JP7379830B2 - Cyclic azine compounds, materials for organic electroluminescent devices, and electron transport materials for organic electroluminescent devices - Google Patents

Description

The present invention relates to a cyclic azine compound, a material for organic electroluminescent devices, and an electron transport material for organic electroluminescent devices.

Organic electroluminescent elements are used not only in small displays but also in large televisions, lighting, and other applications, and their development is being actively pursued.

For example, Patent Document 1 discloses a cyclic azine compound having a specific substituent that has excellent heat resistance, reduces driving voltage, and contributes to providing a long-life organic electroluminescent device as a material for an organic electroluminescent device. There is.
Patent Document 2 discloses a cyclic azine compound having a non-planar structure.

Japanese Patent Application Publication No. 2011-063584 Special Publication No. 2007-520875

However, in recent years, market demands for organic electroluminescent devices have become increasingly high, and materials with excellent current efficiency characteristics, driving voltage characteristics, and long life characteristics are being sought.
Here, although the organic electroluminescent devices using cyclic azine compounds disclosed in Patent Documents 1 and 2 exhibit excellent driving voltage characteristics, further improvements are required in terms of device life and current efficiency. .

One aspect of the present invention aims to provide a cyclic azine compound, a material for an organic electroluminescent device, and an electron transport material for an organic electroluminescent device, which have excellent durability and current efficiency.

The cyclic azine compound according to one embodiment of the present invention is represented by formula (1):

In formula (1),
Ar ¹ each independently represents a phenylene group, a naphthylene group, a pyridylene group, or a single bond;
Ar ² is each independently,
A monocyclic ring that may be connected, a condensed ring that may be connected, or a structure in which these are connected,
aromatic hydrocarbon group having 6 to 24 carbon atoms,
A nitrogen-containing heteroaromatic group having 4 to 25 carbon atoms consisting of only a 6-membered ring, or
Represents a heteroaromatic group having 3 to 25 carbon atoms composed of atoms selected from the atomic group consisting of H, C, O, and S;
Y in the divalent groups L ¹ and L ² each independently represents CH or N;
Ar ³ represents a hydrogen atom, a phenyl group, a naphthyl group, or a pyridyl group;
Ar ⁴ and Ar ⁵ are each independently,
Hydrogen atom, phenyl group, naphthyl group, pyridyl group, or
Represents the bonding position of the triazine ring and any one of the divalent groups L ¹ and L ² ;
m represents 0 or 1;
If m is 0, n is 0;
If m is 1, n is 0, 1, or 2;
When n is 2, the plurality of L ² may be the same or different from each other;
Each group represented by Ar ¹ , Ar ³ , Ar ⁴ , Ar ⁵ , L ¹ , and L ² may be independently substituted with a fluorine atom, a methyl group, or a phenyl group;
Each group represented by Ar ² is independently a phenyl group, a tolyl group, a pyridyl group, a methylpyridyl group, a dimethylpyridyl group, a fluorine atom, an alkyl group having 1 to 4 carbon atoms, or an alkyl group having 1 to 4 carbon atoms. It may be substituted with an alkoxy group.

A material for an organic electroluminescent device according to another aspect of the present invention includes the above-mentioned cyclic azine compound.

An electron transport material for an organic electroluminescent device according to yet another aspect of the present invention contains the above-mentioned cyclic azine compound.

According to one aspect of the present invention, it is possible to provide a cyclic azine compound, a material for an organic electroluminescent device, and an electron transport material for an organic electroluminescent device that have excellent durability and current efficiency.

FIG. 1 is a schematic cross-sectional view showing an example of a stacked structure of an organic electroluminescent device containing a cyclic azine compound according to one embodiment of the present invention. FIG. 2 is a schematic cross-sectional view showing another example (device example 1) of a stacked structure of an organic electroluminescent device containing a cyclic azine compound according to one embodiment of the present invention. FIG. 3 is a schematic cross-sectional view showing yet another example (device example 3) of a stacked structure of an organic electroluminescent device containing a cyclic azine compound according to one embodiment of the present invention.

Hereinafter, the cyclic azine compound according to one embodiment of the present invention will be explained in detail.

<Cyclic azine compound>
The cyclic azine compound according to one embodiment of the present invention is represented by formula (1):

In formula (1),
Ar ¹ each independently represents a phenylene group, a naphthylene group, a pyridylene group, or a single bond;
Ar ² is each independently,
A monocyclic ring that may be connected, a condensed ring that may be connected, or a structure in which these are connected,
aromatic hydrocarbon group having 6 to 24 carbon atoms,
A nitrogen-containing heteroaromatic group having 4 to 25 carbon atoms consisting of only a 6-membered ring, or
Represents a heteroaromatic group having 3 to 25 carbon atoms composed of atoms selected from the atomic group consisting of H, C, O, and S;
Y in the divalent groups L ¹ and L ² each independently represents CH or N;
Ar ³ represents a hydrogen atom, a phenyl group, a naphthyl group, or a pyridyl group;
Ar ⁴ and Ar ⁵ are each independently,
Hydrogen atom, phenyl group, naphthyl group, pyridyl group, or
Represents the bonding position of the triazine ring and any one of the divalent groups L ¹ and L ² ;
m represents 0 or 1;
If m is 0, n is 0;
If m is 1, n is 0, 1, or 2;
When n is 2, the plurality of L ² may be the same or different from each other;
Each group represented by Ar ¹ , Ar ³ , Ar ⁴ , Ar ⁵ , L ¹ , and L ² may be independently substituted with a fluorine atom, a methyl group, or a phenyl group;
Each group represented by Ar ² is independently a phenyl group, a tolyl group, a pyridyl group, a methylpyridyl group, a dimethylpyridyl group, a fluorine atom, an alkyl group having 1 to 4 carbon atoms, or an alkyl group having 1 to 4 carbon atoms. It may be substituted with an alkoxy group.

Hereinafter, the cyclic azine compound represented by formula (1) may be referred to as a cyclic azine compound (1). Definitions of the substituents in the cyclic azine compound (1) and preferred specific examples thereof are as follows.

[About Ar ¹ ]
In formula (1), Ar ¹ each independently represents a phenylene group, a naphthylene group, a pyridylene group, or a single bond. These groups may be substituted with a fluorine atom, a methyl group, or a phenyl group.
It is more preferable that Ar ¹ is each independently a phenylene group or a single bond in terms of excellent electron transporting material properties.
Two Ar ¹ 's may be the same or different.

[About Ar ² ]
Ar ² is each independently,
(i) An aromatic hydrocarbon group having 6 to 24 carbon atoms, which is an optionally connected monocyclic ring, an optionally connected condensed ring, or a structure in which these are connected;
(ii) a nitrogen-containing heteroaromatic group having 4 to 25 carbon atoms and consisting only of a 6-membered ring, which is an optionally connected monocyclic ring, an optionally connected condensed ring, or a structure in which these are connected;
(iii) Consisting of atoms selected from the atomic group consisting of H, C, O, and S, which is a monocyclic ring that may be connected, a condensed ring that may be connected, or a structure in which these are connected. Represents a heteroaromatic group having 3 to 25 carbon atoms.

Each group (i) to (iii) represented by Ar ² is a phenyl group, tolyl group, pyridyl group, methylpyridyl group, dimethylpyridyl group, fluorine atom, an alkyl group having 1 to 4 carbon atoms, or a carbon number It may have 1 to 4 alkoxy groups.

The aromatic hydrocarbon group in (i) above is not particularly limited, but includes, for example, a phenyl group, a naphthyl group, a fluorenyl group, an anthryl group, a phenanthryl group, a benzofluorenyl group, a pyrenyl group, and a triphenylenyl group. , chrysenyl group, perylenyl group, fluoranthenyl group, acenaphthyl group, etc. are mentioned as preferable examples. As mentioned above, these substituents (aromatic hydrocarbon groups) include phenyl group, tolyl group, pyridyl group, methylpyridyl group, dimethylpyridyl group, fluorine atom, alkyl group having 1 to 4 carbon atoms, or carbon It may be substituted with one to four alkoxy groups.

The nitrogen-containing heteroaromatic group (ii) is not particularly limited, but includes, for example, a pyridyl group, a pyrazyl group, a pyrimidyl group, a pyridazyl group, a quinolyl group, an isoquinolyl group, a phenanthridyl group, and a benzoquinolyl group. , acridinyl group, etc. are mentioned as preferred examples. Note that a heteroaromatic group containing a 5-membered ring (for example, a carbazolyl group, etc.) is not included in (ii) nitrogen-containing heteroaromatic group, and is not included in the cyclic azine compound represented by formula (1). Furthermore, as mentioned above, these substituents (nitrogen-containing heteroaromatic group) include phenyl group, tolyl group, pyridyl group, methylpyridyl group, dimethylpyridyl group, fluorine atom, alkyl group having 1 to 4 carbon atoms, or It may be substituted with an alkoxy group having 1 to 4 carbon atoms.

The heteroaromatic group in (iii) above is not particularly limited, but includes, for example, a thienyl group, a furyl group, a bitienyl group, a bifryl group, a benzothienyl group, a benzofuryl group, a dibenzothienyl group, a dibenzofuryl group, etc. are given as preferred examples. As mentioned above, these substituents (heteroaromatic groups) include phenyl group, tolyl group, pyridyl group, methylpyridyl group, dimethylpyridyl group, fluorine atom, alkyl group having 1 to 4 carbon atoms, or It may be substituted with 1 to 4 alkoxy groups.

The alkyl group having 1 to 4 carbon atoms in Ar ² is not particularly limited, but preferably includes, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a t-butyl group, etc. Examples include:
The alkoxy group having 1 to 4 carbon atoms in Ar ² is not particularly limited, but includes methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, t-butoxy group, etc. This is mentioned as a preferable example.
Two Ar ² 's may be the same or different.

Specifically, Ar ² is each independently a phenyl group, tolyl group, pyridyl group, methylpyridyl group, dimethylpyridyl group, fluorine atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms. Phenyl group, naphthyl group, fluorenyl group, anthryl group, phenanthryl group, benzofluorenyl group, pyrenyl group, perylenyl group, fluoranthenyl group, triphenylenyl group, chrysenyl group, acenaphthyl group, pyrimidyl, which may be substituted with A pyrazyl group, a pyridyl group, a quinolyl group, an isoquinolyl group, a benzofuryl group, a benzothienyl group, a dibenzofuryl group, and a dibenzothienyl group. Ar ² is a phenyl group, a naphthyl group, a fluorenyl group, an anthryl group, a phenanthryl group, a benzofluorenyl group, a pyrenyl group, a perylenyl group, a fluoranthenyl group, a triphenylenyl group, a pyrimidyl group, a pyrazyl group, a pyridyl group, a quinolyl group , an isoquinolyl group, a benzofuryl group, a benzothienyl group, a dibenzofuryl group, a dibenzothienyl group, a biphenyl group, or a pyridylphenyl group.

Specific examples of the group represented by -Ar ¹ -Ar ² are not particularly limited, but preferable examples include the groups (1) to (44) shown below, each independently. .

(1): Phenyl group, p-tolyl group, m-tolyl group, o-tolyl group, 2,4-dimethylphenyl group, 3,5-dimethylphenyl group, mesityl group, 2-ethylphenyl group, 3-ethyl group Phenyl group, 4-ethylphenyl group, 2,4-diethylphenyl group, 3,5-diethylphenyl group, 2-propylphenyl group, 3-propylphenyl group, 4-propylphenyl group, 2,4-dipropylphenyl group 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-butyl Phenyl group, 2,4-di-tert-butylphenyl group, 3,5-di-tert-butylphenyl group.

(2): biphenyl-2-yl group, biphenyl-3-yl group, biphenyl-4-yl group, 3-methylbiphenyl-4-yl group, 2'-methylbiphenyl-4-yl group, 4'-methyl biphenyl-4-yl group, 2,2'-dimethylbiphenyl-4-yl group, 6-methylbiphenyl-3-yl group, 5-methylbiphenyl-3-yl group, 2'-methylbiphenyl-3-yl group , 4'-methylbiphenyl-3-yl group, 6,2'-dimethylbiphenyl-3-yl group, 5-methylbiphenyl-2-yl group, 6-methylbiphenyl-2-yl group, 2'-methylbiphenyl group -2-yl group, 4'-methylbiphenyl-2-yl group, 6,2'-dimethylbiphenyl-2-yl group, 3-ethylbiphenyl-4-yl group, 6-ethylbiphenyl-3-yl group, 5-ethylbiphenyl-2-yl group, 3-propylbiphenyl-4-yl group, 6-propylbiphenyl-3-yl group, 5-propylbiphenyl-2-yl group, 3-isopropylbiphenyl-4-yl group, 6-isopropylbiphenyl-3-yl group, 5-isopropylbiphenyl-2-yl group, 3-butylbiphenyl-4-yl group, 6-butylbiphenyl-3-yl group, 5-butylbiphenyl-2-yl group, 3-tert-butylbiphenyl-4-yl group, 4'-tert-butylbiphenyl-4-yl group, 6-tert-butylbiphenyl-3-yl group, 5-tert-butylbiphenyl-2-yl group.

(3): 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 2-methylpyridin-3-yl group, 2-methylpyridin-4-yl group, 2-methylpyridin-5-yl group, 2 -Methylpyridin-6-yl group, 3-methylpyridin-2-yl group, 3-methylpyridin-4-yl group, 3-methylpyridin-5-yl group, 3-methylpyridin-6-yl group, 4 -Methylpyridin-2-yl group, 4-methylpyridin-3-yl group, 2,6-dimethylpyridin-3-yl group, 2,6-dimethylpyridin-4-yl group, 3,6-dimethylpyridin- 2-yl group, 3,6-dimethylpyridin-4-yl group, 3,6-dimethylpyridin-5-yl group.

(4): 2-phenylpyridin-6-yl group, 3-phenylpyridin-6-yl group, 4-phenylpyridin-6-yl group, 5-phenylpyridin-6-yl group, 2-phenylpyridin-3 -yl group, 2-phenylpyridin-5-yl group, 3-phenylpyridin-5-yl group, 4-phenylpyridin-3-yl group, 3-phenylpyridin-4-yl group, 2-phenylpyridin-4 -yl group, 2-(2-pyridyl)phenyl group, 3-(2-pyridyl)phenyl group, 4-(2-pyridyl)phenyl group, 2-(3-pyridyl)phenyl group, 3-(3-pyridyl) ) phenyl group, 4-(3-pyridyl) phenyl group, 2-(4-pyridyl) phenyl group, 3-(4-pyridyl) phenyl group, 4-(4-pyridyl) phenyl group, 2-(3-methyl -2-pyridyl) phenyl group, 3-(3-methyl-2-pyridyl) phenyl group, 4-(3-methyl-2-pyridyl) phenyl group, 2-(4-methyl-2-pyridyl) phenyl group, 3-(4-methyl-2-pyridyl)phenyl group, 4-(4-methyl-2-pyridyl)phenyl group, 2-(5-methyl-2-pyridyl)phenyl group, 3-(5-methyl-2 -pyridyl)phenyl group, 4-(5-methyl-2-pyridyl)phenyl group, 2-(6-methyl-2-pyridyl)phenyl group, 3-(6-methyl-2-pyridyl)phenyl group, 4- (6-methyl-2-pyridyl) phenyl group, 2-(2-methyl-3-pyridyl) phenyl group, 3-(2-methyl-3-pyridyl) phenyl group, 4-(2-methyl-3-pyridyl) ) phenyl group, 2-(4-methyl-3-pyridyl) phenyl group, 3-(4-methyl-3-pyridyl) phenyl group, 4-(4-methyl-3-pyridyl) phenyl group, 2-(5 -Methyl-3-pyridyl)phenyl group, 3-(5-methyl-3-pyridyl)phenyl group, 4-(5-methyl-3-pyridyl)phenyl group, 2-(6-methyl-3-pyridyl)phenyl group, 3-(6-methyl-3-pyridyl)phenyl group, 4-(6-methyl-3-pyridyl)phenyl group, 2-(2-methyl-4-pyridyl)phenyl group, 3-(2-methyl -4-pyridyl) phenyl group, 4-(2-methyl-4-pyridyl) phenyl group, 2-(3-methyl-4-pyridyl) phenyl group, 3-(3-methyl-4-pyridyl) phenyl group, 4-(3-methyl-4-pyridyl)phenyl group, 2,6-diphenylpyridin-3-yl group, 2,6-diphenylpyridin-4-yl group, 4,6-diphenylpyridin-2-yl group, 3,6-diphenylpyridin-4-yl group, 3,6-diphenylpyridin-5-yl group.

