KR20160040826A - 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 the compound for an organic electroluminescent device, which is capable of being used as a host and a hole transfer material improving a light emitting efficiency of a phosphorescence emitting material by having excellent electrical stability and hole transfer ability, and having high triplet state energy. Also, the organic electroluminescent device is also provided.

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,

Ring a is an aromatic ring,

X ¹ is a nitrogen atom or a carbon atom,

,

,

,

, 또는

이고, X ² and X ⁴ may be the same or different from each other, and X ² and X ⁴ are each independently an oxygen atom, a sulfur atom, a nitrogen atom,

,

,

,

, or

ego,

R ⁶ to R ¹² may be the same or different from each other and each of R ⁶ to R ¹² 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,

,

,

,

, 또는

이고, X ³ represents an oxygen atom, a sulfur atom, a nitrogen atom,

,

,

,

, or

ego,

R ¹³ 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, a substituted or unsubstituted C1 to C30 heterocycloalkyl group, a substituted or unsubstituted C6 to C30 an aryl group, or is substituted or unsubstituted C1 to C30 heteroaryl group, or R ¹³ is R ¹³ a in conjunction with the adjacent carbon atoms and more carbon atoms substituted or unsubstituted fused bonding a 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 heteroaryl group,

R ¹⁴ to R ¹⁹ may be the same or different from each other, and each of R ¹⁴ to R ¹⁹ 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,

L is a valence-bonded, substituted or unsubstituted C6 to C30 arylene group, or a substituted or unsubstituted C1 to C30 heteroarylene group,

A represents a hydrogen atom, a deuterium atom, a substituted or unsubstituted C12 to C30 arylamine group, a substituted or unsubstituted C2 to C30 heteroarylamine group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 aryl group, C30 cycloalkyl group, a substituted or 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,

R ¹ and R ² may be the same or different from each other, R ¹ and R ² are each independently a substituted or unsubstituted C1 to C30 alkyl group,

R ³ to R ⁵ may be the same or different from one another and each of R ³ to R ⁵ 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.

Preferably, R ¹³ is 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 unsubstituted C1 to C30 heterocycloalkyl group, a C6 to C30 aryl group, or a substituted or unsubstituted or C1 to C30 heteroaryl ring, or R ¹³ is R ¹³ is combined with the adjacent carbon atoms and more characters combined carbon substituted or unsubstituted ring fused benzene ring . ≪ / RTI >

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.

The compound for an organic electroluminescence device may be any one selected from compounds 1 to 337 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.

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: Compound 183 Synthesis

(One) Production Example 1 -1: Synthesis of intermediate A

2,6-dibromobenzamide (2.8 g, 0.010 mol), Pd (dba) 2 (0.5 g, 0.0005 mol) and sodium chloride were added to a solution of 3-chloro-1,1,2-trimethyl- -tert-butoxide (1.9 g, 0.020 mol) was added 70 ml of TOL, and the mixture was reacted at 95 ° C for 4 hours with stirring. After completion of the reaction, the reaction mixture was separated into H ₂ O: MC and purified by column (n-HEXANE: MC) to obtain 2.7 g (yield: 79%) of intermediate A.

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

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

To the intermediate A (3.4 g, 0.010 mol) was added potassium hydroxide (1.7 g, 0.030 mol) in 50 ml of water and the mixture was reacted at 90 ° C for 2 hours with stirring. After completion of the reaction, the reaction mixture was cooled to room temperature and then subjected to column purification (n-HEXANE: MC) to obtain 2.0 g (yield: 61%) of intermediate A-1.

LC / MS: m / z = 326 [(M + 1) ^< ^{+ &}

(3) Manufacturing example  1-3: Synthesis of intermediate A-2

50 ml of water was added to iodomethane (2.6 g, 0.020 mol) in Intermediate A-1 (3.3 g, 0.010 mol) and the mixture was reacted at 0 ° C for 24 hours with stirring. After completion of the reaction, the reaction mixture was separated into H ₂ O: MC and purified by column (n-HEXANE: MC) to obtain 2.2 g (yield: 62%) of intermediate A-2.

LC / MS: m / z = 354 [(M + 1) ^< ^{+ &}

(4) Manufacturing example  1-4: Synthesis of intermediate A-3

Bromobenzene (1.6 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 100 ml of DMF, 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 3.5 g (yield: 81%) of Intermediate A-3.

LC / MS: m / z = 430 [(M + 1) ^< ^{+ &}

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

(Biphenyl-4-yl) -9,9-dimethyl-9H-fluoren-2-amine (3.6 g, 0.010 mol) was added to 1,4-dibromobenzene (2.4 g, 0.010 mol) (Intermediate 1-1) (4.0 g, Yield: 77%).

LC / MS: m / z = 516 [(M + 1) ^< ^{+ &}

(6) Manufacturing example  1-6: Synthesis of intermediate 1-2

To a solution of bis (pinacolato) dibron (2.5 g, 0.012 mol) PdCl2 (dppf) (0.4 g, 0.0005 mol) and potassium acetate (2.7 g, 0.020 mol) -dioxane (100 ml), and the mixture was reacted at 95 DEG 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 4.0 g (yield: 71%) of Intermediate 1-2.

LC / MS: m / z = 563 [(M + 1) ^< ^{+ &}

(7) Manufacturing example  1-7: Compound 183 Synthesis

100 ml of THF was added to Intermediate 1-2 (6.8 g, 0.012 mol), Pd (pph3) 4 (0.6 g, 0.0005 mol) and potassium carbonate (2.8 g, 0.020 mol) And the mixture was reacted at 65? For 18 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 5.5 g (yield 70%) of <compound 183>.

_{H-NMR (200MHz, CDCl 3} ): δ ppm, 1H (7.87 / d, 7.62 / d, 7.56 / d, 7.55 / d, 7.42 / d, 7.41 / m, 7.38 / m, 7.38 / d, 7.33 / m 7.52 / d, 7.51 / m, 7.23 / m, 6.60 / d, 1.72 / , 1.69 / s, 1.40 / s) 4H (7.54 / d, 6.69 / d)

LC / MS: m / z = 788 [(M + 1) ^&lt; ^{+ &}

Example  2: Compound 184 Synthesis

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

2-bromonaphthalene (2.1 g, 0.010 mol) was added to 4'-bromobiphenyl-4-amine (2.5 g, 0.010 mol) and synthesized in the same manner as in Production Example 1-1 to give 3.0 g Yield: 81%).

LC / MS: m / z = 374 [(M + 1) ^&lt; ^{+ &}

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

Bromobenzene (1.6 g, 0.010 mol) was added to Intermediate 2-1 (3.7 g, 0.010 mol), and 3.3 g (yield 73%) of Intermediate 2-2 was obtained in the same manner as in Production Example 1-1 .

LC / MS: m / z = 450 [(M + 1) ^&lt; ^{+ &}

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

(Pinacolato) dibron (3.0 g, 0.012 mol) was added to Intermediate 2-2 (4.5 g, 0.010 mol), and 3.6 g (yield 72 %).

LC / MS: m / z = 497 [(M + 1) ^&lt; ^{+ &}

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

Intermediate 2-3 (6.0 g, 0.012 mol) was added to Intermediate A-3 (4.3 g, 0.010 mol), and 5.2 g (yield 72%) of Compound 184 was synthesized in the same manner as in Production Example 1-7 .

