KR20160041223A - 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 comprising the same. Accordingly, provided is a compound for an organic electroluminescent device, which can be used as a host and a hole transport material having excellent electrical stability and hole transporting capability and improving light emitting efficiency of a phosphorescent material by having a high triplet energy. An organic electroluminescent device is also provided. The compound for an organic electroluminescent device is represented by structural formula 1.

Description

TECHNICAL FIELD [0001] The present invention relates to a compound for a novel organic electroluminescent device and an organic electroluminescent device including the same. BACKGROUND OF THE INVENTION [0002]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a compound for an organic electroluminescent device and an organic electroluminescent device including the same, and more particularly to a compound for an organic electroluminescent device capable of improving the luminous efficiency of the organic electroluminescent device, Device.

As the move to the information society accelerates, the proportion of flat panel displays is gradually increasing. LCD (liquid crystal display) is the most widely used method, but it is a method to make a screen by applying voltage to liquid crystal and passing light from backlight through color filter to obtain three primary colors. Organic light emitting diodes (OLED) As a self-luminous element, it has excellent viewing angle and contrast ratio, is lightweight and thin, can be used for a substrate having a bending property, and is capable of transparent and flexible display, and has attracted attention as a next generation display element.

Organic EL is a phenomenon in which excitons are formed by recombination of electrons and holes injected through a cathode and an anode into an organic thin film, and light of a specific wavelength is generated from the excitons formed. In 1963, Pope et al. Reported that an anthracene single crystal (CW Tang, SA Vanslyke, Applied Physics Letters, Vol. 51, No. 913p, 1987) by Eastman Kodak Co., Ltd. (CW Tang) et al.

Organic materials used in organic electroluminescent devices are classified into polymer and small molecule, and small molecules can be divided into pure organic material and metal complex which forms metal and chelate.

Polymers can combine diverse functional units into polymer chains to produce multifunctional materials. However, it is difficult to purify compounds or to form devices, while low-molecular materials can synthesize materials of various properties. There is a limit to the synthesis of the substances.

The organic electroluminescent device can be formed in a laminated structure. In general, the device structure is formed by forming a hole injecting layer, a hole transporting layer, a light emitting layer, an electron transporting layer, and an electron injecting layer between an anode and a cathode to form a light emitting layer The exciton formation can be facilitated and the emission efficiency can be enhanced.

The luminescent material can be roughly divided into a host material and a luminescent material (dopant) material, and the luminescent material is distinguished by fluorescence and phosphorescence depending on the luminescence mechanism.

The excited state of the electrons in the compound is 1: 3 ratio of singlet to triplet, and triplet state is generated about 3 times more. Thus, the internal quantum efficiency of phosphorescence falling from the triplet state to the base state is 75% while the internal quantum efficiency of the fluorescence falling from the singlet state to the ground state is only 25%. In addition, the theoretical limit of internal quantum efficiency reaches 100% when the interplanar transition from singlet state to triplet state occurs. A light emitting material that improves the light emitting efficiency by using this point is a phosphorescent material.

Due to the nature of organic materials, it is difficult to emit phosphorescence. As a phosphorescent material, transition metal (iridium) is utilized as an organometallic compound, and an organic material is used as a host material to assist it. The material that assists the phosphorescent material (host) should have a wide bandgap and a high triplet state energy. A phosphorescent material having excellent current efficiency and luminous efficiency is received in the spotlight, but the electron transporting ability, the hole transporting ability, the host material which is thermally and electrically stable, and the organic electroluminescent device It is necessary to develop a compound for use.

The present invention relates to a compound capable of being used for a light emitting layer as a host which is excellent in electrical stability, electron and hole transporting ability, and has high triplet state energy and can improve the luminous efficiency of a phosphorescent light emitting material, A light emitting element can be provided.

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

However, the problems to be solved by the present invention are not limited to the above-mentioned problems, and other problems not mentioned can 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 electroluminescence device represented by the following structural formula 1 may be provided.

[Structural formula 1]

In the above formula 1,

L is a valence-bonded, 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 aryl aryl 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 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, 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 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 A substituted or unsubstituted fused C3 to C30 cycloalkyl group, a substituted or unsubstituted fused C1 to C30 heterocycloalkyl group, a substituted or unsubstituted fused C6 to C30 aryl group, or a substituted or unsubstituted fused C1 to C30 hetero To form an aryl group,

R ³ to R ⁶ may be the same or different from each other and each of R ³ to R ⁶ independently represents a hydrogen atom, a deuterium atom, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, 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 the substituent include a methyl group, an ethyl group, a propyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an isoamyl group, a hexyl group, a heptyl group, A halogen atom, a hydroxyl group, a nitro group, a cyano group, a trifluoromethyl group, a silyl group (in this case, an "alkylsilyl group"), a hydroxyl group ), Amino group (-NH2, -NH (R), -N (R ') (R "), R' and R" are independently an alkyl group having 1 to 20 carbon atoms, 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 alkoxy group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aryloxy group having 1 to 20 carbon atoms, A heteroalkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, An arylalkyl group having 6 to 60 carbon atoms, a heteroaryl group having 4 to 40 carbon atoms, or a heteroarylalkyl group having 4 to 40 carbon atoms.

Specific examples of the cycloalkyl group as a substituent may include 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 the substituent may be methoxy, ethoxy, propoxy, isobutyloxy, sec-butyloxy, pentyloxy, isoamyloxy or hexyloxy.

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

Examples of the C6 to C30 aryl group include a phenyl group, a biphenyl group, a terphenyl group, a naphthalenyl group, an anthracenyl group, a phenanthrenyl group, a fluorenyl group, a spirobifluorenyl group, a chrysene group, a tetracene group, a pentacene group, 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, A benzothiazolyl group, a benzothiazolyl group, a benzimidazolyl group, an indazolyl group, a phenothiazinyl group, a phenazinyl group, a carbazolyl group, a dibenzothiophenyl group, an imidazolyl group, a triazolyl group, A thiazolyl group, a thiazolyl group, a benzothiazolyl group, a pyrazinyl group, a pyridazinyl group, a purinyl group, a quinolinyl group, an isoquinolinyl group, a phthalazinyl group, a naphthyridinyl group, a quinoxalinyl group, 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] A pyridinyl group, a benzimidazolyl group, an indazolyl group, a phenothiazinyl group, Group, may be a carbazolyl group, or dibenzo-thio group.

According to another aspect of the present invention, there is provided a compound for an organic electroluminescence device, which is selected from among compounds 1 to 238 represented by the following formulas.

According to another aspect of the present invention, there is provided an organic electroluminescent device comprising the compound for an organic electroluminescent device.

According to another aspect of the present invention, there is provided an organic electroluminescent device comprising a first electrode, a second electrode, and a single or a plurality of organic layers between the first electrode and the second electrode, The organic electroluminescent device may further include at least one organic compound layer including the organic electroluminescent compound.