(5): 1-naphthyl group, 2-naphthyl group, 1-phenylnaphthalen-2-yl group, 1-phenylnaphthalen-3-yl group, 1-phenylnaphthalen-4-yl group, 1-phenylnaphthalen-5 -yl group, 1-phenylnaphthalen-6-yl group, 1-phenylnaphthalen-7-yl group, 1-phenylnaphthalen-8-yl group, 2-phenylnaphthalen-1-yl group, 2-phenylnaphthalen-3 -yl group, 2-phenylnaphthalen-4-yl group, 2-phenylnaphthalen-5-yl group, 2-phenylnaphthalen-6-yl group, 2-phenylnaphthalen-7-yl group, 2-phenylnaphthalen-8 -yl group, 1-methylnaphthalen-4-yl group, 1-methylnaphthalen-5-yl group, 1-methylnaphthalen-6-yl group, 1-methylnaphthalen-7-yl group, 1-methylnaphthalen-8 -yl group, 2-methylnaphthalen-1-yl group, 2-methylnaphthalen-3-yl group, 2-methylnaphthalen-4-yl group, 2-methylnaphthalen-5-yl group, 2-methylnaphthalen-6 -yl group, 2-methylnaphthalen-7-yl group, 2-methylnaphthalen-8-yl group.

(6): 1-phenanthryl group, 2-phenanthryl group, 3-phenanthryl group, 4-phenanthryl group, 9-phenanthryl group, 1-phenylphenanthren-2-yl group, 1-phenylphenanthren-3-yl group, 1 -phenylphenanthren-4-yl group, 1-phenylphenanthren-5-yl group, 1-phenylphenanthren-6-yl group, 1-phenylphenanthren-7-yl group, 1-phenylphenanthren-8-yl group, 1 -phenylphenanthren-9-yl group, 1-phenylphenanthren-10-yl group, 2-phenylphenanthren-1-yl group, 2-phenylphenanthren-3-yl group, 2-phenylphenanthren-4-yl group, 2 -phenylphenanthren-5-yl group, 2-phenylphenanthren-6-yl group, 2-phenylphenanthren-7-yl group, 2-phenylphenanthren-8-yl group, 2-phenylphenanthren-9-yl group, 2 -phenylphenanthren-10-yl group, 3-phenylphenanthren-1-yl group, 3-phenylphenanthren-2-yl group, 3-phenylphenanthren-4-yl group, 3-phenylphenanthren-5-yl group, 3 -phenylphenanthren-6-yl group, 3-phenylphenanthren-7-yl group, 3-phenylphenanthren-8-yl group, 3-phenylphenanthren-9-yl group, 3-phenylphenanthren-10-yl group, 4 -phenylphenanthren-1-yl group, 4-phenylphenanthren-2-yl group, 4-phenylphenanthren-3-yl group, 4-phenylphenanthren-5-yl group, 4-phenylphenanthren-6-yl group, 4 -phenylphenanthren-7-yl group, 4-phenylphenanthren-8-yl group, 4-phenylphenanthren-9-yl group, 4-phenylphenanthren-10-yl group, 1-methylphenanthren-2-yl group, 1 -Methylphenanthren-3-yl group, 1-methylphenanthren-4-yl group, 1-methylphenanthren-5-yl group, 1-methylphenanthren-6-yl group, 1-methylphenanthren-7-yl group, 1 -Methylphenanthren-8-yl group, 1-methylphenanthren-9-yl group, 1-methylphenanthren-10-yl group, 2-methylphenanthren-1-yl group, 2-methylphenanthren-3-yl group, 2 -Methylphenanthren-4-yl group, 2-methylphenanthren-5-yl group, 2-methylphenanthren-6-yl group, 2-methylphenanthren-7-yl group, 2-methylphenanthren-8-yl group, 2 -Methylphenanthren-9-yl group, 2-methylphenanthren-10-yl group, 3-methylphenanthren-1-yl group, 3-methylphenanthren-2-yl group, 3-methylphenanthren-4-yl group, 3 -Methylphenanthren-5-yl group, 3-methylphenanthren-6-yl group, 3-methylphenanthren-7-yl group, 3-methylphenanthren-8-yl group, 3-methylphenanthren-9-yl group, 3 -Methylphenanthren-10-yl group, 4-methylphenanthren-1-yl group, 4-methylphenanthren-2-yl group, 4-methylphenanthren-3-yl group, 4-methylphenanthren-5-yl group, 4 -Methylphenanthren-6-yl group, 4-methylphenanthren-7-yl group, 4-methylphenanthren-8-yl group, 4-methylphenanthren-9-yl group, 4-methylphenanthren-10-yl group.

(7): 1-anthryl group, 2-anthryl group, 9-anthryl group, 1-phenylanthracen-2-yl group, 1-phenylanthracen-3-yl group, 1-phenylanthracen-4-yl group, 1 -phenylanthracen-5-yl group, 1-phenylanthracen-6-yl group, 1-phenylanthracen-7-yl group, 1-phenylanthracen-8-yl group, 1-phenylanthracen-9-yl group, 1 -phenylanthracen-10-yl group, 2-phenylanthracen-1-yl group, 2-phenylanthracen-3-yl group, 2-phenylanthracen-4-yl group, 2-phenylanthracen-5-yl group, 2 -phenylanthracen-6-yl group, 2-phenylanthracen-7-yl group, 2-phenylanthracen-8-yl group, 2-phenylanthracen-9-yl group, 2-phenylanthracen-10-yl group, 9 -phenylanthracen-1-yl group, 9-phenylanthracen-2-yl group, 9-phenylanthracen-3-yl group, 9-phenylanthracen-4-yl group, 9-phenylanthracen-5-yl group, 9 -(2-pyridyl)-anthracen-10-yl group, 9-(3-pyridyl)-anthracen-10-yl group, 9-(4-pyridyl)-anthracen-10-yl group.

(8): 1-pyrenyl group, 2-pyrenyl group, 4-pyrenyl group, 1-phenylpyren-2-yl group, 1-phenylpyren-3-yl group, 1-phenylpyren-4-yl group, 1 -phenylpyren-5-yl group, 1-phenylpyren-6-yl group, 1-phenylpyren-7-yl group, 1-phenylpyren-8-yl group, 1-phenylpyren-9-yl group, 1 -phenylpyren-10-yl group, 2-phenylpyren-1-yl group, 2-phenylpyren-3-yl group, 2-phenylpyren-4-yl group, 2-phenylpyren-5-yl group, 2 -phenylpyren-6-yl group, 2-phenylpyren-7-yl group, 2-phenylpyren-8-yl group, 2-phenylpyren-9-yl group, 2-phenylpyren-10-yl group, 9 -phenylpyren-1-yl group, 9-phenylpyren-2-yl group, 9-phenylpyren-3-yl group, 9-phenylpyren-4-yl group, 9-phenylpyren-5-yl group, 9 -phenylpyren-6-yl group, 9-phenylpyren-7-yl group, 9-phenylpyren-8-yl group, 9-phenylpyren-10-yl group, 1-methylpyren-2-yl group, 1- Methylpyren-3-yl group, 1-methylpyren-4-yl group, 1-methylpyren-5-yl group, 1-methylpyren-6-yl group, 1-methylpyren-7-yl group, 1-methylpyren-8-yl group group, 1-methylpyren-9-yl group, 1-methylpyren-10-yl group, 2-methylpyren-1-yl group, 2-methylpyren-3-yl group, 2-methylpyren-4-yl group, 2-methylpyrene -5-yl group, 2-methylpyren-6-yl group, 2-methylpyren-7-yl group, 2-methylpyren-8-yl group, 2-methylpyren-9-yl group, 2-methylpyren-10-yl group , 9-methylpyren-1-yl group, 9-methylpyren-2-yl group, 9-methylpyren-3-yl group, 9-methylpyren-4-yl group, 9-methylpyren-5-yl group, 9-methylpyren-yl group 6-yl group, 9-methylpyren-7-yl group, 9-methylpyren-8-yl group, 9-methylpyren-10-yl group.

(9): Fluoranthen-1-yl group, Fluoranthen-1-yl group, Fluoranthen-2-yl group, Fluoranthen-3-yl group, Fluoranthen-4-yl group, Fluoranthen-5-yl group, Fluoranthen-6-yl group. yl group, fluoranthene-7-yl group, fluoranthene-8-yl group, fluoranthene-9-yl group, fluoranthene-10-yl group.

(10): triphenylen-1-yl group, triphenylen-2-yl group, acenaphthylen-1-yl group, acenaphthylen-3-yl group, acenaphthylen-4-yl group, acenaphthylen-5-yl group, chrysen-1-yl group chrysen-yl group, chrysen-2-yl group, chrysen-5-yl group, chrysen-6-yl group.

(11): 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, quinoxalin-2-yl group, quinoxalin-5-yl group, quinoxalin-6-yl group, quinazolin-2-yl group group, quinazolin-4-yl group, quinazolin-5-yl group, quinazolin-6-yl group, quinazolin-7-yl group, quinazolin-8-yl group, pyrazin-2-yl group, 5-methylpyrazine-2 -yl group, 5,6-diphenylpyrazin-2-yl group, pyrimidin-2-yl group, pyrimidin-4-yl group, pyrimidin-5-yl group, 2,4-diphenylpyrimidin-6-yl group, 4 , 6-diphenylpyrimidin-2-yl group, acridin-1-yl group, acridin-1-yl group, acridin-2-yl group, acridin-3-yl group, acridin-4-yl group, acridin-9-yl group yl group, phenanthridin-1-yl group, phenanthridin-1-yl group, phenanthridin-2-yl group, phenanthridin-3-yl group, phenanthridin-4-yl group, phenanthridin-yl group Lysin-6-yl group, phenanthridin-7-yl group, phenanthridin-8-yl group, phenanthridin-9-yl group, phenanthridin-10-yl group, phenazin-1-yl group, Phenazin-2-yl group, benzo[h]quinolin-2-yl group, benzo[h]quinolin-3-yl group, benzo[h]quinolin-4-yl group, benzo[h]quinolin-5-yl group , benzo[h]quinolin-6-yl group, benzo[h]quinolin-7-yl group, benzo[h]quinolin-8-yl group, benzo[h]quinolin-9-yl group, benzo[h]quinoline -10-yl group.

(12): 2-thienyl group, 3-thienyl group, 2-furyl group, 3-furyl group, benzothiophen-2-yl group, benzothiophen-3-yl group, benzothiophen-4-yl group, benzothiophene -5-yl group, benzothiophen-6-yl group, benzothiophen-7-yl group, benzofuran-2-yl group, benzofuran-3-yl group, benzofuran-4-yl group, benzofuran-5-yl group, Benzofuran-6-yl group, benzofuran-7-yl group, dibenzothiophen-1-yl group, dibenzothiophen-2-yl group, dibenzothiophen-3-yl group, dibenzofuran-1-yl group, dibenzofuran-2-yl group group, dibenzofuran-3-yl group, 3-methylthiophen-2-yl group, 4-methylthiophen-2-yl group, 5-methylthiophen-2-yl group, 2-methylthiophen-3-yl group, 4 -Methylthiophen-3-yl group, 5-methylthiophen-3-yl group, 3-methylfuran-2-yl group, 4-methylfuran-2-yl group, 5-methylfuran-2-yl group, 2 -Methylfuran-3-yl group, 4-methylfuran-3-yl group, 5-methylfuran-3-yl group.

(13): 3-methylbenzothiophen-2-yl group, 4-methylbenzothiophen-2-yl group, 5-methylbenzothiophen-2-yl group, 6-methylbenzothiophen-2-yl group, 7- Methylbenzothiophen-2-yl group, 2-methylbenzothiophen-3-yl group, 4-methylbenzothiophen-3-yl group, 5-methylbenzothiophen-3-yl group, 6-methylbenzothiophen-3-yl group yl group, 7-methylbenzothiophen-3-yl group, 2-methylbenzothiophen-4-yl group, 3-methylbenzothiophen-4-yl group, 5-methylbenzothiophen-4-yl group, 6-methyl Benzothiophen-4-yl group, 7-methylbenzothiophen-4-yl group, 2-methylbenzothiophen-5-yl group, 3-methylbenzothiophen-5-yl group, 4-methylbenzothiophen-5-yl group group, 6-methylbenzothiophen-5-yl group, 7-methylbenzothiophen-5-yl group, 2-methylbenzothiophen-6-yl group, 3-methylbenzothiophen-6-yl group, 4-methylbenzo Thiophen-6-yl group, 5-methylbenzothiophen-6-yl group, 7-methylbenzothiophen-6-yl group, 2-methylbenzothiophen-7-yl group, 3-methylbenzothiophen-7-yl group , 4-methylbenzothiophen-7-yl group, 5-methylbenzothiophen-7-yl group, 6-methylbenzothiophen-7-yl group.

(14): 3-methylbenzofuran-2-yl group, 4-methylbenzofuran-2-yl group, 5-methylbenzofuran-2-yl group, 6-methylbenzofuran-2-yl group, 7-methylbenzofuran-2-yl group -yl group, 2-methylbenzofuran-3-yl group, 4-methylbenzofuran-3-yl group, 5-methylbenzofuran-3-yl group, 6-methylbenzofuran-3-yl group, 7-methylbenzofuran-3 -yl group, 2-methylbenzofuran-4-yl group, 3-methylbenzofuran-4-yl group, 5-methylbenzofuran-4-yl group, 6-methylbenzofuran-4-yl group, 7-methylbenzofuran-4-yl group -yl group, 2-methylbenzofuran-5-yl group, 3-methylbenzofuran-5-yl group, 4-methylbenzofuran-5-yl group, 6-methylbenzofuran-5-yl group, 7-methylbenzofuran-5 -yl group, 2-methylbenzofuran-6-yl group, 3-methylbenzofuran-6-yl group, 4-methylbenzofuran-6-yl group, 5-methylbenzofuran-6-yl group, 7-methylbenzofuran-6-yl group -yl group, 2-methylbenzofuran-7-yl group, 3-methylbenzofuran-7-yl group, 4-methylbenzofuran-7-yl group, 5-methylbenzofuran-7-yl group, 6-methylbenzofuran-7-yl group -yl group.

