WO2013191177A1 - Cyclic azine compound, method for producing same, and organic electroluminescent element containing same - Google Patents

Abstract

Provided are a 1,3,5-cyclic triazine compound represented by formula (1), an organic electroluminescent element which uses this compound as an electron transport material and which can be operated for a long period of time, and use of this compound as a constituent component of an organic electroluminescent element. (In the formula, Cz is an (n+1) valent carbazole group or an (n+1) valent carboline group (these groups may each independently have a substituent group such as a fluorine atom), Ar¹ and Ar² are each independently an aromatic hydrocarbon group having 6-30 carbon atoms (these groups may each independently have a substituent group such as a fluorine atom), Ar³ is an arylene group having 6-30 carbon atoms (and may have a substituent group such as a fluorine atom), the Ar⁴ groups are each independently a nitrogen-containing heteroaryl group having 3-30 carbon atoms (these groups may each independently have a substituent group such as a fluorine atom) or a substituent group represented by general formula (A), and Y and Z are each independently a nitrogen atom or CH. However, at least one of Y and Z is a nitrogen atom. n is an integer between 1 and [maximum number of bonds able to be formed on Cz -1]) (In the formula, Ar⁵ is an (m+1) valent aryl group having 6-30 carbon atoms (these groups may each independently have a substituent group such as a fluorine atom), the Ar⁶ groups are each independently a nitrogen-containing heteroaryl group having 3-30 carbon atoms (these groups may each independently have a substituent group such as a fluorine atom), and m is an integer between 1 and [maximum number of bonds able to be formed on Ar⁵ -1]).

Description

Cyclic azine compound, method for producing the same, and organic electroluminescent device containing the same

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

An organic electroluminescent element has a basic structure in which a light-emitting layer containing a light-emitting material is sandwiched between a hole transport layer and an electron transport layer, and an anode and a cathode are attached to the outside of the light-emitting layer. This element utilizes light emission (fluorescence or phosphorescence) accompanying exciton deactivation caused by recombination of holes and electrons, and is applied to displays and the like. The hole transport layer is divided into a hole transport layer and a hole injection layer, the light emitting layer is divided into an electron blocking layer, a light emitting layer and a hole blocking layer, and the electron transport layer is divided into an electron transport layer and an electron injection layer. May be configured.

In recent years, many organic electroluminescent devices using triazine and pyrimidine compounds in the light emitting layer and the electron transporting layer have been reported, but they completely satisfy the market requirements in terms of luminous efficiency characteristics, driving voltage characteristics, and long life characteristics. However, there is a need for better materials.

As electron transport materials and the like, cyclic azine compounds in which a carbazolyl group is substituted via an arylene group have been disclosed (see, for example, Patent Documents 1 to 4), and proposals have been made to improve the lifetime of devices using these. ing. However, improvement is desired in that the device has a higher driving voltage and a longer life expectancy.

In addition, an example in which a 1,3,5-triazine compound having a carbazolyl group is used in an organic electroluminescent device (see, for example, Patent Document 5) is disclosed, but the compound has a carbazolyl group at the 2-position of the triazine ring. Nitrogen atoms are directly bonded. For this reason, when used as an electron transport material, there is a tendency that the electron acceptability essential for the electron transport material is lowered and the device has a high driving voltage, and improvement is required.

International Publication No. 2003/078541 Pamphlet International Publication No. 2003/080760 Pamphlet Japanese Unexamined Patent Publication No. 2009-21336 Japanese Unexamined Patent Publication No. 2002-193952 International Publication No. 2008/123189 Pamphlet

Organic electroluminescence devices have begun to be used in various display devices, but further improvements in device performance are required, such as longer life, higher luminous efficiency, and lower drive voltage. More specifically, development of a carrier transport material that achieves a long life, high luminous efficiency, and low driving voltage is required.
In particular, regarding an electron injection material and an electron transport material, there is a demand for a new material that can drive an element at a low voltage due to excellent electron injectability and electron transport characteristics, has high light emission efficiency, and can drive the element for a long time.
An object of the present invention is to provide an electron injecting material and an electron transporting material for achieving long life, high luminous efficiency, and low driving voltage.

As a result of intensive studies to solve the above problems, the present inventors have included a nitrogen-containing heteroaryl group on the carbazolyl group in a cyclic azine compound substituted with a carbazolyl group via a conventionally known arylene group. It has been found that the electron injecting property and the electron transporting property of the cyclic azine compound are remarkably improved by providing the substituent.
Further, when such a compound (cyclic azine compound represented by the general formula (1) of the present invention) is used as an electron transport layer in an organic electroluminescence device, compared to the case where a known or general-purpose electron transport material is used. Thus, the present inventors have found that the organic electroluminescent device driving voltage is significantly reduced, the luminous efficiency is improved, and the organic electroluminescent device has a long life, and the present invention has been completed.

（式中、
Ｃｚは（ｎ＋１）価のカルバゾール基又は（ｎ＋１）価のカルボリン基（これらの基は、各々独立して、フッ素原子、炭素数１～４のアルキル基、炭素数６～１８の芳香族炭化水素基、フッ素原子を有する炭素数６～１８の芳香族炭化水素基、又は炭素数１～４のアルキル基が置換した炭素数６～１８の芳香族炭化水素基を置換基として有してもよい）を表す。
Ａｒ^１及びＡｒ^２は、各々独立して、炭素数６～３０の芳香族炭化水素基（各々独立して、フッ素原子、炭素数１～４のアルキル基、炭素数３～１８の芳香族基、フッ素原子を有する炭素数３～１８の芳香族基、又は炭素数１～４のアルキル基が置換した炭素数３～１８の芳香族基を置換基として有してもよい）を表す。
Ａｒ^３は炭素数６～３０のアリーレン基（フッ素原子、炭素数１～４のアルキル基、炭素数３～１８の芳香族基、フッ素原子を有する炭素数３～１８の芳香族基、又は炭素数１～４のアルキル基が置換した炭素数３～１８の芳香族基を置換基として有してもよい）を表す。
Ａｒ^４は、各々独立して、炭素数３～３０の含窒素ヘテロアリール基（各々独立して、フッ素原子、炭素数１～４のアルキル基、炭素数３～１８の芳香族基、フッ素原子を有する炭素数３～１８の芳香族基、又は炭素数１～４のアルキル基が置換した炭素数３～１８の芳香族基を置換基として有してもよい）、又は一般式（Ａ）で示される置換基を表す。
Ｙ及びＺは、各々独立して、窒素原子又はＣＨを表す。但し、Ｙ及びＺのうち少なくとも一方は窒素原子である。
ｎは１～［Ｃｚ上に形成できる最大の結合数－１］の整数を表す。） 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. is there.

(Where
Cz is an (n + 1) -valent carbazole group or an (n + 1) -valent carboline group (these groups are each independently a fluorine atom, an alkyl group having 1 to 4 carbon atoms, or an aromatic hydrocarbon having 6 to 18 carbon atoms). Group, a fluorine atom-containing aromatic hydrocarbon group having 6 to 18 carbon atoms, or an aromatic hydrocarbon group having 6 to 18 carbon atoms substituted by an alkyl group having 1 to 4 carbon atoms may be used as a substituent. ).
Ar ¹ and Ar ² are each independently an aromatic hydrocarbon 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) And an aromatic group having 3 to 18 carbon atoms having a fluorine atom, or an aromatic group having 3 to 18 carbon atoms substituted by an alkyl group having 1 to 4 carbon atoms may be used as a substituent.
Ar ³ is 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 a fluorine atom, or carbon An aromatic group having 3 to 18 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms may be substituted).
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) An aromatic group having 3 to 18 carbon atoms, or an aromatic group having 3 to 18 carbon atoms substituted by an alkyl group having 1 to 4 carbon atoms), or a general formula (A) The substituent shown by is represented.
Y and Z each independently represent a nitrogen atom or CH. However, at least one of Y and Z is a nitrogen atom.
n represents an integer of 1 to [the maximum number of bonds -1 that can be formed on Cz-1]. )

（式中、
Ａｒ^５は、各々独立して（ｍ＋１）価の炭素数６～３０のアリール基（各々独立して、フッ素原子、炭素数１～４のアルキル基、フッ素原子を有してもよい炭素数３～１８の芳香族基、又は炭素数１～４のアルキル基が置換してもよい炭素数３～１８の芳香族基を置換基として有してもよい）を表す。
Ａｒ^６は、各々独立して、炭素数３～３０の含窒素ヘテロアリール基（各々独立して、フッ素原子、炭素数１～４のアルキル基、炭素数３～１８の芳香族基、フッ素原子を有する炭素数３～１８の芳香族基、又は炭素数１～４のアルキル基が置換した炭素数３～１８の芳香族基を置換基として有してもよい）を表す。
ｍは、各々独立して、１～［Ａｒ^５上に形成できる最大の結合数－１］の整数を表す。）

(Where
Ar ⁵ is each independently an (m + 1) -valent aryl group having 6 to 30 carbon atoms (each independently having a fluorine atom, an alkyl group having 1 to 4 carbon atoms, or an optionally substituted fluorine atom having 3 carbon atoms). Or an aromatic group having 3 to 18 carbon atoms, which may be substituted by an alkyl group having 1 to 4 carbon atoms or an alkyl group having 1 to 4 carbon atoms, may be substituted.
Ar ⁶ is each independently 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 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.
Each m independently represents 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, the organic electroluminescence device can be driven at a lower voltage, has a higher luminous efficiency, and has a longer life than an organic electroluminescence device using a conventionally known electron transport material. Can be provided.

FIG. 46 is a schematic cross-sectional view of a single-layer element manufactured in Example-45. FIG. 46 is a schematic cross-sectional view of a single-layer element manufactured in Example-50 or the like.

Hereinafter, the present invention will be described in detail.
The present invention relates to the above cyclic azine compound (1), a method for producing the same, and an organic electroluminescent device containing the same.
The cyclic azine compound (1) of the present invention is a cyclic azine compound represented by the following general formula (B), (C), or (D) in that the performance as a material for an organic electroluminescent element is good. It is preferable.

（一般式（Ｂ）、（Ｃ）、及び（Ｄ）中、Ａｒ^１、Ａｒ^２、Ａｒ^３、Ａｒ^４、Ｙ、Ｚ、及びｎは、各々独立して、一般式（１）と同じ定義の置換基を示す。一般式（Ｄ）中、Ｃｂは（ｎ＋１）価のカルボリン基を表す。）

(In General Formulas (B), (C), and (D), Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , Y, Z, and n are each independently the same definition as in General Formula (1). (In the general formula (D), Cb represents an (n + 1) -valent carboline group.)

The substituents in the cyclic azine compound (1) of the present invention are defined as follows, respectively.
The alkyl group having 1 to 4 carbon atoms is not particularly limited, and examples thereof include a methyl group, a trifluoromethyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, A tert-butyl group may be mentioned.
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, or A triphenylenyl group etc. can be mentioned.

The aromatic hydrocarbon group having 6 to 18 carbon atoms having a fluorine atom is not particularly limited, and examples thereof include 2-fluorophenyl group, 3-fluorophenyl group, 4-fluorophenyl group, 2,3- Difluorophenyl group, 2,4-difluorophenyl group, 2,5-difluorophenyl group, 2,6-difluorophenyl group, 3,4-difluorophenyl group, 3,5-difluorophenyl group, 2,3,4- 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- Trifluorophenyl group, pentafluorophenyl group, 4-fluoronaphthalen-1-yl group, 5-fluoronaphthalen-1-yl group, 6-fluoronaphthalen-1-yl group, 7-fluoronaphthalen-1-yl group, 4-fluoronaphthalen-2-yl group, 5-fluoronaphthalen-2-yl group, 6-fluoronaphthalen-2-yl group, 7-fluoronaphthalen-2-yl group, anthryl group, pyrenyl group, phenanthryl group, perylenyl Group, triphenylenyl group and the like.

As the aromatic hydrocarbon group having 6 to 18 carbon atoms substituted by the alkyl group having 1 to 4 carbon atoms, the above-described alkyl group having 1 to 4 carbon atoms is the same aromatic hydrocarbon having 6 to 18 carbon atoms as described above. Represents a substituent on the group, and is not particularly limited, for example, p-tolyl group, m-tolyl group, o-tolyl group, 4-trifluoromethylphenyl group, 3-trifluoromethylphenyl group, 2-trifluoromethylphenyl group, 2,4-dimethylphenyl group, 3,5-dimethylphenyl group, 2,6-dimethylphenyl group, mesityl group, 2-ethylphenyl group, 3-ethylphenyl group, 4-ethyl Phenyl group, 2,4-diethylphenyl group, 3,5-diethylphenyl group, 2-propylphenyl group, 3-propylphenyl group, 4-propylphenyl group, 2,4-dip Pyrphenyl group, 3,5-dipropylphenyl group, 2-isopropylphenyl group, 3-isopropylphenyl group, 4-isopropylphenyl group, 2,4-diisopropylphenyl group, 3,5-diisopropylphenyl group, 2-butylphenyl Group, 3-butylphenyl group, 4-butylphenyl group, 2,4-dibutylphenyl group, 3,5-dibutylphenyl group, 2-tert-butylphenyl group, 3-tert-butylphenyl group, 4-tert- Butylphenyl group, 2,4-di-tert-butylphenyl group, 3,5-di-tert-butylphenyl group, 4-methylnaphthalen-1-yl group, 4-trifluoromethylnaphthalen-1-yl group, 4-ethylnaphthalen-1-yl group, 4-propylnaphthalen-1-yl group, 4-butylnaphthalene -1-yl group, 4-tert-butylnaphthalen-1-yl group, 5-methylnaphthalen-1-yl group, 5-trifluoromethylnaphthalen-1-yl group, 5-ethylnaphthalen-1-yl group, 5-propylnaphthalen-1-yl group, 5-butylnaphthalen-1-yl group, 5-tert-butylnaphthalen-1-yl group, 6-methylnaphthalen-2-yl group, 6-trifluoromethylnaphthalene-2 -Yl group, 6-ethylnaphthalen-2-yl group, 6-propylnaphthalen-2-yl group, 6-butylnaphthalen-2-yl group, 6-tert-butylnaphthalen-2-yl group, 7-methylnaphthalene -2-yl group, 7-trifluoromethylnaphthalen-2-yl group, 7-ethylnaphthalen-2-yl group, 7-propylnaphthalen-2-yl group, 7 Examples thereof include -butylnaphthalen-2-yl group, 7-tert-butylnaphthalen-2-yl group, anthryl group, pyrenyl group, phenanthryl group, perylenyl group, and triphenylenyl group.

The aromatic hydrocarbon group having 6 to 30 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 perenylenyl group, and a triphenylenyl group. Groups and the like.

The aromatic group having 3 to 18 carbon atoms is not particularly limited, and examples thereof include furanyl group, benzofuranyl group, dibenzofuranyl group, thienyl group, benzothienyl group, dibenzothienyl group, 2-pyridyl group, 3 -Pyridyl group, 4-pyridyl group, 2-pyrimidyl group, 4-pyrimidyl group, 5-pyrimidyl group, 2-pyrazyl group, 4-pyrazyl group, 5-pyrazyl group, 2-quinolyl group, 3-quinolyl group, 4 -Quinolyl group, 5-quinolyl group, 6-quinolyl group, 7-quinolyl group, 8-quinolyl group, 1-isoquinolyl group, 3-isoquinolyl group, 4-isoquinolyl group, 5-isoquinolyl group, 6-isoquinolyl group, 7 -Isoquinolyl group, 8-isoquinolyl group, 9-acridyl group, 2-thiazolyl group, 4-thiazolyl group, 5-thiazolyl group, 2-benzothiazolyl group 4-benzothiazolyl group, 5-benzothiazolyl group, 6-benzothiazolyl group, 7-benzothiazolyl group, quinazolyl group, quinoxalyl group, 1,6-naphthyridin-2-yl group, 1,8-naphthyridin-2-yl group, 4 -Thiazolyl group, 5-thiazolyl group, imidazo [1,2-a] pyridin-2-yl group, 2-thiazolyl group, indolizyl group, azaindolidyl group and the like.

The aromatic group having 3 to 18 carbon atoms having a fluorine atom is not particularly limited, and examples thereof include a fluorofuranyl group, a fluorobenzofuranyl group, a fluorodibenzofuranyl group, a fluorothienyl group, and a fluorobenzothienyl. Group, fluorodibenzothienyl group, 3-fluoro-2-pyridyl group, 4-fluoro-2-pyridyl group, 5-fluoro-2-pyridyl group, 6-fluoro-2-pyridyl group, 2-fluoro-3-pyridyl group Group, 4-fluoro-3-pyridyl group, 5-fluoro-3-pyridyl group, 6-fluoro-3-pyridyl group, 2-fluoro-4-pyridyl group, 3-fluoro-4-pyridyl group, 3,4 -Difluoro-2-pyridyl group, 3,5-difluoro-2-pyridyl group, 3,6-difluoro-2-pyridyl group, 2,4-difluoro- -Pyridyl group, 2,5-difluoro-3-pyridyl group, 2,6-difluoro-3-pyridyl group, 4,5-difluoro-3-pyridyl group, 4,6-difluoro-3-pyridyl group, 5, 6-difluoro-3-pyridyl group, 2,3-difluoro-4-pyridyl group, 2,5-difluoro-4-pyridyl group, 2,6-difluoro-4-pyridyl group, 3,5-difluoro-4- Pyridyl group, 3,6-difluoro-4-pyridyl group, 3,4,5-trifluoro-2-pyridyl group, 3,4,6-trifluoro-2-pyridyl group, 3,5,6-trifluoro -2-pyridyl group, 4,5,6-trifluoro-2-pyridyl group, tetrafluoro-2-pyridyl group, 2,4,5-trifluoro-3-pyridyl group, 2,4,6-trifluoro -3-pyridyl group, 2,5 6-trifluoro-3-pyridyl group, 4,5,6-trifluoro-3-pyridyl group, tetrafluoro-3-pyridyl group, 2,3,5-trifluoro-4-pyridyl group, 2,3, 6-trifluoro-4-pyridyl group, tetrafluoro-4-pyridyl group, 4-fluoro-2-pyrimidyl group, 5-fluoro-2-pyrimidyl group, 2-fluoro-4-pyrimidyl group, 5-fluoro-4 -Pyrimidyl group, 6-fluoro-4-pyrimidyl group, 2-fluoro-5-pyrimidyl group, 4-fluoro-5-pyrimidyl group, 2-fluoropyrazyl group, 4-fluoropyrazyl group, 5-fluoropyrazyl group Group, 3-fluoro-2-quinolyl group, 4-fluoro-2-quinolyl group, 5-fluoro-2-quinolyl group, 6-fluoro-2-quinolyl group, 7-fluoro-2-quinolyl group Group, 8-fluoro-2-quinolyl group, 2-fluoro-3-quinolyl group, 4-fluoro-3-quinolyl group, 5-fluoro-3-quinolyl group, 6-fluoro-3-quinolyl group, 7-fluoro -3-quinolyl group, 8-fluoro-3-quinolyl group, 2-fluoro-4-quinolyl group, 3-fluoro-4-quinolyl group, 5-fluoro-4-quinolyl group, 6-fluoro-4-quinolyl group 7-fluoro-4-quinolyl group, 8-fluoro-4-quinolyl group, 3-fluoro-1-isoquinolyl group, 4-fluoro-1-isoquinolyl group, 5-fluoro-1-isoquinolyl group, 6-fluoro- 1-isoquinolyl group, 7-fluoro-1-isoquinolyl group, 8-fluoro-1-isoquinolyl group, 1-fluoro-3-isoquinolyl group, 4-fluoro-3-isoquinolyl group, -Fluoro-3-isoquinolyl group, 6-fluoro-3-isoquinolyl group, 7-fluoro-3-isoquinolyl group, 8-fluoro-3-isoquinolyl group, 1-fluoro-4-isoquinolyl group, 3-fluoro-4- Isoquinolyl group, 5-fluoro-4-isoquinolyl group, 6-fluoro-4-isoquinolyl group, 7-fluoro-4-isoquinolyl group, 8-fluoro-4-isoquinolyl group, fluoroacridyl group, fluorothiazolyl group, Examples thereof include a fluorobenzothiazolyl group, a fluoroquinazolyl group, a fluoroquinoxalyl group, a fluoronaphthylidyl group, a fluorothanthrenyl group, a fluoroindolidyl group, and a fluoroazaindolidyl group.

In the aromatic group having 3 to 18 carbon atoms substituted by the alkyl group having 1 to 4 carbon atoms, the above-described alkyl group having 1 to 4 carbon atoms is substituted on the above-described aromatic group having 3 to 18 carbon atoms. For example, methylfuranyl group, methylbenzofuranyl group, methyldibenzofuranyl group, methylthienyl group, methylbenzothienyl group, methyldibenzothienyl group, 3-methyl-2-pyridyl group Group, 4-methyl-2-pyridyl group, 5-methyl-2-pyridyl group, 6-methyl-2-pyridyl group, 2-methyl-3-pyridyl group, 4-methyl-3-pyridyl group, 5-methyl -3-pyridyl group, 6-methyl-3-pyridyl group, 2-methyl-4-pyridyl group, 3-methyl-4-pyridyl group, 3,4-dimethyl-2-pyridyl group, 3,5-dimethyl- -Pyridyl group, 3,6-dimethyl-2-pyridyl group, 2,4-dimethyl-3-pyridyl group, 2,5-dimethyl-3-pyridyl group, 2,6-dimethyl-3-pyridyl group, 4, 5-dimethyl-3-pyridyl group, 4,6-dimethyl-3-pyridyl group, 5,6-dimethyl-3-pyridyl group, 2,3-dimethyl-4-pyridyl group, 2,5-dimethyl-4- Pyridyl group, 2,6-dimethyl-4-pyridyl group, 3,5-dimethyl-4-pyridyl group, 3,6-dimethyl-4-pyridyl group, 4-methyl-2-pyrimidyl group, 5-methyl-2 -Pyrimidyl group, 2-methyl-4-pyrimidyl group, 5-methyl-4-pyrimidyl group, 6-methyl-4-pyrimidyl group, 2-methyl-5-pyrimidyl group, 4-methyl-5-pyrimidyl group, 2 -Methylpyrazyl group, 4-methyl Lazyl group, 5-methylpyrazyl group, 3-methyl-2-quinolyl group, 4-methyl-2-quinolyl group, 5-methyl-2-quinolyl group, 6-methyl-2-quinolyl group, 7-methyl-2- Quinolyl group, 8-methyl-2-quinolyl group, 2-methyl-3-quinolyl group, 4-methyl-3-quinolyl group, 5-methyl-3-quinolyl group, 6-methyl-3-quinolyl group, 7- Methyl-3-quinolyl group, 8-methyl-3-quinolyl group, 2-methyl-4-quinolyl group, 3-methyl-4-quinolyl group, 5-methyl-4-quinolyl group, 6-methyl-4-quinolyl group Group, 7-methyl-4-quinolyl group, 8-methyl-4-quinolyl group, 2-methyl-5-quinolyl group, 3-methyl-5-quinolyl group, 4-methyl-5-quinolyl group, 6-methyl -5-quinolyl group, 7-methyl-5-ki Noryl group, 8-methyl-5-quinolyl group, 2-methyl-6-quinolyl group, 3-methyl-6-quinolyl group, 4-methyl-6-quinolyl group, 5-methyl-6-quinolyl group, 7- Methyl-6-quinolyl group, 8-methyl-6-quinolyl group, 2-methyl-7-quinolyl group, 3-methyl-7-quinolyl group, 4-methyl-7-quinolyl group, 5-methyl-7-quinolyl group Group, 6-methyl-7-quinolyl group, 8-methyl-7-quinolyl group, 2-methyl-8-quinolyl group, 3-methyl-8-quinolyl group, 4-methyl-8-quinolyl group, 5-methyl -8-quinolyl group, 6-methyl-8-quinolyl group, 7-methyl-8-quinolyl group, 3-methyl-1-isoquinolyl group, 4-methyl-1-isoquinolyl group, 5-methyl-1-isoquinolyl group 6-Methyl-1-isoquinolyl 7-methyl-1-isoquinolyl group, 8-methyl-1-isoquinolyl group, 1-methyl-3-isoquinolyl group, 4-methyl-3-isoquinolyl group, 5-methyl-3-isoquinolyl group, 6-methyl- 3-isoquinolyl group, 7-methyl-3-isoquinolyl group, 8-methyl-3-isoquinolyl group, 1-methyl-4-isoquinolyl group, 3-methyl-4-isoquinolyl group, 5-methyl-4-isoquinolyl group, 6-methyl-4-isoquinolyl group, 7-methyl-4-isoquinolyl group, 8-methyl-4-isoquinolyl group, methylacridyl group, methylthiazolyl group, methylbenzothiazolyl group, methylquinazolyl group, methylquinoxalyl group , Methylnaphthylidyl group, methylthiantenyl group, methylindolidyl group, methylazaindolidyl group, etc. It can be.

The arylene group having 6 to 30 carbon atoms is not particularly limited, and examples thereof include a phenylene group, a biphenylylene group, a naphthalene diyl group, an anthracenediyl group, a pyrenediyl group, a terphenylylene group, a phenanthracenediyl group, a perylene diyl group, A triphenylenediyl group etc. can be mentioned.

The nitrogen-containing heteroaryl group having 3 to 30 carbon atoms is not particularly limited, and examples thereof include 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 2-pyrimidyl group, 4-pyrimidyl group, 5 -Pyrimidyl group, 2-pyrazyl group, 4-pyrazyl group, 5-pyrazyl group, 2-quinolyl group, 3-quinolyl group, 4-quinolyl group, 5-quinolyl group, 6-quinolyl group, 7-quinolyl group, 8 -Quinolyl group, 1-isoquinolyl group, 3-isoquinolyl group, 4-isoquinolyl group, 5-isoquinolyl group, 6-isoquinolyl group, 7-isoquinolyl group, 8-isoquinolyl group, 9-acridyl group, 2-benzothiazolyl group, 4 -Benzothiazolyl group, 5-benzothiazolyl group, 6-benzothiazolyl group, 7-benzothiazolyl group, quinazolyl group, quinoxalyl group, naphthyridine It can be exemplified group, thianthrenyl group, indolizyl group, a Azaindorijiru group.

The (m + 1) -valent aryl group having 6 to 30 carbon atoms (where m is an integer from 1 to [the maximum number of bonds that can be formed on Ar ⁵ −1]) is not particularly limited Examples thereof include an arylene group having 6 to 30 carbon atoms, an aryltriyl group having 6 to 30 carbon atoms, and an aryltetrayl 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.
In addition, m is preferably 1 or 2 and more preferably 1 in terms of good performance as a material for an organic electroluminescent element.

Examples of the arylene group having 6 to 30 carbon atoms include the same substituents as the specific examples represented by the arylene group having 6 to 30 carbon atoms.
The aryltriyl group having 6 to 30 carbon atoms is not particularly limited, and examples thereof include benzenetriyl group, biphenyltriyl group, naphthalenetriyl group, anthracentriyl group, pyrenetriyl group, and terphenyl. A triyl group, a phenanthracenyl group, a perylenetriyl group, a triphenylenetriyl group, and the like can be given.
The aryltetrayl group having 6 to 30 carbon atoms is not particularly limited, and examples thereof include a benzenetetrayl group, a biphenyltetrayl group, a naphthalenetetrayl group, an anthracenetetrayl group, and a pyrenetetrayl group. Group, terphenyltetrayl group, phenanthracenetetrayl group, perylenetetrayl group, triphenylenetetrayl group and the like.

(N + 1) -valent carbazole group in Cz (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 6 to 18 carbon atoms substituted by an alkyl group having 1 to 4 carbon atoms as a substituent), but is not particularly limited. Yl group, carbazoletetrayl group, and the like.
(N + 1) -valent carboline group in Cz (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 6 to 18 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms may be used as a substituent), but is not particularly limited, but includes a carboline diyl group, carboline tri Yl group, carboline tetrayl group and the like.

N represents an integer of 1 to [the maximum number of bonds that can be formed on Cz-1], and in the cyclic azine compound (1), Cz- (Ar ⁴ ) _n represents n Ar ⁴ substituents represented by Cz Indicates that it is bound to. n is preferably 1, 2, or 3, more preferably 1 or 2, and even more preferably 1 in terms of good performance as a material for an organic electroluminescent element.

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-2,7-diyl group, N-phenylcarbazole-2,7-diyl group, N-phenylcarbazole-3,6-diyl group, α-carboline-2,9-diyl group, α-carboline-3,9-diyl group, α-carboline- 4,9-diyl group, α-carboline-5,9-diyl group, α-carboline-6,9-diyl group, α-carboline-7,9-diyl group, α-carboline-8,9-diyl group , Β-carboline-1,9-diyl group, β-carboline-3,9-diyl group, β-carboline-4,9-diyl group, β-carboline-5,9-diyl group, β-carboline-6 , 9-Diyl group β-carboline-7,9-diyl group, β-carboline-8,9-diyl group, γ-carboline-1,9-diyl group, γ-carboline-2,9-diyl group, γ-carboline-4, 9-diyl group, γ-carboline-5,9-diyl group, γ-carboline-6,9-diyl group, γ-carboline-7,9-diyl group, γ-carboline-8,9-diyl group, δ -Carboline-1,9-diyl group, δ-carboline-2,9-diyl group, δ-carboline-3,9-diyl group, δ-carboline-5,9-diyl group, δ-carboline-6,9 -Diyl group, δ-carboline-7,9-diyl group, δ-carboline-8,9-diyl group and the like.

Cz is a carbazole-2,9-diyl group, carbazole-3,9-diyl group, carbazole-4,9-diyl group, carbazole-3,6-, because it has good performance as a material for an organic electroluminescent device. Diyl group, carbazole-3,6,9-triyl group, α-carboline-7,9-diyl group, β-carboline-6,9-diyl group, β-carboline-7,9-diyl group, δ-carboline -3,6-diyl group, δ-carboline-3,9-diyl group, or δ-carboline-6,9-diyl group (these groups are each independently a fluorine atom, having 1 to 4 carbon atoms) An aromatic group having 6 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms having a fluorine atom, or an aromatic group having 6 to 18 carbon atoms substituted by an alkyl group having 1 to 4 carbon atoms Having a hydrocarbon group as a substituent Carbazole-2,9-diyl group, carbazole-3,9-diyl group, carbazole-4,9-diyl group, carbazole-3,6-diyl group, β-carboline-6 , 9-diyl group, δ-carboline-3,9-diyl group, or δ-carboline-6,9-diyl group (these groups are each independently an aromatic hydrocarbon group having 6 to 18 carbon atoms) Is more preferable as a substituent.

In the cyclic azine compound (1), Ar ¹ or Ar ² is not particularly limited, but each independently includes, for example, a phenyl group, a biphenylyl group, a naphthyl group, an anthryl group, a pyrenyl group, a terphenyl group, Phenanthryl group, perylenyl group, triphenylenyl group, methylphenyl group, methylbiphenylyl group, methylnaphthyl group, methylanthryl group, methylterphenyl group, methylphenanthryl group, methylperenylenyl group, methyltriphenylenyl group, fluorophenyl group , Fluorobiphenylyl group, fluoronaphthyl group, fluoroanthryl group, fluoroterphenyl group, fluorophenanthryl group, fluoroperenylenyl group, fluorotriphenylenyl group and the like.

Ar ^{1 and} Ar ² are each independently a phenyl group, a biphenylyl group, a naphthyl group, an anthryl group, a pyrenyl group, a terphenyl group, or a phenanthryl group (these are those that have good performance as a material for an organic electroluminescent device. The group is 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. A substituted aromatic group having 3 to 18 carbon atoms may be used as a substituent, and each independently represents a phenyl group, a naphthyl group or a biphenylyl group (these groups are a fluorine atom, a carbon 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 substituted with 3 to 18 carbon atoms. Replace aromatic group More preferably to also be) have a, each independently, a phenyl group, methylphenyl group, more preferably a naphthyl group, or a biphenylyl group.

The above-mentioned phenyl group, biphenylyl group, naphthyl group, anthryl group, pyrenyl group, terphenyl group, or phenanthryl group (these groups are a fluorine atom, an alkyl group having 1 to 4 carbon atoms, an aromatic group having 3 to 18 carbon atoms) Group, an aromatic group having 3 to 18 carbon atoms having a fluorine atom, or an aromatic group having 3 to 18 carbon atoms substituted by an alkyl group having 1 to 4 carbon atoms may be used as a substituent. Examples of the substituent include, but are not particularly limited to, for example, phenyl group, biphenylyl group, naphthyl group, anthryl group, pyrenyl group, terphenyl group, phenanthryl group, perylenyl group, methylphenyl group, methylbiphenylyl group, Methyl naphthyl group, methyl anthryl group, methyl terphenyl group, methyl phenanthryl group, methyl perylenyl group, fluorophenyl group, Orobifeniriru group, fluoro naphthyl group, fluoro anthryl group, fluorophenyl terphenyl group, fluoro phenanthryl group, and a fluoro peri Les sulfonyl group.

In addition, the above phenyl group or biphenylyl group (these groups are 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) is not particularly limited, And phenyl group, biphenylyl group, methylphenyl group, methylbiphenylyl group, fluorophenyl group, fluorobiphenylyl group and the like.

In the cyclic azine compound (1), Ar ³ is not particularly limited. For example, phenylene group, biphenylylene group, naphthalene diyl group, anthracenediyl group, pyrenediyl group, terphenylylene group, fluorophenylene group, fluorophenyl biphenyl Examples thereof include a rylene group, a fluoronaphthalene dil group, a phenyl phenylene group, a phenyl biphenylylene group, a phenyl naphthalene dil group, a naphthyl phenylene group, a naphthyl biphenylylene group, and a naphthyl naphthalene dil group.

Ar ³ is a phenylene group or a biphenylylene group (these groups are a fluorine atom, an alkyl group having 1 to 4 carbon atoms, an aromatic group having 3 to 18 carbon atoms) in terms of good performance as a material for an organic electroluminescent device. Or 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. Preferably, each independently, a phenylene group, a biphenylylene group, or a fluorophenylene group is more preferable.

The above phenylene group or biphenylylene group (however, these groups are 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) is not particularly limited, Phenylene group, biphenylylene group, naphthalene dil group, terphenylylene group, fluorophenylene group, fluoro naphthalene dil group, phenylphenylene group, phenyl naphthalene dil group, naphthyl phenylene group, naphthyl naphthalene dil group and the like.

In the cyclic azine compound (1), Ar ⁵ is not particularly limited. For example, (m + 1) -valent benzene group, (m + 1) -valent biphenyl group, (m + 1) -valent naphthalene group, (m + 1) -Valent anthracene group, (m + 1) -valent pyrene group, (m + 1) -valent terphenyl group, (m + 1) -valent fluorobenzene group, (m + 1) -valent fluorophenylbiphenylyl group, (m + 1) -valent fluoronaphthalene group (M + 1) -valent phenylbiphenyl group, (m + 1) -valent phenylnaphthalene group, (m + 1) -valent naphthylbenzene group, (m + 1) -valent naphthylbiphenyl group, (m + 1) -valent naphthylnaphthalene group (these groups are , Each independently, a fluorine atom, an alkyl group having 1 to 4 carbon atoms, an aromatic group having 3 to 18 carbon atoms, and 3 to 1 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 used as a substituent.

As Ar ⁵ , when m = 1, phenylene group, methylphenylene group, biphenylylene group, naphthylene group, anthracenediyl group, pyrenediyl group, terphenyldiyl group, fluorophenylene group, fluorophenylbiphenylylene group, fluoronaphthylene group Phenylbiphenylylene group, phenylnaphthylene group, naphthylphenylene group, naphthylbiphenylylene group, naphthylnaphthylene group, and the like.

When m = 2, each independently, benzenetriyl group, methylbenzenetriyl group, biphenyltriyl group, naphthalenetriyl group, anthracentriyl group, pyrenetriyl group, terphenyltriyl group, fluorobenzenetriyl Group, fluorophenylbiphenyltriyl group, fluoronaphthalenetriyl group, phenylbiphenyltriyl group, phenylnaphthalenetriyl group, naphthylbenzenetriyl group, naphthylbiphenyltriyl group, naphthylnaphthalenetriyl group, and the like.

Ar ⁵ is a (m + 1) -valent benzene group or a (m + 1) -valent biphenyl group (these groups are each independently a fluorine atom, carbon number 1 in that the performance as an organic electroluminescent device material is good. An alkyl 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 having a fluorine atom, or an aromatic group having 3 to 18 carbon atoms substituted by an alkyl group having 1 to 4 carbon atoms Group may be present as a substituent). Note that an (m + 1) -valent benzene group (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 1 carbon atom) An aromatic group having 3 to 18 carbon atoms substituted with an alkyl group of 4 to 4 may be used as a substituent) when m = 1, a phenylene group, a methylphenylene group, a fluorophenylene group, a naphthylphenylene group Are preferable, and a phenylene group is more preferable. When m = 2, a benzenetriyl group, a methylbenzenetriyl group, a fluorobenzenetriyl group, and a naphthylbenzenetriyl group are preferable, and a benzenetriyl group is more preferable. And an (m + 1) -valent biphenyl group (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 1 carbon atom) An aromatic group having 3 to 18 carbon atoms substituted by an alkyl group of 4 to 4 may be used as a substituent), when m = 1, a biphenylylene group, a terphenyldiyl group, a fluorophenylbiphenylylene group, A naphthylbiphenylylene group is preferred, and a biphenylylene group is more preferred. 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), a 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, or 3 to 18 carbon atoms) Or a C 3-18 aromatic group substituted with a C 1-4 alkyl group having a fluorine atom, or a C 3-18 aromatic group substituted with a C 1-4 alkyl group as a substituent. Although the substituent represented by is not particularly limited, for example, each independently, pyridyl group, pyrimidyl group, pyrazyl group, quinolyl group, isoquinolyl group, acridyl group, thiazolyl group, benzothiazolyl group, quinazolyl group Quinoxalyl group, naphthyridyl group, thiantenyl group, indolizyl group, azaindolidyl group, fluoropyridyl group, fluoropyrimidyl group, fluoropyrazyl group, full Loquinolyl group, fluoroisoquinolyl group, fluoroacridyl group, fluorothiazolyl group, fluorobenzothiazolyl group, fluoroquinazolyl group, fluoroquinoxalyl group, fluoronaphthylidyl group, fluorothiantenyl group, Fluoroindolidyl group, fluoroazaindolidyl group, methylpyridyl group, methylpyrimidyl group, methylpyrazyl group, methylquinolyl group, methylisoquinolyl group, methylacridyl group, methylthiazolyl group, methylbenzothiazolyl group, methylquinazolyl group, methylquinoyl group Xalyl group, methylnaphthyridyl group, methylthanthrenyl group, methylindolidyl group, methylazaindolidyl group, phenylpyridyl group, phenylpyrimidyl group, phenylpyrazyl group, phenylquinolyl group, phenylisoquinolyl group Group, fe Nylacridyl group, phenylthiazolyl group, phenylbenzothiazolyl group, phenylquinazolyl group, phenylquinoxalyl group, phenylnaphthylidyl group, phenylthianthrenyl group, phenylindolidyl group, phenylazaindolidyl group, Phenylpyridyl group, phenylpyrimidyl group, phenylpyrazyl group, phenylquinolyl group, phenylisoquinolyl group, phenylacridyl group, phenylthiazolyl group, phenylbenzothiazolyl group, phenylquinazolyl group, Phenylquinoxalyl group, phenylnaphthylidyl group, phenylthiantrenyl group, phenylindolidyl group, phenylazaindolidyl group, pyridylphenyl group, 1- (3,5-dipyridyl) phenyl group, pyrimidylphenyl group, Pyrazylphenyl group, pyridylbiphenylyl group, Limidylbiphenylyl, pyrazylbiphenylyl, quinolylbiphenylyl, isoquinolylbiphenylyl, acridylbiphenylyl, thiazolylbiphenylyl, benzothiazolylbiphenylyl, quinazolylbiphenyl Examples thereof include a ryl group, a quinoxalyl biphenylyl group, a naphthyridyl biphenylyl group, a thiantenyl biphenylyl group, an indolizyl biphenylyl group, and an azaindolidyl biphenylyl group.

