KR102022437B1 - Electron transport material and organic electroluminescent element using same - Google Patents

Abstract

식(1)에 있어서, a, b, c, 및 d는 1 또는 0이되, a 및 b가 동시에 0이 되지는 않으며; Py¹ 및 Py²는 피리딜 또는 비피리딜이며; Ar¹은 a가 0일 때 수소 또는 아릴이고, a가 1일 때 아릴렌이며, Ar²는 b가 0일 때 수소 또는 아릴이고, b가 1일 때 알릴렌이며; A는 아릴; R¹∼R⁸은 수소, 알킬, 시클로알킬, 아릴, 또는 헤테로 아릴이다.The benzo [a] carbazole compound represented by formula (1) of the present invention is an electron transporting material that contributes to high luminous efficiency, long life, and the like of an organic electroluminescent device. By manufacturing the organic electroluminescent device using the compound, high luminous efficiency and stable driving over a long period of time are possible.

In formula (1), a, b, c, and d are 1 or 0, but a and b are not simultaneously 0; Py ¹ and Py ² are pyridyl or bipyridyl; Ar ¹ is hydrogen or aryl when a is 0, arylene when a is 1, Ar ² is hydrogen or aryl when b is 0, and allylene when b is 1; A is aryl; R ¹ to R ⁸ are hydrogen, alkyl, cycloalkyl, aryl, or hetero aryl.

Description

Electron transport material and organic electroluminescent element using the same {ELECTRON TRANSPORT MATERIAL AND ORGANIC ELECTROLUMINESCENT ELEMENT USING SAME}

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

In recent years, organic EL devices have attracted attention as the next generation of full color flat panel displays, and are being actively studied. In order to promote the practical use of the organic EL device, it is essential to reduce the device driving voltage and extend the lifespan, and in order to achieve this, a new electron transport material has been developed. In particular, it is essential to lower the driving voltage and extend the life of the blue device. Patent Document 1 (Japanese Laid-Open Patent Publication No. 2003-123983) uses a 2,2'-bipyridyl compound, which is a phenanthroline derivative or an analog thereof, in an electron transporting material to drive an organic EL device at a low voltage. It is written. However, the characteristic (driving voltage, luminous efficiency, etc.) of the element reported in the Example of this document is a relative value based on a comparative example only, and the actual value which can be judged as a practical value is not described. In addition, 2,2'-bipyridyl with an example compound in the electron transporting material, and Non-Patent Document 1 (Proceedings of the 10 ^th International Workshop on Inorganic and Organic Electroluminescence), Patent Document 2 (Japanese Laid-Open Patent Publication No. 2002-158093 Korean Patent Publication No. 1) and Patent Document 3 (International Publication 2007/86552 Pamphlet). The compound described in Nonpatent Document 1 has a low Tg and is not practical. Although the compounds described in Patent Literatures 2 and 3 can drive organic EL devices at relatively low voltages, higher efficiency and longer lifetimes are required for practical use.

Japanese Laid-Open Patent Publication No. 2003-123983 Japanese Patent Application Laid-Open No. 2002-158093 International Publication 2007/86552 Brochure

Proceedings of the 10th International Workshop on Inorganic and Organic Electroluminescence (2000)

This invention is made | formed in order to solve the problem which this prior art has. An object of this invention is to provide the electron carrying material which contributes to high luminous efficiency, long lifetime, etc. of an organic electroluminescent element. Moreover, this invention makes it a subject to provide the organic electroluminescent element using this electron carrying material.

The present inventors have diligently studied to find that a compound in which pyridyl or bipyridyl is linked to position 3 and / or 9 of benzo [a] carbazole, directly or through allylene, is used as an organic EL device. By using it for the electron transport layer of the present invention, it has been found that an organic EL device capable of driving with high luminous efficiency and long life can be obtained. Based on this finding, the present invention has been completed.

The said subject is solved by each term shown below.

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

[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;

Py ¹ and Py ² are independently pyridyl or bipyridyl, and any hydrogen of this pyridyl or bipyridyl is alkyl having 1 to 6 carbons, cycloalkyl having 3 to 6 carbons, aryl having 6 to 14 carbon atoms, Or substituted with heteroaryl having 2 to 12 carbon atoms;

Ar ¹ is hydrogen or aryl having 6 to 20 carbon atoms when a is 0, arylene is 6 to 20 carbon atoms when a is 1, and Ar ² is hydrogen or aryl having 6 to 20 carbon atoms when b is 0; and, when b is 1, allylene having 6 to 20 carbon atoms, and these aryl or any hydrogen of allylene are substituted with alkyl having 1 to 6 carbon atoms, cycloalkyl having 3 to 6 carbon atoms, or aryl having 6 to 14 carbon atoms. May be present;

A is C6-C20 aryl, and arbitrary hydrogen of this aryl may be substituted by C1-C6 alkyl, C3-C6 cycloalkyl, or C6-C14 aryl;

R ¹ to R ⁸ are independently hydrogen, alkyl of 1 to 6 carbon atoms, cycloalkyl of 3 to 6 carbon atoms, aryl of 6 to 14 carbon atoms, or hetero aryl of 2 to 10 carbon atoms, and any of this aryl or hetero aryl. Hydrogen may be substituted with alkyl of 1 to 6 carbon atoms or cycloalkyl of 3 to 6 carbon atoms; Also,

At least 1 hydrogen in the compound represented by Formula (1) may be substituted by deuterium.

[2] The benzo [a] carbazole compound according to the above [1], which is represented by the following Formula (1-1).

[Formula 2]

In formula (1-1),

Py ¹ and Py ² are independently pyridyl or bipyridyl, and any hydrogen of this pyridyl or bipyridyl is alkyl having 1 to 6 carbons, cycloalkyl having 3 to 6 carbons, aryl having 6 to 14 carbon atoms, Or substituted with heteroaryl having 2 to 12 carbon atoms;

Ar ¹ and Ar ² are independently allylene having 6 to 20 carbon atoms, and any hydrogen of the allylene is substituted with alkyl having 1 to 6 carbon atoms, cycloalkyl having 3 to 6 carbon atoms, or aryl having 6 to 14 carbon atoms. May be present;

A is C6-C20 aryl, and arbitrary hydrogen of this aryl may be substituted by C1-C6 alkyl, C3-C6 cycloalkyl, or C6-C14 aryl;

R ¹ to R ⁸ are independently hydrogen, alkyl of 1 to 6 carbon atoms, cycloalkyl of 3 to 6 carbon atoms, aryl of 6 to 14 carbon atoms, or hetero aryl of 2 to 10 carbon atoms, and any of this aryl or hetero aryl. Hydrogen may be substituted with alkyl of 1 to 6 carbon atoms or cycloalkyl of 3 to 6 carbon atoms; And,

c and d are independently 1 or 0.

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

[Formula 3]

In formula (1-2),

Py ² is pyridyl or bipyridyl, and any hydrogen of this pyridyl or bipyridyl is alkyl having 1 to 6 carbon atoms, cycloalkyl having 3 to 6 carbon atoms, aryl having 6 to 14 carbon atoms, or 2 to 12 carbon atoms. May be substituted with a hetero aryl;

Ar ¹ is hydrogen or aryl having 6 to 20 carbon atoms, and any hydrogen of this aryl may be substituted with alkyl having 1 to 6 carbon atoms, cycloalkyl having 3 to 6 carbon atoms, or aryl having 6 to 14 carbon atoms;

Ar ² is allylene having 6 to 20 carbon atoms, and arbitrary hydrogen of this allylene may be substituted with alkyl having 1 to 6 carbon atoms, cycloalkyl having 3 to 6 carbon atoms, or aryl having 6 to 14 carbon atoms;

A is C6-C20 aryl, and arbitrary hydrogen of this aryl may be substituted by C1-C6 alkyl, C3-C6 cycloalkyl, or C6-C14 aryl;

R ¹ to R ⁸ are independently hydrogen, alkyl of 1 to 6 carbon atoms, cycloalkyl of 3 to 6 carbon atoms, aryl of 6 to 14 carbon atoms, or hetero aryl of 2 to 10 carbon atoms, and any of this aryl or hetero aryl. Hydrogen may be substituted with alkyl of 1 to 6 carbon atoms or cycloalkyl of 3 to 6 carbon atoms; And,

d is 1 or 0.

[4] The benzo [a] carbazole compound according to the above [1], which is represented by the following Formula (1-3).

[Formula 4]

In formula (1-3),

Py ¹ is pyridyl or bipyridyl, and any hydrogen of this pyridyl or bipyridyl is alkyl having 1 to 6 carbon atoms, cycloalkyl having 3 to 6 carbon atoms, aryl having 6 to 14 carbon atoms, or 2 to 12 carbon atoms. May be substituted with a hetero aryl;

Ar ¹ is allylene having 6 to 20 carbon atoms, and any hydrogen of the allylene may be substituted with alkyl having 1 to 6 carbon atoms, cycloalkyl having 3 to 6 carbon atoms, or aryl having 6 to 14 carbon atoms;

Ar ² is hydrogen or aryl having 6 to 20 carbon atoms, and any hydrogen of this aryl may be substituted with alkyl having 1 to 6 carbon atoms, cycloalkyl having 3 to 6 carbon atoms, or aryl having 6 to 14 carbon atoms;

A is C6-C20 aryl, and arbitrary hydrogen of this aryl may be substituted by C1-C6 alkyl, C3-C6 cycloalkyl, or C6-C14 aryl;

R ¹ to R ⁸ are independently hydrogen, alkyl of 1 to 6 carbon atoms, cycloalkyl of 3 to 6 carbon atoms, aryl of 6 to 14 carbon atoms, or hetero aryl of 2 to 10 carbon atoms, and any of this aryl or hetero aryl. Hydrogen may be substituted with alkyl of 1 to 6 carbon atoms or cycloalkyl of 3 to 6 carbon atoms; And,

c is 1 or 0.

[5] Py ¹ and Py ² are independently represented by the following formulas (Py-1-1) to (Py-1-3) and formulas (Py-2-1) to (Py-2-18) It is one chosen from the group of groups,

[Formula 5]

[Formula 6]

Any of the hydrogens in these groups may be substituted with methyl, ethyl, isopropyl, tert-butyl, cyclohexyl, phenyl, naphthyl, or pyridyl;

Ar ¹ and Ar ² are independently phenylene, naphthalenediyl, anthracenediyl, or chrysendiyl, and any hydrogen of these groups is methyl, ethyl, isopropyl, tert-butyl, cyclohexyl, phenyl, or naphthyl May be substituted;

A is phenyl, naphthyl or phenanthryl, and any hydrogen in these groups may be substituted with methyl, ethyl, isopropyl, tert-butyl, cyclohexyl, phenyl, or naphthyl;

R ¹ to R ⁸ are independently hydrogen, methyl, ethyl, isopropyl, tert-butyl, cyclohexyl, or phenyl; And,

The benzo [a] carbazole compound according to the above [2], wherein c and d are independently 1 or 0.

[6] Py ² is selected from the group of the group represented by the following formula (Py-1-1) to formula (Py-1-3) and formula (Py-2-1) to formula (Py-2-18) It is one,

[Formula 7]

[Formula 8]

Any of the hydrogens in these groups may be substituted with methyl, ethyl, isopropyl, tert-butyl, cyclohexyl, phenyl, naphthyl, or pyridyl;

Ar ¹ is hydrogen, phenyl, naphthyl, anthryl, phenanthryl, or chrysenyl, and any hydrogen in these groups is substituted with methyl, ethyl, isopropyl, tert-butyl, cyclohexyl, phenyl, or naphthyl May be present;

Ar ² is phenylene, naphthalenediyl, anthracenediyl, or chrysendiyl, and any hydrogen of these groups may be substituted with methyl, ethyl, isopropyl, tert-butyl, cyclohexyl, phenyl, or naphthyl ;

A is phenyl, naphthyl or phenanthryl, and any hydrogen in these groups may be substituted with methyl, ethyl, isopropyl, tert-butyl, cyclohexyl, phenyl, or naphthyl;

R ¹ to R ⁸ are independently hydrogen, methyl, ethyl, isopropyl, tert-butyl, cyclohexyl, or phenyl; And,

The benzo [a] carbazole compound according to the above [3], wherein d is 1 or 0.

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

[Formula 9]

[Formula 10]

Any of the hydrogens in these groups may be substituted with methyl, ethyl, isopropyl, tert-butyl, cyclohexyl, phenyl, naphthyl, or pyridyl;

Ar ¹ is phenylene, naphthalenediyl, anthracenediyl, or chrysendiyl, and any hydrogen of these groups may be substituted with methyl, ethyl, isopropyl, tert-butyl, cyclohexyl, phenyl, or naphthyl ;

Ar ² is hydrogen, phenyl, naphthyl, anthryl, phenanthryl, or chrysenyl, and any hydrogen of these groups is substituted with methyl, ethyl, isopropyl, tert-butyl, cyclohexyl, phenyl, or naphthyl May be present;

A is phenyl, naphthyl or phenanthryl, and any hydrogen in these groups may be substituted with methyl, ethyl, isopropyl, tert-butyl, cyclohexyl, phenyl, or naphthyl;

R ¹ to R ⁸ are independently hydrogen, methyl, ethyl, isopropyl, tert-butyl, cyclohexyl, or phenyl; And,

The benzo [a] carbazole compound according to the above [4], wherein c is 1 or 0.

[8] Py ¹ and Py ² are independently formula (Py-1-1), formula (Py-1-2), formula (Py-1-3), formula (Py-2-1), formula (Py -2-2), formula (Py-2-3), formula (Py-2-7), formula (Py-2-8), formula (Py-2-9), formula (Py-2-10) , And one selected from the group represented by the formula (Py-2-11) and formula (Py-2-12), and any hydrogen of these groups is methyl, tert-butyl, phenyl, naphthyl, Or may be substituted with 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, and any hydrogen of these groups may be substituted with methyl, tert-butyl, or phenyl;

A is phenyl, 1-naphthyl, 2-naphthyl, or 9-phenanthryl, and any hydrogen in these groups may be substituted with methyl, tert-butyl, or phenyl;

R ¹ to R ⁸ are all hydrogen; And,

The benzo [a] carbazole compound according to the above [5], wherein c and d are independently 1 or 0.

[9] Py ² is formula (Py-1-1), formula (Py-1-2), formula (Py-1-3), formula (Py-2-1), formula (Py-2-2) , Formula (Py-2-3), formula (Py-2-7), formula (Py-2-8), formula (Py-2-9), formula (Py-2-10), formula (Py- 2-11), and one group selected from the group represented by the formula (Py-2-12), and any hydrogen of these groups is substituted with methyl, tert-butyl, phenyl, naphthyl, or pyridyl May be;

Ar ¹ is hydrogen, phenyl, 1-naphthyl, 2-naphthyl, or 9-phenanthryl, and any hydrogen in these groups may be substituted with methyl, tert-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, and any hydrogen of these groups may be substituted with methyl, tert-butyl, or phenyl;

A is phenyl, 1-naphthyl, 2-naphthyl, or 9-phenanthryl, and any hydrogen in these groups may be substituted with methyl, tert-butyl, or phenyl;

R ¹ to R ⁸ are all hydrogen; And,

The benzo [a] carbazole compound according to the above [6], wherein d is 1 or 0.

[10] Py ¹ is formula (Py-1-1), formula (Py-1-2), formula (Py-1-3), formula (Py-2-1), formula (Py-2-2) , Formula (Py-2-3), formula (Py-2-7), formula (Py-2-8), formula (Py-2-9), formula (Py-2-10), formula (Py- 2-11), and one group selected from the group represented by the formula (Py-2-12), and any hydrogen of these groups is substituted with methyl, tert-butyl, phenyl, naphthyl, or pyridyl May be;

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, and any hydrogen of these groups may be substituted with methyl, tert-butyl, or phenyl;

Ar ² is hydrogen, phenyl, 1-naphthyl, 2-naphthyl, or 9-phenanthryl, and any hydrogen in these groups may be substituted with methyl, tert-butyl, cyclohexyl, or phenyl;

A is phenyl, 1-naphthyl, 2-naphthyl, or 9-phenanthryl, and any hydrogen in these groups may be substituted with methyl, tert-butyl, or phenyl;

R ¹ to R ⁸ are all hydrogen; And,

The benzo [a] carbazole compound according to the above [7], wherein c is 1 or 0.

