KR101640478B1 - Novel compound for organic electroluminescent device and organic electroluminescent device comprising the same - Google Patents

Abstract

An organic electroluminescent device compound and an organic electroluminescent device comprising the same are provided. As a result, it can be used as a host, a hole transporting material, and an organic light emitting device which can be used as an electron transporting material, which can improve the luminous efficiency of a phosphorescent light emitting material because of its excellent electrical stability, electron and hole transporting ability, A compound and an organic electroluminescent device can be 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 a heteroaromatic ring of five nuclear atoms,

이고, 나머지 하나는 질소원자 또는

이고, X < ^{1 >} and X < ² >

And the other is a nitrogen atom or

ego,

Ar ¹ is each independently selected from the group consisting of hydrogen, deuterium, cyano, halogen atom, hydroxy, substituted or unsubstituted C1 to C30 alkoxy, Substituted or unsubstituted C 1 to C 30 arylalkylamino groups, substituted or unsubstituted C 2 to C 30 alkenyl groups, substituted or unsubstituted silyl groups, substituted or unsubstituted C 1 to C 30 alkyl groups, 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 ⁵ is each independently selected from the group consisting of hydrogen, deuterium, 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, C30 aryl group, or a substituted or unsubstituted C1 to C30 heteroaryl group,

,

,

이고,Y ¹ And Y ² may be the same or different from each other, and Y ¹ And Y ² each independently represent an oxygen atom, a sulfur atom,

,

,

ego,

Ar ² is independently 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 aryl group, Or a substituted or unsubstituted C1 to C30 heteroaryl group,

R ⁶ to R ⁹ may be the same or different from each other and each of R ⁶ to R ⁹ is independently hydrogen, deuterium, 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 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 and each of R ¹ and R ² is independently hydrogen, deuterium, 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 aryl group, or a substituted or unsubstituted C1 to C30 heteroaryl group,

R ³ and R ⁴ may be the same or different from each other, and R ³ and R ⁴ are each independently selected from the group consisting of hydrogen, deuterium, substituted or unsubstituted C1 to C30 alkyl groups, substituted or unsubstituted C3 to C30 cycloalkyl groups, 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 ³ and R ⁴ is a substituted or unsubstituted C1 to C30 heterocycloalkyl group, 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 heteroaryl group.

According to an embodiment of the present invention, preferably,

The organic electroluminescent device compound is represented by any one of the following Structural Formulas 2 to 6,

In the above Structural Formulas 2 to 6,

, 또는

이고,A ¹ to A ¹¹ may be the same or different from each other, and A ¹ to A ¹¹ each independently represent a valence bond,

, or

ego,

R ¹⁶ to R ²¹ may be the same or different from each other and each of R ¹⁶ to R ²¹ independently represents hydrogen, deuterium, 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 aryl group, or a substituted or unsubstituted C1 to C30 heteroaryl group,

이고,Y ¹ And Y ² may be the same or different from each other, and Y ¹ And Y < ² > are each independently a sulfur atom or

ego,

Ar ² is independently 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 aryl group, Or a substituted or unsubstituted C1 to C30 heteroaryl group,

Ar ³ to Ar ⁹ may be the same or different from each other, Ar ³ to Ar ⁹ each independently represent a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, C30 heterocycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C1 to C30 heteroaryl group,

R ¹ to R ⁴ may be the same or different from each other and each of R ¹ to R ⁴ independently represents hydrogen, deuterium, 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 aryl group, or a substituted or unsubstituted C1 to C30 heteroaryl group,

R ¹⁰ to R ¹⁵ may be the same or different from each other and each of R ¹⁰ to R ¹⁵ independently represents hydrogen, deuterium, 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 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.

The organic electroluminescent device compound may be any one selected from compounds 1 to 133 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 a light emitting device comprising a first electrode, a second electrode, and a light emitting layer and a hole transporting layer between the first electrode and the second electrode, wherein at least one of the light emitting layer and the hole transporting layer comprises: The organic electroluminescent device according to the present invention can be provided as an organic electroluminescent device.

The organic electroluminescent device may further include at least one selected from the group consisting of an electron injecting layer, an electron transporting layer, a hole blocking layer, an electron blocking layer, and a hole injecting layer between the first electrode and the second electrode.

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, "covalent 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 C1 to C30 alkyl group, a C1 to C30 alkylsilyl group, a C3 to C30 cycloalkyl group, a C6 to C30 aryl group, a C1 to C20 aryl group, a C1 to C30 aryl group, a C1 to C30 aryl group, An alkoxy group, a C1 to C10 trifluoroalkyl group or a cyano group may be fused to form a 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 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, .

Will be described with reference to Figs. 1 and 2. Fig. According to an embodiment of the present invention, the organic electroluminescent device 1 including the compound for an organic electroluminescent device can be provided.

According to another embodiment of the present invention, a light emitting layer 134 and a hole transporting layer 136 are provided between a first electrode 110, a second electrode 150, and the first and second electrodes, An organic electroluminescent device 1 may be provided, wherein at least one of the hole transporting layers includes the compound for an organic electroluminescent device.

The organic electroluminescent device 1 further includes an electron injecting layer 131, an electron transporting layer 132, a hole blocking layer 133, an electron blocking layer 135, and a hole injecting layer 132 between the first electrode and the second electrode. (137) may be further included.

The light emitting layer 134 may include a host and a dopant.

At least one of the electron injecting layer 131, the electron transporting layer 132, the hole blocking layer 133, the light emitting layer 134, the electron blocking layer 135, the hole transporting layer 136 and the hole injecting layer 137, (130).

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 depending on the characteristics of the material, but may be determined usually within a 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 7

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

200 ml of THF / H ₂ O was added to potassium fluoride (1.7 g, 0.029 mol) in 3,5-dibromobenzene-1,2-diamine (5.0 g, 0.019 mol) and refluxed under nitrogen for 2 hours. After cooling the reaction mixture, water was added by the amount of the reaction solvent, and the mixture was extracted and purified by column (hexane: ethylene acetate) to obtain 2.7 g (yield: 70%) of Intermediate 7-1.

