WO2014002871A1

WO2014002871A1 - Electron transport material and organic electroluminescent element using same

Info

Publication number: WO2014002871A1
Application number: PCT/JP2013/066978
Authority: WO
Inventors: 国防王; 洋平小野
Original assignee: Jnc株式会社
Priority date: 2012-06-28
Filing date: 2013-06-20
Publication date: 2014-01-03
Also published as: KR20150024811A; CN104379572B; CN104379572A; JPWO2014002871A1; TW201406746A; KR102022437B1; TWI541238B; JP6183363B2

Abstract

A benzo[a]carbazole compound represented by formula (1) of the present invention is an electron transport material that contributes to increasing the lifespan, the high light-emitting efficiency, and the like of an organic electroluminescent element. Use of the compound in the production of an organic electroluminescent element enables the production of an organic electroluminescent element having high light-emitting efficiency and stabling operating characteristics over a long period of time. In formula (1): a, b, c, and d are 1 or 0; a and b are not 0 simultaneously; Py¹ and Py² are a pyridyl or bipyridyl; if a is 0, Ar¹ is hydrogen or an aryl, if a is 1, Ar¹ is an arylene, if b is 0, Ar² is hydrogen or an aryl, and if b is 1, Ar² is an arylene; A is an aryl; and R¹-R⁸ each represent hydrogen, an alkyl, a cycloalkyl, an aryl, or a heteroaryl.

Description

Electron transport material and organic electroluminescent device using the same

The present invention relates to a novel electron transport material having a pyridyl group, an organic electroluminescence device using the electron transport material (hereinafter, sometimes abbreviated as an organic EL device or simply a device), and the like.

In recent years, organic EL elements have attracted attention as next-generation full-color flat panel displays, and active research has been conducted. In order to promote the practical use of organic EL elements, it is indispensable to reduce the drive voltage and extend the life of the elements, and new electron transport materials have been developed to achieve these. In particular, it is essential to lower the driving voltage and extend the life of the blue element. Patent Document 1 (Japanese Patent Application Laid-Open No. 2003-123983) discloses that an organic EL device can be driven at a low voltage by using a 2,2′-bipyridyl compound, which is a phenanthroline derivative or an analog thereof, as an electron transport material. It is stated that it can be done. However, the element characteristics (driving voltage, light emission efficiency, etc.) reported in the examples of this document are only relative values based on comparative examples, and no actual measurement values that can be judged as practical values are described. Alternatively, example of using 2,2'-bipyridyl compound to the electron transport material, non-patent document ^{1 (Proceedings of the 10 th International} Workshop on Inorganic and Organic Electroluminescence), Patent Document 2 (JP 2002-158093 JP ) And Patent Document 3 (International Publication No. 2007/86552 pamphlet). The compound described in Non-Patent Document 1 has a low Tg and is not practical. Although the compounds described in Patent Documents 2 and 3 can drive an organic EL device at a relatively low voltage, further higher efficiency and longer life are desired for practical use.

JP 2003-123983 A JP 2002-158093 A International Publication 2007/86552 Pamphlet

The present invention has been made in view of the problems of such conventional techniques. An object of the present invention is to provide an electron transport material that contributes to high luminous efficiency and long life of an organic EL element. Furthermore, this invention makes it a subject to provide the organic EL element using this electron transport material.

As a result of intensive studies, the present inventors have used a compound in which pyridyl or bipyridyl is linked to the 3-position and / or 9-position of benzo [a] carbazole, directly or via arylene, in the electron transport layer of the organic EL device. Thus, it was found that an organic EL element having high luminous efficiency and capable of being driven with a long lifetime was obtained, and the present invention was completed based on this finding.
Said subject is solved by each item shown below.

[1] A benzo [a] carbazole compound represented by the following formula (1).

In equation (1),
a, b, c, and d are independently 1 or 0, but a and b are not 0 at the same time;
Py ¹ and Py ² are independently pyridyl or bipyridyl, and any hydrogen of the pyridyl or bipyridyl is alkyl having 1 to 6 carbons, cycloalkyl having 3 to 6 carbons, aryl having 6 to 14 carbons, or Optionally substituted with heteroaryl having 2 to 12 carbons;
Ar ¹ is hydrogen or aryl having 6 to 20 carbon atoms when a is 0; Ar ¹ is arylene having 6 to 20 carbon atoms when a is 1; Ar ² is hydrogen or carbon when b is 0 An aryl having 6 to 20 carbon atoms and an arylene having 6 to 20 carbon atoms when b is 1, any hydrogen of these aryls or arylenes is an alkyl having 1 to 6 carbon atoms or a cyclohexane having 3 to 6 carbon atoms; Optionally substituted with alkyl or aryl of 6 to 14 carbon atoms;
A is aryl having 6 to 20 carbon atoms, and any hydrogen in the aryl may be replaced by alkyl having 1 to 6 carbon atoms, cycloalkyl having 3 to 6 carbon atoms, or aryl having 6 to 14 carbon atoms ;
R ¹ to R ⁸ are independently hydrogen, alkyl having 1 to 6 carbons, cycloalkyl having 3 to 6 carbons, aryl having 6 to 14 carbons, or heteroaryl having 2 to 10 carbons, and the aryl Or any hydrogen of heteroaryl may be replaced by alkyl having 1 to 6 carbons or cycloalkyl having 3 to 6 carbons;
At least one hydrogen in the compound represented by the formula (1) may be replaced with deuterium.

[2] The benzo [a] carbazole compound according to item [1], represented by the following formula (1-1):

In formula (1-1),
Py ¹ and Py ² are independently pyridyl or bipyridyl, and any hydrogen of the pyridyl or bipyridyl is alkyl having 1 to 6 carbons, cycloalkyl having 3 to 6 carbons, aryl having 6 to 14 carbons, or Optionally substituted with heteroaryl having 2 to 12 carbons;
Ar ¹ and Ar ² are each independently arylene having 6 to 20 carbon atoms, and any hydrogen of the arylene is alkyl having 1 to 6 carbon atoms, cycloalkyl having 3 to 6 carbon atoms, or 6 to 14 carbon atoms Optionally substituted with aryl;
A is aryl having 6 to 20 carbon atoms, and any hydrogen in the aryl may be replaced by alkyl having 1 to 6 carbon atoms, cycloalkyl having 3 to 6 carbon atoms, or aryl having 6 to 14 carbon atoms ;
R ¹ to R ⁸ are independently hydrogen, alkyl having 1 to 6 carbons, cycloalkyl having 3 to 6 carbons, aryl having 6 to 14 carbons, or heteroaryl having 2 to 10 carbons, and the aryl Or any hydrogen in the heteroaryl may be replaced by alkyl of 1 to 6 carbons or cycloalkyl of 3 to 6 carbons; and
c and d are each independently 1 or 0.

[3] The benzo [a] carbazole compound according to the item [1], represented by the following formula (1-2).

In formula (1-2),
Py ² is pyridyl or bipyridyl, and any hydrogen of the pyridyl or bipyridyl is alkyl having 1 to 6 carbons, cycloalkyl having 3 to 6 carbons, aryl having 6 to 14 carbons, or 2 to 12 carbons Optionally substituted with heteroaryl;
Ar ¹ is hydrogen or aryl having 6 to 20 carbon atoms, and any hydrogen in the aryl is replaced by alkyl having 1 to 6 carbon atoms, cycloalkyl having 3 to 6 carbon atoms, or aryl having 6 to 14 carbon atoms May be;
Ar ² is aryl having 6 to 20 carbon atoms, and any hydrogen in the arylene is replaced by alkyl having 1 to 6 carbons, cycloalkyl having 3 to 6 carbons, or aryl having 6 to 14 carbons Well;
A is aryl having 6 to 20 carbon atoms, and any hydrogen in the aryl may be replaced by alkyl having 1 to 6 carbon atoms, cycloalkyl having 3 to 6 carbon atoms, or aryl having 6 to 14 carbon atoms ;
R ¹ to R ⁸ are independently hydrogen, alkyl having 1 to 6 carbons, cycloalkyl having 3 to 6 carbons, aryl having 6 to 14 carbons, or heteroaryl having 2 to 10 carbons, and the aryl Or any hydrogen in the heteroaryl may be replaced by alkyl of 1 to 6 carbons or cycloalkyl of 3 to 6 carbons; and
d is 1 or 0.

[4] The benzo [a] carbazole compound according to item [1], represented by the following formula (1-3):

In formula (1-3),
Py ¹ is pyridyl or bipyridyl, and any hydrogen of the pyridyl or bipyridyl is alkyl having 1 to 6 carbons, cycloalkyl having 3 to 6 carbons, aryl having 6 to 14 carbons, or 2 to 12 carbons Optionally substituted with heteroaryl;
Ar ¹ is an arylene having 6 to 20 carbon atoms, and any hydrogen of the arylene is replaced by an alkyl having 1 to 6 carbons, a cycloalkyl having 3 to 6 carbon atoms, or an aryl having 6 to 14 carbon atoms Well;
Ar ² is hydrogen or aryl having 6 to 20 carbon atoms, and any hydrogen in the aryl is replaced by alkyl having 1 to 6 carbon atoms, cycloalkyl having 3 to 6 carbon atoms, or aryl having 6 to 14 carbon atoms May be;
A is aryl having 6 to 20 carbon atoms, and any hydrogen in the aryl may be replaced by alkyl having 1 to 6 carbon atoms, cycloalkyl having 3 to 6 carbon atoms, or aryl having 6 to 14 carbon atoms ;
R ¹ to R ⁸ are independently hydrogen, alkyl having 1 to 6 carbons, cycloalkyl having 3 to 6 carbons, aryl having 6 to 14 carbons, or heteroaryl having 2 to 10 carbons, and the aryl Or any hydrogen in the heteroaryl may be replaced by alkyl of 1 to 6 carbons or cycloalkyl of 3 to 6 carbons; and
c is 1 or 0.

[5] Py ¹ and Py ² are independently groups represented by the following formulas (Py-1-1) to (Py-1-3) and (Py-2-1) to (Py-2-18) One selected from the group of

Any hydrogen in these groups may be replaced by methyl, ethyl, isopropyl, t-butyl, cyclohexyl, phenyl, naphthyl, or pyridyl;
Ar ¹ and Ar ² are independently phenylene, naphthalenediyl, anthracenediyl, or chrysenediyl, and any hydrogen in these groups is replaced with methyl, ethyl, isopropyl, t-butyl, cyclohexyl, phenyl, or naphthyl May be;
A is phenyl, naphthyl or phenanthryl, and any hydrogen in these groups may be replaced by methyl, ethyl, isopropyl, t-butyl, cyclohexyl, phenyl, or naphthyl;
R ¹ to R ⁸ are independently hydrogen, methyl, ethyl, isopropyl, t-butyl, cyclohexyl, or phenyl; and
The benzo [a] carbazole compound according to item [2], wherein c and d are each independently 1 or 0.

[6] Py ² is selected from the group of groups represented by the following formulas (Py-1-1) to (Py-1-3) and (Py-2-1) to (Py-2-18) And

Any hydrogen in these groups may be replaced by methyl, ethyl, isopropyl, t-butyl, cyclohexyl, phenyl, naphthyl, or pyridyl;
Ar ¹ is hydrogen, phenyl, naphthyl, anthryl, phenanthryl, or chrycenyl, and any hydrogen in these groups may be replaced with methyl, ethyl, isopropyl, t-butyl, cyclohexyl, phenyl, or naphthyl;
Ar ² is phenylene, naphthalenediyl, anthracenediyl, or chrysenediyl, and any hydrogen in these groups may be replaced with methyl, ethyl, isopropyl, t-butyl, cyclohexyl, phenyl, or naphthyl;
A is phenyl, naphthyl or phenanthryl, and any hydrogen in these groups may be replaced by methyl, ethyl, isopropyl, t-butyl, cyclohexyl, phenyl, or naphthyl;
R ¹ to R ⁸ are independently hydrogen, methyl, ethyl, isopropyl, t-butyl, cyclohexyl, or phenyl; and
The benzo [a] carbazole compound according to item [3], wherein d is 1 or 0.

[7] Py ¹ is selected from the group of groups represented by the following formulas (Py-1-1) to (Py-1-3) and (Py-2-1) to (Py-2-18) And

Any hydrogen in these groups may be replaced by methyl, ethyl, isopropyl, t-butyl, cyclohexyl, phenyl, naphthyl, or pyridyl;
Ar ¹ is phenylene, naphthalenediyl, anthracenediyl, or chrysenediyl, and any hydrogen in these groups may be replaced with methyl, ethyl, isopropyl, t-butyl, cyclohexyl, phenyl, or naphthyl;
Ar ² is hydrogen, phenyl, naphthyl, anthryl, phenanthryl, or chrysenyl, and any hydrogen in these groups may be replaced with methyl, ethyl, isopropyl, t-butyl, cyclohexyl, phenyl, or naphthyl;
A is phenyl, naphthyl or phenanthryl, and any hydrogen in these groups may be replaced by methyl, ethyl, isopropyl, t-butyl, cyclohexyl, phenyl, or naphthyl;
R ¹ to R ⁸ are independently hydrogen, methyl, ethyl, isopropyl, t-butyl, cyclohexyl, or phenyl; and
The benzo [a] carbazole compound according to item [4], wherein c is 1 or 0.

[8] Py ¹ and Py ² are independently represented by the formulas (Py-1-1), (Py-1-2), (Py-1-3), (Py-2-1), (Py-2- 2), (Py-2-3), (Py-2-7), (Py-2-8), (Py-2-9), (Py-2-10), (Py-2-11) And any one of the groups represented by (Py-2-12), wherein any hydrogen of these groups may be replaced by methyl, t-butyl, phenyl, naphthyl, or pyridyl Often;
Ar ¹ and Ar ² are independently 1,4-phenylene, 1,3-phenylene, naphthalene-1,4-diyl, naphthalene-1,6-diyl, naphthalene-2,6-diyl, naphthalene-2,7 -Diyl, or anthracene-9,10-diyl, any hydrogen of these groups may be replaced by methyl, t-butyl, or phenyl;
A is phenyl, 1-naphthyl, 2-naphthyl, or 9-phenanthryl, and any hydrogen in these groups may be replaced by methyl, t-butyl, or phenyl;
R ¹ to R ⁸ are all hydrogen; and
The benzo [a] carbazole compound according to item [5], wherein c and d are each independently 1 or 0.

[9] Py ² is represented by the formula (Py-1-1), (Py-1-2), (Py-l-3), (Py-2-1), (Py-2-2), (Py- 2-3), (Py-2-7), (Py-2-8), (Py-2-9), (Py-2-10), (Py-2-11), and (Py-2) -12) is one selected from the group of groups, and any hydrogen of these groups may be replaced by methyl, t-butyl, phenyl, naphthyl, or pyridyl;
Ar ¹ is hydrogen, phenyl, 1-naphthyl, 2-naphthyl, or 9-phenanthryl, and any hydrogen in these groups may be replaced by methyl, t-butyl, or phenyl;
Ar ² is 1,4-phenylene, 1,3-phenylene, naphthalene-1,4-diyl, naphthalene-1,6-diyl, naphthalene-2,6-diyl, naphthalene-2,7-diyl, or anthracene- 9,10-diyl, any hydrogen of these groups may be replaced by methyl, t-butyl, or phenyl;
A is phenyl, 1-naphthyl, 2-naphthyl, or 9-phenanthryl, and any hydrogen in these groups may be replaced by methyl, t-butyl, or phenyl;
R ¹ to R ⁸ are all hydrogen; and
The benzo [a] carbazole compound according to item [6], wherein d is 1 or 0.

[10] Py ¹ is represented by the formula (Py-1-1), (Py-1-2), (Py-1-3), (Py-2-1), (Py-2-2), (Py- 2-3), (Py-2-7), (Py-2-8), (Py-2-9), (Py-2-10), (Py-2-11), and (Py-2) -12) is one selected from the group of groups, and any hydrogen of these groups may be replaced by methyl, t-butyl, phenyl, naphthyl, or pyridyl;
Ar ¹ is 1,4-phenylene, 1,3-phenylene, naphthalene-1,4-diyl, naphthalene-1,6-diyl, naphthalene-2,6-diyl, naphthalene-2,7-diyl, or anthracene- 9,10-diyl, any hydrogen of these groups may be replaced by methyl, t-butyl, or phenyl;
Ar ² is hydrogen, phenyl, 1-naphthyl, 2-naphthyl, or 9-phenanthryl, and any hydrogen in these groups may be replaced by methyl, t-butyl, cyclohexyl, or phenyl;
A is phenyl, 1-naphthyl, 2-naphthyl, or 9-phenanthryl, and any hydrogen in these groups may be replaced by methyl, t-butyl, or phenyl;
R ¹ to R ⁸ are all hydrogen; and
The benzo [a] carbazole compound according to item [7], wherein c is 1 or 0.

[11] Py ¹ and Py ² are independently represented by the formulas (Py-1-1), (Py-1-2), (Py-1-3), (Py-2-2), (Py-2- 3) one selected from the group of groups represented by (Py-2-8), (Py-2-9), (Py-2-11), and (Py-2-12);
Ar ¹ and Ar ² are independently 1,4-phenylene, 1,3-phenylene, naphthalene-1,4-diyl, naphthalene-2,6-diyl, naphthalene-2,7-diyl, or anthracene-9, 10-diyl;
A is phenyl, 2-biphenylyl, 3-biphenylyl, 4-biphenylyl, m-terphenyl-5′-yl, 1-naphthyl, 2-naphthyl, or 9-phenanthryl;
R ¹ to R ⁸ are all hydrogen; and
The benzo [a] carbazole compound according to item [5], wherein c and d are each independently 1 or 0.

[12] Py ¹ and Py ² are independently represented by the formulas (Py-1-1), (Py-1-2), (Py-1-3), (Py-2-2), (Py-2- 3) one selected from the group of groups represented by (Py-2-8), (Py-2-9), (Py-2-11), and (Py-2-12);
Ar ¹ is hydrogen, phenyl, 1-naphthyl, 2-naphthyl, or 9-phenanthryl;
Ar ² is 1,4-phenylene, 1,3-phenylene, naphthalene-1,4-diyl, naphthalene-2,6-diyl, naphthalene-2,7-diyl, or anthracene-9,10-diyl;
A is phenyl, 2-biphenylyl, 3-biphenylyl, 4-biphenylyl, m-terphenyl-5′-yl, 1-naphthyl, 2-naphthyl, or 9-phenanthryl;
R ¹ to R ⁸ are all hydrogen; and
The benzo [a] carbazole compound according to item [6], wherein d is 1 or 0.