[11] Py ¹ and Py ² are independently formula (Py-1-1), formula (Py-1-2), formula (Py-1-3), formula (Py-2-2), formula (Py -2-3), selected from the group of the groups represented by formula (Py-2-8), formula (Py-2-9), formula (Py-2-11), and formula (Py-2-12) Is one;

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 the above [5], wherein c and d are independently 1 or 0.

[12] Py ¹ and Py ² independently represent formula (Py-1-1), formula (Py-1-2), formula (Py-1-3), formula (Py-2-2), and formula (Py -2-3), selected from the group of the groups represented by formula (Py-2-8), formula (Py-2-9), formula (Py-2-11), and formula (Py-2-12) Is one;

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 the above [6], wherein d is 1 or 0.

[13] Py ¹ and Py ² independently represent formula (Py-1-1), formula (Py-1-2), formula (Py-1-3), formula (Py-2-2), and formula (Py -2-3), selected from the group of the groups represented by formula (Py-2-8), formula (Py-2-9), formula (Py-2-11), and formula (Py-2-12) Is one;

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 the above [7], wherein c is 1 or 0.

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

[Formula 11]

[15] The benzo [a] carbazole compound according to the above [6], which is represented by the following Formula (1-2-8) or Formula (1-2-28).

[Formula 12]

[16] The benzo [a] carbazole compound according to the above [7], which is represented by the following Formula (1-3-206) or Formula (1-3-300).

[Formula 13]

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

[Formula 14]

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

[Formula 15]

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

[Formula 16]

[20] The benzo [a] carbazole compound according to the above [5], represented by the following Formula (1-1-973).

[Formula 17]

[21] The benzo [a] carbazole compound according to the above [6], represented by the following Formula (1-2-125).

[Formula 18]

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

[23] a pair of electrodes comprising an anode and a cathode;

A light emitting layer disposed between the pair of electrodes; And

An electron transporting layer and / or an electron injection layer disposed between the cathode and the light emitting layer and containing the electron transporting material according to the above [22].

Organic electroluminescent device having a.

[24] At least one of the electron transporting layer and the electron injecting 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. The organic electroluminescent element of Claim.

[25] At least one of the electron transport layer and the electron injection layer may be an alkali metal, an alkaline earth metal, a rare earth metal, an oxide of an alkali metal, a halide of an alkali metal, an oxide of an alkaline earth metal, a halide of an alkaline earth metal, or a rare earth metal. The organic electric field according to the above [23], further containing at least one selected from the group consisting of an oxide of an oxide, a halide of a rare earth metal, an organic complex of an alkali metal, an organic complex of an alkaline earth metal, and an organic complex of a rare earth metal. Light emitting element.

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 ability. The compound of the present invention is suitable as a charge transport material in an organic EL device. By using the compound of this invention for the electron carrying layer and / or the electron injection layer of organic electroluminescent element, the organic electroluminescent element which has high luminous efficiency and long lifetime can be obtained. By using the organic electroluminescent element of this invention, high performance display apparatuses, such as a full-color display, can be created.

In the following, the present invention is described in more detail. In addition, in this specification, "a compound represented by Formula (1-1-66)" may be called "a compound (1-1-66)", for example. "Compound represented by Formula (1-1-758)" may be called "compound (1-1-758)." The same applies to other expression symbols and expression numbers.

The term "arbitrary" used in the definition of a compound may mean "a thing which can be selected freely not only in position but also in number." For example, the expression "any hydrogen of phenyl may be substituted with alkyl having 1 to 6 carbon atoms" means not only "one hydrogen may be substituted with alkyl" but also "plural hydrogens". May be substituted with the same alkyl, or different alkyl, respectively. "

The symbols Me, Et, i-Pr, tert-Bu, Cy, and Ph used in the structural formulas, chemical reaction schemes, etc. of the present specification are methyl, ethyl, isopropyl, tertiary butyl, cyclohexyl, and phenyl, respectively. Indicates.

<Compound represented by Formula (1)>

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

[Formula 19]

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 aspect of a = b = 1, a = 0 and b = 1, and a = 1 and b = 0.

In Formula (1), the aspect of a = b = 1 is a compound represented by following formula (1-1).

[Formula 20]

In the compound represented by the formula (1-1), pyridyl or bipyridyl is linked to positions 3 and 9 of benzo [a] carbazole, directly or through allylene. When the compound of the present invention is used in the electron transporting 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 transporting layer or the electron injection layer easily occurs, so that the driving voltage is lowered. It is believed to bring an effect. In the aspect of the present invention, the structure of formula (1-1) in which pyridyl or bipyridyl is connected to both ends of the molecule is more preferable. Even if allylene is interposed between benzo [a] carbazole and pyridyl or bipyridyl, there is no big change characteristically, c and d in the formula may be 0 or 1 may be used. On the other hand, as described below, the compound in which bipyridyl is directly linked to benzo [a] carbazole has a limitation in the intermediate raw material that can be used, and thus the production method that can be selected is limited. In the case of a compound in which the other or both of Py ¹ and Py ² are bipyridyl, from the viewpoint of ease of production, the side to which bipyridyl is connected is preferably via allylene.

In Formula (1), the aspect of a = 0 and b = 1 is a compound represented by following formula (1-2).

[Formula 21]

In Formula (1), the aspect of a = 1 and b = 0 is a compound represented by following formula (1-3).

[Formula 22]

In the compound represented by the formula (1-2), pyridyl or bipyridyl is linked to position 9 of benzo [a] carbazole, directly or through allylene. In the compound represented by the formula (1-3), pyridyl or bipyridyl is linked to position 3 of benzo [a] carbazole, directly or through allylene. Compounds in which pyridyl or bipyridyl are linked to one end of these molecules are preferably used in the electron transporting layer or the electron injection layer, following the compound represented by the formula (1-1). The position of the benzo [a] carbazole to which pyridyl and bipyridyl are connected may be 3rd position, and 9th position may be sufficient as it. Even if allylene is interposed between benzo [a] carbazole and pyridyl or bipyridyl, there is no large variation in characteristics, but from the viewpoint of ease of manufacture, the description of the compound represented by the formula (1-1) For the same reason as described in the above, when bipyridyl is linked, it is preferable to interpose allylene.

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

[Formula 23]

[Formula 24]

[Formula 25]

Arbitrary hydrogen of this pyridyl or bipyridyl may be substituted by C1-C6 alkyl, C3-C6 cycloalkyl, C6-C14 aryl, or C2-C12 heteroaryl. The number of substituents is the maximum number which can be substituted, for example, Preferably it is 1-3, More preferably, it is 1-2, More preferably, it is one.

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

Examples of the cycloalkyl having 3 to 6 carbon atoms include cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. In these, cyclohexyl is preferable in consideration of the availability of a raw material and the ease of manufacture.

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

Examples of the heteroaryl having 2 to 12 carbon atoms include heterocyclic groups containing 1 to 5 heteroatoms selected from oxygen, sulfur and nitrogen in addition to carbon as ring constituent atoms. Specifically, furyl, thienyl, pyrrolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, oxadiazolyl, thiadiazolyl, triazolyl, tetrazolyl, pyrazolyl, pyridyl, Pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, indolyl, isoindolyl, 1H-indazolyl, benzoimidazolyl, benzooxazolyl, benzothiazolyl, 1H-benzotriazolyl, quinolinyl, iso Quinolinyl, Cynolyl, Quinazolyl, Quinoxalinyl, Phthalaginyl, Naphthyridinyl, Purinyl, Pteridinyl, Carbazolyl, Acridinyl, Phenoxazinyl, Phenothiazinyl, Phenazinyl, Indolididi Neil, furazanyl, benzofuranyl, isobenzofuranyl, benzo [b] thienyl, phenoxatiinyl, thianthrenyl and the like can be given. Among these, pyridyl, quinolinyl and isoquinolinyl are preferable, and pyridyl is more preferable.

In the aspect of 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 preparation of the compound. Even when Py ¹ and Py ² are the same or even when they are different groups, each is represented by (Py-1-1) to (Py-1-3) and (Py-2-1) to (Py-2-18). It is preferable that it is selected from the group of the group which becomes, and (Py-1-1)-(Py-1-3), (Py-2-1)-(Py-2-3) and (Py-2-7) It is more preferable to select from the group of group represented by (Py-2-12).

Even in a = 1 and b = 0 and a = 0 and b = 1, Py ¹ or Py ² is represented by (Py-1-1) to (Py-1-3) and (Py-2-1). It is preferable that it is selected from the group of the group represented by (Py-2-18), (Py-1-1)-(Py-1-3), (Py-2-1)-(Py-2) More preferably selected from the group of the groups represented by -3) and (Py-2-7) to (Py-2-12).

In the formula ^(1), Ar 1 and Ar ^2, in the aspect of a = b = 1, it is allyl alkylene of 6 to 20 carbon atoms. In the aspect of a = 0 In addition, b = ^1, Ar 1 is an aryl of 6 to 20 carbon atoms or hydrogen, preferably in the 6 to 20 carbon atoms and aryl, Ar ² is allyl alkylene of 6 to 20 carbon atoms. In a = 1 and b = 0, Ar ¹ is allylene having 6 to 20 carbon atoms, Ar ² is hydrogen or aryl having 6 to 20 carbon atoms, and preferably aryl having 6 to 20 carbon atoms.

Examples of the aryl having 6 to 20 carbon atoms include phenyl, naphthyl, anthryl, phenanthryl, triphenylenyl, pyrenyl, chrysenyl, naphthacenyl and peryllenyl. Of these, phenyl, naphthyl, anthryl and phenanthryl are preferred, and phenyl, naphthyl and anthryl are more preferred.

Examples of the allylene having 6 to 20 carbon atoms include phenylene, naphthalenediyl, anthracenediyl, phenanthrenediyl, pyrendiyl, chrysendiyl, naphthacediyl, perylenediyl and the like. Among these, phenylene, naphthalenediyl, anthracenediyl and chrysendiyl are preferable, and phenylene, naphthalenediyl and anthracenediyl are more preferable.

Arbitrary hydrogen of the said aryl or allylene may be substituted by C1-C6 alkyl, C3-C6 cycloalkyl, or C6-C14 aryl. Specific examples of these substituents include the groups exemplified as the substituents of the aforementioned pyridyl or bipyridyl, and include methyl, ethyl, isopropyl, tert-butyl, cyclohexyl, phenyl, naphthyl, anthryl, and phenanthryl Methyl, ethyl, isopropyl, tert-butyl, cyclohexyl, phenyl, and naphthyl are more preferred, and methyl, tert-butyl and phenyl are more preferred. The number of substituents is the maximum number which can be substituted, for example, Preferably it is 1-3, More preferably, it is 1-2, More preferably, it is one.

When Ar ¹ and Ar ² are aryl, also include aryl having a substituent, and include phenyl, 1-naphthyl, 2-naphthyl, 2-biphenylyl, 3-biphenylyl, 4-biphenylyl, m -Terphenyl-5'-yl 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 allylene, 1,4-phenylene, 1,3-phenylene, 1,4-naphthalenediyl, 2,7-naphthalenediyl, and 9,10-anthracenediyl are preferable. , 1,4-phenylene, 1,4-naphthalenediyl and 9,10-anthracenediyl are more preferred.

In Formula (1), A is C6-C20 aryl, and arbitrary hydrogen of this aryl may be substituted by C1-C6 alkyl, C3-C6 cycloalkyl, or C6-C14 aryl. have. Examples of the aryl having 6 to 20 carbon atoms include the groups exemplified for Ar ¹ and Ar ² . The group illustrated as a substituent of the above-mentioned pyridyl or bipyridyl also has a C1-C6 alkyl, a C3-C6 cycloalkyl, and a C6-C14 aryl which is a substituent.

A includes aryl having a substituent, phenyl, 1-naphthyl, 2-naphthyl, 2-biphenylyl, 3-biphenylyl, 4-biphenylyl, m-terphenyl-5'-yl, And 9-phenanthryl, with phenyl, 1-naphthyl, 2-naphthyl, 3-biphenylyl, and 4-biphenylyl being more preferred.

In the formula ^(1), R 1 ~R ⁸ are independently hydrogen, heteroaryl-aryl, or 2 to 10 carbon atoms having 1 to 6 carbon atoms, cycloalkyl, having 6 to 14 carbon atoms having a carbon number of 3 to 6, the Any hydrogen of aryl or heteroaryl may be substituted with alkyl of 1 to 6 carbon atoms or cycloalkyl of 3 to 6 carbon atoms. 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 of the aforementioned pyridyl or bipyridyl. The same applies to alkyl having 1 to 6 carbon atoms and cycloalkyl having 3 to 6 carbon atoms as substituents.

R ¹ to R ⁸ are preferably hydrogen, methyl, ethyl, isopropyl, tert-butyl, cyclohexyl, and phenyl, more preferably hydrogen, methyl, tert-butyl, cyclohexyl, and phenyl, all of which are hydrogen More preferred.

In addition, Py ¹ , Py ² , Ar ¹ , Ar ² , A substituted with a hydrogen atom in benzo [a] carbazole, benzo [a] carbazole constituting the compound represented by the formula (1), and Deuterium may be sufficient as all or one part of the hydrogen atoms in R <^1> -R <^8> .

<Example of Compound>

Specific examples of the compound represented by formula (1-1) in the aspect of the present invention include compounds (1-1-1) to (1-1-861) and (1-1-871) to ( 1-1-1019). Among these, preferable compounds are (1-1-1) to (1-1-56), (1-1-65) to (1-1-67), and (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)-(1-1-113), (1-1-118), (1-1-119), (1-1-123)-(1-1-133), ( 1-1-137)-(1-1-141), (1-1-145)-(1-1-150), (1-1-154)-(1-1-159), (1- 1-163)-(1-1-177), (1-1-181)-(1-1-183), (1-1-205), (1-1-206), (1-1- 208)-(1-1-213), (1-1-215)-(1-1-220), (1-1-222)-(1-1-227), (1-1-230) -(1-1-233), (1-1-236)-(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), (1-1-630) to (1-1-635), ( 1-1-638)-(1-1-641), (1-1-644)-(1-1-647), (1-1-650)-(1-1-653), (1- 1-656)-(1-1-659), (1-1-662)-(1-1-665), (1-1-668)-(1-1-671), (1-1- 673)-(1-1-678), (1-1-680)-(1-1-685), (1-1-687) (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).

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Specific examples of the compound represented by formula (1-2) in the aspect of the present invention include compounds (1-2-1) to (1-2-365) and (1-2-381) to ( 1-2-656). Among these, preferable 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)-(1-2-212), (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).

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Specific examples of the compound represented by formula (1-3) in the aspect of the present invention include compounds (1-3-1) to (1-3-352) and (1-3-361) to ( 1-3-654). Among these, preferable compounds are (1-3-1) to (1-3-132), (1-3-136) 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)-(1-3-189), (1-3-193)-(1-3-198), (1-3-201), (1-3-202), ( 1-3-205)-(1-3-207), (1-3-211)-(1-3-214), (1-3-225)-(1-3-352), and (1 -3-479) to (1-3-620).

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<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 synthesize | combine along the route shown to the following reactions 1-8. Moreover, it can also synthesize | combine along the route shown to the following reactions 9-17.

First, as a synthesis example of the compound in which the same group was connected to the 3rd and 9th positions of the benzo [a] carbazole of formula (1), the route of reaction 1-8 is demonstrated.

[Formula 212]

Reaction 1

In reaction 1, using a palladium catalyst, (6-methoxynaphthalen-2-yl) boronic acid is reacted with a halide or triplet of 2-nitro-4-methoxybenzene in the presence of a base to cause a Suzuki coupling reaction. And compound (a-1) are synthesized. R <^1> -R <^8> in a formula is as above-mentioned including also after.

[Formula 213]

Reaction 2

In reaction 2, nitro group of compound (a-1) is reduced cyclization by triphenylphosphine: PPh ₃ or triethoxyphosphine: P (OEt) ₃ , and compound (a-2) ) Is synthesized.

Formula 214

Reaction 3

In reaction 3, a bromide or iodide of A is reacted with compound (a-2) in the presence of a base and a reaction promoter using a palladium catalyst or a copper catalyst to synthesize compound (a-3). A in Formula is the same as that mentioned above including after.

[Formula 215]

Reaction 4

In reaction 4, methyl of the methoxy group of a compound (a-3) is desorbed using a pyridine hydrochloride, and a compound (a-4) is synthesize | combined.

