used. Can be lifted.

In the organic electroluminescent device of the present invention, the electron injection layer, the electron transport layer, the hole transport layer, and the hole injection layer are formed as a single layer containing one or more types of the above compounds, or are stacked with different types of compounds. It may be composed of a plurality of layers containing.

Examples of the luminescent material include photoluminescent fluorescent materials, fluorescent whitening agents, laser dyes, organic scintillators, and reagents for fluorescence analysis. Specifically, carbazole-based compounds, phosphine oxide-based compounds, carbazole-based phosphine oxide compounds, bis((3,5-difluoro-4-cyanophenyl)pyridine) iridium picolinate(FCNIrpic), tris(8-hydroxyquinoline) aluminum( Alq ₃ ), polyaromatic compounds such as anthracene, phenanthrene, pyrene, chrysene, perylene, coronene, rubrene and quinacridone, oligophenylene compounds such as quiterphenyl, 1,4-bis(2-methyl Styryl)benzene, 1,4-bis(4-methylstyryl)benzene, 1,4-bis(4-methyl-5-phenyl-2-oxazolyl)benzene, 1,4-bis(5-phenyl- 2-oxazolyl)benzene, 2,5-bis(5-t-butyl-2-benzoxazolyl)thiophene, 1,4-diphenyl-1,3-butadiene, 1,6-diphenyl-1, Liquid scintillators such as 3,5-hexatriene, 1,1,4,4-tetraphenyl-1,3-butadiene, metal complexes of auxin derivatives, coumarin dyes, dicyanomethylenepyran dyes, dicyanomethylene And a thiopyran dye, a polymethine dye, an oxobenzanthracene dye, a xanthene dye, a carbostyryl dye, a perylene dye, an oxazine compound, a stilbene derivative, a spiro compound, an oxadiazole compound, and the like.

Each layer constituting the organic EL device of the present invention may be formed into a thin film through a known method such as vacuum deposition, spin coating, or casting, or may be manufactured using a material used in each layer. There is no particular limitation on the thickness of each of these layers, and may be appropriately selected according to the properties of the material, but may be determined in the range of 2 nm to 5,000 nm.

Since the compound for an organic light emitting diode according to the present invention can be formed by a vacuum evaporation method, the thin film formation process is simple and can be easily obtained as a homogeneous thin film with almost no pin holes.

[Example]

Hereinafter, the compound for an organic electroluminescent device according to the present invention and a method of manufacturing an organic electroluminescent device including the same will be described in more detail through examples. However, this is for illustrative purposes, and the scope of the present invention is not limited thereby.

Example 1: compound 1 synthesis

(One) Manufacturing example 1-1: Synthesis of Intermediate 1-1

2-aminobenzamide (1.4 g, 0.010 mol) dibromochloromethane (2.1 g, 0.010 mol) dibejzo-18-crown-6 (1.1 g, 0.0030 mol), copper(2) (1.2 g, 0.020 mol), potassium acetate (2.8 g, 0.020 mol) was added to 100 ml of DMF and stirred at 120° C. for 4 hours to react. After completion of the reaction, the mixture was cooled, H ₂ 0: layer separated on MC, and then column-purified (n-Hexane:MC) to obtain 1.1 g (62% yield) of Intermediate 1-1.

LC/MS: m/z= 180[(M+1) ⁺ ]

(2) Manufacturing example 1-2: intermediate 1-2 synthesis

Intermediate 1-1 (1.8g, 0.010mol) in trifluoromethane sulfonic anhydride (3.1g, 0.011mol), pyridine (1.0g, 0.013mol) potassium carbonate (4.1g, 0.030mol) in 100ml of methyl chloride and stirred at 0℃ And reacted. After the reaction was completed, the mixture was cooled, H ₂ 0: layer-separated on MC, followed by column purification (n-Hexane:MC) to obtain 2.2g (yield 70%) of <Intermediate 1-2>.

LC/MS: m/z= 312[(M+1) ⁺ ]

(3) Manufacturing example 1-3: Synthesis of intermediate 1-3

Intermediate 1-2 (3.1 g, 0.008 mol) bis (pinacolato) dibron (2.5 g, 0.010 mol) PdCl2 (dppf) (0.3 g, 0.0004 mol), potassium-acetate (2.2 g, 0.016 mol) 1,4 80 ml of -dioxane was added and stirred at 95? for 24 hours to react. After the reaction was completed, the mixture was cooled, H ₂ 0: layer separated to MC, and then purified by column (n-Hexane: MC) to obtain 2.1 g (71% yield) of Intermediate 1-3.

LC/MS: m/z= 290[(M+1) ⁺ ]

(4) Manufacturing example 1-4: Intermediate 1 -4 synthesis

3-bromonaphthalen-1-ol (2.2g, 0.010mol) in phenyl boronic acid (1.4g, 0.012mol) Pd(pph3)4 (0.3g, 0.0003mol), potassium carbonate (4.1g, 0.030mol) in THF 80ml And stirred at 65° C. for 18 hours to react. After the reaction was completed, the mixture was cooled, H ₂ 0: layer-separated on MC, and then column-purified (n-Hexane:MC) to obtain 1.6 g (73% yield) of <Intermediate 1-4>.

LC/MS: m/z= 220[(M+1) ⁺ ]

(5) Manufacturing example 1-5: Synthesis of intermediate 1-5

<Intermediate 1-5> 2.6g (yield 73%) was synthesized by the same method used in Preparation Example 1-2, except that the intermediate 1-4 (2.2g, 0.010mol) was used instead of the intermediate 1-1. Got it.

LC/MS: m/z= 220[(M+1) ⁺ ]

(6) Manufacturing example 1-6: Synthesis of intermediate 1-6

Intermediate 1-5 (2.8g, 0.008mol) was added to Intermediate 1-3 (2.9g, 0.010mol) and synthesized by the same method used in Preparation Example 1-4 <Intermediate 1-6> 1.9g (yield 66%) ).

LC/MS: m/z= 366[(M+1) ⁺ ]

(7) Manufacturing example 1-7: Synthesis of intermediate 1-7

1,4-dibromobenzene (2.4g, 0.010mol) was added to 1H-indol-3-ylboronic acid (1.3g, 0.008mol) and synthesized by the same method used in Preparation Example 1-4 <Intermediate 1-7> 1.6 g (73% yield) was obtained.

