JP2021161116A - Cyclic azine compound, method for production thereof and applications thereof - Google Patents

Abstract

To provide a cyclic azine compound that contributes to making an organic electroluminescent element with high current efficiency and long service life.SOLUTION: For example, a cyclic azine compound of the following structural formula is illustrated.SELECTED DRAWING: Figure 1

Description

The present disclosure relates to a cyclic azine compound, a method for producing the same, and an organic electroluminescent device using the same.

Organic electroluminescent devices are used not only for small displays but also for large televisions, lighting, and the like, and their development is being vigorously carried out.
For example, Patent Document 1 discloses a cyclic azine compound having a specific substituent as a material for an organic electroluminescent device, which has excellent heat resistance, a reduced driving voltage, and contributes to the provision of an organic electroluminescent device having a long life. There is.

Japanese Unexamined Patent Publication No. 2011-063584

However, in recent years, the market demand for organic electroluminescent elements has been increasing, and there is a demand for materials having excellent luminous efficiency characteristics, drive voltage characteristics, and long life characteristics.
Here, the organic electroluminescent device using the cyclic azine compound disclosed in Patent Document 1 exhibits excellent drive voltage characteristics, but further improvement in device life and current efficiency is required.
One aspect of the present disclosure is directed to providing cyclic azine compounds and materials for organic electroluminescent devices that contribute to the production of organic electroluminescent devices with excellent durability and current efficiency.
Another aspect of the present disclosure is directed to providing a method for producing the cyclic azine compound.
Yet another aspect of the present disclosure is directed to providing an organic electroluminescent device with excellent durability and current efficiency.

According to one aspect of the present disclosure, cyclic azine compounds represented by the formulas (1-A) to (1-E) are provided:

During the ceremony
Ar ¹ and Ar ² are independent of each other.
(I) Aromatic hydrocarbon groups of monocyclic, linked or condensed rings having 6 to 20 carbon atoms,
(Ii) Aromatic heterocyclic groups of monocycles, linking rings, or condensed rings having 4 to 20 carbon atoms, or
(Iii) The aromatic hydrocarbon group or aromatic heterocyclic group is a fluorine atom, an alkyl group having 1 to 10 carbon atoms, an alkyl halide group having 1 to 3 carbon atoms, or an aromatic hydrocarbon having 6 to 30 carbon atoms. Represents a group substituted with one or more groups selected from the group consisting of groups and aromatic heterocyclic groups having 4 to 30 carbon atoms;
R is
(Iv) Halogen atom, alkyl group having 1 to 10 carbon atoms, alkyloxy group having 1 to 10 carbon atoms, cyano group, amino group, nitro group, acyl group having 1 to 10 carbon atoms,
(V) Aromatic hydrocarbon groups of a monocyclic ring, a linking ring, or a condensed ring having 6 to 30 carbon atoms.
(Vi) An aromatic heterocyclic group having a monocyclic ring, a linking ring, or a condensed ring having 4 to 30 carbon atoms, or
(Vii) The aromatic hydrocarbon group or aromatic heterocyclic group is a fluorine atom, an alkyl group having 1 to 10 carbon atoms, an alkyl halide group having 1 to 3 carbon atoms, or an aromatic hydrocarbon having 6 to 30 carbon atoms. Represents a group substituted with one or more groups selected from the group consisting of groups and aromatic heterocyclic groups having 4 to 30 carbon atoms;
Ra is
(A1) Hydrogen atom, halogen atom, alkyl group having 1 to 10 carbon atoms, alkyloxy group having 1 to 10 carbon atoms, cyano group, amino group, nitro group, acyl group having 1 to 10 carbon atoms,
(A2) An aromatic hydrocarbon group having a monocyclic ring, a linking ring, or a condensed ring having 6 to 30 carbon atoms.
(A3) An aromatic heterocyclic group having a monocycle, a linking ring, or a condensed ring having 4 to 30 carbon atoms, or
(A4) The aromatic hydrocarbon group or aromatic heterocyclic group is a fluorine atom, an alkyl group having 1 to 10 carbon atoms, an alkyl halide group having 1 to 3 carbon atoms, or an aromatic hydrocarbon having 6 to 30 carbon atoms. Represents a group substituted with one or more groups selected from the group consisting of groups and aromatic heterocyclic groups having 4 to 30 carbon atoms;
n represents an integer from 1 to 8.
However, if Ra is a hydrogen atom, n represents an integer from 2 to 8;
Multiple Rs may be the same or different;
Y ¹ and Y ² independently represent a nitrogen atom or CH, respectively.
At ^{least one of Y 1} and Y ² is a nitrogen atom.

During the ceremony
Ar ¹ and Ar ² are independent of each other.
(I) Aromatic hydrocarbon groups of monocyclic, linked or condensed rings having 6 to 20 carbon atoms,
(Ii) Aromatic heterocyclic groups of monocycles, linking rings, or condensed rings having 4 to 20 carbon atoms, or
(Iii) The aromatic hydrocarbon group or aromatic heterocyclic group is a fluorine atom, an alkyl group having 1 to 10 carbon atoms, an alkyl halide group having 1 to 3 carbon atoms, or an aromatic hydrocarbon having 6 to 30 carbon atoms. Represents a group substituted with one or more groups selected from the group consisting of groups and aromatic heterocyclic groups having 4 to 30 carbon atoms;
R is
(Iv) Halogen atom, alkyl group having 1 to 10 carbon atoms, alkyloxy group having 1 to 10 carbon atoms, cyano group, amino group, nitro group, acyl group having 1 to 10 carbon atoms,
(V) Aromatic hydrocarbon groups of a monocyclic ring, a linking ring, or a condensed ring having 6 to 30 carbon atoms.
(Vi) An aromatic heterocyclic group having a monocyclic ring, a linking ring, or a condensed ring having 4 to 30 carbon atoms, or
(Vii) The aromatic hydrocarbon group or aromatic heterocyclic group is a fluorine atom, an alkyl group having 1 to 10 carbon atoms, an alkyl halide group having 1 to 3 carbon atoms, or an aromatic hydrocarbon having 6 to 30 carbon atoms. Represents a group substituted with one or more groups selected from the group consisting of groups and aromatic heterocyclic groups having 4 to 30 carbon atoms;
Rb is
(B1) Hydrogen atom, halogen atom, alkyl group having 1 to 10 carbon atoms, alkyloxy group having 1 to 10 carbon atoms, cyano group, amino group, nitro group, acyl group having 1 to 10 carbon atoms,
(B2) An aromatic hydrocarbon group having a monocyclic ring, a linking ring, or a condensed ring having 6 to 30 carbon atoms.
(B3) An aromatic heterocyclic group having a monocycle, a linking ring, or a condensed ring having 4 to 30 carbon atoms, or
(B4) The aromatic hydrocarbon group or aromatic heterocyclic group is a fluorine atom, an alkyl group having 1 to 10 carbon atoms, an alkyl halide group having 1 to 3 carbon atoms, or an aromatic hydrocarbon having 6 to 30 carbon atoms. Represents a group substituted with one or more groups selected from the group consisting of groups and aromatic heterocyclic groups having 4 to 30 carbon atoms;
n represents an integer from 1 to 8.
However, when Rb is a hydrogen atom, n represents an integer from 2 to 8;
Multiple Rs may be the same or different;
Y ¹ and Y ² independently represent a nitrogen atom or CH, respectively.
At ^{least one of Y 1} and Y ² is a nitrogen atom.

During the ceremony
Ar ¹ and Ar ² are independent of each other.
(I) Aromatic hydrocarbon groups of monocyclic, linked or condensed rings having 6 to 20 carbon atoms,
(Ii) Aromatic heterocyclic groups of monocycles, linking rings, or condensed rings having 4 to 20 carbon atoms, or
(Iii) The aromatic hydrocarbon group or aromatic heterocyclic group is a fluorine atom, an alkyl group having 1 to 10 carbon atoms, an alkyl halide group having 1 to 3 carbon atoms, or an aromatic hydrocarbon having 6 to 30 carbon atoms. Represents a group substituted with one or more groups selected from the group consisting of groups and aromatic heterocyclic groups having 4 to 30 carbon atoms;
R is
(Iv) Halogen atom, alkyl group having 1 to 10 carbon atoms, alkyloxy group having 1 to 10 carbon atoms, cyano group, amino group, nitro group, acyl group having 1 to 10 carbon atoms,
(V) Aromatic hydrocarbon groups of a monocyclic ring, a linking ring, or a condensed ring having 6 to 30 carbon atoms.
(Vi) An aromatic heterocyclic group having a monocyclic ring, a linking ring, or a condensed ring having 4 to 30 carbon atoms, or
(Vii) The aromatic hydrocarbon group or aromatic heterocyclic group is a fluorine atom, an alkyl group having 1 to 10 carbon atoms, an alkyl halide group having 1 to 3 carbon atoms, or an aromatic hydrocarbon having 6 to 30 carbon atoms. Represents a group substituted with one or more groups selected from the group consisting of groups and aromatic heterocyclic groups having 4 to 30 carbon atoms.
However, the Rc is a monocyclic ring having 6 to 30 carbon atoms or an aromatic hydrocarbon group having a linking ring, or the aromatic hydrocarbon group having a monocyclic ring or a linking ring having a fluorine atom and 1 to 10 carbon atoms. One or more groups selected from the group consisting of an alkyl group, an alkyl halide group having 1 to 3 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, and an aromatic heterocyclic group having 4 to 30 carbon atoms. When the group is substituted with R and the 9-position of the phenanthrene is substituted with R, the R substituted at the 9-position of the phenanthrene represents a group other than the unsubstituted phenyl group;
Rc is
(C1) Hydrogen atom, halogen atom, alkyl group having 1 to 10 carbon atoms, alkyloxy group having 1 to 10 carbon atoms, cyano group, amino group, nitro group, acyl group having 1 to 10 carbon atoms,
(C2) An aromatic hydrocarbon group having a monocyclic ring, a linking ring, or a condensed ring having 6 to 30 carbon atoms.
(C3) An aromatic heterocyclic group having a monocycle, a linking ring, or a condensed ring having 4 to 30 carbon atoms, or
(C4) The aromatic hydrocarbon group or aromatic heterocyclic group is a fluorine atom, an alkyl group having 1 to 10 carbon atoms, an alkyl halide group having 1 to 3 carbon atoms, or an aromatic hydrocarbon having 6 to 30 carbon atoms. Represents a group substituted with one or more groups selected from the group consisting of groups and aromatic heterocyclic groups having 4 to 30 carbon atoms;
n represents an integer from 1 to 8.
However, when Rc is a hydrogen atom, n represents an integer from 2 to 8;
Multiple Rs may be the same or different,
However, the 9th and 10th places of phenanthrene are different;
Y ¹ and Y ² independently represent a nitrogen atom or CH, respectively.
At ^{least one of Y 1} and Y ² is a nitrogen atom.

During the ceremony
Ar ¹ and Ar ² are independent of each other.
(I) Aromatic hydrocarbon groups of monocyclic, linked or condensed rings having 6 to 20 carbon atoms,
(Ii) Aromatic heterocyclic groups of monocycles, linking rings, or condensed rings having 4 to 20 carbon atoms, or
(Iii) The aromatic hydrocarbon group or aromatic heterocyclic group is a fluorine atom, an alkyl group having 1 to 10 carbon atoms, an alkyl halide group having 1 to 3 carbon atoms, or an aromatic hydrocarbon having 6 to 30 carbon atoms. Represents a group substituted with one or more groups selected from the group consisting of groups and aromatic heterocyclic groups having 4 to 30 carbon atoms;
R is
(Iv) Halogen atom, alkyl group having 1 to 10 carbon atoms, alkyloxy group having 1 to 10 carbon atoms, cyano group, amino group, nitro group, acyl group having 1 to 10 carbon atoms,
(V) Aromatic hydrocarbon groups of a monocyclic ring, a linking ring, or a condensed ring having 6 to 30 carbon atoms.
(Vi) An aromatic heterocyclic group having a monocyclic ring, a linking ring, or a condensed ring having 4 to 30 carbon atoms, or
(Vii) The aromatic hydrocarbon group or aromatic heterocyclic group is a fluorine atom, an alkyl group having 1 to 10 carbon atoms, an alkyl halide group having 1 to 3 carbon atoms, or an aromatic hydrocarbon having 6 to 30 carbon atoms. Represents a group substituted with one or more groups selected from the group consisting of groups and aromatic heterocyclic groups having 4 to 30 carbon atoms.
However, the R substituted at the 10-position of phenylene is an aromatic hydrocarbon group having a monocycle or a linking ring having 6 to 30 carbon atoms, or an aromatic hydrocarbon group having the monocycle or a linking ring. A group consisting of a fluorine atom, an alkyl group having 1 to 10 carbon atoms, an alkyl halide group having 1 to 3 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, and an aromatic heterocyclic group having 4 to 30 carbon atoms. When the group is substituted with one or more groups selected from the above and the 9-position of the phenanthrene is substituted with R, the R substituted with the 9-position of the phenanthrene is an unsubstituted phenyl group. Represents a group other than;
Rd is
(D1) Hydrogen atom, halogen atom, alkyl group having 1 to 10 carbon atoms, alkyloxy group having 1 to 10 carbon atoms, cyano group, amino group, nitro group, acyl group having 1 to 10 carbon atoms,
(D2) An aromatic hydrocarbon group having a monocyclic ring, a linking ring, or a condensed ring having 6 to 30 carbon atoms.
(D3) An aromatic heterocyclic group having a monocyclic ring, a linking ring, or a condensed ring having 4 to 30 carbon atoms, or
(D4) The aromatic hydrocarbon group or aromatic heterocyclic group is a fluorine atom, an alkyl group having 1 to 10 carbon atoms, an alkyl halide group having 1 to 3 carbon atoms, or an aromatic hydrocarbon having 6 to 30 carbon atoms. Represents a group substituted with one or more groups selected from the group consisting of groups and aromatic heterocyclic groups having 4 to 30 carbon atoms;
n represents an integer from 1 to 8.
However, when Rd is a hydrogen atom, n represents an integer from 2 to 8;
Multiple Rs may be the same or different,
However, the 9th and 10th places of phenanthrene are different;
Y ¹ and Y ² independently represent a nitrogen atom or CH, respectively.
At ^{least one of Y 1} and Y ² is a nitrogen atom.

During the ceremony
Ar ¹ and Ar ² are independent of each other.
(I) Aromatic hydrocarbon groups of monocyclic, linked or condensed rings having 6 to 20 carbon atoms,
(Ii) Aromatic heterocyclic groups of monocycles, linking rings, or condensed rings having 4 to 20 carbon atoms, or
(Iii) The aromatic hydrocarbon group or aromatic heterocyclic group is a fluorine atom, an alkyl group having 1 to 10 carbon atoms, an alkyl halide group having 1 to 3 carbon atoms, or an aromatic hydrocarbon having 6 to 30 carbon atoms. Represents a group substituted with one or more groups selected from the group consisting of groups and aromatic heterocyclic groups having 4 to 30 carbon atoms;
R is
(Iv) Halogen atom, alkyl group having 1 to 10 carbon atoms, alkyloxy group having 1 to 10 carbon atoms, cyano group, amino group, nitro group, acyl group having 1 to 10 carbon atoms,
(V) Aromatic hydrocarbon groups of a monocyclic ring, a linking ring, or a condensed ring having 6 to 30 carbon atoms.
(Vi) An aromatic heterocyclic group having a monocyclic ring, a linking ring, or a condensed ring having 4 to 30 carbon atoms, or
(Vii) The aromatic hydrocarbon group or aromatic heterocyclic group is a fluorine atom, an alkyl group having 1 to 10 carbon atoms, an alkyl halide group having 1 to 3 carbon atoms, or an aromatic hydrocarbon having 6 to 30 carbon atoms. Represents a group substituted with one or more groups selected from the group consisting of groups and aromatic heterocyclic groups having 4 to 30 carbon atoms.
However, the R substituted at the 10-position of phenylene is an aromatic hydrocarbon group having a monocycle or a linking ring having 6 to 30 carbon atoms, or an aromatic hydrocarbon group having the monocycle or a linking ring. A group consisting of a fluorine atom, an alkyl group having 1 to 10 carbon atoms, an alkyl halide group having 1 to 3 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, and an aromatic heterocyclic group having 4 to 30 carbon atoms. When the group is substituted with one or more groups selected from the above and the 9-position of the phenanthrene is substituted with R, the R substituted with the 9-position of the phenanthrene is an unsubstituted phenyl group. Represents a group other than;
Re is
(E1) Hydrogen atom, halogen atom, alkyl group having 1 to 10 carbon atoms, alkyloxy group having 1 to 10 carbon atoms, cyano group, amino group, nitro group, acyl group having 1 to 10 carbon atoms,
(E2) An aromatic hydrocarbon group having a monocyclic ring, a linking ring, or a condensed ring having 6 to 30 carbon atoms.
(E3) An aromatic heterocyclic group having a monocyclic ring, a linking ring, or a condensed ring having 4 to 30 carbon atoms, or
(E4) The aromatic hydrocarbon group or aromatic heterocyclic group is a fluorine atom, an alkyl group having 1 to 10 carbon atoms, an alkyl halide group having 1 to 3 carbon atoms, or an aromatic hydrocarbon having 6 to 30 carbon atoms. Represents a group substituted with one or more groups selected from the group consisting of groups and aromatic heterocyclic groups having 4 to 30 carbon atoms;
n represents an integer from 1 to 8.
However, when Re is a hydrogen atom, n represents an integer from 2 to 8;
Multiple Rs may be the same or different,
However, the 9th and 10th places of phenanthrene are different;
Y ¹ and Y ² independently represent a nitrogen atom or CH, respectively.
At ^{least one of Y 1} and Y ² is a nitrogen atom.

According to another aspect of the present disclosure, there is provided a material for an organic electroluminescent device containing a cyclic azine compound represented by the above formula (1).
According to another aspect of the present disclosure, an organic electroluminescent device containing the cyclic azine compound represented by the above formula (1) is provided.

According to another aspect of the present disclosure, it is a method for producing a cyclic azine compound represented by the formula (1).
In the presence of a metal catalyst, the coupling reaction between the compound represented by the formula (2) and the compound represented by the formula (3) is included.
The cyclic azine compound represented by the formula (1) is a cyclic azine compound, and a method for producing a cyclic azine compound is provided:

During the ceremony
Ar ¹ , Ar ² , R, n, Y ¹ and Y ² are synonymous with equations (1-A)-(1-E);
L represents the group corresponding to the phenanthrenyl group contained in the cyclic azine compounds of the formulas (1-A) to (1-E);
X ¹ represents a chlorine atom, a bromine atom, a trifluoromethanesulfonyloxy group or an iodine atom;
M ¹ represents ZnZ ¹ , MgZ ² , Sn (Z ³ ) ₃ , or B (OZ ⁴ ) ₂ ;
Z ¹ and Z ² independently represent a chlorine atom, a bromine atom or an iodine atom;
Z ³ represents the same or different alkyl or phenyl group having 1-4 carbon atoms;
Z ⁴ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a phenyl group, which is the same or different from each other;
However, when M ¹ represents B (OZ ⁴ ) ₂ , the two (OZ ⁴ ) groups may be integrated to form a ring together with the boron atom.