(15): 2-methyldibenzothiophen-1-yl group, 3-methyldibenzothiophen-1-yl group, 4-methyldibenzothiophen-1-yl group, 6-methyldibenzothiophen-1-yl group, 7- Methyldibenzothiophen-1-yl group, 8-methyldibenzothiophen-1-yl group, 9-methyldibenzothiophen-1-yl group, 1-methyldibenzothiophen-2-yl group, 3-methyldibenzothiophen-2-yl group yl group, 4-methyldibenzothiophen-2-yl group, 6-methyldibenzothiophen-2-yl group, 7-methyldibenzothiophen-2-yl group, 8-methyldibenzothiophen-2-yl group, 9-methyl Dibenzothiophen-2-yl group, 1-methyldibenzothiophen-3-yl group, 2-methyldibenzothiophen-3-yl group, 4-methyldibenzothiophen-3-yl group, 6-methyldibenzothiophen-3-yl group group, 7-methyldibenzothiophen-3-yl group, 8-methyldibenzothiophen-3-yl group, 9-methyldibenzothiophen-3-yl group.

(16): 2-methyldibenzofuran-1-yl group, 3-methyldibenzofuran-1-yl group, 4-methyldibenzofuran-1-yl group, 6-methyldibenzofuran-1-yl group, 7-methyldibenzofuran-1 -yl group, 8-methyldibenzofuran-1-yl group, 9-methyldibenzofuran-1-yl group, 1-methyldibenzofuran-2-yl group, 3-methyldibenzofuran-2-yl group, 4-methyldibenzofuran-2 -yl group, 6-methyldibenzofuran-2-yl group, 7-methyldibenzofuran-2-yl group, 8-methyldibenzofuran-2-yl group, 9-methyldibenzofuran-2-yl group, 1-methyldibenzofuran-3 -yl group, 2-methyldibenzofuran-3-yl group, 4-methyldibenzofuran-3-yl group, 6-methyldibenzofuran-3-yl group, 7-methyldibenzofuran-3-yl group, 8-methyldibenzofuran-3 -yl group, 9-methyldibenzofuran-3-yl group.

(17): 3-phenylthiophen-2-yl group, 4-phenylthiophen-2-yl group, 5-phenylthiophen-2-yl group, 2-phenylthiophen-3-yl group, 4-phenylthiophen-3 -yl group, 5-phenylthiophen-3-yl group.

(18): 3-phenylfuran-2-yl group, 4-phenylfuran-2-yl group, 5-phenylfuran-2-yl group, 2-phenylfuran-3-yl group, 4-phenylfuran-3 -yl group, 5-phenylfuran-3-yl group.

(19): 3-phenylbenzothiophen-2-yl group, 4-phenylbenzothiophen-2-yl group, 5-phenylbenzothiophen-2-yl group, 6-phenylbenzothiophen-2-yl group, 7- Phenylbenzothiophen-2-yl group, 2-phenylbenzothiophen-3-yl group, 4-phenylbenzothiophen-3-yl group, 5-phenylbenzothiophen-3-yl group, 6-phenylbenzothiophen-3-yl group yl group, 7-phenylbenzothiophen-3-yl group, 2-phenylbenzothiophen-4-yl group, 3-phenylbenzothiophen-4-yl group, 5-phenylbenzothiophen-4-yl group, 6-phenyl group Benzothiophen-4-yl group, 7-phenylbenzothiophen-4-yl group, 2-phenylbenzothiophen-5-yl group, 3-phenylbenzothiophen-5-yl group, 4-phenylbenzothiophen-5-yl group group, 6-phenylbenzothiophen-5-yl group, 7-phenylbenzothiophen-5-yl group, 2-phenylbenzothiophen-6-yl group, 3-phenylbenzothiophen-6-yl group, 4-phenylbenzo Thiophen-6-yl group, 5-phenylbenzothiophen-6-yl group, 7-phenylbenzothiophen-6-yl group, 2-phenylbenzothiophen-7-yl group, 3-phenylbenzothiophen-7-yl group , 4-phenylbenzothiophen-7-yl group, 5-phenylbenzothiophen-7-yl group, 6-phenylbenzothiophen-7-yl group.

(20): 3-phenylbenzofuran-2-yl group, 4-phenylbenzofuran-2-yl group, 5-phenylbenzofuran-2-yl group, 6-phenylbenzofuran-2-yl group, 7-phenylbenzofuran-2-yl group -yl group, 2-phenylbenzofuran-3-yl group, 4-phenylbenzofuran-3-yl group, 5-phenylbenzofuran-3-yl group, 6-phenylbenzofuran-3-yl group, 7-phenylbenzofuran-3 -yl group, 2-phenylbenzofuran-4-yl group, 3-phenylbenzofuran-4-yl group, 5-phenylbenzofuran-4-yl group, 6-phenylbenzofuran-4-yl group, 7-phenylbenzofuran-4-yl group -yl group, 2-phenylbenzofuran-5-yl group, 3-phenylbenzofuran-5-yl group, 4-phenylbenzofuran-5-yl group, 6-phenylbenzofuran-5-yl group, 7-phenylbenzofuran-5-yl group -yl group, 2-phenylbenzofuran-6-yl group, 3-phenylbenzofuran-6-yl group, 4-phenylbenzofuran-6-yl group, 5-phenylbenzofuran-6-yl group, 7-phenylbenzofuran-6-yl group -yl group, 2-phenylbenzofuran-7-yl group, 3-phenylbenzofuran-7-yl group, 4-phenylbenzofuran-7-yl group, 5-phenylbenzofuran-7-yl group, 6-phenylbenzofuran-7-yl group -yl group.

(21): 2-phenyldibenzothiophen-1-yl group, 3-phenyldibenzothiophen-1-yl group, 4-phenyldibenzothiophen-1-yl group, 6-phenyldibenzothiophen-1-yl group, 7- Phenyldibenzothiophen-1-yl group, 8-phenyldibenzothiophen-1-yl group, 9-phenyldibenzothiophen-1-yl group, 1-phenyldibenzothiophen-2-yl group, 3-phenyldibenzothiophen-2-yl group yl group, 4-phenyldibenzothiophen-2-yl group, 6-phenyldibenzothiophen-2-yl group, 7-phenyldibenzothiophen-2-yl group, 8-phenyldibenzothiophen-2-yl group, 9-phenyl group Dibenzothiophen-2-yl group, 1-phenyldibenzothiophen-3-yl group, 2-phenyldibenzothiophen-3-yl group, 4-phenyldibenzothiophen-3-yl group, 6-phenyldibenzothiophen-3-yl group group, 7-phenyldibenzothiophen-3-yl group, 8-phenyldibenzothiophen-3-yl group, 9-phenyldibenzothiophen-3-yl group.

(22): 2-phenyldibenzofuran-1-yl group, 3-phenyldibenzofuran-1-yl group, 4-phenyldibenzofuran-1-yl group, 6-phenyldibenzofuran-1-yl group, 7-phenyldibenzofuran-1-yl group -yl group, 8-phenyldibenzofuran-1-yl group, 9-phenyldibenzofuran-1-yl group, 1-phenyldibenzofuran-2-yl group, 3-phenyldibenzofuran-2-yl group, 4-phenyldibenzofuran-2-yl group -yl group, 6-phenyldibenzofuran-2-yl group, 7-phenyldibenzofuran-2-yl group, 8-phenyldibenzofuran-2-yl group, 9-phenyldibenzofuran-2-yl group, 1-phenyldibenzofuran-3 -yl group, 2-phenyldibenzofuran-3-yl group, 4-phenyldibenzofuran-3-yl group, 6-phenyldibenzofuran-3-yl group, 7-phenyldibenzofuran-3-yl group, 8-phenyldibenzofuran-3-yl group -yl group, 9-phenyldibenzofuran-3-yl group.

(23): 3-(2-pyridyl)thiophen-2-yl group, 4-(2-pyridyl)thiophen-2-yl group, 5-(2-pyridyl)thiophen-2-yl group, 2-(2-pyridyl)thiophen-2-yl group, -pyridyl)thiophen-3-yl group, 4-(2-pyridyl)thiophen-3-yl group, 5-(2-pyridyl)thiophen-3-yl group, 3-(2-pyridyl)furan-2-yl group, 4-(2-pyridyl)furan-2-yl group, 5-(2-pyridyl)furan-2-yl group, 2-(2-pyridyl)furan-3-yl group, 4-(2-pyridyl) ) Furan-3-yl group, 5-(2-pyridyl)furan-3-yl group.

(24): 3-(2-pyridyl)benzothiophen-2-yl group, 4-(2-pyridyl)benzothiophen-2-yl group, 5-(2-pyridyl)benzothiophen-2-yl group, 6 -(2-pyridyl)benzothiophen-2-yl group, 7-(2-pyridyl)benzothiophen-2-yl group, 2-(2-pyridyl)benzothiophen-3-yl group, 4-(2-pyridyl) ) benzothiophen-3-yl group, 5-(2-pyridyl)benzothiophen-3-yl group, 6-(2-pyridyl)benzothiophen-3-yl group, 7-(2-pyridyl)benzothiophene-3 -yl group, 2-(2-pyridyl)benzothiophen-4-yl group, 3-(2-pyridyl)benzothiophen-4-yl group, 5-(2-pyridyl)benzothiophen-4-yl group, 6 -(2-pyridyl)benzothiophen-4-yl group, 7-(2-pyridyl)benzothiophen-4-yl group, 2-(2-pyridyl)benzothiophen-5-yl group, 3-(2-pyridyl) ) benzothiophen-5-yl group, 4-(2-pyridyl)benzothiophen-5-yl group, 6-(2-pyridyl)benzothiophen-5-yl group, 7-(2-pyridyl)benzothiophene-5 -yl group, 2-(2-pyridyl)benzothiophen-6-yl group, 3-(2-pyridyl)benzothiophen-6-yl group, 4-(2-pyridyl)benzothiophen-6-yl group, 5 -(2-pyridyl)benzothiophen-6-yl group, 7-(2-pyridyl)benzothiophen-6-yl group, 2-(2-pyridyl)benzothiophen-7-yl group, 3-(2-pyridyl) ) benzothiophen-7-yl group, 4-(2-pyridyl)benzothiophen-7-yl group, 5-(2-pyridyl)benzothiophen-7-yl group, 6-(2-pyridyl)benzothiophene-7 -yl group.

(25): 3-(2-pyridyl)benzofuran-2-yl group, 4-(2-pyridyl)benzofuran-2-yl group, 5-(2-pyridyl)benzofuran-2-yl group, 6-(2 -pyridyl)benzofuran-2-yl group, 7-(2-pyridyl)benzofuran-2-yl group, 2-(2-pyridyl)benzofuran-3-yl group, 4-(2-pyridyl)benzofuran-3-yl group group, 5-(2-pyridyl)benzofuran-3-yl group, 6-(2-pyridyl)benzofuran-3-yl group, 7-(2-pyridyl)benzofuran-3-yl group, 2-(2-pyridyl ) benzofuran-4-yl group, 3-(2-pyridyl)benzofuran-4-yl group, 5-(2-pyridyl)benzofuran-4-yl group, 6-(2-pyridyl)benzofuran-4-yl group, 7-(2-pyridyl)benzofuran-4-yl group, 2-(2-pyridyl)benzofuran-5-yl group, 3-(2-pyridyl)benzofuran-5-yl group, 4-(2-pyridyl)benzofuran -5-yl group, 6-(2-pyridyl)benzofuran-5-yl group, 7-(2-pyridyl)benzofuran-5-yl group, 2-(2-pyridyl)benzofuran-6-yl group, 3- (2-pyridyl)benzofuran-6-yl group, 4-(2-pyridyl)benzofuran-6-yl group, 5-(2-pyridyl)benzofuran-6-yl group, 7-(2-pyridyl)benzofuran-6 -yl group, 2-(2-pyridyl)benzofuran-7-yl group, 3-(2-pyridyl)benzofuran-7-yl group, 4-(2-pyridyl)benzofuran-7-yl group, 5-(2 -pyridyl)benzofuran-7-yl group, 6-(2-pyridyl)benzofuran-7-yl group.

(26): 2-(2-pyridyl)dibenzothiophen-1-yl group, 3-(2-pyridyl)dibenzothiophen-1-yl group, 4-(2-pyridyl)dibenzothiophen-1-yl group, 6 -(2-pyridyl)dibenzothiophen-1-yl group, 7-(2-pyridyl)dibenzothiophen-1-yl group, 8-(2-pyridyl)dibenzothiophen-1-yl group, 9-(2-pyridyl) ) Dibenzothiophen-1-yl group, 1-(2-pyridyl)dibenzothiophen-2-yl group, 3-(2-pyridyl)dibenzothiophen-2-yl group, 4-(2-pyridyl)dibenzothiophene-2 -yl group, 6-(2-pyridyl)dibenzothiophen-2-yl group, 7-(2-pyridyl)dibenzothiophen-2-yl group, 8-(2-pyridyl)dibenzothiophen-2-yl group, 9 -(2-pyridyl)dibenzothiophen-2-yl group, 1-(2-pyridyl)dibenzothiophen-3-yl group, 2-(2-pyridyl)dibenzothiophen-3-yl group, 4-(2-pyridyl) ) Dibenzothiophen-3-yl group, 6-(2-pyridyl)dibenzothiophen-3-yl group, 7-(2-pyridyl)dibenzothiophen-3-yl group, 8-(2-pyridyl)dibenzothiophene-3 -yl group, 9-(2-pyridyl)dibenzothiophen-3-yl group.

(27): 2-(2-pyridyl)dibenzofuran-1-yl group, 3-(2-pyridyl)dibenzofuran-1-yl group, 4-(2-pyridyl)dibenzofuran-1-yl group, 6-(2 -pyridyl)dibenzofuran-1-yl group, 7-(2-pyridyl)dibenzofuran-1-yl group, 8-(2-pyridyl)dibenzofuran-1-yl group, 9-(2-pyridyl)dibenzofuran-1-yl group group, 1-(2-pyridyl)dibenzofuran-2-yl group, 3-(2-pyridyl)dibenzofuran-2-yl group, 4-(2-pyridyl)dibenzofuran-2-yl group, 6-(2-pyridyl) ) dibenzofuran-2-yl group, 7-(2-pyridyl)dibenzofuran-2-yl group, 8-(2-pyridyl)dibenzofuran-2-yl group, 9-(2-pyridyl)dibenzofuran-2-yl group, 1-(2-pyridyl)dibenzofuran-3-yl group, 2-(2-pyridyl)dibenzofuran-3-yl group, 4-(2-pyridyl)dibenzofuran-3-yl group, 6-(2-pyridyl)dibenzofuran -3-yl group, 7-(2-pyridyl)dibenzofuran-3-yl group, 8-(2-pyridyl)dibenzofuran-3-yl group, 9-(2-pyridyl)dibenzofuran-3-yl group.

(28): 3-(3-pyridyl)thiophen-2-yl group, 4-(3-pyridyl)thiophen-2-yl group, 5-(3-pyridyl)thiophen-2-yl group, 2-(3-pyridyl)thiophen-2-yl group, -pyridyl)thiophen-3-yl group, 4-(3-pyridyl)thiophen-3-yl group, 5-(3-pyridyl)thiophen-3-yl group.