[13] Py ¹ and Py ² are independently represented by the formulas (Py-1-1), (Py-1-2), (Py-1-3), (Py-2-2), (Py-2- 3) one selected from the group of groups represented by (Py-2-8), (Py-2-9), (Py-2-11), and (Py-2-12);
Ar ¹ is 1,4-phenylene, 1,3-phenylene, naphthalene-1,4-diyl, naphthalene-2,6-diyl, naphthalene-2,7-diyl, or anthracene-9,10-diyl;
Ar ² is hydrogen, phenyl, 1-naphthyl, 2-naphthyl, or 9-phenanthryl;
A is phenyl, 2-biphenylyl, 3-biphenylyl, 4-biphenylyl, m-terphenyl-5′-yl, 1-naphthyl, 2-naphthyl, or 9-phenanthryl;
R ¹ to R ⁸ are all hydrogen; and
The benzo [a] carbazole compound according to item [7], wherein c is 1 or 0.

[14] The benzo [a] carbazole compound represented by the following formula (1-1-66) or (1-1-758) according to the item [5].

[15] The benzo [a] carbazole compound according to the above item [6], represented by the following formula (1-2-8) or (1-2-28):

[16] The benzo [a] carbazole compound according to the above item [7], represented by the following formula (1-3-206) or (1-3-300):

[17] The benzo [a] carbazole compound according to item [5], represented by the following formula (1-1-2).

[18] The benzo [a] carbazole compound according to item [5], represented by the following formula (1-1-765).

[19] The benzo [a] carbazole compound according to item [5], represented by the following formula (1-1-893).

[20] The benzo [a] carbazole compound according to item [5], represented by the following formula (1-1-973):

[21] The benzo [a] carbazole compound according to item [6], represented by the following formula (1-2-125):

[22] An electron transport material containing the compound according to any one of [1] to [21].

[23] A pair of electrodes composed of an anode and a cathode, a light emitting layer disposed between the pair of electrodes, an electron transport material according to the item [22], disposed between the cathode and the light emitting layer. An organic electroluminescent device having an electron transport layer and / or an electron injection layer containing

[24] At least one of the electron transport layer and the electron injection layer further contains at least one selected from the group consisting of a quinolinol-based metal complex, a bipyridine derivative, a phenanthroline derivative, and a borane derivative, [23] The organic electroluminescent element according to item.

[25] At least one of the electron transport layer and the electron injection layer further includes an alkali metal, an alkaline earth metal, a rare earth metal, an alkali metal oxide, an alkali metal halide, an alkaline earth metal oxide, or alkaline earth. Containing at least one selected from the group consisting of metal halides, rare earth metal oxides, rare earth metal halides, alkali metal organic complexes, alkaline earth metal organic complexes and rare earth metal organic complexes The organic electroluminescence device as described in the item [23].

The compound of the present invention is stable even when a voltage is applied in a thin film state and has a feature of high charge transport capability. The compound of the present invention is suitable as a charge transport material in an organic EL device. By using the compound of the present invention for an electron transport layer and / or an electron injection layer of an organic EL device, an organic EL device having high luminous efficiency and a long lifetime can be obtained. By using the organic EL element of the present invention, a high-performance display device such as full-color display can be created.

Hereinafter, the present invention will be described in more detail. In the present specification, for example, the “compound represented by the formula (1-1-66)” may be referred to as “compound (1-1-66)”. The “compound represented by formula (1-1-758)” may be referred to as “compound (1-1-758)”. Other formula symbols and formula numbers are handled in the same manner.

The term “arbitrary” used in the definition of a compound may mean “can be freely selected not only by position but also by number”. For example, the expression “any hydrogen of phenyl may be substituted with alkyl having 1 to 6 carbon atoms” not only means “one hydrogen may be substituted with alkyl”, but also “ It may also mean “same alkyl, or each may be replaced by a different alkyl”.
The symbols Me, Et, i-Pr, t-Bu, Cy, and Ph used in the structural formulas, chemical reaction formulas, and the like of this specification represent methyl, ethyl, isopropyl, tertiary butyl, cyclohexyl, and phenyl, respectively. .

<Compound represented by Formula (1)>
A first invention of the present application is a benzo [a] carbazole compound having pyridyl or bipyridyl represented by the following formula (1).

In formula (1), a, b, c and d are independently 1 or 0, but a and b are not 0 at the same time. The compound represented by formula (1) has an embodiment in which a = b = 1, an embodiment in which a = 0 and b = 1, and an embodiment in which a = 1 and b = 0.

In the formula (1), an embodiment where a = b = 1 is a compound represented by the following formula (1-1).

In the compound represented by the formula (1-1), pyridyl or bipyridyl is linked to the 3rd and 9th positions of benzo [a] carbazole directly or via arylene. When the compound of the present invention is used in the electron transport layer or the electron injection layer of the organic EL device, the LUMO level is lowered, and the injection of electrons from the cathode to the electron transport layer or the electron injection layer is likely to occur. It is thought to bring about effects such as lowering. In the embodiment of the present invention, a structure of the formula (1-1) in which pyridyl or bipyridyl is connected to both ends of the molecule is more preferable. Even if arylene is interposed between benzo [a] carbazole and pyridyl or bipyridyl, there is no significant characteristic variation, and c and d in the formula may be 0 or 1. On the other hand, as will be described later, a compound in which bipyridyl is directly linked to benzo [a] carbazole has limitations on the intermediate materials that can be used, and thus the production methods that can be selected are limited. In the case of a compound in which one or both of Py ¹ and Py ² is bipyridyl, from the viewpoint of ease of production, the side to which bipyridyl is linked is preferably via arylene.

In the formula (1), an embodiment where a = 0 and b = 1 is a compound represented by the following formula (1-2).

In the formula (1), an embodiment where a = 1 and b = 0 is a compound represented by the following formula (1-3).

In the compound represented by the formula (1-2), pyridyl or bipyridyl is linked to the 9-position of benzo [a] carbazole directly or via arylene. In the compound represented by the formula (1-3), pyridyl or bipyridyl is linked to the 3-position of benzo [a] carbazole directly or via arylene. A compound having pyridyl or bipyridyl linked to one end of these molecules is preferable next to the compound represented by the above formula (1-1) as a material used for the electron transport layer or the electron injection layer. The position of benzo [a] carbazole to which pyridyl and bipyridyl are linked may be the 3rd position or the 9th position. Even if arylene is interposed between benzo [a] carbazole and pyridyl or bipyridyl, there is no significant variation in characteristics. However, from the viewpoint of ease of production, in the description of the compound represented by formula (1-1), For the same reason as described, in the case where bipyridyl is linked, it is preferable to use arylene.

In formula (1), Py ¹ and Py ² are independently pyridyl or bipyridyl. Specifically, pyridyl is 2-pyridyl, 3-pyridyl and 4-pyridyl represented by the following formulas (Py-1-1), (Py-1-2) and (Py-1-3). Bipyridyl is specifically a group represented by the following formulas (Py-2-1) to (Py-2-30).

Any hydrogen of this pyridyl or bipyridyl may be replaced by alkyl having 1 to 6 carbons, cycloalkyl having 3 to 6 carbons, aryl having 6 to 14 carbons, or heteroaryl having 2 to 12 carbons . The number of substituents is, for example, the maximum possible number of substitution, preferably 1 to 3, more preferably 1 to 2, and still more preferably 1.

Examples of the alkyl having 1 to 6 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, isopentyl, neopentyl, t-pentyl, n-hexyl, Examples thereof include 1-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl and the like. Among these, methyl, ethyl, isopropyl, and t-butyl are preferable, methyl and t-butyl are more preferable, and methyl is particularly preferable.

Examples of the cycloalkyl having 3 to 6 carbon atoms include cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. Among these, cyclohexyl is preferable because of easy availability of raw materials and ease of production.

Examples of the aryl having 6 to 14 carbon atoms include phenyl, naphthyl, anthryl, phenanthryl and the like. Among these, phenyl and naphthyl are preferable, and phenyl is more preferable because of easy availability of raw materials and ease of production.

Examples of the heteroaryl having 2 to 12 carbon atoms include a heterocyclic group containing 1 to 5 heteroatoms selected from oxygen, sulfur and nitrogen in addition to carbon as a ring constituent atom. Specifically, furyl, thienyl, pyrrolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, oxadiazolyl, thiadiazolyl, triazolyl, tetrazolyl, pyrazolyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, indolyl, isoindolyl, 1H-indazolyl, , Benzoxazolyl, benzothiazolyl, 1H-benzotriazolyl, quinolinyl, isoquinolinyl, cinnolyl, quinazolyl, quinoxalinyl, phthalazinyl, naphthyridinyl, purinyl, pteridinyl, carbazolyl, acridinyl, phenoxazinyl, phenothiazinyl, phenazinyl, furanazinyl, furanazinyl Isobenzofuranyl, benzo [b] thieni , Phenoxathiinyl, etc. thianthrenyl and the like. Among these, pyridyl, quinolinyl and isoquinolinyl are preferable, and pyridyl is more preferable.

In the embodiment where a = b = 1, Py ¹ and Py ² may be the same or different groups, but are preferably the same in terms of ease of production of the compound. Whether Py ¹ and Py ² are the same or different, (Py-1-1) to (Py-1-3) and (Py-2-1) to (Py-2- 18) is preferably selected from the group of groups represented by (Py-1-1) to (Py-1-3), (Py-2-1) to (Py-2-3) and (Py It is more preferably selected from the group of groups represented by -2-7) to (Py-2-12).

Also in the embodiment in which a = 1 and b = 0 and the embodiment in which a = 0 and b = 1, Py ¹ or Py ² is (Py-1-1) to (Py-1-3) and (Py-2-1). ) To (Py-2-18) are preferably selected from the group of groups represented by (Py-1-1) to (Py-1-3), (Py-2-1) to (Py--). It is more preferable that the group is selected from the group of groups represented by 2-3) and (Py-2-7) to (Py-2-12).

In the formula (1), Ar ¹ and Ar ² are arylene having 6 to 20 carbon atoms in an embodiment where a = b = 1. In an embodiment in which a = 0 and b = 1, Ar ¹ is hydrogen or aryl having 6 to 20 carbon atoms, preferably aryl having 6 to 20 carbon atoms, and Ar ² is arylene having 6 to 20 carbon atoms. is there. In an embodiment in which a = 1 and b = 0, Ar ¹ is arylene having 6 to 20 carbon atoms, Ar ² is hydrogen or aryl having 6 to 20 carbon atoms, and aryl having 6 to 20 carbon atoms preferable.

Examples of the aryl having 6 to 20 carbon atoms include phenyl, naphthyl, anthryl, phenanthryl, triphenylenyl, pyrenyl, chrycenyl, naphthacenyl, perylenyl and the like. Among these, phenyl, naphthyl, anthryl, and phenanthryl are preferable, and phenyl, naphthyl, and anthryl are more preferable.

Examples of the arylene having 6 to 20 carbon atoms include phenylene, naphthalenediyl, anthracenediyl, phenanthrene diyl, pyrenediyl, chrysenediyl, naphthacene diyl, perylene diyl and the like. Among these, phenylene, naphthalenediyl, anthracenediyl and chrysenediyl are preferable, and phenylene, naphthalenediyl and anthracenediyl are more preferable.

Any hydrogen in the above aryl or arylene may be replaced with alkyl having 1 to 6 carbon atoms, cycloalkyl having 3 to 6 carbon atoms, or aryl having 6 to 14 carbon atoms. Specific examples of these substituents include those exemplified as the above-mentioned pyridyl or bipyridyl substituents, and methyl, ethyl, isopropyl, t-butyl, cyclohexyl, phenyl, naphthyl, anthryl and phenanthryl are preferred, and methyl, ethyl , Isopropyl, t-butyl, cyclohexyl, phenyl, and naphthyl are more preferable, and methyl, t-butyl, and phenyl are more preferable. The number of substituents is, for example, the maximum possible number of substitution, preferably 1 to 3, more preferably 1 to 2, and still more preferably 1.

When Ar ¹ and Ar ² are aryl, including aryl having a substituent, phenyl, 1-naphthyl, 2-naphthyl, 2-biphenylyl, 3-biphenylyl, 4-biphenylyl, m-terphenyl-5 ′ -Iyl and 9-phenanthryl are preferred, with phenyl, 1-naphthyl, 2-naphthyl, 3-biphenylyl, and m-terphenyl-5'-yl being more preferred.

When Ar ¹ and Ar ² are arylene, 1,4-phenylene, 1,3-phenylene, 1,4-naphthalenediyl, 2,7-naphthalenediyl, and 9,10-anthracenediyl are preferred, 4-phenylene, 1,4-naphthalenediyl and 9,10-anthracenediyl are more preferred.

In the formula (1), A is aryl having 6 to 20 carbon atoms, and any hydrogen of the aryl is alkyl having 1 to 6 carbon atoms, cycloalkyl having 3 to 6 carbon atoms or aryl having 6 to 14 carbon atoms. It may be replaced. Examples of the aryl having 6 to 20 carbon atoms include the groups exemplified for Ar ¹ and Ar ² above. Examples of the substituents of alkyl having 1 to 6 carbon atoms, cycloalkyl having 3 to 6 carbon atoms, and aryl having 6 to 14 carbon atoms include the groups exemplified as the substituents for the above-mentioned pyridyl or bipyridyl.

A is preferably phenyl, 1-naphthyl, 2-naphthyl, 2-biphenylyl, 3-biphenylyl, 4-biphenylyl, m-terphenyl-5′-yl, and 9-phenanthryl, including aryl having a substituent. More preferred are phenyl, 1-naphthyl, 2-naphthyl, 3-biphenylyl, and 4-biphenylyl.

In the formula (1), R ¹ to R ⁸ are independently hydrogen, alkyl having 1 to 6 carbons, cycloalkyl having 3 to 6 carbons, aryl having 6 to 14 carbons, or heteroaryl having 2 to 10 carbons. Aryl, and any hydrogen of the aryl or heteroaryl may be replaced by alkyl having 1 to 6 carbons or cycloalkyl having 3 to 6 carbons. Examples of the alkyl having 1 to 6 carbon atoms, cycloalkyl having 3 to 6 carbon atoms, aryl having 6 to 14 carbon atoms, and heteroaryl having 2 to 10 carbon atoms include the groups exemplified as the substituents for the above-mentioned pyridyl or bipyridyl. . The same applies to alkyl having 1 to 6 carbon atoms and cycloalkyl having 3 to 6 carbon atoms as a substituent.

R ¹ to R ⁸ are preferably hydrogen, methyl, ethyl, isopropyl, t-butyl, cyclohexyl and phenyl, more preferably hydrogen, methyl, t-butyl, cyclohexyl and phenyl, and even more preferably all hydrogen.

Moreover, the hydrogen atom in benzo [a] carbazole and Py ¹ , Py ² , Ar ¹ , Ar ² , A, and R ¹ that substitute for benzo [a] carbazole, which constitute the compound represented by the above formula (1). All or some of the hydrogen atoms in ~ R ⁸ may be deuterium.

<Specific examples of compounds>
Specific examples of the compound represented by the formula (1-1) in the embodiment of the present invention include the following compounds (1-1-1) to (1-1-861) and (1-1-871) to ( 1-1-1019). Among these, preferred compounds are (1-1-1) to (1-1-56), (1-1-65) to (1-1-67), (1-1-71) to (1-1 -76), (1-1-86) to (1-1-88), (1-1-92) to (1-1-97), (1-1-102) to (1-1-104) ), (1-1-108) to (1-1-113), (1-1-118), (1-1-119), (1-1-123) to (1-1-133), (1-1-137) to (1-1-141), (1-1-145) to (1-1-150), (1-1-154) to (1-1-159), (1 -1-163) to (1-1-177), (1-1-181) to (1-1-183), (1-1-205), (1-1-206), (1-1 -208) to (1-1-213), (1-1-215) to (1 1-220), (1-1-222) to (1-1-227), (1-1-230) to (1-1-233), (1-1-236) to (1-1- 239), (1-1-242), (1-1-243), (1-1-262), (1-1-263), (1-1-266) to (1-1-269) , (1-1-272) to (1-1-275), (1-1-278) to (1-1-281), (1-1-284) to (1-1-287), ( 1-1-290) to (1-1-293), (1-1-296) to (1-1-315), (1-1-325) to (1-1-351), (1- 1-361) to (1-1-387), (1-1-397) to (1-1-423), (1-1-433) to (1-1-621), (1-1) 624), (1-1-625), (1-1- 30) to (1-1-635), (1-1-638) to (1-1-641), (1-1-644) to (1-1-647), (1-1-650) (1-1-653), (1-1-656) to (1-1-659), (1-1-662) to (1-1-665), (1-1-668) to (1-1) 1-1-671), (1-1-673) to (1-1-678), (1-1-680) to (1-1-685), (1-1-687) to (1- 1-692), (1-1-695) to (1-1-698), (1-1-701) to (1-1-704), (1-1-707) to (1-1) 720), (1-1-733) to (1-1-780), (1-1-784) to (1-1-819), (1-1-871) to (1-1-880) , (1-1-885) to (1-1-888) , (1-1-891) to (1-1-894), (1-1-897), (1-1-898), (1-1-901) to (1-1-940), and (1-1-945) to (1-1-974).

Specific examples of the compound represented by the formula (1-2) in the embodiment of the present invention include the following compounds (1-2-1) to (1-2-365) and (1-2-381) to ( 1-2-656). Of these, preferred compounds are (1-2-1) to (1-2-146), (1-2-149), (1-2-150), (1-2-153) to (1-2). -157), (1-2-162) to (1-2-165), (1-2-169) to (1-2-175), (1-2-179) to (1-2-182) ), (1-2-185), (1-2-186), (1-2-189), (1-2-190), (1-2-193) to (1-2-195), (1-2-199)-(1-2-205), (1-2-209)-(1-2212), (1-2-225)-(1-2-365), (1 -2-451) to (1-2-460), (1-2-485) to (1-2-514) and (1-2-539) to (1-2-636).

Specific examples of the compound represented by the formula (1-3) in the embodiment of the present invention include the following compounds (1-3-1) to (1-3-352) and (1-3-361) to ( 1-3-654). Among these, preferred compounds are (1-3-1) to (1-3-132), (1-136) to (1-3-141), (1-3-144) to (1-3 -161), (1-3-165) to (1-3-170), (1-3-173), (1-3-174), (1-3-177) to (1-3-179) ), (1-3-183) to (1-3-189), (1-3-193) to (1-3-198), (1-3-201), (1-3-202), (1-3-205) to (1-3-207), (1-3-211) to (1-3-214), (1-3-225) to (1-3-352), and ( 1-3-479) to (1-3-620).

<Method for Producing Compound Represented by Formula (1)>
The compound represented by Formula (1) can be manufactured using a known synthesis method. For example, it can be synthesized by following the routes shown in the following reactions 1 to 8. It can also be synthesized by following the routes shown in the following reactions 9 to 17.

First, as a synthesis example of a compound in which the same group is linked to the 3-position and the 9-position of benzo [a] carbazole of the formula (1), pathways of reactions 1 to 8 will be described.