According to another aspect of the present disclosure, it is a method for producing a cyclic azine compound represented by the formula (1).
In the presence of a metal catalyst, the coupling reaction between the compound represented by the formula (4) and the compound represented by the formula (5) is included.
The cyclic azine compound represented by the formula (1) is a cyclic azine compound, and a method for producing a cyclic azine compound is provided:

During the ceremony
Ar ¹ , Ar ² , R, n, Y ¹ and Y ² are synonymous with equations (1-A)-(1-E);
L represents the group corresponding to the phenanthrenyl group contained in the cyclic azine compounds of the formulas (1-A) to (1-E);
X ² represents a chlorine atom, a bromine atom, a trifluoromethanesulfonyloxy group or an iodine atom. ;
M ² represents ZnZ ¹ , MgZ ² , Sn (Z ³ ) ₃ , or B (OZ ⁴ ) ₂ ;
Z ¹ and Z ² independently represent a chlorine atom, a bromine atom or an iodine atom;
Z ³ represents the same or different alkyl or phenyl group with 1 to 4 carbon atoms;
Z ⁴ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a phenyl group, which is the same or different from each other;
However, when M ² represents B (OZ ⁴ ) ₂ , the two (OZ ⁴ ) groups may be integrated to form a ring together with the boron atom.

According to one aspect of the present disclosure, it is possible to provide a cyclic azine compound and a material for an organic electroluminescent device, which contribute to the production of an organic electroluminescent device having excellent durability and current efficiency.
According to another aspect of the present disclosure, a method for producing the cyclic azine compound can be provided.
According to still another aspect of the present disclosure, it is possible to provide an organic electroluminescent device having excellent durability and current efficiency.

It is schematic cross-sectional view which shows an example of the laminated structure of the organic electroluminescent element containing the cyclic azine compound which concerns on one aspect of this disclosure. It is a schematic cross-sectional view which shows an example (element Example-1) of the laminated structure of the organic electroluminescent device containing the cyclic azine compound which concerns on one aspect of this disclosure.

Hereinafter, the cyclic azine compound according to one aspect of the present disclosure will be described in detail.

<Cyclic azine compound>
Cyclic azine compounds according to one aspect of the present disclosure, represented by formulas (1-A)-(1-E):

During the ceremony
Ar ¹ and Ar ² are independent of each other.
(I) Aromatic hydrocarbon groups of monocyclic, linked or condensed rings having 6 to 20 carbon atoms,
(Ii) Aromatic heterocyclic groups of monocycles, linking rings, or condensed rings having 4 to 20 carbon atoms, or
(Iii) The aromatic hydrocarbon group or aromatic heterocyclic group is a fluorine atom, an alkyl group having 1 to 10 carbon atoms, an alkyl halide group having 1 to 3 carbon atoms, or an aromatic hydrocarbon having 6 to 30 carbon atoms. Represents a group substituted with one or more groups selected from the group consisting of groups and aromatic heterocyclic groups having 4 to 30 carbon atoms;
R is
(Iv) Halogen atom, alkyl group having 1 to 10 carbon atoms, alkyloxy group having 1 to 10 carbon atoms, cyano group, amino group, nitro group, acyl group having 1 to 10 carbon atoms,
(V) Aromatic hydrocarbon groups of a monocyclic ring, a linking ring, or a condensed ring having 6 to 30 carbon atoms.
(Vi) An aromatic heterocyclic group having a monocyclic ring, a linking ring, or a condensed ring having 4 to 30 carbon atoms, or
(Vii) The aromatic hydrocarbon group or aromatic heterocyclic group is a fluorine atom, an alkyl group having 1 to 10 carbon atoms, an alkyl halide group having 1 to 3 carbon atoms, or an aromatic hydrocarbon having 6 to 30 carbon atoms. Represents a group substituted with one or more groups selected from the group consisting of groups and aromatic heterocyclic groups having 4 to 30 carbon atoms;
Ra ~ Re are
(A1) to (e1) Hydrogen atom, halogen atom, alkyl group having 1 to 10 carbon atoms, alkyloxy group having 1 to 10 carbon atoms, cyano group, amino group, nitro group, acyl group having 1 to 10 carbon atoms,
(A2)-(e2) Aromatic hydrocarbon groups having a monocyclic ring, a linking ring, or a condensed ring having 6 to 30 carbon atoms.
(A3) to (e3) Aromatic heterocyclic groups of monocyclic, linked or condensed rings having 4 to 30 carbon atoms, or
(A4) to (e4) The aromatic hydrocarbon group or aromatic heterocyclic group has a fluorine atom, an alkyl group having 1 to 10 carbon atoms, an alkyl halide group having 1 to 3 carbon atoms, and 6 to 30 carbon atoms. Represents a group substituted with one or more groups selected from the group consisting of aromatic hydrocarbon groups and aromatic heterocyclic groups having 4 to 30 carbon atoms;
n represents an integer from 1 to 8.
However, when Ra to Re are hydrogen atoms, n represents an integer from 2 to 8;
Multiple Rs may be the same or different,
Y ¹ and Y ² independently represent a nitrogen atom or CH, respectively.
At ^{least one of Y 1} and Y ² is a nitrogen atom.

However, in the formulas (1-C) to (1-E), the R substituted at the 10-position of phenanthrene is an aromatic hydrocarbon group having a monocycle or a linking ring having 6 to 30 carbon atoms, or an aromatic hydrocarbon group. The aromatic hydrocarbon group of the single ring or the linking ring is a fluorine atom, an alkyl group having 1 to 10 carbon atoms, an alkyl halide group having 1 to 3 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, and the like. And if it is a group substituted with one or more groups selected from the group consisting of aromatic heterocyclic groups having 4 to 30 carbon atoms and the 9-position of the phenanthrene is substituted with R, the phenanthrene The R substituted at the 9-position represents a group other than the unsubstituted phenyl group.

Hereinafter, the cyclic azine compound according to one aspect of the present disclosure represented by the formulas (1-A) to (1-E) may be collectively referred to as the cyclic azine compound (1). Definitions of substituents in the cyclic azine compound (1), preferred embodiments thereof, and preferred specific examples are as follows.

[About Ar ¹ and Ar ² ]
Ar ¹ and Ar ² are independent of each other.
(I) Aromatic hydrocarbon groups of monocyclic, linked or condensed rings having 6 to 20 carbon atoms,
(Ii) Aromatic heterocyclic groups of monocycles, linking rings, or condensed rings having 4 to 20 carbon atoms, or
(Iii) The aromatic hydrocarbon group or aromatic heterocyclic group is a fluorine atom, an alkyl group having 1 to 10 carbon atoms, an alkyl halide group having 1 to 3 carbon atoms, or an aromatic hydrocarbon having 6 to 30 carbon atoms. Represents a group substituted with one or more groups selected from the group consisting of groups and aromatic heterocyclic groups having 4 to 30 carbon atoms.

[[(I): About aromatic hydrocarbon groups]]
The aromatic hydrocarbon group of a monocyclic ring, a linking ring, or a fused ring having 6 to 20 carbon atoms is not particularly limited, but is not particularly limited, but is a phenyl group, a biphenylyl group, a terphenylyl group, a naphthylphenyl group, a naphthyl group, or an acenaphthylenyl. Examples thereof include a group, a phenylenyl group, an anthryl group, a fluoranthenyl group, a pyrenyl group, a triphenylenyl group, a chrysenyl group, a fluorenyl group, a tryptisenyl group, a perylenel group and the like. Among these, a phenyl group, a naphthyl group, or a biphenylyl group is preferable because it has excellent properties as an electron transporting material.

[[(Ii): About aromatic heterocyclic groups]]
The aromatic heterocyclic group of a monocycle, a linking ring, or a condensed ring having 4 to 20 carbon atoms is not particularly limited, but is a thienyl group, a frill group, a benzofuranyl group, a benzothienyl group, or a dibenzofuranyl group. , Dibenzothienyl group, pyrimidyl group, pyrazinel group, pyridyl group, bipyridyl group, turpyridinyl group, quinolinyl group, isoquinolinyl group, phthalazinyl group, naphthyldinyl group, quinoxalinyl group, quinazolinyl group, acridinyl group, phenanthrolinyl group, phthalazinyl group, etc. Can be mentioned.

[[(Iii): groups in which (i) and (ii) are substituted with predetermined groups]]
-Group in which (i) is substituted with a predetermined group The aromatic hydrocarbon group having 6 to 20 carbon atoms, a monocyclic ring, a linking ring, or a fused ring has a fluorine atom, an alkyl group having 1 to 10 carbon atoms, and a carbon number of carbon atoms. Substituted with one or more groups selected from the group consisting of 1-3 alkyl halide groups, 6-30 carbon aromatic hydrocarbon groups, and 4-30 aromatic heterocyclic groups. May be good. Specific examples are not particularly limited, but for example, a phenyl group, a p-tolyl group, an m-tolyl group, an o-tolyl group, a p-trifluoromethylphenyl group, an m-trifluoromethylphenyl group, and the like. o-Trifluoromethylphenyl group, 2,4-dimethylphenyl group, 3,5-dimethylphenyl group, mesityl group, 2-ethylphenyl group, 3-ethylphenyl group, 4-ethylphenyl group, 2,4-diethyl Phenyl group, 3,5-dipropylphenyl group, 2-propylphenyl group, 3-propylphenyl group, 4-propylphenyl group, 2,4-dipropylphenyl group, 3,5-dipropylphenyl group, 2-( 1-Methylethyl) phenyl group, 3- (1-methylethyl) phenyl group, 4- (1-methylethyl) phenyl group, 2,4-di (1-methylethyl) phenyl group, 3,5-di ( 1-Methylethyl) phenyl group, 2-butylphenyl group, 3-butylphenyl group, 4-butylphenyl group, 2,4-dibutylphenyl group, 3,5-dibutylphenyl group, 2-t-butylphenyl group, 3-t-butylphenyl group, 4-t-butylphenyl group, 2,4-di-t-butylphenyl group, 3,5-di-t-butylphenyl group, biphenyl-4-yl group, biphenyl-3 -Il group, biphenyl-2-yl group, 2-methylbiphenyl-4-yl group, 3-methylbiphenyl-4-yl group, 2'-methylbiphenyl-4-yl group, 4'-methylbiphenyl-4- Il group, 2,2'-dimethylbiphenyl-4-yl group, 2', 4', 6'-trimethylbiphenyl-4-yl group, 6-methylbiphenyl-3-yl group, 5-methylbiphenyl-3- Il group, 2'-methylbiphenyl-3-yl group, 4'-methylbiphenyl-3-yl group, 6,2'-dimethylbiphenyl-3-yl group, 2', 4', 6'-trimethylbiphenyl- 3-yl group, 5-methylbiphenyl-2-yl group, 6-methylbiphenyl-2-yl group, 2'-methylbiphenyl-2-yl group, 4'-methylbiphenyl-2-yl group, 6,2 '-Dimethylbiphenyl-2-yl group, 2', 4', 6'-trimethylbiphenyl-2-yl group, 2-trifluoromethylbiphenyl-4-yl group, 3-trifluoromethylbiphenyl-4-yl group , 2'-trifluoromethylbiphenyl-4-yl group, 4'-trifluoromethylbiphenyl-4-yl group, 6-trifluoromethylbiphenyl-3-yl group, 5-Trifluoromethylbiphenyl-3-yl group, 2'-trifluoromethylbiphenyl-3-yl group, 4'-trifluoromethylbiphenyl-3-yl group, 5-trifluoromethylbiphenyl-2-yl group, 6-Trifluoromethylbiphenyl-2-yl group, 2'-trifluoromethylbiphenyl-2-yl group, 4'-trifluoromethylbiphenyl-2-yl group, 3-ethylbiphenyl-4-yl group, 4' -Ethylbiphenyl-4-yl group, 2', 4', 6'-triethylbiphenyl-4-yl group, 6-ethylbiphenyl-3-yl group, 4'-ethylbiphenyl-3-yl group, 5-ethyl Biphenyl-2-yl group, 4'-ethylbiphenyl-2-yl group, 2', 4', 6'-triethylbiphenyl-2-yl group, 3-propylbiphenyl-4-yl group, 4'-propylbiphenyl -4-Il group, 2', 4', 6'-tripropylbiphenyl-4-yl group, 6-propylbiphenyl-3-yl group, 4'-propylbiphenyl-3-yl group, 5-propylbiphenyl- 2-yl group, 4'-propylbiphenyl-2-yl group, 2', 4', 6'-tripropylbiphenyl-2-yl group, 3- (1-methylethyl) biphenyl-4-yl group, 4 '-(1-Methylethyl) biphenyl-4-yl group, 2', 4', 6'-tri (1-methylethyl) biphenyl-4-yl group, 6- (1-methylethyl) biphenyl-3-3 Il group, 4'-(1-methylethyl) biphenyl-3-yl group, 5- (1-methylethyl) biphenyl-2-yl group, 4'-(1-methylethyl) biphenyl-2-yl group, 2', 4', 6'-tri (1-methylethyl) biphenyl-2-yl group, 3-butylbiphenyl-4-yl group, 4'-butylbiphenyl-4-yl group, 2', 4', 6'-Tributylbiphenyl-4-yl group, 6-butylbiphenyl-3-yl group, 4'-butylbiphenyl-3-yl group, 5-butylbiphenyl-2-yl group, 4'-butylbiphenyl-2- Il group, 2', 4', 6'-tributylbiphenyl-2-yl group, 3-t-butylbiphenyl-4-yl group, 4'-t-butylbiphenyl-4-yl group, 2', 4' , 6'-tri-t-butylbiphenyl-4-yl group, 6-t-butylbiphenyl-3-yl group, 4'-t-butylbiphenyl-3-yl group, 5-t-butylbiphenyl-2- Ethyl group, 4'-t-butylbiphenyl-2-i Lu group, 2', 4', 6'-tri-t-butylbiphenyl-2-yl group, fluorophenyl group, difluorophenyl group, trifluorophenyl group, tetrafluorophenyl group, pentafluorophenyl group, 1-naphthyl Group, 4-trifluoromethylnaphthalene-1-yl group, 4-ethylnaphthalene-1-yl group, 4-propylnaphthalene-1-yl group, 4-butylnaphthalene-1-yl group, 4-t-butylnaphthalene -1-yl group, 5-trifluoromethylnaphthalene-1-yl group, 5-ethylnaphthalen-1-yl group, 5-propylnaphthalene-1-yl group, 5-butylnaphthalene-1-yl group, 5-yl group. t-butylnaphthalen-1-yl group, 2-naphthyl group, 6-trifluoromethylnaphthalene-2-yl group, 6-ethylnaphthalen-2-yl group, 6-propylnaphthalene-2-yl group, 6-butyl Naphthalen-2-yl group, 6-t-butylnaphthalen-2-yl group, 7-trifluoromethylnaphthalen-2-yl group, 7-ethylnaphthalen-2-yl group, 7-propylnaphthalen-2-yl group , 7-Butylnaphthalen-2-yl group, 7-t-butylnaphthalen-2-yl group, 1-phenylnaphthalen-2-yl group, 1-phenylnaphthalene-3-yl group, 1-phenylnaphthalene-4-yl group Il group, 1-Phenylnaphthalen-5-Il group, 1-Phenylnaphthalen-6-Il group, 1-Phenylnaphthalen-7-Il group, 1-Phenylnaphthalen-8-Il group, 2-Phenylnaphthalene-1- Il group, 2-Phenylnaphthalen-3-yl group, 2-Phenylnaphthalen-4-yl group, 2-Phenylnaphthalen-5-yl group, 2-Phenylnaphthalene-6-yl group, 2-Phenylnaphthalene-7- Il group, 2-phenylnaphthalen-8-yl group, 1-methylnaphthalen-4-yl group, 1-methylnaphthalen-5-yl group, 1-methylnaphthalen-6-yl group, 1-methylnaphthalene-7- Il group, 1-methylnaphthalen-8-yl group, 2-methylnaphthalen-1-yl group, 2-methylnaphthalen-3-yl group, 2-methylnaphthalen-4-yl group, 2-methylnaphthalene-5-yl group Il group, 2-methylnaphthalen-6-yl group, 2-methylnaphthalen-7-yl group, 2-methylnaphthalen-8-yl group, 1,1': 4', 1 "-terphenyl-2'- Il group, 1,1': 3', 1 "-terphenyl-2'-yl group, 1,1': 3', 1"- Tarphenyl-4'-yl group, 1,1': 3', 1 "-terphenyl-5'-yl group, 1,1': 2', 1"-terphenyl-3'-yl group, 1 , 1': 2', 1 "-terphenyl-4'-yl group, 1-phenanthrenyl group, 2-phenanthrenyl group, 3-phenanthrenyl group, 4-phenanthrenyl group, 9-phenanthrenyl group, 10-phenylphenanthren-9 -Il group, 10- (2-naphthyl) phenanthrene-9-yl group, 7- (9-phenanthrenyl) phenanthren-2-yl group, 1-anthryl group, 2-anthryl group, 9-anthryl group, 10-methyl Examples thereof include an anthracene-9-yl group, a 10-phenylanthracene-9-yl group, and a 10- (2-naphthyl) anthracene-9-yl group. Of these groups, a phenyl group, a biphenyl-3-yl group, a biphenyl-4-yl group, a 1-naphthyl group, or a 2-naphthyl group is more preferable because of its excellent properties as an electron transporting material.