The singular or plural organic layers may include a light emitting layer.

The plurality of organic layers may include a light emitting layer, and the plurality of organic layers may further include at least one selected from an electron injecting layer, an electron transporting layer, a hole blocking layer, an electron blocking layer, a hole transporting layer, and a hole injecting layer.

The light emitting layer may include a host and a dopant.

The present invention relates to a compound for an organic electroluminescent device which can be used for a light emitting layer as a host which is excellent in electrical stability and electron and hole transporting ability and has high triplet state energy and can improve the luminous efficiency of a phosphorescent light emitting material, An organic electroluminescent device can be provided.

In addition, the present invention can provide an organic electroluminescent compound which can be used for an electron transporting material and a hole transporting material of an organic electroluminescent device, and an organic electroluminescent device including the same.

1 is a cross-sectional view illustrating an organic electroluminescent device according to an embodiment of the present invention.
2 is a cross-sectional view illustrating an organic electroluminescent device according to another embodiment of the present invention.

The invention is capable of various modifications and may have various embodiments, and particular embodiments are exemplified and will be described in detail in the detailed description. It is to be understood, however, that the invention is not to be limited to the specific embodiments, but includes all modifications, equivalents, and alternatives falling within the spirit and scope of the invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in detail with reference to the accompanying drawings.

Furthermore, terms including an ordinal number such as first, second, etc. to be used below can be used to describe various elements, but the constituent elements are not limited by the terms. The terms are used only for the purpose of distinguishing one component from another. For example, without departing from the scope of the present invention, the first component may be referred to as a second component, and similarly, the second component may also be referred to as a first component.

Also, when an element is referred to as being "formed" or "laminated" on another element, it may be directly attached or laminated to the front surface or one surface of the other element, It will be appreciated that other components may be present in the < / RTI >

The singular expressions include plural expressions unless the context clearly dictates otherwise. In the present application, the terms "comprises" or "having" and the like are used to specify that there is a feature, a number, a step, an operation, an element, a component or a combination thereof described in the specification, But do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, or combinations thereof.

As used herein, "atomic bond" means a single bond, a double bond or a triple bond, unless otherwise defined.

As used herein, unless otherwise defined, "substituent" means that at least one hydrogen in the substituent or the compound for organic electroluminescence device is at least one selected from the group consisting of deuterium, a halogen group, a hydroxyl group, an amino group, a C1 to C30 amine group, a nitro group, , A C1 to C30 alkyl group, a C1 to C30 alkylsilyl group, a C6 to C30 arylsilyl group, a C7 to C30 alkylarylsilyl group, a C7 to C30 arylalkylsilyl group, a C3 to C30 cycloalkyl group, a C1 to C30 heterocycloalkyl group, To C30 aryl group, a C1 to C30 heteroaryl group, a C1 to C20 alkoxy group, a C1 to C10 trifluoroalkyl group, or a cyano group.

A substituted or unsubstituted C1-C30 alkyl group, a C1-C30 alkylsilyl group, a C3-C30 cycloalkyl group, a C6-C30 aryl group, a C1-C20 alkoxy group, Two adjacent substituents of a C1 to C10 trifluoroalkyl group or cyano group may be fused to form a fused ring.

As used herein, unless otherwise defined, it is meant that one functional group contains 1 to 4 heteroatoms selected from the group consisting of N, O, S, and P, and the remainder is carbon.

In the present specification, the term "combination thereof" means that two or more substituents are bonded to each other via a linking group or two or more substituents are condensed and bonded.

As used herein, "hydrogen" means monohydrogen, double hydrogen, or tritium, unless otherwise defined.

As used herein, unless otherwise defined, the term "alkyl group" means an aliphatic hydrocarbon group.

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

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

"Alkynylene group" means a functional group in which at least two carbon atoms are composed of at least one carbon-carbon double bond, and "alkynylene group" means that at least two carbon atoms have at least one carbon- Quot; means a functional group formed by bonding. The alkyl group, 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, the C1 to C4 alkyl groups may have 1 to 4 carbon atoms in the alkyl chain, i.e., the alkyl chain may be optionally substituted with one or more substituents selected from the group consisting of methyl, ethyl, propyl, iso-propyl, n-butyl, Indicating that they are selected from the group.

Specific examples of the alkyl group include a methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, hexyl group, ethenyl group, Butyl group, cyclopentyl group, cyclohexyl group, and the like.

The "amine group" includes an arylamine group, an alkylamine group, an arylalkylamine group, or an alkylarylamine group.

"Cycloalkyl group" includes monocyclic or fused-ring polycyclic (i. E., Rings that divide adjacent pairs of carbon atoms) functional groups.

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

"An aromatic group" means a functional group in which all elements of a functional group in the form of a ring have a p-orbital, and these p-orbital forms a conjugation. Specific examples thereof include an aryl group and a heteroaryl group.

An "aryl group" includes a monocyclic or fused ring polycyclic (i. E., A ring that divides adjacent pairs of carbon atoms) functional groups.

"Heteroaryl group" means that the aryl group contains 1 to 4 hetero atoms 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 of the fused rings may contain from 1 to 4 heteroatoms.

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

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

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

The term "alkylaryl group " means an alkyl substituted aryl radical and is included in the aryl group.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT Hereinafter, embodiments of the present invention will be described with reference to the accompanying drawings. Referring to the accompanying drawings, the same or corresponding components are denoted by the same reference numerals, .

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

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

Here, the single or plural organic layers 130 may include a light emitting layer 134.

The plurality of organic layers 130 may include a light emitting layer 134 and the plurality of organic layers may include an electron injection layer 131, an electron transport layer 132, a hole blocking layer 133, an electron blocking layer 135, Transporting layer 136 and hole-injecting layer 137 may be further included.

The light emitting 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. Specific examples thereof include glass, transparent plastic film, and the like.

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

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 less than 4 eV may be used. Specifically, Na, Na-K alloy, calcium, magnesium, lithium, lithium alloy, indium, aluminum, magnesium alloy and aluminum alloy can be mentioned. In addition, aluminum / AlO ₂ , aluminum / lithium, magnesium / silver or magnesium / indium may 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, at least one electrode preferably has a light transmittance of 10% or more. The sheet resistance of the electrode is preferably several hundreds? / Mm or less. The thickness of the electrode is 10 nm to 1 탆, more preferably 10 to 400 nm. Such an electrode can be manufactured by forming the electrode material into a thin film by a vapor deposition method such as chemical vapor deposition (CVD) or physical vapor deposition (PVD) or a sputtering method.

When the compound for an organic electroluminescence device of the present invention is used for the purpose of the present invention, the known hole transporting material, hole injecting material, light emitting layer material, host material of the light emitting layer, electron transporting material, Or may be used in combination with the organic electroluminescent device compound of the present invention selectively.