In the reaction 1, a compound of 6-methoxynaphthalen-2-yl) boronic acid was subjected to a Suzuki coupling reaction with a halide or triflate of 2-nitro-4-methoxybenzene in the presence of a base using a palladium catalyst. Synthesize (a-1). R ¹ to R ⁸ in the formula are the same as described above including the following.

In reaction 2, the nitro group of compound (a-1) is reductively cyclized with triphenylphosphine: PPh ₃ or triethoxyphosphine: P (OEt) ₃ to synthesize compound (a-2).

In Reaction 3, using a palladium catalyst or a copper catalyst, compound (a-2) is reacted with bromide or iodide of A in the presence of a base and a reaction accelerator to synthesize compound (a-3). A in the formula is the same as described above including the following.

In Reaction 4, methyl of the methoxy group of compound (a-3) is eliminated using pyridine hydrochloride to synthesize compound (a-4).

In Reaction 5, compound (a-5) is synthesized by reacting compound (a-4) with trifluoromethanesulfonic anhydride in the presence of a base.

In reaction 6, compound (a-6) is synthesized by reacting compound (a-5) with bis (pinacolato) diboron in the presence of a base using a palladium catalyst.

Reaction 7 is the final step. Compound (a-6) obtained in Reaction 6 is subjected to Suzuki coupling reaction with 2 moles of pyridyl, bipyridyl halide or pyridylaryl (A ⁰ ) halide or triflate, and the compound represented by Formula (1) Is synthesized.

Further, as in Reaction 8, the compound (a-5) obtained in Reaction 5 was added to a boronic acid of 2-fold moles of pyridyl, bipyridyl or pyridylaryl (A ⁰ ) in the presence of a base using a palladium catalyst or A boronic ester can also be subjected to a Suzuki coupling reaction to synthesize a compound represented by the formula (1). However, when A ⁰ is 2-pyridyl or bipyridyl, the reaction 7 is preferred in view of the stability of the reaction intermediate.

Next, routes of reactions 9 to 17 will be described as synthesis examples of compounds in which different groups are linked to the 3rd and 9th positions of benzo [a] carbazole of the formula (1).

In Reaction 9, by using a palladium catalyst in the presence of a base, (6-methoxynaphthalen-2-yl) boronic acid was subjected to Suzuki coupling reaction with a dihalo form of benzene having a nitro group to obtain compound (b-1). Is synthesized. At this time, the halogen of the dihalo compound is selected so that the reactivity is X> Y. Similarly to the above, R ¹ to R ⁸ are the same as the above including the following.

In Reaction 10, the nitro group of compound (b-1) is reductively cyclized with triphenylphosphine: PPh ₃ or triethoxyphosphine: P (OEt) ₃ to synthesize compound (b-2).

In Reaction 11, compound (b-3) is synthesized by reacting compound (b-2) with a bromide or iodide of A in the presence of a base and a reaction accelerator using a palladium catalyst or a copper catalyst. A in the formula is the same as described above including the following.

In Reaction 12, using a palladium catalyst, compound (b-3) is reacted with boronic acid or boronic acid ester of pyridylaryl or aryl (A ⁰² ) in the presence of a base to synthesize compound (b-4). To do. This reaction can be used even when A ⁰² is pyridyl or bipyridyl. However, in consideration of the stability of the reaction intermediate, Y of compound (b-3) is lithiated or used as a Grignard reagent, and then a boronic ester is used according to a conventional method. Alternatively, it is preferable to obtain a compound (b-4) by a Suzuki coupling reaction between boronic acid and pyridyl or bipyridyl halide.

In reaction 13, methyl of the methoxy group of compound (b-4) is eliminated using pyridine hydrochloride to synthesize compound (b-5).

In Reaction 14, trifluoromethanesulfonic anhydride is reacted with compound (b-5) in the presence of a base to synthesize compound (b-6).

In Reaction 15, compound (b-7) is synthesized by reacting compound (b-6) with bis (pinacolato) diboron in the presence of a base using a palladium catalyst.

Reaction 16 is the final step. The compound (b-7) obtained in Reaction 15 is subjected to Suzuki coupling reaction with a pyridyl, bipyridyl, pyridylaryl, or aryl (A ⁰¹ ) halide or triflate to synthesize a compound represented by Formula (1). .

Further, the compound (b-6) obtained in the reaction 14 was subjected to a Suzuki coupling reaction with a boronic acid or boronic acid ester of pyridylaryl or aryl (A ⁰¹ ) in the presence of a base using a palladium catalyst to obtain a compound of the formula The compound represented by (1) can also be synthesized. This reaction can be used even when A ⁰¹ is pyridyl or bipyridyl, but reaction 16 is preferred in view of the stability of the reaction intermediate.

A method for synthesizing a compound in which Ar ^{1 in} formula (1-2) is hydrogen will be described. When synthesizing via the routes of Reactions 1 to 8, instead of (6-methoxynaphthalen-2-yl) boronic acid used in Reaction 1, naphthalen-2-ylboronic acid in which the 6-position of the naphthalene ring is hydrogen is used. do it. When synthesizing via the route of reactions 9 to 17, in place of (6-methoxynaphthalen-2-yl) boronic acid used in reaction 9, naphthalen-2-ylboronic acid in which the 6-position of the naphthalene ring is hydrogen is used. do it.

A method for synthesizing a compound of formula (1-3) in which Ar ² is hydrogen will be described. When synthesizing via the routes of Reactions 1 to 8, instead of the 2-nitro-4-methoxybenzene halide or triflate of Reaction 1, a compound in which the 4-position of the benzene ring is hydrogen may be used. In the case of synthesis through the routes of reactions 9 to 17, a halide or triflate in which Y of nitrobenzene, which is the starting material of reaction 9, is hydrogen may be used.

In addition, the compound represented by the formula (1) can be synthesized by a route other than the above route. 2-nitrohalobenzene or triflate previously substituted at the 4-position with pyridyl, bipyridyl, pyridylaryl, aryl (A ⁰² ), etc., and the 6-position previously substituted with pyridyl, bipyridyl, pyridylaryl, aryl (A ⁰¹ ), etc. Naphthalen-2-ylboronic acid is synthesized, respectively, and subjected to Suzuki coupling reaction according to a conventional method. Thereafter, the nitro group is reductively cyclized using PPh ₃ or P (OEt) ₃ to obtain an 11H-benzo [a] carbazole derivative. Finally, by reacting 11H-benzo [a] carbazole derivative with bromide or iodide of A using a palladium catalyst or a copper catalyst in the presence of a base and a reaction accelerator, the formula (1) of the present invention Can be synthesized. This reaction route is suitable for synthesizing a compound in which the 3-position and 9-position groups of benzo [c] carbazole are different, but can also be applied to a compound in which the 3-position and 9-position groups are the same. In either case, when a compound in which pyridyl or bipyridyl is linked to the 9-position of benzo [c] carbazole is synthesized, it is preferable to go through this reaction route.

The palladium catalyst used in the above-described Suzuki coupling reaction (reactions 1, 7, 8, 9, 12, 16, and 17) is tetrakis (triphenylphosphine) palladium (0): Pd (PPh ₃ ) ₄ , bis ( Triphenylphosphine) dichloropalladium (II): PdCl ₂ (PPh ₃ ) ₂ , palladium acetate (II): Pd (OAc) ₂ , tris (dibenzylideneacetone) dipalladium (0): Pd ₂ (dba) ₃ , Tris (Dibenzylideneacetone) dipalladium (0) chloroform complex: Pd ₂ (dba) ₃ .CHCl ₃ , bis (dibenzylideneacetone) palladium (0): Pd (dba) ₂ , bis (tri-t-butylphosphino) palladium (0): Pd (P ( t-Bu) 3) 2 or [1,1'-bis (diphenyl Niruhosufino) ferrocene] palladium (II) dichloride lithograph dichloromethane complex _(1: 1): and the like can be exemplified _{PdCl 2 (dppf) · CH 2} Cl 2.

In order to accelerate the reaction, a phosphine compound may be added to these palladium compounds in some cases. Specific examples of the phosphine compound include tri (t-butyl) phosphine: t-Bu ₃ P, tricyclohexylphosphine: PCy ₃ , 1- (N, N-dimethylaminomethyl) -2- (di-t-butylphosphino ) Ferrocene, 1- (N, N-dibutylaminomethyl) -2- (di-t-butylphosphino) ferrocene, 1- (methoxymethyl) -2- (di-t-butylphosphino) ferrocene, 1,1 ′ -Bis (di-t-butylphosphino) ferrocene, 2,2'-bis (di-t-butylphosphino) -1,1'-binaphthyl, 2-methoxy-2 '-(di-t-butylphosphino)- 1,1′-binaphthyl, and 2-dicyclohexylphosphino-2 ′, 6′-dimethoxybiphenyl.

Specific examples of bases used in the reaction include sodium carbonate, potassium carbonate, cesium carbonate, sodium hydrogen carbonate, sodium hydroxide, potassium hydroxide, barium hydroxide, sodium ethoxide, sodium t-butoxide, sodium acetate, phosphorus Examples include tripotassium acid: K ₃ PO ₄ , and potassium fluoride.

Solvents used in the reaction include benzene, toluene, xylene, N, N-dimethylformamide, N, N-dimethylacetamide, tetrahydrofuran, diethyl ether, t-butyl methyl ether, 1,4-dioxane, methanol, ethanol, Examples thereof include isopropyl alcohol and cyclopentyl methyl ether. These solvents may be used alone or as a mixed solvent. The reaction is usually carried out in the temperature range of 50 to 180 ° C, more preferably 70 to 130 ° C.

Examples of the reaction solvent used in Reaction 2 and Reaction 10 include toluene, xylene, chlorobenzene, o-dichlorobenzene, N, N-dimethylformamide, N, N-dimethylacetamide, and 1-methyl-2-pyrrolidone. A solvent may be used independently and may be used as a mixed solvent. The reaction temperature is usually in the range of 100 ° C to 220 ° C. More preferably, it is 130 to 190 ° C.

When a copper catalyst is used in Reaction 3 and Reaction 11, copper powder, copper oxide, copper halide, or the like is used. The base used at the same time is potassium carbonate, sodium carbonate, sodium bicarbonate, sodium hydride and the like, and the reaction accelerator is crown ether (for example, 18-crown-6-ether), polyethylene glycol (PEG), polyethylene glycol dialkyl. And ether (PEGDM). As the reaction solvent, N, N-dimethylformamide, N, N-dimethylacetamide, nitrobenzene, dimethyl sulfoxide, dichlorobenzene, quinoline and the like are used. The reaction temperature is 160 to 250 ° C. However, when the reactivity of the substrate is low, a higher temperature reaction may be performed using an autoclave or the like.

When a palladium catalyst is used in Reaction 3 and Reaction 11, palladium (II) acetate: Pd (OAc) ₂ , palladium chloride: PdCl ₂ , palladium bromide PdBr ₂ , tris (dibenzylideneacetone) dipalladium (0): Pd ₂ (dba) ₃ , tris (dibenzylideneacetone) dipalladium (0) chloroform complex: Pd ₂ (dba) ₃ .CHCl ₃ , bis (dibenzylideneacetone) palladium (0): Pd (dba) ₂ , bis ( Tri-t-butylphosphino) palladium (0): Pd (P (t-Bu) ₃ ) ₂ or [1.1′-bis (diphenylphosphino) ferrocene] palladium (II) dichloride dichloromethane complex (1: 1 ): PdCl ₂ (dppf) · CH ₂ Cl ₂ or the like is used.

The bases used at the same time are lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate, cesium carbonate, sodium hydrogen carbonate, sodium hydride, alkoxy potassium (for example, methoxy potassium, ethoxy potassium, normal propoxy potassium, isopropoxy potassium, n- Butoxy potassium, etc.), and alkoxy sodium (eg, methoxy sodium, ethoxy sodium, normal propoxy sodium, isopropoxy sodium, n-butoxy sodium, and t-butoxy sodium).

The reaction accelerator is 2,2 ′-(diphenylphosphino) -1,1′-binaphthyl, 1,1 ′-(diphenylphosphino) ferrocene, dicyclohexylphosphinobiphenyl, di-t-butylphosphinobiphenyl, tri ( t-butyl) phosphine: t-Bu ₃ P, 1- (N, N-dimethylaminomethyl) -2- (di-t-butylphosphino) ferrocene, 1- (N, N-dibutylaminomethyl) -2 -(Di-t-butylphosphino) ferrocene, 1- (methoxymethyl) -2- (di-t-butylphosphino) ferrocene, 1,1'-bis (di-t-butylphosphino) ferrocene, , 2'-bis (di-t-butylphosphino) -1,1'-binaphthyl, 2-methoxy-2 '-(di-t-butylphosphino) -1,1'-binaphthyl, or 2-dicyclo Kishiruhosufino -2 ', 6'-like dimethoxybiphenyl is used.

As the reaction solvent, an aromatic hydrocarbon solvent such as benzene, toluene, xylene, or mesitylene is used. A solvent may be used independently and may be used as a mixed solvent. The reaction temperature is usually 50 to 200 ° C., more preferably 80 to 140 ° C.

Examples of the reaction solvent used in Reaction 4 and Reaction 13 include 1-methyl-2-pyrrolidone, N, N-dimethylacetamide, nitrobenzene, dimethyl sulfoxide, dichlorobenzene, quinoline and the like. A solvent may be used independently and may be used as a mixed solvent. In some cases, the reaction may be performed without a solvent. The reaction is usually carried out in a temperature range of 150 to 220 ° C, more preferably 180 to 200 ° C.

When a base is used in Reaction 5 and Reaction 14, sodium carbonate, potassium carbonate, cesium carbonate, sodium bicarbonate, sodium hydroxide, potassium hydroxide, barium hydroxide, sodium acetate, potassium acetate: KOAc, tripotassium phosphate : K ₃ PO ₄ , potassium fluoride, cesium fluoride, trimethylamine, triethylamine, pyridine and the like can be used.

Examples of the solvent used in Reaction 5 and Reaction 14 include pyridine, toluene, xylene, N, N-dimethylformamide, N, N-dimethylacetamide, CH ₂ Cl ₂ , CHCl ₃ , and CH ₃ CN. These solvents may be used alone or as a mixed solvent. The reaction is usually carried out in the temperature range of −10 to 50 ° C., more preferably 0 to 30 ° C.

As the palladium catalyst used in Reaction 6 and Reaction 15, tetrakis (triphenylphosphine) palladium (0): Pd (PPh ₃ ) ₄ , bis (triphenylphosphine) dichloropalladium (II): PdCl ₂ (PPh ₃ ) ₂ , Palladium (II) acetate: Pd (OAc) ₂ , tris (dibenzylideneacetone) dipalladium (0): Pd ₂ (dba) ₃ , tris (dibenzylideneacetone) dipalladium (0) chloroform complex: Pd ₂ (dba ₃ · CHCl ₃ , bis (dibenzylideneacetone) palladium (0): Pd (dba) ₂ , bis (tri-t-butylphosphino) palladium (0): Pd (P (t-Bu) ₃ ) ₂ , or [1.1'-bis (diphenylphosphino) ferrocene] palladium (II) dic Loritodichloromethane complex (1: 1): PdCl ₂ (dppf) · CH ₂ Cl _{2 and the} like.

In order to accelerate the reaction, a phosphine compound may be added to these palladium compounds. The phosphine compound includes tri (t-butyl) phosphine: t-Bu ₃ P, tricyclohexylphosphine: PCy ₃ , 1- (N, N-dimethylaminomethyl) -2- (di-t-butylphosphino) ferrocene, 1- (N, N-dibutylaminomethyl) -2- (di-t-butylphosphino) ferrocene, 1- (methoxymethyl) -2- (di-t-butylphosphino) ferrocene, 1,1′-bis ( Di-t-butylphosphino) ferrocene, 2,2′-bis (di-t-butylphosphino) -1,1′-binaphthyl, 2-methoxy-2 ′-(di-t-butylphosphino) -1,1 Examples include '-binaphthyl and 2-dicyclohexylphosphino-2', 6'-dimethoxybiphenyl.

The bases used in Reaction 6 and Reaction 15 are sodium carbonate, potassium carbonate, cesium carbonate, sodium bicarbonate, sodium hydroxide, potassium hydroxide, barium hydroxide, sodium ethoxide, sodium t-butoxide, sodium acetate, potassium acetate. : KOAc, tripotassium phosphate: K ₃ PO ₄ , potassium fluoride and the like.

Solvents used in Reaction 6 and Reaction 15 are benzene, toluene, xylene, N, N-dimethylformamide, N, N-dimethylacetamide, tetrahydrofuran, diethyl ether, t-butyl methyl ether, 1,4-dioxane, methanol, Ethanol, isopropyl alcohol, cyclopentyl methyl ether and the like. These solvents may be used alone or as a mixed solvent. The reaction temperature is usually 50 to 180 ° C, more preferably 70 to 130 ° C.

In the above description, the Suzuki coupling reaction is used in the step of bonding rings such as aryl and heteroaryl, but Negishi coupling reaction can be used depending on the types of available raw materials and reagents.

When the compound of the present invention is used for an electron injection layer or an electron transport layer in an organic EL device, it is stable when an electric field is applied. These represent that the compound of the present invention is excellent as an electron injecting material or an electron transporting material for an electroluminescent device. The electron injection layer mentioned here is a layer for receiving electrons from the cathode to the organic layer, and the electron transport layer is a layer for transporting the injected electrons to the light emitting layer. The electron transport layer can also serve as the electron injection layer. The material used for each layer is referred to as an electron injection material and an electron transport material.

<Description of organic EL element>
2nd invention of this application is an organic EL element containing the compound represented by Formula (1) of this invention in an electron injection layer or an electron carrying layer. The organic EL element of the present invention has a low driving voltage and high durability during driving.

Although the structure of the organic EL device of the present invention has various modes, it is basically a multilayer structure in which at least a hole transport layer, a light emitting layer, and an electron transport layer are sandwiched between an anode and a cathode. Examples of the specific configuration of the device are (1) anode / hole transport layer / light emitting layer / electron transport layer / cathode, (2) anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer. / Cathode, (3) anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode, etc.

Since the compound of the present invention has high electron injecting property and electron transporting property, it can be used for an electron injecting layer or an electron transporting layer alone or in combination with other materials. The organic EL device of the present invention emits blue, green, red and white light by combining a hole injection layer, a hole transport layer, a light emitting layer, etc. using other materials with the electron transport material of the present invention. It can also be obtained.

The light-emitting material or light-emitting dopant that can be used in the organic EL device of the present invention is daylight fluorescence as described in the Polymer Society of Japan, Polymer Functional Materials Series “Optical Functional Materials”, Joint Publication (1991), P236. Materials, fluorescent brighteners, laser dyes, organic scintillators, various fluorescent analysis reagents and other luminescent materials, supervised by Koji Koji, “Organic EL materials and displays” published by CMMC (2001) P155-156 And a light emitting material of a triplet material as described in P170 to 172.

