KR102424458B1 - 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:

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

wherein R is a hydrogen atom or a methyl group; Any one of R ¹ to R ³ is a 4-dibenzothienyl group, 4-dibenzofuranyl group, 9-phenanthryl group, or a substituent of the following formula (2) (R represents a hydrogen atom or a methyl group), and the rest 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, which may have a methyl group or a methoxy group:

.

Description

2-Aminocarbazole compounds and uses thereof

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

The organic EL device is a surface light-emitting device in which an organic thin film is held between a pair of electrodes, has characteristics such as thin, light weight, high viewing angle, high-speed response, and the like, and is expected to be applied to various display devices. Moreover, in recent years, some practical applications, such as a display of a mobile phone, are also starting. The organic EL device uses light emitted when holes injected from an anode and electrons injected from a cathode recombine in a light emitting layer, and the structure of the organic EL device is a multilayer stack type in which a hole transport layer, a light emitting layer, an electron transport layer, etc. are stacked. Here, the charge transport layer called the hole transport layer or the electron transport layer does not emit light by itself, but facilitates charge injection into the light emitting layer and also traps the energy of charges injected into the light emitting layer or excitons generated in the light emitting layer. is playing a role

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

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

In recent years, development of an organic EL device using a phosphorescent light emitting material as a light emitting layer is also progressing, and a hole transporting material having a high triplet level is required for a device using phosphorescent light emission. It has been reported that NPD is not sufficient even in terms of the triplet level, and for example, in an organic EL device in which a green phosphorescent material and NPD are combined, the luminous efficiency decreases (for example, See Patent Document 1).

From this background, recently, an amine compound in which a carbazole ring is introduced into a molecule has been reported. Specifically, a 2-aminocarbazole compound is mentioned (for example, refer patent documents 1 - 4).

In Patent Documents 1 and 2, 2-aminocarbazole compounds each containing a pyrene ring and an anthracene ring are disclosed for use as a light emitting material. Since these compounds containing a pyrene ring or anthracene ring have low triplet levels of the pyrene ring and the anthracene ring themselves, high luminous efficiency cannot be obtained in an element using a green phosphorescent material.

On the other hand, the 2-aminocarbazole compounds disclosed in Patent Documents 3 and 4 have a triplet level higher than that of NPD. For this reason, it is known that an element using a green phosphorescent material generally tends to exhibit higher luminous efficiency than NPD.

Moreover, the 3-aminocarbazole compound which combined dibenzothiophene, dibenzofuran, and carbazole is also disclosed (for example, patent document 5).

However, for organic EL devices, further lower driving voltage, higher luminous efficiency, longer life, and the like are desired, and development of a hole transporting material for this purpose is desired.

[Prior art literature]

[Patent Literature]

(Patent Document 1) JP2008-078362 A

(Patent Document 2) JP2008-195841 A

(Patent Document 3) KR10-2009-0129799 A

(Patent Document 4) JP2011-001349 A

(Patent Document 5) WO2011/122132 A

[Non-patent literature]

(Non-Patent Document 1) 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 lifespan of an organic EL device, compared to the conventionally known 2-aminocarbazole compound or 3-aminocarbazole compound. . Another object of the present invention is to provide an organic EL device having an excellent long life using the 2-aminocarbazole compound having the specific chemical structure.

MEANS TO SOLVE THE PROBLEM As a result of earnest examination, the present inventors found the 2-aminocarbazole compound which is a novel compound represented by following formula (1), and came to complete this invention. That is, the present invention relates to a 2-aminocarbazole compound represented by the following formula (1) and uses thereof:

(R each 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 the following formula (2) is a substituent represented by , 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 these 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 is remarkably superior in device lifetime compared to the organic EL device using the conventionally known 2-aminocarbazole compound or 3-aminocarbazole. For this reason, the 2-aminocarbazole compound of this invention can be utilized as an organic electroluminescent material excellent in durability.

Moreover, compared with NPD which is a conventionally well-known hole transport material, the life span of an organic electroluminescent element can be made long, a low driving voltage, and high luminous efficiency can be improved.

That is, according to the present invention, an organic EL device having low power consumption and excellent device lifetime can be provided.

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. Moreover, it is preferable that all R are hydrogen atoms from the point of a hole transport characteristic and the easiness of availability of a raw material.

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

(R represents a hydrogen atom or a methyl group.)

Further, in view of hole transport characteristics and ease of raw material availability, any one of R ¹ to R ³ is a 4-dibenzothienyl group, 4-dibenzofuranyl group, 9-phenanthryl group, or Formula (2) It is a substituent represented by , and the remainder is preferably a hydrogen atom.

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

Although it does not specifically limit as a C6-C18 aromatic hydrocarbon group (they may have a methyl group or a methoxy group) in Ar< ¹ > and Ar< ² >, For example, For example, a phenyl group, a biphenylyl group, a terphenylyl group, naph a tyl group, a fluorenyl group, a phenanthryl group, a benzofluorenyl group (these may have a methyl group or a methoxy group), etc. are mentioned.

Specific examples of Ar ¹ and Ar ² include a phenyl group, 4-methylphenyl group, 3-methylphenyl group, 2-methylphenyl group, 2,4-dimethylphenyl group, 2,5-dimethylphenyl group, 3,4-dimethylphenyl group, 3,5-dimethylphenyl group, 2,6-dimethylphenyl group, 2,3,5-trimethylphenyl group, 2,3,6-trimethylphenyl group, 3,4,5-trimethylphenyl group, 4-methoxy Phenyl group, 3-methoxyphenyl group, 2-methoxyphenyl group, 2-methyl-4-methoxyphenyl group, 2-methyl-5-methoxyphenyl group, 3-methyl-4-methoxyphenyl group, 3-methyl-5- Methoxyphenyl group, 2-methoxy-4-methylphenyl group, 3-methoxy-4-methylphenyl group, 2,4-dimethoxyphenyl group, 2,5-dimethoxyphenyl group, 2,6-dimethoxyphenyl group , 3,4-dimethoxyphenyl group, 3,5-dimethoxyphenyl group, 3,4,5-trimethoxyphenyl group, 4-biphenylyl group, 3-biphenylyl group, 2-biphenylyl group, 2- Methyl-1,1'-biphenyl-4-yl group, 3-methyl-1,1'-biphenyl-4-yl group, 2'-methyl-1,1'-biphenyl-4-yl group, 3'- 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'-dimethyl-1,1'-biphenyl-4-yl group, 2,3'-dimethyl-1,1'-biphenyl-4-yl group, 2,4'-dimethyl-1, 1'-biphenyl-4-yl group, 3,2'-dimethyl-1,1'-biphenyl-4-yl group, 2',3'-dimethyl-1,1'-biphenyl-4-yl group , 2',4'-dimethyl-1,1'-biphenyl-4-yl group, 2',5'-dimethyl-1,1'-biphenyl-4-yl group, 2',6'-di Methyl-1,1'-biphenyl-4-yl group, p-terphenyl group, m-terphenyl group, o-terphenyl group, 1-naphthyl group, 2-naphthyl group, 2-methylnaphthalen-1-yl group, 4- Methylnaphthalen-1-yl group, 6-methylnaphthalen-2-yl group, 2-anthryl group, 9-anthryl group, 1-triphenylenyl group, 2-triphenylenyl group, 2-fluorenyl group, 9, 9-dimethyl-9H-fluoren-2-yl group, 9-phenanthryl group, 2-phenanthryl group, benzofluorenyl group, fluoranthenyl group, pyrenyl group, chrysenyl group and the like can be exemplified, is not limited to

In terms of hole transport properties, Ar ¹ and Ar ² in the 2-aminocarbazole compound represented by Formula (1) of the present invention are each independently a phenyl group, which may have a methyl group or a methoxy group, a methyl group, or It has 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 It is preferable that it is a fluorenyl group which may exist. In addition, as Ar ¹ and Ar ² , each independently represents a phenyl group, a 4-methylphenyl group, a 1-naphthyl group, a 9-phenanthryl group, a 4-biphenylyl group, a p-terphenyl-4-yl group, and a m-terphenyl group. A -4-yl group or a 9,9-dimethyl-9H-fluoren-2-yl group is more preferable.

The 2-aminocarbazole compound represented by the formula (1) is a light emitting host material in a light emitting layer of an organic EL device, a hole transport material in a hole transport layer, or a hole transport material in a hole injection layer (specifically limited). However, these materials can be collectively used as a material for an organic EL device). Moreover, it is preferable that the 2-aminocarbazole compound represented by the said Formula (1) is high purity from the point of a hole transport characteristic and element lifetime.

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

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

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

As a method of forming a hole injection layer, a hole transport layer or a light emitting layer containing the 2-aminocarbazole compound represented by the formula (1), for example, a known method such as a vacuum deposition method, a spin coating method, a casting method can be applied.