LC/MS: m/z= 272[(M+1) ⁺ ]

(8) Manufacturing example 1-8: Synthesis of Intermediate 1-8

In 2-bromo-2'-nitrobiphenyl (5.0g, 0.017mol), triphenylphosphine (4.5g, 0.017mol) was added to 100ml of 1,2-dichlorobenzene and stirred at 180°C for 24 hours to react. After the reaction was completed, the mixture was cooled, and H ₂ 0: layer was separated on MC, followed by column purification (n-Hexane:MC) to obtain 4.2 g (yield 83%) of Intermediate 1-8.

LC/MS: m/z= 246[(M+1) ⁺ ]

(9) Manufacturing example 1-9: Synthesis of Intermediate 1-9

Bromobenzene (1.6g, 0.010mol) was added to Intermediate 1-8 (2.1g, 0.010mol) and synthesized by the same method used in Preparation Example 1-1 to obtain 2.3g (yield 77%) of <Intermediate 1-9> Got it.

LC/MS: m/z= 322[(M+1) ⁺ ]

(10) Manufacturing example 1-10: Synthesis of intermediate 1-10

Intermediate 1-9 (3.2g, 0.010mol) bis(pinacolato)dibron (3.0g, 0.012mol) was added and <Intermediate 1-10> 2.7g (73% yield) was obtained by the same method used in Preparation Example 1-3 I did.

LC/MS: m/z= 369[(M+1) ⁺ ]

(11) Manufacturing example 1-11: Synthesis of Intermediate 1-11

Intermediate 1-10 (4.4g, 0.012mol) was added to Intermediate 1-7 (2.7g, 0.010mol) and synthesized by the same method used in Preparation Example 1-4 <Intermediate 1-11> 3.1g (yield 72%) ).

LC/MS: m/z= 434[(M+1) ⁺ ]

(12) Manufacturing example 1-12: compound 1 synthesis

Intermediate 1-11 (4.3g, 0.010mol) was added to Intermediate 1-6 (3.6g, 0.010mol) and synthesized by the same method used in Preparation Example 1 to obtain 5.5g (yield 72%) of <Compound 1> .

H-NMR (200MHz, CDCl ₃ ): δ ppm, 1H (8.17/d, 8.16/d, 8.08/d, 7.94/d, 7.85/s, 7.76/s, 7.71/d, 7.60/m, 7.59/d , 7.45/m, 7.43/m, 7.41/m, 7.36/s, 7.33/m) 2H(8.55/d, 7.80/d, 7.58/m, 7.55/m, 7.50/d, 7.42/m) 3H(7.79 /d) 5H (7.25d)

LC/MS: m/z= 765[(M+1) ⁺ ]

Example 2: compound 2 synthesis

(One) Manufacturing example 2-1: Synthesis of intermediate 2-1

After dissolving in 30ml of anhydrous THF in Intermediate 1-8 (3.0g, 0.012mol), 5.9ml of n-BuLi(2.5M) was slowly added dropwise at -78°C. After holding for 1 hour, triisopropyl borate (3.4g, 0.018mol) was added, followed by stirring at room temperature for 24 hours. After completion of the reaction, 1N HCl was added and stirred for 1 hour, and then layer-separated in EA: H ₂ O and recrystallized with n-Hexane to give 1.8 g (yield 70%) of <Intermediate 2-1>.

LC/MS: m/z= 211[(M+1) ⁺ ]

(2) Manufacturing example 2-2: Synthesis of intermediate 2-2

Intermediate 2-1 (2.1g, 0.010mol) was added 2-bromo-9,9-dimethyl-9H-fluorene (2.7g, 0.010mol) and synthesized by the same method used in Preparation Example 1-1 <Intermediate 2 -2> 2.9g (72% yield) was obtained.

LC/MS: m/z= 403[(M+1) ⁺ ]

(3) Manufacturing example 2-3: Synthesis of intermediate 2-3

Intermediate 2-2 (4.0g, 0.010mol) was added to Intermediate 1-7 (2.7g, 0.008mol) and synthesized by the same method used in Preparation Example 1-4. <Intermediate 2-3> 2.9g (yield 65%) ).

LC/MS: m/z= 550[(M+1) ⁺ ]

(4) Manufacturing example 2-4: compound 2 synthesis

Intermediate 2-3 (5.5g, 0.010mol) was added to Intermediate 1-6 (3.7g, 0.010mol), synthesized by the same method used in Preparation Example 1-1, <Compound 2> 6.8g (yield 77%) Got it.

H-NMR (200MHz, CDCl ₃ ): δ ppm, 1H (8.17/d, 8.16/d, 8.08/d, 7.94/d, 7.85/d, 7.76/s, 7.71/d, 7.59/d, 7.43/m , 7.41/m, 7.36/s, 7.33/m, 7.30/m, 7.25/m) 2H(7.80/d, 7.55/m, 7.51/m, 7.50/s, 7.42/m, 7.40/d, 1.72/s ) 3H(7.79/d) 4H(7.25/d)

LC/MS: m/z=882 [(M+1) ⁺ ]

Example 3: Synthesis of compound 3

(One) Manufacturing example 3-1: Synthesis of intermediate 3-1

Bromobenzene (1.6g, 0.010mol) was added to 4-bromo-1H-indole (2.0g, 0.010mol) and synthesized by the same method used in Preparation Example 1-1 <Intermediate 3-1> 2.1g (yield 77 %).

LC/MS: m/z= 272[(M+1) ⁺ ]

(2) Manufacturing example 3-2: Synthesis of intermediate 3-2

Intermediate 3-1 (2.7g, 0.010mol) bis(pinacolato)dibron (3.0g, 0.012mol) was added and <Intermediate 3-2> 2.3g (yield 73%) was obtained by the same method used in Preparation Example 1-3. I did.

LC/MS: m/z= 319[(M+1) ⁺ ]

(3) Manufacturing example 3-3: Synthesis of intermediate 3-3

Intermediate 1-7 (2.2g, 0.008mol) was added to Intermediate 3-2 (3.2g, 0.010mol) and synthesized by the same method used in Preparation Example 1-4 <Intermediate 3-3> 2.8g (yield 72%) ).

LC/MS: m/z= 384[(M+1) ⁺ ]

(4) Manufacturing example 3-4: compound 3 synthesis

Intermediate 3-3 (3.8g, 0.010mol) was added to Intermediate 1-6 (3.7g, 0.010mol), synthesized by the same method used in Preparation Example 1-1, <Compound 3> 5.5g (yield 77%) Got it.