Formula 216

Reaction 5

In reaction 5, compound (a-5) is synthesize | combined by making trifluoromethanesulfonic anhydride react with compound (a-4) in presence of a base.

[Formula 217]

Reaction 6

In reaction 6, a bis (pinacholate) diborone is reacted with compound (a-5) in presence of a base using a palladium catalyst, and compound (a-6) is synthesize | combined.

[Formula 218]

Reaction 7

Reaction 7 is the final process. Suzuki coupling reaction of compound (a-6) obtained in Reaction 6 with 2 times mole of pyridyl, bipyridyl halide or pyridylaryl (A ⁰ ) to Suzuki coupling reaction is represented by formula (1). The compound which becomes is synthesize | combined.

[Formula 219]

Reaction 8

In addition, as in reaction 8, using a palladium catalyst to compound (a-5) obtained in reaction 5, in the presence of a base, 2 times mole of pyridyl, bipyridyl or pyridylaryl (A ⁰ ) boron A compound represented by Formula (1) can also be synthesize | combined by suzuki coupling reaction of an acid or a boric acid ester. However, when A ⁰ is 2-pyridyl or bipyridyl, considering the stability of the reaction intermediate, the reaction 7 is preferable.

Next, the route of reaction 9-17 is demonstrated as an example of the synthesis | combination of the compound in which the group different from 3rd position and 9th position of benzo [a] carbazole of Formula (1) was connected.

[Formula 220]

Reaction 9

In reaction 9, (6-methoxynaphthalen-2-yl) boronic acid is subjected to Suzuki coupling reaction to dihalo of benzene having a nitro group in the presence of a base using a palladium catalyst to give compound (b-1). Synthesize At this time, the halogen of the dihalo is selected so that the reactivity becomes X> Y. In the same manner to the above, R ¹ to R ⁸ are the same as described above including the following.

Formula 221

Reaction 10

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

Formula 222

Reaction 11

In reaction 11, a bromide or iodide of A is reacted with compound (b-2) in the presence of a base and a reaction accelerator using a palladium catalyst or a copper catalyst to synthesize compound (b-3). A in Formula is the same as that mentioned above including after.

[Formula 223]

Reaction 12

In reaction 12, using a palladium catalyst, the compound (b-4) is reacted with boric acid or a boric acid ester of pyridylaryl or aryl (A ⁰² ) in the presence of a base to synthesize compound (b-4). do. This reaction can be used even when A ⁰² is pyridyl or bipyridyl, but in view of the stability of the reaction intermediate, Y of compound (b-3) is rethioated or made into Grignard reagent, followed by It is preferable to make a boric acid ester or a boric acid according to a specific method, and to obtain compound (b-4) by the Suzuki coupling reaction of this and the halide of a pyridyl or bipyridyl.

Formula 224

Reaction 13

In reaction 13, methyl of the methoxy group of compound (b-4) is desorbed using pyridine hydrochloride, and compound (b-5) is synthesize | combined.

Formula 225

Reaction 14

In reaction 14, trifluoromethanesulfonic anhydride is reacted with compound (b-5) in presence of a base, and compound (b-6) is synthesize | combined.

[Formula 226]

Reaction 15

In reaction 15, a bis (pinacholate) diborone is reacted with compound (b-6) in the presence of a base using a palladium catalyst to synthesize compound (b-7).

[Formula 227]

Reaction 16

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

[Formula 228]

Reaction 17

In addition, compound (b-6) obtained in reaction 14 was subjected to Suzuki coupling reaction of a boric acid or boric acid ester of pyridylaryl or aryl (A ⁰¹ ) in the presence of a base using a palladium catalyst. You may synthesize | combine the compound represented by 1). This reaction can be used even when A ⁰¹ is pyridyl or bipyridyl, but in view of the stability of the reaction intermediate, reaction 16 is preferable.

The synthesis | combining method of the compound whose Ar <^1> of Formula (1-2) is hydrogen is demonstrated. When synthesize | combining by the route of reaction 1-8, instead of the (6-methoxynaphthalen-2-yl) boronic acid used by reaction 1, when naphthalene-2-ylboronic acid whose position 6 of a naphthalene ring is hydrogen is used do. When synthesize | combining by the route of reaction 9-17, when naphthalene-2-ylboronic acid in which the 6th position of a naphthalene ring is hydrogen is used instead of the (6-methoxynaphthalen-2-yl) boronic acid used by reaction 9 do.

The synthesis | combining method of the compound whose Ar <^2> of Formula (1-3) is hydrogen is demonstrated. When synthesize | combining by the route of reaction 1-8, the compound whose position 4 of a benzene ring is hydrogen may be used instead of the halide or triplelate of 2-nitro-4-methoxybenzene of reaction 1. In addition, when synthesize | combining by the route of reaction 9-17, what is necessary is just to use halide or triplelate whose Y of nitrobenzene which is a starting material of reaction 9 is hydrogen.

Moreover, the compound represented by Formula (1) can be synthesize | combined other than the path mentioned above. 2-nitrohalobenzene or triplelate in which the position 4 is previously substituted with pyridyl, bipyridyl, pyridylaryl, aryl (A ⁰² ), and the like, and the position 6 in advance is pyridyl, bipyridyl, Naphthalen-2-ylboronic acid substituted by pyridylaryl, aryl (A ⁰¹ ), etc. are synthesize | combined, respectively, and these are 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 11H-benzo [a] carbazole derivative. Finally, by reacting the bromide or iodide of A with 11H-benzo [a] carbazole derivative in the presence of a base and a reaction accelerator, using a palladium catalyst or a copper catalyst, the formula (1) of the present invention The compound represented by can be synthesized. This reaction route is suitable for synthesizing compounds having different groups at positions 3 and 9 of benzo [c] carbazole, but can also be applied to compounds having the same positions at positions 3 and 9. In either case, in the case of synthesizing a compound in which pyridyl or bipyridyl is linked to position 9 of benzo [c] carbazole, it is preferable to pass through this reaction route.

The palladium catalyst used in the Suzuki coupling reaction (reactions 1, 7, 8, 9, 12, 16, and 17) described above 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) 2 palladium (0): Pd ₂ ( dba) _3, tris (dibenzylideneacetone) 2 palladium (0) chloroform _{complex: Pd 2 (dba) 3 ·} CHCl 3, bis (dibenzylideneacetone) palladium (0): Pd (dba) _2, bis (tri tert-butylphosphino) palladium (0): Pd (P (tert-Bu) ₃ ) ₂ , or [1,1'-bis (diphenylphosphino) ferrocene] palladium (II) dichloridedichloromethane complex (1 : 1): PdCl ₂ (dppf) .CH ₂ Cl ₂ may be exemplified.

In order to promote the reaction, a phosphine compound may be added to these palladium compounds in some cases. Specific examples of the phosphine compound include tri (tert-butyl) phosphine: tert-Bu ₃ P, tricyclohexylphosphine: PCy ₃ , 1- (N, N-dimethylaminomethyl) -2- (di-tert- Butylphosphino) ferrocene, 1- (N, N-dibutylaminomethyl) -2- (di-tert-butylphosphino) ferrocene, 1- (methoxymethyl) -2- (di-tert-butylphosphino Ferrocene, 1,1'-bis (di-tert-butylphosphino) ferrocene, 2,2'-bis (di-tert-butylphosphino) -1,1'-binafyl, 2-methoxy- 2 '-(di-tert-butylphosphino) -1,1'-binafyl, and 2-dicyclohexylphosphino-2', 6'- dimethoxybiphenyl are mentioned.

Specific examples of the base used in the reaction include sodium carbonate, potassium carbonate, cesium carbonate, sodium bicarbonate, sodium hydroxide, potassium hydroxide, barium hydroxide, sodium ethoxide, sodium tert-butoxide, sodium acetate, tripotassium phosphate: K ₃ PO ₄ , and potassium fluoride.

As the solvent used in the reaction, benzene, toluene, xylene, N, N-dimethylformamide, N, N-dimethylacetamide, tetrahydrofuran, diethyl ether, tert-butylmethyl ether, 1,4-di Oxane, methanol, ethanol, isopropyl alcohol, cyclopentyl methyl ether, etc. are mentioned. These solvents may be used alone, or may be used as a mixed solvent. Although reaction is normally performed in 50-180 degreeC temperature range, it is more preferable to carry out at 70-130 degreeC.

As the reaction solvent used in the reaction 2 and the reaction 10, toluene, xylene, chlorobenzene, o-dichloro benzene, N, N-dimethylformamide, N, N-dimethylacetamide, 1-methyl-2-pyrrolidone are Is illustrated. The solvent may be used alone or in a mixed solvent. Reaction temperature is normally implemented in 100 degreeC-220 degreeC. More preferably, it is 130-190 degreeC.

When using a copper catalyst in reaction 3 and reaction 11, copper powder, copper oxide, copper halide, etc. are used. Simultaneously used bases are potassium carbonate, sodium carbonate, sodium bicarbonate, sodium hydride and the like, and the reaction accelerator is crown ether (e.g., 18-crown-6-ether), polyethylene glycol (PEG), polyethylene glycol dialkyl ether (PEGDM) etc. are mentioned. N, N-dimethylformamide, N, N-dimethylacetamide, nitrobenzene, dimethyl sulfoxide, dichlorobenzene, quinoline and the like are used as the reaction solvent. Although reaction temperature is 160-250 degreeC, when the reactivity of a board | substrate is low, it can also react at higher temperature using an autoclave etc.

In the case of using a palladium catalyst in reactions 3 and 11, palladium acetate (II): Pd (OAc) ₂ , palladium chloride: PdCl ₂ , palladium bromide PdBr ₂ , tris (dibenzylideneacetone) 2 palladium (0) : Pd ₂ (dba) ₃ , tris (dibenzylidene acetone) 2 palladium (0) chloroform complex: Pd ₂ (dba) ₃ CHCl ₃ , bis (dibenzylidene acetone) palladium (0): Pd (dba) ₂ , Bis (tritert-butylphosphino) palladium (0): Pd (P (tert-Bu) ₃ ) ₂ , or [1.1'-bis (diphenylphosphino) ferrocene] palladium (II) dichloridedichloromethane complex (1: 1): PdCl ₂ (dppf) .CH ₂ Cl ₂ or the like is used.

Bases used simultaneously include lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate, cesium carbonate, sodium hydrogen carbonate, sodium hydride, alkoxy potassium (e.g. methoxy potassium, ethoxy potassium, normal propoxy potassium, isopropoxy) Potassium, n-butoxypotassium and tert-butoxypotassium and the like, sodium alkoxy (e.g. methoxy sodium, ethoxy sodium, normal propoxy sodium, isopropoxy sodium, n-butoxy sodium and tert-part Sodium oxy) and the like.

Reaction accelerators include 2,2 '-(diphenylphosphino) -1,1'-binafyl, 1,1'-(diphenylphosphino) ferrocene, dicyclohexylphosphinobiphenyl, di-tert-butyl Phosphinobiphenyl, tri (tert-butyl) phosphine: tert-Bu ₃ P, 1- (N, N-dimethylaminomethyl) -2- (di-tert-butylphosphino) ferrocene, 1- (N, N-dibutylaminomethyl) -2- (di-tert-butylphosphino) ferrocene, 1- (methoxymethyl) -2- (di-tert-butylphosphino) ferrocene, 1,1'-bis (di -tert-butylphosphino) ferrocene, 2,2'-bis (di-tert-butylphosphino) -1,1'-vinaphthyl, 2-methoxy-2 '-(di-tert-butylphosphino ) -1,1'-binafthyl, 2-dicyclohexylphosphino-2 ', 6'- dimethoxybiphenyl, etc. are used.

As the reaction solvent, aromatic hydrocarbon solvents such as benzene, toluene, xylene and mesitylene are used. The solvent may be used alone or in a mixed solvent. Although reaction is normally performed at 50-200 degreeC, it is more preferable to carry out at 80-140 degreeC.

Examples of the reaction solvent used in the reaction 4 and the reaction 13 include 1-methyl-2-pyrrolidone, N, N-dimethylacetamide, nitrobenzene, dimethyl sulfoxide, dichlorobenzene, quinoline and the like. The solvent may be used alone or in a mixed solvent. In some cases, it may be performed without a solvent. Although reaction is normally performed in the temperature range of 150 degreeC-220 degreeC, it is more preferable to carry out at 180-200 degreeC.

When using a base 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 the reaction 5 and the reaction 14 include pyridine, toluene, xylene, N, N-dimethylformamide, N, N-dimethylacetamide, CH ₂ Cl ₂ , CHCl ₃ , and CH ₃ CN. have. These solvents may be used alone, or may be used as a mixed solvent. Although reaction is normally performed in the temperature range of -10-50 degreeC, it is more preferable to carry out at 0-30 degreeC.

As a palladium catalyst used in reaction 6 and 15, 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) 2palladium (0): Pd ₂ (dba) ₃ , tris (dibenzylideneacetone) 2palladium (0) chloroform complex : Pd ₂ (dba) ₃ CHCl ₃ , bis (dibenzylideneacetone) palladium (0): Pd (dba) ₂ , bis (tritert-butylphosphino) palladium (0): Pd (P (tert-Bu ₃ ) ₂ , or [1.1'-bis (diphenylphosphino) ferrocene] palladium (II) dichloridedichloromethane complex (1: 1): PdCl ₂ (dppf) .CH ₂ Cl ₂ . .

In order to promote the reaction, a phosphine compound may be added to these palladium compounds in some cases. This phosphine compound is tri (tert- butyl) phosphine: tert-Bu ₃ P, tricyclohexyl phosphine: PCy ₃ , 1- (N, N-dimethylaminomethyl) -2- (di-tert-butyl Phosphino) ferrocene, 1- (N, N-dibutylaminomethyl) -2- (di-tert-butylphosphino) ferrocene, 1- (methoxymethyl) -2- (di-tert-butylphosphino) Ferrocene, 1,1'-bis (di-tert-butylphosphino) ferrocene, 2,2'-bis (di-tert-butylphosphino) -1,1'-binafyl, 2-methoxy-2 '-(Di-tert-butylphosphino) -1,1'-binafyl, 2-dicyclohexylphosphino-2', 6'-dimethoxybiphenyl, etc. are mentioned.

Bases used in the reaction 6 and the reaction 15 are sodium carbonate, potassium carbonate, cesium carbonate, sodium hydrogen carbonate, sodium hydroxide, potassium hydroxide, barium hydroxide, sodium ethoxide, sodium tert-butoxide, sodium acetate, potassium acetate : KOAc, tripotassium phosphate: K ₃ PO ₄ , potassium fluoride and the like.

The solvent used in reaction 6 and reaction 15 is benzene, toluene, xylene, N, N- dimethylformamide, N, N- dimethylacetamide, tetrahydrofuran, diethyl ether, tert- butylmethyl ether, 1, 4-dioxane, methanol, ethanol, isopropyl alcohol, cyclopentyl methyl ether, and the like. These solvents may be used alone, or may be used as a mixed solvent. Although reaction is normally performed in 50-180 degreeC temperature range, it is more preferable to carry out at 70-130 degreeC.

In addition, although Suzuki coupling reaction was used in the process of bonding rings, such as aryl and heteroaryl, in the above, Negishi coupling reaction can also be used according to the kind of raw material and reagent which can be obtained.

When the compound of this invention is used for the electron injection layer or the electron carrying layer in organic electroluminescent element, it is stabilized at the time of an electric field application. This fact indicates that the compound of the present invention is excellent as an electron injection material or an electron transporting material of an electroluminescent device. The electron injection layer mentioned here is a layer which receives an electron from a cathode to an organic layer, and an electron carrying layer is a layer for conveying the injected electron to a light emitting layer. The electron transport layer may also serve as an electron injection layer. The material used for each layer is called electron injection material and electron transport material.

<Description of Organic EL Element>

2nd invention of this application is an organic electroluminescent element which contains the compound represented by Formula (1) of this invention in an electron injection layer or an electron carrying layer. The organic EL device of the present invention has a low driving voltage and high durability at the time of driving.

Although the structure of the organic electroluminescent element of this invention has various aspects, it is basically a multilayer structure which clamped at least the positive hole transport layer, the light emitting layer, and the electron carrying layer between an anode and a cathode. Examples of the specific structure of the device include (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 transporting layer / light emitting layer / electron transporting layer / electron injection layer / cathode.

