KR20160051742A - 2-aminocarbazole compound and use thereof - Google Patents

Abstract

식 중, R은 수소 원자 또는 메틸기이고; R¹ 내지 R³ 중 어느 하나는 4-다이벤조티에닐기, 4-다이벤조퓨라닐기, 9-페난트릴기 또는 하기 식 (2)의 치환기(R은, 수소 원자 또는 메틸기를 나타냄)이고, 나머지는 수소 원자 또는 메틸기이며; Ar¹, Ar²는, 독립적으로, 탄소수 6 내지 18의 방향족 탄화수소기이고, 이들은 메틸기 또는 메톡시기를 가지고 있어도 된다:

.A 2-aminocarbazole compound suitable for a hole transporting material of an organic EL device and an organic EL device excellent in driving voltage, luminous efficiency, and device life using the compound are provided. A 2-aminocarbazole compound represented by the following formula (1):

Wherein R is a hydrogen atom or a methyl group; One of R ¹ to R ³ is a 4-dibenzothienyl group, a 4-dibenzofuranyl group, a 9-phenanthryl group or a substituent group of the following formula (2) (R represents a hydrogen atom or a methyl group) Is a hydrogen atom or a methyl group; Ar ¹ and Ar ² are independently an aromatic hydrocarbon group having 6 to 18 carbon atoms and may have a methyl group or a methoxy group:

.

Description

2-AMINOCARBASE COMPOUND AND USE THEREOF FIELD OF THE INVENTION [0001]

The present invention relates to a 2-aminocarbazole compound and an organic EL device using the same.

BACKGROUND ART An organic EL element is a surface-emitting type element in which an organic thin film is held between a pair of electrodes. The organic EL element has characteristics such as a thin and light weight, a high viewing angle, and a high speed response and is expected to be applied to various display elements. In recent years, some practical applications such as a display of a mobile phone have been started. The organic EL element uses light emitted when holes injected from the anode and electrons injected from the cathode recombine in the light emitting layer. The structure of the organic EL element is a multi-layer lamination type in which a hole transporting layer, a light emitting layer and an electron transporting layer are laminated. Here, the charge transport layer, which is referred to as a hole transport layer or an electron transport layer, does not emit light per se, but facilitates charge injection into the light emitting layer and keeps the exciton energy generated in the light emitting layer injected into the light emitting layer .

That is, the charge transport layer plays a very important role in improving the low driving voltage and the light emitting efficiency of the organic EL device.

As the hole transporting material, an amine compound having an appropriate ionization potential and hole transporting ability is used. For example, 4,4'-bis [N- (1-naphthyl) NPD ") is well known. However, the driving voltage, luminous efficiency and durability of a device using NPD as a hole transport layer are not sufficient, and development of new materials is required.

In addition, in recent years, development of organic EL devices using a phosphorescent light emitting material in a light emitting layer is under development, and a hole transporting material having a high triplet level is required in a device using phosphorescent light emission. NPD is not sufficient even in terms of triplet state. For example, it has been reported that an organic EL device in which a phosphorescent material having green luminescence and NPD are combined causes a decrease in luminous efficiency (for example, Patent Document 1).

From this background, recently, an amine compound having a carbazole ring introduced into a molecule has been reported. Specifically, 2-aminocarbazole compounds can be mentioned (for example, see Patent Documents 1 to 4).

In Patent Documents 1 and 2, a 2-aminocarbazole compound containing a pyrene ring and an anthracene ring is disclosed as a light-emitting material. These compounds containing a pyrene ring or an anthracene ring have low triplet levels of the pyrene ring and the anthracene ring itself, so that a high luminous efficiency can not be obtained in a device using a green phosphorescent material.

On the other hand, the 2-aminocarbazole compounds disclosed in Patent Documents 3 and 4 have higher triplet levels than NPD. Therefore, it is generally known that a device using a green phosphorescent material tends to exhibit higher luminescence efficiency than NPD.

Further, 3-aminocarbazole compounds in which dibenzothiophene or dibenzofuran and carbazole are combined are disclosed (for example, Patent Document 5).

However, for organic EL devices, further lowering of the driving voltage, higher light emission efficiency, longevity and the like are required, and development of a hole transporting material for this purpose is desired.

JP 2008-078362 A JP 2008-195841 A KR 10-2009-0129799 A JP 2011-001349 A WO2011 / 122132A

 Journal of Applied Physics, 2004, Volume 95, page 7798

An object of the present invention is to provide a 2-aminocarbazole compound having a specific chemical structure that significantly improves the lifetime of an organic EL element compared with a conventionally known 2-aminocarbazole compound or 3-aminocarbazole compound . It is another object of the present invention to provide an organic EL device having excellent lifetime by using a 2-aminocarbazole compound having the specific chemical structure.

As a result of extensive studies, the present inventors have found a 2-aminocarbazole compound, which is a novel compound represented by the following formula (1), to complete the present invention. Namely, the present invention relates to a 2-aminocarbazole compound represented by the following formula (1) and its use:

(Wherein R represents, independently of each other, a hydrogen atom or a methyl group, any one of R ¹ to R ³ represents a 4-dibenzothienyl group, a 4-dibenzofuranyl group, And Ar ¹ and Ar ² are each independently an aromatic hydrocarbon group having 6 to 18 carbon atoms and may have a methyl group or a methoxy group.

(R represents a hydrogen atom or a methyl group)

The organic EL device using the 2-aminocarbazole compound of the present invention has remarkably excellent lifetime as compared with an organic EL device using a conventionally known 2-aminocarbazole compound or 3-aminocarbazole. Therefore, the 2-aminocarbazole compound of the present invention can be used as an organic EL material having excellent durability.

In addition, compared with NPD which is a conventionally known hole transporting material, it is possible to make the organic electroluminescent device longevity, lower driving voltage, and higher luminous efficiency.

That is, according to the present invention, it is possible to provide an organic EL device having low power consumption and excellent device lifetime.

In the 2-aminocarbazole compound represented by the formula (1), R (including R in the formula (2)) each independently represents a hydrogen atom or a methyl group. From the viewpoints of the hole transporting property and the ease of obtaining the raw material, it is preferable that all R are hydrogen atoms.

In the 2-aminocarbazole compound represented by the above formula (1), any one of R ¹ to R ³ is preferably a 4-dibenzothienyl group, a 4-dibenzofuranyl group, a 9-phenanthryl group, 2), and the remainder is a hydrogen atom or a methyl group:

(R represents a hydrogen atom or a methyl group)

Any one of R ¹ to R ³ is preferably a 4-dibenzothienyl group, a 4-dibenzofuranyl group, a 9-phenanthryl group or a group represented by the formula (2) in terms of the hole transporting property and ease of obtaining a raw material. And the rest is preferably a hydrogen atom.

In the 2-aminocarbazole compound represented by the above formula (1), Ar ¹ and Ar ² each independently represent an aromatic hydrocarbon group having 6 to 18 carbon atoms, which may have a methyl group or a methoxy group.

The aromatic hydrocarbon group having 6 to 18 carbon atoms in Ar ¹ and Ar ² (which may have a methyl group or a methoxy group) is not particularly limited, and examples thereof include a phenyl group, a biphenyl group, a terphenyl group, A t-butyl group, a fluorenyl group, a phenanthryl group, and a benzofluorenyl group (these may have a methyl group or a methoxy group).

Specific examples of Ar ¹ and Ar ² include a phenyl group, a 4-methylphenyl group, a 3-methylphenyl group, a 2-methylphenyl group, a 2,4-dimethylphenyl group, A 3,5-dimethylphenyl group, a 2,6-dimethylphenyl group, a 2,3,5-trimethylphenyl group, a 2,3,6-trimethylphenyl group, a 3,4,5-trimethylphenyl group, Methyl-5-methoxyphenyl, 3-methyl-4-methoxyphenyl, 3-methyl-5-methoxyphenyl, 3-methoxyphenyl, 2-methoxyphenyl, Methoxy-4-methylphenyl group, 2,4-dimethoxyphenyl group, 2,5-dimethoxyphenyl group, 2,6-dimethoxyphenyl group, , 4-dimethoxyphenyl group, 3,5-dimethoxyphenyl group, 3,4,5-trimethoxyphenyl group, 4-biphenylyl group, 3-biphenylyl group, 2- Methyl-1,1'-biphenyl-4-yl group, 3'-methyl-1,1'-biphenyl-4-yl group, Methyl-1,1'-biphenyl-4-yl group, 4'-methyl- 1,1'-biphenyl-4-yl group, 2,6-dimethyl-1,1'-biphenyl-4-yl group, 2,2'- , 2,3'-dimethyl-1,1'-biphenyl-4-yl group, 2,4'-dimethyl-1,1'-biphenyl-4-yl group, , 1'-biphenyl-4-yl group, 2 ', 3'-dimethyl-1,1'-biphenyl-4-yl group, 2' - diethyl, 1,1'-biphenyl-4-yl group, 2 ', 6'-dimethyl- methyl naphthalene-1-yl group, a 6-methylnaphthalen-2-yl group, a 2-naphthyl group, a 2-naphthyl group, Triphenylenyl group, a 2-fluorenyl group, a 9,9-dimethyl-9H-fluoren-2-yl group, a 9-phenanthryl group , A 2-phenanthryl group, a benzofluorenyl group, a fluoranthenyl group, a pyrenyl group, a klycenyl group, and the like, but are not limited thereto.

In terms of the hole transporting property, Ar ¹ and Ar ² in the 2-aminocarbazole compound represented by the formula (1) of the present invention are each independently a phenyl group, a methyl group or a methyl group which may have a methyl group or a methoxy group A naphthyl group which may have a methoxy group, a phenanthryl group which may have a methyl group or a methoxy group, a biphenylyl group which may have a methyl group or a methoxy group, a terphenyl group which may have a methyl group or a methoxy group or a methyl group or a methoxy group Or a fluorenyl group which may be substituted. Each of Ar ¹ and Ar ^{2 is} independently a phenyl group, a 4-methylphenyl group, a 1-naphthyl group, a 9-phenanthryl group, a 4-biphenylyl group, a p- Yl group or a 9,9-dimethyl-9H-fluoren-2-yl group.

The 2-aminocarbazole compound represented by the above-mentioned formula (1) can be used as a light-emitting host material in the light-emitting layer of the organic EL device, a hole-transporting material in the hole-transporting layer, or a hole- However, these materials may be collectively used as a material for an organic EL device). The 2-aminocarbazole compound represented by the above formula (1) is preferably highly pure in terms of hole transporting property and device life.

A conventionally known fluorescent or phosphorescent material may be used for the light-emitting layer when the 2-aminocarbazole compound represented by the above formula (1) is used as the hole-injection layer and / or the hole-transport layer of the organic EL device . The light emitting layer may be formed of only one kind of light emitting material or may be doped with one or more kinds of light emitting materials in the host material.

When forming the hole injection layer and / or the hole transport layer containing the 2-aminocarbazole compound represented by the above formula (1), two or more kinds of materials may be contained or laminated as required, and for example, molybdenum oxide , Oxides such as 7,7,8,8-tetracyanoquinodimethane, 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane, hexacyanohexa Or a known electron-accepting material such as azapropylene, may be contained or laminated.

The 2-aminocarbazole compound represented by the formula (1) of the present invention can also be used as a light emitting layer of an organic EL device. When the 2-aminocarbazole compound represented by the above formula (1) is used as a light emitting layer of an organic EL device, an arylamine compound may be used alone, or may be doped into a known light emitting host material, (dopant) can be used by doping.