Although there is no restriction|limiting in particular in the manufacturing method of the thin film for organic electroluminescent element which consists of the 2-aminocarbazole compound represented by said Formula (1) of this invention, The film-forming by the vacuum deposition method is possible. Film formation by the vacuum deposition method can be performed by using a general-purpose vacuum deposition apparatus. The vacuum degree of the vacuum chamber when the film is formed by the vacuum deposition method can be reached by generally used diffusion pumps, turbomolecular pumps, cryopumps, etc., in consideration of the manufacturing tact time and manufacturing cost of manufacturing the organic electroluminescent device. . The degree of vacuum is preferably about 1×10 ^-2 to 1×10 ^-6 Pa, and more preferably 1×10 ^-4 to 1×10 ^-6 Pa.

Although vapor deposition rate depends on the thickness of the film|membrane to form, 0.005-1.0 nm/sec is preferable and 0.01-0.3 nm/sec is more preferable. Moreover, since the 2-aminocarbazole compound represented by the said Formula (1) of this invention has high heat resistance, it is hard to generate|occur|produce thermal decomposition also at the time of high-speed film-forming, and the influence on element 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, an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and a cathode.

The anode and the cathode of the organic EL element are connected to a power supply via an electrical conductor. By applying an electric potential between the anode and the cathode, the organic EL device operates.

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

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

The substrate may be 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 the substrate. The substrate may have a composite structure including multiple material layers. When electroluminescent light emission is identified through an anode, the anode is formed by passing or substantially passing the light emission therethrough.

The general 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 can also be used. In addition to these oxides, a metal nitride, for example, gallium nitride, a metal selenide, for example, zinc selenide, or a metal sulfide, for example, zinc emulsification, can be used as the anode.

The anode can be modified with plasma-deposited fluorocarbon. When electroluminescence emission is confirmed only through the cathode, the transmissive property of the anode is not important, and any electrically conductive material, transparent, opaque or reflective, may be used. Gold, iridium, molybdenum, palladium, platinum, etc. are mentioned as an example of the conductor for this use.

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

In the organic EL device of the present invention, the hole transport layer and/or the hole injection layer contain the 2-aminocarbazole compound represented by the formula (1).

For the hole transport layer and/or the hole injection layer, it can be used in combination with the 2-aminocarbazole compound represented by the formula (1), selecting any one from known hole transport materials and/or hole injection materials.

Known hole injection materials and hole transport materials include, for example, triazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives and pyrazolone derivatives, phenylene diamine derivatives, arylamine derivatives, and amino-substituted chalcone derivatives, oxazole derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aniline copolymers, electrically conductive polymer oligomers, and thiophene oligomers.

As the hole injecting material and the hole transporting material, those described above can be used, but a porphyrin compound, an aromatic tertiary amine compound, a styrylamine compound, etc. can also be used, and it is particularly preferable to use an aromatic tertiary amine compound.

Representative examples of the aromatic tertiary amine compound and the styrylamine compound include N,N,N',N'-tetraphenyl-4,4'-diaminophenyl, N,N'-diphenyl-N,N'- Bis(3-methylphenyl)-[1,1'-biphenyl]-4,4'-diamine (TPD), 2,2-bis(4-di-p-tolylaminophenyl)propane, 1,1- Bis(4-di-p-tolylaminophenyl)cyclohexane, N,N,N',N'-tetra-p-tolyl-4,4'-diaminobiphenyl, 1,1-bis(4-di -p-tolylaminophenyl)-4-phenylcyclohexane, bis(4-dimethylamino-2-methylphenyl)phenylmethane, bis(4-di-p-tolylaminophenyl)phenylmethane, N,N'-di Phenyl-N,N'-di(4-methoxyphenyl)-4,4'-diaminobiphenyl, N,N,N',N'-tetraphenyl-4,4'-diaminodiphenylether , 4,4'-bis(diphenylamino)quadriphenyl, N,N,N-tri(p-tolyl)amine, 4-(di-p-tolylamino)-4'-[4-(di- p-tolylamino) styryl] stilbene, 4-N,N-diphenylamino-(2-diphenylvinyl)benzene, 3-methoxy-4'-N,N-diphenylaminostilbenzene, N- Phenylcarbazole, 4,4′-bis[N-(1-naphthyl)-N-phenylamino]biphenyl (NPD), 4,4′,4″-tris[N-(3-methylphenyl)-N -phenylamino]triphenylamine (MTDATA) etc. are mentioned.

In addition, inorganic compounds such as p-Si and p-SiC can also be used as the hole injecting material and the hole transporting material.

The hole injection layer and/or the hole transport layer may have a single-layer structure composed of one or two or more of the above materials, or a laminate structure composed of multiple layers of the same composition or different compositions.

The light emitting layer of the organic EL element contains a phosphorescent material or a fluorescent material, and emits light as a result of recombination of electron-hole pairs in this region.

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

As the host material of the light emitting layer, the 2-aminocarbazole compound represented by the formula (1) can be used, and as other compounds, for example, a biphenyl group, a fluorenyl group, a triphenylsilyl group, a carbazole group, and a pyrethane group and compounds having a nyl group or an anthranyl group. Specifically, DPVBi(4,4'-bis(2,2-diphenylvinyl)-1,1'-biphenyl), BCzVBi(4,4'-bis(9-ethyl-3-carbazovinylene) ) 1,1'-biphenyl), TBADN (2-tert-butyl-9,10-di (2-naphthyl) anthracene), ADN (9,10-di (2-naphthyl) anthracene), CBP ( 4,4'-bis(carbazol-9-yl)biphenyl), CDBP (4,4'-bis(carbazol-9-yl)-2,2'-dimethylbiphenyl), or 9,10 -bis(biphenyl)anthracene etc. are mentioned.

The host material in the light emitting layer may be an electron transporting material defined below, a hole transporting material defined above, another material that assists (supporting) hole/electron recombination, 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, pyrylium or thiapyrylium compound. , fluorene derivatives, periflanthene derivatives, indenoperylene derivatives, bis(azinyl)amine boron compounds, bis(azinyl)methane compounds, carbostyryl compounds, and the like.

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

As an example of a dopant, Alq ₃ (tris(8-hydroxyquinoline)aluminum))), DPAVBi (4,4′-bis[4-(di-para-tolylamino)styryl]biphenyl), perylene, Ir (PPy) ₃ (tris(2-phenylpyridine)iridium(III) or FlrPic(bis(3,5-difluoro-2-(2-pyridyl)phenyl-(2-carboxypyridyl)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 earth metal complex include 8-hydroxyquinolinatolithium (Liq), bis(8-hydroxyquinolinato)zinc, and bis(8-hydroxyquinolinato). ) Copper, bis(8-hydroxyquinolinato)manganese, tris(8-hydroxyquinolinato)aluminum, tris(2-methyl-8-hydroxyquinolinato)aluminum, tris(8-hydroxyquinolinato)aluminum Nolinato) gallium, bis (10-hydroxybenzo [h] quinolinato) beryllium, bis (10-hydroxybenzo [h] quinolinato) zinc, bis (2-methyl-8-quinolinato) chloro Gallium, bis(2-methyl-8-quinolinato)(o-crezolato)gallium, bis(2-methyl-8-quinolinato)-1-naphtolatoaluminum, bis(2-methyl-8-qui nolinato)-2-naphtolatogallium; and the like.

Between the light emitting layer and the electron transport layer, a hole blocking layer may be formed for the purpose of improving carrier balance. Preferred compounds as 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-(phenylphenollato)aluminum) or bis(10-hydroxybenzo[h]quinolinato)beryllium).

In the organic EL device of the present invention, an electron injection layer may be formed in order to improve electron injection properties and improve device characteristics (eg, luminous efficiency, constant voltage driving, or high durability).

Preferred compounds for the electron injection layer include fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, fluorenylidenemethane, anthraqui. Nodimethane, anthrone, etc. are mentioned.

In addition, the above-described metal complexes, alkali metal oxides, alkaline earth oxides, rare earth oxides, alkali metal halides, alkaline earth halides, rare earth halides, SiO ₂ , AlO, SiN, SiON, AlON, GeO, LiO, LiON, TiO , TiON, TaO, TaON, TaN, various oxides such as C, and inorganic compounds such as nitrides and oxynitrides can also be used.

When 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, magnesium/copper mixture, magnesium/silver mixture, magnesium/aluminum mixture, magnesium/indium mixture, aluminum/aluminum oxide (Al ₂ O ₃ ) mixture, indium, lithium/aluminum mixtures, rare earth metals, and the like.

Further, as specific examples of the 2-aminocarbazole compound represented by the formula (1), the 2-aminocarbazole compound represented by the following formula (1A) and the 2-aminocarbazole compound represented by the formula (1B) compounds can be represented.

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, and these 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.)

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

The 2-aminocarbazole compound represented by the formula (1A) is a compound in which 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, R ³ is a hydrogen atom or a methyl group.

In the 2-aminocarbazole compound represented by the formula (1A), R ^1A to R ^7A each independently represent a hydrogen atom or a methyl group. Further, in terms of hole transport characteristics and the ease of obtaining raw materials, R ^1A , R ^2A , R ^4A , R ^5A , R ^6A and R ^7A are preferably hydrogen atoms, and R ^1A to R ^7A are all hydrogen atoms. more preferably.