Since the compound of this invention has high electron injection property and electron transport property, it can be used for an electron injection layer or an electron carrying layer in combination with a single body or another material. In the organic EL device of the present invention, light emission of blue, green, red or white can be obtained by combining a hole injection layer, a hole transport layer, a light emitting layer and the like using different materials for the electron transporting material of the present invention.

The luminescent material or luminescent dopant which can be used for the organic EL device of the present invention can be prepared by the polymer society edition, the polymer functional material series "optical functional material", Kyodo publication (1991), P236 Luminescent materials, such as brighteners, laser dyes, organic scintillators and various fluorescence assay reagents, supernatant reduction, dopant materials described in "Organic EL Materials and Displays" CMC Publishing (2001) P155-156, P170- Light emitting materials of the triplet material described in 172, and the like.

Compounds that can be used as light emitting materials or light emitting dopants include polycyclic aromatic compounds, heteroaromatic compounds, organometallic complexes, pigments, polymeric light emitting materials, styryl derivatives, aromatic amine derivatives, coumarin derivatives, borane derivatives, oxazine derivatives, Compounds having a spiro ring, oxadiazole derivatives, fluorene derivatives and the like. Examples of the polycyclic aromatic compound include anthracene derivatives, phenanthrene derivatives, naphthacene derivatives, pyrene derivatives, chrysene derivatives, perylene derivatives, coronene derivatives, rubrene derivatives and the like. Examples of heteroaromatic compounds include oxadiazole derivatives having a dialkylamino group or a diarylamino group, pyrazoloquinoline derivatives, pyridine derivatives, pyran derivatives, phenanthroline derivatives, silol derivatives, thiophene derivatives having a triphenylamino group, and quina Clidone derivatives, and the like. Examples of the organometallic complex include zinc, aluminum, beryllium, europium, terbium, dysprosium, iridium, platinum, osmium, gold and the like, quinolinol derivatives, benzoxazole derivatives, benzothiazole derivatives, oxadiazole derivatives, thiadia It is a complex with a sol derivative, a benzimidazole derivative, a pyrrole derivative, a pyridine derivative, a phenanthroline derivative, etc. Examples of the dye include xanthene derivatives, polymethine derivatives, porphyrin derivatives, coumarin derivatives, dicyano methylenepyran derivatives, dicyano methylenethiopyran derivatives, oxobenzanthracene derivatives, carbostyryl derivatives, perylene derivatives, and benzoxazole derivatives. And dyes such as benzothiazole derivatives and benzoimidazole derivatives. Examples of the polymer-based light emitting material include polyparaphenylvinylene derivatives, polythiophene derivatives, polyvinylcarbazole derivatives, polysilane derivatives, polyfluorene derivatives, polyparaphenylene derivatives, and the like. Examples of styryl derivatives include amine-containing styryl derivatives and styryl allylene derivatives.

The other electron transporting material used for the organic EL device of the present invention may be arbitrarily selected from a compound that can be used as an electron transporting compound in a photoconductive material, a compound that can be used for the electron transporting layer and the electron injection layer of the organic EL device. Can be.

Specific examples of such electron transport materials include quinolinol-based metal complexes, 2,2'-bipyridyl derivatives, phenanthroline derivatives, diphenylquinone derivatives, perylene derivatives, oxadiazole derivatives, thiophene derivatives, and tria Sol derivatives, thiadiazole derivatives, metal complexes of auxin derivatives, 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.

About the hole injection material and the hole transport material used for the organic electroluminescent element of this invention, in a photoconductive material, it is used for the compound conventionally commonly used as a charge transport material of a hole, and the hole injection layer and the hole transport layer of an organic electroluminescent element. It can select arbitrarily and use from the well-known thing used. Specific examples thereof include carbazole derivatives, triarylaryl derivatives, and phthalocyanine derivatives.

Each layer which comprises the organic electroluminescent element of this invention can be formed by making the material which comprises each layer into a thin film by methods, such as a vapor deposition method, a spin coating method, or the casting method. It does not specifically limit about the film thickness of each layer formed in this way, Although it can set suitably according to the property of a material, it is the range of 2 nm-5000 nm normally. In the method of thinning the light emitting material, it is preferable to employ a vapor deposition method in that a homogeneous film can be easily obtained and pinholes are hardly produced. When thinning using the vapor deposition method, the vapor deposition conditions differ depending on the kind of light emitting material of the present invention. Deposition conditions generally range from boat heating temperature of 50 to 400 ° C., vacuum degree of 10 to ⁶ to 10 ⁻³ Pa, deposition rate of 0.01 to 50 nm / sec, substrate temperature of −150 to + 300 ° C., and film thickness of 5 nm to 5 μm. It is preferable to set appropriately.

It is preferable that the organic electroluminescent element of this invention is supported by the board | substrate in any structure mentioned above. The substrate should just have mechanical strength, thermal stability, and transparency, and glass, a transparent plastic film, etc. can be used. The anode material may use metals, alloys, electrically conductive compounds and mixtures thereof having a work function greater than 4 eV. Specific examples thereof include metals such as Au, CuI, indium tin oxide (hereinafter abbreviated as ITO), SnO ₂ , ZnO, and the like.

The negative electrode material may use metals, alloys, electrically conductive compounds, and mixtures thereof of work functions 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, magnesium / indium and the like. In order to take out light emission of an organic EL element efficiently, it is preferable that at least one of the electrodes has a light transmittance of 10% or more. It is preferable that sheet resistance as an electrode shall be several hundred ohm / square or less. The film thickness is also limited to the properties of the electrode material, but is usually set in the range of 10 nm to 1 탆, preferably 10 to 400 nm. Such an electrode can be produced by forming a thin film by a method such as vapor deposition, sputtering or the like 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, a method for producing an organic EL device comprising the above-described anode / hole injection layer / hole transport layer / light emitting layer / electron transport material / cathode of the present invention It demonstrates. On a suitable substrate, a thin film of positive electrode material is formed by vapor deposition to fabricate an anode, and then a thin film of a hole injection layer and a hole transport layer is formed on this anode. A thin film of the light emitting layer is formed thereon. The electron transport material of this invention is vacuum-deposited on this light emitting layer, a thin film is formed, and it is set as an electron carrying layer. In addition, the target organic EL device can be obtained by forming a thin film made of a cathode material by a vapor deposition method to form a cathode. Incidentally, in the production of the organic EL device described above, the production procedure may be reversed and the cathode, the electron transport layer, the light emitting layer, the hole transport layer, the hole injection layer, and the anode may be produced in this order.

In the case of applying a DC voltage to the organic EL device thus obtained, an anode may be applied with a polarity of + and a cathode of-, and when a voltage of about 2 to 40 V is applied, a transparent or translucent electrode side (anode or Luminescence can be observed from the cathode and both). In addition, this organic EL element emits light even when an alternating voltage is applied. In addition, the waveform of alternating current to apply may be arbitrary waveform.

Example

In the following, the present invention will be described in more detail based on examples. First, the synthesis example of the benzo [a] carbazole compound used in the Example is demonstrated below.

Synthesis Example 1 Synthesis of Compound (1-1-66)

<Synthesis of 2-methoxy-6- (4-methoxy-2-nitrophenyl) naphthalene>

[Formula 229]

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

<Synthesis of 3,9-dimethoxy-11H-benzo [a] carbazole>

[Formula 230]

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 added to the flask, and the mixture was refluxed for 7 hours. After the completion of heating, the reaction solution was cooled, and pure water was added to the reaction mixture, and the precipitated solid was filtered. The solid was washed with pure water and then with methanol to obtain a crude product. This crude product was purified by a silica gel short column (solvent: toluene) to obtain 15.7 g (yield: 93%) of an intermediate compound (a-2a): 3,9-dimethoxy-11H-benzo [a] carbazole.

<Synthesis of 3,9-dimethoxy-11-phenyl-11H-benzo [a] carbazole>

[Formula 231]

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 , tri (tert-butyl) phosphine: tert-Bu ₃ P 1.70 g, phosphoric acid 35.59 g of tripotassium and 170 ml of xylene were placed in a flask, stirred, and refluxed for 10 hours. The reaction solution was cooled, the solid was removed by filtration, and the crude product obtained by distilling off the solvent under reduced pressure was purified by a silica gel column (solvent: heptane / toluene = 1/1 (volume ratio)) to obtain an intermediate compound (a- 3a): 16.4 g (yield: 83%) of 3,9-dimethoxy-11-phenyl-11H-benzo [a] carbazole were obtained.

<Synthesis of 11-phenyl-11H-benzo [a] carbazole-3,9-diol>

[Formula 232]

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 completion of 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 drying agent was removed by filtration, and the crude product obtained by distilling off the solvent under reduced pressure was purified by a silica gel short column (solvent: toluene / ethyl acetate = 6/1 (volume ratio)) to obtain an intermediate compound (a-4a): 11 14.2 g (yield: 100%) of -phenyl-11H-benzo [a] carbazole-3,9-diol were obtained.

<Synthesis of 11-phenyl-11H-benzo [a] carbazole-3,9-didibis (trifluoromethanesulfonate)>

[Formula 233]

In 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. Then, the reaction solution was stirred overnight at 0 ° C. at room temperature. Pure water was added to the reaction solution, and the precipitated solid was filtered. The obtained solid was purified by a silica gel short column (solvent: toluene), and the compound (a-5a) of the intermediate: 11-phenyl-11H-benzo [a] carbazole-3,9-diylbis (trifluoromethanesulfonate ) 25.5 g (yield: 99%).

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

Formula 234

Under a nitrogen atmosphere, 15 g of compound (a-5a), 14.21 g of bis (pinacholate) diboron, [1.1'-bis (diphenylphosphino) ferrocene] palladium (II) dichloridedichloromethane complex (1: 1) 1.25 g of (PdCl ₂ (dppf) .CH ₂ Cl ₂ ), 14.98 g of potassium acetate, and 127 ml of cyclopentylmethylether were put into a flask, stirred, and refluxed for 4 hours. After the completion of 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 drying agent was removed, and the crude product obtained by distilling off the solvent under reduced pressure was purified by a silica gel short column (solvent: toluene). Furthermore, reprecipitation was carried out with heptane, and the compound (a-6a) of the intermediate: 11-phenyl-3,9-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolane- 12 g (yield: 87%) of 2-yl) -11H-benzo [a] carbazole were obtained.

<Compound (1-1-66): Synthesis of 3,9-di ([2,3'-bipyridin] -6-yl) -11-phenyl-11H-benzo [a] carbazole>

[Formula 235]

Under a nitrogen atmosphere, 2.73 g of Compound (a-6a), 2.47 g of 6-brom-2,3'-bipyridine, 0.29 g of tetrakis (triphenylphosphine) palladium (0) (Pd (PPh ₃ ) ₄ ), 4.24 g of tripotassium phosphate and 20 ml of N, N-dimethylacetamide were added to the flask and stirred, and heated at 120 ° C for 3 hours. After the completion of the reaction, pure water was added to the reaction solution, the precipitated solid was filtered, and the obtained solid was purified by a silica gel column (solvent: toluene / ethyl acetate = 2/1 (volume ratio)), and further subjected to sublimation and purification. Compound (1-1-66): 0.5 g of 3,9-di ([2,3'-bipyridin] -6-yl) -11-phenyl-11H-benzo [a] carbazole (yield: 16% ) 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), 8.51-8.49 (m, 1H), 8.44- 8.41 (m, 1H), 8.31 (d, 2H), 8.17 (d, 1H), 8.07 (d, 1H), 7.95 (s, 1H), 7.90-7.85 (m, 12H), 7.55 (d, 1H) , 7.46-7.41 (m, 2H).

Glass transition temperature (Tg): 115 ° C

MEASURING DEVICE: Diamond DSC (made 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): Synthesis of 11-phenyl-3,9-bis (3-pyridin-3-yl) phenyl-11H-benzo [a] carbazole>

Formula 236

Under a nitrogen atmosphere, 2.0 g of compound (a-5a) 2 g, 3- (3- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl) pyridine , 0.20 g of tetrakis (triphenylphosphine) palladium (0) (Pd (PPh ₃ ) ₄ ), 2.89 g of tripotassium phosphate, and 14 ml of N, N-dimethylacetamide were added to the flask and stirred, at 120 ° C. Heated for 4 hours. After the completion of the reaction, pure water was added to the reaction solution, the precipitated solid was filtered, and the obtained solid was purified by a silica gel column (solvent: toluene / ethyl acetate = 2/1 (volume ratio)), and further subjected to sublimation and purification. Compound (1-1-758): 0.53 g (yield: 25%) of 11-phenyl-3,9-bis (3-pyridin-3-yl) phenyl-11H-benzo [a] carbazole was obtained. 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), 8.30-8.26 (m, 3H), 7.96-7.89 (m, 3H), 7.83-7.80 (m, 2H), 7.75-7.47 (m, 14H), 7.40-7.73 (m, 3H).

Glass transition temperature (Tg): 99.4 ° C

MEASURING DEVICE: Diamond DSC (made by PERKIN-ELMER); Measurement Condition: Cooling Rate 200 ° C / Min., Heating 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>

[Formula 237]

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), 7.42 g of potassium phosphate, and 70 ml of N, N-dimethylacetamide were placed in a flask, stirred for 5 minutes, and refluxed for 7 hours. After completion of the reaction, pure water was added to the reaction solution, and the precipitated solid (crude) was collected by filtration, and the obtained solid was purified by NH-DM1020 (manufactured by Fujisilsia Chemical Co., Ltd.) column (solvent: toluene) to obtain an intermediate. Compound (b-1b): 6.17 g (yield: 88%) of 3-methoxy-11-phenyl-9- (pyridin-3-yl) -11H-benzo [a] carbazole were obtained.

<Synthesis of 11-phenyl-9- (pyridin-3-yl) -11H-benzo [a] carbazole-3-ol>

Formula 238

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 completion of heating, the reaction solution was cooled, 100 ml of pure water was added, and the precipitated solid was filtered to obtain a crude product. The crude product was purified by a silica gel short column (solvent: toluene) to obtain compound (b-2b) of the intermediate: 11-phenyl-9- (pyridin-3-yl) -11H-benzo [a] carbazole-3-ol. 5.4 g (yield: 90.8%) was obtained.

Synthesis of 11-phenyl-9- (pyridin-3-yl) -11H-benzo [a] carbazol-3-yl trifluoro methane sulfonate

[Formula 239]

Under a nitrogen atmosphere, 5.4 g of compound (b-2b) and 56 ml of pyridine were placed in a flask, and 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 drying agent was removed by filtration, and the crude product obtained by distilling off the solvent under reduced pressure was purified by a silica gel column (solvent: toluene / ethyl acetate = 2/1 (volume ratio)) to obtain an intermediate compound (b-3b): 11- 6.65 g (yield: 91.8%) of phenyl-9- (pyridin-3-yl) -11H-benzo [a] carbazol-3-yl trifluoromethanesulfonate were obtained.

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

[Formula 240]

Under a nitrogen atmosphere, 2.2 g of compound (b-3b), 0.80 g of 2-naphthalene boronic acid, 0.15 g of tetrakis (triphenylphosphine) palladium (0) (Pd (PPh ₃ ) ₄ ), 1.80 g of tripotassium phosphate, and 21 ml (toluene / ethanol = 4/1 (volume ratio)) of a mixed solvent of toluene and ethanol was 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, pure water was added, and the precipitated solid was filtered to obtain crude product 1. The organic layer of the filtrate was separated and dried over anhydrous sodium sulfate. The drying agent was removed by filtration, and the solid obtained by distilling off the solvent under reduced pressure was used as crude product 2. Next, Preparations 1 and 2 were combined and purified by a silica gel column (solvent: toluene / ethyl acetate = 10/1 (volume ratio)). Thereafter, the mixture is recrystallized from toluene and further subjected to sublimation purification to obtain the desired compound (1-2-8): 3-([naphthalen-2-yl) -11-phenyl-9- (pyridin-3-yl) 0.8 g (yield: 38%) of -11H-benzo [a] carbazole 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), 8.30-8.28 (dd, 2H), 8.15 (s, 1H), 7.95- 7.84 (m, 6H), 7.73-7.48 (m, 10H), 7.35-7.73 (m, 2H).

Glass transition temperature (Tg): 98.2 ° C

MEASURING DEVICE: Diamond DSC (made by PERKIN-ELMER); Measurement Condition: Cooling Rate 200 ° C / Min., Heating Rate 10 ° C / Min.]