Examples of the method for forming the hole injection layer, the hole transporting layer or the light emitting layer containing the 2-aminocarbazole compound represented by the above formula (1) include known methods such as a vacuum evaporation method, a spin coating method and a casting method Can be applied.

The method for producing a thin film for an organic electroluminescence device comprising a 2-aminocarbazole compound represented by the above formula (1) of the present invention is not particularly limited, but a film can be formed by a vacuum evaporation method. The film formation by the vacuum vapor deposition method can be performed by using a general-purpose vacuum vapor deposition apparatus. The degree of vacuum of the vacuum chamber at the time of forming the film by the vacuum vapor deposition method can be reached by a generally used diffusion pump, turbo molecular pump, cryo pump, etc. in consideration of manufacturing tact time and manufacturing cost of the organic electroluminescent device . As the degree of vacuum, 1 × 10 ^-2 to 1 × 10 ^-6 ㎩ degree it is preferably, 1 × 10 ^-4 to 1 × 10 ^-6 ㎩ is the more preferred.

The deposition rate depends on the thickness of the film to be formed, but is preferably 0.005 to 1.0 nm / second, more preferably 0.01 to 0.3 nm / second. In addition, the 2-aminocarbazole compound represented by the formula (1) of the present invention has high heat resistance, so it is difficult to cause thermal decomposition even at the time of high-speed film formation, and the influence on the device performance is also small.

The basic structure of the organic EL device in which the effect of the present invention is obtained includes a substrate, a positive electrode, a hole injecting layer, a hole transporting layer, a light emitting layer, an electron transporting layer and a negative electrode.

The positive electrode and the negative electrode of the organic EL element are connected to a power source via an electrical conductor. By applying a potential between the anode and the cathode, the organic EL element operates.

The holes are injected from the anode into the organic EL element, and electrons are injected into the organic EL element from the cathode.

The organic EL element is typically coated on a substrate, and the anode or the cathode can be in contact with the substrate. An electrode in contact with the substrate is referred to as a lower electrode for convenience. Generally, the lower electrode is an anode, but the organic EL device of the present invention is not limited to such an embodiment.

The substrate may be light-transmissive or opaque depending on the intended light emission direction. The light transmission characteristic can be confirmed by electroluminescence light emission through the substrate. In general, transparent glass or plastic is used as a substrate. The substrate may be a composite structure including multiple material layers. When the electroluminescence emission is confirmed through the anode, the anode is formed by passing or substantially passing the light emission.

The transparent anode (anode) material used in the present invention is not particularly limited, and examples thereof include indium-tin oxide (ITO), indium-zinc oxide (IZO) and tin oxide. Other metal oxides such as aluminum or indium-doped tin oxide, magnesium-indium oxide or nickel-tungsten oxide may also be used. In addition to these oxides, metal nitrides such as gallium nitride, metal selenide, for example, zinc selenide, or metal sulfides such as zinc sulfide can be used as the anode.

The anode can be reformed into a plasma deposited fluorocarbon. When the electroluminescence emission is confirmed only through the cathode, the transparent property of the anode is not critical and any transparent conductive, opaque or reflective electrically conductive material can be used. Examples of conductors for this application include gold, iridium, molybdenum, palladium, platinum and the like.

Between the anode and the light emitting layer, a plurality of layers having hole transporting properties, such as a hole injecting layer and a hole transporting layer, can be formed. The hole injecting layer or the hole transporting layer has a function of transferring holes injected from the anode to the light emitting layer. By interposing these layers between the anode and the light emitting layer, many holes in a lower electric field can be injected into the light emitting layer.

In the organic EL device of the present invention, the hole transporting layer and / or the hole injecting layer include a 2-aminocarbazole compound represented by the above formula (1).

The hole transporting layer and / or the hole injecting layer may be used by combining any of the known hole transporting materials and / or hole injecting materials together with the 2-aminocarbazole compound represented by the formula (1).

Examples of known hole injecting materials and hole transporting materials include triazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives and pyrazolone derivatives, phenylene diamine derivatives, arylamine derivatives, Amide-substituted chalcone derivatives, oxazole derivatives, styryl anthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aniline-based copolymers, electrically conductive polymer oligomers and thiophenol oligomers.

As the hole injecting material and the hole transporting material, the above-mentioned materials can be used, but a porphyrin compound, an aromatic tertiary amine compound, a styrylamine compound and the like can be used, and in particular, an aromatic tertiary amine compound is preferably used.

Representative examples of the aromatic tertiary amine compound and the styrylamine compound include N, N, N ', N'-tetraphenyl-4,4'-diaminophenyl, N, N'- Bis (3-methylphenyl) - [1,1'-biphenyl] -4,4'-diamine (TPD), 2,2- N, N ', N'-tetra-p-tolyl-4,4'-diaminobiphenyl, 1,1-bis (4-dicarboxylic acid) (4-dimethylamino-2-methylphenyl) phenyl methane, bis (4-di-p- tolylaminophenyl) phenyl methane, N, N'-dicyclohexyl Phenyl-N, N'-di (4-methoxyphenyl) -4,4'-diaminobiphenyl, N, N, N ', N'-tetraphenyl- , 4,4'-bis (diphenylamino) quadriphenyl, N, N, N-tri (p- stilyl] stilbene, 4-N, N-diphenylamino- (2-diphenylvinyl) benzene, 3-methoxy (NPD), 4,4'-bis [N- (1-naphthyl) -N-phenylamino] biphenyl , 4 "-tris [N- (3-methylphenyl) -N-phenylamino] triphenylamine (MTDATA).

Further, inorganic compounds such as p-type-Si and p-type-SiC can also be used as a hole injecting material and a hole transporting material.

The hole injecting layer and / or the hole transporting layer may have a single layer structure composed of one or more of the above materials, or a laminated structure composed of plural layers of the same composition or different compositions.

The light-emitting layer of the organic EL device includes a phosphorescent material or a fluorescent material, and causes light emission as a result of recombination of electron-hole pairs in this region.

The light emitting layer may be formed of a single material including both a low molecular weight and a polymer, but is more generally formed of a host material doped with a guest compound, and the light emission mainly occurs from the dopant and may have any color.

As the host material of the light-emitting layer, a 2-aminocarbazole compound represented by the above formula (1) can be used. Examples of other compounds include a biphenyl group, a fluorenyl group, a triphenylsilyl group, a carbazole group, A thiophene group or a thiophene group. Specific examples thereof include DPVBi (4,4'-bis (2,2-diphenylvinyl) -1,1'-biphenyl), BCzVBi (4,4'-bis (9- Biphenyl), TBADN (2-tert-butyl-9,10-di (2-naphthyl) anthracene), ADN (9,10- Carbazole-9-yl) biphenyl), CDBP (4,4'-bis (carbazol-9-yl) -2,2'-dimethylbiphenyl), or 9,10 -Bis (biphenyl) anthracene, and the like.

The host material in the light emitting layer may be an electron transporting material as defined below, a hole transporting material as defined above, a separate material for assisting in hole / electron recombination (support), or a combination of these materials.

Examples of the fluorescent dopant include anthracene, tetracene, xanthene, perylene, rubrene, coumarin, rhodamine, quinacridone, dicyanomethylenepyran compound, thiopyran compound, polymethine compound, , A fluorene derivative, a periflanthene derivative, an indenopearylene derivative, a bis (azinyl) amine boron compound, a bis (azinyl) methane compound, and a carbostyril compound.

Examples of phosphorescent dopants include organometallic complexes of transition metals such as aluminum, iridium, platinum, palladium, and osmium.

Examples of the dopant include Alq ₃ (tris (8-hydroxyquinoline) aluminum), DPAVBi (4,4'-bis [4- (di- para- tolylamino) styryl] biphenyl) (PPy) ₃ (tris (2-phenylpyridine) iridium (III) or FlrPic (bis (2- (2-pyridyl 3,5-difluoro) phenyl- (2-carboxy-pyridyl) iridium (III) And the like.

Examples of the electron transporting material include alkali metal complexes, alkaline earth metal complexes, and earth metal complexes. Examples of the alkali metal complex, alkaline earth metal complex or the earth metal complex include 8-hydroxyquinolinato lithium (Liq), bis (8-hydroxyquinolinato) zinc, bis (8-hydroxyquinolinato ) Copper, bis (8-hydroxyquinolinato) manganese, tris (8-hydroxyquinolinato) aluminum, tris (2-methyl-8-hydroxyquinolinato) aluminum, tris (8- Bis (10-hydroxybenzo [h] quinolinato) beryllium, bis (10-hydroxybenzo [h] quinolinato) zinc, bis (2-methyl-8-quinolinato) (o-cresolato) gallium, bis Nolinato-2-naphthol ratogallium, and the like.

A hole blocking layer may be formed between the light emitting layer and the electron transporting layer for the purpose of improving the carrier balance. Preferred compounds for the hole blocking layer are BCP (2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline), Bphen (4,7-diphenyl-1,10-phenanthroline) , BAlq (bis (2-methyl-8-quinolinolato) -4- (phenylphenolato) aluminum) or bis (10-hydroxybenzo [h] quinolinato) beryllium).

In the organic EL device of the present invention, an electron injecting layer may be formed for the purpose of improving the electron injecting property and improving the device characteristics (for example, luminous efficiency, constant voltage driving, or high durability).

Examples of preferable compounds for the electron injecting layer include fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylene tetracarboxylic acid, fluorenylidenemethane, Nodai Methane, and Anthrone.

Further, the metal complex or the alkali metal oxides, alkaline earth oxides, rare earth oxides, alkali metal halides, alkaline earth halides, rare earth halides described above, SiO _2, AlO, SiN, SiON, AlON, GeO, LiO, LiON, TiO , Various oxides such as TiON, TaO, TaON, TaN, and C, and inorganic compounds such as nitride and oxynitride.

When the light emission is confirmed only through the anode, the cathode used in the present invention can be formed of any electrically conductive material. Preferred negative electrode materials include sodium, sodium-potassium alloy, magnesium, lithium, a magnesium / copper mixture, a magnesium / silver mixture, a magnesium / aluminum mixture, a magnesium / indium mixture, an aluminum / aluminum oxide (Al ₂ O ₃ ) Lithium / aluminum mixtures, and rare earth metals.

Specific examples of the 2-aminocarbazole compound represented by the formula (1) include 2-aminocarbazole compounds represented by the following formula (1A) and 2-aminocarbazole compounds represented by the formula (1B) ≪ / RTI >

The 2-aminocarbazole compound represented by the following formula (1A) will be described below.

(R ^1A to R ^7A each independently represents a hydrogen atom or a methyl group. Ar ¹ and Ar ² are, each independently, an aromatic hydrocarbon group having 6 to 18 carbon atoms, which are optionally has a methyl group or a methoxy group. One of R ^8A and R ^9A is a group represented by the following formula (2A), and the other is a hydrogen atom.)

(R ^10A represents a hydrogen atom or a methyl group)

The 2-aminocarbazole compound represented by the formula (1A) is a compound wherein one of R ¹ or R ² in the formula (1) is a group of the formula (2) and the other is a hydrogen atom, and R ³ Is a hydrogen atom or a methyl group.

In the 2-aminocarbazole compound represented by the above formula (1A), R ^1A to R ^7A each independently represent a hydrogen atom or a methyl group. It is preferable that R ^{1 A} , R ^{2 A} , R ^{4 A} , R ^{5 A} , R ^{6 A} and R ^{7 A} are each a hydrogen atom in view of the hole transporting property and the ease of obtaining the raw material, and R ^{1 A} to R ^{7 A} are all hydrogen atoms Is more preferable.