N-dicarbazolyl-3,5-benzene (mCP), poly (3,4-ethylenedioxythiophene): polystyrenesulfonate (PEDOT: PSS), N, N'- (NPD), N, N'-diphenyl-N, N'-di (3-methylphenyl) -4,4'- diaminobiphenyl (TPD) N, N'N'-tetra-p-tolyl-4,4'-diaminobiphenyl, N, N'N'N'N'- Porphyrin compound derivatives such as tetraphenyl-4,4'-diaminobiphenyl, copper (II) 1,10,15,20-tetraphenyl-21H, 23H-porphyrin and the like, aromatic tertiary (4-di-p-tolylaminophenyl) cyclohexane, N, N, N-tri (3-methylphenyl) -N-phenylamino] triphenylamine, carbazole derivatives such as N-phenylcarbazole and polyvinylcarbazole, phthalocyanine derivatives such as nonmetal phthalocyanine and copper phthalocyanine, An aminostilbene derivative, a derivative of an aromatic tertiary amine and a styrylamine compound, and polysilane.

The diphenylphosphine oxide-4- (triphenylsilyl) phenyl (TSPO1), Alq 3, 2,5- diaryl silole derivatives (PyPySPyPy), perfluoro rineyi suited compound (PF-6P), Octasubstituted cyclooctatetraene compound (COTs) as an electron transport material .

In the organic electroluminescent device of the present invention, the electron injecting layer, the electron transporting layer, the hole transporting layer, and the hole injecting layer may be formed of a single layer containing at least one kind of the above-mentioned compounds, And the like.

Examples of the light emitting material include a phosphorescent fluorescent material, a fluorescent whitening agent, a laser dye, an organic scintillator, and a reagent for fluorescence analysis. Specifically, a carbazole compound, a phosphine oxide compound, a carbazole-based phosphine oxide compound, 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 quaterphenyl, 1,4- Bis (4-methylstyryl) benzene, 1,4-bis (4-methyl- Bis (5-t-butyl-2-benzoxazolyl) thiophene, 1,4-diphenyl-1,3-butadiene, 1,6- Liquid scintillation scintillators such as 3,5-hexatriene and 1,1,4,4-tetraphenyl-1,3-butadiene, metal complexes of oxine derivatives, coumarin dyes, dicyanomethylenepyran dyes, dicyanomethylene Cyopyran pigment, polymethine pigment, oxobenzanthracene There may be mentioned a colorant, a xanthene colorant, a carbostyryl colorant, a perylene colorant, an oxazine compound, a stilbene derivative, a spiro compound, and an oxadiazole compound.

Each layer constituting the organic EL device of the present invention can be formed into a thin film through a known method such as vacuum deposition, spin coating or casting, or can be manufactured using a material used in each layer. The thickness of each of these layers is not particularly limited and may be appropriately selected according to the characteristics of the material, but may be determined usually in the range of 2 nm to 5,000 nm.

The compound for an organic electroluminescence device according to the present invention can be formed by a vacuum deposition method, so that it is advantageous that a thin film forming process is simple and a homogeneous thin film having almost no pinhole can be easily obtained.

[Example]

Hereinafter, the compound for an organic electroluminescent device according to the present invention and the method for manufacturing the organic electroluminescent device including the same will be described in more detail with reference to the following examples. However, this is for the purpose of illustration only and is not intended to limit the scope of the invention.

Example  1: Synthesis of compound 1

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

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), DMF (100 ml) was added, and the mixture was reacted at 120 DEG C for 4 hours with stirring. After completion of the reaction, the reaction mixture was cooled, separated into H ₂ O: MC, and subjected to column purification (n-hexane: MC) to obtain 1.1 g (yield: 62%) of Intermediate 1-1.

LC / MS: m / z = 180 [(M + 1) ^< ^{+ &}

(2) Manufacturing example  1-2: Intermediate 1-2 Synthesis

100 ml of methyl chloride was added to trifluoromethane sulfonic anhydride (3.1 g, 0.011 mol), pyridine (1.0 g, 0.013 mol) and potassium carbonate (4.1 g, 0.030 mol) Lt; / RTI > After completion of the reaction, the reaction mixture was cooled, separated into H ₂ O: MC and subjected to column purification (n-hexane: MC) to obtain 2.2 g (yield 70%) of Intermediate 1-2.

LC / MS: m / z = 312 [(M + 1) ^< ^{+ &}

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

To the intermediate 1-2 (3.1 g, 0.008 mol) was added bis (pinacolato) dibron (2.5 g, 0.010 mol) PdCl2 (dppf) (0.3 g, 0.0004 mol) and potassium acetate (2.2 g, 0.016 mol) -dioxane (80 ml) were added and the mixture was stirred at 95? for 24 hours. After completion of the reaction, the reaction mixture was cooled, separated into H ₂ O: MC and subjected to column purification (n-hexane: MC) to obtain 2.1 g (yield: 71%) of Intermediate 1-3.

LC / MS: m / z = 290 [(M + 1) ^< ^{+ &}

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

Pd (PPh3) 4 (0.3g, 0.0003mol) and potassium carbonate (4.1g, 0.030mol) were added to a solution of phenyl boronic acid (1.4g, 0.012mol), 3-bromonaphthalen-1-ol And the mixture was reacted at 65 ° C for 18 hours with stirring. After completion of the reaction, the reaction mixture was cooled, separated into H ₂ O: MC and column-purified (n-hexane: MC) to obtain 1.6 g (yield: 73%) of Intermediate 1-4.

LC / MS: m / z = 220 [(M + 1) ^< ^{+ &}

(5) Manufacturing example  1-5: Intermediate 1-5 Synthesis

(Yield: 73%) was synthesized in the same manner as in Production Example 1-2, except that Intermediate 1-4 (2.2 g, 0.010 mol) was used instead of Intermediate 1-1 .

LC / MS: m / z = 220 [(M + 1) ^< ^{+ &}

(6) Manufacturing example  1-6: Intermediate 1-6 Synthesis

Intermediate 1-5 (2.8 g, 0.008 mol) was added to Intermediate 1-3 (2.9 g, 0.010 mol), and 1.9 g of Intermediate 1-6 (yield 66% ).

LC / MS: m / z = 366 [(M + 1) ^< ^{+ &}

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

1,4-dibromobenzene (2.4 g, 0.010 mol) was added to 1H-indol-3-ylboronic acid (1.3 g, 0.008 mol) g (yield: 73%).