H-NMR (200MHz, CDCl ₃ ): δ ppm, 1H (8.55/d, 8.17/d, 8.16/d, 8.10/d, 8.08/d, 7.90/d, 7.85/s, 7.76/s, 7.71/d , 7.60/d, 7.60/m, 7.45/m, 7.41/m, 7.39/m, 7.36/s, 6.52/d) 2H(7.80/d, 7.79/d, 7.58/m, 7.55/m, 7.51/m , 7.50/d, 7.42/m) 4H (7.25/d)

LC/MS: m/z= 715[(M+1) ⁺ ]

Example 4: Synthesis of compound 4

(One) Manufacturing example 4-1: Synthesis of intermediate 4-1

Biphenyl-4-ylboronic acid (2.4g, 0.012mol) was added to 4-bromonaphthalen-2-ol (2.2g, 0.010mol) and synthesized by the same method used in Preparation Example 1-4 <Intermediate 4-1> 2.1 g (72% yield) was obtained.

LC/MS: m/z= 296[(M+1) ⁺ ]

(2) Manufacturing example 4-2: Synthesis of intermediate 4-2

<Intermediate 4-2> 3.0g (yield 70%) was synthesized by the same method used in Preparation Example 1-2, except that intermediate 4-1 (3.0g, 0.010mol) was used instead of intermediate 1-1. Got it.

LC/MS: m/z= 428[(M+1) ⁺ ]

(3) Manufacturing example 4-3: Synthesis of intermediate 4-3

Intermediate 4-2 (3.4g, 0.008mol) was added to Intermediate 1-3 (2.9g, 0.010mol) and synthesized by the same method used in Preparation Example 1-4 <Intermediate 4-3> 3.2g (yield 72%) ).

LC/MS: m/z= 442[(M+1) ⁺ ]

(4) Manufacturing example 4-4: compound 4 synthesis

Intermediate 3-3 (3.8g, 0.010mol) was added to Intermediate 4-3 (4.4g, 0.010mol) and synthesized by the same method used in Preparation Example 1-1 <Compound 4> 6.1g (yield 77%) Got it.

H-NMR (200MHz, CDCl ₃ ): δ ppm, 1H (8.17/d, 8.16/d, 8.10/d, 8.08/d, 7.90/d, 7.85/s, 7.76/d, 7.71/d, 7.60/m , 7.60/d, 7.45/m, 7.41/m, 7.39/m, 7.36/s, 6.52/d) 2H(7.80/d, 7.58/m, 7.55/m, 7.52/d, 7.51/m, 7.50/d , 7.42/m) 8H(7.25/d)

LC/MS: m/z=792 [(M+1) ⁺ ]

Example 5: compound 5 synthesis

(One) Manufacturing example 5-1: Synthesis of intermediate 5-1

9H-carbazole (1.7g, 0.010mol) was added to 3-bromo-9H-carbazole (2.4g, 0.010mol), synthesized by the same method used in Preparation Example 1-1, <Intermediate 5-1> 2.8g ( Yield 84%).

LC/MS: m/z= 332[(M+1) ⁺ ]

(2) Manufacturing example 5-2: Synthesis of intermediate 5-2

Intermediate 1-7 (2.7g, 0.010mol) was added to Intermediate 5-1 (3.3g, 0.010mol), synthesized by the same method used in Preparation Example 1-1, <Intermediate 5-2> 4.0g (yield 77 %).

LC/MS: m/z= 523[(M+1) ⁺ ]

(3) Manufacturing example 5-3: Synthesis of compound 5

Intermediate 5-2 (5.2g, 0.010mol) was added to Intermediate 1-6 (3.6g, 0.010mol), synthesized by the same method used in Preparation Example 1-1, <Compound 5> 6.2g (73% yield) Got it.

H-NMR (200MHz, CDCl ₃ ): δ ppm, 1H (8.55/m, 8.17/d, 8.16/d, 8.12/d, 8.08/d, 7.85/s, 7.76/s, 7.71/d, 7.60/m , 7.50/s, 7.50/d, 7.41/m, 7.36/s, 7.31/d, 7.29/m) 2H (8.55/d, 7.94/d, 7.80/d, 7.68/d, 7.63/d, 7.55/m) , 7.51/m, 7.42/m, 7.33/m, 7.25/m) 4H(7.79/d)

LC/MS: m/z=855 [(M+1) ⁺ ]

Example 6: compound 6 synthesis

(One) Manufacturing example 6-1: Synthesis of intermediate 6-1

Phenanthren-9-ylboronic acid (2.7g, 0.012mol) was added to Intermediate 1-7 (2.7g, 0.008mol) and synthesized by the same method used in Preparation Example 1-4 <Intermediate 6-1> 2.7g (yield 72%).

LC/MS: m/z= 369[(M+1) ⁺ ]

(2) Manufacturing example 6-2: Synthesis of compound 6

Intermediate 6-1 (3.7g, 0.010mol) was added to Intermediate 1-6 (3.7g, 0.010mol), synthesized by the same method used in Preparation Example 1-1, <Compound 6> 5.5g (79% yield) Got it.

H-NMR (200MHz, CDCl ₃ ): δ ppm, 1H (8.55/d, 8.17/d, 8.16/d, 8.08/d, 7.93/d, 7.85/s, 7.76/s, 7.71/d, 7.60/m , 7.41/m, 7.36/s) 2H (8.93/d, 8.12/d, 7.88/m, 7.82/m, 7.80/d, 7.79/d, 7.55/m, 7.51/m, 7.42/m) 4H (7.25 /d)

LC/MS: m/z= 700[(M+1) ⁺ ]

Example 7: compound 7 synthesis

(One) Manufacturing example 7-1: Synthesis of Intermediate 7-1

1H-indol-3-ylboronic acid (1.9g, 0.012mol) was added 4-bromo-2,6-diphenylpyridine (3.1g, 0.010mol) and synthesized by the same method used in Preparation Example 1-4 <Intermediate 7 -1> 2.5g (72% yield) was obtained.

LC/MS: m/z= 346[(M+1) ⁺ ]

(2) Manufacturing example 7-2: Synthesis of compound 7

Intermediate 7-1 (3.5g, 0.010mol) was added to Intermediate 1-6 (3.7g, 0.010mol), synthesized by the same method used in Preparation Example 1-1, <Compound 7> 5.2g (yield 77%) Got it.