-A group in which (ii) is substituted with a predetermined group The aromatic heterocyclic group having a monocycle, a linking ring, or a fused ring having 4 to 20 carbon atoms is a fluorine atom, an alkyl group having 1 to 10 carbon atoms, or a carbon number of carbon atoms. Substituted with one or more groups selected from the group consisting of 1-3 alkyl halide groups, 6-30 carbon aromatic hydrocarbon groups, and 4-30 aromatic heterocyclic groups. May be good. Specific examples thereof are not particularly limited, but for example, 2-thienyl group, 5-methylthiophen-2-yl group, 2-furyl group, 5-methylfuran-2-yl group, 2-benzothienyl group. Group, 3-benzothienyl group, 4-benzothienyl group, 5-benzothienyl group, 6-benzothienyl group, 7-benzothienyl group, 2-benzofuranyl group, 5-benzofuranyl group, 1-dibenzothienyl group, 2- Dibenzothienyl group, 3-dibenzothienyl group, 4-dibenzothienyl group, 1-dibenzofuranyl group, 2-dibenzofuranyl group, 3-dibenzofuranyl group, 4-dibenzofuranyl group, 2-pyrimidyl group, 3 , 5-Dimethylpyrimidin-2-yl group, 3,5-diphenylpyrimidin-2-yl group, 3,5-bis (trifluoromethyl) pyrimidin-2-yl group, 2-pyrazinyl group, 5,6-dimethyl Pyrazine-2-yl group, 3-phenylpyrazin-2-yl group, 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 2-methylpyridin-3-yl group, 2-methylpyridin-4-yl group 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 Group, 3-methylpyridin-6-yl group, 4-methylpyridin-2-yl group, 4-methylpyridin-3-yl group, 2,6-dimethylpyridine-3-yl group, 2,6-dimethylpyridine -4-yl group, 3,6-dimethylpyridin-2-yl group, 3,6-dimethylpyridin-4-yl group, 3,6-dimethylpyridin-5-yl group, 3-phenylpyridine-2-yl group Group, 4-phenylpyridine-2-yl group, 5-phenylpyridine-2-yl group, 6-phenylpyridine-2-yl group, 3,6-diphenylpyridine-2-yl group, 4,6-diphenylpyridine -2-yl group, 3,5-diphenylpyridine-2-yl group, 4,5,6-triphenylpyridine-2-yl group, 2-phenylpyridine-3-yl group, 4-phenylpyridine-3-yl group Il group, 5-phenylpyridine-3-yl group, 6-phenylpyridine-3-yl group, 2,4-diphenylpyridine-3-yl group, 2,5-diphenylpyridine-3-yl group, 2,6 −Diphenylpyridine-3-yl group, 4,6-diphenylpyridine-3-yl group, 2,4,6-triphenylpyridine-3-yl group, 2,5,6-triphenylpyridine- 3-Il group, 2-phenylpyridine-4-yl group, 3-phenylpyridine-4-yl group, 2,3-diphenylpyridine-4-yl group, 2,5-diphenylpyridine-4-yl group, 2 , 6-Diphenylpyridine-4-yl group, 3,5-diphenylpyridine-4-yl group, 2,3,5,6-tetraphenylpyridine-4-yl group, 2,2'-bipyridine-6-yl Group, 2,2'-bipyridin-5-yl group, 2,2'-bipyridin-4-yl group, 2,4'-bipyridin-5-yl group, 2,3'-bipyridine-5-yl group, 2,4'-bipyridine-3'-yl group, 2,2': 6'2 "-terpyridine-6-yl group, 2,2': 6'2"-terpyridine-4'-yl group, 2- Minolyl 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, quinazoline-2-yl group, quinazoline-4- Examples thereof include an yl group, a quinazoline-5-yl group, a quinazoline-6-yl group, a quinazoline-7-yl group, and a quinazoline-8-yl group.

[About R]
R is
(Iv) Halogen atom, alkyl group having 1 to 10 carbon atoms, alkyloxy group having 1 to 10 carbon atoms, cyano group, amino group, nitro group, acyl group having 1 to 10 carbon atoms,
(V) Aromatic hydrocarbon groups of a monocyclic ring, a linking ring, or a condensed ring having 6 to 30 carbon atoms.
(Vi) An aromatic heterocyclic group having a monocyclic ring, a linking ring, or a condensed ring having 4 to 30 carbon atoms, or
(Vii) The aromatic hydrocarbon group or aromatic heterocyclic group is a fluorine atom, an alkyl group having 1 to 10 carbon atoms, an alkyl halide group having 1 to 3 carbon atoms, or an aromatic hydrocarbon having 6 to 30 carbon atoms. Represents a group substituted with one or more groups selected from the group consisting of groups and aromatic heterocyclic groups having 4 to 30 carbon atoms.

In the case of (vii), the carbon number of the substituent contained in the aromatic hydrocarbon group having 6 to 30 carbon atoms or the aromatic heterocyclic group having 4 to 30 carbon atoms is the aromatic hydrocarbon group or the aromatic complex. It is not included in the number of carbon atoms of the ring group.

The aromatic hydrocarbon group of the monocyclic ring, linking ring, or fused ring having 6 to 30 carbon atoms in (v) is not particularly limited, but is, for example, a phenyl group, a naphthyl group, a fluorenyl group, or anthryl. Examples thereof include a group, a phenanthryl group, a benzofluorenyl group, a pyrenyl group, a triphenylenyl group, a chrysenyl group, a perylenel group, a fluoranthenyl group, an acenaphthylenyl group, a biphenylyl group, a terphenylyl group, a naphthylphenyl group and a tryptisenyl group. Here, the aromatic hydrocarbon group means a monocycle containing no heteroatom, a fused ring containing no heteroatom, and a linked ring in which these are linked (that is, rings that do not contain a heteroatom are linked). ..

The aromatic heterocyclic group of the monocyclic, linking ring, or fused ring having 4 to 30 carbon atoms in (vi) is not particularly limited, but is a pyridyl group, a pyrazinyl group, a pyrimidyl group, a pyridadyl group, and the like. Kinolyl group, isoquinolyl group, phenanthridyl group, benzoquinolyl group, acridinyl group, thienyl group, furyl group, benzofuranyl group, benzothienyl group, dibenzofuranyl group, dibenzothienyl group, bipyridyl group, turpyridinyl group, phthalazinyl group, naphthyldinyl group , Kinoxalinyl group, quinazolinyl group, phenanthrolinyl group, phthalazinyl group, thienyl group, frill group, bitienyl group, bifuryl group, benzothienyl group, benzofuryl group, dibenzothienyl group, dibenzofuryl group, phenyltriazyl group, diphenyltoria Jill group and the like can be mentioned. Here, the aromatic heterocyclic group means a monocycle containing a heteroatom, a condensed ring containing a heteroatom, and a linked ring in which these are linked (that is, all rings containing a heteroatom are linked).
That is, the aromatic heterocyclic group includes a monocycle containing a heteroatom, a condensed ring containing a heteroatom, a linking ring, and the like.

As the aromatic hydrocarbon group or aromatic heterocyclic group of (vii), for example, the group mentioned in (v) or (vi) is a fluorine atom, an alkyl group having 1 to 10 carbon atoms, and 1 to 1 carbon atoms. Examples include groups substituted with one or more groups selected from the group consisting of 3 alkyl halide groups, 6-30 carbon aromatic hydrocarbon groups, and 4-30 aromatic heterocyclic groups. Be done.

The alkyl group having 1 to 10 carbon atoms in (iv) is not particularly limited, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, and a t-butyl group. ..

The alkyloxy group having 1 to 10 carbon atoms in (iv) is not particularly limited, but is a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, and a t-butoxy group. And so on.

The acyl group having 1 to 10 carbon atoms in (iv) is not particularly limited, and examples thereof include a metanoyl group, an etanoyl group, a propanoyl group, and a benzoyl group.

R is preferably a group selected from either (vi) or (vii) having no substituent in that the glass transition temperature is high.

Specifically, R is selected from the group consisting of 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 and an alkoxy group having 1 to 4 carbon atoms. A phenyl group, a naphthyl group, a fluorenyl group, an anthryl group, a phenanthryl group, a benzofluorenyl group, a pyrenyl group, a peryleneyl group, a fluoranthenyl group, a triphenylenyl group, which may be substituted with one or more groups. It may be a chrysenyl group, an acenaphthyl group, a pyrimidyl group, a pyrazil group, a pyridyl group, a quinolyl group, an isoquinolyl group, a benzofuryl group, a benzothienyl group, a dibenzofuryl group, a dibenzothienyl group, a phenyltriazyl group, a diphenyltriazyl group; preferable. R is a phenyl group, a naphthyl group, a fluorenyl group, an anthryl group, a phenanthryl group, a benzofluorenyl group, a pyrenyl group, a peryleneyl group, a fluoranthenyl group, a triphenylenyl group, a pyrimidyl group, a pyrazil group, a pyridyl group, a quinolyl group, More preferably, it is an isoquinolyl group, a benzofuryl group, a benzothienyl group, a dibenzofuryl group, a dibenzothienyl group, a biphenyl group, a phenyltriazil group, a diphenyltriazil group, or a pyridylphenyl group.
The plurality of Rs may be the same or different from each other.

[About Ra ~ Re]
Ra ~ Re are
(A1) to (e1) Hydrogen atom, halogen atom, alkyl group having 1 to 10 carbon atoms, alkyloxy group having 1 to 10 carbon atoms, cyano group, amino group, nitro group, acyl group having 1 to 10 carbon atoms,
(A2)-(e2) Aromatic hydrocarbon groups having a monocyclic ring, a linking ring, or a condensed ring having 6 to 30 carbon atoms.
(A3) to (e3) Aromatic heterocyclic groups of monocyclic, linked or condensed rings having 4 to 30 carbon atoms, or
(A4) to (e4) The aromatic hydrocarbon group or aromatic heterocyclic group has a fluorine atom, an alkyl group having 1 to 10 carbon atoms, an alkyl halide group having 1 to 3 carbon atoms, and 6 to 30 carbon atoms. Represents a group substituted with one or more groups selected from the group consisting of aromatic hydrocarbon groups and aromatic heterocyclic groups having 4 to 30 carbon atoms.

Here, the aromatic hydrocarbon group and the aromatic heterocyclic group in Ra to Re are the same as the aromatic hydrocarbon group and the aromatic heterocyclic group in R.

In one aspect of the cyclic azine compound represented by formula (1-A), Ra is:
Phenyl group,
Pyridyl group or
The phenyl or pyridyl group is a fluorine atom, an alkyl group having 1 to 10 carbon atoms, an alkyl halide group having 1 to 3 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, and an aromatic group having 4 to 30 carbon atoms. A group substituted with one or more groups selected from the group consisting of group heterocyclic groups.
In another embodiment of the cyclic azine compound represented by the formula (1-A), Ra is a fluorine atom, an alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 3 carbon atoms, and 6 carbon atoms. A pyridyl group which may be substituted with one or more groups selected from the group consisting of ~ 30 aromatic hydrocarbon groups and 4-30 carbon aromatic heterocyclic groups.
Furthermore, in yet another embodiment of the cyclic azine compound represented by the formula (1-A), Ra is a hydrogen atom.

[About n]
n is an integer of 1-8. However, when Ra to Re are hydrogen atoms, n represents an integer of 2 to 8.
More preferably, n is an integer of 1 to 4.

[About Y ¹ and Y ² ]
Y ¹ and Y ² each independently represent a nitrogen atom or CH. Here, ^{at least one of Y 1} and Y ² is a nitrogen atom.
It is preferable that Y ¹ is a nitrogen atom. It is more preferable that both Y ¹ and Y ^{2 are nitrogen atoms.}

[About each formula]
However, in the formulas (1-C) to (1-E),
Phenanthrene's 9th and 10th places are different;
The R substituted at the 10-position of phenylene is an aromatic hydrocarbon group having 6 to 30 carbon atoms in a monocyclic or linking ring, or the aromatic hydrocarbon group in the monocyclic or linking ring is a fluorine atom. , Select from the group consisting of an alkyl group having 1 to 10 carbon atoms, an alkyl halide group having 1 to 3 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, and an aromatic heterocyclic group having 4 to 30 carbon atoms. When the group is substituted with one or more groups and the 9-position of the phenanthrene is substituted with R, the R substituted at the 9-position of the phenanthrene is other than the unsubstituted phenyl group. Represents a group.

In the formulas (1-A) and (1-B), the 9-position and the 10-position of phenanthrene may be different from each other.

In the formula (1-B), Rb is a monocyclic or linking ring aromatic hydrocarbon group having 6 to 30 carbon atoms, or the monocyclic or linking ring aromatic hydrocarbon group is a fluorine atom. , Select from the group consisting of an alkyl group having 1 to 10 carbon atoms, an alkyl halide group having 1 to 3 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, and an aromatic heterocyclic group having 4 to 30 carbon atoms. When the group is substituted with one or more groups and the 9-position of the phenanthrene is substituted with R, the R substituted at the 9-position of the phenanthrene is other than the unsubstituted phenyl group. It may represent a group.

In the formulas (1-B) to (1-E), the 9th and 10th positions of phenanthrene are simultaneously placed at the 9th position and the 10th position.
Aromatic hydrocarbon groups with 6 to 30 carbon atoms in a single ring or a linking ring, as well as
The aromatic hydrocarbon group of the single ring or the linking ring is a fluorine atom, an alkyl group having 1 to 10 carbon atoms, an alkyl halide group having 1 to 3 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, and the like. And a group substituted with one or more groups selected from the group consisting of aromatic heterocyclic groups having 4 to 30 carbon atoms may not be taken.

[Specific Examples of Preferred Compounds]
Among the compounds represented by the formula (1), specific examples of the preferable compounds include compounds having the structures represented by the following formulas (1-1) to (1-87), but the cyclic azine compound (1) is It is not limited to these.

Among these, cyclic azine compounds represented by any one of the formulas (1-1) to (1-26), (1-48), and (1-85) are particularly preferable.

Next, a method for producing a cyclic azine compound according to another aspect of the present disclosure (hereinafter, referred to as a method for producing a cyclic azine compound (1)) will be described.
The cyclic azine compound (1) can be produced by the method shown in the following reaction pathway 1 or 2.
That is, the method for producing the cyclic azine compound (1) is as follows.
Including or coupling reaction of the cyclic azine intermediate represented by the formula (2) with the compound represented by the formula (3), or
This includes a coupling reaction between the cyclic azine intermediate represented by the formula (4) and the compound represented by the formula (5).
Both coupling reactions are preferably carried out in the presence of a palladium catalyst.

In equations (2) to (5),
^{Ar 1, Ar 2, R,} n, Y 1, and the definition of ^{Y 2,} respectively, ^{Ar 1,} Ar 2, R in the formula (1-A) ~ (1 -E), n, Y 1, and Y Same as the definition of ^2;
L represents the group corresponding to the phenanthrenyl group contained in the cyclic azine compounds of the formulas (1-A) to (1-E);
X ¹ and X ² independently represent a chlorine atom, a bromine atom, a trifluoromethanesulfonyloxy group or an iodine atom;
M ¹ and M ² independently represent ZnZ ¹ , MgZ ² , Sn (Z ³ ) ₃ , or B (OZ ⁴ ) ₂ ;
Z ¹ and Z ² independently represent a chlorine atom, a bromine atom or an iodine atom;
Z ³ represents the same or different alkyl or phenyl group having 1-4 carbon atoms;
Z ⁴ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a phenyl group, which is the same or different from the above.

Further, when M ¹ and M ² represent B (OZ ⁴ ) ₂ , the two (OZ ⁴ ) groups may be integrated to form a ring together with the boron atom.
Among these, B (OZ ⁴ ) ₂ is preferable.

The ZnZ ¹ and MgZ ² are not particularly limited, and examples thereof include ZnCl, ZnBr, ZnI, MgCl, MgBr, and MgI.
The Sn (Z ³ ) ₃ is not particularly limited, and examples thereof include Sn (Me) ₃ and Sn (Bu) ₃ .
The B (OZ ⁴ ) ₂ is not particularly limited, but is, for example, B (OH) ₂ , B (OMe) ₂ , B (O ⁱ Pr) ₂ , B (OBu) ₂ , B (OPh). _2nd class can be mentioned. Me is a methyl group, ⁱ Pr is an isopropyl group, Bu is a butyl group, and Ph is a phenyl group. ^{Further, the example of B (OZ 4} ) _{2 in} the case where two (OZ ⁴ ) groups are integrally formed with a boron atom is not particularly limited, but for example, the following ( The groups represented by I) to (VI) can be mentioned, and the group represented by (II) is preferable in terms of good yield.

In the reaction pathway 1, the cyclic azine intermediate (2) and the compound (3) are coupled to each other in the presence of a palladium catalyst, if necessary, to produce the cyclic azine compound (1). By applying the reaction conditions of general coupling reactions such as Suzuki-Miyaura reaction, Negishi reaction, Tamao-Kumada reaction, and Stille reaction, the target product can be obtained in good yield. When the reaction conditions of the Suzuki-Miyaura reaction are applied to the reaction pathway 1, it is preferably carried out in the presence of a base.

The cyclic azine intermediate represented by the formula (2) used in the reaction pathway 1 is, for example, Dye Pigment. It can be synthesized according to 2018, Vol. 157, pp. 377-384. Further, a commercially available product may be used.
Examples of the cyclic azine intermediate represented by the formula (2) include compounds having the structures shown in 2-1 to 2-15 below, but the present invention is not limited thereto. In equations (2-1) to (2-15), X ¹ has the same definition as described above.

Examples of the group represented by X ¹ include a chlorine atom, a bromine atom, a trifluoromethanesulfonyloxy group and an iodine atom. A chlorine atom is preferable because the yield of the cyclic azine compound (1) is good.

The compound (3) used in the reaction pathway 1 is, for example, J.A. Org. Chem. It can be manufactured in accordance with 2015, Volume 80, pp. 11706-11717. Moreover, you may use a commercially available product.
Examples of the compound (3) include the following 3-1 to 3-21, but the present invention is not limited thereto. In equations (3-1) to (3-21), M ¹ has the same definition as described above.

The ^{group represented by M 1} is not particularly limited, but for example, ZnZ ¹ , MgZ ² , Sn (Z ³ ) ₃ or two (OZ ⁴ ) groups are integrally ringed together with a boron atom. ^{B (OZ 4} ) _{2 and the} like which may form B (OZ 4) 2 and the like may be mentioned. Among these, B (OZ ⁴ ) ₂ is preferable.

The palladium catalyst that can be used in the reaction pathway 1 is not particularly limited, but specifically,
Palladium salts such as palladium chloride, palladium acetate, palladium trifluoroacetate, palladium nitrate;
Complex compounds such as π-allyl palladium chloride dimer, palladium acetylacetonato, tris (dibenzylideneacetone) dipalladium, bis (dibenzylideneacetone) palladium, dichlorobis (acetonitrile) palladium, dichlorobis (benzonitrile) palladium;
Dichlorobis (triphenylphosphine) palladium, tetrakis (triphenylphosphine) palladium, dichloro (1,1'-bis (diphenylphosphino) ferrocene) palladium, bis (tri-t-butylphosphine) palladium, bis (tricyclohexylphosphine) Palladium complex having a tertiary phosphine such as palladium, dichlorobis (tricyclohexylphosphine) palladium as a ligand;
Can be mentioned.

A palladium complex having a tertiary phosphine as a ligand can also be prepared in a reaction system by adding a tertiary phosphine to a palladium salt or a complex compound. Examples of the tertiary phosphine that can be used at this time include triphenylphosphine, trimethylphosphine, tributylphosphine, tri (t-butyl) phosphine, tricyclohexylphosphine, t-butyldiphenylphosphine, 9,9-dimethyl-4, 5-bis (diphenylphosphino) xanthene, 2- (diphenylphosphino) -2'-(N, N-dimethylamino) biphenyl, 2- (di-t-butylphosphino) biphenyl, 2- (dicyclohexylphosphino) ) Biphenyl, bis (diphenylphosphino) methane, 1,2-bis (diphenylphosphino) ethane, 1,3-bis (diphenylphosphino) propane, 1,4-bis (diphenylphosphino) butane, 1,1 '-Bis (diphenylphosphine) ferrocene, tri (2-furyl) phosphine, tri (o-tolyl) phosphine, tris (2,5-kisilyl) phosphine, (±) -2,2'-bis (diphenylphosphine) ) -1,1'-binaphthyl, 2-dicyclohexylphosphino-2', 4', 6'-triisopropylbiphenyl and the like.