_{H-NMR (200MHz, CDCl 3} ): δ ppm, 1H (7.88 / d, 7.84 / d, 7.77 / d, 7.74 / s, 7.56 / d, 7.50 / m, 7.49 / d, 7.42 / d, 7.38 / d 7.26 / m, 7.26 / m, 6.81 / m, 6.77 / m) 2H (7.54 / d, 7.23 / m, 7.20 / m, 6.69 / d, 6.63 / , 6.60 / d, 1.69 / s, 1.40 / s)

LC / MS: m / z = 721 [(M + 1) ^&lt; ^{+ &}

Example  3: Compound 185 Synthesis

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

Biphenyl-4-amine (1.7 g, 0.010 mol) was added to 2,7-dibromo-9,9-dimethyl-9H-fluorene (3.5 g, 0.010 mol) 3.6 g (yield: 81%) of <Intermediate 3-1> was obtained.

LC / MS: m / z = 440 [(M + 1) ^&lt; ^{+ &}

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

Intermediate 3-2 (4.3 g, yield 76%) 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 3-1 (4.4 g, 0.010 mol) &Lt; / RTI >

LC / MS: m / z = 566 [(M + 1) ^&lt; ^{+ &}

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

(Pinacolato) dibron (3.0 g, 0.012 mol) was added to Intermediate 3-2 (5.9 g, 0.010 mol), and 4.4 g (yield: 71%) of Intermediate 2-3 was synthesized in the same manner as in Production Example 1-6 %).

LC / MS: m / z = 613 [(M + 1) ^&lt; ^{+ &}

(4) Manufacturing example  3-4: Compound 185 Synthesis

Intermediate 3-3 (7.4 g, 0.012 mol) was added to Intermediate A-3 (4.3 g, 0.010 mol), and 5.5 g (yield 66%) of Compound 185 was synthesized in the same manner as in Production Example 1-7 .

_{H-NMR (200MHz, CDCl 3} ): δ ppm, 1H (7.93 / d, 7.88 / d, 7.84 / d, 7.77 / d, 7.74 / s, 7.63 / d, 7.62 / d, 7.56 / d, 7.50 / m 7.54 / d, 7.52 / d, 7.51 / m, 7.23 / m, 6.69 / d, 7.31 / , 6.60 / d, 1.72 / s, 1.69 / s, 1.40 / s)

LC / MS: m / z = 837 [(M + 1) ^&lt; ^{+ &}

Example  4: Compound 186 Synthesis

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

Biphenyl-4-amine (1.7 g, 0.010 mol) was added to 2-bromo-9,9-dimethyl-9H-fluorene (2.7 g, 0.010 mol) 4-1> 2.9 g (yield: 81%).

LC / MS: m / z = 361 [(M + 1) ^&lt; ^{+ &}

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

2,6-dibromonaphthalene (2.9 g, 0.010 mol) was added to Intermediate 4-1 (3.6 g, 0.010 mol) and synthesized in the same manner as in Production Example 1-1 to obtain 4.6 g of Intermediate 4-2 %).

LC / MS: m / z = 566 [(M + 1) ^&lt; ^{+ &}

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

(Pinacolato) dibron (3.0 g, 0.012 mol) was added to Intermediate 4-2 (5.7 g, 0.010 mol), and 4.4 g of Intermediate 4-3 (yield 72 %).

LC / MS: m / z = 613 [(M + 1) ^&lt; ^{+ &}

(4) Manufacturing example  4-4: Synthesis of compound 186

Intermediate 4-3 (7.3 g, 0.012 mol) was added to Intermediate A-3 (4.3 g, 0.010 mol), and 5.4 g of Intermediate 186 (yield 65%) was synthesized in the same manner as in Production Example 1-7 .

_{H-NMR (200MHz, CDCl 3} ): δ ppm, 1H (7.87 / d, 7.84 / d, 7.74 / s, 7.69 / d, 7.64 / d, 7.62 / d, 7.56 / d, 7.55 / d, 7.49 / d M, 7.27 / m, 7.22 / m, 6.77 / m, 6.75 / s, 6.77 / m, 7.48 / / m) 2H (7.54 / d, 7.52 / d, 7.51 / m, 7.23 / m, 6.69 / d, 6.60 / d, 1.72 / s, 1.69 / s, 1.40 / s)

LC / MS: m / z = 838 [(M + 1) ^&lt; ^{+ &}

Example  5: Compound 187 Synthesis

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

Intermediate 5-1> 2.4 (3-bromo-1-chlorophenylanthracene) was synthesized in the same manner as in Example 1 (1) except that 3-bromo-1-chloronaphthalene (2.4 g, 0.010 mol) g (yield: 71%).

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

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

(Pinacolato) dibron (3.0 g, 0.012 mol) was added to Intermediate 5-1 (3.3 g, 0.010 mol), and 2.7 g of Intermediate 5-2 (yield 72 %).

LC / MS: m / z = 379 [(M + 1) ^&lt; ^{+ &}

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

Intermediate 5-2 (3.8 g, 0.010 mol) was added with phenyl boronic acid (1.4 g, 0.012 mol) to obtain 2.9 g (yield 70%) of Intermediate 5-3, &Lt; / RTI >

LC / MS: m / z = 421 [(M + 1) ^&lt; ^{+ &}

(4) Manufacturing example  5-4: Intermediate 5-4 Synthesis

(1.6 g, 0.010 mol) was added to Intermediate 5-3 (4.2 g, 0.010 mol), and 3.7 g (yield: 74%) of Intermediate 5-4 was obtained in the same manner as in Production Example 1-1 .

LC / MS: m / z = 497 [(M + 1) ^&lt; ^{+ &}

(5) Manufacturing example  5-5: Synthesis of compound 187

Intermediate 5-4 (6.0 g, 0.012 mol) was added to Intermediate A-3 (4.3 g, 0.010 mol), and 5.0 g (yield 70%) of Compound 187 was synthesized in the same manner as in Production Example 1-7 .

_{H-NMR (200MHz, CDCl 3} ): δ ppm, 1H (8.43 / d, 7.85 / d, 7.56 / d, 7.46 / m, 7.42 / d, 7.41 / m, 7.38 / d, 7.33 / m, 7.32 / m M, 7.30 / d, 7.27 / m, 7.22 / m, 6.99 / s, 6.81 / , 6.69 / d, 6.63 / d, 6.60 / d, 1.69 / s, 1.40 / s)

LC / MS: m / z = 721 [(M + 1) ^&lt; ^{+ &}

Example  6: Compound 188 Synthesis

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

Synthesis was conducted in the same manner as in Preparation Example 1-1, except that 2-bromo-9,9-dimethyl-9H-fluorene (2.7 g, 0.010 mol) was added to Intermediate 5-3 (4.2 g, 0.010 mol) -1> 4.5 g (yield: 74%).

LC / MS: m / z = 613 [(M + 1) ^&lt; ^{+ &}

(2) Manufacturing example  6-2: Synthesis of Compound 188

Intermediate 6-1 (7.3 g, 0.012 mol) was added to Intermediate A-3 (4.3 g, 0.010 mol), and 5.2 g (yield 62%) of Compound 188 was synthesized in the same manner as in Production Example 1-7 .

_{H-NMR (200MHz, CDCl 3} ): δ ppm, 1H (8.43 / d, 7.87 / d, 7.85 / d, 7.62 / d, 7.56 / d, 7.55 / d, 7.46 / m, 7.42 / d, 7.41 / m 7.38 / d, 7.32 / m, 7.28 / m, 7.27 / m, 7.22 / d, 6.99 / d, 6.77 / m, 6.76 / d, 6.75 / s, 6.58 / (7.79 d, 7.54 d, 7.51 m, 7.23 m, 6.69 d, 6.60 d, 1.72 s, 1.69 s, 1.40 s)

LC / MS: m / z = 838 [(M + 1) ^&lt; ^{+ &}

Example  7: Compound 189 Synthesis

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

2,5-dibromobenzamide (2.8 g, 0.010 mol) was added to 3-chloro-1,1,2-trimethyl-1H-indene (1.9 g, 0.010 mol) &Lt; Intermediate B > 2.6 g (yield: 76%) was obtained.