The compounds that can be used as the light emitting material or the light emitting dopant are polycyclic aromatic compounds, heteroaromatic compounds, organometallic complexes, dyes, polymer light emitting materials, styryl derivatives, aromatic amine derivatives, coumarin derivatives, borane derivatives, oxazines. Derivatives, compounds having a spiro ring, oxadiazole derivatives, fluorene derivatives and the like. Examples of the polycyclic aromatic compound are anthracene derivatives, phenanthrene derivatives, naphthacene derivatives, pyrene derivatives, chrysene derivatives, perylene derivatives, coronene derivatives, rubrene derivatives, and the like. Examples of heteroaromatic compounds are oxadiazole derivatives having a dialkylamino group or diarylamino group, pyrazoloquinoline derivatives, pyridine derivatives, pyran derivatives, phenanthroline derivatives, silole derivatives, thiophene derivatives having a triphenylamino group, quinacridone derivatives Etc. Examples of organometallic complexes are zinc, aluminum, beryllium, europium, terbium, dysprosium, iridium, platinum, osmium, gold, etc., quinolinol derivatives, benzoxazole derivatives, benzothiazole derivatives, oxadiazole derivatives, thiadiazole derivatives, A complex with a benzimidazole derivative, a pyrrole derivative, a pyridine derivative, a phenanthroline derivative, or the like. Examples of dyes are xanthene derivatives, polymethine derivatives, porphyrin derivatives, coumarin derivatives, dicyanomethylenepyran derivatives, dicyanomethylenethiopyran derivatives, oxobenzanthracene derivatives, carbostyril derivatives, perylene derivatives, benzoxazole derivatives, benzothiazole derivatives, benzimidazoles And pigments such as derivatives. Examples of the polymer light-emitting material are polyparaphenyl vinylene derivatives, polythiophene derivatives, polyvinyl carbazole derivatives, polysilane derivatives, polyfluorene derivatives, polyparaphenylene derivatives, and the like. Examples of styryl derivatives are amine-containing styryl derivatives, styrylarylene derivatives, and the like.

Other electron transport materials used in the organic EL device of the present invention are arbitrarily selected from compounds that can be used as electron transport compounds in photoconductive materials and compounds that can be used in the electron transport layer and electron injection layer of organic EL devices. Can be used.

Specific examples of such electron transport materials include quinolinol metal complexes, 2,2′-bipyridyl derivatives, phenanthroline derivatives, diphenylquinone derivatives, perylene derivatives, oxadiazole derivatives, thiophene derivatives, triazole derivatives, thiadiazole derivatives, oxine derivatives. Metal complexes, quinoxaline derivatives, polymers of quinoxaline derivatives, benzazole compounds, gallium complexes, pyrazole derivatives, perfluorinated phenylene derivatives, triazine derivatives, pyrazine derivatives, benzoquinoline derivatives, imidazopyridine derivatives, borane derivatives, and the like.

Regarding the hole injection material and the hole transport material used in the organic EL device of the present invention, in a photoconductive material, a compound conventionally used as a charge transport material for holes or a hole injection of an organic EL device is used. Any known material used for the layer and the hole transport layer can be selected and used. Specific examples thereof are carbazole derivatives, triarylamine derivatives, phthalocyanine derivatives and the like.

Each layer constituting the organic EL element of the present invention can be formed by forming a material to constitute each layer into a thin film by a method such as a vapor deposition method, a spin coating method, or a casting method. The film thickness of each layer thus formed is not particularly limited and can be appropriately set according to the properties of the material, but is usually in the range of 2 nm to 5000 nm. Note that it is preferable to employ a vapor deposition method as a method of thinning the light emitting material from the standpoint that a homogeneous film can be easily obtained and pinholes are hardly generated. When thinning using the vapor deposition method, the vapor deposition conditions differ depending on the type of the light emitting material of the present invention. Deposition conditions generally include boat heating temperature 50 to 400 ° C., vacuum degree 10 ⁻⁶ to 10 ⁻³ Pa, deposition rate 0.01 to 50 nm / second, substrate temperature −150 to + 300 ° C., film thickness 5 nm to 5 μm. It is preferable to set appropriately within the range.

The organic EL device of the present invention is preferably supported by a substrate in any of the structures described above. The substrate only needs to have mechanical strength, thermal stability, and transparency, and glass, a transparent plastic film, and the like can be used. As the anode material, metals, alloys, electrically conductive compounds and mixtures thereof having a work function larger than 4 eV can be used. Specific examples thereof include metals such as Au, CuI, indium tin oxide (hereinafter abbreviated as ITO), SnO ₂ , ZnO, and the like.

Cathode materials can use metals, alloys, electrically conductive compounds, and mixtures thereof with work functions of less than 4 eV. Specific examples thereof are aluminum, calcium, magnesium, lithium, magnesium alloy, aluminum alloy and the like. Specific examples of the alloy include aluminum / lithium fluoride, aluminum / lithium, magnesium / silver, and magnesium / indium. In order to efficiently extract light emitted from the organic EL element, it is desirable that at least one of the electrodes has a light transmittance of 10% or more. The sheet resistance as the electrode is preferably several hundred Ω / □ or less. Although the film thickness depends on the properties of the electrode material, it is usually set in the range of 10 nm to 1 μm, preferably 10 to 400 nm. Such an electrode can be produced by forming a thin film by a method such as vapor deposition or sputtering using the electrode material described above.

Next, as an example of a method for producing an organic EL device using the light emitting material of the present invention, the organic material comprising the above-mentioned anode / hole injection layer / hole transport layer / light emitting layer / electron transport material of the present invention / cathode A method for creating an EL element will be described. A thin film of an anode material is formed on a suitable substrate by vapor deposition to produce an anode, and then a thin film of a hole injection layer and a hole transport layer is formed on the anode. A light emitting layer thin film is formed thereon. On this light emitting layer, the electron transport material of this invention is vacuum-deposited, a thin film is formed, and it is set as an electron carrying layer. Furthermore, the target organic EL element is obtained by forming the thin film which consists of a substance for cathodes by a vapor deposition method, and making it a cathode. In the production of the organic EL element described above, the production order can be reversed, and the cathode, the electron transport layer, the light emitting layer, the hole transport layer, the hole injection layer, and the anode can be produced in this order.

When a DC voltage is applied to the organic EL device thus obtained, the anode may be applied with a positive polarity and the cathode with a negative polarity. When a voltage of about 2 to 40 V is applied, a transparent or translucent electrode is applied. Luminescence can be observed from the side (anode or cathode and both). The organic EL element also emits light when an alternating voltage is applied. The alternating current waveform to be applied may be arbitrary.

Hereinafter, the present invention will be described in more detail based on examples. First, synthesis examples of the benzo [a] carbazole compounds used in the examples are described below.

[Synthesis Example 1] Synthesis of Compound (1-1-66) <Synthesis of 2-methoxy-6- (4-methoxy-2-nitrophenyl) naphthalene>

Under a nitrogen atmosphere, 13.13 g of 1-chloro-4-methoxy-2-nitrobenzene, 15.56 g of (6-methoxynaphthalen-2-yl) boronic acid, tetrakis (triphenylphosphine) palladium (0) (Pd (PPh ₃ ₄ ) 2.43 g, tripotassium phosphate 29.72 g, and 280 ml of a mixed solvent of toluene and ethanol (toluene / ethanol = 4/1 (volume ratio)) were placed in a flask and stirred for 5 minutes. Next, 28 ml of pure water was added and refluxed for 5 hours. After completion of the heating, the reaction solution was cooled, and the precipitated solid was separated by filtration to obtain a crude product 1. The filtrate was separated and the organic layer was dried over anhydrous sodium sulfate. The desiccant was removed by filtration, and the solid obtained by distilling off the solvent under reduced pressure was used as crude product 2. These crude products 1 and 2 were combined, purified with a silica gel short column (solvent: toluene), and reprecipitated with heptane to obtain intermediate compound (a-1a): 2-methoxy-6- (4 19.52 g (yield: 91%) of -methoxy-2-nitrophenyl) naphthalene was obtained.

Under a nitrogen atmosphere, 18.9 g of the compound (a-1a), 40.1 g of triphenylphosphine and 120 ml of 1-methyl-2-pyrrolidone were placed in a flask and stirred, and the mixture was refluxed for 7 hours. After completion of the heating, the reaction solution was cooled, pure water was added to the reaction mixture, and the precipitated solid was separated by filtration. The solid was washed with pure water and then with methanol to obtain a crude product. The crude product was purified by a silica gel short column (solvent: toluene) to obtain 15.7 g of intermediate compound (a-2a): 3,9-dimethoxy-11H-benzo [a] carbazole (yield: 93%). Obtained.

Under a nitrogen atmosphere, 15.5 g of compound (a-2a), 13.2 g of bromobenzene, 0.63 g of palladium (II) acetate Pd (OAc) ₂ , 1.70 g of tri (t-butyl) phosphine t-Bu ₃ P, phosphorus 35.59 g of tripotassium acid and 170 ml of xylene were placed in a flask and stirred and refluxed for 10 hours. After cooling the reaction solution and removing solids by filtration, the solvent was distilled off under reduced pressure, and the resulting crude product was purified with a silica gel column (solvent: heptane / toluene = 1/1 (volume ratio)). Intermediate compound (a-3a): 3,9-dimethoxy-11-phenyl-11H-benzo [a] carbazole 16.4 g (yield: 83%) was obtained.

Under a nitrogen atmosphere, 15.4 g of compound (a-3a) and 100.7 g of pyridine hydrochloride were placed in a flask and heated at 200 ° C. for 6 hours. After the heating, the reaction solution was cooled, and 100 ml of pure water was added. The reaction mixture was extracted with ethyl acetate, and the organic layer was dried over anhydrous sodium sulfate. The desiccant was removed by filtration, the solvent was distilled off under reduced pressure, and the resulting crude product was purified by a silica gel short column (solvent: toluene / ethyl acetate = 6/1 (volume ratio)) to obtain an intermediate compound. (A-4a): 11.2 g (yield: 100%) of 11-phenyl-11H-benzo [a] carbazole-3,9-diol was obtained.

Under a nitrogen atmosphere, 14.2 g of compound (a-4a) and 110 ml of pyridine were placed in a flask, cooled to 0 ° C., and 30.7 g of trifluoromethanesulfonic anhydride was slowly added dropwise. Thereafter, the reaction solution was stirred at 0 ° C. for 1 hour and at room temperature overnight. Pure water was added to the reaction solution, and the precipitated solid was separated by filtration. The obtained solid was purified with a silica gel short column (solvent: toluene) to obtain an intermediate compound (a-5a): 11-phenyl-11H-benzo [a] carbazole-3,9-diylbis (trifluoromethanesulfonate). -G) 25.5 g (yield: 99%) was obtained.

Under a nitrogen atmosphere, 15 g of compound (a-5a), 14.21 g of bis (pinacolato) diboron, [1.1′-bis (diphenylphosphino) ferrocene] palladium (II) dichloride dichloromethane complex (1: 1) (PdCl ₂ (Dppf) · CH ₂ Cl ₂ ) (1.25 g), potassium acetate (14.98 g), and cyclopentyl methyl ether (127 ml) were placed in a flask and stirred, and refluxed for 4 hours. After the heating, the reaction solution was cooled and 150 ml of pure water was added. The reaction mixture was extracted with ethyl acetate, the organic layer was dried over anhydrous sodium sulfate, the desiccant was removed, the solvent was distilled off under reduced pressure, and the resulting crude product was purified with a silica gel short column (solvent: toluene). did. Further, reprecipitation was performed with heptane, and intermediate compound (a-6a): 11-phenyl-3,9-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolane-2- Yl) -11H-benzo [a] carbazole (12 g, yield: 87%) was obtained.

Under a nitrogen atmosphere, 2.73 g of compound (a-6a), 2.47 g of 6-bromo-2,3′-bipyridine, 0.29 g of tetrakis (triphenylphosphine) palladium (0) (Pd (PPh ₃ ) ₄ ), Tripotassium phosphate (4.24 g) and N, N-dimethylacetamide (20 ml) were placed in a flask, stirred, and heated at 120 ° C. for 3 hours. After completion of the reaction, pure water was added to the reaction solution, the precipitated solid was filtered off, and the obtained solid was purified with a silica gel column (solvent: toluene / ethyl acetate = 2/1 (volume ratio)), and further sublimated. The purified compound (1-1-66): 3,9-di ([2,3′-bipyridin] -6-yl) -11-phenyl-11H-benzo [a] carbazole 0.5 g (Yield: 16%) was obtained. The structure of the compound (1-1-66) was confirmed by MS spectrum and NMR measurement.

¹ H-NMR (CDCl ₃ ): δ = 9.36 (s, 1H), 9.31 (s, 1H), 8.76 (s, 1H), 8.67 (t, 2H), 8.51 To 8.49 (m, 1H), 8.44 to 8.41 (m, 1H), 8.31 (d, 2H), 8.17 (d, 1H), 8.07 (d, 1H), 7.95 (s, 1H), 7.90-7.65 (m, 12H), 7.55 (d, 1H), 7.46-7.41 (m, 2H).
Glass transition temperature (Tg): 115 ° C
[Measurement equipment: Diamond DSC (manufactured by PERKIN-ELMER); Measurement conditions: Cooling rate 200 ° C / Min., Temperature rising rate 10 ° C / Min.]

Synthesis Example 2 Synthesis of Compound (1-1-758) <Compound (1-1-758): 11-Phenyl-3,9-bis (3-pyridin-3-yl) phenyl-11H-benzo [a Synthesis of carbazole>

Under a nitrogen atmosphere, 2 g of compound (a-5a), 2.01 g of 3- (3- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl) pyridine, tetrakis ( Triphenylphosphine) palladium (0) (Pd (PPh ₃ ) ₄ ) 0.20 g, tripotassium phosphate 2.89 g, and N, N-dimethylacetamide 14 ml were stirred in a flask and heated at 120 ° C. for 4 hours. did. After completion of the reaction, pure water was added to the reaction solution, the precipitated solid was filtered off, and the obtained solid was purified with a silica gel column (solvent: toluene / ethyl acetate = 2/1 (volume ratio)), and further sublimated. After purification, 0.53 g of the target compound (1-1-758): 11-phenyl-3,9-bis (3-pyridin-3-yl) phenyl-11H-benzo [a] carbazole (yield: 25%). The structure of the compound (1-1-758) was confirmed by MS spectrum and NMR measurement.

¹ H-NMR (CDCl ₃ ): δ = 8.93 (s, 1H), 8.90 (s, 1H), 8.62 (t, 2H), 8.30 to 8.26 (m, 3H) 7.96-7.89 (m, 3H), 7.83-7.80 (m, 2H), 7.75-7.47 (m, 14H), 7.40-7.37 (m, 3H).
Glass transition temperature (Tg): 99.4 ° C
[Measurement equipment: Diamond DSC (manufactured by PERKIN-ELMER); Measurement conditions: Cooling rate 200 ° C / Min., Temperature rising rate 10 ° C / Min.]

Synthesis Example 3 Synthesis of Compound (1-2-8) <Synthesis of 3-methoxy-11-phenyl-9- (pyridin-3-yl) -11H-benzo [a] carbazole>

Under a nitrogen atmosphere, 6.25 g of compound (b-3a), 2.58 g of 3-pyridineboronic acid, 0.50 g of bis (dibenzylideneacetone) palladium (0) (Pd (dba) ₂ ), tricyclohexylphosphine (PCy ₃ ) 0.37 g, potassium phosphate 7.42 g, and N, N-dimethylacetamide 70 ml were placed in a flask and stirred for 5 minutes and refluxed for 7 hours. After completion of the reaction, pure water is added to the reaction solution, the precipitated solid (crude product) is collected by filtration, and the obtained solid is purified by NH-DM1020 (Fuji Silysia Chemical Ltd.) column (solvent: toluene). Intermediate compound (b-1b): 6.17 g (yield: 88%) of 3-methoxy-11-phenyl-9- (pyridin-3-yl) -11H-benzo [a] carbazole was obtained.

Under a nitrogen atmosphere, 6.17 g of compound (b-1b) and 26.7 g of pyridine hydrochloride were placed in a flask and heated at 200 ° C. for 7 hours. After the heating, the reaction solution was cooled, 100 ml of pure water was added, and the precipitated solid was collected by filtration to obtain a crude product. The crude product was purified with a silica gel short column (solvent: toluene), and the intermediate compound (b-2b): 11-phenyl-9- (pyridin-3-yl) -11H-benzo [a] carbazole-3- 5.4 g (yield: 90.8%) of ol was obtained.

Under a nitrogen atmosphere, 5.4 g of compound (b-2b) and 56 ml of pyridine were placed in a flask, cooled to 0 ° C., and 7.89 g of trifluoromethanesulfonic anhydride was slowly added dropwise. Thereafter, the reaction solution was stirred at 0 ° C. for 1 hour and at room temperature for 2 hours. Pure water was added to the reaction solution, followed by extraction with ethyl acetate, and the organic layer was dried over anhydrous sodium sulfate. The desiccant was removed by filtration, the solvent was distilled off under reduced pressure, and the resulting crude product was purified by a silica gel column (solvent: toluene / ethyl acetate = 2/1 (volume ratio)) to obtain an intermediate compound ( b-3b): 11.65 g (yield: 91.8%) of 11-phenyl-9- (pyridin-3-yl) -11H-benzo [a] carbazol-3-yl trifluoromethanesulfonate It was.

Under a nitrogen atmosphere, 2.2 g of compound (b-3b), 0.80 g of 2-naphthaleneboronic acid, 0.15 g of tetrakis (triphenylphosphine) palladium (0) (Pd (PPh ₃ ) ₄ ), tripotassium phosphate 1 .80 g and 21 ml of a mixed solvent of toluene and ethanol (toluene / ethanol = 4/1 (volume ratio)) were placed in a flask and stirred for 5 minutes. Thereafter, 2 ml of pure water was added and refluxed for 5 hours. The reaction liquid was cooled after completion | finish of a heating, the pure solid was added and the depositing solid was filtered, and it was set as the crude product 1. The organic layer of the filtrate was separated and dried over anhydrous sodium sulfate. The desiccant was removed by filtration, and the solvent was distilled off under reduced pressure to obtain a crude product 2. Next, the crude products 1 and 2 were combined and purified by a silica gel column (solvent: toluene / ethyl acetate = 10/1 (volume ratio)). Thereafter, the product is recrystallized from toluene and further purified by sublimation to obtain the target compound (1-2-8): 3-([naphthalen-2-yl) -11-phenyl-9- (pyridin-3-yl). ) -11H-benzo [a] carbazole 0.8 g (yield: 38%) was obtained. The structure of the compound (1-2-8) was confirmed by MS spectrum and NMR measurement.