Synthesis Example 4 Synthesis of Compound (1-2-28)

<Compound (1-2-28): Synthesis of 3- (4- (naphthalen-2-yl) phenyl) -11-phenyl-9- (pyridin-3-yl) -11H-benzo [a] carbazole>

[Formula 241]

Under 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, tripotassium phosphate 1.80 g, and 21 ml (toluene / ethanol = 4/1 (volume ratio)) of a mixed solvent of toluene and ethanol 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, pure water was added, and the precipitated solid was collected by filtration, washed with pure water and then with methanol, dissolved in heated toluene, and the undissolved one was removed by high temperature filtration. Furthermore, after purifying 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 was carried out with ethyl acetate and further sublimation purification was carried out to obtain the desired 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), 7.95-7.80 (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 to 7.33 (m, 2H).

No glass transition temperature (Tg) was observed.

Synthesis Example 5 Synthesis of Compound (1-3-206)

<Synthesis of 2- (4-chloro-2-nitrophenyl) -6-methoxynaphthalene>

[Formula 242]

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 placed in a flask, stirred for 5 minutes, and 38 ml of pure water was added and refluxed for 5 hours. After the completion of heating, the reaction solution was cooled and the precipitated solid was filtered to obtain crude product 1. The organic layer of the filtrate was separated, dried over anhydrous sodium sulfate, the drying agent was removed by filtration, and the solid obtained by distilling off the solvent under reduced pressure was used as crude product 2. Thereafter, Preparations 1 and 2 were combined and purified by a silica gel short column (solvent: toluene). Furthermore, reprecipitation was carried out with heptane to give 12.9 g (yield: 85.7%) of intermediate compound (b-1a): 2- (4-chloro-2-nitrophenyl) -6-methoxynaphthalene.

<Synthesis of 9-chloro-3-methoxy-11H-benzo [a] carbazole>

[Formula 243]

Under a nitrogen atmosphere, 12.9 g of the compound (b-1a), 26.96 g of triphenylphosphine and 82 ml of o-dichlorobenzene were put into a flask and stirred, and the mixture was refluxed for 7.5 hours. After the completion of 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) to obtain 10.3 g (yield: 89%) of intermediate compound (b-2a): 9-chloro-3-methoxy-11H-benzo [a] carbazole. .

<Synthesis of 9-chloro-3-methoxy-11-phenyl-11H-benzo [a] carbazole>

[Formula 244]

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

<9-([1,1'-biphenyl] -3-yl) -3-methoxy-11-phenyl-11H-benzo [a] carbazole

Formula 245

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, 6.16 g of tripotassium phosphate, and 58 ml of toluene 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 the reaction was completed, the reaction solution was cooled and 50 ml of pure water was added. The reaction mixture was extracted with toluene, the organic layer was dried over anhydrous sodium sulfate, the drying agent was removed by filtration, and the solvent was distilled off under reduced pressure. A crude product obtained was subjected to silica gel column (solvent: heptane / toluene = 3/1 (volume ratio)). Compound of the intermediate (b-4a): 9-([1,1'-biphenyl] -3-yl) -3-methoxy-11-phenyl-11H-benzo [a] carbazole 6.66 g (yield: 97%) was obtained.

<9-([1,1'-biphenyl] -3-yl) -11-phenyl-11H-benzo [a] carbazole-3-ol

Formula 246

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 completion of the heating, the reaction solution was cooled, 100 ml of pure water was added, and the precipitated solid was filtered to obtain a crude product. The crude product was purified by a silica gel short column (solvent: toluene) to obtain compound (b-5a) of the intermediate: 9-([1,1'-biphenyl] -3-yl) -11-phenyl-11H-benzo [ a] 6.32 g (yield: 100%) of carbazole-3-ol were obtained.

<Synthesis of 9-([1,1'-biphenyl] -3-yl) -11-phenyl-11H-benzo [a] carbazol-3-yl trifluoromethanesulfonate>

Formula 247

Under a nitrogen atmosphere, 6.32 g of compound (b-5a) and 35 ml of pyridine were placed in a flask, and cooled to 0 ° C, followed by slowly dropping 7.73 g of trifluoromethanesulfonic anhydride. 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 drying agent was removed by filtration, and the crude product obtained by distilling off the solvent under reduced pressure was purified by a silica gel short column (solvent: toluene) to obtain compound (b-6a) of the intermediate: 9-([1,1'-biphenyl). 7.4 g (yield: 91%) of] -3-yl) -11-phenyl-11H-benzo [a] carbazol-3-yl trifluoromethanesulfonate.

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

Formula 248

Under a nitrogen atmosphere, 5.2 g of the compound (b-6a), 2.7 g of bis (pinacholate) diborane, [1.1'-bis (diphenylphosphino) ferrocene] palladium (II) dichloridedichloromethane complex (1: 1) 0.21 g of (PdCl ₂ (dppf) .CH ₂ Cl ₂ ), 2.58 g of potassium acetate, and 45 ml of cyclopentylmethyl ether were put into a flask, stirred, and refluxed for 4 hours. After the 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 drying agent was removed by filtration, and the crude product obtained by distilling off the solvent under reduced pressure was purified by an activated carbon short column (solvent: toluene) to obtain compound (b-7a) of the intermediate: 9-([1,1'-biphenyl). ] -3-yl) -11-phenyl-3- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -11H-benzo [a] carbazole 4.53 g (yield: 90.6%) was obtained.

<Compound (1-3-206): 9-([1,1'-biphenyl] -3-yl) -3-([2,3'-bipyridin] -6-yl) -11-phenyl- Synthesis of 11H-benzo [a] carbazole>

[Formula 249]

Under a nitrogen atmosphere, 1.94 g of Compound (b-7a), 0.88 g of 6-brom-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 the reaction was completed, pure water was added to the reaction solution, and the precipitated solid (crude) was filtered. The obtained solid was purified by a silica gel column (solvent: toluene / ethyl acetate = 10/1 (volume ratio)), and further sublimed to purify the target compound (1-3-206): 9-([1,1 ' 0.89 g (yield: 44%) of -biphenyl] -3-yl) -3-([2,3'-bipyridin] -6-yl) -11-phenyl-11H-benzo [a] carbazole was obtained. . 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), 8.31-8.27 (q, 2H), 8.07 ( dd, 1H), 7.90-7.88 (m, 3H), 7.83 (s, 1H), 7.73-7.35 (m, 18H).

Glass transition temperature (Tg): 107.4 ° C

MEASURING DEVICE: Diamond DSC (made by PERKIN-ELMER); Measurement Condition: Cooling Rate 200 ° C / Min., Heating 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- (pyridin-3-yl) phenyl) -11H-benzo [a] Synthesis of Carbazole>

[Formula 250]

Under a nitrogen atmosphere, 2 g of compound (b-6a) and 0.95 g of 3- (3- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl) pyridine 0.12 g of tetrakis (triphenylphosphine) palladium (0) (Pd (PPh ₃ ) ₄ ), 1.43 g of tripotassium phosphate, and 15 ml of N, N-dimethylacetamide were added to the flask, followed by stirring. Heated for 4 hours. After the reaction was completed, pure water was added to the reaction solution, extraction was performed with toluene, and the organic layer was dried over anhydrous sodium sulfate. The drying agent was removed by filtration, and the crude product obtained by distilling off the solvent under reduced pressure was purified by a silica gel column (solvent: toluene / ethyl acetate = 10/1 (volume ratio)), and further subjected to sublimation purification to obtain a target compound ( 1-3-300): 9-([1,1'-biphenyl] -3-yl) -11-phenyl-3- (3- (pyridin-3-yl) phenyl) -11H-benzo [a] 1.29 g (yield: 64%) of carbazole were 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), 8.31-8.26 (m, 3H), 7.95 (dt, 1H), 7.90 (s, 1H), 7.83- 7.82 (m, 2 H), 7.76-7.39 (m, 21 H).

Glass transition temperature (Tg): 99.6 degrees Celsius

MEASURING DEVICE: Diamond DSC (made by PERKIN-ELMER); Measurement Condition: Cooling Rate 200 ° C / Min., Heating Rate 10 ° C / Min.]

Synthesis Example 7 Synthesis of Compound (1-1-2)

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

[Formula 251]

Under a nitrogen atmosphere, 2.95 g of compound (a-5a), 1.23 g of 3-pyridineboronic acid, 0.14 g of bis (dibenzylideneacetone) palladium (0) (Pd (dba) ₂ ), tricyclohexylphosphine (PCy ₃₎ 0.11 g), 4.25 g of tripotassium phosphate, and 25 ml of N, N-dimethylacetamide were placed in a flask, stirred for 5 minutes, and heated at 120 ° C for 5 hours. After the reaction was completed, pure water was added to the reaction solution, and the precipitated solid was filtered. The obtained solid was purified by a silica gel column (solvent: toluene / ethyl acetate = 2/1 (volume ratio)) and further reprecipitated with heptane. Finally, sublimation purification was carried out to obtain target compound (1-1-2): 0.90 g of 11-phenyl-3,9-di (pyridin-3-yl) -11H-benzo [a] carbazole (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), 7.62-7.58 (m, 3H), 7.52-7.47 (m, 2H) , 7.40 to 7.33 (m, 3H).

Glass transition temperature (Tg): 91.2 ° C

MEASURING DEVICE: Diamond DSC (made by PERKIN-ELMER); Measurement Condition: Cooling Rate 200 ° C / Min., Heating Rate 10 ° C / Min.]

Synthesis Example 8 Synthesis of Compound (1-1-765)

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

[Formula 252]

Under a nitrogen atmosphere, 2.5 g of compound (a-6a), 2.15 g of 4- (4-bromophenyl) pyridine, 0.26 g of tetrakis (triphenylphosphine) palladium (0) (Pd (PPh ₃ ) ₄ ), phosphoric acid 3.89 g of tripotassium and 20 ml of N, N-dimethylacetamide were placed in a flask and stirred, and heated at 120 ° C for 6 hours. After the reaction was completed, pure water was added to the reaction solution, and the precipitated solid was filtered. The obtained solid was purified by NH-DM1020 (manufactured by Fujisilsia Chemical Co., Ltd.) column (solvent: toluene), and further reprecipitated with ethyl acetate. Finally, sublimation purification is carried out to obtain the desired compound (1-1-765): 11-phenyl-3,9-bis (4- (pyridin-4-yl) phenyl) -11H-benzo [a] carbazole 1.4 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 7.82 (m, 15H), 7.58 to 7.48 (m, 6H), 7.41 (s , 1H).

Synthesis Example 9 Synthesis of Compound (1-1-893)

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

Formula 253

Under 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, 3.89 g of tripotassium phosphate and 25 ml of N, N-dimethylacetamide were placed in a flask and stirred, and heated at 120 ° C for 6 hours. After the reaction was completed, pure water was added to the reaction solution, and the precipitated solid was filtered. The obtained solid was purified by NH-DM1020 (manufactured by Fujisilsia Chemical Co., Ltd.) column (solvent: toluene / ethyl acetate = 8/1 (volume ratio)), and further reprecipitated with ethyl acetate. Finally, sublimation purification is carried out to obtain the desired compound (1-1-893): 3,9-bis (5'-methyl- [2,3'-bipyridin] -6-yl) -11-phenyl- 1.6 g (yield: 56%) of 11H-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), 8.30-8.26 (m, 3H), 7.82-7.81 (m, 3H), 7.75-7.82 (m, 11H), 7.56-7.41 (m , 4H), 7.36 (dd, 2H), 2.65 (s, 6H).

Glass transition temperature (Tg): 114.0 ° C

MEASURING DEVICE: Diamond DSC (made by PERKIN-ELMER); Measurement Condition: Cooling Rate 200 ° C / Min., Heating Rate 10 ° C / Min.]

Synthesis Example 10 Synthesis of Compound (1-1-973)

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

Formula 254

Under a nitrogen atmosphere, 2.5 g of Compound (a-6a), 2.1 g of 4- (4-chlorophenyl) -2-methylpyridine, 0.16 g of bis (dibenzylideneacetone) palladium (0) (Pd (dba) ₂ ), 0.12 g of tricyclohexylphosphine (PCy ₃ ), 4.0 g of tripotassium phosphate, 25 ml of 1,2,4-trimethylbenzene, 2.5 ml of tert-butyl alcohol and 2.5 ml of water were put in a flask and refluxed for 6 hours. After the reaction was completed, pure water was added to the reaction solution, and the precipitated solid was filtered. The obtained solid was purified by NH-DM1020 (manufactured by Fujisilsia Chemical Co., Ltd.) column (solvent: toluene / ethyl acetate = 10/1 (volume ratio)), and further reprecipitated with ethyl acetate. Finally, sublimation purification is carried out to obtain the desired compound (1-1-973): 3,9-bis (4- (2-methylpyridin-4-yl) phenyl) -11-phenyl-11H-benzo [a ] 1.8 g (yield: 60%) of carbazole were 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), 7.90-77.6 (m, 14H), 7.57 (d, 1H), 2.48 (s, 3H), 2.45 (s, 3H).

Glass transition temperature (Tg): 116.2 ° C

MEASURING DEVICE: Diamond DSC (made by PERKIN-ELMER); Measurement Condition: Cooling Rate 200 ° C / Min., Heating Rate 10 ° C / Min.]

<Compound (1-2-125): Synthesis of 11-phenyl-3- (10-phenylanthracene 9-yl) -9- (pyridin-3-yl) -11H-benzo [a] carbazole>

[Formula 255]

Under a nitrogen atmosphere, 2.2 g of the compound (b-3b), 1.64 g of 10-phenylanthracene 9-yl) boronic acid, 0.15 g of tetrakis (triphenylphosphine) palladium (0) (Pd (PPh ₃ ) ₄ ), phosphoric acid 1.80 g of tripotassium and 21 ml (toluene / ethanol = 4/1 (volume ratio)) of a mixed solvent of toluene and ethanol 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 heating, the pure water was added, and the precipitated solid was filtered. The obtained solid was purified by a silica gel column (solvent: toluene / ethyl acetate = 4/1 (volume ratio)), and further reprecipitated with ethyl acetate. Finally, sublimation purification is carried out to obtain the desired compound (1-2-125): 11-phenyl-3- (10-phenylanthracene-9-yl) -9- (pyridin-3-yl) -11H-benzo 0.81 g (yield: 31%) of [a] 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

MEASURING DEVICE: Diamond DSC (made by PERKIN-ELMER); Measurement Condition: Cooling Rate 200 ° C / Min., Heating Rate 10 ° C / Min.]

By selecting the compound of a raw material suitably, the other compound of this invention can be synthesize | combined by the method according to the said synthesis example.

Hereinafter, in order to demonstrate this invention further in detail, the Example of the organic electroluminescent element using the compound of this invention is shown, but this invention is not limited to these.

An organic EL device according to Examples 1 to 3 and Comparative Examples 1 to 3 was fabricated, and measurement of voltage (V), which is a characteristic at 1000 cd / m ² light emission, EL emission wavelength (nm), and external quantum efficiency (% ) Was measured, and then the brightness half time (hour (hr)) when the constant current was driven at a current density capable of obtaining a luminance of 2000 cd / m ² was measured. Hereinafter, an Example and a comparative example are explained in full detail.

The quantum efficiency of the light emitting device includes an internal quantum efficiency and an external quantum efficiency. However, the internal quantum efficiency represents a ratio in which external energy injected as electrons (or holes) into the light emitting layer of the light emitting device is purely converted to photons. On the other hand, it is the external quantum efficiency that is calculated based on the amount of photons emitted to the outside of the light emitting element, and a part of the photons generated in the light emitting layer is absorbed or continuously reflected inside the light emitting element, and thus the outside of the light emitting element Since it is not emitted as, the external quantum efficiency is lower than the internal quantum efficiency.

The measuring method of external quantum efficiency is as follows. Using a voltage / current generator R6144 manufactured by Advantest, the device was made to emit light by applying a current whose luminance is 1000 cd / m ² . The spectral radiance of the visible light region was measured from the perpendicular direction with respect to the light emitting surface using the spectral radiance luminance meter SR-3AR manufactured by TOPCON. Assuming that the light emitting surface is a fully diffusive surface, the value of the spectral radiance luminance of each wavelength component measured is divided by the wavelength energy and multiplied by π is the number of photons at each wavelength. Subsequently, photon number was integrated in all the observed wavelength ranges, and it was set as the total photon number emitted from the element. The external quantum efficiency is the number obtained by dividing the applied current value by the low charge as the number of carriers injected into the device, and the total number of photons emitted from the device divided by the number of carriers injected into the device.