In the 2-aminocarbazole compound represented by the formula (1A), Ar ¹ and Ar ² each independently represent an aromatic hydrocarbon group having 6 to 18 carbon atoms, and these may have a methyl group or a methoxy group. Although it does not specifically limit as a C6-C18 aromatic hydrocarbon group in Ar< ¹ > and Ar< ² >, For example, a phenyl group, a biphenylyl group, a terphenylyl group, a naphthyl group, a fluorenyl group, a phenanthryl group, benzo fluorenyl group (these groups may have a methyl group or a methoxy group, and the number of substituents is not specifically limited) etc. are mentioned.

Specific examples of Ar ¹ and Ar ² include a phenyl group, 4-methylphenyl group, 3-methylphenyl group, 2-methylphenyl group, 2,4-dimethylphenyl group, 2,5-dimethylphenyl group, 3,4-dimethylphenyl group, 3,5-dimethylphenyl group, 2,6-dimethylphenyl group, 2,3,5-trimethylphenyl group, 2,3,6-trimethylphenyl group, 3,4,5-trimethylphenyl group, 4-methoxy Phenyl group, 3-methoxyphenyl group, 2-methoxyphenyl group, 2-methyl-4-methoxyphenyl group, 2-methyl-5-methoxyphenyl group, 3-methyl-4-methoxyphenyl group, 3-methyl-5- Methoxyphenyl group, 2-methoxy-4-methylphenyl group, 3-methoxy-4-methylphenyl group, 2,4-dimethoxyphenyl group, 2,5-dimethoxyphenyl group, 2,6-dimethoxyphenyl group , 3,4-dimethoxyphenyl group, 3,5-dimethoxyphenyl group, 3,4,5-trimethoxyphenyl group, 4-biphenylyl group, 3-biphenylyl group, 2-biphenylyl group, 2- Methyl-1,1'-biphenyl-4-yl group, 3-methyl-1,1'-biphenyl-4-yl group, 2'-methyl-1,1'-biphenyl-4-yl group, 3'- 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'-dimethyl-1,1'-biphenyl-4-yl group, 2,3'-dimethyl-1,1'-biphenyl-4-yl group, 2,4'-dimethyl-1, 1'-biphenyl-4-yl group, 3,2'-dimethyl-1,1'-biphenyl-4-yl group, 2',3'-dimethyl-1,1'-biphenyl-4-yl group , 2',4'-dimethyl-1,1'-biphenyl-4-yl group, 2',5'-dimethyl-1,1'-biphenyl-4-yl group, 2',6'-di Methyl-1,1'-biphenyl-4-yl group, p-terphenyl group, m-terphenyl group, o-terphenyl group, 1-naphthyl group, 2-naphthyl group, 2-methylnaphthalen-1-yl group, 4- Methylnaphthalen-1-yl group, 6-methylnaphthalen-2-yl group, 2-anthryl group, 9-anthryl group, 2-fluorenyl group, 9,9-dimethyl-9H-fluoren-2-yl group, 9-phenanthryl group, 2-phenanthryl group, benzofluorenyl group, fluoranthenyl group, pyrenyl group, chrysenyl group and the like can be exemplified, but the present invention is not limited thereto.

In terms of hole transport properties, 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 which may have a methyl group or a methoxy group, a methyl group, or It is preferably a biphenylyl group which may have a methoxy group, a methyl group or a terphenyl group which may have a methoxy group, or a fluorenyl group which may have a methyl group or a methoxy group, a phenyl group, 4-biphenylyl group, p-terphenyl- A 4-yl group, a m-terphenyl-4-yl group, or a 9,9-dimethyl-9H-fluoren-2-yl group is more preferable.

Although the preferable example of the 2-aminocarbazole compound represented by Formula (1A) is shown below, it is not limited to these compounds.

Among these compounds, in terms of triplet level and hole transport properties, compound (A25), compound (A26), compound (A27), compound (A28), compound (A29), compound (A47), or compound (A53) This is more preferable.

The 2-aminocarbazole compound represented by the formula (1A) can be prepared by a known method (Tetrahedron Letters, 1998, Vol. 39) using, for example, a 9H-carbazole compound having the 2-position halogenated as a raw material. , page 2367) can be synthesized. Specifically, it can be synthesized by the following route.

A 9H-carbazole compound in which the 2-position represented by the formula (3A) is halogenated 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, A 2-halogenated-9-substituted carbazole compound represented by the formula (5A) is obtained. Further, the obtained 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 .

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

The compound represented by Formula (3A) can be synthesize|combined based on a general well-known method (For example, Unexamined-Japanese-Patent No. 2011-1349).

The compound represented by Formula (4A) can be synthesize|combined based on a general well-known method (for example, WO2008-013399).

A commercially available compound may be used for the compound represented by Formula (6A), and it can also synthesize|combine it based on a general well-known method.

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 transport layer, or a hole injection layer of an organic EL device. Further, the 2-aminocarbazole compound represented by the formula (1A) is preferably of high purity in terms of hole transport properties and device lifetime.

For the light emitting layer when the 2-aminocarbazole compound represented by the formula (1A) is used as a hole injection layer and/or a hole transport layer of an organic EL device, a conventionally used fluorescent or phosphorescent light emitting material can be used. . The light-emitting layer may be formed of only one type of light-emitting material, or one or more types of light-emitting materials may be doped in the host material.

When forming the hole injection layer and/or the hole transport layer made of the 2-aminocarbazole compound represented by the formula (1A), two or more types of materials may be contained or laminated as needed, for example, molybdenum oxide, etc. Oxide of, 7,7,8,8-tetracyanoquinodimethane, 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane, hexacyanohexaaza A known electron-accepting material such as triphenylene may be contained or laminated.

When the 2-aminocarbazole compound represented by the formula (1A) is used as a light emitting layer of an organic EL device, the 2-aminocarbazole compound is used alone, or doped with a known light emitting host material, or A known light emitting dopant can be doped and used.

As a method of forming a hole injection layer, a hole transport layer or a light emitting layer containing the 2-aminocarbazole compound represented by the formula (1A), for example, a known method such as a vacuum deposition method, a spin coating method, a casting method can be applied.

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

(Any one of R ^1B to R ^3B is a 4-dibenzothienyl group, a 4-dibenzofuranyl group or a 9-phenanthryl group, and the rest is a hydrogen atom. Ar ¹ and Ar ² are each independently, each having a carbon number It is an aromatic hydrocarbon group of 6-18, and these may have a methyl group or a methoxy group.)

In the 2-aminocarbazole compound represented by the formula (1B), 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, or 4-dibenzo represents a compound of a furanyl group or a 9-phenanthryl group, and the remainder is a hydrogen atom.

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

Although it does not specifically limit as a C6-C18 aromatic hydrocarbon group in Ar< ¹ > and Ar< ² >, For example, a phenyl group, a biphenylyl group, a terphenylyl group, a naphthyl group, a fluorenyl group, a phenanthryl group, benzo A fluorenyl group, a triphenylenyl group, a fluoranthenyl group (These substituents may have a methyl group or a methoxy group, and the number of the said methyl group or a methoxy group is not specifically limited.) etc. are mentioned.

Specific examples of Ar ¹ and Ar ² include a phenyl group, 4-methylphenyl group, 3-methylphenyl group, 2-methylphenyl group, 2,4-dimethylphenyl group, 2,5-dimethylphenyl group, 3,4-dimethylphenyl group, 3,5-dimethylphenyl group, 2,6-dimethylphenyl group, 2,3,5-trimethylphenyl group, 2,3,6-trimethylphenyl group, 3,4,5-trimethylphenyl group, 4-methoxy Phenyl group, 3-methoxyphenyl group, 2-methoxyphenyl group, 2-methyl-4-methoxyphenyl group, 2-methyl-5-methoxyphenyl group, 3-methyl-4-methoxyphenyl group, 3-methyl-5- Methoxyphenyl group, 2-methoxy-4-methylphenyl group, 3-methoxy-4-methylphenyl group, 2,4-dimethoxyphenyl group, 2,5-dimethoxyphenyl group, 2,6-dimethoxyphenyl group , 3,4-dimethoxyphenyl group, 3,5-dimethoxyphenyl group, 3,4,5-trimethoxyphenyl group, 4-biphenylyl group, 3-biphenylyl group, 2-biphenylyl group, 2- Methyl-1,1'-biphenyl-4-yl group, 3-methyl-1,1'-biphenyl-4-yl group, 2'-methyl-1,1'-biphenyl-4-yl group, 3'- 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'-dimethyl-1,1'-biphenyl-4-yl group, 2,3'-dimethyl-1,1'-biphenyl-4-yl group, 2,4'-dimethyl-1, 1'-biphenyl-4-yl group, 3,2'-dimethyl-1,1'-biphenyl-4-yl group, 2',3'-dimethyl-1,1'-biphenyl-4-yl group , 2',4'-dimethyl-1,1'-biphenyl-4-yl group, 2',5'-dimethyl-1,1'-biphenyl-4-yl group, 2',6'-di Methyl-1,1'-biphenyl-4-yl group, p-terphenyl group, m-terphenyl group, o-terphenyl group, 1-naphthyl group, 2-naphthyl group, 2-methylnaphthalen-1-yl group, 4- Methylnaphthalen-1-yl group, 6-methylnaphthalen-2-yl group, 2-anthryl group, 9-anthryl group, 1-triphenylenyl group, 2-triphenylenyl group, 2-fluorenyl group, 9, 9-dimethyl-9H-fluoren-2-yl group, 9-phenanthryl group, 2-phenanthryl group, benzofluorenyl group, fluoranthenyl group, pyrenyl group, chrysenyl group and the like can be exemplified, is not limited to

Ar ¹ and Ar ² are each independently 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 which may have a methyl group or a methoxy group, in terms of hole transport properties It is preferably a biphenylyl group which may have a group, 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 phenyl group, a 4-methylphenyl group, 1- naphthyl group, 9-phenanthryl group, 4-biphenylyl group, p-terphenyl-4-yl group, m-terphenyl-4-yl group, or 9,9-dimethyl-9H-fluoren-2-yl group more preferably.