Ar ⁴ and Ar ⁶ are each independently a nitrogen-containing heteroaryl group having 3 to 30 carbon atoms consisting of carbon, hydrogen, and nitrogen (independently from the viewpoint of good performance as a material for an organic electroluminescent device. 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. An aromatic group having 3 to 18 carbon atoms as a substituent), or a nitrogen-containing heteroaryl group having 3 to 30 carbon atoms composed of only carbon, hydrogen, nitrogen, and sulfur (each independently fluorine 3 carbon atoms substituted by an 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 To 18 aromatic groups as substituents). It is preferable. Of these, each independently a nitrogen-containing heteroaryl group having 3 to 30 carbon atoms consisting of only carbon, hydrogen and nitrogen (each independently a fluorine atom, an alkyl group having 1 to 4 carbon atoms, 3 to 3 carbon atoms) An aromatic group having 18 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 by an alkyl group having 1 to 4 carbon atoms may be used as a substituent. ) Is more preferable.

Furthermore, Ar ⁴ and Ar ⁶ are each independently a pyridyl group, a pyrimidyl group, a quinolyl group, an isoquinolyl group, a pyridylphenyl group, or a compound that is easy to synthesize and has good performance as a material for an organic electroluminescent device. 1- (3,5-dipyridyl) phenyl group (these groups are each independently a fluorine atom, an alkyl group having 1 to 4 carbon atoms, an aromatic group having 3 to 18 carbon atoms, or a carbon number having a fluorine atom) An aromatic group having 3 to 18 carbon atoms or an aromatic group having 3 to 18 carbon atoms substituted by an alkyl group having 1 to 4 carbon atoms may be preferably used as a substituent. A pyridyl group, a pyrimidyl group, a quinolyl group, an isoquinolyl group, a pyridylphenyl group, or a 1- (3,5-dipyridyl) phenyl group is more preferable, and a pyridyl group is still more preferable.

The aforementioned nitrogen-containing heteroaryl group having 3 to 30 carbon atoms (only having a fluorine atom, an alkyl group having 1 to 4 carbon atoms, an aromatic group having 3 to 18 carbon atoms, or a fluorine atom) consisting of only carbon, hydrogen, and nitrogen An aromatic group having 3 to 18 carbon atoms, or an aromatic group having 3 to 18 carbon atoms substituted by an alkyl group having 1 to 4 carbon atoms), or carbon, hydrogen, nitrogen, and A nitrogen-containing heteroaryl group having 3 to 30 carbon atoms (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) A substituent represented by a group 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, For example, pyridyl group, pyrimidyl group, pyrazyl group, quino Group, isoquinolyl group, acridyl group, thiazolyl group, benzothiazolyl group, quinazolyl group, quinoxalyl group, naphthyridyl group, thiantenyl group, indolizyl group, azaindolidyl group, fluoropyridyl group, fluoropyrimidyl group, fluoropyrazyl group, Fluoroquinolyl group, fluoroisoquinolyl group, fluoroacridyl group, fluorothiazolyl group, fluorobenzothiazolyl group, fluoroquinazolyl group, fluoroquinoxalyl group, fluoronaphthylidyl group, fluorothianthenyl Group, fluoroindolidyl group, fluoroazaindolidyl group, methylpyridyl group, methylpyrimidyl group, methylpyrazyl group, methylquinolyl group, methylisoquinolyl group, methylacridyl group, methylthiazolyl group, methylbenzothiazolyl group, methyl Nazolyl group, methylquinoxalyl group, methylnaphthyridyl group, methylthianthrenyl group, methylindolidyl group, methylazaindolidyl group, phenylpyridyl group, phenylpyrimidyl group, phenylpyrazyl group, phenylquinolyl group , Phenylisoquinolyl group, phenylacridyl group, phenylthiazolyl group, phenylbenzothiazolyl group, phenylquinazolyl group, phenylquinoxalyl group, phenylnaphthylidyl group, phenylthianthenyl group, phenylindo Lysyl group, phenylazaindolidyl group, phenylpyridyl group, phenylpyrimidyl group, phenylpyrazyl group, phenylquinolyl group, phenylisoquinolyl group, phenylacridyl group, phenylthiazolyl group, phenylbenzothiazolyl Group, phenylquinazolyl group, phenylquino Xalyl group, phenylnaphthylidyl group, phenylthanthrenyl group, phenylindolidyl group, phenylazaindolidyl group, pyridylphenyl group, 1- (3,5-dipyridyl) phenyl group, pyrimidylphenyl group, pyrazylphenyl Group, pyridyl biphenylyl group, pyrimidyl biphenylyl group, pyrazyl biphenylyl group, quinolyl biphenylyl group, isoquinolyl biphenylyl group, acridyl biphenylyl group, thiazolyl biphenylyl group, benzothiazolyl A biphenylyl group, a quinazolyl biphenylyl group, a quinoxalyl biphenylyl group, a naphthyridyl biphenylyl group, a thiantenyl biphenylyl group, an indolizyl biphenylyl group, an azaindolidyl biphenylyl group, and the like can be given.

The nitrogen-containing heteroaryl group having 3 to 30 carbon atoms composed of only carbon, hydrogen, and nitrogen (however, these groups are a fluorine atom, an alkyl group having 1 to 4 carbon atoms, an aromatic group having 3 to 18 carbon atoms) Group, an aromatic group having 3 to 18 carbon atoms having a fluorine atom, or an aromatic group having 3 to 18 carbon atoms substituted by an alkyl group having 1 to 4 carbon atoms may be used as a substituent. Examples of the substituent include, but are not limited to, for example, pyridyl group, pyrimidyl group, pyrazyl group, quinolyl group, isoquinolyl group, fluoropyridyl group, fluoropyrimidyl group, fluoropyrazyl group, fluoroquinolyl group , Fluoroisoquinolyl group, methylpyridyl group, methylpyrimidyl group, methylpyrazyl group, methylquinolyl group, methylisoquinolyl group, phenylpyridyl group, phenylpyrimidi Group, phenylpyrazyl group, phenylquinolyl group, phenylisoquinolyl group, pyridylphenyl group, 1- (3,5-dipyridyl) phenyl group, pyrimidylphenyl group, pyrazylphenyl group, quinolylphenyl group, An isoquinolylphenyl group is mentioned.

Y and Z each independently represent a nitrogen atom or CH. However, at least one of Y and Z is a nitrogen atom. Y and Z are preferably nitrogen atoms, or Y is CH and Z is a nitrogen atom in terms of good performance as a material for an organic electroluminescent element.
In addition, any hydrogen atom in the cyclic azine compound (1) of the present invention may be substituted with a deuterium atom.

Next, the manufacturing method of the cyclic azine compound of this invention is demonstrated.
The cyclic azine compound (1) of the present invention is prepared by the following reaction formula (1), reaction formula (2), reaction formula (3), or reaction formula in the presence of a metal catalyst or a base and a metal catalyst. It can be produced by the method shown in (4).
Hereinafter, the compound represented by the general formula (2) is referred to as a compound (2). The same applies to compounds (3) to (9).

（一般式（１）、（２）、（３）、（４）、（５）、（６）、（７）、（８）、及び（９）中、Ｃｚ、Ａｒ^１、Ａｒ^２、Ａｒ^３、Ａｒ^４、ｎ、Ｙ、及びＺは、各々独立して、前記の一般式（１）と同じ定義を表す。Ｘ^１、Ｘ^２、Ｘ^３、Ｘ^４、及びＭは、各々独立して、脱離基を表す。Ｈ^ＮはＣｚにおける窒素原子上の水素原子を表す。）

(In the general formulas (1), (2), (3), (4), (5), (6), (7), (8), and (9), Cz, Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , n, Y, and Z each independently represent the same definition as in the general formula (1), and X ¹ , X ² , X ³ , X ⁴ , and M are each independently H ^N represents a hydrogen atom on a nitrogen atom in Cz.)

^{X 1, X 2, X 3} , and examples of the leaving group represented by X ^4, is not particularly limited, for example, a chlorine atom, a bromine atom, and an triflate or iodine atom. Among these, a bromine atom or a chlorine atom is preferable in that the reaction yield is good.

The leaving group represented by M is not particularly limited, but 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 , Etc.), Si (R ⁴ ) ₃ , BF ₃ K, B (OR ¹ ) ₂ , B (OR ² ) _{3 and the} like.
Examples of the metal-containing group represented by M include B (OR ¹ ) ₂ , B (OR ² ) ₃ , ZnR ³ , Si (R ⁴ ) _3, etc. Examples of ZnR ³ include ZnCl, ZnBr, and ZnI. Can be illustrated. In addition, ligands such as ethers and amines may be coordinated with these metal-containing groups, and the type of ligand is not limited as long as it does not inhibit the reaction formula (1). Absent.

Examples of 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 .
In addition, B (OR ¹ ) ₂ in the case where two R ¹ are combined to form a ring containing an oxygen atom and a boron atom can be exemplified by the following (I) to (VII): The compound represented by (II) is preferable in that the yield is good.

　前記Ｂ（ＯＲ^２）_３としては次の（Ｉ）から（ＩＩＩ）で示されるものが例示できる。

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

Among these leaving groups, chlorine atom, bromine atom, triflate, iodine atom, B (OR ¹ ) ₂ , or B (OR ² ) in terms of ease of processing after reaction, easy procurement of raw materials, etc. ₃ is preferred.
As shown in the reaction formula (1) and the reaction formula (3), the cyclic azine compound (1) of the present invention is prepared by reacting the compound (2) and the compound in the presence of a metal catalyst or in the presence of a base and a metal catalyst. (3), or compound (6) and compound (7) can be synthesized by carrying out a coupling reaction as described in each reaction formula.

In addition, it is preferable that a metal catalyst is a palladium catalyst or a copper catalyst in the reaction of Reaction Formula (1) and Reaction Formula (3) in that the efficiency of the coupling reaction is excellent.
In addition, in reaction of Reaction formula (1) and Reaction formula (3), it is also possible to react by adding a base, and it is preferable to add a base from the point which the reaction yield improves. In particular, when M is a chlorine atom, bromine atom, triflate, iodine atom, B (OR ¹ ) ₂ or Si (R ⁴ ) ₃ , it is essential to add a base.
In addition, as shown in the reaction formulas (2) and (4), the cyclic azine compound (1) of the present invention is compound (4) in the presence of a metal catalyst or in the presence of a base and a metal catalyst. And compound (5), or compound (8) and compound (9) can be synthesized by performing a coupling reaction as described in each reaction formula.

In addition, in the reaction of reaction formula (2) and reaction formula (4), the metal catalyst is preferably a palladium catalyst or a nickel catalyst in that the efficiency of the coupling reaction is excellent.
In addition, in reaction of Reaction formula (2) and Reaction formula (4), it is also possible to react by adding a base, and it is preferable to add a base from the point which the reaction yield improves. In particular, when M is a chlorine atom, bromine atom, triflate, iodine atom, B (OR ¹ ) ₂ or Si (R ⁴ ) ₃ , it is essential to add a base.
In addition, a phase transfer catalyst may be added in the reactions of the reaction formulas (1) to (4). The phase transfer catalyst is not particularly limited. For example, 18-crown-6-ether or the like can be used. The amount added 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.
Although it does not specifically limit as a palladium catalyst, For example, salts, such as palladium chloride, palladium acetate, trifluoroacetate palladium, palladium nitrate, can be illustrated. Further, π-allyl palladium chloride dimer, palladium acetylacetonato, bis (dibenzylideneacetone) palladium, tris (dibenzylideneacetone) dipalladium, dichlorobis (triphenylphosphine) palladium, tetrakis (triphenylphosphine) 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 as a ligand, such as dichlorobis (triphenylphosphine) palladium, tetrakis (triphenylphosphine) palladium, tri (tert-butyl) phosphinepalladium, is preferable in terms of high yield, and is available. In terms of ease, tri (tert-butyl) phosphine palladium is more preferable.

The copper catalyst is not particularly limited, and examples thereof include copper chloride, copper bromide, copper iodide, copper oxide, and copper triflate. Among these, copper oxide and copper iodide are preferable from the viewpoint of excellent coupling reaction efficiency and the like, and copper oxide is more preferable from the viewpoint of easy availability.
The nickel catalyst is not particularly limited. For example, nickel chloride, nickel bromide, nickel chloride hydrate, dichloro (dimethoxyethane) nickel, dichloro [1,2-bis (diphenylphosphino) ethane] nickel Dichloro [1,3-bis (diphenylphosphino) propane] nickel, dichloro [1,4-bis (diphenylphosphino) butane] nickel, dichloro [1,1′-bis (diphenylphosphino) ferrocene] nickel ( Examples of the four include nickel complexes having tertiary phosphine as a ligand) and dichloro (N, N, N ′, N′-tetramethylethylenediamine) nickel. Among them, dichloro (dimethoxyethane) nickel, dichloro [1,4-bis (diphenylphosphino) butane] nickel, dichloro (N, N, N ′, N′-tetramethylethylenediamine) nickel are effective in coupling reaction, etc. Is preferable from the viewpoint of superiority, and dichloro [dimethoxyethane) nickel and dichloro [1,4-bis (diphenylphosphino) butane] nickel are more preferable from the viewpoint of availability.

In addition, about the palladium complex which has the above-mentioned tertiary phosphine as a ligand, and the nickel complex which has tertiary phosphine as a ligand, tertiary phosphine is added to palladium salt, nickel salt or their complex compounds. Can be prepared. The preparation can be performed separately from the reaction and then added to the reaction system, or can be performed in the reaction system.
The tertiary phosphine is not particularly limited. For example, triphenylphosphine, trimethylphosphine, tributylphosphine, tri (tert-butyl) phosphine, tricyclohexylphosphine, tert-butyldiphenylphosphine, 9,9-dimethyl -4,5-bis (diphenylphosphino) xanthene, 2- (diphenylphosphino) -2 '-(N, N-dimethylamino) biphenyl, 2- (di-tert-butylphosphino) biphenyl, 2- ( Dicyclohexylphosphino) biphenyl, bis (diphenylphosphino) methane, 1,2-bis (diphenylphosphino) ethane, 1,3-bis (diphenylphosphino) propane, 1,4-bis (diphenylphosphino) butane, 1,1'-bis (diphenylphos Fino) ferrocene, tri (2-furyl) phosphine, tri (o-tolyl) phosphine, tris (2,5-xylyl) phosphine, (±) -2,2′-bis (diphenylphosphino) -1,1 ′ -Binaphthyl, 2-dicyclohexylphosphino-2 ', 4', 6'-triisopropylbiphenyl and the like can be exemplified. Of these, (tert-butyl) phosphine or 2-dicyclohexylphosphino-2 ′, 4 ′, 6′-triisopropylbiphenyl is preferred because it is readily available and yields are good.

When a tertiary phosphine is added to a palladium salt, nickel salt or complex thereof, the addition amount of the tertiary phosphine is 1 mol of palladium salt, nickel salt or complex thereof (in terms of palladium or nickel atom). On the other hand, the amount is preferably 0.1 to 10 times mol, and more preferably 0.3 to 5 times mol in terms of good yield.

In addition, it is also possible to add a ligand separately to said copper catalyst. The ligand added to the copper catalyst is not particularly limited. For example, 2,2′-bipyridine, 1,10-phenanthroline, N, N, N ′, N′-tetramethylethylenediamine, triphenyl Examples include phosphine, 2- (dicyclohexylphosphino) biphenyl, and the like. Of these, 1,10-phenanthroline is preferred because it is readily available and yields are good.

The base that can be used in the reactions of the reaction formulas (1) to (4) is not particularly limited, and examples thereof include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate, and cesium carbonate. , Potassium acetate, sodium acetate, potassium phosphate, sodium phosphate, sodium fluoride, potassium fluoride, cesium fluoride and the like. Among these, potassium carbonate, potassium phosphate, or sodium hydroxide is preferable in terms of a good yield.

The reactions of reaction formulas (1) to (4) are preferably carried out in a solvent. Examples of the solvent include, but are not limited to, water, dimethyl sulfoxide, dimethylformamide, tetrahydrofuran, toluene, benzene, diethyl ether, 1,4-dioxane, ethanol, butanol, xylene, and the like. You may use it combining suitably. Of these, a mixed solvent of 1,4-dioxane, xylene, toluene and butanol or a mixed solvent of xylene and butanol is preferable in terms of a good yield.
The purity of the cyclic azine compound (1) of the present invention can be increased by carrying out treatments such as reprecipitation, concentration, filtration, and purification after completion of the reactions of the reaction formulas (1) to (4). In order to further increase the purity, purification by recrystallization, silica gel column chromatography, sublimation, or the like may be performed as necessary.

Hereinafter, the reaction of the reaction formula (1) will be described.
The compound (2) can be produced, for example, using the method disclosed in Hiroshi Yamanaka, “New edition of heterocyclic compounds”, Kodansha, 2004.
Arbitrary hydrogen atoms in compound (2) may be substituted with deuterium atoms.
The compound (3) is not particularly limited, but for example, the following 3-1 to 3-17 (each independently a fluorine atom, an alkyl group having 1 to 4 carbon atoms, or a carbon atom having 6 to 18 carbon atoms) An aromatic hydrocarbon group, an aromatic hydrocarbon group having 6 to 18 carbon atoms having a fluorine atom, an aromatic hydrocarbon group having 6 to 18 carbon atoms substituted by an alkyl group having 1 to 4 carbon atoms, or 3 to 18 carbon atoms Or a C 3-18 aromatic group substituted with an alkyl group having 1 to 4 carbon atoms or a C 3-18 aromatic group having a fluorine atom. These substituents are the same as those described above.).

Compound (3) is, for example, J.I. Tsuji, "Palladium Reagents and Catalysts", John Wiley & Sons, 2004, Journal of Organic Chemistry, 60, 7508-7510, 1995, Journal of Organic, 16th. 10, 941-944, 2008, or Chemistry of Materials, 20, 5951-5953, 2008.
In addition, any hydrogen atom in 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 a so-called catalyst amount, but is 0.1 to 0.01 with respect to 1 mol of the compound (2) in terms of good yield. It is preferably a double mole (in terms of palladium atom).
The amount of the base used in the reaction formula (1) is not particularly limited, but is preferably 1 to 10 times mol per mol of the compound (3), and 1 to 3 in terms of good yield. More preferably, it is a double mole.
There is no particular limitation on the molar ratio of the compound (2) and the compound (3) used in the reaction formula (1), but it is preferably 0.2 to 5 times mol per mol of the compound (2). From the viewpoint of good yield, it is more preferably 1 to 3 moles.

Below, Reaction formula (2) is demonstrated.
Compound (4) can be produced, for example, according to the method shown in Synthesis Example-1 in the Examples.
In addition, any hydrogen atom in the compound (4) may be substituted with a deuterium atom.
The compound (5) is not particularly limited, but for example, the following 5-1 to 5-15 (each independently, a fluorine atom, an alkyl group having 1 to 4 carbon atoms, or a group having 3 to 18 carbon atoms) An aromatic group, an aromatic group having 3 to 18 carbon atoms having a fluorine atom, or an aromatic group having 3 to 18 carbon atoms substituted by an alkyl group having 1 to 4 carbon atoms may be used as a substituent. The compound of can be illustrated.

（例示式（５－１）～（５－１５）中、Ｍは、上記一般式（５）におけるＭと同じ定義である。）

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

Compound (5) is described in, for example, J. Org. Tsuji, "Palladium Reagents and Catalysts", John Wiley & Sons, 2004, Journal of Organic Chemistry, 60, 7508-7510, 1995, Journal of Organic, 16th. 10, 941-944, 2008, or Chemistry of Materials, 20, 5951-5953, 2008.
In addition, any hydrogen atom in the compound (5) may be substituted with a deuterium atom.

Reaction formula (2) is a method for producing the cyclic azine compound (1) of the present invention by reacting the compound (4) with the compound (5) in the presence of a palladium catalyst in the presence of a base. Yes, by applying the reaction conditions of the Suzuki-Miyaura reaction, the target 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 a so-called catalyst amount, but is 0.1 to 0.01 with respect to 1 mol of the compound (5) in terms of good yield. It is preferable that it is a double mole (palladium atom conversion).
The amount of the base to be used is not particularly limited, but is preferably 0.5 to 10 times mol for 1 mol of compound (5), and 1 to 3 times mol for a good yield. Is more preferable.
There is no particular limitation on the molar ratio of the compound (4) and the compound (5) used in the reaction formula (2), but it is preferably 0.2 to 5 times moles with respect to 1 mole of the compound (2). More preferably, the molar ratio is 0.3 to 3 times in terms of good yield.

Below, Reaction formula (3) is demonstrated.
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.
The compound (7) is not particularly limited, but for example, the following 7-1 to 7-21 (each independently a fluorine atom, an alkyl group having 1 to 4 carbon atoms, or a group having 3 to 18 carbon atoms) An aromatic group, an aromatic group having 3 to 18 carbon atoms having a fluorine atom, or an aromatic group having 3 to 18 carbon atoms substituted by an alkyl group having 1 to 4 carbon atoms may be used as a substituent. The compound of can be illustrated.

（例示式（７－１）～（７－２１）中、Ｘ^３は、上記一般式（７）におけるＸ^３と同じ定義である。）

(In the exemplary formulas (7-1) to (7-21), X ³ has the same definition as X ³ in the general formula (7).)

Compound (7) is described in, for example, J. Org. Org. Chem. 48, 1064-1069, 1983 can be used for the production.
In addition, any hydrogen atom in the compound (7) may be substituted with a deuterium atom.
Reaction formula (3) is a method of 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. be able to.
The amount of the palladium catalyst used in the reaction formula (3) is not particularly limited as long as it is a so-called catalyst amount, but is 0.01 to 0.1 to 1 mol of the compound (6) in terms of a good yield. It is preferable that it is a double mole (palladium atom conversion). The amount of the base to be used is not particularly limited, but is preferably 0.5 to 10 times mol and more preferably 1 to 3 times mol for 1 mol of the compound (6).

In the reaction formula (3), a phase transfer catalyst represented by 18-crown-6-ether may be added.
The reaction of reaction formula (3) is preferably carried out in a solvent in terms of good yield.

Below, Reaction formula (4) is demonstrated.
Compound (8) can be produced, for example, according to the method shown in Synthesis Example 1 in the Examples.
In addition, any hydrogen atom in compound (8) may be substituted with a deuterium atom.
The compound (9) is not particularly limited. For example, the compound (9) includes the following 9-1 to 9-12 (each independently a fluorine atom, an alkyl group having 1 to 4 carbon atoms, an alkyl group having 6 to 18 carbon atoms). An aromatic hydrocarbon group, an aromatic hydrocarbon group having 6 to 18 carbon atoms having a fluorine atom, an aromatic hydrocarbon group having 6 to 18 carbon atoms substituted by an alkyl group having 1 to 4 carbon atoms, and 3 to 18 carbon atoms Or a C 3-18 aromatic group substituted with an alkyl group having 1 to 4 carbon atoms or a C 3-18 aromatic group having a fluorine atom. These substituents are the same as those described above.).

（例示式（９－１）～（９－１２）中、Ｘ^４は、上記一般式（７）におけるＸ^４と同じ定義である。）

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

Compound (9) is described in, for example, J. Org. Tsuji, "Palladium Reagents and Catalysts", John Wiley & Sons, 2004, Journal of Organic Chemistry, 60, 7508-7510, 1995, Journal of Organic, 16th. 10, 941-944, 2008, or Chemistry of Materials, 20, 5951-5953, 2008.
In addition, any hydrogen atom in the compound (9) may be substituted with a deuterium atom.

Reaction formula (4) is a method for producing the cyclic azine compound (1) of the present invention by reacting compound (8) with compound (9) in the presence of a palladium catalyst, optionally in the presence of a base. Yes, by applying the reaction conditions of the Suzuki-Miyaura reaction, the target product can be obtained in high yield.
The amount of the palladium catalyst used in the reaction formula (4) is not particularly limited as long as it is a so-called catalyst amount, but is 0.1 to 0.01 with respect to 1 mol of the compound (9) in terms of a good yield. It is preferably a double mole (in terms of palladium atom).
The amount of the base used is not particularly limited, but it is preferably 0.5 to 10 times by mole with respect to 1 mole of compound (9), and 1 to 3 times by mole in terms of good yield. Is more preferable.
There is no particular limitation on the molar ratio of the compound (8) and the compound (9) used in the reaction formula (4), but it is preferably 0.2 to 5 times mol per mol of the compound (8). More preferably, it is 0.3 to 3 moles in terms of good yield.

Although there is no limitation in particular in the manufacturing method of the organic electroluminescent element thin film which consists of cyclic azine compound (1) of this invention, The film-forming by a vacuum evaporation method can be mentioned as a preferable example.
Film formation by the vacuum evaporation method can be performed by using a general-purpose vacuum evaporation apparatus. The vacuum degree of the vacuum chamber when forming a film by the vacuum evaporation method is a diffusion pump and a turbo molecular pump that are generally used in that the production tact time in the production of the organic electroluminescent device is short and the production cost is superior. It is preferably about 1 × 10 ⁻² to 1 × 10 ⁻⁶ Pa that can be reached by a cryopump or the like.
Further, the deposition rate is preferably 0.005 to 10 nm / second depending on the thickness of the film to be formed.

In addition, a thin film for an organic electroluminescence device comprising the 1,3,5-triazine compound (1) can also be produced by a solution coating method. For example, the cyclic azine compound (1) is dissolved in an organic solvent such as chloroform, dichloromethane, 1,2-dichloroethane, chlorobenzene, toluene, ethyl acetate or tetrahydrofuran, and a spin coating method, an inkjet method, a cast using a general-purpose apparatus. Film formation by a method, a dip method or the like is also possible.

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 construed as being limited thereto.

　アルゴン気流下、２－（４－ブロモフェニル）－４，６－ジフェニル－１，３，５－トリアジン（６２１ｍｇ）、２－クロロカルバゾール（３３９ｍｇ）、酢酸パラジウム（７．２ｍｇ）、１Ｍ－トリ（ｔｅｒｔ－ブチル）ホスフィンのトルエン溶液（９６μＬ）、炭酸カリウム（３３２ｍｇ）、及び１８－クラウン－６－エーテル（８４．６ｍｇ）を、キシレン（８．０ｍＬ）に懸濁し、１２０℃で２１時間撹拌した。反応混合物を放冷後、水を加えた。析出した固体を水、次いでメタノール、その後ヘキサンで洗浄し、目的物である２－クロロ－９－［４－（４，６－ジフェニルトリアジン－２－イル）フェニル］カルバゾールの白色粉末（収量７２９ｍｇ，収率９０％）を得た。
　^１Ｈ－ＮＭＲ（ＣＤＣｌ_３）：δ７．３２（ｄ，Ｊ＝８．４Ｈｚ，１Ｈ），７．３７（ｔ，Ｊ＝７．４Ｈｚ，１Ｈ），７．４９（ｔ，Ｊ＝７．６Ｈｚ，１Ｈ），７．５５－７．５７（ｍ，２Ｈ），７．６２－７．６８（ｍ，６Ｈ），７．８２（ｄ，Ｊ＝８．４Ｈｚ，２Ｈ），８．０９（ｄ，Ｊ＝８．４Ｈｚ，１Ｈ），８．１６（ｄ，Ｊ＝７．６Ｈｚ，１Ｈ），８．８５（ｄ，Ｊ＝６．４Ｈｚ，４Ｈ），９．０６（ｄ，Ｊ＝８．４Ｈｚ，２Ｈ）． Synthesis example-1

Under an argon stream, 2- (4-bromophenyl) -4,6-diphenyl-1,3,5-triazine (621 mg), 2-chlorocarbazole (339 mg), palladium acetate (7.2 mg), 1M-tri ( (tert-butyl) phosphine in toluene (96 μL), potassium carbonate (332 mg), and 18-crown-6-ether (84.6 mg) were suspended in xylene (8.0 mL) and stirred at 120 ° C. for 21 hours. . The reaction mixture was allowed to cool and water was added. The precipitated solid was washed with water, then with methanol and then with hexane, and white powder of the desired product 2-chloro-9- [4- (4,6-diphenyltriazin-2-yl) phenyl] carbazole (yield 729 mg, Yield 90%).
¹ H-NMR (CDCl ₃ ): δ 7.32 (d, J = 8.4 Hz, 1H), 7.37 (t, J = 7.4 Hz, 1H), 7.49 (t, J = 7.6 Hz) 1H), 7.55-7.57 (m, 2H), 7.62-7.68 (m, 6H), 7.82 (d, J = 8.4 Hz, 2H), 8.09 (d , J = 8.4 Hz, 1H), 8.16 (d, J = 7.6 Hz, 1H), 8.85 (d, J = 6.4 Hz, 4H), 9.06 (d, J = 8. 4Hz, 2H).

　アルゴン気流下、２－［４－（４，４，５，５－テトラメチル－１，３，２－ジオキサボロラン－２－イル）フェニル］－４，６－ジフェニル－１，３，５－トリアジン（１．０ｇ）、３－ブロモカルバゾール（６２２ｍｇ）、及びテトラキス（トリフェニルホスフィン）パラジウム（２３８ｍｇ）を、１，４－ジオキサン（１２ｍＬ）及び３Ｍ－リン酸カリウム水溶液（１．１ｍＬ）の混合溶媒に懸濁し、２０時間加熱還流した。室温まで冷却後、水を加えた。析出した固体を水、次いでメタノール、その後ヘキサンで洗浄し、目的物である３－［４－（４，６－ジフェニルトリアジン－２－イル）フェニル］カルバゾールの褐色固体（収量７９４ｍｇ，収率７０％）を得た。
　^１Ｈ－ＮＭＲ（ＤＭＳＯ－ｄ_６）：δ７．２３（ｔ，Ｊ＝７．４Ｈｚ，１Ｈ），７．４４（ｔ，Ｊ＝７．６Ｈｚ，１Ｈ），７．５４（ｄ，Ｊ＝８．１Ｈｚ，１Ｈ），７．６４（ｄ，Ｊ＝８．４Ｈｚ，１Ｈ），７．６３－７．７５（ｍ、６Ｈ），７．８９（ｄ，Ｊ＝８．５Ｈｚ，１Ｈ），８．１０（ｄ，Ｊ＝８．３Ｈｚ，２Ｈ），８．２９（ｄ，Ｊ＝７．８Ｈｚ，１Ｈ），８．６５（ｓ，１Ｈ），８．７９（ｄ，Ｊ＝７．０Ｈｚ，４Ｈ），８．８５（ｄ，Ｊ＝８．３Ｈｚ，２Ｈ），１１．４５（ｓ，１Ｈ）． Synthesis Example-2

Under an argon stream, 2- [4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl] -4,6-diphenyl-1,3,5-triazine ( 1.0 g), 3-bromocarbazole (622 mg), and tetrakis (triphenylphosphine) palladium (238 mg) in a mixed solvent of 1,4-dioxane (12 mL) and 3M aqueous potassium phosphate (1.1 mL). Suspended and 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, and the target product 3- [4- (4,6-diphenyltriazin-2-yl) phenyl] carbazole was a brown solid (yield 794 mg, yield 70%). )
¹ H-NMR (DMSO-d ₆ ): δ 7.23 (t, J = 7.4 Hz, 1H), 7.44 (t, J = 7.6 Hz, 1H), 7.54 (d, J = 8 .1 Hz, 1H), 7.64 (d, J = 8.4 Hz, 1H), 7.63-7.75 (m, 6H), 7.89 (d, J = 8.5 Hz, 1H), 8 .10 (d, J = 8.3 Hz, 2H), 8.29 (d, J = 7.8 Hz, 1H), 8.65 (s, 1H), 8.79 (d, J = 7.0 Hz, 4H), 8.85 (d, J = 8.3 Hz, 2H), 11.45 (s, 1H).

　アルゴン気流下、３－ブロモカルバゾール（４．９２ｇ）、ビスピナコラートジボロン（１０．２ｇ）、酢酸カリウム（７．８５ｇ）、及びジクロロビストリフェニルホスフィンパラジウム（２８１ｍｇ）を、１，４－ジオキサン（１００ｍＬ）に懸濁し、２時間加熱還流した。室温まで冷却後、不溶物をろ別した。次いで、ろ液をシリカゲルクロマトグラフィー（展開溶媒；クロロホルム）で精製し、３－（４，４，５，５－テトラメチル－１，３，２－ジオキサボロラン－２－イル）－カルバゾールの白色固体（収量３．９４ｇ，収率６７％）を得た。
　^１Ｈ－ＮＭＲ（ＤＭＳＯ－ｄ_６）：δ１．１７（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＝８．２Ｈｚ，１Ｈ），８．２０（ｄ，Ｊ＝７．８Ｈｚ，１Ｈ），８．４６（ｓ，１Ｈ），１１．４３（ｓ，１Ｈ）． Synthesis example-3

Under a stream of argon, 3-bromocarbazole (4.92 g), bispinacolatodiboron (10.2 g), potassium acetate (7.85 g), and dichlorobistriphenylphosphine palladium (281 mg) were added to 1,4-dioxane ( 100 mL) and heated to reflux for 2 hours. After cooling to room temperature, insolubles were filtered off. The filtrate was then purified by silica gel chromatography (developing solvent; chloroform), and a white solid of 3- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -carbazole ( Yield 3.94 g, 67% yield).
¹ H-NMR (DMSO-d ₆ ): δ 1.17 (s, 12H), 7.18 (t, J = 7.4 Hz, 1H), 7.40 (t, J = 7.6 Hz, 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).

　アルゴン気流下、３－（４，４，５，５－テトラメチル－１，３，２－ジオキサボロラン－２－イル）－カルバゾール（５８６ｍｇ）、２－ブロモピリジン（３４８ｍｇ）、及びテトラキス（トリフェニルホスフィン）パラジウム（４６ｍｇ）を、ＴＨＦ（１０ｍＬ）及び４Ｎ－水酸化ナトリウム水溶液（１．０ｍＬ）の混合溶媒に懸濁し、２３時間加熱還流した。室温まで冷却後、クロロホルムで抽出した。有機層をシリカゲルクロマトグラフィー（展開溶媒；トルエン、次いでクロロホルム、その後メタノール）で精製し、３－（２－ピリジル）カルバゾールの黄色固体（収量４７４ｍｇ，収率９７％）を得た。
　^１Ｈ－ＮＭＲ（ＤＭＳＯ－ｄ_６）：δ７．２０（ｔ，Ｊ＝７．４Ｈｚ，１Ｈ），７．２９（ｄｄ，Ｊ＝７．４，４．８Ｈｚ，１Ｈ），７．４１（ｔ，Ｊ＝７．６Ｈｚ，１Ｈ），７．５０（ｄ，Ｊ＝８．１Ｈｚ，１Ｈ），７．５６（ｄ、Ｊ＝８．５Ｈｚ，１Ｈ），７．８７（ｔ，Ｊ＝７．７Ｈｚ，１Ｈ），８．０５（ｄ，Ｊ＝８．１Ｈｚ，１Ｈ），８．１８（ｄ，Ｊ＝８．６Ｈｚ，１Ｈ），８．２２（ｄ，Ｊ＝７．８Ｈｚ，１Ｈ），８．６６（ｄ，Ｊ＝４．８Ｈｚ，１Ｈ），８．８８（ｓ，１Ｈ），１１．４１（ｓ，１Ｈ）． Synthesis example 4

Under an argon stream, 3- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-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 heated under reflux 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, then chloroform, and then methanol) to obtain a yellow solid (yield 474 mg, yield 97%) of 3- (2-pyridyl) carbazole.
¹ H-NMR (DMSO-d ₆ ): δ 7.20 (t, J = 7.4 Hz, 1H), 7.29 (dd, J = 7.4, 4.8 Hz, 1H), 7.41 (t , J = 7.6 Hz, 1H), 7.50 (d, J = 8.1 Hz, 1H), 7.56 (d, J = 8.5 Hz, 1H), 7.87 (t, J = 7. 7 Hz, 1H), 8.05 (d, J = 8.1 Hz, 1H), 8.18 (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 (s, 1H).

　アルゴン気流下、２－（３－ブロモフェニル）－４，６－ジフェニル－１，３，５－トリアジン（１．１７ｇ）、３－（４，４，５，５－テトラメチル－１，３，２－ジオキサボロラン－２－イル）カルバゾール（９６７ｍｇ）、及びテトラキス（トリフェニルホスフィン）パラジウム（１０４ｍｇ）を、１，４－ジオキサン（１５ｍＬ）に懸濁し、３Ｍ－炭酸カリウム水溶液（２．５ｍＬ）を添加し、１７時間加熱還流した。反応混合物を放冷後、水を加えた。析出した固体を水、次いでメタノール、その後ヘキサンで洗浄し、目的物である３－［３－（４，６－ジフェニル－１，３，５－トリアジン－２－イル）フェニル］カルバゾールの白色粉末（収量１．３７ｇ，収率９６％）を得た。
　^１Ｈ－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，１Ｈ），７．８１（ｄ，Ｊ＝８．４Ｈｚ，１Ｈ），７．９４（ｄ，Ｊ＝７．８Ｈｚ，１Ｈ），８．１５（ｂｓ，１Ｈ），８．１７（ｄ，Ｊ＝７．８Ｈｚ，１Ｈ），８．４１（ｓ，１Ｈ），８．７５（ｄ，Ｊ＝７．８Ｈｚ，１Ｈ），８．８０（ｄ，Ｊ＝７．８Ｈｚ，４Ｈ），９．０７（ｓ，１Ｈ）． Synthesis example-5

Under an argon stream, 2- (3-bromophenyl) -4,6-diphenyl-1,3,5-triazine (1.17 g), 3- (4,4,5,5-tetramethyl-1,3, 2-Dioxaborolan-2-yl) carbazole (967 mg) and tetrakis (triphenylphosphine) palladium (104 mg) are suspended in 1,4-dioxane (15 mL), and 3M aqueous potassium carbonate solution (2.5 mL) is added. And heated to reflux for 17 hours. The reaction mixture was allowed to cool and water was added. The precipitated solid was washed with water, then with methanol and then with hexane, and a white powder of 3- [3- (4,6-diphenyl-1,3,5-triazin-2-yl) phenyl] carbazole, which was the target product ( Yield 1.37 g, yield 96%).
¹ H-NMR (CDCl ₃ ): δ, 7.29 (t, J = 7.0 Hz, 1H), 7.43-7.50 (m, 2H), 7.55-7.61 (m, 7H) ), 7.66 (t, J = 7.8 Hz, 1H), 7.81 (d, J = 8.4 Hz, 1H), 7.94 (d, J = 7.8 Hz, 1H), 8.15. (Bs, 1H), 8.17 (d, J = 7.8 Hz, 1H), 8.41 (s, 1H), 8.75 (d, J = 7.8 Hz, 1H), 8.80 (d , J = 7.8 Hz, 4H), 9.07 (s, 1H).