The material structure of each layer in the produced organic EL element which concerns on Examples 1-3 and Comparative Examples 1-3 is shown in Table 1 below.

TABLE 1

In Table 1, "HI" is N ^4, N ^{4 '-} diphenyl -N ^4, N ^4' - bis (9-phenyl -9H- carbazole-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'-ratio Phenyl] -4,4'-diamine, "BH1" is 9- (4- (naphthalen-1-yl) phenyl) -10-phenylanthracene, and "BH2" is 9-phenyl-10- (4-phenylnaphthalene- 1-yl) anthracene, "BD1" means 4,4 '-(7,7-diphenyl-7H-benzo [c] fluorene-5,9-diyl) bis (phenylazanediyl) 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. A chemical structure is shown below with quinolinol lithium "Liq".

[Formula 256]

Example 1 Device Using Compound (1-1-66) as Electron Transport Layer

A 26 mm x 28 mm x 0.7 mm glass substrate (manufactured by Offscience Co., Ltd.), which was polished to 150 nm by ITO formed into a film at a thickness of 180 nm by sputtering, was used as a transparent support substrate. The transparent support substrate is fixed to a substrate holder of a commercial vapor deposition apparatus manufactured by Showa Vacuum Co., Ltd., and a molybdenum vapor deposition boat with HI, a molybdenum vapor deposition boat with HT, and a molybdenum vapor deposition with BH1 is used. Boat, evaporation boat made of molybdenum containing BD1, evaporation boat made of molybdenum containing compound (1-1-66) of the present invention, evaporation boat made of molybdenum containing quinolinol lithium (Liq) and tungsten made of aluminum Evaporation boats were mounted.

The following each layer was formed sequentially on the ITO film | membrane of a transparent support substrate. The vacuum chamber was decompressed to 5 × 10 ⁻⁴ Pa, first, the deposition boat containing HI was heated to be deposited so as to have a film thickness of 40 nm to form a hole injection layer, and then the deposition boat containing HT was heated. The film was deposited to have a 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 simultaneously heated to be deposited so as to have a film thickness of 25 nm to form a light emitting layer. The deposition rate was adjusted so that the weight ratio of BH1 and BD1 was approximately 95: 5. Next, the evaporation boat containing compound (1-1-66) and the evaporation boat containing Liq were simultaneously heated to be deposited so as to have a film thickness of 20 nm to form an electron transporting layer. The deposition rate was adjusted so that the weight ratio of 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 deposition boat containing Liq was heated and deposited at a deposition rate of 0.01 to 0.1 nm / second so that the film thickness was 1 nm. Subsequently, a vapor deposition boat containing aluminum was heated to deposit aluminum at a deposition rate of 0.01 to 2 nm / second so that the film thickness was 100 nm, thereby forming a cathode to obtain an organic EL device.

When the ITO electrode was used as an anode and the Liq / aluminum electrode was used as a cathode, the characteristics at 1000 cd / m ² light emission were measured. As a result, the driving voltage was 3.8 V and the external quantum efficiency was 4.3% (blue light emission having a wavelength of about 451 nm). ). In addition, when the constant current drive test was conducted with the current density for obtaining the 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 by the method according to Example 1, except that compound (1-1-66) of the electron transport layer was changed to compound (ET1). The ITO electrode was used as the anode and the quinolinolithium / aluminum electrode as the cathode, and the characteristics at 1000 cd / m ² light emission were measured. As a result, the driving voltage was 5.5 V and the external quantum efficiency was 3.2% (blue with a wavelength of about 451 nm). Luminescence). In addition, when the constant current drive test was conducted with the current density for obtaining the 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 Device Using Compound (1-1-758) as Electron Transport Layer

Compound (BH1), the host material of the light emitting layer, was changed to Compound (BH2), and compound (BD1), the dopant material of the light emitting layer, was changed to Compound (BD2), and compound (1-1, which is the electron transporting material of the electron transporting layer). An organic EL device was obtained by the method according to Example 1, except that -66) was changed to compound (1-1-758). When the ITO electrode was used as the anode and the quinolinolithium / aluminum electrode was used as the cathode, the characteristics at 1000 cd / m ² emission were measured. As a result, the driving voltage was 5.8 V and the external quantum efficiency was 5.1% (wavelength: about 455 nm). Blue light emission). In addition, when the constant current drive test was conducted with the current density for obtaining the 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 Electron Transport Layer

The same transparent support substrate as that used in Example 1 was fixed to a substrate holder of a commercially available deposition apparatus (manufactured by Showa Vacuum Co., Ltd.), and a molybdenum deposition boat with HI, a molybdenum deposition boat with HT, BH1 Molybdenum evaporation boats containing tungsten, molybdenum evaporation boats containing BD1, molybdenum evaporation boats containing compound (1-1-66) of the present invention, molybdenum evaporation boats containing Liq and tungsten containing aluminum Evaporation boats were mounted.

The following each layer was formed sequentially on the ITO film | membrane of a transparent support substrate. The vacuum chamber was decompressed to 5 × 10 ^-4 Pa, first, the deposition boat containing HI was heated to be deposited so as to have a film thickness of 40 nm to form a hole injection layer, and then the deposition boat containing HT. Was heated to deposit 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 simultaneously heated to be deposited so as to have a film thickness of 25 nm to form a light emitting layer. The deposition rate was adjusted so that the weight ratio of BH1 and BD1 was approximately 95: 5. Next, the evaporation boat containing compound (1-1-66) was heated to deposit a film thickness of 20 nm to form an electron transporting layer. The deposition rate of each layer was 0.01 to 1 nm / second.

Thereafter, the deposition boat containing Liq was heated and deposited at a deposition rate of 0.01 to 0.1 nm / second so that the film thickness was 1 nm. Subsequently, a vapor deposition boat containing aluminum was heated to deposit aluminum at a deposition rate of 0.01 to 2 nm / second so that the film thickness was 100 nm, thereby forming a cathode to obtain an organic EL device.

When the ITO electrode was used as an anode and the Liq / aluminum electrode was used as a cathode, the characteristics at 1000 cd / m ² light emission were measured. As a result, the driving voltage was 3.7 V and the external quantum efficiency was 4.5% (blue light emission having a wavelength of about 451 nm). ). Moreover, when the constant current drive test was done with the current density for obtaining initial luminance 2000 cd / m <^2> , the time to hold | maintain the brightness | luminance of 77% (1540 cd / m <^2> ) or more of initial value was 345 hours.

Comparative Example 2

An organic EL device was obtained by the method according to Example 3, except that compound (1-1-66), which is an electron transporting material of the electron transporting layer, was changed to compound (ET1). When the ITO electrode was used as the anode and the quinolinolithium / aluminum electrode was used as the cathode, the characteristics at 1000 cd / m ² emission were measured. As a result, the driving voltage was 5.4 V and the external quantum efficiency was 2.5% (wavelength: about 453 nm Blue light emission). In addition, when the constant current drive test was conducted with the current density for obtaining the 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 hour.

Comparative Example 3

An organic EL device was obtained by the method according to Example 3, except that compound (1-1-66), which is an electron transporting material of the electron transporting layer, was changed to compound (ET2). When the ITO electrode was used as an anode and the quinolinolithium / aluminum electrode was used as a cathode, the characteristics at 1000 cd / m ² emission were measured. As a result, the driving voltage was 5.4 V and the external quantum efficiency was 2.2% (wavelength: about 453 nm). Blue light emission). Moreover, when the constant current drive test was done with the current density for obtaining initial luminance 2000 cd / m <^2> , the time to hold | maintain the brightness | luminance of 77% (1540 cd / m <^2> ) or more of initial value was 22 hours.

The above result was put together in Table 2 and shown.

TABLE 2

The material structure of each layer in the organic electroluminescent element produced according to Examples 4-8 and Comparative Examples 4-7 is shown in Table 3 below.

TABLE 3

In Table 3, "HI2" is 1,4,5,8,9,12-hexaazatriphenylene-2,3,6,7,10,11-hexacarbonitrile, and "ET3" is 5,9- Di ([2,3'-bipyridin] -6-yl) -7-phenyl-7H-benzo [c] carbazole, "ET4" is 3- (6- (10-phenylanthracene-9-yl) naphthalene 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.

Formula 257

Example 4 Device Using Compound (1-1-66) as Electron Transport Layer

A 26 mm x 28 mm x 0.7 mm glass substrate (manufactured by Offscience Co., Ltd.), which was polished to 150 nm by ITO formed into a film at a thickness of 180 nm by sputtering, was used as a transparent support substrate. The transparent support substrate is fixed to a substrate holder of a commercially available deposition apparatus (manufactured by Showa Vacuum Co., Ltd.), and a molybdenum deposition boat containing HI, a molybdenum deposition boat containing HI2, and a molybdenum deposition container containing HT are used. Boat, molybdenum deposition boat with BH2, molybdenum deposition boat with BD2, molybdenum deposition boat with compound (1-1-66) of the present invention, molybdenum deposition boat with Liq and aluminum A tungsten vapor deposition boat was mounted.

The following each layer was formed sequentially on the ITO film | membrane of a transparent support substrate. The vacuum chamber was decompressed to 5 × 10 ⁻⁴ Pa, first, the deposition boat containing HI was heated to be deposited so as to have a film thickness of 40 nm to form a first hole injection layer, and the deposition boat containing HI 2 was further formed. Was heated to deposit a film thickness of 5 nm to form a second hole injection layer, and then a deposition boat containing HT was heated to deposit a film thickness of 25 nm to form a hole transport layer. Next, the vapor deposition boat containing BH2 and the vapor deposition boat containing BD2 were simultaneously heated to be deposited so as to have a film thickness of 20 nm to form a light emitting layer. The deposition rate was adjusted so that the weight ratio of BH2 and BD2 was approximately 95: 5. Next, the evaporation boat containing compound (1-1-66) and the evaporation boat containing Liq were simultaneously heated to deposit a film thickness of 30 nm to form an electron transporting layer. The deposition rate was adjusted so that the weight ratio of 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 deposition boat containing Liq was heated and deposited at a deposition rate of 0.01 to 0.1 nm / second so that the film thickness was 1 nm. Subsequently, a vapor deposition boat containing aluminum was heated to deposit aluminum at a deposition rate of 0.01 to 2 nm / second so that the film thickness was 100 nm, thereby forming a cathode to obtain an organic EL device.

When the ITO electrode was used as an anode and the Liq / aluminum electrode was used as a cathode, the characteristics at 1000 cd / m ² light emission were measured. As a result, the driving voltage was 3.8 V and the external quantum efficiency was 5.1% (blue light emission having a wavelength of about 454 nm). ). Moreover, when the constant current drive test was done with the current density for obtaining the initial luminance of 2000 cd / m <^2> , time to hold | maintain 80% (1600 cd / m <^2> ) or more of brightness | luminance of an initial value was 396 hours.

[Comparative Example 4]

An organic EL device was obtained by the method according to Example 4, except that compound (1-1-66) of the electron transport layer was changed to compound (ET3). When the ITO electrode was used as an anode and the Liq / aluminum electrode was used as a cathode, the characteristics at 1000 cd / m ² light emission were measured. As a result, the driving voltage was 4.0 V and the external quantum efficiency was 4.6% (blue light emission having a wavelength of about 458 nm). ). Moreover, when the constant current drive test was conducted with the current density for obtaining initial luminance 2000 cd / m <^2> , time to hold | maintain 80% (1600 cd / m <^2> ) or more of brightness | luminance of an initial value was 279 hours.

Example 5 Device Using Compound (1-2-125) as Electron Transport Layer

A 26 mm x 28 mm x 0.7 mm glass substrate (manufactured by Offscience Co., Ltd.), which was polished to 150 nm by ITO formed into a film at a thickness of 180 nm by sputtering, was used as a transparent support substrate. The transparent support substrate is fixed to a substrate holder of a commercially available deposition apparatus (manufactured by Showa Vacuum Co., Ltd.), and a molybdenum deposition boat with HI, a molybdenum deposition boat with HI2, and a molybdenum deposition container with HT are used. Boat, molybdenum deposition boat with BH2, molybdenum deposition boat with BD2, molybdenum deposition boat with compound (1-2-125) of the present invention, molybdenum deposition boat with Liq, magnesium A molybdenum vapor deposition boat containing silver and a molybdenum vapor deposition boat containing silver were mounted.

The following each layer was formed sequentially on the ITO film | membrane of a transparent support substrate. The vacuum chamber was decompressed to 5 × 10 ⁻⁴ Pa, first, the deposition boat containing HI was heated to be deposited so as to have a film thickness of 40 nm to form a first hole injection layer, and the deposition boat containing HI 2 was further formed. Was heated to deposit a film thickness of 5 nm to form a second hole injection layer, and then a deposition boat containing HT was heated to deposit a film thickness of 25 nm to form a hole transport layer. Next, the vapor deposition boat containing BH2 and the vapor deposition boat containing BD2 were simultaneously heated to be deposited so as to have a film thickness of 20 nm to form a light emitting layer. The deposition rate was adjusted so that the weight ratio of BH2 and BD2 was approximately 95: 5. Next, the evaporation boat containing compound (1-2-125) and the evaporation boat containing Liq were simultaneously heated to be deposited so as to have a film thickness of 30 nm to form an electron transporting layer. The deposition rate was adjusted so that the weight ratio of 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 deposition boat containing Liq was heated and deposited at a deposition rate of 0.01 to 0.1 nm / second so that the film thickness was 1 nm. Subsequently, the boat containing magnesium and the boat containing silver were simultaneously heated to be deposited so that the film thickness was 100 nm to form a cathode. At this time, the deposition rate was adjusted so that the atomic ratio of magnesium and silver was 10: 1, and the deposition rate was 0.01-2 nm / second to obtain an organic EL device.

The ITO electrode was used as an anode, and the Liq / magnesium + silver electrode was used as a cathode. As a result of measuring characteristics at 1000 cd / m ² emission, the driving voltage was 3.8 V and the external quantum efficiency was 6.0% (wavelength of about 458 nm). Blue light emission). Moreover, as a result of the constant current drive test by the current density for obtaining the 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 by the method according to Example 5, except that compound (1-2-125) of the electron transport layer was changed to compound (ET4). When the ITO electrode was used as an anode and the Liq / magnesium + silver electrode was used as a cathode, the characteristics at 1000 cd / m ² emission were measured. As a result, the driving voltage was 3.5 V and the external quantum efficiency was 5.5% (wavelength of about 454 nm). Blue light emission). Moreover, when the constant current drive test was done with the current density for obtaining initial luminance 2000 cd / m <^2> , the time to hold | maintain 80% (1600 cd / m <^2> ) or more of brightness | luminance of initial value was 170 hours.

Example 6 Device Using Compound (1-3-206) in an Electron Transport Layer

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 (1-3-206). The ITO electrode was used as an anode, and the Liq / magnesium + silver electrode was used as a cathode. As a result of measuring characteristics at 1000 cd / m ² emission, the driving voltage was 3.8 V and the external quantum efficiency was 5.3% (wavelength of about 455 nm). Blue light emission). Moreover, as a result of the constant current drive test by the current density for obtaining the 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 compound (1-2-125) of the electron transport layer was changed to compound (ET5). The ITO electrode was used as an anode, and the Liq / magnesium + silver electrode was used as a cathode. As a result of measuring characteristics at 1000 cd / m ² emission, the driving voltage was 3.9 V and the external quantum efficiency was 4.4% (wavelength of about 456 nm). Blue light emission). In addition, when the constant current drive test was conducted with the current density for obtaining the 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 Device Using Compound (1-1-893) as Electron Transport Layer

A 26 mm x 28 mm x 0.7 mm glass substrate (manufactured by Offscience Co., Ltd.), which was polished to 150 nm by ITO formed into a film at a thickness of 180 nm by sputtering, was used as a transparent support substrate. The transparent support substrate is fixed to a substrate holder of a commercially available deposition apparatus (manufactured by Showa Vacuum Co., Ltd.), and a molybdenum deposition boat containing HI, a molybdenum deposition boat containing HI2, and a molybdenum deposition container containing HT are used. Boat, molybdenum deposition boat with BH2, molybdenum deposition boat with BD2, molybdenum deposition boat with compound (1-1-893) of the present invention, molybdenum deposition boat with Liq, magnesium A molybdenum vapor deposition boat containing silver and a molybdenum vapor deposition boat containing silver were mounted.