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

(2) Manufacturing example  7-2: Synthesis of Compound B-1

Intermediate B (3.4 g, 0.010 mol) was added thereto and synthesized in the same manner as in Production Example 1-2 to obtain 1.9 g (yield: 58%) of Intermediate B-1.

LC / MS: m / z = 326 [(M + 1) ^&lt; ^{+ &}

(3) Manufacturing example  7-3: Synthesis of intermediate B-2

Intermediate B-1 (3.3 g, 0.010 mol) was added thereto and synthesized in the same manner as in Production Example 1-3 to obtain 1.9 g (yield: 55%) of Intermediate B-2.

LC / MS: m / z = 354 [(M + 1) ^&lt; ^{+ &}

(4) Manufacturing example  7-4: Synthesis of intermediate B-3

Bromobenzene (1.6 g, 0.010 mol) was added to B-2 (3.5 g, 0.010 mol), and 3.2 g (yield: 74%) of Intermediate B-3 was obtained in the same manner as in Production Example 1-4.

LC / MS: m / z = 430 [(M + 1) ^&lt; ^{+ &}

(5) Manufacturing example  7-5: Intermediate 7-1 Synthesis

3.0 g (yield: 81%) of <Intermediate 7-1> was synthesized in the same manner as in Production Example 1-1, except that dip-tolylamine (2.0 g, 0.010 mol) was added to 3,5-dibromoaniline (2.5 g, 0.010 mol) ).

LC / MS: m / z = 367 [(M + 1) ^&lt; ^{+ &}

(6) Manufacturing example  7-6: Intermediate 7-2 Synthesis

Intermediate 7-2 (3.7 g, yield 76%) was synthesized by the same method as in Preparation Example 1-1, except that 1-bromonaphthalene (2.1 g, 0.010 mol) was added to Intermediate 7-1 (3.7 g, 0.010 mol) &Lt; / RTI >

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

(7) Manufacturing example  7-7: Intermediate 7-3 Synthesis

4-methylbenzene (1.7 g, 0.010 mol) was added to Intermediate 7-2 (4.9 g, 0.010 mol), and 4.5 g of Intermediate 7-3 was synthesized in the same manner as in Production Example 1-1 Yield: 77%).

LC / MS: m / z = 583 [(M + 1) ^&lt; ^{+ &}

(8) Manufacturing example  7-8: Intermediate 7 -4 synthesis

(Pinacolato) dibron (3.0 g, 0.012 mol) was added to Intermediate 7-3 (5.8 g, 0.010 mol), and 4.5 g of Intermediate 7-4 (yield 72 %).

LC / MS: m / z = 630 [(M + 1) ^&lt; ^{+ &}

(9) Manufacturing example  7-9: Synthesis of compound 189

Intermediate 7-4 (7.6 g, 0.012 mol) was added to Intermediate B-3 (4.3 g, 0.010 mol), and 6.1 g (yield 71%) of Compound 189 was synthesized in the same manner as in Production Example 1-7 .

_{H-NMR (200MHz, CDCl 3} ): δ ppm, 1H (8.07 / d, 8.02 / d, 7.86 / m, 7.57 / d, 7.54 / s, 7.53 / m, 7.48 / d, 7.46 / d, 7.42 / d , 7.30 / d, 7.27 / m, 7.22 / m, 6.77 / m) 2H (7.23 / m, 6.60 / d, 6.25 / s, 1.69 / s, 1.40 / s) ) &Lt; / RTI &gt; 7H (6.98 / d)

LC / MS: m / z = 855 [(M + 1) ^&lt; ^{+ &}

Example  8: Compound 190 Synthesis

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

Synthesis was carried out in the same manner as in Production Example 1-1, except that 2-bromo-9,9-dimethyl-9H-fluorene (2.7 g, 0.010 mol) was added to 4-bromoaniline (1.7 g, 0.010 mol) 1 &gt; (yield: 81%).

LC / MS: m / z = 364 [(M + 1) ^&lt; ^{+ &}

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

1-bromo-5-phenylnaphthalene (2.8 g, 0.010 mol) was added to Intermediate 8-1 (3.6 g, 0.010 mol) and the compound was synthesized in the same manner as in Production Example 1-1 to give 4.1 g Yield: 73%).

LC / MS: m / z = 566 [(M + 1) ^&lt; ^{+ &}

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

(Pinacolato) dibron (3.0 g, 0.012 mol) was added to Intermediate 8-2 (5.7 g, 0.010 mol), and 4.1 g (Intermediate 8-3) %).

LC / MS: m / z = 613 [(M + 1) ^&lt; ^{+ &}

(4) Manufacturing example  8-4: Compound 190 Synthesis

Intermediate 8-3 (7.3 g, 0.012 mol) was added to Intermediate B-3 (4.3 g, 0.010 mol), and 5.9 g (Yield: 70%) of Compound 190 was synthesized in the same manner as in Production Example 1-7 .

_{H-NMR (200MHz, CDCl 3} ): δ ppm, 1H (8.40 / d, 8.04 / d, 8.03 / d, 7.87 / d, 7.86 / s, 7.62 / d, 7.60 / m, 7.55 / d, 7.48 / d , 7.46 / d, 7.42 / d, 7.41 / m, 7.30 / d, 7.28 / m, 7.27 / m, 7.22 / m, 6.98 / d, 6.75 / s, 6.58 / , 7.51 m, 7.38 m, 7.23 m, 6.69 d, 6.60 d, 1.72 s, 1.69 s, 1.40 s)

LC / MS: m / z = 838 [(M + 1) ^&lt; ^{+ &}

Example  9: Synthesis of compound 1

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

2-bromo-6-chlorobenzamide (2.3 g, 0.010 mol) was added to 3,5-dibromo-4H-1,2,4-triazole (2.3 g, 0.010 mol) To obtain 2.3 g (yield 76%) of < Intermediate C >.

LC / MS: m / z = 300 [(M + 1) ^&lt; ^{+ &}

(2) Manufacturing example  9-2: Synthesis of intermediate C-1

Intermediate C (3.0 g, 0.010 mol) was added thereto, and the reaction mixture was synthesized in the same manner as in Production Example 1-2 to give 1.7 g (yield: 58%) of Intermediate C-1.

LC / MS: m / z = 285 [(M + 1) ^&lt; ^{+ &}

(3) Manufacturing example  9-3: Synthesis of intermediate C-2

Intermediate C-1 (2.9 g, 0.010 mol) was added thereto, and 1.7 g (yield 55%) of Intermediate C-2 was obtained in the same manner as in Production Example 1-3.

LC / MS: m / z = 313 [(M + 1) ^&lt; ^{+ &}

(4) Manufacturing example  9-4: Synthesis of intermediate C-3

Intermediate C-3 (3.2 g, yield 81%) was obtained by the same method as in Preparation Example 1-4, with bromobenzene (1.6 g, 0.010 mol) added to Intermediate C-2 (3.1 g, 0.010 mol) .

LC / MS: m / z = 389 [(M + 1) ^&lt; ^{+ &}

(5) Manufacturing example  9-5: Synthesis of intermediate C-4

Intermediate C-4 (2.7 g, yield 70%) was synthesized in the same manner as in Preparation Example 1-7, except that phenyl boronic acid (1.4 g, 0.012 mol) was added to Intermediate C-3 (3.9 g, 0.010 mol) &Lt; / RTI >

LC / MS: m / z = 386 [(M + 1) ^&lt; ^{+ &}

(6) Manufacturing example  9-6: Synthesis of intermediate 9-1

2-ylboronic acid (3.3 g, 0.012 mol) was added to 1,3-dibromobenzene (1.6 g, 0.010 mol), and 2.7 g of Intermediate 9-1 Yield: 71%).