　アルゴン気流下、３－［３－クロロ－５－（４，６－ジフェニル－１，３，５－トリアジン－２－イル）フェニル］カルバゾール（２．００ｇ）、２－ブロモピリジン（７４５ｍｇ）、酸化銅（５６．２３ｍｇ）、１，１０－フェナントロリン（７０．８２ｍｇ）、１８－クラウン－６－エーテル（２０７．７６ｍｇ）、及び炭酸カリウム（１３５８ｍｇ）を、キシレン（２０ｍＬ）に懸濁し、１６時間加熱還流した。反応混合物を放冷後、水を加えた。析出した固体を水、次いでメタノール、その後ヘキサンで洗浄し、目的物であるＮ－（２－ピリジル）－３－［３－クロロ－５－（４，６－ジフェニル－１，３，５－トリアジン－２－イル）フェニル］カルバゾールの黄色粉末（収量２１１０ｍｇ，収率９２％）を得た。
　^１Ｈ－ＮＭＲ（ＣＤＣｌ_３）：δ７．３３－７．３９（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＝８．０Ｈｚ，１Ｈ），７．８６（ｄ，Ｊ＝７．６Ｈｚ，１Ｈ），７．９２（ｓ，１Ｈ），７．９５－８．００（ｍ，２Ｈ），８．２２（ｄ，Ｊ＝７．６Ｈｚ，１Ｈ），８．４１（ｓ，１Ｈ），８．７１（ｓ，１Ｈ），８．７８－８．８０（ｍ，５Ｈ），８．９７（ｓ，１Ｈ）． Synthesis example-6

Under an argon stream, 3- [3-chloro-5- (4,6-diphenyl-1,3,5-triazin-2-yl) phenyl] carbazole (2.00 g), 2-bromopyridine (745 mg), oxidation Copper (56.23 mg), 1,10-phenanthroline (70.82 mg), 18-crown-6-ether (207.76 mg), and potassium carbonate (1358 mg) were suspended in xylene (20 mL) and heated for 16 hours. Refluxed. The reaction mixture was allowed to cool and water was added. The precipitated solid was washed with water, then with methanol and then with hexane, and the target product N- (2-pyridyl) -3- [3-chloro-5- (4,6-diphenyl-1,3,5-triazine) A yellow powder of (-2-yl) phenyl] carbazole (yield 2110 mg, yield 92%) was obtained.
¹ H-NMR (CDCl ₃ ): δ 7.33-7.39 (m, 2H), 7.48 (t, J = 7.2 Hz, 1H), 7.56-7.64 (m, 6H), 7.69 (d, J = 8.0 Hz, 1H), 7.80 (d, J = 8.0 Hz, 1H), 7.86 (d, J = 7.6 Hz, 1H), 7.92 (s , 1H), 7.95-8.00 (m, 2H), 8.22 (d, J = 7.6 Hz, 1H), 8.41 (s, 1H), 8.71 (s, 1H), 8.78-8.80 (m, 5H), 8.97 (s, 1H).

　アルゴン気流下、３－［３－クロロ－５－（４，６－ジフェニル－１，３，５－トリアジン－２－イル）フェニル］－９－（２－ピリジル）カルバゾール（１．９０ｇ）、ビスピナコラートジボロン（０．９０ｇ）、トリス（ジベンジリデンアセトン）ジパラジウム（２９．７ｍｇ）、２－ジシクロヘキシルホスフィノ－２’，４’，６’－トリイソプロピルビフェニル（３０．９ｍｇ）、及び酢酸カリウム（０．９５ｇ）を、１，４－ジオキサン（２４ｍＬ）に懸濁し、５時間加熱還流した。反応混合物を放冷後、水を加えた。析出した固体をろ別し、水、次いでメタノールで洗浄した。減圧下において溶媒を留去し、目的物である３－［３－（４，４，５，５－テトラメチル－１，３，２－ジオキサボロラン－２－イル）－５－（４，６－ジフェニル－１，３，５－トリアジン－２－イル）フェニル］－９－（２－ピリジル）カルバゾールの白色粉末（収量１．９８ｇ，収率９０％）を得た。
　^１Ｈ－ＮＭＲ（ＣＤＣｌ_３）：δ，１．４５（ｓ，１２Ｈ），７．３１－７．３７（ｍ，２Ｈ），７．４７（ｔ，Ｊ＝７．４Ｈｚ，１Ｈ），７．５６－７．６１（ｍ，６Ｈ），７．７０（ｄ，Ｊ＝８．２Ｈｚ，１Ｈ），７．８５－７．８９（ｍ，２Ｈ），７．９６（ｔ，Ｊ＝８．２Ｈｚ，２Ｈ），８．２４（ｄ，Ｊ＝７．４Ｈｚ，１Ｈ），８．４０（ｓ，１Ｈ），８．４８（ｓ，１Ｈ）、８．７５－８．８３（ｍ，５Ｈ），９．１３（ｓ，１Ｈ），９．１８（ｓ，１Ｈ）． Synthesis example-7

Under an argon stream, 3- [3-chloro-5- (4,6-diphenyl-1,3,5-triazin-2-yl) phenyl] -9- (2-pyridyl) carbazole (1.90 g), bi Spinacolatodiboron (0.90 g), tris (dibenzylideneacetone) dipalladium (29.7 mg), 2-dicyclohexylphosphino-2 ′, 4 ′, 6′-triisopropylbiphenyl (30.9 mg), and acetic acid Potassium (0.95 g) was suspended in 1,4-dioxane (24 mL) and heated to reflux for 5 hours. The reaction mixture was allowed to cool and water was added. The precipitated solid was filtered off and washed with water and then methanol. The solvent was distilled off under reduced pressure, and the desired product 3- [3- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -5- (4,6- A white powder (yield 1.98 g, yield 90%) of diphenyl-1,3,5-triazin-2-yl) phenyl] -9- (2-pyridyl) carbazole was obtained.
¹ H-NMR (CDCl ₃ ): δ, 1.45 (s, 12H), 7.31-7.37 (m, 2H), 7.47 (t, J = 7.4 Hz, 1H), 7. 56-7.61 (m, 6H), 7.70 (d, J = 8.2 Hz, 1H), 7.85-7.89 (m, 2H), 7.96 (t, J = 8.2 Hz) , 2H), 8.24 (d, J = 7.4 Hz, 1H), 8.40 (s, 1H), 8.48 (s, 1H), 8.75-8.83 (m, 5H), 9.13 (s, 1H), 9.18 (s, 1H).

　アルゴン気流下、２－［３－クロロ－５－（４，４，５，５－テトラメチル－１，３，２－ジオキサボロラン－２－イル）フェニル］－４，６－ジフェニル－１，３，５－トリアジン（９３ｍｇ）、６－ブロモ－９－（２－ピリジル）－β－カルボリン（５４ｍｇ）、テトラキス（トリフェニルホスフィン）パラジウム（５．７ｍｇ）、及び炭酸カリウム（５７ｍｇ）を、１，４－ジオキサン（３．３ｍＬ）に懸濁し、水（１５０μＬ）を添加し、１４時間加熱還流した。反応混合物を放冷後、水を加えた。析出した固体を水、次いでメタノール、その後ヘキサンで洗浄し、減圧下において溶媒を留去した。シリカゲルカラムクロマトグラフィー（溶離液；酢酸エチル）による精製を行い、目的物である９－（２－ピリジル）－６－［３－クロロ－５－（４，６－ジフェニルトリアジン－２－イル）フェニル］－β－カルボリンの白色粉末（収量７０ｍｇ，収率７１％）を得た。
　^１Ｈ－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＝８．４Ｈｚ，１Ｈ），８．０１（ｔ，Ｊ＝７．８Ｈｚ，１Ｈ），
８．０６－８．０９（ｍ，２Ｈ），８．４５（ｓ，１Ｈ），８．６０（ｄ，Ｊ＝５．２Ｈｚ，１Ｈ），８．７２（ｓ，１Ｈ），８．７６－８．７８（ｍ，５Ｈ），８．９３（ｓ，１Ｈ），９．３２（ｓ，１Ｈ）． Synthesis example-8

Under an argon stream, 2- [3-chloro-5- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl] -4,6-diphenyl-1,3 5-triazine (93 mg), 6-bromo-9- (2-pyridyl) -β-carboline (54 mg), tetrakis (triphenylphosphine) palladium (5.7 mg), and potassium carbonate (57 mg) -Suspended in dioxane (3.3 mL), added water (150 μL) and heated to reflux for 14 hours. The reaction mixture was allowed to cool and water was added. The precipitated solid was washed with water, then methanol, and then hexane, and the solvent was distilled off under reduced pressure. 9- (2-pyridyl) -6- [3-chloro-5- (4,6-diphenyltriazin-2-yl) phenyl, the target product, was purified by silica gel column chromatography (eluent: ethyl acetate). ] -Β-carboline white powder (yield 70 mg, yield 71%) was obtained.
¹ H-NMR (CDCl ₃ ): δ, 7.39 (dd, J = 7.4, 5.0 Hz, 1H), 7.55-7.62 (m, 6H), 7.72 (d, J = 7.4 Hz, 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 (s, 1H), 8.60 (d, J = 5.2 Hz, 1H), 8.72 (s, 1H), 8.76- 8.78 (m, 5H), 8.93 (s, 1H), 9.32 (s, 1H).

　アルゴン気流下、２－［３－クロロ－５－（４，４，５，５－テトラメチル－１，３，２－ジオキサボロラン－２－イル）フェニル］－４，６－ジフェニル－１，３，５－トリアジン（７０６ｍｇ）、３－ブロモ－９－フェニル－６－（２－ピリジル）カルバゾール（５００ｍｇ）、テトラキス（トリフェニルホスフィン）パラジウム（２８．９ｍｇ）、及び炭酸カリウム（５７ｍｇ）を、１，４－ジオキサン（６．５ｍＬ）に懸濁し、水（１．３ｍＬ）を添加し、２０時間加熱還流した。反応混合物を放冷後、水を加えた。析出した固体をろ別し、水、次いでメタノール、その後ヘキサンで洗浄した。減圧下において溶媒を留去し、目的物である３－［３－クロロ－５－（４，６－ジフェニル－１，３，５－トリアジン－２－イル）フェニル］－９－フェニル－６－（２－ピリジル）カルバゾールの白色粉末（収量７５４ｍｇ，収率９１％）を得た。
　^１Ｈ－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＝８．４Ｈｚ，２Ｈ），７．８８（ｄ，Ｊ＝８．４Ｈｚ，１Ｈ），７．９２（ｓ，１Ｈ），８．１１（ｄ，Ｊ＝８．４Ｈｚ，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-9

Under an argon stream, 2- [3-chloro-5- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl] -4,6-diphenyl-1,3 5-triazine (706 mg), 3-bromo-9-phenyl-6- (2-pyridyl) carbazole (500 mg), tetrakis (triphenylphosphine) palladium (28.9 mg), and potassium carbonate (57 mg) The mixture was suspended in 4-dioxane (6.5 mL), water (1.3 mL) was added, and the mixture was heated to reflux for 20 hours. The reaction mixture was allowed to cool and water was added. The precipitated solid was filtered off and washed with water, then methanol, and then hexane. The solvent was distilled off under reduced pressure, and the desired product 3- [3-chloro-5- (4,6-diphenyl-1,3,5-triazin-2-yl) phenyl] -9-phenyl-6- A white powder of (2-pyridyl) carbazole (yield 754 mg, yield 91%) was obtained.
¹ H-NMR (CDCl ₃ ): δ, 7.21 (t, J = 7.4 Hz, 1H), 7.52 (t, J = 8.4 Hz, 2H), 7.55-7.69 (m 11H), 7.76 (t, J = 8.4 Hz, 2H), 7.88 (d, J = 8.4 Hz, 1H), 7.92 (s, 1H), 8.11 (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).

　アルゴン気流下、２－（５－クロロビフェニル－３－イル）－４，６－ジフェニル－１，３，５－トリアジン（１２．６ｇ）、ビスピナコラートジボロン（８．４ｇ）、トリス（ジベンジリデンアセトン）ジパラジウム（８２４ｍｇ）、２－ジシクロヘキシルホスフィノ－２’，４’，６’－トリイソプロピルビフェニル（１．３ｇ）、及び酢酸カリウム（６．５ｇ）を、１，４－ジオキサン（１５０ｍＬ）に懸濁し、３．５時間加熱還流した。反応混合物を放冷後、水を加えた。析出した固体をろ別し、水、次いでメタノールで洗浄した。減圧下において溶媒を留去し、目的物である２－［５－（４，４，５，５－テトラメチル－１，３，２－ジオキサボロラン－２－イル）－ビフェニル－３－イル－４，６－ジフェニル－１，３，５－トリアジン（以下、化合物（Ｅ－１））の白色粉末（収量１４．８ｇ，収率９６％）を得た。
　^１Ｈ－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＝８．１Ｈｚ，２Ｈ），８．３３（ｓ，１Ｈ），８．８５（ｄ，Ｊ＝７．９Ｈｚ，４Ｈ），９．１２（ｓ，１Ｈ），９．１６（ｓ，１Ｈ）． Synthesis Example-10

Under an argon stream, 2- (5-chlorobiphenyl-3-yl) -4,6-diphenyl-1,3,5-triazine (12.6 g), bispinacolatodiboron (8.4 g), tris (di Benzylideneacetone) dipalladium (824 mg), 2-dicyclohexylphosphino-2 ′, 4 ′, 6′-triisopropylbiphenyl (1.3 g), and potassium acetate (6.5 g) were added to 1,4-dioxane (150 mL). ) And heated to reflux for 3.5 hours. The reaction mixture was allowed to cool and water was added. The precipitated solid was filtered off and washed with water and then methanol. The solvent was distilled off under reduced pressure, and the desired product 2- [5- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -biphenyl-3-yl-4 , 6-Diphenyl-1,3,5-triazine (hereinafter referred to as compound (E-1)) was obtained as a white powder (yield 14.8 g, yield 96%).
¹ H-NMR (CDCl ₃ ): δ, 1.47 (s, 12H), 7.45 (t, J = 7.4 Hz, 1H), 7.55 (t, J = 7.4 Hz, 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 (s, 1H).

　アルゴン気流下、３－［３－クロロ－５－（４，６－ジフェニル－１，３，５－トリアジン－２－イル）フェニル］カルバゾール（４．００ｇ）、フェニルボロン酸（１．２５ｇ）、酢酸パラジウム（５３ｍｇ）、及び２－ジシクロヘキシルホスフィノ－２’，４’，６’－トリイソプロピルビフェニル（２２５ｍｇ）を、１，４－ジオキサン（８０ｍＬ）に懸濁し、３Ｍ－炭酸カリウム水溶液（６．８ｍＬ）を添加し、２７時間加熱還流した。反応混合物を放冷後、水を加えた。析出した固体をろ別し、水、次いでメタノール、その後ヘキサンで洗浄した。減圧下において溶媒を留去し、目的物である３－［５－（４，６－ジフェニル－１，３，５－トリアジン－２－イル）－ビフェニル－３－イル］カルバゾールの白色粉末（収量３．２７ｇ，収率７６％）を得た。
　^１Ｈ－ＮＭＲ（ＣＤＣｌ_３）：δ７．３２（ｄｄ，Ｊ＝７．９，６．２Ｈｚ，１Ｈ），７．４７－７．５１（ｍ，２Ｈ），７．５９－７．６８（ｍ，１０Ｈ），７．８７－７．９１（ｍ，３Ｈ），８．１８（ｓ，１Ｈ），８．１９（ｓ，１Ｈ），８．２２（ｄ，Ｊ＝７．７Ｈｚ，１Ｈ），８．５０（ｓ，１Ｈ），８．８４－８．８７（ｍ，４Ｈ），９．００（ｓ，１Ｈ），９．０９（ｓ，１Ｈ）． Synthesis Example-11

Under an argon stream, 3- [3-chloro-5- (4,6-diphenyl-1,3,5-triazin-2-yl) phenyl] carbazole (4.00 g), phenylboronic acid (1.25 g), Palladium acetate (53 mg) and 2-dicyclohexylphosphino-2 ′, 4 ′, 6′-triisopropylbiphenyl (225 mg) were suspended in 1,4-dioxane (80 mL), and 3M aqueous potassium carbonate solution (6. 8 mL) was added and heated to reflux for 27 hours. The reaction mixture was allowed to cool and water was added. The precipitated solid was filtered off and washed with water, then methanol, and then hexane. The solvent was distilled off under reduced pressure, and the desired product 3- [5- (4,6-diphenyl-1,3,5-triazin-2-yl) -biphenyl-3-yl] carbazole was obtained as a white powder (yield) 3.27 g, yield 76%).
¹ H-NMR (CDCl ₃ ): δ 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 (m, 3H), 8.18 (s, 1H), 8.19 (s, 1H), 8.22 (d, J = 7.7 Hz, 1H), 8.50 (s, 1H), 8.84-8.87 (m, 4H), 9.00 (s, 1H), 9.09 (s, 1H).

　アルゴン気流下、９－（２－ピリジル）－δ－カルボリン（７００ｍｇ）、及びＮ－ブロモスクシンイミド（５５９ｍｇ）を、ＤＭＦ（５．７ｍＬ）に懸濁し、３０℃で１０時間撹拌した。その後、水を加え、析出した固体をろ別し、水、次いでヘキサンで洗浄した。減圧下において溶媒を留去し、目的物である６－ブロモ－９－（２－ピリジル）－δ－カルボリンの褐色粉末（収量７６１ｍｇ，収率８２％）を得た。
　^１Ｈ－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＝８．８Ｈｚ，１Ｈ），７．８０（ｄ，Ｊ＝８．８Ｈｚ，１Ｈ），７．８０（ｔ，Ｊ＝７．６Ｈｚ，１Ｈ），８．２２（ｄ，Ｊ＝８．４Ｈｚ，１Ｈ），８．５９（ｓ，１Ｈ），８．６６（ｄ，Ｊ＝４．７Ｈｚ，１Ｈ），８．７５（ｄ，Ｊ＝４．９Ｈｚ，１Ｈ）． Synthesis example-12

Under an argon stream, 9- (2-pyridyl) -δ-carboline (700 mg) and N-bromosuccinimide (559 mg) were suspended in DMF (5.7 mL) and stirred at 30 ° C. for 10 hours. Thereafter, water was added and the precipitated solid was filtered off and washed with water and then with hexane. The solvent was distilled off under reduced pressure to obtain 6-bromo-9- (2-pyridyl) -δ-carboline brown powder (yield 761 mg, yield 82%), which was the target product.
¹ H-NMR (CDCl ₃ ): δ, 7.38 (dd, J = 7.5, 4.9 Hz, 1H), 7.42 (dd, J = 8.4, 4.7 Hz, 1H), 7 .62 (d, J = 8.2 Hz, 1H), 7.65 (d, J = 8.8 Hz, 1H), 7.80 (d, J = 8.8 Hz, 1H), 7.80 (t, J = 7.6 Hz, 1H), 8.22 (d, J = 8.4 Hz, 1H), 8.59 (s, 1H), 8.66 (d, J = 4.7 Hz, 1H), 8. 75 (d, J = 4.9 Hz, 1H).

　アルゴン気流下、９－フェニル－３－（２－ピリジル）カルバゾール（７５７ｍｇ）、及びＮ－ブロモスクシンイミド（４６３ｍｇ）を、ＤＭＦ（４．７ｍＬ）に懸濁し、３０℃で７時間撹拌した。その後、水を加え、析出した固体をろ別し、水、次いでヘキサンで洗浄した。減圧下において溶媒を留去し、目的物である３－ブロモ－９－フェニル－６－（２－ピリジル）カルバゾールの褐色粉末（収量８５２ｍｇ，収率９０％）を得た。
　^１Ｈ－ＮＭＲ（ＣＤＣｌ_３）：δ，７．２７－７．３０（ｍ，１Ｈ），７．３１７．１３１（ｄ，Ｊ＝８．５Ｈｚ，１Ｈ），７．４９（ｄ，Ｊ＝８．６Ｈｚ，１Ｈ），７．５１－７．５５（ｍ，２Ｈ），７．５７－７．６０（ｍ，２Ｈ），７．６４－７．６８（ｍ，２Ｈ），７．８４（ｔ，Ｊ＝７．６Ｈｚ，１Ｈ），７．８９（ｄ，Ｊ＝８．０Ｈｚ，１Ｈ），８．１４（ｄ，Ｊ＝８．５Ｈｚ，１Ｈ），８．３７（ｓ，１Ｈ），８．７７（ｄ，Ｊ＝４．８Ｈｚ，１Ｈ），８．８０（ｓ，１Ｈ）． Synthesis Example-13

Under an argon stream, 9-phenyl-3- (2-pyridyl) carbazole (757 mg) and N-bromosuccinimide (463 mg) were suspended in DMF (4.7 mL) and stirred at 30 ° C. for 7 hours. Thereafter, water was added and the precipitated solid was filtered off and washed with water and then with hexane. The solvent was distilled off under reduced pressure to obtain a brown powder (yield 852 mg, yield 90%) of 3-bromo-9-phenyl-6- (2-pyridyl) carbazole as a target product.
¹ H-NMR (CDCl ₃ ): δ, 7.27-7.30 (m, 1H), 7.317.131 (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 (d, J = 8.0 Hz, 1H), 8.14 (d, J = 8.5 Hz, 1H), 8.37 (s, 1H), 8 .77 (d, J = 4.8 Hz, 1H), 8.80 (s, 1H).

　アルゴン気流下、３－［３－クロロ－５－（４，６－ジフェニル－１，３，５－トリアジン－２－イル）フェニル］カルバゾール（２．５５ｇ）、４－（２－ピリジル）フェニルボロン酸（１．１９ｇ）、酢酸パラジウム（２２．５ｍｇ）、２－ジシクロヘキシルホスフィノ－２’，４’，６’－トリイソプロピルビフェニル（１４３ｍｇ）を１，４－ジオキサン（２５ｍＬ）に懸濁し、次いで３Ｍ－炭酸カリウム水溶液（４．０ｍＬ）を添加し、１４時間加熱還流した。反応混合物を放冷後、水を加えた。析出した固体をろ別し、水、メタノール、ヘキサンで洗浄した。得られた固体をｏ－キシレンで再結晶することで、目的の３－［５－（４，６－ジフェニル－１，３，５－トリアジン－２－イル）－４’－（２－ピリジル）ビフェニル－３－イル］カルバゾール（以下、化合物（Ｅ－２））の白色粉末（収量２．３１ｇ，収率７４％）を得た。
　^１Ｈ－ＮＭＲ（ＤＭＳＯ－ｄ_６）：δ７．２１（ｔ，Ｊ＝７．４Ｈｚ，１Ｈ），７．４１（ｄｄ，Ｊ＝７．４，４．７Ｈｚ，１Ｈ），７．４４（ｔ，Ｊ＝７．６Ｈｚ，１Ｈ），７．５５（ｄ，Ｊ＝８．１Ｈｚ，１Ｈ），７．６６－７．７６（ｍ，７Ｈ），７．９２－７．９７（ｍ，２Ｈ），８．０７－８．１０（ｍ，３Ｈ），８．３０－８．３２（ｍ，３Ｈ），８．４８（ｓ，１Ｈ），８．７１（ｓ，１Ｈ），８．７４（ｄ，Ｊ＝４．７Ｈｚ，１Ｈ），８．７７－８．８０（ｍ，４Ｈ），８．９４（ｓ，１Ｈ），９．００（ｓ，１Ｈ），１１．４３（ｓ，１Ｈ）． Synthesis example-14

Under an argon stream, 3- [3-chloro-5- (4,6-diphenyl-1,3,5-triazin-2-yl) phenyl] carbazole (2.55 g), 4- (2-pyridyl) phenylboron Acid (1.19 g), palladium acetate (22.5 mg), 2-dicyclohexylphosphino-2 ′, 4 ′, 6′-triisopropylbiphenyl (143 mg) are suspended in 1,4-dioxane (25 mL), then 3M aqueous potassium carbonate solution (4.0 mL) was added, and the mixture was heated to reflux for 14 hours. The reaction mixture was allowed to cool and water was added. The precipitated solid was filtered off and washed with water, methanol and hexane. The obtained solid was recrystallized from o-xylene to give the desired 3- [5- (4,6-diphenyl-1,3,5-triazin-2-yl) -4 '-(2-pyridyl) A white powder (yield 2.31 g, yield 74%) of biphenyl-3-yl] carbazole (hereinafter compound (E-2)) was obtained.
¹ H-NMR (DMSO-d ₆ ): δ 7.21 (t, J = 7.4 Hz, 1H), 7.41 (dd, J = 7.4, 4.7 Hz, 1H), 7.44 (t , J = 7.6 Hz, 1H), 7.55 (d, J = 8.1 Hz, 1H), 7.66-7.76 (m, 7H), 7.92-7.97 (m, 2H) , 8.07-8.10 (m, 3H), 8.30-8.32 (m, 3H), 8.48 (s, 1H), 8.71 (s, 1H), 8.74 (d , J = 4.7 Hz, 1H), 8.77-8.80 (m, 4H), 8.94 (s, 1H), 9.00 (s, 1H), 11.43 (s, 1H).

　アルゴン気流下、３－（４，４，５，５－テトラメチル－１，３，２－ジオキサボロラン－２－イル）カルバゾール（１．１７ｇ）、８－クロロキノリン（７２０ｍｇ）、酢酸パラジウム（１８．０ｍｇ）、２－ジシクロヘキシルホスフィノ－２’，４’，６’－トリイソプロピルビフェニル（１１４ｍｇ）をＴＨＦ（１０ｍＬ）に懸濁し、３Ｍ－炭酸カリウム水溶液（２．７ｍＬ）を添加し、１５時間加熱還流した。反応混合物を放冷後、水を加えクロロホルムで抽出した。有機層を硫酸マグネシウムで乾燥したのち、ろ過した。溶媒を減圧留去することで析出した固体をろ取することで、目的の３－（キノリン－８－イル）カルバゾールの黄色粉末（収量７８０ｍｇ，収率６６％）を得た。
　^１Ｈ－ＮＭＲ（ＣＤＣｌ_３）：δ７．２２（ｄｄ，Ｊ＝７．９，６．６Ｈｚ，１Ｈ），７．３６（ｄ，Ｊ＝８．０Ｈｚ，１Ｈ），７．４０（ｄｄ，Ｊ＝８．１，６．６Ｈｚ，１Ｈ），７．４４（ｄｄ，Ｊ＝８．４Ｈｚ，１Ｈ），７．４６（ｄｄ，Ｊ＝８．３，４．２Ｈｚ，１Ｈ），７．６７（ｄｄ，Ｊ＝８．２，７．０Ｈｚ，１Ｈ），７．７６（ｄ，８．３Ｈｚ，１Ｈ），７．８６（ｄ，Ｊ＝４．３Ｈｚ，１Ｈ），７．８８（ｄ，Ｊ＝４．３Ｈｚ，１Ｈ），８．０５（ｄ，Ｊ＝７．８Ｈｚ，１Ｈ），８．２７（ｄ，Ｊ＝８．３Ｈｚ，１Ｈ），８．３５（ｓ，１Ｈ），８．４５（ｓ，１Ｈ），９．０２（ｄ，Ｊ＝４．２Ｈｚ，１Ｈ）． Synthesis Example-15

Under an argon stream, 3- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) carbazole (1.17 g), 8-chloroquinoline (720 mg), palladium acetate (18. 0 mg), 2-dicyclohexylphosphino-2 ′, 4 ′, 6′-triisopropylbiphenyl (114 mg) suspended in THF (10 mL), 3M aqueous potassium carbonate solution (2.7 mL) was added, and the mixture was heated for 15 hours. Refluxed. The reaction mixture was allowed to cool, water was added, and the mixture was extracted with chloroform. The organic layer was dried over magnesium sulfate and then filtered. The solvent was distilled off under reduced pressure, and the precipitated solid was collected by filtration to obtain the desired yellow powder (yield 780 mg, 66%) of 3- (quinolin-8-yl) carbazole.
¹ H-NMR (CDCl ₃ ): δ 7.22 (dd, J = 7.9, 6.6 Hz, 1H), 7.36 (d, J = 8.0 Hz, 1H), 7.40 (dd, J = 8.1, 6.6 Hz, 1H), 7.44 (dd, J = 8.4 Hz, 1H), 7.46 (dd, J = 8.3, 4.2 Hz, 1H), 7.67 ( dd, J = 8.2, 7.0 Hz, 1H), 7.76 (d, 8.3 Hz, 1H), 7.86 (d, J = 4.3 Hz, 1H), 7.88 (d, J = 4.3 Hz, 1H), 8.05 (d, J = 7.8 Hz, 1H), 8.27 (d, J = 8.3 Hz, 1H), 8.35 (s, 1H), 8.45. (S, 1H), 9.02 (d, J = 4.2 Hz, 1H).

　アルゴン気流下、３－（キノリン－８－イル）カルバゾール（７３６ｍｇ）、２－ブロモピリジン（４７４ｍｇ）、酸化銅（Ｉ）（１７．９ｍｇ）、１，１０－フェナントロリン（４５ｍｇ）、１８－クラウン－６－エーテル（１３２ｍｇ）、炭酸カリウム（６９１ｍｇ）をキシレン（６．２ｍＬ）に懸濁し、１５時間加熱還流した。反応混合物を放冷後、不要物をセライトでろ過することで除去した。濾液を減圧留去し、カラムクロマトグラフィー（展開溶媒：クロロホルム）で精製することで、目的の９－（２－ピリジル）－３－（キノリン－８－イル）カルバゾールの黄色粉末（収量９２９ｍｇ，収率１００％）を得た。
　^１Ｈ－ＮＭＲ（ＣＤＣｌ_３）：δ７．３２－７．３６（ｍ，２Ｈ），７．４６－７．５０（ｍ，２Ｈ），７．６９（ｄｄ，Ｊ＝８．１，７．１Ｈｚ，１Ｈ），７．７４（ｄ，Ｊ＝８．１Ｈｚ，１Ｈ），７．８２（ｄ，Ｊ＝８．５Ｈｚ，１Ｈ），７．８７－７．９２（ｍ，２Ｈ），７．９３（ｄ，Ｊ＝８．４Ｈｚ，１Ｈ），７，９７（ｄｄ，Ｊ＝８．０，７．５Ｈｚ，１Ｈ），７．９７（ｄ，Ｊ＝８．５Ｈｚ，１Ｈ），８，１６（ｄ，Ｊ＝７．７Ｈｚ，１Ｈ），８．２９（ｄ，Ｊ＝８．３Ｈｚ，１Ｈ），８．４４（ｓ，１Ｈ），８．７８（ｄ，Ｊ＝４．７Ｈｚ，１Ｈ），９．０４（ｄ，Ｊ＝４．１Ｈｚ，１Ｈ）． Synthesis Example-16

Under an argon stream, 3- (quinolin-8-yl) carbazole (736 mg), 2-bromopyridine (474 mg), copper (I) oxide (17.9 mg), 1,10-phenanthroline (45 mg), 18-crown- 6-ether (132 mg) and potassium carbonate (691 mg) were suspended in xylene (6.2 mL), and the mixture was heated to reflux for 15 hours. The reaction mixture was allowed to cool, and unnecessary substances were removed by filtration through celite. The filtrate was evaporated under reduced pressure, and purified by column chromatography (developing solvent: chloroform) to give the desired 9- (2-pyridyl) -3- (quinolin-8-yl) carbazole yellow powder (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, 7.1 Hz) , 1H), 7.74 (d, J = 8.1 Hz, 1H), 7.82 (d, J = 8.5 Hz, 1H), 7.87-7.92 (m, 2H), 7.93 (D, J = 8.4 Hz, 1H), 7, 97 (dd, J = 8.0, 7.5 Hz, 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 (s, 1H), 8.78 (d, J = 4.7 Hz, 1H), 9.04 (d, J = 4.1 Hz, 1H).

　アルゴン気流下、９－（２－ピリジル）－３－（キノリン－８－イル）カルバゾール（９２９ｍｇ）、Ｎ－ブロモスクシンイミド（４６７ｍｇ）をＤＭＦ（１０ｍＬ）に懸濁し、６０℃で３時間撹拌した。その後、水を加え析出した固体をろ別し、水、ヘキサンで洗浄した。減圧下において溶媒を留去し、目的の３－ブロモ－９－（２－ピリジル）－６－（キノリン－８－イル）カルバゾールの褐色粉末（収量９８６ｍｇ，収率８８％）を得た。
　^１Ｈ－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＝７．８，７．５Ｈｚ，１Ｈ），７．７０（ｄ，Ｊ＝８．１Ｈｚ，１Ｈ），７．８２（ｄ，Ｊ＝８．５Ｈｚ，１Ｈ），７．８３－７．９０（ｍ，３Ｈ），７．９３（ｄ，Ｊ＝８．５Ｈｚ，１Ｈ），７．９８（ｄｄ，Ｊ＝８．０，７．５Ｈｚ，１Ｈ），８．２７（ｓ，１Ｈ），８．２９（ｄ，Ｊ＝８．３Ｈｚ，１Ｈ），８．４０（ｓ，１Ｈ），８．７６（ｄ，Ｊ＝４．９Ｈｚ，１Ｈ），９．０２（ｄ，Ｊ＝４．２Ｈｚ，１Ｈ）． Synthesis Example-17

Under an argon stream, 9- (2-pyridyl) -3- (quinolin-8-yl) carbazole (929 mg) and N-bromosuccinimide (467 mg) were suspended in DMF (10 mL) and stirred at 60 ° C. for 3 hours. Thereafter, water was added and the precipitated solid was filtered off and washed with water and hexane. The solvent was distilled off under reduced pressure to obtain the desired 3-bromo-9- (2-pyridyl) -6- (quinolin-8-yl) carbazole brown powder (yield 986 mg, 88%).
¹ H-NMR (CDCl ₃ ): δ, 7.35 (dd, J = 7.4, 4.9 Hz, 1H), 7.48 (dd, J = 8.3, 4.2 Hz, 1H), 7 .55 (d, J = 8.8 Hz, 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 (m, 3H), 7.93 (d, J = 8.5 Hz, 1H), 7.98 (dd, J = 8 0.0, 7.5 Hz, 1 H), 8.27 (s, 1 H), 8.29 (d, J = 8.3 Hz, 1 H), 8.40 (s, 1 H), 8.76 (d, J = 4.9 Hz, 1H), 9.02 (d, J = 4.2 Hz, 1H).

　アルゴン気流下、３－［４－（２－ピリジル）フェニル］カルバゾール（３．２０ｇ）、２－ブロモピリジン（１．９０ｇ）、酸化銅（Ｉ）（７１．５ｍｇ）、１，１０－フェナントロリン（１８０ｍｇ）、１８－クラウン－６－エーテル（５２９ｍｇ）、炭酸カリウム（２．７６ｇ）をキシレン（２５ｍＬ）に懸濁し、１５時間加熱還流した。反応混合物を放冷後、水及びメタノールを加え、不要物をろ過することで除去した。濾液をクロロホルムで抽出し、有機層を硫酸ナトリウムで乾燥した後、ろ過した。溶媒を減圧留去し、カラムクロマトグラフィー（展開溶媒：クロロホルム）で精製することで、目的の９－（２－ピリジル）－３－［４－（２－ピリジル）フェニル］カルバゾールの黄色粉末（収量３．６２ｇ，収率９１％）を得た。
　^１Ｈ－ＮＭＲ（ＣＤＣｌ_３）：δ７．２６－７．３０（ｍ，１Ｈ），７．３５（ｄｄ，Ｊ＝７．４，４．９Ｈｚ，１Ｈ），７．３８（ｔ，Ｊ＝７．５Ｈｚ，１Ｈ），７．５０（ｔ，Ｊ＝７．７Ｈｚ，１Ｈ），７．７０（ｄ，Ｊ＝８．１Ｈｚ，１Ｈ），７．７８（ｄ，Ｊ＝８．６Ｈｚ，１Ｈ），７．８１－７．９１（ｍ，５Ｈ），７．９５（ｄ，Ｊ＝８．６Ｈｚ，１Ｈ），７．９８（ｔ，Ｊ＝７．８Ｈｚ，１Ｈ），８．１６（ｄ，Ｊ＝８．５Ｈｚ，２Ｈ），８．２２（ｄ，Ｊ＝７．５Ｈｚ，１Ｈ），８．４２（ｓ，１Ｈ），８．７５－８．７９（ｍ，２Ｈ）． Synthesis Example-18

Under an argon stream, 3- [4- (2-pyridyl) phenyl] carbazole (3.20 g), 2-bromopyridine (1.90 g), copper (I) oxide (71.5 mg), 1,10-phenanthroline ( 180 mg), 18-crown-6-ether (529 mg) and potassium carbonate (2.76 g) were suspended in xylene (25 mL), and the mixture was heated to reflux for 15 hours. The reaction mixture was allowed to cool, water and methanol were added, and unnecessary substances were 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 purification by column chromatography (developing solvent: chloroform) gave the desired 9- (2-pyridyl) -3- [4- (2-pyridyl) phenyl] carbazole yellow powder (yield) 3.62 g, 91% yield).
¹ H-NMR (CDCl ₃ ): δ 7.26-7.30 (m, 1H), 7.35 (dd, J = 7.4, 4.9 Hz, 1H), 7.38 (t, J = 7 .5 Hz, 1H), 7.50 (t, J = 7.7 Hz, 1H), 7.70 (d, J = 8.1 Hz, 1H), 7.78 (d, 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 (s, 1H), 8.75-8.79 (m, 2H).

