WO2017196081A1

WO2017196081A1 - Compound for organic electroluminescent device and organic electroluminescent device comprising the same

Info

Publication number: WO2017196081A1
Application number: PCT/KR2017/004840
Authority: WO
Inventors: Yu-Mi Chang; Jeong Ho Park; Ju-Sik Kang; Nam-Choul Yang; Jae-Kyun Park; Song Lee
Original assignee: Sk Chemicals Co., Ltd.
Priority date: 2016-05-11
Filing date: 2017-05-10
Publication date: 2017-11-16

Abstract

This invention provides a compound for an organic electroluminescent device and an organic electroluminescent device including the same. This invention provides a compound for an organic EL device, which may have high thermal stability, improved light emission efficiency and lifetime and hole transport capability. Further, when this compound is used as a hole transport layer material in contact with a light emitting layer, thereby increasing a triplet energy, ultimately improving efficiency of the organic EL device and lifetime.

Description

COMPOUND FOR ORGANIC ELECTROLUMINESCENT DEVICE AND ORGANIC ELECTROLUMINESCENT DEVICE COMPRISING THE SAME

The present invention relates to a compound for an organic electroluminescent device and an organic electroluminescent device including the same, and more particularly, to an amine-based compound for an organic electroluminescent device, having excellent light emission efficiency and lifetime, and to an organic electroluminescent device including the same.

Organic electroluminescent (EL) devices have a simpler structure, various processing advantages, higher brightness, superior viewing angle properties, quicker response rate, and a lower driving voltage compared to other flat panel displays such as liquid crystal displays (LCDs), plasma display panels (PDPs), field emission displays (FEDs), etc., and are thus being thoroughly developed so as to be utilized as light sources of flat panel displays such as wall-mountable TVs, etc. or backlight units of the displays, illuminators, advertisement boards and so on.

Typically, when a direct-current voltage is applied to an organic EL device, holes injected from an anode and electrons injected from a cathode recombine to form electron-hole pairs, namely, excitons. While the excitons return to a stable ground state, energy corresponding thereto is transferred to a light emitting material and is thereby converted into light.

In order to increase efficiency and stability of an organic EL device, since C. W. Tang et al. of Eastman Kodak Company made an organic EL device operating at low voltage by forming a tandem organic thin film between two opposite electrodes (C. W. Tang, S. A. Vanslyke, Applied Physics Letters, vol. 51, pp. 913, 1987), extensive and intensive research into organic materials for organic EL devices having a multilayered thin-film structure has been ongoing. The efficiency and lifetime of such a tandem organic EL device are closely related to the molecular structure of a material for the thin film. For example, quantum efficiency may greatly vary depending on the structure of the material for the thin film, particularly a light emitting material, a hole transport layer material or an electron transport layer material. When thermal stability of the material decreases, the material may be crystallized at a high temperature or a driving temperature, undesirably shortening the lifetime of the device.

Hole transport materials for use in organic EL devices, which have been known to date, are problematic because thin films formed therefrom using vacuum deposition are thermally and electrically unstable, and thus may rapidly crystallize due to heat generated upon device driving and also the film materials may change, undesirably deteriorating the light emission efficiency of the devices. Further, non-emission parts referred to as dark spots may increasingly occur, and the voltage may increase upon constant-current driving, undesirably damaging the devices.

Also, organic EL devices using a phosphorescent light emitting material do not confine a triplet exciton produced in the light emitting material of a light emitting layer due to low triplet energy, undesirably lowering the light emission efficiency of the devices.

Accordingly, an object of the present invention is to provide a compound for an organic EL device, which may have high thermal stability, improved light emission efficiency and lifetime and hole transport capability.

Another object of the present invention is to provide an organic EL device, which includes the compound as above and in which the above compound is used as a hole transport layer material in contact with a light emitting layer, thereby increasing a triplet energy, ultimately improving efficiency of the organic EL device and lifetime.

In order to accomplish the above objects, an aspect of the present invention provides a compound for an organic EL device, as represented by Chemical Formula 1 below.

[Chemical Formula 1]

In Chemical Formula 1, R¹ to R⁶ are identical to or different from each other, and R¹ to R⁶ are each independently a hydrogen atom, a deuterium atom, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or 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 bond, a substituted or unsubstituted C1 to C30 alkylene group, a substituted or unsubstituted C3 to C30 cycloalkylene group, a substituted or unsubstituted C2 to C30 heterocycloalkylene group, a substituted or unsubstituted C6 to C30 arylene group, or a substituted or unsubstituted C2 to C30 heteroarylene group,

X is an oxygen atom or a sulfur atom, and

Ar¹ to Ar³ are identical to or different from each other, and Ar¹ to Ar³ are each independently a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C1 to C30 heteroaryl group.

According to a preferred embodiment of the present invention, the compound for an organic EL device is represented by Chemical Formula 2 below.

[Chemical Formula 2]

In Chemical Formula 2, R¹ to R⁶ are identical to or different from each other, and R¹ to R⁶ are each independently a hydrogen atom, a deuterium atom, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or 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 is an oxygen atom or a sulfur atom, and

According to a preferred embodiment of the present invention, the compound for an organic EL device is represented by Chemical Formulas 3 below.

[Chemical Formula 3]

In Chemical Formula 3, R¹ to R⁶ are identical to or different from each other, and R¹ to R⁶ are each independently a hydrogen atom, a deuterium atom, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or 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 is an oxygen atom or a sulfur atom, and

According to a preferred embodiment of the present invention, in Chemical Formulas 2 and 3, Ar¹ and Ar² are identical to or different from each other, and Ar¹ and Ar² are a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C1 to C30 heteroaryl group, and Ar³ is each independently

,

,

,

,

,

or

,

wherein R⁷ to R³⁸, and R^29' to R^31' are identical to or different from each other, and R⁷ to R³⁸, and R^29' to R^31' are each independently a hydrogen atom, a deuterium atom, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or 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.

According to a preferred embodiment of the present invention, in Chemical Formulas 2 and 3, Ar¹ to Ar³ are identical to or different from each other, and Ar¹ to Ar³ are each independently

,

,

,

,

,

or

,

According to a preferred embodiment of the present invention, in Chemical Formulas 2 and 3, Ar¹ to Ar² are identical to or different from each other, and Ar¹ to Ar² are each independently

,

,

,

,

,

or

, and

Ar³ is identical to or different from each other, and Ar³ is each independently

,

or

,

In a preferred embodiment of the present invention, in Chemical Formulas 2 and 3, R⁷ to R¹⁶, R¹⁸ to R³⁸, and R^29' to R^31' are identical to or different from each other, and R⁷ to R¹⁶, R¹⁸ to R³⁸, and R^29' to R^31' are each independently a hydrogen atom, a deuterium atom, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or 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, and

R¹⁷ is a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C1 to C30 heteroaryl group.

According to a preferred embodiment of the present invention, the compound for an organic EL device is any one selected from among compounds 1 to 159 represented by the following chemical formulas.

According to another preferred embodiment of the present invention, the compound for an organic EL device is any one selected from among compounds 2, 6, 38, 39, and 63 to 159 represented by the following chemical formulas.

According to an embodiment of the present invention, an organic electroluminescent (EL) device including the compounds for an organic EL device according to the present invention may be provided.

According to an embodiment of the present invention, an organic EL device may include a first electrode, a second electrode, and a single organic layer or a plurality of organic layers between the first electrode and the second electrode, and one or more organic layers selected from among the single organic layer or the plurality of organic layers may include the compound for an organic EL device according to the present invention.

According to an embodiment of the present invention, the single organic layer or the plurality of organic layers may include a light emitting layer.

According to an embodiment of the present invention, the plurality of organic layers may include a light emitting layer, and the plurality of organic layers may further include one or more selected from among an electron injection layer, an electron transport layer, a hole blocking layer, an electron blocking layer, a hole transport layer and a hole injection layer.

According to an embodiment of the present invention, the light emitting layer may include a host and a dopant.

The present invention may provide a compound for an organic EL device, which may have high thermal stability, improved light emission efficiency and lifetime and hole transport capability.

Moreover, the present invention may improve light emission efficiency of the organic EL device and lifetime by increasing a triplet energy using the above compound as a hole transport layer material which may contact with light emitting layer.

The above and other objects, features and advantages of the present invention will be more clearly understood from the following detailed description taken in conjunction with the accompanying drawings, in which:

FIG. 1 is a cross-sectional view illustrating an organic EL device according to an embodiment of the present invention; and

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

The present invention may be variously modified, and may have a variety of embodiments, and is intended to illustrate specific embodiments. However, the following description does not limit the present invention to specific embodiments, and should be understood to include all variations, equivalents or substitutions within the spirit and scope of the present invention. Furthermore, in the description of the present invention, when it is determined that the detailed description of the related art would obscure the gist of the present invention, the description thereof will be omitted.