LC / MS: m / z = 205 [(M + 1) ^< ^{+ &}

(2) Manufacturing example  1-2: Intermediate 7-2 Synthesis

Tert-butoxide (2.9 g, 0.030 mol), Pd ₂ (dba) ₃ (0.3 g, 0.0003 mol) and ethyl 3-mercaptopropanoate (2.4 g, 0.018 mol) Was added 120 ml of TOL and refluxed under nitrogen for 16 hours. After cooling the reaction mixture, water was added by the amount of the reaction solvent, and the mixture was extracted and purified by column (hexane: ethylene acetate) to obtain 3.5 g (yield: 90%) of Intermediate 7-2.

LC / MS: m / z = 258 [(M + 1) ^< ^{+ &}

(3) Manufacturing example  1-3: Intermediate 7-3 Synthesis

1-bromo-3-fluorobenzene (3.0 g, 0.017 mol) was synthesized in the same manner as in Production Example 1-2 to give 2.7 g (yield: 70%) of Intermediate 7-3.

LC / MS: m / z = 228 [(M + 1) ^< ^{+ &}

(4) Manufacturing example  1-4: Intermediate 7-4 Synthesis

Intermediate 7-2 (3.0g, 0.012mol) and stirred for 30 minutes or more into a 120ml diethylether at a low temperature n-BuLi (0.1g, 0.001mol) and then stirred for at least 1 hour at a low temperature and then slowly dropped CuBr ₂ (5.4g , 0.024 mol) were added and stirred for 1 hour or longer. Then, nitrobenzene (1.6 g, 0.013 mol) and intermediate 7-3 (3.0 g, 0.013 mol) were added at room temperature and refluxed under nitrogen for 16 hours or longer. After the reaction mixture was cooled, water was added by the amount of the reaction solvent, and after extraction, column purification (hexane: ethylene acetate) was conducted to obtain 4.1 g (yield: 70%) of Intermediate 7-4.

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

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

STBT (2.9 g, 0.030 mol) and TOL (200 ml) were added to Intermediate 7-4 (5.0 g, 0.010 mol), stirred for 1 minute under nitrogen, treated with 10% HCl and then washed with MeOH to obtain Intermediate 7-5 : 80%).

LC / MS: m / z = 284 [(M + 1) ^< ^{+ &}

(6) Manufacturing example  1-6: Intermediate 7-6 Synthesis

Cs ₂ CO ₃ (13 g, 0.040 mol) and 120 ml of DMSO were added to Intermediate 7-5 (3.0 g, 0.010 mol), stirred at 50 ° C for 1 hour or more, and then refluxed at 150 ° C for 5 hours under nitrogen. After cooling the reaction mixture, water was added by the amount of the reaction solvent, and the mixture was extracted and purified by column (hexane: ethylene acetate) to obtain 1.8 g (yield: 72%) of intermediate 7-6.

LC / MS: m / z = 254 [(M + 1) ^< ^{+ &}

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

120 ml of nitroacetyl was added to intermediate 7-6 (3.0 g, 0.012 mol), benzaldehyde (1.5 g, 0.014 mol) and zinc acetate (0.1 g, 0.0006 mol), refluxed under nitrogen for 1 hour and stirred at room temperature for 10 minutes. After cooling the reaction mixture, water was added by the amount of the reaction solvent, and the mixture was extracted and purified by column (hexane) to obtain 3.2 g (yield: 80%) of intermediate 7-7.

LC / MS: m / z = 330 [(M + 1) ^< ^{+ &}

(8) Manufacturing example  1-8: Synthesis of Compound 7

Intermediate 7-7 (5.0g, 0.015mol) 2- ( 4-bromophenyl) triphenylene (6.9g, 0.018mol), Pd 2 (dba) 3 (0.3g, 0.0003mol), STBT (2.9g, 0.030mol) in Was added 200 ml of TOL and refluxed under nitrogen for 5 hours or more. After cooling the reaction mixture, water was added by the amount of the reaction solvent, and the mixture was extracted and purified by column (hexane: ethylene acetate) to obtain 6.4 g (yield: 68%) of Compound 7.

^{1 H-NMR (200MHz, CDCl} 3): δ ppm, 1H (9.20 (s) / 8.18 (d) / 8.04 (d) / 7.98 (d) / 7.50 (m) / 7.45 (d) / 7.41 (d) / 7.33 (s)), 2H (8.93 d / 8.28 d / 8.12 d / 7.88 m / 7.82 d / 7.68 d / 7.51 m)

LC / MS: m / z = 632 [(M + 1) ^< ^{+ &}

Example  2: Compound 8 Synthesis

(One) Manufacturing example  2-1: Intermediate 8-1 Synthesis

2,4,6-trichloro-1,3,5-triazine (3.0 g, 0.016 mol) and 9H-carbazole (5.9 g, 0.035 mol) were added thereto and the intermediate 8 -1 (3.7 g, yield: 52%).

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

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

Intermediate 8-1 (6.7 g, 0.015 mol) was added to Intermediate 7-7 (5.0 g, 0.015 mol), and 8.6 g (Yield: 70%) of Compound 8 was obtained by the same method as in Production Example 1-8 Respectively.

^{1 H-NMR (200MHz, CDCl} 3): δ ppm, 1H (7.98 (d) / 7.45 (d) / 7.41 (m)), 2H (8.55 (d) / 8.28 (d) / 8.12 (d) / 7.94 (d) / 7.79 (d) / 7.68 (d) / 7.63 (d) / 7.51 (m) / 7.29 (m) / 7.25 (m)

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

Example  3: Compound 13 Synthesis

(One) Manufacturing example  3-1: Synthesis of Intermediate 13-1

4,5-diamine (2.0 g, 0.018 mol) was used in place of Intermediate 7-6 used in Preparation Example 1-7, to obtain 2.8 g (yield: 80%) of Intermediate 13-1 %).