Among these, a palladium complex having a tertiary phosphine as a ligand is preferable in terms of good yield, and 2-dicyclohexylphosphino-2', 4', 6'-triisopropylbiphenyl or triphenylphosphine is coordinated. A palladium complex having as a child is more preferable.

The molar ratio of the tertiary phosphine to the palladium salt or complex compound is preferably in the range of 1:10 to 10: 1, and more preferably in the range of 1: 2 to 3: 1 in terms of good yield. preferable. The amount of the palladium catalyst used in the reaction pathway 1 is not limited, but the molar equivalent of the palladium catalyst is preferably in the range of 0.005 to 0.5 molar equivalent with respect to the boron compound in terms of good yield.

The base used in the reaction pathway 1 is not particularly limited, but for example, metal hydroxide salts such as sodium hydroxide, potassium hydroxide, and calcium hydroxide; sodium carbonate, potassium carbonate, lithium carbonate, and carbonic acid. Metal carbonates such as cesium; Metal acetates such as potassium acetate and sodium acetate; Metal phosphates such as potassium phosphate and sodium phosphate; Metal fluoride salts such as sodium fluoride, potassium fluoride and cesium fluoride; Metal alkoxides such as sodium methoxydo, potassium methoxydo, sodium ethoxydo, potassium isopropyl oxide, potassium tert-butoxide; and the like can be mentioned. Among them, metal carbonate and metal phosphate are preferable, and potassium carbonate or potassium phosphate is more preferable in terms of good reaction yield. The amount of the base is not particularly limited, but the molar ratio of the base to the boron compound is preferably in the range of 1: 2 to 10: 1 and 1: 1 to 4: 1 in terms of good reaction yield. It is more preferable that it is in the range of.

Reaction pathway 1 can be carried out in a solvent, which includes water; diisopropyl ether, dibutyl ether, cyclopentyl methyl ether (CPME), tetrahydrofuran (THF), 2-methyl tetrahydrofuran, 1,4-dioxane, dimethoxy. Ethers such as ethane; aromatic hydrocarbons such as benzene, toluene, xylene, mesityrene, tetraline; carbonates such as ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethylmethyl carbonate, 4-fluoroethylene carbonate; ethyl acetate, Esters such as butyl acetate, methyl propionate, ethyl propionate, methyl butyrate, γ-lactone; amides such as N, N-dimethylformamide (DMF), dimethylacetamide (DMAc), N-methylpyrrolidone (NMP); N, Ureas such as N, N', N'-tetramethylurea (TMU), N, N'-dimethylpropylene urea (DMPU); and dimethylsulfoxide (DMSO), methanol, ethanol, isopropyl alcohol, butanol, octanol, benzyl Examples thereof include alcohols, ethylene glycols, propylene glycols, diethylene glycols, triethylene glycols, alcohols such as 2,2,2-trifluoroethanol; and the like. These may be mixed and used in arbitrary ratios. There is no particular limitation on the amount of solvent used. Of these, water, ether, amide, alcohol or a mixed solvent thereof is preferable from the viewpoint of good reaction yield, and a mixed solvent of THF and water is more preferable.

The reaction route 1 can be carried out at a temperature appropriately selected from 0 ° C. to 200 ° C., and is preferably carried out at a temperature appropriately selected from 40 ° C. to 150 ° C. in terms of good reaction yield.
The reaction pathway 1 is obtained by carrying out a usual treatment after the reaction is completed. If necessary, it may be purified by recrystallization, column chromatography, sublimation, preparative HPLC or the like.

Next, the reaction pathway 2 will be described.
In the reaction pathway 2, the cyclic azine intermediate represented by the formula (4) and the compound represented by the formula (5) are coupled to each other in the presence of a palladium catalyst, if necessary, and the cyclic azine compound (the cyclic azine compound ( 1) is manufactured. In the reaction route 2, the desired product can be obtained in good yield by applying the reaction conditions of general coupling reactions such as Suzuki-Miyaura reaction, Negishi reaction, Tamao-Kumada reaction, and Stille reaction. When the reaction conditions of the Suzuki-Miyaura reaction are applied to the reaction pathway 2, it is preferably carried out in the presence of a base.

The cyclic azine intermediate represented by the formula (4) used in the reaction pathway 2 can be produced, for example, according to the method disclosed in Korean Application Publication No. 2017/0049441.
Examples of the cyclic azine intermediate represented by the formula (4) include compounds having the structures shown in 4-1 to 4-24 below, but the present invention is not limited thereto. In equations (4-1) to (4-24), X ² has the same definition as described above.

The ^{leaving group represented by X 2} is a chlorine atom, a bromine atom, a trifluoromethanesulfonyloxy group or an iodine atom. A chlorine atom or a bromine atom is preferable because the yield of the cyclic azine compound (1) is good.

The compound represented by the formula (5) used in the reaction pathway 2 is, for example, J.A. Org. Chem. It can be manufactured in accordance with 2017, Vol. 82, pp. 9258-9262. Further, it is synthesized by using a reaction for synthesizing a general organometallic compound from the compound represented by the formula (7) (for example, Angew. Chem. Int. Ed. 2007, Vol. 46, pp. 5359-5363). A commercially available product may be used.

Examples of the compound represented by the formula (5) include compounds having the structures shown in 5-1 to 5-24 below, but the present invention is not limited thereto. In equations (5-1) to (5-24), M ² has the same definition as described above.

As the palladium catalyst, base, solvent, reaction temperature, and post-treatment (purification) that can be used in the reaction pathway 2, the same ones as those exemplified in the reaction pathway 1 can be exemplified, and the preferable configuration thereof is also described. The same is true.

The cyclic azine compound (1) can be used, for example, in organic electronic device applications such as organic electroluminescent devices (OLEDs) and photoelectric devices. Among these, the cyclic azine compound (1) is preferably used as a material for an organic electroluminescent device. When the cyclic azine compound (1) is used as a part of the constituent components of the organic electroluminescent device, effects such as high current efficiency and long life can be obtained. In particular, when the cyclic azine compound (1) is used as an electron transport layer, these effects are further exhibited.

Hereinafter, the use of the cyclic azine compound (1) will be described.

<Materials for organic electroluminescent devices, electron transport materials for organic electroluminescent devices>
The cyclic azine compound (1) is not particularly limited, but 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 an organic electroluminescent device.
That is, the material for an organic electroluminescent device according to one aspect of the present disclosure includes a cyclic azine compound (1). Further, the electron transport material for an organic electroluminescent device according to one aspect of the present disclosure includes a cyclic azine compound (1). The material for an organic electroluminescent element and the electron transporting material for an organic electroluminescent element containing the cyclic azine compound (1) contribute to the production of an organic electroluminescent element having excellent durability and current efficiency.

<Organic electroluminescent device>
The organic electroluminescent device according to one aspect of the present disclosure includes a cyclic azine compound (1).
The configuration of the organic electroluminescent device is not particularly limited, and examples thereof include the configurations (a) to (f) shown below.
(A): anode / light emitting layer / cathode (b): anode / hole transport layer / light emitting layer / cathode (c): anode / light emitting layer / electron transport layer / cathode (d): anode / hole transport layer / Light emitting layer / electron transport layer / cathode (e): anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode (f): anode / hole injection layer / charge generation layer / Hole transport layer / Light emitting layer / Electron transport layer / Cathode.

Hereinafter, the organic electroluminescent device according to one aspect of the present disclosure will be described in more detail with reference to FIG. 1 by taking the configuration of the above (f) as an example.
The organic electroluminescent device shown in FIG. 1 has a so-called bottom emission type element configuration, but the organic electroluminescent device according to one aspect of the present disclosure is not limited to the bottom emission type element configuration. No. That is, the organic electroluminescent device according to one aspect of the present disclosure may have another known device configuration such as a top emission type.
FIG. 1 is a schematic cross-sectional view showing an example of a laminated structure of an organic electroluminescent device containing a cyclic azine compound according to one aspect of the present disclosure.

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, and 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, the charge generation layer 4 is omitted, and the hole transport layer 5 is directly provided on the hole injection layer 3. May be good. Further, for example, a single layer having a function of a plurality of layers, such as an electron injection / transport layer having a function of an electron injection layer and a function of an electron transport layer in a single layer, is formed into the plurality of layers. It may be a configuration provided instead of. Further, 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 cyclic azine compound (1)]
The organic electroluminescent device contains the cyclic azine compound (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 contains 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). The cyclic azine compound (1) may be contained in a plurality of layers included in the organic electroluminescent element, and when an electron injection layer is provided between the electron transport layer and the cathode, the electron injection layer is provided. The cyclic azine compound (1) may be contained.
In the following, the organic electroluminescent device 100 in which the electron transport layer 7 contains the cyclic azine compound (1) will be described.

[Board 1]
The substrate is not particularly limited, and examples thereof include a glass plate, a quartz plate, and a plastic plate. Further, in the case of a configuration in which light emission is taken out from the substrate 1 side, the substrate 1 is transparent with respect to the wavelength of light.
Examples of the light-transmitting plastic film include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyethersulfone (PES), polyetherimide, polyetheretherketone, polyphenylene sulfide, polyarylate, polyimide, and polycarbonate (Plastic film). PC), a film composed of cellulose triacetate (TAC), cellulose acetate propionate (CAP) and the like can be mentioned.

[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 light emission is taken out through an anode, the anode is formed of a material that allows or substantially passes the light emission.
The transparent material used for the anode is not particularly limited, but for example, indium-tin oxide (ITO; Indium Tin Oxide), indium-zinc oxide (IZO; Indium Zinc Oxide), tin oxide, aluminum.・ Dope-type tin oxide, magnesium-indium oxide, nickel-tungsten oxide, other metal oxides, metal nitrides such as gallium nitride, metal serene products such as zinc selenium, and metal sulfides such as zinc sulfide. Can be mentioned.
In the case of an organic electroluminescent device having a configuration in which light is extracted only from the cathode side, the transmission characteristics of the anode are not important. Therefore, examples of the material 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 the light emitting layer 6 described later, a hole injection layer 3, a charge generating layer 4 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, more holes are injected into the light emitting layer at a lower electric field.
The hole injection layer and the hole transport layer also function as electron barrier layers. That is, the electrons injected from the cathode and transported from the electron injecting layer and / or the electron transporting layer to the light emitting layer are generated by the electron barrier existing at the interface between the light emitting layer and the hole injecting layer and / or the hole transporting layer. , Leakage into the hole injection layer and / or the hole transport layer is suppressed. As a result, the electrons are accumulated at the interface in the light emitting layer to bring about effects such as improvement of luminous efficiency, and an organic electroluminescent element having excellent light emitting performance can be obtained.

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

Specific examples of materials for the hole injection layer and the hole transport layer include triazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, and amino-substituted chalcones. Derivatives, oxazole derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilben derivatives, silazane derivatives, aniline copolymers, conductive polymer oligomers (particularly thiophene oligomers), porphyrin compounds, aromatic tertiary amine compounds, styryl Examples include amine compounds. Among these, a porphyrin compound, an aromatic tertiary amine compound, and a styrylamine compound are preferable, and an aromatic tertiary amine compound is particularly preferable.

Specific examples of the aromatic tertiary amine compound and the styrylamine compound 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] Stilben, 4-N, N-diphenyl Amino- (2-diphenylvinyl) benzene, 3-methoxy-4'-N, N-diphenylaminostillbenzene, 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.

Inorganic compounds such as p-type-Si and p-type-SiC can also be mentioned as examples of the material of the hole injection layer and the material of the hole transport layer.

The hole injection layer and the hole transport layer may have a single-layer structure made of one or more kinds of materials, or may have a laminated structure made of a plurality of 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.
The material of the charge generation layer is not particularly limited, but for example, 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 a plurality of 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 the electron transport layer 7, which will be described later.
Examples of the material of the light emitting layer include a phosphorescent light emitting material, a fluorescent light emitting material, and a thermal activated delayed fluorescent light emitting material. In the light emitting layer, electron-hole pairs are recombined, resulting in light emission.

The light emitting layer may consist of a single small molecule material or a single polymer material, but more generally it consists of a host material doped with a guest compound. The luminescence comes 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-carbazobinylene) 1, 1'-biphenyl), TBADN (2-t-butyl-9,10-di (2-naphthyl) anthracene), ADN (9,10-di (2-naphthyl) anthracene), CBP (4,4'-bis) (Carbazole-9-yl) biphenyl), CDBP (4,4'-bis (carbazole-9-yl) -2,2'-dimethylbiphenyl), 2- (9-phenylcarbazole-3-yl) -9- [Examples include 4- (4-phenylphenylquinazoline-2-yl) carbazole, 9,10-bis (biphenyl) anthracene and the like.

Examples of the fluorescent dopant include anthracene, pyrene, tetracene, xanthene, perylene, lubrene, coumarin, rhodamine, quinacridone, dicyanomethylenepyran compound, thiopyran compound, polymethine compound, pyrylium, thiapyrrylium compound, fluorene derivative, perifrantene derivative and indenoperylene. Examples thereof 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 transition metal complexes such as iridium, platinum, palladium, and osmium.

Specific examples of the fluorescent dopant and phosphorescent dopant include Alq3 (tris (8-hydroxyquinoline) aluminum), DPAVBi (4,5'-bis [4- (di-p-tolylamino) styryl] biphenyl), perylene, and bis [ 2- (4-n-Hexylphenyl) quinoline] (acetylacetonate) 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 can be mentioned.

Further, the light emitting material is not limited to being contained only in the light emitting layer. For example, the light emitting material may contain a layer (hole transport layer 5 or electron transport layer 7) adjacent to the light emitting layer. This makes it possible to further increase the luminous 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 a plurality of 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 the cathode 8 described later.
The electron transport layer has a function of transferring electrons injected from the cathode to the light emitting layer. By interposing the electron transport layer between the cathode and the light emitting layer, electrons are injected into the light emitting layer with a lower electric field.
As described above, the electron transport layer preferably contains the cyclic azine compound (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, 8-hydroxyquinolinate lithium (Liq), bis (8-hydroxyquinolinate) zinc, bis (8-hydroxyquinolinate) copper, and bis (8-hydroxyquinoli). Nart) manganese, tris (8-hydroxyquinolinate) aluminum, tris (2-methyl-8-hydroxyquinolinate) aluminum, tris (8-hydroxyquinolinate) gallium, bis (10-hydroxybenzo [h]] Kinolinate) berylium, 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) -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- Il) -4,6-diphenyl-1,3,5-triazine, BCP (2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline), Bphenyl (4,7-diphenyl-1,10-) Phenantroline), BAlq (bis (2-methyl-8-quinolinolate) -4- (phenylphenolate) aluminum), bis (10-hydroxybenzo [h] quinolinate) berylium) and the like.

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

When the electron transport layer has a two-layer structure in which the light emitting layer side is the first electron transport layer and the cathode side is the second electron transport layer, the second electron transport layer preferably 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 electroluminescence device having a configuration in which only light emitted through 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, indium. , Lithium / aluminum mixture, 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]
For each layer except the electrodes (anode, cathode) described above, the material of each layer (with a material such as a binder resin and a solvent if necessary) can be used, for example, by vacuum deposition method, spin coating method, casting method, LB ( It can be formed by thinning by a known method such as the Langmuir-Projet) method. The film thickness of each layer is not particularly limited, but is usually about 5 nm to 5 μm.
The film thickness of each layer thus formed is not particularly limited and may be appropriately selected depending on the situation, but is usually in the range of 5 nm to 5 μm.
The anode and cathode can be formed by thinning the electrode material 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 the cathode is preferably 1 μm or less, and more preferably 10 nm or more and 200 nm or less.

The organic electroluminescent element according to one aspect of the present disclosure may be used as a kind of lamp such as an illumination or an exposure light source, a projection device of a type for projecting an image, or a still image or a moving image can be directly visually recognized. It may be used as a display device (display) of the type to be used. When used as a display device for video reproduction, the drive method may be either a simple matrix (passive matrix) method or an active matrix method. Further, a full-color display device can be manufactured by using two or more kinds of organic electroluminescent devices of this embodiment having different emission colors.

The cyclic azine compound (1) can be synthesized by appropriately combining known reactions (for example, Suzuki-Miyaura cross-coupling reaction).

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not construed as being limited to these examples.

¹ Bruker ASCEND 400 (400 MHz; manufactured by BRUKER) was used for 1 H-NMR measurement. ^{1 1} H-NMR was _{measured using deuterated chloroform (CDCl 3} ) as a measurement solvent and tetramethylsilane (TMS) as an internal standard substance. For HPLC, Shimadzu LC-2040C 3D was used.

The light emitting characteristics of the organic electroluminescent element were evaluated by applying a direct current to the manufactured element at room temperature and using a luminance meter (product name: BM-9, manufactured by Topcon Technohouse Co., Ltd.). In the present specification, the room temperature is 15 ° C. to 30 ° C., particularly 25 ° C.

Synthesis Example-1

9-Bromo-2-chloro-10-phenylphenanthrene (500 mg, 1.4 mmol) was dissolved in THF (10 mL) under an argon atmosphere. This solution is cooled to −78 ° C., 1.64 M n-butyllithium-hexane solution (0.92 mL, 1.5 mmоl) is added, and after stirring at −78 ° C. for 30 minutes, zinc chloride (222 mg, 1. A solution prepared by dissolving 6 mmol) in THF (5 mL) was added, and the mixture was further stirred at the same temperature for 30 minutes. The reaction solution was heated to room temperature and then stirred for 30 minutes, where 2-chloro-4,6-diphenyl-1,3,5-triazine (400 mg, 1.5 mmol) and tetrakistriphenylphosphine palladium (78 mg, 70 μmol) was added, and the mixture was heated under reflux for 14 hours. After cooling to room temperature, the low boiling point was distilled off under reduced pressure, ethyl acetate and an aqueous sodium hydroxide solution were added to the residue, and the mixture was stirred for 15 minutes. By filtering the solid and washing with methanol, the desired 2- (2-chloro-10-phenylphenanthrene-9-yl) -4,6-diphenyl-1,3,5-triazine white solid ( Yield 0.58 g, yield 82%) was obtained.

^{1 1} H-NMR (CDCl ₃ ): δ8.76-8.79 (m, 2H), 8.52 (d, J = 7.0Hz, 4H), 7.73 (d, J = 7.8Hz, 2H) ), 7.65-7.70 (m, 2H), 7.56 (m, 1H), 7.56 (d, J = 7.5Hz, 2H), 7.49 (dd, J = 7.0) , 1.4Hz, 4H), 7.36 (d, J = 7.0Hz, 2H), 7.24 (t, J = 6.0Hz, 2H), 7.14 (dd, J = 7.4, 1.3Hz, 1H).