　アルゴン気流下、９－（２－ピリジル）－３－［４－（２－ピリジル）フェニル］カルバゾール（１．９９ｇ）、Ｎ－ブロモスクシンイミド（９７９ｍｇ）をＤＭＦ（２０ｍＬ）に懸濁し、６０℃で４時間撹拌した。その後、水を加え析出した固体をろ別し、水、メタノール、ヘキサンで洗浄することで、目的の３－ブロモ－９－（２－ピリジル）－６－［４－（２－ピリジル）フェニル］カルバゾールの褐色粉末（収量２．１２ｇ，収率８９％）を得た。
　^１Ｈ－ＮＭＲ（ＣＤＣｌ_３）：δ７．２６－７．３０（ｍ，１Ｈ），７．３６（ｄｄ，Ｊ＝７．４，４．９Ｈｚ，１Ｈ），７．５６（ｄ，Ｊ＝８．８Ｈｚ，１Ｈ），７．６６（ｄ，Ｊ＝８．１Ｈｚ，１Ｈ），７．７８－７．８３（ｍ，４Ｈ），７．８５（ｄ，Ｊ＝８．５Ｈｚ，２Ｈ），７．９１（ｄ，Ｊ＝８．５Ｈｚ，１Ｈ），７．９８（ｄｄ，Ｊ＝８．０，７．５Ｈｚ，１Ｈ），８．１５（ｄ，Ｊ＝８．５Ｈｚ，２Ｈ），８．３２（ｓ，１Ｈ），８．３５（ｓ，１Ｈ），８．７５－８．７７（ｍ，２Ｈ）． Synthesis Example-19

Under an argon stream, 9- (2-pyridyl) -3- [4- (2-pyridyl) phenyl] carbazole (1.99 g) and N-bromosuccinimide (979 mg) were suspended in DMF (20 mL) at 60 ° C. Stir for 4 hours. Thereafter, water is added and the precipitated solid is filtered off and washed with water, methanol, and hexane to give the desired 3-bromo-9- (2-pyridyl) -6- [4- (2-pyridyl) phenyl]. A carbazole brown powder (yield 2.12 g, yield 89%) was obtained.
¹ H-NMR (CDCl ₃ ): δ 7.26-7.30 (m, 1H), 7.36 (dd, J = 7.4, 4.9 Hz, 1H), 7.56 (d, J = 8 .8 Hz, 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 (d, J = 8.5 Hz, 1H), 7.98 (dd, J = 8.0, 7.5 Hz, 1H), 8.15 (d, J = 8.5 Hz, 2H), 8. 32 (s, 1H), 8.35 (s, 1H), 8.75-8.77 (m, 2H).

　アルゴン気流下、ベンズアミジン塩酸塩（３１３ｍｇ）、１－（４－ブロモフェニル）－３－（１－ナフチル）－２－プロペン－１－オン（１．４２ｇ）を２Ｍ－水酸化カリウムのエタノール溶液（２．０ｍＬ）及びエタノール（４．０ｍＬ）の混合溶液に懸濁し、１７時間還流した。放冷後、水を加え、クロロホルムで抽出した。有機層をカラムクロマトグラフィー（展開溶媒：クロロホルム、ヘキサン）で精製することで、目的の４－（４－ブロモフェニル）－６－（１－ナフチル）－２－フェニルピリミジンの黄色粉末（収量４５９ｍｇ，収率５２％）を得た。
　^１Ｈ－ＮＭＲ（ＣＤＣｌ_３）：δ７．５３－７．６１（ｍ，５Ｈ），７．６５（ｄｄ，Ｊ＝８．２，７．２Ｈｚ，１Ｈ），７．７２（ｄ，Ｊ＝８．６Ｈｚ，２Ｈ），７．８２（ｄ，Ｊ＝７．１Ｈｚ，１Ｈ），７．８９（ｓ，１Ｈ），７．９８－８．００（ｍ，１Ｈ），８．０３（ｄ，Ｊ＝８．２Ｈｚ，１Ｈ），８．２１（ｄ，Ｊ＝８．６Ｈｚ，２Ｈ），８．３６－８．３８（ｍ，１Ｈ），８．６９－８．７２（ｍ，２Ｈ）． Synthesis Example-20

Under an argon stream, benzamidine hydrochloride (313 mg), 1- (4-bromophenyl) -3- (1-naphthyl) -2-propen-1-one (1.42 g) were added to an ethanol solution of 2M potassium hydroxide (1.42 g). 2.0 mL) and ethanol (4.0 mL), and the mixture was refluxed for 17 hours. After allowing to cool, water was added and the mixture was extracted with chloroform. The organic layer was purified by column chromatography (developing solvent: chloroform, hexane) to give the desired 4- (4-bromophenyl) -6- (1-naphthyl) -2-phenylpyrimidine yellow powder (yield 459 mg, Yield 52%).
¹ H-NMR (CDCl ₃ ): δ 7.53-7.61 (m, 5H), 7.65 (dd, J = 8.2, 7.2 Hz, 1H), 7.72 (d, J = 8 .6 Hz, 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, 1H), 8.69-8.72 (m, 2H).

　アルゴン気流下、３－［５－（４，６－ジフェニル－１，３，５－トリアジン－２－イル）－ビフェニル－３－イル］カルバゾール（１．１０ｇ）、ブロモベンゼン（３７７ｍｇ）、酢酸パラジウム（９．０ｍｇ）、トリ（ｔｅｒｔ－ブチルホスフィン）１Ｍ－トルエン溶液）（１２０μＬ）、１８－クラウン－６－エーテル（１０６ｍｇ）、炭酸カリウム（５５３ｍｇ）をキシレン（１０ｍＬ）に懸濁し、１５時間加熱還流した。反応混合物を放冷後、水を加えた。析出した固体を水、メタノール、ヘキサンで洗浄し、目的の９－フェニル－３－［５－（４，６－ジフェニル－１，３，５－トリアジン－２－イル）－ビフェニル－３－イル］カルバゾール（以下、ＥＴＬ－４）の黄色粉末（収量１．２１ｇ，収率９７％）を得た。
　^１Ｈ－ＮＭＲ（ＣＤＣｌ_３）：δ７．３４－７．３８（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＝７．７Ｈｚ，１Ｈ），８．５６（ｓ，１Ｈ），８．８４（ｄ，Ｊ＝８．０Ｈｚ，４Ｈ），９．００（ｓ，１Ｈ），９．１０（ｓ，１Ｈ）． Synthesis Example-21

Under an argon stream, 3- [5- (4,6-diphenyl-1,3,5-triazin-2-yl) -biphenyl-3-yl] carbazole (1.10 g), bromobenzene (377 mg), palladium acetate (9.0 mg), tri (tert-butylphosphine) 1M-toluene solution) (120 μL), 18-crown-6-ether (106 mg), potassium carbonate (553 mg) are suspended in xylene (10 mL) and heated for 15 hours. Refluxed. The reaction mixture was allowed to cool and water was added. The precipitated solid was washed with water, methanol and hexane, and the desired 9-phenyl-3- [5- (4,6-diphenyl-1,3,5-triazin-2-yl) -biphenyl-3-yl] was obtained. A yellow powder (yield 1.21 g, yield 97%) of carbazole (hereinafter referred to as ETL-4) was obtained.
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, 1H), 8.56 (s, 1H), 8.84 (d, J = 8.0 Hz, 4H), 9.00 (s, 1H), 9.10 (s, 1H).

　アルゴン気流下、２－（３－ブロモフェニル）－４，６－ジフェニル－１，３，５－トリアジン（５００ｍｇ）、３－［４－（２－ピリジル）フェニル］カルバゾール（６０６ｍｇ）、酢酸パラジウム（７．０ｍｇ）、１Ｍ－トリ（ｔｅｒｔ－ブチル）ホスフィンのトルエン溶液（９４μＬ）、炭酸カリウム（４３１ｍｇ）、及び１８－クラウン－６－エーテル（８２．５ｍｇ）を、キシレン（７．８ｍＬ）に懸濁し、４時間加熱還流した。反応混合物を放冷後、水を加えた。析出した固体を水、次いでメタノール、その後ヘキサンで洗浄し、目的物である３－［４－（２－ピリジル）フェニル］－９－［３－（４，６－ジフェニルトリアジン－２－イル）フェニル］カルバゾール（Ａ－１）の黄色粉末（収量８６７ｍｇ，収率８８％）を得た。
　^１Ｈ－ＮＭＲ（ＤＭＳＯ－ｄ_６）：δ７．３６－７．３９（ｍ，２Ｈ），７．４８－７．５３（ｍ，２Ｈ），７．５７（ｄ，Ｊ＝８．８Ｈｚ，１Ｈ），７．６４（ｔ，Ｊ＝７．４Ｈｚ，４Ｈ），７．６９－７．７３（ｍ，２Ｈ），７．８８－７．９４（ｍ，２Ｈ），７．９７（ｄ，Ｊ＝８．５Ｈｚ，２Ｈ），８．０１－８．０６（ｍ，３Ｈ），８．２４（ｄ，Ｊ＝８．４Ｈｚ，２Ｈ），８．４５（ｄ，Ｊ＝７．９Ｈｚ，１Ｈ），８．７１（ｍ，６Ｈ），８．９１－８．９３（ｍ，２Ｈ）． Example 1

Under an argon stream, 2- (3-bromophenyl) -4,6-diphenyl-1,3,5-triazine (500 mg), 3- [4- (2-pyridyl) phenyl] carbazole (606 mg), palladium acetate ( 7.0 mg), 1M-tri (tert-butyl) phosphine in toluene (94 μL), potassium carbonate (431 mg), and 18-crown-6-ether (82.5 mg) suspended in xylene (7.8 mL). It became cloudy and heated to reflux for 4 hours. The reaction mixture was allowed to cool and water was added. The precipitated solid was washed with water, then with methanol and then with hexane, and the desired product 3- [4- (2-pyridyl) phenyl] -9- [3- (4,6-diphenyltriazin-2-yl) phenyl A yellow powder of carbazole (A-1) (yield 867 mg, yield 88%) was obtained.
¹ H-NMR (DMSO-d ₆ ): δ 7.36-7.39 (m, 2H), 7.48-7.53 (m, 2H), 7.57 (d, J = 8.8 Hz, 1H ), 7.64 (t, J = 7.4 Hz, 4H), 7.69-7.73 (m, 2H), 7.88-7.94 (m, 2H), 7.97 (d, J = 8.5 Hz, 2H), 8.01-8.06 (m, 3H), 8.24 (d, J = 8.4 Hz, 2H), 8.45 (d, J = 7.9 Hz, 1H) , 8.71 (m, 6H), 8.91-8.93 (m, 2H).

　アルゴン気流下、２－（４－ブロモフェニル）－４，６－ジフェニル－１，３，５－トリアジン（７００ｍｇ）、３－［４－（２－ピリジル）フェニル］カルバゾール（６３５ｍｇ）、酢酸パラジウム（８．１ｍｇ）、１Ｍ－トリ（ｔｅｒｔ－ブチル）ホスフィンのトルエン溶液（１０８μＬ）、炭酸カリウム（４９８ｍｇ）、及び１８－クラウン－６エーテル（１０５ｍｇ）を、キシレン（９．０ｍＬ）に懸濁し、２．５時間加熱還流した。反応混合物を放冷後、水を加えた。析出した固体を水、次いでメタノール、その後ヘキサンで洗浄し、目的物である３－［４－（２－ピリジル）フェニル］－９－［４－（４，６－ジフェニルトリアジン－２－イル）フェニル］カルバゾール（Ａ－２）の黄色粉末（収量１１０８ｍｇ，収率９８％）を得た。
　^１Ｈ－ＮＭＲ（ＣＤＣｌ_３）：δ７．２６－７．３０（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＝８．４Ｈｚ，２Ｈ），８．２７（ｄ，Ｊ＝７．６Ｈｚ，１Ｈ），８．４８（ｓ，１Ｈ），８．７６（ｄ，Ｊ＝４．７Ｈｚ，１Ｈ），８．８６（ｄ，Ｊ＝６．４Ｈｚ，４Ｈ），９．０８（ｄ，Ｊ＝８．６Ｈｚ，２Ｈ）． Example-2

Under an argon stream, 2- (4-bromophenyl) -4,6-diphenyl-1,3,5-triazine (700 mg), 3- [4- (2-pyridyl) phenyl] carbazole (635 mg), palladium acetate ( 8.1 mg), 1M-tri (tert-butyl) phosphine in toluene (108 μL), potassium carbonate (498 mg), and 18-crown-6 ether (105 mg) were suspended in xylene (9.0 mL). Heated to reflux for 5 hours. The reaction mixture was allowed to cool and water was added. The precipitated solid was washed with water, then with methanol and then with hexane, and the desired product 3- [4- (2-pyridyl) phenyl] -9- [4- (4,6-diphenyltriazin-2-yl) phenyl A yellow powder (1108 mg, 98% yield) of carbazole (A-2) was obtained.
¹ H-NMR (CDCl ₃ ): δ 7.26-7.30 (m, 1H), 7.40 (t, J = 7.8 Hz, 1H), 7.51 (t, J = 7.7 Hz, 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, 1H), 8.48 (s, 1H), 8.76 (d, J = 4.7 Hz, 1H), 8.86 (d , J = 6.4 Hz, 4H), 9.08 (d, J = 8.6 Hz, 2H).

　アルゴン気流下、２－（５－クロロビフェニル－３－イル）－４，６－ジフェニル－１，３，５－トリアジン（５００ｍｇ）、３－［４－（２－ピリジル）フェニル］カルバゾール（４２０ｍｇ）、酢酸パラジウム（５．３ｍｇ）、１Ｍ－トリ（ｔｅｒｔ－ブチル）ホスフィンのトルエン溶液（７１μＬ）、炭酸カリウム（３２９ｍｇ）、及び１８－クラウン－６エーテル（６９ｍｇ）を、キシレン（６ｍＬ）に懸濁し、２１．５時間加熱還流した。反応混合物を放冷後、水を加えた。析出した固体を水、次いでメタノール、その後ヘキサンで洗浄し、目的物である３－［４－（２－ピリジル）フェニル］－９－［５－（４，６－ジフェニルトリアジン－２－イル）ビフェニル－３－イル］カルバゾール（Ａ－３）の黄色粉末（収量８００ｍｇ，収率９５％）を得た。
　^１Ｈ－ＮＭＲ（ＣＤＣｌ_３）：δ７．２８（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＝８．４Ｈｚ，２Ｈ），８．０８（ｓ，１Ｈ），８．１７（ｄ，Ｊ＝８．３Ｈｚ，２Ｈ），８．３０（ｄ，Ｊ＝７．７Ｈｚ，１Ｈ），８．５１（ｓ，１Ｈ），８．７８（ｄ，Ｊ＝４．７Ｈｚ，１Ｈ），８．８１（ｄ，Ｊ＝６．７Ｈｚ，４Ｈ），９．０２（ｓ，１Ｈ），９．１４（ｓ，１Ｈ）． Example-3

Under an argon stream, 2- (5-chlorobiphenyl-3-yl) -4,6-diphenyl-1,3,5-triazine (500 mg), 3- [4- (2-pyridyl) phenyl] carbazole (420 mg) , Palladium acetate (5.3 mg), 1M-tri (tert-butyl) phosphine in toluene (71 μL), potassium carbonate (329 mg), and 18-crown-6 ether (69 mg) were suspended in xylene (6 mL). The mixture was heated to reflux for 21.5 hours. The reaction mixture was allowed to cool and water was added. The precipitated solid was washed with water, then with methanol and then with hexane, and the target product 3- [4- (2-pyridyl) phenyl] -9- [5- (4,6-diphenyltriazin-2-yl) biphenyl was obtained. A yellow powder (yield 800 mg, yield 95%) of -3-yl] carbazole (A-3) was obtained.
¹ H-NMR (CDCl ₃ ): δ 7.28 (t, J = 6.2 Hz, 1H), 7.41 (t, J = 7.3 Hz, 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 (s, 1H) ), 8.17 (d, J = 8.3 Hz, 2H), 8.30 (d, J = 7.7 Hz, 1H), 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).

　アルゴン気流下、２－（４’－クロロビフェニル－４－イル）－４，６－ジフェニル－１，３，５－トリアジン（７７０ｍｇ）、３－［４－（２－ピリジル）フェニル］カルバゾール（６４６ｍｇ）、酢酸パラジウム（８．２ｍｇ）、１Ｍ－トリ（ｔｅｒｔ－ブチル）ホスフィンのトルエン溶液（１１０μＬ）、炭酸カリウム（５０７ｍｇ）、及び１８－クラウン－６エーテル（９７ｍｇ）を、キシレン（９ｍＬ）に懸濁し、４時間加熱還流した。反応混合物を放冷後、水を加えた。析出した固体を水、次いでメタノール、その後ヘキサンで洗浄し、目的物である３－［４－（２－ピリジル）フェニル］－９－［４’－（４，６－ジフェニルトリアジン－２－イル）ビフェニル－４－イル］カルバゾール（Ａ－４）の黄色粉末（収量１１４０ｍｇ，収率８８％）を得た。
　^１Ｈ－ＮＭＲ（ＣＤＣｌ_３）：δ７．２６－７．２９（ｍ，１Ｈ），７．３８（ｔ，Ｊ＝７．４Ｈｚ，１Ｈ），７．５１（ｔ，Ｊ＝７．１Ｈｚ，１Ｈ），７．５７（ｄ，Ｊ＝８．２Ｈｚ，１Ｈ），７．６１－７．６９（ｍ，７Ｈ），７．７６－７．８６（ｍ，５Ｈ），７．８９（ｄ，Ｊ＝８．４Ｈｚ，２Ｈ），７．９５（ｄ，Ｊ＝８．４Ｈｚ，２Ｈ），８．００（ｄ，Ｊ＝８．４Ｈｚ，２Ｈ），８．１７（ｄ，Ｊ＝８．４Ｈｚ，２Ｈ），８．２７（ｄ，Ｊ＝７．７Ｈｚ，１Ｈ），８．４８（ｓ，１Ｈ），８．７７（ｄ，Ｊ＝４．７Ｈｚ，１Ｈ），８．８６（ｄ，Ｊ＝７．７Ｈｚ，４Ｈ），８．９５（ｄ，Ｊ＝８．４Ｈｚ，２Ｈ）． Example-4

Under an argon stream, 2- (4′-chlorobiphenyl-4-yl) -4,6-diphenyl-1,3,5-triazine (770 mg), 3- [4- (2-pyridyl) phenyl] carbazole (646 mg) ), Palladium acetate (8.2 mg), 1M-tri (tert-butyl) phosphine in toluene (110 μL), potassium carbonate (507 mg), and 18-crown-6 ether (97 mg) suspended in xylene (9 mL). It became cloudy and heated to reflux for 4 hours. The reaction mixture was allowed to cool and water was added. The precipitated solid was washed with water, then with methanol and then with hexane, and the target product 3- [4- (2-pyridyl) phenyl] -9- [4 ′-(4,6-diphenyltriazin-2-yl) A yellow powder (yield 1140 mg, yield 88%) of biphenyl-4-yl] carbazole (A-4) was obtained.
¹ H-NMR (CDCl ₃ ): δ 7.26-7.29 (m, 1H), 7.38 (t, J = 7.4 Hz, 1H), 7.51 (t, J = 7.1 Hz, 1H) ), 7.57 (d, J = 8.2 Hz, 1H), 7.61-7.69 (m, 7H), 7.76-7.86 (m, 5H), 7.89 (d, J = 8.4 Hz, 2H), 7.95 (d, J = 8.4 Hz, 2H), 8.00 (d, J = 8.4 Hz, 2H), 8.17 (d, J = 8.4 Hz, 2H), 8.27 (d, J = 7.7 Hz, 1H), 8.48 (s, 1H), 8.77 (d, J = 4.7 Hz, 1H), 8.86 (d, J = 7.7 Hz, 4H), 8.95 (d, J = 8.4 Hz, 2H).

　アルゴン気流下、合成例－１で合成した２－クロロ－９－［４－（４，６－ジフェニルトリアジン－２－イル）フェニル］カルバゾール（７１５ｍｇ）、４－（２－ピリジル）フェニルボロン酸（３３６ｍｇ）、酢酸パラジウム（６．３ｍｇ）及び２－ジシクロヘキシルホスフィノ－２’，４’，６’－トリイソプロピルビフェニル（４０ｍｇ）を、３Ｍ－リン酸カリウム水溶液（１．３ｍＬ）及び１，４－ジオキサン（７ｍＬ）の混合溶液に懸濁し、１６時間加熱還流した。反応混合物を放冷後、水を加えた。析出した固体をろ別し、水、次いでメタノール、その後ヘキサンで洗浄し、目的物である２－［４－（２－ピリジル）フェニル］－９－［４－（４，６－ジフェニルトリアジン－２－イル）フェニル］カルバゾール（Ａ－５）の白色粉末（収量８４２ｍｇ，収率９６％）を得た。
　^１Ｈ－ＮＭＲ（ＣＤＣｌ_３）：δ７．２４－７．２７（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＝８．６Ｈｚ，２Ｈ），８．１２（ｄ，Ｊ＝８．５Ｈｚ，２Ｈ），８．２３（ｄ，Ｊ＝７．６Ｈｚ，１Ｈ），８．２７（ｄ，Ｊ＝８．１Ｈｚ，１Ｈ），８．７４（ｄ，Ｊ＝４．６Ｈｚ，１Ｈ），８．８６（ｄ，Ｊ＝８．０Ｈｚ，４Ｈ），９．０９（ｄ，Ｊ＝８．６Ｈｚ，２Ｈ）． Example-5

Under a stream of argon, 2-chloro-9- [4- (4,6-diphenyltriazin-2-yl) phenyl] carbazole (715 mg), 4- (2-pyridyl) phenylboronic acid synthesized in Synthesis Example 1 ( 336 mg), palladium acetate (6.3 mg) and 2-dicyclohexylphosphino-2 ′, 4 ′, 6′-triisopropylbiphenyl (40 mg), 3M-potassium phosphate aqueous solution (1.3 mL) and 1,4- It was suspended in a mixed solution of dioxane (7 mL) and heated to reflux for 16 hours. The reaction mixture was allowed to cool and water was added. The precipitated solid was filtered off, washed with water, then methanol, and then with hexane, and the target product 2- [4- (2-pyridyl) phenyl] -9- [4- (4,6-diphenyltriazine-2) A white powder (yield 842 mg, yield 96%) of -yl) phenyl] carbazole (A-5) was obtained.
¹ H-NMR (CDCl ₃ ): δ 7.24-7.27 (m, 1H), 7.38 (t, J = 7.4 Hz, 1H), 7.50 (t, J = 7.4 Hz, 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 (d, J = 7.6 Hz, 1H), 8.27 (d, 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).

　アルゴン気流下、４－クロロ－９－［４－（４，６－ジフェニルトリアジン－２－イル）フェニル］カルバゾール（６７５ｍｇ）、４－（２－ピリジル）フェニルボロン酸（３１７ｍｇ）、酢酸パラジウム（６．０ｍｇ）及び２－ジシクロヘキシルホスフィノ－２’，４’，６’－トリイソプロピルビフェニル（３８ｍｇ）を、３Ｍ－リン酸カリウム水溶液（１．１ｍＬ）及び１，４－ジオキサン（１３ｍＬ）の混合溶液に懸濁し、１８時間加熱還流した。反応混合物を放冷後、水を加えた。析出した固体をろ別し、水、次いでメタノール、その後ヘキサンで洗浄し、目的物である４－［４－（２－ピリジル）フェニル］－９－［４－（４，６－ジフェニルトリアジン－２－イル）フェニル］カルバゾール（Ａ－６）の白色粉末（収量８３０ｍｇ，収率１００％）を得た。
　^１Ｈ－ＮＭＲ（ＣＤＣｌ_３）：δ７．１０（ｔ，Ｊ＝７．６Ｈｚ，１Ｈ），７．２８（ｄ，Ｊ＝７．５Ｈｚ，１Ｈ），７．３１－７．３４（ｍ，１Ｈ），７．４２（ｄ，Ｊ＝７．７Ｈｚ，１Ｈ），７．５１－７．７１（ｍ，１０Ｈ），７．８４－７．８９（ｍ，５Ｈ），７．９３（ｄ，Ｊ＝８．０Ｈｚ，１Ｈ），８．２５（ｄ，Ｊ＝８．３Ｈｚ，２Ｈ），８．８１（ｄ，Ｊ＝４．４Ｈｚ，１Ｈ），８．８７（ｄ，Ｊ＝８．０Ｈｚ，４Ｈ），９．０８（ｄ，Ｊ＝８．６Ｈｚ，２Ｈ）． Example-6

Under a stream of argon, 4-chloro-9- [4- (4,6-diphenyltriazin-2-yl) phenyl] carbazole (675 mg), 4- (2-pyridyl) phenylboronic acid (317 mg), palladium acetate (6 0.0 mg) and 2-dicyclohexylphosphino-2 ′, 4 ′, 6′-triisopropylbiphenyl (38 mg) in a mixed solution of 3M aqueous potassium phosphate (1.1 mL) and 1,4-dioxane (13 mL) And heated to reflux for 18 hours. The reaction mixture was allowed to cool and water was added. The precipitated solid was filtered off, washed with water, then methanol, and then with hexane, and the target 4- [4- (2-pyridyl) phenyl] -9- [4- (4,6-diphenyltriazine-2) A white powder (yield 830 mg, yield 100%) of -yl) phenyl] carbazole (A-6) was obtained.
¹ H-NMR (CDCl ₃ ): δ 7.10 (t, J = 7.6 Hz, 1H), 7.28 (d, J = 7.5 Hz, 1H), 7.31-7.34 (m, 1H ), 7.42 (d, J = 7.7 Hz, 1H), 7.51-7.71 (m, 10H), 7.84-7.89 (m, 5H), 7.93 (d, J = 8.0 Hz, 1H), 8.25 (d, J = 8.3 Hz, 2H), 8.81 (d, J = 4.4 Hz, 1H), 8.87 (d, J = 8.0 Hz, 4H), 9.08 (d, J = 8.6 Hz, 2H).

　アルゴン気流下、２－（４－ブロモフェニル）－４，６－ジ（ビフェニル－４－イル）－１，３，５－トリアジン（５００ｍｇ）、３－［４－（２－ピリジル）フェニル］カルバゾール（３２６ｍｇ）、酢酸パラジウム（４．２ｍｇ）、１Ｍ－トリ（ｔｅｒｔ－ブチル）ホスフィンのトルエン溶液（５６μＬ）、炭酸カリウム（２５６ｍｇ）、及び１８－クラウン－６エーテル（４９ｍｇ）を、キシレン（４．６ｍＬ）に懸濁し、３時間加熱還流した。反応混合物を放冷後、水を加えた。析出した固体を水、次いでメタノール、その後ヘキサンで洗浄し、目的物である３－［４－（２－ピリジル）フェニル］－９－［４－（４，６－ジ（ビフェニル－４－イル）フェニルトリアジン－２－イル）フェニル］カルバゾール（Ａ－７）の黄色粉末（収量６７３ｍｇ，収率９３％）を得た。
　^１Ｈ－ＮＭＲ（ＣＤＣｌ_３）：δ７．２８（ｔ，Ｊ＝５．９Ｈｚ，１Ｈ），７．４０（ｔ，Ｊ＝７．６Ｈｚ，１Ｈ），７．４６（ｔ，Ｊ＝７．４Ｈｚ，２Ｈ），７．５１（ｄ，Ｊ＝８．４Ｈｚ，１Ｈ），７．５５（ｔ，Ｊ＝７．５Ｈｚ，４Ｈ），７．６３（ｄ，Ｊ＝８．２Ｈｚ，１Ｈ），７．６８（ｄ，Ｊ＝８．５Ｈｚ，１Ｈ），７．７７（ｄ，Ｊ＝７．２Ｈｚ，４Ｈ），７．７９－７．９１（ｍ，１１Ｈ），８．１７（ｄ，Ｊ＝８．４Ｈｚ，２Ｈ），８．２８（ｄ，Ｊ＝７．７Ｈｚ，１Ｈ），８．４８（ｓ，１Ｈ），８．７７（ｄ，Ｊ＝４．６Ｈｚ，１Ｈ），８．９４（ｄ，Ｊ＝８．４Ｈｚ，４Ｈ），９．１０（ｄ，Ｊ＝８．５Ｈｚ，２Ｈ）． Example-7

Under an argon stream, 2- (4-bromophenyl) -4,6-di (biphenyl-4-yl) -1,3,5-triazine (500 mg), 3- [4- (2-pyridyl) phenyl] carbazole (326 mg), palladium acetate (4.2 mg), 1M-tri (tert-butyl) phosphine in toluene (56 μL), potassium carbonate (256 mg), and 18-crown-6 ether (49 mg) were added to xylene (4. 6 mL) and heated to reflux for 3 hours. The reaction mixture was allowed to cool and water was added. The precipitated solid was washed with water, then with methanol and then with hexane, and the desired product 3- [4- (2-pyridyl) phenyl] -9- [4- (4,6-di (biphenyl-4-yl) A yellow powder (yield 673 mg, 93%) of phenyltriazin-2-yl) phenyl] carbazole (A-7) was obtained.
¹ H-NMR (CDCl ₃ ): δ 7.28 (t, J = 5.9 Hz, 1H), 7.40 (t, J = 7.6 Hz, 1H), 7.46 (t, J = 7.4 Hz) , 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 = 8.5 Hz, 1H), 7.77 (d, J = 7.2 Hz, 4H), 7.79-7.91 (m, 11H), 8.17 (d, J = 8.4 Hz, 2H), 8.28 (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).

　アルゴン気流下、２－（３，５－ジブロモフェニル）－４，６－ジ（４－メチルフェニル）－１，３，５－トリアジン（１０００ｍｇ）、４－メチル－１－ナフタレンボロン酸（４８６ｍｇ）、及びテトラキス（トリフェニルホスフィン）パラジウム（４７ｍｇ）を、３Ｍ－リン酸カリウム水溶液（１ｍＬ）、ＴＨＦ（８ｍＬ）及びエタノール（２ｍＬ）の混合溶媒に懸濁し、７２時間４０℃で撹拌した。反応混合物を放冷後、析出した固体をろ過した。得られた固体を水、次いでメタノール、その後ヘキサンで洗浄し、黄白色固体を９７８ｍｇ得た。
　得られた黄白色固体（９５０ｍｇ）、３－［４－（２－ピリジル）フェニル］カルバゾール（６０２ｍｇ）、酢酸パラジウム（７．７ｍｇ）、１Ｍ－トリ（ｔｅｒｔ－ブチル）ホスフィンのトルエン溶液（１０３μＬ）、炭酸カリウム（４７３ｍｇ）、及び１８－クラウン－６－エーテル（９０ｍｇ）をキシレン（８．６ｍＬ）に懸濁し、４．５時間加熱還流した。反応混合物を放冷後、水を加え、析出した固体濾別した。次いで、濾液をクロロホルムで抽出し、有機層をシリカゲルクロマトグラフィー（展開溶媒；クロロホルム）で精製し、目的物である３－［４－（２－ピリジル）フェニル］－９－［３－（４，６－ジ（４－メチルフェニル）トリアジン－２－イル）－５－（４－メチルナフタレン－１－イル）］フェニルカルバゾール（Ａ－８）の黄色粉末（収量６４０ｍｇ，収率４０％）を得た。
　^１Ｈ－ＮＭＲ（ＣＤＣｌ_３）：δ２．５０（ｓ，６Ｈ），２．８５（ｓ，３Ｈ），７．２８（ｔ，Ｊ＝６．０Ｈｚ，１Ｈ），７．３５（ｄ，Ｊ＝８．０Ｈｚ，４Ｈ），７．４１（ｔ，Ｊ＝７．５Ｈｚ，１Ｈ），７．５２（ｄ，Ｊ＝７．２Ｈｚ，１Ｈ），７．５３（ｔ，Ｊ＝７．７Ｈｚ，１Ｈ），７．５１－７．６８（ｍ，３Ｈ），７．７０（ｄ，Ｊ＝８．２Ｈｚ，１Ｈ），７．７５（ｄ，Ｊ＝８．５Ｈｚ，１Ｈ），７．７７－７．８５（ｍ，３Ｈ），７．９１（ｄ，Ｊ＝８．５Ｈｚ，２Ｈ），７．９９（ｓ，１Ｈ），８．１８（ｄ，Ｊ＝８．６Ｈｚ，４Ｈ），８．３１（ｄ，Ｊ＝７．６Ｈｚ，１Ｈ），８．５２（ｓ，１Ｈ），８．６８（ｄ，Ｊ＝８．２Ｈｚ，４Ｈ），８．７９（ｄ，Ｊ＝４．８Ｈｚ，１Ｈ），９．０５（ｓ，１Ｈ），９．１３（ｓ，１Ｈ）． Example-8

Under an argon stream, 2- (3,5-dibromophenyl) -4,6-di (4-methylphenyl) -1,3,5-triazine (1000 mg), 4-methyl-1-naphthaleneboronic acid (486 mg) And tetrakis (triphenylphosphine) palladium (47 mg) were suspended in a mixed solvent of 3M aqueous potassium phosphate (1 mL), THF (8 mL) and ethanol (2 mL), and the mixture was stirred at 40 ° C. for 72 hours. The reaction mixture was allowed to cool, and the precipitated solid was filtered. The obtained solid was washed with water, then with methanol, and then with hexane to obtain 978 mg of a pale yellow solid.
The obtained yellowish white solid (950 mg), 3- [4- (2-pyridyl) phenyl] carbazole (602 mg), palladium acetate (7.7 mg), toluene solution of 1M-tri (tert-butyl) phosphine (103 μL) , Potassium carbonate (473 mg) and 18-crown-6-ether (90 mg) were suspended in xylene (8.6 mL) and heated to reflux for 4.5 hours. The reaction mixture was allowed to cool, 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), and the desired product 3- [4- (2-pyridyl) phenyl] -9- [3- (4, A yellow powder of 6-di (4-methylphenyl) triazin-2-yl) -5- (4-methylnaphthalen-1-yl)] phenylcarbazole (A-8) (yield 640 mg, yield 40%) was obtained. It was.
¹ H-NMR (CDCl ₃ ): δ 2.50 (s, 6H), 2.85 (s, 3H), 7.28 (t, J = 6.0 Hz, 1H), 7.35 (d, J = 8.0 Hz, 4H), 7.41 (t, J = 7.5 Hz, 1H), 7.52 (d, J = 7.2 Hz, 1H), 7.53 (t, J = 7.7 Hz, 1H) ), 7.51-7.68 (m, 3H), 7.70 (d, J = 8.2 Hz, 1H), 7.75 (d, J = 8.5 Hz, 1H), 7.77-7 .85 (m, 3H), 7.91 (d, J = 8.5 Hz, 2H), 7.99 (s, 1H), 8.18 (d, J = 8.6 Hz, 4H), 8.31 (D, J = 7.6 Hz, 1H), 8.52 (s, 1H), 8.68 (d, J = 8.2 Hz, 4H), 8.79 (d, J = 4.8 Hz, 1H) 9.05 (s, 1H), 9. 3 (s, 1H).

　アルゴン気流下、合成例－２で合成した３－［４－（４，６－ジフェニルトリアジン－２－イル）フェニル］カルバゾール（６５０ｍｇ）、３，５－ジ（２－ピリジル）ブロモベンゼン（４６９ｍｇ）、酢酸パラジウム（６．２ｍｇ）、１Ｍ－トリ（ｔｅｒｔ－ブチル）ホスフィンのトルエン溶液（８２μＬ）、炭酸カリウム（３７９ｍｇ）、及び１８－クラウン－６－エーテル（７２ｍｇ）を、キシレン（６．９ｍＬ）に懸濁し、５．５時間加熱還流した。反応混合物を放冷後、水を加えた。次いで、析出した固体をろ過し、水、次いでメタノール、その後ヘキサンで洗浄して、目的物である３－［４－（４，６－ジ（ビフェニル－４－イル）フェニルトリアジン－２－イル）フェニル］－９－［３，５－ジ（２－ピリジル）フェニル］カルバゾール（Ａ－９）の褐色固体（収量８８８ｍｇ，収率９２％）を得た。
　^１Ｈ－ＮＭＲ（ＣＤＣｌ_３）：δ７．３２－７．３６（ｍ，２Ｈ），７．３８（ｔ，Ｊ＝７．４Ｈｚ，１Ｈ），７．５０（ｔ，Ｊ＝７．６Ｈｚ，１Ｈ），７．５８（ｄ，Ｊ＝８．２Ｈｚ，１Ｈ），７．６０－７．６８（ｍ，７Ｈ），７．８１－７．８７（ｍ，３Ｈ），７．９５（ｄ，Ｊ＝８．０Ｈｚ，２Ｈ），７．９８（ｄ，Ｊ＝８．６Ｈｚ，２Ｈ），８．２９（ｄ，Ｊ＝７．５Ｈｚ，１Ｈ），８．３６（ｓ，２Ｈ），８．５３（ｓ，１Ｈ），８．７８（ｄ，Ｊ＝４．８Ｈｚ，２Ｈ），８．８４（ｓ，１Ｈ），８．８５（ｄ，Ｊ＝７．８Ｈｚ，４Ｈ），８．９１（ｄ，Ｊ＝８．５Ｈｚ，２Ｈ）． Example-9

3- [4- (4,6-diphenyltriazin-2-yl) phenyl] carbazole (650 mg), 3,5-di (2-pyridyl) bromobenzene (469 mg) synthesized in Synthesis Example 2 under an argon stream , Palladium acetate (6.2 mg), 1M-tri (tert-butyl) phosphine in toluene (82 μL), potassium carbonate (379 mg), and 18-crown-6-ether (72 mg) in xylene (6.9 mL) And heated to reflux for 5.5 hours. The reaction mixture was allowed to cool and water was added. Next, the precipitated solid is filtered, washed with water, then methanol, and then with hexane to give the desired product 3- [4- (4,6-di (biphenyl-4-yl) phenyltriazin-2-yl). A brown solid (yield 888 mg, yield 92%) of phenyl] -9- [3,5-di (2-pyridyl) phenyl] carbazole (A-9) was obtained.
¹ H-NMR (CDCl ₃ ): δ 7.32-7.36 (m, 2H), 7.38 (t, J = 7.4 Hz, 1H), 7.50 (t, J = 7.6 Hz, 1H) ), 7.58 (d, J = 8.2 Hz, 1H), 7.60-7.68 (m, 7H), 7.81-7.87 (m, 3H), 7.95 (d, J = 8.0 Hz, 2H), 7.98 (d, J = 8.6 Hz, 2H), 8.29 (d, J = 7.5 Hz, 1H), 8.36 (s, 2H), 8.53 (S, 1H), 8.78 (d, J = 4.8 Hz, 2H), 8.84 (s, 1H), 8.85 (d, J = 7.8 Hz, 4H), 8.91 (d , J = 8.5 Hz, 2H).