LC / MS: m / z = 196 [(M + 1) ^< ^{+ &}

(2) Manufacturing example  3-2: Intermediate 13-2 Synthesis

The intermediate 13-1 (4.3 g, 0.022 mol) was added to 3,6-dibromo-9- (4-bromophenyl) -9H-carbazole (5.0 g, 0.010 mol) 3.8 g (yield: 60%) of 13-2 was obtained.

LC / MS: m / z = 631 [(M + 1) ^< ^{+ &}

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

Synthesis was conducted in the same manner as in Example 1-8, except that Intermediate 13-2 (5.0 g, 0.008 mol) was used instead of 2- (4-bromophenyl) triphenylene to obtain 5.8 g (Yield: 75% ).

^{1 H-NMR (200MHz, CDCl} 3): δ ppm, 1H (7.98 (d) / 7.94 (d) / 7.63 (d) / 7.45 (d) / 7.33 (s) / 7.31 (d), 3H (7.50 ( (d) / 7.51 (m)), 6H (8.28 (d) / 7.51 (m)

LC / MS: m / z = 960 [(M + 1) ^< ^{+ &}

Example  4: Compound 17 Synthesis

Except that 2- (4-bromophenyl) -4,6-diphenyl-1,3,5-triazine (5.0 g, 0.013 mol) was used instead of 2- (4-bromophenyl) triphenylene used in Production Example 1-8 Were synthesized in the same way to obtain 5.5 g (Yield: 67%) of Compound 17.

^{1 H-NMR (200MHz, CDCl} 3): δ ppm, 1H (7.98 (d) / 7.50 (m) / 7.45 (d) / 7.33 (s)), 2H (7.79 (d) / 7.68 (d)), 3H (7.41 (m)), 6H (8.28 (d) / 7.51 (m)

LC / MS: m / z = 637 [(M + 1) ^< ^{+ &}

Example  5: Compound 25 Synthesis

(One) Manufacturing example  5-1: Synthesis of intermediate 25-1

Except that 3,5-dibromoaniline (3.0 g, 0.012 mol) was used instead of 3,5-dibromobenzene-1,2-diamine used in the synthesis method of Preparation Example 1-1, to obtain Intermediate 25-1 (Yield: 70%).

LC / MS: m / z = 190 [(M + 1) ^< ^{+ &}

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

Synthesis was carried out in the same manner except that Intermediate 25-1 (3.0 g, 0.016 mol) was used instead of Intermediate 7-1 used in Preparation Example 1-2 to obtain 3.1 g (yield: 80%) of Intermediate 25-2 Respectively.

LC / MS: m / z = 243 [(M + 1) ^< ^{+ &}

(3) Manufacturing example  5-3: Intermediate 25-3 Synthesis

Synthesis was conducted in the same manner as Intermediate 25-2 (3.0 g, 0.012 mol) in place of Intermediate 7-2 used in Preparation Example 1-4 to obtain 2.9 g (yield: 52%) of Intermediate 25-3 Respectively.

LC / MS: m / z = 469 [(M + 1) ^< ^{+ &}

(4) Manufacturing example  5-4: Intermediate 25-4 Synthesis

Synthesis was conducted in the same manner except that Intermediate 25-3 (3.0 g, 0.006 mol) was used instead of Intermediate 7-4 used in Preparation Example 1-5 to obtain 1.2 g (yield: 76%) of Intermediate 25-4 Respectively.

LC / MS: m / z = 269 [(M + 1) ^< ^{+ &}

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

(2.5 g, 0.011 mol) was used instead of Intermediate 7-5 used in Production Example 1-6, 1.8 g (yield: 71%) of Intermediate 25-5 was obtained .

LC / MS: m / z = 229 [(M + 1) ^< ^{+ &}

(6) Manufacturing example  5-6: Intermediate 25-6 Synthesis

1-phenylpropan-2-one (2.1 g, 0.016 mol) and 120 ml of TOL were added to Intermediate 25-5 (3.0 g, 0.013 mol) and refluxed under nitrogen for 5 hours or more. After cooling the reaction mixture, water was added by the amount of the reaction solvent, and the mixture was extracted and purified by column (hexane: ethylene acetate) to obtain 3.6 g (yield: 80%) of intermediate 25-6.

LC / MS: m / z = 345 [(M + 1) ^< ^{+ &}

(7) Manufacturing example  5-7: Intermediate 25-7 Synthesis

200 ml of DMSO was added to intermediate 25-6 (5.0 g, 0.014 mol) and Cu (OAc) ₂ (2.6 g, 0.042 mol) and catalyst Pd (OAc) ₂ (0.3 g, 0.0014 mol) Lt; / RTI > After cooling the reaction mixture, water was added by the amount of the reaction solvent, and the mixture was extracted and subjected to column purification (hexane: ethylene acetate) to obtain 3.4 g (yield: 74%) of intermediate 25-7.

LC / MS: m / z = 329 [(M + 1) ^< ^{+ &}

(8) Manufacturing example  5-8: Compound 25 Synthesis

Was synthesized in the same way except that 25-7 (5.0 g, 0.015 mol) was used in place of Intermediate 7-7 used in Production Example 1-8 to obtain 6.9 g (yield: 73%) of Compound 25.

8.08 (d) / 7.98 (d) / 7.50 (m) / 7.45 (d) / 7.41 (m) ¹ H-NMR (200 MHz, CDCl ₃ ) / 7.36 (s) / 7.33 (s)), 2H (8.93 (d) /8.12 (d) /7.88 (m) / 7.82 (d) / 7.68 (m)

LC / MS: m / z = 631 [(M + 1) ^< ^{+ &}

Example  6: Compound 42 Synthesis

(One) Manufacturing example  6-1: Synthesis of Intermediate 42-1

Synthesis was carried out in the same manner except that 2,4-dibromoaniline (3.0 g, 0.012 mol) was used instead of 3,5-dibromoaniline used in the synthesis of Intermediate 25-1 to obtain 2.8 g (yield: 80 %).