LC / MS: m / z = 383 [(M + 1) ^&lt; ^{+ &}

(7) Manufacturing example  9-7: Intermediate 9-2 Synthesis

Intermediate 9-1 (3.8 g, 0.010 mol) was added with bis (pinacolato) dibron (3.0 g, 0.012 mol) to obtain 3.1 g of Intermediate 9-2 (yield 72 %).

LC / MS: m / z = 430 [(M + 1) ^&lt; ^{+ &}

(8) Manufacturing example  9-8: Synthesis of compound 1

Intermediate 9-2 (5.2 g, 0.012 mol) was added to Intermediate C-4 (3.9 g, 0.010 mol), and 4.6 g (Yield: 70%) of Compound 1 was synthesized in the same manner as in Production Example 1-7 .

_{H-NMR (200MHz, CDCl 3} ): δ ppm, 1H (9.15 / s, 8.18 / d, 8.04 / d, 7.71 / d, 7.70 / s, 7.57 / m, 7.33 / m, 7.22 / d, 6.77 / m M, 7.51 / m, 7.48 / d, 7.33 / d, 7.23 / m, 1.40 / s)

LC / MS: m / z = 655 [(M + 1) ^&lt; ^{+ &}

Example  10: Synthesis of compound 2

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

Biphenyl-4-ylboronic acid (2.4 g, 0.012 mol) was added to 2,4-dibromo-6- (4-bromophenyl) -1,3,5-triazine (3.9 g, 0.010 mol) (Intermediate 10-1) (3.3 g, Yield: 70%).

LC / MS: m / z = 467 [(M + 1) ^&lt; ^{+ &}

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

Intermediate 10-2 (3.2 g, 70%) was synthesized in the same manner as in Preparation Example 1-7, except that phenyl boronic acid (1.4 g, 0.012 mol) was added to Intermediate 10-1 (4.7 g, 0.010 mol) &Lt; / RTI >

LC / MS: m / z = 464 [(M + 1) ^&lt; ^{+ &}

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

(Pinacolato) dibron (3.0 g, 0.012 mol) was added to Intermediate 10-2 (4.6 g, 0.010 mol) and synthesized in the same manner as in Production Example 1-6 to give 3.7 g of Intermediate 10-3 %).

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

(4) Manufacturing example  10-4: Synthesis of compound 2

Intermediate 10-3 (6.1 g, 0.012 mol) was added to Intermediate C-4 (3.9 g, 0.010 mol), and 5.0 g (yield 68%) of Compound 2 was synthesized in the same manner as in Production Example 1-7 .

_{H-NMR (200MHz, CDCl 3} ): δ ppm, 1H (7.71 / d, 7.33 / m, 7.22 / d) 2H (7.52 / d, 7.33 / d, 7.23 / m) 3H (7.41 / m) 4H (8.28 / d, 7.85 / d, 7.25 / d) 6H (7.51 / m)

LC / MS: m / z = 736 [(M + 1) ^&lt; ^{+ &}

Example  11: Synthesis of compound 3

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

2-bromo-4,6-diphenyl-1,3,5-triazine (3.1 g, 0.010 mol) was added to 9H-carbazol-3-ylboronic acid (2.1 g, 0.010 mol) Synthesis was conducted in the same manner to obtain 3.1 g (yield: 71%) of Intermediate 11-1.

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

(2) Manufacturing example  11-2: Synthesis of compound 3

Intermediate 11-1 (5.3 g, 0.012 mol) was added to Intermediate C-5 (4.6 g, 0.010 mol), and 6.0 g (yield 73%) of Compound 3 was synthesized in the same manner as in Production Example 1-7 .

_{H-NMR (200MHz, CDCl 3} ): δ ppm, 1H (8.55 / d, 7.94 / d, 7.87 / d, 7.77 / s, 7.71 / d, 7.69 / d, 7.25 / m, 7.22 / d, 6.77 / m ) 2H (7.85 / d, 7.52 / d, 7.33 / m, 7.33 / d, 7.25 / d, 7.23 / m, 1.40 / s)

LC / MS: m / z = 825 [(M + 1) ^&lt; ^{+ &}

Example  12: Synthesis of compound 4

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

4-bromo-2,6-diphenylpyridine (3.1 g, 0.010 mol) was added to 9H-carbazol-3-ylboronic acid (2.1 g, 0.010 mol) -1> (yield: 67%).

LC / MS: m / z = 440 [(M + 1) ^&lt; ^{+ &}

(2) Manufacturing example  12-2: Synthesis of compound 4

Intermediate 12-1 (5.3 g, 0.012 mol) was added to Intermediate C-5 (4.6 g, 0.010 mol) and the compound 4 was synthesized in the same manner as in Production Example 1-7 to give 5.7 g (yield 69%) of Compound 4 .

_{H-NMR (200MHz, CDCl 3} ): δ ppm, 1H (8.55 / d, 7.94 / d, 7.87 / d, 7.77 / s, 7.71 / d, 7.69 / d, 7.25 / m, 7.22 / d, 6.77 / m 7H (8.30 / d, 7.54 / d, 7.52 / d, 7.51 / m, 7.47 / m, 7.33 / d, 7.33 / m, 7.25 / d, 7.23 / / m)

LC / MS: m / z = 823 [(M + 1) ^&lt; ^{+ &}

Example  13: Synthesis of compound 5

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

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 13-1.

LC / MS: m / z = 246 [(M + 1) ^&lt; ^{+ &}

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

(1.6 g, 0.010 mol) was added to Intermediate 2-1 (2.1 g, 0.010 mol), and 2.3 g (yield 77%) of Intermediate 2-2 was obtained by the same method as in Production Example 1-4 .

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

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

After dissolving in 30 ml of anhydrous THF to intermediate 2-2 (3.9 g, 0.012 mol), 5.9 ml of n-BuLi (2.5 M) was slowly added dropwise at -78 °. 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. After separating into EA: H ₂ O, 2.0 g (yield 70%) of Intermediate 2-3 was obtained by recrystallization with n-hexane.

LC / MS: m / z = 287 [(M + 1) ^&lt; ^{+ &}

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

(1.9 g, 0.008 mol) was added to Intermediate 13-3 (2.9 g, 0.010 mol), and 2.3 g (yield: 71%) of Intermediate 13-4 was synthesized in the same manner as in Preparation Example 1-7 %).

LC / MS: m / z = 398 [(M + 1) ^&lt; ^{+ &}

(5) Manufacturing example  13-5: Intermediate 13-5 Synthesis

(Pinacolato) dibron (3.0 g, 0.012 mol) was added to Intermediate 13-4 (4.0 g, 0.010 mol), and 3.2 g (yield: 72%) of Intermediate 13-5 %).

LC / MS: m / z = 445 [(M + 1) ^&lt; ^{+ &}

(6) Manufacturing example  13-6: Synthesis of compound 5

Intermediate 13-5 (5.3 g, 0.012 mol) was added to Intermediate C-5 (4.7 g, 0.010 mol), and 5.2 g (yield 70%) of Compound 5 was synthesized in the same manner as in Production Example 1-7 .

_{H-NMR (200MHz, CDCl 3} ): δ ppm, 1H (8.55 / d, 7.94 / d, 7.79 / d, 7.71 / d, 7.59 / d, 7.45 / m, 7.43 / m, 7.41 / m, 7.33 / m 7.52 / d, 7.51 / m, 7.50 / d, 7.33 / d, 7.23 / m, 1.40 / s ) 6H (7.25 / d)

LC / MS: m / z = 746 [(M + 1) ^&lt; ^{+ &}

Example  14: Synthesis of Compound 6

Intermediate 2-3 (6.1 g, 0.012 mol) was added to Intermediate C-5 (4.7 g, 0.010 mol), and 5.4 g (yield 73%) of Compound 6 was synthesized in the same manner as in Production Example 1-7 .

