KR20150018776A - Cyclic azine compound, method for producing same, and organic electroluminescent element containing same - Google Patents

Abstract

(식 중, Cz는 (n+1)가의 카바졸기 또는 (n+1)가의 카볼린기(이들 기는, 각각 독립적으로, 불소 원자 등을 치환기로서 지녀도 됨)를 나타내고; Ar¹ 및 Ar²는, 각각 독립적으로, 탄소수 6 내지 30의 방향족 탄화수소기(각각 독립적으로, 불소 원자 등을 치환기로서 지녀도 됨)를 나타내며; Ar³은 탄소수 6 내지 30의 아릴렌기(불소 원자 등을 치환기로서 지녀도 됨)를 나타내고; Ar⁴는, 각각 독립적으로, 탄소수 3 내지 30의 질소 함유 헤테로아릴기(각각 독립적으로, 불소 원자 등을 치환기로서 지녀도 됨) 또는 하기 일반식 (A)로 표시되는 치환기를 나타내며; Y 및 Z는, 각각 독립적으로, 질소 원자 또는 CH를 나타낸다. 단, Y 및 Z 중 적어도 한쪽은 질소 원자이다. n은 1 내지 [Cz 상에 형성할 수 있는 최대의 결합수-1]의 정수를 나타낸다.)

(식 중, Ar⁵는, (m+1)가의 탄소수 6 내지 30의 아릴기(각각 독립적으로, 불소 원자 등을 치환기로서 지녀도 됨)를 나타내고; Ar⁶은, 각각 독립적으로, 탄소수 3 내지 30의 질소 함유 헤테로아릴기(각각 독립적으로, 불소 원자 등을 치환기로서 지녀도 됨)를 나타내며; m은 1 내지 [Ar⁵ 상에 형성할 수 있는 최대의 결합수-1]의 정수를 나타낸다.)A 1,3,5-cyclic triazine compound represented by the following formula (1), an organic electroluminescent device capable of long-time driving using it as an electron transport material, and its use as a constituent component of an organic electroluminescent device to provide:

(Wherein these groups each independently represent a fluorine atom or the like as a substituent); Ar < ¹ > and Ar < ² > Each independently represent an aromatic hydrocarbon group having 6 to 30 carbon atoms (each independently having a fluorine atom or the like as a substituent), Ar ³ represents an arylene group having 6 to 30 carbon atoms And Ar ⁴ each independently represent a nitrogen-containing heteroaryl group having 3 to 30 carbon atoms (each independently having a fluorine atom or the like as a substituent) or a substituent represented by the following formula (A) Y and Z each independently represent a nitrogen atom or CH, provided that at least one of Y and Z is a nitrogen atom, n is an integer from 1 to [the maximum number of bonds that can be formed on Cz-1 ].)

(Wherein Ar ⁵ represents an aryl group having 6 to 30 carbon atoms (each independently, a fluorine atom or the like may be substituted) as the (m + 1) th group; Ar ⁶ is, independently, (Each of which may independently have a fluorine atom or the like as a substituent), and m represents an integer of 1 to [the maximum number of bonds which can be formed on the Ar ⁵ ] -1]. )

Description

CYCLIC AZINE COMPOUND, METHOD FOR PRODUCING SAME, AND ORGANIC ELECTROLUMINESCENT ELEMENT CONTAINING SAME. The present invention relates to a cyclic azine compound,

The present invention relates to a cyclic azine compound having a carbazolyl group substituted with a nitrogen-containing heteroaryl group useful as a constituent component of an organic electroluminescent device, a process for producing the same, and an organic electroluminescent device containing the same.

The organic electroluminescent element has a basic structure in which a light emitting layer containing a light emitting material is disposed between a hole transporting layer and an electron transporting layer and an anode and a cathode are attached to the outside of the hole transporting layer and the electron transporting layer. (Fluorescence or phosphorescence) accompanying the excitation of excitons, and is applied to displays and the like. The hole transporting layer may be constituted by a hole transporting layer and a hole injecting layer, the light emitting layer may be divided into an electron blocking layer, a light emitting layer and a hole blocking layer, and an electron transporting layer may be divided into an electron transporting layer and an electron injecting layer.

Recently, many organic electroluminescent devices using triazine and pyrimidine compounds in a light emitting layer, an electron transporting layer, and the like have been reported. However, it can not be said that the organic electroluminescent device satisfies the market demand completely in the light emitting efficiency, drive voltage, In addition, excellent materials are required.

As an electron transporting material and the like, a cyclic azine compound substituted with a carbazolyl group via an arylene group has been disclosed (see, for example, Patent Documents 1 to 4), and proposals have been made to improve the lifetime of the device using these compounds. However, improvements have been demanded in that devices are subjected to high-voltage coercive voltage and further longer life is demanded.

Furthermore, an example of using a 1,3,5-triazine compound having a carbazolyl group in an organic electroluminescent device (see, for example, Patent Document 5) is disclosed. However, The nitrogen atom of the zolyl group is directly bonded. Therefore, when it is used as an electron transporting material, the electron acceptability which is indispensable for the electron transporting material is lowered, and the device tends to be subjected to high-voltage co-electrification, and improvement is demanded.

WO 2003078541 A WO 2003080760 A JP 2009-21336 A JP 2002-193952 A WO 2008123189 A

Organic electroluminescent devices have begun to be used in various display devices. However, higher performance of devices is demanded, such as longevity, high luminous efficiency, low voltage electrification, and the like. More specifically, development of a carrier transporting material which achieves a long life, a high efficiency of light emission and a low electrification voltage is required.

Particularly, for electron injecting materials and electron transporting materials, a new material for driving an element at a low voltage due to its excellent electron injecting property and electron transporting property, high luminous efficiency and driving the element for a long time is desired. It is an object of the present invention to provide an electron injecting material and an electron transporting material for achieving long life, high efficiency of light emission, low voltage electrification.

DISCLOSURE OF THE INVENTION The present inventors have intensively studied in order to solve the above problems. As a result, it has been found that, in a cyclic azine compound in which a carbazolyl group has been substituted through a conventionally known arylene group, a nitrogen-containing heteroaryl group It has been found that the electron injecting property and the electron transporting property of the cyclic azine compound are remarkably improved by having a substituent. In addition, when such a compound (cyclic azine compound represented by the general formula (1) of the present invention) is used as an electron transporting layer in an organic electroluminescent device, as compared with the case of using a known or general electron transporting material, The inventors have found that the device driving voltage is remarkably reduced, the luminous efficiency is improved, and the life of the organic electroluminescent device is lengthened, thereby completing the present invention.

That is, the present invention relates to a cyclic azine compound represented by the following general formula (1) (hereinafter referred to as "cyclic azine compound (1)"), a production method thereof and an organic electroluminescent device containing the same:

(Wherein,

Cz represents a carbazole group of the (n + 1) valence or a valine group of the (n + 1) valence (these groups each independently represent a fluorine atom, an alkyl group of 1 to 4 carbon atoms, an aromatic hydrocarbon group of 6 to 18 carbon atoms, May have, as a substituent, an aromatic hydrocarbon group having 6 to 18 carbon atoms or an aromatic hydrocarbon group having 6 to 18 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms.

Ar ¹ and Ar ² each independently represent an aromatic hydrocarbon group having 6 to 30 carbon atoms (each independently selected from the group consisting of a fluorine atom, an alkyl group having 1 to 4 carbon atoms, an aromatic group having 3 to 18 carbon atoms, Or an aromatic group having 3 to 18 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms as the substituent).

Ar ³ represents an arylene group having 6 to 30 carbon atoms (a fluorine atom, an alkyl group having 1 to 4 carbon atoms, an aromatic group having 3 to 18 carbon atoms, an aromatic group having 3 to 18 carbon atoms having fluorine atom or an alkyl group having 1 to 4 carbon atoms Or an aromatic group having 3 to 18 carbon atoms as a substituent).

Ar ⁴ each independently represents a nitrogen-containing heteroaryl group having 3 to 30 carbon atoms (each independently a fluorine atom, an alkyl group having 1 to 4 carbon atoms, an aromatic group having 3 to 18 carbon atoms, a fluorine atom-containing 3 to 18 carbon atoms An aromatic group or an aromatic group having 3 to 18 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms as a substituent) or a substituent represented by the following formula (A).

Y and Z each independently represent a nitrogen atom or CH. Provided that at least one of Y and Z is a nitrogen atom.

and n represents an integer of 1 to [the maximum number of bonds that can be formed on Cz-1].

(Wherein,

Ar ⁵ is independently an aryl group having 6 to 30 carbon atoms (each independently, a fluorine atom, an alkyl group having 1 to 4 carbon atoms, an aromatic group having 3 to 18 carbon atoms which may have a fluorine atom, or Or an aromatic group having 3 to 18 carbon atoms which may be substituted with alkyl having 1 to 4 carbon atoms).

Ar ⁶ each independently represents a nitrogen-containing heteroaryl group having 3 to 30 carbon atoms (each independently, a fluorine atom, an alkyl group having 1 to 4 carbon atoms, an aromatic group having 3 to 18 carbon atoms, a fluorine atom- An aromatic group or an aromatic group having 3 to 18 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms).

m each independently represent an integer of 1 to [the maximum number of bonds that can be formed on Ar ⁵ ] -1).

By using the cyclic azine compound of the present invention, there is provided an organic electroluminescent device which is driven at a lower voltage and has higher luminous efficiency and longer life than an organic electroluminescent device using a conventionally known electron transporting material .

1 is a schematic sectional view of a single-layer element manufactured in Example-45 or the like;
2 is a schematic cross-sectional view of a single-layer element manufactured in Example-50 and the like.

Hereinafter, the present invention will be described in detail.

The present invention relates to the cyclic azine compound (1), a production method thereof, and an organic electroluminescent device containing the same.

The cyclic azine compound (1) of the present invention is preferably a cyclic azine compound represented by the following general formula (B), (C) or (D) from the viewpoint of good performance as a material for an organic electroluminescence device:

(In the formulas (B), (C) and (D), Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , Y, Z and n each independently represent a substituent In the general formula (D), Cb represents a carboline group of the (n + 1) -valent.

The substituents in the cyclic azine compound (1) of the present invention are each defined as follows.

Examples of the alkyl group having 1 to 4 carbon atoms include, but are not limited to, methyl group, trifluoromethyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, .

The aromatic hydrocarbon group having 6 to 18 carbon atoms is not particularly limited and examples thereof include a phenyl group, a biphenylyl group, a naphthyl group, an anthryl group, a pyrenyl group, a terphenyl group, a phenanthryl group, a perylenyl group, Nylon and the like.

The aromatic hydrocarbon group having 6 to 18 carbon atoms and having a fluorine atom is not particularly limited and examples thereof include a 2-fluorophenyl group, a 3-fluorophenyl group, a 4-fluorophenyl group, a 2,3-difluorophenyl group , 2,4-difluorophenyl group, 2,5-difluorophenyl group, 2,6-difluorophenyl group, 3,4-difluorophenyl group, 3,5-difluorophenyl group, 4-trifluorophenyl group, 2,3,5-trifluorophenyl group, 2,3,6-trifluorophenyl group, 2,4,5-trifluorophenyl group, 2,4,6-trifluorophenyl group , 3,4,5-trifluorophenyl group, 2,3,4,5-tetrafluorophenyl group, 2,3,4,6-tetrafluorophenyl group, 2,3,5,6-tetrafluorophenyl group , A pentafluorophenyl group, a 4-fluoronaphthalen-1-yl group, a 5-fluoronaphthalen-1-yl group, a 6-fluoronaphthalen-1-yl group, a 7-fluoronaphthalen- Naphthalene-2-yl group, 5-fluoro Fluorenylnaphthalene-2-yl group, anthryl group, pyrenyl group, phenanthryl group, perylenyl group, triphenylenyl group and the like can be given .

As the aromatic hydrocarbon group having 6 to 18 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms, the above-mentioned alkyl group having 1 to 4 carbon atoms is likewise substituted on the above-mentioned aromatic hydrocarbon group having 6 to 18 carbon atoms. But are not limited to, for example, p-tolyl, m-tolyl, o-tolyl, 4-trifluoromethylphenyl, 3-trifluoromethylphenyl, 2-trifluoromethylphenyl, Dimethylphenyl group, 3,5-dimethylphenyl group, 2,6-dimethylphenyl group, mesityl group, 2-ethylphenyl group, 3-ethylphenyl group, 4-ethylphenyl group, Isopropylphenyl group, 3-isopropylphenyl group, 4-tert-butylphenyl group, 4-ethylphenyl group, Isopropylphenyl group, 2,4-diisopropylphenyl group, 3,5-diisopropylphenyl group, 2-butyl Butylphenyl group, 2-tert-butylphenyl group, 3-tert-butylphenyl group, 2-tert-butylphenyl group, 2-tert-butylphenyl group, 2-tert- Di-tert-butylphenyl group, 3,5-di-tert-butylphenyl group, 4-methylnaphthalen-1-yl group, 4-trifluoromethylnaphthalen- , 4-propylnaphthalen-1-yl group, 4-butylnaphthalen-1-yl group, 4-tert-butylnaphthalen-1-yl group, 5-methylnaphthalen-1-yl group, 5-trifluoromethylnaphthalen- Naphthalene-1-yl group, a 5-ethylnaphthalen-1-yl group, a 5-ethylnaphthalen-1-yl group, Butyl naphthalene-2-yl group, 6-ethyl naphthalene-2-yl group, 6- Methylnaphthalen-2-yl group, 7-trifluoromethylnaphthalen-2-yl group, 7-ethylnaphthalen- Anthryl group, pyrenyl group, phenanthryl group, perylenyl group, triphenylenyl group, and the like can be used in combination with at least one member selected from the group consisting of a methyl group, an ethyl group, .

The aromatic hydrocarbon group having 6 to 30 carbon atoms is not particularly limited and examples thereof include a phenyl group, a biphenyl group, a naphthyl group, an anthryl group, a pyrenyl group, a terphenyl group, a phenanthryl group, a perylenyl group, Nylon and the like.

The aromatic group having 3 to 18 carbon atoms is not particularly limited and examples thereof include a furanyl group, a benzofuranyl group, a dibenzofuranyl group, a thienyl group, a benzothienyl group, a dibenzothienyl group, a 2-pyridyl group, A pyrimidyl group, a 4-pyridyl group, a 4-pyridyl group, a 2-pyrimidyl group, a 4-pyrimidyl group, a 5-pyrimidyl group, Quinolyl group, 8-quinolyl group, 1-isoquinolyl group, 3-isoquinolyl group, 4-isoquinolyl group, 4-quinolyl group, Isoquinolyl group, 8-isoquinolyl group, 9-acridyl group, 2-thiazolyl group, 4-thiazolyl group, Benzothiazolyl group, 7-benzothiazolyl group, quinazolyl group, quinoxalyl group, 1-benzothiazolyl group, 2-benzothiazolyl group, 4-benzothiazolyl group, Naphthyridin-2-yl group, a 4-thiazolyl group, a 5-thiazolyl group, An imidazo [1,2-a] pyridin-2-yl group, a 2-thiazolyl group, an indolizyl group, and azaindolizyl group.

The aromatic group having 3 to 18 carbon atoms and having a fluorine atom is not particularly limited, and examples thereof include a fluorofuranyl group, a fluorobenzofuranyl group, a fluorodibenzofuranyl group, a fluorothienyl group, a fluorobenzothiene group, Fluoro-2-pyridyl group, 6-fluoro-2-pyridyl group, 2-fluoro-2-pyridyl group, 3-pyridyl group, 2-fluoro-4-pyridyl group, 3-fluoro-3-pyridyl group, 3-fluoro- 2-pyridyl group, 3,6-difluoro-2-pyridyl group, 2, 3-difluoro-2-pyridyl group, 4-difluoro-3-pyridyl group, 2,5-difluoro-3-pyridyl group, 2,6-difluoro-3-pyridyl group, A 4,6-difluoro-3-pyridyl group, a 5,6-difluoro-3-pyridyl group, 4-pyridyl group, 3,5-difluoro-4-pyridyl group, 3,6-difluoro-4-pyridyl group, 4-pyridyl group, 3,4,5-trifluoro-2-pyridyl group, 3,4,6-trifluoro-2-pyridyl group, 3,5,6-trifiuoro- Pyridyl group, a 4,5,6-trifluoro-2-pyridyl group, a tetrafluoro-2-pyridyl group, a 2,4,5-trifluoro- 3-pyridyl group, tetrafluoro-3-pyridyl group, 2,5,6-trifluoro-3-pyridyl group, 4,5,6- 4-pyridyl group, 4-fluoro-2-pyrimidyl group, 5- (trifluoromethyl) Fluoro-4-pyrimidyl, 2-fluoro-4-pyrimidyl, 5-fluoro-4-pyrimidyl, 4-fluoro-5-pyrimidyl, 2-fluoropyridyl , 4-fluoro-2-quinolyl group, 5-fluoro-2-quinolyl group, 6-fluoro-2-quinolyl group, Fluoro-2-quinolyl group, 2-fluoro-3-quinolyl group, 4-fluoro-3-quinolyl group, Fluoro-3-quinolyl group, 8-fluoro-3-quinolyl group, 2-fluoro-3-quinolyl group, Quinolyl group, 3-fluoro-4-quinolyl group, 5-fluoro-4-quinolyl group, 6-fluoro-4- Fluoro-1-isoquinolyl group, a 5-fluoro-1-isoquinolyl group, a 6-fluoro-1-isoquinolyl group, Fluoro-1-isoquinolyl group, 1-fluoro-3-isoquinolyl group, 4-fluoro-1-isoquinolyl group, 3-isoquinolyl group, 5-fluoro-3-isoquinolyl group, 6-fluoro-3- Fluoro-4-isoquinolyl group, 3-fluoro-4-isoquinolyl group, 3-fluoro-4-isoquinolyl group, Isoquinolyl group, a 5-fluoro-4-isoquinolyl group, a 6-fluoro-4-isoquinolyl group, A fluoroaryl group, a fluoroaryl group, a fluoroaryl group, a fluoroaryl group, a fluoroaryl group, a fluoroacridyl group, a fluorothiazolyl group, a fluorobenzothiazolyl group, a fluoroquinazolyl group, a fluoroquinoxalyl group, a fluoronaphthyridyl group, Azaindolizine and the like.

The aromatic group having 3 to 18 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms indicates that the above-mentioned alkyl group having 1 to 4 carbon atoms is similarly substituted with the above-mentioned aromatic group having 3 to 18 carbon atoms, For example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-propyl group, an isobutyl group, Methyl-3-pyridyl, 5-methyl-3-pyridyl, 6-methyl-2-pyridyl, Pyridyl group, 3-methyl-4-pyridyl group, 3,4-dimethyl-2-pyridyl group, 3,5-dimethyl- Pyridyl group, 2,4-dimethyl-3-pyridyl group, 2,5-dimethyl-3-pyridyl group, 2,6- Methyl-3-pyridyl group, 4,6-dimethyl-3-pyridyl group, 5,6- Dimethyl-4-pyridyl group, 2,5-dimethyl-4-pyridyl group, 2,6- Methyl-2-pyrimidyl, 2-methyl-4-pyrimidyl, 5-methyl-4-pyrimidyl, Methyl-4-pyrimidyl, 2-methyl-5-pyrimidyl, 4-methyl-5-pyrimidyl, 2- methylpyridyl, 4- methylpyridyl, 5- Methyl-2-quinolyl group, 7-methyl-2-quinolyl group, 8- Methyl-3-quinolyl group, 6-methyl-3-quinolyl group, 7-methyl-3-quinolyl group, Methyl-4-quinolyl group, 5-methyl-4-quinolyl group, 6-methyl-4-quinolyl group, Methyl-4-quinolyl group, 3-methyl-5-quinolyl group, 4- Methyl-5-quinolyl group, 6-methyl-5-quinolyl group, 7-methyl- Methyl-6-quinolyl group, 4-methyl-6-quinolyl group, 5-methyl-6-quinolyl group Methyl-6-quinolyl group, 8-methyl-6-quinolyl group, 2-methyl-7-quinolyl group, 3-methyl- Methyl-7-quinolyl group, 6-methyl-7-quinolyl group, 8-methyl-7-quinolyl group, 2- Methyl-8-quinolyl group, a 5-methyl-8-quinolyl group, a 6-methyl- Methyl-1-isoquinolyl group, a 5-methyl-1-isoquinolyl group, a 6-methyl- Isoquinolyl group, 1-methyl-3-isoquinolyl group, 4-methyl-3-isoquinolyl group, Isoquinolyl group, 3-methyl-4-isoquinolyl group, 5-methyl-4-isoquinolyl group, -Isoquinolyl group, 6-methyl-4- An isoquinolyl group, an isoquinolyl group, an isoquinolyl group, a 7-methyl-4-isoquinolyl group, an 8-methyl-4-isoquinolyl group, A thienyl group, a thienyl group, a salicyl group, a methylnaphthyridyl group, a methylthianthrenyl group, a methylindolizyl group, and a methyl azahydronyl group.

The arylene group having 6 to 30 carbon atoms is not particularly limited and includes, for example, a phenylene group, a biphenylene group, a naphthalenediyl group, an anthracene diyl group, a pyrandiyl group, a terphenylrenylene group, A naphthyl group, a neopentyl group, a neopentyl group, a neopentyl group, a neopentyl group,

The nitrogen-containing heteroaryl group having 3 to 30 carbon atoms is not particularly limited, and examples thereof include a 2-pyridyl group, a 3-pyridyl group, a 4-pyridyl group, a 2-pyrimidyl group, A pyrimidyl group, a 4-pyrazinyl group, a 5-pyrazyl group, a 2-quinolyl group, a 3-quinolyl group, a 4-quinolyl group, a 5-quinolyl group, Isoquinolyl group, 6-isoquinolyl group, 6-isoquinolyl group, 7-isoquinolyl group, 8-quinolyl group, Benzothiazolyl group, 6-benzothiazolyl group, 6-benzothiazolyl group, 7-benzothiazolyl group, 4-benzothiazolyl group, A quinazolyl group, a quinoxalyl group, a naphthyridyl group, a thianthrenyl group, an indolizyl group, and azaindolizyl group.

(m + 1) represents an aryl group having 6 to 30 carbon atoms (provided that m represents an integer of 1 to [the maximum number of bonds capable of forming on the Ar ⁵ phase-1]). However, Include an arylene group having 6 to 30 carbon atoms, an aryltriyl group having 6 to 30 carbon atoms, and an aryltetrile group having 6 to 30 carbon atoms.

In the cyclic azine compound (1), Ar ⁵ - (Ar ⁶ ) _m represents that m Ar ⁶ substituents are bonded to Ar ⁵ . That is, although not particularly limited, for example, when Ar ⁵ is a phenylene group, m represents an integer of 1 to 5.

Furthermore, m is preferably 1 or 2, and more preferably 1, from the viewpoint of good performance as a material for an organic electroluminescence device.

As the above-mentioned arylene group having 6 to 30 carbon atoms, there can be mentioned, for example, substituents such as the specific examples represented by the above-mentioned arylene group having 6 to 30 carbon atoms.

The aryltriyl group having 6 to 30 carbon atoms is not particularly limited and includes, for example, a benzene triyl group, a biphenyltriyl group, a naphthalenetriyl group, an anthracene triyl group, a pyrenyltriyl group, a terphenyltriyl group, A perylene group, a perylene group, a perylene group, a perylene group, a perylene group, and a perylene group.

The aryltetrile group having 6 to 30 carbon atoms is not particularly limited and includes, for example, benzene tetrayl group, biphenyltetrayl group, naphthalene tetrayl group, anthracene tetrayl group, pyrenetetrayl group, A phenanthracene tetrayl group, a perylene tetrayl group, and a triphenylenetetrayl group.

(N + 1) -valent carbazole group (a fluorine atom, an alkyl group having 1 to 4 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms having a fluorine atom or an aromatic hydrocarbon group having 1 to 4 carbon atoms An aromatic hydrocarbon group having 6 to 18 carbon atoms substituted with an alkyl group as a substituent) may be used without particular limitation, and examples thereof include a carbazoyldiaryl group, a carbazole triyl group and a carbazole tetrayl group.

(N + 1) -valent carboline group (a fluorine atom, an alkyl group having 1 to 4 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms having a fluorine atom or an aromatic hydrocarbon group having 1 to 4 carbon atoms May have an aromatic hydrocarbon group substituted with an alkyl group having 6 to 18 carbon atoms as a substituent) is not particularly limited, and examples thereof include a carbolynyldiol group, a carbolynyltriyl group, and a carbolenetetryl group.

In the cyclic azine compound (1), Cz- (Ar ⁴ ) _n represents an integer of n Ar ⁴ substituents of Cz (Ar ⁴ ) _n wherein _n represents an integer of 1 to [the maximum number of bonds that can be formed on Cz- In Fig. n is preferably 1, 2 or 3, more preferably 1 or 2, and further preferably 1, from the viewpoint of good performance as a material for an organic electroluminescence device.