Although the preferable example of the 2-aminocarbazole compound represented by Formula (1B) is shown below, it is not limited to these compounds.

Among these compounds, compound (B2), compound (B5), compound (B25), compound (B26), compound (B27), compound (B28), compound (B29) in terms of triplet level and hole transport properties , compound (B34), compound (B46), compound (B53), compound (B77), compound (B79), compound (B103), compound (B106), compound (B122) or compound (B138) is more preferable.

The 2-aminocarbazole compound represented by the formula (1B) is prepared by a known method (Tetrahedron Letters, 1998, vol. 39) using, for example, a 9H-carbazole compound having the 2-position halogenated as a raw material. , page 2367) can be synthesized.

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 Formula (1B) above. A and B each independently represent a halogen atom (iodine, bromine, chlorine or fluorine). )

As in the above route, the 9H-carbazole compound in which the 2-position represented by the formula (2B) is halogenated and the compound having a halogen atom represented by the formula (3B) are reacted with a copper catalyst or a palladium catalyst in the presence of a base. and reacted 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 Formula (2B) can be synthesize|combined based on a general well-known method (For example, Unexamined-Japanese-Patent No. 2011-1349).

The compound represented by Formula (3B) can be synthesize|combined based on a general well-known method (For example, WO2009-133007 and Chemistry Letters, 2011, Vol. 40, page 1050).

A commercially available compound can also be used for the compound represented by Formula (5B), and it can also synthesize|combine it based on a general well-known method.

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

Moreover, it is preferable that this compound is high purity from the point of a hole transport characteristic or organic electroluminescent element lifetime. Distillation, sublimation purification, recrystallization, silica gel chromatography, etc. can refine|purify by a well-known method, and can achieve high purity.

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

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

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

As a method of forming a hole injection layer, a hole transport layer or a light emitting layer containing the 2-aminocarbazole compound represented by the formula (1B), for example, a known method such as a vacuum deposition method, a spin coating method, 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 by these Examples.

¹ H-NMR and ¹³ C-NMR measurements were performed using Gemini200 manufactured by Varian Corporation using tetramethylsilane as an internal standard.

The FDMS (field escape mass spectrometry) measurement was performed using M-80B manufactured by Hitachi Seisakusho Corporation. The light emitting characteristics of the organic EL element were measured and evaluated using a luminance meter of LUMINANCE METER (BM-9) manufactured by Topcon, by applying a set direct current to the produced element.

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

In a 50 ml three-necked flask under a nitrogen stream, 5.2 g (26.0 mmol) of 2-chlorocarbazole, 7.7 g (27.3 mmol) of 1-bromo-4-(1-naphthyl) benzene, 5.2 of potassium carbonate g (38.2 mmol), o-xylene 25 ml, palladium acetate 61 mg (0.27 mmol) and tri(tert-butyl) phosphine 193 mg (0.95 mmol) were added, and the mixture was stirred at 140° C. 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 sequentially 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 8.7 g of a white powder of 2-chloro-9-(4-(1-naphthyl)phenyl)carbazole. (21.5 mmol) was isolated (yield 83%).

Identification of the compound was performed by ¹ H-NMR measurement and ¹³ C-NMR measurement (hereinafter the same applies).

¹ H-NMR (CDCl ₃ )δ (ppm); 8.10(d, 1H), 8.03(d, 2H), 7.87-7.95(m, 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, 10.12.

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

In a 50 ml three-necked flask under a nitrogen stream, 1.5 g (7.7 mmol) of 2-chlorocarbazole, 2.3 g (7.7 mmol) of 1-bromo-4- (2-methylnaphthalen-1-yl) benzene , potassium carbonate 1.5 g (10.8 mmol), o-xylene 10 ml, palladium acetate 17 mg (0.07 mmol) and tri(tert-butyl) phosphine 54 mg (0.27 mmol) were added, and at 140 ° C. The mixture was 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 sequentially 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 give 2-chloro-9-(4-(2-methylnaphthalen-1-yl)phenyl)carbazole as a white color. 1.9 g (4.6 mmol) of the powder was isolated (yield 59%).

¹ H-NMR (CDCl ₃ )δ (ppm); 8.12 (d, 1H), 8.06 (d, 1H), 7.81-7.90 (m, 2H), 7.65 (d, 2H), 7.23-7.55 (m, 11H), 2.36 (s, 3H)

¹³ C-NMR (CDCl ₃ )δ (ppm); 140.89, 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, 119.79, 124.46, 119.79, 120.71, 12.55, 120.48. 121.55 20.58

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

In a 100 ml three-necked flask under a nitrogen stream, 5.9 g (29.43 mmol) of 2-chlorocarbazole, 8.3 g (29.4 mmol) of 1-bromo-3-(1-naphthyl) benzene, 5.6 of potassium carbonate g (41.2 mmol), o-xylene 35 ml, palladium acetate 66 mg (0.29 mmol) and tri(tert-butyl) phosphine 207 mg (1.0 mmol) were added, and the mixture was stirred at 140° C. 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 sequentially 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 7.6 g of a white powder of 2-chloro-9-(3-(1-naphthyl)phenyl)carbazole. (18.8 mmol) was isolated (yield 63%).

Identification of the compound was performed by FDMS measurement (the same applies hereafter).

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

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

5.3 g (26.3 mmol) of 2-chlorocarbazole, 7.8 g (26.3 mmol) of 2-chlorocarbazole, 1-bromo-3-(2-methylnaphthalen-1-yl) benzene in a 50 ml three-necked flask under a nitrogen stream , potassium carbonate 5.1 g (36.8 mmol), o-xylene 25 ml, palladium acetate 59 mg (0.26 mmol) and tri(tert-butyl) phosphine 185 mg (0.92 mmol) were added, and at 140 ° C. The mixture was stirred 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 sequentially 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 give 2-chloro-9-(3-(2-methylnaphthalen-1-yl)phenyl)carbazole white 10.5 g (25.1 mmol) of the powder was isolated (95% yield).

¹ H-NMR (CDCl ₃ )δ (ppm); 8.02(d, 1H), 7.95(d, 1H), 7.64-7.83(m, 3H), 7.14-7.58(m, 12H), 2.33(s, 3H)

¹³ C-NMR (CDCl ₃ )δ (ppm); 141.48, 140.87, 140.65, 136.79, 136.29, 132.69, 132.26, 131.55, 131.28, 129.61, 129.19, 128.16, 127.49, 127.28, 125.82, 125.76, 125.29, 125.05, 124.05, 119.75. 20.64

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

In a 200 ml three-necked flask under a nitrogen stream, 7.1 g (35.5 mmol) of 2-chlorocarbazole, 12.0 g (35.5 mmol) of 1-bromo-4-(4-dibenzothienyl) benzene, carbonic acid Potassium 9.8g (71.0mmol), o-xylene 100ml, palladium acetate 239mg (1.0mmol) and tri(tert-butyl)phosphine 752mg (3.7mmol) were added, and it was 140 degreeC for 14 hours. stirred. After cooling to room temperature, 60 ml of pure water was added, and the organic layer was separated. The organic layer was washed sequentially 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 = 1:2)), and white powder of 2-chloro-9-(4-(4-dibenzothienyl)phenyl)carbazole 14.0 g (30.5 mmol) was isolated (yield 86%).

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

¹ H-NMR (CDCl ₃ )δ (ppm); 7.96-8.15(m,4H), 7.89(d, 2H), 7.79-7.83(m, 1H), 7.37-7.60(m,8H), 7.12-7.32(m, 3H)

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. 109.63, 109.56.

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

In a 50 ml three-necked flask under a nitrogen stream, 3.0 g (14.9 mmol) of 2-chlorocarbazole, 4.8 g (14.9 mmol) of 1-bromo-4-(4-dibenzofuranyl) benzene, carbonic acid Potassium 4.1g (29.8mmol), o-xylene 25ml, palladium acetate 67mg (0.29mmol) and tri(tert-butyl)phosphine 210mg (1.0mmol) were added, and it was 140 degreeC for 6 hours. stirred. After cooling to room temperature, 10 ml of pure water was added, and the organic layer was separated. The organic layer was washed sequentially 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 = 1:2)), and white powder of 2-chloro-9-(4-(4-dibenzofuranyl)phenyl)carbazole was isolated 5.4 g (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); 155.69, 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, 119.81.29, 120.69, 120.81. 109.67, 109.59

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

In a 200 ml three-necked flask under a nitrogen stream, 5.6 g (28.4 mmol) of 2-chlorocarbazole, 9.6 g (28.4 mmol) of 1-bromo-3-(4-dibenzothienyl) benzene, carbonic acid Potassium 7.8 g (56.8 mmol), o-xylene 80 ml, palladium acetate 191 mg (0.80 mmol), and tri(tert-butyl) phosphine 601 mg (2.9 mmol) were added, and 10 hours at 140° C. stirred. After cooling to room temperature, 50 ml of pure water was added, and the organic layer was separated. The organic layer was washed sequentially 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 = 1:2)), and white powder of 2-chloro-9-(3-(4-dibenzothienyl)phenyl)carbazole 10.0 g (21.8 mmol) was isolated (yield 77%).