In the 2-aminocarbazole compound represented by the above formula (1A), Ar ¹ and Ar ² each independently represent an aromatic hydrocarbon group having 6 to 18 carbon atoms, which may have a methyl group or a methoxy group. The aromatic hydrocarbon group having 6 to 18 carbon atoms in Ar ¹ and Ar ² is not particularly limited and examples thereof include a phenyl group, a biphenylyl group, a terphenyl group, a naphthyl group, a fluorenyl group, a phenanthryl group, A fluorenyl group (these groups may have a methyl group or a methoxy group, and the number of substituents is not particularly limited).

Specific examples of Ar ¹ and Ar ² include a phenyl group, a 4-methylphenyl group, a 3-methylphenyl group, a 2-methylphenyl group, a 2,4-dimethylphenyl group, A 3,5-dimethylphenyl group, a 2,6-dimethylphenyl group, a 2,3,5-trimethylphenyl group, a 2,3,6-trimethylphenyl group, a 3,4,5-trimethylphenyl group, Methyl-5-methoxyphenyl, 3-methyl-4-methoxyphenyl, 3-methyl-5-methoxyphenyl, 3-methoxyphenyl, 2-methoxyphenyl, Methoxy-4-methylphenyl group, 2,4-dimethoxyphenyl group, 2,5-dimethoxyphenyl group, 2,6-dimethoxyphenyl group, , 4-dimethoxyphenyl group, 3,5-dimethoxyphenyl group, 3,4,5-trimethoxyphenyl group, 4-biphenylyl group, 3-biphenylyl group, 2- Methyl-1,1'-biphenyl-4-yl group, 3'-methyl-1,1'-biphenyl-4-yl group, Methyl-1,1'-biphenyl-4-yl group, 4'-methyl- 1,1'-biphenyl-4-yl group, 2,6-dimethyl-1,1'-biphenyl-4-yl group, 2,2'- , 2,3'-dimethyl-1,1'-biphenyl-4-yl group, 2,4'-dimethyl-1,1'-biphenyl-4-yl group, , 1'-biphenyl-4-yl group, 2 ', 3'-dimethyl-1,1'-biphenyl-4-yl group, 2' - diethyl, 1,1'-biphenyl-4-yl group, 2 ', 6'-dimethyl- methyl naphthalene-1-yl group, a 6-methylnaphthalen-2-yl group, a 2-naphthyl group, a 2-naphthyl group, Fluorenyl group, 9-anthryl group, 2-fluorenyl group, 9,9-dimethyl-9H-fluoren-2-yl group, 9-phenanthryl group, A thienyl group, a pyrenyl group, a klycenyl group, and the like, but are not limited thereto.

In terms of the hole transporting property, Ar ¹ and Ar ² in the 2-aminocarbazole compound represented by the formula (1A) of the present invention are each independently a phenyl group, a methyl group or a methyl group which may have a methyl group or a methoxy group A biphenylyl group which may have a methoxy group, a terphenyl group which may have a methyl group or a methoxy group, or a fluorenyl group which may have a methyl group or a methoxy group, and a phenyl group, a 4-biphenylyl group, Yl group, an m-terphenyl-4-yl group or a 9,9-dimethyl-9H-fluoren-2-yl group.

Hereinafter, preferred examples of the 2-aminocarbazole compounds represented by the formula (1A) are shown, but the present invention is not limited to these compounds.

Among these compounds, the compound (A25), the compound (A26), the compound (A27), the compound (A28), the compound (A29), the compound (A47), or the compound (A53) in terms of triplet level and hole- Is more preferable.

The 2-aminocarbazole compound represented by the formula (1A) can be obtained by a known method (Tetrahedron Letters, 1998, vol. 39, 1998) using 9H-carbazole compounds in which the 2-position is halogenated, , Page 2367). Specifically, it can be synthesized by the following route.

A 9H-carbazole compound in which the 2-position is halogenated and represented by the formula (3A) and a compound having a halogen atom represented by the formula (4A) are reacted in the presence of a base using a copper catalyst or a palladium catalyst, To obtain a 2-halogenated-9-substituted carbazole compound represented by the formula (5A). Further, the 2-halogenated-9-substituted carbazole compound represented by the formula (5A) and the secondary amine compound represented by the formula (6A) are reacted in the presence of a base using a copper catalyst or a palladium catalyst .

(Wherein Ar ¹ , Ar ² , and R ^1A to R ^9A represent the same definitions as in the above formula (1). A and B each independently represent a halogen atom (iodine, bromine, chlorine or fluorine) .)

The compound represented by the formula (3A) can be synthesized according to a generally known method (for example, Japanese Patent Laid-Open Publication No. 2011-1349).

The compound represented by the formula (4A) can be synthesized according to a generally known method (for example, WO2008-013399).

The compound represented by the formula (6A) may be a commercially available compound or may be synthesized according to generally known methods.

The 2-aminocarbazole compound represented by the formula (1A) of the present invention can be used as a material for a light emitting layer, a hole transporting layer, or a hole injecting layer of an organic EL device. The 2-aminocarbazole compound represented by the above formula (1A) is preferably high in purity in terms of hole transporting property and device life.

For the light-emitting layer when the 2-aminocarbazole compound represented by the above formula (1A) is used as the hole-injecting layer and / or the hole-transporting layer of the organic EL device, conventionally known fluorescent or phosphorescent materials can be used . The light emitting layer may be formed of only one kind of light emitting material or may be doped with one or more kinds of light emitting materials in the host material.

In forming the hole injecting layer and / or the hole transporting layer made of the 2-aminocarbazole compound represented by the above formula (1A), two or more kinds of materials may be contained or laminated if necessary. For example, molybdenum oxide , Oxides such as 7,7,8,8-tetracyanoquinodimethane, 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodiacetane, hexacyanohexaaza A known electron-accepting material such as triphenylene may be contained or laminated.

When the 2-aminocarbazole compound represented by the above formula (1A) is used as a light emitting layer of an organic EL device, the 2-aminocarbazole compound may be used singly or doped into a known light emitting host material, or A known luminescent dopant can be used by doping.

Examples of the method for forming the hole injection layer, the hole transporting layer or the light emitting layer containing the 2-aminocarbazole compound represented by the above formula (1A) include known methods such as a vacuum evaporation method, a spin coating method, and a casting method Can be applied.

Next, the 2-aminocarbazole compound represented by the following formula (1B) will be described below.

(Wherein one of R ^1B to R ^3B is a 4-dibenzothienyl group, a 4-dibenzofuranyl group or a 9-phenanthryl group, and the remainder is a hydrogen atom, Ar ¹ and Ar ² each independently represent a An aromatic hydrocarbon group having 6 to 18 carbon atoms, which may have a methyl group or a methoxy group.

The 2-aminocarbazole compound represented by the formula (1B) is a compound in which a part of R in the formula (1) is a hydrogen atom, and any one of R ¹ to R ³ is a 4-dibenzothienyl group, A furanyl group or a 9-phenanthryl group, and the remainder are hydrogen atoms.

In the 2-aminocarbazole compound represented by the above formula (1B), Ar ¹ and Ar ² are each independently an aromatic hydrocarbon group having 6 to 18 carbon atoms and may have a methyl group or a methoxy group.

The aromatic hydrocarbon group having 6 to 18 carbon atoms in Ar ¹ and Ar ² is not particularly limited and examples thereof include a phenyl group, a biphenylyl group, a terphenyl group, a naphthyl group, a fluorenyl group, a phenanthryl group, A fluorenyl group, a fluorenyl group, a fluorenyl group, a fluorenyl group, a fluorenyl group, a fluorenyl group, a triphenylenyl group, and a fluoranthenyl group (the substituent thereof may have a methyl group or a methoxy group and the number of the methyl group or methoxy group is not particularly limited).

Specific examples of Ar ¹ and Ar ² include a phenyl group, a 4-methylphenyl group, a 3-methylphenyl group, a 2-methylphenyl group, a 2,4-dimethylphenyl group, A 3,5-dimethylphenyl group, a 2,6-dimethylphenyl group, a 2,3,5-trimethylphenyl group, a 2,3,6-trimethylphenyl group, a 3,4,5-trimethylphenyl group, Methyl-5-methoxyphenyl, 3-methyl-4-methoxyphenyl, 3-methyl-5-methoxyphenyl, 3-methoxyphenyl, 2-methoxyphenyl, Methoxy-4-methylphenyl group, 2,4-dimethoxyphenyl group, 2,5-dimethoxyphenyl group, 2,6-dimethoxyphenyl group, , 4-dimethoxyphenyl group, 3,5-dimethoxyphenyl group, 3,4,5-trimethoxyphenyl group, 4-biphenylyl group, 3-biphenylyl group, 2- Methyl-1,1'-biphenyl-4-yl group, 3'-methyl-1,1'-biphenyl-4-yl group, Methyl-1,1'-biphenyl-4-yl group, 4'-methyl- 1,1'-biphenyl-4-yl group, 2,6-dimethyl-1,1'-biphenyl-4-yl group, 2,2'- , 2,3'-dimethyl-1,1'-biphenyl-4-yl group, 2,4'-dimethyl-1,1'-biphenyl-4-yl group, , 1'-biphenyl-4-yl group, 2 ', 3'-dimethyl-1,1'-biphenyl-4-yl group, 2' - diethyl, 1,1'-biphenyl-4-yl group, 2 ', 6'-dimethyl- methyl naphthalene-1-yl group, a 6-methylnaphthalen-2-yl group, a 2-naphthyl group, a 2-naphthyl group, Triphenylenyl group, a 2-fluorenyl group, a 9,9-dimethyl-9H-fluoren-2-yl group, a 9-phenanthryl group , A 2-phenanthryl group, a benzofluorenyl group, a fluoranthenyl group, a pyrenyl group, a klycenyl group, and the like, but are not limited thereto.

Ar ¹ and Ar ² each independently represent a phenyl group which may have a methyl group or a methoxy group, a naphthyl group which may have a methyl group or a methoxy group, a phenanthryl group which may have a methyl group or a methoxy group A phenyl group which may have a methyl group or a methoxy group, a terphenyl group which may have a methyl group or a methoxy group or a fluorenyl group which may have a methyl group or a methoxy group, and a phenyl group, a 4-methylphenyl group, A naphthyl group, a 9-phenanthryl group, a 4-biphenylyl group, a p-terphenyl-4-yl group, an m-terphenyl-4-yl group or a 9,9-dimethyl-9H- More preferable.

Hereinafter, preferred examples of the 2-aminocarbazole compounds represented by formula (1B) are shown, but the present invention is not limited thereto.

Of these compounds, compound (B2), compound (B5), compound (B25), compound (B26), compound (B27), compound (B28), compound (B29) (B34), compound (B46), compound (B53), compound (B77), compound (B79), compound (B103), compound (B106), compound (B122) or compound (B138) are more preferable.

The 2-aminocarbazole compound represented by the above formula (1B) can be obtained by a known method (Tetrahedron Letters, 1998, vol. 39, 1998) using, for example, a 9H- , Page 2367).

Specifically, it can be synthesized by the following route.

(R ^1B to R ^3B , Ar ¹ and Ar ² have the same definitions as in the formula (1B). A and B each independently represent a halogen atom (iodine, bromine, chlorine or fluorine). )

A compound having a halogen atom in the 2-position halogenated 9H-carbazole compound represented by the formula (2B) and a halogen atom represented by the formula (3B) is reacted with a copper catalyst or a palladium catalyst To obtain a 2-halogenated-9-substituted carbazole compound represented by the formula (4B).

Further, the obtained 2-halogenated-9-substituted carbazole compound represented by the formula (4B) and the secondary amine compound represented by the formula (5B) are reacted in the presence of a base using a copper catalyst or a palladium catalyst .