Cz is not particularly limited, and examples thereof include carbazole-1,9-diyl group, carbazole-2,9-diyl group, carbazole-1,3-diyl group, carbazole- N-phenylcarbazole-2,7-diyl group, N-phenylcarbazole-3,6-diyl group,? -Carboline-2,9-diyl group,? -Carboline- A-carboben-4,9-diyl group, an? -Cabolin-5,9-diyl group,? -Cabolin-6,9-diyl group,? -Carboline-7,9-diyl group ,? -carboline-8,9-diyl group,? -carboline-1,9-diyl group,? -carboline-3,9-diyl group,? -carboline-4,9-diyl group,? -Carboline-5,9-diyl group,? -Carboline-6,9-diyl group,? -Carboline-7,9-diyl group,? -Carboline-8,9-diyl group, 9-diyl group,? -Cabolin-5,9-diyl group,? -Cabolin-9,9-diyl group, 6,9-diyl group,? -Cabolin-7,9-diyl group,? -Carboline-8,9-diyl group,? -Carboline-1,9-diyl group, A 9-diyl group, a? -Cabolin-3,9-diyl group, a carbene-5,9-diyl group, a? -carboline-6,9-diyl group, a? -carboline-7,9-diyl group, a? .

Cz is preferably a carbazole-2,9-diyl group, a carbazole-3,9-diyl group, a carbazole-4,9-diyl group, a carbazole-3,9-diyl group, , A 6-diyl group, a carbazole-3,6,9-triyl group, an a-carbolin-7,9-diyl group, a -carboline-6,9-diyl group, A divalent group, a 隆 -carboline-3,6-diyl group, a 隆 -carboline-3,9-diyl group or a 隆 -carboline-6,9-diyl group (these groups each independently represent a fluorine atom, An aromatic hydrocarbon group having 6 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms having a fluorine atom, or an aromatic hydrocarbon group having 6 to 18 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms as a substituent Is preferably a carbazole-2,9-diyl group, a carbazole-3,9-diyl group, a carbazole-4,9-diyl group, a carbazole-3,6-diyl group, 6,9-diyl group,? -Carboline-3,9-diyl group or? -Carboline-6,9 -Diiyl group (each of these groups may independently have an aromatic hydrocarbon group having 6 to 18 carbon atoms as a substituent).

In the cyclic azine compound (1), Ar ¹ or Ar ² is not particularly limited, and each independently, for example, a phenyl group, a biphenylyl group, a naphthyl group, an anthryl group, a pyrenyl group, a terphenyl group, A methylphenyl group, a methylphenyl group, a methylphenyl group, a methylphenyl group, a methylphenyl group, a methylphenyl group, a methylphenyl group, a methylphenyl group, a methylthiophenyl group, A fluorophenyl group, a fluorophenyl group, a fluorophenyl group, a fluorophenyl group, a fluorophenyl group, a fluorophenyl group, a fluorophenyl group, a fluorophenyl group, a fluorophenyl group, a fluorophenanthryl group and the like.

Each of Ar ¹ and Ar ² is independently a phenyl group, a biphenyl group, a naphthyl group, an anthryl group, a pyrenyl group, a terphenyl group or a phenanthryl group (these groups are, for example, A fluorine atom, an alkyl group having 1 to 4 carbon atoms, an aromatic group having 3 to 18 carbon atoms, an aromatic group having 3 to 18 carbon atoms bearing a fluorine atom or an aromatic group having 3 to 18 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms A phenyl group, a naphthyl group or a biphenylyl group (these groups may be substituted with a fluorine atom, an alkyl group having 1 to 4 carbon atoms, an aromatic group having 3 to 18 carbon atoms, a cycloalkyl group having 3 to 18 carbon atoms having a fluorine atom More preferably an aromatic group or an aromatic group having 3 to 18 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms as a substituent), and each independently represents a phenyl group, A naphthyl group, or a biphenylyl group.

A fluorenyl group, a fluorenyl group, a fluorenyl group, a fluorenyl group, a fluorenyl group, a fluorenyl group, a phenyl group, a biphenyl group, a naphthyl group, an anthryl group, An aromatic group having 3 to 18 carbon atoms or an aromatic group having 3 to 18 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms may be used as a substituent) is not particularly limited, and examples thereof include a phenyl group, A methylphenyl group, a methylphenyl group, a methyl naphthyl group, a methyl anthryl group, a methyl terphenyl group, a methyl phenanthryl group, a methylphenyl group, a methylphenyl group, a methylphenyl group, A fluorenyl group, a fluorenyl group, a fluorenyl group, a fluorenyl group, a fluorenyl group, a fluorenyl group, a fluorenyl group, a fluorenyl group, a fluorenyl group,

The phenyl group or the biphenylyl group may be substituted with a substituent selected from the group consisting of a fluorine atom, an alkyl group having 1 to 4 carbon atoms, an aromatic group having 3 to 18 carbon atoms, an aromatic group having 3 to 18 carbon atoms having a fluorine atom or an alkyl group having 1 to 4 carbon atoms Which may have an aromatic group having 3 to 18 carbon atoms as the substituent, is not particularly limited, and examples thereof include a phenyl group, a biphenylyl group, a methylphenyl group, a methylbiphenylyl group, a fluorophenyl group, a fluoro And a biphenylyl group.

In the cyclic azine compound (1), Ar ³ is not particularly limited and examples thereof include a phenylene group, a biphenylene group, a naphthalenediyl group, an anthracene diyl group, a pyrandiyl group, a terphenylrenylene group, a fluoro A phenylphenyl group, a phenylphenyl group, a phenylene group, a fluorophenylbiphenylene group, a fluoronaphthalenediyl group, a phenylphenylene group, a phenylbiphenylene group, a phenylnaphthalenediyl group, a naphthylphenylene group, a naphthylbiphenylene group, .

Ar ³ is preferably a phenylene group or a biphenylylene group in which a fluorine atom, an alkyl group having 1 to 4 carbon atoms, an aromatic group having 3 to 18 carbon atoms, a fluorine atom having a fluorine atom An aromatic group having 3 to 18 carbon atoms or an aromatic group having 3 to 18 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms as a substituent), and each independently represents a phenylene group, a biphenylene group or a fluorophenyl group It is more preferable that R < 1 >

The phenylene group or the biphenylene group is preferably a fluorine atom, an alkyl group having 1 to 4 carbon atoms, an aromatic group having 3 to 18 carbon atoms, an aromatic group having 3 to 18 carbon atoms or an alkyl group having 1 to 4 carbon atoms May have a substituted aromatic group having 3 to 18 carbon atoms as a substituent) is not particularly limited, and examples thereof include a phenylene group, a biphenyllylene group, a naphthalenediyl group, a terphenylrenylene group, a fluoro Include a phenylene group, a fluoronaphthalenediyl group, a phenylphenylene group, a phenylnaphthalenediyl group, a naphthylphenylene group, and a naphthylnaphthalenediyl group.

In the cyclic azine compound (1), Ar ⁵ is not particularly limited, and examples thereof include a benzene group of an (m + 1) valence, a biphenyl group of an (m + 1) valence, a naphthalene group of an (m + (m + 1) valent anthracene group, (m + 1) valent pyrene group, (m + 1) valent terphenyl group, (m + 1) valent fluorobenzene group, (m + 1) valent naphthylbenzene group, (m + 1) valent naphthyl group, (m + 1) valent naphthyl group, Naphthylnaphthalene group of the formula (m + 1) (these groups each independently represent a fluorine atom, an alkyl group of 1 to 4 carbon atoms, an aromatic group of 3 to 18 carbon atoms, an aromatic group of 3 to 18 carbon atoms having a fluorine atom Or an aromatic group having 3 to 18 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms as a substituent).

As Ar ⁵ , it is preferable that when m is 1, a group selected from the group consisting of a phenylene group, a methylphenylene group, a biphenylrenylene group, a naphthylene group, an anthracene dylyl group, a pyrandiyl group, a terphenyldiyl group, a fluorophenylene group, , A fluoronaphthylene group, a phenylbiphenylene group, a phenylnaphthylene group, a naphthylphenylene group, a naphthylbiphenylene group, a naphthylnaphthylene group and the like.

when m = 2, each independently represents a benzene triyl group, a methylbenzene triyl group, a biphenyltriyl group, a naphthalenetriyl group, an anthracenetriyl group, a pyrenyltriyl group, a terphenyltriyl group, a fluorobenzene triyl group, A biphenyltriyl group, a fluoronaphthalenetriyl group, a phenylbiphenyltriyl group, a phenylnaphthalenetriyl group, a naphthylbenzenetriyl group, a naphthylbiphenyltriyl group, and a naphthylnaphthalenetriyl group.

Ar ⁵ is preferably a benzene group of the (m + 1) valency or a biphenyl group of the (m + 1) valence (these groups each independently represent a fluorine atom, An aromatic group having 3 to 18 carbon atoms, an aromatic group having 3 to 18 carbon atoms having a fluorine atom, or an aromatic group having 3 to 18 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms as the substituent). The benzene group of the (m + 1) valency (a fluorine atom, an alkyl group having 1 to 4 carbon atoms, an aromatic group having 3 to 18 carbon atoms, an aromatic group having 3 to 18 carbon atoms bearing a fluorine atom or an alkyl group having 1 to 4 carbon atoms And an aromatic group having 3 to 18 carbon atoms as a substituent), when m = 1, a phenylene group, a methylphenylene group, a fluorophenylene group or a naphthylphenylene group is preferable, and a phenylene group is more preferable. When m = 2, a benzene triyl group, a methylbenzene triyl group, a fluorobenzene triyl group, and a naphthylbenzene triyl group are preferable, and a benzene triyl group is more preferable. (B) a biphenyl group of the formula (m + 1) in which a fluorine atom, an alkyl group of 1 to 4 carbon atoms, an aromatic group of 3 to 18 carbon atoms, an aromatic group of 3 to 18 carbon atoms bearing a fluorine atom or an alkyl group of 1 to 4 carbon atoms And an aromatic group having 3 to 18 carbon atoms as a substituent), when m = 1, a biphenyllylene group, a terphenyldiyl group, a fluorophenylbiphenyllylene group or a naphthylbiphenyllylene group is preferable, More preferred is a lylene group. When m = 2, a biphenyltriyl group, a terphenyltriyl group, a fluorophenylbiphenyltriyl group, and a naphthylbiphenyltriyl group are preferable, and a biphenyltriyl group is more preferable.

In the cyclic azine compound (1), the nitrogen-containing heteroaryl group having 3 to 30 carbon atoms represented by Ar ⁴ and Ar ⁶ (each independently a fluorine atom, an alkyl group having 1 to 4 carbon atoms, an aromatic group having 3 to 18 carbon atoms, An aromatic group having 3 to 18 carbon atoms or an aromatic group having 3 to 18 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms) may be used as the substituent. Examples of the substituent include, but are not limited to, Independently, a group selected from the group consisting of pyridyl, pyrimidyl, pyrazyl, quinolyl, isoquinolyl, acridyl, thiazolyl, benzothiazolyl, quinazolyl, quinoxalyl, naphthyridyl, , An indolyl group, an azaindolizyl group, a fluoropyridyl group, a fluoropyrimidyl group, a fluoropyrazyl group, a fluoroquinolyl group, a fluoro isoquinolyl group, a fluoroacridyl group, a fluoro thiazolyl group, A fluoroaryl group, a fluorobenzothiazolyl group, a fluoroquinazolyl group, a fluoroquinoxalyl group, a fluoronaphthyridyl group, a fluorothianthrenyl group, a fluoroindolyl group, a fluoroazindolinyl group, a methylpyridyl group, A methylthiazolyl group, a methylbenzothiazolyl group, a methylquinazolyl group, a methylquinoxalyl group, a methylnaphthyridyl group, a methylthiazolyl group, a methylthiazolyl group, a methylthiazolyl group, a methylthiazolyl group, , A phenylthiazolyl group, a phenylthiazolyl group, a phenylthiazolyl group, a phenylthiazolyl group, a phenylthiazolyl group, a phenylthiazolyl group, a phenylthiazolyl group, a phenylthiazolyl group, a phenylthiazolyl group, , Phenylbenzothiazolyl group, phenylquinazolyl group, phenylquinoxalyl group, phenylnaphthyridyl group, phenylthianthrenyl group, phenylindolyl group, phenyl azaindolyl group, phenylpyridyl group, phenylpyrimidyl group, , Phenylquinolyl group, phenyliso A phenylthiazolyl group, a phenylthiazolyl group, a phenylquinazolyl group, a phenylquinoxalyl group, a phenylnaphthyridyl group, a phenylthiotrenyl group, a phenylindolinyl group, a phenylindolinyl group, a phenylthiazolyl group, A pyridylphenyl group, a pyrazylbiphenylyl group, a quinolylbiphenylyl group, a quinolylbiphenylyl group, a quinolylbiphenylyl group, a quinolylbiphenylyl group, a quinolylbiphenylyl group, A thiazolyl biphenylyl group, a benzothiazolyl biphenylyl group, a quinazolyl biphenylyl group, a quinoxalyl biphenyl group, a naphthyridyl biphenyl group, a thianthrenyl biphenylyl group, a thiazolyl biphenylyl group, , An indolylbiphenylyl group, and an azaindolizylbiphenylyl group.

Ar ⁴ and Ar ⁶ each independently represent a nitrogen-containing heteroaryl group having 3 to 30 carbon atoms consisting only of carbon, hydrogen and nitrogen (each independently a fluorine atom, a carbon number An aromatic group having 3 to 18 carbon atoms, an aromatic group having 3 to 18 carbon atoms having a fluorine atom, or an aromatic group having 3 to 18 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms) , A nitrogen-containing heteroaryl group having 3 to 30 carbon atoms consisting of hydrogen, nitrogen and sulfur (each independently a fluorine atom, an alkyl group having 1 to 4 carbon atoms, an aromatic group having 3 to 18 carbon atoms, a fluorine atom- An aromatic group or an aromatic group having 3 to 18 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms as a substituent). Each independently represent a fluorine atom, an alkyl group having 1 to 4 carbon atoms, an aromatic group having 3 to 18 carbon atoms, a fluorine atom, a fluorine atom, or an alkyl group having 3 to 30 carbon atoms, More preferably an aromatic group having 3 to 18 carbon atoms or an aromatic group having 3 to 18 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms as a substituent).

Ar ⁴ and Ar ⁶ each independently represent a pyridyl group, a pyrimidyl group, a quinolyl group, an isoquinolyl group, a pyridylphenyl group or a pyridylphenyl group in view of ease of synthesis and excellent performance as a material for an organic electroluminescence device These groups each independently represent a fluorine atom, an alkyl group having 1 to 4 carbon atoms, an aromatic group having 3 to 18 carbon atoms, an aromatic group having 3 to 18 carbon atoms having a fluorine atom or Or an aromatic group having 3 to 18 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms as a substituent), and each independently represents a pyridyl group, a pyrimidyl group, a quinolyl group, an isoquinolyl group, a pyridylphenyl group Or a 1- (3,5-dipyridyl) phenyl group, and more preferably a pyridyl group.

The nitrogen-containing heteroaryl group having 3 to 30 carbon atoms consisting of carbon, hydrogen and nitrogen only (the fluorine atom, the alkyl group having 1 to 4 carbon atoms, the aromatic group having 3 to 18 carbon atoms, the aromatic group having 3 to 18 carbon atoms having fluorine atom Or an aromatic group having 3 to 18 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms as a substituent) or a nitrogen-containing heteroaryl group having 3 to 30 carbon atoms consisting of carbon, hydrogen, nitrogen and sulfur (fluorine atom, An aromatic group having 3 to 18 carbon atoms, an aromatic group having 3 to 18 carbon atoms having a fluorine atom or an aromatic group having 3 to 18 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms) Is not particularly limited and includes, for example, a pyridyl group, a pyrimidyl group, a pyrazyl group, a quinolyl group, an isoquinolyl group, an acridyl group, a thiazole A thiazolyl group, a benzothiazolyl group, a quinazolyl group, a quinoxalyl group, a naphthyridyl group, a thianthrenyl group, an indolizyl group, an azaindolizyl group, a fluoropyridyl group, a fluoropyrimidyl group, A fluoroaryl group, a fluoroaryl group, a fluoroaryl group, a quinolyl group, a fluoro isoquinolyl group, a fluoroacridyl group, a fluorothiazolyl group, a fluorobenzothiazolyl group, a fluoroquinazolyl group, a fluoroquinoxalyl group, A methylpyridyl group, a methylpyridyl group, a methylquinolyl group, a methyl isoquinolyl group, a methylacridyl group, a methylthiazolyl group, a thiomorpholinyl group, a thiazolyl group, A phenylthiomorpholinyl group, a phenylthiomorpholinyl group, a benzylthiazolyl group, a methylbenzothiazolyl group, a methylquinazolyl group, a methylquinoxalyl group, a methylnaphthyridyl group, a methylthiotranyl group, a methylindolizyl group, a methyl azaindolizyl group, Phenylquinolyl group, phenyliso A phenylthiazolyl group, a phenylthiazolyl group, a phenylquinazolyl group, a phenylquinoxalyl group, a phenylnaphthyridyl group, a phenylthiotrenyl group, a phenylindolinyl group, a phenylindolinyl group, a phenylthiazolyl group, A phenylpyridyl group, a phenylpyrimidyl group, a phenylpyrazyl group, a phenylquinolyl group, a phenylisoquinolyl group, a phenylacryidyl group, a phenylthiazolyl group, a phenylbenzothiazolyl group, a phenylquinazolyl group, a phenylquinoxalyl group, A phenylthiophenyl group, a pyridylphenyl group, a pyridylphenyl group, a pyrimidylphenyl group, a pyrimidylphenyl group, a pyrimidylphenyl group, a pyrimidylphenyl group, a pyrimidylphenyl group, A thiazolidinylphenyl group, a thiazolyl biphenylyl group, a benzothiazolyl biphenylyl group, a quinazolyl biphenyl group, a thiazolyl biphenylyl group, a benzothiazolyl biphenyl group, a quinazolyl biphenyl group, A phenylyl group, a quinoxalylbiphenyl group, a Ridil tea and the like biphenyl group, Tian tray carbonyl biphenyl group, indole rijil biphenyl group, a biphenyl group-aza the dolly quality.

A nitrogen-containing heteroaryl group having 3 to 30 carbon atoms consisting of carbon, hydrogen and nitrogen alone, provided that these groups are a fluorine atom, an alkyl group having 1 to 4 carbon atoms, an aromatic group having 3 to 18 carbon atoms, Or an aromatic group having 3 to 18 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms as the substituent) is not particularly limited, and examples thereof include a pyridyl group, a pyrimidyl group, A fluorine atom, a fluorine atom, a cyano group, a cyano group, a cyano group, a cyano group, a cyano group, a fluorine atom, A substituted or unsubstituted phenyl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted heterocyclic group, Pyridyl) Group, there may be mentioned a pyrimidyl group, a pyrazyl group, quinolyl group, isoquinolyl group.

Y and Z each independently represent a nitrogen atom or CH. Provided that at least one of Y and Z is a nitrogen atom. It is also preferable that Y and Z are nitrogen atoms, or Y is CH and Z is a nitrogen atom, from the viewpoint of good performance as a material for an organic electroluminescence device.

In addition, any hydrogen atom in the cyclic azine compound (1) of the present invention may be substituted with a deuterium atom.

Next, a method for producing the cyclic azine compound of the present invention will be described. The cyclic azine compound (1) of the present invention can be produced by reacting the cyclic azine compound (1) in the presence of a metal catalyst or in the presence of a base and a metal catalyst by a method represented by the following Reaction Formula (1), Reaction Formula . ≪ / RTI >

Hereinafter, the compound represented by the general formula (2) is hereinafter referred to as the compound (2). The same applies to the compounds (3) to (9).

(Formula (1), 2 and 3, 4, 5, 6, 7, 8 and 9 of, Cz, Ar ^1, Ar ^2, Ar ³ , Ar ^4, n, Y, and Z are, each independently, represents the same definition as the above-mentioned general formula ^{(1). X 1, X} 2, X 3, X 4, and M are, each independently, a leaving group H ^N represents a hydrogen atom on the nitrogen atom in Cz.)

The leaving group represented by X ¹ , X ² , X ³ and X ⁴ is not particularly limited and includes, for example, a chlorine atom, a bromine atom, a triflate or an iodine atom. Among them, a bromine atom or a chlorine atom is preferable from the viewpoint of a good reaction yield.

The leaving group represented by M is not particularly limited and includes, for example, a chlorine atom, a bromine atom, a triflate, an iodine atom, a metal containing group (for example, Li, Na, MgCl, MgBr, MgI, CuCl, _{CuBr, CuI, AlCl 2, AlBr} 2, Al (Me) 2, Al (Et) 2, Al (i Bu) 2, Sn (Me) 3, Sn (Bu) 3, SnF 3, ZnR 3 (R 3 is A halogen atom), Si (R ⁴ ) ₃ , BF ₃ K, B (OR ¹ ) ₂ and B (OR ² ) ₃ . Examples of the metal containing group represented by M include B (OR ¹ ) ₂ , B (OR ² ) ₃ , ZnR ³ and Si (R ⁴ ) _3. Examples of the ZnR ³ include ZnCl, ZnBr, For example. These metal-containing groups may be coordinated with ligands such as ethers or amines, and the ligand is not limited as long as it does not inhibit the reaction formula (1).

Examples of the Si (R ⁴ ) ₃ include SiMe ₃ , SiPh ₃ , SiMePh ₂ , SiCl ₃ , SiF ₃ , Si (OMe) ₃ , Si (OEt) ₃ and Si (OMe) ₂ OH. Examples of B (OR ¹ ) ₂ include B (OH) ₂ , B (OMe) ₂ , B (O ⁱ Pr) ₂ , B (OBu) ₂ and B (OPh) ₂ . Examples of B (OR ¹ ) ₂ in the case where two R ¹ are combined to form a ring including an oxygen atom and a boron atom include those represented by the following (I) to (VII) (II) in view of good yield.

Examples of the B (OR ² ) ₃ include those represented by the following (I) to (III).

Of these leaving groups, a chlorine atom, a bromine atom, a triflate, an iodine atom, B (OR ¹ ) ₂ or B (OR ² ) ₃ are preferable from the viewpoints of ease of treatment after the reaction and ease of procurement of raw materials.

As shown in the reaction of the reaction formulas (1) and (3), the cyclic azine compound (1) of the present invention can be obtained by reacting the compound (2) with the compound (3) in the presence of a metal catalyst or in the presence of a base and a metal catalyst. ) Or compound (6) and compound (7), as described in the respective reaction schemes.

It is preferable that the metal catalyst is a palladium catalyst or a copper catalyst in the reaction of the reaction formula (1) and the reaction formula (3) from the viewpoint of good coupling efficiency and the like.

Further, in the reaction of the reaction formula (1) and the reaction formula (3), it is also possible to carry out the reaction by adding a base, and from the viewpoint of improving the reaction yield, it is preferable to add a base. In particular, when M is a chlorine atom, a bromine atom, a triflate, an iodine atom, B (OR ¹ ) ₂ or Si (R ⁴ ) ₃ , it is essential to add a base. The cyclic azine compound (1) of the present invention can be obtained by reacting the compound (4) with the compound (4) in the presence of a metal catalyst or in the presence of a base and a metal catalyst, 5), or the compound (8) and the compound (9), as described in the respective reaction schemes.

In the reaction of the reaction formula (2) and the reaction formula (4), it is preferable that the metal catalyst is a palladium catalyst or a nickel catalyst in view of good coupling efficiency and the like.

Further, in the reaction of the reaction formula (2) and the reaction formula (4), it is also possible to carry out the reaction by adding a base, and from the viewpoint of improving the reaction yield, it is preferable to add a base. Particularly, when M is a chlorine atom, a bromine atom, a triflate, an iodine atom, B (OR ¹ ) ₂ or Si (R ⁴ ) ₃ , it is essential to add a base. Further, in the reaction of the reaction formulas (1) to (4), a correlated transfer catalyst may be added. The correlated transfer catalyst is not particularly limited, but for example, 18-crown-6-ether can be used. The addition amount is an arbitrary amount within a range that does not significantly inhibit the reaction.

The metal catalyst used in the reactions of the reaction formulas (1) to (4) is not particularly limited, and examples thereof include a palladium catalyst, a copper catalyst and a nickel catalyst.