_{H-NMR (200MHz, CDCl 3} ): δ ppm, 1H (7.71 / d, 7.33 / m, 7.22 / d, 6.77 / m) 2H (8.28 / d, 7.33 / d, 7.23 / m, 1.40 / s) 3H (7.41 / m) 4H (7.85 / d, 7.52 / d, 7.25 / d) 6H (7.51 /

LC / MS: m / z = 736 [(M + 1) ^&lt; ^{+ &}

Example  15: Synthesis of Compound 7

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

Phenylmethanamine (7.0 g, 0.066 mol) and ferric chloride (0.07 g, 0.0004 mol) were added to 2-nitroaniline (3.0 g, 0.022 mol) and the mixture was reacted at 120 ° C for 48 hours with stirring. After completion of the reaction, the mixture was cooled to room temperature, and 50 ml of M. C was added thereto, followed by stirring for 30 minutes, followed by filtration. The obtained solid was subjected to column purification (n-hexane: EA) to obtain 3.1 g (yield 80%) of Intermediate 15-1.

LC / MS: m / z = 194 [(M + 1) ^&lt; ^{+ &}

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

To the intermediate 15-1 (2.0 g, 0.010 mol) was added methyl 2,6-dibromobenzoate (3.0 g, 0.015 mol), potassium carbonate (2.8 g, 0.020 mol), copper (0.1 g, 0.0020 mol), iodine copper , 0.006 mol) were dissolved in 70 ml of n-butyl ether and reacted under nitrogen for 48 hours with stirring. After completion of the reaction, the reaction mixture was cooled to room temperature, and subjected to column separation (n-hexane: EA) after separation of H ₂ O: MC layer to obtain 2.8 g (yield: 68%) of Intermediate 15-2.

LC / MS: m / z = 407 [(M + 1) ^&lt; ^{+ &}

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

Intermediate 15-2 (4.0 g, 0.010 mol) was dissolved in 30 ml of ether, cooled to -78 캜, and 2.5 M BuLi (0.01 ml, 0.0005 mol) was dropwise added thereto, followed by stirring for 1 hour. The mixture was slowly warmed to room temperature and stirred for 4 hours. After completion of the reaction, the reaction mixture was extracted with 100 ml of water and the organic layer was dried under reduced pressure. This was recrystallized from EtOH: Acetone to give Intermediate 15-3 (2.7 g, 67%).

LC / MS: m / z = 407 [(M + 1) ^&lt; ^{+ &}

(4) Manufacturing example  15-4: Intermediate 15-4 Synthesis

Intermediate 15-3 (4.0 g, 0.010 mol) was dissolved in 50 ml of concentrated H ₃ PO ₄ and stirred for 5 hours. This was extracted with 100 ml of water and 100 ml of Ethyl Acetate, and the organic layer was dried under reduced pressure. This was recrystallized from 100 ml of EtOH to obtain 2.8 g (yield 72%) of Intermediate 15-4.

LC / MS: m / z = 389 [(M + 1) ^&lt; ^{+ &}

(5) Manufacturing example  15-5: Intermediate 15-5 Synthesis

(Pinacolato) dibron (3.0 g, 0.012 mol) was added to Intermediate 15-4 (3.9 g, 0.010 mol), and 3.1 g (yield 72 %).

LC / MS: m / z = 436 [(M + 1) ^&lt; ^{+ &}

(6) Manufacturing example  15-6: Intermediate 15-6 Synthesis

Intermediate 15-5 (4.4 g, 0.010 mol) was added 1,4-dibromobenzene (1.9 g, 0.008 mol), and the reaction mixture was reacted in the same manner as in Preparation Example 1-7 to give 2.7 g of Intermediate 15-6 %).

LC / MS: m / z = 465 [(M + 1) ^&lt; ^{+ &}

(7) Manufacturing example  15-7: Intermediate 15-7 Synthesis

(3.5 g, 0.012 mol) of bis (pinacolato) dibron (3.0 g, 0.012 mol) was added to Intermediate 15-6 (4.7 g, 0.010 mol) in the same manner as in Preparation Example 1-6 to give 3.6 g %). (M / z = 512)

LC / MS: m / z = 512 [(M + 1) ^&lt; ^{+ &}

(8) Manufacturing example  15-8: Synthesis of Compound 7

Intermediate 15-7 (6.1 g, 0.012 mol) was added to Intermediate C-5 (4.7 g, 0.010 mol), and 5.7 g (Yield: 70%) of Compound 7 was synthesized in the same manner as in Production Example 1-7 .

_{H-NMR (200MHz, CDCl 3} ): δ ppm, 1H (7.61 / d, 7.41 / d, 7.14 / m, 6.77 / m) 2H (8.28 / d, 7.85 / d, 7.71 / d, 7.52 / d, 7.41 m, 7.33 / d, 7.23 / m, 7.22 / d, 1.72 / s, 1.40 / s)

LC / MS: m / z = 813 [(M + 1) ^&lt; ^{+ &}

Example  16: Synthesis of compound 8

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

Bis (pinacolato) dibron (3.0 g, 0.012 mol) was added to 1- (4-bromophenyl) -2-phenyl-1H-benzo [d] imidazole (3.5 g, 0.010 mol) To obtain 2.9 g (yield: 72%) of Intermediate 16-1.

LC / MS: m / z = 396 [(M + 1) ^&lt; ^{+ &}

(2) Manufacturing example  16-2: Compound 8 Synthesis

Intermediate 16-1 (4.8 g, 0.012 mol) was added to Intermediate C-6 (4.7 g, 0.010 mol), and 4.7 g (Yield: 70%) of Compound 8 was synthesized in the same manner as in Production Example 1-7 .

_{H-NMR (200MHz, CDCl 3} ): δ ppm, 1H (8.56 / d, 7.71 / d, 7.59 / d, 7.33 / m, 7.22 / d, 6.77 / m) 2H (8.28 / d, 7.85 / d, 7.79 m, 7.22 / m, 1.40 / s) 4H (7.51 / m)

LC / MS: m / z = 697 [(M + 1) ^&lt; ^{+ &}

Example  17: Compound 9 Synthesis

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

2-bromo-6-chlorobenzamide (2.3 g, 0.010 mol) was added to 2,5-dibromo-1H-pyrrole (2.2 g, 0.010 mol) 2.1 g (yield: 72%) of Intermediate D was obtained.

LC / MS: m / z = 297 [(M + 1) ^&lt; ^{+ &}

(2) Manufacturing example  17-2: Synthesis of intermediate D-1

Intermediate D (3.0 g, 0.010 mol) was added thereto and synthesized in the same manner as in Production Example 1-2 to obtain 1.6 g (yield: 58%) of Intermediate D-1.

LC / MS: m / z = 283 [(M + 1) ^&lt; ^{+ &}

(3) Manufacturing example  17-3: Synthesis of intermediate D-2

Intermediate D-1 (2.8 g, 0.010 mol) was added thereto, and 1.6 g (yield: 52%) of Intermediate D-2 was obtained in the same manner as in Production Example 1-3.

LC / MS: m / z = 311 [(M + 1) ^&lt; ^{+ &}

(4) Manufacturing example  17-4: Synthesis of intermediate D-3

3.0 g (yield 81%) of Intermediate D-3 was obtained by the same procedure as in Preparation Example 1-4, except that bromobenzene (1.6 g, 0.010 mol) was added to Intermediate D-2 (3.1 g, 0.010 mol) .