Synthesis Example-2

Under an argon atmosphere, 2- (2-chloro-10-phenylphenanthrene-9-yl) -4,6-diphenyl-1,3,5-triazine (2.00 g, 3.8 mmol), 3-pyridylboronic acid ( 614 mg, 4.9 mmol), palladium acetate (43 mg, 0.19 mmol) and 2-dicyclohexylphosphino-2', 4', 6'-triisopropylphenyl (183 mg, 0.38 mmol) with THF (40 mL) and 2. A 0M-potassium phosphate aqueous solution (5.7 mL) was added, and the mixture was stirred under heating and reflux for 18 hours. After cooling to room temperature, the low boiling point was distilled off under reduced pressure, and the residue was washed with water and methanol. The obtained crude product was suspended in xylene, heated to 150 ° C., and then filtered by heat. After allowing the filtrate to cool, the resulting solid was filtered off. After washing this solid with methanol, it is dried under reduced pressure to obtain the desired 2,4-diphenyl-6- [10-phenyl-2- (3-pyridyl) phenanthrene-9-yl] -1,3,5. -A white solid of triazine (yield 1.40 g, yield 63%) was obtained.

¹ H-NMR (CDCl ₃ ): δ8.95 (d, J = 8.6Hz, 1H), 8.85-8.87 (m, 2H), 8.57 (dd, J = 4.8,1) .5Hz, 1H), 8.54 (d, J = 5.2Hz, 4H), 7.96 (dd, J = 8.6, 1.9Hz, 1H), 7.92 (s, 1H), 7 .87 (dt, J = 8.0, 1.9Hz, 1H), 7.76 (d, J = 8.6Hz, 1H), 7.72 (d, J = 7.0Hz, 1H), 7. 55-7.59 (m, 3H), 7.50 (dd, J = 8.6, 1.2Hz, 4H), 7.43 (dd, J = 7.6, 1.2Hz, 2H), 7 .34 (dd, J = 8.0, 4.8Hz, 1H), 7.25 (t, J = 8.0Hz, 2H), 7.14 (dd, J = 8.0, 1.2Hz, 1H) ).

Synthesis Example-3

Under an argon atmosphere, 2- (2-chloro-10-phenylphenanthrene-9-yl) -4,6-diphenyl-1,3,5-triazine (1.30 g, 2.5 mmol), 9-phenanthrene boronic acid ( 675 mg, 3.0 mmol), palladium acetate (28 mg, 0.12 mmol) and 2-dicyclohexylphosphino-2', 4', 6'-triisopropylphenyl (120 mg, 0.25 mmol) in THF (26 mL). Made turbid. A 2M aqueous potassium phosphate solution (3.8 mL) was sequentially added to this suspension, and the mixture was stirred under heating under reflux for 18 hours. After cooling to room temperature, the solvent was distilled off under reduced pressure, and the obtained residue was washed with water and methanol to obtain a crude product. The obtained crude product was suspended in xylene, heated to 150 ° C., and then filtered by heat. After allowing the filtrate to cool, the resulting solid was filtered off. By drying this solid under reduced pressure, a white solid of 2,4-diphenyl-6- (10-phenyl- [2,9'-biphenanthrene] -9-yl) -1,3,5-triazine (yield). 1.30 g, yield 78%) was obtained.

¹ H-NMR (CDCl ₃ ): δ8.97 (d, J = 8.5Hz, 1H), 8.92 (d, J = 8.5Hz, 1H), 8.76 (d, J = 8.2Hz) , 1H), 8.70 (d, J = 8.2Hz, 1H), 8.54 (d, J = 8.0Hz, 4H), 8.86-8.93 (m, 4H), 7.79 (D, J = 7.5Hz, 1H), 7.75 (t, J = 7.5Hz, 1H), 7.70 (s, 1H), 7.66 (dd, J = 8.5,7. 5Hz, 2H), 7.47-7.61 (m, 9H), 7.43 (dd, J = 8.2, 1.2Hz, 2H), 7.15 (t, J = 7.8Hz, 2H) ), 7.01 (J = 7.5, 1.2Hz, 1H).

Synthesis Example-4

2- (2-Chloro-10-phenylphenanthrene-9-yl) -4,6-diphenyl-1,3,5-triazine (2.50 g, 4.8 mmol), biphenylboronic acid (1. 23 g, 6.2 mmol), palladium acetate (32 mg, 0.14 mmol) and 2-dicyclohexylphosphino-2', 4', 6'-triisopropylphenyl (140 mg, 0.29 mmol) suspended in THF (20 mL). I let you. A 2.0 M-potassium phosphate aqueous solution (7.2 mL) was sequentially added to this suspension, and the mixture was stirred under heating under reflux for 20 hours. After allowing to cool to room temperature, water and methanol were added, and the precipitated solid was collected by filtration and washed with water and methanol to obtain a crude product. The crude product and 1 g of activated carbon were suspended in toluene and heated and stirred at 110 ° C. for 30 minutes. After stirring, Celite filtration was performed, and a low boiling point was distilled off under reduced pressure from the obtained solution. By washing the obtained solid with toluene, 2- (2-([1,1'-biphenyl] -4-yl) -10-phenylphenanthrene-9-yl) -4,6-diphenyl-1 , 3,5-Triazine white solid (yield 1.59 g, yield 44%) was obtained.

^{1 1} H-NMR (CDCl ₃ ): δ8.93 (d, J = 8.7Hz, 1H), 8.87 (d, J = 8.2Hz, 1H), 8.54 (d, J = 7.0Hz) , 4H), 8.04 (dd, J = 8.6, 1.9Hz, 1H), 7.97 (d, J = 1.8Hz, 1H), 7.71-7.77 (m, 2H) , 7.64-7.69 (m, 4H), 7.62 (dd, J = 8.5, 1.4Hz, 2H), 7.53-7.59 (m, 1H), 7.56 ( dd, J = 7.4, 2.4Hz, 2H), 7.51 (dd, J = 6.2, 1.4Hz, 3H), 7.43-7.48 (m, 5H), 7.36 (T, J = 5.4Hz, 1H), 7.23-7.27 (m, 2H), 7.14 (t, J = 7.4Hz, 1H).

Synthesis Example-5

2- (2-Chloro-10-phenylphenanthrene-9-yl) -4,6-diphenyl-1,3,5-triazine (100 mg, 0.19 mmol), trifluoromethylphenylboronic acid (48 mg) under an argon atmosphere , 0.25 mmol), palladium acetate (2.2 mg, 9.6 μmol) and 2-dicyclohexylphosphino-2', 4', 6'-triisopropylphenyl (9.2 mg, 19 μmol) in THF (0.8 mL). Suspended in. A 2.0 M-potassium phosphate aqueous solution (0.3 mL) was sequentially added to this suspension, and the mixture was stirred overnight under heating under reflux. After allowing to cool to room temperature, water and chloroform were added, the organic layer was extracted, and the organic layer was washed with water and then saturated brine. Sodium sulfate was added to the extract, and the mixture was stirred at room temperature for a while, then the desiccant was filtered off, and the low boiling point was distilled off under reduced pressure from the filtrate. The obtained crude product was purified by column chromatography (developing solution: chloroform / hexane) and 2,4-diphenyl-6- (10-phenyl-2- (4- (trifluoromethyl) phenyl) phenanthrene- A white solid of 9-yl) -1,3,5-triazine (yield 88 mg, yield 73%) was obtained.

^{1 1} H-NMR (CDCl ₃ ): δ8.94 (d, J = 8.6Hz, 1H), 8.87 (d, J = 8.6Hz, 1H), 8.53 (d, J = 8.6Hz) , 4H), 7.98 (d, J = 8.6Hz, 1H), 7.92 (s, 1H), 7.55 (dd, J = 12.8, 8.2Hz, 2H), 7.65 -7.70 (m, 4H), 7.58 (t, J = 7.4Hz, 3H), 7.50 (t, J = 7.6Hz, 4H), 7.43 (d, J = 6. 9Hz, 2H), 7.23-7.27 (m, 2H), 7.14 (t, J = 7.4Hz, 1H).

Synthesis Example-6

2- (2-Chloro-10-phenylphenanthrene-9-yl) -4,6-diphenyl-1,3,5-triazine (100 mg, 0.19 mmol), 4-t-butylphenylboronic acid under an argon atmosphere (45 mg, 0.25 mmol), palladium acetate (2.2 mg, 9.6 μmol) and 2-dicyclohexylphosphino-2', 4', 6'-triisopropylphenyl (9.2 mg, 19 μmol) in THF (1. It was suspended in 3 mL). A 2.0 M-potassium phosphate aqueous solution (290 μL) was sequentially added to this suspension, and the mixture was stirred overnight under heating under reflux. After allowing to cool to room temperature, water and chloroform were added, the organic layer was extracted, and the organic layer was washed with water and then saturated brine. Sodium sulfate was added to the extract, and the mixture was stirred at room temperature for a while, then the desiccant was filtered off, and the low boiling point was distilled off under reduced pressure from the filtrate. The obtained crude product was purified by column chromatography (developing solution: chloroform / hexane) and 2- {2- [4- (tert-butyl) phenyl] -10-phenylphenanthrene-9-yl} -4. , 6-Diphenyl-1,3,5-triazine was obtained as a white solid (yield 61 mg, yield 51%).

^{1 1} H-NMR (CDCl ₃ ): δ8.88 (d, J = 8.6Hz, 1H), 8.85 (d, J = 8.3Hz, 1H), 8.53 (d, J = 8.6Hz) , 4H), 7.72 (dd, J = 16.1, 8.0Hz, 2H), 7.41-7.58 (m, 14H), 7.20-7.24 (m, 3H), 7 .12 (t, J = 6.2Hz, 1H), 1.34 (s, 9H).

Synthesis Example-7

2- (2-Chloro-10-phenylphenanthrene-9-yl) -4,6-diphenyl-1,3,5-triazine (100 mg, 0.19 mmol), 2-aminopyridine-5-boron under an argon atmosphere Acid pinacol ester (55 mg, 0.25 mmol), palladium acetate (2 mg, 9.6 μmol) and 2-dicyclohexylphosphino-2', 4', 6'-triisopropylphenyl (9 mg, 19 μmol) in THF (1.3 mL) ) Was suspended. A 2.0 M-potassium phosphate aqueous solution (0.3 mL) was sequentially added to this suspension, and the mixture was stirred overnight under heating under reflux. After allowing to cool to room temperature, water and chloroform were added, the organic layer was extracted, and the organic layer was washed with water and then saturated brine. Sodium sulfate was added to the extract, and the mixture was stirred at room temperature for a while, then the desiccant was filtered off, and the low boiling point was distilled off under reduced pressure from the filtrate. The obtained crude product was separated and purified by column chromatography (developing solution: chloroform / hexane) and 5- (9- (4,6-diphenyl-1,3,5-triazine-2-yl) -10. A white solid (yield 51 mg, yield 46%) of −phenylphenanthrene-2-yl) pyridine-2-amine was obtained.

^{1 1} H-NMR (CDCl ₃ ): δ8.88 (d, J = 8.6Hz, 1H), 8.84 (d, J = 8.3Hz, 1H), 8.53 (d, J = 8.5Hz) , 4H), 8.32 (s, 1H), 7.89 (dd, J = 8.6, 1.9Hz, 1H), 7.81 (s, 1H), 7.73 (t, J = 8) .6Hz, 2H), 7.66 (dd, J = 7.2, 1.2Hz, 1H), 7.58-7.54 (m, 3H), 7.47-7.52 (m, 4H) , 7.41 (d, J = 8.3Hz, 2H), 7.23-7.21 (m, 2H), 7.13 (t, J = 5.4Hz, 1H), 6.55 (d, J = 8.5Hz, 1H), 4.48 (s, 2H).

Synthesis Example-8

2- (2-Chloro-10-phenylphenanthrene-9-yl) -4,6-diphenyl-1,3,5-triazine (100 mg, 0.19 mmol), 2-thiopheneboronic acid pinacol ester (2-thiophenanthrene-9-yl), 2-thiophenanthrene pinacol ester, under an argon atmosphere. 53 mg, 0.25 mmol), palladium acetate (2 mg, 9.6 μmol) and 2-dicyclohexylphosphino-2', 4', 6'-triisopropylphenyl (9 mg, 19 μmol) suspended in THF (1.3 mL) I let you. A 2.0 M-potassium phosphate aqueous solution (290 μL) was sequentially added to this suspension, and the mixture was stirred overnight under heating under reflux. After allowing to cool to room temperature, water and chloroform were added, the organic layer was extracted, and the organic layer was washed with water and then saturated brine. Sodium sulfate was added to the extract, and the mixture was stirred at room temperature for a while, then the desiccant was filtered off, and the low boiling point was distilled off under reduced pressure from the filtrate. The obtained crude product was separated and purified by column chromatography (developing solution: chloroform / hexane) and 2,4-diphenyl-6- (10-phenyl-2- (thiophen-2-yl) phenanthrene-9-). A white solid of yl) -1,3,5-triazine (yield 93 mg, yield 86%) was obtained.

^{1 1} H-NMR (CDCl ₃ ): δ8.83 (d, J = 8.6Hz, 1H), 8.82 (d, J = 8.2Hz, 1H), 8.54 (d, J = 8.6Hz) , 4H), 7.98 (dd, J = 8.6, 1.9Hz, 1H), 7.92 (s, 1H), 7.74 (d, J = 8.5Hz, 1H), 7.70 (D, J = 8.2Hz, 1H), 7.54-7.59 (m, 3H), 7.50 (dd, J = 8.5Hz, 4H), 7.42 (d, J = 8. 3Hz, 2H), 7.23-7.29 (m, 4H), 7.16 (t, J = 7.5Hz, 1H), 7.06 (dd, J = 5.0, 3.6Hz, 1H) ).

Synthesis Reference Example-1

Under an argon atmosphere, 2- (2-chloro-10-phenylphenanthrene-9-yl) -4,6-diphenyl-1,3,5-triazine (7.9 g, 15 mmol), bis (pinacholate) diboron (4. 6 g, 18 mmol), palladium acetate (100 mg, 0.46 mmol) and 2-dicyclohexylphosphino-2', 4', 6'-triisopropylphenyl (0.44 mg, 0.91 mmol), potassium acetate (5.4 g, 55 mmol) was suspended in THF (150 mL) and stirred under heating and reflux for 18 hours. The low boiling point was distilled off from the reaction solution under reduced pressure, and the obtained solid was washed with water, methanol and hexane, dissolved in chloroform, activated carbon was added, and the mixture was stirred for 30 minutes. After removing the activated carbon by Celite filtration, the low boiling point was distilled off from the filtrate under reduced pressure to obtain 2,4-diphenyl-6- (10-phenyl-2- (4,4,5,5-tetramethyl-1). , 3,2-Dioxaborolan-2-yl) Phenanthrene-9-yl) -1,3,5-triazine white solid (yield 5.6 g, yield 66%) was obtained.

^{1 1} H-NMR (CDCl ₃ ): δ8.88 (d, J = 8.4Hz, 1H), 8.83 (d, J = 8.4Hz, 1H), 8.52 (brd, J = 8.1Hz) , 4H), 8.20 (d, J = 0.8Hz, 1H), 8.12 (dd, J = 8.4, 1.2Hz, 1H), 7.74 (dd, J = 8.4) 0.8Hz, 1H), 7.70 (ddd, J = 8.4, 7.0, 1.2Hz, 1H), 7.60-7.46 (m, 7H), 7.40 (brd, J) = 7.8Hz, 2H), 7.23 (dd, J = 7.8, 7.5Hz, 2H), 7.12 (brt, J = 7.5Hz, 1H) 1.33 (s, 12H).

Synthesis Example-9

2,4-Diphenyl-6- (10-Phenyl-2- (4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenanthrene-9-yl)-under an argon atmosphere 1,3,5-triazine (5.6 g, 9.2 mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine (2.6 g, 9.7 mmol), tetrakis (triphenylphosphine) Palladium (320 mg, 0.28 mmol) was suspended in THF (90 mL). A 2.0 M-potassium carbonate aqueous solution (17 mL) was added to this suspension, and the mixture was stirred under heating under reflux for 18 hours. After allowing to cool to room temperature, the solid obtained by filtration was washed with water, methanol and hexane. The obtained solid was dissolved in toluene heated to 110 ° C., activated carbon was added, and the mixture was hot-filtered with Celite and then allowed to stand. By filtering the precipitated solid, a white solid of 2,9-bis (4,6-diphenyl-1,3,5-triazine-2-yl) -10-phenylphenanthrene (yield 4.0 g, yield 61) %) Was obtained.

^{1 1} H-NMR (CDCl ₃ ): δ9.25 (d, J = 1.3Hz, 1H), 9.05 (dd, J = 8.7, 1.5Hz, 1H), 9.01 (d, J) = 8.7Hz, 1H), 8.94 (d, J = 8.3Hz, 1H), 8.67 (brd, J = 7.7Hz, 4H), 8.57 (brd, J = 7.7Hz, 4H), 7.84 (brd, J = 8.3Hz, 1H), 7.78 (brdd, J = 8.3, 7.1Hz, 1H), 7.66-7.47 (m, 15H), 7.38 (dd, J = 8.0, 7.5Hz, 2H), 7.31 (brt, J = 7.5Hz, 1H).

Synthesis Reference Example-2

Under an argon atmosphere, 9-biphenyl-2-chloro-10-phenylphenanthrene (2.48 g, 5.6 mmol), bis (pinacholate) diboron (1.70 g, 6.7 mmol), potassium acetate (1.66 g, 17 mmol). , Tris (dibenzylideneacetone) dipalladium (128 mg, 0.14 mmol) and 2-dicyclohexylphosphino-2', 4', 6'-triisopropylphenyl (267 mg, 0.56 mmol) dissolved in THF (30 mL). , Heated and refluxed for 16 hours. After allowing to cool to room temperature, water and methanol were added, and the precipitated solid was collected by filtration and washed with water and methanol to obtain a crude product. By purifying the crude product by column chromatography (developing solution: hexane / chloroholom), 2- (9-([1,1'-biphenyl] -4-yl) -10-phenylphenanthrene-2-yl) ) -4,4,5,5-Tetramethyl-1,3,2-dioxaborolane (B-1) was obtained as a white solid (yield 1.47 g, yield 49%).

^{1 1} H-NMR (CDCl ₃ ): δ8.85 (d, J = 8.3Hz, 1H), 8.80 (d, J = 8.9Hz, 1H), 8.06 (dd, J = 7.3) , 1Hz, 2H), 7.59-7.69 (m, 2H), 7.67 (t, J = 8.2Hz, 1H), 7.59 (s, 1H), 7.53 (m, 1H) ), 7.48 (d, J = 8.4Hz, 2H), 7.43 (t, J = 7.3Hz, 2H), 7.33 (t, J = 7.3Hz, 1H), 7.18 -7.23 (m, 7H), 1.31 (s, 12H).