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

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

In a 100 ml three-necked flask under a nitrogen stream, 6.0 g (29.8 mmol) of 2-chlorocarbazole, 9.6 g (29.8 mmol) of 1-bromo-3-(4-dibenzofuranyl) benzene, carbonic acid Potassium 8.2 g (59.6 mmol), o-xylene 50 ml, palladium acetate 134 mg (0.58 mmol) and tri(tert-butyl) phosphine 420 mg (2.0 mmol) were added, and stirred at 140° C. for 8 hours. did. After cooling to room temperature, 30 ml of pure water was added, and the organic layer was separated. The organic layer was washed sequentially 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 = 1:2)), and white powder of 2-chloro-9-(3-(4-dibenzofuranyl)phenyl)carbazole 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 the following synthesis route])

In a nitrogen stream, in a 300 ml three-necked flask, 10.6 g (39.8 mmol) of 2-nitro-5,4'-dichlorobiphenyl, 10.0 g (43.8 mmol) of 4-dibenzothiophenboronic acid, 0.46 g (0.39 mmol) of tetrakis (triphenylphosphine) palladium, 50 ml of tetrahydrofuran and 52.8 g (99.6 mmol) of a 40% by weight aqueous solution of tripotassium phosphate were added, followed by heating and refluxing for 10 hours. After cooling to room temperature, the water layer and the organic layer were separated, and the organic layer was washed with a saturated aqueous ammonia chloride solution and a 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 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'-chlorobiphenyl. mol) isolated (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 (m, 8H)

¹³ C-NMR (CDCl ₃ ); 147.48, 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, 124.5726, 124.26, 121.37, 122.

Synthesis Example 6B (Synthesis of 2-chloro-6- (4-dibenzothienyl) carbazole [see the following synthetic route])

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

¹ H-NMR (acetone-d ₆ ); 8.50(s, 1H), 8.27-8.38(m, 2H), 8.22(d, 1H), 7.93-7.98(m, 1H), 7.82(d, 1H), 7.71(d, 1H), 7.54-7.65( m, 3H), 7.47-7.56 (m, 2H), 7.23 (d, 1H)

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, 111.81, 120.57

Synthesis Example 7B (Synthesis of 2-chloro-6-(4-dibenzothienyl)-9-phenylcarbazole [see the following synthetic route])

4.5 g (11.7 mmol) of 2-chloro-6- (4-dibenzothienyl) carbazole obtained in Synthesis Example 6B, 2.0 g (12.9 mmol) of bromobenzene in a 50 mL three-necked flask under a nitrogen stream ), potassium carbonate 3.2 g (23.4 mmol), o-xylene 25 ml, palladium acetate 52 mg (0.23 mmol) and tri(tert-butyl) phosphine 165 mg (0.81 mmol) were added, and 140 ° C. was stirred 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 sequentially 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)), and a pale yellow powder of 2-chloro-6-(4-dibenzothienyl)-9-phenylcarbazole 5.0 g (10.8 mmol) was isolated (yield 92%).

¹ H-NMR (CDCl ₃ ); 8.44(s, 1H), 8.13-8.21(m, 2H), 8.06(d, 1H) 7.76-7.85(m, 2H), 7.39-7.68(m, 11H), 7.27(d, 1H)

¹³ C-NMR (CDCl ₃ ); 141.40, 140.41, 139.09, 138.47, 137.01, 136.46, 135.67, 135.41, 132.59, 131.53, 129.59, 127.50, 126.62, 126.55, 126.22, 126.11, 124.65, 123.84, 121.26, 122.80, 120. 109.72, 109.58

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

In a 200 ml three-necked flask under a nitrogen stream, 6.0 g (30.1 mmol) of 2-chlorocarbazole, 10.0 g (30.1 mmol) of 1-bromo-4-(9-phenanthryl) benzene, 6.2 potassium carbonate g (45.1 mmol), o-xylene 40 ml, palladium acetate 135 mg (0.60 mmol) and tri(tert-butyl) phosphine 425 mg (2.1 mmol) were added, and the mixture was stirred at 140° C. 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 sequentially 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)phenyl)carbazole. 7.5 g (16.5 mmol) was isolated (yield 55%).

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

¹ H-NMR (CDCl ₃ )δ (ppm); 8.75(d, 1H), 8.68(d, 1H), 7.98-8.09(m, 3H), 7.89(d, 1H), 7.37-7.74(m, 12H), 7.23-7.32(m, 2H)

¹³ C-NMR (CDCl ₃ )δ (ppm); 141.76, 141.59, 140.69, 138.03, 136.61, 132.14, 131.99, 131.81, 131.19, 131.08, 130.45, 129.10, 128.23, 127.35, 127.22, 127.09, 127.04, 126.65, 123.42, 126.65, 123.42, 121.6894, 122.88, 122.6894, 120.88 110.44, 110.35

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

In a 200 ml three-necked flask under a nitrogen stream, 8.2 g (41.0 mmol) of 2-chlorocarbazole, 15.0 g (45.1 mmol) of 1-bromo-3-(9-phenanthryl) benzene, 8.5 of potassium carbonate g (61.5 mmol), o-xylene 60 ml, palladium acetate 184 mg (0.82 mmol) and tri(tert-butyl) phosphine 579 mg (2.8 mmol) were added, and the mixture was stirred at 140° C. 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 sequentially 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 a white powder of 2-chloro-9-(3-(9-phenanthryl)phenyl)carbazole. 12.4 g (27.3 mmol) was isolated (yield 66%).

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

¹ H-NMR (CDCl ₃ )δ (ppm); 8.77(d, 1H), 8.71(d, 1H), 8.01-8.10(m, 3H), 7.90(d, 1H), 7.40-7.77(m, 12H), 7.23-7.31(m, 2H)

¹³ C-NMR (CDCl ₃ )δ (ppm); 143.20, 141.66, 141.45, 137.71, 137.46, 132.05, 131.66, 131.00, 130.40, 130.31, 129.76, 129.05, 128.73, 128.17, 127.29, 127.21, 127.07, 127.00, 126.82, 126.10, 123.57, 86, 126.15, 126.57, 86. 121.48, 120.78, 120.59, 110.27

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

In a 200 ml three-necked flask under a nitrogen stream, 9.6 g (36.0 mmol) of 2-nitro-5,4'-dichlorobiphenyl, 9.60 g (43.2 mmol) of 9-phenathrenboronic acid, tetrakis 0.41 g (0.36 mmol) of (triphenylphosphine) palladium, 40 ml of tetrahydrofuran and 47.7 g (90.0 mmol) of a 40% by weight aqueous solution of tripotassium phosphate were added, followed by heating and refluxing for 24 hours. After cooling to room temperature, the water layer and the organic layer were separated, and the organic layer was washed with a saturated aqueous ammonia chloride solution and a saturated aqueous sodium chloride solution, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. 14 g of the obtained dark brown oil of 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 the following synthetic route])

11.0 g (26.8 mmol) of 2-nitro-5-(9-phenanthryl)-4'-chlorobiphenyl obtained in Synthesis Example 10B, 17.6 triphenylphosphine in a 200 ml three-necked flask under a nitrogen stream g (67.2 mmol) and 60 ml of o-dichlorobenzene were injected, and the mixture was stirred at 150° C. for 40 hours. o-dichlorobenzene was distilled off under reduced pressure, and then toluene was added to the obtained residue, followed by purification by silica gel column chromatography (toluene). The obtained pale yellow powder was further washed with hexane, and 7.3 g (19.3 mmol) of a pale yellow powder of 2-chloro-6-(9-phenanthryl)carbazole was isolated (yield 72%).

¹ H-NMR (acetone-d ₆ ); 10.81(s, 1H), 8.89(d, 1H), 8.83(d, 1H), 8.27(s, 1H), 8.14(d, 1H), 7.98(d, 2H), 7.81(s, 1H), 7.55 -7.71(m,7H), 7.19(d, 1H)

¹³ C-NMR (acetone-d ₆ ); 141.49, 140.18, 139.73, 132.20, 132.08, 131.94, 131.17, 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, 111.21.51

Synthesis Example 12B (Synthesis of 2-chloro-6-(9-phenanthryl)-9-phenylcarbazole [see the following synthetic route])

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, Potassium carbonate 7.6 g (55.6 mmol), o-xylene 50 ml, palladium acetate 62 mg (0.27 mmol) and tri(tert-butyl) phosphine 196 mg (0.97 mmol) were added, and 14 at 140° C. time was stirred. After cooling to room temperature, 25 ml of pure water was added, and the organic layer was separated. The organic layer was washed sequentially 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)-9-phenylcarbazole to 5.8 g (12.8 mmol) was isolated (yield 69%).