H-NMR (200MHz, CDCl ₃ ): δ ppm, 1H (8.16/d, 8.08/d, 7.94/d, 7.85/s, 7.76/s, 7.41/m, 7.33/m, 7.25/m) 2H (8.55 /d, 8.20/s, 7.80/d, 7.79/d, 7.60/s, 7.55/m, 7.51/m, 7.47/m) 4H (8.30/d, 7.54/m)

LC/MS: m/z= 677[(M+1) ⁺ ]

Example 8: compound 8 synthesis

(One) Manufacturing example 8-1: Synthesis of intermediate 8-1

Add phenanthren-9-ylboronic acid (2.7 g, 0.012 mol) to 1,3-dibromobenzene (2.4 g, 0.010 mol) and synthesized by the same method used in Preparation Example 1-4 <Intermediate 8-1> 2.4 g ( Yield 72%).

LC/MS: m/z= 333[(M+1) ⁺ ]

(2) Manufacturing example 8-2: Synthesis of intermediate 8-2

Intermediate 8-1 (3.3g, 0.010mol) was added 1H-indol-3-ylboronic acid (1.9g, 0.012mol) and synthesized by the same method used in Preparation Example 1-4 <Intermediate 8-2> 2.7g (Yield 72%) was obtained.

LC/MS: m/z= 369[(M+1) ⁺ ]

(3) Manufacturing example 8-3: Synthesis of intermediate 8-3

Phenyl boronic acid (1.4g, 0.012mol) was added to 6-bromonaphthalen-2-ol (2.2g, 0.010mol) and synthesized by the same method used in Preparation Example 1-4 <Intermediate 8-3> 1.6g (yield 72%).

LC/MS: m/z= 220[(M+1) ⁺ ]

(4) Manufacturing example 8-4: Synthesis of intermediate 8-4

Intermediate 8-3 (2.2g, 0.010mol) was added and synthesized by the same method used in Preparation Example 1-5 to obtain 2.4g (yield 67%) of <Intermediate 8-4>.

LC/MS: m/z= 352[(M+1) ⁺ ]

(5) Manufacturing example 8-5: Synthesis of intermediate 8-5

Intermediate 1-3 (3.5g, 0.012mol) was added to Intermediate 8-4 (3.5g, 0.010mol) and synthesized by the same method used in Preparation Example 1-4. <Intermediate 8-5> 2.6g (yield 72%) ).

LC/MS: m/z= 366[(M+1) ⁺ ]

(6) Manufacturing example 8-6: compound 8 synthesis

Intermediate 8-2 (3.7 g, 0.010 mol) was added to Intermediate 8-5 (3.6 g, 0.010 mol), synthesized by the same method used in Preparation Example 1-1, <Compound 8> 5.4 g (yield 77%) Got it.

H-NMR (200MHz, CDCl ₃ ): δ ppm, 1H (8.34/s, 8.17/d, 8.16/d, 7.93/s, 7.87/d, 7.73/d, 7.71/d, 7.70/s, 7.60/m , 7.58/d, 7.57/m, 7.41/m, 7.36/s) 2H(8.93/d, 8.12/d, 7.92/d, 7.88/m, 7.82/m, 7.80/d, 7.52/d, 7.51/m , 7.48/d, 7.42/m)

LC/MS: m/z=700[(M+1) ⁺ ]

Example 9: Synthesis of compound 9

(One) Manufacturing example 9-1: Synthesis of intermediate 9-1

Dibromochloromethane (2.1g, 0.010mol) was added to 1-amino-2-naphthamide (1.9g, 0.010mol), synthesized by the same method used in Preparation Example 1-1, <Intermediate 9-1> 1.2g (yield 53 %).

LC/MS: m/z= 230[(M+1) ⁺ ]

(2) Manufacturing example 9-2: Synthesis of intermediate 9-2

<Intermediate 9-2> 2.6g (yield 73%) was synthesized by the same method used in Preparation Example 1-2, except that intermediate 9-1 (2.3g, 0.010mol) was used instead of intermediate 1-1. Got it.

LC/MS: m/z= 362[(M+1) ⁺ ]

(3) Manufacturing example 9-3: Synthesis of intermediate 9-3

Intermediate 9-2 (3.6g, 0.010mol) bis(pinacolato)dibron (3.0g, 0.012mol) was added and <Intermediate 9-3> 2.4g (yield 70%) was obtained by the same method used in Preparation Example 1-3. I did.

LC/MS: m/z= 340[(M+1) ⁺ ]

(4) Manufacturing example 9-4: Synthesis of intermediate 9-4

Intermediate 1-5 (3.5g, 0.010mol) was added to Intermediate 9-3 (4.1g, 0.012mol) and synthesized by the same method used in Preparation Example 1-4 <Intermediate 9-4> 2.8g (yield 67%) ).

LC/MS: m/z= 416[(M+1) ⁺ ]

(5) Manufacturing example 9-5: Synthesis of compound 9

Intermediate 1-11 (4.3g, 0.010mol) was added to Intermediate 9-4 (4.2g, 0.010mol), synthesized by the same method used in Preparation Example 1-1, <Compound 9> 6.3g (yield 77%) Got it.

H-NMR (200MHz, CDCl ₃ ): δ ppm, 1H (8.51/d, 8.17/d, 8.16/d, 8.08/d, 7.94/d, 7.85/s, 7.80/d, 7.76/s, 7.71/d , 7.60/d, 7.59/d, 7.45/m, 7.43/m, 7.41/m, 7.36/s, 7.33/m, 7.25/d) 2H(8.55/d, 7.67/m, 7.58/m, 7.55/m , 7.51/m, 7.50/d, 7.42/m) 3H(7.79/d) 4H(7.25/d)

LC/MS: m/z=815[(M+1) ⁺ ]

Example 10: compound 10 synthesis

(One) Manufacturing Example 10 -1: Synthesis of intermediate 10-1

Intermediate 1-8 (2.4g, 0.010mol) 3-(4-bromophenyl)pyridine (2.3g, 0.010mol) was added and synthesized by the same method used in Preparation Example 1-1 <Intermediate 10-1> 3.1g (Yield 77%) was obtained.

LC/MS: m/z= 400[(M+1) ⁺ ]

(2) Manufacturing example 10-2: Synthesis of intermediate 10-2

Intermediate 10-1 (4.0g, 0.010mol) bis(pinacolato)dibron (3.0g, 0.012mol) was added and <Intermediate 10-2> 3.3g (yield 73%) was obtained by the same method used in Preparation Example 1-3 I did.

LC/MS: m/z= 446[(M+1) ⁺ ]

(3) Manufacturing example 10-3: Synthesis of intermediate 10-3

Intermediate 1-7 (2.2g, 0.008mol) was added to Intermediate 10-2 (4.5g, 0.010mol) and synthesized by the same method used in Preparation Example 1-(4) <Intermediate 10-3> 3.7g (yield 72%).