The compound represented by the formula (2B) can be synthesized according to a generally known method (for example, Japanese Patent Laid-Open No. 2011-1349).

The compound represented by the formula (3B) can be synthesized according to a generally known method (for example, WO2009-133007 and Chemistry Letters, 2011, vol. 40, page 1050).

The compound represented by the formula (5B) may be a commercially available compound or may be synthesized according to generally known methods.

The 2-aminocarbazole compound represented by the formula (1B) of the present invention can be used as a light emitting layer, a hole transporting layer, or a hole injecting layer of an organic EL device. That is, the compound represented by the formula (1B) can be effectively used as a light emitting material, a light emitting host material, a hole transporting material, or a hole injecting material.

In addition, the compound is preferably high in purity, in view of the hole transporting property and the lifetime of the organic EL device. Purification can be carried out by a generally known method such as distillation, sublimation purification, recrystallization, silica gel chromatography, and the like, and high purity can be obtained.

As a light-emitting layer when the 2-aminocarbazole compound represented by the above formula (1B) is used as the hole injection layer and / or the hole transport layer of the organic EL device, conventionally known fluorescent or phosphorescent materials can be used . The light emitting layer may be formed of only one kind of light emitting material or may be doped with one or more kinds of light emitting materials in the host material.

When forming the hole injection layer and / or the hole transport layer containing the 2-aminocarbazole compound represented by the above formula (1B), two or more kinds of materials may be contained or laminated as required. For example, oxides such as molybdenum oxide, oxides such as 7,7,8,8-tetracyanoquinodimethane, 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodi Methane, hexacyanohexaazatriphenylene, or other known electron-accepting material may be contained or laminated.

When the 2-aminocarbazole compound represented by the above formula (1B) is used as a light emitting layer of an organic EL device, the 2-aminocarbazole compound may be used singly or doped into a known light emitting host material, or A known luminescent dopant can be used by doping.

Examples of the method of forming the hole injection layer, the hole transporting layer or the light emitting layer containing the 2-aminocarbazole compound represented by the above formula (1B) include known methods such as a vacuum evaporation method, a spin coating method, and a casting method Can be applied.

[ Example ]

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.

¹ H-NMR and ¹³ C-NMR measurements were carried out using Gemini 200 of Barien product using tetramethylsilane as an internal standard.

The FDMS (off-center mass analysis) measurement was carried out using M-80B manufactured by Hitachi Seisakusho Co., Ltd. The luminescent characteristics of the organic EL device were evaluated by applying a set direct current to the fabricated device and measuring the luminance using a luminometer of LUMINANCE METER (BM-9) manufactured by Topcon Corporation.

Synthesis Example 1A (Synthesis of 2-chloro-9- (4- (1-naphthyl) phenyl) carbazole [

5.2 g (26.0 mmol) of 2-chlorocarbazole, 7.7 g (27.3 mmol) of 1-bromo-4- (1-naphthyl) benzene and 5.2 g , 25 mg of o-xylene, 61 mg (0.27 mmol) of palladium acetate and 193 mg (0.95 mmol) of tri (tert-butyl) phosphine were added to the solution, and the mixture was stirred at 140 占 폚 for 18 hours . After cooling to room temperature, 30 ml of pure water was added, and the organic layer was separated. The organic layer was washed successively with water and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (mixed solvent of toluene and hexane (volume ratio = 1: 2)) to obtain 8.7 g of a white powder of 2-chloro-9- (4- (1-naphthyl) phenyl) carbazole (21.5 mmol) (yield: 83%).

The compound was identified by ¹ H-NMR measurement and ¹³ C-NMR measurement (the same applies hereinafter).

_{^{1 H-NMR (CDCl 3)}} δ (ppm); 2H), 7.70 (d, 2H), 7.40-7.62 (m, 9H), 7.20-7. 34 (m, 2H)

_{^{13 C-NMR (CDCl 3)}} δ (ppm); 140.93, 140.74, 139.85, 138.62, 135.67, 133.38, 131.28, 131.15, 130.98, 127.94, 127.61, 126.64, 126.26, 125.87, 125.80, 125.49, 125.27, 124.94, 122.38, 121.55, 120.71, 120.01, 119.81,

Synthesis Example 2A Synthesis of (2-chloro-9- (4- (2-methylnaphthalen-1-yl) phenyl) carbazole [

(7.7 mmol) of 2-chlorocarbazole and 2.3 g (7.7 mmol) of 1-bromo-4- (2-methylnaphthalen-1-yl) benzene were placed in a 50 ml three- (10.8 mmol) of potassium carbonate, 10 ml of o-xylene, 17 mg (0.07 mmol) of palladium acetate and 54 mg (0.27 mmol) of tri (tert-butyl) phosphine were added, And stirred for 13 hours. After cooling to room temperature, 10 ml of pure water was added, and the organic layer was separated. The organic layer was washed successively with water and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (a mixed solvent of toluene and hexane (volume ratio = 1: 2)) to give 2-chloro-9- (4- (2-methylnaphthalen- 1.9 g (4.6 mmol) of the powder was isolated (yield: 59%).

_{^{1 H-NMR (CDCl 3)}} δ (ppm); 2H), 7.65 (d, 2H), 7.23-7.55 (m, 11H), 2.36 (s, 3H)

_{^{13 C-NMR (CDCl 3)}} δ (ppm); 140.94, 140.74, 139.00, 136.51, 135.41, 132.83, 132.32, 131.50, 131.35, 131.22, 128.14, 127.39, 127.16,126.39,125.76,125.62,125.38,124.46,122.36,121.55,120.71,201.00, 119.79,109.58,109.48, 20.58

Synthesis Example 3A Synthesis of (2-chloro-9- (3- (1-naphthyl) phenyl) carbazole [

(29.43 mmol) of 2-chlorocarbazole, 8.3 g (29.4 mmol) of 1-bromo-3- (1-naphthyl) benzene and 5.6 g 35 mg of o-xylene, 66 mg (0.29 mmol) of palladium acetate and 207 mg (1.0 mmol) of tri (tert-butyl) phosphine were added and the mixture was stirred at 140 캜 for 15 hours . After cooling to room temperature, 30 ml of pure water was added, and the organic layer was separated. The organic layer was washed successively with water and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (mixed solvent of toluene and hexane (volume ratio = 1: 2)) to obtain 7.6 g of a white powder of 2-chloro-9- (3- (1-naphthyl) phenyl) carbazole (18.8 mmol) (yield: 63%).

Identification of the compound was carried out by FDMS measurement (the same applies hereinafter).

FDMS (m / z); 403 (M < + >)

Synthesis Example 4A Synthesis of (2-chloro-9- (3- (2-methylnaphthalen-1-yl) phenyl) carbazole [

(26.3 mmol) of 2-chlorocarbazole and 7.8 g (26.3 mmol) of 1-bromo-3- (2-methylnaphthalen-1-yl) benzene were placed in a 50 ml three- (36.8 mmol) of potassium carbonate, 25 ml of o-xylene, 59 mg (0.26 mmol) of palladium acetate and 185 mg (0.92 mmol) of tri (tert-butyl) Followed by stirring for 14 hours. After cooling to room temperature, 20 ml of pure water was added, and the organic layer was separated. The organic layer was washed successively with water and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (a mixed solvent of toluene and hexane (volume ratio = 1: 2)) to obtain 2-chloro-9- (3- (2-methylnaphthalen- 10.5 g (25.1 mmol) of the powder was isolated (yield: 95%).

_{^{1 H-NMR (CDCl 3)}} δ (ppm); (M, 3H), 7.14-7.58 (m, 12H), 2.33 (s, 3H)

_{^{13 C-NMR (CDCl 3)}} δ (ppm); 129.19, 128.16, 127.49, 127.28, 125.82, 125.76, 125.29, 125.05, 124.54, 122.43, 121.59, 120.75, 120.05, 119.85, 109.54, 20.64

Synthesis Example 1B Synthesis of (2-chloro-9- (4- (4-dibenzothienyl) phenyl) carbazole [

(35.5 mmol) of 2-chlorocarbazole, 12.0 g (35.5 mmol) of 1-bromo-4- (4-dibenzothienyl) benzene, 100 mg of o-xylene, 239 mg (1.0 mmol) of palladium acetate and 752 mg (3.7 mmol) of tri (tert-butyl) phosphine were added, and the mixture was stirred at 140 占 폚 for 14 hours Lt; / RTI > After cooling to room temperature, 60 ml of pure water was added, and the organic layer was separated. The organic layer was washed successively with water and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography (a mixed solvent of toluene and hexane (volume ratio = 1: 2)) to obtain a white powder of 2-chloro-9- (4- (4-dibenzothienyl) 14.0 g (30.5 mmol) of the title compound was obtained (yield: 86%).

FDMS (m / z); 459 (M < + >)

_{^{1 H-NMR (CDCl 3)}} δ (ppm); (M, 4H), 7.89 (d, 2H), 7.79-7.83 (m, 1H), 7.37-7.60 (m, 8H), 7.12-7.32

_{^{13 C-NMR (CDCl 3)}} δ (ppm); 140.82, 140.65, 139.52, 138.95, 137.96, 136.26, 135.96, 135.38, 135.25, 131.33, 129.39, 127.76, 126.68, 126.50, 125.86, 124.78, 124.06, 122.43, 122.17, 121.63, 121.35, 120.73, 120.42, 120.12, 119.85, 109.63, 109.56

Synthesis Example 2B Synthesis of (2-chloro-9- (4- (4-dibenzofuranyl) phenyl) carbazole [

(14.9 mmol) of 2-chlorocarbazole, 4.8 g (14.9 mmol) of 1-bromo-4- (4-dibenzofuranyl) benzene, (29.8 mmol) of potassium, 25 mg of o-xylene, 67 mg (0.29 mmol) of palladium acetate and 210 mg (1.0 mmol) of tri (tert-butyl) Lt; / RTI > After cooling to room temperature, 10 ml of pure water was added, and the organic layer was separated. The organic layer was washed successively with water and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (a mixed solvent of toluene and hexane (volume ratio = 1: 2)) to obtain a white powder of 2-chloro-9- (4- (4-dibenzofuranyl) (12.1 mmol) (yield: 81%).

FDMS (m / z); 443 (M < + >)

_{^{1 H-NMR (CDCl 3)}} δ (ppm); 7.90-8.11 (m, 6H), 7.62 (d, 4H), 7.08-7.49 (m, 8H)

_{^{13 C-NMR (CDCl 3)}} δ (ppm); 125.69, 152.81, 140.89, 140.71, 136.02, 135.41, 131.31, 129.83, 126.94, 126.57, 126.26, 125.82, 124.68, 124.21, 123.64, 122.91, 122.47, 122.41, 121.59, 120.69, 120.29, 120.07, 119.81, 119.68, 111.43, 109.67, 109.59

Synthesis Example 3B Synthesis of (2-chloro-9- (3- (4-dibenzothienyl) phenyl) carbazole [

(28.4 mmol) of 2-chlorocarbazole, 9.6 g (28.4 mmol) of 1-bromo-3- (4-dibenzothienyl) benzene, , 801 ml of o-xylene, 191 mg (0.80 mmol) of palladium acetate and 601 mg (2.9 mmol) of tri (tert-butyl) phosphine were added, Lt; / RTI > After cooling to room temperature, 50 ml of pure water was added, and the organic layer was separated. The organic layer was washed successively with water and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography (a mixed solvent of toluene and hexane (volume ratio = 1: 2)) to obtain a white powder of 2-chloro-9- (3- (4-dibenzothienyl) (21.8 mmol) (yield: 77%).