　アルゴン気流下、２－（４－ブロモフェニル）－４，６－ジフェニル－１，３，５－トリアジン（６６０ｍｇ）、３－（２－ピリジル）カルバゾール（４５７ｍｇ）、酢酸パラジウム（７．６ｍｇ）、１Ｍ－トリ（ｔｅｒｔ－ブチル）ホスフィンのトルエン溶液（１０２μＬ）、炭酸カリウム（４７０ｍｇ）、及び１８－クラウン－６－エーテル（９０ｍｇ）を、キシレン（８．５ｍＬ）に懸濁し、２時間加熱還流した。反応混合物を放冷後、クロロホルムで抽出した。有機層を減圧留去した後、メタノールを加えて、固体を析出させた。析出した固体をはろ過し、メタノール、次いでヘキサンで洗浄して、目的物である３－（２－ピリジル）－９－［４－（４，６－ジフェニルトリアジン－２－イル）フェニル］カルバゾール（Ａ－１０）の黄色粉末（収量９１７ｍｇ，収率９８％）を得た。
　^１Ｈ－ＮＭＲ（ＣＤＣｌ_３）：δ７．２６（ｄｄ，Ｊ＝７．４，４．８Ｈｚ，１Ｈ），７．３９（ｔ，Ｊ＝７．４Ｈｚ，１Ｈ），７．５０（ｔ，Ｊ＝７．７Ｈｚ，１Ｈ），７．６０－７．６９（ｍ，８Ｈ），７．８１（ｔ，Ｊ＝７．７Ｈｚ，１Ｈ），７．８７（ｄ，Ｊ＝８．７Ｈｚ，２Ｈ），７．９０（ｄ，Ｊ＝８．０Ｈｚ，１Ｈ），８．１３（ｄ，Ｊ＝８．７Ｈｚ，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-10

Under an argon stream, 2- (4-bromophenyl) -4,6-diphenyl-1,3,5-triazine (660 mg), 3- (2-pyridyl) carbazole (457 mg), palladium acetate (7.6 mg), 1M-tri (tert-butyl) phosphine in toluene (102 μL), potassium carbonate (470 mg), and 18-crown-6-ether (90 mg) were suspended in xylene (8.5 mL) and heated to reflux for 2 hours. . The reaction mixture was allowed to cool and extracted with chloroform. After the organic layer was distilled off under reduced pressure, methanol was added to precipitate a solid. The precipitated solid was filtered, washed with methanol and then with hexane, and the target product 3- (2-pyridyl) -9- [4- (4,6-diphenyltriazin-2-yl) phenyl] carbazole ( A-10) yellow powder (yield 917 mg, yield 98%) was obtained.
¹ H-NMR (CDCl ₃ ): δ 7.26 (dd, J = 7.4, 4.8 Hz, 1H), 7.39 (t, J = 7.4 Hz, 1H), 7.50 (t, J = 7.7 Hz, 1H), 7.60-7.69 (m, 8H), 7.81 (t, J = 7.7 Hz, 1H), 7.87 (d, 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 = 7.6 Hz, 1H), 8.77 ( d, J = 4.8 Hz, 1H), 8.84-8.696 (m, 5H), 9.07 (d, J = 8.6 Hz, 2H).

　アルゴン気流下、３－［３－（４，６－ジフェニル－１，３，５－トリアジン－２－イル）フェニル］カルバゾール（１．１９ｇ）、２－ブロモピリジン（４７４ｍｇ）、酸化銅（３６ｍｇ）、１，１０－フェナントロリン（４５ｍｇ）、１８－クラウン－６－エーテル（１３２ｍｇ）、及び炭酸カリウム（８６４ｍｇ）を、キシレン（１２．５ｍＬ）に懸濁し、１５時間加熱還流した。反応混合物を放冷後、水を加えた。析出した固体はろ過し、水、次いでメタノール、その後ヘキサンで洗浄して、目的物である９－（２－ピリジル）－３－［３－（４，６－ジフェニル－１，３，５－トリアジン－２－イル）フェニル］カルバゾール（Ａ－１１）の黄色粉末（収量１．２９ｇ，収率９３％）を得た。
　^１Ｈ－ＮＭＲ（ＣＤＣｌ_３）：δ７．３２－７．３７（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＝８．０Ｈｚ，１Ｈ），７．８７（ｄ，Ｊ＝８．０Ｈｚ，１Ｈ），７．９４－７．９９（ｍ，３Ｈ），８．２１（ｄ，Ｊ＝７．６Ｈｚ，１Ｈ），８．４４（ｓ，１Ｈ），８．７５－８．８１（ｍ，２Ｈ），８．８０（ｄ，Ｊ＝７．８Ｈｚ，４Ｈ），９．０８（ｓ，１Ｈ）． Example-11

Under an argon stream, 3- [3- (4,6-diphenyl-1,3,5-triazin-2-yl) phenyl] carbazole (1.19 g), 2-bromopyridine (474 mg), copper oxide (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 heated to reflux for 15 hours. The reaction mixture was allowed to cool and water was added. The precipitated solid was filtered, washed with water, then methanol, and then with hexane to give the desired 9- (2-pyridyl) -3- [3- (4,6-diphenyl-1,3,5-triazine A yellow powder of (-2-yl) phenyl] carbazole (A-11) was obtained (yield 1.29 g, yield 93%).
¹ H-NMR (CDCl ₃ ): δ 7.32-7.37 (m, 2H), 7.48 (t, J = 7.6 Hz, 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), 8.44 (s, 1H), 8.75-8.81 (m, 2H), 8.80 (d, J = 7.8 Hz, 4H), 9.08 (s, 1H).

　アルゴン気流下、２－［５－（４，４，５，５－テトラメチル－１，３，２－ジオキサボロラン－２－イル）ビフェニル］－４，６－ジフェニル－１，３，５－トリアジン（１．０８ｇ）、３－ブロモ－９－（２－ピリジル）カルバゾール（５７０ｍｇ）、及びテトラキス（トリフェニルホスフィン）パラジウム（１０２ｍｇ）を、１，４－ジオキサン（９．０ｍＬ）に懸濁し、さらに、３Ｍ－リン酸カリウム水溶液（１．８ｍＬ）を添加し、２７時間加熱還流した。反応混合物を放冷後、水を加えた。析出した固体はろ過し、水、次いでメタノール、その後ヘキサンで洗浄して、目的物である９－（２－ピリジル）－３－［５－（４，６－ジフェニル－１，３，５－トリアジン－２－イル）ビフェニル－３－イル］カルバゾール（Ａ－１２）の灰色粉末（収量８００ｍｇ，収率６０％）を得た。
　^１Ｈ－ＮＭＲ（ＣＤＣｌ_３）：δ７．３２－７．３５（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＝８．４，２Ｈ），７．８７（ｄ，Ｊ＝８．４，２Ｈ），７．９６（ｔ，Ｊ＝７．８，１Ｈ），８．００（ｄ，Ｊ＝８．４Ｈｚ，１Ｈ），８．１６（ｓ，１Ｈ），８．２２（ｄ，Ｊ＝７．６Ｈｚ，１Ｈ），８．４９（ｓ，１Ｈ），８．７６（ｄ，Ｊ＝６．０Ｈｚ，１Ｈ），８．８１（ｄ，Ｊ＝８．０Ｈｚ，４Ｈ），８．９７（ｓ，１Ｈ），９．０７（ｓ，１Ｈ）． Example-12

Under an argon stream, 2- [5- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) biphenyl] -4,6-diphenyl-1,3,5-triazine ( 1.08 g), 3-bromo-9- (2-pyridyl) carbazole (570 mg), and tetrakis (triphenylphosphine) palladium (102 mg) were suspended in 1,4-dioxane (9.0 mL), and 3M aqueous potassium phosphate solution (1.8 mL) was added, and the mixture was heated to reflux for 27 hours. The reaction mixture was allowed to cool and water was added. The precipitated solid was filtered, washed with water, then with methanol and then with hexane, and the desired product 9- (2-pyridyl) -3- [5- (4,6-diphenyl-1,3,5-triazine) A gray powder (yield 800 mg, yield 60%) of -2-yl) biphenyl-3-yl] carbazole (A-12) was obtained.
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 = 8.0 Hz, 1H), 7.84 (d, J = 8.4, 2H), 7.87 (d, J = 8.4, 2H), 7.96 (t, J = 7.8, 1H), 8.00 (d, J = 8.4 Hz, 1H), 8.16 (s, 1H), 8.22 (d, J = 7.6 Hz, 1H), 8.49. (S, 1H), 8.76 (d, J = 6.0 Hz, 1H), 8.81 (d, J = 8.0 Hz, 4H), 8.97 (s, 1H), 9.07 (s , 1H).

　アルゴン気流下、３－［１－クロロ－５－（４，６－ジフェニル－１，３，５－トリアジン－２－イル）－３－イル］－９－（２－ピリジル）カルバゾール（１．４７ｇ）、４－（２－ピリジル）フェニルボロン酸（５９７ｍｇ）、酢酸パラジウム（１１ｍｇ）、及び２－ジシクロヘキシルホスフィノ－２’，４’，６’－トリイソプロピルビフェニル（７２ｍｇ）を、キシレン（２２．５ｍＬ）及び１－ブタノール（２．５ｍＬ）の混合溶媒に懸濁し、さらに３Ｍ－炭酸カリウム水溶液（２．５ｍＬ）を添加し、２４時間加熱還流した。反応混合物を放冷後、水を加えた。析出した固体はろ過し、水、次いでメタノール、その後ヘキサンで洗浄して、目的物である９－（２－ピリジル）－３－［５－（４，６－ジフェニル－１，３，５－トリアジン－２－イル）－４’－（２－ピリジル）ビフェニル－３－イル］カルバゾール（Ａ－１３）の灰色粉末（収量１．５０ｇ，収率６０％）を得た。
　^１Ｈ－ＮＭＲ（ＣＤＣｌ_３）：δ７．２６－７．２８（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＝８．０Ｈｚ，１Ｈ），７．７７－７．８５（ｍ，２Ｈ），７．８８－７．９１（ｍ，２Ｈ），７．９６－８．００（ｍ，３Ｈ），８．０２（ｄ，Ｊ＝８．０Ｈｚ，１Ｈ），８．１８－８．２４（ｍ，３Ｈ），８．２４（ｄ，Ｊ＝７．４Ｈｚ，１Ｈ），８．５０（ｓ，１Ｈ），８．７５（ｄ，Ｊ＝４．６Ｈｚ，１Ｈ），８．７７（ｄ，Ｊ＝４．６Ｈｚ，１Ｈ），８．８２（ｄ，Ｊ＝８．０Ｈｚ，４Ｈ），９．０４（ｓ，１Ｈ），９．０８（ｓ，１Ｈ）． Example-13

Under an argon stream, 3- [1-chloro-5- (4,6-diphenyl-1,3,5-triazin-2-yl) -3-yl] -9- (2-pyridyl) carbazole (1.47 g ), 4- (2-pyridyl) phenylboronic acid (597 mg), palladium acetate (11 mg), and 2-dicyclohexylphosphino-2 ′, 4 ′, 6′-triisopropylbiphenyl (72 mg) were added to xylene (22. 5 mL) and 1-butanol (2.5 mL) were suspended in the mixture, 3M-potassium carbonate aqueous solution (2.5 mL) was further added, and the mixture was heated to reflux for 24 hours. The reaction mixture was allowed to cool and water was added. The precipitated solid was filtered, washed with water, then methanol, and then hexane, and the desired product 9- (2-pyridyl) -3- [5- (4,6-diphenyl-1,3,5-triazine) was obtained. A gray powder (yield 1.50 g, yield 60%) of -2-yl) -4 ′-(2-pyridyl) biphenyl-3-yl] carbazole (A-13) was obtained.
¹ H-NMR (CDCl ₃ ): δ 7.26-7.28 (m, 1H), 7.33-7.38 (m, 2H), 7.48 (t, J = 7.2 Hz, 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 (m, 3H), 8.02 (d, J = 8.0 Hz, 1H), 8.18-8.24 (m, 3H), 8.24 (d , J = 7.4 Hz, 1H), 8.50 (s, 1H), 8.75 (d, J = 4.6 Hz, 1H), 8.77 (d, J = 4.6 Hz, 1H), 8 .82 (d, J = 8.0 Hz, 4H), 9.04 (s, 1H), 9.08 (s, 1H).

　アルゴン気流下、６－［３－クロロ－５－（４，６－ジフェニル－１，３，５－トリアジン－２－イル）フェニル］－９－（２－ピリジル）－β－カルボリン（８４５ｍｇ）、４－（２－ピリジル）フェニルボロン酸（８７３ｍｇ）、酢酸パラジウム（９．７ｍｇ）、及び２－ジシクロヘキシルホスフィノ－２’，４’，６’－トリイソプロピルビフェニル（６１．７ｍｇ）を、ＴＨＦ（３０ｍＬ）に懸濁し、さらに３Ｍ－炭酸カリウム水溶液（１．５ｍＬ）を添加し、６０時間加熱還流した。反応混合物を放冷後、水を加えた。析出した固体はろ過し、水、次いでメタノール、その後ヘキサンで洗浄し、さらに減圧下において溶媒を留去した。その後、シリカゲルカラムクロマトグラフィー（溶離液；酢酸エチル）による精製を行い、目的物である６－［５－（４，６－ジフェニル－１，３，５－トリアジン－２－イル）－４’－（２－ピリジル）ビフェニル－３－イル］－９－（２－ピリジル）－β－カルボリン（Ａ－１４）の白色粉末（収量８３４ｍｇ，収率８２％）を得た。
　^１Ｈ－ＮＭＲ（ＣＤＣｌ_３）：δ７．２７－７．２９（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＝８．４Ｈｚ，２Ｈ），８．００－８．０６（ｍ，２Ｈ），８．１０－８．１２（ｍ，２Ｈ），８．１９－８．２１（ｍ，３Ｈ），８．５６（ｓ，１Ｈ），８．６０（ｄ，Ｊ＝５．２Ｈｚ，１Ｈ），８．７５（ｄ，Ｊ＝４．８Ｈｚ，１Ｈ），８．７９（ｄ，Ｊ＝４．８Ｈｚ，１Ｈ），８．８３（ｄ，Ｊ＝８．０Ｈｚ，４Ｈ），９．０６（ｓ，２Ｈ），９．３５（ｓ，１Ｈ）． Example-14

Under an argon stream, 6- [3-chloro-5- (4,6-diphenyl-1,3,5-triazin-2-yl) phenyl] -9- (2-pyridyl) -β-carboline (845 mg), 4- (2-pyridyl) phenylboronic acid (873 mg), palladium acetate (9.7 mg), and 2-dicyclohexylphosphino-2 ′, 4 ′, 6′-triisopropylbiphenyl (61.7 mg) were added to THF ( 30 mL), 3M aqueous potassium carbonate solution (1.5 mL) was added, and the mixture was heated to reflux for 60 hours. The reaction mixture was allowed to cool and water was added. The precipitated solid was filtered, washed with water, then methanol, and then hexane, and the solvent was distilled off under reduced pressure. Thereafter, purification by silica gel column chromatography (eluent: ethyl acetate) was performed, and 6- [5- (4,6-diphenyl-1,3,5-triazin-2-yl) -4′- A white powder (yield 834 mg, yield 82%) of (2-pyridyl) biphenyl-3-yl] -9- (2-pyridyl) -β-carboline (A-14) was obtained.
¹ H-NMR (CDCl ₃ ): δ 7.27-7.29 (m, 1H), 7.39 (dd, J = 7.4, 5.0 Hz, 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 (m, 3H), 8.56 (s, 1H), 8.60 (d, J = 5.2 Hz, 1H), 8.75 (d , J = 4.8 Hz, 1H), 8.79 (d, J = 4.8 Hz, 1H), 8.83 (d, J = 8.0 Hz, 4H), 9.06 (s, 2H), 9 .35 (s, 1H).

　アルゴン気流下、３－［３－（４，４，５，５－テトラメチル－１，３，２－ジオキサボロラン－２－イル）－５－（４，６－ジフェニル－１，３，５－トリアジン－２－イル）フェニル］－９－（２－ピリジル）カルバゾール（１．９８ｇ）、及び２－ブロモピリジン（０．５６ｇ）、テトラキス（トリフェニルホスフィン）パラジウム（１０１．５ｍｇ）を、１，４－ジオキサン（１５ｍＬ）に懸濁し、さらに３Ｍ－炭酸カリウム水溶液（３ｍＬ）を添加し、１７時間加熱還流した。反応混合物を放冷後、水を加えた。析出した固体はろ別し、水、次いでメタノール、その後ヘキサンで洗浄した。さらに、減圧下において溶媒を留去することで、目的物である３－［３－（２－ピリジル）－５－（４，６－ジフェニル－１，３，５－トリアジン－２－イル）フェニル］－９－（２－ピリジル）カルバゾール（Ａ－１５）の灰色粉末（収量１．７２ｇ，収率９３％）を得た。
　^１Ｈ－ＮＭＲ（ＣＤＣｌ_３）：δ７．３２－７．３８（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＝８．４Ｈｚ，１Ｈ），７．９７（ｔ，Ｊ＝７．４Ｈｚ，１Ｈ），８．０３（ｔ，Ｊ＝７．４Ｈｚ，２Ｈ），８．２４（ｄ，Ｊ＝８．４Ｈｚ，１Ｈ），８．５４（ｓ，１Ｈ），８．６４（ｓ，１Ｈ），８．７７（ｄ，Ｊ＝４．４Ｈｚ，１Ｈ），８．８１－８．８（ｍ，５Ｈ），９．１５（ｓ，１Ｈ），９．３０（ｓ，１Ｈ）． Example-15

3- [3- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -5- (4,6-diphenyl-1,3,5-triazine under argon flow -2-yl) phenyl] -9- (2-pyridyl) carbazole (1.98 g), 2-bromopyridine (0.56 g), tetrakis (triphenylphosphine) palladium (101.5 mg), -Suspended in dioxane (15 mL), further added 3M aqueous potassium carbonate solution (3 mL), and heated to reflux for 17 hours. The reaction mixture was allowed to cool and water was added. The precipitated solid was filtered off and washed with water, then methanol, and then hexane. Furthermore, by distilling off the solvent under reduced pressure, the desired product 3- [3- (2-pyridyl) -5- (4,6-diphenyl-1,3,5-triazin-2-yl) phenyl is obtained. ] -9- (2-pyridyl) carbazole (A-15) gray powder (1.72 g, 93% yield) was obtained.
¹ H-NMR (CDCl ₃ ): δ 7.32-7.38 (m, 3H), 7.50 (t, J = 7.4 Hz, 1H), 7.56-7.62 (m, 6H), 7.71 (d, J = 8.4 Hz, 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 (t, J = 7.4 Hz, 2H), 8.24 (d, J = 8.4 Hz, 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 (s, 1H), 9.30 (s, 1H) ).

　アルゴン気流下、３－［３－クロロ－５－（４，６－ジフェニル－１，３，５－トリアジン－２－イル）フェニル］－９－フェニル－６－（２－ピリジル）カルバゾール（７５４ｍｇ）、フェニルボロン酸（１６７ｍｇ）、酢酸パラジウム（５．１ｍｇ）、及び２－ジシクロヘキシルホスフィノ－２’，４’，６’－トリイソプロピルビフェニル（３２．６ｍｇ）を、キシレン（９ｍＬ）に懸濁し、さらに３Ｍ－炭酸カリウム水溶液（１．２ｍＬ）を添加し、４８時間加熱還流した。反応混合物を放冷後、水を加えた。析出した固体はろ別し、水、次いでメタノール、その後ヘキサンで洗浄した。さらに、減圧下において溶媒を留去することで、目的物である３－［５－（４，６－ジフェニル－１，３，５－トリアジン－２－イル）ビフェニル－３－イル］－９－フェニル－６－（２－ピリジル）カルバゾール（Ａ－１６）の黄白色粉末（収量２９７．９ｍｇ，収率３７％）を得た。
　マススペクトル（質量分析）測定の結果は、分子量が７０３であり、得られた化合物はＡ－１６であることを確認した。 Example-16

Under an argon stream, 3- [3-chloro-5- (4,6-diphenyl-1,3,5-triazin-2-yl) phenyl] -9-phenyl-6- (2-pyridyl) carbazole (754 mg) , Phenylboronic acid (167 mg), palladium acetate (5.1 mg), and 2-dicyclohexylphosphino-2 ′, 4 ′, 6′-triisopropylbiphenyl (32.6 mg) were suspended in xylene (9 mL), Further, 3M-potassium carbonate aqueous solution (1.2 mL) was added, and the mixture was heated to reflux for 48 hours. The reaction mixture was allowed to cool and water was added. The precipitated solid was filtered off and washed with water, then methanol, and then hexane. Further, by distilling off the solvent under reduced pressure, the desired product 3- [5- (4,6-diphenyl-1,3,5-triazin-2-yl) biphenyl-3-yl] -9- A yellowish white powder (yield 297.9 mg, yield 37%) of phenyl-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.

　アルゴン気流下、３－［５－（４，６－ジフェニル－１，３，５－トリアジン－２－イル）－ビフェニル－３－イル］カルバゾール（１．５０ｇ）、２－ブロモピリジン（５１５ｍｇ）、酸化銅（Ｉ）（２０ｍｇ）、１，１０－フェナントロリン（４９ｍｇ）、１８－クラウン－６－エーテル（１４３ｍｇ）、及び炭酸カリウム（７５２ｍｇ）を、キシレン（１４ｍＬ）に懸濁し、１５時間加熱還流した。反応混合物を放冷後、水を加えた。析出した固体はろ過し、水、次いでメタノール、その後ヘキサンで洗浄して、目的物である９－（２－ピリジル）－３－［５－（４，６－ジフェニル－１，３，５－トリアジン－２－イル）－ビフェニル－３－イル］カルバゾール（Ａ－１２）の黄色粉末（収量１．２８ｇ，収率９６％）を得た。
　^１Ｈ－ＮＭＲ（ＣＤＣｌ_３）：δ７．３２－７．３５（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＝８．４，２Ｈ），７．８７（ｄ，Ｊ＝８．４，２Ｈ），７．９６（ｔ，Ｊ＝７．８，１Ｈ），８．００（ｄ，Ｊ＝８．４Ｈｚ，１Ｈ），８．１６（ｓ，１Ｈ），８．２２（ｄ，Ｊ＝７．６Ｈｚ，１Ｈ），８．４９（ｓ，１Ｈ），８．７６（ｄ，Ｊ＝６．０Ｈｚ，１Ｈ），８．８１（ｄ，Ｊ＝８．０Ｈｚ，４Ｈ），８．９７（ｓ，１Ｈ），９．０７（ｓ，１Ｈ）． Example-17

Under an argon stream, 3- [5- (4,6-diphenyl-1,3,5-triazin-2-yl) -biphenyl-3-yl] carbazole (1.50 g), 2-bromopyridine (515 mg), Copper (I) oxide (20 mg), 1,10-phenanthroline (49 mg), 18-crown-6-ether (143 mg) and potassium carbonate (752 mg) were suspended in xylene (14 mL) and heated to reflux for 15 hours. . The reaction mixture was allowed to cool and water was added. The precipitated solid was filtered, washed with water, then methanol, and then hexane, and the desired product 9- (2-pyridyl) -3- [5- (4,6-diphenyl-1,3,5-triazine) was obtained. A yellow powder (yield 1.28 g, yield 96%) of -2-yl) -biphenyl-3-yl] carbazole (A-12) was obtained.
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 = 8.0 Hz, 1H), 7.84 (d, J = 8.4, 2H), 7.87 (d, J = 8.4, 2H), 7.96 (t, J = 7.8, 1H), 8.00 (d, J = 8.4 Hz, 1H), 8.16 (s, 1H), 8.22 (d, J = 7.6 Hz, 1H), 8.49. (S, 1H), 8.76 (d, J = 6.0 Hz, 1H), 8.81 (d, J = 8.0 Hz, 4H), 8.97 (s, 1H), 9.07 (s , 1H).

　アルゴン気流下、化合物（Ｅ－１）（１．１３ｇ）、６－ブロモ－９－（２－ピリジル）－δ－カルボリン（７４９ｍｇ）、及びビス（トリフェニルホスフィン）パラジウムジクロライド（３１ｍｇ）を、１，４－ジオキサン（１１ｍＬ）に懸濁し、さらに３Ｍ－炭酸カリウム水溶液（１．５ｍＬ）を添加し、１８時間加熱還流した。反応混合物を放冷後、水を加えた。析出した固体はろ別し、水、次いでメタノール、その後ヘキサンで洗浄した。
　さらに、減圧下において溶媒を留去することで、目的物である６－［５－（４，６－ジフェニル－１，３，５－トリアジン－２－イル）ビフェニル－３－イル］－９－（２－ピリジル）－δ－カルボリン（Ａ－１７）の灰色粉末（収量１．３０ｇ，収率９４％）を得た。
　^１Ｈ－ＮＭＲ（ＣＤＣｌ_３）：δ７．３９（ｄｄ，Ｊ＝７．４，４．９Ｈｚ，１Ｈ），７．４５（ｄｄ，Ｊ＝８．４，４．７Ｈｚ，１Ｈ），７．４８（ｔ，Ｊ＝７．４Ｈｚ，１Ｈ），７．５５－７．６７（ｍ，８Ｈ），７．７３（ｄ，Ｊ＝８．１Ｈｚ，１Ｈ），７．８７（ｄ，Ｊ＝７．７Ｈｚ，２Ｈ），８．０１（ｔ，Ｊ＝７．７Ｈｚ，１Ｈ），８．０５－８．０６（ｍ，２Ｈ），８．２４（ｓ，１Ｈ），８．３２（ｄ，Ｊ＝８．４Ｈｚ，１Ｈ），８．７０（ｄ，Ｊ＝４．７Ｈｚ，１Ｈ），８．７８（ｄ，Ｊ＝４．９Ｈｚ，１Ｈ），８．８４（ｄ，Ｊ＝７．９Ｈｚ，４Ｈ），８．９５（ｓ，１Ｈ），９．０１（ｓ，１Ｈ），９．１１（ｓ，１Ｈ）． Example-18

Under an argon stream, compound (E-1) (1.13 g), 6-bromo-9- (2-pyridyl) -δ-carboline (749 mg), and bis (triphenylphosphine) palladium dichloride (31 mg) , 4-Dioxane (11 mL), 3M aqueous potassium carbonate solution (1.5 mL) was added, and the mixture was heated to reflux for 18 hours. The reaction mixture was allowed to cool and water was added. The precipitated solid was filtered off and washed with water, then methanol, and then hexane.
Further, by distilling off the solvent under reduced pressure, 6- [5- (4,6-diphenyl-1,3,5-triazin-2-yl) biphenyl-3-yl] -9- A gray powder (yield 1.30 g, yield 94%) of (2-pyridyl) -δ-carboline (A-17) was obtained.
¹ H-NMR (CDCl ₃ ): δ 7.39 (dd, J = 7.4, 4.9 Hz, 1H), 7.45 (dd, J = 8.4, 4.7 Hz, 1H), 7.48 (T, J = 7.4 Hz, 1H), 7.55-7.67 (m, 8H), 7.73 (d, J = 8.1 Hz, 1H), 7.87 (d, J = 7. 7 Hz, 2H), 8.01 (t, J = 7.7 Hz, 1H), 8.05-8.06 (m, 2H), 8.24 (s, 1H), 8.32 (d, J = 8.4 Hz, 1H), 8.70 (d, J = 4.7 Hz, 1H), 8.78 (d, J = 4.9 Hz, 1H), 8.84 (d, J = 7.9 Hz, 4H) ), 8.95 (s, 1H), 9.01 (s, 1H), 9.11 (s, 1H).

　アルゴン気流下、化合物（Ｅ－１）（４１８ｍｇ）、３－クロロ－９－（２－ピリジル）－δ－カルボリン（２４０ｍｇ）、酢酸パラジウム（３．７ｍｇ）、及び２－ジシクロヘキシルホスフィノ－２’，４’，６’－トリイソプロピルビフェニル（２２．９ｍｇ）を、１，４－ジオキサン（４．１ｍＬ）に懸濁し、さらに３Ｍ－炭酸カリウム水溶液（０．５４ｍＬ）を添加し、２時間加熱還流した。反応混合物を放冷後、水を加えた。析出した固体はろ別し、水、次いでメタノール、その後ヘキサンで洗浄した。さらに、減圧下において溶媒を留去することで、目的物である３－［５－（４，６－ジフェニル－１，３，５－トリアジン－２－イル）ビフェニル－３－イル］－９－（２－ピリジル）－δ－カルボリン（Ａ－１８）の灰色粉末（収量４４７ｍｇ，収率８７％）を得た。
　^１Ｈ－ＮＭＲ（ＣＤＣｌ_３）：δ７．３９（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，１Ｈ），７．９３－７．９７（ｍ，３Ｈ），８．０２（ｔ，Ｊ＝７．６Ｈｚ，１Ｈ），８．１０（ｄ，Ｊ＝８．７Ｈｚ，１Ｈ），８．４２（ｄ，Ｊ＝８．６Ｈｚ，１Ｈ），８．６６（ｄ，Ｊ＝４．３Ｈｚ，１Ｈ），８．７８（ｓ，１Ｈ），８．７９（ｄ，Ｊ＝４．９Ｈｚ，１Ｈ），８．８７（ｄ，Ｊ＝７．９Ｈｚ，４Ｈ），９．０７（ｓ，１Ｈ），９．４６（ｓ，１Ｈ）． Example-19

Under an argon stream, compound (E-1) (418 mg), 3-chloro-9- (2-pyridyl) -δ-carboline (240 mg), palladium acetate (3.7 mg), and 2-dicyclohexylphosphino-2 ′ , 4 ′, 6′-triisopropylbiphenyl (22.9 mg) is suspended in 1,4-dioxane (4.1 mL), 3M aqueous potassium carbonate solution (0.54 mL) is added, and the mixture is heated under reflux for 2 hours. did. The reaction mixture was allowed to cool and water was added. The precipitated solid was filtered off and washed with water, then methanol, and then hexane. Further, by distilling off the solvent under reduced pressure, the desired product 3- [5- (4,6-diphenyl-1,3,5-triazin-2-yl) biphenyl-3-yl] -9- A gray powder (yield 447 mg, yield 87%) of (2-pyridyl) -δ-carboline (A-18) was obtained.
¹ H-NMR (CDCl ₃ ): δ 7.39 (dd, J = 7.4, 4.9 Hz, 1H), 7.46-7.52 (m, 2H), 7.59-7.68 (m 9H), 7.74 (d, J = 8.1 Hz, 1H), 7.93-7.97 (m, 3H), 8.02 (t, J = 7.6 Hz, 1H), 8.10 (D, J = 8.7 Hz, 1H), 8.42 (d, J = 8.6 Hz, 1H), 8.66 (d, J = 4.3 Hz, 1H), 8.78 (s, 1H) , 8.79 (d, J = 4.9 Hz, 1H), 8.87 (d, J = 7.9 Hz, 4H), 9.07 (s, 1H), 9.46 (s, 1H).

　アルゴン気流下、化合物（Ｅ－１）（１．０２ｇ）、３－ブロモ－６－フェニル－９－（２－ピリジル）カルバゾール（８３９ｇ）、及びビス（トリフェニルホスフィン）パラジウムジクロライド（２８ｍｇ）を、１，４－ジオキサン（１０ｍＬ）に懸濁し、さらに３Ｍ－炭酸カリウム水溶液（１．３ｍＬ）を添加し、５時間加熱還流した。反応混合物を放冷後、水を加えた。析出した固体はろ別し、水、次いでメタノール、その後ヘキサンで洗浄した。さらに、減圧下において溶媒を留去することで、目的物である３－［５－（４，６－ジフェニル－１，３，５－トリアジン－２－イル）ビフェニル－３－イル］－６－フェニル－９－（２－ピリジル）カルバゾール（Ａ－１９）の灰色粉末（収量１．３４ｇ，収率９５％）を得た。
　^１Ｈ－ＮＭＲ（ＣＤＣｌ_３）：δ７．３９（ｔ，Ｊ＝７．４Ｈｚ，１Ｈ），７．４０－７．４３（ｍ，１Ｈ），７．４７－７．５４（ｍ，３Ｈ），７．５８－７．６８（ｍ，８Ｈ），７．７７－７．８１（ｍ，４Ｈ），７．８９（ｄ，Ｊ＝８．２Ｈｚ，２Ｈ），７．９５（ｄ，Ｊ＝８．６Ｈｚ，１Ｈ），７．９８（ｄ，Ｊ＝８．６Ｈｚ，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，１Ｈ），９．１２（ｓ，１Ｈ）． Example-20

Under an argon stream, compound (E-1) (1.02 g), 3-bromo-6-phenyl-9- (2-pyridyl) carbazole (839 g), and bis (triphenylphosphine) palladium dichloride (28 mg) were The suspension was suspended in 1,4-dioxane (10 mL), 3M-potassium carbonate aqueous solution (1.3 mL) was further added, and the mixture was heated to reflux for 5 hours. The reaction mixture was allowed to cool and water was added. The precipitated solid was filtered off and washed with water, then methanol, and then hexane. Further, by distilling off the solvent under reduced pressure, the desired product 3- [5- (4,6-diphenyl-1,3,5-triazin-2-yl) biphenyl-3-yl] -6- A gray powder (yield 1.34 g, yield 95%) of phenyl-9- (2-pyridyl) carbazole (A-19) was obtained.
¹ H-NMR (CDCl ₃ ): δ 7.39 (t, J = 7.4 Hz, 1H), 7.40-7.43 (m, 1H), 7.47-7.54 (m, 3H), 7.58-7.68 (m, 8H), 7.77-7.81 (m, 4H), 7.89 (d, J = 8.2 Hz, 2H), 7.95 (d, 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, 1H), 9.12 (s, 1H).

　アルゴン気流下、化合物（Ｅ－１）（１．３４ｇ）、６－ブロモ－３－フェニル－９－（２－ピリジル）－δ－カルボリン（１．００ｇ）、及びビス（トリフェニルホスフィン）パラジウムジクロライド（３５．１ｍｇ）を、１，４－ジオキサン（１６．７ｍＬ）に懸濁し、さらに３Ｍ－炭酸カリウム水溶液（１．８ｍＬ）を添加し、１９時間加熱還流した。反応混合物を放冷後、水を加えた。析出した固体はろ別し、水、次いでメタノール、その後ヘキサンで洗浄し、さらに、減圧下において溶媒を留去した。得られた固体をｏ－キシレンで再結晶することで、目的物である６－［５－（４，６－ジフェニル－１，３，５－トリアジン－２－イル）ビフェニル－３－イル］－３－フェニル－９－（２－ピリジル）－δ－カルボリン（Ａ－２０）の灰色粉末（収量１．７ｇ，収率９７％）を得た。
　^１Ｈ－ＮＭＲ（ＣＤＣｌ_３）：δ７．３９（ｄｄ，Ｊ＝７．４，４．９Ｈｚ，１Ｈ），７．４５（ｔ，Ｊ＝７．３Ｈｚ，１Ｈ），７．４９（ｔ，Ｊ＝７．４Ｈｚ，１Ｈ），７．５４－７．６８（ｍ，１０Ｈ），７．７６（ｄ，Ｊ＝８．１Ｈｚ，１Ｈ），７．８９（ｄ，Ｊ＝８．６Ｈｚ，１Ｈ），７．９０（ｄ，Ｊ＝８．０Ｈｚ，２Ｈ），８．０１－８．０６（ｍ，２Ｈ），８．１０（ｄ，Ｊ＝８．６Ｈｚ，１Ｈ），８．２４（ｄ，Ｊ＝８．１Ｈｚ，２Ｈ），８．２７（ｓ，１Ｈ），８．３５（ｄ，Ｊ＝８．７Ｈｚ，１Ｈ），８．８０（ｄ，Ｊ＝４．９Ｈｚ，１Ｈ），８．８６（ｄ，Ｊ＝８．１Ｈｚ，４Ｈ），８．９８（ｓ，１Ｈ），９．０２（ｓ，１Ｈ），９．１５（ｓ，１Ｈ）． Example-21

Under an argon stream, compound (E-1) (1.34 g), 6-bromo-3-phenyl-9- (2-pyridyl) -δ-carboline (1.00 g), and bis (triphenylphosphine) palladium dichloride (35.1 mg) was suspended in 1,4-dioxane (16.7 mL), 3M-potassium carbonate aqueous solution (1.8 mL) was further added, and the mixture was heated to reflux for 19 hours. The reaction mixture was allowed to cool and water was added. The precipitated solid was separated by filtration, washed with water, then methanol, and then hexane, and the solvent was distilled off under reduced pressure. The obtained solid was recrystallized from o-xylene to give the desired product, 6- [5- (4,6-diphenyl-1,3,5-triazin-2-yl) biphenyl-3-yl]- A gray powder (yield 1.7 g, yield 97%) of 3-phenyl-9- (2-pyridyl) -δ-carboline (A-20) was obtained.
¹ H-NMR (CDCl ₃ ): δ 7.39 (dd, J = 7.4, 4.9 Hz, 1H), 7.45 (t, J = 7.3 Hz, 1H), 7.49 (t, J = 7.4 Hz, 1 H), 7.54-7.68 (m, 10 H), 7.76 (d, J = 8.1 Hz, 1 H), 7.89 (d, J = 8.6 Hz, 1 H) , 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 (s, 1H), 8.35 (d, J = 8.7 Hz, 1H), 8.80 (d, J = 4.9 Hz, 1H), 8. 86 (d, J = 8.1 Hz, 4H), 8.98 (s, 1H), 9.02 (s, 1H), 9.15 (s, 1H).

　アルゴン気流下、化合物（Ｅ－１）（７０１ｍｇ）、６－ブロモ－９－フェニル－３－（２－ピリジル）－δ－カルボリン（５５０ｍｇ）、及びビス（トリフェニルホスフィン）パラジウムジクロライド（１９ｍｇ）を、１，４－ジオキサン（７ｍＬ）に懸濁し、さらに３Ｍ－炭酸カリウム水溶液（１ｍＬ）を添加し、４０時間加熱還流した。反応混合物を放冷後、水を加えた。析出した固体はろ別し、水、次いでメタノール、その後ヘキサンで洗浄し、さらに、減圧下において溶媒を留去した。得られた固体をトルエンで再結晶することで、目的物である６－［５－（４，６－ジフェニル－１，３，５－トリアジン－２－イル）ビフェニル－３－イル］－９－フェニル－３－（２－ピリジル）－δ－カルボリン（Ａ－２１）の灰色粉末（収量４００ｍｇ，収率４１％）を得た。
　^１Ｈ－ＮＭＲ（ＣＤＣｌ_３）：δ７．３２（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，４Ｈ），８．００（ｄ，Ｊ＝８．６Ｈｚ，１Ｈ），８．２６（ｓ，１Ｈ），８．５８（ｄ，Ｊ＝８．７Ｈｚ，１Ｈ），８．７３（ｄ，Ｊ＝４．８Ｈｚ，１Ｈ），８．７９（ｄ，８．０Ｈｚ，１Ｈ），８．８４－８．８６（ｍ，４Ｈ），８．９６（ｓ，１Ｈ），９．０２（ｓ，１Ｈ），９．１４（ｓ，１Ｈ）． Example-22

Under an argon stream, compound (E-1) (701 mg), 6-bromo-9-phenyl-3- (2-pyridyl) -δ-carboline (550 mg), and bis (triphenylphosphine) palladium dichloride (19 mg) were added. The suspension was suspended in 1,4-dioxane (7 mL), 3M aqueous potassium carbonate solution (1 mL) was added, and the mixture was heated to reflux for 40 hours. The reaction mixture was allowed to cool and water was added. The precipitated solid was separated by filtration, washed with water, then methanol, and then hexane, and the solvent was distilled off under reduced pressure. The obtained solid was recrystallized from toluene to obtain 6- [5- (4,6-diphenyl-1,3,5-triazin-2-yl) biphenyl-3-yl] -9- A gray powder (yield 400 mg, yield 41%) of phenyl-3- (2-pyridyl) -δ-carboline (A-21) was obtained.
¹ H-NMR (CDCl ₃ ): δ 7.32 (dd, J = 7.4, 4.8 Hz, 1H), 7.50 (t, J = 7.4 Hz, 1H), 7.55-7.73 (M, 14H), 7.86-7.91 (m, 4H), 8.00 (d, J = 8.6 Hz, 1H), 8.26 (s, 1H), 8.58 (d, J = 8.7 Hz, 1H), 8.73 (d, J = 4.8 Hz, 1H), 8.79 (d, 8.0 Hz, 1H), 8.84-8.86 (m, 4H), 8 .96 (s, 1H), 9.02 (s, 1H), 9.14 (s, 1H).