LC/MS: m/z= 511[(M+1) ⁺ ]

(4) Manufacturing example 10-4: compound 10 synthesis

Intermediate 10-3 (3.7g, 0.010mol) was added to Intermediate 9-4 (4.2g, 0.010mol), synthesized by the same method used in Preparation Example 1-1, <Compound 10> 6.6g (yield 74%) Got it.

H-NMR (200MHz, CDCl ₃ ): δ ppm, 1H (9.24/s, 8.70/d, 8.51/d, 8.42/s, 8.17/d, 8.16/d, 8.08/d, 7.94/d, 7.85/s , 7.80/d, 7.76/s, 7.71/d, 7.60/d, 7.59/d, 7.43/m, 7.41/m, 7.36/s, 7.33/m, 7.25/d) 2H(8.55/d, 7.79/d , 7.68/d, 7.67/m, 7.55/m, 7.51/m, 7.42/m) 3H(7.79/d) 4H(7.25/d)

LC/MS: m/z=893[(M+1) ⁺ ]

Example 11: Synthesis of compound 11

(One) Manufacturing example 11-1: Synthesis of Intermediate 11-1

Phenyl boronic acid (1.4g, 0.012mol) was added to 3-bromonaphthalen-1-ol (2.2g, 0.010mol) and synthesized by the same method used in Preparation Example 1-4 <Intermediate 11-1> 1.6g (yield 72%).

LC/MS: m/z= 220[(M+1) ⁺ ]

(2) Manufacturing example 11-2: Synthesis of Intermediate 11-2

<Intermediate 11-2> 2.3g (yield 66%) was synthesized in the same manner as used in Preparation Example 1-2, except that intermediate 11-1 (2.2g, 0.010mol) was used instead of intermediate 1-1. Got it.

LC/MS: m/z= 352[(M+1) ⁺ ]

(3) Manufacturing example 11-3: Synthesis of Intermediate 11-3

Intermediate 11-2 (3.5g, 0.010mol) was added to Intermediate 9-3 (4.1g, 0.012mol) and synthesized by the same method used in Preparation Example 1-4 <Intermediate 11-3> 3.0g (yield 72%) ).

LC/MS: m/z= 416[(M+1) ⁺ ]

(4) Manufacturing example 11-4: Synthesis of intermediate 11-4

Add 9-phenyl-9H-carbazol-2-ylboronic acid (3.3g, 0.012mol) to Intermediate 1-7 (2.7g, 0.010mol) and synthesized by the same method used in Preparation Example 1-4 <Intermediate 11- 4> 3.0g (68% yield) was obtained.

LC/MS: m/z= 434[(M+1) ⁺ ]

(5) Manufacturing example 11-5: Synthesis of compound 11

Intermediate 11-4 (4.3g, 0.010mol) was added to Intermediate 11-3 (4.2g, 0.010mol), synthesized by the same method used in Preparation Example 1-1, <Compound 11> 6.4g (79% yield) Got it.

H-NMR (200MHz, CDCl ₃ ): δ ppm, 1H (8.55/d, 8.51/d, 8.49/d, 8.17/d, 8.16/d, 8.12/d, 8.10/d, 8.08/d, 7.85/s , 7.80/d, 7.76/s, 7.71/d, 7.63/d, 7.62/s, 7.60/d, 7.45/m, 7.41/m, 7.36/s) 2H(7.67/m, 7.58/m, 7.55/m , 7.52/d, 7.51/m, 7.42/m) 3H(7.50/d) 4H(7.25/d)

LC/MS: m/z=815 [(M+1) ⁺ ]

Example 12: compound 12 synthesis

(One) Manufacturing example 12-1: Synthesis of Intermediate 12-1

Dibromochloromethane (2.1g, 0.010mol) was added to 2-amino-1-naphthamide (1.8g, 0.010mol), synthesized by the same method used in Preparation Example 1-1, <Intermediate 12-1> 1.8g (yield 77 %).

LC/MS: m/z= 230[(M+1) ⁺ ]

(2) Manufacturing example 12-2: Synthesis of Intermediate 12-2

<Intermediate 12-2> 2.6g (yield 73%) was synthesized by the same method used in Preparation Example 1-2, except that intermediate 12-1 (2.3g, 0.010 mol) was used instead of intermediate 1-1. Got it.

LC/MS: m/z= 362[(M+1) ⁺ ]

(3) Manufacturing example 12-3: Synthesis of Intermediate 12-3

Intermediate 12-2 (3.6g, 0.010mol) bis(pinacolato)dibron (3.0g, 0.012mol) was added and <Intermediate 12-3> 2.4g (70% yield) was obtained by the same method used in Preparation Example 1-3. I did.

LC/MS: m/z= 340[(M+1) ⁺ ]

(4) Manufacturing example 12-4: Synthesis of intermediate 12-4

Intermediate 1-5 (3.5g, 0.010mol) was added to Intermediate 12-3 (4.1g, 0.012mol) and synthesized by the same method used in Preparation Example 1-4 <Intermediate 12-4> 3.0g (yield 72%) ).

LC/MS: m/z= 416[(M+1) ⁺ ]

(5) Manufacturing example 12-5: compound 12 synthesis

Intermediate 1-11 (4.3g, 0.010mol) was added to Intermediate 12-4 (4.2g, 0.010mol), synthesized by the same method used in Preparation Example 1-1, <Compound 12> 7.1g (80% yield) Got it.

H-NMR (200MHz, CDCl ₃ ): δ ppm, 1H (8.54/d, 8.17/d, 8.08/d, 7.94/d, 7.85/d, 7.80/d, 7.76/s, 7.71/d, 7.59/d , 7.45/m, 7.43/m, 7.33/m, 7.25/m) 2H(8.55/d, 8.16/d, 7.67/m, 7.58/m, 7.55/m, 7.50/d, 7.42/m, 7.41/m ) 4H(7.51/m, 7.25/d) 5H(7.79/d)

LC/MS: m/z=892[(M+1) ⁺ ]

Example 13: Synthesis of compound 13

(One) Manufacturing example 13-1: Synthesis of Intermediate 13-1

2-bromonaphthalene (2.1g, 0.010mol) was added to Intermediate 1-8 (2.5g, 0.010mol), synthesized by the same method used in Preparation Example 1-1, <Intermediate 13-1> 3.2g (yield 86%) ).

LC/MS: m/z= 372[(M+1) ⁺ ]

(2) Manufacturing example 13-2: Synthesis of Intermediate 13-2

Intermediate 13-1 (3.7g, 0.010mol) bis(pinacolato)dibron (3.0g, 0.012mol) was added and <Intermediate 13-2> 3.1g (yield 73%) was obtained by the same method used in Preparation Example 1-3. I did.