LC / MS: m / z = 272 [(M + 1) ^< ^{+ &}

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

100 ml of 1,2-dichlorobenzene was added to triphenylphosphine (4.5 g, 0.017 mol) in 2-bromo-2'-nitrobiphenyl (5.0 g, 0.017 mol) and reacted at 180 ° C for 24 hours with stirring. After completion of the reaction, the reaction mixture was cooled, separated into H ₂ O: MC and subjected to 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: Intermediate 1-9 Synthesis

2.3 g (yield: 77%) of <Intermediate 1-9> was synthesized in the same manner as in Production Example 1-1 except that bromobenzene (1.6 g, 0.010 mol) was added to Intermediate 1-8 (2.1 g, 0.010 mol) .

LC / MS: m / z = 322 [(M + 1) ^&lt; ^{+ &}

(10) Manufacturing example  1-10: Intermediate 1-10 Synthesis

Intermediate 1-9 (3.2 g, 0.010 mol) bis (pinacolato) dibron (3.0 g, 0.012 mol) was added and 2.7 g (yield 73%) of Intermediate 1-10 was obtained in the same manner as in Preparation Example 1-3 Respectively.

LC / MS: m / z = 369 [(M + 1) ^&lt; ^{+ &}

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

Intermediate 1-10 (4.4g, 0.012mol) was added to Intermediate 1-7 (2.7g, 0.010mol), and 3.1g (yield 72%) of Intermediate 1-11 was synthesized in the same manner as in Preparation Example 1-4, ).

LC / MS: m / z = 434 [(M + 1) ^&lt; ^{+ &}

(12) Manufacturing example  1-12: Synthesis of compound 1

Intermediate 1-11 (4.3 g, 0.010 mol) was added to Intermediate 1-6 (3.6 g, 0.010 mol) and synthesized according to the same method as in Production Example 1- to obtain 5.5 g (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 (7.55 / 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) ^&lt; ^{+ &}

Example  2: Synthesis of compound 2

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

After dissolving in 30 ml of anhydrous THF to intermediate 1-8 (3.0 g, 0.012 mol), 5.9 ml of n-BuLi (2.5 M) was slowly added dropwise at -78 ° C. After maintaining for 1 hour, triisopropyl borate (3.4 g, 0.018 mol) was added, and the mixture was stirred at room temperature for 24 hours. After completion of the reaction, 1N HCl was added and the mixture was stirred for 1 hour. Then, the mixture was separated into EA: H ₂ O and recrystallized with n-hexane to obtain 1.8 g (yield 70%) of Intermediate 2-1.

LC / MS: m / z = 211 [(M + 1) ^&lt; ^{+ &}

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

2-bromo-9,9-dimethyl-9H-fluorene (2.7 g, 0.010 mol) was added to Intermediate 2-1 (2.1 g, 0.010 mol) -2> 2.9 g (yield: 72%).

LC / MS: m / z = 403 [(M + 1) ^&lt; ^{+ &}

(3) Manufacturing example  2-3: Intermediate 2-3 Synthesis

Intermediate 2-2 (4.0 g, 0.010 mol) was added to Intermediate 1-7 (2.7 g, 0.008 mol), and 2.9 g of Intermediate 2-3 (yield 65% ).

LC / MS: m / z = 550 [(M + 1) ^&lt; ^{+ &}

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

6.8 g (yield: 77%) of Compound 2 was synthesized in the same manner as in Production Example 1-1, except that Intermediate Compound 2-3 (5.5 g, 0.010 mol) was added to Intermediate 1-6 (3.7 g, 0.010 mol) &Lt; / RTI >

_{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 7.51 / 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) ^&lt; ^{+ &}

Example  3: Synthesis of compound 3

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

Bromobenzene (1.6 g, 0.010 mol) was added to 4-bromo-1H-indole (2.0 g, 0.010 mol) and synthesized in the same manner as in Production Example 1-1 to give 2.1 g of Intermediate 3-1 %).

LC / MS: m / z = 272 [(M + 1) ^&lt; ^{+ &}

(2) Manufacturing example  3-2: Intermediate 3-2 Synthesis

Intermediate 3-1 (2.7 g, 0.010 mol) bis (pinacolato) dibron (3.0 g, 0.012 mol) was added and 2.3 g (yield 73%) of Intermediate 3-2 was obtained in the same manner as in Production Example 1-3 Respectively.

LC / MS: m / z = 319 [(M + 1) ^&lt; ^{+ &}

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

Intermediate 1-7 (2.2 g, 0.008 mol) was added to Intermediate 3-2 (3.2 g, 0.010 mol), and 2.8 g of Intermediate 3-3 (yield: 72% ).

LC / MS: m / z = 384 [(M + 1) ^&lt; ^{+ &}

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

5.5 g (yield: 77%) of <Compound 3> was synthesized in the same manner as in Production Example 1-1 except that Intermediate 3-3 (3.8 g, 0.010 mol) was added to Intermediate 1-6 (3.7 g, 0.010 mol) &Lt; / RTI &gt;

_{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 7.80 / 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) ^&lt; ^{+ &}

Example  4: Synthesis of compound 4

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

Biphenyl-4-ylboronic acid (2.4 g, 0.012 mol) was added to 4-bromonaphthalen-2-ol (2.2 g, 0.010 mol) g (yield: 72%).

LC / MS: m / z = 296 [(M + 1) ^&lt; ^{+ &}

(2) Manufacturing example  4-2: Intermediate 4-2 Synthesis

3.0 g (yield 70%) of Intermediate 4-2 was synthesized in the same manner as in Preparation Example 1-2, except that Intermediate 4-1 (3.0 g, 0.010 mol) was used instead of Intermediate 1-1 .

LC / MS: m / z = 428 [(M + 1) ^&lt; ^{+ &}

(3) Manufacturing example  4-3: Intermediate 4-3 Synthesis

Intermediate 4-2 (3.4 g, 0.008 mol) was added to Intermediate 1-3 (2.9 g, 0.010 mol), and 3.2 g of Intermediate 4-3 (yield: 72% ).

LC / MS: m / z = 442 [(M + 1) ^&lt; ^{+ &}

(4) Manufacturing example  4-4: Compound 4 Synthesis

Intermediate 3-3 (3.8 g, 0.010 mol) was added to Intermediate 4-3 (4.4 g, 0.010 mol), and 6.1 g (yield 77%) of Compound 4 was synthesized in the same manner as in Production Example 1-1, &Lt; / RTI >

_{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 M, 7.52 / d, 7.51 / m, 7.50 / d, 7.60 / d, 7.45 / m, 7.41 / m, 7.39 / , 7.42 / m) 8H (7.25 / d)

LC / MS: m / z = 792 [(M + 1) ^&lt; ^{+ &}

Example  5: Synthesis of compound 5

(One) Manufacturing example  5-1: Intermediate 5-1 Synthesis

Synthesis was conducted in the same manner as in Production Example 1-1, except that 9H-carbazole (1.7 g, 0.010 mol) was added to 3-bromo-9H-carbazole (2.4 g, 0.010 mol) Yield: 84%).