LC / MS: m / z = 387 [(M + 1) ^&lt; ^{+ &}

(5) Manufacturing example  17-5: Synthesis of intermediate D-4

2.7 g (yield 70%) of Intermediate D-4 was synthesized by the same method as in Preparation Example 1-7, except that phenyl boronic acid (1.4 g, 0.012 mol) was added to Intermediate D-3 (3.9 g, 0.010 mol) &Lt; / RTI >

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

(6) Manufacturing example  17-6: Compound 9 Synthesis

Intermediate 10-3 (6.1 g, 0.012 mol) was added to Intermediate D-4 (3.8 g, 0.010 mol), and 5.1 g (yield 70%) of Compound 9 was synthesized in the same manner as in Production Example 1-7 .

_{H-NMR (200MHz, CDCl 3} ): δ ppm, 1H (7.71 / d, 7.33 / m, 7.22 / d, 6.77 / m, 6.58 / d, 6.20 / d) 2H (8.28 / d, 7.79 / d, 7.52 m), 7H (7.85 / d, 7.25 / d), 6H (7.51 / m)

LC / MS: m / z = 734 [(M + 1) ^&lt; ^{+ &}

Example  18: Compound 10 Synthesis

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

Carbazole (3.3 g, 0.020 mol) was added to 3,4 ', 5-tribromobiphenyl (3.9 g, 0.010 mol) and the compound was synthesized in the same manner as in Preparation Example 1-4 to give 4.7 g Yield: 84%). (M / z = 563)

LC / MS: m / z = 563 [(M + 1) ^&lt; ^{+ &}

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

(Pinacolato) dibron (3.0 g, 0.012 mol) was added to Intermediate 18-1 (5.6 g, 0.010 mol), and 4.0 g (yield: 66%) of Intermediate 18-2 %).

LC / MS: m / z = 610 [(M + 1) ^&lt; ^{+ &}

(3) Manufacturing example  18-3: Compound 10 Synthesis

5.8 g (Yield: 70%) of Compound 10 was synthesized in the same manner as in Preparation Example 1-7, except that Intermediate 18-2 (7.3 g, 0.012 mol) was added to Intermediate C-5 (4.7 g, 0.010 mol) .

_{H-NMR (200MHz, CDCl 3} ): δ ppm, 1H (7.71 / d, 7.41 / m, 7.33 / m, 7.22 / d, 7.20 / s, 6.77 / m) 2H (8.55 / d, 8.12 / d, 8.09 m / s, 7.94 / d, 7.85 / d, 7.63 / d, 7.52 / d, 7.51 / m, 7.50 / m, 7.33 / d, 7.33 / m, 7.29 / m, 7.25 / d, 7.25 / , 1.40 / s)

LC / MS: m / z = 835 [(M + 1) ^&lt; ^{+ &}

Example  19: Compound 11 Synthesis

(One) Manufacturing example  19-1: Synthesis of intermediate 19-1

Bromobenzene (1.6 g, 0.010 mol) was added to Intermediate 13-1 (2.5 g, 0.010 mol), and 2.8 g (yield: 87%) of Intermediate 19-1 was obtained in the same manner as in Production Example 1-4 .

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

(2) Manufacturing example  19-2: Intermediate 19-2 Synthesis

3-ylboronic acid (2.1 g, 0.010 mol) was added to Intermediate 19-1 (3.2 g, 0.010 mol), and the intermediate 19-2 was synthesized in the same manner as in Preparation Example 1-4 to give 3.9 g (Yield: 87%).

LC / MS: m / z = 452 [(M + 1) ^&lt; ^{+ &}

(3) Manufacturing example  19-3: Compound 11 Synthesis

Intermediate 19-2 (5.4 g, 0.012 mol) was added to Intermediate C-5 (4.7 g, 0.010 mol) and the compound was synthesized by the same method as in Preparation Example 1-7 to give 5.9 g (Yield: 70%) of Compound 11 .

_{H-NMR (200MHz, CDCl 3} ): δ ppm, 1H (7.77 / s, 7.71 / d, 7.41 / m, 7.34 / m, 7.22 / d) 2H (8.55 / d, 7.94 / d, 7.85 / d, 7.58 7.33 / d, 7.25 / d, 7.25 / m, 1.40 / s) 3H (7.23 / d)

LC / MS: m / z = 836 [(M + 1) ^&lt; ^{+ &}

Example  20: Compound 12 Synthesis

(One) Manufacturing example  20-1: Synthesis of intermediate 20-1

3-ylboronic acid (2.9 g, 0.024 mol) was added to 1,3-dibromo-2,5-dichlorobenzene (3.0 g, 0.010 mol) -1> (yield: 70%).

LC / MS: m / z = 301 [(M + 1) ^&lt; ^{+ &}

(2) Manufacturing example  20-2: Intermediate 20-2 Synthesis

4,6-diphenyl-1,3,5-triazin-2-ylboronic acid (3.3 g, 0.012 mol) was added to Intermediate 20-1 (3.0 g, 0.010 mol) 3.0 g (yield: 61%) of Intermediate 20-2 was obtained (m / z = 497)

LC / MS: m / z = 497 [(M + 1) ^&lt; ^{+ &}

(3) Manufacturing example  20-3: Intermediate 20-3 Synthesis

(Pinacolato) dibron (3.0 g, 0.012 mol) was added to Intermediate 20-2 (5.0 g, 0.010 mol), and 4.2 g of Intermediate 20-3 (yield 72 %).

LC / MS: m / z = 589 [(M + 1) ^&lt; ^{+ &}

(4) Manufacturing example  20-4: Compound 12 Synthesis

Intermediate 20-3 (7.1 g, 0.012 mol) was added to Intermediate C-5 (4.7 g, 0.010 mol) and synthesized by the same method as in Production Example 1-7 to obtain 5.6 g (yield: 63%) of Compound 12 .

_{H-NMR (200MHz, CDCl 3} ): δ ppm, 1H (7.71 / d, 7.57 / d, 7.33 / m, 7.22 / d, 6.77 / m) 2H (9.24 / s, 8.70 / d, 8.42 / d, 7.85 m, 7.41 / m, 7.41 / m, 7.41 / m,

LC / MS: m / z = 891 [(M + 1) ^&lt; ^{+ &}

Example  21: Compound 13 Synthesis

(One) Manufacturing example  21-1: Synthesis of Intermediate 21-1

2-bromotriphenylene (3.1 g, 0.010 mol) was added to 1,4-9H-carbazol-3-ylboronic acid (2.1 g, 0.010 mol) > 3.5 g (yield: 81%). (M / z = 437)

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

(2) Manufacturing example  21-2: Compound 13 Synthesis

Intermediate 21-1 (5.2 g, 0.012 mol) was added to Intermediate C-5 (4.7 g, 0.010 mol), and 5.6 g (Yield: 68%) of Compound 13 was synthesized in the same manner as in Production Example 1-7 .

_{H-NMR (200MHz, CDCl 3} ): δ ppm, 1H (8.93 / d, 8.55 / d, 8.12 / d, 7.94 / d, 7.90 / m, 7.88 / m, 7.87 / d, 7.82 / m, 7.77 / s 7.71 / d, 7.69 / d, 7.41 / m, 7.33 / d, 7.33 / m, 7.25 / m, 7.22 / d, 6.77 / m) 2H (8.90 / s, 8.10 / s, 7.85 / , 7.52 / d, 7.51 / m, 7.33 / d, 7.25 / d, 7.23 / m, 1.40 / s)

LC / MS: m / z = 820 [(M + 1) ^&lt; ^{+ &}

Example  22: Compound 14 Synthesis

(One) Manufacturing example  22-1: Intermediate E Synthesis

2-bromobenzamide (2.0 g, 0.010 mol) was added to 3,5-dibromo-4H-1,2,4-triazole (2.3 g, 0.010 mol) E> 1.9 g (yield: 71%). (M / z = 265)

LC / MS: m / z = 265 [(M + 1) ^&lt; ^{+ &}

(2) Manufacturing example  22-2: Synthesis of intermediate E-1

1.5 g (yield: 58%) of Intermediate E-1 (m / z = 251) was obtained by adding the intermediate E (2.7 g, 0.010 mol)

LC / MS: m / z = 251 [(M + 1) ^&lt; ^{+ &}

(3) Manufacturing example  22-3: Synthesis of intermediate E-2

(M / z = 279) 1.5 g (yield: 55%) of Intermediate E-1 (2.5 g, 0.010 mol) was synthesized in the same manner as in Production Example 1-3.