　アルゴン気流下、化合物（Ｅ－１）（１．０２ｇ）、３－ブロモ－９－フェニル－６－（２－ピリジル）カルバゾール（８３９ｇ）、及びビス（トリフェニルホスフィン）パラジウムジクロライド（２８ｍｇ）を、１，４－ジオキサン（１０ｍＬ）に懸濁し、さらに３Ｍ－炭酸カリウム水溶液（１．３ｍＬ）を添加し、５時間加熱還流した。反応混合物を放冷後、水を加えた。析出した固体はろ別し、水、次いでメタノール、その後ヘキサンで洗浄し、さらに、減圧下において溶媒を留去した。得られた固体をシリカゲルカラムクロマトグラフィー（溶離液；クロロホルム）で精製し、目的物である３－［５－（４，６－ジフェニル－１，３，５－トリアジン－２－イル）ビフェニル－３－イル］－９－フェニル－６－（２－ピリジル）カルバゾール（Ａ－１６）の灰色粉末（収量１．０６ｇ，収率７５％）を得た。
　^１Ｈ－ＮＭＲ（ＣＤＣｌ_３）：δ７．２６－７．３０（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＝８．０Ｈｚ，１Ｈ），８．１８（ｄ，Ｊ＝８．７Ｈｚ，１Ｈ），８．２１（ｓ，１Ｈ），８．６６（ｓ，１Ｈ），８．７８（ｄ，Ｊ＝４．８Ｈｚ，１Ｈ），８．８５（ｄ，Ｊ＝７．９Ｈｚ，４Ｈ），８．９８（ｓ，１Ｈ），９．０２（ｓ，１Ｈ），９．１１（ｓ，１Ｈ）． Example-23

Under an argon stream, compound (E-1) (1.02 g), 3-bromo-9-phenyl-6- (2-pyridyl) carbazole (839 g), and bis (triphenylphosphine) palladium dichloride (28 mg) The suspension was suspended in 1,4-dioxane (10 mL), 3M-potassium carbonate aqueous solution (1.3 mL) was further added, and the mixture was heated to reflux for 5 hours. The reaction mixture was allowed to cool and water was added. The precipitated solid was separated by filtration, washed with water, then methanol, and then hexane, and the solvent was distilled off under reduced pressure. The obtained solid was purified by silica gel column chromatography (eluent: chloroform), and the target 3- [5- (4,6-diphenyl-1,3,5-triazin-2-yl) biphenyl-3 was obtained. A gray powder (yield 1.06 g, yield 75%) of -yl] -9-phenyl-6- (2-pyridyl) carbazole (A-16) was obtained.
¹ H-NMR (CDCl ₃ ): δ 7.26-7.30 (m, 1H), 7.50 (t, J = 7.4 Hz, 1H), 7.54-7.71 (m, 15H), 7.85 (t, J = 7.6 Hz, 1H), 7.89-7.93 (m, 3H), 7.95 (d, J = 8.0 Hz, 1H), 8.18 (d, J = 8.7 Hz, 1H), 8.21 (s, 1H), 8.66 (s, 1H), 8.78 (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).

　アルゴン気流下、化合物（Ｅ－１）（１．５３ｇ）、３－ブロモ－９－フェニル－６－（ピラジニル）カルバゾール（１．２０ｇ）、及びビス（トリフェニルホスフィン）パラジウムジクロライド（４２．１ｍｇ）を、１，４－ジオキサン（１５ｍＬ）に懸濁し、さらに３Ｍ－炭酸カリウム水溶液（２．０ｍＬ）を添加し、７時間加熱還流した。反応混合物を放冷後、水を加えた。析出した固体はろ別し、水、次いでメタノール、その後ヘキサンで洗浄し、さらに、減圧下において溶媒を留去した。得られた固体をシリカゲルカラムクロマトグラフィー（溶離液；クロロホルム）で精製し、目的物である３－［５－（４，６－ジフェニル－１，３，５－トリアジン－２－イル）ビフェニル－３－イル］－９－フェニル－６－（ピラジニル）カルバゾール（Ａ－２２）の灰色粉末（収量１．５９ｇ，収率７５％）を得た。
　^１Ｈ－ＮＭＲ（ＣＤＣｌ_３）：δ７．５０（ｔ，Ｊ＝７．４Ｈｚ，１Ｈ），７．５６－７．７２（ｍ，１５Ｈ），７．８９（ｄ，Ｊ＝８．３Ｈｚ，２Ｈ），７．９２（ｄ，Ｊ＝８．６Ｈｚ，１Ｈ），８．１５（ｄ，Ｊ＝８．７Ｈｚ，１Ｈ），８．２０（ｓ，１Ｈ），８．５１（ｄ、Ｊ＝２．５Ｈｚ，１Ｈ），８．６５（ｓ、１Ｈ），８．６８（ｄ、Ｊ＝２．５Ｈｚ，１Ｈ），８．８４（ｄ、Ｊ＝８．０Ｈｚ，４Ｈ），８．９９（ｓ、１Ｈ），９．００（ｓ、１Ｈ），９．１０（ｓ，１Ｈ），９．２１（ｓ、１Ｈ）． Example-24

Under an argon stream, compound (E-1) (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-potassium carbonate aqueous solution (2.0 mL) was further added, and the mixture was heated to reflux for 7 hours. The reaction mixture was allowed to cool and water was added. The precipitated solid was separated by filtration, washed with water, then methanol, and then hexane, and the solvent was distilled off under reduced pressure. The obtained solid was purified by silica gel column chromatography (eluent: chloroform), and the target 3- [5- (4,6-diphenyl-1,3,5-triazin-2-yl) biphenyl-3 was obtained. A gray powder (yield 1.59 g, yield 75%) of -yl] -9-phenyl-6- (pyrazinyl) carbazole (A-22) was obtained.
¹ H-NMR (CDCl ₃ ): δ 7.50 (t, J = 7.4 Hz, 1H), 7.56-7.72 (m, 15H), 7.89 (d, J = 8.3 Hz, 2H) ), 7.92 (d, J = 8.6 Hz, 1H), 8.15 (d, J = 8.7 Hz, 1H), 8.20 (s, 1H), 8.51 (d, J = 2) .5 Hz, 1H), 8.65 (s, 1H), 8.68 (d, J = 2.5 Hz, 1H), 8.84 (d, J = 8.0 Hz, 4H), 8.99 (s) 1H), 9.00 (s, 1H), 9.10 (s, 1H), 9.21 (s, 1H).

　アルゴン気流下、前記化合物（Ｅ－２）（６２８ｍｇ）、ヨードピラジン（３０９ｍｇ）、酸化銅（Ｉ）（７．２ｍｇ）、１，１０－フェナントロリン（１８ｍｇ）、１８－クラウン－６－エーテル（５３ｍｇ）、炭酸カリウム（２７６ｍｇ）をキシレン（５．０ｍＬ）に懸濁し、１８時間加熱還流した。反応混合物を放冷後、水及びメタノールを加えた。析出した固体を水、メタノール、ヘキサンで洗浄した後、キシレンで再結晶をすることで、目的の９－ピラジル－３－［５－（４，６－ジフェニル－１，３，５－トリアジン－２－イル）－４’－（２－ピリジル）ビフェニル－３－イル］カルバゾール（Ａ－２３）の褐色粉末（収量６９１ｍｇ，収率９８％）を得た。
　^１Ｈ－ＮＭＲ（ＣＤＣｌ_３）：δ７．３１－７．３５（ｍ，１Ｈ），７．４５（ｔ，Ｊ＝７．４Ｈｚ，１Ｈ），７．５６（ｔ，Ｊ＝７．７Ｈｚ，１Ｈ），７．６１－７．６８（ｍ，６Ｈ），７．８６－７．８９（ｍ，２Ｈ），７．９４－７．９８（ｍ，２Ｈ），８．００（ｄ，Ｊ＝８．３Ｈｚ，２Ｈ），８．１０（ｄ，Ｊ＝８．６Ｈｚ，１Ｈ），８．２２（ｄ，Ｊ＝８．５Ｈｚ，２Ｈ），８．２４（ｓ，１Ｈ），８．２８（ｄ，Ｊ＝７．６Ｈｚ，１Ｈ），８．５４（ｓ，１Ｈ），８．６３（ｓ，１Ｈ），８．７６（ｓ，１Ｈ），８．８１（ｄ，Ｊ＝４．３Ｈｚ，１Ｈ），８．８５（ｄ，Ｊ＝７．８Ｈｚ，４Ｈ），９．０８（ｓ，１Ｈ）， Example-25

Under an argon stream, the compound (E-2) (628 mg), iodopyrazine (309 mg), copper (I) oxide (7.2 mg), 1,10-phenanthroline (18 mg), 18-crown-6-ether (53 mg) ), Potassium carbonate (276 mg) was suspended in xylene (5.0 mL) and heated to reflux for 18 hours. After allowing the reaction mixture to cool, water and methanol were added. The precipitated solid is washed with water, methanol and hexane, and then recrystallized with xylene to give the desired 9-pyrazyl-3- [5- (4,6-diphenyl-1,3,5-triazine-2 A brown powder (yield 691 mg, yield 98%) of -yl) -4 ′-(2-pyridyl) biphenyl-3-yl] carbazole (A-23) was obtained.
¹ H-NMR (CDCl ₃ ): δ 7.31-7.35 (m, 1H), 7.45 (t, J = 7.4 Hz, 1H), 7.56 (t, J = 7.7 Hz, 1H) ), 7.61-7.68 (m, 6H), 7.86-7.89 (m, 2H), 7.94-7.98 (m, 2H), 8.00 (d, J = 8 .3 Hz, 2H), 8.10 (d, J = 8.6 Hz, 1H), 8.22 (d, J = 8.5 Hz, 2H), 8.24 (s, 1H), 8.28 (d , J = 7.6 Hz, 1H), 8.54 (s, 1H), 8.63 (s, 1H), 8.76 (s, 1H), 8.81 (d, J = 4.3 Hz, 1H) ), 8.85 (d, J = 7.8 Hz, 4H), 9.08 (s, 1H),

　アルゴン気流下、前記化合物（Ｅ－２）（６２８ｍｇ）、２－ブロモピリミジン（２３８ｍｇ）、酸化銅（Ｉ）（７．２ｍｇ）、１，１０－フェナントロリン（１８.０ｍｇ）、炭酸カリウム（２７６ｍｇ）、１８－クラウン－６（５２．９ｍｇ）をキシレン（５．０ｍＬ）に懸濁し、１５０℃で６０時間加熱した。反応混合物を放冷後、メタノールを加え、析出した固体をろ取した。得られた固体を水、メタノール、ヘキサンで洗浄し、トルエン３０ｍｌで再結晶することで、目的の３－[５－（４，６－ジフェニル－１，３，５－トリアジン－２－イル）－４’－（２－ピリジル）ビフェニル－３－イル]－９－（２－ピリミジル）カルバゾール（Ａ－２４）の灰色粉末（収量６３６ｍｇ，収率９０％）を得た。
　^１Ｈ－ＮＭＲ（ＣＤＣｌ_３）：δ７．１６（ｔ，Ｊ＝５．０Ｈｚ，１Ｈ），７．３１（ｍ，１Ｈ），７．４１（ｔ，Ｊ＝７．０Ｈｚ，１Ｈ），７．５４－７．６６（ｍ，７Ｈ），７．８２－７．８９（ｍ，２Ｈ），７．９５－８．００（ｍ，３Ｈ），８．２０－８．２３（ｍ，４Ｈ），８．６４（ｄ，Ｊ＝１８Ｈｚ，１Ｈ），８．７８－８．８４（ｍ，５Ｈ），８．８９－８．９４（ｍ，３Ｈ），９．０２－９．０６（ｍ，２Ｈ），９．１１（ｓ，１Ｈ）． Example-26

Under an argon stream, the compound (E-2) (628 mg), 2-bromopyrimidine (238 mg), copper (I) oxide (7.2 mg), 1,10-phenanthroline (18.0 mg), potassium carbonate (276 mg) , 18-crown-6 (52.9 mg) was suspended in xylene (5.0 mL) and heated at 150 ° C. for 60 hours. The reaction mixture was allowed to cool, methanol was added, and the precipitated solid was collected by filtration. The obtained solid was washed with water, methanol and hexane, and recrystallized with 30 ml of toluene to obtain the desired 3- [5- (4,6-diphenyl-1,3,5-triazin-2-yl)- A gray powder (yield 636 mg, yield 90%) of 4 ′-(2-pyridyl) biphenyl-3-yl] -9- (2-pyrimidyl) carbazole (A-24) was obtained.
¹ H-NMR (CDCl ₃ ): δ 7.16 (t, J = 5.0 Hz, 1H), 7.31 (m, 1H), 7.41 (t, J = 7.0 Hz, 1H), 7. 54-7.66 (m, 7H), 7.82-7.89 (m, 2H), 7.95-8.00 (m, 3H), 8.20-8.23 (m, 4H), 8.64 (d, J = 18 Hz, 1H), 8.78-8.84 (m, 5H), 8.89-8.94 (m, 3H), 9.02-9.06 (m, 2H) ), 9.11 (s, 1H).

　アルゴン気流下、９－ピラジル－３－［３－クロロ－５－（４，６－ジフェニル－１，３，５－トリアジン－２－イル）フェニル］カルバゾール（２．００ｇ）、４－ビフェニルボロン酸（８７５ｍｇ）、酢酸パラジウム（２３ｍｇ）、２－ジシクロヘキシルホスフィノ－２’，４’，６’－トリイソプロピルビフェニル（９７ｍｇ）をトルエン（３４ｍＬ）及び１－ブタノール（３．０ｍＬ）の混合溶媒に懸濁し、３Ｍ－炭酸カリウム水溶液（３．０ｍＬ）を添加し、２４時間加熱還流した。反応混合物を放冷後、水を加えた。析出した固体を水、メタノール、ヘキサンで洗浄した。得られた固体をトルエンで再結晶した後、昇華精製することで目的の９－ピラジル－３－［５－（４，６－ジフェニル－１，３，５－トリアジン－２－イル）－１，１’：４’，１”－ターフェニル－３－イル］カルバゾール（Ａ－２５）の薄黄色粉末（収量３２９ｍｇ，収率１４％）を得た。
　^１Ｈ－ＮＭＲ（ＣＤＣｌ_３）：δ７．４３（ｔ，Ｊ＝７．６Ｈｚ，１Ｈ），７．４６（ｄ，Ｊ＝７．８Ｈｚ，１Ｈ），７．５２（ｄ，Ｊ＝７．８Ｈｚ，１Ｈ），７．５４－７．５８（ｍ，２Ｈ），７．６１－７．６７（ｍ，６Ｈ），７．７４（ｄ，Ｊ＝８．０Ｈｚ，２Ｈ），７．８３（ｄ，Ｊ＝８．４Ｈｚ，２Ｈ），７．９４－７．９９（ｍ，４Ｈ），８．１０（ｄ，Ｊ＝８．６Ｈｚ，１Ｈ），８．２３（ｓ，１Ｈ），８．２７（ｄ，Ｊ＝７．４Ｈｚ，１Ｈ），８．５３（ｓ，１Ｈ），８．６３（ｓ，１Ｈ），８．７７（ｓ，１Ｈ），８．８５（ｄ，Ｊ＝８．０Ｈｚ，４Ｈ），９．０７（ｓ，１Ｈ），９．１０（ｓ，１Ｈ），９．１６（ｓ，１Ｈ）． Example-27

Under an argon stream, 9-pyrazyl-3- [3-chloro-5- (4,6-diphenyl-1,3,5-triazin-2-yl) phenyl] carbazole (2.00 g), 4-biphenylboronic acid (875 mg), palladium acetate (23 mg), 2-dicyclohexylphosphino-2 ′, 4 ′, 6′-triisopropylbiphenyl (97 mg) suspended in a mixed solvent of toluene (34 mL) and 1-butanol (3.0 mL). The solution became cloudy, 3M-potassium carbonate aqueous solution (3.0 mL) was added, and the mixture was heated to reflux for 24 hours. The reaction mixture was allowed to cool and water was added. The precipitated solid was washed with water, methanol and hexane. The obtained solid was recrystallized from toluene and purified by sublimation to obtain the desired 9-pyrazyl-3- [5- (4,6-diphenyl-1,3,5-triazin-2-yl) -1, 1 ′: 4 ′, 1 ″ -terphenyl-3-yl] carbazole (A-25) was obtained as a pale yellow powder (yield 329 mg, 14%).
¹ H-NMR (CDCl ₃ ): δ 7.43 (t, J = 7.6 Hz, 1H), 7.46 (d, J = 7.8 Hz, 1H), 7.52 (d, J = 7.8 Hz) , 1H), 7.54-7.58 (m, 2H), 7.61-7.67 (m, 6H), 7.74 (d, J = 8.0 Hz, 2H), 7.83 (d , J = 8.4 Hz, 2H), 7.94-7.99 (m, 4H), 8.10 (d, J = 8.6 Hz, 1H), 8.23 (s, 1H), 8.27 (D, J = 7.4 Hz, 1H), 8.53 (s, 1H), 8.63 (s, 1H), 8.77 (s, 1H), 8.85 (d, J = 8.0 Hz) , 4H), 9.07 (s, 1H), 9.10 (s, 1H), 9.16 (s, 1H).

　アルゴン気流下、前記のＮ－（２－ピリジル）－３－［３－クロロ－５－（４，６－ジフェニル－１，３，５－トリアジン－２－イル）フェニル］カルバゾール（５８６ｍｇ）、４－ビフェニルボロン酸（２５７ｍｇ）、酢酸パラジウム（４．５ｍｇ）、２－ジシクロヘキシルホスフィノ－２’，４’，６’－トリイソプロピルビフェニル（２８．６ｍｇ）をトルエン（２０ｍＬ）及び１－ブタノール（０．９ｍＬ）の混合溶媒に懸濁し、３Ｍ－炭酸カリウム水溶液（０．９ｍＬ）を添加し、１８時間加熱還流した。反応混合物を放冷後、水を加えた。析出した固体を水、メタノール、ヘキサンで洗浄した。得られた固体をトルエンで再結晶した後、昇華精製することで目的の９－（２－ピリジル）－３－［５－（４，６－ジフェニル－１，３，５－トリアジン－２－イル）－１，１’：４’，１”－ターフェニル－３－イル］カルバゾール（Ａ－２６）の薄黄色粉末（収量１７１ｍｇ，収率２４％）を得た。
　^１Ｈ－ＮＭＲ（ＣＤＣｌ_３）：δ７．３８－７．４５（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＝７．１Ｈｚ，１Ｈ），７．８３（ｄ，Ｊ＝８．４Ｈｚ，２Ｈ），７．９２（ｄ，Ｊ＝８．３Ｈｚ，１Ｈ），７．９３（ｄ，Ｊ＝８．５Ｈｚ，１Ｈ），７．９７（ｄ，Ｊ＝８．４Ｈｚ，２Ｈ），８．００－８．０４（ｍ，１Ｈ），８．０５（ｄ，Ｊ＝８．５Ｈｚ，１Ｈ），８．２４（ｓ，１Ｈ），８．２７（ｄ，Ｊ＝７，１Ｈｚ，１Ｈ），８．５４（ｓ，１Ｈ），８．８１－８．８２（ｍ，１Ｈ），８．８５（ｄ，Ｊ＝７．９Ｈｚ，４Ｈ），９．０６（ｓ，１Ｈ），９．１１（ｓ，１Ｈ）． Example-28

N- (2-pyridyl) -3- [3-chloro-5- (4,6-diphenyl-1,3,5-triazin-2-yl) phenyl] carbazole (586 mg), 4 -Biphenylboronic acid (257 mg), palladium acetate (4.5 mg), 2-dicyclohexylphosphino-2 ', 4', 6'-triisopropylbiphenyl (28.6 mg) in toluene (20 mL) and 1-butanol (0 (9 mL), a 3M aqueous potassium carbonate solution (0.9 mL) was added, and the mixture was heated to reflux for 18 hours. The reaction mixture was allowed to cool and water was added. The precipitated solid was washed with water, methanol and hexane. The obtained solid was recrystallized from toluene and purified by sublimation to obtain the desired 9- (2-pyridyl) -3- [5- (4,6-diphenyl-1,3,5-triazin-2-yl). ) -1,1 ′: 4 ′, 1 ″ -terphenyl-3-yl] carbazole (A-26) was obtained as a pale yellow powder (Yield 171 mg, Yield 24%).
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 = 8.2 Hz, 2H), 7.76 (d, J = 7.1 Hz, 1H), 7.83 (d, J = 8.4 Hz, 2H), 7.92 (d, J = 8.3 Hz, 1H), 7.93 (d, J = 8.5 Hz, 1H), 7.97 (d, J = 8.4 Hz, 2H), 8.00-8.04 (m, 1H) , 8.05 (d, J = 8.5 Hz, 1H), 8.24 (s, 1H), 8.27 (d, J = 7, 1 Hz, 1H), 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).

　アルゴン気流下、前記のＮ－（２－ピリジル）－３－［３－クロロ－５－（４，６－ジフェニル－１，３，５－トリアジン－２－イル）フェニル］カルバゾール（５８６ｍｇ）、９－フェナントレンボロン酸（２６７ｍｇ）、酢酸パラジウム（２．３ｍｇ）、２－ジシクロヘキシルホスフィノ－２’，４’，６’－トリイソプロピルビフェニル（９．５ｍｇ）をトルエン（２０．０ｍＬ）及び１－ブタノール（０．６ｍＬ）の混合溶媒に懸濁し、３Ｍ－炭酸カリウム水溶液（０．６ｍＬ）を添加し、５時間加熱還流した。その後、９－フェナントレンボロン酸（２６７ｍｇ）、酢酸パラジウム（２．３ｍｇ）、２－ジシクロヘキシルホスフィノ－２’，４’，６’－トリイソプロピルビフェニル（９．５ｍｇ）を追加し、さらに５時間加熱還流した。反応混合物を放冷後、メタノールを加え、析出した固体をろ取した。得られた固体を水、メタノール、ヘキサンで洗浄し、シリカゲルカラムクロマトグラフィー（展開溶媒クロロホルム：ヘキサン＝１：９）で精製した。これをトルエンで再結晶することで、目的の３－［５－（９－フェナントリル）－３－（４，６－ジフェニル－１，３，５－トリアジン－２－イル）フェニル］－９－（２－ピリジル）カルバゾール（Ａ－２７）の灰色粉末（収量１１９ｍｇ，収率１６％）を得た。
　^１Ｈ－ＮＭＲ（ＣＤＣｌ_３）：δ７．３５－７．４２（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＝８．３Ｈｚ，１Ｈ），７．９４－８．１０（ｍ，６Ｈ），８．１５（ｔ，Ｊ＝１．９Ｈｚ，１Ｈ），８．２０（ｄ，Ｊ＝７．７Ｈｚ，１Ｈ），８．５２（ｄ，Ｊ＝１．３Ｈｚ，１Ｈ），８．７９－８．８７（ｍ，８Ｈ），８．９４（ｔ，Ｊ＝１．５Ｈｚ，１Ｈ），９．２２（ｔ，Ｊ＝１．７Ｈｚ，１Ｈ）． Example-29

N- (2-pyridyl) -3- [3-chloro-5- (4,6-diphenyl-1,3,5-triazin-2-yl) phenyl] carbazole (586 mg), 9 -Phenanthreneboronic acid (267 mg), palladium acetate (2.3 mg), 2-dicyclohexylphosphino-2 ', 4', 6'-triisopropylbiphenyl (9.5 mg) in toluene (20.0 mL) and 1-butanol Suspended in a mixed solvent (0.6 mL), 3M aqueous potassium carbonate solution (0.6 mL) was added, and the mixture was heated to reflux for 5 hours. Thereafter, 9-phenanthreneboronic acid (267 mg), palladium acetate (2.3 mg), 2-dicyclohexylphosphino-2 ′, 4 ′, 6′-triisopropylbiphenyl (9.5 mg) were added, and the mixture was further heated for 5 hours. Refluxed. The reaction mixture was allowed to cool, 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). By recrystallizing this from toluene, the desired 3- [5- (9-phenanthryl) -3- (4,6-diphenyl-1,3,5-triazin-2-yl) phenyl] -9- ( A gray powder (yield 119 mg, yield 16%) of 2-pyridyl) carbazole (A-27) was obtained.
¹ H-NMR (CDCl ₃ ): δ 7.35-7.42 (m, 2H), 7.50 (t, J = 7.5 Hz, 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), 8.20 (d, J = 7.7 Hz, 1H), 8.52 (d, J = 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).

　アルゴン気流下、前記のＮ－（２－ピリジル）－３－［３－クロロ－５－（４，６－ジフェニル－１，３，５－トリアジン－２－イル）フェニル］カルバゾール（５８６ｍｇ）、９－アントラセンボロン酸（６６６ｍｇ）、酢酸パラジウム（２．３ｍｇ）、２－ジシクロヘキシルホスフィノ－２’，４’，６’－トリイソプロピルビフェニル（９．５ｍｇ）をトルエン（２０．０ｍＬ）及び１－ブタノール（０．６ｍＬ）の混合溶媒に懸濁し、３Ｍ－炭酸カリウム水溶液（０．６ｍＬ）を添加し、３．５時間加熱還流した。反応混合物を放冷後、メタノールを加え、析出した固体をろ取した。得られた固体を水、メタノール、ヘキサンで洗浄し、次いでトルエンで再結晶することで、目的の３－［５－（９－アントラシル）－３－（４，６－ジフェニル－１，３，５－トリアジン－２－イル）フェニル］－９－（２－ピリジル）カルバゾール（Ａ－２８）の灰色粉末（収量５７５ｍｇ，収率７９％）を得た。
　^１Ｈ－ＮＭＲ（ＣＤＣｌ_３）：δ７．３５（ｔ，Ｊ＝７．１Ｈｚ，１Ｈ），７．４０－７．６１（ｍ，１３Ｈ），７．８９（ｄ，Ｊ＝８．４Ｈｚ，３Ｈ），７．９７－８．０７（ｍ，４Ｈ），８．１３（ｄ，Ｊ＝８．９Ｈｚ，２Ｈ），８．１８（ｄ，Ｊ＝８．２Ｈｚ，１Ｈ），８．５２（ｓ，１Ｈ），８．６１（ｓ，１Ｈ），８．７６－８．７８（ｍ，５Ｈ），８．８４（ｓ，１Ｈ），９．３１（ｓ，１Ｈ）． Example-30

N- (2-pyridyl) -3- [3-chloro-5- (4,6-diphenyl-1,3,5-triazin-2-yl) phenyl] carbazole (586 mg), 9 Anthraceneboronic acid (666 mg), palladium acetate (2.3 mg), 2-dicyclohexylphosphino-2 ′, 4 ′, 6′-triisopropylbiphenyl (9.5 mg) in toluene (20.0 mL) and 1-butanol The mixture was suspended in a mixed solvent (0.6 mL), 3M-potassium carbonate aqueous solution (0.6 mL) was added, and the mixture was heated to reflux for 3.5 hours. The reaction mixture was allowed to cool, methanol was added, and the precipitated solid was collected by filtration. The obtained solid was washed with water, methanol and hexane, and then recrystallized with toluene to obtain the desired 3- [5- (9-anthracyl) -3- (4,6-diphenyl-1,3,5). A gray powder (yield 575 mg, 79% yield) of -triazin-2-yl) phenyl] -9- (2-pyridyl) carbazole (A-28) was obtained.
¹ H-NMR (CDCl ₃ ): δ 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 (m, 4H), 8.13 (d, J = 8.9 Hz, 2H), 8.18 (d, J = 8.2 Hz, 1H), 8.52 (s) , 1H), 8.61 (s, 1H), 8.76-8.78 (m, 5H), 8.84 (s, 1H), 9.31 (s, 1H).

　アルゴン気流下、前記のＮ－（２－ピリジル）－３－［３－クロロ－５－（４，６－ジフェニル－１，３，５－トリアジン－２－イル）フェニル］カルバゾール（５８６ｍｇ）、４－ジベンゾチオフェンボロン酸（２７４ｍｇ）、酢酸パラジウム（２．３ｍｇ）、２－ジシクロヘキシルホスフィノ－２’，４’，６’－トリイソプロピルビフェニル（９．５ｍｇ）をトルエン（２０．０ｍＬ）及び１－ブタノール（０．６ｍＬ）の混合溶媒に懸濁し、３Ｍ－炭酸カリウム水溶液（０．６ｍＬ）を添加し、５時間加熱還流した。その後、４－ジベンゾチオフェンボロン酸（２７４ｍｇ）、酢酸パラジウム（２．３ｍｇ）、２－ジシクロヘキシルホスフィノ－２’，４’，６’－トリイソプロピルビフェニル（９．５ｍｇ）を追加し、さらに５時間加熱還流した。反応混合物を放冷後、メタノールを加え、析出した固体をろ取した。得られた固体を水、メタノール、ヘキサンで洗浄し、次いでクロロホルムで熱時ろ過することで、目的の３－［５－（ジベンゾチオフェン－４－イル）－３－（４，６－ジフェニル－１，３，５－トリアジン－２－イル）フェニル］－９－（２－ピリジル）カルバゾール（Ａ－２９）の灰色粉末（収量２１３ｍｇ，収率２９％）を得た。
　^１Ｈ－ＮＭＲ（ＣＤＣｌ_３）：δ７．３８（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＝８．３Ｈｚ，２Ｈ），７．９４－８．０４（ｍ，３Ｈ），８．２３－８．２８（ｍ，３Ｈ），８．３５（ｄ，Ｊ＝１．６Ｈｚ，１Ｈ），８．５４（ｄ，Ｊ＝１．４Ｈｚ，１Ｈ），８．８０－８．８４（ｍ，６Ｈ），９．１７（ｄ，Ｊ＝７．３Ｈｚ，２Ｈ）． Example-31

N- (2-pyridyl) -3- [3-chloro-5- (4,6-diphenyl-1,3,5-triazin-2-yl) phenyl] carbazole (586 mg), 4 -Dibenzothiopheneboronic acid (274 mg), palladium acetate (2.3 mg), 2-dicyclohexylphosphino-2 ', 4', 6'-triisopropylbiphenyl (9.5 mg) in toluene (20.0 mL) and 1- The mixture was suspended in a mixed solvent of butanol (0.6 mL), 3M-potassium carbonate aqueous solution (0.6 mL) was added, and the mixture was heated to reflux for 5 hours. Thereafter, 4-dibenzothiopheneboronic acid (274 mg), palladium acetate (2.3 mg), 2-dicyclohexylphosphino-2 ′, 4 ′, 6′-triisopropylbiphenyl (9.5 mg) were added, and the mixture was further added for 5 hours. Heated to reflux. The reaction mixture was allowed to cool, methanol was added, and the precipitated solid was collected by filtration. The obtained solid was washed with water, methanol and hexane, and then filtered while hot with chloroform to obtain the desired 3- [5- (dibenzothiophen-4-yl) -3- (4,6-diphenyl-1 , 3,5-Triazin-2-yl) phenyl] -9- (2-pyridyl) carbazole (A-29) was obtained as a gray powder (yield 213 mg, yield 29%).
¹ H-NMR (CDCl ₃ ): δ 7.38 (t, J = 7.9 Hz, 1H), 7.48-7.52 (m, 3H), 7.56-7.63 (m, 6H), 7.67 (t, J = 7.2 Hz, 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 (m, 3H), 8.35 (d, J = 1.6 Hz, 1H), 8.54 (d, J = 1.4 Hz, 1H), 8 .80-8.84 (m, 6H), 9.17 (d, J = 7.3 Hz, 2H).

　アルゴン気流下、前記のＮ－（２－ピリジル）－３－［３－クロロ－５－（４，６－ジフェニル－１，３，５－トリアジン－２－イル）フェニル］カルバゾール（５８６ｍｇ）、３－キノリンボロン酸（３４６ｍｇ）、酢酸パラジウム（２．３ｍｇ）、２－ジシクロヘキシルホスフィノ－２’，４’，６’－トリイソプロピルビフェニル（９．５ｍｇ）をトルエン（２０．０ｍＬ）及び１－ブタノール（０．６ｍＬ）の混合溶媒に懸濁し、３Ｍ－炭酸カリウム水溶液（０．６ｍＬ）を添加し、９時間加熱還流した。反応混合物を放冷し、メタノールを加えて析出した固体をろ取した。得られた固体と、３－キノリンボロン酸（３４６ｍｇ）、酢酸パラジウム（２．３ｍｇ）、２－ジシクロヘキシルホスフィノ－２’，４’，６’－トリイソプロピルビフェニル（９．５ｍｇ）をトルエン（２０．０ｍＬ）及び１－ブタノール（０．６ｍＬ）の混合溶媒に懸濁し、３Ｍ－炭酸カリウム水溶液（０．６ｍＬ）を添加し、再度３時間加熱還流した。反応混合物を放冷後、メタノールを加え、析出した固体をろ取した。得られた固体を水、メタノール、ヘキサンで洗浄し、次いでトルエンで再結晶することで、目的の３－［５－（４，６－ジフェニル－１，３，５－トリアジン－２－イル）－３－（３－キノリル）フェニル］－９－（２－ピリジル）カルバゾール（Ａ－３０）の灰色粉末（収量５４１ｍｇ，収率８０％）を得た。
　^１Ｈ－ＮＭＲ（ＣＤＣｌ_３）：δ７．３５－７．４１（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＝８．５Ｈｚ，２Ｈ），７．９８－８．０６（ｍ，３Ｈ），８．２６－８．３３（ｍ，３Ｈ），８．５３（ｓ，１Ｈ），８．６５（ｓ，１Ｈ），８．７９－８．８３（ｍ，５Ｈ），９．１０（ｓ，１Ｈ），９．１８（ｓ，１Ｈ），９．４８（ｓ，１Ｈ）． Example-32

N- (2-pyridyl) -3- [3-chloro-5- (4,6-diphenyl-1,3,5-triazin-2-yl) phenyl] carbazole (586 mg), 3 -Quinolineboronic acid (346 mg), palladium acetate (2.3 mg), 2-dicyclohexylphosphino-2 ', 4', 6'-triisopropylbiphenyl (9.5 mg) in toluene (20.0 mL) and 1-butanol The mixture was suspended in a mixed solvent (0.6 mL), 3M-potassium carbonate aqueous solution (0.6 mL) was added, and the mixture was heated to reflux for 9 hours. The reaction mixture was allowed to cool, methanol was added, and the precipitated solid was collected by filtration. The obtained solid was mixed with 3-quinolineboronic acid (346 mg), palladium acetate (2.3 mg), 2-dicyclohexylphosphino-2 ′, 4 ′, 6′-triisopropylbiphenyl (9.5 mg) in toluene (20 mg). 0.0 mL) and 1-butanol (0.6 mL), 3M-potassium carbonate aqueous solution (0.6 mL) was added, and the mixture was heated to reflux again for 3 hours. The reaction mixture was allowed to cool, methanol was added, and the precipitated solid was collected by filtration. The obtained solid was washed with water, methanol, and hexane, and then recrystallized with toluene to obtain the desired 3- [5- (4,6-diphenyl-1,3,5-triazin-2-yl)- A gray powder (yield 541 mg, yield 80%) of 3- (3-quinolyl) phenyl] -9- (2-pyridyl) carbazole (A-30) was obtained.
¹ H-NMR (CDCl ₃ ): δ 7.35-7.41 (m, 2H), 7.50 (t, J = 7.4 Hz, 1H), 7.58-7.74 (m, 8H), 7.83 (t, J = 6.9 Hz, 1H), 7.91 (t, J = 8.5 Hz, 2H), 7.98-8.06 (m, 3H), 8.26-8.33 (M, 3H), 8.53 (s, 1H), 8.65 (s, 1H), 8.79-8.83 (m, 5H), 9.10 (s, 1H), 9.18 ( s, 1H), 9.48 (s, 1H).

　アルゴン気流下、前記の３－［３－（４，４，５，５－テトラメチル－１，３，２－ジオキサボロラン－２－イル）－５－（４，６－ジフェニル－１，３，５－トリアジン－２－イル）フェニル］－９－（２－ピリジル）カルバゾール（３３９ｍｇ）、３－ブロモ－６－フェニルピリジン（１２９ｍｇ）、テトラキス（トリフェニルホスフィン）パラジウム（１１．６ｍｇ）を１，４－ジオキサン（２．５ｍＬ）に懸濁し、３Ｍ－炭酸カリウム水溶液（０．３３ｍＬ）を添加し、２０時間加熱還流した。反応混合物を放冷後、水を加えた。析出した固体をろ別し、水、メタノール、ヘキサンで洗浄し、減圧下において加熱乾燥した。これをトルエンで再結晶することで、目的の３－［５－（６－フェニルピリジン－３－イル）－３－（４，６－ジフェニル－１，３，５－トリアジン－２－イル）フェニル］－９－（２－ピリジル）カルバゾール（Ａ－３１）の褐色粉末（収量２０７ｍｇ，収率５９％）を得た。
　^１Ｈ－ＮＭＲ（ＣＤＣｌ_３）：δ７．３７－７．４３（ｍ，２Ｈ），７．４９－７．６９（ｍ，１０Ｈ），７．７５（ｄ，Ｊ＝７．８Ｈｚ，１Ｈ），７．９１－７．９３（ｍ，２Ｈ），７．９９（ｄ，Ｊ＝８．３Ｈｚ，１Ｈ），８．０２（ｔ，Ｊ＝７．７Ｈｚ，１Ｈ），８．０６（ｄ，Ｊ＝８．４Ｈｚ，１Ｈ），８．１６（ｄ，Ｊ＝７．３Ｈｚ，２Ｈ），８．２３（ｓ，１Ｈ），８．２７－８，３１（ｍ，２Ｈ），８．５４（ｓ，１Ｈ），８．８１－８．８６（ｍ，５Ｈ），９．０７（ｓ，１Ｈ），９．１７（ｓ，１Ｈ），９．２７（ｓ，１Ｈ）． Example-33

Under the argon stream, the above 3- [3- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -5- (4,6-diphenyl-1,3,5) -Triazin-2-yl) phenyl] -9- (2-pyridyl) carbazole (339 mg), 3-bromo-6-phenylpyridine (129 mg), tetrakis (triphenylphosphine) palladium (11.6 mg) -Suspended in dioxane (2.5 mL), added with 3M aqueous potassium carbonate solution (0.33 mL), and heated to reflux for 20 hours. The reaction mixture was allowed to cool and water was added. The precipitated solid was separated by filtration, washed with water, methanol and hexane, and dried by heating under reduced pressure. By recrystallizing this from toluene, the desired 3- [5- (6-phenylpyridin-3-yl) -3- (4,6-diphenyl-1,3,5-triazin-2-yl) phenyl is obtained. ] -9- (2-pyridyl) carbazole (A-31) was obtained as a brown powder (yield 207 mg, yield 59%).
¹ H-NMR (CDCl ₃ ): δ 7.37-7.43 (m, 2H), 7.49-7.69 (m, 10H), 7.75 (d, J = 7.8 Hz, 1H), 7.91-7.93 (m, 2H), 7.99 (d, J = 8.3 Hz, 1H), 8.02 (t, J = 7.7 Hz, 1H), 8.06 (d, J = 8.4 Hz, 1H), 8.16 (d, J = 7.3 Hz, 2H), 8.23 (s, 1H), 8.27-8, 31 (m, 2H), 8.54 (s) , 1H), 8.81-8.86 (m, 5H), 9.07 (s, 1H), 9.17 (s, 1H), 9.27 (s, 1H).