LC/MS: m/z= 419[(M+1) ⁺ ]

(3) Manufacturing example 13-3: Synthesis of Intermediate 13-3

Intermediate 13-2 (5.0g, 0.012mol) was added to Intermediate 1-7 (2.7g, 0.010mol) and synthesized by the same method used in Preparation Example 1-4 <Intermediate 13-3> 3.5g (yield 72%) ).

LC/MS: m/z= 484[(M+1) ⁺ ]

(4) Manufacturing example 13-4: compound 13 synthesis

Intermediate 13-3 (4.8g, 0.010mol) was added to Intermediate 12-4 (4.2g, 0.010mol), synthesized by the same method used in Preparation Example 1-1, <Compound 13> 6.7g (yield 77%) Got it.

H-NMR (200MHz, CDCl ₃ ): δ ppm, 1H (8.54/s, 8.17/d, 8.08/d, 7.94/d, 7.85/d, 7.83/s, 7.80/d, 7.76/s, 7.71/d , 7.43/m, 7.41/m, 7.36/d, 7.36/s, 7.33/m) 2H(8.55/d, 8.16/d, 7.67/m, 7.55/m, 7.51/m, 7.42/m) 3H(8.00 /d, 7.79/d, 7.59/m) 5H (7.25/d)

LC/MS: m/z=866[(M+1) ⁺ ]

Example 14: compound 14 synthesis

(One) Manufacturing example 14-1: Synthesis of Intermediate 14-1

Add 2,7-dibromo-9,9-dimethyl-9H-fluorene (3.5g, 0.010mol) to 1H-indol-3-ylboronic acid (1.9g, 0.012mol) and the same method used in Preparation Example 1-4 And <Intermediate 14-1> 2.8g (72% yield) was obtained.

LC/MS: m/z= 388[(M+1) ⁺ ]

(2) Manufacturing example 14-2: Synthesis of intermediate 14-2

Intermediate 1-10 (4.4g, 0.012mol) was added to Intermediate 14-1 (3.9g, 0.010mol) and synthesized by the same method used in Preparation Example 1-4 <Intermediate 14-2> 4.0g (yield 72%) ).

LC/MS: m/z= 550[(M+1) ⁺ ]

(3) Manufacturing example 14-3: Synthesis of compound 14

Intermediate 14-2 (5.5g, 0.010mol) was added to Intermediate 12-4 (4.2g, 0.010mol), synthesized by the same method used in Preparation Example 1-1, <Compound 14> 6.6g (71% yield) Got it.

H-NMR (200MHz, CDCl ₃ ): δ ppm, 1H (8.54/s, 8.17/d, 8.08/d, 7.94/d, 7.85/d, 7.80/d, 7.76/s, 7.71/d, 7.59/d , 7.45/m, 7.43/m, 7.41/m, 7.36/s, 7.33/m, 7.25/m) 2H(8.55/d, 8.16/d, 7.93/d, 7.77/s, 7.67/m, 7.63/d , 7.55/m, 7.51/m, 7.42/m, 7.58/m, 7.50/d, 1.72/s) 3H(7.79/d)

LC/MS: m/z=932[(M+1) ⁺ ]

Example 15: compound 15 synthesis

(One) Manufacturing example 15-1: Synthesis of intermediate 15-1

3,6-dibromo-9-phenyl-9H-carbazole (4.0g, 0.010mol) was added to 1H-indol-3-ylboronic acid (1.9g, 0.012mol) and synthesized by the same method used in Preparation Example 1-4. Thus, 3.1 g of <Intermediate 15-1> (72% yield) was obtained.

LC/MS: m/z=437[(M+1) ⁺ ]

(2) Manufacturing example 15-2: Synthesis of intermediate 15-2

Intermediate 1-10 (4.4g, 0.012mol) was added to Intermediate 15-1 (4.4g, 0.010mol) and synthesized by the same method used in Preparation Example 1-4 <Intermediate 15-2> 4.3g (yield 72%) ).

LC/MS: m/z=600[(M+1) ⁺ ]

(3) Manufacturing example 15-3: Synthesis of compound 15

Intermediate 15-2 (6.0g, 0.010mol) was added to Intermediate 12-4 (4.2g, 0.010mol), synthesized by the same method used in Preparation Example 1-1, <Compound 15> 7.6g (yield 77%) Got it.

H-NMR (200MHz, CDCl ₃ ): δ ppm, 1H (8.54/s, 8.18/d, 8.17/d, 8.08/d, 8.00/d, 7.94/d, 7.87/d, 7.85/d, 7.80/m , 7.76/s, 7.71/d, 7.69/d, 7.59/d, 7.43/m, 7.36/s, 7.33/m, 7.25/m) 2H (8.55/d, 8.16/d, 7.77/s, 7.67/m , 7.55/m, 7.51/m, 7.45/m, 7.42/m) 3H(7.79/d) 4H(7.58/m, 7.50/d)

LC/MS: m/z=981[(M+1) ⁺ ]

Example 16: compound 16 synthesis

(One) Manufacturing example 16-1: Synthesis of intermediate 16-1

Dibromochloromethane (2.1g, 0.010mol) was added to 3-amino-2-naphthamide (1.9g, 0.010mol), synthesized by the same method used in Preparation Example 1-1, <Intermediate 16-1> 1.8g (yield 77) %).

LC/MS: m/z=230[(M+1) ⁺ ]

(2) Manufacturing example 16-2: Synthesis of intermediate 16-2

<Intermediate 16-2> 2.6g (yield 73%) was synthesized by the same method used in Preparation Example 1-2, except that intermediate 16-1 (2.2g, 0.010mol) was used instead of intermediate 1-1. Got it.

LC/MS: m/z=362[(M+1) ⁺ ]

(3) Manufacturing example 16-3: Synthesis of intermediate 16-3

Intermediate 16-2 (3.6g, 0.010mol) bis(pinacolato)dibron (3.0g, 0.012mol) was added and <Intermediate 16-3> 2.5g (73% yield) was obtained by the same method used in Preparation Example 1-3. I did.

LC/MS: m/z=340[(M+1) ⁺ ]

(4) Manufacturing example 16-4: Synthesis of intermediate 16-4

Intermediate 1-5 (3.5g, 0.010mol) was added to Intermediate 16-3 (4.1g, 0.012mol) and synthesized by the same method used in Preparation Example 1-4 <Intermediate 16-4> 3.0g (yield 72%) ).