Also, in the following description, the terms "first," "second" and the like are used to differentiate a certain component from other components, but the configuration of such components should not be construed to be limited by the terms. For example, a first component may be referred to as a second component, and a second component may be referred to as a first component, within the scope of the present invention.

Also, when any one component is mentioned to be "on another component", "formed on another component" or "laminated on another component", it may be directly attached to the entire surface or one surface of another component, or a further component may be additionally interposed therebetween.

Unless otherwise stated, the singular expression includes a plural expression. In this application, the terms "include" and "have" are used to designate the presence of features, numbers, steps, operations, components, parts or combinations thereof described in the specification, not intending to exclude the presence or additional possibility of one or more different features, numbers, steps, operations, components, parts or combinations thereof are not excluded.

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

As used herein, unless otherwise defined, the term "substituted" means that at least one hydrogen is substituted with a substituent selected from the group consisting of a deuterium, a C1 to C30 alkyl group, a C3 to C30 cycloalkyl group, a C2 to C30 heterocycloalkyl group, a C1 to C30 alkyl halide group, a C6 to C30 aryl group, a C1 to C30 heteroaryl group, a C1 to C30 alkoxy group, a C2 to C30 alkenyl group, a C2 to C30 alkynyl group, a C6 to C30 aryloxy group, a silyloxy group(-OSiH₃), -OSiR¹H₂(R¹ is a C1 to C30 alkyl group or C6 to C30 aryl group), -OSiR¹R²H(R¹ and R² are each independently a C1 to C30 alkyl group or a C6 to C30 aryl group), -OSiR¹R²R³, (R¹, R², and R³are each independently a C1 to C30 alkyl group or a C6 to C30 aryl group), a C1 to C30 acyl group, a C2 to C30 acyloxy group, a C2 to C30 heteroaryloxy group, a C1 to C30 sulfonyl group, a C1 to C30 alkylthiol group, a C6 to C30 arylthiol group, a C1 to C30 heterocyclothiol group, a C1 to C30 phosphoramide group, silyl group(-SiH₃), -SiR¹H₂(R¹ is a C1 to C30 alkyl group or a C6 to C30 aryl group), -SiR¹R²H(R¹ and R² are each independently a C1 to C30 alkyl group or a C6 to C30 aryl group), -SiR¹R²R³, (R¹, R², and R³ are each independently a C1 to C30 alkyl group or a C6 to C30 aryl group), amine group-NRR'(wherein R and R' are each independently a substituent selected from the group consisting of a hydrogen atom, a C1 to C30 alkyl group and a C6 to C30 aryl group), a carboxyl group, a halogen group, a cyano group, a nitro group, a azo group and a hydroxyl group.

Further, among the substituents, two adjacent substituents may be fused to form a saturated or unsaturated ring.

Further, in the "substituted or unsubstituted fused C1 to C30 alkyl group" or "substituted or unsubstituted C6 to C30 aryl group", “C1 to C30" or "C6 to C30" means the number of carbon of alkyl or aryl group except the substituent. For example, butyl substituted phenyl group (C6) means a phenyl group of carbon number 6 substituted by a butyl group.

Further, in the "substituted or unsubstituted C6 to C30 fused aryl group", “C6 to C30" means the number of carbon of fused aryl group except the substituent.

As used herein, unless otherwise defined, the term "hetero" means a functional group containing 1 ~ 4 heteroatoms selected from the group consisting of N, O, S and P, the remainder being carbon.

As used herein, unless otherwise defined, the term "combination thereof" means that two or more substituents are coupled with each other by a linker or two or more substituents are condensed to each other.

As used herein, unless otherwise defined, the term "hydrogen" means hydrogen, deuterium or tritium.

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

The alkyl group may be a "saturated alkyl group" without any double bond or triple bond.

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

The term "alkenylene group" means a functional group having at least one carbon-carbon double bond between at least two carbon atoms, and the term "alkynylene group" means a functional group having at least one carbon-carbon triple bond between at least two carbon atoms. The alkyl group may be branched, linear or cyclic, regardless of whether it is saturated or unsaturated.

The alkyl group may be a C1 to C30 alkyl group, preferably a C1 to C20 alkyl, more preferably a C1 to C10 alkyl group, and much more preferably a C1 to C6 alkyl group.

For example, a C1 to C4 alkyl group indicates an alkyl chain containing 1 ~ 4 carbon atoms, particularly an alkyl chain which is selected from the group consisting of methyl, ethyl, propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl and t-butyl.

Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a pentyl group, a hexyl group, an ethenyl group, a propenyl group, a butenyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, etc.

The "amine group" includes an amino group, and arylamine group, an alkylamine group, an arylalkylamine group, or an alkylarylamine group and is denoted by -NRR', wherein R and R` are each independently a substituent selected from the group consisting of a hydrogen atom, a C1 to C30 alkyl group and a C6 to C30 aryl group.

The term "cycloalkyl group" refers to a monocyclic or fused-ring polycyclic (i.e., rings which share adjacent pairs of carbon atoms) functional group.

The term "heterocycloalkyl group" means a cycloalkyl group containing 1 ~ 4 heteroatoms selected from the group consisting of N, O, S and P, the remainder being carbon. In the case where the heterocycloalkyl group is a fused ring, at least one ring may contain 1 ~ 4 heteroatoms.

The term "aromatic group" means a cyclic functional group where all ring atoms have p-orbitals, and these p-orbitals form conjugation. Specific examples thereof include an aryl group and a heteroaryl group.

The term "aryl group" refers to a monocyclic or fused-ring polycyclic (i.e., rings which share adjacent pairs of carbon atoms) functional group.

The term "heteroaryl group" means an aryl group containing 1 ~ 4 heteroatoms selected from the group consisting of N, O, S and P, the remainder being carbon. In the case where the heteroalkyl group is a fused ring, at least one ring may contain 1 ~ 4 heteroatoms.

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

When alkyl and aryl are used in combination as in "alkylaryl group" or "arylalkyl group," "alkyl" and "aryl" respectively have the meanings as above.

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

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

Below is a description of embodiments of the present invention with reference to the appended drawings, wherein the same or similar components are designated by the same reference numerals and the overlapping description thereof is omitted.

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

According to another embodiment of the present invention, an organic EL device includes a first electrode 110, a second electrode 150, and a single organic layer or a plurality of organic layers 130 between the first electrode and the second electrode, and one or more organic layers selected from among the single organic layer or the plurality of organic layers 130 may include the compound for an organic EL device according to the present invention.

As such, the single organic layer or the plurality of organic layers 130 may include a light emitting layer 134.

The plurality of organic layers 130 include a light emitting layer 134, and the plurality of organic layers 130 may further include one or more selected from among an electron injection layer 131, an electron transport layer 132, a hole blocking layer 133, an electron blocking layer 135, a hole transport layer 136 and a hole injection layer 137.

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

The organic EL device is preferably supported by a transparent substrate. The material for the transparent substrate is not particularly limited so long as it has good mechanical strength, thermal stability and transparency. Specific examples thereof may include glass, a transparent plastic film, etc.

The anode material of the organic EL device according to the present invention may include a metal, an alloy, an electrically conductive compound or a mixture thereof, having a work function of 4 eV or more. Specific examples thereof may include Au metal or a transparent conductive material such as CuI, ITO (indium tin oxide), SnO₂ and ZnO. The thickness of the anode film is preferably set to 10 ~ 200 nm.

The cathode material of the organic EL device according to the present invention may include a metal, an alloy, an electrically conductive compound or a mixture thereof, having a work function of less than 4 eV. Specific examples thereof may include Na, a Na-K alloy, calcium, magnesium, lithium, a lithium alloy, indium, aluminum, a magnesium alloy, or an aluminum alloy. In addition, aluminum/AlO₂, aluminum/lithium, magnesium/silver or magnesium/indium may be used. The thickness of the cathode film is preferably set to 10 ~ 200 nm.

In order to increase light emission efficiency of the organic EL device, one or more electrodes preferably have a light transmittance of 10% or more. The sheet resistance of the electrodes is preferably hundreds of Ω/mm or less. The thickness of the electrodes falls in the range of 10 nm ~ 1 ㎛, and preferably 10 ~ 400 nm. Such electrodes may be manufactured in the form of a thin film using the above electrode material via vapor deposition such as chemical vapor deposition (CVD), physical vapor deposition (PVD) or the like, or sputtering.