¹ H-NMR (CDCl ₃ ): δ = 8.89 (d, 1H), 8.57 (d, 1H), 8.34 (s, 1H), 8.30 to 8.28 (dd, 2H) 8.15 (s, 1H), 7.95-7.84 (m, 6H), 7.73-7.48 (m, 10H), 7.35-7.33 (m, 2H).
Glass transition temperature (Tg): 98.2 ° C
[Measurement equipment: Diamond DSC (manufactured by PERKIN-ELMER); Measurement conditions: Cooling rate 200 ° C / Min., Temperature rising rate 10 ° C / Min.]

Synthesis Example 4 Synthesis of Compound (1-228) <Compound (1-228): 3- (4- (Naphthalen-2-yl) phenyl) -11-phenyl-9- (pyridine-3 -Yl) -11H-benzo [a] carbazole synthesis>

Under a nitrogen atmosphere, 2.2 g of compound (b-3b), 1.16 g of 4- (naphthalen-2-yl) phenyl) boronic acid, tetrakis (triphenylphosphine) palladium (0) (Pd (PPh ₃ ) ₄ ) 0 .15 g, 1.80 g of tripotassium phosphate and 21 ml of a mixed solvent of toluene and ethanol (toluene / ethanol = 4/1 (volume ratio)) were placed in a flask and stirred for 5 minutes. Thereafter, 2 ml of pure water was added and refluxed for 5 hours. After completion of the heating, the reaction solution was cooled and pure water was added. The precipitated solid was collected by filtration, washed with pure water and then with methanol, dissolved in heated toluene, and the insoluble matter was removed by hot filtration. . Further, after purification with a silica gel column (solvent: toluene / ethyl acetate = 3/1 (volume ratio)), it was decolorized by treatment with activated carbon in a hot toluene solution. Thereafter, reprecipitation is performed with ethyl acetate, and further purification by sublimation is performed to obtain the target compound (1-2-28): 3- (4- (naphthalen-2-yl) phenyl) -11-phenyl-9- 1.2 g (yield: 50%) of (pyridin-3-yl) -11H-benzo [a] carbazole was obtained. The structure of the compound (1-2-28) was confirmed by MS spectrum and NMR measurement.

¹ H-NMR (CDCl ₃ ): δ = 8.89 (d, 1H), 8.57 (dd, 1H), 8.30-8.28 (m, 3H), 8.11 (s, 1H) 7.95 to 7.80 (m, 10H), 7.74 to 7.70 (m, 3H), 7.64 to 7.58 (m, 4H), 7.54 to 7.48 (m, 3H), 7.36-7.33 (m, 2H).
A glass transition temperature (Tg) was not observed.

Synthesis Example 5 Synthesis of Compound (1-3-206) <Synthesis of 2- (4-Chloro-2-nitrophenyl) -6-methoxynaphthalene>

Under a nitrogen atmosphere, 11.35 g of 1-bromo-4-chloro-2-nitrobenzene, 9.7 g of (6-methoxynaphthalen-2-yl) boronic acid, tetrakis (triphenylphosphine) palladium (0) (Pd (PPh ₃ ₄ ) 1.66 g, 10.18 g of sodium carbonate, and 197 ml of toluene were put in a flask and stirred for 5 minutes, and then 38 ml of pure water was added and refluxed for 5 hours. After completion of the heating, the reaction solution was cooled and the precipitated solid was filtered off to obtain crude product 1. The organic layer of the filtrate was separated and dried over anhydrous sodium sulfate, the desiccant was removed by filtration, and the solvent was distilled off under reduced pressure to obtain the solid product 2. Thereafter, the crude products 1 and 2 were combined and purified with a silica gel short column (solvent: toluene). Further, reprecipitation was performed with heptane to obtain 12.9 g of intermediate compound (b-1a): 2- (4-chloro-2-nitrophenyl) -6-methoxynaphthalene (yield: 85.7%). It was.

Under a nitrogen atmosphere, 12.9 g of the compound (b-1a), 26.96 g of triphenylphosphine and 82 ml of o-dichlorobenzene were placed in a flask and stirred, and refluxed for 7.5 hours. After heating, the reaction solution was cooled and the precipitated solid was filtered to obtain a crude product. The crude product was purified by a silica gel column (solvent: toluene), and the intermediate compound (b-2a): 9-chloro-3-methoxy-11H-benzo [a] carbazole 10.3 g (yield: 89%) Got.

Under a nitrogen atmosphere, compound (b-2a) 10.25 g, bromobenzene 8.57 g, palladium (II) acetate (Pd (OAc) ₂ ) 0.327 g, tri (t-butyl) phosphine (t-Bu ₃ P) 0.88 g, 30.89 g of tripotassium phosphate, and 110 ml of xylene were placed in a flask and stirred, and refluxed for 6 hours. The reaction mixture was cooled and filtered to remove the solid, and then the filtrate was concentrated under reduced pressure. The resulting crude product was purified by a silica gel short column (solvent: toluene) to obtain an intermediate compound (b-3a): 12.2 g (yield: 93.8%) of 9-chloro-3-methoxy-11-phenyl-11H-benzo [a] carbazole was obtained.

Under a nitrogen atmosphere, 5.19 g of compound (b-3a), 3.45 g of 3-biphenylboronic acid, 0.42 g of bis (dibenzylideneacetone) palladium (0) (Pd (dba) ₂ ), tricyclohexylphosphine (PCy ₃ ) 0.30 g, tripotassium phosphate 6.16 g, and toluene 58 ml were placed in a flask and stirred for 5 minutes. Thereafter, 5.8 ml of pure water was added and refluxed for 7 hours. After completion of the reaction, the reaction solution was cooled and 50 ml of pure water was added. The reaction solution was extracted with toluene, and the organic layer was dried over anhydrous sodium sulfate. Then, the desiccant was removed by filtration, and the solvent was distilled off under reduced pressure. 3/1 (volume ratio)) to give intermediate compound (b-4a): 9-([1,1′-biphenyl] -3-yl) -3-methoxy-11-phenyl-11H- 6.66 g (yield: 97%) of benzo [a] carbazole was obtained.

Under a nitrogen atmosphere, 6.51 g of compound (b-4a) and 23.7 g of pyridine hydrochloride were placed in a flask and heated at 200 ° C. for 6 hours. After heating, the reaction solution was cooled, 100 ml of pure water was added, and the precipitated solid was collected by filtration to obtain a crude product. The crude product was purified by a silica gel short column (solvent: toluene), and the intermediate compound (b-5a): 9-([1,1′-biphenyl] -3-yl) -11-phenyl-11H-benzo [A] 6.32 g (yield: 100%) of carbazol-3-ol was obtained.

Under a nitrogen atmosphere, 6.32 g of compound (b-5a) and 35 ml of pyridine were placed in a flask, cooled to 0 ° C., and then 7.73 g of trifluoromethanesulfonic anhydride was slowly added dropwise. Thereafter, the reaction solution was stirred at 0 ° C. for 1 hour and at room temperature for 2 hours. After adding pure water to the reaction solution, the reaction mixture was extracted with toluene, and the organic layer was dried over anhydrous sodium sulfate. The desiccant was removed by filtration, and the crude product obtained by distilling off the solvent under reduced pressure was purified with a silica gel short column (solvent: toluene) to obtain an intermediate compound (b-6a): 9-([1 , 1′-biphenyl] -3-yl) -11-phenyl-11H-benzo [a] carbazol-3-yl trifluoromethanesulfonate (yield: 91%) was obtained.

<9-([1,1′-biphenyl] -3-yl) -11-phenyl-3- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -11H -Synthesis of Benzo [a] carbazole>

Under a nitrogen atmosphere, compound (b-6a) 5.2 g, bis (pinacolado) diborane 2.7 g, [1.1′-bis (diphenylphosphino) ferrocene] palladium (II) dichlorodichloromethane complex (1: 1) 0.21 g of (PdCl ₂ (dppf) · CH ₂ Cl ₂ ), 2.58 g of potassium acetate, and 45 ml of cyclopentyl methyl ether were placed in a flask and stirred, and refluxed for 4 hours. After completion of heating, the reaction solution was cooled and 150 ml of pure water was added. The reaction mixture was extracted with ethyl acetate, and the organic layer was dried over anhydrous sodium sulfate. The desiccant was removed by filtration, and the crude product obtained by distilling off the solvent under reduced pressure was purified with an activated carbon short column (solvent: toluene) to obtain an intermediate compound (b-7a): 9-([1, 1′-biphenyl] -3-yl) -11-phenyl-3- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -11H-benzo [a] carbazole 4 0.53 g (yield: 90.6%) was obtained.

Under a nitrogen atmosphere, 1.94 g of compound (b-7a), 0.88 g of 6-bromo-2,3′-bipyridine, 0.16 g of tetrakis (triphenylphosphine) palladium (0) (Pd (PPh ₃ ) ₄ ), 1.44 g of tripotassium phosphate and 14 ml of N, N-dimethylacetamide were placed in a flask and stirred and heated at 120 ° C. for 6 hours. After completion of the reaction, pure water was added to the reaction solution, and the precipitated solid (crude product) was collected by filtration. The obtained solid was purified with a silica gel column (solvent: toluene / ethyl acetate = 10/1 (volume ratio)), and further purified by sublimation to obtain the target compound (1-3-206): 9-([ 1,1′-biphenyl] -3-yl) -3-([2,3′-bipyridin] -6-yl) -11-phenyl-11H-benzo [a] carbazole 0.89 g (yield: 44% ) The structure of the compound (1-3-206) was confirmed by MS spectrum and NMR measurement.

¹ H-NMR (CDCl ₃ ): δ = 9.36 (s, 1H), 8.76 (s, 1H), 8.69 (dd, 1H), 8.50 (dt, 1H), 8.31 To 8.27 (q, 2H), 8.07 (dd, 1H), 7.90 to 7.88 (m, 3H), 7.83 (s, 1H), 7.73 to 7.35 (m) , 18H).
Glass transition temperature (Tg): 107.4 ° C
[Measurement equipment: Diamond DSC (manufactured by PERKIN-ELMER); Measurement conditions: Cooling rate 200 ° C / Min., Temperature rising rate 10 ° C / Min.]

[Synthesis Example 6] Synthesis of Compound (1-3-300) <Compound (1-3-300): 9-([1,1′-biphenyl] -3-yl) -11-phenyl-3- (3 Synthesis of — (pyridin-3-yl) phenyl) -11H-benzo [a] carbazole>

Under a nitrogen atmosphere, 2 g of compound (b-6a), 0.95 g of 3- (3- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl) pyridine, tetrakis ( Triphenylphosphine) palladium (0) (Pd (PPh ₃ ) ₄ ) 0.12 g, tripotassium phosphate 1.43 g, and N, N-dimethylacetamide 15 ml were stirred in a flask and heated at 120 ° C. for 4 hours. did. After completion of the reaction, pure water was added to the reaction solution, extracted with toluene, and the organic layer was dried over anhydrous sodium sulfate. The crude product obtained by removing the desiccant by filtration and distilling off the solvent under reduced pressure was purified with a silica gel column (solvent: toluene / ethyl acetate = 10/1 (volume ratio)), and further purified by sublimation. The target compound (1-3-300): 9-([1,1′-biphenyl] -3-yl) -11-phenyl-3- (3- (pyridin-3-yl) phenyl) -11H -1.29 g (yield: 64%) of benzo [a] carbazole was obtained. The structure of the compound (1-3-300) was confirmed by MS spectrum and NMR measurement.

¹ H-NMR (CDCl ₃ ): δ = 8.94 (s, 1H), 8.64 (dd, 1H), 8.31 to 8.26 (m, 3H), 7.95 (dt, 1H) 7.90 (s, 1H), 7.83 to 7.82 (m, 2H), 7.76 to 7.39 (m, 21H).
Glass transition temperature (Tg): 99.6 ° C.
[Measurement equipment: Diamond DSC (manufactured by PERKIN-ELMER); Measurement conditions: Cooling rate 200 ° C / Min., Temperature rising rate 10 ° C / Min.]

Synthesis Example 7 Synthesis of Compound (1-1-2) <Compound (1-1-2): 11-Phenyl-3,9-di (pyridin-3-yl) -11H-benzo [a] carbazole Synthesis>

Under nitrogen atmosphere, compound (a-5a) 2.95 g, 3-pyridineboronic acid 1.23 g, bis (dibenzylideneacetone) palladium (0) (Pd (dba) ₂ ) 0.14 g, tricyclohexylphosphine (PCy ₃ ) 0.11 g, tripotassium phosphate 4.25 g, and N, N-dimethylacetamide 25 ml were placed in a flask, stirred for 5 minutes, and heated at 120 ° C. for 5 hours. After completion of the reaction, pure water was added to the reaction solution, and the precipitated solid was separated by filtration. The obtained solid was purified with a silica gel column (solvent: toluene / ethyl acetate = 2/1 (volume ratio)), and further reprecipitated with heptane. Finally, purification by sublimation was performed to obtain the target compound (1-1-2): 11-phenyl-3,9-di (pyridin-3-yl) -11H-benzo [a] carbazole 0.90 g (yield) : 40%). The structure of the compound (1-1-2) was confirmed by MS spectrum and NMR measurement.

¹ H-NMR (CDCl ₃ ): δ = 8.96 (s, 1H), 8.88 (s, 1H), 8.61 (dd, 1H), 8.58 (dd, 1H), 8.30 (Dd, 2H), 8.21 (s, 1H), 7.97 (dt, 1H), 7.91 (dt, 1H), 7.83 (d, 1H), 7.74-7.70 ( m, 3H), 7.62 to 7.58 (m, 3H), 7.52 to 7.47 (m, 2H), 7.40 to 7.33 (m, 3H).
Glass transition temperature (Tg): 91.2 ° C
[Measurement equipment: Diamond DSC (manufactured by PERKIN-ELMER); Measurement conditions: Cooling rate 200 ° C / Min., Temperature rising rate 10 ° C / Min.]

[Synthesis Example 8] Synthesis of Compound (1-1-765) <Compound (1-1-765): 11-Phenyl-3,9-bis (4- (pyridin-4-yl) phenyl) -11H-benzo [A] Synthesis of carbazole>

Under nitrogen atmosphere, compound (a-6a) 2.5 g, 4- (4-bromophenyl) pyridine 2.15 g, tetrakis (triphenylphosphine) palladium (0) (Pd (PPh ₃ ) ₄ ) 0.26 g, phosphorus 3.89 g of tripotassium acid and 20 ml of N, N-dimethylacetamide were placed in a flask, stirred and heated at 120 ° C. for 6 hours. After completion of the reaction, pure water was added to the reaction solution, and the precipitated solid was separated by filtration. The obtained solid was purified with an NH-DM1020 (Fuji Silysia Chemical Ltd.) column (solvent: toluene), and further reprecipitated with ethyl acetate. Finally, purification by sublimation gave the target compound (1-1-765): 11-phenyl-3,9-bis (4- (pyridin-4-yl) phenyl) -11H-benzo [a] carbazole 1 0.4 g (yield: 49.6%) was obtained. The structure of the compound (1-1-765) was confirmed by MS spectrum and NMR measurement.

¹ H-NMR (CDCl ₃ ): δ = 8.69 to 8.67 (m, 4H), 8.31 to 8.27 (m, 3H), 7.84 to 7.62 (m, 15H), 7.58-7.48 (m, 6H), 7.41 (s, 1H).

Synthesis Example 9 Synthesis of Compound (1-1-893) <Compound (1-1-893): 3,9-bis (5′-methyl- [2,3′-bipyridin] -6-yl)- Synthesis of 11-phenyl-11H-benzo [a] carbazole>

In a nitrogen atmosphere, 2.5 g of compound (a-6a), 2.51 g of 6-bromo-5′-methyl-2,3′-bipyridine, tetrakis (triphenylphosphine) palladium (0) (Pd (PPh ₃ ) ₄ ) 0.32 g, tripotassium phosphate 3.89 g and N, N-dimethylacetamide 25 ml were stirred in a flask and heated at 120 ° C. for 6 hours. After completion of the reaction, pure water was added to the reaction solution, and the precipitated solid was separated by filtration. The obtained solid was purified with an NH-DM1020 (Fuji Silysia Chemical Ltd.) column (solvent: toluene / ethyl acetate = 8/1 (volume ratio)), and further reprecipitated with ethyl acetate. Finally, by sublimation purification, the target compound (1-1-893): 3,9-bis (5′-methyl- [2,3′-bipyridin] -6-yl) -11-phenyl-11H -1.6 g (yield: 56%) of benzo [a] carbazole was obtained. The structure of the compound (1-1-893) was confirmed by MS spectrum and NMR measurement.

¹ H-NMR (CDCl ₃ ): δ = 8.56 (t, 2H), 8.30 to 8.26 (m, 3H), 7.82 to 7.81 (m, 3H), 7.75 to 7.62 (m, 11H), 7.56 to 7.41 (m, 4H), 7.36 (dd, 2H), 2.65 (s, 6H).
Glass transition temperature (Tg): 114.0 ° C
[Measurement equipment: Diamond DSC (manufactured by PERKIN-ELMER); Measurement conditions: Cooling rate 200 ° C / Min., Temperature rising rate 10 ° C / Min.]

[Synthesis Example 10] Synthesis of Compound (1-1-973) <Compound (1-1-973): 3,9-bis (4- (2-methylpyridin-4-yl) phenyl) -11-phenyl- Synthesis of 11H-benzo [a] carbazole>

Under a nitrogen atmosphere, compound (a-6a) 2.5 g, 4- (4-chlorophenyl) -2-methylpyridine 2.1 g, bis (dibenzylideneacetone) palladium (0) (Pd (dba) ₂ ) 0.16 g , 0.12 g of tricyclohexylphosphine (PCy ₃ ), 4.0 g of tripotassium phosphate, 25 ml of 1,2,4-trimethylbenzene, 2.5 ml of t-butyl alcohol and 2.5 ml of water were refluxed for 6 hours. did. After completion of the reaction, pure water was added to the reaction solution, and the precipitated solid was separated by filtration. The obtained solid was purified with an NH-DM1020 (Fuji Silysia Chemical Ltd.) column (solvent: toluene / ethyl acetate = 10/1 (volume ratio)), and reprecipitated with ethyl acetate. Finally, sublimation purification was performed to obtain the target compound (1-1-973): 3,9-bis (4- (2-methylpyridin-4-yl) phenyl) -11-phenyl-11H-benzo [a Thus, 1.8 g (yield: 60%) of carbazole was obtained. The structure of the compound (1-1-973) was confirmed by MS spectrum and NMR measurement.

¹ H-NMR (CDCl ₃ ): δ = 9.14 (s, 1H), 9.09 (s, 1H), 8.75 (s, 1H), 8.51 (dd, 2H), 8.32 To 8.26 (m, 4H), 8.15 (dd, 1H), 8.07 (dd, 1H), 8.01 (s, 1H), 7.90 to 7.66 (m, 14H), 7.57 (d, 1H), 2.48 (s, 3H), 2.45 (s, 3H).
Glass transition temperature (Tg): 116.2 ° C
[Measurement equipment: Diamond DSC (manufactured by PERKIN-ELMER); Measurement conditions: Cooling rate 200 ° C / Min., Temperature rising rate 10 ° C / Min.]