Examples of the palladium catalyst include, but are not limited to, palladium chloride, palladium acetate, palladium trifluoroacetate, and palladium nitrate. In addition, it is also possible to use palladium complexes such as π-arylpalladium chloride dimer, palladium acetylacetonate, bis (dibenzylideneacetone) palladium, tris (dibenzylideneacetone) dipalladium, dichlorobis (triphenylphosphine) palladium, Palladium, tri (tert-butyl) phosphine palladium, dichloro (1,1'-bis (diphenylphosphino) ferrocene) palladium, and the like. Among them, a palladium complex having a tertiary phosphine such as dichlorobis (triphenylphosphine) palladium, tetrakis (triphenylphosphine) palladium, and tri (tert-butyl) phosphine palladium as a ligand has good yield , And tri (tert-butyl) phosphine palladium is more preferable in that it is easily available.

The copper catalyst is not particularly limited, and examples thereof include copper chloride, copper bromide, copper iodide, copper oxide and copper triflate. Of these, copper oxide and copper iodide are preferred because of their good coupling efficiency and the like, and copper oxide is more preferable in view of easy availability.

The nickel catalyst is not particularly limited and examples thereof include nickel chloride, nickel bromide, nickel chloride hydrate, dichloro (dimethoxyethane) nickel, dichloro [1,2-bis (diphenylphosphino) (Diphenylphosphino) propane] nickel, dichloro [1,4-bis (diphenylphosphino) butane] nickel, dichloro [1,1'-bis (N, N, N ', N'-tetramethylethylenediamine) nickel (the above four are nickel complexes having a tertiary phosphine as a ligand) and dichloro have. Among them, preferred are dichloro (dimethoxyethane) nickel, dichloro [1,4-bis (diphenylphosphino) butane] nickel, dichloro (N, N, N ', N'-tetramethylethylenediamine) Nickel is preferable from the viewpoint of good coupling efficiency and the like and it is preferable to use nickel dichloride such as dichloro (dimethoxyethane) nickel, dichloro [1,4-bis (diphenylphosphino) Is more preferable.

The palladium complex having the tertiary phosphine as the ligand and the nickel complex having the tertiary phosphine as the ligand can be prepared by adding tertiary phosphine to the palladium salt, the nickel salt or the complex compound thereof . Further, the preparation may be carried out separately from the reaction and then added to the reaction system, or may be carried out in the reaction system.

Examples of the tertiary phosphine include, but are not limited to, triphenylphosphine, trimethylphosphine, tributylphosphine, tri (tert-butyl) phosphine, tricyclohexylphosphine, (Diphenylphosphino) -2'- (N, N-dimethylamino) biphenyl, 2, 3'- Bis (diphenylphosphino) ethane, 1,3- (di-tert-butylphosphino) biphenyl, 2- (dicyclohexylphosphino) Bis (diphenylphosphino) propane, 1,1'-bis (diphenylphosphino) ferrocene, tri (2-furyl) phosphine, tri- (2,5-xylyl) phosphine, (±) -2,2'-bis (diphenylphosphino) -1,1'-binaphthyl, 2-dicyclohexylphosphino -2 ', 4', 6'-triisopropylbiphenyl, and the like There. Among them, (tert-butyl) phosphine or 2-dicyclohexylphosphino-2 ', 4', 6'-triisopropylbiphenyl is preferred in view of easy availability and good yield.

When the tertiary phosphine is added to the palladium salt, the nickel salt or the complex thereof, the amount of the tertiary phosphine to be added is preferably 0.1 to 5 mol per 1 mol of the palladium salt, the nickel salt or the complex compound thereof (in terms of palladium or nickel atom) It is preferably 10-fold molar, and more preferably 0.3 to 5-fold molar in view of good yield.

It is also possible to add a ligand separately to the copper catalyst. The ligand to be added to the copper catalyst is not particularly limited, and examples thereof include aliphatic ligands such as 2,2'-bipyridine, 1,10-phenanthroline, N, N, N ', N'-tetramethylethylenediamine, Triphenylphosphine, 2- (dicyclohexylphosphino) biphenyl, and the like. Of these, 1,10-phenanthroline is preferable because it is easy to obtain and the yield is good.

In the reactions of the reaction formulas (1) to (4), the base which can be used is not particularly limited, and examples thereof include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate and cesium carbonate) , Sodium acetate, potassium phosphate, sodium phosphate, sodium fluoride, potassium fluoride, cesium fluoride and the like. Among them, potassium carbonate, potassium phosphate or sodium hydroxide is preferable in view of good yield.

The reaction of the reaction formulas (1) to (4) is preferably carried out in a solvent. Examples of the solvent include, but are not limited to, water, dimethylsulfoxide, dimethylformamide, tetrahydrofuran, toluene, benzene, diethylether, 1,4-dioxane, ethanol, And the like, and they may be appropriately combined and used. Among them, a mixed solvent of 1,4-dioxane, xylene, toluene and butanol, or a mixed solvent of xylene and butanol is preferable in terms of good yield.

The purity of the cyclic azine compound (1) of the present invention can be increased by performing re-precipitation, concentration, filtration, purification, and the like after completion of the reaction of the reaction formulas (1) to (4). In order to further increase the purity, it may be purified by recrystallization, silica gel column chromatography, sublimation or the like, if necessary.

Hereinafter, the reaction of the reaction formula (1) will be described.

The compound (2) can be produced, for example, by a method disclosed in Yamanaka Hiroshi, " New Heterocyclic Compound Basic Foundation ", Kodansha, 2004.

Any hydrogen atom in the compound (2) may be substituted with a deuterium atom. Examples of the compound (3) include, but are not limited to, the following 3-1 to 3-17 (independently, a fluorine atom, an alkyl group having 1 to 4 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, fluorine An aromatic hydrocarbon group having 6 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms, an aromatic group having 3 to 18 carbon atoms, an aromatic group having 3 to 18 carbon atoms, An aromatic group having 3 to 18 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms as a substituent, and these substituents are the same as described above).

Compound (3) can be synthesized by a method described in, for example, J.Tsuji, Palladium Reagents and Catalysts, John Wiley & Sons, 2004, Journal of Organic Chemistry, vol. 60, 7508-7510, Chemistry, 65, 164-168, 2000, Organic Letters, Vol. 10, 941-944, 2008, or Chemistry of Materials, Vol. 20, 5951-5953, 2008 .

In addition, any hydrogen atom in the compound (3) may be substituted with a deuterium atom.

The amount of the palladium catalyst used in the reaction formula (1) is not particularly limited as long as it is the so-called catalyst amount, but it is preferably 0.1 to 0.01 moles (in terms of palladium atom) relative to 1 mole of the compound (2) from the viewpoint of good yield. The amount of the base to be used in the reaction formula (1) is not particularly limited, but it is preferably 1 to 10 times the molar amount per 1 mole of the compound (3), more preferably 1 to 3 times the molar amount Do.

Although the molar ratio of the compound (2) to the compound (3) used in the reaction formula (1) is not particularly limited, it is preferably 0.2 to 5 times the molar amount per 1 mole of the compound (2) It is more preferable that it is distributed.

The reaction formula (2) will be described below.

Compound (4) can be produced, for example, in accordance with the method shown in Synthesis Example-1 in the Examples.

Any hydrogen atom in the compound (4) may be substituted with a deuterium atom.

The compound (5) is not particularly limited, and for example, the following 5-1 to 5-15 (each independently represents a fluorine atom, an alkyl group having 1 to 4 carbon atoms, an aromatic group having 3 to 18 carbon atoms, May have, as a substituent, an aromatic group having 3 to 18 carbon atoms or an aromatic group having 3 to 18 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms.

(In the formulas (5-1) to (5-15), M has the same definition as M in the general formula (5).)

Compound (5) can be prepared by the method described in, for example, J.Tsuji, Palladium Reagents and Catalysts, John Wiley & Sons, 2004, Journal of Organic Chemistry, vol. 60, 7508-7510, Chemistry, 65, 164-168, 2000, Organic Letters, Vol. 10, 941-944, 2008 or Chemistry of Materials, Vol. 20, 5951-5953, 2008 have.

In addition, any hydrogen atom in the compound (5) may be substituted with a deuterium atom.

Reaction formula (2) is a method for producing cyclic azine compound (1) of the present invention by reacting compound (4) with compound (5) optionally in the presence of a base in the presence of a palladium catalyst, -Siuki-Miyaura reaction, the desired product can be obtained in good yield. The amount of the palladium catalyst used in the reaction formula (2) is not particularly limited as long as it is the so-called catalyst amount, but it is preferably 0.1 to 0.01 moles (in terms of palladium atom) relative to 1 mole of the compound (5) from the viewpoint of good yield. The amount of the base to be used is not particularly limited, but it is preferably 0.5 to 10 times the molar amount per mole of the compound (5), more preferably 1 to 3 times the molar amount in view of the good yield. The molar ratio of the compound (4) to the compound (5) used in the reaction formula (2) is not particularly limited, but is preferably 0.2 to 5 times the molar amount per mole of the compound (2) It is more preferable that it is distributed.

The reaction formula (3) will be described below.

Compound (6) can be produced, for example, according to the method shown in Synthesis Example-2 in the Examples.

In addition, any hydrogen atom in the compound (6) may be substituted with a deuterium atom.

Examples of the compound (7) include, but are not limited to, the following 7-1 to 7-21 (each independently represents a fluorine atom, an alkyl group having 1 to 4 carbon atoms, an aromatic group having 3 to 18 carbon atoms, May have, as a substituent, an aromatic group having 3 to 18 carbon atoms or an aromatic group having 3 to 18 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms.

(Of, X ³ illustrates the formula (7-1) to (7-21) is defined as X ³ in the general formula (7).)

Compound (7) can be prepared, for example, by the method described in J. Org. Chem. 48, 1064-1069, 1983).

In addition, any hydrogen atom in the compound (7) may be substituted with a deuterium atom.

Scheme (3) is a method for obtaining the cyclic azine compound (1) of the present invention by reacting the compound (6) with the compound (7) in the presence of a palladium catalyst and a base to obtain the desired product in good yield.

The amount of the palladium catalyst used in the reaction formula (3) is not particularly limited as long as it is the so-called catalyst amount, but it is preferably 0.01 to 0.1 times mol (in terms of palladium atom) relative to 1 mol of the compound (6) from the viewpoint of good yield. The amount of the base to be used is not particularly limited, but it is preferably 0.5 to 10 times by mole based on 1 mole of the compound (6), more preferably 1 to 3 times by mole in view of good yield.

In the reaction formula (3), an interphase transfer catalyst typified by 18-crown-6-ether may be added.

The reaction of the reaction formula (3) is preferably carried out in a solvent in view of good yield.

The reaction formula (4) will be described below.

Compound (8) can be produced, for example, in accordance with the method shown in Synthesis Example-1 in the Examples.

In addition, any hydrogen atom in the compound (8) may be substituted with a deuterium atom.

Examples of the compound (9) include, but are not limited to, the following 9-1 to 9-12 (each independently represents a fluorine atom, an alkyl group having 1 to 4 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, fluorine An aromatic hydrocarbon group having 6 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms, an aromatic group having 3 to 18 carbon atoms, an aromatic group having 3 to 18 carbon atoms, Or an aromatic group having 3 to 18 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms as a substituent. These substituents are the same as those described above).

(In the formulas (9-1) to (9-12), X ⁴ has the same definition as X ⁴ in the general formula (7).)

Compound (9) can be prepared by the method described in, for example, J.Tsuji, Palladium Reagents and Catalysts, John Wiley & Sons, 2004, Journal of Organic Chemistry, Vol. 60, 7508-7510, Chemistry, 65, 164-168, 2000, Organic Letters, Vol. 10, 941-944, 2008 or Chemistry of Materials, Vol. 20, 5951-5953, 2008 have.

Any hydrogen atom in the compound (9) may be substituted with a deuterium atom.

Reaction formula (4) is a method for producing cyclic azine compound (1) of the present invention by reacting compound (8) with compound (9) optionally in the presence of a base in the presence of a palladium catalyst, - Miyaura reaction, the target product can be obtained in a satisfactory yield.

The amount of the palladium catalyst used in the reaction formula (4) is not particularly limited as long as it is the so-called catalyst amount, but it is preferably 0.1 to 0.01 times mole (in terms of palladium atom) relative to 1 mole of the compound (9) from the viewpoint of good yield. The amount of the base to be used is not particularly limited, but it is preferably 0.5 to 10 times the molar amount per mole of the compound (9), more preferably 1 to 3 times the molar amount in view of the good yield.

Although the molar ratio of the compound (8) and the compound (9) used in the reaction formula (4) is not particularly limited, it is preferably 0.2 to 5 times the molar amount per 1 mole of the compound (8) It is more preferable that it is distributed.

The method for producing the thin film for an organic electroluminescence device comprising the cyclic azine compound (1) of the present invention is not particularly limited, but a preferable example is a film formation by a vacuum evaporation method.

The film formation by the vacuum vapor deposition method can be performed by using a general-purpose vacuum vapor deposition apparatus. The vacuum degree of the vacuum chamber at the time of forming the film by the vacuum vapor deposition method is not particularly limited because the production tact time in manufacturing the organic electroluminescent device is short and the manufacturing cost is superior, Or the like, which can be attained by, for example, about 1 x 10 ^-2 to 1 x 10 ^-6 Pa.

The deposition rate depends on the thickness of the film to be formed, but is preferably 0.005 to 10 nm / sec.

Further, a thin film for an organic electroluminescence device comprising the 1,3,5-triazine compound (1) can also be prepared by a solution coating method. For example, a cyclic azine compound (1) is dissolved in an organic solvent such as chloroform, dichloromethane, 1,2-dichloroethane, chlorobenzene, toluene, ethyl acetate or tetrahydrofuran, It is also possible to form a film by a spin coating method, an ink jet method, a casting method, a dipping method or the like.

[Example]

Hereinafter, the present invention will be described in more detail with reference to synthesis examples, examples, comparative examples and reference examples, but the present invention is not limited to these examples.

Synthesis Example 1

2- (4-bromophenyl) -4,6-diphenyl-1,3,5-triazine (621 mg), 2- chlorocarbazole (339 mg), palladium acetate (7.2 mg) , Potassium carbonate (332 mg) and 18-crown-6-ether (84.6 mg) were suspended in xylene (8.0 ml), and a solution of 120 C < / RTI > for 21 hours. After cooling the reaction mixture, water was added. The precipitated solid was washed with water, then with methanol and then with hexane to obtain a white powder of the objective product, 2-chloro-9- [4- (4,6-diphenyltriazin-2-yl) phenyl] Yield 729 mg, yield 90%).

_{^{1 H-NMR (CDCl 3)}} : δ 7.32 (d, J = 8.4Hz, 1H), 7.37 (t, J = 7.4Hz, 1H), 7.49 (t, J = 7.6Hz, 1H), 7.55-7.57 ( J = 8.4 Hz, 1H), 8.16 (d, J = 7.6 Hz, 1 H), 8.02 (d, J = 8.85 (d, J = 6.4 Hz, 4H), 9.06 (d, J = 8.4 Hz, 2H).

Synthesis Example 2

2- [4- (4,4,5,5-tetramethyl-1,3,2-dioxaballolan-2-yl) phenyl] -4,6-diphenyl-1,3,5 -Triazine (1.0 g), 3-bromocarbazole (622 mg) and tetrakis (triphenylphosphine) palladium (238 mg) were dissolved in 1,4-dioxane (12 ml) and 3M- potassium phosphate aqueous solution Ml), and the mixture was heated to reflux for 20 hours. After cooling to room temperature, water was added. The precipitated solid was washed with water, then with methanol and then with hexane to obtain a brown solid (yield: 794 mg, yield 79%) of 3- [4- (4,6-diphenyltriazin- Yield: 70%).

^{1 H-NMR (DMSO-d} 6): δ 7.23 (t, J = 7.4Hz, 1H), 7.44 (t, J = 7.6Hz, 1H), 7.54 (d, J = 8.1Hz, 1H), 7.64 ( J = 8.4 Hz, 1H), 7.63-7.75 (m, 6H), 7.89 (d, J = 8.5 Hz, 1H) 1H), 8.65 (s, 1H), 8.79 (d, J = 7.0 Hz, 4H), 8.85 (d, J = 8.3 Hz, 2H), 11.45

Synthesis Example 3

(4.92 g), bispinacolatodiboron (10.2 g), potassium acetate (7.85 g) and dichlorobistriphenylphosphine palladium (281 mg) were added to a solution of 1,4-dioxane (100 ml), and the mixture was heated under reflux for 2 hours. After cooling to room temperature, insoluble materials were separated by filtration. Next, the filtrate was purified by silica gel chromatography (developing solvent: chloroform) to obtain 3- (4,4,5,5-tetramethyl-1,3,2-dioxaballolan-2-yl) White solids (yield 3.94 g, yield 67%) of the sol were obtained.

^{1 H-NMR (DMSO-d} 6): δ 1.17 (s, 12H), 7.18 (t, J = 7.4Hz, 1H), 7.40 (t, J = 7.6Hz, 1H), 7.46-7.51 (m, 2H ), 7.70 (d, J = 8.2 Hz, 1H), 8.20 (d, J = 7.8 Hz, 1H), 8.46 (s, 1H), 11.43 (s, 1H).

Synthesis Example 4

A solution of 3- (4,4,5,5-tetramethyl-1,3,2-dioxaballol-2-yl) -carbazole (586 mg), 2- bromopyridine (348 mg) and Tetrakis (triphenylphosphine) palladium (46 mg) was suspended in a mixed solvent of THF (10 ml) and 4N aqueous sodium hydroxide solution (1.0 ml) and refluxed for 23 hours. After cooling to room temperature, the mixture was extracted with chloroform. The organic layer was purified by silica gel chromatography (developing solvent; toluene, followed by chloroform, then methanol) to give 3- (2-pyridyl) carbazole as a yellow solid (yield 474 mg, yield 97%).

^{1 H-NMR (DMSO-d} 6): δ 7.20 (t, J = 7.4Hz, 1H), 7.29 (dd, J = 7.4, 4.8Hz, 1H), 7.41 (t, J = 7.6Hz, 1H), J = 8.1 Hz, 1H), 7.58 (d, J = 8.1 Hz, 1H), 7.56 (d, J = 8.6 Hz, 1H), 8.22 (d, J = 7.8 Hz, 1H), 8.66 (d, J = 4.8 Hz, 1H), 8.88 (s, 1H), 11.41

Synthesis Example 5

(1.17 g), 2- (3-bromophenyl) -4,6-diphenyl-1,3,5-triazine (1.17 g) and 3- (4,4,5,5- (967 mg) and tetrakis (triphenylphosphine) palladium (104 mg) were suspended in 1,4-dioxane (15 ml) and 3M-carbonic acid Potassium aqueous solution (2.5 ml) was added, and the mixture was heated under reflux for 17 hours. After cooling the reaction mixture, water was added. The precipitated solid was washed with water, then with methanol, and then with hexane to obtain a white product of the objective 3- [3- (4,6-diphenyl-1,3,5-triazin-2-yl) phenyl] carbazole Powder (yield: 1.37 g, yield: 96%).

_{^{1 H-NMR (CDCl 3)}} : δ, 7.29 (t, J = 7.0Hz, 1H), 7.43-7.50 (m, 2H), 7.55-7.61 (m, 7H), 7.66 (t, J = 7.8Hz, J = 7.8 Hz, 1H), 8.15 (d, J = 7.8 Hz, 1H), 7.81 (d, J = 1H), 8.75 (d, J = 7.8 Hz, 1H), 8.80 (d, J = 7.8 Hz, 4H), 9.07 (s, 1H).

Synthesis Example 6

A solution of 3- [3-chloro-5- (4,6-diphenyl-1,3,5-triazin-2-yl) phenyl] carbazole (2.00 g), 2-bromopyridine Crown-6-ether (207.76 mg) and potassium carbonate (1358 mg) were suspended in xylene (20 ml) And refluxed for 16 hours. After cooling the reaction mixture, water was added. The precipitated solid was washed with water, followed by methanol and then with hexane to obtain the objective product, N- (2-pyridyl) -3- [3-chloro-5- (4,6-diphenyl- Triazin-2-yl) phenyl] carbazole (yield: 2110 mg, yield 92%).

_{^{1 H-NMR (CDCl 3)}} : δ 7.33-7.39 (m, 2H), 7.48 (t, J = 7.2Hz, 1H), 7.56-7.64 (m, 6H), 7.69 (d, J = 8.0Hz, 1H ), 7.80 (d, J = 8.0 Hz, 1 H), 7.86 (d, J = 7.6 Hz, 1 H), 7.92 , 8.41 (s, 1H), 8.71 (s, 1H), 8.78-8.80 (m, 5H), 8.97 (s, 1H).

Synthesis Example-7

A solution of 3- [3-chloro-5- (4,6-diphenyl-1,3,5-triazin-2-yl) phenyl] -9- (2- pyridyl) carbazole ), Bispinacolatodiaboron (0.90 g), tris (dibenzylideneacetone) dipalladium (29.7 mg), 2-dicyclohexylphosphino-2 ', 4', 6'- triisopropylbiphenyl 30.9 mg) and potassium acetate (0.95 g) were suspended in 1,4-dioxane (24 ml) and refluxed for 5 hours. After cooling the reaction mixture, water was added. The precipitated solid was separated by filtration, washed with water and then with methanol. The solvent was distilled off under reduced pressure to obtain the desired product, 3- [3- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) Diphenyl-1,3,5-triazin-2-yl) phenyl] -9- (2-pyridyl) carbazole was obtained (Yield 1.98 g, yield 90%).

¹ H-NMR (CDCl ₃ ):?, 1.45 (s, 12H), 7.31-7.37 (m, 2H), 7.47 (t, J = 7.4 Hz, 1H), 7.56-7.61 (d, J = 8.2 Hz, 1H), 7.85-7.89 (m, 2H), 7.96 (t, J = 8.2 Hz, 2H), 8.24 8.48 (s, 1H), 8.75-8.83 (m, 5H), 9.13 (s, 1H), 9.18 (s, 1H).

Synthesis Example-8

Dioxaborolan-2-yl) phenyl] -4,6-diphenyl-1, 4- , 3,5-triazine (93 mg), 6-bromo-9- (2- pyridyl) -? - carbene (54 mg), tetrakis (triphenylphosphine) palladium Potassium (57 mg) was suspended in 1,4-dioxane (3.3 ml), water (150 μl) was added, and the mixture was refluxed for 14 hours. After cooling the reaction mixture, water was added. The precipitated solid was washed with water, then with methanol, and then with hexane, and the solvent was distilled off under reduced pressure. Purification by silica gel column chromatography (eluent: ethyl acetate) gave 9- (2-pyridyl) -6- [3-chloro-5- (4,6-diphenyltriazin- Phenyl] - [beta] -carboline (yield 70 mg, yield 71%).

_{^{1 H-NMR (CDCl 3)}} : δ, 7.39 (dd, J = 7.4, 5.0Hz, 1H), 7.55-7.62 (m, 6H), 7.72 (d, J = 7.4Hz, 1H), 7.89 (s, 1H), 7.92 (d, J = 8.4 Hz, 1H), 8.01 (t, J = 7.8 Hz, 1H), 8.06-8.09 (m, 2H), 8.45 1H), 8.72 (s, 1H), 8.76-8.78 (m, 5H), 8.93 (s, 1H), 9.32 (s, 1H).

Synthesis Example-9

Dioxaborolan-2-yl) phenyl] -4,6-diphenyl-1, 4- , 3,5-triazine (706 mg), 3-bromo-9-phenyl-6- (2- pyridyl) carbazole (500 mg), tetrakis (triphenylphosphine) palladium Potassium carbonate (57 mg) was suspended in 1,4-dioxane (6.5 ml), water (1.3 ml) was added, and the mixture was refluxed for 20 hours. After cooling the reaction mixture, water was added. The precipitated solid was separated by filtration and washed with water, then methanol, and then with hexane. The solvent was distilled off under reduced pressure to obtain the desired product, 3- [3-chloro-5- (4,6-diphenyl-1,3,5-triazin-2-yl) phenyl] (2-pyridyl) carbazole (yield 754 mg, yield 91%).

_{^{1 H-NMR (CDCl 3)}} : δ, 7.21 (t, J = 7.4Hz, 1H), 7.52 (t, J = 8.4Hz, 2H), 7.55-7.69 (m, 11H), 7.76 (t, J = (D, J = 8.4 Hz, 1H), 8.54 (s, 1H), 8.71-8.73 (m, 2H), 8.75-8.80 (m, 4H), 8.91 (s, 1H), 8.96 (s, 1H).

Synthesis Example-10

(12.6 g), bispinacolatodiborone (8.4 g), tris (2,4-dichlorobenzophenone) Dicyclohexylphosphino-2 ', 4', 6'-triisopropylbiphenyl (1.3 g) and potassium acetate (6.5 g) were added to a solution of 1, Was suspended in 4-dioxane (150 ml), and the mixture was heated under reflux for 3.5 hours. After cooling the reaction mixture, water was added. The precipitated solid was separated by filtration, washed with water and then with methanol. The solvent was distilled off under reduced pressure to obtain the desired product, 2- [5- (4,4,5,5-tetramethyl-1,3,2-dioxaballolan-2-yl) (Yield 14.8 g, yield 96%) of 4,6-diphenyl-1,3,5-triazine (hereinafter referred to as compound (E-1)) was obtained.