When the compound for an organic EL device according to the present invention is used so as to be adapted for the purposes of the present invention, a hole transport material, a hole injection material, a light emitting layer material, a host material for a light emitting layer, an electron transport material, and an electron injection material, which are known, may be used alone in each organic layer, or may be used in selective combination with the compound for an organic EL device according to the present invention.

Examples of the hole transport material may include porphyrin compound derivatives including N,N-dicarbazolyl-3,5-benzene (mCP), poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS), N,N'-di(1-naphthyl)-N,N'-diphenylbenzidine (NPD), N,N'-diphenyl-N,N'-di(3-methylphenyl)-4,4'-diaminobiphenyl (TPD), N,N'-diphenyl-N,N'-dinaphthyl-4,4'-diaminobiphenyl, N,N,N',N'-tetra-p-tolyl-4,4'-diaminobiphenyl, N,N,N'N'-tetraphenyl-4,4'-diaminobiphenyl, 1,10,15,20-tetraphenyl-21H,23H-porphyrin copper(II), etc., triarylamine derivatives including polymers having an aromatic tertiary amine in the main chain or side chain thereof, 1,1-bis(4-di-p-tolylaminophenyl)cyclohexane, N,N,N-tri(p-tolyl)amine and 4,4',4'-tris[N-(3-methylphenyl)-N-phenylamino]triphenylamine, carbazole derivatives including N-phenylcarbazole and polyvinylcarbazole, phthalocyanine derivatives including metal-free phthalocyanine and copper phthalocyanine, starburst amine derivatives, enaminestilbene-based derivatives, aromatic tertiary amine-containing styrylamine compound derivatives, polysilane, etc.

Examples of the electron transport material may include diphenylphosphine oxide-4-(triphenylsilyl)phenyl (TSPO1), Alq₃, 2,5-diaryl sylol derivatives (PyPySPyPy), perfluorinated compounds (PF-6P), octasubstituted cyclooctatetraene compounds (COTs), etc.

In the organic EL device according to the present invention, an electron injection layer, an electron transport layer, a hole transport layer and a hole injection layer may be provided in the form of a single layer containing one or more kinds of the above compound, or may be provided in the form of a plurality of stacked layers containing different kinds of compounds.

The light emitting material may include, for example, photoluminescent fluorescent materials, fluorescent brighteners, laser dyes, organic scintillators and fluorescence analysis reagents. Specific examples thereof include carbazole-based compounds, phosphine oxide-based compounds, carbazole-based phosphine oxide compounds, polyaromatic compounds including bis((3,5-difluoro-4-cyanophenyl)pyridine)iridium picolinate (FCNIrpic), tris(8-hydroxyquinoline) aluminum (Alq₃), anthracene, phenanthrene, pyrene, chrysene, perylene, coronene, rubrene and quinacridone, oligophenylene compounds including quaterphenyl, scintillators for liquid scintillation including 1,4-bis(2-methylstyryl)benzene, 1,4-bis(4-methylstyryl)benzene, 1,4-bis(4-methyl-5-phenyl-2-oxazolyl)benzene, 1,4-bis(5-phenyl-2-oxazolyl)benzene, 2,5-bis(5-t-butyl-2-benzoxazolyl)thiophene, 1,4-diphenyl-1,3-butadiene, 1,6-diphenyl-1,3,5-hexatriene and 1,1,4,4-tetraphenyl-1,3-butadiene, metal complexes of oxine derivatives, coumarine dyes, dicyanomethylenepyran dyes, dicyanomethylenethiopyran dyes, polymethine dyes, oxobenzanthracene dyes, xanthene dyes, carbostyryl dyes, perylene dyes, oxazine compounds, stilbene derivatives, spiro compounds, oxadiazole compounds, etc.

Each layer of the organic EL device according to the present invention may be provided in the form of a thin film using a known process such as vacuum deposition, spin coating or casting, or may be manufactured using each layer material. The thickness of each layer is not particularly limited, but may be appropriately set depending on the material properties, and may be typically determined in the range of 2 ~ 5,000 nm.

Because the compound for an organic EL device according to the present invention may be subjected to vacuum deposition, a thin film formation process is simple and a uniform thin film which does not substantially have pin holes may be easily obtained.

A better understanding of the present invention regarding the synthesis of the compound for an organic EL device and the manufacture of the organic EL device including the same may be obtained through the following examples which are set forth to illustrate, but are not to be construed as limiting, the present invention.

[Example]

Preparation Example 1. Synthesis of Intermediate 1 (4- bromo -2,6-diiodobenzene)

In a 1 L round-bottom three-neck flask, 45.5 g of 4-bromophenol, 100 g of iodine, 77.7 g of 34.5% hydrogen peroxide and 800 ml of cyclohexane were placed, and stirred at 50℃ for 12 hrs. After completion of the reaction, layers were separated with sodium thiosulfate saturated solution and ethyl acetate, after which the ethyl acetate was distilled under reduced pressure, thus obtaining 106 g of Intermediate 1 (yield 95%).

MS (ESI) : [M+H]⁺ 425

Preparation Example 2. Synthesis of Intermediate 2 (4- bromo -2,6- diiodo anisole)

In a 1 L round-bottom three-neck flask under a nitrogen atmosphere, 106 g of Intermediate 1, 55.4 g of methane iodide, 71.9 g of potassium carbonate and 800 ml of acetone were placed, and stirred under reflux for 4 hrs. The reaction solution was cooled and layers were separated with water and dichloromethane. The layer of dichloromethane was concentrated and then subjected to column chromatography with a solvent mixture of dichloromethane and n-hexane, thus obtaining 64.6 g of Intermediate 2 (yield 59%).

MS (ESI) : [M+H]⁺ 439

Preparation Example 3. Synthesis of Intermediate 3 (2-(4,4,5,5- tetramethyl-1,3,2-dioxaborolane-2-yl)aniline)

In a 1000 ml round-bottom three-neck flask under a nitrogen atmosphere, 39.3 g of 2-bromoaniline, 69.7 g of bis(pinacolato)diboron, 1.0 g, 67.3 g of potassium acetate and 600 ml of DMSO were placed, and stirred at 85℃ for 12 hrs. The reaction solution was cooled and layers were separated with water and dichloromethane. The layer of dichloromethane was concentrated and then subjected to column chromatography with a solvent mixture of dichloromethane and n-hexane, thus obtaining 43.5 g of Intermediate 3 (yield 87%).

MS (ESI) : [M+H]⁺ 220

Preparation Example 4. Synthesis of Intermediate 4 (5'- bromo -3'- iodo -2'-methoxy-[1,1'-biphenyl]-2-amine)

In a 1000 ml round-bottom three-neck flask, 55.9 g of Intermediate 2, 27.9 g of Intermediate 3, 52.8 g of potassium carbonate, 600 ml of THF and 200 ml of water were placed, and stirred under reflux for 48 hrs. The reaction solution was cooled and layers were separated with water and dichloromethane. The layer of dichloromethane was concentrated and then subjected to column chromatography with a solvent mixture of dichloromethane and n-hexane, thus obtaining 20.3 g of Intermediate 4 (yield 39%).

MS (ESI) : [M+H]⁺ 404

Preparation Example 5. Synthesis of Intermediate 5 (2- bromo -4-iododibenzofuran)

In a 250 ml round-bottom three-neck flask under a nitrogen atmosphere, 20.0 g of Intermediate 4, 10.5 g of borontrifluoride-diethyl ether and 100 ml of o-dichlorobenzene were placed, and stirred at room temperature for 1 hr. The reaction solution was cooled below 0℃, and 6.1 g of butyl nitrite was slowly added dropwise, and stirred at 0℃ for 1 hr. After completion of the reaction, stirred at 105℃ for 12 hrs, filtered with silica gel, concentrated and then subjected to column chromatography with a n-hexane, thus obtaining 17.0 g of Intermediate 5 (yield 92%).

MS (ESI) : [M+H]⁺ 373

Preparation Example 6. Synthesis of Intermediate 6 (2- bromo -4-phenyldibenzofuran)

In a 500 ml round-bottom three-neck flask under a nitrogen atmosphere, 8.3 g of Intermediate 5, 3.0 g of phenylboronic acid, 9.2 g of potassium carbonate, 0.8 g of tetrakistriphenylphosphinepalladium, 180 ml of tetrahydrofuran and 60 ml of water were placed, and stirred under reflux for 48 hrs. The reaction solution was cooled and then extracted with dichloromethane and water. The extracted solution was concentrated, subjected to column chromatography using a solvent mixture of dichloromethane and n-hexane and then concentrated, thus obtaining 4.2 g of Intermediate 6 (yield 59%).