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

(2) Manufacturing example  6-2: Intermediate 42-2 Synthesis

Synthesis was conducted in the same manner as Intermediate 42-1 (3.0 g, 0.010 mol) instead of Intermediate 42-1 used in Preparative Example 5-2 to give 1.8 g (Yield: 76%) of Intermediate 42-2 Respectively.

LC / MS: m / z = 243 [(M + 1) ^< ^{+ &}

(3) Manufacturing example  6-3: Intermediate 42-3 Synthesis

Synthesis was conducted in the same manner except that Intermediate 42-2 (3.0 g, 0.012 mol) was used instead of Intermediate 25-2 used in Production Example 5-3 to obtain 3.3 g (yield: 70%) of Intermediate 42-3 Respectively.

LC / MS: m / z = 469 [(M + 1) ^< ^{+ &}

(4) Manufacturing example  6-4: Intermediate 42-4 Synthesis

Synthesis was conducted in the same manner except that Intermediate 42-3 (5.0 g, 0.010 mol) was used in place of Intermediate 25-3 used in Production Example 5-4 to obtain 1.9 g (yield: 72%) of Intermediate 42-4 Respectively.

LC / MS: m / z = 269 [(M + 1) ^< ^{+ &}

(5) Manufacturing example  6-5: Intermediate 42-5 Synthesis

Synthesis was conducted in the same manner except that Intermediate 42-4 (3.0 g, 0.011 mol) was used instead of Intermediate 25-4 used in Production Example 5-5 to obtain 2.0 g (yield: 80%) of Intermediate 42-5 Respectively.

LC / MS: m / z = 229 [(M + 1) ^< ^{+ &}

(6) Manufacturing example  6-6: Intermediate 42-6 Synthesis

Intermediate 42-5 (3.0 g, 0.013 mol) and 1-bromopropan-2-one (2.2 g, 0.016 mol) were used instead of Intermediate 25-5 used in Preparative Example 5-6 (Yield: 81%) of Intermediate 42-6 was obtained.

LC / MS: m / z = 348 [(M + 1) ^< ^{+ &}

(7) Manufacturing example  6-7: Intermediate 42-7 Synthesis

Synthesis was conducted in the same manner except that Intermediate 42-6 (5.0 g, 0.014 mol) was used instead of Intermediate 25-6 used in Preparation 5-7 to obtain 3.6 g (yield: 77%) of Intermediate 42-7 Respectively.

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

(8) Manufacturing example  6-8: Intermediate 42-8 Synthesis

Except that bromobenzene (2.4 g, 0.015 mol) was used instead of 42-7 (5.0 g, 0.015 mol) and 2- (4-bromophenyl) triphenylene in place of Intermediate 7-7 used in Preparation Example 1-8 To obtain 4.5 g (yield: 73%) of Intermediate 42-8.

LC / MS: m / z = 408 [(M + 1) ^< ^{+ &}

(9) Manufacturing example  6-9: Compound 42 Synthesis

(5.0 g, 0.012 mol) instead of Intermediate 7-7 used in Preparation Example 1-8, 3- (4-bromophenyl) -9-phenyl-9H-carbazole 4.8 g, 0.012 mol) was used in place of the compound obtained in Example 1 to obtain 5.8 g (yield: 75%) of Compound 42.

^{1 H-NMR (200MHz, CDCl} 3): δ ppm, 1H (8.55 (d) / 7.98 (d) / 7.94 (d) / 7.87 (d) / 7.77 (d) / 7.69 (d) / 7.36 (s) 7.55 (d)), 2H (7.33 (s, 1H / m, 1H), 3H (7.45

LC / MS: m / z = 646 [(M + 1) ^< ^{+ &}

Example  7: Compound 60 Synthesis

(One) Manufacturing example  7-1: Synthesis of intermediate 60-1

2-nitrophenylboronic acid (3.0g, 0.018mol ) in 4-bromo-3-nitrobenzene- 1,2-diamine (5.0g, 0.022mol), Pd (PPh3) 4 (1.0g, 00009mol), K 2 CO 3 ( 7.5 g, 0.054 mol), 2-nitrophenylboronic acid and 150 ml of THF were added and refluxed under nitrogen for 16 hours. After cooling the reaction mixture, water was added by the amount of the reaction solvent, and the mixture was extracted and purified by column (hexane: ethylene acetate) to obtain 4.4 g (yield 90%) of intermediate 60-1 (m / z = 274).

LC / MS: m / z = 274 [(M + 1) ^< ^{+ &}

(2) Manufacturing example  7-2: Intermediate 60-2 Synthesis

Triphenylphosphine (10.0 g, 0.040 mol) and 1,2-dichlorobezene (120 ml) were added to the intermediate 60-1 (3.0 g, 0.010 mol) and refluxed under nitrogen for 16 hours or longer. After cooling the reaction mixture, water was added by the amount of the reaction solvent, and the mixture was extracted and purified by column (hexane: ethylene acetate) to obtain 1.6 g (yield: 74%) of Intermediate 60-2.

LC / MS: m / z = 210 [(M + 1) ^< ^{+ &}

(3) Manufacturing example  7-3: Intermediate 60-3 Synthesis

Iodobezene (5.5 g, 0.028 mol) and K ₂ CO ₃ (6.1 g, 0.044 mol) were added to 120 ml of DMF and refluxed under nitrogen for 16 hours. After the reaction mixture was cooled, water was added by the amount of the reaction solvent, and the mixture was extracted and then subjected to column purification (hexane: ethylene acetate) to obtain 1.0 g (yield: 25%) of Intermediate 60-3.