¹ H-NMR (CDCl ₃ ); 8.79(d, 1H), 8.73(d, 1H), 8.25(s, 1H), 7.89-8.03(m, 3H), 7.78(s, 1H), 7.41-7.69(m, 12H), 7.25(d, 1H)

¹³ C-NMR (CDCl ₃ ); 142.17, 140.94, 139.40, 137.39, 133.42, 132.23, 131.96, 130.98, 130.42, 130.19, 128.91, 128.77, 128.29, 128.18, 127.43, 127.38, 127.15, 126.78, 126.70, 123.57, 122.85, 122.20, 123.21, 123.16. 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, N,N-bis( 4-biphenyl)amine 6.3g (19.8mmol), sodium-tert-butoxide 2.6g (27.7mmol), o-xylene 45ml, palladium acetate 44mg (0.19mmol) and tri(tert-butyl) ) Phosphine 139 mg (0.69 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. Further, it was recrystallized from o-xylene, and 11.0 g (16.0 mmol) of a pale yellow powder of compound (A25) was isolated (yield 81%).

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); 146.84, 145.50, 141.40, 140.96, 140.10, 139.33, 138.67, 136.13, 134.57, 133.36, 131.04, 130.98, 128.29, 127.91, 127.52, 127.28, 126.68, 126.35, 126.17, 125.84, 125.43, 125.29, 126.08, 125.05. 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 Synthesis Example 2A in a 50 ml three-necked flask under a nitrogen stream, N, N-bis(4-biphenyl)amine 2.7 g (8.3 mmol), sodium-tert-butoxide 1.1 g (11.7 mmol), o-xylene 20 ml, palladium acetate 18 mg (0.08 mmol) and tri 59 mg (0.29 mmol) of (tert-butyl)phosphine was added, and the mixture was stirred at 140°C for 10 hours. After cooling to room temperature, the precipitated product was collected by filtration and washed with pure water and ethanol. Further, it was recrystallized from o-xylene, and 3.5 g (4.9 mmol) of white powder of compound (A26) was isolated (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))

In a 100 ml three-necked flask under a nitrogen stream, 5.0 g (12.4 mmol) of 2-chloro-9-(3-(1-naphthyl)phenyl)carbazole obtained in Synthesis Example 3A, N,N-bis( 4-biphenyl)amine 3.9g (12.4mmol), sodium-tert-butoxide 1.6g (17.3mmol), o-xylene 30ml, palladium acetate 27mg (0.12mmol) and tri(tert-butyl) ) Phosphine 87 mg (0.43 mmol) was added, and the mixture was stirred at 140° C. 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 sequentially 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)), and 4.5 g (6.5 mmol) of a pale yellow free solid of compound (A27) was isolated (yield 52%).

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

¹ H-NMR (CDCl ₃ )δ (ppm); 8.00(t, 2H), 7.88(d, 1H), 7.77(d, 1H), 7.68(t, 1H), 7.59(s, 1H), 7.05-751(m, 30H)

¹³ C-NMR (CDCl ₃ )δ (ppm); 146.88, 145.61, 142.23, 141.40, 140.91, 140.14, 138.47, 137.17, 134.65, 133.31, 130.89, 129.30, 128.68, 128.36, 127.94, 127.80, 127.63, 127.34, 126.61, 125.24, 125.18, 126. 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 Synthesis Example 4A in a 100 ml three-necked flask under a nitrogen stream, N, N-bis(4-biphenyl)amine 7.6 g (23.9 mmol), sodium-tert-butoxide 3.2 g (33.5 mmol), o-xylene 50 ml, palladium acetate 75 mg (0.12 mmol) and tri (tert-butyl)phosphine 236 mg (1.1 mmol) was added, and the mixture was stirred at 140° C. 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 sequentially 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)), and 8.0 g (11.3 mmol) of a pale yellow free solid of Compound (A28) was isolated (yield 47%).

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

¹ H-NMR (CDCl ₃ )δ (ppm); 8.03(t, 2H), 7.76(d, 1H), 7.54-7.68(m,7H), 7.06-7.49(m, 25H), 2.04(s, 3H)

¹³ C-NMR (CDCl ₃ )δ (ppm); 146.71, 145.52, 141.27, 141.24, 140.69, 140.03, 137.08, 136.26, 134.55, 132.63, 132.08, 131.31, 129.37, 128.55, 128.22, 128.05, 127.81, 127.25, 127.16, 126.31, 125.13, 126.53, 126.95, 126.18 124.79, 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))

4.0 g (9.9 mmol) of 2-chloro-9-(4-(1-naphthyl)phenyl)carbazole obtained in Synthesis Example 1A, N-phenyl-N-, in a 50 ml three-necked flask under a nitrogen stream (p-terphenyl-4-yl)amine 3.1 g (9.9 mmol), sodium-tert-butoxide 1.3 g (13.8 mmol), o-xylene 25 ml, palladium acetate 22 mg (0.09 mmol) and Tri (tert-butyl) phosphine 69 mg (0.34 mmol) was added, and the mixture was stirred at 140°C 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 sequentially 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)), and 5.1 g (7.4 mmol) of a pale yellow free solid of Compound (A29) was isolated (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))

1.0 g (2.4 mmol) of 2-chloro-9- (3- (1-naphthyl) phenyl) carbazole obtained in Synthesis Example 3A in a 50 mL three-necked flask under a nitrogen stream, N- (4-bi Phenyl)-N-(m-terphenyl-4-yl)amine 0.98 g (2.4 mmol), sodium-tert-butoxide 0.32 g (3.4 mmol), o-xylene 10 ml, palladium acetate 5 mg ( 0.02 mmol) and tri(tert-butyl)phosphine 17 mg (0.08 mmol) were added, and the mixture was stirred at 140° C. for 4 hours. After cooling to room temperature, 5 ml of pure water was added, and the organic layer was separated. The organic layer was washed sequentially 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)), and 1.4 g (1.9 mmol) of a pale yellow free solid of Compound (A47) was isolated (yield 79%).

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

¹ H-NMR (CDCl ₃ )δ (ppm); 8.01 (t, 2H), 7.90 (d, 1H), 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, N-phenyl-N- (9,9-dimethylfluoren-2-yl)amine 1.7 g (6.2 mmol), sodium-tert-butoxide 0.8 g (8.6 mmol), o-xylene 15 ml, palladium acetate 13 mg (0.06) mmol) and tri(tert-butyl)phosphine 43 mg (0.21 mmol) were added, and the mixture was stirred at 140° C. for 8 hours. After cooling to room temperature, 5 ml of pure water was added, and the organic layer was separated. The organic layer was washed sequentially 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)), and 3.2 g (5.0 mmol) of a pale yellow free solid of compound (A53) was isolated (yield 81%).

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

Example 1B (Synthesis of Compound (B25))

5.5 g (11.9 mmol) of 2-chloro-9-(4-(4-dibenzothienyl)phenyl)carbazole obtained in Synthesis Example 1B, N,N- Bisbiphenylamine 3.8g (11.9mmol), sodium-tert-butoxide 1.6g (16.7mmol), o-xylene 35ml, palladium acetate 53mg (0.23mmol) and tri(tert-butyl)phos 162 mg (0.80 mmol) of a pin was added, and it stirred at 140 degreeC for 6 hours. After cooling to room temperature, the precipitated product was collected by filtration and washed with pure water and ethanol. Then, it was recrystallized from o-xylene, and 6.5 g (8.7 mmol) of a pale yellow powder of compound (B25) was isolated (yield 72%).

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); 146.80, 145.56, 141.27, 140.80, 140.10, 138.97, 138.93, 137.92, 136.68, 135.89, 135.41, 135.19, 134.59, 129.22, 128.27, 127.28, 126.46, 126.39, 126.31, 125.05, 124.72. 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))

5.0 g (11.2 mmol) of 2-chloro-9-(4-(4-dibenzofuranyl)phenyl)carbazole obtained in Synthesis Example 2B, N,N- Bisbiphenylamine 3.6g (11.2mmol), sodium-tert-butoxide 1.5g (15.7mmol), o-xylene 25ml, palladium acetate 50mg (0.22mmol) and tri(tert-butyl)phos 155 mg (0.77 mmol) of a pin was added, and it stirred at 140 degreeC for 6 hours. After cooling to room temperature, the precipitated product was collected by filtration and washed with pure water and ethanol. Then, it was recrystallized from o-xylene, and 6.4 g (8.7 mmol) of a pale yellow powder of compound (B26) was isolated (yield 77%).

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

¹ H-NMR (CDCl ₃ )δ (ppm); 7.98-8.07 (m, 4H), 7.87 (t, 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, 121, 122. 120.27, 119.98, 119.59, 119.48, 118.60, 111.46, 109.52, 106.61

Example 3B (Synthesis of Compound (B27))

1.8 g (3.9 mmol) of 2-chloro-9-(3-(4-dibenzothienyl)phenyl)carbazole obtained in Synthesis Example 3B, N,N- Bisbiphenylamine 1.2g (3.9mmol), sodium-tert-butoxide 0.5g (5.5mmol), o-xylene 10ml, palladium acetate 17mg (0.07mmol) and tri(tert-butyl)phos Pin 54 mg (0.26 mmol) was added, and it stirred at 140 degreeC 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 sequentially 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)), and 2.3 g (3.1 mmol) of a pale yellow free solid of compound (B27) was isolated (yield 81%). ).