MS (ESI) : [M+H]⁺ 323

Preparation Example 7. Synthesis of Intermediate 7 (3-(2-bromodibenzofuran-4-yl)-9-phenyl-9 H -carbazole)

In a 100 ml round-bottom three-neck flask under a nitrogen atmosphere, 1.6 g of Intermediate 5, 1.2 g of (3-(9H-carbazole-9-yl)phenyl)boronic acid, 1.8 g of potassium carbonate, 0.2 g of tetrakistriphenylphosphinepalladium(0), 45 ml of tetrahydrofuran and 15 ml of water were placed, and stirred under reflux for 18 hrs. The reaction solution was cooled and then extracted with dichloromethane and water. The extracted solution was concentrated, subjected to column chromatography using a solvent mixture of ethyl acetate and n-hexane and then concentrated, thus obtaining 1.3 g of Intermediate 7 (yield 61%).

MS (ESI) : [M+H]⁺ 488

Preparation Example 8. Synthesis of Intermediate 8 (2- bromo -4-(9,9-dimethyl-9 H -fluoren-2-yl)dibenzofuran)

In a 100 ml round-bottom three-neck flask under a nitrogen atmosphere, 2.0 g of Intermediate 5, 1.7 g of 2-(9,9-dimethyl-9H-fluoren-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane, 2.2 g of potassium carbonate, 0.2 g of tetrakistriphenylphosphinepalladium(0), 45 ml of tetrahydrofuran and 15 ml of water were placed, and stirred under reflux for 48 hrs. The reaction solution was cooled and then extracted with dichloromethane and water. The extracted solution was concentrated, subjected to column chromatography using a solvent mixture of dichloromethane and n-hexane and then concentrated, thus obtaining 1.5 g of Intermediate 8 (yield 63%).

MS (ESI) : [M+H]⁺ 440

Preparation Example 9. Synthesis of Intermediate 9 (9-(2-bromodibenzofuran-4-yl)-9 H -carbazole)

In a 100 ml round-bottom three-neck flask under a nitrogen atmosphere, 2.0 g of Intermediate 5, 1.0 g of 9H-carbazole, 0.2 g of trisdibenzylidenedipalladium, 0.4 g of 50% tris(tert-butyl)phosphine, 2.0 g of sodium t-butoxide and 30 ml of xylene were placed, and stirred under reflux for 48 hrs. The reaction solution was cooled and then extracted with dichloromethane and water. The extracted solution was concentrated, subjected to column chromatography using a solvent mixture of ethyl acetate and n-hexane and then concentrated, thus obtaining 0.8 g of Intermediate 9 (yield 36%).

MS (ESI) : [M+H]⁺ 412

Preparation Example 10. Synthesis of Intermediate 10 (9-(2-bromodibenzofuran-4-yl)-9 H -carbazole)

In a 100 ml round-bottom three-neck flask under a nitrogen atmosphere, 2.0 g of Intermediate 5, 1.9 g of 4,4,5,5-tetramethyl-2-(triphenylene-2-yl)-1,3,2-dioxaborolane, 2.2 g of potassium carbonate, 0.2 g of tetrakistriphenylphosphinepalladium(0), 45 ml of tetrahydrofuran and 15 ml of water were placed, and stirred under reflux for 48 hrs. The reaction solution was cooled and then extracted with dichloromethane and water. The extracted solution was concentrated, subjected to column chromatography using a solvent mixture of ethyl acetate and n-hexane and then concentrated, thus obtaining 1.4 g of Intermediate 10 (yield 55%).

MS (ESI) : [M+H]⁺ 473

Preparation Example 11. Synthesis of Intermediate 11 (N-([1,1'-biphenyl]-4-yl)-N-(4-(2-bromodibenzofuran-4-yl)phenyl)-[1,1'-biphenyl]-4-amine)

In a 100 ml round-bottom three-neck flask under a nitrogen atmosphere, 1.8 g of Intermediate 5, 2.1 g of (4-(di([1,1'-biphenyl]-4-yl)amino)phenyl) boronic acid, 2.0 g of potassium carbonate, 0.2 g of tetrakistriphenylphosphinepalladium(0), 45 ml of tetrahydrofuran and 15 ml of water were placed, and stirred under reflux for 18 hrs. The reaction solution was cooled and then extracted with dichloromethane and water. The extracted solution was concentrated, subjected to column chromatography using a solvent mixture of dichloromethane and n-hexane and then concentrated, thus obtaining 1.9 g of Intermediate 11 (yield 63%).

MS (ESI) : [M+H]⁺ 642

Preparation Example 12. Synthesis of Intermediate 12 ( dibenzothiophene -5- oxide)

In a 2000 ml round-bottom three-neck flask under a nitrogen atmosphere, 36.8 g of dibenzothiophene, 138 g of 34.5% hydrogen peroxide and 1500 ml of methanol were placed, and maintained at 0℃. 92.3g of zirconium(IV) chloride was slowly added to the reaction solution and stirred at room temperature for 2 hrs. The reaction was completed, filtered with silica gel, concentrated and then subjected to column chromatography with a dichloromethane, thus obtaining 17.5 g of Intermediate 12 (yield 44%).

MS (ESI) : [M+H]⁺ 201

Preparation Example 13. Synthesis of Intermediate 13 (3- nitrobenzothiophene-5-oxide)

In a 500 ml round-bottom three-neck flask under a nitrogen atmosphere, 16.8 g of Intermediate 11, 58.8 g of acetic acid and 199 g of sulfuric acid were placed, and maintained at 0℃. 18 g of 70% nitric acid solution was slowly added dropwise and stirred below 5℃ for 1 hr. After completion of the reaction, water was added, crystal was formed, filtered, thus obtaining 18.0 g of Intermediate 13 (yield 87%).

MS (ESI) : [M+H]⁺ 246

Preparation Example 14. Synthesis of Intermediate 14 ( dibenzothiophene -3-amine)

In a 500 ml round-bottom three-neck flask under a nitrogen atmosphere, 18.0 g of Intermediate 12, 180 g of acetic acid and 108 g of 35% tin(II) chloride hydrate were placed, and stirred at room temperature. 120 ml of 35% hydrogen chloride was slowly added dropwise, and stirred at room temperature for 24 hrs. The reaction was completed and then extracted with sodium hydroxide solution and ethyl acetate. The extracted solution was concentrated, thus obtaining 12.6 g of Intermediate 14 (yield 86%).

MS (ESI) : [M+H]⁺ 200

Preparation Example 15. Synthesis of Intermediate 15 (2-bromodibenzothiophene-3-amine)

In a 250 ml round-bottom three-neck flask under a nitrogen atmosphere, 12.0 g of Intermediate 13, 23 ml of 2N sodium hydroxide solution and 175 ml of dioxane were placed and 7.3 g of bromine was slowly added dropwise at 0℃. After completion of the reaction, the reaction solution was stirred at room temperature for 24 hrs and then extracted with dichloromethane and water. The extracted solution was concentrated, subjected to column chromatography with a solvent mixture of ethyl acetate and n-hexane, thus obtaining 6.2 g of Intermediate 15 (yield 37%).

MS (ESI) : [M+H]⁺ 278

Preparation Example 16. Synthesis of Intermediate 16 (2- bromo -4-iododibenzothiophene-3-amine)

In a 100 ml round-bottom three-neck flask, 5.6 g of Intermediate 14, 5.1 g of iodine, 2.0 g of 34.5% hydrogen peroxide and 50 ml of cyclohexane were placed, and stirred at 50℃ for 24 hrs. After completion of the reaction, layers were separated with sodium thiosulfate and ethyl acetate, after which the ethyl acetate layer was distilled under reduced pressure, thus obtaining 6.5 g of Intermediate 16 (yield 81%).

MS (ESI) : [M+H]⁺ 404

Preparation Example 17. Synthesis of Intermediate 17 (2- bromo -4-iododibenzothiophene)

In a 250 ml round-bottom three-neck flask, 3.8 g of t-butyl nitrite is placed in 52 ml of DMF and maintained at 50℃. 6.0 g of Intermediate 15 and 52 ml of DMF were slowly added dropwise, and stirred at 50℃ for 48 hrs. The reaction solution was cooled and then extracted with dichloromethane and water, after which the extracted solution was concentrated and then subjected to column chromatography using n-hexane, thus obtaining 2.2 g of Intermediate 16 (yield 38%).