LC/MS: m/z=416[(M+1) ⁺ ]

(5) Manufacturing example 16-5: compound 16 synthesis

Intermediate 1-11 (4.3g, 0.010mol) was added to Intermediate 16-4 (4.2g, 0.010mol), synthesized by the same method used in Preparation Example 1-1, <Compound 16> 7.3g (82% yield) Got it.

H-NMR (200MHz, CDCl ₃ ): δ ppm, 1H (8.17/d, 8.08/d, 8.00/s, 7.94/d, 7.85/s, 7.80/s, 7.76/s, 7.71/d, 7.59/d , 7.45/m, 7.43/m, 7.33/m) 2H (8.55/d, 8.16/d, 7.67/m, 7.58/m, 7.55/m, 7.50/d, 7.42/m, 7.41/m) 4H (7.51 /m) 5H (7.79/d, 7.25/d)

LC/MS: m/z=892[(M+1) ⁺ ]

Example 17: compound 17 synthesis

(One) Manufacturing example 17-1: Synthesis of intermediate 17-1

Biphenyl-3-ylboronic acid (2.4g, 0.012mol) was added to 4-bromonaphthalen-2-ol (2.2g, 0.010mol) and synthesized by the same method used in Preparation Example 1-4 <Intermediate 17-1> 2.0 g (66% yield) was obtained.

LC/MS: m/z=296[(M+1) ⁺ ]

(2) Manufacturing example 17-2: Synthesis of intermediate 17-2

<Intermediate 17-2> 3.1g (yield 73%) was synthesized by the same method used in Preparation Example 1-2, except that intermediate 17-1 (3.0g, 0.010mol) was used instead of intermediate 1-1. Got it.

LC/MS: m/z=428[(M+1) ⁺ ]

(3) Manufacturing example 17-3: Synthesis of intermediate 17-3

Intermediate 17-2 (4.3g, 0.010mol) was added to Intermediate 16-3 (4.1g, 0.012mol) and synthesized by the same method used in Preparation Example 1-4 <Intermediate 17-3> 3.5g (yield 72%) ).

LC/MS: m/z=493[(M+1) ⁺ ]

(4) Manufacturing example 16-4: Synthesis of compound 17

Intermediate 1-11 (4.3g, 0.010mol) was added to Intermediate 17-3 (4.9g, 0.010mol), synthesized by the same method used in Preparation Example 1-1, <Compound 17> 6.3g (yield 71%) Got it.

H-NMR (200MHz, CDCl ₃ ): δ ppm, 1H (8.17/d, 8.08/d, 8.00/s, 7.94/d, 7.85/s, 7.80/s, 7.79/d, 7.76/s, 7.71/d , 7.70/s, 7.59/d, 7.57/m, 7.45/m, 7.43/m, 7.41/m, 7.36/s, 7.33/m, 7.25/m) 2H(8.16/d, 7.67/m, 7.58/m , 7.55/m, 7.52/d, 7.51/m, 7.50/d, 7.48/d, 7.42/m) 4H (8.55/d, 7.25/d)

LC/MS: m/z= 892[(M+1) ⁺ ]

Example 18: compound 18 synthesis

(One) Manufacturing example 18-1: Synthesis of intermediate 18-1

Dibromochloromethane (2.1g, 0.010mol) was added to 10-amino-5,8-dihydrophenanthrene-9-carboxamide (2.4g, 0.010mol) and synthesized by the same method used in Preparation Example 1-1 <Intermediate 18-1 > 2.2g (77% yield) was obtained.

LC/MS: m/z= 282[(M+1) ⁺ ]

(2) Manufacturing example 18-2: Synthesis of intermediate 18-2

<Intermediate 18-2> 3.0g (yield 73%) was synthesized by the same method used in Preparation Example 1-2, except that intermediate 18-1 (2.2g, 0.010mol) was used instead of intermediate 1-1. Got it.

LC/MS: m/z= 414[(M+1) ⁺ ]

(3) Manufacturing example 18-3: Synthesis of intermediate 18-3

Intermediate 18-2 (4.1g, 0.010mol) bis(pinacolato)dibron (3.0g, 0.012mol) was added and <Intermediate 18-3> 2.7g (70% yield) was obtained by the same method used in Preparation Example 1-3 I did.

LC/MS: m/z= 392[(M+1) ⁺ ]

(4) Manufacturing example 18-4: Synthesis of intermediate 18-4

Intermediate 1-5 (3.5g, 0.010mol) was added to Intermediate 18-3 (4.7g, 0.012mol) and synthesized by the same method used in Preparation Example 1-4. <Intermediate 18-4> 3.4g (yield 72%) ).

LC/MS: m/z= 466[(M+1) ⁺ ]

(5) Manufacturing example 5: compound 18 synthesis

Intermediate 1-11 (4.3g, 0.010mol) was added to Intermediate 18-4 (4.7g, 0.010mol), synthesized by the same method used in Preparation Example 1-1, <Compound 18> 6.2g (72% yield) Got it.

H-NMR (200MHz, CDCl ₃ ): δ ppm, 1H (8.17/d, 8.08/d, 7.94/d, 7.76/s, 7.71/d, 7.59/d, 7.45/m, 7.43/m, 7.41/m , 7.36/s, 7.33/m) 2H(8.93/d, 8.55/d, 8.12/d, 7.88/m, 7.82/m, 7.58/m, 7.55/m, 7.51/m, 7.50/d, 7.42/m ) 3H(7.79/d) 5H(7.25/d)

LC/MS: m/z=866[(M+1) ⁺ ]

Abbreviations used in the embodiments of the present invention are as follows.

Copper Phthalocyanine (CuPc)

α-NPD (N4,N4'-di(naphthalen-1-yl)-N4,N4'-diphenylbiphenyl-4,4'-diamine)

Ir(btp)2(acac)(bis(2-(2'-benzothienyl)-pyridinato-N,C3')iridium(acetylacetonate))

NPB: N,N'-Bis(naphthalen-1-yl)-N,N'-bis(phenyl)benzidine

Ir(ppy) ₃ : Iridium, tris(2-phenylpyidine)

Balq: Bis(2-methyl-8-quinolinolato-N1,O8)-(1,1'-Biphenyl-4-olato)aluminum

Alq ₃ : tris(8-quinolinolato)-aluminium(III)

CBP: (4,4-N,N-dicarbazole)biphenyl

Structures of the hole injection layer material CuPc, the hole transport material NPB, the emission host material CBP, and the red dopant Ir(btp)2(acac) used in the device embodiment or device comparison example are as follows.