　アルゴン気流下、前記の３－［３－（４，４，５，５－テトラメチル－１，３，２－ジオキサボロラン－２－イル）－５－（４，６－ジフェニル－１，３，５－トリアジン－２－イル）フェニル］－９－（２－ピリジル）カルバゾール（６７８ｍｇ）、２－ブロモジベンゾチオフェン（３１６ｍｇ）、酢酸パラジウム（２．３ｍｇ）、２－ジシクロヘキシルホスフィノ－２’，４’，６’－トリイソプロピルビフェニル（９．５ｍｇ）をトルエン（２０．０ｍＬ）及び１－ブタノール（０．６ｍＬ）の混合溶媒に懸濁し、３Ｍ－炭酸カリウム水溶液（０．６ｍＬ）を添加し、２４時間加熱還流した。反応混合物を放冷後、メタノールを加え、析出した固体をろ取した。得られた固体を水、メタノール、ヘキサンで洗浄し、次いでトルエンで再結晶することで、目的の３－［５－（ジベンゾチオフェン－２－イル）－３－（４，６－ジフェニル－１，３，５－トリアジン－２－イル）フェニル］－９－（２－ピリジル）カルバゾール（Ａ－３２）の灰色粉末（収量６４０ｍｇ，収率８７％）を得た。
　^１Ｈ－ＮＭＲ（ＣＤＣｌ_３）：δ７．３８－７．４１（ｍ，２Ｈ），７．５０－７．５３（ｍ，３Ｈ），７．５８－７．６４（ｍ，６Ｈ），７．８９－７．９７（ｍ，４Ｈ），８．００－８．０６（ｍ，３Ｈ），８．２２－８．２８（ｍ，２Ｈ），８．３４（ｔ，Ｊ＝５．８Ｈｚ，１Ｈ），８．５０－８．５９（ｍ，２Ｈ），８．７８－８．８５（ｍ，６Ｈ），９．０８－９．１３（ｍ，２Ｈ）． Example-34

Under the argon stream, the above 3- [3- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -5- (4,6-diphenyl-1,3,5) -Triazin-2-yl) phenyl] -9- (2-pyridyl) carbazole (678 mg), 2-bromodibenzothiophene (316 mg), palladium acetate (2.3 mg), 2-dicyclohexylphosphino-2 ', 4' , 6′-triisopropylbiphenyl (9.5 mg) is suspended in a mixed solvent of toluene (20.0 mL) and 1-butanol (0.6 mL), and 3M aqueous potassium carbonate solution (0.6 mL) is added. Heated to reflux for hours. The reaction mixture was allowed to cool, methanol was added, and the precipitated solid was collected by filtration. The obtained solid was washed with water, methanol, and hexane, and then recrystallized with toluene to obtain the desired 3- [5- (dibenzothiophen-2-yl) -3- (4,6-diphenyl-1, A gray powder (yield 640 mg, yield 87%) of 3,5-triazin-2-yl) phenyl] -9- (2-pyridyl) carbazole (A-32) was obtained.
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, 4H), 8.00-8.06 (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 (m, 2H).

　アルゴン気流下、前記化合物（Ｅ－１）（１．０２ｇ）、合成例－１７で合成した３－ブロモ－９－（２－ピリジル）－６－（キノリン－８－イル）カルバゾール（９４６ｍｇ）、テトラキス（トリフェニルホスフィン）パラジウム（４６．２ｍｇ）を１，４－ジオキサン（１０ｍＬ）に懸濁し、３Ｍ－炭酸カリウム水溶液（１．３ｍＬ）を添加し、１３時間加熱還流した。反応混合物を放冷後、水及びメタノールを加えた。析出した固体をろ別し、水、メタノール、ヘキサンで洗浄し、ろ取物を減圧下において過熱乾燥した。得られた固体をキシレンで再結晶することで、目的の３－［５－（４，６－ジフェニル－１，３，５－トリアジン－２－イル）ビフェニル－３－イル］－９－（２－ピリジル）－６－（キノリン－８－イル）カルバゾール（Ａ－３３）の黄褐色粉末（収量１．０８ｇ，収率７２％）を得た。
　^１Ｈ－ＮＭＲ（ＣＤＣｌ_３）：δ７．３９（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，１Ｈ），７．８３（ｄ，Ｊ＝８．１Ｈｚ，１Ｈ），７．８６－７．９１（ｍ，４Ｈ），７．９３－７．９６（ｍ，２Ｈ），８．００－８．０５（ｍ，１Ｈ），８．０３（ｄ，Ｊ＝８．６Ｈｚ，１Ｈ），８．１１（ｄ，Ｊ＝８．６Ｈｚ，１Ｈ），８．２０（ｓ，１Ｈ），８．３１（ｄ，Ｊ＝８．１Ｈｚ，１Ｈ），８．５６（ｓ，１Ｈ），８．５８（ｓ，１Ｈ），８．８２－８．８５（ｍ，５Ｈ），９．００（ｓ，１Ｈ），９．０６－９．０７（ｍ，１Ｈ），９．１１（ｓ，１Ｈ）． Example-35

Under an argon stream, the compound (E-1) (1.02 g), 3-bromo-9- (2-pyridyl) -6- (quinolin-8-yl) carbazole (946 mg) synthesized in Synthesis Example-17, Tetrakis (triphenylphosphine) palladium (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 to reflux for 13 hours. After allowing the reaction mixture to cool, water and methanol were added. The precipitated solid was collected by filtration, washed with water, methanol, and hexane, and the filtered product was dried by heating under reduced pressure. The obtained solid was recrystallized from xylene to give the desired 3- [5- (4,6-diphenyl-1,3,5-triazin-2-yl) biphenyl-3-yl] -9- (2 A yellow-brown powder (yield 1.08 g, yield 72%) of -pyridyl) -6- (quinolin-8-yl) carbazole (A-33) was obtained.
¹ H-NMR (CDCl ₃ ): δ 7.39 (dd, J = 7.4, 4.9 Hz, 1H), 7.45-7.51 (m, 2H), 7.56-7.65 (m 8H), 7.71 (t, J = 7.3 Hz, 1H), 7.83 (d, J = 8.1 Hz, 1H), 7.86-7.91 (m, 4H), 7.93. -7.96 (m, 2H), 8.00-8.05 (m, 1H), 8.03 (d, J = 8.6 Hz, 1H), 8.11 (d, J = 8.6 Hz, 1H), 8.20 (s, 1H), 8.31 (d, J = 8.1 Hz, 1H), 8.56 (s, 1H), 8.58 (s, 1H), 8.82-8 .85 (m, 5H), 9.00 (s, 1H), 9.06-9.07 (m, 1H), 9.11 (s, 1H).

　アルゴン気流下、２－［４－（４，４，５，５－テトラメチル－１，３，２－ジオキサボロラン－２－イル）フェニル］－４，６－ジフェニル－１，３，５－トリアジン（１．３１ｇ）、３－ブロモ－９－（２－ピリジル）－６－［４－（２－ピリジル）フェニル］カルバゾール（１．５７ｇ）、テトラキス（トリフェニルホスフィン）パラジウム（６９．３ｍｇ）を１，４－ジオキサン（２０ｍＬ）及び３Ｍ－炭酸カリウム水溶液（２．０ｍＬ）の混合溶媒に懸濁し、１３時間加熱還流した。室温まで冷却後、水及びメタノールを加えた。析出した固体を水、メタノール、ヘキサンで洗浄し、ろ取物をキシレンで再結晶することで、目的の３－［４－（４，６－ジフェニル－１，３，５－トリアジン－２－イル）フェニル］－９－（２－ピリジル）－６－［４－（２－ピリジル）フェニル］カルバゾール（Ａ－３４）の褐色固体（収量１．３３ｇ，収率６３％）を得た。
　^１Ｈ－ＮＭＲ（ＤＭＳＯ－ｄ_６）：δ７．２６－７．２９（ｍ，１Ｈ），７．３８（ｄｄ，Ｊ＝７．５Ｈｚ，４．９Ｈｚ，１Ｈ），７．６０－７．６８（ｍ，６Ｈ），７．７４（ｄ，Ｊ＝８．０Ｈｚ，１Ｈ），７．８１（ｄ，Ｊ＝８．７Ｈｚ，２Ｈ），７．８３－７．８６（ｍ，２Ｈ），７．９０（ｄ，Ｊ＝８．５Ｈｚ，２Ｈ），７．９６－８．０３（ｍ，５Ｈ），８．１６（ｄ，Ｊ＝８．５Ｈｚ，２Ｈ），８．５１（ｓ，１Ｈ），８．５４（ｓ，１Ｈ），８．７６（ｄ，Ｊ＝４．６Ｈｚ，１Ｈ），８．８０（ｄ，Ｊ＝４．９Ｈｚ，１Ｈ），８．８３（ｄ，Ｊ＝７．９Ｈｚ，４Ｈ），８．９１（ｄ，Ｊ＝８．５Ｈｚ，２Ｈ）． Example-36

Under an argon stream, 2- [4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-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) , 4-Dioxane (20 mL) and a 3M-potassium carbonate aqueous solution (2.0 mL) were suspended in a mixed solvent and heated to reflux for 13 hours. After cooling to room temperature, water and methanol were added. The precipitated solid is washed with water, methanol and hexane, and the filtered product is recrystallized with xylene to give the desired 3- [4- (4,6-diphenyl-1,3,5-triazin-2-yl]. ) Phenyl] -9- (2-pyridyl) -6- [4- (2-pyridyl) phenyl] carbazole (A-34) was obtained as a brown solid (1.33 g, 63% yield).
¹ H-NMR (DMSO-d ₆ ): δ 7.26-7.29 (m, 1H), 7.38 (dd, J = 7.5 Hz, 4.9 Hz, 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 (m, 5H), 8.16 (d, J = 8.5 Hz, 2H), 8.51 (s, 1H) , 8.54 (s, 1H), 8.76 (d, J = 4.6 Hz, 1H), 8.80 (d, J = 4.9 Hz, 1H), 8.83 (d, J = 7. 9 Hz, 4H), 8.91 (d, J = 8.5 Hz, 2H).

　アルゴン気流下、前記化合物（Ｅ－１）（１．０２ｇ）、３－ブロモ－６，９－ジ（２－ピリジル）カルバゾール（９６１ｍｇ）、酢酸パラジウム（４．５ｍｇ）、２－ジシクロヘキシルホスフィノ－２’，４’，６’－トリイソプロピルビフェニル（１９．０ｍｇ）を１，４－ジオキサン（４０．０ｍＬ）に懸濁し、３Ｍ－炭酸カリウム水溶液（１．３ｍＬ）を添加し、９５℃で４時間加熱した。反応混合物を放冷後、メタノールを加え、析出した固体をろ取した。得られた固体を水、メタノール、ヘキサンで洗浄し、次いでトルエンで再結晶することで、目的の６－[５－（４，６－ジフェニル－１，３，５－トリアジン－２－イル）ビフェニル－３－イル]－３，９－ジ（２－ピリジル）カルバゾール（Ａ－３５）の灰色粉末（収量４９２ｍｇ，収率３５％）を得た。
　^１Ｈ－ＮＭＲ（ＣＤＣｌ_３）：δ７．２６－７．２９（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＝８．０Ｈｚ，１Ｈ），７．８４（ｔ，Ｊ＝７．７Ｈｚ，１Ｈ），７．８８－７．９２（ｍ，２Ｈ），７．９５（ｄ，Ｊ＝８．６Ｈｚ，２Ｈ），８．００（ｄ，Ｊ＝８．６Ｈｚ，１Ｈ），８．０４（ｔ，Ｊ＝７．７Ｈｚ，１Ｈ），８．０６（ｄ，Ｊ＝８．６Ｈｚ，１Ｈ），８．１８－８．２３（ｍ，２Ｈ），８．６４（ｓ，１Ｈ），８．７８（ｄ，Ｊ＝４．８Ｈｚ，１Ｈ），８．８３（ｄ，Ｊ＝４．９Ｈｚ，１Ｈ），８．８５（ｄ，Ｊ＝７．８Ｈｚ，４Ｈ），８．９５（ｓ，１Ｈ），９．０２（ｓ，１Ｈ），９．１１（ｓ，１Ｈ）． Example-37

Under an argon stream, the compound (E-1) (1.02 g), 3-bromo-6,9-di (2-pyridyl) carbazole (961 mg), palladium acetate (4.5 mg), 2-dicyclohexylphosphino- 2 ′, 4 ′, 6′-triisopropylbiphenyl (19.0 mg) was suspended in 1,4-dioxane (40.0 mL), 3M aqueous potassium carbonate solution (1.3 mL) was added, and the mixture was added at 95 ° C. for 4 hours. Heated for hours. The reaction mixture was allowed to cool, methanol was added, and the precipitated solid was collected by filtration. The obtained solid was washed with water, methanol and hexane, and then recrystallized with toluene to obtain the desired 6- [5- (4,6-diphenyl-1,3,5-triazin-2-yl) biphenyl. A gray powder (yield 492 mg, yield 35%) of -3-yl] -3,9-di (2-pyridyl) carbazole (A-35) was obtained.
¹ H-NMR (CDCl ₃ ): δ 7.26-7.29 (m, 1H), 7.41 (dd, J = 7.4, 4.9 Hz, 1H), 7.50 (t, J = 7 .4 Hz, 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 (m, 2H), 7.95 (d, J = 8.6 Hz, 2H), 8.00 (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 (m, 2H), 8.64 (s, 1H), 8.78 (d, J = 4.8 Hz, 1H), 8.83 (d, J = 4.9 Hz, 1H), 8.85 (d, J = 7.8 Hz, 4H), 8.95 (s, 1H), 9. 02 (s, 1H), 9.11 (s 1H).

　アルゴン気流下、２－（３，５－ジブロモフェニル）－４，６－ジフェニルピリミジン（４６６ｍｇ）、９－アントラセンボロン酸（２３３ｍｇ）、及びテトラキス（トリフェニルホスフィン）パラジウム（２３ｍｇ）を、４Ｎ－水酸化ナトリウム水溶液（０．５ｍＬ）とＴＨＦ（２．０ｍＬ）の混合溶媒に懸濁し、３０℃で３時間撹拌した。その後、水を加え、析出した固体はろ過し、水、次いでメタノール、その後ヘキサンで洗浄して、黄白色固体を５００ｍｇ得た。
　得られた黄白色固体（５００ｍｇ）、３－［４－（２－ピリジル）フェニル］カルバゾール（２８５ｍｇ）、酢酸パラジウム（４ｍｇ）、１Ｍ－トリ（ｔｅｒｔ－ブチル）ホスフィンのトルエン溶液（５３μＬ）、炭酸カリウム（２４６ｍｇ）、及び１８－クラウン－６－エーテル（４７ｍｇ）をキシレン（４．４ｍＬ）に懸濁し、５時間加熱還流した。反応混合物を放冷後、クロロホルムで抽出した。有機層をシリカゲルクロマトグラフィー（展開溶媒；クロロホルム）で精製し、３－［４－（２－ピリジル）フェニル］－９－［３－（４，６－ジフェニルピリミジン－２－イル）－５－（アントラセン－９－イル）］フェニルカルバゾール（Ｂ－１）の黄色固体（収量５８０ｍｇ，収率７２％）を得た。
　^１Ｈ－ＮＭＲ（ＣＤＣｌ_３）：δ７．２９（ｔ，Ｊ＝５．９Ｈｚ，１Ｈ），７．４８（ｔ，Ｊ＝７．４Ｈｚ，１Ｈ），７．５４－７．６４（ｍ，１１Ｈ），７．７９（ｔ，Ｊ＝８．０Ｈｚ，１Ｈ），７．８３（ｄ，Ｊ＝７．９Ｈｚ，１Ｈ），７．８６－７．０７（ｍ，６Ｈ），８．１２（ｄ，Ｊ＝７．５Ｈｚ，２Ｈ），８．１６（ｓ，１Ｈ），８．１９－８．２４（ｍ，４Ｈ），８．３３－８．３８（ｍ，５Ｈ），８．５８（ｓ，１Ｈ），８．６７（ｓ，１Ｈ），８．８４（ｄ，Ｊ＝４．８Ｈｚ，１Ｈ），９．１３（ｓ，１Ｈ），９．３８（ｓ，１Ｈ）． Example-38

Under an argon stream, 2- (3,5-dibromophenyl) -4,6-diphenylpyrimidine (466 mg), 9-anthraceneboronic acid (233 mg), and tetrakis (triphenylphosphine) palladium (23 mg) were added to 4N-water. The mixture was suspended in a mixed solvent of an aqueous sodium oxide solution (0.5 mL) and THF (2.0 mL), and stirred at 30 ° C. for 3 hours. Thereafter, water was added, and the precipitated solid was filtered, washed with water, then methanol, and then hexane to obtain 500 mg of a yellowish white solid.
The obtained yellowish white solid (500 mg), 3- [4- (2-pyridyl) phenyl] carbazole (285 mg), palladium acetate (4 mg), toluene solution (53 μL) of 1M-tri (tert-butyl) phosphine, carbonic acid Potassium (246 mg) and 18-crown-6-ether (47 mg) were suspended in xylene (4.4 mL) and heated to reflux for 5 hours. The reaction mixture was allowed to cool and extracted with chloroform. The organic layer was purified by silica gel chromatography (developing solvent; chloroform), and 3- [4- (2-pyridyl) phenyl] -9- [3- (4,6-diphenylpyrimidin-2-yl) -5- ( An anthracen-9-yl)] phenylcarbazole (B-1) was obtained as a yellow solid (yield 580 mg, yield 72%).
¹ H-NMR (CDCl ₃ ): δ 7.29 (t, J = 5.9 Hz, 1H), 7.48 (t, J = 7.4 Hz, 1H), 7.54-7.64 (m, 11H) ), 7.79 (t, J = 8.0 Hz, 1H), 7.83 (d, J = 7.9 Hz, 1H), 7.86-7.07 (m, 6H), 8.12 (d , J = 7.5 Hz, 2H), 8.16 (s, 1H), 8.19-8.24 (m, 4H), 8.33-8.38 (m, 5H), 8.58 (s) , 1H), 8.67 (s, 1H), 8.84 (d, J = 4.8 Hz, 1H), 9.13 (s, 1H), 9.38 (s, 1H).

　アルゴン気流下、２－（５－クロロビフェニル－３－イル）－４，６－ジフェニルピリミジン（３．２５ｇ）、３－［４－（２－ピリジル）フェニル］カルバゾール（２．７３ｇ）、酢酸パラジウム（３４．８ｍｇ）、１Ｍ－トリ（ｔｅｒｔ－ブチル）ホスフィンのトルエン溶液（４６５μＬ）、炭酸カリウム（２．１４ｇ）、及び１８－クラウン－６－エーテル（４１０ｍｇ）を、キシレン（３９ｍＬ）に懸濁し、１８時間加熱還流した。反応混合物を放冷後、クロロホルムで抽出した。有機層をシリカゲルクロマトグラフィー（展開溶媒；クロロホルム）で精製し、目的物である３－［４－（２－ピリジル）フェニル］－９－［５－（４，６－ジフェニルピリミジン－２－イル）ビフェニル－３－イル］カルバゾール（Ｂ－２）の褐色粉末（収量５．０３ｇ，収率９２％）を得た。
　^１Ｈ－ＮＭＲ（ＣＤＣｌ_３）：δ７．２８（ｄｄ，Ｊ＝７．０，４．８Ｈｚ，１Ｈ），７．３９（ｔ，Ｊ＝７．４Ｈｚ，１Ｈ），７．４７（ｔ，Ｊ＝７．４Ｈｚ，１Ｈ），７．５１（ｔ，Ｊ＝７．７Ｈｚ，１Ｈ），７．５５－７．６４（ｍ，９Ｈ），７．６８（ｄ，Ｊ＝８．６Ｈｚ，１Ｈ），７．７８－７．８７（ｍ，５Ｈ），７．９０（ｄ，Ｊ＝８．５Ｈｚ，２Ｈ），８．００（ｓ，１Ｈ），８．１３（ｓ、１Ｈ），８．１７（ｄ，Ｊ＝８．５Ｈｚ，２Ｈ），８．３２９－８．３５（ｍ，５Ｈ），８．５１（ｓ，１Ｈ），８．７６（ｄ，Ｊ＝４．８Ｈｚ，１Ｈ），８．９７（ｓ，１Ｈ），９．１２（ｓ，１Ｈ）． Example-39

Under an argon stream, 2- (5-chlorobiphenyl-3-yl) -4,6-diphenylpyrimidine (3.25 g), 3- [4- (2-pyridyl) phenyl] carbazole (2.73 g), palladium acetate (34.8 mg) 1M-tri (tert-butyl) phosphine in toluene (465 μL), potassium carbonate (2.14 g), and 18-crown-6-ether (410 mg) were suspended in xylene (39 mL). And heated to reflux for 18 hours. The reaction mixture was allowed to cool and extracted with chloroform. The organic layer was purified by silica gel chromatography (developing solvent; chloroform), and the target product 3- [4- (2-pyridyl) phenyl] -9- [5- (4,6-diphenylpyrimidin-2-yl) A brown powder of biphenyl-3-yl] carbazole (B-2) was obtained (yield 5.03 g, yield 92%).
¹ H-NMR (CDCl ₃ ): δ 7.28 (dd, J = 7.0, 4.8 Hz, 1H), 7.39 (t, J = 7.4 Hz, 1H), 7.47 (t, J = 7.4 Hz, 1H), 7.51 (t, J = 7.7 Hz, 1H), 7.55-7.64 (m, 9H), 7.68 (d, J = 8.6 Hz, 1H) , 7.78-7.87 (m, 5H), 7.90 (d, J = 8.5 Hz, 2H), 8.00 (s, 1H), 8.13 (s, 1H), 8.17 (D, J = 8.5 Hz, 2H), 8.329-8.35 (m, 5H), 8.51 (s, 1H), 8.76 (d, J = 4.8 Hz, 1H), 8 .97 (s, 1H), 9.12 (s, 1H).

　アルゴン気流下、２－（５－クロロビフェニル－３－イル）－４，６－ジフェニルピリミジン（１．２０ｇ）、３－（２－ピリジル）カルバゾール（７７０ｍｇ）、酢酸パラジウム（１２．８ｍｇ）、１Ｍ－トリ（ｔｅｒｔ－ブチル）ホスフィンのトルエン溶液（１７２μＬ）、炭酸カリウム（７９１ｍｇ）、及び１８－クラウン－６－エーテル（１５１ｍｇ）を、キシレン（１４ｍＬ）に懸濁し、４４時間加熱還流した。反応混合物を放冷後、クロロホルムで抽出した。有機層をシリカゲルクロマトグラフィー（展開溶媒；クロロホルム）で精製し、目的物である３－（２－ピリジル）－９－［５－（４，６－ジフェニルピリミジン－２－イル）ビフェニル－３－イル］カルバゾール（Ｂ－３）の褐色粉末（収量９４９ｍｇ，収率５３％）を得た。
　^１Ｈ－ＮＭＲ（ＣＤＣｌ_３）：δ７．２５（ｄｄ，Ｊ＝７．２，４．８Ｈｚ，１Ｈ），７．３８（ｔ，Ｊ＝７．４Ｈｚ，１Ｈ），７．４７（ｔ，Ｊ＝７．４Ｈｚ，１Ｈ），７．５０（ｔ，Ｊ＝７．７Ｈｚ，１Ｈ），７．５４－７．６２（ｍ，９Ｈ），７．６６（ｄ，Ｊ＝８．８Ｈｚ，１Ｈ），７．８１（ｔ，Ｊ＝７．７Ｈｚ，１Ｈ），７．８４（ｄ，Ｊ＝８．０Ｈｚ，２Ｈ），７．９０（ｄ，Ｊ＝８．０Ｈｚ，１Ｈ），７．９９（ｓ，１Ｈ），８．１２（ｄ，Ｊ＝８．６Ｈｚ，１Ｈ），８．１３（ｓ、１Ｈ），８．２９－８．３３（ｍ，５Ｈ），８．７７（ｄ，Ｊ＝４．８Ｈｚ，１Ｈ），８．９１（ｓ，１Ｈ），８．９６（ｓ，１Ｈ），９．１１（ｓ，１Ｈ）． Example-40

Under an argon stream, 2- (5-chlorobiphenyl-3-yl) -4,6-diphenylpyrimidine (1.20 g), 3- (2-pyridyl) carbazole (770 mg), palladium acetate (12.8 mg), 1M -Toluene solution of tri (tert-butyl) phosphine (172 μL), potassium carbonate (791 mg), and 18-crown-6-ether (151 mg) were suspended in xylene (14 mL) and heated to reflux for 44 hours. The reaction mixture was allowed to cool and extracted with chloroform. The organic layer was purified by silica gel chromatography (developing solvent; chloroform), and the target product 3- (2-pyridyl) -9- [5- (4,6-diphenylpyrimidin-2-yl) biphenyl-3-yl was obtained. A brown powder of carbazole (B-3) (yield 949 mg, yield 53%) was obtained.
¹ H-NMR (CDCl ₃ ): δ 7.25 (dd, J = 7.2, 4.8 Hz, 1H), 7.38 (t, J = 7.4 Hz, 1H), 7.47 (t, J = 7.4 Hz, 1H), 7.50 (t, J = 7.7 Hz, 1H), 7.54-7.62 (m, 9H), 7.66 (d, J = 8.8 Hz, 1H) , 7.81 (t, J = 7.7 Hz, 1H), 7.84 (d, J = 8.0 Hz, 2H), 7.90 (d, J = 8.0 Hz, 1H), 7.99 ( s, 1H), 8.12 (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).

　アルゴン気流下、９－（２－ピリジル）－９－［３－クロロ－５－（４，６－ジフェニルピリミジン－２－イル）フェニル］カルバゾール（１．１７ｇ）、フェニルボロン酸（２９３ｍｇ）、酢酸パラジウム（９．０ｍｇ）、２－ジシクロヘキシルホスフィノ－２’，４’，６’－トリイソプロピルビフェニル（５７ｍｇ）、及び３Ｍ－炭酸カリウム水溶液（１．６ｍＬ）を、トルエン（９．０ｍＬ）及びｎ－ブタノール（１．０ｍＬ）の混合溶媒に懸濁し、３時間加熱還流した。反応混合物を放冷後、水を加え、クロロホルムで抽出した。次いで、有機層を硫酸マグネシウムで乾燥させた後、ろ過し、溶媒を減圧留去した。その後、濃縮した有機層にヘキサンを加え、固体を再沈殿させることで、目的物である９－（２－ピリジル）－３－［５－（４，６－ジフェニルピリミジン－２－イル）ビフェニル－３－イル］カルバゾール（Ｂ－４）の褐色粉末（収量９００ｍｇ，収率７２％）を得た。
　^１Ｈ－ＮＭＲ（ＣＤＣｌ_３）：δ７．２８（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＝８．１Ｈｚ，１Ｈ），７．８９－７．９４（ｍ，４Ｈ），７．９８（ｔ，Ｊ＝７．７Ｈｚ，１Ｈ），８．０２（ｄ，Ｊ＝８．５Ｈｚ，１Ｈ），８．０７（ｓ、１Ｈ），８．１２（ｓ，１Ｈ），８．２５（ｄ，Ｊ＝７．４Ｈｚ，１Ｈ），８．３４９－８．３７（ｍ，４Ｈ），８．５４（ｓ，１Ｈ），８．８１（ｄ，Ｊ＝４．９Ｈｚ，１Ｈ），８．９９（ｓ，１Ｈ），９．０８（ｓ，１Ｈ）． Example-41

Under an argon stream, 9- (2-pyridyl) -9- [3-chloro-5- (4,6-diphenylpyrimidin-2-yl) phenyl] carbazole (1.17 g), phenylboronic acid (293 mg), acetic acid Palladium (9.0 mg), 2-dicyclohexylphosphino-2 ′, 4 ′, 6′-triisopropylbiphenyl (57 mg), and 3M aqueous potassium carbonate solution (1.6 mL) were added to toluene (9.0 mL) and n -Suspended in a mixed solvent of butanol (1.0 mL) and heated to reflux for 3 hours. The reaction mixture was allowed to cool, water was added, and the mixture was extracted with chloroform. Next, the organic layer was dried over magnesium sulfate and filtered, and the solvent was distilled off under reduced pressure. Thereafter, hexane is added to the concentrated organic layer, and the solid is reprecipitated, whereby the target product 9- (2-pyridyl) -3- [5- (4,6-diphenylpyrimidin-2-yl) biphenyl- A brown powder (yield 900 mg, yield 72%) of 3-yl] carbazole (B-4) was obtained.
¹ H-NMR (CDCl ₃ ): δ 7.28 (dd, J = 7.4, 4.9 Hz, 1H), 7.40 (t, J = 7.4 Hz, 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, 1H), 8.02 (d, J = 8.5 Hz, 1H), 8.07 (s, 1H), 8.12 (s, 1H), 8.25 (d , J = 7.4 Hz, 1H), 8.349-8.37 (m, 4H), 8.54 (s, 1H), 8.81 (d, J = 4.9 Hz, 1H), 8.99. (S, 1H), 9.08 (s, 1H).

　アルゴン気流下、９－（２－ピリジル）－９－［３－クロロ－５－（４，６－ジフェニルピリミジン－２－イル）フェニル］カルバゾール（５８５ｍｇ）、４－（２－ピリジル）フェニルボロン酸（２３９ｍｇ）、酢酸パラジウム（４．５ｍｇ）、２－ジシクロヘキシルホスフィノ－２’，４’，６’－トリイソプロピルビフェニル（２９ｍｇ）、及び３Ｍ－炭酸カリウム水溶液（０．８ｍＬ）を、トルエン（４．５ｍＬ）及びｎ－ブタノール（０．５ｍＬ）の混合溶媒に懸濁し、３時間加熱還流した。反応混合物を放冷後、水及びメタノールを加えてスラリーとし、固体を析出させた。析出した固体はろ過し、水、次いでメタノール、その後ヘキサンで洗浄して、目的物である９－（２－ピリジル）－３－［５－（４，６－ジフェニルピリミジン－２－イル）－４’－（２－ピリジル）ビフェニル－３－イル］カルバゾール（Ｂ－５）の褐色粉末（収量６７６ｍｇ，収率９６％）を得た。
　^１Ｈ－ＮＭＲ（ＣＤＣｌ_３）：δ７．２８（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＝７．５Ｈｚ，１Ｈ），７．５６－７．６３（ｍ，６Ｈ），７．７１（ｄ，Ｊ＝８．０Ｈｚ，１Ｈ），７．７８－７．８５（ｍ，２Ｈ），７．９１－８．０２（ｍ，６Ｈ），８．０５（ｓ，１Ｈ），８．１５（ｓ、１Ｈ），８．２１（ｄ，Ｊ＝８．３Ｈｚ，２Ｈ），８．２５（ｄ，Ｊ＝７．７Ｈｚ，１Ｈ），８．３５（ｄ，Ｊ＝７．８Ｈｚ，４Ｈ），８．５３（ｓ，１Ｈ），８．７８（ｄ，Ｊ＝４．８Ｈｚ，１Ｈ），８．８０（ｄ＝４．４Ｈｚ，１Ｈ），９．０３（ｓ，１Ｈ），９．０８（ｓ，１Ｈ）． Example-42

Under an argon stream, 9- (2-pyridyl) -9- [3-chloro-5- (4,6-diphenylpyrimidin-2-yl) phenyl] carbazole (585 mg), 4- (2-pyridyl) phenylboronic acid (239 mg), palladium acetate (4.5 mg), 2-dicyclohexylphosphino-2 ′, 4 ′, 6′-triisopropylbiphenyl (29 mg), and 3M aqueous potassium carbonate solution (0.8 mL) were added to toluene (4 mL). 0.5 mL) and n-butanol (0.5 mL), and the mixture was heated to reflux for 3 hours. After allowing the reaction mixture to cool, water and methanol were added to form a slurry, and a solid was precipitated. The precipitated solid was filtered, washed with water, then methanol, and then with hexane, and the desired product, 9- (2-pyridyl) -3- [5- (4,6-diphenylpyrimidin-2-yl) -4 A brown powder (yield 676 mg, yield 96%) of '-(2-pyridyl) biphenyl-3-yl] carbazole (B-5) was obtained.
¹ H-NMR (CDCl ₃ ): δ 7.28 (t, J = 6.0 Hz, 1H), 7.34 (dd, J = 7.2, 5.0 Hz, 1H), 7.39 (t, J = 7.5 Hz, 1 H), 7.52 (t, J = 7.5 Hz, 1 H), 7.56-7.63 (m, 6 H), 7.71 (d, J = 8.0 Hz, 1 H) , 7.78-7.85 (m, 2H), 7.91-8.02 (m, 6H), 8.05 (s, 1H), 8.15 (s, 1H), 8.21 (d , J = 8.3 Hz, 2H), 8.25 (d, J = 7.7 Hz, 1H), 8.35 (d, J = 7.8 Hz, 4H), 8.53 (s, 1H), 8 .78 (d, J = 4.8 Hz, 1H), 8.80 (d = 4.4 Hz, 1H), 9.03 (s, 1H), 9.08 (s, 1H).

　アルゴン気流下、９－（２－ピリジル）－９－［３－クロロ－５－（４，６－ジフェニルピリミジン－２－イル）フェニル］カルバゾール（１．１７ｇ）、４－（２－ピラジル）フェニルボロン酸（４８０ｍｇ）、酢酸パラジウム（９．０ｍｇ）、２－ジシクロヘキシルホスフィノ－２’，４’，６’－トリイソプロピルビフェニル（５７ｍｇ）、及び３Ｍ－炭酸カリウム水溶液（１．６ｍＬ）を、トルエン（９．０ｍＬ）及びｎ－ブタノール（１．０ｍＬ）の混合溶媒に懸濁し、２時間加熱還流した。反応混合物を放冷後、水を加えた。析出した固体はろ過し、水、次いでメタノール、その後ヘキサンで洗浄して、目的物である９－（２－ピリジル）－３－［５－（４，６－ジフェニルピリミジン－２－イル）－４’－（２－ピラジル）ビフェニル－３－イル］カルバゾール（Ｂ－６）の褐色粉末（収量１．２５ｇ，収率８９％）を得た。
　^１Ｈ－ＮＭＲ（ＣＤＣｌ_３）：δ７．３４－７．４０（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＝８．５Ｈｚ，１Ｈ），７．９２（ｄ，Ｊ＝８．２Ｈｚ，１Ｈ），７．９６－８．０３（ｍ，４Ｈ），８．０６（ｓ、１Ｈ），８．１３（ｓ，１Ｈ），８．２１－８．２５（ｍ，３Ｈ），８．３３－８．３５（ｍ，４Ｈ），８．５２（ｓ，１Ｈ），８．５６（ｓ，１Ｈ），８．７０（ｓ，１Ｈ），８．８０（ｄ，Ｊ＝４．８Ｈｚ，１Ｈ），９．０１（ｓ，１Ｈ），９．０８（ｓ，１Ｈ），９．１５（ｓ，１Ｈ）． Example-43

Under argon flow, 9- (2-pyridyl) -9- [3-chloro-5- (4,6-diphenylpyrimidin-2-yl) phenyl] carbazole (1.17 g), 4- (2-pyrazyl) phenyl Boronic acid (480 mg), palladium acetate (9.0 mg), 2-dicyclohexylphosphino-2 ′, 4 ′, 6′-triisopropylbiphenyl (57 mg), and 3M aqueous potassium carbonate solution (1.6 mL) were added to toluene. (9.0 mL) and n-butanol (1.0 mL) were suspended in a mixed solvent and heated to reflux for 2 hours. The reaction mixture was allowed to cool and water was added. The precipitated solid was filtered, washed with water, then methanol, and then with hexane, and the desired product, 9- (2-pyridyl) -3- [5- (4,6-diphenylpyrimidin-2-yl) -4 A brown powder (yield 1.25 g, yield 89%) of '-(2-pyrazyl) biphenyl-3-yl] carbazole (B-6) was obtained.
¹ H-NMR (CDCl ₃ ): δ 7.34-7.40 (m, 2H), 7.51 (t, J = 7.7 Hz, 1H), 7.56-7.63 (m, 6H), 7.72 (d, J = 8.0 Hz, 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), 8.13 (s, 1H), 8.21-8.25 (m, 3H), 8.33-8.35 (m, 4H) ), 8.52 (s, 1H), 8.56 (s, 1H), 8.70 (s, 1H), 8.80 (d, J = 4.8 Hz, 1H), 9.01 (s, 1H), 9.08 (s, 1H), 9.15 (s, 1H).

　アルゴン気流下、合成例－２０で合成した４－（４－ブロモフェニル）－６－（１－ナフチル）－２－フェニルピリミジン（２１９ｍｇ）、合成例－１５で合成した３－（キノリン－８－イル）カルバゾール（１６２ｍｇ）、酢酸パラジウム（２．２ｍｇ）、１Ｍ－トリ（ｔｅｒｔ－ブチル）ホスフィンのトルエン溶液（３０μＬ）、炭酸カリウム（１５２ｍｇ）、１８－クラウン－６－エーテル（２６ｍｇ）をキシレン（２．５ｍＬ）に懸濁し、２０時間加熱還流した。反応混合物を放冷後、ろ過することで不要物を除去した。濾液をシリカゲルクロマトグラフィー（展開溶媒　クロロホルム）で精製し、目的の９－［４－（６－ナフチル－２－フェニルピリミジン－４－イル）フェニル］－３－（キノリン－８－イル）カルバゾール（Ｂ－７）の黄色粉末（収量２９７ｍｇ，収率９１％）を得た。
　^１Ｈ－ＮＭＲ（ＣＤＣｌ_３）：δ７．３５（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＝８．５Ｈｚ，１Ｈ），７．８８（ｄ，Ｊ＝８．６Ｈｚ，２Ｈ），７．８６－７．９３（ｍ，３Ｈ），８．００－８．０２（ｍ，１Ｈ），８．０４（ｓ，１Ｈ），８．０６（ｄ，Ｊ＝８．２Ｈｚ，１Ｈ），８．２１（ｄ，Ｊ＝７．６Ｈｚ，１Ｈ），８．２９（ｄ，Ｊ＝８．３Ｈｚ，１Ｈ），８．４３－８．４６（ｍ，１Ｈ），８．４８（ｓ，１Ｈ），８．６０（ｄ，Ｊ＝８．６Ｈｚ，２Ｈ），８．７６－８．７９（ｍ，２Ｈ），９．０４（ｄ，Ｊ＝４．１Ｈｚ，１Ｈ）．
＜環状アジンを構成成分とする有機電界発光素子の作製と性能評価＞
　以下の実施例、参考例、及び比較例は、有機電界発光素子の作製と性能評価に関するものである。
　用いた化合物の構造式は、以下に示す通りである。 Example-44

Under an argon stream, 4- (4-bromophenyl) -6- (1-naphthyl) -2-phenylpyrimidine (219 mg) synthesized in Synthesis Example-20, 3- (quinoline-8-) synthesized in Synthesis Example-15 Yl) carbazole (162 mg), palladium acetate (2.2 mg), toluene solution (30 μL) of 1M-tri (tert-butyl) phosphine, potassium carbonate (152 mg), 18-crown-6-ether (26 mg) in xylene ( 2.5 mL) and heated to reflux for 20 hours. The reaction mixture was allowed to cool and then filtered to remove unnecessary substances. The filtrate was purified by silica gel chromatography (developing solvent: chloroform), and the desired 9- [4- (6-naphthyl-2-phenylpyrimidin-4-yl) phenyl] -3- (quinolin-8-yl) carbazole (B A yellow powder of -7) (yield 297 mg, yield 91%) was obtained.
¹ H-NMR (CDCl ₃ ): δ 7.35 (t, J = 7.4 Hz, 1H), 7.47 (d, J = 8.0 Hz, 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 (m, 1H), 8.04 (s, 1H), 8.06 (d, J = 8.2 Hz, 1H), 8.21 (d, J = 7.6 Hz, 1H), 8.29 (d, J = 8.3 Hz, 1H), 8.43-8.46 (m, 1H) , 8.48 (s, 1H), 8.60 (d, J = 8.6 Hz, 2H), 8.76-8.79 (m, 2H), 9.04 (d, J = 4.1 Hz, 1H).
<Preparation and performance evaluation of organic electroluminescence device comprising cyclic azine as a constituent>
The following examples, reference examples, and comparative examples relate to the fabrication and performance evaluation of organic electroluminescent elements.
The structural formula of the compound used is as shown below.