MS (ESI) : [M+H]⁺ 389

Preparation Example 18. Synthesis of Intermediate 18 (2- bromo -4-phenyldibenzothiophene)

In a 100 ml round-bottom three-neck flask under a nitrogen atmosphere, 2.2 g of Intermediate 16, 0.7 g of phenylboronic acid, 2.3 g of potassium carbonate, 0.2 g of tetrakistriphenylphosphinepalladium(0), 50 ml of tetrahydrofuran and 17 ml of water were placed, and stirred under reflux for 48 hrs. The reaction solution was cooled and then extracted with dichloromethane and water. The extracted solution was concentrated, subjected to column chromatography using a solvent mixture of dichloromethane and n-hexane and then concentrated, thus obtaining 1.0 g of Intermediate 18 (yield 52%).

MS (ESI) : [M+H]⁺ 339

Preparation Example 19. Synthesis of Intermediate 19 (4- bromo -2'-nitro-1,1'-biphenyl)

In a 250 ml round-bottom three-neck flask under a nitrogen atmosphere, 10.0 g of 2-iodo-1-nitrobenzene, 8.1 g of 4-bromophenylboronic acid, 16.7 g of potassium carbonate, 1.4 g of tetrakistriphenylphosphinepalladium(0), 180 ml of tetrahydrofuran and 60 ml of water were placed, and stirred under reflux for 12 hrs. The reaction solution was cooled and then extracted with dichloromethane and water. The extracted solution was concentrated, subjected to column chromatography using a solvent mixture of dichloromethane and n-hexane and then concentrated, thus obtaining 10.5 g of Intermediate 19 (yield 94%).

MS (ESI) : [M+H]⁺ 278

Preparation Example 20. Synthesis of Intermediate 20 (2- bromo -9 H -carbazole)

In a 250 ml round-bottom three-neck flask under a nitrogen atmosphere, 10.5 g of Intermediate 19, 24.8 g of triphenylphosphine and 230 ml of o-dichlorobenzene were placed, and stirred at 180℃ for 18 hrs. The reaction solution was concentrated and then subjected to column chromatography using a solvent mixture of dichloromethane and n-hexane, thus obtaining 4.2 g of Intermediate 20 (yield 45%).

MS (ESI) : [M+H]⁺ 246

Preparation Example 21. Synthesis of Intermediate 21 (2- bromo -9-phenyl-9 H -carbazole)

In a 100 ml round-bottom three-neck flask under a nitrogen atmosphere, 4.2 g of Intermediate 20, 5.2 g of iodobenzene, 0.3 g of copper iodide, 0.3 g of 1,10-phenanthroline, 7.1 g of potassium carbonate and 50 ml of dimethylformamide were placed, and reacted at 80℃ for 24 hrs. The reaction solution was cooled and then extracted with dichloromethane and water. The extracted solution was concentrated, subjected to column chromatography using a solvent mixture of dichloromethane and n-hexane and then concentrated, thus obtaining 4.8 g of Intermediate 21 (yield 81%).

MS (ESI) : [M+H]⁺ 322

Preparation Example 22. Synthesis of Intermediate 22 (9-phenyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolane-2-yl)-9 H -carbazole)

In a 100 ml round-bottom three-neck flask under a nitrogen atmosphere, 2.0 g of Intermediate 21, 2.4 g of bis(pinacolato)diboron, 1.8 g of potassium acetate and 60 ml of 1,4-dioxane were placed, and stirred at 100℃ for 12 hrs. The reaction solution was cooled and then layers were separated with dichloromethane and water, after which the dichloromethane layer was concentrated and then subjected to column chromatography using a solvent mixture of dichloromethane and n-hexane, thus obtaining 1.5 g of Intermediate 22 (yield 63%).

MS (ESI) : [M+H]⁺ 369

Preparation Example 23. Synthesis of Intermediate 23 (2- bromo -2'-nitro-1,1'-biphenyl)

In a 250 ml round-bottom three-neck flask under a nitrogen atmosphere, 7.0 g of 2-iodo-1-nitrobenzene, 5.6 g of 2-bromophenylboronic acid, 5.9 g of potassium carbonate, 0.5 g of tetrakistriphenylphosphinepalladium(0), 120 ml of tetrahydrofuran and 40 ml of water were placed, and stirred under reflux for 24 hrs. The reaction solution was cooled and then extracted with dichloromethane and water. The extracted solution was concentrated, subjected to column chromatography using a solvent mixture of dichloromethane and n-hexane and then concentrated, thus obtaining 7.2 g of Intermediate 23 (yield 92%).

MS (ESI) : [M+H]⁺ 278

Preparation Example 24. Synthesis of Intermediate 24 (4- bromo -9 H -carbazole)

In a 250 ml round-bottom three-neck flask under a nitrogen atmosphere, 7.2 g of Intermediate 22, 6.8 g of triphenylphosphine and 160 ml of o-dichlorobenzene were placed, and stirred at 180℃ for 18 hrs. The reaction solution was concentrated and then subjected to column chromatography using a solvent mixture of dichloromethane and n-hexane, thus obtaining 2.6 g of Intermediate 24 (yield 86%).

MS (ESI) : [M+H]⁺ 246

Preparation Example 25. Synthesis of Intermediate 25 (4- bromo -9-phenyl-9 H -carbazole)

In a 100 ml round-bottom three-neck flask under a nitrogen atmosphere, 2.6 g of Intermediate 24, 2.6 g of iodobenzene, 0.2 g of copper iodide, 0.2 g of 1,10-phenanthroline, 4.4 g of potassium carbonate and 30 ml of dimethylformamide were placed, and reacted at 80℃ for 24 hrs. The reaction solution was cooled and then extracted with dichloromethane and water. The extracted solution was concentrated, subjected to column chromatography using a solvent mixture of dichloromethane and n-hexane and then concentrated, thus obtaining 2.7 g of Intermediate 25 (yield 81%).

MS (ESI) : [M+H]⁺ 322

Preparation Example 26. Synthesis of Intermediate 26 (9-phenyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolane-2-yl)-9 H -carbazole)

In a 100 ml round-bottom three-neck flask under a nitrogen atmosphere, 2.6 g of Intermediate 26, 3.1 g of bis(pinacolato)diboron, 2.2 g of potassium acetate and 80 ml of 1,4-dioxane were placed, and stirred at 100℃ for 12 hrs. The reaction solution was cooled and then layers were separated with water and dichloromethane, after which the dichloromethane layer was concentrated and then subjected to column chromatography using a solvent mixture of dichloromethane and n-hexane, thus obtaining 1.8 g of Intermediate 26 (yield 59%).

MS (ESI) : [M+H]⁺ 369

Preparation Example 27. Synthesis of Intermediate 27 (2-(2-bromodibenzofuran-4-yl)-9-phenyl-9 H -carbazole)

In a 100 ml round-bottom three-neck flask under a nitrogen atmosphere, 1.5 g of Intermediate 5, 1.5 g of Intermediate 22, 1.6 g of potassium carbonate, 0.2 g of tetrakistriphenylphosphinepalladium(0), 45 ml of tetrahydrofuran and 15 ml of water were placed, and stirred under reflux for 18 hrs. The reaction solution was cooled and then extracted with dichloromethane and water. The extracted solution was concentrated, subjected to column chromatography using a solvent mixture of dichloromethane and n-hexane and then concentrated, thus obtaining 1.3 g of Intermediate 27 (yield 69%).

MS (ESI) : [M+H]⁺ 488

Preparation Example 28. Synthesis of Intermediate 28 (4-(2-bromodibenzofuran-4-yl)-9-phenyl-9 H -carbazole)

In a 100 ml round-bottom three-neck flask under a nitrogen atmosphere, 0.8 g of Intermediate 5, 19 g of Intermediate 26, 1.0 g of potassium carbonate, 0.1 g of tetrakistriphenylphosphinepalladium(0), 30 ml of tetrahydrofuran and 10 ml of water were placed, and stirred under reflux for 18 hrs. The reaction solution was cooled and then extracted with dichloromethane and water. The extracted solution was concentrated, subjected to column chromatography using a solvent mixture of dichloromethane and n-hexane and then concentrated, thus obtaining 0.9 g of Intermediate 28 (yield 88%).

MS (ESI) : [M+H]⁺ 488

Preparation Example 29. Synthesis of Intermediate 29 (2- bromo -4,4'-bidibenzofuran)

In a 100 ml round-bottom three-neck flask under a nitrogen atmosphere, 2.0 g of Intermediate 5, 1.1 g of 4-dibenzofuran boronic acid, 2.2 g of potassium carbonate, 0.2 g of tetrakistriphenylphosphinepalladium(0), 45 ml of tetrahydrofuran and 15 ml of water were placed, and stirred under reflux for 18 hrs. The reaction solution was cooled and then extracted with dichloromethane and water. The extracted solution was concentrated, subjected to column chromatography using a solvent mixture of dichloromethane and n-hexane and then concentrated, thus obtaining 1.2 g of Intermediate 29 (yield 54%).