LC / MS: m / z = 279 [(M + 1) ^&lt; ^{+ &}

(4) Manufacturing example  22-4: Synthesis of intermediate E-3

2.5 g (yield 70%) of Intermediate E-3 was obtained by the same procedure as in Preparation Example 1-4, except that bromobenzene (1.6 g, 0.010 mol) was added to Intermediate E-2 (2.8 g, 0.010 mol) . < / RTI > (m / z = 355)

LC / MS: m / z = 355 [(M + 1) ^&lt; ^{+ &}

(5) Manufacturing example  22-5: Compound 14 Synthesis

Intermediate 10-3 (6.1 g, 0.012 mol) was added to Intermediate E-3 (3.6 g, 0.010 mol), and 4.6 g (Yield: 70%) of Compound 14 was synthesized in the same manner as in Production Example 1-7 .

_{H-NMR (200MHz, CDCl 3} ): δ ppm, 1H (7.40 / m, 7.37 / m, 7.30 / d, 7.26 / d, 6.77 / m) 2H (8.28 / d, 7.52 / d, 7.41 / m, 7.25 / d, 7.23 / m, 1.40 / s) 4H (7.51 / m) 6H (7.85 / d)

LC / MS: m / z = 660 [(M + 1) ^&lt; ^{+ &}

Example  23: Compound 15 Synthesis

(One) Manufacturing example  23-1: Synthesis of Intermediate 23-1

9a-boronic acid (2.7g, 0.012mol) was added to 1,4-dibromobenzene (2.4g, 0.010mol) Yield: 70%).

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

(2) Manufacturing example  23-2: Intermediate 23-2 Synthesis

(Pinacolato) dibron (3.0 g, 0.012 mol) was added to Intermediate 23-1 (3.3 g, 0.010 mol), and 2.7 g of Intermediate 23-2 (yield 72 %).

LC / MS: m / z = 380 [(M + 1) ^&lt; ^{+ &}

(3) Manufacturing example  23-3: Compound 15 Synthesis

Intermediate 23-2 (4.6 g, 0.012 mol) was added to Intermediate C-4 (3.9 g, 0.010 mol), and 4.3 g (yield 72%) of Compound 15 was synthesized in the same manner as in Production Example 1-7 .

_{H-NMR (200MHz, CDCl 3} ): δ ppm, 1H (7.93 / d, 7.71 / d, 7.41 / m, 7.33 / m, 7.22 / d, 6.77 / m) 2H (8.93 / d, 8.28 / d, 8.12 7.8 / m, 7.51 / m, 7.33 / d, 7.23 / m, 1.40 / s)

LC / MS: m / z = 604 [(M + 1) ^&lt; ^{+ &}

Example  24: Compound 16 Synthesis

Intermediate 18-2 (7.3 g, 0.012 mol) was added to Intermediate C-4 (3.9 g, 0.010 mol), and 5.6 g (Yield 67%) of Compound 16 was synthesized in the same manner as in Production Example 1-7 .

_{H-NMR (200MHz, CDCl 3} ): δ ppm, 1H (7.71 / d, 7.41 / m, 7.34 / m, 7.22 / d, 7.20 / s) 2H (8.55 / d, 8.28 / d, 8.12 / d, 8.09 7.23 / m, 7.40 / d, 7.63 / d, 7.51 / m, 7.50 / m, 7.33 /

LC / MS: m / z = 837 [(M + 1) ^&lt; ^{+ &}

Example  25: Compound 17 Synthesis

(One) Manufacturing example  25-1: Intermediate F Synthesis

2,6-dibromobenzamide (2.8 g, 0.010 mol) was added to 2-chloro-3-methylbenzofuran (1.7 g, 0.010 mol) and the reaction was conducted in the same manner as in Production Example 1-1 to give 2.4 g 76%). (M / z = 314)

LC / MS: m / z = 314 [(M + 1) ^&lt; ^{+ &}

(2) Manufacturing example  25-2: Synthesis of intermediate F-1

Intermediate F (3.1 g, 0.010 mol) was added thereto, and 1.7 g (yield: 58%) of Intermediate F-1 was obtained in the same manner as in Production Example 1-2.

LC / MS: m / z = 300 [(M + 1) ^&lt; ^{+ &}

(3) Manufacturing example  25-3: Synthesis of intermediate F-2

Intermediate F-1 (3.0 g, 0.010 mol) was added thereto and synthesized in the same manner as in Production Example 1-3 to obtain 1.8 g (yield: 55%) of Intermediate F-2.

LC / MS: m / z = 328 [(M + 1) ^&lt; ^{+ &}

(4) Manufacturing example  25-4: Synthesis of intermediate 25-1

Intermediate 25-1 (3.9 g, 81%) was synthesized by the same method as in Preparation Example 1-4, except that 4-bromobiphenyl (2.3 g, 0.010 mol) was added to Intermediate F-2 (3.3 g, 0.010 mol) &Lt; / RTI >

LC / MS: m / z = 480 [(M + 1) ^&lt; ^{+ &}

(5) Manufacturing example  25-5: Intermediate 25-2 Synthesis

(3.3 g, 0.012 mol) of triphenylen-2-ylboronic acid was added to 1,4-dibromobenzene (2.4 g, 0.010 mol) Yield: 70%).

LC / MS: m / z = 383 [(M + 1) ^&lt; ^{+ &}

(6) Manufacturing example  25-6: Intermediate 25-3 Synthesis

Intermediate 25-3 (3.1 g, yield 72%) was obtained by synthesizing bis (pinacolato) dibron (3.0 g, 0.012 mol) in Intermediate 25-2 (3.8 g, 0.010 mol) %).

LC / MS: m / z = 430 [(M + 1) ^&lt; ^{+ &}

(7) Manufacturing example  25-7: Compound 17 Synthesis

Intermediate 25-3 (5.2 g, 0.012 mol) was added to Intermediate 25-1 (4.8 g, 0.010 mol) and the compound 17 was synthesized in the same manner as in Production Example 1-7 to give 4.4 g (yield: 63%) of Compound 17 .

_{H-NMR (200MHz, CDCl 3} ): δ ppm, 1H (9.15 / s, 8.18 / d, 8.04 / d, 7.89 / d, 7.66 / d, 7.41 / m, 7.39 / m, 7.38 / m, 7.32 / m ), 2H (8.93 / d, 8.12 / d, 7.88 / m, 7.82 / m, 7.67 / d, 7.57 / d, 7.52 / d, 7.51 / m, 6.61 / d, 1.40 / s)

LC / MS: m / z = 704 [(M + 1) ^&lt; ^{+ &}

Example  26: Compound 18 Synthesis

Intermediate 10-3 (6.1 g, 0.012 mol) was added to Intermediate 25-1 (4.8 g, 0.010 mol), and 5.1 g (yield 65%) of Compound 18 was synthesized in the same manner as in Production Example 1-7 .