Synthesis reference example-3

Under an argon atmosphere, 10-biphenyl-3-chloro-9-phenylphenanthrene (1.90 g, 4.3 mmol), bis (pinacholate) diboron (1.30 g, 5.1 mmol), potassium acetate (1.27 g, 13 mmol) , Tris (dibenzylideneacetone) dipalladium (100 mg, 0.11 mmol) and 2-dicyclohexylphosphino-2', 4', 6'-triisopropylphenyl (200 mg, 0.42 mmol) dissolved in THF (30 mL). , 9.5 hours heating and refluxing. After allowing to cool to room temperature, water and methanol were added, and the precipitated solid was collected by filtration and washed with water and methanol to obtain a crude product. By purifying the crude product by column chromatography (developing solution: hexane / chloroholom), 2- (10-([1,1'-biphenyl] -4-yl) -9-phenylphenanthrene-3-yl) ) -4,4,5,5-Tetramethyl-1,3,2-dioxaborolane (B-2) was obtained as a white solid (yield 1.45 g, yield 63%).

^{1 1} H-NMR (CDCl ₃ ): δ9.31 (s, 1H), 8.98 (d, J = 8.3Hz, 1H), 7.88 (dd, J = 8.2,1.0Hz, 1H) ), 7.68 (t, J = 8.3Hz, 1H), 7.63-7.60 (m, 3H), 7.57 (dd, J = 8.2,1.0Hz, 1H), 7 .50 (dd, J = 8.3, 1.8Hz, 2H), 7.49 (m, 1H), 7.43 (t, J = 7.3Hz, 2H), 7.32 (t, J = 7.3Hz, 1H), 7.17-7.25 (m, 7H), 1.43 (s, 12H).

Synthesis Example-10

Under an argon atmosphere, with 2,4-diphenyl-6- (2'-(phenylethynyl)-[1,1'-biphenyl] -4-yl) -1,3,5-triazine (12.4 g, 26 mmol). Copper (II) bromide (17.6 g, 79 mmol) and potassium phosphate (2.72 g, 13 mmol) were suspended in nitromethane (240 mL) and stirred under heating and reflux for 2 days. After allowing to cool to room temperature, chloroform was added to the reaction solution, copper salts were removed by filtration through Celite, and the low boiling point was distilled off under reduced pressure. By recrystallizing the obtained crude product with toluene, a white solid of 2- (9-bromo-10-phenylphenanthrene-2-yl) -4,6-diphenyl-1,3,5-triazine ( Yield 8.77 g, yield 61%) was obtained.

^{1 1} H-NMR (CDCl ₃ ): 8.87-8.89 (m, 2H), 8.81 (d, J = 8.6Hz, 1H), 8.77-8.80 (m, 1H), 8.61 (d, J = 7.0Hz, 4H), 8.55-8.58 (m, 1H), 7.75-7.80 (m, 2H), 7.67-7.68 (m) , 3H), 7.60 (t, J = 7.2Hz, 2H), 7.48-7.55 (m, 6H).

Synthesis Example-11

2- (9-Bromo-10-phenylphenanthrene-2-yl) -4,6-diphenyl-1,3,5-triazine (300 mg, 0.53 mmol), 2-thiophenanthrene acid (82 mg,) under an argon atmosphere. 0.64 mmol), palladium acetate (12 mg, 53 μmol), tri (cyclohexyl) phosphine toluene solution (0.6 M, 180 μL), and 2.0 M-potassium phosphate aqueous solution (800 μL) were suspended in dimethylformamide (2 mL). The mixture was heated and stirred at 110 ° C. for 15 hours. After cooling to room temperature, separation was performed by column chromatography and size exclusion chromatography to obtain a crude product. When this crude product was analyzed by HPLC, the crude product was 2,4-diphenyl-6- (10-phenyl-9- (thiophen-2-yl) phenanthrene-2-yl) -1,3, 5-Triazine was contained in a yield of 23%.

^{1 1} H-NMR (CDCl ₃ ): δ9.09 (s, 1H), 8.98 (m, 1H), 8.95 (d, J = 8.7Hz, 1H), 8.88 (d, J = 8.7Hz, 1H), 8.65 (d, J = 6.9Hz, 4H), 7.88 (t, J = 8.2Hz, 1H), 7.75 (t, J = 8.2Hz, 1H) ), 7.53-7.65 (m, 7H), 7.44-7.48 (m, 3H), 7.37-7.39 (m, 2H), 7.31 (dd, J = 5) .1,1.2Hz, 1H), 7.00 (dd, J = 5.1,3.4Hz, 1H), 6.96 (dd, J = 3.4,1.2Hz, 1H).

Synthesis Example-12

2- (9-Bromo-10-phenylphenanthrene-2-yl) -4,6-diphenyl-1,3,5-triazine (300 mg, 0.53 mmol), benzofuran-2-boronic acid pinacol ester under an argon atmosphere (103 mg, 0.64 mmol), palladium acetate (12 mg, 53 μmol), tri (cyclohexyl) phosphenyl toluene solution (0.6 M, 180 μL), and 2.0 M-potassium phosphate aqueous solution (800 μL) in dimethylformamide (2 mL). It was suspended and heated and stirred at 110 ° C. for 15 hours. After cooling to room temperature, separation was performed by wet column chromatography and size exclusion chromatography to obtain a crude product. When this crude product was analyzed by HPLC, the crude product was 2- (9- (benzofuran-2-yl) -10-phenylphenanthrene-2-yl) -4,6-diphenyl-1,3. 5-Triazine was contained in a yield of 4%.

^{1 1} H-NMR (CDCl ₃ ): δ9.18 (s, 1H), 9.02 (dd, J = 8.7, 1.7Hz, 1H), 8.96 (d, J = 8.2Hz, 1H) ), 8.89 (d, J = 8.2Hz, 1H), 8.66 (d, J = 6.9Hz, 4H), 7.81 (d, J = 8.2Hz, 1H), 7.76 (T, J = 8.2Hz, 1H), 7.55-7.65 (m, 7H), 7.49-7.54 (m, 3H), 7.43-7.47 (m, 4H) , 7.29 (m, 1H), 7.22 (m, 1H), 6.56 (s, 1H).

Synthesis Example-13

2- (9-Bromo-10-phenylphenanthrene-2-yl) -4,6-diphenyl-1,3,5-triazine (300 mg, 0.53 mmol), 2-phenylpyridine-5-boron under an argon atmosphere Acid pinacol ester (179 mg, 0.64 mmol), palladium acetate (12 mg, 53 μmol), tri (cyclohexyl) phosphenyl toluene solution (0.6 M, 180 μL), and 2.0 M-potassium phosphate aqueous solution (800 μL) were added to dimethylformamide (800 μL). It was suspended in 2 mL) and heated and stirred at 110 ° C. for 15 hours. After cooling to room temperature, separation was performed by column chromatography and size exclusion chromatography to obtain a crude product. When this crude product was analyzed by HPLC, the crude product was 2,4-diphenyl-6- (10-phenyl-9- (6-phenylpyridine-3-yl) phenanthrene-2-yl) -1. , 3,5-Triazine was contained in a yield of 9%.

^{1 1} H-NMR (CDCl ₃ ): δ9.11 (s, 1H), 8.96-9.00 (m, 2H), 8.92 (d, J = 8.2Hz, 1H), 8.64 ( d, J = 7.0Hz, 4H), 8.04 (d, J = 7.1Hz, 2H), 7.77 (t, J = 8.2Hz, 1H), 7.31-7.72 (m) , 19H).

Synthesis Example-14

2- (9-Bromo-10-phenylphenanthrene-2-yl) -4,6-diphenyl-1,3,5-triazine (300 mg, 0.53 mmol), 1.2 molar equivalents of triphenylene boron under an argon atmosphere Acid (173 mg, 0.64 mmol), palladium acetate (12 mg, 53 μmol), tri (cyclohexylphosphyl) phosphine toluene solution (0.6 M, 180 μL), and 2.0 M-potassium phosphate aqueous solution (800 μL) in dimethylformamide (2 mL) It was suspended in 1 and heated and stirred at 110 ° C. for 15 hours. After cooling to room temperature, the mixture was separated by wet column chromatography to obtain a crude product. When this crude product was analyzed by HPLC, the crude product was 2,4-diphenyl-6- (10-phenyl-9- (triphenylene-2-yl) phenanthrene-2-yl) -1,3, 5-Triazine was contained in a yield of 6%.

^{1 1} H-NMR (CDCl ₃ ): δ9.17 (s, 1H), 9.02 (s, 2H), 8.95 (d, J = 8.0Hz, 1H), 8.58-8.67 ( m, 7H), 8.69 (d, J = 8.2Hz, 2H), 8.59 (d, J = 7.9Hz, 1H), 7.52-7.77 (m, 14H), 7. 39-7.42 (m, 2H), 7.35 (t, J = 6.8Hz, 1H), 7.28-7.30 (m, 2H).

Synthesis Reference Example-4

Under an argon atmosphere, 3- (2-chloro-10-phenylphenanthrene-9-yl) pyridine (874 mg, 2.4 mmol), bis (pinacholate) diboron (728 mg, 2.9 mmol), potassium acetate (1.66 g, 17 mmol). ), Tris (dibenzylideneacetone) dipalladium (128 mg, 60 μmol) and 2-dicyclohexylphosphino-2', 4', 6'-triisopropylphenyl (267 mg, 0.24 mmol) are dissolved in THF (10 mL). Heat reflux was performed for 14 hours. After allowing to cool to room temperature, water and methanol were added, and the precipitated solid was collected by filtration and washed with water and methanol to obtain a crude product. The obtained crude product was purified by wet column chromatography (developing solution: hexane / chloroholom) to 3- (10-phenyl-2- (4,4,5,5-tetramethyl-1,3). , 2-Dioxaborolan-2-yl) phenanthrene-9-yl) A white solid of pyridine (yield 731 mg, yield 67%) was obtained.

^{1 1} H-NMR (CDCl ₃ ): δ8.86 (d, J = 8.2Hz, 1H), 8.80 (d, J = 8.2Hz, 1H), 6.44 (d, J = 6.5Hz) , 1H), 8.42 (s, 1H), 8.08 (d, J = 8.3Hz, 1H), 8.05 (s, 1H), 7.69 (t, J = 8.3Hz, 1H) ), 7.53 (dt, J = 8.2,1.1 Hz, 1H), 7.44-7.48 (m, 2H), 7.12-7.28 (m, 6H), 1.31 (S, 12H).

Synthesis Example-15

3- (10-Phenyl-2- (4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenanthrene-9-yl) pyridine (100 mg, 0.22 mmol) under an argon atmosphere ), 2-Chloro-4,6-diphenyl-1,3,5-triazine (70 mg, 0.26 mmol), tetrakistriphenylphosphine palladium (25 mg, 22 μmol), and 2.0 M-potassium phosphate aqueous solution (330 μL). Was suspended in 1,4-dioxane (1 mL) and heated and stirred for 12 hours. After allowing to cool to room temperature, water and methanol were added, and the precipitated solid was collected by filtration and washed with water and methanol to obtain a crude product. By purifying the obtained crude product by column chromatography (developing solution: ethyl acetate / chloroholom), 2,4-diphenyl-6- (10-phenyl-9- (pyridin-3-yl) phenanthrene- A white solid of 2-yl) -1,3,5-triazine (yield 71 mg, yield 58%) was obtained.

^{1 1} H-NMR (CDCl ₃ ): δ9.11 (s, 1H), 8.99-9.02 (m, 2H), 8.93 (d, J = 8.2Hz, 1H), 8.64- 8.67 (m, 4H), 8.54 (m, 1H), 8.51 (dd, J = 4.9, 1.7Hz, 1H), 7.77 (t, J = 8.3Hz, 1H) ), 7.52-7.63 (m, 10H), 7.40-7.42 (m, 3H), 7.28-7.33 (m, 2H).

Synthesis Example-16

3- (10-Phenyl-2- (4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenanthrene-9-yl) pyridine (100 mg, 0.22 mmol) under an argon atmosphere ), 2,4-Di ([1,1'-biphenyl] -4-yl) -6-chloro-1,3,5-triazine (110 mg, 0.26 mmol), tetrakistriphenylphosphine palladium (25 mg, 22 μmol) ), And 2.0 M-potassium phosphate aqueous solution (330 μL) were suspended in 1,4-dioxane (1 mL), and heated and stirred for 12 hours. After allowing to cool to room temperature, water and methanol were added, and the precipitated solid was collected by filtration and washed with water and methanol to obtain a crude product. The obtained crude product was purified by column chromatography (developing solution: ethyl acetate / chloroholom) to result in 2,4-di ([1,1'-biphenyl] -4-yl) -6- (10). A white solid (yield 130 mg, yield 83%) of −phenyl-9- (pyridin-3-yl) phenanthrene-2-yl) -1,3,5-triazine was obtained.

^{1 1} H-NMR (CDCl ₃ ): δ9.12 (s, 1H), 8.97-9.03 (m, 2H), 8.93 (d, J = 8.3Hz, 1H), 8.71 ( d, J = 7.8Hz, 4H), 8.54 (s, 1H), 8.51 (dd, J = 4.9, 1.7Hz, 1H), 7.76 (m, 5H), 7. 71 (d, J = 7.4Hz, 4H), 7.56-7.62 (m, 3H), 7.51 (t, J = 7.2Hz, 4H), 7.40-7.44 (m) , 5H), 7.28-7.35 (m, 2H), 7.24-7.27 (m, 1H).

Synthesis Example-17

3- (10-Phenyl-2- (4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenanthrene-9-yl) pyridine (100 mg, 0.22 mmol) under an argon atmosphere ), 2,4-Bis (4- (t-butyl) phenyl) -6-chloro-1,3,5-triazine (100 mg, 0.26 mmol, tetrakistriphenylphosphenyl palladium (25 mg, 22 μmol), and 2. A 0M-potassium phosphate aqueous solution (330 μL) was suspended in 1,4-dioxane (1 mL), heated and stirred for 12 hours. After allowing to cool to room temperature, water and methanol were added, and the precipitated solid was collected by filtration, and water and stirring were performed. The crude product was washed with methanol to obtain a crude product. The obtained crude product was purified by column chromatography (developing solution: ethyl acetate / chlorophorome) to obtain 2,4-bis (4- (t-butyl)). A white solid (yield 91 mg, yield 61%) of phenyl) -6- (10-phenyl-9- (pyridin-3-yl) phenanthrene-2-yl) -1,3,5-triazine was obtained.

^{1 1} H-NMR (CDCl ₃ ): δ9.08 (s, 1H), 8.98-9.01 (m, 2H), 8.93 (d, J = 8.2Hz, 1H), 8.54- 8.57 (m, 1H), 8.55 (d, J = 8.6Hz, 4H), 8.51 (dd, J = 5.0, 1.7Hz, 1H), 7.77 (t, J) = 6.6Hz, 1H), 7.57-7.61 (m, 3H), 7.55 (d, J = 8.6Hz, 4H), 7.40-7.44 (m, 3H), 7 .31-7.33 (m, 2H), 7.27-7.30 (m, 1H), 1.41 (s, 18H).

Synthesis Example-18

3- (10-Phenyl-2- (4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenanthrene-9-yl) pyridine (100 mg, 0.22 mmol) under an argon atmosphere ), 2-Chloro-4,6-bis (4-methoxyphenyl) -1,3,5-triazine (86 mg, 0.26 mmol), tetrakistriphenylphosphine palladium (25 mg, 22 μmol), and 2.0 M-phosphorus. An aqueous potassium phosphate solution (330 μL) was suspended in 1,4-dioxane (1 mL), and the mixture was heated and stirred for 12 hours. After allowing to cool to room temperature, water and methanol were added, and the precipitated solid was collected by filtration and washed with water and methanol to obtain a crude product. The obtained crude product was purified by column chromatography (developing solution: ethyl acetate / chloroholom) to obtain 2,4-bis (4-methoxyphenyl) -6- (10-phenyl-9- (pyridine-). A white solid (yield 95 mg, yield 70%) of 3-yl) phenylanthren-2-yl) -1,3,5-triazine was obtained.

^{1 1} H-NMR (CDCl ₃ ): δ9.06 (s, 1H), 8.96 (m, 2H), 8.92 (d, J = 8.3Hz, 1H), 8.58 (d, J = 8.8Hz, 4H), 8.55 (s, 1H), 8.52 (dd, J = 4.9, 1.6Hz, 1H), 7.77 (t, J = 8.0Hz, 1H), 7.56-7.63 (m, 3H), 7.40-7.43 (m, 3H), 7.29-7.34 (m, 2H), 7.25 (m, 1H), 7. 03 (d, J = 8.8Hz, 4H), 3.94 (s, 6H).

Synthesis Example-19

3- (10-Phenyl-2- (4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenanthrene-9-yl) pyridine (100 mg, 0.22 mmol) under an argon atmosphere ), 2-Chloro-4,6-bis (4- (neopentylthio) phenyl) -1,3,5-triazine (116 mg, 0.26 mmol), tetrakistriphenylphosphine palladium (25 mg, 22 μmol), and 2 A 0.0M-potassium phosphate aqueous solution (330 μL) was suspended in 1,4-dioxane (1 mL), and the mixture was heated and stirred for 12 hours. After allowing to cool to room temperature, water and methanol were added, and the precipitated solid was collected by filtration and washed with water and methanol to obtain a crude product. Obtained. By purifying the crude product by column chromatography (developing solution: ethyl acetate / chloroholom), 2,4-bis (4- (neopentylthio) phenyl) -6- (10-phenyl-9- (pyridine) −3-Il) Phenanthrene-2-yl) -1,3,5-triazine was obtained as a white solid (yield 107 mg, yield 64%).

^{1 1} H-NMR (CDCl ₃ ): δ9.05 (s, 1H), 8.96 (m, 2H), 8.92 (d, J = 8.3Hz, 1H), 8.54 (s, 1H) , 8.52 (m, 1H), 8.50 (d, J = 8.5Hz, 4H), 7.76 (t, J = 8.3Hz, 1H), 7.62-7.51 (m, 3H), 7.43-7.40 (m, 3H), 7.42 (d, J = 8.5Hz, 4H), 7.32-7.24 (m, 3H), 3.00 (s,, 4H), 1.11 (s, 18H).

Synthesis Example-20

3- (10-Phenyl-2- (4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenanthrene-9-yl) pyridine (100 mg, 0.22 mmol) under an argon atmosphere ), 4-Chloro-2,6-diphenylpyrimidine (70 mg, 0.26 mmol), tetrakistriphenylphosphine palladium (25 mg, 22 μmol), and 2.0 M-potassium phosphate aqueous solution (330 μL), 1,4-dioxane ( It was suspended in 1 mL) and heated and stirred for 12 hours. After allowing to cool to room temperature, water and methanol were added, and the precipitated solid was collected by filtration and washed with water and methanol to obtain a crude product. By purifying the obtained crude product by column chromatography (developing solution: ethyl acetate / chloroholom), 2,4-biphenyl-6- (10-phenyl-9- (pyridin-3-yl) phenanthrene- A white solid of 2-yl) pyrimidine (yield 105 mg, yield 85%) was obtained.