The following each layer was formed sequentially on the ITO film | membrane of a transparent support substrate. The vacuum chamber was decompressed to 5 × 10 ⁻⁴ Pa, first, the deposition boat containing HI was heated to be deposited so as to have a film thickness of 40 nm to form a first hole injection layer, and the deposition boat containing HI 2 was further formed. Was heated to deposit a film thickness of 5 nm to form a second hole injection layer, and then a deposition boat containing HT was heated to deposit a film thickness of 25 nm to form a hole transport layer. Next, the vapor deposition boat containing BH2 and the vapor deposition boat containing BD2 were simultaneously heated to be deposited so as to have a film thickness of 20 nm to form a light emitting layer. The deposition rate was adjusted so that the weight ratio of BH2 and BD2 was approximately 95: 5. Next, the evaporation boat containing compound (1-1-893) was heated to deposit a film thickness of 30 nm to form an electron transporting layer. The deposition rate of each layer was 0.01 to 1 nm / second.

Thereafter, the deposition boat containing Liq was heated and deposited at a deposition rate of 0.01 to 0.1 nm / second so that the film thickness was 1 nm. Subsequently, the boat containing magnesium and the boat containing silver were simultaneously heated to be deposited so that the film thickness was 100 nm to form a cathode. At this time, the deposition rate was adjusted so that the atomic ratio of magnesium and silver was 10: 1, and the deposition rate was 0.01-2 nm / second to obtain an organic EL device.

The ITO electrode was used as an anode, and the Liq / magnesium + silver electrode was used as a cathode. As a result of measuring characteristics at 1000 cd / m ² emission, the driving voltage was 3.3 V and the external quantum efficiency was 3.6% (wavelength of about 456 nm). Blue light emission). In addition, when the constant current drive test was conducted with the current density for obtaining the 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 Device Using Compound (1-1-973) for Electron Transport Layer

An organic EL device was obtained by the method according to Example 7 except that the compound (1-1-893) of the electron transport layer was changed to the compound (1-1-973). The ITO electrode was used as an anode, and the Liq / magnesium + silver electrode was used as a cathode. As a result of measuring characteristics at 1000 cd / m ² emission, the driving voltage was 4.2 V and the external quantum efficiency was 4.8% (wavelength of about 456 nm). Blue light emission). In addition, when the constant current drive test was conducted with the current density for obtaining the 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 by the method according to Example 7 except that the compound (1-1-893) of the electron transport layer was changed to the compound (ET6). The ITO electrode was used as an anode, and the Liq / magnesium + silver electrode was used as a cathode. As a result of measuring characteristics at 1000 cd / m ² emission, the driving voltage was 5.6 V and the external quantum efficiency was 4.8% (wavelength of about 455 nm). Blue light emission). In addition, when the constant current drive test was conducted with the current density for obtaining the 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 result was put together in Table 4 and shown.

TABLE 4

* Time to keep luminance above 90% of initial luminance

The material structure of each layer in the organic electroluminescent element produced according to Example 9, 10 and Comparative Examples 8 and 9 is shown in Table 5 below.

TABLE 5

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 '-(dimethyl boryl)-[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.

Formula 258

Example 9 Device Using Compound (1-1-765) as Electron Transport Layer

A 26 mm x 28 mm x 0.7 mm glass substrate (manufactured by Offscience Co., Ltd.), which was polished to 150 nm by ITO formed into a film at a thickness of 180 nm by sputtering, was used as a transparent support substrate. The transparent support substrate is fixed to a substrate holder of a commercially available deposition apparatus (manufactured by Showa Vacuum Co., Ltd.), and a molybdenum deposition boat containing HI, a molybdenum deposition boat containing HI2, and a molybdenum deposition container containing HT are used. Boat, Molybdenum deposition boat with BH2, Molybdenum deposition boat with BD2, Molybdenum deposition boat with compound (1-1-765) of the present invention, Molybdenum deposition boat with ET7, Lithium fluoride A molybdenum vapor deposition boat containing (LiF) and a tungsten vapor deposition boat containing aluminum were mounted.

The following each layer was formed sequentially on the ITO film | membrane of a transparent support substrate. The vacuum chamber was decompressed to 5 × 10 ⁻⁴ Pa, first, the deposition boat containing HI was heated to be deposited so as to have a film thickness of 40 nm to form a first hole injection layer, and the deposition boat containing HI 2 was further formed. Was heated to deposit a film thickness of 5 nm to form a second hole injection layer, and then a deposition boat containing HT was heated to deposit a film thickness of 25 nm to form a hole transport layer. Next, the vapor deposition boat containing BH2 and the vapor deposition boat containing BD2 were simultaneously heated to be deposited so as to have a film thickness of 20 nm to form a light emitting layer. The deposition rate was adjusted so that the weight ratio of BH2 and BD2 was approximately 95: 5. Next, the deposition boat containing the compound (1-1-765) was heated to be deposited so that the film thickness was 20 nm to form the first electron transport layer, and the deposition boat containing ET7 was heated to increase the film thickness. It deposited so that it might be set to 10 nm, and the 2nd layer electron carrying layer was formed. The deposition rate of each layer was 0.01 to 1 nm / second.

Thereafter, the deposition boat containing LiF was heated and deposited at a deposition rate of 0.01 to 0.1 nm / second so that the film thickness was 1 nm. Subsequently, a vapor deposition boat containing aluminum was heated to deposit aluminum at a deposition rate of 0.01 to 2 nm / second so that the film thickness was 100 nm, thereby forming a cathode to obtain an organic EL device.

When the ITO electrode was used as the anode and the LiF / aluminum electrode was used as the cathode, the characteristics at 1000 cd / m ² emission were measured. As a result, the driving voltage was 3.8 V and the external quantum efficiency was 5.3% (blue light emission having a wavelength of about 456 nm). ). Moreover, as a result of the constant current drive test by the current density for obtaining the 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 by the method according to Example 9, except that compound (1-1-765) of the electron transport layer was changed to compound (ET8). When the ITO electrode was used as an anode and the LiF / aluminum electrode was used as a cathode, the characteristics at 1000 cd / m ² light emission were measured. As a result, the driving voltage was 5.3 V and the external quantum efficiency was 4.3% (blue light emission having a wavelength of about 455 nm). ). In addition, when the constant current drive test was conducted with the current density for obtaining the 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 Device Using Compound (1-1-973) as Electron Transport Layer

A 26 mm x 28 mm x 0.7 mm glass substrate (manufactured by Offscience Co., Ltd.), which was polished to 150 nm by ITO formed into a film at a thickness of 180 nm by sputtering, was used as a transparent support substrate. The transparent support substrate is fixed to a substrate holder of a commercially available deposition apparatus (manufactured by Showa Vacuum Co., Ltd.), and a molybdenum deposition boat containing HI, a molybdenum deposition boat containing HI2, and a molybdenum deposition container containing HT are used. Boat, molybdenum deposition boat with BH2, molybdenum deposition boat with BD2, molybdenum deposition boat with ET9, molybdenum deposition boat with compound (1-1-973) of the present invention, lithium fluoride A molybdenum vapor deposition boat containing (LiF) and a tungsten vapor deposition boat containing aluminum were mounted.

The following each layer was formed sequentially on the ITO film | membrane of a transparent support substrate. The vacuum chamber was decompressed to 5 × 10 ⁻⁴ Pa, first, the deposition boat containing HI was heated to be deposited so as to have a film thickness of 40 nm to form a first hole injection layer, and the deposition boat containing HI 2 was further formed. Was heated to deposit a film thickness of 5 nm to form a second hole injection layer, and then a deposition boat containing HT was heated to deposit a film thickness of 25 nm to form a hole transport layer. Next, the vapor deposition boat containing BH2 and the vapor deposition boat containing BD2 were simultaneously heated to be deposited so as to have a film thickness of 20 nm to form a light emitting layer. The deposition rate was adjusted so that the weight ratio of BH2 and BD2 was approximately 95: 5. Next, the deposition boat containing the compound (ET9) was heated to be deposited so that the film thickness was 20 nm to form the first electron transport layer, and the deposition boat containing the compound (1-1-973) was heated to The film was deposited to have a thickness of 10 nm to form an electron transport layer for the second layer. The deposition rate of each layer was 0.01 to 1 nm / second.

Thereafter, the deposition boat containing LiF was heated and deposited at a deposition rate of 0.01 to 0.1 nm / second so that the film thickness was 1 nm. Subsequently, a vapor deposition boat containing aluminum was heated to deposit aluminum at a deposition rate of 0.01 to 2 nm / second so that the film thickness was 100 nm, thereby forming a cathode to obtain an organic EL device.

When the ITO electrode was used as the anode and the LiF / aluminum electrode was used as the cathode, the characteristics at 1000 cd / m ² light emission were measured. As a result, the driving voltage was 4.3 V and the external quantum efficiency was 5.9% (blue light emission having a wavelength of about 457 nm). ). In addition, when the constant current drive test was conducted with the current density for obtaining the 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 the method according to Example 10, except that compound (1-1-973) of the electron transport layer was changed to compound (ET10). When the ITO electrode was used as an anode and the LiF / aluminum electrode was used as a cathode, the characteristics at 1000 cd / m ² light emission were measured. As a result, the driving voltage was 4.3 V and the external quantum efficiency was 5.4% (blue light emission having a wavelength of about 455 nm). ). In addition, when the constant current drive test was conducted with the current density for obtaining the 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 result was put together in Table 6 and shown.

TABLE 6

The material structure of each layer in the organic EL element produced according to Examples 11-15 is shown in Table 7 below.

TABLE 7

Example 11 Device Using Compound (1-1-765) as Electron Transport Layer

A 26 mm x 28 mm x 0.7 mm glass substrate (manufactured by Offscience Co., Ltd.), which was polished to 150 nm by ITO formed into a film at a thickness of 180 nm by sputtering, was used as a transparent support substrate. The transparent support substrate is fixed to a substrate holder of a commercially available deposition apparatus (manufactured by Showa Vacuum Co., Ltd.), and a molybdenum deposition boat containing HI, a molybdenum deposition boat containing HI2, and a molybdenum deposition container containing HT are used. Boat, molybdenum deposition boat with BH2, molybdenum deposition boat with BD2, molybdenum deposition boat with compound (1-1-765) of the present invention, molybdenum deposition boat with Liq and aluminum A tungsten vapor deposition boat was mounted.

The following each layer was formed sequentially on the ITO film | membrane of a transparent support substrate. The vacuum chamber was decompressed to 5 × 10 ⁻⁴ Pa, first, the deposition boat containing HI was heated to be deposited so as to have a film thickness of 40 nm to form a first hole injection layer, and the deposition boat containing HI 2 was further formed. Was heated to deposit a film thickness of 5 nm to form a second hole injection layer, and then a deposition boat containing HT was heated to deposit a film thickness of 25 nm to form a hole transport layer. Next, the vapor deposition boat containing BH2 and the vapor deposition boat containing BD2 were simultaneously heated to be deposited so as to have a film thickness of 20 nm to form a light emitting layer. The deposition rate was adjusted so that the weight ratio of BH2 and BD2 was approximately 95: 5. Next, the evaporation boat containing compound (1-1-765) and the evaporation boat containing Liq were simultaneously heated to be deposited so as to have a film thickness of 20 nm to form an electron transport layer. The deposition rate was adjusted so that the weight ratio of compound (1-1-765) and Liq was approximately 1: 1. The deposition rate of each layer was 0.01 to 1 nm / second.

Thereafter, the deposition boat containing Liq was heated and deposited at a deposition rate of 0.01 to 0.1 nm / second so that the film thickness was 1 nm. Subsequently, a vapor deposition boat containing aluminum was heated to deposit aluminum at a deposition rate of 0.01 to 2 nm / second so that the film thickness was 100 nm, thereby forming a cathode to obtain an organic EL device.

When the ITO electrode was used as an anode and the Liq / aluminum electrode was used as a cathode, the characteristics of 1000 cd / m ² light emission were measured. As a result, the driving voltage was 3.7 V and the external quantum efficiency was 7.4% (blue light emission of about 456 nm wavelength). ). In addition, when the constant current drive test was conducted with the current density for obtaining the 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 by the method according to Example 11 except that Compound (1-1-765) in the electron transport layer was changed to Compound (1-2-125). When the ITO electrode was used as the anode and the Liq / aluminum electrode was used as the cathode, the characteristics at 1000 cd / m ² light emission were measured. As a result, the driving voltage was 4.3 V and the external quantum efficiency was 6.2% (blue light emission having a wavelength of about 456 nm). ). In addition, when the constant current drive test was conducted with the current density for obtaining the 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 Device Using Compound (1-1-2) as Electron Transport Layer

A 26 mm x 28 mm x 0.7 mm glass substrate (manufactured by Offscience Co., Ltd.), which was polished to 150 nm by ITO formed into a film at a thickness of 180 nm by sputtering, was used as a transparent support substrate. The transparent support substrate is fixed to a substrate holder of a commercially available deposition apparatus (manufactured by Showa Vacuum Co., Ltd.), and a molybdenum deposition boat containing HI, a molybdenum deposition boat containing HI2, and a molybdenum deposition container containing HT are used. Boat, molybdenum deposition boat with BH2, molybdenum deposition boat with BD2, molybdenum deposition boat with compound (1-1-2) of the present invention, molybdenum deposition boat with Liq, magnesium A molybdenum vapor deposition boat containing silver and a molybdenum vapor deposition boat containing silver were mounted.

The following each layer was formed sequentially on the ITO film | membrane of a transparent support substrate. The vacuum chamber was decompressed to 5 × 10 ⁻⁴ Pa, first, the deposition boat containing HI was heated to be deposited so as to have a film thickness of 40 nm to form a first hole injection layer, and the deposition boat containing HI 2 was further formed. Was heated to deposit a film thickness of 5 nm to form a second hole injection layer, and then a deposition boat containing HT was heated to deposit a film thickness of 25 nm to form a hole transport layer. Next, the vapor deposition boat containing BH2 and the vapor deposition boat containing BD2 were simultaneously heated to be deposited so as to have a film thickness of 20 nm to form a light emitting layer. The deposition rate was adjusted so that the weight ratio of BH2 and BD2 was approximately 95: 5. Next, the evaporation boat containing compound (1-1-2) and the evaporation boat containing Liq were simultaneously heated to deposit a film thickness of 20 nm to form an electron transporting layer. The deposition rate was adjusted so that the weight ratio of compound (1-1-2) and Liq was approximately 1: 1. The deposition rate of each layer was 0.01 to 1 nm / second.

Thereafter, the deposition boat containing Liq was heated and deposited at a deposition rate of 0.01 to 0.1 nm / second so that the film thickness was 1 nm. Subsequently, the boat containing magnesium and the boat containing silver were simultaneously heated to be deposited so that the film thickness was 100 nm to form a cathode. At this time, the deposition rate was adjusted so that the atomic ratio of magnesium and silver was 10: 1, and the deposition rate was 0.01-2 nm / second to obtain an organic EL device.

The ITO electrode was used as an anode, and the Liq / magnesium + silver electrode was used as a cathode. As a result of measuring characteristics at 1000 cd / m ² emission, the driving voltage was 3.9 V and the external quantum efficiency was 6.2% (wavelength of about 458 nm). Blue light emission). In addition, when the constant current drive test was conducted with the current density for obtaining the 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 by the method according to Example 13, except that compound (1-1-2) of the electron transport layer was changed to compound (1-1-765). The ITO electrode was used as an anode, and the Liq / magnesium + silver electrode was used as a cathode. As a result of measuring characteristics at 1000 cd / m ² emission, the driving voltage was 3.5 V and the external quantum efficiency was 6.7% (wavelength of about 457 nm). Blue light emission). In addition, when the constant current drive test was conducted with the current density for obtaining the 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 the method according to Example 13, except that compound (1-1-2) of the electron transport layer was changed to compound (1-1-973). The ITO electrode was used as an anode, and the Liq / magnesium + silver electrode was used as a cathode. As a result of measuring characteristics at 1000 cd / m ² emission, the driving voltage was 3.8 V and the external quantum efficiency was 6.7% (wavelength of about 455 nm). Blue light emission). Moreover, when the constant current drive test was done with the current density for obtaining initial luminance 2000 cd / m <^2> , the time to hold | maintain 80% (1600 cd / m <^2> ) or more of brightness | luminance of initial value was 170 hours.

The above result was put together in Table 8 and shown.