LC / MS: m / z = 332 [(M + 1) ^&lt; ^{+ &}

(2) Manufacturing example  5-2: Intermediate 5-2 Synthesis

Intermediate 1-7 (2.7 g, 0.010 mol) was added to Intermediate 5-1 (3.3 g, 0.010 mol) and synthesized in the same manner as in Production Example 1-1 to give 4.0 g (Intermediate 5-2) %).

LC / MS: m / z = 523 [(M + 1) ^&lt; ^{+ &}

(3) Manufacturing example  5-3: Compound 5 Synthesis

(5.2 g, 0.010 mol) was added to Intermediate 1-6 (3.6 g, 0.010 mol), and 6.2 g (yield 73%) of Compound 5 was synthesized in the same manner as in Production Example 1-1, &Lt; / RTI >

_{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 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) ^&lt; ^{+ &}

Example  6: Synthesis of Compound 6

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

9a-boronic acid (2.7g, 0.012mol) was added to Intermediate 1-7 (2.7g, 0.008mol), and 2.7g of Intermediate 6-1 (yield: 72%).

LC / MS: m / z = 369 [(M + 1) ^&lt; ^{+ &}

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

Intermediate 6-1 (3.7 g, 0.010 mol) was added to Intermediate 1-6 (3.7 g, 0.010 mol), and 5.5 g (yield 79%) of Compound 6 was synthesized in the same manner as in Production Example 1-1, &Lt; / RTI >

_{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 M, 7.46 / s) 2H (8.93 / d, 8.12 / d, 7.88 / m, 7.82 / m, 7.80 / d, 7.79 / d, 7.55 / / d)

LC / MS: m / z = 700 [(M + 1) ^&lt; ^{+ &}

Example  7: Synthesis of Compound 7

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

4-bromo-2,6-diphenylpyridine (3.1 g, 0.010 mol) was added to 1H-indol-3-ylboronic acid (1.9 g, 0.012 mol) -1> 2.5 g (yield: 72%).

LC / MS: m / z = 346 [(M + 1) ^&lt; ^{+ &}

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

Intermediate 7-1 (3.5 g, 0.010 mol) was added to Intermediate 1-6 (3.7 g, 0.010 mol), and 5.2 g (yield 77%) of Compound 7 was synthesized in the same manner as in Production Example 1-1, &Lt; / RTI >

_{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, 7.50 / m, 7.51 / m, 7.47 / m) 4H (8.30 / d, 7.54 /

LC / MS: m / z = 677 [(M + 1) ^&lt; ^{+ &}

Example  8: Compound 8 Synthesis

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

9a-boronic acid (2.7g, 0.012mol) was added to 1,3-dibromobenzene (2.4g, 0.010mol), and 2.4g (0.012mol) of Intermediate 8-1 Yield: 72%).

LC / MS: m / z = 333 [(M + 1) ^&lt; ^{+ &}

(2) Manufacturing example  8-2: Intermediate 8-2 Synthesis

1H-indol-3-ylboronic acid (1.9 g, 0.012 mol) was added to Intermediate 8-1 (3.3 g, 0.010 mol) (Yield: 72%).

LC / MS: m / z = 369 [(M + 1) ^&lt; ^{+ &}

(3) Manufacturing example  8-3: Intermediate 8-3 Synthesis

Phenylboronic acid (1.4 g, 0.012 mol) was added to 6-bromonaphthalen-2-ol (2.2 g, 0.010 mol) and the compound was synthesized in the same manner as in Preparation Example 1-4 to give 1.6 g 72%).

LC / MS: m / z = 220 [(M + 1) ^&lt; ^{+ &}

(4) Manufacturing example  8-4: Intermediate 8-4 Synthesis

Intermediate 8-3 (2.2 g, 0.010 mol) was added thereto, and 2.4 g (yield 67%) of Intermediate 8-4 was obtained by the same method as in Production Example 1-5.

LC / MS: m / z = 352 [(M + 1) ^&lt; ^{+ &}

(5) Manufacturing example  8-5: Intermediate 8-5 Synthesis

(2.7 g, 0.012 mol) was added to Intermediate 8-4 (3.5 g, 0.010 mol), and 2.6 g (yield 72%) of Intermediate 8-5 was synthesized in the same manner as in Preparation Example 1-4, ).

LC / MS: m / z = 366 [(M + 1) ^&lt; ^{+ &}

(6) Manufacturing example  8-6: Synthesis of compound 8

Intermediate 8-2 (3.7 g, 0.010 mol) was added to Intermediate 8-5 (3.6 g, 0.010 mol) and the compound 8 was synthesized in the same manner as in Production Example 1-1 to obtain 5.4 g (yield: 77% &Lt; / RTI >

_{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) ^&lt; ^{+ &}

Example  9: Synthesis of Compound 9

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

Dibromochloromethane (2.1 g, 0.010 mol) was added to 1-amino-2-naphthamide (1.9 g, 0.010 mol), and 1.2 g (yield: 53%) of Intermediate 9-1 %).

LC / MS: m / z = 230 [(M + 1) ^&lt; ^{+ &}

(2) Manufacturing example  9-2: Intermediate 9-2 Synthesis

Intermediate 9-1 (2.3 g, 0.010 mol) was used instead of Intermediate 1-1, and 2.6 g (yield: 73%) of Intermediate 9-2 was synthesized in the same manner as in Preparation Example 1-2 .

LC / MS: m / z = 362 [(M + 1) ^&lt; ^{+ &}

(3) Manufacturing example  9-3: Intermediate 9-3 Synthesis

Intermediate 9-2 (3.6 g, 0.010 mol) bis (pinacolato) dibron (3.0 g, 0.012 mol) was added and 2.4 g (yield 70%) of Intermediate 9-3 was obtained in the same manner as in Preparation Example 1-3 Respectively.

LC / MS: m / z = 340 [(M + 1) ^&lt; ^{+ &}

(4) Manufacturing example  9-4: Intermediate 9-4 Synthesis

Intermediate 1-5 (3.5 g, 0.010 mol) was added to Intermediate 9-3 (4.1 g, 0.012 mol), and 2.8 g of Intermediate 9-4 (yield 67% ).

LC / MS: m / z = 416 [(M + 1) ^&lt; ^{+ &}

(5) Manufacturing example  9-5: Compound 9 Synthesis

6.3 g (yield: 77%) of Compound 9 was synthesized in the same manner as in Production Example 1-1 except that Intermediate 1-11 (4.3 g, 0.010 mol) was added to Intermediate 9-4 (4.2 g, 0.010 mol) &Lt; / RTI >

_{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 7.55 / m, 7.45 / m, 7.36 / s, 7.33 / m, 7.25 / , 7.51 / m, 7.50 / d, 7.42 / m) 3H (7.79 / d) 4H (7.25 / d)

LC / MS: m / z = 815 [(M + 1) ^&lt; ^{+ &}

Example  10: Compound 10 Synthesis

(One) Production Example 10 -1: Intermediate 10-1 Synthesis

Intermediate 1-8 (2.4g, 0.010mol) 3- (4-bromophenyl) pyridine (2.3g, 0.010mol) was added thereto and synthesized in the same manner as in Production Example 1-1 to give 3.1g (Yield: 77%).