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

(4) Manufacturing example  7-4: Intermediate 60-4 Synthesis

Except that 60-3 (5.0 g, 0.014 mol) was used instead of pyridazine-4,5-diamine used in Production Example 3-1, to obtain 4.4 g (yield: 70%) of Intermediate 60-4, ).

LC / MS: m / z = 448 [(M + 1) ^< ^{+ &}

(5) Manufacturing example  7-5: Compound 60 Synthesis

Except that 60-4 (5.0 g, 0.011 mol) was used instead of 42-8 used in Production Example 6-9, 5.5 g (yield: 65%) of Compound 60 was obtained.

^{1 H-NMR (200MHz, CDCl} 3): δ ppm, 1H (8.55 (d) / 7.87 (d) / 7.77 (d) / 7.70 (s) / 7.69 (d) / 7.54 (d) / 7.41 (m) / 7.25 (m), 2H (8.28 (d) / 7.94 (d) / 7.79 (d) / 7.68 (d) / 7.51 (m) / 7.33 m) / 7.50 (d)

LC / MS: m / z = 765 [(M + 1) ^< ^{+ &}

Example  8: Compound 61 Synthesis

Except that 60-4 (5.0 g, 0.011 mol) was used instead of 7-7 used in Production Example 1-8 to obtain 5.6 g (Yield: 68%) of Compound 61.

^{1 H-NMR (200MHz, CDCl} 3): δ ppm, 1H (9.15 (s) / 8.18 (d) / 8.04 (d) / 7.94 (d) / 7.70 (s) / 7.54 (d) / 7.41 (m) / 7.33 (m)), 2H (8.93 (d) / 8.28 (d) /8.12 (d) /7.88 (m) / 7.82 (d) /7.68 (m)), 4H (7.58 (m) / 7.50 (d)).

LC / MS: m / z = 750 [(M + 1) ^< ^{+ &}

Example  9: Compound 67 Synthesis

Instead of 2- (4-bromophenyl) -1-phenyl-1H-benzo [d (4-bromophenyl) ] imidazole (3.8 g, 0.011 mol) was used in place of the compound obtained in Example 1 to obtain 5.6 g (Yield: 68%) of Compound 67.

^{1 H-NMR (200MHz, CDCl} 3): δ ppm, 1H (8.56 (d) / 7.94 (d) / 7.70 (s) / 7.59 (d) / 7.54 (d) / 7.41 (m) / 7.33 (m) 7.58 (m)), 3H (7.45 m), 6H (7.58 (m), 7.50 (d)), 2H (8.28 (d)

LC / MS: m / z = 750 [(M + 1) ^< ^{+ &}

Example  10: Compound 77 Synthesis

(One) Manufacturing example  10-1: Synthesis of Intermediate 77-1

Except that 3-bromo-2-nitroaniline (3.0 g, 0.014 mol) was used instead of 4-bromo-3-nitrobenzene-1,2-diamine used in Preparation Example 7-1 to obtain Intermediate 77 -1 (3.3 g, yield: 90%).

LC / MS: m / z = 259 [(M + 1) ^< ^{+ &}

(2) Manufacturing example  10-2: Intermediate 77-2 Synthesis

Except that 77-1 (3.0 g, 0.012 mol) was used instead of 60-1 used in Production Example 7-2, 1.8 g (yield: 75%) of Intermediate 77-2 was obtained.

LC / MS: m / z = 195 [(M + 1) ^< ^{+ &}

(3) Manufacturing example  10-3: Intermediate 77-3 Synthesis

Except that 77-2 (3.0 g, 0.015 mol) was used instead of 60-2 used in Production Example 7-3, 1.6 g (yield: 30%) of Intermediate 77-3 was obtained.

LC / MS: m / z = 347 [(M + 1) ^< ^{+ &}

(4) Manufacturing example  10-4: Intermediate 77-4 Synthesis

Synthesis was carried out in the same manner except that Intermediate 77-3 (3.0 g, 0.009 mol) was used instead of Intermediate 42-5 used in Preparation Example 6-6 to obtain 3.1 g (yield: 74%) of Intermediate 77-4 Respectively.

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

(5) Manufacturing example  10-5: Intermediate 77-5 Synthesis

Synthesis was conducted in the same manner as Intermediate 77-4 except that Intermediate 77-4 (5.0 g, 0.011 mol) was used instead of Intermediate 42-6 used in Preparation Example 6-7 to obtain 3.5 g (yield: 71%) of Intermediate 77-5 Respectively.

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

(6) Manufacturing example  10-6: Compound 77 Synthesis

1-yl) phenylboronic acid (4.1 g, 0.013 mol), Catalyst Pd (PPh3), and the like were added to Intermediate 77-5 (5.0 g, 0.011 mol) 4 (0.6 g, 0.0006 mol) and K ₂ CO ₃ (4.6 g, 0.033 mol) were added and refluxed under nitrogen for 5 hours. After cooling the reaction mixture, water was added by the amount of the reaction solvent, and the mixture was extracted and purified by column (hexane: ethylene acetate) to obtain 5.7 g (yield: 72%) of Compound 77.

^{1 H-NMR (200MHz, CDCl} 3): δ ppm, 1H (8.87 (s) / 8.43 (d) / 7.94 (d) / 7.54 (d) / 7.41 (m) / 7.36 (s) / 7.33 (m) 7.58 (d) / 7.57 (d)), 2H ((8.28 (d) / 7.79 (d) / 7.68 )

LC / MS: m / z = 716 [(M + 1) ^< ^{+ &}

Example  11: Synthesis of compound 80

(9-phenyl-9H-carbazol-3-yl) phenylboronic acid instead of 4- (2-phenyl-1H-imidazo [4,5- phenylboronic acid (4.7g, 0.013mol) was used in place of the compound obtained in Example 1, and 7.5g (yield: 76%) of Compound 80 was obtained.