TABLE 8

[Industry availability]

According to the preferable aspect of this invention, the organic electroluminescent element excellent in luminous efficiency and element lifetime, the display apparatus provided with this, the illuminating device provided with this, etc. can be provided.

Claims (25)

Benzo [a] carbazole compounds represented by the following formula (1):
[Formula 1]

In the formula (1),
a, b, c, and d are independently 1 or 0, a and b are not 0 at the same time, a and c are not 0 at the same time, and b and d are not 0 at the same time;
Py ¹ and Py ² are independently pyridyl or bipyridyl, and any hydrogen of this pyridyl or bipyridyl is alkyl having 1 to 6 carbons, cycloalkyl having 3 to 6 carbons, aryl having 6 to 14 carbon atoms, Or substituted with heteroaryl having 2 to 12 carbon atoms;
Ar ¹ is aryl having 6 to 20 carbon atoms when a is 0, arylene is 6 to 20 carbon atoms when a is 1, Ar ² is hydrogen or aryl having 6 to 20 carbon atoms when b is 0, b Is arylene having 6 to 20 carbon atoms, and any of these aryl or arylene may be substituted with alkyl having 1 to 6 carbon atoms, cycloalkyl having 3 to 6 carbon atoms, or aryl having 6 to 14 carbon atoms. There is;
A is C6-C20 aryl, and arbitrary hydrogen of this aryl may be substituted by C1-C6 alkyl, C3-C6 cycloalkyl, or C6-C14 aryl;
R ¹ to R ⁸ are independently hydrogen, alkyl of 1 to 6 carbon atoms, cycloalkyl of 3 to 6 carbon atoms, aryl of 6 to 14 carbon atoms, or hetero aryl of 2 to 10 carbon atoms, and any of this aryl or hetero aryl. Hydrogen may be substituted with alkyl of 1 to 6 carbon atoms or cycloalkyl of 3 to 6 carbon atoms; Also,
At least 1 hydrogen in the compound represented by said Formula (1) may be substituted by deuterium. The method of claim 1,
Benzo [a] carbazole compounds represented by the following formula (1-1):
[Formula 2]

In the formula (1-1),
Py ¹ and Py ² are independently pyridyl or bipyridyl, and any hydrogen of this pyridyl or bipyridyl is alkyl having 1 to 6 carbons, cycloalkyl having 3 to 6 carbons, aryl having 6 to 14 carbon atoms, Or substituted with heteroaryl having 2 to 12 carbon atoms;
Ar ¹ and Ar ² are independently arylene having 6 to 20 carbon atoms, and any hydrogen of the arylene is substituted with alkyl having 1 to 6 carbon atoms, cycloalkyl having 3 to 6 carbon atoms, or aryl having 6 to 14 carbon atoms. There may be;
A is C6-C20 aryl, and arbitrary hydrogen of this aryl may be substituted by C1-C6 alkyl, C3-C6 cycloalkyl, or C6-C14 aryl;
R ¹ to R ⁸ are independently hydrogen, alkyl of 1 to 6 carbon atoms, cycloalkyl of 3 to 6 carbon atoms, aryl of 6 to 14 carbon atoms, or hetero aryl of 2 to 10 carbon atoms, and any of this aryl or hetero aryl. Hydrogen may be substituted with alkyl of 1 to 6 carbon atoms or cycloalkyl of 3 to 6 carbon atoms; And,
c and d are independently 1 or 0. The method of claim 1,
Benzo [a] carbazole compounds represented by the following formula (1-2):
[Formula 3]

In the formula (1-2),
Py ² is pyridyl or bipyridyl, and any hydrogen of this pyridyl or bipyridyl is alkyl having 1 to 6 carbon atoms, cycloalkyl having 3 to 6 carbon atoms, aryl having 6 to 14 carbon atoms, or 2 to 12 carbon atoms. May be substituted with a hetero aryl;
Ar ¹ is C6-C20 aryl, and arbitrary hydrogen of this aryl may be substituted by C1-C6 alkyl, C3-C6 cycloalkyl, or C6-C14 aryl;
Ar ² is arylene having 6 to 20 carbon atoms, and arbitrary hydrogen of this arylene may be substituted with alkyl having 1 to 6 carbon atoms, cycloalkyl having 3 to 6 carbon atoms, or aryl having 6 to 14 carbon atoms;
A is C6-C20 aryl, and arbitrary hydrogen of this aryl may be substituted by C1-C6 alkyl, C3-C6 cycloalkyl, or C6-C14 aryl;
R ¹ to R ⁸ are independently hydrogen, alkyl of 1 to 6 carbon atoms, cycloalkyl of 3 to 6 carbon atoms, aryl of 6 to 14 carbon atoms, or hetero aryl of 2 to 10 carbon atoms, and any of this aryl or hetero aryl. Hydrogen may be substituted with alkyl of 1 to 6 carbon atoms or cycloalkyl of 3 to 6 carbon atoms; And,
d is 1 or 0. The method of claim 1,
Benzo [a] carbazole compounds represented by the following formula (1-3):
[Formula 4]

In the formula (1-3),
Py ¹ is pyridyl or bipyridyl, and any hydrogen of this pyridyl or bipyridyl is alkyl having 1 to 6 carbon atoms, cycloalkyl having 3 to 6 carbon atoms, aryl having 6 to 14 carbon atoms, or 2 to 12 carbon atoms. May be substituted with a hetero aryl;
Ar ¹ is arylene having 6 to 20 carbon atoms, and arbitrary hydrogen of the arylene may be substituted with alkyl having 1 to 6 carbon atoms, cycloalkyl having 3 to 6 carbon atoms, or aryl having 6 to 14 carbon atoms;
Ar ² is hydrogen or aryl having 6 to 20 carbon atoms, and any hydrogen of this aryl may be substituted with alkyl having 1 to 6 carbon atoms, cycloalkyl having 3 to 6 carbon atoms, or aryl having 6 to 14 carbon atoms;
A is C6-C20 aryl, and arbitrary hydrogen of this aryl may be substituted by C1-C6 alkyl, C3-C6 cycloalkyl, or C6-C14 aryl;
R ¹ to R ⁸ are independently hydrogen, alkyl of 1 to 6 carbon atoms, cycloalkyl of 3 to 6 carbon atoms, aryl of 6 to 14 carbon atoms, or hetero aryl of 2 to 10 carbon atoms, and any of this aryl or hetero aryl. Hydrogen may be substituted with alkyl of 1 to 6 carbon atoms or cycloalkyl of 3 to 6 carbon atoms; And,
c is 1 or 0. The method of claim 2,
Py ¹ and Py ² are the groups of groups independently represented by the following formulas (Py-1-1) to (Py-1-3) and formulas (Py-2-1) to (Py-2-18) It is one chosen from,
[Formula 5]

[Formula 6]

Any of the hydrogens in these groups may be substituted with methyl, ethyl, isopropyl, tert-butyl, cyclohexyl, phenyl, naphthyl, or pyridyl;
Ar ¹ and Ar ² are independently phenylene, naphthalenediyl, anthracenediyl, or chrysendiyl, and any hydrogen of these groups is methyl, ethyl, isopropyl, tert-butyl, cyclohexyl, phenyl, or naphthyl May be substituted;
A is phenyl, naphthyl or phenanthryl, and any hydrogen in these groups may be substituted with methyl, ethyl, isopropyl, tert-butyl, cyclohexyl, phenyl, or naphthyl;
R ¹ to R ⁸ are independently hydrogen, methyl, ethyl, isopropyl, tert-butyl, cyclohexyl, or phenyl; And,
A benzo [a] carbazole compound, wherein c and d are independently 1 or 0. The method of claim 3,
Py ² is one selected from the group of groups represented by the following formula (Py-1-1) to formula (Py-1-3) and formula (Py-2-1) to formula (Py-2-18). Is,
[Formula 7]

[Formula 8]

Any of the hydrogens in these groups may be substituted with methyl, ethyl, isopropyl, tert-butyl, cyclohexyl, phenyl, naphthyl, or pyridyl;
Ar ¹ is hydrogen, phenyl, naphthyl, anthryl, phenanthryl, or chrysenyl, and any hydrogen in these groups is substituted with methyl, ethyl, isopropyl, tert-butyl, cyclohexyl, phenyl, or naphthyl May be present;
Ar ² is phenylene, naphthalenediyl, anthracenediyl, or chrysendiyl, and any hydrogen of these groups may be substituted with methyl, ethyl, isopropyl, tert-butyl, cyclohexyl, phenyl, or naphthyl ;
A is phenyl, naphthyl or phenanthryl, and any hydrogen in these groups may be substituted with methyl, ethyl, isopropyl, tert-butyl, cyclohexyl, phenyl, or naphthyl;
R ¹ to R ⁸ are independently hydrogen, methyl, ethyl, isopropyl, tert-butyl, cyclohexyl, or phenyl; And,
A benzo [a] carbazole compound, wherein d is 1 or 0. The method of claim 4, wherein
Py ¹ is one selected from the group of groups represented by the following formula (Py-1-1) to formula (Py-1-3) and formula (Py-2-1) to formula (Py-2-18) Is,
[Formula 9]

[Formula 10]

Any of the hydrogens in these groups may be substituted with methyl, ethyl, isopropyl, tert-butyl, cyclohexyl, phenyl, naphthyl, or pyridyl;
Ar ¹ is phenylene, naphthalenediyl, anthracenediyl, or chrysendiyl, and any hydrogen of these groups may be substituted with methyl, ethyl, isopropyl, tert-butyl, cyclohexyl, phenyl, or naphthyl ;
Ar ² is hydrogen, phenyl, naphthyl, anthryl, phenanthryl, or chrysenyl, and any hydrogen of these groups is substituted with methyl, ethyl, isopropyl, tert-butyl, cyclohexyl, phenyl, or naphthyl May be present;
A is phenyl, naphthyl or phenanthryl, and any hydrogen in these groups may be substituted with methyl, ethyl, isopropyl, tert-butyl, cyclohexyl, phenyl, or naphthyl;
R ¹ to R ⁸ are independently hydrogen, methyl, ethyl, isopropyl, tert-butyl, cyclohexyl, or phenyl; And,
benzo [a] carbazole compound wherein c is 1 or 0. The method of claim 5,
Py ¹ and Py ² are independently formula (Py-1-1), formula (Py-1-2), formula (Py-1-3), formula (Py-2-1), formula (Py-2- 2), formula (Py-2-3), formula (Py-2-7), formula (Py-2-8), formula (Py-2-9), formula (Py-2-10), formula ( Py-2-11), and one group selected from the group represented by the formula (Py-2-12), and any hydrogen of these groups is methyl, tert-butyl, phenyl, naphthyl, or pyridyl May be substituted with;
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, and any hydrogen of these groups may be substituted with methyl, tert-butyl, or phenyl;
A is phenyl, 1-naphthyl, 2-naphthyl, or 9-phenanthryl, and any hydrogen in these groups may be substituted with methyl, tert-butyl, or phenyl;
R ¹ to R ⁸ are all hydrogen; And,
A benzo [a] carbazole compound, wherein c and d are independently 1 or 0. The method of claim 6,
Py ² is formula (Py-1-1), formula (Py-1-2), formula (Py-1-3), formula (Py-2-1), formula (Py-2-2), formula ( Py-2-3), formula (Py-2-7), formula (Py-2-8), formula (Py-2-9), formula (Py-2-10), formula (Py-2-11 ) And one group selected from the group represented by the formula (Py-2-12), and any hydrogen of these groups may be substituted with methyl, tert-butyl, phenyl, naphthyl, or pyridyl. There is;
Ar ¹ is hydrogen, phenyl, 1-naphthyl, 2-naphthyl, or 9-phenanthryl, and any hydrogen in these groups may be substituted with methyl, tert-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, and any hydrogen of these groups may be substituted with methyl, tert-butyl, or phenyl;
A is phenyl, 1-naphthyl, 2-naphthyl, or 9-phenanthryl, and any hydrogen in these groups may be substituted with methyl, tert-butyl, or phenyl;
R ¹ to R ⁸ are all hydrogen; And,
A benzo [a] carbazole compound, wherein d is 1 or 0. The method of claim 7, wherein
Py ¹ is formula (Py-1-1), formula (Py-1-2), formula (Py-1-3), formula (Py-2-1), formula (Py-2-2), formula ( Py-2-3), formula (Py-2-7), formula (Py-2-8), formula (Py-2-9), formula (Py-2-10), formula (Py-2-11 ) And one group selected from the group represented by the formula (Py-2-12), and any hydrogen of these groups may be substituted with methyl, tert-butyl, phenyl, naphthyl, or pyridyl. There is;
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, and any hydrogen of these groups may be substituted with methyl, tert-butyl, or phenyl;
Ar ² is hydrogen, phenyl, 1-naphthyl, 2-naphthyl, or 9-phenanthryl, and any hydrogen in these groups may be substituted with methyl, tert-butyl, cyclohexyl, or phenyl;
A is phenyl, 1-naphthyl, 2-naphthyl, or 9-phenanthryl, and any hydrogen in these groups may be substituted with methyl, tert-butyl, or phenyl;
R ¹ to R ⁸ are all hydrogen; And,
benzo [a] carbazole compound wherein c is 1 or 0. The method of claim 5,
Py ¹ and Py ² independently represent formula (Py-1-1), formula (Py-1-2), formula (Py-1-3), formula (Py-2-2), and formula (Py-2- 3), one selected from the group of groups represented by formula (Py-2-8), formula (Py-2-9), formula (Py-2-11), and formula (Py-2-12) Is;
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,
A benzo [a] carbazole compound, wherein c and d are independently 1 or 0. The method of claim 6,
Py ² independently represents formula (Py-1-1), formula (Py-1-2), formula (Py-1-3), formula (Py-2-2), formula (Py-2-3), One selected from the group of the groups represented by formula (Py-2-8), formula (Py-2-9), formula (Py-2-11), and formula (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,
A benzo [a] carbazole compound, wherein d is 1 or 0. The method of claim 7, wherein
Py ¹ independently represents formula (Py-1-1), formula (Py-1-2), formula (Py-1-3), formula (Py-2-2), formula (Py-2-3), One selected from the group of the groups represented by formula (Py-2-8), formula (Py-2-9), formula (Py-2-11), and formula (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,
benzo [a] carbazole compound wherein c is 1 or 0. The method of claim 5,
Benzo [a] carbazole compounds represented by the following formula (1-1-66) or formula (1-1-758):
[Formula 11]

. The method of claim 6,
Benzo [a] carbazole compounds represented by the following formula (1-2-8) or formula (1-2-28):
[Formula 12]

. The method of claim 7, wherein
Benzo [a] carbazole compounds represented by the following formula (1-3-206) or formula (1-3-300):
[Formula 13]

. The method of claim 5,
Benzo [a] carbazole compounds represented by the following formula (1-1-2):
[Formula 14]

. The method of claim 5,
Benzo [a] carbazole compounds represented by the following formula (1-1-765):
[Formula 15]

. The method of claim 5,
Benzo [a] carbazole compounds represented by the following formula (1-1-893):
[Formula 16]

. The method of claim 5,
Benzo [a] carbazole compounds represented by the following formula (1-1-973):
[Formula 17]

. The method of claim 6,
Benzo [a] carbazole compounds represented by the following formula (1-2-125):
[Formula 18]

. An electron transporting material containing the compound according to any one of claims 1 to 21. A pair of electrodes consisting of an anode and a cathode;
A light emitting layer disposed between the pair of electrodes; And
The electron transport layer, the electron injection layer, or the electron transport layer and the electron injection layer which are arrange | positioned between the said cathode and the said light emitting layer, and contain the electron carrying material of Claim 22
Organic electroluminescent device having a. The method of claim 23, wherein
At least one of the said electron carrying layer and an electron injection layer further contains at least 1 selected from the group which consists of a quinolinol type metal complex, a bipyridine derivative, a phenanthroline derivative, and a borane derivative. The method of claim 23, wherein
At least one of the electron transport layer and the electron injection layer is an alkali metal, an alkaline earth metal, a rare earth metal, an oxide of an alkali metal, a halide of an alkali metal, an oxide of an alkaline earth metal, an halide of an alkaline earth metal, an oxide of a rare earth metal, An organic electroluminescent device further comprising at least one selected from the group consisting of halides of rare earth metals, organic complexes of alkali metals, organic complexes of alkaline earth metals, and organic complexes of rare earth metals.