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

Example 4B (Synthesis of Compound (B28))

3.0 g (6.7 mmol) of 2-chloro-9- (3- (4-dibenzofuranyl) phenyl) carbazole obtained in Synthesis Example 4B in a 50 mL three-neck flask under a nitrogen stream, N,N- Bisbiphenylamine 2.1g (6.7mmol), sodium-tert-butoxide 0.90g (9.4mmol), o-xylene 15ml, palladium acetate 30mg (0.13mmol) and tri(tert-butyl)phos Pin 93 mg (0.46 mmol) was added, followed by stirring at 140°C 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 sequentially 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)), and 4.2 g (5.8 mmol) of a pale yellow powder of compound (B28) was isolated (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, N-phenyl- N-(p-terphenylamine) 0.73 g (2.3 mmol), sodium-tert-butoxide 0.32 g (3.3 mmol), o-xylene 10 ml, palladium acetate 10 mg (0.04 mmol) and tri( 32 mg (0.26 mmol) of tert-butyl) phosphine 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, it was recrystallized from o-xylene, and 0.99 g (1.3 mmol) of a pale yellow powder of compound (B29) was isolated (yield 58%).

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

Example 6B (Synthesis of Compound (B34))

2.5 g (5.6 mmol) of 2-chloro-9- (4- (4-dibenzofuranyl) phenyl) carbazole obtained in Synthesis Example 2B, N-biphenyl in a 50 mL three-necked flask under a nitrogen stream -N-(p-terphenyl)amine 2.2g (5.6mmol), sodium-tert-butoxide 0.75g (7.8mmol), o-xylene 15ml, palladium acetate 25mg (0.11mmol) and tri (tert-butyl)phosphine 77 mg (0.38 mmol) was added, and the mixture was stirred at 140°C for 6 hours. After cooling to room temperature, the precipitated product was collected by filtration and washed with pure water and ethanol. Then, it was recrystallized from o-xylene, and 3.1 g (3.9 mmol) of a pale yellow powder of compound (B34) was isolated (yield 70%).

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

Example 7B (Synthesis of Compound (B46))

1.0 g (2.2 mmol) of 2-chloro-9- (4- (4-dibenzofuranyl) phenyl) carbazole obtained in Synthesis Example 2B, N-biphenyl in a 50 mL three-necked flask under a nitrogen stream -N-(m-terphenyl)amine 0.88g (2.2mmol), sodium-tert-butoxide 0.3g (3.1mmol), o-xylene 10ml, palladium acetate 10mg (0.04mmol) and tri 31 mg (0.15 mmol) of (tert-butyl)phosphine was added, and the mixture was stirred at 140°C for 2 hours. After cooling to room temperature, 5 ml of pure water was added, and the organic layer was separated. The organic layer was washed sequentially 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)), and 1.4 g (1.8 mmol) of a pale yellow free solid of compound (B46) was isolated (yield 83%). ).

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, N-phenyl- N-(9,9-dimethylfluoren-2-yl)amine 0.65 g (2.3 mmol), sodium-tert-butoxide 0.32 g (3.3 mmol), o-xylene 10 ml, palladium acetate 10 mg (0.04 mmol) and tri(tert-butyl)phosphine 32 mg (0.16 mmol) were added, and the mixture was stirred at 140°C for 4 hours. After cooling to room temperature, 5 ml of pure water was added, and the organic layer was separated. The organic layer was washed sequentially 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)), and 1.2 g (1.8 mmol) of a pale yellow free solid of compound (B53) was isolated (yield 79%).

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

Example 9B (Synthesis of Compound (B77))

In a 50 ml three-necked flask under a nitrogen stream, 4.0 g (8.7 mmol) of 2-chloro-6-(4-dibenzothienyl)-9-phenylcarbazole obtained in Synthesis Example 7B, N,N-bis Biphenylamine 2.8g (8.7mmol), sodium-tert-butoxide 1.1g (12.1mmol), o-xylene 25ml, palladium acetate 19mg (0.08mmol) and tri(tert-butyl)phosphine 56 mg (0.28 mmol) was added, and it stirred at 140 degreeC 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 sequentially 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)), and 4.9 g (6.5 mmol) of a pale yellow free solid of compound (B77) was isolated (yield 75%). ).

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

¹ H-NMR (CDCl ₃ )δ (ppm); 8.41(s, 1H), 8.11-8.20(m, 2H), 8.07(d, 1H), 7.81(t, 1H), 7.72(d, 1H), 7.10-7.59(m, 30H)

¹³ C-NMR (CDCl ₃ )δ (ppm); 146.73, 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, 126.84, 126.13, 123. 122.14, 121.26, 120.80, 119.46, 119.30, 119.12, 118.53, 109.47, 106.37

Example 10B (Synthesis of Compound (B79))

1.2 g (2.6 mmol) of 2-chloro-6-(4-dibenzothienyl)-9-phenylcarbazole obtained in Synthesis Example 7B, N-phenyl-N in a 50 ml three-necked flask under a nitrogen stream -(p-terphenylamine) 0.8 g (2.6 mmol), sodium-tert-butoxide 0.33 g (3.6 mmol), o-xylene 10 ml, palladium acetate 5 mg (0.02 mmol) and tri(tert) -Butyl)phosphine 16 mg (0.08 mmol) was added, and the mixture was stirred at 140° C. for 8 hours. After cooling to room temperature, 5 ml of pure water was added, and the organic layer was separated. The organic layer was washed sequentially 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)), and 1.5 g (2.1 mmol) of a pale yellow free solid of compound (B79) was isolated (yield 81%). ).

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

Example 11B (Synthesis of Compound (B2))

1.0 g (2.2 mmol) of 2-chloro-9-(4-(4-dibenzofuranyl)phenyl)carbazole obtained in Synthesis Example 2B, N-phenyl- N-(1-naphthyl)amine 0.48 g (2.2 mmol), sodium-tert-butoxide 0.3 g (3.1 mmol), o-xylene 10 ml, palladium acetate 10 mg (0.04 mmol) and tri( 31 mg (0.15 mmol) of tert-butyl) phosphine was added, and the mixture was stirred at 140° C. for 3 hours. After cooling to room temperature, 5 ml of pure water was added, and the organic layer was separated. The organic layer was washed sequentially 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 = 2:3)), and 1.0 g (1.6 mmol) of a pale yellow free solid of compound (B2) was isolated (yield 74%). ).

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

Example 12B (Synthesis of Compound (B5))

In a 50 ml three-necked flask under a nitrogen stream, 4.0 g (8.7 mmol) of 2-chloro-9-(4-(4-dibenzothienyl)phenyl)carbazole obtained in Synthesis Example 1B, N-phenyl- N-(9-phenanthryl)amine 2.3g (8.7mmol), sodium-tert-butoxide 1.1g (12.1mmol), o-xylene 25ml, palladium acetate 19mg (0.08mmol) and tri( 56 mg (0.28 mmol) of tert-butyl) phosphine was added, and the mixture was stirred at 140° C. for 16 hours. After cooling to room temperature, 15 ml of pure water was added, and the organic layer was separated. The organic layer was washed sequentially 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)), and 4.7 g (6.8 mmol) of a pale yellow free solid of compound (B5) was isolated (yield 79%). ).

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

Example 13B (Synthesis of compound (B103))

1.0 g (2.2 mmol) of 2-chloro-9-(4-(9-phenanthryl)phenyl)carbazole obtained in Synthesis Example 8B, N-(4-methylphenyl) in a 100 ml three-necked flask under a nitrogen stream )-N-(4-biphenyl)amine 0.57 g (2.2 mmol), sodium-tert-butoxide 0.28 g (3.0 mmol), o-xylene 10 ml, palladium acetate 5 mg (0.02 mmol) and Tri (tert-butyl) phosphine 15 mg (0.07 mmol) was added, and the mixture was stirred at 140°C for 2 hours. After cooling to room temperature, 5 ml of pure water was added, and the organic layer was separated. The organic layer was washed sequentially 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 = 4:5)), and 1.2 g (1.8 mmol) of a pale yellow free solid of compound (B103) was isolated (yield 83%). ).

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

Example 14B (Synthesis of Compound (B106))

7.0 g (15.4 mmol) of 2-chloro-9-(4-(9-phenanthryl)phenyl)carbazole obtained in Synthesis Example 8B, N,N-bis( 4-biphenyl)amine 4.6g (15.4mmol), sodium-tert-butoxide 2.0g (21.6mmol), o-xylene 35ml, palladium acetate 34mg (0.15mmol) and tri(tert-butyl) ) 108 mg (0.54 mmol) of phosphine was added, and the mixture was stirred at 140°C for 9 hours. After cooling to room temperature, the precipitated product was collected by filtration and washed with pure water and ethanol. Next, it was recrystallized from o-xylene, and 10.4 g (14.0 mmol) of white powder of compound (B106) was isolated (yield 91%).