^{1 H-NMR (200MHz, CDCl} 3): δ ppm, 1H (8.55 (d) / 7.87 (d) / (7.77 (s) / 7.69 (d) / 7.54 (d) / 7.36 (s) / 7.17 (s 7.58 (m)), 2H (7.94 (d) / 7.33 (m)), 4H (7.45

LC / MS: m / z = 764 [(M + 1) ^< ^{+ &}

Example  12: Compound 82 Synthesis

4- (triphenylen-2-yl) phenylboronic acid (4.5 g, 0.1 mmol) instead of 4- (2-phenyl-1H- imidazo [4,5- c] pyridin- 0.013 mol) was used in place of the compound obtained in Example 1 to obtain 5.5 g (yield: 67%) of Compound 82.

^{1 H-NMR (200MHz, CDCl} 3): δ ppm, 1H (9.15 (s) / 8.18 (d) / 8.04 (d) / 7.94 (d) / 7.54 (d) / 7.36 (s) / 7.33 (m) (7.18 (s)), 2H (8.93 (d) /8.12 (d) /7.88 m), 7.50 (d)

LC / MS: m / z = 749 [(M + 1) ^< ^{+ &}

Example  13: Compound 88 Synthesis

4- (4,6-diphenyl-1,3,5-triazol-4-yl) phenylboronic acid was used instead of 4- (2-phenyl- triazin-2-yl) phenylboronic acid (4.6 g, 0.013 mol) was used to obtain 5.0 g of the compound 88 (yield: 60%).

^{1 H-NMR (200MHz, CDCl} 3): δ ppm, 1H (7.94 (d) / 7.54 (d) / 7.36 (s) / 7.33 (m) / 7.17 (s)), 2H (7.85 (d), 7.41 (m) / 7.25 (d)), 3H (7.45 m), 4H (8.28 (d) / 7.51 (m)

LC / MS: m / z = 754 [(M + 1) ^< ^{+ &}

Example  14: Compound 89 Synthesis

4- (4,6-di (9H-carbazol-9-yl) phenylboronic acid was used in place of 4- (2-phenyl-1H-imidazo [4,5- yl) -1,3,5-triazin-2-yl) phenylboronic acid (6.9g, 0.013mol) was used to give 6.4g (Yield: 62%) of compound 89.

^{1 H-NMR (200MHz, CDCl} 3): δ ppm, 1H (7.54 (d) / 7.36 (s) / 7.17 (s)), 2H (8.55 (d) / 8.12 (d) / 7.85 (d) / 7.63 (d) / 7.29 (m)), 3H (7.94 (d) / 7.45 (m) / 7.33 (m)), 4H (7.25 )

LC / MS: m / z = 933 [(M + 1) ^< ^{+ &}

Example  15: Compound 101 Synthesis

(One) Manufacturing example  15-1: Synthesis of Intermediate 101-1

Except that 2-fluoro-6-nitrophenylboronic acid (3.0 g, 0.016 mol) was used instead of 77-5 used in Production Example 10-6, thereby obtaining 4.2 g (yield: 85%) of Intermediate 101-1 %).

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

(2) Manufacturing example  15-2: Intermediate 101-2 Synthesis

Synthesis was conducted in the same manner as Intermediate 101-1 (3.0, 0.010 mol), except that Intermediate 101-1 (3.0, 0.010 mol) was used instead of Intermediate 25-1 used in the synthesis of Preparation Example 5-2 to give 2.8 g (Yield: 76% .

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

(3) Manufacturing example  15-3: Intermediate 101-3 Synthesis

(3.0 g, 0.008 mol) was used instead of Intermediate 25-3 used in Production Example 5-4, 1.7 g (Yield: 80%) of Intermediate 101-3 was obtained .

LC / MS: m / z = 264 [(M + 1) ^< ^{+ &}

(4) Manufacturing example  15-4: Intermediate 101-4 Synthesis

(3.0 g, 0.011 mol) and triphenylphosphine (5.5 g, 0.022 mol) were used instead of 60-1 used in Production Example 7-2, 2.0 g of Intermediate 101-4 (Yield: 79%).

LC / MS: m / z = 232 [(M + 1) ^< ^{+ &}

(5) Manufacturing example  15-5: Intermediate 101-5 Synthesis

Except that Intermediate 7-5 was replaced with Intermediate 101-4 (3.0 g, 0.013 mol) and Cs ₂ CO ₃ (8.5 g, 0.026 mol) instead of Intermediate 7-5 used in Preparation Example 1-6. (Yield: 71%).

LC / MS: m / z = 212 [(M + 1) ^< ^{+ &}

(6) Manufacturing example  15-6: Intermediate 101-6 Synthesis

Intermediate 101-5 (3.0 g, 0.014 mol) and 1-bromopropan-2-one (1.9 g, 0.014 mol) were used instead of Intermediate 25-5 used in Preparative Example 5-6 (Yield: 77%) of intermediate 101-6 was obtained.

LC / MS: m / z = 331 [(M + 1) ^< ^{+ &}

(7) Manufacturing example  15-7: Synthesis of intermediate 101-7

Synthesis was conducted in the same manner except that Intermediate 101-6 (3.0 g, 0.009 mol) was used instead of Intermediate 25-6 used in Preparation 5-7 to obtain 2.0 g (yield: 70%) of Intermediate 101-7 Respectively.

LC / MS: m / z = 315 [(M + 1) ^< ^{+ &}

(8) Manufacturing example  15-8: Synthesis of Intermediate 101-8

Was synthesized in the same manner as in Production Example 7-3, except that 101-7 (3.0 g, 0.010 mol) was used instead of 60-2, thereby obtaining 2.8 g (yield: 60%) of Intermediate 101-8.