_{^{1 H-NMR (CDCl 3)}} : δ, 1.47 (s, 12H), 7.45 (t, J = 7.4Hz, 1H), 7.55 (t, J = 7.4Hz, 2H), 7.60-7.68 (m, 6H) , 7.82 (d, J = 8.1 Hz, 2H), 8.33 (s, 1H), 8.85 (d, J = 7.9 Hz, 4H), 9.12 (s, 1H), 9.16

Synthesis Example-11

Phenyl) carbazole (4.00 g), phenylboronic acid (1.25 g) and triethylamine , 2-dicyclohexylphosphino-2 ', 4', 6'-triisopropylbiphenyl (225 mg) were suspended in 1,4-dioxane (80 ml) and 3M - potassium carbonate aqueous solution (6.8 ml) was added, and the mixture was heated to reflux for 27 hours. After cooling the reaction mixture, water was added. The precipitated solid was separated by filtration and washed with water, then methanol, and then with hexane. The solvent was distilled off under reduced pressure to obtain a white powder of the objective 3- [5- (4,6-diphenyl-1,3,5-triazin-2-yl) (Yield 3.27 g, yield 76%).

¹ H-NMR (CDCl ₃ ):? 7.32 (dd, J = 7.9, 6.2 Hz, 1H), 7.47-7.51 (m, 2H), 7.59-7.68 (m, 10H), 7.87-7.91 , 8.18 (s, 1H), 8.19 (s, 1H), 8.22 (d, J = 7.7 Hz, 1H), 8.50 (s, 1H), 8.84-8.87 9.09 (s, 1 H).

Synthesis Example-12

(700 mg) and N-bromosuccinimide (559 mg) were suspended in DMF (5.7 ml) under argon atmosphere, and the mixture was stirred at 30 ° C for 10 hours Lt; / RTI > Thereafter, water was added, and the precipitated solid was separated by filtration, washed with water, and then with hexane. The solvent was distilled off under reduced pressure to obtain a brown powder of the desired product, 6-bromo-9- (2-pyridyl) -? - carbene (yield 761 mg, yield 82%).

_{^{1 H-NMR (CDCl 3)}} : δ, 7.38 (dd, J = 7.5, 4.9Hz, 1H), 7.42 (dd, J = 8.4, 4.7Hz, 1H), 7.62 (d, J = 8.2Hz, 1H) , 7.65 (d, J = 8.8 Hz, 1H), 7.80 (d, J = 8.8 Hz, 1H) (s, 1H), 8.66 (d, J = 4.7 Hz, 1H), 8.75 (d, J = 4.9 Hz, 1H).

Synthesis Example-13

(757 mg) and N-bromosuccinimide (463 mg) were suspended in DMF (4.7 ml) under argon atmosphere, and the mixture was stirred at 30 ° C for 7 hours Lt; / RTI > Thereafter, water was added, and the precipitated solid was separated by filtration, washed with water, and then with hexane. The solvent was distilled off under reduced pressure to obtain 3-bromo-9-phenyl-6- (2-pyridyl) carbazole brown powder (yield 852 mg, yield 90%).

¹ H-NMR (CDCl ₃ ):?, 7.27-7.30 (m, 1H), 7.31-7.131 (d, J = 8.5 Hz, 1H), 7.49 (d, J = 8.6 Hz, 1H), 7.51-7.55 (m, 2H), 7.57-7.60 (m, 2H), 7.64-7.68 (m, 2H), 7.84 (t, J = 7.6 Hz, 1H), 7.89 J = 8.5 Hz, 1H), 8.37 (s, 1H), 8.77 (d, J = 4.8 Hz, 1H), 8.80 (s, 1H).

Synthesis Example-14

(2.55 g), 4- (2-pyridyl) -1,3,5-triazin-2-yl) ) Phenylboronic acid (1.19 g), palladium acetate (22.5 mg) and 2-dicyclohexylphosphino-2 ', 4', 6'- triisopropylbiphenyl Ml), followed by addition of 3M aqueous potassium carbonate solution (4.0 ml), and the mixture was heated under reflux for 14 hours. After cooling the reaction mixture, water was added. The precipitated solid was separated by filtration and washed with water, methanol, and hexane. The resulting solid was recrystallized from o-xylene to obtain the objective 3- [5- (4,6-diphenyl-1,3,5-triazin-2-yl) (Yield 2.31 g, yield 74%) of the title compound (E-2) as a white powder.

^{1 H-NMR (DMSO-d} 6): δ 7.21 (t, J = 7.4Hz, 1H), 7.41 (dd, J = 7.4, 4.7Hz, 1H), 7.44 (t, J = 7.6Hz, 1H), 7H), 7.92-7.97 (m, 2H), 8.07-8.10 (m, 3H), 8.30-8. 32 (m, 3H), 8.48 (m, 1H), 8.71 (s, 1H), 8.74 (d, J = 4.7 Hz, 1H), 8.77-8.80 (m, 4H) , 1H).

Synthesis Example-15

(1.17 g), 8-chloroquinoline (720 mg), and palladium acetate (1.00 g) were added to a solution of 3- (4,4,5,5-tetramethyl-1,3,2-dioxaballolan- 2-dicyclohexylphosphino-2 ', 4', 6'-triisopropylbiphenyl (114 mg) was suspended in THF (10 ml), and a 3M aqueous potassium carbonate solution (2.7 ml) And the mixture was heated under reflux for 15 hours. After cooling the reaction mixture, water was added and extracted with chloroform. The organic layer was dried over magnesium sulfate and filtered. The solvent was distilled off under reduced pressure, and the precipitated solid was collected by filtration to obtain the intended yellow powder of 3- (quinolin-8-yl) carbazole (yield 780 mg, yield 66%).

_{^{1 H-NMR (CDCl 3)}} : δ 7.22 (dd, J = 7.9, 6.6Hz, 1H), 7.36 (d, J = 8.0Hz, 1H), 7.40 (dd, J = 8.1, 6.6Hz, 1H), (Dd, J = 8.4 Hz, 1H), 7.46 (dd, J = 8.3, 4.2 Hz, 1H), 7.67 7.86 (d, J = 4.3 Hz, 1H), 7.88 (d, J = 4.3 Hz, 1H), 8.05 s, 1 H), 8.45 (s, 1 H), 9.02 (d, J = 4.2 Hz, 1 H).

Synthesis Example-16

(73 mg), 2-bromopyridine (474 mg), copper (I) oxide (17.9 mg) and 1,10-phenanthroline (45 mg ), 18-crown-6-ether (132 mg) and potassium carbonate (691 mg) were suspended in xylene (6.2 ml) and refluxed for 15 hours. After cooling the reaction mixture, the unnecessary material was removed by filtration through celite. The filtrate was distilled off under reduced pressure and the residue was purified by column chromatography (developing solvent: chloroform) to obtain the objective yellow powder of 9- (2-pyridyl) -3- (quinolin- Yield 929 mg, yield 100%).

_{^{1 H-NMR (CDCl 3)}} : δ 7.32-7.36 (m, 2H), 7.46-7.50 (m, 2H), 7.69 (dd, J = 8.1, 7.1Hz, 1H), 7.74 (d, J = 8.1Hz J = 8.0 Hz, 1H), 7.82 (d, J = 8.5 Hz, 1H), 7.87-7.92 1H), 7.97 (d, J = 8.5 Hz, 1H), 8,16 (d, J = 7.7 Hz, 1H), 8.29 (d, J = 8.3 Hz, 1H), 8.44 d, J = 4.7 Hz, 1H), 9.04 (d, J = 4.1 Hz, 1H).

Synthesis Example -17

A suspension of 9- (2-pyridyl) -3- (quinolin-8-yl) carbazole (929 mg) and N-bromosuccinimide (467 mg) in DMF (10 ml) Followed by stirring at 60 占 폚 for 3 hours. Thereafter, water was added, and the precipitated solid was separated by filtration and washed with water and hexane. The solvent was distilled off under reduced pressure to obtain a brown powder (yield 986 mg, yield: 88%) of 3-bromo-9- (2- pyridyl) -6- (quinolin- ≪ / RTI >

_{^{1 H-NMR (CDCl 3)}} : δ, 7.35 (dd, J = 7.4, 4.9Hz, 1H), 7.48 (dd, J = 8.3, 4.2Hz, 1H), 7.55 (d, J = 8.8Hz, 1H) , 7.69 (dd, J = 7.8, 7.5 Hz, 1H), 7.70 (d, J = 8.1 Hz, 1H), 7.82 (d, J = 8.5 Hz, 1H), 7.83-7.90 (d, J = 8.5 Hz, 1H), 7.98 (dd, J = 8.0, 7.5 Hz, 1H), 8.27 8.76 (d, J = 4.9 Hz, 1H), 9.02 (d, J = 4.2 Hz, 1H).

Synthesis Example-18

(I) (71.5 mg), 1,10-phenanthroline (1.00 g) and triethylamine 6-ether (529 mg) and potassium carbonate (2.76 g) were suspended in xylene (25 ml), and the mixture was heated under reflux for 15 hours. After the reaction mixture was cooled, water and methanol were added, and unnecessary matter was removed by filtration. The filtrate was extracted with chloroform, and the organic layer was dried over sodium sulfate and filtered. The solvent was distilled off under reduced pressure and the residue was purified by column chromatography (developing solvent: chloroform) to obtain the desired 9- (2-pyridyl) -3- [4- Powder (yield 3.62 g, yield 91%).

_{^{1 H-NMR (CDCl 3)}} : δ 7.26-7.30 (m, 1H), 7.35 (dd, J = 7.4, 4.9Hz, 1H), 7.38 (t, J = 7.5Hz, 1H), 7.50 (t, J J = 8.6 Hz, 1H), 7.81-7.91 (m, 5H), 7.95 (d, J = 8.6 Hz, 1H) ), 7.98 (t, J = 7.8 Hz, 1H), 8.16 (d, J = 8.5 Hz, 2H), 8.22 (d, J = 7.5 Hz, 1H), 8.42 , 2H).

Synthesis Example -19

(1.99 g) and N-bromosuccinimide (979 mg) were dissolved in DMF (20 ml) under argon atmosphere, , And the mixture was stirred at 60 ° C for 4 hours. Thereafter, water was added thereto, and the precipitated solid was separated by filtration and washed with water, methanol and hexane to obtain the objective 3-bromo-9- (2-pyridyl) -6- [4- Dicylphenyl] carbazole (yield 2.12 g, yield 89%).

_{^{1 H-NMR (CDCl 3)}} : δ 7.26-7.30 (m, 1H), 7.36 (dd, J = 7.4, 4.9Hz, 1H), 7.56 (d, J = 8.8Hz, 1H), 7.66 (d, J = 8.1 Hz, 1H), 7.78-7.83 (m, 4H), 7.85 (d, J = 8.5 Hz, 2H), 7.91 , 8.15 (d, J = 8.5 Hz, 2H), 8.32 (s, 1H), 8.35 (s, 1H), 8.75-8.77 (m, 2H).

Synthesis Example-20

(1-naphthyl) -2-propen-1-one (1.42 g) was added to a solution of 2M potassium hydroxide Ethanol solution (2.0 ml) and ethanol (4.0 ml), and refluxed for 17 hours. After cooling, water was added and the mixture was extracted with chloroform. The organic layer was purified by column chromatography (developing solvent: chloroform, hexane) to obtain a yellow powder of the desired 4- (4-bromophenyl) -6- (1-naphthyl) -2-phenylpyrimidine Yield 459 mg, yield 52%).

_{^{1 H-NMR (CDCl 3)}} : δ 7.53-7.61 (m, 5H), 7.65 (dd, J = 8.2, 7.2Hz, 1H), 7.72 (d, J = 8.6Hz, 2H), 7.82 (d, J = 7.1 Hz, 1H), 7.89 (s, 1H), 7.98-8.00 (m, 1H), 8.03 (d, J = 8.2 Hz, 1H), 8.21 (d, J = 8.6 Hz, 2H), 8.36-8.38 (m, 1 H), 8.69-8.72 (m, 2 H).

Synthesis Example-21

(1.10 g), bromobenzene (377 mg, 0.35 mmol) and triethylamine 18-crown-6-ether (106 mg) and potassium carbonate (553 mg) were dissolved in 100 ml of xylene (100 ml) 10 ml), and the mixture was heated under reflux for 15 hours. After cooling the reaction mixture, water was added. The precipitated solid was washed with water, methanol and hexane to obtain the objective 9-phenyl-3- [5- (4,6-diphenyl-1,3,5-triazin-2-yl) 3-yl] carbazole (hereinafter referred to as ETL-4) (yield: 1.21 g, yield 97%).

_{^{1 H-NMR (CDCl 3)}} : δ 7.34-7.38 (m, 1H), 7.47-7.56 (m, 4H), 7.58-7.69 (m, 13H), 7.87-7.89 (m, 3H), 8.19 (s, 1H), 8.29 (d, J = 7.7 Hz, IH), 8.56 (s, IH), 8.84 (d, J = 8.0 Hz, 4H), 9.00 (s,

Example-1

(500 mg), 3- [4- (2-pyridyl) phenyl] carbazole ( A solution of potassium carbonate (431 mg) and 18-crown-6-ether (82.5 mg) in toluene solution (94 쨉 L) of palladium acetate (7.0 mg), 1M tri- (7.8 ml), and the mixture was heated under reflux for 4 hours. After cooling the reaction mixture, water was added. The precipitated solid was washed with water, then with methanol and then with hexane to obtain the objective 3- [4- (2-pyridyl) phenyl] -9- [3- (4,6-diphenyltriazin- ) Phenyl] carbazole (A-1) (yield 867 mg, yield 88%).

^{1 H-NMR (DMSO-d} 6): δ 7.36-7.39 (m, 2H), 7.48-7.53 (m, 2H), 7.57 (d, J = 8.8Hz, 1H), 7.64 (t, J = 7.4Hz (D, J = 8.5 Hz, 2H), 7.69-7.73 (m, 2H), 7.88-7.94 Hz, 2H), 8.45 (d, J = 7.9 Hz, 1H), 8.71 (m, 6H), 8.91-8.93 (m, 2H).

Example-2

(700 mg), 3- [4- (2-pyridyl) phenyl] carbazole ( (108 mg), potassium carbonate (498 mg) and 18-crown-6-ether (105 mg) of palladium acetate (8.1 mg), 1M tri- Was suspended in phenol (9.0 ml), and the mixture was heated under reflux for 2.5 hours. After cooling the reaction mixture, water was added. The precipitated solid was washed with water, then with methanol and then with hexane to obtain the desired product, 3- [4- (2-pyridyl) phenyl] -9- [4- (4- ) Phenyl] carbazole (A-2) (Yield 1108 mg, yield 98%).

_{^{1 H-NMR (CDCl 3)}} : δ 7.26-7.30 (m, 1H), 7.40 (t, J = 7.8Hz, 1H), 7.51 (t, J = 7.7Hz, 1H), 7.61-7.68 (m, 8H ), 7.79-7.84 (m, 3H), 7.87-7.91 (m, 4H), 8.17 (d, J = 8.4 Hz, 2H), 8.27 (d, J = 7.6 Hz, , 8.76 (d, J = 4.7 Hz, 1H), 8.86 (d, J = 6.4 Hz, 4H), 9.08 (d, J = 8.6 Hz, 2H).

Example-3

(500 mg), 3- [4- (2-pyridyl) phenyl) -1,3,5-triazine ] Carbazole (420 mg), palladium acetate (5.3 mg), a toluene solution of 1M-tri (tert-butyl) phosphine (71 μl), potassium carbonate (329 mg) and 18- ) Was suspended in xylene (6 ml) and heated under reflux for 21.5 hours. After cooling the reaction mixture, water was added. The precipitated solid was washed with water, then with methanol and then with hexane to obtain the objective 3- [4- (2-pyridyl) phenyl] -9- [5- (4,6-diphenyltriazin- ) Biphenyl-3-yl] carbazole (A-3) as a yellow powder (yield: 800 mg, yield 95%).

_{^{1 H-NMR (CDCl 3)}} : δ 7.28 (t, J = 6.2Hz, 1H), 7.41 (t, J = 7.3Hz, 1H), 7.48-7.53 (m, 2H), 7.57-7.66 (m, 10H ), 7.78-7.86 (m, 5H), 7.90 (d, J = 8.4 Hz, 2H), 8.08 , 8.51 (s, 1H), 8.78 (d, J = 4.7 Hz, 1H), 8.81 (d, J = 6.7 Hz, 4H), 9.02 (s, 1H), 9.14 (s, 1H).

Example-4

4- (2-pyridyl) -4,6-diphenyl-1,3,5-triazine (770 mg), 2- (4'-chlorobiphenyl- Crown-6-ether (976 mg), palladium acetate (8.2 mg), 1 M-tri (tert- Mg) was suspended in xylene (9 ml), and the mixture was heated under reflux for 4 hours. After cooling the reaction mixture, water was added. The precipitated solid was washed with water, then with methanol and then with hexane to obtain the desired product 3- [4- (2-pyridyl) phenyl] -9- [4 '- (4,6-diphenyltriazin- Yl) carbazole (A-4) as a yellow powder (yield: 1140 mg, yield 88%).

_{^{1 H-NMR (CDCl 3)}} : δ 7.26-7.29 (m, 1H), 7.38 (t, J = 7.4Hz, 1H), 7.51 (t, J = 7.1Hz, 1H), 7.57 (d, J = 8.2 (D, J = 8.4 Hz, 2H), 7.95 (d, J = 8.4 Hz, 2H), 8.00 (d, J = 8.7 Hz, 2H), 8.17 (d, J = 8.4 Hz, 2H), 8.27 (d, J = 7.7 Hz, 1H), 8.48 ), 8.86 (d, J = 7.7 Hz, 4H), 8.95 (d, J = 8.4 Hz, 2H).

Example 5

(4,6-diphenyltriazin-2-yl) phenyl] carbazole (715 mg) synthesized in Synthesis Example-1, 4- (2-pyridyl ) Phenylboronic acid (336 mg), palladium acetate (6.3 mg) and 2-dicyclohexylphosphino-2 ', 4', 6'- triisopropylbiphenyl (40 mg) 1.3 ml) and 1,4-dioxane (7 ml), and the mixture was heated under reflux for 16 hours. After cooling the reaction mixture, water was added. The precipitated solid was isolated by filtration, washed with water, then with methanol, and then with hexane to obtain the desired product, 2- [4- (2-pyridyl) phenyl] -9- [4- (4,6-diphenyltri Azin-2-yl) phenyl] carbazole (A-5) (yield 842 mg, yield 96%).

_{^{1 H-NMR (CDCl 3)}} : δ 7.24-7.27 (m, 1H), 7.38 (t, J = 7.4Hz, 1H), 7.50 (t, J = 7.4Hz, 1H), 7.59-7.69 (m, 8H ), 7.78-7.84 (m, 5H), 7.90 (d, J = 8.6 Hz, 2H), 8.12 (d, J = 8.5 Hz, 2H), 8.23 J = 8.1 Hz, 1H), 8.74 (d, J = 4.6 Hz, 1H), 8.86 (d, J = 8.0 Hz, 4H), 9.09 (d, J = 8.6 Hz, 2H).

Example-6

Phenylboronic acid (675 mg) and 4- (2-pyridyl) phenylboronic acid (317 mg) in a stream of argon were added to a solution of 4-chloro-9- [4- (4,6-diphenyltriazin- ), Palladium acetate (6.0 mg) and 2-dicyclohexylphosphino-2 ', 4', 6'-triisopropylbiphenyl (38 mg) were dissolved in a 3 M aqueous potassium phosphate solution (1.1 ml) -Dioxane (13 ml), and the mixture was heated under reflux for 18 hours. After cooling the reaction mixture, water was added. The precipitated solid was separated by filtration and washed with water, then with methanol, and then with hexane to obtain the objective 4- [4- (2-pyridyl) phenyl] -9- [4- (4,6- Azin-2-yl) phenyl] carbazole (A-6) (yield 830 mg, yield 100%).

_{^{1 H-NMR (CDCl 3)}} : δ 7.10 (t, J = 7.6Hz, 1H), 7.28 (d, J = 7.5Hz, 1H), 7.31-7.34 (m, 1H), 7.42 (d, J = 7.7 J = 8.0 Hz, 1H), 8.25 (d, J = 8.3 Hz, 2H), 8.81 (d, J = 8.0 Hz, 1H), 7.51-7.71 (m, 10H), 7.84-7.89 , J = 4.4 Hz, 1H), 8.87 (d, J = 8.0 Hz, 4H), 9.08 (d, J = 8.6 Hz, 2H).

Example-7

(Biphenyl-4-yl) -1,3,5-triazine (500 mg), 3- [4- (2-pyridyl) Crown-6-ether (166 mg), palladium acetate (4.2 mg), 1M-tri (tert-butyl) phosphine in toluene (49 mg) were suspended in xylene (4.6 ml), and the mixture was heated under reflux for 3 hours. After cooling the reaction mixture, water was added. The precipitated solid was washed with water, then with methanol and then with hexane to obtain the desired product, 3- [4- (2-pyridyl) phenyl] -9- [4- (4,6- ) Phenyl triazin-2-yl) phenyl] carbazole (A-7) as a yellow powder (yield 673 mg, yield 93%).

_{^{1 H-NMR (CDCl 3)}} : δ 7.28 (t, J = 5.9Hz, 1H), 7.40 (t, J = 7.6Hz, 1H), 7.46 (t, J = 7.4Hz, 2H), 7.51 (d, J = 8.4 Hz, 1H), 7.55 (t, J = 7.5 Hz, 4H), 7.63 (d, J = 8.2 Hz, 1H), 7.68 (D, J = 7.7 Hz, 1H), 8.48 (s, 1H), 8.77 (d, J = 4.6 Hz, 1H), 8.94 (d, J = 8.4 Hz, 4H), 9.10 (d, J = 8.5 Hz, 2H).

Example-8

(4-methylphenyl) -1,3,5-triazine (1000 mg), 4-methyl-1-naphthaleneboronic acid ( (48 mg) and tetrakis (triphenylphosphine) palladium (47 mg) were suspended in a mixed solvent of 3M aqueous potassium phosphate solution (1 ml), THF (8 ml) and ethanol (2 ml) Lt; 0 > C. After cooling the reaction mixture, the precipitated solid was filtered off. The obtained solid was washed with water, then with methanol, and then with hexane to obtain 978 mg of a yellowish white solid.

A toluene solution (103 ml) of the obtained yellowish white solid (950 mg), 3- [4- (2-pyridyl) phenyl] carbazole (602 mg), palladium acetate (7.7 mg) and IM- , Potassium carbonate (473 mg) and 18-crown-6-ether (90 mg) were suspended in xylene (8.6 ml) and heated under reflux for 4.5 hours. After cooling the reaction mixture, water was added and the precipitated solid was separated by filtration. Next, the filtrate was extracted with chloroform and the organic layer was purified by silica gel chromatography (developing solvent: chloroform) to obtain the objective 3- [4- (2-pyridyl) phenyl] -9- [3- (Yield: 640 mg, yield 40%) was obtained as yellow powders of 4,6-di (4-methylphenyl) triazin-2-yl) -5- (4-methylnaphthalen- %).

_{^{1 H-NMR (CDCl 3)}} : δ 2.50 (s, 6H), 2.85 (s, 3H), 7.28 (t, J = 6.0Hz, 1H), 7.35 (d, J = 8.0Hz, 4H), 7.41 ( J = 7.7 Hz, 1H), 7.51-7.68 (m, 3H), 7.70 (d, J = 8.2 Hz, 1H) 1H), 7.75 (d, J = 8.5 Hz, 1H), 7.77-7.85 (m, 3H), 7.91 (d, J = 8.5 Hz, 2H) = 8.6 Hz, 4H), 8.31 (d, J = 7.6 Hz, 1H), 8.52 9.05 (s, 1 H), 9.13 (s, 1 H).

Example-9

(4,6-diphenyltriazin-2-yl) phenyl] carbazole (650 mg) synthesized in Synthesis Example-2, 3,5-di (2-pyridyl) (72 mg), potassium carbonate (379 mg) and 18-crown-6-ether (72 mg) were added to a toluene solution of palladium ) Was suspended in xylene (6.9 ml), and the mixture was heated under reflux for 5.5 hours. After cooling the reaction mixture, water was added. Subsequently, the precipitated solid was filtered, washed with water, then with methanol, and then with hexane to obtain the desired product, 3- [4- (4,6-di (biphenyl-4-yl) phenyltriazin- ) Phenyl] -9- [3,5-di (2-pyridyl) phenyl] carbazole (A-9) as a brown solid (Yield 888 mg, yield 92%).