(29): 3-(3-pyridyl)furan-2-yl group, 4-(3-pyridyl)furan-2-yl group, 5-(3-pyridyl)furan-2-yl group, 2-(3 -pyridyl)furan-3-yl group, 4-(3-pyridyl)furan-3-yl group, 5-(3-pyridyl)furan-3-yl group.

(30): 3-(3-pyridyl)benzothiophen-2-yl group, 4-(3-pyridyl)benzothiophen-2-yl group, 5-(3-pyridyl)benzothiophen-2-yl group, 6 -(3-pyridyl)benzothiophen-2-yl group, 7-(3-pyridyl)benzothiophen-2-yl group, 2-(3-pyridyl)benzothiophen-3-yl group, 4-(3-pyridyl) ) benzothiophen-3-yl group, 5-(3-pyridyl)benzothiophen-3-yl group, 6-(3-pyridyl)benzothiophen-3-yl group, 7-(3-pyridyl)benzothiophene-3 -yl group, 2-(3-pyridyl)benzothiophen-4-yl group, 3-(3-pyridyl)benzothiophen-4-yl group, 5-(3-pyridyl)benzothiophen-4-yl group, 6 -(3-pyridyl)benzothiophen-4-yl group, 7-(3-pyridyl)benzothiophen-4-yl group, 2-(3-pyridyl)benzothiophen-5-yl group, 3-(3-pyridyl) ) benzothiophen-5-yl group, 4-(3-pyridyl)benzothiophen-5-yl group, 6-(3-pyridyl)benzothiophen-5-yl group, 7-(3-pyridyl)benzothiophene-5 -yl group, 2-(3-pyridyl)benzothiophen-6-yl group, 3-(3-pyridyl)benzothiophen-6-yl group, 4-(3-pyridyl)benzothiophen-6-yl group, 5 -(3-pyridyl)benzothiophen-6-yl group, 7-(3-pyridyl)benzothiophen-6-yl group, 2-(3-pyridyl)benzothiophen-7-yl group, 3-(3-pyridyl) ) benzothiophen-7-yl group, 4-(3-pyridyl)benzothiophen-7-yl group, 5-(3-pyridyl)benzothiophen-7-yl group, 6-(3-pyridyl)benzothiophene-7 -yl group.

(31): 3-(3-pyridyl)benzofuran-2-yl group, 4-(3-pyridyl)benzofuran-2-yl group, 5-(3-pyridyl)benzofuran-2-yl group, 6-(3 -pyridyl)benzofuran-2-yl group, 7-(3-pyridyl)benzofuran-2-yl group, 2-(3-pyridyl)benzofuran-3-yl group, 4-(3-pyridyl)benzofuran-3-yl group, 5-(3-pyridyl)benzofuran-3-yl group, 6-(3-pyridyl)benzofuran-3-yl group, 7-(3-pyridyl)benzofuran-3-yl group, 2-(3-pyridyl) ) benzofuran-4-yl group, 3-(3-pyridyl)benzofuran-4-yl group, 5-(3-pyridyl)benzofuran-4-yl group, 6-(3-pyridyl)benzofuran-4-yl group, 7-(3-pyridyl)benzofuran-4-yl group, 2-(3-pyridyl)benzofuran-5-yl group, 3-(3-pyridyl)benzofuran-5-yl group, 4-(3-pyridyl)benzofuran -5-yl group, 6-(3-pyridyl)benzofuran-5-yl group, 7-(3-pyridyl)benzofuran-5-yl group, 2-(3-pyridyl)benzofuran-6-yl group, 3- (3-pyridyl)benzofuran-6-yl group, 4-(3-pyridyl)benzofuran-6-yl group, 5-(3-pyridyl)benzofuran-6-yl group, 7-(3-pyridyl)benzofuran-6 -yl group, 2-(3-pyridyl)benzofuran-7-yl group, 3-(3-pyridyl)benzofuran-7-yl group, 4-(3-pyridyl)benzofuran-7-yl group, 5-(3 -pyridyl)benzofuran-7-yl group, 6-(3-pyridyl)benzofuran-7-yl group.

(32): 2-(3-pyridyl)dibenzothiophen-1-yl group, 3-(3-pyridyl)dibenzothiophen-1-yl group, 4-(3-pyridyl)dibenzothiophen-1-yl group, 6 -(3-pyridyl)dibenzothiophen-1-yl group, 7-(3-pyridyl)dibenzothiophen-1-yl group, 8-(3-pyridyl)dibenzothiophen-1-yl group, 9-(3-pyridyl) ) Dibenzothiophen-1-yl group, 1-(3-pyridyl)dibenzothiophen-2-yl group, 3-(3-pyridyl)dibenzothiophen-2-yl group, 4-(3-pyridyl)dibenzothiophene-2 -yl group, 6-(3-pyridyl)dibenzothiophen-2-yl group, 7-(3-pyridyl)dibenzothiophen-2-yl group, 8-(3-pyridyl)dibenzothiophen-2-yl group, 9 -(3-pyridyl)dibenzothiophen-2-yl group, 1-(3-pyridyl)dibenzothiophen-3-yl group, 2-(3-pyridyl)dibenzothiophen-3-yl group, 4-(3-pyridyl) ) Dibenzothiophen-3-yl group, 6-(3-pyridyl)dibenzothiophen-3-yl group, 7-(3-pyridyl)dibenzothiophen-3-yl group, 8-(3-pyridyl)dibenzothiophene-3 -yl group, 9-(3-pyridyl)dibenzothiophen-3-yl group.

(33): 2-(3-pyridyl)dibenzofuran-1-yl group, 3-(3-pyridyl)dibenzofuran-1-yl group, 4-(3-pyridyl)dibenzofuran-1-yl group, 6-(3 -pyridyl)dibenzofuran-1-yl group, 7-(3-pyridyl)dibenzofuran-1-yl group, 8-(3-pyridyl)dibenzofuran-1-yl group, 9-(3-pyridyl)dibenzofuran-1-yl group group, 1-(3-pyridyl)dibenzofuran-2-yl group, 3-(3-pyridyl)dibenzofuran-2-yl group, 4-(3-pyridyl)dibenzofuran-2-yl group, 6-(3-pyridyl) ) dibenzofuran-2-yl group, 7-(3-pyridyl)dibenzofuran-2-yl group, 8-(3-pyridyl)dibenzofuran-2-yl group, 9-(3-pyridyl)dibenzofuran-2-yl group, 1-(3-pyridyl)dibenzofuran-3-yl group, 2-(3-pyridyl)dibenzofuran-3-yl group, 4-(3-pyridyl)dibenzofuran-3-yl group, 6-(3-pyridyl)dibenzofuran -3-yl group, 7-(3-pyridyl)dibenzofuran-3-yl group, 8-(3-pyridyl)dibenzofuran-3-yl group, 9-(3-pyridyl)dibenzofuran-3-yl group.

(34): 3-(4-pyridyl)thiophen-2-yl group, 4-(4-pyridyl)thiophen-2-yl group, 5-(4-pyridyl)thiophen-2-yl group, 2-(4-pyridyl)thiophen-2-yl group, -pyridyl)thiophen-3-yl group, 4-(4-pyridyl)thiophen-3-yl group, 5-(4-pyridyl)thiophen-3-yl group.

(35): 3-(4-pyridyl)furan-2-yl group, 4-(4-pyridyl)furan-2-yl group, 5-(4-pyridyl)furan-2-yl group, 2-(4-pyridyl)furan-2-yl group, -pyridyl)furan-3-yl group, 4-(4-pyridyl)furan-3-yl group, 5-(4-pyridyl)furan-3-yl group.

(36): 3-(4-pyridyl)benzothiophen-2-yl group, 4-(4-pyridyl)benzothiophen-2-yl group, 5-(4-pyridyl)benzothiophen-2-yl group, 6 -(4-pyridyl)benzothiophen-2-yl group, 7-(4-pyridyl)benzothiophen-2-yl group, 2-(4-pyridyl)benzothiophen-3-yl group, 4-(4-pyridyl) ) benzothiophen-3-yl group, 5-(4-pyridyl)benzothiophen-3-yl group, 6-(4-pyridyl)benzothiophen-3-yl group, 7-(4-pyridyl)benzothiophene-3 -yl group, 2-(4-pyridyl)benzothiophen-4-yl group, 3-(4-pyridyl)benzothiophen-4-yl group, 5-(4-pyridyl)benzothiophen-4-yl group, 6 -(4-pyridyl)benzothiophen-4-yl group, 7-(4-pyridyl)benzothiophen-4-yl group, 2-(4-pyridyl)benzothiophen-5-yl group, 3-(4-pyridyl) ) benzothiophen-5-yl group, 4-(4-pyridyl)benzothiophen-5-yl group, 6-(4-pyridyl)benzothiophen-5-yl group, 7-(4-pyridyl)benzothiophene-5 -yl group, 2-(4-pyridyl)benzothiophen-6-yl group, 3-(4-pyridyl)benzothiophen-6-yl group, 4-(4-pyridyl)benzothiophen-6-yl group, 5 -(4-pyridyl)benzothiophen-6-yl group, 7-(4-pyridyl)benzothiophen-6-yl group, 2-(4-pyridyl)benzothiophen-7-yl group, 3-(4-pyridyl) ) benzothiophen-7-yl group, 4-(4-pyridyl)benzothiophen-7-yl group, 5-(4-pyridyl)benzothiophen-7-yl group, 6-(4-pyridyl)benzothiophene-7 -yl group.

(37): 3-(4-pyridyl)benzofuran-2-yl group, 4-(4-pyridyl)benzofuran-2-yl group, 5-(4-pyridyl)benzofuran-2-yl group, 6-(4 -pyridyl)benzofuran-2-yl group, 7-(4-pyridyl)benzofuran-2-yl group, 2-(4-pyridyl)benzofuran-3-yl group, 4-(4-pyridyl)benzofuran-3-yl group group, 5-(4-pyridyl)benzofuran-3-yl group, 6-(4-pyridyl)benzofuran-3-yl group, 7-(4-pyridyl)benzofuran-3-yl group, 2-(4-pyridyl) ) benzofuran-4-yl group, 3-(4-pyridyl)benzofuran-4-yl group, 5-(4-pyridyl)benzofuran-4-yl group, 6-(4-pyridyl)benzofuran-4-yl group, 7-(4-pyridyl)benzofuran-4-yl group, 2-(4-pyridyl)benzofuran-5-yl group, 3-(4-pyridyl)benzofuran-5-yl group, 4-(4-pyridyl)benzofuran -5-yl group, 6-(4-pyridyl)benzofuran-5-yl group, 7-(4-pyridyl)benzofuran-5-yl group, 2-(4-pyridyl)benzofuran-6-yl group, 3- (4-pyridyl)benzofuran-6-yl group, 4-(4-pyridyl)benzofuran-6-yl group, 5-(4-pyridyl)benzofuran-6-yl group, 7-(4-pyridyl)benzofuran-6 -yl group, 2-(4-pyridyl)benzofuran-7-yl group, 3-(4-pyridyl)benzofuran-7-yl group, 4-(4-pyridyl)benzofuran-7-yl group, 5-(4 -pyridyl)benzofuran-7-yl group, 6-(4-pyridyl)benzofuran-7-yl group.

(38): 2-(4-pyridyl)dibenzothiophen-1-yl group, 3-(4-pyridyl)dibenzothiophen-1-yl group, 4-(4-pyridyl)dibenzothiophen-1-yl group, 6 -(4-pyridyl)dibenzothiophen-1-yl group, 7-(4-pyridyl)dibenzothiophen-1-yl group, 8-(4-pyridyl)dibenzothiophen-1-yl group, 9-(4-pyridyl) ) Dibenzothiophen-1-yl group, 1-(4-pyridyl)dibenzothiophen-2-yl group, 3-(4-pyridyl)dibenzothiophen-2-yl group, 4-(4-pyridyl)dibenzothiophene-2 -yl group, 6-(4-pyridyl)dibenzothiophen-2-yl group, 7-(4-pyridyl)dibenzothiophen-2-yl group, 8-(4-pyridyl)dibenzothiophen-2-yl group, 9 -(4-pyridyl)dibenzothiophen-2-yl group, 1-(4-pyridyl)dibenzothiophen-3-yl group, 2-(4-pyridyl)dibenzothiophen-3-yl group, 4-(4-pyridyl) ) Dibenzothiophen-3-yl group, 6-(4-pyridyl)dibenzothiophen-3-yl group, 7-(4-pyridyl)dibenzothiophen-3-yl group, 8-(4-pyridyl)dibenzothiophene-3 -yl group, 9-(4-pyridyl)dibenzothiophen-3-yl group.

(39): 2-(4-pyridyl)dibenzofuran-1-yl group, 3-(4-pyridyl)dibenzofuran-1-yl group, 4-(4-pyridyl)dibenzofuran-1-yl group, 6-(4 -pyridyl)dibenzofuran-1-yl group, 7-(4-pyridyl)dibenzofuran-1-yl group, 8-(4-pyridyl)dibenzofuran-1-yl group, 9-(4-pyridyl)dibenzofuran-1-yl group group, 1-(4-pyridyl)dibenzofuran-2-yl group, 3-(4-pyridyl)dibenzofuran-2-yl group, 4-(4-pyridyl)dibenzofuran-2-yl group, 6-(4-pyridyl) ) dibenzofuran-2-yl group, 7-(4-pyridyl)dibenzofuran-2-yl group, 8-(4-pyridyl)dibenzofuran-2-yl group, 9-(4-pyridyl)dibenzofuran-2-yl group, 1-(4-pyridyl)dibenzofuran-3-yl group, 2-(4-pyridyl)dibenzofuran-3-yl group, 4-(4-pyridyl)dibenzofuran-3-yl group, 6-(4-pyridyl)dibenzofuran -3-yl group, 7-(4-pyridyl)dibenzofuran-3-yl group, 8-(4-pyridyl)dibenzofuran-3-yl group, 9-(4-pyridyl)dibenzofuran-3-yl group.

(40): 1-fluorenyl group, 2-fluorenyl group, 3-fluorenyl group, 4-fluorenyl group, 9,9-dimethylfluoren-1-yl group, 9,9-dimethylfluoren-2-yl group, 9, 9-dimethylfluoren-3-yl group, 9,9-dimethylfluoren-4-yl group, 9,9-diphenylfluoren-1-yl group, 9,9-diphenylfluoren-2-yl group, 9,9- diphenylfluoren-3-yl group, 9,9-diphenylfluoren-4-yl group.