Device Example 1: compound 1 Light emitting layer With red host material Organic light emitting device Produce

After forming a hole transport layer of 80nm CuPc, 30nm α-NPD on a glass substrate coated with ITO, and mixing <Compound 1> + 6% red dopant <Ir(btp)2(acac)> 25nm thickness, deposition rate 0.1 After forming a light emitting layer at m/sec, an electron transport layer of 40 nm thickness with Alq ₃ , an electron injection layer of 1 nm thickness with LiF, and a cathode Al of 120 nm thickness were sequentially formed to manufacture an organic electroluminescent device. At this time, the deposition rate of each material was 0.1 nm/sec for CuPc, α-NPD, and Alq ₃ , 0.01 nm/sec for LiF, and 0.5 nm/sec for Al.

Device Example 2 to 18

Organic electroluminescent devices of Device Examples 2 to 18 were manufactured in the same manner as in Device Example 1, except that the light-emitting materials shown in Table 1 were used instead of Compound 1.

Element comparison example One

An organic electroluminescent device of Device Comparative Example 1 was manufactured in the same manner as in Device Example 1, except that (4,4-N,N-dicarbazole)biphenyl (CBP) was used as a light emitting material instead of Compound 1.

Hereinafter, the results of comparing the characteristics of the organic electroluminescent devices manufactured according to Device Examples 1 to 18 and Device Comparative Example 1 are shown in Table 1 below.

division Emitting material Driving voltage (V)
(at 1000cd/m ² ) Luminous efficiency
(cd/A) Color coordinates
(CIE(x, y)) Device Example 1 Compound 1 5.1 17.6 (0.62 ,0.35) Device Example 2 Compound 2 6.1 18.1 (0.61 ,0.36) Device Example 3 Compound 3 5.3 15.7 (0.63 ,0.34) Device Example 4 Compound 4 4.5 14.8 (0.62 ,0.35) Device Example 5 Compound 5 5.5 16.2 (0.61 ,0.33) Device Example 6 Compound 6 5.1 19.5 (0.60 ,0.33) Device Example 7 Compound 7 5.9 18.8 (0.62 ,0.35) Device Example 8 Compound 8 5.6 18.1 (0.61 ,0.34) Device Example 9 Compound 9 4.1 17.6 (0.62 ,0.34) Device Example 10 Compound 10 5.8 18.9 (0.63 ,0.36) Device Example 11 Compound 11 5.5 16.4 (0.61 ,0.33) Device Example 12 Compound 12 5.9 16.5 (0.61 ,0.33) Device Example 13 Compound 13 5.4 16.8 (0.62 ,0.32) Device Example 14 Compound 14 4.6 18.5 (0.63 ,0.32) Device Example 15 Compound 15 4.9 17.1 (0.61 ,0.34) Device Example 16 Compound 16 4.1 19.1 (0.60 ,0.35) Device Example 17 Compound 17 5.9 16.1 (0.61 ,0.34) Device Example 18 Compound 18 5.8 19.1 (0.60 ,0.35) Device Comparative Example 1 C B P 6.8 12.3 (0.61 ,0.35)

Measurement of driving voltage and luminous efficiency

After fixing the above-made organic light-emitting device (substrate size: 25*25mm ² / deposition area: 2*2mm ² ) to the IVL measurement set (CS-2000+jig+IVL program), evaporate while increasing the current by 1mA/m ² Measure the luminance (cd/m ² ), driving voltage (V), current density (A/m ² ), and luminous efficiency (cd/A) of the surface to determine the driving voltage and luminous efficiency when the luminance is 1000 cd/m ² . It is shown in Table 1 above.

According to Table 1, it was found that when the compound for an organic light emitting diode according to the present invention was used as a red light emitting material for an organic light emitting device, the driving voltage was considerably lower than when using the conventional CBP as a light emitting material, and the luminous efficiency was significantly improved. I can. Therefore, it can be seen that it can be usefully used for display devices, display devices, and lighting.

Claims (7)

A compound for an organic electroluminescent device represented by the following structural formula 1.
[Structural Formula 1]

In the above structural formula 1,
L is a valent bond, a substituted or unsubstituted C6 to C30 arylene group, or a substituted or unsubstituted C1 to C30 heteroarylene group,
Ar ¹ is a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C12 to C30 arylaryl group, a substituted or unsubstituted C7 to C30 heteroaryl aryl group, a substituted or unsubstituted C1 to C30 heteroaryl group , A substituted or unsubstituted C7 to C30 arylheteroaryl group, or a substituted or unsubstituted C2 to C30 heteroarylheteroaryl group,
R ¹ and R ² may be the same as or different from each other, and R ¹ and R ² are each independently a hydrogen atom, a deuterium atom, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted Or an unsubstituted C1 to C30 heterocycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C1 to C30 heteroaryl group, or at least any one of R ¹ and R ² is any one substituted with a combination of carbon atoms (C _b 1) neighboring carbon atom (C _b 2) and added to the combined carbon atom (C _b 1) and the neighboring carbon atom (C _b 2) coupled to the or Unsubstituted fused C3 to C30 cycloalkyl group, substituted or unsubstituted fused C1 to C30 heterocycloalkyl group, substituted or unsubstituted fused C6 to C30 aryl group, or substituted or unsubstituted fused C1 to C30 hetero Forming an aryl group,
R ³ to R ⁶ may be the same as or different from each other, and R ³ to R ⁶ are each independently a hydrogen atom, a deuterium atom, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted Or an unsubstituted C1 to C30 heterocycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C1 to C30 heteroaryl group. A compound for an organic electroluminescent device, which is any one selected from compounds 1 to 238 represented by the following formula.

An organic electroluminescent device comprising the compound for an organic electroluminescent device according to any one of claims 1 and 2. In the organic electroluminescent device comprising a first electrode, a second electrode, and a single or a plurality of organic material layers between the first electrode and the second electrode,
The organic electroluminescent device comprising the compound for an organic electroluminescent device according to any one of claims 1 and 2, wherein at least one organic material layer selected from the single or plurality of organic material layers. The method of claim 4,
The organic electroluminescent device, characterized in that the single or plurality of organic material layers include an emission layer. The method of claim 4,
The plurality of organic material layers include an emission layer, and the plurality of organic material layers further comprise at least one selected from an electron injection layer, an electron transport layer, a hole blocking layer, an electron blocking layer, a hole transport layer, and a hole injection layer. Organic electroluminescent device. The method of claim 5,
The organic electroluminescent device, wherein the emission layer includes a host and a dopant.

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