Compound (b-3b) 2.2 g, 10-phenylanthracen-9-yl) boronic acid 1.64 g, tetrakis (triphenylphosphine) palladium (0) (Pd (PPh ₃ ) ₄ ) 0.15 g under nitrogen atmosphere Then, 1.80 g of tripotassium phosphate and 21 ml of a mixed solvent of toluene and ethanol (toluene / ethanol = 4/1 (volume ratio)) were placed in a flask and stirred for 5 minutes. Thereafter, 2 ml of pure water was added and refluxed for 5 hours. After the heating, the reaction solution was cooled, pure water was added and the precipitated solid was collected by filtration. The obtained solid was purified with a silica gel column (solvent: toluene / ethyl acetate = 4/1 (volume ratio)), and reprecipitated with ethyl acetate. Finally, by sublimation purification, the target compound (1-2-125): 11-phenyl-3- (10-phenylanthracen-9-yl) -9- (pyridin-3-yl) -11H-benzo [A] 0.81 g (yield: 31%) of carbazole was obtained. The structure of the compound (1-2-125) was confirmed by MS spectrum and NMR measurement.

¹ H-NMR (CDCl ₃ ): δ = 8.92 (s, 1H), 8.59 (dd, 1H), 8.35 (d, 2H), 8.13 (s, 1H), 7.93 (Dt, 1H), 7.81 (d, 1H), 7.76-7.49 (m, 16H), 7.39-7.29 (m, 7H).
Glass transition temperature (Tg): 179.6 ° C.
[Measurement equipment: Diamond DSC (manufactured by PERKIN-ELMER); Measurement conditions: Cooling rate 200 ° C / Min., Temperature rising rate 10 ° C / Min.]

By appropriately selecting the starting compounds, other compounds of the present invention can be synthesized by a method according to the above synthesis example.

Hereinafter, in order to describe the present invention in more detail, examples of the organic EL device using the compound of the present invention are shown, but the present invention is not limited thereto.

Organic EL devices according to Examples 1 to 3 and Comparative Examples 1 to 3 were prepared, and the voltage (V), which is a characteristic at 1000 cd / m ² emission, was measured, the EL emission wavelength (nm), the external quantum efficiency (% ), And then the luminance half time (time) when driven at a constant current at a current density at which a luminance of 2000 cd / m ² was obtained was measured. Hereinafter, examples and comparative examples will be described in detail.

Note that the quantum efficiency of a light-emitting element includes an internal quantum efficiency and an external quantum efficiency. The ratio of external energy injected as electrons (or holes) into the light-emitting layer of the light-emitting element is converted into photons purely. What is shown is the internal quantum efficiency. On the other hand, the external quantum efficiency is calculated based on the amount of photons emitted to the outside of the light emitting element, and some of the photons generated in the light emitting layer are absorbed inside the light emitting element. The external quantum efficiency is lower than the internal quantum efficiency because it is continuously reflected and is not emitted outside the light emitting element.

The external quantum efficiency is measured as follows. Using a voltage / current generator R6144 manufactured by Advantest, a current was applied so that the luminance of the device was 1000 cd / m ² , and the device was caused to emit light. Using a spectral radiance meter SR-3AR manufactured by TOPCON, the spectral radiance in the visible light region was measured from the direction perpendicular to the light emitting surface. Assuming that the light emitting surface is a completely diffusing surface, the value obtained by dividing the measured spectral radiance value of each wavelength component by the wavelength energy and multiplying by π is the number of photons at each wavelength. Next, the number of photons in the entire wavelength region observed was integrated to obtain the total number of photons emitted from the device. The value obtained by dividing the applied current value by the elementary charge is the number of carriers injected into the device, and the number obtained by dividing the total number of photons emitted from the device by the number of carriers injected into the device is the external quantum efficiency.

Table 1 below shows the material configuration of each layer in the manufactured organic EL elements according to Examples 1 to 3 and Comparative Examples 1 to 3.

In Table 1, “HI” refers to N ⁴ , N ^{4 ′} -diphenyl-N ⁴ , N ^{4 ′} -bis (9-phenyl-9H-carbazol-3-yl)-[1,1′-biphenyl] -4, 4′-diamine, “HT” is N ⁴ , N ⁴ , N ^{4 ′} , N ^{4 ′} -tetra [1,1′-biphenyl] -4-yl)-[1,1′-biphenyl] -4,4 '-Diamine, “BH1” is 9- (4- (naphthalen-1-yl) phenyl) -10-phenylanthracene, “BH2” is 9-phenyl-10- (4-phenylnaphthalen-1-yl) anthracene, “BD1” 4,4 ′-((7,7-diphenyl-7H-benzo [c] fluorene-5,9-diyl) bis (phenylazanezyl)) dibenzonitrile, “BD2” is 7,7, − dimethyl ^-N 5, ^{N 9} - diphenyl ^-N 5, ^{N 9} - Bis (4- (trimethylsilanyl) phenyl) -7H-benzo [c] fluorene-5,9-diamine, “ET1” is 5,9-di ([bipyridin] -6-yl) -7-phenyl-7H -Benzo [c] carbazole, “ET2” is 2- (4- (9,10-di (naphthalen-2-yl) anthracen-2-yl) phenyl) -1-phenyl-1H-benzo [d] imidazole is there. The chemical structure is shown below together with quinolinol lithium “Liq”.

[Example 1] A glass substrate (26 mm x 28 mm x 0.7 mm) obtained by polishing ITO having a thickness of 180 nm by element sputtering using the compound (1-1-66) as an electron transport layer to 150 nm (( Opt Science Co., Ltd.) was used as a transparent support substrate. This transparent support substrate is fixed to a substrate holder of a commercially available vapor deposition apparatus (made by Showa Vacuum Co., Ltd.), a molybdenum vapor deposition boat containing HI, a molybdenum vapor deposition boat containing HT, and a molybdenum vapor vessel containing BH1. Vapor deposition boat, molybdenum vapor deposition boat containing BD1, molybdenum vapor deposition boat containing compound (1-1-66) of the present invention, molybdenum vapor deposition boat containing quinolinol lithium (Liq), and aluminum A tungsten vapor deposition boat was installed.

The following layers were sequentially formed on the ITO film of the transparent support substrate. The vacuum chamber was depressurized to 5 × 10 ⁻⁴ Pa, first, the vapor deposition boat containing HI was heated to deposit to a film thickness of 40 nm to form a hole injection layer, and then HT entered. The vapor deposition boat was heated and vapor-deposited to a film thickness of 25 nm to form a hole transport layer. Next, the vapor deposition boat containing BH1 and the vapor deposition boat containing BD1 were heated at the same time to form a light emitting layer by vapor deposition to a film thickness of 25 nm. The deposition rate was adjusted so that the weight ratio of BH1 to BD1 was approximately 95: 5. Next, an evaporation boat containing the compound (1-1-66) and an evaporation boat containing Liq were simultaneously heated to evaporate to a thickness of 20 nm to form an electron transport layer. The deposition rate was adjusted so that the weight ratio of the compound (1-1-66) and Liq was approximately 1: 1. The deposition rate of each layer was 0.01 to 1 nm / second.

Thereafter, the evaporation boat containing Liq was heated to deposit at a deposition rate of 0.01 to 0.1 nm / second so as to have a film thickness of 1 nm. Next, a vapor deposition boat containing aluminum was heated, and aluminum was deposited at a deposition rate of 0.01 to 2 nm / second so as to have a film thickness of 100 nm to form a cathode, thereby obtaining an organic EL device.

Using the ITO electrode as the anode and the Liq / aluminum electrode as the cathode, the characteristics at 1000 cd / m ² emission were measured. It was. Further, as a result of conducting a constant current driving test with a current density for obtaining an initial luminance of 2000 cd / m ² , the time for maintaining the luminance of 77% (1540 cd / m ² ) or more of the initial value was 321 hours.

[Comparative Example 1]
An organic EL device was obtained in the same manner as in Example 1 except that the compound (1-1-66) in the electron transport layer was changed to the compound (ET1). Using the ITO electrode as the anode and the quinolinol lithium / aluminum electrode as the cathode, the characteristics at 1000 cd / m ² emission were measured. The drive voltage was 5.5 V and the external quantum efficiency was 3.2% (blue emission with a wavelength of about 451 nm). there were. Further, as a result of conducting a constant current driving test with a current density for obtaining an initial luminance of 2000 cd / m ² , the time for maintaining the luminance of 77% (1540 cd / m ² ) or more of the initial value was 63 hours.

[Example 2] The compound (BH1), which is the host material of the device light emitting layer using the compound (1-1-758) for the electron transport layer, is replaced with the compound (BH2), and the compound (BD1) which is the dopant material of the light emitting layer ) Was replaced with compound (BD2), and compound (1-1-66), which was an electron transport material for the electron transport layer, was replaced with compound (1-1-758). An organic EL device was obtained. Using the ITO electrode as the anode and the quinolinol lithium / aluminum electrode as the cathode, the characteristics at 1000 cd / m ² emission were measured. The drive voltage was 5.8 V and the external quantum efficiency was 5.1% (blue emission with a wavelength of about 455 nm). there were. Further, as a result of conducting a constant current driving test with a current density for obtaining an initial luminance of 2000 cd / m ² , the time for maintaining the luminance of 77% (1540 cd / m ² ) or more of the initial value was 170 hours.

[Example 3] Device using compound (1-1-66) as an electron transport layer The same transparent support substrate as used in Example 1 was used as a substrate holder of a commercially available vapor deposition apparatus (manufactured by Showa Vacuum Co., Ltd.). Molybdenum deposition boat with HI and fixed, molybdenum deposition boat with HT, molybdenum deposition boat with BH1, molybdenum deposition boat with BD1, compound of the present invention (1- A molybdenum vapor deposition boat containing 1-66), a molybdenum vapor deposition boat containing Liq, and a tungsten vapor deposition boat containing aluminum were mounted.

The following layers were sequentially formed on the ITO film of the transparent support substrate. The vacuum chamber was depressurized to 5 × 10 ⁻⁴ Pa, and first, a vapor deposition boat containing HI was heated to deposit to a film thickness of 40 nm to form a hole injection layer, and then HT entered. The vapor deposition boat was heated and vapor-deposited to a film thickness of 25 nm to form a hole transport layer. Next, the vapor deposition boat containing BH1 and the vapor deposition boat containing BD1 were heated at the same time to form a light emitting layer by vapor deposition to a film thickness of 25 nm. The deposition rate was adjusted so that the weight ratio of BH1 to BD1 was approximately 95: 5. Next, the vapor deposition boat containing the compound (1-1-66) was heated and vapor-deposited to a film thickness of 20 nm to form an electron transport layer. The deposition rate of each layer was 0.01 to 1 nm / second.

Using the ITO electrode as the anode and the Liq / aluminum electrode as the cathode, the characteristics at 1000 cd / m ² emission were measured. The drive voltage was 3.7 V and the external quantum efficiency was 4.5% (blue emission with a wavelength of about 451 nm). It was. In addition, as a result of conducting a constant current driving test with a current density for obtaining an initial luminance of 2000 cd / m ² , the time for maintaining the luminance of 77% (1540 cd / m ² ) or more of the initial value was 345 hours.

[Comparative Example 2]
An organic EL device was obtained in the same manner as in Example 3, except that the compound (1-1-66), which was the electron transport material for the electron transport layer, was changed to the compound (ET1). Using the ITO electrode as the anode and the quinolinol lithium / aluminum electrode as the cathode, the characteristics at 1000 cd / m ² emission were measured. there were. In addition, as a result of conducting a constant current driving test with a current density for obtaining an initial luminance of 2000 cd / m ² , the time for maintaining the luminance of 77% (1540 cd / m ² ) or more of the initial value was 0.5 hours. It was.

[Comparative Example 3]
An organic EL device was obtained in the same manner as in Example 3 except that the compound (1-1-66), which was the electron transport material for the electron transport layer, was changed to the compound (ET2). Using the ITO electrode as the anode and the quinolinol lithium / aluminum electrode as the cathode, measuring the characteristics at 1000 cd / m ² emission, the drive voltage is 5.4 V, the external quantum efficiency is 2.2% (blue emission with a wavelength of about 453 nm) there were. Further, as a result of conducting a constant current driving test with a current density for obtaining an initial luminance of 2000 cd / m ² , the time for maintaining the luminance of 77% (1540 cd / m ² ) or more of the initial value was 22 hours.

The above results are summarized in Table 2.

Table 3 below shows the material configuration of each layer in the manufactured organic EL elements according to Examples 4 to 8 and Comparative Examples 4 to 7.

In Table 3, “HI2” is 1,4,5,8,9,12-hexaazatriphenylene-2,3,6,7,10,11-hexacarbonitrile, “ET3” is 5,9-di ( [2,3′-bipyridin] -6-yl) -7-phenyl-7H-benzo [c] carbazole, “ET4” is 3- (6- (10-phenylanthracen-9-yl) naphthalen-2-yl ) Pyridine, “ET5” is 2-([1,1′-biphenyl] -3-yl) -7-([2,3′-bipyridin] -6-yl) -9-phenyl-9H-carbazole, “ “ET6” is 9-phenyl-2,7-bis (4- (pyridin-4-yl) naphthalen-1-yl) -9H-carbazole. The chemical structure is shown below.

[Example 4] A glass substrate (26 mm x 28 mm x 0.7 mm) obtained by polishing ITO having a thickness of 180 nm by element sputtering using the compound (1-1-66) as an electron transport layer to 150 nm (( Opt Science Co., Ltd.) was used as a transparent support substrate. This transparent support substrate is fixed to a substrate holder of a commercially available vapor deposition apparatus (manufactured by Showa Vacuum Co., Ltd.), a molybdenum vapor deposition boat containing HI, a molybdenum vapor deposition boat containing HI2, and a molybdenum vapor containing HT. Vapor deposition boat, molybdenum vapor deposition boat with BH2, molybdenum vapor deposition boat with BD2, molybdenum vapor deposition boat with compound (1-1-66) of the present invention, molybdenum with Liq A vapor deposition boat and a tungsten vapor deposition boat containing aluminum were mounted.

The following layers were sequentially formed on the ITO film of the transparent support substrate. The vacuum chamber is depressurized to 5 × 10 ⁻⁴ Pa, and first, a vapor deposition boat containing HI is heated and vapor-deposited to a film thickness of 40 nm to form a first hole injection layer. Is heated to a thickness of 5 nm to form a second hole injection layer, and then the evaporation boat containing HT is heated to a thickness of 25 nm. Thus, a hole transport layer was formed by vapor deposition. Next, the vapor deposition boat containing BH2 and the vapor deposition boat containing BD2 were heated at the same time to form a light emitting layer by vapor deposition to a film thickness of 20 nm. The deposition rate was adjusted so that the weight ratio of BH2 to BD2 was approximately 95: 5. Next, the vapor deposition boat containing the compound (1-1-66) and the vapor deposition boat containing Liq were heated at the same time so as to have a film thickness of 30 nm to form an electron transport layer. The deposition rate was adjusted so that the weight ratio of the compound (1-1-66) and Liq was approximately 1: 1. The deposition rate of each layer was 0.01 to 1 nm / second.

Using the ITO electrode as the anode and the Liq / aluminum electrode as the cathode, the characteristics at 1000 cd / m ² emission were measured. The drive voltage was 3.8 V and the external quantum efficiency was 5.1% (blue emission with a wavelength of about 454 nm). It was. Further, as a result of conducting a constant current driving test with a current density for obtaining an initial luminance of 2000 cd / m ² , the time for maintaining the luminance of 80% (1600 cd / m ² ) or more of the initial value was 396 hours.

[Comparative Example 4]
An organic EL device was obtained in the same manner as in Example 4 except that the compound (1-1-66) in the electron transport layer was changed to the compound (ET3). Using the ITO electrode as the anode and the Liq / aluminum electrode as the cathode, the characteristics at 1000 cd / m ² emission were measured. The drive voltage was 4.0 V and the external quantum efficiency was 4.6% (blue emission with a wavelength of about 458 nm). It was. In addition, as a result of conducting a constant current driving test with a current density for obtaining an initial luminance of 2000 cd / m ² , the time for maintaining the luminance of 80% (1600 cd / m ² ) or more of the initial value was 279 hours.

[Example 5] A glass substrate (26 mm x 28 mm x 0.7 mm) obtained by polishing ITO having a thickness of 180 nm formed by element sputtering using the compound (1-2-125) as an electron transport layer to 150 nm (( Opt Science Co., Ltd.) was used as a transparent support substrate. This transparent support substrate is fixed to a substrate holder of a commercially available vapor deposition apparatus (manufactured by Showa Vacuum Co., Ltd.), a molybdenum vapor deposition boat containing HI, a molybdenum vapor deposition boat containing HI2, and a molybdenum vapor containing HT. Vapor deposition boat, molybdenum vapor deposition boat with BH2, molybdenum vapor deposition boat with BD2, molybdenum vapor deposition boat with compound of the present invention (1-225), molybdenum with Liq A vapor deposition boat, a molybdenum vapor deposition boat containing magnesium, and a molybdenum vapor deposition boat containing silver were mounted.

The following layers were sequentially formed on the ITO film of the transparent support substrate. The vacuum chamber is depressurized to 5 × 10 ⁻⁴ Pa, and first, a vapor deposition boat containing HI is heated and vapor-deposited to a film thickness of 40 nm to form a first hole injection layer. Is heated to a thickness of 5 nm to form a second hole injection layer, and then the evaporation boat containing HT is heated to a thickness of 25 nm. Thus, a hole transport layer was formed by vapor deposition. Next, the vapor deposition boat containing BH2 and the vapor deposition boat containing BD2 were heated at the same time to form a light emitting layer by vapor deposition to a film thickness of 20 nm. The deposition rate was adjusted so that the weight ratio of BH2 to BD2 was approximately 95: 5. Next, the vapor deposition boat containing the compound (1-2-125) and the vapor deposition boat containing Liq were heated at the same time to be vapor-deposited to a film thickness of 30 nm to form an electron transport layer. The deposition rate was adjusted so that the weight ratio of the compound (1-2-125) and Liq was approximately 1: 1. The deposition rate of each layer was 0.01 to 1 nm / second.

Thereafter, the evaporation boat containing Liq was heated to deposit at a deposition rate of 0.01 to 0.1 nm / second so as to have a film thickness of 1 nm. Next, a boat containing magnesium and a boat containing silver were heated at the same time and evaporated to a film thickness of 100 nm to form a cathode. At this time, the vapor deposition rate was adjusted so that the atomic ratio of magnesium and silver was 10: 1, and an organic EL device was obtained so that the vapor deposition rate was 0.01 to 2 nm / second.