LC / MS: m / z = 400 [(M + 1) ^&lt; ^{+ &}

(2) Manufacturing example  10-2: Intermediate 10-2 Synthesis

Intermediate 10-1 (4.0 g, 0.010 mol) bis (pinacolato) dibron (3.0 g, 0.012 mol) was added and 3.3 g (yield: 73%) of Intermediate 10-2 was obtained in the same manner as in Preparation Example 1-3 Respectively.

LC / MS: m / z = 446 [(M + 1) ^&lt; ^{+ &}

(3) Manufacturing example  10-3: Intermediate 10-3 Synthesis

Intermediate 1-7 (2.2 g, 0.008 mol) was added to Intermediate 10-2 (4.5 g, 0.010 mol) and synthesized in the same manner as in Production Example 1- (4) 72%).

LC / MS: m / z = 511 [(M + 1) ^&lt; ^{+ &}

(4) Manufacturing example  10-4: Compound 10 Synthesis

Intermediate 10-3 (3.7 g, 0.010 mol) was added to Intermediate 9-4 (4.2 g, 0.010 mol), and 6.6 g (yield 74%) of Compound 10 was synthesized in the same manner as in Production Example 1-1, &Lt; / RTI >

_{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 D, 7.79 / d, 7.75 / d, 7.59 / d, 7.43 / m, 7.41 / m, 7.36 / s, 7.33 / m, 7.25 / M, 7.52 / m, 7.52 / m) 3H (7.79 / d) 4H (7.25 / d)

LC / MS: m / z = 893 [(M + 1) ^&lt; ^{+ &}

Example  11: Compound 11 Synthesis

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

Phenylboronic acid (1.4 g, 0.012 mol) was added to 3-bromonaphthalen-1-ol (2.2 g, 0.010 mol) and the compound was synthesized in the same manner as in Preparation Example 1-4 to give 1.6 g 72%).

LC / MS: m / z = 220 [(M + 1) ^&lt; ^{+ &}

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

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

LC / MS: m / z = 352 [(M + 1) ^&lt; ^{+ &}

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

Intermediate 11-2 (3.5 g, 0.010 mol) was added to Intermediate 9-3 (4.1 g, 0.012 mol) and synthesized in the same manner as in Preparation Example 1-4 to give 3.0 g (yield: 72% ).

LC / MS: m / z = 416 [(M + 1) ^&lt; ^{+ &}

(4) Manufacturing example  11-4: Intermediate 11-4 Synthesis

Synthesis was conducted in the same manner as in Preparation Example 1-4 except that 9-phenyl-9H-carbazol-2-ylboronic acid (3.3 g, 0.012 mol) was added to Intermediate 1-7 (2.7 g, 0.010 mol) 4> 3.0 g (yield: 68%).

LC / MS: m / z = 434 [(M + 1) ^&lt; ^{+ &}

(5) Manufacturing example  11-5: Compound 11 Synthesis

6.4 g (Yield: 79%) of Compound 11 was synthesized in the same manner as in Production Example 1-1, except that Intermediate 11-4 (4.3 g, 0.010 mol) was added to Intermediate 11-3 (4.2 g, 0.010 mol) &Lt; / RTI >

_{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 M, 7.58 / m, 7.75 / m, 7.80 / d, 7.76 / s, 7.71 / d, 7.63 / d, 7.62 / , 7.52 / d, 7.51 / m, 7.42 / m) 3H (7.50 / d) 4H (7.25 / d)

LC / MS: m / z = 815 [(M + 1) ^&lt; ^{+ &}

Example  12: Compound 12 Synthesis

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

Dibromochloromethane (2.1 g, 0.010 mol) was added to 2-amino-1-naphthamide (1.8 g, 0.010 mol) and synthesized in the same manner as in Production Example 1-1 to obtain 1.8 g of Intermediate 12-1 %).

LC / MS: m / z = 230 [(M + 1) ^&lt; ^{+ &}

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

(Yield: 73%) was synthesized in the same manner as in Production Example 1-2, except that Intermediate 12-1 (2.3 g, 0.010 mol) was used instead of Intermediate 1-1 .

LC / MS: m / z = 362 [(M + 1) ^&lt; ^{+ &}

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

Intermediate 12-2 (3.6 g, 0.010 mol) bis (pinacolato) dibron (3.0 g, 0.012 mol) was added and 2.4 g (yield 70%) of Intermediate 12-3 was obtained in the same manner as in Preparation Example 1-3 Respectively.

LC / MS: m / z = 340 [(M + 1) ^&lt; ^{+ &}

(4) Manufacturing example  12-4: Intermediate 12-4 Synthesis

Intermediate 1-5 (3.5 g, 0.010 mol) was added to Intermediate 12-3 (4.1 g, 0.012 mol) and synthesized in the same manner as in Production Example 1-4 to give 3.0 g (yield: 72% ).

LC / MS: m / z = 416 [(M + 1) ^&lt; ^{+ &}

(5) Manufacturing example  12-5: Compound 12 Synthesis

Intermediate 1-11 (4.3 g, 0.010 mol) was added to Intermediate 12-4 (4.2 g, 0.010 mol), and 7.1 g (yield 80%) of Compound 12 was synthesized in the same manner as in Production Example 1-1, &Lt; / RTI >

_{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 M, 7.50 / d, 7.42 / m, 7.41 / m, 7.45 / ) 4H (7.51 / m, 7.25 / d) 5H (7.79 / d)

LC / MS: m / z = 892 [(M + 1) ^&lt; ^{+ &}

Example  13: Compound 13 Synthesis

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

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

LC / MS: m / z = 372 [(M + 1) ^&lt; ^{+ &}

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

Intermediate 13-1 (3.7 g, 0.010 mol) bis (pinacolato) dibron (3.0 g, 0.012 mol) was added and 3.1 g (yield: 73%) of Intermediate 13-2 was obtained in the same manner as in Production Example 1-3 Respectively.

LC / MS: m / z = 419 [(M + 1) ^&lt; ^{+ &}

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

Intermediate 13-2 (5.0 g, 0.012 mol) was added to Intermediate 1-7 (2.7 g, 0.010 mol), and 3.5 g (yield: 72%) of Intermediate 13-3 was synthesized in the same manner as in Preparation Example 1-4, ).