_{H-NMR (200MHz, CDCl 3} ): δ ppm, 1H (7.89 / d, 7.66 / d, 7.39 / m, 7.38 / m, 7.32 / m) 2H (8.28 / d, 7.67 / d, 7.57 / d, 6.66 / d, 1.40 / s) 4H (7.85 / d, 7.52 / d, 7.25 / d) 6H (7.51 /

LC / MS: m / z = 784 [(M + 1) ^&lt; ^{+ &}

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

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 Ir (ppy) ₃ , CBP and NPB used in the above are as follows.

Device Example  1: Compound 1 With hole transport material  So Organic electroluminescent device  Produce

<Compound 183> was deposited on a glass substrate coated with ITO to form a hole transporting layer having a thickness of 120 nm, followed by deposition of Ir (ppy) ₃ as a dopant at a deposition rate of 0.009 nm / sec and using CBP as a host The deposition rate was 0.1 nm / sec, and Ir (ppy) ₃ was doped so that the deposition rate ratio was 9% to form a light emitting layer with a thickness of 30 nm on the hole transport layer.

Balq was deposited thereon to a thickness of 10 nm to form a hole blocking layer for preventing holes from moving to the electron transporting layer through the light emitting layer, and Alq ₃ was deposited thereon to form an electron transporting layer of 40 nm, and lithium fluoride Thereby forming an electron injection layer having a thickness of 1 nm. Aluminum was deposited on the electron injecting layer to form a 120 nm cathode, thereby fabricating an organic electroluminescent device.

At this time, the deposition rate of each material was set to 0.1 nm / sec for CBP, compound 1, Alq ₃ , Balq, 0.01 nm / sec for lithium fluoride, and 0.5 nm / sec for aluminum, which are organic materials.

Device Example  2 to 8

Except that CBP was used as a light emitting material instead of Compound 183 and the hole transporting material shown in Table 1 was used instead of NPB, the compound for organic electroluminescence devices of Device Examples 2 to 8 was obtained in the same manner as in Example 1 .

Device Example  9 to 26

The organic electroluminescent devices of the device embodiments 9 to 26 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 183.

Device comparison example  One

An organic electroluminescent device of Comparative Example 1 was manufactured in the same manner as in Example 1 except that (4,4-N, N-dicarbazole) biphenyl (CBP) was used instead of the compound 183 as a light emitting material.

Hereinafter, the characteristics of the organic electroluminescent device manufactured according to the device embodiments 1 to 26 and the device comparative example 1 are compared, and the results are shown in Table 1 below.

division Emitting material Hole transport material The driving voltage (V)
(at 1000 cd / m ² ) Luminous efficiency
(cd / A) Color coordinates
(CIE (x, y)) Device Embodiment 1 C B P Compound 183 5.1 58 (0.31, 0.63) Device Example 2 C B P Compound 184 6.1 46 (0.31, 0.63) Device Embodiment 3 C B P Compound 185 5.3 47 (0.32, 0.64) Device Example 4 C B P Compound 186 4.5 61 (0.32, 0.64) Element Embodiment 5 C B P Compound 187 5.5 47 (0.32, 0.64) Device Example 6 C B P Compound 188 5.9 47 (0.32, 0.64) Device Example 7 C B P Compound 189 5.9 45 (0.34, 0.62) Device Example 8 C B P Compound 190 5.6 46 (0.35, 0.63) Device Example 9 Compound 1 N P B 4.1 61 (0.34, 0.62) Element Embodiment 10 Compound 2 N P B 5.8 47 (0.34, 0.64) Element Embodiment 11 Compound 3 N P B 5.5 45 (0.33, 0.62) Device Example 12 Compound 4 N P B 5.9 48 (0.34, 0.64) Device Embodiment 13 Compound 5 N P B 5.4 48 (0.34, 0.62) Device Embodiment 14 Compound 6 N P B 4.6 54 (0.35, 0.63) Device Example 15 Compound 7 N P B 4.9 51 (0.34, 0.63) Device Embodiment 16 Compound 8 N P B 4.1 60 (0.32, 0.64) Device Example 17 Compound 9 N P B 5.9 44 (0.34, 0.64) Element Embodiment 18 Compound 10 N P B 5.8 46 (0.33, 0.63) Element Embodiment 19 Compound 11 N P B 5.7 45 (0.33, 0.61) Device Embodiment 20 Compound 12 N P B 5.9 46 (0.34, 0.62) Device Example 21 Compound 13 N P B 4.3 62 (0.34, 0.64) Device Embodiment 22 Compound 14 N P B 4.4 61 (0.33, 0.62) Device Example 23 Compound 15 N P B 5.1 45 (0.34, 0.64) Device Embodiment 24 Compound 16 N P B 5.6 45 (0.34, 0.62) Device Example 25 Compound 17 N P B 5.8 46 (0.35, 0.63) Device Embodiment 26 Compound 18 N P B 5.7 47 (0.34, 0.64) Device Comparative Example 1 C B P N P B 6.8 37 (0.33, 0.62)

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 electroluminescence device according to the present invention is used as a host material or a hole transporting material of a light emitting layer of an organic electroluminescence device, the conventional CBP is used as a light emitting material, or when NPB is used as a hole transporting material It can be seen that the driving voltage is significantly lowered and the luminous efficiency is significantly improved.

Claims (8)

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

In the above formula 1,
Ring a is an aromatic five-membered ring,
X ¹ is a nitrogen atom or a carbon atom,
X ² and X ⁴ may be the same or different from each other, and X ² and X ⁴ are each independently an oxygen atom, a sulfur atom, a nitrogen atom,

,

,

,

, or

ego,
R ⁶ to R ¹² may be the same or different from each other and each of R ⁶ to R ¹² 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,
X ³ represents an oxygen atom, a sulfur atom, a nitrogen atom,

,

,

,

, or

ego,
R ¹³ 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, a substituted or unsubstituted C1 to C30 heterocycloalkyl group, a substituted or unsubstituted C6 to C30 an aryl group, or is substituted or unsubstituted C1 to C30 heteroaryl group, or R ¹³ is R ¹³ a in conjunction with the adjacent carbon atoms and more carbon atoms substituted or unsubstituted fused bonding a 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 heteroaryl group,
R ¹⁴ to R ¹⁹ may be the same or different from each other, and each of R ¹⁴ to R ¹⁹ 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,
L is a valence-bonded, substituted or unsubstituted C6 to C30 arylene group, or a substituted or unsubstituted C1 to C30 heteroarylene group,
A represents a hydrogen atom, a deuterium atom, a substituted or unsubstituted C12 to C30 arylamine group, a substituted or unsubstituted C2 to C30 heteroarylamine group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 aryl group, C30 cycloalkyl group, a substituted or 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,
R ¹ and R ² may be the same or different from each other, R ¹ and R ² are each independently a substituted or unsubstituted C1 to C30 alkyl group,
R ³ to R ⁵ may be the same or different from one another and each of R ³ to R ⁵ 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. The method according to claim 1,
R ¹³ 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, a substituted or unsubstituted C1 to C30 heterocycloalkyl group, a substituted or unsubstituted C6 to C30 an aryl group, or a substituted or unsubstituted or C1 to C30 heteroaryl ring, or R ¹³ is the formation of a substituted or unsubstituted ring fused a benzene ring in combination with R ¹³ the adjacent carbon atom and the additional party that the combined carbon Wherein the organic electroluminescent device is a compound for an organic electroluminescent device. The method according to claim 1,
Wherein the compound for an organic electroluminescence device is any one selected from compounds 1 to 337 represented by the following formula.

An organic electroluminescent device comprising the compound for an organic electroluminescent device according to any one of claims 1 to 3. 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. 6. The method of claim 5,
Wherein the single or plural organic layers include a light emitting layer. 6. The method of claim 5,
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. The method according to claim 6,
Wherein the light emitting layer comprises a host and a dopant.

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