_{^{1 H-NMR (CDCl 3)}} : δ 7.32-7.36 (m, 2H), 7.38 (t, J = 7.4Hz, 1H), 7.50 (t, J = 7.6Hz, 1H), 7.58 (d, J = 8.2 7.98 (d, J = 8.0 Hz, 2H), 7.98 (d, J = 8.6 Hz, 2H), 8.29 (m, , 8.85 (d, J = 7.8 Hz, 2H), 8.84 (s, 1H) , 4H), 8.91 (d, J = 8.5 Hz, 2H).

Example-10

(4-bromophenyl) -4,6-diphenyl-1,3,5-triazine (660 mg), 3- (2-pyridyl) carbazole (457 mg) and acetic acid (8.5 ml) of palladium (7.6 mg), 1M-tri (tert-butyl) phosphine in toluene solution (102 μl), potassium carbonate (470 mg) and 18- ≪ / RTI > and refluxed for 2 hours. The reaction mixture was cooled and extracted with chloroform. The organic layer was distilled off under reduced pressure, and then methanol was added to precipitate a solid. The precipitated solid was filtered and washed with methanol and then with hexane to obtain the desired product 3- (2-pyridyl) -9- [4- (4,6-diphenyltriazin-2-yl) phenyl] A-10) (Yield 917 mg, yield 98%).

_{^{1 H-NMR (CDCl 3)}} : δ 7.26 (dd, J = 7.4, 4.8Hz, 1H), 7.39 (t, J = 7.4Hz, 1H), 7.50 (t, J = 7.7Hz, 1H), 7.60- J = 8.7 Hz, 2H), 7.90 (d, J = 8.0 Hz, 1H), 8.13 (d, J = 8.7 Hz, 1H), 8.28 (d, J = 7.6Hz, 1H), 8.77 (d, J = 4.8Hz, 1H), 8.84-8.696 (m, 5H), 9.07 (d, J = 8.6Hz, 2H).

Example-11

(1.19 g), 2-bromopyridine (474 mg), and triethylamine were added to a solution of 3- [3- (4,6-diphenyl-1,3,5-triazin- (36 mg), 1,10-phenanthroline (45 mg), 18-crown-6-ether (132 mg) and potassium carbonate (864 mg) were suspended in xylene (12.5 ml) And the mixture was heated to reflux. After cooling the reaction mixture, water was added. The precipitated solid was filtered, washed with water, then with methanol, and then with hexane to obtain the desired product, 9- (2-pyridyl) -3- [3- (4,6-diphenyl-1,3,5-tri Azin-2-yl) phenyl] carbazole (A-11) (yield 1.29 g, yield 93%).

_{^{1 H-NMR (CDCl 3)}} : δ 7.32-7.37 (m, 2H), 7.48 (t, J = 7.6Hz, 1H), 7.58-7.61 (m, 6H), 7.66-7.71 (m, 2H), 7.83 (d, J = 8.0 Hz, 1H), 7.87 (d, J = 8.0 Hz, 1H), 7.94-7.99 (m, 3H), 8.21 (d, J = 7.6 Hz, 1H) , 8.75-8.81 (m, 2H), 8.80 (d, J = 7.8 Hz, 4H), 9.08 (s, 1H).

Example-12

Dioxaborolan-2-yl) biphenyl] -4,6-diphenyl-1,3,5- 5-Triflazine (1.08 g), 3-bromo-9- (2-pyridyl) carbazole (570 mg) and tetrakis (triphenylphosphine) palladium (102 mg) 9.0 ml), and a 3M-potassium phosphate aqueous solution (1.8 ml) was further added, and the mixture was heated under reflux for 27 hours. After cooling the reaction mixture, water was added. The precipitated solid was filtered, washed with water, then with methanol, and then with hexane to obtain the desired product, 9- (2-pyridyl) -3- [5- (4,6-diphenyl-1,3,5-tri Azine-2-yl) biphenyl-3-yl] carbazole (A-12) (yield: 800 mg, yield 60%).

_{^{1 H-NMR (CDCl 3)}} : δ 7.32-7.35 (m, 2H), 7.44-7.50 (m, 2H), 7.54-7.62 (m, 8H), 7.71 (d, J = 8.0Hz, 1H), 7.84 (d, J = 8.4 Hz, 2H), 7.87 (d, J = 8.4 Hz, 2H), 7.96 J = 8.0 Hz, 4H), 8.97 (s, 1H), 8.22 (d, J = 7.6 Hz, 1H), < / RTI > 9.07 (s, 1H).

Example-13

Under argon stream, a solution of 3- [1-chloro-5- (4,6-diphenyl-1,3,5-triazin- (1.47 g), 4- (2-pyridyl) phenylboronic acid (597 mg), palladium acetate (11 mg) and 2-dicyclohexylphosphino-2 ', 4', 6'- triisopropylbiphenyl (72 mg) was suspended in a mixed solvent of xylene (22.5 ml) and 1-butanol (2.5 ml), and further 3 M aqueous potassium carbonate solution (2.5 ml) was added and refluxed for 24 hours. After cooling the reaction mixture, water was added. The precipitated solid was filtered, washed with water, then with methanol, and then with hexane to obtain the desired product, 9- (2-pyridyl) -3- [5- (4,6-diphenyl-1,3,5-tri Azine-2-yl) -4'- (2-pyridyl) biphenyl-3-yl] carbazole (A-13) was obtained (yield 1.50 g, yield 60%).

_{^{1 H-NMR (CDCl 3)}} : δ 7.26-7.28 (m, 1H), 7.33-7.38 (m, 2H), 7.48 (t, J = 7.2Hz, 1H), 7.57-7.63 (m, 6H), 7.71 (d, J = 8.0 Hz, 1H), 7.77-7.85 (m, 2H), 7.88-7.91 (m, 2H), 7.96-8.00 J = 4.6 Hz, 1H), 8.15-8.24 (m, 3H), 8.24 (d, J = 7.4 Hz, 1H) ), 8.82 (d, J = 8.0 Hz, 4H), 9.04 (s, 1H), 9.08 (s, 1H).

Example-14

Under a stream of argon, a solution of 6- [3-chloro-5- (4,6-diphenyl-1,3,5-triazin-2-yl) phenyl] (845 mg), 4- (2-pyridyl) phenylboronic acid (873 mg), palladium acetate (9.7 mg) and 2-dicyclohexylphosphino-2 ', 4', 6'-triisopropylbiphenyl (61.7 mg) was suspended in THF (30 ml), 3M aqueous potassium carbonate solution (1.5 ml) was added, and the mixture was heated under reflux for 60 hours. After cooling the reaction mixture, water was added. The precipitated solid was filtered off, washed with water, then methanol, then with hexane, and the solvent was distilled off under reduced pressure. Thereafter, purification was carried out by silica gel column chromatography (eluent: ethyl acetate) to obtain the desired product, 6- [5- (4,6-diphenyl-1,3,5-triazin- (Yield: 834 mg, yield 82%) of 2- (2-pyridyl) biphenyl-3-yl] -9- (2- pyridyl) -? - carboline (A- 14).

_{^{1 H-NMR (CDCl 3)}} : δ 7.27-7.29 (m, 1H), 7.39 (dd, J = 7.4, 5.0Hz, 1H), 7.57-7.74 (m, 6H), 7.74-7.85 (m, 3H) , 7.96 (d, J = 8.4 Hz, 2H), 8.00-8.06 (m, 2H), 8.10-8.12 (m, 2H), 8.19-8.21 J = 8.8 Hz, 1H), 8.75 (d, J = 4.8 Hz, 1H), 8.79 ), 9.35 (s, 1 H).

Example-15

Dioxaborolan-2-yl) -5- (4,6-diphenyl-1,3,4,5-tetramethyl- (2-pyridyl) carbazole (1.98 g) and 2-bromopyridine (0.56 g), tetrakis (triphenylphosphine) palladium (101.5 mg) Was suspended in 1,4-dioxane (15 ml), 3M aqueous potassium carbonate solution (3 ml) was added, and the mixture was heated under reflux for 17 hours. After cooling the reaction mixture, water was added. The precipitated solid was separated by filtration, washed with water, then with methanol, and then with hexane. The solvent was distilled off under reduced pressure to obtain the desired product, 3- [3- (2-pyridyl) -5- (4,6-diphenyl-1,3,5-triazin- -9- (2-pyridyl) carbazole (A-15) (yield 1.72 g, yield 93%).

_{^{1 H-NMR (CDCl 3)}} : δ 7.32-7.38 (m, 3H), 7.50 (t, J = 7.4Hz, 1H), 7.56-7.62 (m, 6H), 7.71 (d, J = 8.4Hz, 1H ), 7.87-7.89 (m, 2H), 7.92 (d, J = 8.4 Hz, 1H), 7.97 (t, J = 7.4 Hz, 1H), 8.03 1H), 8.54 (s, 1H), 8.64 (s, 1H), 8.77 (d, J = 4.4 Hz, 1H), 8.81-8.8 (m, 5H), 9.15 , 9.30 (s, 1 H).

Example-16

Phenyl) -9-phenyl-6- (2-pyridyl) carbamate under an argon atmosphere was added to a solution of 3- [3-chloro-5- 2, 4 ', 6'-triisopropylbiphenyl (32.6 mg) was added to a solution of the sol (754 mg), phenylboronic acid (167 mg), palladium acetate (5.1 mg), and 2-dicyclohexylphosphino- (9 ml), 3M aqueous potassium carbonate solution (1.2 ml) was added, and the mixture was heated under reflux for 48 hours. After cooling the reaction mixture, water was added. The precipitated solid was separated by filtration, washed with water, then with methanol, and then with hexane. Further, the solvent was distilled off under reduced pressure to obtain the objective product, 3- [5- (4,6-diphenyl-1,3,5-triazin-2-yl) biphenyl- White powder (yield 297.9 mg, yield 37%) of 6- (2-pyridyl) carbazole (A-16) was obtained.

As a result of mass spectrum (mass spectrometry) measurement, it was confirmed that the molecular weight was 703 and the obtained compound was A-16.

Example-17

Under argon stream, a solution of 3- [5- (4,6-diphenyl-1,3,5-triazin-2-yl) (I) (20 mg), 1,10-phenanthroline (49 mg), 18-crown-6-ether (143 mg) and potassium carbonate (752 mg) 14 ml), and the mixture was heated under reflux for 15 hours. After cooling the reaction mixture, water was added. The precipitated solid was filtered, washed with water, then with methanol, and then with hexane to obtain the desired product, 9- (2-pyridyl) -3- [5- (4,6-diphenyl-1,3,5-tri Azine-2-yl) -biphenyl-3-yl] carbazole (A-12) (yield 1.28 g, yield 96%).

_{^{1 H-NMR (CDCl 3)}} : δ 7.32-7.35 (m, 2H), 7.44-7.50 (m, 2H), 7.54-7.62 (m, 8H), 7.71 (d, J = 8.0Hz, 1H), 7.84 (d, J = 8.4 Hz, 2H), 7.87 (d, J = 8.4 Hz, 2H), 7.96 (D, J = 6.0 Hz, 1H), 8.22 (d, J = 7.6 Hz, 1H), 8.49 , ≪ / RTI > 1H), 9.07 (s, 1H).

Example -18

Compound (E-1) (1.13 g), 6-bromo-9- (2-pyridyl) -? - carboline (749 mg) and bis (triphenylphosphine) palladium dichloride Was suspended in 1,4-dioxane (11 ml), and further 3 M aqueous potassium carbonate solution (1.5 ml) was added, and the mixture was heated under reflux for 18 hours. After cooling the reaction mixture, water was added. The precipitated solid was separated by filtration, washed with water, then with methanol, and then with hexane. The solvent was distilled off under reduced pressure to obtain the desired product, 6- [5- (4,6-diphenyl-1,3,5-triazin-2-yl) biphenyl- (Yield: 1.30 g, yield 94%) of 2-pyridyl) -? - carboline (A-17).

_{^{1 H-NMR (CDCl 3)}} : δ 7.39 (dd, J = 7.4, 4.9Hz, 1H), 7.45 (dd, J = 8.4, 4.7Hz, 1H), 7.48 (t, J = 7.4Hz, 1H), J = 7.7 Hz, 2H), 8.01 (t, J = 7.7 Hz, 1H), 8.05-8.06 (m, 1H), 7.57-7.67 J = 4.7 Hz, 1H), 8.84 (d, J = 4.9 Hz, 1H), 8.24 , J = 7.9 Hz, 4H), 8.95 (s, IH), 9.01 (s, IH), 9.11 (s, IH).

Example-19

Compound (E-1) (418 mg), 3-chloro-9- (2-pyridyl) -? - carboline (240 mg), palladium acetate (3.7 mg) and 2-dicyclohexylphosphine (22.9 mg) was suspended in 1,4-dioxane (4.1 ml), and a 3M aqueous potassium carbonate solution (0.54 ml) was further added thereto to obtain 2 Lt; / RTI > After cooling the reaction mixture, water was added. The precipitated solid was separated by filtration, washed with water, then with methanol, and then with hexane. The solvent was distilled off under reduced pressure to obtain the desired product, 3- [5- (4,6-diphenyl-1,3,5-triazin-2-yl) biphenyl- (Yield 447 mg, yield 87%) of 2-pyridyl) -? - carbolin (A-18).

_{^{1 H-NMR (CDCl 3)}} : δ 7.39 (dd, J = 7.4, 4.9Hz, 1H), 7.46-7.52 (m, 2H), 7.59-7.68 (m, 9H), 7.74 (d, J = 8.1Hz (D, J = 8.6 Hz, 1H), 7.93-7.97 (m, 3H), 8.02 (t, J = 7.6 Hz, 1H), 8.10 (d, J = 4.3 Hz, 1H), 8.78 (s, 1H), 8.79 (d, J = 4.9 Hz, 1H) (s, 1 H).

Example-20

Compound (E-1) (1.02 g), 3-bromo-6-phenyl-9- (2- pyridyl) carbazole (839 g) and bis (triphenylphosphine) palladium dichloride Mg) was suspended in 1,4-dioxane (10 ml), 3M aqueous potassium carbonate solution (1.3 ml) was added, and the mixture was heated under reflux for 5 hours. After cooling the reaction mixture, water was added. The precipitated solid was separated by filtration, washed with water, then with methanol, and then with hexane. Further, the solvent was distilled off under reduced pressure to obtain the objective product, 3- [5- (4,6-diphenyl-1,3,5-triazin-2-yl) biphenyl- -9- (2-pyridyl) carbazole (A-19) (yield 1.34 g, yield 95%).

_{^{1 H-NMR (CDCl 3)}} : δ 7.39 (t, J = 7.4Hz, 1H), 7.40-7.43 (m, 1H), 7.47-7.54 (m, 3H), 7.58-7.68 (m, 8H), 7.77 J = 8.6 Hz, 1H), 7.98 (d, J = 8.6 Hz, 1H), 8.04-8.08 (m, 2H), 8.21 (s, 1H), 8.48 (s, 1H), 8.58 (s, 1H), 8.83-8.87 (m, 5H), 9.02 (s,

Example -21

(1.34 g), 6-bromo-3-phenyl-9- (2-pyridyl) -? - carbene (1.00 g) and bis (triphenylphosphine) palladium Dichloride (35.1 mg) was suspended in 1,4-dioxane (16.7 ml), and further 3 M aqueous potassium carbonate solution (1.8 ml) was added and refluxed for 19 hours. After cooling the reaction mixture, water was added. The precipitated solid was separated by filtration, washed with water, then with methanol, and then with hexane, and the solvent was distilled off under reduced pressure. The resulting solid was recrystallized from o-xylene to obtain the desired product, 6- [5- (4,6-diphenyl-1,3,5-triazin-2-yl) biphenyl- -9- (2-pyridyl) -? - carboline (A-20) (yield 1.7 g, yield 97%).

_{^{1 H-NMR (CDCl 3)}} : δ 7.39 (dd, J = 7.4, 4.9Hz, 1H), 7.45 (t, J = 7.3Hz, 1H), 7.49 (t, J = 7.4Hz, 1H), 7.54- J = 8.6 Hz, 1H), 7.90 (d, J = 8.0 Hz, 2H), 8.01-8.06 (m, 2H ), 8.10 (d, J = 8.6 Hz, 1H), 8.24 (d, J = 8.1 Hz, 2H), 8.27 = 4.9 Hz, 1H), 8.86 (d, J = 8.1 Hz, 4H), 8.98 (s, 1H), 9.02 (s, 1H), 9.15 (s, 1H).

Example-22

(701 mg), 6-bromo-9-phenyl-3- (2-pyridyl) -? - carboline (550 mg) and bis (triphenylphosphine) palladium Dichloride (19 mg) was suspended in 1,4-dioxane (7 ml), and further 3 M aqueous potassium carbonate solution (1 ml) was added, and the mixture was heated under reflux for 40 hours. After cooling the reaction mixture, water was added. The precipitated solid was separated by filtration, washed with water, then with methanol, and then with hexane, and the solvent was distilled off under reduced pressure. The resulting solid was recrystallized using toluene to obtain the target product, 6- [5- (4,6-diphenyl-1,3,5-triazin-2-yl) biphenyl- (Yield 400 mg, yield 41%) of 3- (2-pyridyl) -? - carboline (A-21).

_{^{1 H-NMR (CDCl 3)}} : δ 7.32 (dd, J = 7.4, 4.8Hz, 1H), 7.50 (t, J = 7.4Hz, 1H), 7.55-7.73 (m, 14H), 7.86-7.91 (m (D, J = 8.7 Hz, 1H), 8.00 (d, J = 8.6 Hz, 1H), 8.26 , 8.0 Hz, IH), 8.84-8.86 (m, 4H), 8.96 (s, IH), 9.02 (s, IH), 9.14 (s, IH).

Example-23

Compound (E-1) (1.02 g), 3-bromo-9-phenyl-6- (2- pyridyl) carbazole (839 g) and bis (triphenylphosphine) palladium dichloride Mg) was suspended in 1,4-dioxane (10 ml), 3M aqueous potassium carbonate solution (1.3 ml) was added, and the mixture was heated under reflux for 5 hours. After cooling the reaction mixture, water was added. The precipitated solid was separated by filtration, washed with water, then with methanol, and then with hexane, and the solvent was distilled off under reduced pressure. The obtained solid was purified by silica gel column chromatography (eluent: chloroform) to obtain the objective 3- [5- (4,6-diphenyl-1,3,5-triazin- (Yield: 1.06 g, yield 75%) was obtained in the same manner as in Example 1,

_{^{1 H-NMR (CDCl 3)}} : δ 7.26-7.30 (m, 1H), 7.50 (t, J = 7.4Hz, 1H), 7.54-7.71 (m, 15H), 7.85 (t, J = 7.6Hz, 1H ), 7.89-7.93 (m, 3H), 7.95 (d, J = 8.0 Hz, 1 H), 8.18 (d, J = 8.7 Hz, 1 H), 8.21 (d, J = 4.8 Hz, 1H), 8.85 (d, J = 7.9 Hz, 4H), 8.98 (s, 1H), 9.02 (s, 1H), 9.11 (s, 1H).

Example -24

(1.53 g), 3-bromo-9-phenyl-6- (pyrazinyl) carbazole (1.20 g) and bis (triphenylphosphine) palladium dichloride (42.1 mg ) Was suspended in 1,4-dioxane (15 ml), 3M aqueous potassium carbonate solution (2.0 ml) was added, and the mixture was heated under reflux for 7 hours. After cooling the reaction mixture, water was added. The precipitated solid was separated by filtration, washed with water, then with methanol, and then with hexane, and the solvent was distilled off under reduced pressure. The resulting solid was purified by silica gel column chromatography (eluent: chloroform) to obtain the desired product, 3- [5- (4,6-diphenyl-1,3,5-triazin- (Yield 1.59 g, yield 75%) of 3- (4-fluorophenyl) -6- (pyrazinyl) carbazole (A-22).

_{^{1 H-NMR (CDCl 3)}} : δ 7.50 (t, J = 7.4Hz, 1H), 7.56-7.72 (m, 15H), 7.89 (d, J = 8.3Hz, 2H), 7.92 (d, J = 8.6 (D, J = 2.5 Hz, 1H), 8.65 (d, J = 8.7 Hz, 1H), 8.20 1H), 8.84 (d, J = 8.0 Hz, 4H), 8.99 (s, 1H), 9.00 (s, 1H), 9.10 (s, 1H), 9.21

Example-25

(I-2) (628 mg), iodopyrazine (309 mg), copper (I) (7.2 mg), 1,10-phenanthroline (18 mg), 18- 6-ether (53 mg) and potassium carbonate (276 mg) were suspended in xylene (5.0 ml) and heated to reflux for 18 hours. After cooling the reaction mixture, water and methanol were added. The precipitated solid was washed with water, methanol and hexane and then recrystallized with xylene to obtain the objective 9-pyrazyl-3- [5- (4,6-diphenyl-1,3,5-triazine -2-yl) -4 '- (2-pyridyl) biphenyl-3-yl] carbazole (A-23) was obtained (yield 691 mg, yield 98%).

_{^{1 H-NMR (CDCl 3)}} : δ 7.31-7.35 (m, 1H), 7.45 (t, J = 7.4Hz, 1H), 7.56 (t, J = 7.7Hz, 1H), 7.61-7.68 (m, 6H J = 8.6 Hz, 1H), 8.22 (d, J = 8.3 Hz, 2H), 7.86-7.89 (m, 2H), 7.94-7.98 1H), 8.83 (s, 1H), 8.28 (d, J = 7.6Hz, 1H), 8.54 J = 4.3 Hz, 1H), 8.85 (d, J = 7.8 Hz, 4H), 9.08 (s, 1H).

Example-26

(628 mg), 2-bromopyrimidine (238 mg), copper (I) chloride (7.2 mg), 1,10-phenanthroline (18.0 mg), carbonic acid Potassium (276 mg) and 18-crown-6 (52.9 mg) were suspended in xylene (5.0 ml) and heated at 150 캜 for 60 hours. After cooling the reaction mixture, methanol was added, and the precipitated solid was collected by filtration. The resulting solid was washed with water, methanol, and hexane, and recrystallized from 30 ml of toluene to obtain the target 3- [5- (4,6-diphenyl-1,3,5-triazin- (Yield 636 mg, yield 90%) of 3- (2-pyridyl) biphenyl-3-yl] -9- (2- pyrimidyl) carbazole (A-24).

_{^{1 H-NMR (CDCl 3)}} : δ 7.16 (t, J = 5.0Hz, 1H), 7.31 (m, 1H), 7.41 (t, J = 7.0Hz, 1H), 7.54-7.66 (m, 7H), 1H), 8.78-8.84 (m, 5H), 8.89-8.94 (m, 2H), 7.82-7.89 (m, 3H), 9.02-9.06 (m, 2H), 9.11 (s, 1H).

Example-27

3- (3-chloro-5- (4,6-diphenyl-1,3,5-triazin-2-yl) phenyl] carbazole (2.00 g) and 4- 2-dicyclohexylphosphino-2 ', 4', 6'-triisopropylbiphenyl (97 mg) was dissolved in toluene (34 ml) and 1 -Butanol (3.0 ml), 3 M aqueous potassium carbonate solution (3.0 ml) was added, and the mixture was refluxed for 24 hours. After cooling the reaction mixture, water was added. The precipitated solid was washed with water, methanol, and hexane. The resulting solid was recrystallized from toluene and then purified by sublimation to obtain the objective 9-pyrazyl-3- [5- (4,6-diphenyl-1,3,5-triazin-2-yl) (Yield 329 mg, yield 14%) of 1,1 ': 4', 1 "-terphenyl-3-yl] carbazole (A-25).

_{^{1 H-NMR (CDCl 3)}} : δ 7.43 (t, J = 7.6Hz, 1H), 7.46 (d, J = 7.8Hz, 1H), 7.52 (d, J = 7.8Hz, 1H), 7.54-7.58 ( (d, J = 8.4 Hz, 2H), 7.94-7.99 (m, 4H), 8.10 (d, J = 1H, J = 8.6 Hz, 1H), 8.23 (s, 1H), 8.27 (d, J = 7.4 Hz, 1H), 8.53 (d, J = 8.0 Hz, 4H), 9.07 (s, IH), 9.10 (s, IH), 9.16 (s, IH).