FDMS (m / z); 459 (M < + >)

Synthesis Example 4B (Synthesis of 2-chloro-9- (3- (4-dibenzofuranyl) phenyl) carbazole [

(29.8 mmol) of 2-chlorocarbazole, 9.6 g (29.8 mmol) of 1-bromo-3- (4-dibenzofuranyl) benzene, 82 mg (59.6 mmol) of potassium, 50 mg of o-xylene, 134 mg (0.58 mmol) of palladium acetate and 420 mg (2.0 mmol) of tri (tert-butyl) phosphine were added and stirred at 140 ° C for 8 hours Respectively. After cooling to room temperature, 30 ml of pure water was added, and the organic layer was separated. The organic layer was washed successively with water and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (a mixed solvent of toluene and hexane (volume ratio = 1: 2)) to obtain a white powder of 2-chloro-9- (3- (4-dibenzofuranyl) 11.2 g (25.3 mmol) was isolated (yield: 85%).

FDMS (m / z); 443 (M < + >)

Synthesis Example 5B (Synthesis of 2-nitro-5- (4-dibenzothienyl) -4'-chlorobiphenyl [see synthesis route below]

In a 300 ml three-necked flask under a nitrogen gas stream were introduced 10.6 g (39.8 mmol) of 2-nitro-5,4'-dichlorobiphenyl, 10.0 g (43.8 mmol) of 4-dibenzothiophene boronic acid, 0.46 g (0.39 mmol) of tetrakis (triphenylphosphine) palladium, 50 ml of tetrahydrofuran, and 52.8 g (99.6 mmol) of a tripotassium phosphate aqueous solution of 40% by weight were added and refluxed for 10 hours. After cooling to room temperature, the water layer and the organic layer were separated, and the organic layer was washed with saturated aqueous ammonium chloride solution and saturated aqueous sodium chloride solution, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. Toluene was added to the obtained residue and the residue was purified by silica gel column chromatography (toluene) to obtain 11.1 g (26.7 m) of a yellow powder of 2-nitro-5- (4-dibenzothienyl) -4'- ㏖) (yield: 67%).

_{^{1 H-NMR (CDCl 3)}} ; 8.15-8.21 (m, 2H), 8.02 (d, 1H), 7.77-7.86 (m, 3H), 7.30-7.60

_{^{13 C-NMR (CDCl 3)}} ; 134.48, 144.50, 138.55, 137.76, 136.15, 135.38, 135.25, 134.92, 134.10, 133.71, 131.13, 128.82, 128.47, 127.69, 126.75, 126.48, 124.81, 124.57, 124.26, 122.16, 121.37, 121.26

Synthesis Example 6B Synthesis of (2-chloro-6- (4-dibenzothienyl) carbazole [see synthesis route below]

To a 200 ml three-necked flask under a nitrogen gas stream were added 10.6 g (25.5 mmol) of 2-nitro-5- (4-dibenzothienyl) -4'-chlorobiphenyl obtained in Synthesis Example 5B, 16.7 g (63.8 mmol) of pin and 60 ml of o-dichlorobenzene were charged, and the mixture was stirred at 150 占 폚 for 24 hours. The o-dichlorobenzene was distilled off under reduced pressure, and then toluene was added to the obtained residue, and the residue was purified by silica gel column chromatography (toluene). The resulting pale yellow powder was further washed with hexane to isolate 5.0 g (13.0 mmol) of pale yellow powder of 2-chloro-6- (4-dibenzothienyl) carbazole (yield: 51%).

¹ H-NMR (acetone -d _6); (D, 1H), 7.50-7.65 (m, 1H), 8.50 (s, 1H), 8.27-8.38 m, 3H), 7.47-7.56 (m, 2H), 7.23 (d, IH)

¹³ C-NMR (acetone-d ₆ ); 141.89, 140.88, 140.02, 138.52, 137.64, 136.87, 136.59, 132.68, 131.74, 127.91, 127.66, 126.96, 126.14, 125.28, 123.61, 123.30, 122.62, 122.57, 122.22, 120.81, 120.57, 120.08, 112.17, 111.67

Synthesis Example 7B Synthesis of (2-chloro-6- (4-dibenzothienyl) -9-phenylcarbazole [see synthesis route below]

In a 50 ml three-necked flask under a nitrogen gas stream, 4.5 g (11.7 mmol) of 2-chloro-6- (4-dibenzothienyl) carbazole obtained in Synthesis Example 6B, 2.0 g ), 3.2 g (23.4 mmol) of potassium carbonate, 25 ml of o-xylene, 52 mg (0.23 mmol) of palladium acetate and 165 mg (0.81 mmol) of tri (tert- Lt; / RTI > for 14 hours. After cooling to room temperature, 20 ml of pure water was added, and the organic layer was separated. The organic layer was washed successively with pure water and saturated brine, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography (a mixed solvent of toluene and hexane (volume ratio = 1: 1)) to obtain a pale yellow powder of 2-chloro-6- (4-dibenzothienyl) Was isolated (5.0 g, 10.8 mmol) (yield: 92%).

_{^{1 H-NMR (CDCl 3)}} ; 2H), 7.39-7.68 (m, 11H), 7.27 (d, IH), 8.14-8.21 (m,

_{^{13 C-NMR (CDCl 3)}} ; 126.42, 126.16, 126.55, 126.22, 126.11, 124.65, 123.84, 122.65, 122.10, 121.44, 121.26, 120.80, 120.18, 119.54, 129.59, 127.59, 131.53, 129.59, 127.59, 109.72, 109.58

Synthesis Example 8B (Synthesis of 2-chloro-9- (4- (9-phenanthryl) phenyl) carbazole [

(30.1 mmol) of 2-chlorocarbazole, 10.0 g (30.1 mmol) of 1-bromo-4- (9-phenanthryl) benzene and 6.2 g 40 ml of o-xylene, 135 mg (0.60 mmol) of palladium acetate and 425 mg (2.1 mmol) of tri (tert-butyl) phosphine were added and the mixture was stirred at 140 占 폚 for 10 hours . After cooling to room temperature, 30 ml of pure water was added, and the organic layer was separated. The organic layer was washed successively with water and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (a mixed solvent of toluene and hexane (volume ratio = 1: 3)) to obtain a white powder of 2-chloro-9- (4- (9-phenanthryl) 7.5 g (16.5 mmol) of the compound was isolated (yield: 55%).

FDMS (m / z); 453 (M < + >)

_{^{1 H-NMR (CDCl 3)}} δ (ppm); 2H), 7.23-7.32 (m, 2H), 7.75 (d, IH)

_{^{13 C-NMR (CDCl 3)}} δ (ppm); 131.19, 131.08, 130.45, 129.10, 128.23, 127.35, 127.22, 127.09, 127.04, 126.65, 123.42, 123.23, 122.94, 122.41, 121.56, 120.88, 120.68, 127.04, 141.76, 141.59, 140.69, 138.03, 136.61, 132.14, 131.08, 110.44, 110.35

Synthesis Example 9B (Synthesis of 2-chloro-9- (3- (9-phenanthryl) phenyl) carbazole [

(41.0 mmol) of 2-chlorocarbazole, 15.0 g (45.1 mmol) of 1-bromo-3- (9-phenanthryl) benzene, 60 ml of o-xylene, 184 mg (0.82 mmol) of palladium acetate and 579 mg (2.8 mmol) of tri (tert-butyl) phosphine were added, and the mixture was stirred at 140 占 폚 for 12 hours . After cooling to room temperature, 30 ml of pure water was added, and the organic layer was separated. The organic layer was washed successively with water and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (a mixed solvent of toluene and hexane (volume ratio = 1: 1)) to obtain a white powder of 2-chloro-9- (3- (9-phenanthryl) 12.4 g (27.3 mmol) was isolated (yield: 66%).

FDMS (m / z); 453 (M < + >)

_{^{1 H-NMR (CDCl 3)}} δ (ppm); 2H), 7.23-7.31 (m, 2H), 7.90 (d, 1H)

_{^{13 C-NMR (CDCl 3)}} δ (ppm); 127.21, 127.07, 127.00, 126.82, 126.57, 126.10, 123.37, 123.15, 122.86, 122.31, 128.37, 121.48, 120.78, 120.59, 110.27

Synthesis Example 10B (Synthesis of 2-nitro-5- (9-phenanthryl) -4'-chlorobiphenyl [see synthesis route below]

9.6 g (36.0 mmol) of 2-nitro-5,4'-dichlorobiphenyl, 9.60 g (43.2 mmol) of 9-phenanthrenorbic acid, (0.36 mmol) of tetrakis (triphenylphosphine) palladium, 40 ml of tetrahydrofuran and 47.7 g (90.0 mmol) of a tripotassium phosphate aqueous solution of 40% by weight were added and refluxed for 24 hours. After cooling to room temperature, the water layer and the organic layer were separated, and the organic layer was washed with saturated aqueous ammonium chloride solution and saturated aqueous sodium chloride solution, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. 14 g of the resulting 2-nitro-5- (9-phenanthryl) -4'-chlorobiphenyl was used as a raw material for the next step without purification.

Synthesis Example 11B (Synthesis of 2-chloro-6- (9-phenanthryl) carbazole [see synthesis route below]

To a 200 ml three-necked flask under a nitrogen gas stream were added 11.0 g (26.8 mmol) of 2-nitro-5- (9-phenanthryl) -4'-chlorobiphenyl obtained in Synthesis Example 10B, g (67.2 mmol) of p-toluenesulfonic acid and 60 ml of o-dichlorobenzene, and the mixture was stirred at 150 占 폚 for 40 hours. The o-dichlorobenzene was distilled off under reduced pressure, and then toluene was added to the obtained residue, and the residue was purified by silica gel column chromatography (toluene). The resulting pale yellow powder was further washed with hexane to obtain 7.3 g (19.3 mmol) of pale yellow powder of 2-chloro-6- (9-phenanthryl) carbazole (yield: 72%).

¹ H-NMR (acetone -d _6); 1H), 7.81 (d, 1H), 7.81 (d, 1H), 8.83 (d, -7.71 (m, 7 H), 7.19 (d, 1 H)

¹³ C-NMR (acetone-d ₆ ); 131.14, 131.00, 130.09, 128.89, 128.46, 127.96, 127.22, 126.83, 123.31, 122.95, 122.86, 122.20, 121.73, 119.51, 111.21

Synthesis Example 12B (Synthesis of 2-chloro-6- (9-phenanthryl) -9-phenylcarbazole [see synthesis route below]

7.0 g (18.5 mmol) of 2-chloro-6- (9-phenanthryl) carbazole obtained in Synthesis Example 11B, 4.3 g (27.8 mmol) of bromobenzene, (35.7 mmol) of potassium carbonate, 50 ml of o-xylene, 62 mg (0.27 mmol) of palladium acetate and 196 mg (0.97 mmol) of tri (tert-butyl) Lt; / RTI > After cooling to room temperature, 25 ml of pure water was added, and the organic layer was separated. The organic layer was washed successively with pure water and saturated brine, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography (a mixed solvent of toluene and hexane (volume ratio = 1: 1)) to obtain a white powder of 2-chloro-6- (9-phenanthryl) g (12.8 mmol) (yield 69%).