^{1 1} H-NMR (CDCl ₃ ): δ8.97 (d, J = 8.8Hz, 1H), 8.90 (d, J = 8.2Hz, 1H), 8.68 (s, 1H), 8. 58-8.54 (m, 3H), 8.52 (s, 1H), 8.50 (d, J = 2.8Hz, 1H), 8.22-8.25 (m, 2H), 7. 97 (s, 1H), 7.76 (t, J = 8.2Hz, 1H), 7.54-7.61 (m, 6H), 7.55-7.52 (m, 3H), 7. 35-7.41 (m, 3H), 7.22-7.31 (m, 3H).

Synthesis Example-21

3- (10-Phenyl-2- (4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenanthrene-9-yl) pyridine (100 mg, 0.22 mmol) under an argon atmosphere ), 2-([1,1'-biphenyl] -4-yl) -4-chloro-6-phenyl-1,3,5-triazine (67 mg, 0.19 mmol), tetrakistriphenylphosphine palladium (19 mg, 16 μmol) and 2.0 M-potassium phosphate aqueous solution (240 μL) were suspended in 1,4-dioxane (700 μL), and the mixture was heated and stirred for 12 hours. After allowing to cool to room temperature, water and methanol were added, and the precipitated solid was collected by filtration and washed with water and methanol to obtain a crude product. The obtained crude product was purified by column chromatography (developing solution: ethyl acetate / chloroholom) to 2-([1,1'-biphenyl] -4-yl) -4-phenyl-6-(. A white solid of 10-phenyl-9- (pyridin-3-yl) phenanthrene-2-yl) -1,3,5-triazine (yield 67 mg, 65% yield) was obtained.

^{1 1} H-NMR (CDCl ₃ ): δ9.10 (s, 1H), 9.00 (d, J = 8.7Hz, 1H), 8.96 (d, J = 8.7Hz, 1H), 8. 91 (d, J = 8.2Hz, 1H), 8.69 (d, J = 8.4Hz, 2H), 8.65 (d, J = 8.4Hz, 2H), 8.54 (s, 1H) ), 8.50 (d, J = 3.7Hz, 1H), 7.74 (m, 1H), 7.75 (d, J = 8.4Hz, 2H), 7.71 (d, J = 8) .4Hz, 2H), 7.62-7.49 (m, 4H), 7.53 (d, J = 8.2Hz, 2H), 7.50 (d, J = 7.7Hz, 2H), 7 .40-7.44 (m, 4H), 7.23-7.33 (m, 3H).

Synthesis Reference Example-5

4-Bromo-3-iodophenol (16 g, 52 mmol), dichlorobis (triphenylphosphine) palladium (0.70 g, 1.0 mmol), copper (I) iodide (0.38 g, 2.0 mmol) under an argon atmosphere. Was stirred in triethylamine (100 mL) at room temperature for 15 minutes. Phenylacetylene (6.3 mL, 57 mmol) was added to the reaction solution, and the mixture was stirred at room temperature for 18 hours. The low boiling point was distilled off from the reaction solution under reduced pressure, the mixture was quenched with a 28% aqueous ammonia solution, and then extracted with chloroform. The extract was washed with a 1 M aqueous solution of hydrochloric acid and saturated brine, and the low boiling point was distilled off from the extract under reduced pressure to obtain 4-bromo-3- (2-phenylethynyl) phenol (10 g, 71%). ).

^{1 1} H-NMR (CDCl ₃ ): δ7.57 (m, 2H), 7.45 (d, J = 8.6Hz, 1H), 7.36 (m, 3H), 7.04 (d, J = 3.0Hz, 1H), 6.71 (dd, J = 8.6, 3.0Hz, 1H), 4.90 (brs, 1H).

Synthesis Reference Example-6

Under an argon atmosphere, 4-bromo-3- (2-phenylethynyl) phenol (10 g, 37 mmol), 4-chlorophenylboronic acid (6.3 g, 40 ml), dichlorobis (triphenylphosphine) palladium (0.51 g, 0. 73 mmol) was suspended in THF (370 mL). A 2.0 M-potassium carbonate aqueous solution (37 mL, 74 mmol) was added to this suspension, and the mixture was stirred at 80 ° C. for 18 hours. The low boiling point was distilled off from the reaction solution under reduced pressure, the mixture was extracted with chloroform, the extract was dried over sodium sulfate, and the desiccant was removed by filtration. The low boiling point was distilled off from the obtained filtrate under reduced pressure to obtain 4'-chloro-2- (2-phenylethynyl) -1,1'-biphenyl-4-ol (9.5 g, 81%). ..

^{1 1} H-NMR (CDCl ₃ ): δ7.56 (brd, J = 8.4Hz, 2H), 7.40 (brd, J = 8.4Hz, 2H), 7.37-7.29 (m, 5H) ), 7.26 (d, J = 8.2Hz, 1H), 7.11 (d, J = 2.6Hz, 1H), 6.89 (dd, J = 8.2,2.6Hz, 1H) , 5.03 (brs, 1H).

Synthesis Reference Example-7

Dissolve 4'-chloro-2- (2-phenylethynyl) -1,1'-biphenyl-4-ol (2.6 g, 8.5 mmol) in chloroform (20 mL) and add trifluoroacetic acid (20 mL). The mixture was stirred at room temperature for 17 hours. The low boiling point was distilled off from the reaction solution under reduced pressure, and the obtained oily substance was purified by column chromatography (developing solvent: hexane: chloroform: ethyl acetate = 10: 1: 1) to 7-chloro-9-. Phenylphenanthrene-2-ol was obtained (1.6 g, 61%).

^{1 1} H-NMR (CDCl ₃ ): δ8.60 (d, J = 2.2Hz, 1H), 8.52 (d, J = 9.7Hz, 1H), 7.79 (d, J = 8.8Hz) , 1H), 7.56-7.43 (m, 5H), 7.50 (s, 1H), 7.40 (dd, J = 8.8, 2.2Hz, 1H), 7.25-7 .22 (m, 2H).

Synthesis Reference Example-8

7-Chloro-9-phenylphenanthrene-2-ol (0.70 g, 2.3 mmol) was dissolved in chloroform (25 mL), trifluoromethanesulfonic anhydride (0.77 mL, 4.6 mmol) and pyridine (0.74 mL). , 9.2 mmol) was added at 0 ° C., and the mixture was stirred at room temperature for 18 hours. The reaction solution was quenched with a 1 M aqueous hydrochloric acid solution and then extracted with chloroform. The extract was washed with saturated aqueous sodium hydrogen carbonate solution, dried over sodium sulfate, and then the desiccant was removed by filtration. The low boiling point was distilled off from the obtained filtrate under reduced pressure to obtain 7-chloro-9-phenylphenanthrene-2-yltrifluoromethanesulfonate (0.95 g, 95%).

^{1 1} H-NMR (CDCl ₃ ): δ8.71 (d, J = 9.2Hz, 1H), 8.68 (d, J = 2.1Hz, 1H), 7.88 (d, J = 8.8Hz) , 1H), 7.79 (d, J = 2.5Hz, 1H), 7.67 (s, 1H), 7.61-7.46 (m, 7H).

Synthesis Reference Example-9

Under an argon atmosphere, 7-chloro-9-phenylphenanthrene-2-yltrifluoromethanesulfonate (2.6 g, 6.0 mmol), phenylboronic acid (0.79 g, 6.5 mmol), dichlorobis (triphenylphosphine) palladium ( 0.13 g, 0.18 mmol) was suspended in THF (60 mL). A 2.0 M-potassium carbonate aqueous solution (6.0 mL, 12 mmol) was added to this suspension, and the mixture was stirred at 80 ° C. for 17 hours. The low boiling point was distilled off from the reaction solution under reduced pressure, the mixture was extracted with chloroform, the extract was dried over sodium sulfate, and the desiccant was removed by filtration. A crude product of 2-chloro-7,10-diphenylphenanthrene was obtained by distilling off the low boiling point from the obtained filtrate under reduced pressure (2.2 g).
Under an argon atmosphere, this crude product and bispinacolato diboron (1.8 g, 7.2 mmol), palladium acetate (40 mg, 0.18 mmol), 2-dicyclohexylphosphino-2', 4', 6'-tri Isopropylbiphenyl (0.17 g, 0.36 mmol) and potassium acetate (2.1 g, 22 mmol) were suspended in THF (60 mL), and the mixture was stirred at 80 ° C. for 16 hours. The low boiling point was distilled off from the reaction solution under reduced pressure, the mixture was extracted with chloroform, the extract was dried over sodium sulfate, and the desiccant was removed by filtration. After distilling off the low boiling point from the obtained filtrate under reduced pressure, the obtained solid was washed with methanol to 2- (7,10-diphenylphenanthrene-2-yl) -4,4,5,5-. Tetramethyl-1,3,2-dioxaborolane was obtained (2.1 g, 77%).

^{1 1} H-NMR (CDCl ₃ ): δ9.28 (brs, 1H), 8.94 (brd, J = 8.7Hz, 1H), 8.10 (d, J = 2.0Hz, 1H), 7. 96-7.88 (m, 3H), 7.81-7.75 (m, 3H), 7.60-7.44 (m, 7H), 7.40 a (brt, J = 7.4Hz, 1H), 1.43 (s, 12H).

Synthesis Example-22

2- (4-Biphenyl) -4-chloro-6-phenyl-1,3,5-triazine (1.6 g, 4.6 mmol), 2- (7,10-diphenylphenanthrene-2-yl) under an argon atmosphere ) -4,4,5,5-Tetramethyl-1,3,2-dioxaborolane (2.0 g, 4.4 mmol), dichlorobis (triphenylphosphine) palladium (0.15 g, 0.13 mmol) in THF (40 mL) ) Suspended in. A 2.0 M-potassium carbonate aqueous solution (8.0 mL, 16 mmol) was added to this suspension, and the mixture was stirred at 80 ° C. for 18 hours. After allowing to cool to room temperature, water and hexane were added to the reaction mixture, and the precipitated solid was collected by filtration and washed with water, methanol and hexane. The obtained solid is dissolved in toluene heated to 110 ° C., activated charcoal is added, and the mixture is filtered at hot temperature using Celite, then allowed to stand, and the precipitated solid is collected by filtration to obtain 2- (4-biphenyl)-. 4- (7,10-diphenylphenanthrene-2-yl) -6-phenyl-1,3,5-triazine was obtained (1.9 g, 68%).

^{1 1} H-NMR (CDCl ₃ ): δ10.3 (brs, 1H), 9.09 (d, J = 8.5Hz, 1H), 8.95-8.86 (m, 5H), 8.16 ( Brs, 1H), 8.13 (d, J = 8.5Hz, 1H), 8.08 (brd, J = 9.0Hz, 1H), 7.88 (s, 1H), 7.87 (d, J = 8.5Hz, 2H), 7.82 (brd, J = 8.0Hz, 2H), 7.75 (brd, J = 8.0Hz, 2H), 7.68-7.48 (m, 12H) ), 7.43 (m, 2H).

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

Device Example-1 (see FIG. 2)
(Preparation of substrate 1 and anode 2)
As a substrate having an anode on its surface, a glass substrate with an ITO transparent electrode in which a 2 mm wide indium tin oxide (ITO) film (thickness 110 nm) was patterned in a stripe shape was prepared. Then, after cleaning this substrate with isopropyl alcohol, surface treatment was performed by ozone ultraviolet cleaning.

(Preparation for vacuum deposition)
Each layer was vacuum-deposited by a vacuum-film deposition method on the surface-treated substrate after cleaning, and each layer was laminated and formed.
First, the glass substrate was introduced into a vacuum vapor deposition tank, and the pressure was reduced to ^{1.0 × 10 -4 Pa.} Then, each layer was produced in the following order according to the film forming conditions of each layer.

(Preparation of hole injection layer 3)
The sublimated and purified HIL was formed into a 55 nm film at a rate of 0.15 nm / sec to prepare a hole injection layer.

(Preparation of charge generation layer 4)
The sublimated and purified HAT was formed into a 5 nm film at a rate of 0.05 nm / sec to prepare a charge generation layer.

(Preparation of the first hole transport layer 51)
HTL-1 was formed into a 10 nm film at a rate of 0.15 nm / sec to prepare a first hole transport layer.

(Preparation of second hole transport layer 52)
HTL-2 was formed into a 10 nm film at a rate of 0.15 nm / sec to prepare a second hole transport layer.

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

(Preparation of the first electron transport layer 71)
ETL-1 was formed into a 5 nm film at a rate of 0.15 nm / sec to prepare a first electron transport layer 7.

(Preparation of the second electron transport layer 72)
Synthesis The 2,4-diphenyl-6- [10-phenyl-2- (3-pyridyl) phenanthrene-9-yl] -1,3,5-triazine (Compound 1-1) and Liq synthesized in Example-2. Was formed at a ratio of 50:50 (mass ratio) at 25 nm to prepare a second electron transport layer 71. The film forming rate was 0.15 nm / sec.

(Preparation of cathode 8)
Finally, a metal mask was arranged so as to be orthogonal to the ITO stripe on the substrate, and the cathode 8 was formed into a film. As the cathode, silver / magnesium (mass ratio 1/10) and silver were formed in this order at 80 nm and 20 nm, respectively, to form a two-layer structure. The film formation rate of silver / magnesium was 0.5 nm / sec, and the film formation rate of silver was 0.2 nm / sec.

^{As described above, the 2} organic electroluminescent device 100 having a light emitting area of 4 mm as shown in FIG. 2 was manufactured. Each film thickness was measured with a stylus type film thickness measuring meter (DEKTAK, manufactured by Bruker).

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

A direct current was applied to the organic electroluminescent element produced as described above, and the emission characteristics were evaluated using a luminance meter (product name: BM-9, manufactured by Topcon Technohouse Co., Ltd.). As a light emitting characteristic, the current efficiency (cd / A) when a current density of 10 mA / cm ² was passed was measured, and the element life (h) at the time of continuous lighting was measured. Incidentally, Table 1 of element lifetime (h), the luminance decay time at the time of continuous lighting when driving was prepared device at an initial luminance 1000 cd / ^{m 2} was measured, until the luminance (cd / ^{m 2)} is reduced by 15% The time required for was measured. The current efficiency and the device life are relative values using the result in the device reference example 1 described later as a reference value (100). The obtained measurement results are shown in Table 1.

Element Example-2
In the device Example-1, 2,4-diphenyl-6- (10-phenyl- [2,9'-biphenanthrene] -9-yl) -synthesized in Synthesis Example-3 instead of Compound 1-1. An organic electroluminescent device was prepared and evaluated in the same manner as in Device Example-1 except that 1,3,5-triazine (Compound 1-2) was used. The obtained measurement results are shown in Table 1.

Element reference example-1
In Device Example-1, 2- [5- (9-phenanthryl) -3- (3-pyridyl) phenyl] -4,6-diphenyl-1 described in Patent Document 1 instead of Compound 1-1. , 3,5-Triazine (ETL-2) was used, but an organic electroluminescent device was prepared and evaluated in the same manner as in Device Example-1. The obtained measurement results are shown in Table 1.

The cyclic azine compound according to one aspect of the present disclosure is extremely excellent in heat resistance of the film quality, and by using the compound, an organic electroluminescent device having excellent current efficiency can be provided.

Further, the cyclic azine compound according to one aspect of the present disclosure provides a material which is excellent in operability of sublimation purification because it has good thermal stability during sublimation purification and has few impurities which cause element deterioration of the organic electroluminescent element. can do. Further, the cyclic azine compound according to one aspect of the present disclosure can provide an organic electroluminescent device having a long life because the vapor deposition film is excellent in stability.

Further, since the thin film made of the cyclic azine compound according to one aspect of the present disclosure is excellent in electron transporting ability, hole blocking ability, redox resistance, water resistance, oxygen resistance, electron injection characteristics and the like, it is a material for an organic electroluminescent element. It is useful as an electron transporting material, a hole blocking material, a light emitting host material, and the like. It is especially useful when used as an electron transport material.