Example-28

(2-pyridyl) -3- [3-chloro-5- (4,6-diphenyl-1,3,5-triazin-2-yl) phenyl] carbazole 2-dicyclohexylphosphino-2 ', 4', 6'-triisopropylbiphenyl (28.6 mg) was dissolved in toluene (5 ml) 20 ml) and 1-butanol (0.9 ml), 3 M aqueous potassium carbonate solution (0.9 ml) was added, and the mixture was refluxed for 18 hours. After cooling the reaction mixture, water was added. The precipitated solid was washed with water, methanol, and hexane. The resulting solid was recrystallized using toluene and then purified by sublimation to obtain 9- (2-pyridyl) -3- [5- (4,6-diphenyl-1,3,5-triazin- (Yield: 171 mg, yield: 24%) of 1, 1 ': 4', 1 "-tterphenyl-3-yl] carbazole (A-26).

_{^{1 H-NMR (CDCl 3)}} : δ 7.38-7.45 (m, 3H), 7.51-7.55 (m, 3H), 7.60-7.67 (m, 6H), 7.74 (d, J = 8.2Hz, 2H), 7.76 (d, J = 8.3 Hz, 1H), 7.93 (d, J = 8.4 Hz, 1H), 7.97 J = 8.4 Hz, 2H), 8.00-8.04 (m, 1H), 8.05 (d, J = 8.5 Hz, 1H), 8.24 8.54 (s, 1H), 8.81-8.82 (m, 1H), 8.85 (d, J = 7.9 Hz, 4H), 9.06 (s, 1H), 9.11 (s, 1H).

Example-29

(2-pyridyl) -3- [3-chloro-5- (4,6-diphenyl-1,3,5-triazin-2-yl) phenyl] carbazole 2-dicyclohexylphosphino-2 ', 4', 6'-triisopropylbiphenyl (9.5 mg) was dissolved in toluene (2 ml) 20.0 ml) and 1-butanol (0.6 ml), 3 M aqueous potassium carbonate solution (0.6 ml) was added, and the mixture was heated under reflux for 5 hours. Thereafter, 9-phenanthreneboronic acid (267 mg), palladium acetate (2.3 mg) and 2-dicyclohexylphosphino-2 ', 4', 6'-triisopropylbiphenyl , And further refluxed for 5 hours. After cooling the reaction mixture, methanol was added, and the precipitated solid was collected by filtration. The obtained solid was washed with water, methanol and hexane, and purified by silica gel column chromatography (developing solvent: chloroform: hexane = 1: 9). This was recrystallized using toluene to obtain the desired 3- [5- (9-phenanthryl) -3- (4,6-diphenyl-1,3,5-triazin-2-yl) phenyl] (Yield 119 mg, yield 16%) of 9- (2-pyridyl) carbazole (A-27).

_{^{1 H-NMR (CDCl 3)}} : δ 7.35-7.42 (m, 2H), 7.50 (t, J = 7.5Hz, 1H), 7.54-7.63 (m, 6H), 7.66-7.77 (m, 4H), 7.87 (d, J = 8.3 Hz, 1H), 7.94-8.10 (m, 6H), 8.15 (t, J = 1.9 Hz, 1H) 1.3 Hz, 1H), 8.79-8.87 (m, 8H), 8.94 (t, J = 1.5 Hz, 1H), 9.22 (t, J = 1.7 Hz, 1H).

Example-30

(2-pyridyl) -3- [3-chloro-5- (4,6-diphenyl-1,3,5-triazin-2-yl) phenyl] carbazole Dicyclohexylphosphino-2 ', 4', 6'-triisopropylbiphenyl (9.5 mg) was dissolved in toluene (20.0 mg) Ml) and 1-butanol (0.6 ml), and 3M-potassium carbonate aqueous solution (0.6 ml) was added thereto, followed by heating under reflux for 3.5 hours. After cooling the reaction mixture, methanol was added, and the precipitated solid was collected by filtration. The resulting solid was washed with water, methanol, and hexane, and then recrystallized from toluene to obtain the target 3- [5- (9-anthracyl) -3- (4,6-diphenyl- Yl) phenyl] -9- (2-pyridyl) carbazole (A-28) (yield 575 mg, yield 79%).

¹ H-NMR (CDCl ₃ ):? 7.35 (t, J = 7.1 Hz, 1H), 7.40-7.61 (m, 13H), 7.89 (d, J = 8.4 Hz, 3H), 7.97-8.07 ), 8.13 (d, J = 8.9 Hz, 2H), 8.18 (d, J = 8.2 Hz, 1H), 8.52 (s, (s, 1 H), 9.31 (s, 1 H).

Example -31

(2-pyridyl) -3- [3-chloro-5- (4,6-diphenyl-1,3,5-triazin-2-yl) phenyl] carbazole Dicyclohexylphosphino-2 ', 4', 6'-triisopropylbiphenyl (9.5 mg) was added to a solution of the compound Was suspended in a mixed solvent of toluene (20.0 ml) and 1-butanol (0.6 ml), 3M aqueous potassium carbonate solution (0.6 ml) was added and the mixture was heated under reflux for 5 hours. Thereafter, 4-dibenzothiophene boronic acid (274 mg), palladium acetate (2.3 mg) and 2-dicyclohexylphosphino-2 ', 4', 6'-triisopropylbiphenyl And the mixture was heated under reflux for 5 hours. After cooling the reaction mixture, methanol was added, and the precipitated solid was collected by filtration. The obtained solid was washed with water, methanol and hexane and then filtered with heating with chloroform to obtain the target 3- [5- (dibenzothiophen-4-yl) -3- (4,6- (Yield: 213 mg, yield 29%) of the title compound was obtained in the form of a white solid. 1H-NMR (DMSO-d6)?

_{^{1 H-NMR (CDCl 3)}} : δ 7.38 (t, J = 7.9Hz, 1H), 7.48-7.52 (m, 3H), 7.56-7.63 (m, 6H), 7.67 (t, J = 7.2Hz, 1H ), 7.74-7.77 (m, 2H), 7.88 (d, J = 8.3 Hz, 2H), 7.94-8.04 (m, 3H), 8.23-8.28 1H), 8.54 (d, J = 1.4 Hz, 1H), 8.80-8.84 (m, 6H), 9.17 (d, J = 7.3 Hz, 2H).

Example-32

(2-pyridyl) -3- [3-chloro-5- (4,6-diphenyl-1,3,5-triazin-2-yl) phenyl] carbazole 2, 4 ', 6'-triisopropylbiphenyl (9.5 mg) was dissolved in toluene (20.0 mg) in the same manner as in Example 1, Ml) and 1-butanol (0.6 ml), and 3M-potassium carbonate aqueous solution (0.6 ml) was added thereto, followed by heating under reflux for 9 hours. The reaction mixture was quenched, methanol was added and the precipitated solid was filtered off. The obtained solid was reacted with 3-quinolinic acid (346 mg), palladium acetate (2.3 mg) and 2-dicyclohexylphosphino-2 ', 4', 6'- triisopropylbiphenyl (9.5 mg) 20.0 ml) and 1-butanol (0.6 ml), 3 M aqueous potassium carbonate solution (0.6 ml) was added, and the mixture was heated to reflux for 3 hours again. After cooling the reaction mixture, methanol was added, and the precipitated solid was collected by filtration. The resulting solid was washed with water, methanol, and hexane, and then recrystallized from toluene to obtain the target 3- [5- (4,6-diphenyl-1,3,5-triazin-2-yl) (Yield 541 mg, yield 80%) of 3- (3-quinolyl) phenyl] -9- (2-pyridyl) carbazole (A-30).

_{^{1 H-NMR (CDCl 3)}} : δ 7.35-7.41 (m, 2H), 7.50 (t, J = 7.4Hz, 1H), 7.58-7.74 (m, 8H), 7.83 (t, J = 6.9Hz, 1H ), 7.91 (t, J = 8.5 Hz, 2H), 7.98-8.06 (m, 3H), 8.26-8.33 (m, 3H), 8.53 (s, m, 5H), 9.10 (s, IH), 9.18 (s, IH), 9.48 (s, IH).

Example-33

Under an argon stream, the above-mentioned 3- [3- (4,4,5,5-tetramethyl-1,3,2-dioxaballolan-2-yl) Phenyl) -9- (2-pyridyl) carbazole (339 mg), 3-bromo-6-phenylpyridine (129 mg), tetrakis (triphenylphosphine) Palladium (11.6 mg) was suspended in 1,4-dioxane (2.5 ml), 3M aqueous potassium carbonate solution (0.33 ml) was added, and the mixture was refluxed for 20 hours. After cooling the reaction mixture, water was added. The precipitated solid was separated by filtration, washed with water, methanol, hexane, and dried by heating under reduced pressure. This was recrystallized from toluene to give the desired 3- [5- (6-phenylpyridin-3-yl) -3- (4,6-diphenyl-1,3,5-triazin- ) Phenyl] -9- (2-pyridyl) carbazole (A-31) (yield 207 mg, yield 59%).

¹ H-NMR (CDCl ₃ ):? 7.37-7.43 (m, 2H), 7.49-7.69 (m, 10H), 7.75 (d, J = 7.8Hz, 1H), 7.91-7.93 (d, J = 8.3 Hz, 1H), 8.02 (t, J = 7.7 Hz, 1H), 8.06 1H), 9.27 (s, 1H), 8.27-8.31 (m, 2H), 8.54 (s, 1H), 8.81-8.86 ).

Example -34

Under an argon stream, the above-mentioned 3- [3- (4,4,5,5-tetramethyl-1,3,2-dioxaballolan-2-yl) 2-yl) phenyl] -9- (2- pyridyl) carbazole (678 mg), 2- bromodibenzothiophene (316 mg), palladium acetate (2.3 mg) Cyclohexylphosphino-2 ', 4', 6'-triisopropylbiphenyl (9.5 mg) was suspended in a mixed solvent of toluene (20.0 ml) and 1-butanol (0.6 ml), and a 3M aqueous potassium carbonate solution (0.6 ml), and the mixture was heated under reflux for 24 hours. After cooling the reaction mixture, methanol was added, and the precipitated solid was collected by filtration. The resulting solid was washed with water, methanol, and hexane, and then recrystallized from toluene to obtain the target 3- [5- (dibenzothiophen-2-yl) -3- (4,6- Yl) phenyl] -9- (2-pyridyl) carbazole (A-32) (yield 640 mg, yield 87%).

¹ H-NMR (CDCl ₃ ): δ 7.38-7.41 (m, 2H), 7.50-7.53 (m, 3H), 7.58-7.64 (m, 6H), 7.89-7.97 m, 3H), 8.22-8.28 (m, 2H), 8.34 (t, J = 5.8 Hz, 1H), 8.50-8.59 (m, 2H), 8.78-8.85 (m, 6H), 9.08-9.13 2H).

Example -35

9- (2-pyridyl) -6- (quinolin-8-yl) carbazole (946) synthesized in Synthesis Example 17, 1.02 g of the compound (E- (46.2 mg) was suspended in 1,4-dioxane (10 ml), 3M aqueous potassium carbonate solution (1.3 ml) was added, and the mixture was heated under reflux for 13 hours. After cooling the reaction mixture, water and methanol were added. The precipitated solid was separated by filtration, washed with water, methanol, and hexane, and the material taken by filtration was heated to dryness under reduced pressure. The resulting solid was recrystallized from xylene to obtain the target 3- [5- (4,6-diphenyl-1,3,5-triazin-2-yl) biphenyl- -Pyridyl) -6- (quinolin-8-yl) carbazole (A-33) as a yellowish brown powder (yield 1.08 g, yield 72%).

_{^{1 H-NMR (CDCl 3)}} : δ 7.39 (dd, J = 7.4, 4.9Hz, 1H), 7.45-7.51 (m, 2H), 7.56-7.65 (m, 8H), 7.71 (t, J = 7.3Hz , 7.83 (d, J = 8.1 Hz, 1H), 7.86-7.91 (m, 4H), 7.93-7.96 (m, 2H), 8.00-8.05 1H), 8.58 (s, 1H), 8.58 (s, 1H), 8.31 (d, J = 8.82-8.85 (m, 5H), 9.00 (s, 1H), 9.06-9.07 (m, 1H), 9.11 (s, 1H).

Example-36

2- [4- (4,4,5,5-tetramethyl-1,3,2-dioxaballolan-2-yl) phenyl] -4,6-diphenyl-1,3,5 -Triazine (1.31 g), 3-bromo-9- (2- pyridyl) -6- [4- (2- pyridyl) phenyl] carbazole (1.57 g), tetrakis (triphenylphosphine) Palladium (69.3 mg) was suspended in a mixed solvent of 1,4-dioxane (20 ml) and 3M-potassium carbonate aqueous solution (2.0 ml) and refluxed for 13 hours. After cooling to room temperature, water and methanol were added. The precipitated solid was washed with water, methanol, and hexane, and the residue was collected by filtration and recrystallized from xylene to obtain the target 3- [4- (4,6-diphenyl-1,3,5-triazin- (Yield: 1.33 g, yield 63%) of 4- (2-pyridyl) -6- [4- (2- pyridyl) phenyl] Respectively.

^{1 H-NMR (DMSO-d} 6): δ 7.26-7.29 (m, 1H), 7.38 (dd, J = 7.5Hz, 4.9Hz, 1H), 7.60-7.68 (m, 6H), 7.74 (d, J = 8.0 Hz, 1H), 7.81 (d, J = 8.7 Hz, 2H), 7.83-7.86 (m, 2H), 7.90 (d, J = 8.5 Hz, 2H), 7.96-8.03 (d, J = 8.5 Hz, 2H), 8.51 (s, IH), 8.54 (s, IH), 8.76 (d, J = 4.6 Hz, (d, J = 7.9 Hz, 4H), 8.91 (d, J = 8.5 Hz, 2H).

Example-37

(E-1) (1.02 g), 3-bromo-6,9-di (2-pyridyl) carbazole (961 mg), palladium acetate (4.5 mg) (19.0 mg) was suspended in 1,4-dioxane (40.0 ml), 3M aqueous potassium carbonate solution (1.3 ml) was added, and 95 mg of 95 Lt; 0 > C for 4 hours. After cooling the reaction mixture, methanol was added, and the precipitated solid was collected by filtration. The resulting solid was washed with water, methanol, and hexane, and then recrystallized from toluene to obtain the desired 6- [5- (4,6-diphenyl-1,3,5-triazin-2-yl) 3-yl] -3,9-di (2-pyridyl) carbazole (A-35) (yield 492 mg, yield 35%).

_{^{1 H-NMR (CDCl 3)}} : δ 7.26-7.29 (m, 1H), 7.41 (dd, J = 7.4, 4.9Hz, 1H), 7.50 (t, J = 7.4Hz, 1H), 7.58-7.66 (m , 8H), 7.78 (d, J = 8.0 Hz, 1H), 7.84 (t, J = 7.7 Hz, 1H), 7.88-7.92 (d, J = 8.6 Hz, 1H), 8.04 (t, J = 7.7 Hz, 1H), 8.06 (d, J = 8.6 Hz, 1H), 8.18-8.23 , 8.78 (d, J = 4.8 Hz, 1H), 8.83 (d, J = 4.9 Hz, 1H) , 9.11 (s, 1 H).

Example -38

(466 mg), 9-anthracene boronic acid (233 mg), and tetrakis (triphenylphosphine) palladium (23 mg) were added to a solution of 2- (3,5- dibromophenyl) -4,6- Mg) was suspended in a mixed solvent of 4N aqueous sodium hydroxide (0.5 ml) and THF (2.0 ml), and the mixture was stirred at 30 캜 for 3 hours. Then water was added, and the precipitated solid was filtered off and washed with water, then methanol, then hexane to give 500 mg of a yellowish white solid. A toluene solution (53 mg) of the obtained yellowish white solid (500 mg), 3- [4- (2-pyridyl) phenyl] carbazole (285 mg), palladium acetate (4 mg) and IM- (246 mg) and 18-crown-6-ether (47 mg) were suspended in xylene (4.4 ml), and the mixture was heated under reflux for 5 hours. The reaction mixture was cooled and extracted with chloroform. The organic layer was purified by silica gel chromatography (developing solvent: chloroform) to give 3- [4- (2-pyridyl) phenyl] -9- [3- (4,6-diphenylpyrimidin- (Yield: 580 mg, yield 72%) of 5- (anthracen-9-yl)] phenylcarbazole (B-1).

_{^{1 H-NMR (CDCl 3)}} : δ 7.29 (t, J = 5.9Hz, 1H), 7.48 (t, J = 7.4Hz, 1H), 7.54-7.64 (m, 11H), 7.79 (t, J = 8.0 (D, J = 7.5 Hz, 2H), 8.16 (s, 1H), 8.19-8.24 (m, 1H), 7.83 (d, J = 7.9 Hz, 1H), 7.86-7.07 , 8.33-8.38 (m, 5H), 8.58 (s, IH), 8.67 (s, IH), 8.84 (d, J = 4.8 Hz, 1H), 9.13 1H).

Example-39

2- (5-chlorobiphenyl-3-yl) -4,6-diphenylpyrimidine (3.25 g) and 3- [4- (2- pyridyl) phenyl] carbazole (2.73 g) , Potassium carbonate (2.14 g) and 18-crown-6-ether (410 mg) were added to a toluene solution of xylene (39 mg), 1M-tri (tert- 0.0 > mL) < / RTI > and heated to reflux for 18 hours. The reaction mixture was cooled and extracted with chloroform. The organic layer was purified by silica gel chromatography (developing solvent: chloroform) to obtain the objective 3- [4- (2-pyridyl) phenyl] -9- [5- (4,6-diphenylpyrimidin- ) Biphenyl-3-yl] carbazole (B-2) (yield 5.03 g, yield 92%).

_{^{1 H-NMR (CDCl 3)}} : δ 7.28 (dd, J = 7.0, 4.8Hz, 1H), 7.39 (t, J = 7.4Hz, 1H), 7.47 (t, J = 7.4Hz, 1H), 7.51 ( (d, J = 8.6 Hz, 1H), 7.78-7.87 (m, 5H), 7.90 (d, J = 8.5 Hz, 2H), 7.55-7.64 J = 8.5 Hz, 2H), 8.329-8.35 (m, 5H), 8.51 (s, 1H), 8.76 (d, J = 4.8 Hz, 1 H), 8.97 (s, 1 H), 9.12 (s, 1 H).

Example-40

3- (2-pyridyl) carbazole (770 mg), palladium acetate (12.8 g) and triethylamine (172 μl), potassium carbonate (791 mg) and 18-crown-6-ether (151 mg) of 1 M tri (tert-butyl) phosphine were suspended in xylene (14 ml) , And the mixture was heated under reflux for 44 hours. The reaction mixture was cooled and extracted with chloroform. The organic layer was purified by silica gel chromatography (developing solvent: chloroform) to obtain the objective product, 3- (2-pyridyl) -9- [5- (4,6-diphenylpyrimidin- -Vinyl] -carbazole (B-3) (yield 949 mg, yield 53%).

_{^{1 H-NMR (CDCl 3)}} : δ 7.25 (dd, J = 7.2, 4.8Hz, 1H), 7.38 (t, J = 7.4Hz, 1H), 7.47 (t, J = 7.4Hz, 1H), 7.50 ( J = 7.7 Hz, 1H), 7.54-7.62 (m, 9H), 7.66 (d, J = 8.8 Hz, 1H) (D, J = 8.6 Hz, 1H), 8.13 (s, 1H), 8.29-8.33 (m, 5H ), 8.77 (d, J = 4.8 Hz, 1H), 8.91 (s, 1H), 8.96 (s, 1H), 9.11 (s, 1H).

Example-41

Phenylboronic acid (1.17 g), phenylboronic acid (293 < RTI ID = 0.0 > Dicyclohexylphosphino-2 ', 4', 6'-triisopropylbiphenyl (57 mg) and 3M-potassium carbonate aqueous solution (1.6 ml) were dissolved in toluene 9.0 ml) and n-butanol (1.0 ml), and the mixture was heated to reflux for 3 hours. After quenching the reaction mixture, water was added and extracted with chloroform. Then, the organic layer was dried with magnesium sulfate, filtered, and the solvent was distilled off under reduced pressure. Thereafter, hexane was added to the concentrated organic layer, and the solid was reprecipitated to obtain the desired product, 9- (2-pyridyl) -3- [5- (4,6-diphenylpyrimidin- -3-yl] carbazole (B-4) (yield: 900 mg, yield: 72%).

_{^{1 H-NMR (CDCl 3)}} : δ 7.28 (dd, J = 7.4, 4.9Hz, 1H), 7.40 (t, J = 7.4Hz, 1H), 7.47-7.54 (m, 2H), 7.57-7.64 (m , 8H), 7.73 (d, J = 8.1 Hz, 1H), 7.89-7.94 (m, 4H), 7.98 (t, J = 7.7 Hz, (s, 1H), 8.12 (s, 1H), 8.25 (d, J = 7.4 Hz, 1H), 8.349-8.37 (m, 4H), 8.54 1H), 8.99 (s, 1 H), 9.08 (s, 1 H).

Example -42

(2-pyridyl) -9- [3-chloro-5- (4,6-diphenylpyrimidin-2- yl) phenyl] carbazole (585 mg) Pyridyl) phenylboronic acid (239 mg), palladium acetate (4.5 mg), 2-dicyclohexylphosphino-2 ', 4', 6'- triisopropylbiphenyl (0.8 ml) were suspended in a mixed solvent of toluene (4.5 ml) and n-butanol (0.5 ml) and refluxed for 3 hours. After cooling the reaction mixture, water and methanol were added to form a slurry to precipitate a solid. The precipitated solid was filtered and washed with water, then with methanol, and then with hexane to obtain the desired product, 9- (2-pyridyl) -3- [5- (4,6-diphenylpyrimidin- (Yield 676 mg, yield 96%) of 4 '- (2-pyridyl) biphenyl-3-yl] carbazole (B-5) was obtained.

_{^{1 H-NMR (CDCl 3)}} : δ 7.28 (t, J = 6.0Hz, 1H), 7.34 (dd, J = 7.2, 5.0Hz, 1H), 7.39 (t, J = 7.5Hz, 1H), 7.52 ( (t, J = 7.5 Hz, 1H), 7.56-7.63 (m, 6H), 7.71 (d, J = 8.0 Hz, 1H), 7.78-7.85 (m, 2H), 7.91-8.02 (d, J = 7.7 Hz, 1H), 8.15 (s, 1H), 8.21 (d, J = 8.3 Hz, 2H), 8.25 (s, 1H), 8.78 (d, J = 4.8 Hz, 1H), 8.80 (d = 4.4 Hz, 1H), 9.03 (s, 1H), 9.08

Example -43

(2-pyridyl) -9- [3-chloro-5- (4,6-diphenylpyrimidin-2-yl) phenyl] carbazole (1.17 g) (480 mg), palladium acetate (9.0 mg), 2-dicyclohexylphosphino-2 ', 4', 6'- triisopropylbiphenyl (57 mg) and a 3M aqueous potassium carbonate solution (1.6 ml) were suspended in a mixed solvent of toluene (9.0 ml) and n-butanol (1.0 ml), and the mixture was refluxed for 2 hours. After cooling the reaction mixture, water was added. The precipitated solid was filtered and washed with water, then with methanol, and then with hexane to obtain the desired product, 9- (2-pyridyl) -3- [5- (4,6-diphenylpyrimidin- (Yield: 1.25 g, yield 89%) of 4 '- (2-pyrazyl) biphenyl-3-yl] carbazole (B-6).

_{^{1 H-NMR (CDCl 3)}} : δ 7.34-7.40 (m, 2H), 7.51 (t, J = 7.7Hz, 1H), 7.56-7.63 (m, 6H), 7.72 (d, J = 8.0Hz, 1H ), 7.91 (d, J = 8.5 Hz, 1H), 7.92 (d, J = 8.2 Hz, 1H), 7.96-8.03 (m, 4H), 8.06 (s, 1H), 8.50 (s, 1H), 8.70 (s, 1H), 8.80 (d, J = 4.8 Hz, 1H) 9.01 (s, 1 H), 9.08 (s, 1 H), 9.15 (s, 1 H).

Example -44

4- (4-bromophenyl) -6- (1-naphthyl) -2-phenylpyrimidine (219 mg) synthesized in Synthetic Example-20 and 3- ( (2.2 mg), 1 M-tri (tert-butyl) phosphine in toluene (30 L), potassium carbonate (152 mg) and 18-crown- -Ethanol (26 mg) was suspended in xylene (2.5 ml), and the mixture was refluxed for 20 hours. The reaction mixture was filtered, and unnecessary matter was removed. The filtrate was purified by silica gel chromatography (eluent: chloroform) to obtain the desired 9- [4- (6-naphthyl-2-phenylpyrimidin-4-yl) phenyl] -3- (quinolin- -Yl) carbazole (B-7) (Yield 297 mg, yield 91%).