_{^{1 H-NMR (CDCl 3)}} ; (D, 1H), 8.25 (s, 1H), 7.89-8.03 (m, 3H), 7.78 1H)

_{^{13 C-NMR (CDCl 3)}} ; 128.19, 128.47, 128.29, 128.18, 127.43, 127.38, 127.15, 126.78, 126.70, 123.21, 123.16, 122.85, 122.20, 121.90, 121.57, 128.17, 140.94, 139.40, 137.39, 133.42, 132.23, 131.96, 130.98, 120.89, 110.35, 109.98

Example 1A (Synthesis of compound (A25)

8.0 g (19.8 mmol) of 2-chloro-9- (4- (1-naphthyl) phenyl) carbazole obtained in Synthesis Example 1A and 10.0 g Biphenyl) amine, 2.6 g (27.7 mmol) of sodium-tert-butoxide, 45 ml of o-xylene, 44 mg (0.19 mmol) of palladium acetate, ) Phosphine (139 mg, 0.69 mmol) was added, and the mixture was stirred at 140 占 폚 for 4 hours. After cooling to room temperature, the precipitated product was collected by filtration and washed with pure water and ethanol. Further, 11.0 g (16.0 mmol) of pale yellow powder of compound (A25) was isolated (yield: 81%) by recrystallization from o-xylene.

FDMS (m / z); 688 (M +)

_{^{1 H-NMR (CDCl 3)}} δ (ppm); 8.06 (t, 2H), 7.81-7.96 (m, 3H), 7.11-7.59 (m, 31H)

_{^{13 C-NMR (CDCl 3)}} δ (ppm); 126.98, 126.35, 126.17, 126.08, 125.84, 125.43, 125.29, 125.05, 124.94, 126.98, 127.28, 126.68, 126.35,126.17,124.84,145.10, 141.40, 140.96, 140.10,139.33,138.67,133.13,134.57,133.36,131.04,139.98,128.29,127.91,127. 123.24, 123.00, 120.76, 119.92, 119.56, 119.46, 118.53, 109.43, 106.50

Example 2A (Synthesis of compound (A26)

3.5 g (8.3 mmol) of 2-chloro-9- (4- (2-methylnaphthalen-1-yl) phenyl) carbazole obtained in Synthetic Example 2A and 50 ml of N, 2.7 g (8.3 mmol) of N-bis (4-biphenyl) amine, 1.1 g (11.7 mmol) of sodium-tert-butoxide, 20 ml of o-xylene, 18 mg (0.08 mmol) (tert-butyl) phosphine (59 mg, 0.29 mmol) was added, and the mixture was stirred at 140 占 폚 for 10 hours. After cooling to room temperature, the precipitated product was collected by filtration and washed with pure water and ethanol. Further, 3.5 g (4.9 mmol) of a white powder of the compound (A26) was isolated by recrystallization with o-xylene (yield: 59%).

FDMS (m / z); 702 (M < + >)

_{^{1 H-NMR (CDCl 3)}} δ (ppm); 8.05 (t, 2H), 7.12-7.85 (m, 33H), 2.09 (s, 3H)

Example 3A (Synthesis of compound (A27)) [

To a 100 ml three-necked flask under a nitrogen stream were added 5.0 g (12.4 mmol) of 2-chloro-9- (3- (1-naphthyl) phenyl) carbazole obtained in Synthesis Example 3A, (17.4 mmol) of sodium-tert-butoxide, 30 ml of o-xylene, 27 mg (0.12 mmol) of palladium acetate and 0.16 mmol of tri (tert-butyl) ) Phosphine (87 mg, 0.43 mmol) was added and the mixture was stirred at 140 占 폚 for 5 hours. After cooling to room temperature, 20 ml of pure water was added, and the organic layer was separated. The organic layer was washed successively with water and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (mixed solvent of toluene and hexane (volume ratio = 1: 1)) to isolate 4.5 g (6.5 mmol) of pale yellow glassy solid of compound (A27) (yield: 52%).

FDMS (m / z); 688 (M +)

_{^{1 H-NMR (CDCl 3)}} δ (ppm); 1H), 7.05-7.51 (m, 30H), 7.80 (d, IH)

_{^{13 C-NMR (CDCl 3)}} δ (ppm); 126.92, 126.24, 125.91, 125.49, 125.18, 125.05, 125.18, 127.04, 124.98, 123.44, 123.07, 120.80, 119.96, 119.51, 119.43, 118.31, 109.41, 106.15

Example 4A (Synthesis of compound (A28)

10.0 g (23.9 mmol) of 2-chloro-9- (3- (2-methylnaphthalen-1-yl) phenyl) carbazole obtained in Synthetic Example 4A and 10.0 g (33.9 mmol) of sodium-tert-butoxide, 50 ml of o-xylene, 75 mg (0.12 mmol) of palladium acetate, (tert-butyl) phosphine (236 mg, 1.1 mmol) was added, and the mixture was stirred at 140 占 폚 for 8 hours. After cooling to room temperature, 30 ml of pure water was added, and the organic layer was separated. The organic layer was washed successively with water and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (a mixed solvent of toluene and hexane (volume ratio = 1: 1)) to obtain 8.0 g (11.3 mmol) of a pale yellow glassy solid of compound (A28) (yield: 47%).

FDMS (m / z); 702 (M < + >)

_{^{1 H-NMR (CDCl 3)}} δ (ppm); 2H), 7.76 (d, 1H), 7.54-7.68 (m, 7H), 7.06-7.49 (m, 25H), 2.04

_{^{13 C-NMR (CDCl 3)}} δ (ppm); 128.15, 128.22, 128.05, 127.81, 127.25, 127.16, 126.95, 126.31, 126.13, 125.53, 125.18, 124.84, 124.79, 124.30, 123.37, 122.96, 120.56, 119.76, 119.32, 119.14, 117.96, 109.23, 97.49, 20.19

Example 5A (Synthesis of compound (A29)

(9.9 mmol) of 2-chloro-9- (4- (1-naphthyl) phenyl) carbazole obtained in Synthesis Example 1A and N-phenyl-N- (9.9 mmol) of sodium (p-terphenyl-4-yl) amine, 1.3 g (13.8 mmol) of sodium tert-butoxide, 25 ml of o-xylene, 69 mg (0.34 mmol) of tri (tert-butyl) phosphine was added, and the mixture was stirred at 140 占 폚 for 10 hours. After cooling to room temperature, 10 ml of pure water was added, and the organic layer was separated. The organic layer was washed successively with water and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (a mixed solvent of toluene and hexane (volume ratio = 1: 1)) to obtain 5.1 g (7.4 mmol) of a pale yellow glassy solid of Compound (A29) (yield: 75%).

FDMS (m / z); 688 (M +)

_{^{1 H-NMR (CDCl 3)}} δ (ppm); 8.04 (t, 2H), 7.80-7.93 (m, 3H), 7.10-7.57 (m, 31H)

Example 6A (synthesis of compound (A47)

(2.4 mmol) of 2-chloro-9- (3- (1-naphthyl) phenyl) carbazole obtained in Synthesis Example 3A, N- 0.32 g (3.4 mmol) of sodium-tert-butoxide, 10 ml of o-xylene and 5 mg (0.1 mmol) of palladium acetate 0.02 mmol) and tri (tert-butyl) phosphine (17 mg, 0.08 mmol) were added and the mixture was stirred at 140 占 폚 for 4 hours. After cooling to room temperature, pure water (5 ml) was added and the organic layer was separated. The organic layer was washed successively with water and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (mixed solvent of toluene and hexane (volume ratio = 1: 1)) to obtain 1.4 g (1.9 mmol) of a pale yellow glassy solid of the compound (A47) (yield: 79%).

FDMS (m / z); 764 (M < + >)

_{^{1 H-NMR (CDCl 3)}} δ (ppm); 8.01 (t, 2H), 7.90 (d, IH), 7.05-7.79 (m, 37H)

Example 7A (synthesis of compound (A53)

2.5 g (6.2 mmol) of 2-chloro-9- (4- (1-naphthyl) phenyl) carbazole obtained in Synthesis Example 1A and 2.5 g 1.7 g (6.2 mmol) of sodium (9,9-dimethylfluoren-2-yl) amine, 0.8 g (8.6 mmol) of sodium tert- butoxide, 15 ml of o-xylene, (tert-butyl) phosphine (43 mg, 0.21 mmol) were added, and the mixture was stirred at 140 占 폚 for 8 hours. After cooling to room temperature, pure water (5 ml) was added and the organic layer was separated. The organic layer was washed successively with water and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (a mixed solvent of toluene and hexane (volume ratio = 1: 1)) to obtain 3.2 g (5.0 mmol) of a pale yellow glassy solid of the compound (A53) (yield: 81%).

FDMS (m / z); 652 (M < + >)

Example 1B (Synthesis of compound (B25)

To a 100 ml three-necked flask under a nitrogen stream were added 5.5 g (11.9 mmol) of 2-chloro-9- (4- (4-dibenzothienyl) phenyl) carbazole obtained in Synthesis Example 1B, (11.9 mmol) of bisbiphenylamine, 1.6 g (16.7 mmol) of sodium-tert-butoxide, 35 ml of o-xylene, 53 mg (0.23 mmol) of palladium acetate and tri 162 mg (0.80 mmol) of fins was added, and the mixture was stirred at 140 占 폚 for 6 hours. After cooling to room temperature, the precipitated product was collected by filtration and washed with pure water and ethanol. Next, 6.5 g (8.7 mmol) of pale yellow powder of compound (B25) was isolated (yield 72%) by recrystallization with o-xylene.

FDMS (m / z); 744 (M < + >)

_{^{1 H-NMR (CDCl 3)}} δ (ppm); 8.01-8.13 (m, 4H), 7.83 (d, 2H), 7.10-7.69 (m, 30H)

_{^{13 C-NMR (CDCl 3)}} δ (ppm); 126. 24, 126.17, 125.05, 124.72, 123.97, 123.31, 123.04, 128.04, 122.19, 121.26, 120.73, 120.27, 119.96, 119.48, 119.45, 118.44, 109.41, 106.35

Example 2B (Synthesis of compound (B26)

In a 50 ml three-necked flask, 5.0 g (11.2 mmol) of 2-chloro-9- (4- (4-dibenzofuranyl) phenyl) carbazole obtained in Synthesis Example 2B, (11.2 mmol) of bisbiphenylamine, 1.5 g (15.7 mmol) of sodium-tert-butoxide, 25 ml of o-xylene, 50 mg (0.22 mmol) of palladium acetate and tri 155 mg (0.77 mmol) of pyridine was added, and the mixture was stirred at 140 占 폚 for 6 hours. After cooling to room temperature, the precipitated product was collected by filtration and washed with pure water and ethanol. Then, recrystallization from o-xylene was conducted to isolate 6.4 g (8.7 mmol) of pale yellow powder of compound (B26) (yield: 77%).

FDMS (m / z); 728 (M +)

_{^{1 H-NMR (CDCl 3)}} δ (ppm); 2H), 7.60 (d, 2H), 7.09-7.54 (m, 28H)

_{^{13 C-NMR (CDCl 3)}} δ (ppm); 155.65, 152.79, 146.90, 145.60, 141.35, 140.91, 140.14, 136.49, 134.90, 134.55,129.74,128.31,127.32,126.90,126.39,126.19,125.10,124.63,124.26,123.66,123.27,123.05,122.91,122.45,121.80, 120.27, 119.98, 119.59, 119.48, 118.60, 111.46, 109.52, 106.61

Example 3B (Synthesis of compound (B27)

(3.9 mmol) of 2-chloro-9- (3- (4-dibenzothienyl) phenyl) carbazole obtained in Synthesis Example 3B and N, N- (3.9 mmol) of bisbiphenylamine, 0.5 g (5.5 mmol) of sodium-tert-butoxide, 10 ml of o-xylene, 17 mg (0.07 mmol) of palladium acetate, 54 mg (0.26 mmol) of fins was added, and the mixture was stirred at 140 占 폚 for 3 hours. After cooling to room temperature, 10 ml of pure water was added, and the organic layer was separated. The organic layer was washed successively with water and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography (mixed solvent of toluene and hexane (volume ratio = 1: 1)) to obtain 2.3 g (3.1 mmol) of a pale yellow glassy solid of compound (B27) ).