LC / MS: m / z = 484 [(M + 1) ^&lt; ^{+ &}

(4) Manufacturing example  13-4: Compound 13 Synthesis

Intermediate 13-3 (4.8 g, 0.010 mol) was added to Intermediate 12-4 (4.2 g, 0.010 mol), and 6.7 g (yield: 77%) of Compound 13 was synthesized in the same manner as in Production Example 1-1. &Lt; / RTI >

_{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 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 / / d, 7.79 / d, 7.59 / m) 5H (7.25 / d)

LC / MS: m / z = 866 [(M + 1) ^&lt; ^{+ &}

Example  14: Compound 14 Synthesis

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

2,7-dibromo-9,9-dimethyl-9H-fluorene (3.5 g, 0.010 mol) was added to 1H-indol-3-ylboronic acid (1.9 g, 0.012 mol) To obtain 2.8 g (yield: 72%) of Intermediate 14-1.

LC / MS: m / z = 388 [(M + 1) ^&lt; ^{+ &}

(2) Manufacturing example  14-2: Intermediate 14-2 Synthesis

Intermediate 1-10 (4.4g, 0.012mol) was added to Intermediate 14-1 (3.9g, 0.010mol) and synthesized in the same manner as in Preparation Example 1-4 to give 4.0g (yield: 72% ).

LC / MS: m / z = 550 [(M + 1) ^&lt; ^{+ &}

(3) Manufacturing example  14-3: Compound 14 Synthesis

Intermediate 14-2 (5.5 g, 0.010 mol) was added to Intermediate 12-4 (4.2 g, 0.010 mol), and 6.6 g (Yield: 71%) of Compound 14 was synthesized in the same manner as in Production Example 1-1. &Lt; / RTI >

_{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 D, 7.93 / d, 7.77 / s, 7.67 / m, 7.63 / d, 7.45 / 7.55 / m, 7.51 / m, 7.42 / m, 7.58 / m, 7.50 /

LC / MS: m / z = 932 [(M + 1) ^&lt; ^{+ &}

Example  15: Compound 15 Synthesis

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

9,6-dibromo-9-phenyl-9H-carbazole (4.0 g, 0.010 mol) was added to 1H-indol-3-ylboronic acid (1.9 g, 0.012 mol) 3.1 g (yield: 72%) of Intermediate 15-1 was obtained.

LC / MS: m / z = 437 [(M + 1) ^&lt; ^{+ &}

(2) Manufacturing example  15-2: Intermediate 15-2 Synthesis

Intermediate 1-10 (4.4 g, 0.012 mol) was added to Intermediate 15-1 (4.4 g, 0.010 mol), and 4.3 g (yield 72%) of Intermediate 15-2 was synthesized in the same manner as in Preparation Example 1-4, ).

LC / MS: m / z = 600 [(M + 1) ^&lt; ^{+ &}

(3) Manufacturing example  15-3: Compound 15 Synthesis

Intermediate 15-2 (6.0 g, 0.010 mol) was added to Intermediate 12-4 (4.2 g, 0.010 mol) and synthesized in the same manner as in Production Example 1-1 to obtain 7.6 g (yield: 77% &Lt; / RTI >

_{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, 7.59 / d, 7.43 / m, 7.36 / s, 7.33 / , 7.55 / m, 7.51 / m, 7.45 / m, 7.42 / m) 3H (7.79 / d)

LC / MS: m / z = 981 [(M + 1) ^&lt; ^{+ &}

Example  16: Compound 16 Synthesis

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

Dibromochloromethane (2.1 g, 0.010 mol) was added to 3-amino-2-naphthamide (1.9 g, 0.010 mol) and synthesized in the same manner as in Production Example 1-1 to give 1.8 g of Intermediate 16-1 %).

LC / MS: m / z = 230 [(M + 1) ^&lt; ^{+ &}

(2) Manufacturing example  16-2: Intermediate 16-2 Synthesis

(Yield: 73%) was synthesized in the same manner as in Production Example 1-2, except that Intermediate 16-1 (2.2 g, 0.010 mol) was used instead of Intermediate 1-1 .

LC / MS: m / z = 362 [(M + 1) ^&lt; ^{+ &}

(3) Manufacturing example  16-3: Intermediate 16-3 Synthesis

Intermediate 16-2 (3.6 g, 0.010 mol) bis (pinacolato) dibron (3.0 g, 0.012 mol) was added and 2.5 g (yield: 73%) of Intermediate 16-3 was obtained in the same manner as in Preparation Example 1-3 Respectively.

LC / MS: m / z = 340 [(M + 1) ^&lt; ^{+ &}

(4) Manufacturing example  16-4: Intermediate 16-4 Synthesis

Intermediate 1-5 (3.5 g, 0.010 mol) was added to Intermediate 16-3 (4.1 g, 0.012 mol), and 3.0 g (yield 72%) of Intermediate 16-4 was synthesized in the same manner as in Production Example 1-4, ).

LC / MS: m / z = 416 [(M + 1) ^&lt; ^{+ &}

(5) Manufacturing example  16-5: Compound 16 Synthesis

Intermediate 1-11 (4.3 g, 0.010 mol) was added to Intermediate 16-4 (4.2 g, 0.010 mol) and synthesized in the same manner as in Production Example 1-1 to give 7.3 g (82% &Lt; / RTI >

_{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 M, 7.50 / d, 7.42 / m, 7.41 / m) 4H (7.51 / d, 8.16 / d, 7.67 / m, 7.58 / / m) 5H (7.79 d, 7.25 / d)

LC / MS: m / z = 892 [(M + 1) ^&lt; ^{+ &}

Example  17: Compound 17 Synthesis

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

Biphenyl-3-ylboronic acid (2.4 g, 0.012 mol) was added to 4-bromonaphthalen-2-ol (2.2 g, 0.010 mol) g (yield 66%).

LC / MS: m / z = 296 [(M + 1) ^&lt; ^{+ &}

(2) Manufacturing example  17-2: Intermediate 17-2 Synthesis

Intermediate 17-1 (3.1 g, yield: 73%) was synthesized in the same manner as in Production Example 1-2, except that Intermediate 17-1 (3.0 g, 0.010 mol) was used instead of Intermediate 1-1 .

LC / MS: m / z = 428 [(M + 1) ^&lt; ^{+ &}

(3) Manufacturing example  17-3: Intermediate 17-3 Synthesis

Intermediate 17-2 (4.3 g, 0.010 mol) was added to Intermediate 16-3 (4.1 g, 0.012 mol), and 3.5 g (yield: 72% ).

LC / MS: m / z = 493 [(M + 1) ^&lt; ^{+ &}

(4) Manufacturing example  16-4: Compound 17 Synthesis

Intermediate 1-11 (4.3 g, 0.010 mol) was added to Intermediate 17-3 (4.9 g, 0.010 mol), and 6.3 g (yield 71%) of Compound 17 was synthesized in the same manner as in Production Example 1-1, &Lt; / RTI >

_{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 7.36 / 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 /

LC / MS: m / z = 892 [(M + 1) ^&lt; ^{+ &}

Example  18: Compound 18 Synthesis

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

Dibromochloromethane (2.1 g, 0.010 mol) was added to 10-amino-5,8-dihydrophenanthrene-9-carboxamide (2.4 g, 0.010 mol) and synthesized in the same manner as in Production Example 1-1 to obtain Intermediate 18-1 (Yield: 77%).