1 substrate 2 anode 3 hole injection layer 4 charge generation layer 5 hole transport layer 6 light emitting layer 7 electron transport layer 8 cathode 51 first hole transport layer 52 second hole transport layer 71 first electron transport layer 72 second Electron transport layer 100 Organic electroluminescent element

Claims (19)

Cyclic azine compound represented by the formula (1-A):

During the ceremony
Ar ¹ and Ar ² are independent of each other.
(I) Aromatic hydrocarbon groups of monocyclic, linked or condensed rings having 6 to 20 carbon atoms,
(Ii) Aromatic heterocyclic groups of monocycles, linking rings, or condensed rings having 4 to 20 carbon atoms, or
(Iii) The aromatic hydrocarbon group or aromatic heterocyclic group is a fluorine atom, an alkyl group having 1 to 10 carbon atoms, an alkyl halide group having 1 to 3 carbon atoms, or an aromatic hydrocarbon having 6 to 30 carbon atoms. Represents a group substituted with one or more groups selected from the group consisting of groups and aromatic heterocyclic groups having 4 to 30 carbon atoms;
R is
(Iv) Halogen atom, alkyl group having 1 to 10 carbon atoms, alkyloxy group having 1 to 10 carbon atoms, cyano group, amino group, nitro group, acyl group having 1 to 10 carbon atoms,
(V) Aromatic hydrocarbon groups of a monocyclic ring, a linking ring, or a condensed ring having 6 to 30 carbon atoms.
(Vi) An aromatic heterocyclic group having a monocyclic ring, a linking ring, or a condensed ring having 4 to 30 carbon atoms, or
(Vii) The aromatic hydrocarbon group or aromatic heterocyclic group is a fluorine atom, an alkyl group having 1 to 10 carbon atoms, an alkyl halide group having 1 to 3 carbon atoms, or an aromatic hydrocarbon having 6 to 30 carbon atoms. Represents a group substituted with one or more groups selected from the group consisting of groups and aromatic heterocyclic groups having 4 to 30 carbon atoms;
Ra is
(A1) Hydrogen atom, halogen atom, alkyl group having 1 to 10 carbon atoms, alkyloxy group having 1 to 10 carbon atoms, cyano group, amino group, nitro group, acyl group having 1 to 10 carbon atoms,
(A2) An aromatic hydrocarbon group having a monocyclic ring, a linking ring, or a condensed ring having 6 to 30 carbon atoms.
(A3) An aromatic heterocyclic group having a monocycle, a linking ring, or a condensed ring having 4 to 30 carbon atoms, or
(A4) The aromatic hydrocarbon group or aromatic heterocyclic group is a fluorine atom, an alkyl group having 1 to 10 carbon atoms, an alkyl halide group having 1 to 3 carbon atoms, or an aromatic hydrocarbon having 6 to 30 carbon atoms. Represents a group substituted with one or more groups selected from the group consisting of groups and aromatic heterocyclic groups having 4 to 30 carbon atoms;
n represents an integer from 1 to 8.
However, if Ra is a hydrogen atom, n represents an integer from 2 to 8;
Multiple Rs may be the same or different;
Y ¹ and Y ² independently represent a nitrogen atom or CH, respectively.
At ^{least one of Y 1} and Y ² is a nitrogen atom. Cyclic azine compound represented by the formula (1-B):

During the ceremony
Ar ¹ and Ar ² are independent of each other.
(I) Aromatic hydrocarbon groups of monocyclic, linked or condensed rings having 6 to 20 carbon atoms,
(Ii) Aromatic heterocyclic groups of monocycles, linking rings, or condensed rings having 4 to 20 carbon atoms, or
(Iii) The aromatic hydrocarbon group or aromatic heterocyclic group is a fluorine atom, an alkyl group having 1 to 10 carbon atoms, an alkyl halide group having 1 to 3 carbon atoms, or an aromatic hydrocarbon having 6 to 30 carbon atoms. Represents a group substituted with one or more groups selected from the group consisting of groups and aromatic heterocyclic groups having 4 to 30 carbon atoms;
R is
(Iv) Halogen atom, alkyl group having 1 to 10 carbon atoms, alkyloxy group having 1 to 10 carbon atoms, cyano group, amino group, nitro group, acyl group having 1 to 10 carbon atoms,
(V) Aromatic hydrocarbon groups of a monocyclic ring, a linking ring, or a condensed ring having 6 to 30 carbon atoms.
(Vi) An aromatic heterocyclic group having a monocyclic ring, a linking ring, or a condensed ring having 4 to 30 carbon atoms, or
(Vii) The aromatic hydrocarbon group or aromatic heterocyclic group is a fluorine atom, an alkyl group having 1 to 10 carbon atoms, an alkyl halide group having 1 to 3 carbon atoms, or an aromatic hydrocarbon having 6 to 30 carbon atoms. Represents a group substituted with one or more groups selected from the group consisting of groups and aromatic heterocyclic groups having 4 to 30 carbon atoms;
Rb is
(B1) Hydrogen atom, halogen atom, alkyl group having 1 to 10 carbon atoms, alkyloxy group having 1 to 10 carbon atoms, cyano group, amino group, nitro group, acyl group having 1 to 10 carbon atoms,
(B2) An aromatic hydrocarbon group having a monocyclic ring, a linking ring, or a condensed ring having 6 to 30 carbon atoms.
(B3) An aromatic heterocyclic group having a monocycle, a linking ring, or a condensed ring having 4 to 30 carbon atoms, or
(B4) The aromatic hydrocarbon group or aromatic heterocyclic group is a fluorine atom, an alkyl group having 1 to 10 carbon atoms, an alkyl halide group having 1 to 3 carbon atoms, or an aromatic hydrocarbon having 6 to 30 carbon atoms. Represents a group substituted with one or more groups selected from the group consisting of groups and aromatic heterocyclic groups having 4 to 30 carbon atoms;
n represents an integer from 1 to 8.
However, when Rb is a hydrogen atom, n represents an integer from 2 to 8;
Multiple Rs may be the same or different;
Y ¹ and Y ² independently represent a nitrogen atom or CH, respectively.
At ^{least one of Y 1} and Y ² is a nitrogen atom. Cyclic azine compound represented by the formula (1-C):

During the ceremony
Ar ¹ and Ar ² are independent of each other.
(I) Aromatic hydrocarbon groups of monocyclic, linked or condensed rings having 6 to 20 carbon atoms,
(Ii) Aromatic heterocyclic groups of monocycles, linking rings, or condensed rings having 4 to 20 carbon atoms, or
(Iii) The aromatic hydrocarbon group or aromatic heterocyclic group is a fluorine atom, an alkyl group having 1 to 10 carbon atoms, an alkyl halide group having 1 to 3 carbon atoms, or an aromatic hydrocarbon having 6 to 30 carbon atoms. Represents a group substituted with one or more groups selected from the group consisting of groups and aromatic heterocyclic groups having 4 to 30 carbon atoms;
R is
(Iv) Halogen atom, alkyl group having 1 to 10 carbon atoms, alkyloxy group having 1 to 10 carbon atoms, cyano group, amino group, nitro group, acyl group having 1 to 10 carbon atoms,
(V) Aromatic hydrocarbon groups of a monocyclic ring, a linking ring, or a condensed ring having 6 to 30 carbon atoms.
(Vi) An aromatic heterocyclic group having a monocyclic ring, a linking ring, or a condensed ring having 4 to 30 carbon atoms, or
(Vii) The aromatic hydrocarbon group or aromatic heterocyclic group is a fluorine atom, an alkyl group having 1 to 10 carbon atoms, an alkyl halide group having 1 to 3 carbon atoms, or an aromatic hydrocarbon having 6 to 30 carbon atoms. Represents a group substituted with one or more groups selected from the group consisting of groups and aromatic heterocyclic groups having 4 to 30 carbon atoms.
However, the Rc is a monocyclic ring having 6 to 30 carbon atoms or an aromatic hydrocarbon group having a linking ring, or the aromatic hydrocarbon group having a monocyclic ring or a linking ring having a fluorine atom and 1 to 10 carbon atoms. One or more groups selected from the group consisting of an alkyl group, an alkyl halide group having 1 to 3 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, and an aromatic heterocyclic group having 4 to 30 carbon atoms. When the group is substituted with R and the 9-position of the phenanthrene is substituted with R, the R substituted at the 9-position of the phenanthrene represents a group other than the unsubstituted phenyl group;
Rc is
(C1) Hydrogen atom, halogen atom, alkyl group having 1 to 10 carbon atoms, alkyloxy group having 1 to 10 carbon atoms, cyano group, amino group, nitro group, acyl group having 1 to 10 carbon atoms,
(C2) An aromatic hydrocarbon group having a monocyclic ring, a linking ring, or a condensed ring having 6 to 30 carbon atoms.
(C3) An aromatic heterocyclic group having a monocycle, a linking ring, or a condensed ring having 4 to 30 carbon atoms, or
(C4) The aromatic hydrocarbon group or aromatic heterocyclic group is a fluorine atom, an alkyl group having 1 to 10 carbon atoms, an alkyl halide group having 1 to 3 carbon atoms, or an aromatic hydrocarbon having 6 to 30 carbon atoms. Represents a group substituted with one or more groups selected from the group consisting of groups and aromatic heterocyclic groups having 4 to 30 carbon atoms;
n represents an integer from 1 to 8.
However, when Rc is a hydrogen atom, n represents an integer from 2 to 8;
Multiple Rs may be the same or different,
However, the 9th and 10th places of phenanthrene are different;
Y ¹ and Y ² independently represent a nitrogen atom or CH, respectively.
At ^{least one of Y 1} and Y ² is a nitrogen atom. Cyclic azine compound represented by the formula (1-D):

During the ceremony
Ar ¹ and Ar ² are independent of each other.
(I) Aromatic hydrocarbon groups of monocyclic, linked or condensed rings having 6 to 20 carbon atoms,
(Ii) Aromatic heterocyclic groups of monocycles, linking rings, or condensed rings having 4 to 20 carbon atoms, or
(Iii) The aromatic hydrocarbon group or aromatic heterocyclic group is a fluorine atom, an alkyl group having 1 to 10 carbon atoms, an alkyl halide group having 1 to 3 carbon atoms, or an aromatic hydrocarbon having 6 to 30 carbon atoms. Represents a group substituted with one or more groups selected from the group consisting of groups and aromatic heterocyclic groups having 4 to 30 carbon atoms;
R is
(Iv) Halogen atom, alkyl group having 1 to 10 carbon atoms, alkyloxy group having 1 to 10 carbon atoms, cyano group, amino group, nitro group, acyl group having 1 to 10 carbon atoms,
(V) Aromatic hydrocarbon groups of a monocyclic ring, a linking ring, or a condensed ring having 6 to 30 carbon atoms.
(Vi) An aromatic heterocyclic group having a monocyclic ring, a linking ring, or a condensed ring having 4 to 30 carbon atoms, or
(Vii) The aromatic hydrocarbon group or aromatic heterocyclic group is a fluorine atom, an alkyl group having 1 to 10 carbon atoms, an alkyl halide group having 1 to 3 carbon atoms, or an aromatic hydrocarbon having 6 to 30 carbon atoms. Represents a group substituted with one or more groups selected from the group consisting of groups and aromatic heterocyclic groups having 4 to 30 carbon atoms.
However, the R substituted at the 10-position of phenylene is an aromatic hydrocarbon group having a monocycle or a linking ring having 6 to 30 carbon atoms, or an aromatic hydrocarbon group having the monocycle or a linking ring. A group consisting of a fluorine atom, an alkyl group having 1 to 10 carbon atoms, an alkyl halide group having 1 to 3 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, and an aromatic heterocyclic group having 4 to 30 carbon atoms. When the group is substituted with one or more groups selected from the above and the 9-position of the phenanthrene is substituted with R, the R substituted with the 9-position of the phenanthrene is an unsubstituted phenyl group. Represents a group other than;
Rd is
(D1) Hydrogen atom, halogen atom, alkyl group having 1 to 10 carbon atoms, alkyloxy group having 1 to 10 carbon atoms, cyano group, amino group, nitro group, acyl group having 1 to 10 carbon atoms,
(D2) An aromatic hydrocarbon group having a monocyclic ring, a linking ring, or a condensed ring having 6 to 30 carbon atoms.
(D3) An aromatic heterocyclic group having a monocyclic ring, a linking ring, or a condensed ring having 4 to 30 carbon atoms, or
(D4) The aromatic hydrocarbon group or aromatic heterocyclic group is a fluorine atom, an alkyl group having 1 to 10 carbon atoms, an alkyl halide group having 1 to 3 carbon atoms, or an aromatic hydrocarbon having 6 to 30 carbon atoms. Represents a group substituted with one or more groups selected from the group consisting of groups and aromatic heterocyclic groups having 4 to 30 carbon atoms;
n represents an integer from 1 to 8.
However, when Rd is a hydrogen atom, n represents an integer from 2 to 8;
Multiple Rs may be the same or different,
However, the 9th and 10th places of phenanthrene are different;
Y ¹ and Y ² independently represent a nitrogen atom or CH, respectively.
At ^{least one of Y 1} and Y ² is a nitrogen atom. Cyclic azine compound represented by the formula (1-E):

During the ceremony
Ar ¹ and Ar ² are independent of each other.
(I) Aromatic hydrocarbon groups of monocyclic, linked or condensed rings having 6 to 20 carbon atoms,
(Ii) Aromatic heterocyclic groups of monocycles, linking rings, or condensed rings having 4 to 20 carbon atoms, or
(Iii) The aromatic hydrocarbon group or aromatic heterocyclic group is a fluorine atom, an alkyl group having 1 to 10 carbon atoms, an alkyl halide group having 1 to 3 carbon atoms, or an aromatic hydrocarbon having 6 to 30 carbon atoms. Represents a group substituted with one or more groups selected from the group consisting of groups and aromatic heterocyclic groups having 4 to 30 carbon atoms;
R is
(Iv) Halogen atom, alkyl group having 1 to 10 carbon atoms, alkyloxy group having 1 to 10 carbon atoms, cyano group, amino group, nitro group, acyl group having 1 to 10 carbon atoms,
(V) Aromatic hydrocarbon groups of a monocyclic ring, a linking ring, or a condensed ring having 6 to 30 carbon atoms.
(Vi) An aromatic heterocyclic group having a monocyclic ring, a linking ring, or a condensed ring having 4 to 30 carbon atoms, or
(Vii) The aromatic hydrocarbon group or aromatic heterocyclic group is a fluorine atom, an alkyl group having 1 to 10 carbon atoms, an alkyl halide group having 1 to 3 carbon atoms, or an aromatic hydrocarbon having 6 to 30 carbon atoms. Represents a group substituted with one or more groups selected from the group consisting of groups and aromatic heterocyclic groups having 4 to 30 carbon atoms.
However, the R substituted at the 10-position of phenylene is an aromatic hydrocarbon group having a monocycle or a linking ring having 6 to 30 carbon atoms, or an aromatic hydrocarbon group having the monocycle or a linking ring. A group consisting of a fluorine atom, an alkyl group having 1 to 10 carbon atoms, an alkyl halide group having 1 to 3 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, and an aromatic heterocyclic group having 4 to 30 carbon atoms. When the group is substituted with one or more groups selected from the above and the 9-position of the phenanthrene is substituted with R, the R substituted with the 9-position of the phenanthrene is an unsubstituted phenyl group. Represents a group other than;
Re is
(E1) Hydrogen atom, halogen atom, alkyl group having 1 to 10 carbon atoms, alkyloxy group having 1 to 10 carbon atoms, cyano group, amino group, nitro group, acyl group having 1 to 10 carbon atoms,
(E2) An aromatic hydrocarbon group having a monocyclic ring, a linking ring, or a condensed ring having 6 to 30 carbon atoms.
(E3) An aromatic heterocyclic group having a monocyclic ring, a linking ring, or a condensed ring having 4 to 30 carbon atoms, or
(E4) The aromatic hydrocarbon group or aromatic heterocyclic group is a fluorine atom, an alkyl group having 1 to 10 carbon atoms, an alkyl halide group having 1 to 3 carbon atoms, or an aromatic hydrocarbon having 6 to 30 carbon atoms. Represents a group substituted with one or more groups selected from the group consisting of groups and aromatic heterocyclic groups having 4 to 30 carbon atoms;
n represents an integer from 1 to 8.
However, when Re is a hydrogen atom, n represents an integer from 2 to 8;
Multiple Rs may be the same or different,
However, the 9th and 10th places of phenanthrene are different;
Y ¹ and Y ² independently represent a nitrogen atom or CH, respectively.
At ^{least one of Y 1} and Y ² is a nitrogen atom. The cyclic azine compound according to claim 1 or 2, wherein the 9-position and the 10-position of phenanthrene are different. Rb is a monocyclic or linking ring aromatic hydrocarbon group having 6 to 30 carbon atoms, or the monocyclic or linking ring aromatic hydrocarbon group is a fluorine atom and an alkyl group having 1 to 10 carbon atoms. , Substituent with one or more groups selected from the group consisting of alkyl halide groups having 1 to 3 carbon atoms, aromatic hydrocarbon groups having 6 to 30 carbon atoms, and aromatic heterocyclic groups having 4 to 30 carbon atoms. The 9th position of the phenanthrene is substituted with R, and the R substituted at the 9th position of the phenanthrene represents a group other than the unsubstituted phenyl group, according to claim 2. Cyclic hydrocarbon compound. Phenanthrene's 9th and 10th places are at the same time
Aromatic hydrocarbon groups of monocyclic or linked rings with 6 to 30 carbon atoms, or
The aromatic hydrocarbon group of the single ring or the linking ring is a fluorine atom, an alkyl group having 1 to 10 carbon atoms, an alkyl halide group having 1 to 3 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, and the like. The cyclic hydrocarbon according to any one of claims 2 to 5, which cannot take a group substituted with one or more groups selected from the group consisting of an aromatic heterocyclic group having 4 to 30 carbon atoms. Compound. Ra
Phenyl group,
Pyridyl group or
The phenyl group or pyridyl group is a fluorine atom, an alkyl group having 1 to 10 carbon atoms, an alkyl halide group having 1 to 3 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, and an aromatic group having 4 to 30 carbon atoms. The cyclic azine compound according to claim 1, which is a group substituted with one or more groups selected from the group consisting of group heterocyclic groups. Ra is a fluorine atom, an alkyl group having 1 to 10 carbon atoms, an alkyl halide group having 1 to 3 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, and an aromatic heterocyclic group having 4 to 30 carbon atoms. The cyclic hydrocarbon compound according to claim 1, which is a pyridyl group, which may be substituted with one or more groups selected from the group consisting of. The cyclic azine compound according to claim 1, wherein Ra is a hydrogen atom. The cyclic azine compound according to any one of claims 1 to 11, wherein n is an integer of 1 to 4. The cyclic azine compound according to any one of claims 1 to 12, wherein Y ^{1 is a nitrogen atom.} The cyclic azine compound according to any one of claims 1 to 12, wherein Y ¹ and Y ^{2 are both nitrogen atoms.} A cyclic azine compound represented by any one of the formulas (1-1) to (1-26).

A material for an organic electroluminescent device containing the cyclic azine compound according to any one of claims 1 to 15. An organic electroluminescent device comprising the cyclic azine compound according to any one of claims 1 to 15. A method for producing a cyclic azine compound represented by the formula (1).
In the presence of a metal catalyst, the coupling reaction between the compound represented by the formula (2) and the compound represented by the formula (3) is included.
The method for producing a cyclic azine compound, wherein the cyclic azine compound represented by the formula (1) is the cyclic azine compound according to any one of claims 1 to 15.

During the ceremony
Ar ¹ , Ar ² , R, n, Y ¹ and Y ² are synonymous with equations (1-A)-(1-E);
L represents the group corresponding to the phenanthrenyl group contained in the cyclic azine compounds of the formulas (1-A) to (1-E);
X ¹ represents a chlorine atom, a bromine atom, a trifluoromethanesulfonyloxy group or an iodine atom;
M ¹ represents ZnZ ¹ , MgZ ² , Sn (Z ³ ) ₃ , or B (OZ ⁴ ) ₂ ;
Z ¹ and Z ² independently represent a chlorine atom, a bromine atom or an iodine atom;
Z ³ represents the same or different alkyl or phenyl group having 1-4 carbon atoms;
Z ⁴ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a phenyl group, which is the same or different from each other;
However, when M ¹ represents B (OZ ⁴ ) ₂ , the two (OZ ⁴ ) groups may be integrated to form a ring together with the boron atom. A method for producing a cyclic azine compound represented by the formula (1).
In the presence of a metal catalyst, the coupling reaction between the compound represented by the formula (4) and the compound represented by the formula (5) is included.
The method for producing a cyclic azine compound, wherein the cyclic azine compound represented by the formula (1) is the cyclic azine compound according to any one of claims 1 to 15.

During the ceremony
Ar ¹ , Ar ² , R, n, Y ¹ and Y ² are synonymous with equations (1-A)-(1-E);
L represents the group corresponding to the phenanthrenyl group contained in the cyclic azine compounds of the formulas (1-A) to (1-E);
X ² represents a chlorine atom, a bromine atom, a trifluoromethanesulfonyloxy group or an iodine atom. ;
M ² represents ZnZ ¹ , MgZ ² , Sn (Z ³ ) ₃ , or B (OZ ⁴ ) ₂ ;
Z ¹ and Z ² independently represent a chlorine atom, a bromine atom or an iodine atom;
Z ³ represents the same or different alkyl or phenyl group with 1 to 4 carbon atoms;
Z ⁴ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a phenyl group, which is the same or different from each other;
However, when M ² represents B (OZ ⁴ ) ₂ , the two (OZ ⁴ ) groups may be integrated to form a ring together with the boron atom.

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