FDMS (m / z); 744 (M < + >)

Example 4B (synthesis of compound (B28)) < RTI ID = 0.0 >

(6.7 mmol) of 2-chloro-9- (3- (4-dibenzofuranyl) phenyl) carbazole obtained in Synthesis Example 4B and N, N- (6.7 mmol) of bisbiphenylamine, 0.90 g (9.4 mmol) of sodium tert-butoxide, 15 ml of o-xylene, 30 mg (0.13 mmol) of palladium acetate and tri 93 mg (0.46 mmol) of pin was added, and the mixture was stirred at 140 占 폚 for 5 hours. After cooling to room temperature, 10 ml of pure water was added, and the organic layer was separated. The organic layer was washed successively with water and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (mixed solvent of toluene and hexane (volume ratio = 1: 1)) to obtain 4.2 g (5.8 mmol) of pale yellow powder of compound (B28) (yield: 88%).

FDMS (m / z); 728 (M +)

Example 5B (Synthesis of compound (B29)

1.1 g (2.3 mmol) of 2-chloro-9- (4- (4-dibenzothienyl) phenyl) carbazole obtained in Synthesis Example 1B, 0.73 g (2.3 mmol) of N- (p-terphenylamine), 0.32 g (3.3 mmol) of sodium tert-butoxide, 10 ml of o-xylene, 10 mg (0.04 mmol) butyl) phosphine (32 mg, 0.26 mmol) was added, and the mixture was stirred at 140 ° C for 4 hours. After cooling to room temperature, the precipitated product was collected by filtration and washed with pure water and ethanol. Then, the product was recrystallized with o-xylene to obtain 0.99 g (1.3 mmol) of pale yellow powder of compound (B29) (yield: 58%).

FDMS (m / z); 744 (M < + >)

Example 6B (Synthesis of compound (B34)

(5.6 mmol) of 2-chloro-9- (4- (4-dibenzofuranyl) phenyl) carbazole obtained in Synthesis Example 2B, N-biphenyl 2.2 g (5.6 mmol) of N- (p-terphenyl) amine, 0.75 g (7.8 mmol) of sodium-tert-butoxide, 15 ml of o-xylene, 25 mg (0.11 mmol) (tert-butyl) phosphine (77 mg, 0.38 mmol) was added, and the mixture was stirred at 140 占 폚 for 6 hours. After cooling to room temperature, the precipitated product was collected by filtration and washed with pure water and ethanol. Next, 3.1 g (3.9 mmol) of a pale yellow powder of the compound (B34) was isolated (yield 70%) by recrystallization with o-xylene.

FDMS (m / z); 804 (M < + >)

Example 7B (Synthesis of compound (B46)

(2.2 mmol) of the 2-chloro-9- (4- (4-dibenzofuranyl) phenyl) carbazole obtained in Synthesis Example 2B and N-biphenyl (3.1 mmol) of sodium-tert-butoxide, 10 ml of o-xylene, 10 mg (0.04 mmol) of palladium acetate, and 0.8 g (2.2 mmol) (tert-butyl) phosphine (31 mg, 0.15 mmol) was added, and the mixture was stirred at 140 ° C for 2 hours. After cooling to room temperature, pure water (5 ml) was added and the organic layer was separated. The organic layer was washed successively with water and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography (mixed solvent of toluene and hexane (volume ratio = 1: 1)) to obtain 1.4 g (1.8 mmol) of a pale yellow glassy solid of compound (B46) ).

FDMS (m / z); 804 (M < + >)

Example 8B (Synthesis of compound (B53)

1.1 g (2.3 mmol) of 2-chloro-9- (4- (4-dibenzothienyl) phenyl) carbazole obtained in Synthesis Example 1B, 0.65 g (2.3 mmol) of N- (9,9-dimethylfluoren-2-yl) amine, 0.32 g (3.3 mmol) of sodium tert-butoxide, 10 ml of o-xylene, (0.04 mmol) of tri (tert-butyl) phosphine and 32 mg (0.16 mmol) of tri (tert-butyl) phosphine were added and the mixture was stirred at 140 占 폚 for 4 hours. After cooling to room temperature, pure water (5 ml) was added and the organic layer was separated. The organic layer was washed successively with water and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (mixed solvent of toluene and hexane (volume ratio = 1: 1)) to obtain 1.2 g (1.8 mmol) of a pale yellow glassy solid of compound (B53) (yield: 79%).

FDMS (m / z); 708 (M +)

Example 9B (Synthesis of compound (B77)

To a 50 ml three-necked flask under a nitrogen gas stream were added 4.0 g (8.7 mmol) of 2-chloro-6- (4-dibenzothienyl) -9-phenylcarbazole obtained in Synthesis Example 7B, (8.7 mmol) of biphenylamine, 1.1 g (12.1 mmol) of sodium-tert-butoxide, 25 ml of o-xylene, 19 mg (0.08 mmol) of palladium acetate, 56 mg (0.28 mmol) of triethylamine were added, and the mixture was stirred at 140 占 폚 for 16 hours. After cooling to room temperature, 10 ml of pure water was added, and the organic layer was separated.

The organic layer was washed successively with water and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (a mixed solvent of toluene and hexane (volume ratio = 1: 1)) to obtain 4.9 g (6.5 mmol) of a light yellow glassy solid of compound (B77) ).

FDMS (m / z); 744 (M < + >)

_{^{1 H-NMR (CDCl 3)}} δ (ppm); 1H), 7.72 (d, 1H), 7.10-7.59 (m, 30H), 8.41 (s,

_{^{13 C-NMR (CDCl 3)}} δ (ppm); 136.73, 145.78, 141.88, 140.58, 140.08, 139.19, 138.56, 137.30, 136.84, 135.67, 135.47, 134.55, 132.41, 129.46, 128.25, 127.23, 127.06, 126.62, 126.33, 126.20, 126.13, 125.31, 124.65, 123.84, 123.24, 122.14, 121.26, 120.80, 119.46, 119.30, 119.12, 118.53, 109.47, 106.37

Example 10B (Synthesis of compound (B79)

(2.6 mmol) of 2-chloro-6- (4-dibenzothienyl) -9-phenylcarbazole obtained in Synthesis Example 7B and 1.2 g (2.6 mmol) of sodium tert-butoxide, 10 ml of o-xylene, 5 mg (0.02 mmol) of palladium acetate and 0.06 g (Butyl) phosphine (16 mg, 0.08 mmol) was added, and the mixture was stirred at 140 占 폚 for 8 hours. After cooling to room temperature, pure water (5 ml) was added and the organic layer was separated. The organic layer was washed successively with water and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (mixed solvent of toluene and hexane (volume ratio = 1: 1)) to obtain 1.5 g (2.1 mmol) of a pale yellow glassy solid of compound (B79) ).

FDMS (m / z); 744 (M < + >)

Example 11B (synthesis of compound (B2)) < RTI ID = 0.0 >

(2.2 mmol) of 2-chloro-9- (4- (4-dibenzofuranyl) phenyl) carbazole obtained in Synthesis Example 2B and N-phenyl- A mixture of 0.48 g (2.2 mmol) of N- (1-naphthyl) amine, 0.3 g (3.1 mmol) of sodium tert-butoxide, 10 ml of o-xylene, 10 mg (0.04 mmol) tert-butyl) phosphine (31 mg, 0.15 mmol) was added and the mixture was stirred at 140 ° C for 3 hours. After cooling to room temperature, pure water (5 ml) was added and the organic layer was separated. The organic layer was washed successively with water and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (mixed solvent of toluene and hexane (volume ratio = 2: 3)) to obtain 1.0 g (1.6 mmol) of a pale yellow glassy solid of compound (B2) ).

FDMS (m / z); 626 (M < + >)

Example 12B (Synthesis of compound (B5)

(8.7 mmol) of 2-chloro-9- (4- (4-dibenzothienyl) phenyl) carbazole obtained in Synthetic Example 1B and 4.0 g (8.7 mmol) of N-phenyl- 2.3 g (8.7 mmol) of N- (9-phenanthryl) amine, 1.1 g (12.1 mmol) of sodium tert-butoxide, 25 ml of o-xylene, 19 mg (0.08 mmol) tert-butyl) phosphine (56 mg, 0.28 mmol) was added, and the mixture was stirred at 140 占 폚 for 16 hours. After cooling to room temperature, pure water (15 ml) was added and the organic layer was separated. The organic layer was washed successively with water and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (mixed solvent of toluene and hexane (volume ratio = 1: 1)) to obtain 4.7 g (6.8 mmol) of a pale yellow glassy solid of compound (B5) ).

FDMS (m / z); 692 (M < + >)

Example 13B (Synthesis of compound (B103)

To a 100 mL three-necked flask under a nitrogen stream were added 1.0 g (2.2 mmol) of 2-chloro-9- (4- (9-phenanthryl) phenyl) carbazole obtained in Synthesis Example 8B, , 0.57 g (2.2 mmol) of N- (4-biphenyl) amine, 0.28 g (3.0 mmol) of sodium tert-butoxide, 10 ml of o-xylene, 5 mg (0.02 mmol) 15 mg (0.07 mmol) of tri (tert-butyl) phosphine was added, and the mixture was stirred at 140 占 폚 for 2 hours. After cooling to room temperature, pure water (5 ml) was added and the organic layer was separated. The organic layer was washed successively with water and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography (mixed solvent of toluene and hexane (volume ratio = 4: 5)) to obtain 1.2 g (1.8 mmol) of a pale yellow glassy solid of compound (B103) ).

FDMS (m / z); 676 (M < + >)

Example 14B (Synthesis of compound (B106)

To a 100 mL three-necked flask under a nitrogen gas stream was added 7.0 g (15.4 mmol) of 2-chloro-9- (4- (9-phenanthryl) phenyl) carbazole obtained in Synthesis Example 8B, 4-biphenyl) amine, 2.0 g (21.6 mmol) of sodium-tert-butoxide, 35 ml of o-xylene, 34 mg (0.15 mmol) of palladium acetate, ) Phosphine (108 mg, 0.54 mmol) was added, and the mixture was stirred at 140 占 폚 for 9 hours. After cooling to room temperature, the precipitated product was collected by filtration and washed with pure water and ethanol. Next, 10 g (14.0 mmol) of white powder of compound (B106) was isolated (yield 91%) by recrystallization with o-xylene.

FDMS (m / z); 738 (M +)

_{^{1 H-NMR (CDCl 3)}} δ (ppm); 2H), 7.98 (d, 1H), 7.86 (d, 1H), 7.17-7.73 (m, 32H)

_{^{13 C-NMR (CDCl 3)}} δ (ppm); 127.19, 127.09, 126.91, 125.78, 123.93, 123.71, 123.25, 122.81, 121.48, 128.01, 120.62, 120.30, 120.19, 119.32, 110.13, 107.28

Example 15B (Synthesis of compound (B122)

8.0 g (17.6 mmol) of 2-chloro-9- (3- (9-phenanthryl) phenyl) carbazole obtained in Synthetic Example 9B, 8.0 g (17.6 mmol) of sodium-tert-butoxide, 40 ml of o-xylene, 39 mg (0.017 mmol) of palladium acetate, ) Phosphine (124 mg, 0.61 mmol) was added, and the mixture was stirred at 140 占 폚 for 10 hours. After cooling to room temperature, 30 ml of pure water was added, and the organic layer was separated. The organic layer was washed successively with water and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography (mixed solvent of toluene and hexane (volume ratio = 1: 1)) to obtain 9.0 g (12.1 mmol) of a pale yellow glassy solid of compound (B122) ).