MS (ESI) : [M+H]⁺ 413

Example 1. Synthesis of Compound 1

In a 100 ml round-bottom three-neck flask under a nitrogen atmosphere, 1.3 g of Intermediate 6, 1.9 g of (4-(di([1,1'-biphenyl]-4-yl)amino)phenyl)boronic acid, 1.6 g of potassium carbonate, 0.1 g of tetrakistriphenylphosphinepalladium(0), 36 ml of tetrahydrofuran and 12 ml of water were placed, and stirred under reflux for 12 hrs. The reaction solution was cooled and then extracted with dichloromethane and water. The extracted solution was concentrated, subjected to column chromatography using a solvent mixture of dichloromethane and n-hexane and then concentrated, thus obtaining 2.2 g of Compound 1 (yield 86%).

MS (ESI) : [M+H]⁺ 640

¹H NMR(600MHz, CDCl₃): δ 8.13 (s, 1H), 8.03 (d, 1H), 7.97 (d, 2H), 7.83 (s, 1H), 7.66 (d, 2H) 7.62-7.60 (m, 5H), 7.57-7.54 (m, 6H), 7.50-7.43 (m, 6H), 7.38 (t, 1H), 7.33-7.25 (m, 8H)

Example 2. Synthesis of Compound 2

In a 100 ml round-bottom three-neck flask under a nitrogen atmosphere, 1.3 g of Intermediate 7, 1.4 g of (4-(di([1,1'-biphenyl]-4-yl)amino)phenyl)boronic acid, 1.1 g of potassium carbonate, 0.1 g of tetrakistriphenylphosphinepalladium(0), 30 ml of tetrahydrofuran and 10 ml of water were placed, and stirred under reflux for 12 hrs. The reaction solution was cooled and then extracted with dichloromethane and water. The extracted solution was concentrated, subjected to column chromatography using a solvent mixture of dichloromethane and n-hexane and then concentrated, thus obtaining 1.5 g of Compound 2 (yield 71%).

MS (ESI) : [M+H]⁺ 805

¹H NMR(600MHz, CDCl₃): δ 8.70 (s, 1H), 8.26 (d, 1H), 8.12 (s, 1H), 8.06-8.02 (m, 2H), 7.95 (s, 1H), 7.71 (d, 2H) 7.65-7.58 (m, 10H), 7.55 (d, 4H), 7.52-7.42 (m, 8H), 7.39 (t, 1H), 7.35-7.31 (m, 5H), 7.28 (d, 4H)

Example 3. Synthesis of Compound 4

In a 100 ml round-bottom three-neck flask under a nitrogen atmosphere, 1.3 g of Intermediate 8, 1.9 g of (4-(di([1,1'-biphenyl]-4-yl)amino)phenyl)boronic acid, 1.6 g of potassium carbonate, 0.1 g of tetrakistriphenylphosphinepalladium(0), 30 ml of tetrahydrofuran and 10 ml of water were placed, and stirred under reflux for 12 hrs. The reaction solution was cooled and then extracted with dichloromethane and water. The extracted solution was concentrated, subjected to column chromatography using a solvent mixture of dichloromethane and n-hexane and then concentrated, thus obtaining 2.0 g of Compound 4 (yield 89%).

MS (ESI) : [M+H]⁺ 756

¹H NMR(600MHz, CDCl₃): δ 8.13 (s, 1H), 8.04 (d, 1H), 7.98 (d, 2H), 7.91 (d, 1H), 7.88 (s, 1H), 7.81 (d, 1H), 7.69 (d, 2H) 7.64-7.60 (m, 5H), 7.55 (d, 4H). 7.51-7.42 (m, 6H), 7.40-7.31 (m, 7H), 7.28 (d, 4H), 1.60 (s, 6H)

Example 4. Synthesis of Compound 7

In a 100 ml round-bottom three-neck flask under a nitrogen atmosphere, 1.0 g of Intermediate 9, 1.2 g of (4-(di([1,1'-biphenyl]-4-yl)amino)phenyl)boronic acid, 1.0 g of potassium carbonate, 0.1 g of tetrakistriphenylphosphinepalladium(0), 30 ml of tetrahydrofuran and 10 ml of water were placed, and stirred under reflux for 12 hrs. The reaction solution was cooled and then extracted with dichloromethane and water. The extracted solution was concentrated, subjected to column chromatography using a solvent mixture of dichloromethane and n-hexane and then concentrated, thus obtaining 0.8 g of Compound 7 (yield 44%).

MS (ESI) : [M+H]⁺ 729

¹H NMR(600MHz, CDCl₃): δ 8.27 (s, 1H), 8.21 (d, 1H), 8.09 (d, 2H), 7.89 (s, 1H), 7.64 (d, 2H), 7.60 (d, 4H), 7.53 (d, 4H), 7.47-7.40 (m, 9H), 7.34-7.31 (m, 12H)

Example 5. Synthesis of Compound 8

In a 100 ml round-bottom three-neck flask under a nitrogen atmosphere, 0.9 g of Intermediate 6, 1.6 g of (4-(di([1,1'-biphenyl]-4-yl)amino)phenyl)boronic acid, 1.6 g of potassium carbonate, 0.1 g of tetrakistriphenylphosphinepalladium(0), 30 ml of tetrahydrofuran and 10 ml of water were placed, and stirred under reflux for 12 hrs. The reaction solution was cooled and then extracted with dichloromethane and water. The extracted solution was concentrated, subjected to column chromatography using a solvent mixture of dichloromethane and n-hexane and then concentrated, thus obtaining 1.5 g of Compound 8 (yield 75%).

MS (ESI) : [M+H]⁺ 680

¹H NMR(600MHz, CDCl₃): δ 8.13 (s, 1H), 8.03 (d, 1H), 7.97 (d, 2H), 7.83 (s, 1H), 7.67-7.61 (m, 7H), 7.57-7.53 (m, 4H), 7.50-7.37 (m, 6H), 7.37 -7.25 (m, 8H), 7.15 (s, 1H), 1.49 (s, 6H)

Example 6. Synthesis of Compound 12

In a 100 ml round-bottom three-neck flask under a nitrogen atmosphere, 1.4 g of Intermediate 6, 1.6 g of di([1,1'-biphenyl-4-yl)amine, 0.1 g of tris(dibenzylideneacetone)dipalladium(0), 0.1 g of 15% tris(t-butyl)phosphine, 0.8 g of t-butoxy sodium and 25 ml of toluene were placed, and stirred at 100℃ for 12 hrs. The reaction solution was cooled, filtered with silica gel, concentrated and then subjected to column chromatography using a solvent mixture of dichloromethane and n-hexane, thus obtaining 2.0 g of Compound 12 (yield 81%).

¹H NMR(600MHz, CDCl₃): δ 7.87 (dd, 2H), 7.77 (s, 1H), 7.61-7.59 (m, 5H), 7.53-7.49 (m, 8H), 7.47-7.39 (m, 7H), 7.32 (dd, 2H), 7.26 (d, 4H)

MS (ESI) : [M+H]⁺ 564

Example 7. Synthesis of Compound 16

In a 100 ml round-bottom three-neck flask under a nitrogen atmosphere, 1.4 g of Intermediate 10, 1.3 g of (4-(di([1,1'-biphenyl]-4-yl)amino)phenyl)boronic acid, 1.5 g of potassium carbonate, 0.1 g of tetrakistriphenylphosphinepalladium(0), 30 ml of tetrahydrofuran and 10 ml of water were placed, and stirred under reflux for 12 hrs. The reaction solution was cooled and then extracted with dichloromethane and water. The extracted solution was concentrated, subjected to column chromatography using a solvent mixture of dichloromethane and n-hexane and then concentrated, thus obtaining 1.7 g of Compound 16 (yield 72%).

MS (ESI) : [M+H]⁺ 790

¹H NMR(600MHz, CDCl₃): δ 9.25 (s, 1H), 8.84-8.80 (m, 2H), 8.75-8.69 (m, 3H), 8.29 (d, 1H), 8.20 (s, 1H), 8.08 (d, 1H), 8.03 (s, 1H), 7.72-7.67 (m, 7H), 7.61 (d, 4H), 7.56-7.50 (m, 5H), 7.45-7.40 (m, 5H), 7.33-7.22 (m, 8H)

Example 8. Synthesis of Compound 23

In a 100 ml round-bottom three-neck flask under a nitrogen atmosphere, 1.3 g of Intermediate 11, 0.3 g of phenylboronic acid, 0.8 g of potassium carbonate, 0.1 g of tetrakistriphenylphosphinepalladium(0), 25 ml of tetrahydrofuran and 8 ml of water were placed, and stirred under reflux for 12 hrs. The reaction solution was cooled and then extracted with dichloromethane and water. The extracted solution was concentrated, subjected to column chromatography using a solvent mixture of dichloromethane and n-hexane and then concentrated, thus obtaining 1.2 g of Compound 23 (yield 95%).