(41): 2-(1-naphthyl) phenyl group, 3-(1-naphthyl) phenyl group, 4-(1-naphthyl) phenyl group, 2-(2-naphthyl) phenyl group, 3-(2-naphthyl) ) phenyl group, 4-(2-naphthyl) phenyl group, 2-(9-phenanthryl) phenyl group, 3-(9-phenanthryl) phenyl group, 4-(9-phenanthryl) phenyl group, 2-(1-anthryl) ) phenyl group, 3-(1-anthryl) phenyl group, 4-(1-anthryl) phenyl group, 2-(2-anthryl) phenyl group, 3-(2-anthryl) phenyl group, 4-(2-anthryl) ) phenyl group, 2-(9-anthryl) phenyl group, 3-(9-anthryl) phenyl group, 4-(9-anthryl) phenyl group, 2-(1-pyrenyl) phenyl group, 3-(1-pyrenyl) ) phenyl group, 4-(1-pyrenyl) phenyl group, 2-(2-pyrenyl) phenyl group, 3-(2-pyrenyl) phenyl group, 4-(2-pyrenyl) phenyl group, 2-(2-fluor oranthenyl) phenyl group, 3-(2-fluoranthenyl) phenyl group, 4-(2-fluoranthenyl) phenyl group, 2-(3-fluoranthenyl) phenyl group, 3-(3-fluoranthenyl) ) phenyl group, 4-(3-fluoranthenyl) phenyl group, 2-(7-fluoranthenyl) phenyl group, 3-(7-fluoranthenyl) phenyl group, 4-(7-fluoranthenyl) phenyl group, 2-(8-fluoranthenyl) phenyl group, 3-(8-fluoranthenyl) phenyl group, 4-(8-fluoranthenyl) phenyl group, 2-(1-triphenylenyl) phenyl group, 3- (1-triphenylenyl) phenyl group, 4-(1-triphenylenyl) phenyl group, 2-(2-triphenylenyl) phenyl group, 3-(2-triphenylenyl) phenyl group, 4-(2-triphenylenyl) phenyl group.

(42): 2-(2-quinolyl)phenyl group, 3-(2-quinolyl)phenyl group, 4-(2-quinolyl)phenyl group, 2-(3-quinolyl)phenyl group, 3-(3-quinolyl) ) phenyl group, 4-(3-quinolyl) phenyl group, 2-(4-quinolyl) phenyl group, 3-(4-quinolyl) phenyl group, 4-(4-quinolyl) phenyl group, 2-(5-quinolyl) ) phenyl group, 3-(5-quinolyl) phenyl group, 4-(5-quinolyl) phenyl group, 2-(6-quinolyl) phenyl group, 3-(6-quinolyl) phenyl group, 4-(6-quinolyl) ) phenyl group, 2-(7-quinolyl) phenyl group, 3-(7-quinolyl) phenyl group, 4-(7-quinolyl) phenyl group, 2-(8-quinolyl) phenyl group, 3-(8-quinolyl) ) phenyl group, 4-(8-quinolyl) phenyl group, 2-(1-isoquinolyl) phenyl group, 3-(1-isoquinolyl) phenyl group, 4-(1-isoquinolyl) phenyl group, 2-(3-isoquinolyl) ) phenyl group, 3-(3-isoquinolyl)phenyl group, 4-(3-isoquinolyl)phenyl group, 2-(4-isoquinolyl)phenyl group, 3-(4-isoquinolyl)phenyl group, 4-(4-isoquinolyl) ) phenyl group, 2-(5-isoquinolyl)phenyl group, 3-(5-isoquinolyl)phenyl group, 4-(5-isoquinolyl)phenyl group, 2-(6-isoquinolyl)phenyl group, 3-(6-isoquinolyl) ) phenyl group, 4-(6-isoquinolyl)phenyl group, 2-(7-isoquinolyl)phenyl group, 3-(7-isoquinolyl)phenyl group, 4-(7-isoquinolyl)phenyl group, 2-(8-isoquinolyl) ) phenyl group, 3-(8-isoquinolyl)phenyl group, 4-(8-isoquinolyl)phenyl group.

(43): 2-(2-benzothienyl)phenyl group, 3-(2-benzothienyl)phenyl group, 4-(2-benzothienyl)phenyl group, 2-(3-benzothienyl)phenyl group, 3- (3-benzothienyl)phenyl group, 4-(3-benzothienyl)phenyl group, 2-(4-benzothienyl)phenyl group, 3-(4-benzothienyl)phenyl group, 4-(4-benzothienyl) Phenyl group, 2-(5-benzothienyl)phenyl group, 3-(5-benzothienyl)phenyl group, 4-(5-benzothienyl)phenyl group, 2-(6-benzothienyl)phenyl group, 3-( 6-benzothienyl) phenyl group, 4-(6-benzothienyl) phenyl group, 2-(7-benzothienyl) phenyl group, 3-(7-benzothienyl) phenyl group, 4-(7-benzothienyl) phenyl group group, 2-(2-benzofuryl) phenyl group, 3-(2-benzofuryl) phenyl group, 4-(2-benzofuryl) phenyl group, 2-(3-benzofuryl) phenyl group, 3-(3-benzofuryl) phenyl group, 4-(3-benzofuryl) phenyl group, 2-(4-benzofuryl) phenyl group, 3-(4-benzofuryl) phenyl group, 4-(4-benzofuryl) phenyl group, 2-(5-benzofuryl) phenyl group, 3-(5-benzofuryl) phenyl group, 4-(5-benzofuryl) phenyl group, 2-(6-benzofuryl) phenyl group, 3-(6-benzofuryl) phenyl group, 4-(6-benzofuryl) phenyl group group, 2-(7-benzofuryl) phenyl group, 3-(7-benzofuryl) phenyl group, 4-(7-benzofuryl) phenyl group.

(44): 2-(1-dibenzothienyl)phenyl group, 3-(1-dibenzothienyl)phenyl group, 4-(1-dibenzothienyl)phenyl group, 2-(2-dibenzothienyl)phenyl group, 3- (2-dibenzothienyl)phenyl group, 4-(2-dibenzothienyl)phenyl group, 2-(3-dibenzothienyl)phenyl group, 3-(3-dibenzothienyl)phenyl group, 4-(3-dibenzothienyl) Phenyl group, 2-(4-dibenzothienyl)phenyl group, 3-(4-dibenzothienyl)phenyl group, 4-(4-dibenzothienyl)phenyl group, 2-(1-dibenzofuryl)phenyl group, 3-( 1-dibenzofuryl) phenyl group, 4-(1-dibenzofuryl) phenyl group, 2-(2-dibenzofuryl) phenyl group, 3-(2-dibenzofuryl) phenyl group, 4-(2-dibenzofuryl) phenyl group group, 2-(3-dibenzofuryl) phenyl group, 3-(3-dibenzofuryl) phenyl group, 4-(3-dibenzofuryl) phenyl group, 2-(4-dibenzofuryl) phenyl group, 3-(4 -dibenzofuryl) phenyl group, 4-(4-dibenzofuryl) phenyl group.

The groups represented by -Ar ¹ -Ar ² each independently include a phenyl group, tolyl group, biphenyl group, pyridylphenyl group, naphthylphenyl group, pyridyl group, naphthyl group, Preferably, it is a quinolyl group, isoquinolyl group, benzothienyl group, benzofuryl group, anthryl group, phenanthryl group, dibenzothienyl group, dibenzofuryl group, fluoranthenyl group, pyrenyl group, or triphenylenyl group.
In addition, among these substituents, phenyl group, p-tolyl group, biphenyl-2-yl group, biphenyl-3-yl group, biphenyl-4-yl group are each independently selected from the viewpoint of excellent electron transporting material properties. group, 3-(2-pyridyl)phenyl group, 4-(2-pyridyl)phenyl group, 3-(3-pyridyl)phenyl group, 4-(3-pyridyl)phenyl group, 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 2-phenylpyridin-6-yl group, 2-phenylpyridin-5-yl group, 2-phenylpyridin-4-yl group, 3-phenylpyridin-5-yl group, 3-phenyl Pyridin-6-yl group, 2,6-diphenylpyridin-4-yl group, 4,6-diphenylpyridin-2-yl group, 2-pyrimidyl group, 2-pyrazyl group, 1-naphthyl group, 2-naphthyl group , 3-quinolyl group, 4-quinolyl group, 3-isoquinolyl group, 2-benzothienyl group, 2-benzofuryl group, 2-fluorenyl group, 9,9-dimethylfluoren-2-yl group, 9,9-dimethylfluorene -3-yl group, 9,9-dimethylfluoren-4-yl group, 9,9-diphenylfluoren-2-yl group, 9,9-diphenylfluoren-3-yl group, 9,9-diphenylfluoren-4 -yl group, 9-anthryl group, 1-phenanthryl group, 2-phenanthryl group, 3-phenanthryl group, 9-phenanthryl group, 2-dibenzothienyl group, 2-dibenzofuryl group, 4-dibenzothienyl group, 4-dibenzo A furyl group, 3-fluoranthenyl group, 1-pyrenyl group, or 2-triphenylenyl group is preferred.
Furthermore, among these substituents, phenyl group, p-tolyl group, biphenyl-2-yl group, biphenyl-3-yl group, biphenyl-4-yl group, More preferably, it is a 1-naphthyl group or a 2-naphthyl group.

[About divalent groups L ¹ and L ² ]
Y in the divalent groups L ¹ and L ² each independently represents CH or N.
m represents 0 or 1.
If m is 0, n is 0.
When m is 1, n is 0, 1, or 2.
When n is 2, the plurality of ^L2s may be the same or different from each other.
The divalent groups L ¹ and L ² may each be independently substituted with a fluorine atom, a methyl group, or a phenyl group.

Regarding the divalent groups L ¹ and L ² , the following (i) or (ii) is preferable from the viewpoint of easy synthesis.
(i): L ¹ and L ² are each independently a phenylene group or a pyridylene group.
(ii): m=n=0.

[About Ar ³ ]
Ar ³ represents a hydrogen atom, a phenyl group, a naphthyl group, or a pyridyl group. Ar ³ may be substituted with a fluorine atom, a methyl group, or a phenyl group.
Ar ³ is preferably a hydrogen atom because it is easy to synthesize.

[About Ar ⁴ and Ar ⁵ ]
Ar ⁴ and Ar ⁵ are each independently,
Hydrogen atom, phenyl group, naphthyl group, pyridyl group, or
Represents the bonding position of the triazine ring and any one of the divalent groups L ¹ and L ² .
Ar ⁴ and Ar ⁵ are easy to synthesize;
hydrogen atom, or
The bonding position is preferably the triazine ring or any one of the divalent groups L ¹ and L ² .
Ar ⁴ and Ar ⁵ may each be independently substituted with a fluorine atom, a methyl group, or a phenyl group.

When the cyclic azine compound (1) is used as a component of an organic light emitting diode (OLED), effects such as high current efficiency and long life can be obtained. In particular, these effects are even more pronounced when the cyclic azine compound (1) is used as the electron transport layer.

[Specific example of cyclic azine compound (1)]
Among the compounds represented by formula (1), the following (A-1) to (A-1266) can be exemplified as particularly preferable compounds. ) are not limited to these.

The uses of the cyclic azine compound (1) will be explained below.

<Materials for organic electroluminescent devices, electron transport materials for organic electroluminescent devices>
Although the cyclic azine compound (1) is not particularly limited, it can be used, for example, as a material for an organic electroluminescent device. Further, the cyclic azine compound (1) can be used, for example, as an electron transport material for organic electroluminescent devices.
That is, the organic electroluminescent element material according to one embodiment of the present invention contains the cyclic azine compound (1). Further, an electron transport material for an organic electroluminescent device according to one embodiment of the present invention includes a cyclic azine compound (1). The organic electroluminescent device material and the organic electroluminescent device electron transport material containing the cyclic azine compound (1) contribute to the production of an organic electroluminescent device with excellent durability and current efficiency.

<Organic electroluminescent device>
An organic electroluminescent device according to one embodiment of the present invention includes a cyclic azine compound (1).
The structure of the organic electroluminescent device is not particularly limited, and examples thereof include the following structures (i) to (vi).
(i): Anode/Emissive layer/Cathode (ii): Anode/Hole transport layer/Emissive layer/Cathode (iii): Anode/Emissive layer/Electron transport layer/Cathode (iv): Anode/Hole transport layer/ Light emitting layer/electron transport layer/cathode (v): anode/hole injection layer/hole transport layer/light emitting layer/electron transport layer/electron injection layer/cathode (vi): anode/hole injection layer/charge generation layer /Hole transport layer/Light emitting layer/Electron transport layer/Cathode.

Hereinafter, an organic electroluminescent device according to one embodiment of the present invention will be described in more detail with reference to FIG. 1, taking the configuration (vi) above as an example.
FIG. 1 is a schematic cross-sectional view showing an example of a stacked structure of an organic electroluminescent device containing a cyclic azine compound according to one embodiment of the present invention.

The organic electroluminescent device 100 includes a substrate 1, an anode 2, a hole injection layer 3, a charge generation layer 4, a hole transport layer 5, a light emitting layer 6, an electron transport layer 7, and a cathode 8 in this order. However, some of these layers may be omitted, or conversely, other layers may be added. For example, an electron injection layer may be provided between the electron transport layer 7 and the cathode 8, or the charge generation layer 4 may be omitted and the hole transport layer 5 may be provided directly on the hole injection layer 3. Good too. In addition, a single layer that has the functions of multiple layers, such as an electron injection/transport layer that has both the functions of an electron injection layer and an electron transport layer in a single layer, may be used as a layer. A configuration may be provided instead of. Furthermore, for example, the single-layer hole transport layer 5 and the single-layer electron transport layer 7 may each be composed of a plurality of layers.

[Layer containing a cyclic azine compound represented by formula (1)]
The organic electroluminescent device contains a cyclic azine compound represented by the above formula (1) in one or more layers selected from the group consisting of a light emitting layer and a layer between the light emitting layer and the cathode. Therefore, in the configuration example shown in FIG. 1, the organic electroluminescent device 100 includes the cyclic azine compound (1) in at least one layer selected from the group consisting of the light emitting layer 6 and the electron transport layer 7. In particular, it is preferable that the electron transport layer 7 contains the cyclic azine compound (1). Note that the cyclic azine compound (1) may be included in a plurality of layers included in the organic electroluminescent device, and when an electron injection layer is provided between the electron transport layer and the cathode, the electron injection layer is It may also contain a cyclic azine compound (1).
In addition, below, the organic electroluminescent element 100 in which the electron transport layer 7 contains a cyclic azine compound (1) is demonstrated.

[Substrate 1]
The substrate is not particularly limited, and examples thereof include glass plates, quartz plates, plastic plates, and the like. Further, in the case of a configuration in which light emission is extracted from the substrate 1 side, the substrate 1 is transparent to the wavelength of light.

Examples of optically transparent plastic films include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyethersulfone (PES), polyetherimide, polyetheretherketone, polyphenylene sulfide, polyarylate, polyimide, and polycarbonate ( PC), cellulose triacetate (TAC), cellulose acetate propionate (CAP), and the like.

[Anode 2]
An anode 2 is provided on the substrate 1 (on the hole injection layer 3 side).
In the case of an organic electroluminescent device in which the emitted light is extracted through an anode, the anode is formed of a material that is transparent or substantially transparent to the emitted light.

Transparent materials used for the anode are not particularly limited, but include, for example, indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide, and aluminum.・Doped tin oxide, magnesium-indium oxide, nickel-tungsten oxide, other metal oxides, metal nitrides such as gallium nitride, metal selenides such as zinc selenide, metal sulfides such as zinc sulfide, etc. can be mentioned.
Note that in the case of an organic electroluminescent element configured to extract light only from the cathode side, the transmission characteristics of the anode are not important. Therefore, examples of materials used for the anode in this case include gold, iridium, molybdenum, palladium, platinum, and the like.
A buffer layer (electrode interface layer) may be provided on the anode.