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

(9) Manufacturing example  15-9: Compound 101 Synthesis

4- (triphenylen-2-yl) phenylboronic acid (4.5 g, 0.1 mmol) instead of 4- (2-phenyl-1H- imidazo [4,5- c] pyridin- 0.013 mol) was used in place of the compound obtained in Example 1 to obtain 5.8 g (Yield: 76%) of Compound 101.

^{1 H-NMR (200MHz, CDCl} 3): δ ppm, 1H (9.15 (s) / 8.18 (d) / 8.04 (d) / 7.98 () / 7.36 (s)) / 2H (8.93 (d) / 8.12 ( 7.48 (m) / 7.48 (m) / 7.33 (s)), 4H (7.58 (m), 7.25

LC / MS: m / z = 690 [(M + 1) ^< ^{+ &}

Example  16: Compound 112 Synthesis

(One) Manufacturing example  16-1: Synthesis of Intermediate 112-1

Except that 2-phenyl-1H-benzo [d] imidazole (4.3 g, 0.022 mol) was used in place of Intermediate 13-1 used in Preparation Example 3-2, 9.5 g (Yield: 61%).

(2) Manufacturing example  16-2: Intermediate 112-2 Synthesis

To the intermediate 112-1 (5.0 g, 0.007 mol) was added bis (pinacolato) diboron (2.1 g, 0.008 mol), catalyst PdCl ₂ (dppf) (0.4 g, 0.0004 mol), KOAc (2.4 g, 0.021 mol) And refluxed under nitrogen for 5 hours. After cooling the reaction mixture, water was added by the amount of the reaction solvent, and the mixture was extracted and purified by column (hexane: ethylene acetate) to obtain 2.7 g (yield: 52%) of intermediate 112-2.

LC / MS: m / z = 753 [(M + 1) ^< ^{+ &}

(3) Manufacturing example  16-3: Compound 112 Synthesis

Synthesis was carried out in the same manner except that 101-8 (3.7 g, 0.008 mol) was used instead of Intermediate 7-7 used in Production Example 3-3, and 112-1 (6.0 g, 0.008 mol) was used instead of Intermediate 13-2. 3.8 g (Yield: 67%) of Compound 112 was obtained.

^{1 H-NMR (200MHz, CDCl} 3): δ ppm, 1H (7.98 (d) / 7.94 (d) / 7.63 (d) / 7.62 (d) / 7.36 (s) / 7.31 (d)), 2H (8.56 (d) / 7.79 (d) / 7.68 (d) / 7.59 (d) / 7.45 (m) / 7.41 (m) / 7.33 ) / 7.22 (m)), 7H (7.50 (s, 2H / d, 4H /

LC / MS: m / z = 706 [(M + 1) ^< ^{+ &}

Example  17: Compound 120 Synthesis

(One) Manufacturing example  17-1: Synthesis of intermediate 120-1

4-iodobenzene-1,2-diamine (3.0 g, 0.016 mol), 4- (2-phenyl-1H-imidazo [4,5- (yield: 88%) was prepared in the same manner except that 2-fluoro-6-nitrophenylboronic acid (5.0 g, 0.016 mol) was used instead of 2- .

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

(2) Manufacturing example  17-2: Synthesis of intermediate 120-2

Synthesis was conducted in the same manner except that Intermediate 120-1 (3.0 g, 0.009 mol) was used in place of Intermediate 25-1 used in Production Example 5-2 to obtain 2.6 g (yield: 75%) of Intermediate 120-2 Respectively.

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

(3) Manufacturing example  17-3: Intermediate 120-3 Synthesis

(3.0 g, 0.008 mol) was used instead of Intermediate 25-3 used in Production Example 5-4, 1.7 g (yield: 78%) of Intermediate 120-3 was obtained .

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

(4) Manufacturing example  17-4: Intermediate 120-4 Synthesis

Except that 120-3 (2,8 g, 0.010 mol) and triphenylphosphine (5.0 g, 0.020 mol) were used instead of 60-1 used in Preparation Example 7-2 to obtain Intermediate 120-4 in an amount of 1.9 g (yield: 77%).

LC / MS: m / z = 247 [(M + 1) ^< ^{+ &}

(5) Manufacturing example  17-5: Intermediate 120-5 Synthesis

Instead of Intermediate 7-5 used in Preparation Example 1-6 120-4 (2.5g, 0.010mol), Cs 2 CO 3 (6.5g, 0.020mol) and is synthesized in the same manner except that Intermediate 120-5 (Yield: 77%).

LC / MS: m / z = 227 [(M + 1) ^< ^{+ &}

(6) Manufacturing example  17-6: Intermediate 120-6 Synthesis

Except that 120-5 (3.0 g, 0.013 mol) was used instead of 60-2 used in Production Example 7-3, 2.0 g (yield: 50%) of Intermediate 120-6 was obtained.

LC / MS: m / z = 303 [(M + 1) ^< ^{+ &}

(7) Manufacturing example  17-7: Intermediate 120-7 Synthesis

Was synthesized in the same manner as in Production Example 3-1, except that 120-6 (3.0 g, 0.010 mol) was used instead of pyridazine-4,5-diamine to obtain 3.0 g (yield: 78% ).

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

(8) Manufacturing example  17-8: Synthesis of compound 120

Was synthesized in the same manner as Intermediate 120-7 (3.9 g, 0.010 mol) instead of Intermediate 7-7 used in Preparation Example 1-8 to obtain 5.7 g (yield: 82%) of Compound 120.

^{1 H-NMR (200MHz, CDCl} 3): δ ppm, 1H (9.15 (s) / 8.18 (d) / 8.04 (d) / 7.98 (d) / 7.45 (m) / 7.41 (m)), 2H (8.93 (d) / 8.28 (d) /8.12 (d) / 7.88 (m) / 7.82 (m) / 7.79 (d) / 7.68 (d) / 7.58 (m) / 7.51 (m) / 7.33 3H (7.50 (m, 1H / d, 2H))

LC / MS: m / z = 691 [(M + 1) ^< ^{+ &}

Example  18: Synthesis of Compound 121

Intermediate 120-7 (3.9 g, 0.010 mol) and 2- (4-bromophenyl) -1-phenyl-1H-benzo [d] imidazole (3.5 g, 0.010 mol) was used to synthesize Compound 121 (5.3 g, yield: 80%).