MS (ESI) : [M+H]⁺ 640

¹H NMR(600MHz, CDCl₃): δ 8.33 (s, 1H), 8.26-8.24 (m, 1H), 7.87-7.86 (m, 1H), 7.78-7.75 (m, 3H), 7.73 (d, 2H), 7.61 (d, 4H), 7.57 (d, 4H), 7.52-7.48 (m, 4H), 7.45-7.39 (m, 5H), 7.34-7.30 (m, 8H)

Example 9. Synthesis of Compound 34

In a 100 ml round-bottom three-neck flask under a nitrogen atmosphere, 1.0 g of Intermediate 18, 1.4 g of (4-(di([1,1'-biphenyl]-4-yl)amino)phenyl)boronic acid, 1.2 g of potassium carbonate, 0.1 g of tetrakistriphenylphosphinepalladium(0), 30 ml of tetrahydrofuran and 10 ml of water were placed, and stirred under reflux for 12 hrs. The reaction solution was cooled and then extracted with dichloromethane and water. The extracted solution was concentrated, subjected to column chromatography using a solvent mixture of dichloromethane and n-hexane and then concentrated, thus obtaining 1.0 g of Compound 34 (yield 52%).

MS (ESI) : [M+H]⁺ 656

¹H NMR(600MHz, CDCl₃): δ 8.19 (s, 2H), 7.71-7.68 (m, 4H), 7.64-7.60 (m, 8H), 7.54 (d, 4H), 7.48 (t, 2H), 7.43 (t, 4H), 7.37 (t, 1H), 7.33-7.25 (m, 8H)

Example 10. Synthesis of Compound 63

In a 100 ml round-bottom three-neck flask under a nitrogen atmosphere, 1.0 g of Intermediate 27, 1.1 g of (4-(di([1,1'-biphenyl]-4-yl)amino)phenyl)boronic acid, 0.9 g of potassium carbonate, 0.1 g of tetrakistriphenylphosphinepalladium(0), 30 ml of tetrahydrofuran and 10 ml of water were placed, and stirred under reflux for 12 hrs. The reaction solution was cooled and then extracted with dichloromethane and water. The extracted solution was concentrated, subjected to column chromatography using a solvent mixture of dichloromethane and n-hexane and then concentrated, thus obtaining 0.9 g of Compound 63 (yield 88%).

MS (ESI) : [M+H]⁺ 805

¹H NMR(600MHz, CDCl₃): δ 8.31 (d, 1H), 8.21 (d, 1H), 8.11 (s, 1H), 8.03 (d, 1H), 7.98 (s, 1H), 7.88 (d, 1H), 7.85 (s, 1H), 7.67-7.55 (m, 11H), 7.54 (d, 2H) 7.48-7.42 (m, 8H), 7.37 (t, 1H). 7.33-7.25 (m, 8H)

Example 11. Synthesis of Compound 64

In a 100 ml round-bottom three-neck flask under a nitrogen atmosphere, 0.9 g of Intermediate 28, 1.0 g of (4-(di([1,1'-biphenyl]-4-yl)amino)phenyl)boronic acid, 0.8 g of potassium carbonate, 0.1 g of tetrakistriphenylphosphinepalladium(0), 30 ml of tetrahydrofuran and 10 ml of water were placed, and stirred under reflux for 12 hrs. The reaction solution was cooled and then extracted with dichloromethane and water. The extracted solution was concentrated, subjected to column chromatography using a solvent mixture of dichloromethane and n-hexane and then concentrated, thus obtaining 0.9 g of Compound 64 (yield 60%).

MS (ESI) : [M+H]⁺ 805

¹H NMR(600MHz, CDCl₃): δ 8.30 (s, 1H), 8.10 (d, 1H), 7.96 (s, 1H), 7.69 (d, 2H), 7.64-7.58 (m, 8H), 7.55-7.49 (m, 7H), 7.44-7.35 (m, 9H), 7.32-7.25 (m, 10H), 6.88 (t, 1H)

Example 12. Synthesis of Compound 65

In a 100 ml round-bottom three-neck flask under a nitrogen atmosphere, 1.1 g of Intermediate 29, 1.2 g of (4-(di([1,1'-biphenyl]-4-yl)amino)phenyl)boronic acid, 1.1 g of potassium carbonate, 0.1 g of tetrakistriphenylphosphinepalladium(0), 30 ml of tetrahydrofuran and 10 ml of water were placed, and stirred under reflux for 12 hrs. The reaction solution was cooled and then extracted with dichloromethane and water. The extracted solution was concentrated, subjected to column chromatography using a solvent mixture of dichloromethane and n-hexane and then concentrated, thus obtaining 0.9 g of Compound 65 (yield 46%).

MS (ESI) : [M+H]⁺ 730

¹H NMR(600MHz, CDCl₃): δ 8.22 (s, 1H), 8.19 (s, 1H), 8.07-8.03 (m, 3H), 8.00 (d, 1H), 7.71 (d, 2H), 7.60 (d, 2H), 7.57-7.53 (m, 7H), 7.49-7.27 (m, 16H)

Example 13. Synthesis of Compound 74

In a 100 ml round-bottom three-neck flask under a nitrogen atmosphere, 1.2 g of Intermediate 7, 1.4 g of N-([1,1'-biphenyl]-4-yl)-9,9-dimethyl-N-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolane-2-yl)phenyl)-9H-fluorene-2-amine, 1.1 g of potassium carbonate, 0.1 g of tetrakistriphenylphosphinepalladium(0), 40 ml of tetrahydrofuran and 13 ml of water were placed, and stirred under reflux for 12 hrs. The reaction solution was cooled and then extracted with dichloromethane and water. The extracted solution was concentrated, subjected to column chromatography using a solvent mixture of dichloromethane and n-hexane and then concentrated, thus obtaining 1.4 g of Compound 74 (yield 66%).

¹H NMR(600MHz, CDCl₃): δ 8.70 (s, 1H), 8.26 (d, 1H), 8.15 (s, 1H), 8.06-8.02 (m 2H), 7.95 (s, 1H), 7.71-7.25 (m, 32H), 1.47 (s, 6H)

MS (ESI) : [M+H]⁺ 858

Example 14. Synthesis of Compound 92

In a 100 ml round-bottom three-neck flask under a nitrogen atmosphere, 1.6 g of Intermediate 11, 0.7 g of ((3-(9H-carbazol-9-yl)phenyl)boronic acid, 1.0 g of potassium carbonate, 0.1 g of tetrakistriphenylphosphinepalladium(0), 45 ml of tetrahydrofuran and 15 ml of water were placed, and stirred under reflux for 12 hrs. The reaction solution was cooled and then extracted with dichloromethane and water. The extracted solution was concentrated, subjected to column chromatography using a solvent mixture of dichloromethane and n-hexane and then concentrated, thus obtaining 1.5 g of Compound 92 (yield 75%).

MS (ESI) : [M+H]⁺ 805

¹H NMR(600MHz, CDCl₃): δ 8.51 (s, 1H), 8.24 (d, 1H), 8.20 (s, 1H), 8.08 (d, 1H), 7.97-7.95 (m, 3H), 7.78 (d, 1H), 7.64-7.61 (m, 9H), 7.56 (d, 4H) 7.53-7.48 (m, 3H), 7.45-7.31 (m, 16H)

Device Example 1. Manufacture of organic EL device including Compound 1 as second hole transport layer

A glass substrate coated with an ITO thin film having a thickness of 100 nm was ultrasonically washed with an isopropyl alcohol solvent, dried, placed in a plasma cleaning system so that the substrate was cleaned using oxygen plasma for 5 min, and then transferred into a vacuum deposition system.

The ITO transparent electrode thus prepared was used as an anode, and compound HIL and compound IL were vacuum deposited on the ITO substrate to a thickness of 50 nm and 5 nm, respectively, thus forming a hole injection layer. Subsequently, Compound HTL was vacuum deposited to a thickness of 20 nm, thus forming a first hole transport layer, and a second hole transport layer was formed to a thickness of 20 nm using Compound 1 on the first hole transport layer. Compound GH-1 and GH-2 at a ratio as a host and 10 vol% of Compound GD as a dopant were vacuum deposited on the second hole transport layer, thus forming a light emitting layer.