Using the ITO electrode as the anode and the Liq / magnesium + silver electrode as the cathode, the characteristics at 1000 cd / m ² emission were measured. The drive voltage was 3.8 V and the external quantum efficiency was 6.0% (blue emission with a wavelength of about 458 nm). Met. Further, as a result of conducting a constant current driving test with a current density for obtaining an initial luminance of 2000 cd / m ² , the time for maintaining the luminance of 80% (1600 cd / m ² ) or more of the initial value was 220 hours.

[Comparative Example 5]
An organic EL device was obtained in the same manner as in Example 5 except that the compound (1-2-125) in the electron transport layer was changed to the compound (ET4). Using the ITO electrode as the anode and the Liq / magnesium + silver electrode as the cathode, measuring the characteristics at 1000 cd / m ² emission, the drive voltage is 3.5 V, the external quantum efficiency is 5.5% (blue emission with a wavelength of about 454 nm) Met. Further, as a result of conducting a constant current driving test with a current density for obtaining an initial luminance of 2000 cd / m ² , the time for maintaining the luminance of 80% (1600 cd / m ² ) or more of the initial value was 170 hours.

[Example 6] Example 5 except that the compound (1-2-125) in the device electron transport layer was changed to the compound (1-3-206) using the compound (1-3-206) in the electron transport layer. An organic EL device was obtained by a method according to the above. Using the ITO electrode as the anode and the Liq / magnesium + silver electrode as the cathode, the characteristics at 1000 cd / m ² emission were measured. The drive voltage was 3.8 V and the external quantum efficiency was 5.3% (blue emission with a wavelength of about 455 nm). Met. Further, as a result of conducting a constant current driving test with a current density for obtaining an initial luminance of 2000 cd / m ² , the time for maintaining the luminance of 80% (1600 cd / m ² ) or more of the initial value was 307 hours.

[Comparative Example 6]
An organic EL device was obtained by the method according to Example 5 except that the compound (1-2-125) in the electron transport layer was changed to the compound (ET5). Using the ITO electrode as the anode and the Liq / magnesium + silver electrode as the cathode, the characteristics at 1000 cd / m ² emission were measured. The drive voltage was 3.9 V and the external quantum efficiency was 4.4% (blue emission with a wavelength of about 456 nm). Met. In addition, as a result of conducting a constant current driving test with a current density for obtaining an initial luminance of 2000 cd / m ² , the time for maintaining the luminance of 80% (1600 cd / m ² ) or more of the initial value was 201 hours.

[Example 7] A glass substrate (26 mm x 28 mm x 0.7 mm) obtained by polishing ITO having a thickness of 180 nm by element sputtering using the compound (1-1-893) as an electron transport layer to 150 nm (( Opt Science Co., Ltd.) was used as a transparent support substrate. This transparent support substrate is fixed to a substrate holder of a commercially available vapor deposition apparatus (manufactured by Showa Vacuum Co., Ltd.), a molybdenum vapor deposition boat containing HI, a molybdenum vapor deposition boat containing HI2, and a molybdenum vapor containing HT. Vapor deposition boat, molybdenum vapor deposition boat with BH2, molybdenum vapor deposition boat with BD2, molybdenum vapor deposition boat with compound (1-1-893) of the present invention, molybdenum with Liq A vapor deposition boat, a molybdenum vapor deposition boat containing magnesium, and a molybdenum vapor deposition boat containing silver were mounted.

The following layers were sequentially formed on the ITO film of the transparent support substrate. The vacuum chamber is depressurized to 5 × 10 ⁻⁴ Pa, and first, a vapor deposition boat containing HI is heated and vapor-deposited to a film thickness of 40 nm to form a first hole injection layer. Is heated to a thickness of 5 nm to form a second hole injection layer, and then the evaporation boat containing HT is heated to a thickness of 25 nm. Thus, a hole transport layer was formed by vapor deposition. Next, the vapor deposition boat containing BH2 and the vapor deposition boat containing BD2 were heated at the same time to form a light emitting layer by vapor deposition to a film thickness of 20 nm. The deposition rate was adjusted so that the weight ratio of BH2 to BD2 was approximately 95: 5. Next, the evaporation boat containing the compound (1-1-893) was heated and evaporated to a thickness of 30 nm to form an electron transport layer. The deposition rate of each layer was 0.01 to 1 nm / second.

Using the ITO electrode as the anode and the Liq / magnesium + silver electrode as the cathode, measuring the characteristics at 1000 cd / m ² emission, the drive voltage is 3.3 V, the external quantum efficiency is 3.6% (blue emission with a wavelength of about 456 nm) Met. Further, as a result of conducting a constant current driving test with a current density for obtaining an initial luminance of 2000 cd / m ² , the time for maintaining the luminance of 90% (1800 cd / m ² ) or more of the initial value was 56 hours.

[Example 8] Example 7 using compound (1-1-973) in the electron transport layer Example 7 except that compound (1-1-893) in the device electron transport layer was replaced with compound (1-1-973) An organic EL device was obtained by a method according to the above. Using the ITO electrode as the anode and the Liq / magnesium + silver electrode as the cathode, the characteristics at 1000 cd / m ² emission were measured. The drive voltage was 4.2 V and the external quantum efficiency was 4.8% (blue emission with a wavelength of about 456 nm). Met. Further, as a result of conducting a constant current driving test with a current density for obtaining an initial luminance of 2000 cd / m ² , the time for maintaining the luminance of 80% (1600 cd / m ² ) or more of the initial value was 80 hours.

[Comparative Example 7]
An organic EL device was obtained in the same manner as in Example 7 except that the compound (1-1-893) in the electron transport layer was changed to the compound (ET6). Using the ITO electrode as the anode and the Liq / magnesium + silver electrode as the cathode, the characteristics at 1000 cd / m ² emission were measured. The drive voltage was 5.6 V and the external quantum efficiency was 4.8% (blue emission with a wavelength of about 455 nm). Met. Further, as a result of conducting a constant current driving test with a current density for obtaining an initial luminance of 2000 cd / m ² , the time for maintaining the luminance of 80% (1600 cd / m ² ) or more of the initial value was 35 hours.

The above results are summarized in Table 4.

* The time during which the luminance is 90% or more of the initial luminance.

Table 5 below shows the material configuration of each layer in the manufactured organic EL elements according to Examples 9 and 10 and Comparative Examples 8 and 9.

In Table 5, “ET7” is 2-phenyl-9,10-di ([2,2′-bipyridin] -5-yl) anthracene, and “ET8” is 7-phenyl-5,9-bis (3- ( Pyridin-4-yl) phenyl) -7H-benzo [c] carbazole, “ET9” is 9- (4 ′-(dimesitylboryl)-[1,1′-binaphthalene] -4-yl) -9H-carbazole, “ “ET10” is 4,4 ′-((2-phenylanthracene-9,10-diyl) bis (4,1-phenylene)) dipyridine. The chemical structure is shown below.

[Example 9] A glass substrate (26 mm x 28 mm x 0.7 mm) obtained by polishing ITO having a thickness of 180 nm by element sputtering using the compound (1-1-765) as an electron transport layer to 150 nm (( Opt Science Co., Ltd.) was used as a transparent support substrate. This transparent support substrate is fixed to a substrate holder of a commercially available vapor deposition apparatus (manufactured by Showa Vacuum Co., Ltd.), a molybdenum vapor deposition boat containing HI, a molybdenum vapor deposition boat containing HI2, and a molybdenum vapor containing HT. Vapor deposition boat, molybdenum vapor deposition boat with BH2, molybdenum vapor deposition boat with BD2, molybdenum vapor deposition boat with compound (1-1-765) of the present invention, molybdenum with ET7 A vapor deposition boat, a molybdenum vapor deposition boat containing lithium fluoride (LiF), and a tungsten vapor deposition boat containing aluminum were mounted.

The following layers were sequentially formed on the ITO film of the transparent support substrate. The vacuum chamber is depressurized to 5 × 10 ⁻⁴ Pa, and first, a vapor deposition boat containing HI is heated and vapor-deposited to a film thickness of 40 nm to form a first hole injection layer. Is heated to a thickness of 5 nm to form a second hole injection layer, and then the evaporation boat containing HT is heated to a thickness of 25 nm. Thus, a hole transport layer was formed by vapor deposition. Next, the vapor deposition boat containing BH2 and the vapor deposition boat containing BD2 were heated at the same time to form a light emitting layer by vapor deposition to a film thickness of 20 nm. The deposition rate was adjusted so that the weight ratio of BH2 to BD2 was approximately 95: 5. Next, the vapor deposition boat containing the compound (1-1-765) is heated and vapor-deposited to a film thickness of 20 nm to form the first electron transport layer, and further the vapor deposition boat containing ET7 Was heated to a thickness of 10 nm to form a second electron transport layer. The deposition rate of each layer was 0.01 to 1 nm / second.

Thereafter, the evaporation boat containing LiF was heated to deposit at a deposition rate of 0.01 to 0.1 nm / second so as to have a film thickness of 1 nm. Next, a vapor deposition boat containing aluminum was heated, and aluminum was deposited at a deposition rate of 0.01 to 2 nm / second so as to have a film thickness of 100 nm to form a cathode, thereby obtaining an organic EL device.

Using the ITO electrode as the anode and the LiF / aluminum electrode as the cathode, the characteristics at 1000 cd / m ² emission were measured. The drive voltage was 3.8 V and the external quantum efficiency was 5.3% (blue emission with a wavelength of about 456 nm). It was. Further, as a result of conducting a constant current driving test with a current density for obtaining an initial luminance of 2000 cd / m ² , the time for maintaining the luminance of 80% (1600 cd / m ² ) or more of the initial value was 107 hours.

[Comparative Example 8]
An organic EL device was obtained in the same manner as in Example 9 except that the compound (1-1-765) in the electron transport layer was changed to the compound (ET8). Using the ITO electrode as the anode and the LiF / aluminum electrode as the cathode, the characteristics at 1000 cd / m ² emission were measured. The drive voltage was 5.3 V and the external quantum efficiency was 4.3% (blue emission with a wavelength of about 455 nm). It was. In addition, as a result of conducting a constant current driving test with a current density for obtaining an initial luminance of 2000 cd / m ² , the time for maintaining the luminance of 80% (1600 cd / m ² ) or more of the initial value was 48 hours.

[Example 10] A glass substrate (26 mm x 28 mm x 0.7 mm) obtained by polishing ITO having a thickness of 180 nm formed by element sputtering using the compound (1-1-973) as an electron transport layer to 150 nm (( Opt Science Co., Ltd.) was used as a transparent support substrate. This transparent support substrate is fixed to a substrate holder of a commercially available vapor deposition apparatus (manufactured by Showa Vacuum Co., Ltd.), a molybdenum vapor deposition boat containing HI, a molybdenum vapor deposition boat containing HI2, and a molybdenum vapor containing HT. Vapor deposition boat, molybdenum vapor deposition boat containing BH2, molybdenum vapor deposition boat containing BD2, molybdenum vapor deposition boat containing ET9, molybdenum product containing the compound of the present invention (1-1973) A vapor deposition boat, a molybdenum vapor deposition boat containing lithium fluoride (LiF), and a tungsten vapor deposition boat containing aluminum were mounted.

The following layers were sequentially formed on the ITO film of the transparent support substrate. The vacuum chamber is depressurized to 5 × 10 ⁻⁴ Pa, and first, a vapor deposition boat containing HI is heated and vapor-deposited to a film thickness of 40 nm to form a first hole injection layer. Is heated to a thickness of 5 nm to form a second hole injection layer, and then the evaporation boat containing HT is heated to a thickness of 25 nm. Thus, a hole transport layer was formed by vapor deposition. Next, the vapor deposition boat containing BH2 and the vapor deposition boat containing BD2 were heated at the same time to form a light emitting layer by vapor deposition to a film thickness of 20 nm. The deposition rate was adjusted so that the weight ratio of BH2 to BD2 was approximately 95: 5. Next, the vapor deposition boat containing the compound (ET9) was heated and vapor-deposited to a film thickness of 20 nm to form the first electron transport layer, and the compound (1-1-973) was further contained. A vapor deposition boat was heated and vapor-deposited to a film thickness of 10 nm to form a second electron transport layer. The deposition rate of each layer was 0.01 to 1 nm / second.

Using the ITO electrode as the anode and the LiF / aluminum electrode as the cathode, the characteristics at 1000 cd / m ² emission were measured. The drive voltage was 4.3 V and the external quantum efficiency was 5.9% (blue emission with a wavelength of about 457 nm). It was. In addition, as a result of conducting a constant current driving test with a current density for obtaining an initial luminance of 2000 cd / m ² , the time for maintaining the luminance of 80% (1600 cd / m ² ) or more of the initial value was 338 hours.

[Comparative Example 9]
An organic EL device was obtained by a method according to Example 10 except that the compound (1-1 to 973) in the electron transport layer was changed to the compound (ET10). Using the ITO electrode as the anode and the LiF / aluminum electrode as the cathode, the characteristics at 1000 cd / m ² emission were measured. The drive voltage was 4.3 V and the external quantum efficiency was 5.4% (blue emission with a wavelength of about 455 nm). It was. Further, as a result of conducting a constant current driving test with a current density for obtaining an initial luminance of 2000 cd / m ² , the time for maintaining the luminance of 80% (1600 cd / m ² ) or more of the initial value was 200 hours.

The above results are summarized in Table 6.

Table 7 below shows the material structure of each layer in the organic EL elements according to Examples 11 to 15 thus manufactured.

[Example 11] A glass substrate (26 mm x 28 mm x 0.7 mm) obtained by polishing ITO having a thickness of 180 nm formed by element sputtering using the compound (1-1-765) as an electron transport layer to 150 nm (( Opt Science Co., Ltd.) was used as a transparent support substrate. This transparent support substrate is fixed to a substrate holder of a commercially available vapor deposition apparatus (manufactured by Showa Vacuum Co., Ltd.), a molybdenum vapor deposition boat containing HI, a molybdenum vapor deposition boat containing HI2, and a molybdenum vapor containing HT. Vapor deposition boat, molybdenum vapor deposition boat with BH2, molybdenum vapor deposition boat with BD2, molybdenum vapor deposition boat with compound (1-1-765) of the present invention, molybdenum with Liq A vapor deposition boat and a tungsten vapor deposition boat containing aluminum were mounted.

The following layers were sequentially formed on the ITO film of the transparent support substrate. The vacuum chamber is depressurized to 5 × 10 ⁻⁴ Pa, and first, a vapor deposition boat containing HI is heated and vapor-deposited to a film thickness of 40 nm to form a first hole injection layer. Is heated to a thickness of 5 nm to form a second hole injection layer, and then the evaporation boat containing HT is heated to a thickness of 25 nm. Thus, a hole transport layer was formed by vapor deposition. Next, the vapor deposition boat containing BH2 and the vapor deposition boat containing BD2 were heated at the same time to form a light emitting layer by vapor deposition to a film thickness of 20 nm. The deposition rate was adjusted so that the weight ratio of BH2 to BD2 was approximately 95: 5. Next, the vapor deposition boat containing the compound (1-1-765) and the vapor deposition boat containing Liq were heated at the same time to form a 20 nm-thick film, thereby forming an electron transport layer. The deposition rate was adjusted so that the weight ratio of the compound (1-1-765) and Liq was approximately 1: 1. The deposition rate of each layer was 0.01 to 1 nm / second.

Using the ITO electrode as the anode and the Liq / aluminum electrode as the cathode, the characteristics at 1000 cd / m ² emission were measured. The drive voltage was 3.7 V and the external quantum efficiency was 7.4% (blue emission with a wavelength of about 456 nm). It was. Further, as a result of conducting a constant current driving test with a current density for obtaining an initial luminance of 2000 cd / m ² , the time for maintaining the luminance of 80% (1600 cd / m ² ) or more of the initial value was 243 hours.

[Example 12]
An organic EL device was obtained in the same manner as in Example 11 except that the compound (1-1-765) in the electron transport layer was changed to the compound (1-2-125). Using the ITO electrode as the anode and the Liq / aluminum electrode as the cathode, the characteristics at 1000 cd / m ² emission were measured. The drive voltage was 4.3 V and the external quantum efficiency was 6.2% (blue emission with a wavelength of about 456 nm). It was. In addition, as a result of conducting a constant current driving test with a current density for obtaining an initial luminance of 2000 cd / m ² , the time for maintaining the luminance of 80% (1600 cd / m ² ) or more of the initial value was 223 hours.

[Example 13] A glass substrate (26 mm x 28 mm x 0.7 mm) obtained by polishing ITO having a thickness of 180 nm formed by element sputtering using the compound (1-1-2) as an electron transport layer to 150 nm (( Opt Science Co., Ltd.) was used as a transparent support substrate. This transparent support substrate is fixed to a substrate holder of a commercially available vapor deposition apparatus (manufactured by Showa Vacuum Co., Ltd.), a molybdenum vapor deposition boat containing HI, a molybdenum vapor deposition boat containing HI2, and a molybdenum vapor containing HT. Vapor deposition boat, molybdenum vapor deposition boat with BH2, molybdenum vapor deposition boat with BD2, molybdenum vapor deposition boat with compound (1-1-2) of the present invention, molybdenum with Liq A vapor deposition boat, a molybdenum vapor deposition boat containing magnesium, and a molybdenum vapor deposition boat containing silver were mounted.

The following layers were sequentially formed on the ITO film of the transparent support substrate. The vacuum chamber is depressurized to 5 × 10 ⁻⁴ Pa, and first, a vapor deposition boat containing HI is heated and vapor-deposited to a film thickness of 40 nm to form a first hole injection layer. Is heated to a thickness of 5 nm to form a second hole injection layer, and then the evaporation boat containing HT is heated to a thickness of 25 nm. Thus, a hole transport layer was formed by vapor deposition. Next, the vapor deposition boat containing BH2 and the vapor deposition boat containing BD2 were heated at the same time to form a light emitting layer by vapor deposition to a film thickness of 20 nm. The deposition rate was adjusted so that the weight ratio of BH2 to BD2 was approximately 95: 5. Next, the vapor deposition boat containing the compound (1-1-2) and the vapor deposition boat containing Liq were heated at the same time so as to have a film thickness of 20 nm, thereby forming an electron transport layer. The deposition rate was adjusted so that the weight ratio of compound (1-1-2) to Liq was approximately 1: 1. The deposition rate of each layer was 0.01 to 1 nm / second.

Using the ITO electrode as the anode and the Liq / magnesium + silver electrode as the cathode, the characteristics at 1000 cd / m ² emission were measured. The drive voltage was 3.9 V and the external quantum efficiency was 6.2% (blue emission with a wavelength of about 458 nm). Met. Further, as a result of conducting a constant current driving test with a current density for obtaining an initial luminance of 2000 cd / m ² , the time for maintaining the luminance of 80% (1600 cd / m ² ) or more of the initial value was 150 hours.