FDMS (m / z); 738 (M +)

_{^{1 H-NMR (CDCl 3)}} δ (ppm); 2H), 7.92 (d, 1H), 7.78 (d, 1H), 7.09-7.71 (m, 32H)

_{^{13 C-NMR (CDCl 3)}} δ (ppm); 127.01, 126.91, 126.80, 126.02, 125.77, 128.01, 127.01, 127.01, 126.91, 126.80, 123.95, 123.69, 123.25, 122.80, 121.48, 120.60, 120.17, 119.29, 110.06, 107.15

Example 16B (Synthesis of compound (B138)

To a 100 ml three-necked flask under a nitrogen gas stream were added 5.5 g (12.1 mmol) of 2-chloro-6- (9-phenanthryl) -9-phenylcarbazole obtained in Synthesis Example 12B, -Biphenyl) amine, 1.6 g (16.7 mmol) of sodium-tert-butoxide, 30 ml of o-xylene, 27 mg (0.12 mmol) of palladium acetate, 85 mg (0.42 mmol) of phosphine was added, and the mixture was stirred at 140 占 폚 for 11 hours. After cooling to room temperature, 20 ml of pure water was added, and the organic layer was separated. The organic layer was washed successively with water and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (mixed solvent of toluene and hexane (volume ratio = 2: 3)) to obtain 4.6 g (6.2 mmol) of a pale yellow glassy solid of compound (B138) ).

FDMS (m / z); 738 (M +)

_{^{1 H-NMR (CDCl 3)}} δ (ppm); 2H), 7.89 (d, 1H), 7.78 (s, 1H), 7.09-7.67 (m, 31H)

_{^{13 C-NMR (CDCl 3)}} δ (ppm); 128.0, 127.93, 127.56, 127.13, 126.94, 126.78, 126.70, 124.01, 127.03, 131.01, 130.29, 130.19, 129.07, 128.94, 128.12, 128.05, 127.83, 123.71, 123.21, 122.87, 121.56, 120.07, 119.31, 109.75, 107.19

Example 8A (Device evaluation of compound (A25)) [

A glass substrate having a 200 nm thick ITO transparent electrode (positive electrode) laminated thereon was subjected to ultrasonic cleaning with acetone and pure water and boiling cleaning with isopropyl alcohol. Further, the substrate was cleaned with ultraviolet rays / ozone, installed in a vacuum evaporator, and then evacuated with a vacuum pump until the pressure reached 1 × 10 ^-4 Pa. First, copper phthalocyanine was deposited on the ITO transparent electrode at a deposition rate of 0.1 nm / sec to form a hole injection layer of 10 nm, followed by vapor deposition of Compound (A25) at a deposition rate of 0.3 nm / Respectively. Subsequently, a phosphorescent dopant material, tris (2-phenylpyridine) iridium (Ir (ppy)) ₃ ) and 4,4'-bis (N-carbazolyl) biphenyl (CBP) as a host material were mixed at a weight ratio of 1: At a deposition rate of 0.25 nm / sec to form a light emitting layer having a thickness of 30 nm. Next, BAlq (bis (2-methyl-8-quinolinolato) aluminum (p-phenylphenolato) aluminum) was vapor-deposited at a deposition rate of 0.3 nm / sec to form an exciton block layer of 5 nm, (Tris (8-quinolinolato) aluminum) was vapor-deposited at a deposition rate of 0.3 nm / sec to form an electron transport layer having a thickness of 45 nm. Subsequently, lithium fluoride was deposited as an electron injecting layer at a deposition rate of 0.01 nm / second to 1 nm, and further aluminum was deposited at a deposition rate of 0.25 nm / second to a thickness of 100 nm to form a cathode. Further, in a nitrogen atmosphere, a sealing glass plate was bonded with a UV curable resin to obtain an organic EL device for evaluation. A current of 20 mA / cm < 2 > was applied to the thus fabricated device, and the driving voltage and the current efficiency were measured. The luminance halftime of the device was evaluated by applying a current of 6.25 mA / cm < 2 >. The results are shown in Table 1.

Examples 9A to 14A (Device Evaluation)

An organic EL device was fabricated in the same manner as in Example 8A except for using Compound (A26), (A27), (A28), (A29), (A47), or (A53) instead of Compound (A25). Table 1 summarizes the driving voltage and current efficiency when a current of 20 mA / cm < 2 > is applied and the half brightness time when a current of 6.25 mA / cm &

Examples 17B to 41B (Device evaluation)

(B25), (B26), (B27), (B28), (B29), (B34), (B46), (B53), (B77), (B79), ), (B5), (B103), (B106), (B122), or (B138), the organic EL device was fabricated in the same manner as in Example 8A. Table 1 summarizes the driving voltage and current efficiency when a current of 20 mA / cm < 2 > is applied and the half brightness time when a current of 6.25 mA / cm &

Comparative Example 1 (Device evaluation of NPD)

An organic EL device was fabricated in the same manner as in Example 8A except that the compound (A25) was changed to NPD (4,4'-bis [N- (1-naphthyl) -N-phenylamino] biphenyl). Table 1 shows the driving voltage and current efficiency when a current of 20 mA / cm < 2 > is applied and the half-life of brightness when a current of 6.25 mA / cm &

Comparative Example 2 (Device evaluation of compound (a)) [

An organic EL device was fabricated in the same manner as in Example 8A except that the compound (A25) was changed to the following compound (a). Table 1 shows the driving voltage and current efficiency when a current of 20 mA / cm < 2 > is applied and the half-life of brightness when a current of 6.25 mA / cm &

Reference Example 1 (Device evaluation of compound (b)) [

An organic EL device was fabricated in the same manner as in Example 8A except that the compound (A25) was changed to the following compound (b). Table 1 shows the driving voltage and current efficiency when a current of 20 mA / cm < 2 > is applied and the half-life of brightness when a current of 6.25 mA / cm &

The organic EL device using the 2-aminocarbazole compound of the present invention can be used as an organic EL material having remarkably excellent lifetime and excellent durability.

In addition, the organic EL device using the 2-aminocarbazole compound of the present invention as a hole transporting material has a long life, low driving voltage and high luminous efficiency, low power consumption, And can be used in a display field such as a device.

In addition, Japanese Patent Application No. 2013-186686 filed on September 9, 2013, Japanese Patent Application No. 2013-216683 filed on October 17, 2013, and Japanese Patent Application No. 2014-216683 filed on February 18, 2014, 028366, the entire contents of the claims and the abstract are hereby incorporated herein by reference in their entirety.

Claims (20)

A 2-aminocarbazole compound represented by the following formula (1):

Wherein each R independently represents a hydrogen atom or a methyl group;
Any one of R ¹ to R ³ is a 4-dibenzothienyl group, a 4-dibenzofuranyl group, a 9-phenanthryl group or a substituent group represented by the following formula (2) (R represents a hydrogen atom or a methyl group) , And the remainder is a hydrogen atom or a methyl group;
Ar ¹ and Ar ² are each independently an aromatic hydrocarbon group having 6 to 18 carbon atoms and may have a methyl group or a methoxy group:

. The 2-aminocarbazole compound according to claim 1, wherein R in the formula (1) is a hydrogen atom and R in the formula (2) is a hydrogen atom or a methyl group. The compound according to claim 1, wherein one of R ¹ to R ³ is a 4-dibenzothienyl group, a 4-dibenzofuranyl group, a 9-phenanthryl group or a substituent group represented by the following formula (2) Phosphorus, 2-aminocarbazole compounds:

In the formula, R represents a hydrogen atom or a methyl group. The compound according to Claim 1, wherein Ar ¹ and Ar ² each independently represent a phenyl group which may have a methyl group or a methoxy group, a naphthyl group which may have a methyl group or a methoxy group, a phenanthryl group which may have a methyl group or a methoxy group, A 2-aminocarbazole compound which is a biphenylyl group which may have a methyl group or a methoxy group, a terphenyl group which may have a methyl group or a methoxy group, or a fluorenyl group which may have a methyl group or a methoxy group. A material for an organic EL device comprising the 2-aminocarbazole compound according to claim 1. A 2-aminocarbazole compound according to claim 1, which is represented by the following formula (1A):

In the formulas, R ^1A to R ^7A each independently represent a hydrogen atom or a methyl group;
Ar ¹ and Ar ² are each independently an aromatic hydrocarbon group having 6 to 18 carbon atoms, which may have a methyl group or a methoxy group;
One of R ^8A and R ^9A is a group represented by the following formula (2A) and the other is a hydrogen atom:

In the formulas, R ^10A represents a hydrogen atom or a methyl group. A 2-aminocarbazole compound according to claim 6, wherein R ^1A , R ^2A , R ^4A , R ^5A , R ^6A and R ^7A are hydrogen atoms. The compound according to claim 6, wherein Ar ¹ and Ar ² each independently represent a phenyl group which may have a methyl group or a methoxy group, a biphenylyl group which may have a methyl group or a methoxy group, a terphenyl group which may have a methyl group or a methoxy group, A 2-aminocarbazole compound which is a fluorenyl group which may have a methyl group or a methoxy group. 7. The compound according to claim 6, wherein Ar ¹ and Ar ² are each independently a phenyl group, a 4-biphenylyl group, a p-terphenyl-4-yl group, 9H-fluoren-2-yl group. The 2-aminocarbazole compound according to any one of claims 1 to 6, which is any one of compounds represented by the following formulas:

. A hole transporting material, a hole injecting material or a light emitting host material comprising the 2-aminocarbazole compound according to claim 6. An organic EL device comprising a 2-aminocarbazole compound according to any one of claims 1 to 6 in at least one layer of a light-emitting layer, a hole-transporting layer, and a hole-injecting layer. An organic EL device comprising the hole transport layer of the 2-aminocarbazole compound according to claim 6. A 2-aminocarbazole compound according to claim 1, which is represented by the following formula (1B):

In the formula, any one of R ^1B to R ^3B is a 4-dibenzothienyl group, a 4-dibenzofuranyl group or a 9-phenanthryl group, and the remainder is a hydrogen atom;
Ar ¹ and Ar ² are each independently an aromatic hydrocarbon group having 6 to 18 carbon atoms and may have a methyl group or a methoxy group. A compound according to claim 14, wherein Ar ¹ and Ar ² each independently represent a phenyl group which may have a methyl group or a methoxy group, a naphthyl group which may have a methyl group or a methoxy group, a phenanthryl group which may have a methyl group or a methoxy group, A 2-aminocarbazole compound which is a biphenylyl group which may have a methyl group or a methoxy group, a terphenyl group which may have a methyl group or a methoxy group, or a fluorenyl group which may have a methyl group or a methoxy group. A method according to claim 14, wherein Ar ¹ and Ar ² are each independently selected from the group consisting of a phenyl group, a 4-methylphenyl group, a 1-naphthyl group, a 9-phenanthryl group, m-terphenyl-4-yl group or a 9,9-dimethyl-9H-fluoren-2-yl group. The 2-aminocarbazole compound according to any one of claims 1 to 14, which is any one of compounds represented by the following formulas:

. A hole transporting material, a hole injecting material, or a light emitting host material comprising the 2-aminocarbazole compound according to claim 14. An organic EL device comprising the 2-aminocarbazole compound according to claim 14 in any one or two or more layers of a light emitting layer, a hole transporting layer and a hole injecting layer. An organic EL device comprising the 2-aminocarbazole compound according to claim 14 in a hole transport layer.