_{^{1 H-NMR (CDCl 3)}} : δ 7.35 (t, J = 7.4Hz, 1H), 7.47 (d, J = 8.0Hz, 1H), 7.47-7.50 (m, 1H), 7.56-7.63 (m, 6H ), 7.66-7.72 (m, 3H), 7.85 (d, J = 8.5 Hz, 1H), 7.88 (d, J = 8.6 Hz, 2H), 7.86-7.93 (m, 3H), 8.00-8.02 J = 7.6 Hz, 1H), 8.29 (d, J = 8.3 Hz, 1H), 8.43-8.46 (d, 2H), 8.76-8.79 (m, 2H), 9.04 (d, J = 4.1 Hz, 1H), 8.48 (s, 1H), 8.60 (d, J = 8.6 Hz, 2H).

≪ Fabrication and performance evaluation of an organic electroluminescent device using cyclic azine as a component &

The following Examples, Reference Examples, and Comparative Examples relate to the fabrication and performance evaluation of an organic electroluminescent device.

The structural formula of the compound used is as follows.

Example-45

As the substrate, a glass substrate with an ITO transparent electrode, in which an indium tin oxide (ITO) film having a width of 2 mm was patterned in a stripe shape, was used. The substrate was washed with isopropyl alcohol, and then subjected to surface treatment by oxygen plasma cleaning. Vacuum evaporation of each layer was carried out on the cleaned substrate by the vacuum vapor deposition method to produce an organic electroluminescent device having a light emitting area of 4 mm square as shown in Fig.

First, the glass substrate was introduced into a vacuum vapor deposition vessel, and the pressure was reduced to 1.0 × 10 ^-4 Pa. Thereafter, a hole injecting layer 2, a hole transporting layer 3, a light emitting layer 4 and an electron transporting layer 5 are sequentially formed as an organic compound layer on the ITO transparent electrode-coated glass substrate shown in Fig. 1 (1) , And then the cathode layer 6 was formed. The material constituting each layer of the organic electroluminescent device was vacuum evaporated by a resistance heating method.

As the hole injecting layer 2, CuPc sublimed and purified was vacuum-deposited at a deposition rate of 0.06 nm / sec and a film thickness of 25 nm.

As the hole transport layer 3, NPD was vacuum deposited at a film-forming rate of 0.30 nm / sec and a film thickness of 45 nm.

As the light emitting layer 4, EML-1 and EML-2 were vacuum-deposited with a film thickness of 40 nm (co-evaporation of EML-1 / EML-2 = 95/5 (weight ratio)) at a film formation rate of 0.18 nm / sec.

As the electron transport layer 5, A-1 synthesized in Example 1 of the present invention was vacuum deposited at a film formation rate of 0.25 nm / sec and a film thickness of 20 nm.

Finally, a metal mask was disposed so as to be in direct contact with the ITO stripe, and the cathode layer 6 was formed. The cathode layer 6 was made of a two-layer structure in which lithium fluoride and aluminum were vacuum-deposited in this order at a deposition rate of 0.1 nm / sec and 0.25 nm / sec, respectively, to a film thickness of 1.0 nm and 100 nm.

Each film thickness was measured with a stylus type film thickness meter (DEKTAK, Veeco).

Further, the device was sealed in a nitrogen atmosphere glove box with oxygen and moisture concentration of 1 ppm or less. As the sealing, a sealing cap made of glass and an epoxy type ultraviolet curing resin (manufactured by Nagase Chemtech Co., Ltd.) were used.

Example -46

An organic electroluminescent device was fabricated in the same manner as in Example-45, except that A-3 synthesized in Example 3 was used instead of A-1 in the electron transport layer (5) of Example-45.

Example-47

An organic electroluminescent device was fabricated in the same manner as in Example-45 except that, in the electron transport layer (5) of Example-45, A-6 synthesized in Example 6 was used instead of A-1.

Reference Example 1

An organic electroluminescent device was fabricated in the same manner as in Example-45 except that ETL-1, a known electron transporting material, was used in place of A-1 in the electron transport layer (5) of Example-31. A direct current was applied to the fabricated organic electroluminescent device, and the luminescent characteristics were evaluated using a luminometer of LUMINANCE METER (BM-9) manufactured by Topcon Corporation. The luminance decay time at the time of continuous lighting when the current density of 20 mA / cm 2 was allowed to flow was measured. The time when the luminance (cd / m < 2 >) is reduced by 20% is shown below.

From Table 1, it can be seen that the organic electroluminescent device using the cyclic azine derivative of the present invention has excellent lifetime characteristics as compared with the reference example.

Example -48

(EML-1 / EML-2 = 95/5 (weight ratio)) at a film formation rate of 0.18 nm / sec in the light emitting layer (4) (TBADN / EML-2 = 95/5 (co-evaporation deposition) of 40 nm at a film formation rate of 0.18 nm / sec, vacuum evaporation was performed for TBADN and EML-2.

Further, in the same manner as in Example-45, except that A-2 was vacuum-deposited instead of A-1 in the electron-transporting layer 5 at a film-forming rate of 0.25 nm / sec and a film thickness of 20 nm, Respectively.

Example-49

An organic electroluminescent device was fabricated in the same manner as in Example-48 except that A-10 synthesized in Example 10 was used instead of A-2 in the electron transport layer (5) of Example-48.

Comparative Example 1

An organic electroluminescent device was fabricated in the same manner as in Example -48 except that ETL-2 described in Patent Document 4 was used in place of A-2 in the electron transport layer (5) of Example-48. A direct current was applied to the fabricated organic electroluminescent device, and the luminescent characteristics were evaluated using a luminometer of LUMINANCE METER (BM-9) manufactured by Topcon. The time and the voltage and efficiency when the luminance (cd / m 2) is reduced by 20% and the current is caused to flow to the device at a density of 20 mA / cm 2 are shown below.

From Table 2, it can be seen that the cyclic azine compound (1) of the present invention is superior in electron injecting property, electron transporting property, driving voltage (voltage [V]), current efficiency / A]) and device life remarkably and significantly.

Example -50

An ITO transparent electrode-adhered glass substrate on which an indium oxide-tin oxide (ITO) film having a width of 2 mm was patterned in a stripe shape was used as a substrate. The substrate was washed with isopropyl alcohol, and then subjected to surface treatment by oxygen plasma cleaning. Vacuum evaporation of each layer was carried out on the cleaned substrate by a vacuum vapor deposition method, and an organic electroluminescent device having a light emitting area of 4 mm square as shown in Fig. 2 was manufactured.

First, the glass substrate was introduced into a vacuum vapor deposition vessel, and the pressure was reduced to 1.0 × 10 ^-4 Pa. Thereafter, the hole injection layer 12, the first hole transport layer 13, the second hole transport layer 14, the light emitting layer 15, and the light emitting layer 15 are formed as an organic compound layer on the ITO transparent electrode- And the electron transport layer 16 were successively formed, and then the cathode layer 17 was formed. The material constituting each layer of the organic electroluminescent device was vacuum evaporated by a resistance heating method.

As the hole injecting layer 12, HTL-1 was vacuum-deposited at a deposition rate of 0.15 nm / sec and a film thickness of 40 nm.

As the first hole transporting layer 13, HAT-CN was vacuum deposited at a deposition rate of 0.025 nm / sec and a film thickness of 5 nm.

As the second hole transporting layer 14, HTL-2 was vacuum deposited at a deposition rate of 0.15 nm / sec and a film thickness of 25 nm.

As the light emitting layer 15, EML-1 and EML-2 were vacuum deposited at a film-forming rate of 0.18 nm / sec and a film thickness of 40 nm (co-evaporation of EML-1 / EML-2 = 95/5 (weight ratio)).

As the electron transport layer 16, B-2 synthesized in Example 39 of the present invention was vacuum deposited at a film formation rate of 0.15 nm / sec and a film thickness of 30 nm.

Finally, a metal mask was disposed so as to be in direct contact with the ITO stripe, and the cathode layer 17 was formed. The cathode layer 17 was formed in the order of 0.005 nm / sec, 0.5 nm / sec, 0.2 nm / sec, and 0.5 nm, 80 nm, and 0.5 nm at a deposition rate of Liq, magnesium / silver (weight ratio 80/20) Vacuum evaporation was performed at a film thickness of 20 nm to obtain a three-layer structure.

Each film thickness was measured with a stylus type film thickness meter (DEKTAK, Veeco).

The device was also sealed in a nitrogen atmosphere glove box with oxygen and moisture concentration of 1 ppm or less. As the sealing, a sealing cap made of glass and an epoxy type ultraviolet curing resin (manufactured by Nagase Chemtech Co., Ltd.) were used.

Example -51

An organic electroluminescent device was fabricated in the same manner as in Example -50 except that B-3 synthesized in Example 40 was used instead of B-2 in the electron transport layer 16 of Example-50.

Example -52

An organic electroluminescent device was fabricated in the same manner as in Example -50 except that B-4 synthesized in Example 41 was used instead of B-2 in the electron transport layer 16 of Example-50.

Example -53

An organic electroluminescent device was fabricated in the same manner as in Example 50 except that B-5 synthesized in Example 42 was used in place of B-2 in the electron transport layer 16 of Example-50.

Example -54

An organic electroluminescent device was fabricated in the same manner as in Example -50 except that B-6 synthesized in Example 43 was used instead of B-2 in the electron transport layer 16 of Example-50.

Comparative Example 2

An organic electroluminescent device was fabricated in the same manner as in Example -50 except that ETL-3 was used in place of B-2 in the electron transport layer 16 of Example-50.

A direct current was applied to the fabricated organic electroluminescent device, and the luminescent characteristics were evaluated using a luminometer of LUMINANCE METER (BM-9) manufactured by Topcon. The luminance decay time at the time of continuous lighting when the current density of 20 mA / cm 2 was allowed to flow was measured. The voltage and efficiency at the time when the luminance (cd / m < 2 >) was reduced by 10% and when the current was caused to flow to the device at a density of 20 mA /

From Table 3, it can be seen that the cyclic azine compound (1) of the present invention is superior in electron injecting property, electron transporting property, driving voltage (voltage [V]), current efficiency / A]) and device life remarkably and significantly.

Example -55

An ITO transparent electrode-adhered glass substrate on which an indium oxide-tin oxide (ITO) film having a width of 2 mm was patterned in a stripe shape was used as a substrate. The substrate was washed with isopropyl alcohol, and then subjected to surface treatment by oxygen plasma cleaning. Vacuum evaporation of each layer was carried out on the cleaned substrate by a vacuum vapor deposition method to produce an organic electroluminescent device having a light emitting area of 4 mm square as shown in Fig.

First, the glass substrate was introduced into a vacuum vapor deposition vessel, and the pressure was reduced to 1.0 × 10 ^-4 Pa. Thereafter, the hole injection layer 12, the first hole transport layer 13, the second hole transport layer 14, the light emitting layer 15, and the light emitting layer 15 are formed as an organic compound layer on the ITO transparent electrode- And the electron transport layer 16 were successively formed, and then the cathode layer 17 was formed. The material constituting each layer of the organic electroluminescent device was vacuum evaporated by a resistance heating method.

As the hole injecting layer 12, HTL-1 was vacuum deposited at a film-forming rate of 0.15 nm / sec and a film thickness of 45 nm.

As the first hole transporting layer 13, HAT-CN was vacuum deposited at a deposition rate of 0.025 nm / sec and a film thickness of 5 nm.

As the second hole transporting layer 14, HTL-2 was vacuum deposited at a deposition rate of 0.15 nm / sec and a film thickness of 30 nm.

As the light emitting layer 15, EML-1 and EML-2 were vacuum deposited at a film-forming rate of 0.18 nm / sec and a film thickness of 20 nm (co-evaporation of EML-1 / EML-2 = 96/4 (weight ratio)).

As the electron transport layer 16, A-3 synthesized in Example 3 of the present invention was vacuum deposited at a film formation rate of 0.15 nm / sec and a film thickness of 30 nm.

Finally, a metal mask was disposed so as to be in direct contact with the ITO stripe, and the cathode layer 17 was formed. The cathode layer 17 was formed in the order of 0.5 nm and 80 nm at a film formation rate of 0.005 nm / second, 0.5 nm / second and 0.2 nm / second, respectively, in the order of lithium fluoride, magnesium / silver , And vacuum vapor deposited at a film thickness of 20 nm to obtain a three-layer structure.

Each film thickness was measured with a stylus type film thickness meter (DEKTAK, Veeco).

The device was also sealed in a nitrogen atmosphere glove box with oxygen and moisture concentration of 1 ppm or less. As the sealing, a sealing cap made of glass and an epoxy type ultraviolet curing resin (manufactured by Nagase Chemtech Co., Ltd.) were used.

Example -56

An organic electroluminescent device was fabricated in the same manner as in Example 55 except that A-13 synthesized in Example 13 was used instead of A-3 in the electron transport layer 16 of Example-55.

Example -57

An organic electroluminescent device was fabricated in the same manner as in Example 55 except that B-5 synthesized in Example 42 was used in place of A-3 in the electron transport layer 16 of Example-55.

Reference Example-2

An organic electroluminescent device was fabricated in the same manner as in Example 55 except that ETL-1 was used in place of A-3 in the electron transport layer 16 of Example-55.

A direct current was applied to the fabricated organic electroluminescent device, and the luminescent characteristics were evaluated using a luminometer of LUMINANCE METER (BM-9) manufactured by Topcon. The luminance decay time at the time of continuous lighting when the current density of 20 mA / cm 2 was allowed to flow was measured. The time when the luminance (cd / m < 2 >) was reduced by 20% and the voltage and efficiency when the current was flown to the device at a density of 10 mA /

It can be seen from Table 4 that the cyclic azine compound (1) of the present invention has a driving voltage (voltage [V]), current efficiency (efficiency [cd / A]) and lifetime characteristics of the organic electroluminescent device Excellent.

Example -58

An ITO transparent electrode-adhered glass substrate on which an indium oxide-tin oxide (ITO) film having a width of 2 mm was patterned in a stripe shape was used as a substrate. The substrate was washed with isopropyl alcohol, and then subjected to surface treatment by oxygen plasma cleaning. Vacuum vapor deposition of each layer was carried out on the cleaned substrate by a vacuum evaporation method, and a cross-sectional view of the organic electroluminescent device having a light emitting area of 4 mm 2 as shown in Fig. 2 was prepared.

First, the glass substrate was introduced into a vacuum vapor deposition vessel, and the pressure was reduced to 1.0 × 10 ^-4 Pa. Thereafter, the hole injection layer 12, the first hole transport layer 13, the second hole transport layer 14, the light emitting layer 15, and the light emitting layer 15 are formed as an organic compound layer on the ITO transparent electrode- And the electron transport layer 16 were successively formed, and then the cathode layer 17 was formed. The material constituting each layer of the organic electroluminescent device was vacuum evaporated by a resistance heating method.

As the hole injecting layer 12, HTL-1 was vacuum-deposited at a deposition rate of 0.15 nm / sec and a film thickness of 65 nm.

As the first hole transporting layer 13, HAT-CN was vacuum deposited at a deposition rate of 0.025 nm / sec and a film thickness of 5 nm.

As the second hole transporting layer 14, HTL-2 was vacuum deposited at a deposition rate of 0.15 nm / sec and a film thickness of 10 nm.

As the light emitting layer 15, EML-1 and EML-2 were vacuum deposited in a film thickness of 25 nm (co-evaporation of EML-1 / EML-2 = 96/4 (weight ratio)) at a film formation rate of 0.18 nm / sec.

As the electron transport layer 16, A-12 synthesized in Example 12 of the present invention was vacuum deposited at a film formation rate of 0.15 nm / sec and a film thickness of 30 nm. Each of the organic materials was deposited by resistance heating, and the heated compound was vacuum deposited at a deposition rate of 0.3 to 0.5 nm / sec.

Finally, a metal mask was disposed so as to be in direct contact with the ITO stripe, and the cathode layer 17 was formed. The cathode layer 17 was formed in the order of 0.005 nm / sec, 0.5 nm / sec, 0.2 nm / sec, and 0.5 nm, 80 nm, and 0.5 nm at a deposition rate of Liq, magnesium / silver (weight ratio 80/20) Vacuum evaporation was performed at a film thickness of 20 nm to obtain a three-layer structure.

Each film thickness was measured with a stylus type film thickness meter (DEKTAK).

Further, the device was sealed in a nitrogen atmosphere glove box with oxygen and moisture concentration of 1 ppm or less. As the sealing, a sealing cap made of glass and an epoxy type ultraviolet curing resin (manufactured by Nagase Chemtech Co., Ltd.) were used.

Example -59

An organic electroluminescent device was fabricated in the same manner as in Example 58 except that A-16 synthesized in Example 16 was used in place of A-12 in the electron transport layer 16 of Example 58.

Example-60

An organic electroluminescent device was fabricated in the same manner as in Example 58 except that A-17 synthesized in Example 18 was used in place of A-12 in the electron transport layer 16 of Example 58.

Example -61

An organic electroluminescent device was fabricated in the same manner as in Example 58 except that A-18 synthesized in Example 19 was used in place of A-12 in the electron transport layer 16 of Example 58.

Example-62

An organic electroluminescent device was fabricated in the same manner as in Example 58 except that A-19 synthesized in Example 20 was used instead of A-12 in the electron transport layer 16 of Example 58.

Example-63

An organic electroluminescent device was fabricated in the same manner as in Example 58 except that A-20 synthesized in Example 21 was used in place of A-12 in the electron transport layer 16 of Example 58.

Example-64

An organic electroluminescent device was fabricated in the same manner as in Example 58 except that A-22 synthesized in Example 24 was used in place of A-12 in the electron transport layer 16 of Example 58.

Comparative Example 3

An organic electroluminescent device was fabricated in the same manner as in Example 58 except that ETL-4 synthesized in Synthesis Example 21 was used instead of A-12 in the electron transport layer 16 of Example 58.

A direct current was applied to the fabricated organic electroluminescent device, and the luminescent characteristics were evaluated using a luminometer of LUMINANCE METER (BM-9) manufactured by Topcon. The luminance decay time at the time of continuous lighting when the current density of 20 mA / cm 2 was allowed to flow was measured. The time when the luminance (cd / m < 2 >) was reduced by 10% and the voltage when the current was caused to flow to the device at a density of 10 mA /

From Table 5, it was shown that the cyclic azine compound (1) of the present invention is superior in driving voltage (voltage [V]) and lifespan characteristics of an organic electroluminescent device as compared with conventionally known compounds.

As described above, the organic electroluminescent device using the cyclic azine compound (1) of the present invention is remarkably superior in device characteristics such as drive voltage, current efficiency and lifetime of the organic electroluminescent device compared with conventionally known compounds .

INDUSTRIAL APPLICABILITY The organic electroluminescent device using the cyclic azine compound of the present invention can be driven for a long time as compared with an organic electroluminescent device using a conventional material and can be applied not only to devices using a fluorescent light emitting material, It can be applied to an electroluminescent device, and is industrially very useful.

Further, the cyclic azine compound of the present invention has high solubility and can be used not only as an electron transporting layer but also as a light emitting host layer as well as a vacuum deposition method and a device using a coating method. , And is also useful in lighting applications requiring low power consumption.

Japanese Patent Application No. 2012-136711 filed on June 18, 2012, Japanese Patent Application No. 2012-247767 filed on November 9, 2012, and Japanese Patent Application filed on December 21, 2012 The entire contents of the specification, claims, drawings and summary of the present application are hereby incorporated herein by reference as if fully set forth herein.

1: Glass substrate with ITO transparent electrode 2: Hole injection layer
3: hole transport layer 4: light emitting layer
5: electron transport layer 6: cathode layer
11: Glass substrate with ITO transparent electrode 12: Hole injection layer
13: first hole transporting layer 14: second hole transporting layer
15: luminescent layer 16: electron transport layer
17: cathode layer

Claims (22)

A cyclic azine compound represented by the following general formula (1):

(Wherein,
Cz represents a carbazole group of the (n + 1) valence or a valine group of the (n + 1) valence (these groups each independently represent a fluorine atom, an alkyl group of 1 to 4 carbon atoms, an aromatic hydrocarbon group of 6 to 18 carbon atoms, May have, as a substituent, an aromatic hydrocarbon group having 6 to 18 carbon atoms or an aromatic hydrocarbon group having 6 to 18 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms.
Ar ¹ and Ar ² each independently represent an aromatic hydrocarbon group having 6 to 30 carbon atoms (each independently selected from the group consisting of a fluorine atom, an alkyl group having 1 to 4 carbon atoms, an aromatic group having 3 to 18 carbon atoms, Or an aromatic group having 3 to 18 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms as the substituent).
Ar ³ represents an arylene group having 6 to 30 carbon atoms (a fluorine atom, an alkyl group having 1 to 4 carbon atoms, an aromatic group having 3 to 18 carbon atoms, an aromatic group having 3 to 18 carbon atoms having fluorine atom or an alkyl group having 1 to 4 carbon atoms Or an aromatic group having 3 to 18 carbon atoms as a substituent).
Ar ⁴ each independently represents a nitrogen-containing heteroaryl group having 3 to 30 carbon atoms (each independently a fluorine atom, an alkyl group having 1 to 4 carbon atoms, an aromatic group having 3 to 18 carbon atoms, a fluorine atom-containing 3 to 18 carbon atoms An aromatic group or an aromatic group having 3 to 18 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms as a substituent) or a substituent represented by the following formula (A).
Y and Z each independently represent a nitrogen atom or CH.
Provided that at least one of Y and Z is a nitrogen atom.
and n represents an integer of 1 to [the maximum number of bonds that can be formed on Cz-1].

(Wherein,
Ar ⁵ each independently represents an aryl group having 6 to 30 carbon atoms (each independently, a fluorine atom, an alkyl group having 1 to 4 carbon atoms, an aromatic group having 3 to 18 carbon atoms, a carbon number 3 having a fluorine atom, An aromatic group having 1 to 18 carbon atoms or an aromatic group having 3 to 18 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms).
Ar ⁶ each independently represents a nitrogen-containing heteroaryl group having 3 to 30 carbon atoms (each independently, a fluorine atom, an alkyl group having 1 to 4 carbon atoms, an aromatic group having 3 to 18 carbon atoms, a fluorine atom- An aromatic group or an aromatic group having 3 to 18 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms).
m each independently represent an integer of 1 to [the maximum number of bonds that can be formed on Ar ⁵ ] -1). The cyclic azine compound according to claim 1, wherein the general formula (1) is represented by the following general formula (B), (C) or (D)

(In the formula (D), Cb represents a carboline group of the (n + 1) -valent.
Among the formulas (B), (C) and (D)
Ar ¹ and Ar ² each independently represent an aromatic hydrocarbon group having 6 to 30 carbon atoms (each independently selected from the group consisting of a fluorine atom, an alkyl group having 1 to 4 carbon atoms, an aromatic group having 3 to 18 carbon atoms, Or an aromatic group having 3 to 18 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms as the substituent).
And Ar ³ each independently represent an arylene group having 6 to 30 carbon atoms such as a fluorine atom, an alkyl group having 1 to 4 carbon atoms, an aromatic group having 3 to 18 carbon atoms, an aromatic group having 3 to 18 carbon atoms having a fluorine atom, May have, as a substituent, an aromatic group having 3 to 18 carbon atoms substituted with an alkyl group of 1 to 18 carbon atoms).
Ar ⁴ each independently represents a nitrogen-containing heteroaryl group having 3 to 30 carbon atoms (each independently a fluorine atom, an alkyl group having 1 to 4 carbon atoms, an aromatic group having 3 to 18 carbon atoms, a fluorine atom-containing 3 to 18 carbon atoms An aromatic group or an aromatic group having 3 to 18 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms as a substituent) or a substituent represented by the following formula (A).
Y and Z each independently represent a nitrogen atom or CH.
Provided that at least one of Y and Z is a nitrogen atom.
n each independently represent an integer of 1 to 7.)