[Hole injection layer 3, hole transport layer 5]
Between the anode 2 and a light emitting layer 6, which will be described later, a hole injection layer 3, a charge generation layer 4, which will be described later, and a hole transport layer 5 are provided in this order from the anode 2 side.
The hole injection layer and the hole transport layer have a function of transmitting holes injected from the anode to the light emitting layer, and the hole injection layer and the hole transport layer are interposed between the anode and the light emitting layer. As a result, many holes are injected into the light emitting layer at a lower electric field.

Further, the hole injection layer and the hole transport layer also function as electron barrier layers. That is, electrons injected from the cathode and transported from the electron injection layer and/or the electron transport layer to the light emitting layer are transported by the electron barrier existing at the interface between the light emitting layer and the hole injection layer and/or the hole transport layer. , leakage to the hole injection layer and/or hole transport layer is suppressed. As a result, the electrons are accumulated at the interface within the light-emitting layer, resulting in effects such as improved current efficiency (light-emitting efficiency), and an organic electroluminescent device with excellent light-emitting performance can be obtained.

The material for the hole injection layer and the hole transport layer has at least one of hole injection properties, hole transport properties, and electron barrier properties. The material for the hole injection layer and the hole transport layer may be either organic or inorganic.

Specific examples of materials for the hole injection layer and hole transport layer include triazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, and amino-substituted chalcone. Derivatives, oxazole derivatives, styryl anthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aniline copolymers, conductive polymer oligomers (especially thiophene oligomers), porphyrin compounds, aromatic tertiary amine compounds, styryl Examples include amine compounds. Among these, porphyrin compounds, aromatic tertiary amine compounds, and styrylamine compounds are preferred, and aromatic tertiary amine compounds are particularly preferred.

Specific examples of aromatic tertiary amine compounds and styrylamine compounds include N,N,N',N'-tetraphenyl-4,4'-diaminophenyl, N,N'-diphenyl-N,N'- Bis(3-methylphenyl)-[1,1'-biphenyl]-4,4'-diamine (TPD), 2,2-bis(4-di-p-tolylaminophenyl)propane, 1,1-bis (4-di-p-tolylaminophenyl)cyclohexane, N,N,N',N'-tetra-p-tolyl-4,4'-diaminobiphenyl, 1,1-bis(4-di-p-tolyl) aminophenyl)-4-phenylcyclohexane, bis(4-dimethylamino-2-methylphenyl)phenylmethane, bis(4-di-p-tolylaminophenyl)phenylmethane, N,N'-diphenyl-N,N'-di(4-methoxyphenyl)-4,4'-diaminobiphenyl,N,N,N',N'-tetraphenyl-4,4'-diaminodiphenyl ether, 4,4'-bis(diphenylamino)quadri Phenyl, N,N,N-tri(p-tolyl)amine, 4-(di-p-tolylamino)-4'-[4-(di-p-tolylamino)styryl]stilbene, 4-N,N-diphenyl Amino-(2-diphenylvinyl)benzene, 3-methoxy-4'-N,N-diphenylaminostilbenzene, N-phenylcarbazole, 4,4'-bis[N-(1-naphthyl)-N-phenylamino ] biphenyl (NPD), 4,4',4''-tris[N-(3-methylphenyl)-N-phenylamino]triphenylamine (MTDATA), and the like.
Further, inorganic compounds such as p-type Si and p-type SiC can also be cited as examples of materials for the hole injection layer and hole transport layer.

The hole injection layer and the hole transport layer may have a single layer structure made of one or more materials, or may have a laminated structure made of multiple layers having the same composition or different compositions.

[Charge generation layer 4]
A charge generation layer 4 may be provided between the hole injection layer 3 and the hole transport layer 5.
There are no particular limitations on the material for the charge generation layer, but examples include dipyrazino[2,3-f:2',3'-h]quinoxaline-2,3,6,7,10,11-hexacarbonitrile (HAT -CN).
The charge generation layer may have a single layer structure made of one or more kinds of materials, or may have a laminated structure made of multiple layers having the same composition or different compositions.

[Light-emitting layer 6]
A light emitting layer 6 is provided between the hole transport layer 5 and an electron transport layer 7, which will be described later.
Examples of materials for the light-emitting layer include phosphorescent materials, fluorescent materials, and thermally activated delayed fluorescent materials. In the light-emitting layer, electron-hole pairs recombine, resulting in light emission.
The emissive layer may consist of a single small molecule material or a single polymeric material, but more commonly it consists of a host material doped with a guest compound. Luminescence arises primarily from the dopant and can have any color.

Examples of the host material include compounds having a biphenyl group, a fluorenyl group, a triphenylsilyl group, a carbazole group, a pyrenyl group, and an anthryl group. More specifically, DPVBi (4,4'-bis(2,2-diphenylvinyl)-1,1'-biphenyl), BCzVBi (4,4'-bis(9-ethyl-3-carbazovinylene) 1, 1'-biphenyl), TBADN (2-tert-butyl-9,10-di(2-naphthyl)anthracene), ADN (9,10-di(2-naphthyl)anthracene), CBP (4,4'-bis (carbazol-9-yl)biphenyl), CDBP (4,4'-bis(carbazol-9-yl)-2,2'-dimethylbiphenyl), 2-(9-phenylcarbazol-3-yl)-9- [4-(4-phenylphenylquinazolin-2-yl)carbazole, 9,10-bis(biphenyl)anthracene, etc.].

Examples of fluorescent dopants include anthracene, pyrene, tetracene, xanthene, perylene, rubrene, coumarin, rhodamine, quinacridone, dicyanomethylenepyran compound, thiopyran compound, polymethine compound, pyrylium, thiapyrylium compound, fluorene derivative, periflanthene derivative, and indenoperylene. Examples include derivatives, bis(azinyl)amine boron compounds, bis(azinyl)methane compounds, carbostyryl compounds, and the like. The fluorescent dopant may be a combination of two or more selected from these.

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

Specific examples of fluorescent dopants and phosphorescent dopants include Alq3 (tris(8-hydroxyquinoline)aluminum), DPAVBi (4,4'-bis[4-(di-p-tolylamino)styryl]biphenyl), perylene, bis[ 2-(4-n-hexylphenyl)quinoline](acetylacetonato)iridium(III), Ir(PPy)3(tris(2-phenylpyridine)iridium(III)), and FIrPic(bis(3,5- difluoro-2-(2-pyridyl)phenyl-(2-carboxypyridyl)iridium(III)) and the like.

Furthermore, the luminescent material is not limited to being contained only in the luminescent layer. For example, the luminescent material may be contained in a layer adjacent to the luminescent layer (hole transport layer 5 or electron transport layer 7). This further increases the current efficiency of the organic electroluminescent device.

The light-emitting layer may have a single layer structure made of one or more kinds of materials, or may have a laminated structure made of multiple layers having the same composition or different compositions.

[Electron transport layer 7]
An electron transport layer 7 is provided between the light emitting layer 6 and a cathode 8, which will be described later.
The electron transport layer has a function of transmitting electrons injected from the cathode to the light emitting layer. By interposing the electron transport layer between the cathode and the emissive layer, electrons are injected into the emissive layer at a lower electric field.
As described above, the electron transport layer preferably contains a cyclic azine compound represented by the above formula (1).

Further, the electron transport layer may further contain a conventionally known electron transport material in addition to the cyclic azine compound (1). Conventionally known electron transport materials include, for example, lithium 8-hydroxyquinolinate (Liq), zinc bis(8-hydroxyquinolinate), copper bis(8-hydroxyquinolinate), and copper bis(8-hydroxyquinolinate). tris(8-hydroxyquinolinate)aluminum, tris(2-methyl-8-hydroxyquinolinate)aluminum, tris(8-hydroxyquinolinate)gallium, bis(10-hydroxybenzo[h] quinolinate) beryllium, bis(10-hydroxybenzo[h]quinolinate) zinc, bis(2-methyl-8-quinolinate) chlorogallium, bis(2-methyl-8-quinolinate)(o-cresolate) gallium, bis(2-methyl-8-quinolinate)(o-cresolate) gallium, -Methyl-8-quinolinate)-1-naphtholate aluminum, or bis(2-methyl-8-quinolinate)-2-naphtholate gallium, 2-[3-(9-phenanthrenyl)-5-(3-pyridinyl) phenyl]-4,6-diphenyl-1,3,5-triazine, and 2-(4,''-di-2-pyridinyl[1,1':3',1''-terphenyl]-5- yl)-4,6-diphenyl-1,3,5-triazine, BCP (2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline), Bphen(4,7-diphenyl-1,10- phenanthroline), BAlq (bis(2-methyl-8-quinolinolate)-4-(phenylphenolate)aluminum), and bis(10-hydroxybenzo[h]quinolinate)beryllium).

The electron transport layer may have a single layer structure made of one or more kinds of materials, or may have a laminated structure made of multiple layers having the same composition or different compositions.

When the electron transport layer has a two-layer structure with the first electron transport layer on the light emitting layer side and the second electron transport layer on the cathode side, it is preferable that the second electron transport layer contains the cyclic azine compound (1).

[Cathode 8]
A cathode 8 is provided on the electron transport layer 7.
In the case of an organic electroluminescent device configured such that only light emitted from the anode is extracted, the cathode can be formed from any conductive material.
Materials for the cathode include sodium, sodium-potassium alloy, magnesium, lithium, magnesium/copper mixture, magnesium/silver mixture, magnesium/aluminum mixture, magnesium/indium mixture, aluminum/aluminum oxide (Al ₂ O ₃ ) mixture, and indium. , lithium/aluminum mixtures, rare earth metals, and the like.
A buffer layer (electrode interface layer) may be provided on the cathode (electron transport layer side).

[Formation method of each layer]
Each layer except for the electrodes (anode, cathode) described above is prepared by applying the material for each layer (along with materials such as binder resin and solvent as necessary) using, for example, vacuum evaporation, spin coating, casting, LB ( It can be formed by forming a thin film using a known method such as the Langmuir-Blodgett method. The thickness of each layer is not particularly limited, but is usually about 5 nm to 5 μm.
The thickness of each layer formed in this way is not particularly limited and can be appropriately selected depending on the situation, but is usually in the range of 5 nm to 5 μm.

The anode and the cathode can be formed by forming an electrode material into a thin film by a method such as vapor deposition or sputtering. A pattern may be formed through a mask having a desired shape during vapor deposition or sputtering, or a thin film may be formed by vapor deposition or sputtering, and then a pattern having a desired shape may be formed by photolithography.
The film thickness of the anode and cathode is preferably 1 μm or less, more preferably 10 nm or more and 200 nm or less.

The organic electroluminescent element according to one embodiment of the present invention may be used as a type of lamp for illumination or as an exposure light source, or as a type of projection device that projects an image, or for direct viewing of still images or moving images. It may also be used as a type of display device. When used as a display device for video playback, the driving method may be either a simple matrix (passive matrix) method or an active matrix method. Further, by using two or more types of organic electroluminescent elements of this embodiment having different emission colors, it is possible to produce a full-color display device.

Note that the cyclic azine compound (1) according to one embodiment of the present invention can be synthesized by appropriately combining known reactions (eg, Suzuki-Miyaura cross-coupling reaction, etc.).

EXAMPLES Hereinafter, the present invention will be explained in more detail based on Examples, but the present invention should not be interpreted as being limited by these Examples.

¹ H-NMR measurement was performed using Gemini200 (manufactured by Varian).
The luminescence properties of the organic electroluminescent device were evaluated using a luminance meter (product name: BM-9, manufactured by Topcon Technohouse) by applying a direct current to the fabricated device at room temperature.

The glass transition temperature was measured by DSC (Differential Scanning Calorimetry) using DSC7020 (manufactured by Hitachi High-Tech Science).
The measurement conditions of the DSC are as follows. Note that the measurement was performed under a nitrogen atmosphere (flow rate 50 ml/min). Further, first heating, first cooling, and second heating were performed in this order, and the glass transition temperature at the time of second heating was taken as the glass transition temperature of the sample.
Sample amount: 5-10mg
Measurement condition:
<First heating>
Temperature increase rate: 10℃/min
Measurement temperature range: 30℃~400℃
<First cooling>
Rapid cooling with dry ice <second heating>
Temperature increase rate: 5℃/min
Measurement temperature range: 30℃~400℃

Synthesis example-1

Under argon stream, 2-bromo-9,10-dihydro-9,10-[1,2]benzenoanthracene (20.0 g, 60.0 mmol), bis(pinacolato)diboron (21.0 g, 82.5 mmol) , potassium acetate (22.1 g, 225.2 mmol), palladium acetate (170 mg, 0.76 mmol), and 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl (715 mg, 1.50 mmol; -Phos) was suspended in tetrahydrofuran (400 mL) and stirred at 75°C for 22 hours. After cooling to room temperature, the reaction solution was concentrated under reduced pressure. Methanol (200 mL) was added to the resulting slurry, stirred at room temperature, and the solid was filtered off. By washing the obtained solid with methanol, the desired 2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9,10-dihydro-9,10 A white solid of -[1,2]benzenoanthracene (yield: 19.1 g, yield: 84%) was obtained.
¹ H-NMR (CDCl ₃ ) δ (ppm): 1.22 (s, 12H), 5.36 (s, 2H), 6.88-6.92 (m, 4H), 7.25-7. 34 (m, 4H), 7.39-7.42 (m, 1H), 7.76 (s, 2H).

Synthesis Example-1

Under an argon stream, 2-[(1,1'-biphenyl)-4-yl]-4-chloro-6-phenyl-1,3,5-triazine (2.00 g, 5.82 mmol), 2-(4 ,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9,10-dihydro-9,10-[1,2]benzenoanthracene (2.43g, 6.40mmol) , and tetrakis(triphenylphosphine)palladium (0.2 g, 0.175 mmol) were dissolved in tetrahydrofuran (100 mL). A 2M aqueous potassium carbonate solution (8.8 mL, 17.6 mmol) was added to this, and the mixture was stirred at 75°C for 19 hours. After cooling to room temperature, the reaction solution was concentrated under reduced pressure. Water (50 mL) and methanol (20 mL) were added to the obtained concentrate, stirred at room temperature, and the precipitated solid was filtered off. The obtained solid was washed with water (30 mL), methanol (30 mL), and hexane (30 mL). This solid was dissolved in toluene (80 mL), silica gel was added, and the mixture was filtered through Celite, and the filtrate was concentrated under reduced pressure. The solid obtained by drying this concentrated solution is purified once by recrystallization (toluene) to obtain the desired 2-[(1,1'-biphenyl)-4-yl]-4-(9, 10-dihydro-9,10-[1,2]benzenoanthracen-2-yl)-6-phenyl-1,3,5-triazine (compound A-2) as a white solid (yield 2.19 g, yield 67%).

¹ H-NMR (CDCl ₃ ) δ (ppm): 5.54 (d, J = 46 Hz, 2H), 6.94-6.99 (m, 4H), 7.33-7.46 (m, 7H ), 7.49-7.57 (m, 4H), 7.64 (d, J = 7.0Hz, 2H), 7.74 (d, J = 8.4Hz, 2H), 8.43 (d , J=7.8Hz, 1H), 8.69-8.72 (m, 3H), 8.76 (d, J=8.6Hz, 2H).
The glass transition temperature of Compound A-2 was 144°C.