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

¹ H-NMR (CDCl ₃ )δ (ppm); 8.77 (d, 1H), 8.71 (d, 1H), 8.09 (d, 2H), 7.98 (d, 1H), 7.86 (d, 1H), 7.17-7.73 (m, 32H)

¹³ C-NMR (CDCl ₃ )δ (ppm); 147.62, 146.25, 142.17, 141.72, 140.87, 140.15, 138.01, 136.99, 135.31, 131.82, 131.12, 130.95, 130.32, 129.03, 128.12, 128.01, 127.19, 127.09, 126.91, 125.78, 123.25, 123.78, 123.93, 12 120.62, 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 Synthesis Example 9B, N,N-bis( 4-biphenyl)amine 5.3g (17.6mmol), sodium-tert-butoxide 2.3g (17.6mmol), o-xylene 40ml, palladium acetate 39mg (0.017mmol) and tri(tert-butyl) ) Phosphine 124 mg (0.61 mmol) was added, and the mixture was stirred at 140° C. 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 sequentially 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)), and 9.0 g (12.1 mmol) of a pale yellow free solid of compound (B122) was isolated (yield 69%). ).

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

¹ H-NMR (CDCl ₃ )δ (ppm); 8.70 (d, 1H), 8.65 (d, 1H), 8.01-8.08 (m, 2H), 7.92 (d, 1H), 7.78 (d, 1H), 7.09-7.71 (m, 32H)

¹³ C-NMR (CDCl ₃ )δ (ppm); 147.60, 146.23, 143.00, 142.18, 141.71, 140.87, 137.89, 137.82, 135.28, 131.61, 131.01, 130.88, 130.32, 130.10, 129.46, 129.04, 128.61, 128.00, 127.21, 126.80, 127.08, 127.80, 127.08, 127. 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))

In a 100 ml three-necked flask under a nitrogen stream, 5.5 g (12.1 mmol) of 2-chloro-6-(9-phenanthryl)-9-phenylcarbazole obtained in Synthesis Example 12B, N,N-bis(4) -Biphenyl)amine 3.8g (12.1mmol), sodium-tert-butoxide 1.6g (16.7mmol), o-xylene 30ml, palladium acetate 27mg (0.12mmol) and tri(tert-butyl) 85 mg (0.42 mmol) of phosphine was added, and the mixture was stirred at 140°C 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 sequentially 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 = 2:3)), and 4.6 g (6.2 mmol) of a pale yellow free solid of compound (B138) was isolated (yield 51%). ).

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

¹ H-NMR (CDCl ₃ )δ (ppm); 8.78(d, 1H), 8.72(d, 1H), 8.22(s, 1H), 8.02(d, 2H), 7.89(d, 1H), 7.78(s, 1H), 7.09-7.67(m, 31H)

¹³ C-NMR (CDCl ₃ )δ (ppm); 147.60, 146.51, 142.64, 141.11, 140.92, 139.69, 137.78, 135.36, 133.21, 132.11, 132.03, 131.01, 130.29, 130.19, 129.07, 128.94, 128.12, 128.05, 127.83, 127.76, 126.94, 124.78. 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 on which an ITO transparent electrode (anode) having a thickness of 200 nm was laminated was subjected to ultrasonic cleaning with acetone and pure water and boiling cleaning with isopropyl alcohol. Furthermore, after UV/ozone cleaning was performed and installed in a vacuum vapor deposition apparatus, it was evacuated with a vacuum pump until it became 1×10 ⁻⁴ Pa. First, copper phthalocyanine is deposited on an ITO transparent electrode at a deposition rate of 0.1 nm/sec to form a 10 nm hole injection layer, and then Compound (A25) is vapor-deposited at a deposition rate of 0.3 nm/sec to 30 nm at a deposition rate of 0.3 nm/sec to form a hole transport layer was done with Subsequently, tris(2-phenylpyridine)iridium (Ir(ppy)) ₃ ) as a phosphorescent dopant material and 4,4'-bis(N-carbazolyl)biphenyl (CBP) as a host material were mixed in a weight ratio of 1:11.5 It was co-deposited at a deposition rate of 0.25 nm/sec so as to become a light emitting layer of 30 nm. Next, BAlq (bis(2-methyl-8-quinolinolato)(p-phenylphenollato)aluminum) was vapor-deposited at a deposition rate of 0.3 nm/sec to form an exciton-blocking layer of 5 nm, and then Alq3 (Tris(8-quinolinolato)aluminum) was vapor-deposited at a vapor deposition rate of 0.3 nm/sec to obtain an electron transport layer of 45 nm. Next, as an electron injection layer, 1 nm of lithium fluoride was vapor-deposited at the deposition rate of 0.01 nm/sec, and 100 nm of aluminum was vapor-deposited at the vapor deposition rate of 0.25 nm/sec, and the cathode was formed. Moreover, the glass plate for sealing was adhere|attached with UV curing resin in nitrogen atmosphere, and it was set as the organic electroluminescent element for evaluation. A current of 20 mA/cm 2 was applied to the device thus fabricated, and the driving voltage and current efficiency were measured. In addition, the luminance half-life time 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 (element evaluation)

An organic EL device was fabricated in the same manner as in Example 8A except that Compound (A26), (A27), (A28), (A29), (A47) or (A53) was used instead of Compound (A25). Table 1 shows the driving voltage and current efficiency when a current of 20 mA/cm 2 is applied and the luminance half-life time when a current of 6.25 mA/cm 2 is applied.

Examples 17B to 41B (element evaluation)

Instead of compound (A25), compound (B25), (B26), (B27), (B28), (B29), (B34), (B46), (B53), (B77), (B79), (B2) ), (B5), (B103), (B106), (B122) or (B138), an organic EL device was fabricated in the same manner as in Example 8A. Table 1 shows the driving voltage and current efficiency when a current of 20 mA/cm 2 is applied and the luminance half-life time when a current of 6.25 mA/cm 2 is applied.

Comparative Example 1 (Evaluation of NPD devices)

An organic EL device was fabricated in the same manner as in Example 8A except that 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 was applied and the luminance half-life time when a current of 6.25 mA/cm 2 was applied.

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 was applied and the luminance half-life time when a current of 6.25 mA/cm 2 was applied.

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 was applied and the luminance half-life time when a current of 6.25 mA/cm 2 was applied.

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

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

Further, 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 2014- filed on February 18, 2014 The entire contents of the specification, claims and abstract of No. 028366 are incorporated herein by reference and are hereby incorporated as a disclosure of the specification of the present invention.

Claims (10)

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

wherein, any one of R ^1B to R ^3B is a 4-dibenzothienyl group, and the rest is a hydrogen atom;
Ar ¹ and Ar ² are each independently 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 methyl group or a methoxy group, It is the terphenyl group which may have the biphenylyl group which may have a methyl group, or a methoxy group, or the fluorenyl group which may have a methyl group or a methoxy group.
A 2-aminocarbazole compound represented by the following formula (1B);

wherein, any one of R ^1B to R ^3B is a 4-dibenzofuranyl group, and the remainder is a hydrogen atom;
Ar ¹ and Ar ² are each independently 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 methyl group or a methoxy group, It is the terphenyl group which may have the biphenylyl group which may have a methyl group, or a methoxy group, or the fluorenyl group which may have a methyl group or a methoxy group.
delete A 2-aminocarbazole compound represented by the following formula (1A):

wherein R ^1A , R ^2A , R ^4A , R ^5A , R ^6A and R ^7A are methyl groups;
R ^3A represents a hydrogen atom or a methyl group,
Ar ¹ and Ar ² are each independently 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 methyl group or a methoxy group, a terphenyl group which may have an optionally biphenylyl group, a methyl group or a methoxy group, or a fluorenyl group which may have a methyl group or a methoxy group;
R ^8A and R ^9A are either a group represented by the following formula (2A), and the other is a hydrogen atom:

In the formula, R ^10A represents a hydrogen atom or a methyl group.
The method according to any one of claims 1, 2, and 4, wherein Ar ¹ and Ar ² are each independently a phenyl group, a naphthyl group, a phenanthryl group, a biphenylyl group, a terphenyl group, or a fluorenyl group. A phosphorus, 2-aminocarbazole compound.
The method according to any one of claims 1, 2, and 4, wherein Ar ¹ and Ar ² are each independently a phenyl group, 4-methylphenyl group, 1-naphthyl group, 9-phenanthryl group, 4-bi A phenylyl group, a p-terphenyl-4-yl group, a m-terphenyl-4-yl group, or a 9,9-dimethyl-9H-fluoren-2-yl group, the 2-aminocarbazole compound.
A 2-aminocarbazole compound, which is any one of the compounds represented by the following formula:

.
A hole transporting material, a hole injecting material, or a light emitting host material comprising the 2-aminocarbazole compound according to any one of claims 1, 2, and 4.
An organic EL device comprising the 2-aminocarbazole compound according to any one of claims 1, 2, and 4 in any one layer, two or more layers of a light emitting layer, a hole transport layer, and a hole injection layer.
An organic EL device comprising the 2-aminocarbazole compound according to any one of claims 1 to 4 in a hole transporting layer.