(Wherein,
Ar ⁵ represents an aryl group having 6 to 30 carbon atoms of (m + 1) valency (each independently, a fluorine atom, an alkyl group having 1 to 4 carbon atoms, an aromatic group having 3 to 18 carbon atoms, an aromatic group having 3 to 18 carbon atoms having a fluorine atom Or an aromatic group having 3 to 18 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms as a substituent).
Ar ⁶ each independently represents a nitrogen-containing heteroaryl group having 3 to 30 carbon atoms (each independently, a fluorine atom, an alkyl group having 1 to 4 carbon atoms, an aromatic group having 3 to 18 carbon atoms, a fluorine atom- An aromatic group or an aromatic group having 3 to 18 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms).
and m represents an integer of 1 to [the maximum number of bonds that can be formed on Ar ^5-1 ]. The nitrogen-containing heteroaryl group of 3 to 30 carbon atoms represented by Ar ⁴ and Ar ⁶ (each independently a fluorine atom, an alkyl group having 1 to 4 carbon atoms, an aromatic group having 3 to 18 carbon atoms , An aromatic group having 3 to 18 carbon atoms which carries a fluorine atom or an aromatic group having 3 to 18 carbon atoms in which an alkyl group having 1 to 4 carbon atoms is substituted may be used as a substituent group) may be independently selected from the group consisting of carbon, hydrogen and nitrogen (Each independently represent a fluorine atom, an alkyl group having 1 to 4 carbon atoms, an aromatic group having 3 to 18 carbon atoms, an aromatic group having 3 to 18 carbon atoms, or an alkyl group having 1 to 4 carbon atoms) A substituted or unsubstituted aromatic group having 3 to 18 carbon atoms as a substituent) or a nitrogen-containing heteroaryl group having 3 to 30 carbon atoms consisting of carbon, hydrogen, nitrogen and sulfur only A fluorine atom, an alkyl group having 1 to 4 carbon atoms, an aromatic group having 3 to 18 carbon atoms, an aromatic group having 3 to 18 carbon atoms having a fluorine atom, or an aromatic group having 3 to 18 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms Optionally substituted as a substituent). The heterocyclic compound according to any one of claims 1 to 3, wherein the nitrogen-containing heteroaryl group having 3 to 30 carbon atoms represented by Ar ⁴ and Ar ⁶ (each independently a fluorine atom, an alkyl group having 1 to 4 carbon atoms, An aromatic group having 3 to 18 carbon atoms having a fluorine atom or an aromatic group having 3 to 18 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms as the substituent) may be independently selected from the group consisting of carbon, hydrogen and nitrogen A nitrogen-containing heteroaryl group having 3 to 30 carbon atoms (provided that a fluorine atom, an alkyl group having 1 to 4 carbon atoms, an aromatic group having 3 to 18 carbon atoms, an aromatic group having 3 to 18 carbon atoms having a fluorine atom or an aromatic group having 1 to 4 carbon atoms Or an aromatic group having 3 to 18 carbon atoms substituted with an alkyl group as a substituent). The heterocyclic compound according to any one of claims 1 to ⁴ , wherein the nitrogen-containing heteroaryl group having 3 to 30 carbon atoms represented by Ar ⁴ and Ar ⁶ (each independently a fluorine atom, an alkyl group having 1 to 4 carbon atoms, An aromatic group having 3 to 18 carbon atoms having a fluorine atom or an aromatic group having 3 to 18 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms may be substituted as a substituent), each independently represents a pyridyl group, (These groups each independently represent a fluorine atom, an alkyl group having 1 to 4 carbon atoms, an alkyl group having 3 to 6 carbon atoms, or a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms) An aromatic group having 1 to 18 carbon atoms, a fluorine atom-containing aromatic group having 3 to 18 carbon atoms, or an aromatic group having 3 to 18 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms). Any one of claims 1 to A method according to any one of claim 5, wherein, Ar ^4, and a nitrogen-containing heteroaryl group having 3 to 30 represented by Ar ⁶ (each independently, an alkyl group of fluorine atoms, having 1 to 4 carbon atoms, having from 3 to An aromatic group having 3 to 18 carbon atoms having a fluorine atom or an aromatic group having 3 to 18 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms as a substituent) may be independently a pyridyl group An aromatic group having 3 to 18 carbon atoms, an aromatic group having 3 to 18 carbon atoms, or an aromatic group having 3 to 18 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms, as a substituent, in the presence of a fluorine atom, an alkyl group having 1 to 4 carbon atoms, an aromatic group having 3 to 18 carbon atoms, Which is a cyclic azine compound. 7. The compound according to any one of claims 1 to 6, wherein Ar ¹ and Ar ² each independently represent a phenyl group, a biphenyl group, a naphthyl group, an anthryl group, a pyrenyl group, a terphenyl group or a phenanthryl group Each independently represent a fluorine atom, an alkyl group having 1 to 4 carbon atoms, an aromatic group having 3 to 18 carbon atoms, an aromatic group having 3 to 18 carbon atoms having a fluorine atom or an aromatic group having 3 to 18 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms Group may be substituted as a substituent). 8. The compound according to any one of claims 1 to 7, wherein Ar ¹ and Ar ² are each independently a phenyl group or a biphenylyl group (these groups each independently represent a fluorine atom, an alkyl group having 1 to 4 carbon atoms, An aromatic group having 1 to 18 carbon atoms, a fluorine atom-containing aromatic group having 3 to 18 carbon atoms, or an aromatic group having 3 to 18 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms). 9. The cyclic azine compound according to any one of claims 1 to 8, wherein Ar ¹ and Ar ² are each independently a phenyl group, a methylphenyl group or a biphenylyl group. A compound according to any one of claims 1 to 9, wherein Ar ³ is a phenylene group or a biphenylylene group (each of these groups is independently a fluorine atom, an alkyl group having 1 to 4 carbon atoms, an aromatic group having 3 to 18 carbon atoms, An aromatic group having 3 to 18 carbon atoms which carries a fluorine atom or an aromatic group having 3 to 18 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms). The compound according to any one of claims 1 to 10, wherein Ar ⁵ is a benzene group of the formula (m + 1) or a biphenyl group of the formula (m + 1) (these groups each independently represent a fluorine atom, An aromatic group having 3 to 18 carbon atoms, an aromatic group having 3 to 18 carbon atoms having a fluorine atom, or an aromatic group having 3 to 18 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms as a substituent) compound. 12. The cyclic azine compound according to any one of claims 1 to 11, wherein Y and Z are a nitrogen atom, or Y is CH and Z is a nitrogen atom. The cyclic azine compound according to any one of claims 1 to 12, wherein n is 1, 2 or 3. 14. The cyclic azine compound according to any one of claims 1 to 13, wherein m is 1 or 2. A process for producing a compound represented by the following general formula (2), wherein the compound represented by the following general formula (2) and the compound represented by the following general formula (3) are subjected to coupling reaction in the presence of a metal catalyst or in the presence of a base and a metal catalyst (1): < EMI ID =

(Wherein,
Cz represents a carbazole group of the (n + 1) valence or a valine group of the (n + 1) valence (these groups each independently represent a fluorine atom, an alkyl group of 1 to 4 carbon atoms, an aromatic hydrocarbon group of 6 to 18 carbon atoms, May have, as a substituent, an aromatic hydrocarbon group having 6 to 18 carbon atoms or an aromatic hydrocarbon group having 6 to 18 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms.
Ar ¹ and Ar ² each independently represent an aromatic hydrocarbon group having 6 to 30 carbon atoms (each independently selected from the group consisting of a fluorine atom, an alkyl group having 1 to 4 carbon atoms, an aromatic group having 3 to 18 carbon atoms, Or an aromatic group having 3 to 18 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms as the substituent).
Ar ³ represents an arylene group having 6 to 30 carbon atoms (a fluorine atom, an alkyl group having 1 to 4 carbon atoms, an aromatic group having 3 to 18 carbon atoms, an aromatic group having 3 to 18 carbon atoms having fluorine atom or an alkyl group having 1 to 4 carbon atoms Or an aromatic group having 3 to 18 carbon atoms as a substituent).
Ar ⁴ each independently represents a nitrogen-containing heteroaryl group having 3 to 30 carbon atoms (each independently a fluorine atom, an alkyl group having 1 to 4 carbon atoms, an aromatic group having 3 to 18 carbon atoms, a fluorine atom-containing 3 to 18 carbon atoms An aromatic group or an aromatic group having 3 to 18 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms as a substituent) or a substituent represented by the following formula (A).
Y and Z each independently represent a nitrogen atom or CH.
Provided that at least one of Y and Z is a nitrogen atom.
H ^N represents a hydrogen atom on the nitrogen atom in Cz.
X ¹ represents a leaving group.
and n represents an integer of 1 to [the maximum number of bonds that can be formed on Cz-1].

(Wherein,
Ar ⁵ represents an aryl group having 6 to 30 carbon atoms of (m + 1) valency (each independently, a fluorine atom, an alkyl group having 1 to 4 carbon atoms, an aromatic group having 3 to 18 carbon atoms, an aromatic group having 3 to 18 carbon atoms having a fluorine atom Or an aromatic group having 3 to 18 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms as a substituent).
Ar ⁶ each independently represents a nitrogen-containing heteroaryl group having 3 to 30 carbon atoms (each independently, a fluorine atom, an alkyl group having 1 to 4 carbon atoms, an aromatic group having 3 to 18 carbon atoms, a fluorine atom- An aromatic group or an aromatic group having 3 to 18 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms).
and m represents an integer of 1 to [the maximum number of bonds that can be formed on Ar ^5-1 ]. A process for producing a compound represented by the following general formula (5), which comprises subjecting a compound represented by the following general formula (4) and a compound represented by the following general formula (5) to a coupling reaction in the presence of a metal catalyst or in the presence of a base and a metal catalyst (1): < EMI ID =

(Wherein,
Cz represents a carbazole group of the (n + 1) valence or a valine group of the (n + 1) valence (these groups each independently represent a fluorine atom, an alkyl group of 1 to 4 carbon atoms, an aromatic hydrocarbon group of 6 to 18 carbon atoms, May have, as a substituent, an aromatic hydrocarbon group having 6 to 18 carbon atoms or an aromatic hydrocarbon group having 6 to 18 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms.
Ar ¹ and Ar ² each independently represent an aromatic hydrocarbon group having 6 to 30 carbon atoms (each independently selected from the group consisting of a fluorine atom, an alkyl group having 1 to 4 carbon atoms, an aromatic group having 3 to 18 carbon atoms, Or an aromatic group having 3 to 18 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms as the substituent).
Ar ³ represents an arylene group having 6 to 30 carbon atoms (a fluorine atom, an alkyl group having 1 to 4 carbon atoms, an aromatic group having 3 to 18 carbon atoms, an aromatic group having 3 to 18 carbon atoms having fluorine atom or an alkyl group having 1 to 4 carbon atoms Or an aromatic group having 3 to 18 carbon atoms as a substituent).
Ar ⁴ each independently represents a nitrogen-containing heteroaryl group having 3 to 30 carbon atoms (each independently a fluorine atom, an alkyl group having 1 to 4 carbon atoms, an aromatic group having 3 to 18 carbon atoms, a fluorine atom-containing 3 to 18 carbon atoms An aromatic group or an aromatic group having 3 to 18 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms as a substituent) or a substituent represented by the following formula (A).
Y and Z each independently represent a nitrogen atom or CH.
Provided that at least one of Y and Z is a nitrogen atom.
M and X < ² > represent leaving groups.
and n represents an integer of 1 to [the maximum number of bonds that can be formed on Cz-1].

(Wherein,
Ar ⁵ represents an aryl group having 6 to 30 carbon atoms of (m + 1) valency (each independently, a fluorine atom, an alkyl group having 1 to 4 carbon atoms, an aromatic group having 3 to 18 carbon atoms, an aromatic group having 3 to 18 carbon atoms having a fluorine atom Or an aromatic group having 3 to 18 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms as a substituent).
Ar ⁶ each independently represents a nitrogen-containing heteroaryl group having 3 to 30 carbon atoms (each independently, a fluorine atom, an alkyl group having 1 to 4 carbon atoms, an aromatic group having 3 to 18 carbon atoms, a fluorine atom- An aromatic group or an aromatic group having 3 to 18 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms).
and m represents an integer of 1 to [the maximum number of bonds that can be formed on Ar ^5-1 ]. A process for producing a compound represented by the following general formula (7), which is characterized in that a compound represented by the following general formula (6) and a compound represented by the following general formula (7) are subjected to a coupling reaction in the presence of a metal catalyst or in the presence of a base and a metal catalyst (1): < EMI ID =

(Wherein,
Cz represents a carbazole group of the (n + 1) valence or a valine group of the (n + 1) valence (these groups each independently represent a fluorine atom, an alkyl group of 1 to 4 carbon atoms, an aromatic hydrocarbon group of 6 to 18 carbon atoms, May have, as a substituent, an aromatic hydrocarbon group having 6 to 18 carbon atoms or an aromatic hydrocarbon group having 6 to 18 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms.
Ar ¹ and Ar ² each independently represent an aromatic hydrocarbon group having 6 to 30 carbon atoms (each independently selected from the group consisting of a fluorine atom, an alkyl group having 1 to 4 carbon atoms, an aromatic group having 3 to 18 carbon atoms, Or an aromatic group having 3 to 18 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms as the substituent).
Ar ³ represents an arylene group having 6 to 30 carbon atoms (a fluorine atom, an alkyl group having 1 to 4 carbon atoms, an aromatic group having 3 to 18 carbon atoms, an aromatic group having 3 to 18 carbon atoms having fluorine atom or an alkyl group having 1 to 4 carbon atoms Or an aromatic group having 3 to 18 carbon atoms as a substituent).
Ar ⁴ each independently represents a nitrogen-containing heteroaryl group having 3 to 30 carbon atoms (each independently a fluorine atom, an alkyl group having 1 to 4 carbon atoms, an aromatic group having 3 to 18 carbon atoms, a fluorine atom-containing 3 to 18 carbon atoms An aromatic group or an aromatic group having 3 to 18 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms as a substituent) or a substituent represented by the following formula (A).
Y and Z each independently represent a nitrogen atom or CH.
Provided that at least one of Y and Z is a nitrogen atom.
H ^N represents a hydrogen atom on the nitrogen atom in Cz.
X ³ represents a leaving group.
n is 1)

(Wherein,
Ar ⁵ represents an aryl group having 6 to 30 carbon atoms of (m + 1) valency (each independently, a fluorine atom, an alkyl group having 1 to 4 carbon atoms, an aromatic group having 3 to 18 carbon atoms, an aromatic group having 3 to 18 carbon atoms having a fluorine atom Or an aromatic group having 3 to 18 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms as a substituent).
Ar ⁶ each independently represents a nitrogen-containing heteroaryl group having 3 to 30 carbon atoms (each independently, a fluorine atom, an alkyl group having 1 to 4 carbon atoms, an aromatic group having 3 to 18 carbon atoms, a fluorine atom- An aromatic group or an aromatic group having 3 to 18 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms).
and m represents an integer of 1 to [the maximum number of bonds that can be formed on Ar ^5-1 ]. A process for producing a compound represented by the following general formula (9), which comprises subjecting a compound represented by the following general formula (8) and a compound represented by the following general formula (9) to a coupling reaction in the presence of a metal catalyst or in the presence of a base and a metal catalyst (1): < EMI ID =

(Wherein,
Cz represents a carbazole group of the (n + 1) valence or a valine group of the (n + 1) valence (these groups each independently represent a fluorine atom, an alkyl group of 1 to 4 carbon atoms, an aromatic hydrocarbon group of 6 to 18 carbon atoms, May have, as a substituent, an aromatic hydrocarbon group having 6 to 18 carbon atoms or an aromatic hydrocarbon group having 6 to 18 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms.
Ar ¹ and Ar ² each independently represent an aromatic hydrocarbon group having 6 to 30 carbon atoms (each independently selected from the group consisting of a fluorine atom, an alkyl group having 1 to 4 carbon atoms, an aromatic group having 3 to 18 carbon atoms, Or an aromatic group having 3 to 18 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms as the substituent).
Ar ³ represents an arylene group having 6 to 30 carbon atoms (a fluorine atom, an alkyl group having 1 to 4 carbon atoms, an aromatic group having 3 to 18 carbon atoms, an aromatic group having 3 to 18 carbon atoms having fluorine atom or an alkyl group having 1 to 4 carbon atoms Or an aromatic group having 3 to 18 carbon atoms as a substituent).
Ar ⁴ each independently represents a nitrogen-containing heteroaryl group having 3 to 30 carbon atoms (each independently a fluorine atom, an alkyl group having 1 to 4 carbon atoms, an aromatic group having 3 to 18 carbon atoms, a fluorine atom-containing 3 to 18 carbon atoms An aromatic group or an aromatic group having 3 to 18 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms as a substituent) or a substituent represented by the following formula (A).
Y and Z each independently represent a nitrogen atom or CH.
Provided that at least one of Y and Z is a nitrogen atom.
M and X ⁴ represent leaving groups.
and n represents an integer of 1 to [the maximum number of bonds that can be formed on Cz-1].

(Wherein,
Ar ⁵ represents an aryl group having 6 to 30 carbon atoms of (m + 1) valency (each independently, a fluorine atom, an alkyl group having 1 to 4 carbon atoms, an aromatic group having 3 to 18 carbon atoms, an aromatic group having 3 to 18 carbon atoms having a fluorine atom Or an aromatic group having 3 to 18 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms as a substituent).
Ar ⁶ each independently represents a nitrogen-containing heteroaryl group having 3 to 30 carbon atoms (each independently, a fluorine atom, an alkyl group having 1 to 4 carbon atoms, an aromatic group having 3 to 18 carbon atoms, a fluorine atom- An aromatic group or an aromatic group having 3 to 18 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms).
and m represents an integer of 1 to [the maximum number of bonds that can be formed on Ar ^5-1 ]. An organic electroluminescent device comprising a cyclic azine compound represented by the following general formula (1)

(Wherein,
Cz represents a carbazole group of the (n + 1) valence or a valine group of the (n + 1) valence (these groups each independently represent a fluorine atom, an alkyl group of 1 to 4 carbon atoms, an aromatic hydrocarbon group of 6 to 18 carbon atoms, May have, as a substituent, an aromatic hydrocarbon group having 6 to 18 carbon atoms or an aromatic hydrocarbon group having 6 to 18 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms.
Ar ¹ and Ar ² each independently represent an aromatic hydrocarbon group having 6 to 30 carbon atoms (each independently selected from the group consisting of a fluorine atom, an alkyl group having 1 to 4 carbon atoms, an aromatic group having 3 to 18 carbon atoms, Or an aromatic group having 3 to 18 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms as the substituent).
Ar ³ represents an arylene group having 6 to 30 carbon atoms (a fluorine atom, an alkyl group having 1 to 4 carbon atoms, an aromatic group having 3 to 18 carbon atoms, an aromatic group having 3 to 18 carbon atoms having fluorine atom or an alkyl group having 1 to 4 carbon atoms Or an aromatic group having 3 to 18 carbon atoms as a substituent).
Ar ⁴ each independently represents a nitrogen-containing heteroaryl group having 3 to 30 carbon atoms (each independently a fluorine atom, an alkyl group having 1 to 4 carbon atoms, an aromatic group having 3 to 18 carbon atoms, a fluorine atom-containing 3 to 18 carbon atoms An aromatic group or an aromatic group having 3 to 18 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms as a substituent) or a substituent represented by the following formula (A).
Y and Z each independently represent a nitrogen atom or CH.
Provided that at least one of Y and Z is a nitrogen atom.
and n represents an integer of 1 to [the maximum number of bonds that can be formed on Cz-1].

(Wherein,
Ar ⁵ represents an aryl group having 6 to 30 carbon atoms of (m + 1) valency (each independently, a fluorine atom, an alkyl group having 1 to 4 carbon atoms, an aromatic group having 3 to 18 carbon atoms, an aromatic group having 3 to 18 carbon atoms having a fluorine atom Or an aromatic group having 3 to 18 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms as a substituent).
Ar ⁶ each independently represents a nitrogen-containing heteroaryl group having 3 to 30 carbon atoms (each independently, a fluorine atom, an alkyl group having 1 to 4 carbon atoms, an aromatic group having 3 to 18 carbon atoms, a fluorine atom- An aromatic group or an aromatic group having 3 to 18 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms).
and m represents an integer of 1 to [the maximum number of bonds that can be formed on Ar ^5-1 ]. The organic electroluminescent device according to claim 19, wherein the cyclic azine compound represented by the general formula (1) is contained in any one of the hole blocking layer, the electron transporting layer and the electron injecting layer. A longevity increasing method of an organic electroluminescent device, characterized by using a cyclic azine compound represented by the following general formula (1) in an electron transporting layer:

(Wherein,
Cz represents a carbazole group of the (n + 1) valence or a valine group of the (n + 1) valence (these groups each independently represent a fluorine atom, an alkyl group of 1 to 4 carbon atoms, an aromatic hydrocarbon group of 6 to 18 carbon atoms, May have, as a substituent, an aromatic hydrocarbon group having 6 to 18 carbon atoms or an aromatic hydrocarbon group having 6 to 18 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms.
Ar ¹ and Ar ² each independently represent an aromatic hydrocarbon group having 6 to 30 carbon atoms (each independently selected from the group consisting of a fluorine atom, an alkyl group having 1 to 4 carbon atoms, an aromatic group having 3 to 18 carbon atoms, Or an aromatic group having 3 to 18 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms as the substituent).
Ar ³ represents an arylene group having 6 to 30 carbon atoms (a fluorine atom, an alkyl group having 1 to 4 carbon atoms, an aromatic group having 3 to 18 carbon atoms, an aromatic group having 3 to 18 carbon atoms having fluorine atom or an alkyl group having 1 to 4 carbon atoms Or an aromatic group having 3 to 18 carbon atoms as a substituent).
Ar ⁴ each independently represents a nitrogen-containing heteroaryl group having 3 to 30 carbon atoms (each independently a fluorine atom, an alkyl group having 1 to 4 carbon atoms, an aromatic group having 3 to 18 carbon atoms, a fluorine atom-containing 3 to 18 carbon atoms An aromatic group or an aromatic group having 3 to 18 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms as a substituent) or a substituent represented by the following formula (A).
Y and Z each independently represent a nitrogen atom or CH.
Provided that at least one of Y and Z is a nitrogen atom.
and n represents an integer of 1 to [the maximum number of bonds that can be formed on Cz-1].

(Wherein,
Ar ⁵ represents an aryl group having 6 to 30 carbon atoms of (m + 1) valency (each independently, a fluorine atom, an alkyl group having 1 to 4 carbon atoms, an aromatic group having 3 to 18 carbon atoms, an aromatic group having 3 to 18 carbon atoms having a fluorine atom Or an aromatic group having 3 to 18 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms as a substituent).
Ar ⁶ each independently represents a nitrogen-containing heteroaryl group having 3 to 30 carbon atoms (each independently, a fluorine atom, an alkyl group having 1 to 4 carbon atoms, an aromatic group having 3 to 18 carbon atoms, a fluorine atom- An aromatic group or an aromatic group having 3 to 18 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms).
and m represents an integer of 1 to [the maximum number of bonds that can be formed on Ar ^5-1 ]. A method for electroluminescence of an organic electroluminescent device, characterized by using a cyclic azine compound represented by the following general formula (1) in an electron transport layer:

(Wherein,
Cz represents a carbazole group of the (n + 1) valence or a valine group of the (n + 1) valence (these groups each independently represent a fluorine atom, an alkyl group of 1 to 4 carbon atoms, an aromatic hydrocarbon group of 6 to 18 carbon atoms, May have, as a substituent, an aromatic hydrocarbon group having 6 to 18 carbon atoms or an aromatic hydrocarbon group having 6 to 18 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms.
Ar ¹ and Ar ² each independently represent an aromatic hydrocarbon group having 6 to 30 carbon atoms (each independently selected from the group consisting of a fluorine atom, an alkyl group having 1 to 4 carbon atoms, an aromatic group having 3 to 18 carbon atoms, Or an aromatic group having 3 to 18 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms as the substituent).
Ar ³ represents an arylene group having 6 to 30 carbon atoms (a fluorine atom, an alkyl group having 1 to 4 carbon atoms, an aromatic group having 3 to 18 carbon atoms, an aromatic group having 3 to 18 carbon atoms having fluorine atom or an alkyl group having 1 to 4 carbon atoms Or an aromatic group having 3 to 18 carbon atoms as a substituent).
Ar ⁴ each independently represents a nitrogen-containing heteroaryl group having 3 to 30 carbon atoms (each independently a fluorine atom, an alkyl group having 1 to 4 carbon atoms, an aromatic group having 3 to 18 carbon atoms, a fluorine atom-containing 3 to 18 carbon atoms An aromatic group or an aromatic group having 3 to 18 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms as a substituent) or a substituent represented by the following formula (A).
Y and Z each independently represent a nitrogen atom or CH.
Provided that at least one of Y and Z is a nitrogen atom.
and n represents an integer of 1 to [the maximum number of bonds that can be formed on Cz-1].

(Wherein,
Ar ⁵ represents an aryl group having 6 to 30 carbon atoms of (m + 1) valency (each independently, a fluorine atom, an alkyl group having 1 to 4 carbon atoms, an aromatic group having 3 to 18 carbon atoms, an aromatic group having 3 to 18 carbon atoms having a fluorine atom Or an aromatic group having 3 to 18 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms as a substituent).
Ar ⁶ each independently represents a nitrogen-containing heteroaryl group having 3 to 30 carbon atoms (each independently, a fluorine atom, an alkyl group having 1 to 4 carbon atoms, an aromatic group having 3 to 18 carbon atoms, a fluorine atom- An aromatic group or an aromatic group having 3 to 18 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms).
and m represents an integer of 1 to [the maximum number of bonds that can be formed on Ar ^5-1 ].

Images