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 cleaned with isopropyl alcohol and then surface-treated by oxygen plasma cleaning. Each layer was vacuum-deposited on the cleaned substrate by a vacuum deposition method, and an organic electroluminescence device having a light-emitting area of 4 mm ² as shown in FIG.
First, the glass substrate was introduced into a vacuum evaporation tank, and the pressure was reduced to 1.0 × 10 ⁻⁴ Pa. Thereafter, a hole injection layer 2, a hole transport layer 3, a light emitting layer 4, and an electron transport layer 5 are sequentially formed as an organic compound layer on the glass substrate with an ITO transparent electrode shown by 1 in FIG. Layer 6 was deposited. In addition, the material which comprises each layer of an organic electroluminescent element was vacuum-deposited by the resistance heating system.
As the hole injection layer 2, sublimated and purified CuPc was vacuum-deposited at a film thickness of 25 nm with a film formation rate of 0.06 nm / second.
As the hole transport layer 3, NPD was vacuum-deposited with a film thickness of 45 nm at a film formation rate of 0.30 nm / second.
As the light emitting layer 4, EML-1 and EML-2 are vacuum-formed at a film formation rate of 0.18 nm / second and a film thickness of 40 nm (co-evaporation of EML-1 / EML-2 = 95/5 (weight ratio)). Vapor deposited.
As the electron transport layer 5, A-1 synthesized in Example 1 of the present invention was vacuum-deposited with a film thickness of 20 nm at a film formation rate of 0.25 nm / second.
Finally, a metal mask was disposed so as to be orthogonal to the ITO stripe, and the cathode layer 6 was formed. The cathode layer 6 is formed by vacuum deposition of lithium fluoride and aluminum in this order at a film thickness of 1.0 nm and 100 nm at a film formation rate of 0.1 nm / second and 0.25 nm / second, respectively. did.
Each film thickness was measured with a stylus type film thickness meter (DEKTAK, manufactured by Veeco).
Furthermore, this element was sealed in a nitrogen atmosphere glove box having an oxygen and moisture concentration of 1 ppm or less. For the sealing, a glass sealing cap and the above-described film-forming substrate epoxy type ultraviolet curable resin (manufactured by Nagase ChemteX Corporation) were used.

Example-46
An organic electroluminescent device was produced in the same manner as in Example-45, except that A-3 synthesized in Example 3 was used in place of A-1 in the electron transport layer 5 of Example-45.

Example-47
An organic electroluminescent device was produced in the same manner as in Example-45, except that A-6 synthesized in Example 6 was used instead of A-1 in the electron transport layer 5 of Example-45.

Reference example-1
In the electron transport layer 5 of Example-31, an organic electroluminescent element was produced in the same manner as in Example-45, except that ETL-1 which is a known electron transport material was used instead of A-1.
A direct current was applied to the produced organic electroluminescent device, and the light emission characteristics were evaluated using a luminance meter of LUMINANCE METER (BM-9) manufactured by TOPCON. As a lifetime characteristic, the luminance decay time during continuous lighting when a current density of 20 mA / cm ² was passed was measured. The time when the luminance (cd / m ² ) is reduced by 20% is shown below.

　表１より、参考例に比べて、本発明の環状アジン誘導体を使用した有機電界発光素子は寿命特性に優れていることが分かる。

From Table 1, it can be seen that the organic electroluminescent device using the cyclic azine derivative of the present invention is superior in life characteristics as compared with the reference example.

Example-48
In the light-emitting layer 4 of Example-45, EML-1 and EML-2 were mixed at a film formation rate of 0.18 nm / second and a film thickness of 40 nm (EML-1 / EML-2 = 95/5 (weight ratio)). Instead of vacuum vapor deposition, TBADN and EML-2 are vacuum vapor deposited with a film thickness of 0.18 nm / second and a film thickness of 40 nm (co-vapor deposition of TBADN / EML-2 = 95/5 (weight ratio)). did.
In addition, in the electron transport layer 5, organic electroluminescence was produced in the same manner as in Example 45 except that A-2 was vacuum-deposited at a film formation rate of 0.25 nm / second and a film pressure of 20 nm instead of A-1. An element was produced.

Example-49
An organic electroluminescent device was produced in the same manner as in Example-48 except that A-10 synthesized in Example 10 was used in place of A-2 in the electron transport layer 5 of Example-48.

Comparative Example-1
An organic electroluminescent device was produced 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 produced organic electroluminescent device, and the light emission characteristics were evaluated using a luminance meter of LUMINANCE METER (BM-9) manufactured by TOPCON. The time when the luminance (cd / m ² ) is reduced by 20%, and the voltage and efficiency when a current is passed through the element at a density of 20 mA / cm ² are shown below.

　表２より、本発明の環状アジン化合物（１）は、従来公知の化合物に比べて、有機電界発光素子の電子注入性、電子輸送特性、駆動電圧（電圧［Ｖ］）、電流効率（効率［ｃｄ／Ａ］）、及び素子寿命を顕著格別に向上させることが示された。

From Table 2, the cyclic azine compound (1) of the present invention has an electron injection property, electron transport property, driving voltage (voltage [V]), current efficiency (efficiency [efficiency [ cd / A]), and the device lifetime was significantly improved.

Example-50
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 cleaned with isopropyl alcohol and then surface-treated by oxygen plasma cleaning. Each layer was vacuum-deposited on the cleaned substrate by a vacuum deposition method, and an organic electroluminescence device having a light-emitting area of 4 mm ² as shown in FIG.
First, the glass substrate was introduced into a vacuum evaporation tank, and the pressure was reduced to 1.0 × 10 ⁻⁴ Pa. Thereafter, a hole injection layer 12, a first hole transport layer 13, a second hole transport layer 14, a light emitting layer 15, and an electron transport are formed as an organic compound layer on the glass substrate with an ITO transparent electrode indicated by 11 in FIG. The layer 16 was sequentially formed, and then the cathode layer 17 was formed. In addition, the material which comprises each layer of an organic electroluminescent element was vacuum-deposited by the resistance heating system.
As the hole injection layer 12, HTL-1 was vacuum-deposited with a film thickness of 40 nm at a film formation rate of 0.15 nm / second.
As the first hole transport layer 13, HAT-CN was vacuum-deposited with a film thickness of 0.025 nm / second and a film thickness of 5 nm.
As the second hole transport layer 14, HTL-2 was vacuum-deposited with a film thickness of 25 nm at a film formation rate of 0.15 nm / second.
As the light-emitting layer 15, EML-1 and EML-2 were vacuumed with a film thickness of 0.18 nm / second and a film thickness of 40 nm (co-evaporation of EML-1 / EML-2 = 95/5 (weight ratio)). Vapor deposited.
As the electron transport layer 16, B-2 synthesized in Example 39 of the present invention was vacuum-deposited with a film thickness of 30 nm at a film formation rate of 0.15 nm / second.

Finally, a metal mask was arranged so as to be orthogonal to the ITO stripe, and the cathode layer 17 was formed. The cathode layer 17 is composed of Liq, magnesium / silver (weight ratio 80/20), and silver in this order at a film formation rate of 0.005 nm / second, 0.5 nm / second, and 0.2 nm / second, respectively. Vacuum deposition was performed with film thicknesses of 5 nm, 80 nm, and 20 nm to form a three-layer structure.
Each film thickness was measured with a stylus type film thickness meter (DEKTAK, manufactured by Veeco).
Furthermore, this element was sealed in a nitrogen atmosphere glove box having an oxygen and moisture concentration of 1 ppm or less. For the sealing, a glass sealing cap and the above-described film-forming substrate epoxy type ultraviolet curable resin (manufactured by Nagase ChemteX Corporation) were used.

Example-51
An organic electroluminescent device was produced in the same manner as in Example-50 except that B-3 synthesized in Example 40 was used in place of B-2 in the electron transport layer 16 of Example-50.

Example-52
An organic electroluminescent device was produced 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 element was produced 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
In the electron transport layer 16 of Example-50, an organic electroluminescent device was produced in the same manner as in Example-50 except that B-6 synthesized in Example 43 was used instead of B-2.

Comparative Example-2
An organic electroluminescent device was produced 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 produced organic electroluminescent device, and the light emission characteristics were evaluated using a luminance meter of LUMINANCE METER (BM-9) manufactured by TOPCON. As a lifetime characteristic, the luminance decay time during continuous lighting when a current density of 20 mA / cm ² was passed was measured. The time when the luminance (cd / m ² ) is reduced by 10%, and the voltage and efficiency when a current is passed through the device at a density of 20 mA / cm ² are shown below.

　表３より、本発明の環状アジン化合物（１）は、従来公知の化合物に比べて、有機電界発光素子の電子注入性、電子輸送特性、駆動電圧（電圧［Ｖ］）、電流効率（効率［ｃｄ／Ａ］）、及び素子寿命を顕著格別に向上させることが示された。

From Table 3, the cyclic azine compound (1) of the present invention has an electron injection property, electron transport property, driving voltage (voltage [V]), current efficiency (efficiency [efficiency [ cd / A]), and the device lifetime was significantly improved.

Example-55
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 cleaned with isopropyl alcohol and then surface-treated by oxygen plasma cleaning. Each layer was vacuum-deposited on the cleaned substrate by a vacuum deposition method, and an organic electroluminescence device having a light-emitting area of 4 mm ² as shown in FIG.
First, the glass substrate was introduced into a vacuum evaporation tank, and the pressure was reduced to 1.0 × 10 ⁻⁴ Pa. Thereafter, a hole injection layer 12, a first hole transport layer 13, a second hole transport layer 14, a light emitting layer 15, and an electron transport are formed as an organic compound layer on the glass substrate with an ITO transparent electrode indicated by 11 in FIG. The layer 16 was sequentially formed, and then the cathode layer 17 was formed. In addition, the material which comprises each layer of an organic electroluminescent element was vacuum-deposited by the resistance heating system.
As the hole injection layer 12, HTL-1 was vacuum-deposited with a film thickness of 45 nm at a film formation rate of 0.15 nm / second.
As the first hole transport layer 13, HAT-CN was vacuum-deposited with a film thickness of 0.025 nm / second and a film thickness of 5 nm.
As the second hole transport layer 14, HTL-2 was vacuum-deposited with a film thickness of 30 nm at a film formation rate of 0.15 nm / second.
As the light-emitting layer 15, EML-1 and EML-2 were vacuumed with a film thickness of 20 nm (co-evaporation of EML-1 / EML-2 = 96/4 (weight ratio)) at a film formation rate of 0.18 nm / second. Vapor deposited.
As the electron transport layer 16, A-3 synthesized in Example 3 of the present invention was vacuum-deposited with a film thickness of 30 nm at a film formation rate of 0.15 nm / second.

Finally, a metal mask was arranged so as to be orthogonal to the ITO stripe, and the cathode layer 17 was formed. The cathode layer 17 is composed of lithium fluoride, magnesium / silver (weight ratio 80/20), and silver in this order at a film formation rate of 0.005 nm / second, 0.5 nm / second, and 0.2 nm / second, respectively. Vacuum deposition was performed with a film thickness of 0.5 nm, 80 nm, and 20 nm to form a three-layer structure.
Each film thickness was measured with a stylus type film thickness meter (DEKTAK, manufactured by Veeco).
Furthermore, this element was sealed in a nitrogen atmosphere glove box having an oxygen and moisture concentration of 1 ppm or less. For the sealing, a glass sealing cap and the above-described film-forming substrate epoxy type ultraviolet curable resin (manufactured by Nagase ChemteX Corporation) were used.

Example-56
An organic electroluminescent device was produced in the same manner as in Example 55 except that A-13 synthesized in Example 13 was used in place of A-3 in the electron transport layer 16 of Example-55.

Example-57
An organic electroluminescent element was produced 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 element was produced 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 produced organic electroluminescent device, and the light emission characteristics were evaluated using a luminance meter of LUMINANCE METER (BM-9) manufactured by TOPCON. As a lifetime characteristic, the luminance decay time during continuous lighting when a current density of 20 mA / cm ² was passed was measured. The time when the luminance (cd / m ² ) is reduced by 20% and the voltage and efficiency when a current is passed through the element at a density of 10 mA / cm ² are shown below.

　表４より、本発明の環状アジン化合物（１）は、従来公知の化合物に比べて、有機電界発光素子の駆動電圧（電圧［Ｖ］）、電流効率（効率［ｃｄ／Ａ］）、及び寿命特性に優れることが示された。

From Table 4, the cyclic azine compound (1) of the present invention has a driving voltage (voltage [V]), current efficiency (efficiency [cd / A]), and lifetime of the organic electroluminescence device, as compared with conventionally known compounds. It was shown that the properties are excellent.

Example-58
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 cleaned with isopropyl alcohol and then surface-treated by oxygen plasma cleaning. Each layer was vacuum-deposited on the cleaned substrate by a vacuum deposition method, and an organic electroluminescence device having a light-emitting area of 4 mm ² as shown in FIG.
First, the glass substrate was introduced into a vacuum evaporation tank, and the pressure was reduced to 1.0 × 10 ⁻⁴ Pa. Thereafter, a hole injection layer 12, a first hole transport layer 13, a second hole transport layer 14, a light emitting layer 15, and an electron transport are formed as an organic compound layer on the glass substrate with an ITO transparent electrode indicated by 11 in FIG. The layer 16 was sequentially formed, and then the cathode layer 17 was formed. In addition, the material which comprises each layer of an organic electroluminescent element was vacuum-deposited by the resistance heating system.
As the hole injection layer 12, HTL-1 was vacuum-deposited with a film thickness of 65 nm at a film formation rate of 0.15 nm / second.
As the first hole transport layer 13, HAT-CN was vacuum-deposited with a film thickness of 0.025 nm / second and a film thickness of 5 nm.
As the second hole transport layer 14, HTL-2 was vacuum-deposited at a film formation rate of 0.15 nm / second to a film thickness of 10 nm.
As the light-emitting layer 15, EML-1 and EML-2 were vacuumed at a film formation rate of 0.18 nm / second and a film thickness of 25 nm (co-evaporation of EML-1 / EML-2 = 96/4 (weight ratio)). Vapor deposited.
As the electron transport layer 16, A-12 synthesized in Example 12 of the present invention was vacuum-deposited with a film thickness of 30 nm at a film formation rate of 0.15 nm / second.
Each organic material was formed into a film by a resistance heating method, and the heated compound was vacuum-deposited at a film formation rate of 0.3 to 0.5 nm / second.

Finally, a metal mask was arranged so as to be orthogonal to the ITO stripe, and the cathode layer 17 was formed. The cathode layer 7 contains Liq, magnesium / silver (weight ratio 80/20), and silver in this order at a film formation rate of 0.005 nm / second, 0.5 nm / second, and 0.2 nm / second, respectively. Vacuum deposition was performed with film thicknesses of 5 nm, 80 nm, and 20 nm to form a three-layer structure.
Each film thickness was measured with a stylus type film thickness meter (DEKTAK, manufactured by Veeco). Furthermore, this element was sealed in a nitrogen atmosphere glove box having an oxygen and moisture concentration of 1 ppm or less. For the sealing, a glass sealing cap and the above-described film-forming substrate epoxy type ultraviolet curable resin (manufactured by Nagase ChemteX Corporation) were used.

Example-59
An organic electroluminescent device was produced 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 produced 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 element was produced 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 produced in the same manner as in Example 58 except that A-19 synthesized in Example 20 was used in place of A-12 in the electron transport layer 16 of Example-58.
Example-63
An organic electroluminescent device was produced 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
In the electron transport layer 16 of Example-58, an organic electroluminescent element was produced in the same manner as in Example 58 except that A-22 synthesized in Example 24 was used instead of A-12.

Comparative Example-3
An organic electroluminescent element was produced in the same manner as in Example 58 except that ETL-4 synthesized in Synthesis Example-21 was used in place of A-12 in the electron transport layer 16 of Example-58.
A direct current was applied to the produced organic electroluminescent device, and the light emission characteristics were evaluated using a luminance meter of LUMINANCE METER (BM-9) manufactured by TOPCON. As a lifetime characteristic, the luminance decay time during continuous lighting when a current density of 20 mA / cm ² was passed was measured. The time when the luminance (cd / m ² ) is reduced by 10% and the voltage when a current is passed through the element at a density of 10 mA / cm ² are shown below.

From Table 5, it was shown that the cyclic azine compound (1) of the present invention is superior in the driving voltage (voltage [V]) and life characteristics of the organic electroluminescence device as compared with the conventionally known compounds.
As described above, the organic electroluminescent device using the cyclic azine compound (1) of the present invention is more remarkable in device characteristics such as driving voltage, current efficiency, and device lifetime of the organic electroluminescent device than the conventionally known compounds. It turns out that it is exceptional.

The organic electroluminescent element using the cyclic azine compound of the present invention can be driven for a long time compared to the organic electroluminescent element using the existing material, not only the element using the fluorescent light emitting material, The present invention is extremely useful industrially because it can be applied to various organic electroluminescent devices using phosphorescent materials.
In addition, the cyclic azine compound of the present invention has high solubility, and it is possible to produce a device using a coating method as well as a vacuum deposition method, and it can be applied as a light emitting host layer in addition to an electron transport layer, In addition to applications such as flat panel displays, it is also useful in lighting applications that require low power consumption.

In addition, 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 abstract of patent application 2012-279541 are incorporated herein by reference as the disclosure of the specification of the present invention.

1. 1. Glass substrate with ITO transparent electrode 2. hole injection layer Hole transport layer 4. Light emitting layer 5. Electron transport layer 6. Cathode layer 11. 11. Glass substrate with ITO transparent electrode Hole injection layer 13. First hole transport layer 14. Second hole transport layer 15. Light emitting layer 16. Electron transport layer 17. Cathode layer

Claims (22)

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

(Where
Cz is an (n + 1) -valent carbazole group or an (n + 1) -valent carboline group (these groups are each independently a fluorine atom, an alkyl group having 1 to 4 carbon atoms, or an aromatic hydrocarbon having 6 to 18 carbon atoms). Group, a fluorine atom-containing aromatic hydrocarbon group having 6 to 18 carbon atoms, or an aromatic hydrocarbon group having 6 to 18 carbon atoms substituted by an alkyl group having 1 to 4 carbon atoms may be used as a substituent. ).
Ar ¹ and Ar ² are each independently an aromatic hydrocarbon 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) And an aromatic group having 3 to 18 carbon atoms having a fluorine atom, or an aromatic group having 3 to 18 carbon atoms substituted by an alkyl group having 1 to 4 carbon atoms may be used as a substituent.
Ar ³ is 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 a fluorine atom, or carbon An aromatic group having 3 to 18 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms may be substituted).
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) An aromatic group having 3 to 18 carbon atoms, or an aromatic group having 3 to 18 carbon atoms substituted by an alkyl group having 1 to 4 carbon atoms), or a general formula (A) The substituent shown by is represented.
Y and Z each independently represent a nitrogen atom or CH. However, at least one of Y and Z is a nitrogen atom.
n represents an integer of 1 to [the maximum number of bonds -1 that can be formed on Cz-1]. )

(Where
Ar ⁵ each independently represents an (m + 1) -valent 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, 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 used as a substituent.
Ar ⁶ is each independently 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 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.
Each m independently represents 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 general formula (B), (C), or (D).

(In the formula (D), Cb represents an (n + 1) -valent carboline group.
In formulas (B), (C), and (D),
Ar ¹ and Ar ² are each independently an aromatic hydrocarbon 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) And an aromatic group having 3 to 18 carbon atoms having a fluorine atom, or an aromatic group having 3 to 18 carbon atoms substituted by an alkyl group having 1 to 4 carbon atoms may be used as a substituent.
Ar ³ is each independently 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, or a 3 to 18 carbon atom having a fluorine atom). An aromatic group or an aromatic group having 3 to 18 carbon atoms substituted by an alkyl group having 1 to 4 carbon atoms may be used 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) An aromatic group having 3 to 18 carbon atoms, or an aromatic group having 3 to 18 carbon atoms substituted by an alkyl group having 1 to 4 carbon atoms), or a general formula (A) The substituent shown by is represented.
Y and Z each independently represent a nitrogen atom or CH. However, at least one of Y and Z is a nitrogen atom.
n independently represents an integer of 1 to 7. )

(Where
Ar ⁵ is an (m + 1) -valent 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, or a carbon 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 may be used as a substituent.
Ar ⁶ is each independently 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 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.
m represents an integer of 1 to [the maximum number of bonds that can be formed on Ar ⁵ −1]. ) A nitrogen-containing heteroaryl group having 3 to 30 carbon atoms represented by Ar ⁴ and Ar ⁶ (each independently having a fluorine atom, an alkyl group having 1 to 4 carbon atoms, an aromatic group having 3 to 18 carbon atoms, or a fluorine atom) Each having an aromatic group having 3 to 18 carbon atoms or an aromatic group having 3 to 18 carbon atoms substituted by an alkyl group having 1 to 4 carbon atoms as a substituent. , Hydrogen, and nitrogen-containing heteroaryl group having 3 to 30 carbon atoms (each independently including a fluorine atom, an alkyl group having 1 to 4 carbon atoms, an aromatic group having 3 to 18 carbon atoms, and 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), or carbon, hydrogen, nitrogen, And a nitrogen-containing heteroaryl group having 3 to 30 carbon atoms consisting of only sulfur ( 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 alkyl group having 1 to 4 carbon atoms The cyclic azine compound according to claim 1 or 2, which may have a substituted aromatic group having 3 to 18 carbon atoms as a substituent. A nitrogen-containing heteroaryl group having 3 to 30 carbon atoms represented by Ar ⁴ and Ar ⁶ (each independently having a fluorine atom, an alkyl group having 1 to 4 carbon atoms, an aromatic group having 3 to 18 carbon atoms, or a fluorine atom) Each having an aromatic group having 3 to 18 carbon atoms or an aromatic group having 3 to 18 carbon atoms substituted by an alkyl group having 1 to 4 carbon atoms as a substituent. , Hydrogen and nitrogen-containing heteroaryl group having 3 to 30 carbon atoms (however, fluorine atom, alkyl group having 1 to 4 carbon atoms, aromatic group having 3 to 18 carbon atoms, carbon number having fluorine atom) The 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 substituted). The cyclic azine compound according to any one of the above. A nitrogen-containing heteroaryl group having 3 to 30 carbon atoms represented by Ar ⁴ and Ar ⁶ (each independently having a fluorine atom, an alkyl group having 1 to 4 carbon atoms, an aromatic group having 3 to 18 carbon atoms, or a fluorine atom) Each having a C 3-18 aromatic group or a C 3-18 aromatic group substituted with a C 1-4 alkyl group as a substituent. Group, pyrimidyl group, pyrazyl group, quinolyl group, isoquinolyl group, pyridylphenyl group, or 1- (3,5-dipyridyl) phenyl group (these groups are each independently a fluorine atom, having 1 to 4 carbon atoms) Replaced by an alkyl group, 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 by an alkyl group having 1 to 4 carbon atoms As a group) Or cyclic azine compound according to any one of claims 4. A nitrogen-containing heteroaryl group having 3 to 30 carbon atoms represented by Ar ⁴ and Ar ⁶ (each independently having a fluorine atom, an alkyl group having 1 to 4 carbon atoms, an aromatic group having 3 to 18 carbon atoms, or a fluorine atom) Each having 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. (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 alkyl group having 1 to 4 carbon atoms. The cyclic azine compound according to any one of claims 1 to 5, wherein the group may have a substituted C3-C18 aromatic group as a substituent. Ar ¹ and Ar ² are each independently a phenyl group, biphenylyl group, naphthyl group, anthryl group, pyrenyl group, terphenyl group, or phenanthryl group (these groups are each independently a fluorine atom, a carbon number An aromatic group having 3 to 18 carbon atoms substituted by 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 The cyclic azine compound according to any one of claims 1 to 6, which may have a group as a substituent. Ar ¹ and Ar ² are each independently a phenyl group or a biphenylyl group (these groups are each independently a fluorine atom, an alkyl group having 1 to 4 carbon atoms, an aromatic group having 3 to 18 carbon atoms, 3. An aromatic group having 3 to 18 carbon atoms having a fluorine atom, or an aromatic group having 3 to 18 carbon atoms substituted by an alkyl group having 1 to 4 carbon atoms may be used as a substituent. The cyclic azine compound as described in any one of Claims 7 thru | or 7. 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. Ar ³ is a phenylene group or a biphenylylene group (these groups are each independently a fluorine atom, an alkyl group having 1 to 4 carbon atoms, an aromatic group having 3 to 18 carbon atoms, or a 3 to 3 carbon atom having a fluorine atom). The aromatic group having 18 carbon atoms or an aromatic group having 3 to 18 carbon atoms substituted by an alkyl group having 1 to 4 carbon atoms may be substituted). The cyclic azine compound according to Item. Ar ⁵ is an (m + 1) -valent benzene group or an (m + 1) -valent biphenyl group (these groups are each independently 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 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. The cyclic azine compound according to any one of claims 1 to 10. The cyclic azine compound according to any one of claims 1 to 11, wherein Y and Z are nitrogen atoms, 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. The cyclic azine compound according to any one of claims 1 to 13, wherein m is 1 or 2. A compound represented by the general formula (2) and a compound represented by the general formula (3) are subjected to a coupling reaction in the presence of a metal catalyst or in the presence of a base and a metal catalyst. The manufacturing method of the cyclic azine compound shown by (1).

(Where
Cz is an (n + 1) -valent carbazole group or an (n + 1) -valent carboline group (these groups are each independently a fluorine atom, an alkyl group having 1 to 4 carbon atoms, or an aromatic hydrocarbon having 6 to 18 carbon atoms). Group, a fluorine atom-containing aromatic hydrocarbon group having 6 to 18 carbon atoms, or an aromatic hydrocarbon group having 6 to 18 carbon atoms substituted by an alkyl group having 1 to 4 carbon atoms may be used as a substituent. ).
Ar ¹ and Ar ² are each independently an aromatic hydrocarbon 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) And an aromatic group having 3 to 18 carbon atoms having a fluorine atom, or an aromatic group having 3 to 18 carbon atoms substituted by an alkyl group having 1 to 4 carbon atoms may be used as a substituent.
Ar ³ is 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 a fluorine atom, or carbon An aromatic group having 3 to 18 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms may be substituted).
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) An aromatic group having 3 to 18 carbon atoms, or an aromatic group having 3 to 18 carbon atoms substituted by an alkyl group having 1 to 4 carbon atoms), or a general formula (A) The substituent shown by is represented.
Y and Z each independently represent a nitrogen atom or CH. However, 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.
n represents an integer of 1 to [the maximum number of bonds -1 that can be formed on Cz-1]. )

(Where
Ar ⁵ is an (m + 1) -valent 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, or a carbon 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 may be used as a substituent.
Ar ⁶ is each independently 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 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.
m represents an integer of 1 to [the maximum number of bonds that can be formed on Ar ⁵ −1]. ) A compound represented by the general formula (4) and a compound represented by the general formula (5) are subjected to a coupling reaction in the presence of a metal catalyst or in the presence of a base and a metal catalyst. The manufacturing method of the cyclic azine compound shown by (1).

(Where
Cz is an (n + 1) -valent carbazole group or an (n + 1) -valent carboline group (these groups are each independently a fluorine atom, an alkyl group having 1 to 4 carbon atoms, or an aromatic hydrocarbon having 6 to 18 carbon atoms). Group, a fluorine atom-containing aromatic hydrocarbon group having 6 to 18 carbon atoms, or an aromatic hydrocarbon group having 6 to 18 carbon atoms substituted by an alkyl group having 1 to 4 carbon atoms may be used as a substituent. ).
Ar ¹ and Ar ² are each independently an aromatic hydrocarbon 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) And an aromatic group having 3 to 18 carbon atoms having a fluorine atom, or an aromatic group having 3 to 18 carbon atoms substituted by an alkyl group having 1 to 4 carbon atoms may be used as a substituent.
Ar ³ is 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 a fluorine atom, or carbon An aromatic group having 3 to 18 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms may be substituted).
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) An aromatic group having 3 to 18 carbon atoms, or an aromatic group having 3 to 18 carbon atoms substituted by an alkyl group having 1 to 4 carbon atoms), or a general formula (A) The substituent shown by is represented.
Y and Z each independently represent a nitrogen atom or CH. However, at least one of Y and Z is a nitrogen atom.
M and ^{X 2} represents a leaving group.
n represents an integer of 1 to [the maximum number of bonds -1 that can be formed on Cz-1]. )

(Where
Ar ⁵ is an (m + 1) -valent 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, or a carbon 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 may be used as a substituent.
Ar ⁶ is each independently 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 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.
m represents an integer of 1 to [the maximum number of bonds that can be formed on Ar ⁵ −1]. ) A compound represented by the general formula (6) and a compound represented by the general formula (7) are subjected to a coupling reaction in the presence of a metal catalyst or a base and a metal catalyst. The manufacturing method of the cyclic azine compound shown by (1).

(Where
Cz is an (n + 1) -valent carbazole group or an (n + 1) -valent carboline group (these groups are each independently a fluorine atom, an alkyl group having 1 to 4 carbon atoms, or an aromatic hydrocarbon having 6 to 18 carbon atoms). Group, a fluorine atom-containing aromatic hydrocarbon group having 6 to 18 carbon atoms, or an aromatic hydrocarbon group having 6 to 18 carbon atoms substituted by an alkyl group having 1 to 4 carbon atoms may be used as a substituent. ).
Ar ¹ and Ar ² are each independently an aromatic hydrocarbon 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) And an aromatic group having 3 to 18 carbon atoms having a fluorine atom, or an aromatic group having 3 to 18 carbon atoms substituted by an alkyl group having 1 to 4 carbon atoms may be used as a substituent.
Ar ³ is 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 a fluorine atom, or carbon An aromatic group having 3 to 18 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms may be substituted).
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) An aromatic group having 3 to 18 carbon atoms, or an aromatic group having 3 to 18 carbon atoms substituted by an alkyl group having 1 to 4 carbon atoms), or a general formula (A) The substituent shown by is represented.
Y and Z each independently represent a nitrogen atom or CH. However, 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)

(Where
Ar ⁵ is an (m + 1) -valent 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, or a carbon 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 may be used as a substituent.
Ar ⁶ is each independently 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 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.
m represents an integer of 1 to [the maximum number of bonds that can be formed on Ar ⁵ −1]. ) A compound represented by the general formula (8) and a compound represented by the general formula (9) are subjected to a coupling reaction in the presence of a metal catalyst or in the presence of a base and a metal catalyst. A method for producing the cyclic azine compound represented by 1).

(Where
Cz is an (n + 1) -valent carbazole group or an (n + 1) -valent carboline group (these groups are each independently a fluorine atom, an alkyl group having 1 to 4 carbon atoms, or an aromatic hydrocarbon having 6 to 18 carbon atoms). Group, a fluorine atom-containing aromatic hydrocarbon group having 6 to 18 carbon atoms, or an aromatic hydrocarbon group having 6 to 18 carbon atoms substituted by an alkyl group having 1 to 4 carbon atoms may be used as a substituent. ).
Ar ¹ and Ar ² are each independently an aromatic hydrocarbon 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) And an aromatic group having 3 to 18 carbon atoms having a fluorine atom, or an aromatic group having 3 to 18 carbon atoms substituted by an alkyl group having 1 to 4 carbon atoms may be used as a substituent.
Ar ³ is 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 a fluorine atom, or carbon An aromatic group having 3 to 18 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms may be substituted).
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) An aromatic group having 3 to 18 carbon atoms, or an aromatic group having 3 to 18 carbon atoms substituted by an alkyl group having 1 to 4 carbon atoms), or a general formula (A) The substituent shown by is represented.
Y and Z each independently represent a nitrogen atom or CH. However, at least one of Y and Z is a nitrogen atom.
M and X ⁴ represent a leaving group.
n represents an integer of 1 to [the maximum number of bonds -1 that can be formed on Cz-1]. )

(Where
Ar ⁵ is an (m + 1) -valent 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, or a carbon 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 may be used as a substituent.
Ar ⁶ is each independently 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 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.
m represents an integer of 1 to [the maximum number of bonds that can be formed on Ar ⁵ −1]. ) General formula (1)

(Where
Cz is an (n + 1) -valent carbazole group or an (n + 1) -valent carboline group (these groups are each independently a fluorine atom, an alkyl group having 1 to 4 carbon atoms, or an aromatic hydrocarbon having 6 to 18 carbon atoms). Group, a fluorine atom-containing aromatic hydrocarbon group having 6 to 18 carbon atoms, or an aromatic hydrocarbon group having 6 to 18 carbon atoms substituted by an alkyl group having 1 to 4 carbon atoms may be used as a substituent. ).
Ar ¹ and Ar ² are each independently an aromatic hydrocarbon 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) And an aromatic group having 3 to 18 carbon atoms having a fluorine atom, or an aromatic group having 3 to 18 carbon atoms substituted by an alkyl group having 1 to 4 carbon atoms may be used as a substituent.
Ar ³ is 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 a fluorine atom, or carbon An aromatic group having 3 to 18 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms may be substituted).
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) An aromatic group having 3 to 18 carbon atoms, or an aromatic group having 3 to 18 carbon atoms substituted by an alkyl group having 1 to 4 carbon atoms), or a general formula (A) The substituent shown by is represented.
Y and Z each independently represent a nitrogen atom or CH. However, at least one of Y and Z is a nitrogen atom.
n represents an integer of 1 to [the maximum number of bonds -1 that can be formed on Cz-1]. )

(Where
Ar ⁵ is an (m + 1) -valent 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, or a carbon 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 may be used as a substituent.
Ar ⁶ is each independently 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 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.
m represents an integer of 1 to [the maximum number of bonds that can be formed on Ar ⁵ −1]. )
The organic electroluminescent element characterized by including the cyclic azine compound shown by these. The organic electroluminescent element of Claim 19 which contains the cyclic azine compound represented by General formula (1) in either a hole block layer, an electron carrying layer, or an electron injection layer. General formula (1)

(Where
Cz is an (n + 1) -valent carbazole group or an (n + 1) -valent carboline group (these groups are each independently a fluorine atom, an alkyl group having 1 to 4 carbon atoms, or an aromatic hydrocarbon having 6 to 18 carbon atoms). Group, a fluorine atom-containing aromatic hydrocarbon group having 6 to 18 carbon atoms, or an aromatic hydrocarbon group having 6 to 18 carbon atoms substituted by an alkyl group having 1 to 4 carbon atoms may be used as a substituent. ).
Ar ¹ and Ar ² are each independently an aromatic hydrocarbon 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) And an aromatic group having 3 to 18 carbon atoms having a fluorine atom, or an aromatic group having 3 to 18 carbon atoms substituted by an alkyl group having 1 to 4 carbon atoms may be used as a substituent.
Ar ³ is 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 a fluorine atom, or carbon An aromatic group having 3 to 18 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms may be substituted).
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) An aromatic group having 3 to 18 carbon atoms, or an aromatic group having 3 to 18 carbon atoms substituted by an alkyl group having 1 to 4 carbon atoms), or a general formula (A) The substituent shown by is represented.
Y and Z each independently represent a nitrogen atom or CH. However, at least one of Y and Z is a nitrogen atom.
n represents an integer of 1 to [the maximum number of bonds -1 that can be formed on Cz-1]. )

(Where
Ar ⁵ is an (m + 1) -valent 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, or a carbon 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 may be used as a substituent.
Ar ⁶ is each independently 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 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.
m represents an integer of 1 to [the maximum number of bonds that can be formed on Ar ⁵ −1]. )
A method for extending the lifetime of an organic electroluminescent device, characterized in that a cyclic azine compound represented by the formula: General formula (1)

(Where
Cz is an (n + 1) -valent carbazole group or an (n + 1) -valent carboline group (these groups are each independently a fluorine atom, an alkyl group having 1 to 4 carbon atoms, or an aromatic hydrocarbon having 6 to 18 carbon atoms). Group, a fluorine atom-containing aromatic hydrocarbon group having 6 to 18 carbon atoms, or an aromatic hydrocarbon group having 6 to 18 carbon atoms substituted by an alkyl group having 1 to 4 carbon atoms may be used as a substituent. ).
Ar ¹ and Ar ² are each independently an aromatic hydrocarbon 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) And an aromatic group having 3 to 18 carbon atoms having a fluorine atom, or an aromatic group having 3 to 18 carbon atoms substituted by an alkyl group having 1 to 4 carbon atoms may be used as a substituent.
Ar ³ is 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 a fluorine atom, or carbon An aromatic group having 3 to 18 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms may be substituted).
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) An aromatic group having 3 to 18 carbon atoms, or an aromatic group having 3 to 18 carbon atoms substituted by an alkyl group having 1 to 4 carbon atoms), or a general formula (A) The substituent shown by is represented.
Y and Z each independently represent a nitrogen atom or CH. However, at least one of Y and Z is a nitrogen atom.
n represents an integer of 1 to [the maximum number of bonds -1 that can be formed on Cz-1]. )

(Where
Ar ⁵ is an (m + 1) -valent 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, or a carbon 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 may be used as a substituent.
Ar ⁶ is each independently 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 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.
m represents an integer of 1 to [the maximum number of bonds that can be formed on Ar ⁵ −1]. )
A method for reducing the electric charge of an organic electroluminescent device, characterized in that a cyclic azine compound represented by the formula (1) is used for an electron transport layer.

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