Thereafter, an electron transport layer was formed to a thickness of 30 nm using Compound ETL on the light emitting layer. 1.5 nm thick Liq [lithium quinolate] and 100 nm thick Al were sequentially vacuum deposited on the electron transport layer to form a cathode, thereby manufacturing an organic EL device.

Device Example 2. Manufacture of organic EL device including Compound 2 as hole transport layer

An organic EL device was manufactured in the same manner as in Device Example 1, with the exception that Compound 2 was used instead of Compound 1.

Device Example 3. Manufacture of organic EL device including Compound 4 as second hole transport layer

An organic EL device was manufactured in the same manner as in Device Example 1, with the exception that Compound 4 was used instead of Compound 1.

Device Example 4. Manufacture of organic EL device including Compound 8 as second hole transport layer

An organic EL device was manufactured in the same manner as in Device Example 1, with the exception that Compound 8 was used instead of Compound 1.

Device Example 5. Manufacture of organic EL device including Compound 16 as second hole transport layer

An organic EL device was manufactured in the same manner as in Device Example 1, with the exception that Compound 16 was used instead of Compound 1.

Device Example 6. Manufacture of organic EL device including Compound 23 as second hole transport layer

An organic EL device was manufactured in the same manner as in Device Example 1, with the exception that Compound 23 was used instead of Compound 1.

Device Example 7. Manufacture of organic EL device including Compound 63 as second hole transport layer

An organic EL device was manufactured in the same manner as in Device Example 1, with the exception that Compound 63 was used instead of Compound 1.

Device Example 8. Manufacture of organic EL device including Compound 64 as second hole transport layer

An organic EL device was manufactured in the same manner as in Device Example 1, with the exception that Compound 64 was used instead of Compound 1.

Device Example 9. Manufacture of organic EL device including Compound 65 as second hole transport layer

An organic EL device was manufactured in the same manner as in Device Example 1, with the exception that Compound 65 was used instead of Compound 1.

Device Example 10. Manufacture of organic EL device including Compound 74 as second hole transport layer

An organic EL device was manufactured in the same manner as in Device Example 1, with the exception that Compound 74 was used instead of Compound 1.

Device Example 11. Manufacture of organic EL device including Compound 92 as second hole transport layer

An organic EL device was manufactured in the same manner as in Device Example 1, with the exception that Compound 92 was used instead of Compound 1.

Comparative Device Example 1. Manufacture of organic EL device including NPB as second hole transport layer

An organic EL device was manufactured in the same manner as in Device Example 1, with the exception that NPB was used instead of Compound 1.

The chemical formulas of HIL, IL, HTL, NPB, GH-1, GH-2, GD and ETL used in the Device Examples and Comparative Device Examples are represented below.

Evaluation of properties of organic EL device

The properties of the organic EL devices manufactured in Device Examples 1 to 11 and Comparative Device Example 1 were evaluated. The brightness efficiency was measured at the basis of current density, 10 mA/cm². The lifetime was measured as the time when the luminance decreased by 3% by driving at constant current of initial luminance, 4500 cd/m². The results are shown in Table 1 below.

	2^nd Hole transport layer material	Brightness efficiency(cd/A)	Lifetime(hr)
Device Ex. 1	Compound 1	47.9	58
Device Ex. 2	Compound 2	46.0	47
Device Ex. 3	Compound 4	45.4	67
Device Ex. 4	Compound 8	45.3	52
Device Ex. 5	Compound 16	45.6	50
Device Ex. 6	Compound 23	44.7	53
Device Ex. 7	Compound 63	47.5	34
Device Ex. 8	Compound 64	46.9	29
Device Ex. 9	Compound 65	45.9	101
Device Ex. 10	Compound 74	44.8	80
Device Ex. 11	Compound 92	44.0	45
Comp. Device Ex. 1	NPB	25.7	38

According to Table 1, as is apparent from the results of manufacturing organic EL devices using the compounds 1, 2, 4, 8, 16, 23, 63 to 65, 74 and 92 according to the present invention as the material for the hole transport layer, all of the devices exhibited superior properties improving brightness efficiency and lifetime compared to when using NPB as a conventional material.

Although the preferred embodiments of the present invention have been disclosed for illustrative purposes, those skilled in the art will appreciate that various modifications, additions and substitutions are possible, without departing from the scope and spirit of the invention as disclosed in the accompanying claims.

Claims

A compound for an organic electroluminescent device, represented by Chemical Formula 1 below:

[Chemical Formula 1]

wherein R¹ to R⁶ are identical to or different from each other, and R¹ to R⁶ are each independently a hydrogen atom, a deuterium atom, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or 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 bond, a substituted or unsubstituted C1 to C30 alkylene group, a substituted or unsubstituted C3 to C30 cycloalkylene group, a substituted or unsubstituted C2 to C30 heterocycloalkylene group, a substituted or unsubstituted C6 to C30 arylene group, or a substituted or unsubstituted C2 to C30 heteroarylene group,

X is an oxygen atom or a sulfur atom, and

Ar¹ to Ar³ are identical to or different from each other, and Ar¹ to Ar³ are each independently a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C1 to C30 heteroaryl group.
The compound of claim 1, which is represented by Chemical Formula 2 below:

[Chemical Formula 2]

wherein R¹ to R⁶ are identical to or different from each other, and R¹ to R⁶ are each independently a hydrogen atom, a deuterium atom, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or 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 bond, a substituted or unsubstituted C1 to C30 alkylene group, a substituted or unsubstituted C3 to C30 cycloalkylene group, a substituted or unsubstituted C2 to C30 heterocycloalkylene group, a substituted or unsubstituted C6 to C30 arylene group, or a substituted or unsubstituted C2 to C30 heteroarylene group,

X is an oxygen atom or a sulfur atom, and

Ar¹ to Ar³ are identical to or different from each other, and Ar¹ to Ar³ are each independently a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C1 to C30 heteroaryl group.
The compound of claim 1, which is represented by Chemical Formula 3 below:

[Chemical Formula 3]

wherein R¹ to R⁶ are identical to or different from each other, and R¹ to R⁶ are each independently a hydrogen atom, a deuterium atom, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or 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 bond, a substituted or unsubstituted C1 to C30 alkylene group, a substituted or unsubstituted C3 to C30 cycloalkylene group, a substituted or unsubstituted C2 to C30 heterocycloalkylene group, a substituted or unsubstituted C6 to C30 arylene group, or a substituted or unsubstituted C2 to C30 heteroarylene group,

X is an oxygen atom or a sulfur atom, and

Ar¹ to Ar³ are identical to or different from each other, and Ar¹ to Ar³ are each independently a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C1 to C30 heteroaryl group.
The compound of claim 2 or 3, wherein Ar¹ to Ar³ are identical to or different from each other, and Ar¹ to Ar³ are each independently
,
,
,
,
,
,
,
or
,

wherein R⁷ to R³⁸, and R^29' to R^31' are identical to or different from each other, and R⁷ to R³⁸, and R^29' to R^31' are each independently a hydrogen atom, a deuterium atom, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or 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 compound of claim 4, wherein Ar¹ to Ar² are identical to or different from each other, and Ar¹ to Ar² are each independently
,
,
,
,
,
,
,
or
,

Ar³ is identical to or different from each other, and Ar³ is each independently
,
or
,

wherein R⁷ to R³⁸, and R^29' to R^31' are identical to or different from each other, and R⁷ to R³⁸, and R^29' to R^31' are each independently a hydrogen atom, a deuterium atom, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or 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 compound of claim 5, wherein R⁷ to R¹⁶, R¹⁸ to R³⁸, and R^29' to R^31' are identical to or different from each other, and R⁷ to R¹⁶, R¹⁸ to R³⁸, and R^29' to R^31' are each independently a hydrogen atom, a deuterium atom, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or 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, and

R¹⁷ is a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C1 to C30 heteroaryl group.
The compound of claim 1, which is any one selected from among compounds 1 to 159 represented by the following chemical formulas:
An organic electroluminescent device, including the compound of claim 1.
An organic electroluminescent device, comprising a first electrode, a second electrode, and a single organic layer or a plurality of organic layers between the first electrode and the second electrode, wherein one or more organic layers selected from among the single organic layer or the plurality of organic layers include the compound of claim 1.
The organic electroluminescent device of claim 9, wherein the single organic layer or the plurality of organic layers include a light emitting layer.
The organic electroluminescent device of claim 9, wherein the plurality of organic layers include a light emitting layer, and the plurality of organic layers further include one or more selected from among an electron injection layer, an electron transport layer, a hole blocking layer, an electron blocking layer, a hole transport layer and a hole injection layer.
The organic electroluminescent device of claim 10, wherein the light emitting layer includes a host and a dopant.