[Example 14]
An organic EL device was obtained in the same manner as in Example 13 except that the compound (1-1-2) in the electron transport layer was changed to the compound (1-1-765). Using the ITO electrode as the anode and the Liq / magnesium + silver electrode as the cathode, the characteristics at 1000 cd / m ² emission were measured. The drive voltage was 3.5 V and the external quantum efficiency was 6.7% (blue emission with a wavelength of about 457 nm). Met. Further, as a result of conducting a constant current driving test with a current density for obtaining an initial luminance of 2000 cd / m ² , the time for maintaining the luminance of 80% (1600 cd / m ² ) or more of the initial value was 210 hours.

[Example 15]
An organic EL device was obtained by a method according to Example 13 except that the compound (1-1-2) in the electron transport layer was changed to the compound (1-1-973). Using the ITO electrode as the anode and the Liq / magnesium + silver electrode as the cathode, the characteristics at 1000 cd / m ² emission were measured. The drive voltage was 3.8 V and the external quantum efficiency was 6.7% (blue emission with a wavelength of about 455 nm). Met. Further, as a result of conducting a constant current driving test with a current density for obtaining an initial luminance of 2000 cd / m ² , the time for maintaining the luminance of 80% (1600 cd / m ² ) or more of the initial value was 170 hours.

The above results are summarized in Table 8.

According to a preferred aspect of the present invention, it is possible to provide an organic electroluminescent element having excellent luminous efficiency and element lifetime, a display device including the same, a lighting device including the display device, and the like.

Claims

A benzo [a] carbazole compound represented by the following formula (1).

In equation (1),
a, b, c, and d are independently 1 or 0, but a and b are not 0 at the same time;
Py 1 and Py 2 are independently pyridyl or bipyridyl, and any hydrogen of the pyridyl or bipyridyl is alkyl having 1 to 6 carbons, cycloalkyl having 3 to 6 carbons, aryl having 6 to 14 carbons, or Optionally substituted with heteroaryl having 2 to 12 carbons;
Ar 1 is hydrogen or aryl having 6 to 20 carbon atoms when a is 0; Ar 1 is arylene having 6 to 20 carbon atoms when a is 1; Ar 2 is hydrogen or carbon when b is 0 An aryl having 6 to 20 carbon atoms and an arylene having 6 to 20 carbon atoms when b is 1, any hydrogen of these aryls or arylenes is an alkyl having 1 to 6 carbon atoms or a cyclohexane having 3 to 6 carbon atoms; Optionally substituted with alkyl or aryl of 6 to 14 carbon atoms;
A is aryl having 6 to 20 carbon atoms, and any hydrogen in the aryl may be replaced by alkyl having 1 to 6 carbon atoms, cycloalkyl having 3 to 6 carbon atoms, or aryl having 6 to 14 carbon atoms ;
R 1 to R 8 are independently hydrogen, alkyl having 1 to 6 carbons, cycloalkyl having 3 to 6 carbons, aryl having 6 to 14 carbons, or heteroaryl having 2 to 10 carbons, and the aryl Or any hydrogen of heteroaryl may be replaced by alkyl having 1 to 6 carbons or cycloalkyl having 3 to 6 carbons;
At least one hydrogen in the compound represented by the formula (1) may be replaced with deuterium.
The benzo [a] carbazole compound according to claim 1, which is represented by the following formula (1-1).

In formula (1-1),
Py 1 and Py 2 are independently pyridyl or bipyridyl, and any hydrogen of the pyridyl or bipyridyl is alkyl having 1 to 6 carbons, cycloalkyl having 3 to 6 carbons, aryl having 6 to 14 carbons, or Optionally substituted with heteroaryl having 2 to 12 carbons;
Ar 1 and Ar 2 are each independently arylene having 6 to 20 carbon atoms, and any hydrogen of the arylene is alkyl having 1 to 6 carbon atoms, cycloalkyl having 3 to 6 carbon atoms, or 6 to 14 carbon atoms Optionally substituted with aryl;
A is aryl having 6 to 20 carbon atoms, and any hydrogen in the aryl may be replaced by alkyl having 1 to 6 carbon atoms, cycloalkyl having 3 to 6 carbon atoms, or aryl having 6 to 14 carbon atoms ;
R 1 to R 8 are independently hydrogen, alkyl having 1 to 6 carbons, cycloalkyl having 3 to 6 carbons, aryl having 6 to 14 carbons, or heteroaryl having 2 to 10 carbons, and the aryl Or any hydrogen in the heteroaryl may be replaced by alkyl of 1 to 6 carbons or cycloalkyl of 3 to 6 carbons; and
c and d are each independently 1 or 0.
The benzo [a] carbazole compound according to claim 1, which is represented by the following formula (1-2).

In formula (1-2),
Py 2 is pyridyl or bipyridyl, and any hydrogen of the pyridyl or bipyridyl is alkyl having 1 to 6 carbons, cycloalkyl having 3 to 6 carbons, aryl having 6 to 14 carbons, or 2 to 12 carbons Optionally substituted with heteroaryl;
Ar 1 is hydrogen or aryl having 6 to 20 carbon atoms, and any hydrogen in the aryl is replaced by alkyl having 1 to 6 carbon atoms, cycloalkyl having 3 to 6 carbon atoms, or aryl having 6 to 14 carbon atoms May be;
Ar 2 is aryl having 6 to 20 carbon atoms, and any hydrogen in the arylene is replaced by alkyl having 1 to 6 carbons, cycloalkyl having 3 to 6 carbons, or aryl having 6 to 14 carbons Well;
A is aryl having 6 to 20 carbon atoms, and any hydrogen in the aryl may be replaced by alkyl having 1 to 6 carbon atoms, cycloalkyl having 3 to 6 carbon atoms, or aryl having 6 to 14 carbon atoms ;
R 1 to R 8 are independently hydrogen, alkyl having 1 to 6 carbons, cycloalkyl having 3 to 6 carbons, aryl having 6 to 14 carbons, or heteroaryl having 2 to 10 carbons, and the aryl Or any hydrogen in the heteroaryl may be replaced by alkyl of 1 to 6 carbons or cycloalkyl of 3 to 6 carbons; and
d is 1 or 0.
The benzo [a] carbazole compound according to claim 1, which is represented by the following formula (1-3).

In formula (1-3),
Py 1 is pyridyl or bipyridyl, and any hydrogen of the pyridyl or bipyridyl is alkyl having 1 to 6 carbons, cycloalkyl having 3 to 6 carbons, aryl having 6 to 14 carbons, or 2 to 12 carbons Optionally substituted with heteroaryl;
Ar 1 is an arylene having 6 to 20 carbon atoms, and any hydrogen of the arylene is replaced by an alkyl having 1 to 6 carbons, a cycloalkyl having 3 to 6 carbon atoms, or an aryl having 6 to 14 carbon atoms Well;
Ar 2 is hydrogen or aryl having 6 to 20 carbon atoms, and any hydrogen in the aryl is replaced by alkyl having 1 to 6 carbon atoms, cycloalkyl having 3 to 6 carbon atoms, or aryl having 6 to 14 carbon atoms May be;
A is aryl having 6 to 20 carbon atoms, and any hydrogen in the aryl may be replaced by alkyl having 1 to 6 carbon atoms, cycloalkyl having 3 to 6 carbon atoms, or aryl having 6 to 14 carbon atoms ;
R 1 to R 8 are independently hydrogen, alkyl having 1 to 6 carbons, cycloalkyl having 3 to 6 carbons, aryl having 6 to 14 carbons, or heteroaryl having 2 to 10 carbons, and the aryl Or any hydrogen in the heteroaryl may be replaced by alkyl of 1 to 6 carbons or cycloalkyl of 3 to 6 carbons; and
c is 1 or 0.
Py 1 and Py 2 are independently selected from the group of groups represented by the following formulas (Py-1-1) to (Py-1-3) and (Py-2-1) to (Py-2-18) One that is chosen,

Any hydrogen in these groups may be replaced by methyl, ethyl, isopropyl, t-butyl, cyclohexyl, phenyl, naphthyl, or pyridyl;
Ar 1 and Ar 2 are independently phenylene, naphthalenediyl, anthracenediyl, or chrysenediyl, and any hydrogen in these groups is replaced with methyl, ethyl, isopropyl, t-butyl, cyclohexyl, phenyl, or naphthyl May be;
A is phenyl, naphthyl or phenanthryl, and any hydrogen in these groups may be replaced by methyl, ethyl, isopropyl, t-butyl, cyclohexyl, phenyl, or naphthyl;
R 1 to R 8 are independently hydrogen, methyl, ethyl, isopropyl, t-butyl, cyclohexyl, or phenyl; and
The benzo [a] carbazole compound according to claim 2, wherein c and d are each independently 1 or 0.
Py 2 is one selected from the group of groups represented by the following formulas (Py-1-1) to (Py-1-3) and (Py-2-1) to (Py-2-18) ,

Any hydrogen in these groups may be replaced by methyl, ethyl, isopropyl, t-butyl, cyclohexyl, phenyl, naphthyl, or pyridyl;
Ar 1 is hydrogen, phenyl, naphthyl, anthryl, phenanthryl, or chrycenyl, and any hydrogen in these groups may be replaced with methyl, ethyl, isopropyl, t-butyl, cyclohexyl, phenyl, or naphthyl;
Ar 2 is phenylene, naphthalenediyl, anthracenediyl, or chrysenediyl, and any hydrogen in these groups may be replaced with methyl, ethyl, isopropyl, t-butyl, cyclohexyl, phenyl, or naphthyl;
A is phenyl, naphthyl or phenanthryl, and any hydrogen in these groups may be replaced by methyl, ethyl, isopropyl, t-butyl, cyclohexyl, phenyl, or naphthyl;
R 1 to R 8 are independently hydrogen, methyl, ethyl, isopropyl, t-butyl, cyclohexyl, or phenyl; and
The benzo [a] carbazole compound according to claim 3, wherein d is 1 or 0.
Py 1 is one selected from the group of groups represented by the following formulas (Py-1-1) to (Py-1-3) and (Py-2-1) to (Py-2-18) ,

Any hydrogen in these groups may be replaced by methyl, ethyl, isopropyl, t-butyl, cyclohexyl, phenyl, naphthyl, or pyridyl;
Ar 1 is phenylene, naphthalenediyl, anthracenediyl, or chrysenediyl, and any hydrogen in these groups may be replaced with methyl, ethyl, isopropyl, t-butyl, cyclohexyl, phenyl, or naphthyl;
Ar 2 is hydrogen, phenyl, naphthyl, anthryl, phenanthryl, or chrysenyl, and any hydrogen in these groups may be replaced with methyl, ethyl, isopropyl, t-butyl, cyclohexyl, phenyl, or naphthyl;
A is phenyl, naphthyl or phenanthryl, and any hydrogen in these groups may be replaced by methyl, ethyl, isopropyl, t-butyl, cyclohexyl, phenyl, or naphthyl;
R 1 to R 8 are independently hydrogen, methyl, ethyl, isopropyl, t-butyl, cyclohexyl, or phenyl; and
The benzo [a] carbazole compound according to claim 4, wherein c is 1 or 0.
Py 1 and Py 2 are independently represented by the formulas (Py-1-1), (Py-1-2), (Py-1-3), (Py-2-1), (Py-2-2), (Py-2-3), (Py-2-7), (Py-2-8), (Py-2-9), (Py-2-10), (Py-2-11), and ( Py-2-12), and any hydrogen of these groups may be replaced by methyl, t-butyl, phenyl, naphthyl, or pyridyl;
Ar 1 and Ar 2 are independently 1,4-phenylene, 1,3-phenylene, naphthalene-1,4-diyl, naphthalene-1,6-diyl, naphthalene-2,6-diyl, naphthalene-2,7 -Diyl, or anthracene-9,10-diyl, any hydrogen of these groups may be replaced by methyl, t-butyl, or phenyl;
A is phenyl, 1-naphthyl, 2-naphthyl, or 9-phenanthryl, and any hydrogen in these groups may be replaced by methyl, t-butyl, or phenyl;
R 1 to R 8 are all hydrogen; and
The benzo [a] carbazole compound according to claim 5, wherein c and d are each independently 1 or 0.
Py 2 is represented by the formulas (Py-1-1), (Py-1-2), (Py-1-3), (Py-2-1), (Py-2-2), (Py-2-3). ), (Py-2-7), (Py-2-8), (Py-2-9), (Py-2-10), (Py-2-11), and (Py-2-12) Any hydrogen of these groups may be replaced by methyl, t-butyl, phenyl, naphthyl, or pyridyl;
Ar 1 is hydrogen, phenyl, 1-naphthyl, 2-naphthyl, or 9-phenanthryl, and any hydrogen in these groups may be replaced by methyl, t-butyl, or phenyl;
Ar 2 is 1,4-phenylene, 1,3-phenylene, naphthalene-1,4-diyl, naphthalene-1,6-diyl, naphthalene-2,6-diyl, naphthalene-2,7-diyl, or anthracene- 9,10-diyl, any hydrogen of these groups may be replaced by methyl, t-butyl, or phenyl;
A is phenyl, 1-naphthyl, 2-naphthyl, or 9-phenanthryl, and any hydrogen in these groups may be replaced by methyl, t-butyl, or phenyl;
R 1 to R 8 are all hydrogen; and
The benzo [a] carbazole compound according to claim 6, wherein d is 1 or 0.
Py 1 is represented by the formulas (Py-1-1), (Py-1-2), (Py-1-3), (Py-2-1), (Py-2-2), (Py-2-3). ), (Py-2-7), (Py-2-8), (Py-2-9), (Py-2-10), (Py-2-11), and (Py-2-12) Any hydrogen of these groups may be replaced by methyl, t-butyl, phenyl, naphthyl, or pyridyl;
Ar 1 is 1,4-phenylene, 1,3-phenylene, naphthalene-1,4-diyl, naphthalene-1,6-diyl, naphthalene-2,6-diyl, naphthalene-2,7-diyl, or anthracene- 9,10-diyl, any hydrogen of these groups may be replaced by methyl, t-butyl, or phenyl;
Ar 2 is hydrogen, phenyl, 1-naphthyl, 2-naphthyl, or 9-phenanthryl, and any hydrogen in these groups may be replaced by methyl, t-butyl, cyclohexyl, or phenyl;
A is phenyl, 1-naphthyl, 2-naphthyl, or 9-phenanthryl, and any hydrogen in these groups may be replaced by methyl, t-butyl, or phenyl;
R 1 to R 8 are all hydrogen; and
The benzo [a] carbazole compound according to claim 7, wherein c is 1 or 0.
Py 1 and Py 2 are independently represented by the formulas (Py-1-1), (Py-1-2), (Py-1-3), (Py-2-2), (Py-2-3), One selected from the group of groups represented by (Py-2-8), (Py-2-9), (Py-2-11), and (Py-2-12);
Ar 1 and Ar 2 are independently 1,4-phenylene, 1,3-phenylene, naphthalene-1,4-diyl, naphthalene-2,6-diyl, naphthalene-2,7-diyl, or anthracene-9, 10-diyl;
A is phenyl, 2-biphenylyl, 3-biphenylyl, 4-biphenylyl, m-terphenyl-5′-yl, 1-naphthyl, 2-naphthyl, or 9-phenanthryl;
R 1 to R 8 are all hydrogen; and
The benzo [a] carbazole compound according to claim 5, wherein c and d are each independently 1 or 0.
Py 1 and Py 2 are independently represented by the formulas (Py-1-1), (Py-1-2), (Py-1-3), (Py-2-2), (Py-2-3), One selected from the group of groups represented by (Py-2-8), (Py-2-9), (Py-2-11), and (Py-2-12);
Ar 1 is hydrogen, phenyl, 1-naphthyl, 2-naphthyl, or 9-phenanthryl;
Ar 2 is 1,4-phenylene, 1,3-phenylene, naphthalene-1,4-diyl, naphthalene-2,6-diyl, naphthalene-2,7-diyl, or anthracene-9,10-diyl;
A is phenyl, 2-biphenylyl, 3-biphenylyl, 4-biphenylyl, m-terphenyl-5′-yl, 1-naphthyl, 2-naphthyl, or 9-phenanthryl;
R 1 to R 8 are all hydrogen; and
The benzo [a] carbazole compound according to claim 6, wherein d is 1 or 0.
Py 1 and Py 2 are independently represented by the formulas (Py-1-1), (Py-1-2), (Py-1-3), (Py-2-2), (Py-2-3), One selected from the group of groups represented by (Py-2-8), (Py-2-9), (Py-2-11), and (Py-2-12);
Ar 1 is 1,4-phenylene, 1,3-phenylene, naphthalene-1,4-diyl, naphthalene-2,6-diyl, naphthalene-2,7-diyl, or anthracene-9,10-diyl;
Ar 2 is hydrogen, phenyl, 1-naphthyl, 2-naphthyl, or 9-phenanthryl;
A is phenyl, 2-biphenylyl, 3-biphenylyl, 4-biphenylyl, m-terphenyl-5′-yl, 1-naphthyl, 2-naphthyl, or 9-phenanthryl;
R 1 to R 8 are all hydrogen; and
The benzo [a] carbazole compound according to claim 7, wherein c is 1 or 0.
The benzo [a] carbazole compound according to claim 5, which is represented by the following formula (1-1-66) or (1-1-758).
The benzo [a] carbazole compound according to claim 6, represented by the following formula (1-2-8) or (1-2-28).
The benzo [a] carbazole compound according to claim 7, which is represented by the following formula (1-3-206) or (1-3-300).
The benzo [a] carbazole compound according to claim 5, represented by the following formula (1-1-2).
The benzo [a] carbazole compound according to claim 5, which is represented by the following formula (1-1-765).
The benzo [a] carbazole compound according to claim 5, represented by the following formula (1-1-893).
The benzo [a] carbazole compound according to claim 5, which is represented by the following formula (1-1-973).
The benzo [a] carbazole compound according to claim 6, represented by the following formula (1-2-125):
An electron transport material comprising the compound according to any one of claims 1 to 21.
23. Electron transport containing an electron transport material according to claim 22, disposed between a pair of electrodes composed of an anode and a cathode, a light emitting layer disposed between the pair of electrodes, and the cathode and the light emitting layer. An organic electroluminescent device having a layer and / or an electron injection layer.
24. The organic material according to claim 23, wherein at least one of the electron transport layer and the electron injection layer further contains at least one selected from the group consisting of a quinolinol-based metal complex, a bipyridine derivative, a phenanthroline derivative, and a borane derivative. Electroluminescent device.
At least one of the electron transport layer and the electron injection layer is further made of an alkali metal, an alkaline earth metal, a rare earth metal, an alkali metal oxide, an alkali metal halide, an alkaline earth metal oxide, or an alkaline earth metal. The material contains at least one selected from the group consisting of halides, rare earth metal oxides, rare earth metal halides, alkali metal organic complexes, alkaline earth metal organic complexes and rare earth metal organic complexes. 24. The organic electroluminescent device according to 23.