Synthesis Example-2

2-[(1,1'-biphenyl)-4-yl]-4-chloro-6-phenyl-1,3,5-triazine, 2,4-bis[(1,1'-biphenyl)-4 The desired 2,4-bis[(1,1'-biphenyl) -4-yl]-6-(9,10-dihydro-9,10-[1,2]benzenoanthracen-2-yl)-1,3,5-triazine (compound A-81) as a white solid ( 5.60 g (yield: 74%) was obtained.
¹ H-NMR (CDCl ₃ ) δ (ppm): 5.55 (d, J = 48 Hz, 2H), 6.94-6.99 (m, 4H), 7.33-7.46 (m, 10H) ), 7.53 (d, J=7.7Hz, 1H), 7.65 (d, J=7.5Hz, 4H), 7.75 (d, J=8.6Hz, 4H), 8.44 (d, J=7.6Hz, 1H), 8.73 (s, 1H), 8.77 (d, J=8.6Hz, 4H).
The glass transition temperature of Compound A-81 was 159°C.

Synthesis Example-3

2-[(1,1'-biphenyl)-4-yl]-4-chloro-6-phenyl-1,3,5-triazine, 2,4-bis[(1,1'-biphenyl)-4 -yl]-6-(4-chlorophenyl)-1,3,5-triazine, except that tetrakis(triphenylphosphine)palladium was changed to a mixture of palladium acetate/X-Phos (molar ratio 1:2). The same experimental operations as in Synthesis Example 1 were performed to obtain the desired 2,4-bis[(1,1'-biphenyl)-4-yl]-6-[4-(9,10-dihydro-9, A white solid (2.64 g, 67% yield) of 10-[1,2]benzenoanthracen-2-yl)phenyl]-1,3,5-triazine (compound A-425) was obtained.
¹ H-NMR (CDCl ₃ ) δ (ppm): 5.46 (d, J = 17 Hz, 2H), 6.94-6.98 (m, 4H), 7.27 (d, J = 7.5 Hz) , 1H), 7.33-7.46 (m, 11H), 7.64-7.67 (m, 7H), 7.75 (d, J=8.5Hz, 4H), 8.75 (d , J=8.6Hz, 2H), 8.80(d, J=8.4Hz, 4H).
The glass transition temperature of Compound A-425 was 170°C.

Synthesis example-2

2-[(1,1'-biphenyl)-4-yl]-4-chloro-6-phenyl-1,3,5-triazine was changed to 2-bromo-5-chloropyridine, and 2-(4 , 4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9,10-dihydro-9,10-[1,2]benzenoanthracene, 4,6-diphenyl-2 -[4-{(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl}]-Synthesis Example-1 except that it was changed to -1,3,5-triazine The same experimental procedure as above was carried out to obtain the desired white solid of 2-{4-[(5-chloropyridin)-2-yl]phenyl}-4,6-diphenyl-1,3,5-triazine (yield: 5 .66 g, yield 56%) was obtained.
¹ H-NMR (CDCl ₃ ) δ (ppm): 7.57-7.65 (m, 6H), 7.78-7.83 (m, 2H), 8.19 (d, J = 8.9Hz , 2H), 8.71 (s, 1H), 8.80 (d, J = 7.8Hz, 4H), 8.88 (d, J = 8.7Hz, 2H).

Synthesis Example-4

2-[(1,1'-biphenyl)-4-yl]-4-chloro-6-phenyl-1,3,5-triazine was synthesized in Synthesis Example 1 using chloropyridin)-2-yl]phenyl}-4,6-diphenyl-1,3,5-triazine, and tetrakis(triphenylphosphine)palladium was replaced with a mixture of palladium acetate/X-Phos (molar ratio 1: The desired 2-(4-{5-[(9,10-dihydro-9,10-[1,2]benzeno Anthracen-2-yl)]pyridin-2-yl}phenyl)-4,6-diphenyl-1,3,5-triazine (compound A-779) as a white solid (yield 6.64 g, yield 78%). Obtained.
¹ H-NMR (CDCl ₃ ) δ (ppm): 5.44 (s, 1H), 5.48 (s, 1H), 6.94-6.99 (m, 4H), 7.22 (d, J = 7.5Hz, 1H), 7.34-7.40 (m, 4H), 7.45 (d, J = 7.6Hz, 1H), 7.51-7.58 (m, 6H), 7.62 (s, 1H), 7.81-7.87 (m, 2H), 8.18 (d, J = 8.5Hz, 2H), 8.74 (d, J = 7.0Hz, 4H ), 8.81-8.85 (m, 3H).
The glass transition temperature of Compound A-779 was 157°C.

Synthesis example-3

2-[(1,1'-biphenyl)-4-yl]-4-chloro-6-phenyl-1,3,5-triazine was changed to 2-bromo-6-chloropyridine, and 2-(4 , 4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9,10-dihydro-9,10-[1,2]benzenoanthracene, 4,6-diphenyl-2 -[4-{(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl}]-Synthesis Example-1 except that it was changed to -1,3,5-triazine The same experimental procedure as above was carried out to obtain the target 2-{4-[(6-chloropyridin)-2-yl]phenyl}-4,6-diphenyl-1,3,5-triazine as a white solid (yield: 4 .06 g, yield 81%) was obtained.
¹ H-NMR (CDCl ₃ ) δ (ppm): 7.34 (dd, J=6.1Hz, 2.2Hz, 1H), 7.57-7.63 (m, 6H), 7.78 (dd , 2H), 8.22 (d, J = 8.5Hz, 2H), 8.80 (m, 4H), 8.88 (d, J = 8.7Hz, 2H).

Synthesis Example-5

2-{4-[(6- The desired 2-(4- {6-[(9,10-dihydro-9,10-[1,2]benzenoanthracen-2-yl)]pyridin-2-yl}phenyl)-4,6-diphenyl-1,3,5- A white solid (4.60 g, yield 99%) of triazine (compound A-1231) was obtained.
¹ H-NMR (CDCl ₃ ) δ (ppm): 5.51 (s, 1H), 5.59 (s, 1H), 6.99-7.04 (m, 4H), 7.40-7. 46 (m, 4H), 7.52 (d, J=7.6Hz, 1H), 7.58-7.68 (m, 7H), 7.74-7.84 (m, 3H), 8. 27 (s, 1H), 8.35 (d, J = 8.4Hz, 2H), 8.83 (m, 4H), 8.92 (d, J = 8.6Hz, 2H).
The glass transition temperature of compound A-1231 was 156°C.

Synthesis example-4

2-[(1,1'-biphenyl)-4-yl]-4-chloro-6-phenyl-1,3,5-triazine was changed to 2-bromo-6-chloropyridine, and 2-(4 ,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9,10-dihydro-9,10-[1,2]benzenoanthracene, 2-[(1,1 '-biphenyl)-4-yl]-6-phenyl-4-[4-{(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl}]-1, The same experimental procedure as in Synthesis Example 1 was carried out except that 3,5-triazine was used to obtain the desired 2-{4-[(6-chloropyridin)-2-yl]phenyl}-4-[( A white solid of 1,1'-biphenyl)-4-yl]-6-phenyl-1,3,5-triazine (yield: 4.06 g, yield: 81%) was obtained.
¹ H-NMR (CDCl ₃ ) δ (ppm): 7.34 (dd, J = 6.4 Hz, 2.1 Hz 1H), 7.42 (t, J = 7.3 Hz, 1H), 7.51 (t , J=7.9Hz, 2H), 7.58-7.64 (m, 3H), 7.72-7.74 (m, 2H), 7.78-7.84 (m, 4H), 8 .23 (d, J=8.7Hz, 2H), 8.83 (d, J=7.8Hz, 2H), 8.90 (m, 4H).

Synthesis Example-6

2-{4-[(6- Same as Synthesis Example 1 except that chloropyridin)-2-yl]phenyl}-4-[(1,1'-biphenyl)-4-yl]-6-phenyl-1,3,5-triazine was used. Similar experimental procedures were performed to obtain the desired 4-[(1,1'-biphenyl)-4-yl]-2-(4-{6-[(9,10-dihydro-9,10-[1, 2] Benzenoanthracen-2-yl)]pyridin-2-yl}phenyl)-6-phenyl-1,3,5-triazine (compound A-1234) as a white solid (yield: 8.66 g, yield: 87%) ) was obtained.
¹ H-NMR (CDCl ₃ ) δ (ppm): 5.51 (s, 1H), 5.59 (s, 1H), 6.99-7.04 (m, 4H), 7.46-7. 41 (m, 5H), 7.50-7.54 (m, 3H), 7.59-7.68 (m, 4H), 7.72-7.84 (m, 7H), 8.27 ( s, 1H), 8.36 (d, J = 8.5Hz, 2H), 8.83 (m, 2H), 8.88 (d, J = 8.6Hz, 2H), 8.93 (d, J=8.6Hz, 2H).
The glass transition temperature of compound A-1234 was 164°C.

Synthesis example-5

Synthesis example except that 2-[(1,1'-biphenyl)-4-yl]-4-chloro-6-phenyl-1,3,5-triazine was changed to 2-bromo-5-chloropyridine. The same experimental procedure as in -1 was performed to obtain the desired 5-chloro-2-(9,10-dihydro-9,10-[1,2]benzenoanthracen-2-yl)pyridine as a white solid (yield: 3 .83 g, yield 57%) was obtained.
¹ H-NMR (CDCl ₃ ) δ (ppm): 5.50 (d, J = 16 Hz, 2H), 6.98-7.02 (m, 4H), 7.37-7.42 (m, 4H ), 7.45-7.68 (m, 4H), 8.04 (s, 1H), 8.58 (d, J=2.5Hz, 1H).

Synthesis Example-7

2-[(1,1'-biphenyl)-4-yl]-4-chloro-6-phenyl-1,3,5-triazine was converted into 5-chloro-2-(9, 10-dihydro-9,10-[1,2]benzenoanthracen-2-yl)pyridine and 2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolane-2- yl)-9,10-dihydro-9,10-[1,2]benzenoanthracene was converted into 4,6-diphenyl-2-[4'-(4,4,5,5-tetramethyl-1,3 ,2-dioxaborolan-2-yl)biphenyl-4-yl]-1,3,5-triazine, and tetrakis(triphenylphosphine)palladium was replaced with a mixture of palladium acetate/X-Phos (molar ratio 1:2). ) except that the desired 2-(4'-{6-(9,10-dihydro-9,10-[1,2]benzenoanthracene) -2-yl)pyridin-3-yl]biphenyl})-4,6-diphenyl-1,3,5-triazine (compound A-836) as a white solid (yield: 1.51 g, yield: 43%) Ta.
¹ H-NMR (CDCl ₃ ) δ (ppm): 5.43 (s, 1H), 5.49 (s, 1H), 6.93-6.97 (m, 4H), 7.33-7. 37 (m, 4H), 7.44 (d, J = 7.6Hz, 1H), 7.51-7.60 (m, 7H), 7.69 (d, J = 8.3Hz, 3H), 7.78 (t, J = 8.5Hz, 4H), 7.91 (d, J = 8.3Hz, 2.5Hz, 1H), 8.09 (s, 1H), 8.74 (d, J =7.8Hz, 4H), 8.81 (d, J = 8.6Hz, 2H), 8.89 (s, 1H).
The glass transition temperature of Compound A-779 was 168°C.

2-([1,1′-biphenyl]-4-yl)-4-(9,9-diphenyl-9H-fluoren-4-yl)-6-phenyl described in Japanese Patent Publication No. 2017-517486 When compared with -1,3,5-triazine (ETL-2), it can be seen that the cyclic azine compound to which a group having a triptycene structure according to one embodiment of the present invention is bonded has a high glass transition temperature.

Next, element evaluation will be described.
The structural formulas and abbreviations of the compounds used for device evaluation are shown below.

Element example-1 (see Figure 2)
(Preparation of substrate 1 and anode 2)
A glass substrate with an ITO transparent electrode on which a 2 mm wide indium-tin oxide (ITO) film (film thickness: 110 nm) was patterned in stripes was prepared as a substrate having an anode on its surface. Next, this substrate was cleaned with isopropyl alcohol, and then surface-treated by ozone ultraviolet cleaning.

(Preparation for vacuum deposition)
Each layer was vacuum-deposited using a vacuum evaporation method on the surface-treated substrate after cleaning, and each layer was laminated.
First, the glass substrate was introduced into a vacuum deposition tank, and the pressure was reduced to 1.0×10 ⁻⁴ Pa. Then, each layer was manufactured according to the film forming conditions in the following order.

(Preparation of hole injection layer 3)
A 55 nm film of HIL purified by sublimation was formed at a rate of 0.15 nm/sec to produce a hole injection layer.

(Preparation of charge generation layer 4)
HAT purified by sublimation was deposited to a thickness of 5 nm at a rate of 0.05 nm/sec to produce a charge generation layer.

(Preparation of first hole transport layer 51)
HTL-1 was deposited to a thickness of 10 nm at a rate of 0.15 nm/sec to produce a first hole transport layer.

(Preparation of second hole transport layer 52)
HTL-2 was deposited to a thickness of 10 nm at a rate of 0.15 nm/sec to produce a second hole transport layer.

(Preparation of light emitting layer 6)
EML-1 and EML-2 were formed into a 25 nm film at a ratio of 95:5 (mass ratio) to produce a light emitting layer. The film deposition rate was 0.18 nm/sec.

(Preparation of first electron transport layer 71)
ETL-1 was deposited to a thickness of 5 nm at a rate of 0.15 nm/sec to produce the first electron transport layer 7.

(Preparation of second electron transport layer 72)
2-([1,1'-biphenyl]-4-yl)-4-(9,10-dihydro-9,10-[1,2]benzenoanthracen-2-yl synthesized in Synthesis Example-1) )-6-phenyl-1,3,5-triazine (compound A-2) and Liq were deposited to a thickness of 25 nm at a ratio of 50:50 (mass ratio) to produce a second electron transport layer 71. The film deposition rate was 0.15 nm/sec.

(Preparation of cathode 8)
Finally, a metal mask was placed so as to be perpendicular to the ITO stripes on the substrate, and the cathode 8 was formed. The cathode had a two-layer structure by forming films of silver/magnesium (mass ratio 1/10) and silver to have a thickness of 80 nm and 20 nm, respectively, in this order. The deposition rate of silver/magnesium was 0.5 nm/sec, and the deposition rate of silver was 0.2 nm/sec.

As described above, an organic electroluminescent device 100 having a light emitting area of 4 mm ² as shown in FIG. 2 was manufactured. The thickness of each film was measured using a stylus-type film thickness meter (DEKTAK, manufactured by Bruker).

Furthermore, this device was sealed in a nitrogen atmosphere glove box with an oxygen and moisture concentration of 1 ppm or less. Sealing was performed using a glass sealing cap and a film-forming substrate (device) using bisphenol F type epoxy resin (manufactured by Nagase ChemteX).

A direct current was applied to the organic electroluminescent device produced as described above, and its luminescence characteristics were evaluated using a luminance meter (product name: BM-9, manufactured by Topcon Technohouse). As for the luminescence characteristics, the current efficiency (cd/A) when a current density of 10 mA/cm ² was applied was measured, and the element life (h) during continuous lighting was measured. The device life (h) in Table 1 is determined by measuring the brightness decay time during continuous lighting when the fabricated device is driven at an initial brightness of 1000 cd/m ² until the brightness (cd/m ² ) decreases by 20%. The time required was measured. Note that the current efficiency and the element life are relative values with the results in Element Reference Example 1, which will be described later, as a reference value (100). The measurement results obtained are shown in Table 2.