^{1 H-NMR (200MHz, CDCl} 3): δ ppm, 1H (8.56 (d) / 7.98 (d) / 7.59 (d) / 7.41 (m)), 2H (8.28 (d), 7.79 (d), 7.68 1H), 7.51 (m), 7.45 (m) / 7.33 (s) / 7.22

LC / MS: m / z = 657 [(M + 1) ^< ^{+ &}

Example  19: Compound 126 Synthesis

Intermediate 120-7 (3.9 g, 0.010 mol) and 2- (4-bromophenyl) -4,6-diphenyl-1 , And 3,5-triazine (3.9 g, 0.010 mol) were used in place of the compound obtained in the previous step, to obtain 5.6 g (yield: 81%) of the compound 126.

^{1 H-NMR (200MHz, CDCl} 3): δ ppm, 1H (7.98 (d) / 7.45 (m)), 2H (7.79 (d) / 7.68 (d) / 7.58 (m) / 7.33 (s)), (7.50 (d, 2H / m, 1 H)) / 7.41 (m), 6H (8.28 (d) / 7.51

LC / MS: m / z = 696 [(M + 1) ^< ^{+ &}

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

Device Example  1: Compound 7 The light-  As a host material Organic electroluminescent device  Produce

Depositing NPB on the glass substrate coated with ITO to form a hole transport layer was of 120nm, followed by Ir (ppy) the deposition rate of the compound 7 to a ₃ as the dopant 0.1nm / sec, Ir (ppy) ₃ deposition rate 0.009nm / 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 compound 1, NPB, Alq ₃ , Balq, 0.01 nm / sec for lithium fluoride, and 0.5 nm / sec for aluminum.

Device Example  2 to 19

The organic electroluminescent devices of Device Examples 2 to 19 were fabricated in the same manner as in Example 1 except that the compounds described in the following Table 1 were used instead of the above compounds.

Device comparison example  One

The organic light emitting diode device for the comparative example was fabricated in the same manner except that CBP, which is generally used as a phosphorescent host material, was used in place of the compound prepared by the invention in the device structure of the embodiment, and the structure of the CBP is as follows.

(CBP)

Table 1 shows the results of comparing the characteristics of the organic electroluminescent devices manufactured according to the device embodiments 1 to 19 and the device comparison example 1.

Emitting material The driving voltage (V)
(at 1000 cd / m ² ) Luminous efficiency
(cd / A) Color coordinates
(CIE (x, y)) Device Embodiment 1 Compound 7 5.0 63 (0.31, 0.63) Device Example 2 Compound 8 5.1 52 (0.31, 0.63) Device Embodiment 3 Compound 13 5.0 49 (0.32, 0.64) Device Example 4 Compound 17 4.9 61 (0.32, 0.64) Element Embodiment 5 Compound 25 4.5 53 (0.32, 0.64) Device Example 6 Compound 42 4.9 46 (0.32, 0.64) Device Example 7 Compound 60 4.9 51 (0.34, 0.62) Device Example 8 Compound 61 5.1 48 (0.35, 0.63) Device Example 9 Compound 67 5.5 60 (0.34, 0.62) Element Embodiment 10 Compound 77 4.5 55 (0.32, 0.64) Element Embodiment 11 Compound 80 5.1 49 (0.35, 0.64) Device Example 12 Compound 82 5.5 53 (0.32, 0.64) Device Embodiment 13 Compound 88 5.0 49 (0.35, 0.65) Device Embodiment 14 Compound 89 5.2 51 (0.34, 0.62) Device Example 15 Compound 101 5.1 47 (0.33, 0.63) Device Embodiment 16 Compound 112 4.8 48 (0.32, 0.62) Device Example 17 Compound 120 4.9 48 (0.33, 0.62) Element Embodiment 18 Compound 121 4.8 49 (0.31, 0.63) Element Embodiment 19 Compound 126 5.0 55 (0.35, 0.66) Device Comparative Example 1 C B P 6.9 38 (0.31, 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 programs) the current deposition raises by 1mA / m ² were fixed to the surface the light emission luminance (cd / m ^2), 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 the Table 1 shows the results.

According to Table 1, when the compound for an organic electroluminescence device according to the present invention is used as a host material of a light emitting layer of an organic electroluminescence device, the driving voltage is considerably lower than that of the conventional CBP as a light emitting material and the luminous efficiency is considerably improved Able to know.

Claims (7)

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

In the above formula 1,
Ring a is a heteroaromatic ring of five nuclear atoms,
Y ¹ and Y ² may be the same or different from each other, Y ¹ and Y ² are each independently a sulfur atom or

, Ar < ² > is a phenyl group,
R ¹ , R ³ and R ⁴ are hydrogen, R ² is hydrogen or a phenyl group,
X < ^{1 >} and X < ² >

And the other is a nitrogen atom or

ego,
Ar ¹ and R ⁵ are each independently phenyl or any one selected from the following Structural Formula 2.
[Structural formula 2]

delete delete An organic electroluminescent device comprising the compound for organic electroluminescent device according to claim 1. A light emitting layer and a hole transporting layer between the first electrode and the second electrode,
Wherein at least one of the light emitting layer and the hole transporting layer comprises the compound for an organic electroluminescence device according to claim 1. 6. The method of claim 5,
Wherein the organic electroluminescent device further comprises at least one selected from the group consisting of an electron injecting layer, an electron transporting layer, a hole blocking layer, an electron blocking layer, and a hole injecting layer between the first electrode and the second electrode. An electroluminescent device. 6. The method of claim 5,
Wherein the light emitting layer comprises a host and a dopant.

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