LC / MS: m / z = 282 [(M + 1) ^&lt; ^{+ &}

(2) Manufacturing example  18-2: Intermediate 18-2 Synthesis

3.0 g (yield: 73%) of Intermediate 18-2 was synthesized in the same manner as in Production Example 1-2, except that Intermediate 18-1 (2.2 g, 0.010 mol) was used instead of Intermediate 1-1 .

LC / MS: m / z = 414 [(M + 1) ^&lt; ^{+ &}

(3) Manufacturing example  18-3: Intermediate 18-3 Synthesis

Intermediate 18-2 (4.1 g, 0.010 mol) bis (pinacolato) dibron (3.0 g, 0.012 mol) was added and 2.7 g (yield 70%) of Intermediate 18-3 was obtained in the same manner as in Preparation Example 1-3 Respectively.

LC / MS: m / z = 392 [(M + 1) ^&lt; ^{+ &}

(4) Manufacturing example  18-4: Intermediate 18-4 Synthesis

Intermediate 1-5 (3.5 g, 0.010 mol) was added to Intermediate 18-3 (4.7 g, 0.012 mol), and 3.4 g (yield 72%) of Intermediate 18-4 was synthesized in the same manner as in Production Example 1-4, ).

LC / MS: m / z = 466 [(M + 1) ^&lt; ^{+ &}

(5) Manufacturing example  5: Compound 18 Synthesis

Intermediate 1-11 (4.3 g, 0.010 mol) was added to Intermediate 18-4 (4.7 g, 0.010 mol), and 6.2 g (yield 72%) of Compound 18 was synthesized in the same manner as in Production Example 1-1. &Lt; / RTI >

_{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 M, 7.58 / 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) ^&lt; ^{+ &}

Abbreviations used in the embodiment 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,

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

The structures of the hole injection layer material CuPc, the hole transport material NPB, the light emitting host material CBP, and the red dopant Ir (btp) 2 (acac) used in the device example or device comparative example are as follows.

Device Example  1: Compound 1 The light-  As a red host material Organic electroluminescent device  Produce

A hole transport layer having a thickness of 80 nm and a thickness of 30 nm was formed on a glass substrate coated with ITO and then mixed with 6% of a compound 1 and a red dopant Ir (btp) 2 (acac) m / sec. Then, an electron transport layer of 40 nm in thickness of Alq ₃ , an electron injection layer of 1 nm in thickness of LiF, and a thickness of 120 nm of cathode Al were formed in this order. Thus, an organic electroluminescent device was manufactured. At this time, deposition rates of CuPc, α-NPD, Alq ₃ , LiF and Al were 0.5 nm / sec, 0.1 nm / sec, 0.01 nm / sec and 0.5 nm / sec, respectively.

Device Example  2 to 18

The organic electroluminescent devices of the device embodiments 2 to 18 were fabricated in the same manner as in the device example 1, except that the luminescent material described in the following Table 1 was used in place of the compound 1.

Device comparison example  One

An organic electroluminescent device of Comparative Example 1 was prepared in the same manner as in Example 1 except that (4,4-N, N-dicarbazole) biphenyl (CBP)

Hereinafter, the characteristics of the organic electroluminescent device manufactured according to the device embodiments 1 to 18 and the device comparative example 1 are shown in Table 1 below.

division Emitting material The driving voltage (V)
(at 1000 cd / m ² ) Luminous efficiency
(cd / A) Color coordinates
(CIE (x, y)) Device Embodiment 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 Embodiment 3 Compound 3 5.3 15.7 (0.63, 0.34) Device Example 4 Compound 4 4.5 14.8 (0.62, 0.35) Element Embodiment 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) Element Embodiment 10 Compound 10 5.8 18.9 (0.63, 0.36) Element Embodiment 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 Embodiment 13 Compound 13 5.4 16.8 (0.62, 0.32) Device Embodiment 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 Embodiment 16 Compound 16 4.1 19.1 (0.60, 0.35) Device Example 17 Compound 17 5.9 16.1 (0.61, 0.34) Element Embodiment 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

The organic light emitting element made from above (substrate size: 25 * 25mm ² / deposition area: ² * 2mm 2) an IVL measuring set (CS-2000 + fixture + IVL program) by the current deposition raises by 1mA / m ² and then fixed to the the brightness of light emitted by the surface (cd / m ^2), a driving voltage (V), current density (a / m ^2), luminous efficiency (cd / a) drive voltage when measured brightness is 1000cd / m ² days and luminous efficiency Shown in Table 1 above.

According to Table 1, when the compound for an organic electroluminescent device according to the present invention is used as a red light emitting material of an organic electroluminescent device, the driving voltage is significantly lowered and the luminous efficiency is significantly improved as compared with the case of using conventional CBP as a light emitting material . Therefore, it can be seen that the organic EL device can be effectively used for a display device, a display device, and an illumination device.

Claims (7)

A compound for an organic electroluminescence device represented by Structural Formula (1) below.
[Structural formula 1]

In the above formula 1,
L is a valence-bonded, 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 aryl aryl 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 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, 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 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 A substituted or unsubstituted fused C3 to C30 cycloalkyl group, a substituted or unsubstituted fused C1 to C30 heterocycloalkyl group, a substituted or unsubstituted fused C6 to C30 aryl group, or a substituted or unsubstituted fused C1 to C30 hetero To form an aryl group,
R ³ to R ⁶ may be the same or different from each other and each of R ³ to R ⁶ independently represents a hydrogen atom, a deuterium atom, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, 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 of compounds 1 to 238 represented by the following formula:

An organic electroluminescent device comprising the compound for organic electroluminescent device according to any one of claims 1 and 2. 1. An organic electroluminescent device comprising a first electrode, a second electrode, and a single or a plurality of organic layers between the first electrode and the second electrode,
The organic electroluminescent device according to any one of claims 1 to 3, wherein the at least one organic layer selected from the single or plural organic layers comprises the compound for organic electroluminescent devices according to any one of claims 1 to 3. 5. The method of claim 4,
Wherein the single or plural organic layers include a light emitting layer. 5. The method of claim 4,
Wherein the plurality of organic layers include a light emitting layer and the plurality of organic layers further include at least one selected from an electron injecting layer, an electron transporting layer, a hole blocking layer, an electron blocking layer, a hole transporting layer and a hole injecting layer Organic electroluminescent device. 6. The method of claim 5,
Wherein the light emitting layer comprises a host and a dopant.

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