Element example-2
In Device Example-1, 2,4-bis([1,1'-biphenyl]-4-yl)-6-(9,10- An organic electric field was applied in the same manner as in Device Example-1, except that dihydro-9,10-[1,2]benzenoanthracen-2-yl)-1,3,5-triazine (compound A-81) was used. A light emitting device was produced and evaluated. The measurement results obtained are shown in Table 2.

Element reference example-1
In Device Example-1, 2-([1,1'-biphenyl]-4-yl)-4-(9,9- An organic electroluminescent device was prepared in the same manner as in Device Example-1, except that diphenyl-9H-fluoren-4-yl)-6-phenyl-1,3,5-triazine (ETL-2) was used. evaluated. The measurement results obtained are shown in Table 2.

Element example-3 (see Figure 3)
(Preparation of substrate 101 and anode 102)
A glass substrate with an ITO transparent electrode on which a 2 mm wide indium-tin oxide (ITO) film (film thickness: 110 nm) was patterned in stripes was prepared as a substrate having an anode on its surface. Next, this substrate was cleaned with isopropyl alcohol, and then surface-treated by ozone ultraviolet cleaning.

(Preparation for vacuum deposition)
Each layer was vacuum-deposited using a vacuum evaporation method on the surface-treated substrate after cleaning, and each layer was laminated.
First, the glass substrate was introduced into a vacuum deposition tank, and the pressure was reduced to 1.0×10 ⁻⁴ Pa. Then, each layer was manufactured according to the film forming conditions in the following order.

(Preparation of hole injection layer 103)
Sublimation-purified N-[1,1'-biphenyl]-4-yl-9,9-dimethyl-N-[4-(9-phenyl-9H-carbazol-3-yl)phenyl]-9H-fluorene-2 - A 10 nm film of amine and 1,2,3-tris[(4-cyano-2,3,5,6-tetrafluorophenyl)methylene]cyclopropane was formed at a rate of 0.15 nm/sec to form a hole injection layer. 103 was produced.

(Preparation of first hole transport layer 1051)
Sublimation-purified N-[1,1'-biphenyl]-4-yl-9,9-dimethyl-N-[4-(9-phenyl-9H-carbazol-3-yl)phenyl]-9H-fluorene-2 -Amine was deposited to a thickness of 85 nm at a rate of 0.15 nm/sec to produce a first hole transport layer 1051.

(Preparation of second hole transport layer 1052)
A 5 nm film of N-phenyl-N-(9,9-diphenylfluoren-2-yl)-N-(1,1'-biphenyl-4-yl)amine purified by sublimation was formed at a speed of 0.15 nm/sec. , a second hole transport layer 1052 was produced.

(Preparation of light emitting layer 106)
3-(10-phenyl-9-anthryl)-dibenzofuran and 2,7-bis[N,N-di-(4-tertbutylphenyl)]amino-bisbenzofurano-9,9'-spirofluorene purified by sublimation A 20 nm thick film was formed at a ratio of 95:5 (mass ratio) to produce a light-emitting layer 106. The film deposition rate was 0.18 nm/sec.

(Preparation of first electron transport layer 1071)
2-[3'-(9,9-dimethyl-9H-fluoren-2-yl)[1,1'-biphenyl]-3-yl]-4,6-diphenyl-1,3,5- purified by sublimation Triazine was deposited to a thickness of 6 nm at a rate of 0.05 nm/sec to produce a first electron transport layer 1071.

(Preparation of second electron transport layer 1072)
2,4-bis[(1,1'-biphenyl)-4-yl]-6-[4-(9,10-dihydro-9,10-[1,2]benze synthesized in Synthesis Example-3) A 25 nm film of noanthracen-2-yl)phenyl]-1,3,5-triazine (compound A-425) and Liq was formed at a ratio of 50:50 (mass ratio) to produce a second electron transport layer 1072. . The film deposition rate was 0.15 nm/sec.

(Preparation of cathode 108)
Finally, a metal mask was placed so as to be perpendicular to the ITO stripes on the substrate, and a cathode 108 was formed. The cathode had a two-layer structure by forming films of silver/magnesium (mass ratio 1/10) and silver to have a thickness of 80 nm and 20 nm, respectively, in this order. The deposition rate of silver/magnesium was 0.5 nm/sec, and the deposition rate of silver was 0.2 nm/sec.

As described above, an organic electroluminescent device 100 having a light emitting area of 4 mm ² as shown in FIG. 3 was manufactured. The thickness of each film was measured using a stylus-type film thickness meter (DEKTAK, manufactured by Bruker).

Furthermore, this device was sealed in a nitrogen atmosphere glove box with an oxygen and moisture concentration of 1 ppm or less. Sealing was performed using a glass sealing cap and a film-forming substrate (device) using bisphenol F type epoxy resin (manufactured by Nagase ChemteX).

A direct current was applied to the organic electroluminescent device produced as described above, and its luminescence characteristics were evaluated using a luminance meter (product name: BM-9, manufactured by Topcon Technohouse). As for the luminescence characteristics, the current efficiency (cd/A) when a current density of 10 mA/cm ² was applied was measured, and the element life (h) during continuous lighting was measured. The device life (h) in Table 3 is determined by measuring the brightness decay time during continuous lighting when the fabricated device is driven at an initial brightness of 1000 cd/m ² until the brightness (cd/m ² ) decreases by 5%. The time required was measured. Note that the drive voltage, current efficiency, and element life are relative values with the results in Element Reference Example 2 described later as a reference value (100). The measurement results obtained are shown in Table 3.

Element example-4
In Device Example 3, 2-(4-{5-[(9,10-dihydro-9,10-[1,2]benzeno) synthesized in Synthesis Example 4 was used instead of compound A-425. Anthracen-2-yl)]pyridin-2-yl}phenyl)-4,6-diphenyl-1,3,5-triazine (Compound A-779) was used in the same manner as in Device Example-3. An organic electroluminescent device was produced and evaluated. The measurement results obtained are shown in Table 2.

Element example-5
In Device Example 3, 2-(4-{6-[(9,10-dihydro-9,10-[1,2]benzeno) synthesized in Synthesis Example 5 was used instead of compound A-425. Anthracen-2-yl)]pyridin-2-yl}phenyl)-4,6-diphenyl-1,3,5-triazine (compound A-1231) was used in the same manner as in Device Example-3. An organic electroluminescent device was produced and evaluated. The measurement results obtained are shown in Table 3.

Element example-6
In Device Example-3, 4-[(1,1'-biphenyl)-4-yl]-2-(4-{6-[( 9,10-dihydro-9,10-[1,2]benzenoanthracen-2-yl)]pyridin-2-yl}phenyl)-6-phenyl-1,3,5-triazine (compound A-1234) An organic electroluminescent device was produced and evaluated in the same manner as in Device Example-3, except that . The measurement results obtained are shown in Table 3.

Element example-7
In Device Example 3, 42-(4'-{6-(9,10-dihydro-9,10-[1,2]benzeno) synthesized in Synthesis Example 7 was used instead of compound A-425. Anthracen-2-yl)pyridin-3-yl]biphenyl})-4,6-diphenyl-1,3,5-triazine (compound A-836) was used in the same manner as in Device Example-3. An organic electroluminescent device was produced and evaluated. The measurement results obtained are shown in Table 3.

Element reference example-2
In Device Example-3, 2-[5-(9-phenanthryl)-4'-(2-pyrimidyl)biphenyl-3-yl described in JP-A-2011-063584 was used instead of compound A-425. ]-4,6-diphenyl-1,3,5-triazine (ETL-3) was used, but an organic electroluminescent device was produced and evaluated in the same manner as in Device Example-3. The measurement results obtained are shown in Table 3.

The cyclic azine compound (1) according to one embodiment of the present invention has extremely excellent heat resistance in film quality, and by using the compound, an organic electroluminescent device having excellent long life and current efficiency can be provided.
Further, the cyclic azine compound (1) according to one embodiment of the present invention is used as an electron transport material for organic electroluminescent devices that has excellent low driving voltage. Furthermore, according to the cyclic azine compound (1), an organic electroluminescent device with low power consumption can be provided.
In addition, the cyclic azine compound according to one embodiment of the present invention has good thermal stability during sublimation purification, and thus provides excellent operability in sublimation purification, and provides a material with few impurities that cause element deterioration of organic electroluminescent devices. can do. Further, since the cyclic azine compound according to one embodiment of the present invention has excellent stability of a deposited film, it is possible to provide a long-life organic electroluminescent device.
In addition, the thin film made of the cyclic azine compound (1) according to one embodiment of the present invention has excellent electron transport ability, hole blocking ability, redox resistance, water resistance, oxygen resistance, electron injection property, etc. It is useful as a material for devices, and is useful as an electron transport material, a hole blocking material, a light emitting host material, etc. It is particularly useful when used as an electron transport material.
Furthermore, since the cyclic azine compound (1) according to one embodiment of the present invention has a wide bandgap and a high triplet excitation level, it can be used not only for conventional fluorescent devices but also for phosphorescent devices and thermally activated delayed fluorescence ( It can be suitably used for an organic electroluminescent device using TADF).

1,101 Substrate 2,102 Anode 3,103 Hole injection layer
4 Charge generation layer 5,105 Hole transport layer 6,106 Light emitting layer 7,107 Electron transport layer 8,108 Cathode 51,1051 First hole transport layer 52,1052 Second hole transport layer 71,1071 First electron Transport layer 72,1072 Second electron transport layer 100 Organic electroluminescent device

Claims (12)

Cyclic azine compound represented by formula (1):
In formula (1),
Ar ¹ each independently represents a phenylene group, a naphthylene group, a pyridylene group, or a single bond;
Ar ² is each independently,
Single ring, condensed ring, or a structure in which these are connected,
Aromatic hydrocarbon group having 6 to 24 carbon atoms, or
Represents a nitrogen-containing heteroaromatic group with 4 to 25 carbon atoms consisting of only 6-membered rings;
However, two ^Ar2s do not bond to each other;
Y in the divalent groups L ¹ and L ² each independently represents CH or N;
Ar ³ represents a hydrogen atom;
Ar ⁴ and Ar ⁵ are each independently,
Represents a hydrogen atom;
m represents 0 or 1;
If m is 0, n is 0;
If m is 1, n is 0, 1, or 2;
When n is 2, the plurality of L ² may be the same or different from each other;
Each group represented by Ar ¹ , L ¹ , and L ² may be independently substituted with a fluorine atom, a methyl group, or a phenyl group;
Each group represented by Ar ² is independently a phenyl group, a tolyl group, a pyridyl group, a methylpyridyl group, a dimethylpyridyl group, a fluorine atom, an alkyl group having 1 to 4 carbon atoms, or an alkyl group having 1 to 4 carbon atoms. It may be substituted with an alkoxy group. Ar ² is each independently,
It is a monocyclic ring or a structure in which these are linked,
Aromatic hydrocarbon group having 6 to 24 carbon atoms, or
Represents a nitrogen-containing heteroaromatic group consisting of only a 6-membered ring and having 4 to 25 carbon atoms.
The cyclic azine compound according to claim 1, wherein two Ar ² ions do not bond to each other. The cyclic azine compound according to claim 1 or 2, wherein Ar ¹ is each independently a phenylene group or a single bond. Ar ² is each independently substituted with a phenyl group, tolyl group, pyridyl group, methylpyridyl group, dimethylpyridyl group, fluorine atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms; phenyl group, naphthyl group, fluorenyl group, anthryl group, phenanthryl group, benzofluorenyl group, pyrenyl group, perylenyl group, fluoranthenyl group, triphenylenyl group, chrysenyl group, acenaphthyl group, pyrimidyl group, pyrazyl group, The cyclic azine compound according to any one of claims 1 to 3, which is a pyridyl group, a quinolyl group, or an isoquinolyl group. -Ar ¹ -Ar ² each independently represents a phenyl group, tolyl group, biphenyl group, pyridylphenyl group, naphthylphenyl group, pyridyl group, naphthyl group, quinolyl group, isoquinolyl group, anthryl group, phenanthryl group, fluoranthenyl group The cyclic azine compound according to any one of claims 1 to 4, which is a group, a pyrenyl group, or a triphenylenyl group. -Ar ¹ -Ar ² each independently represents a phenyl group, p-tolyl group, biphenyl-2-yl group, biphenyl-3-yl group, biphenyl-4-yl group, 3-(2-pyridyl)phenyl group , 4-(2-pyridyl)phenyl group, 3-(3-pyridyl)phenyl group, 4-(3-pyridyl)phenyl group, 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 2-phenylpyridine -6-yl group, 2-phenylpyridin-5-yl group, 2-phenylpyridin-4-yl group, 3-phenylpyridin-5-yl group, 3-phenylpyridin-6-yl group, 2,6-yl group diphenylpyridin-4-yl group, 4,6-diphenylpyridin-2-yl group, 2-pyrimidyl group, 2-pyrazyl group, 1-naphthyl group, 2-naphthyl group, 3-quinolyl group, 4-quinolyl group, 3-isoquinolyl group, 2-fluorenyl group, 9,9-dimethylfluoren-2-yl group, 9,9-dimethylfluoren-3-yl group, 9,9-dimethylfluoren-4-yl group, 9,9- Diphenylfluoren-2-yl group, 9,9-diphenylfluoren-3-yl group, 9,9-diphenylfluoren-4-yl group, 9-anthryl group, 1-phenanthryl group, 2-phenanthryl group, 3-phenanthryl group The cyclic azine compound according to any one of claims 1 to 5, which is a 9-phenanthryl group, a 3-fluoranthenyl group, a 1-pyrenyl group, or a 2-triphenylenyl group. -Ar ¹ -Ar ² each independently represents a phenyl group, p-tolyl group, biphenyl-2-yl group, biphenyl-3-yl group, biphenyl-4-yl group, 1-naphthyl group, 2-naphthyl group , 2-fluorenyl group, 9,9-dimethylfluoren-2-yl group, 9,9-dimethylfluoren-3-yl group, 9,9-dimethylfluoren-4-yl group, 9,9-diphenylfluoren-2 -yl group, 9,9-diphenylfluoren-3-yl group, 9,9-diphenylfluoren-4-yl group, 9-anthryl group, 1-phenanthryl group, 2-phenanthryl group, 3-phenanthryl group, 9- The cyclic azine compound according to any one of claims 1 to 6, which is a phenanthryl group, a 3-fluoranthenyl group, a 1-pyrenyl group, or a 2-triphenylenyl group. -Ar ¹ -Ar ² each independently represents a phenyl group, p-tolyl group, biphenyl-2-yl group, biphenyl-3-yl group, biphenyl-4-yl group, 1-naphthyl group, or 2-naphthyl group The cyclic azine compound according to any one of claims 1 to 7, which is a group. The cyclic azine compound according to any one of claims 1 to 8, which satisfies the following (i) or (ii):
(i) L ¹ and L ² are each independently a phenylene group or a pyridylene group;
(ii) m=n=0. An organic electroluminescent device material comprising the cyclic azine compound according to any one of claims 1 to 9. An electron transport material for an organic electroluminescent device, comprising the cyclic azine compound according to any one of claims 1 to 9. An organic electroluminescent device comprising the cyclic azine compound according to any one of claims 1 to 9.

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