JP2018158918A - Cyclic azine compound, material for organic electroluminescent element, and electron transport material for organic electroluminescent element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a cyclic azine compound having exceptional heat resistance, a long service life in an organic electroluminescent element, and exceptional low-voltage drive properties or luminous efficiency.SOLUTION: The present invention provides a cyclic azine compound having a specific structure represented by formula (1), where Aris a phenyl group or the like; Aris a C6-24 monocycle or fused-ring aromatic hydrocarbon group, H or the like; Arand Arare a phenyl group, an alkyl group, H or the like, or a single bond; Arand Arare a phenyl group, an alkyl group, H or the like, or a single bond; W, Wand Ware C-H, or N; Xand Xare a phenylene group or the like, or a single bond; Y, Y, Yand Yare C-R, N; R is a phenyl group, H or the like; R's may be bound to each other; Z is N or C-H.SELECTED DRAWING: None

Description

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

An organic electroluminescent element has a basic structure in which a light emitting layer containing a light emitting material is sandwiched between a hole transport layer and an electron transport layer, and an anode and a cathode are attached to the outside, and holes injected into the light emitting layer And a light-emitting element that utilizes light emission (fluorescence or phosphorescence) when excitons generated by electron recombination are deactivated, and are already used for applications such as large televisions and lighting as well as small displays. . The hole transport layer is a hole transport layer and a hole injection layer, the light emitting layer is an electron block layer, a light emitting layer and a hole block layer, and the electron transport layer is an electron transport layer and an electron injection layer. In some cases, it may be divided. In some cases, a co-deposited film doped with a metal, an organometallic compound, or another organic compound may be used as the carrier transport layer (electron transport layer or hole transport layer) of the organic electroluminescence device.
Cyclic azine compounds disclosed in Patent Document 1 or 2 have been reported as materials for organic electroluminescent elements.

JP 2011-063584 A Special table 2007-520875 gazette

  Conventional organic electroluminescent devices have a higher driving voltage than inorganic light emitting diodes, have low luminance and luminous efficiency, have extremely low device lifetime, and have not been put into practical use. Although recent organic electroluminescence devices have been gradually improved, further excellent materials are demanded in terms of luminous efficiency characteristics, driving voltage characteristics, and long life characteristics. Further, depending on the use such as in-vehicle use, extremely high heat resistance may be required, and the material is required to have a high glass transition temperature (Tg). Furthermore, in recent years, active research has been conducted on organic electroluminescent devices using thermally activated delayed fluorescence (TADF) and blue electroluminescent devices using phosphorescence by Adachi et al. In these materials for organic electroluminescence devices, high triplet excitation levels are required for energy confinement.

  Regarding the cyclic azine compound disclosed in Patent Document 1, further improvements are required in terms of the glass transition temperature and the triplet excitation level, and the lifetime of the device when used in an organic electroluminescent device, and the luminous efficiency. Improvement is demanded.

  The cyclic azine compound having a non-planar structure disclosed in Patent Document 2 is required to be further improved in terms of extending the lifetime of the device when used in an organic electroluminescent device and increasing the luminous efficiency. For compounds containing triptycene, specific synthesis examples, characteristics as an electron transport material for organic electroluminescence devices, glass transition temperature, and triplet excitation levels are not described, and their physical properties are unknown. It is.

  The purpose of each aspect of the present invention is to provide a cyclic azine compound having a high glass transition temperature and a high triplet excitation level, a material for an organic electroluminescence device, and an electron transport material for an organic electroluminescence device, as compared with conventionally known compounds. Is to provide.

  As a result of intensive studies to solve the above problems, the present inventors have found that the glass transition temperature of a cyclic azine compound to which a group having a triptycene structure is bonded (hereinafter also referred to as “cyclic azine compound (1)”). An organic electroluminescence device that is extremely high and has a high triplet excitation level and uses the compound as an electron transport material has a lower driving voltage, higher luminous efficiency, and higher performance than when a conventionally known material is used. It has been found that the heat resistance is increased or the life is extended, and each aspect of the present invention has been completed.

  The cyclic azine compound according to the first aspect of the present invention is a cyclic azine compound represented by the formula (1):

In formula (1),
Ar ¹ each independently represents a substituted or unsubstituted phenyl group, naphthyl group, or pyridyl group;
Ar ² is
A substituted or unsubstituted monocyclic or condensed aromatic hydrocarbon group having 6 to 24 carbon atoms,
A monocyclic or condensed nitrogen-containing heteroaromatic group having 4 to 25 carbon atoms consisting of only a substituted or unsubstituted 6-membered ring,
Represents a monocyclic or condensed heteroaromatic group having 3 to 25 carbon atoms or a hydrogen atom composed of an atom selected from the group consisting of substituted, unsubstituted H, C, O, and S;
Ar ³ and Ar ⁴ are each independently
Substituted or unsubstituted phenyl, naphthyl, pyridyl,
Hydrogen atom,
An unsubstituted alkyl group having 1 to 4 carbon atoms, or
Represents a single bond bonded to X ² ;
Ar ⁵ and Ar ⁶ are each independently
Substituted or unsubstituted phenyl, naphthyl, pyridyl,
Hydrogen atom,
An unsubstituted alkyl group having 1 to 4 carbon atoms, or
Represents a single bond bonded to X ² ;
W ¹ , W ² , and W ³ are
Each independently represents C—H or a nitrogen atom;
At least two represent C—H;
X ¹ and X ² are each independently
Substituted or unsubstituted phenylene group, naphthylene group, biphenylene group, pyridylene group, or
Represents a single bond;
Y ¹ , Y ² , Y ³ , and Y ⁴ are each independently
A group represented by C—R, or
Represents a nitrogen atom;
Each R is independently
Substituted or unsubstituted phenyl, naphthyl, pyridyl,
Hydrogen atom,
An unsubstituted alkyl group having 1 to 4 carbon atoms, or
Represents an unsubstituted alkenyl group having 1 to 4 carbon atoms;
R may be bonded to each other to form an aromatic ring;
Z represents a nitrogen atom or C—H;
When Ar ¹ , Ar ^{3 to} Ar ⁶ , X ^{1 to} X ² , or R has a substituent, the substituent is a fluorine atom, a methyl group, or a phenyl group;
When Ar ² has a substituent, the substituent is a phenyl group, a tolyl group, a pyridyl group, a methylpyridyl group, a dimethylpyridyl group, a fluorine atom, an alkyl group having 1 to 4 carbon atoms, or an alkyl group having 1 to 4 carbon atoms. An alkoxy group;

The cyclic azine compound according to the second aspect of the present invention is:
The cyclic azine compound according to the first aspect, wherein Z is a nitrogen atom.

The cyclic azine compound according to the third aspect of the present invention is:
Two Ar ¹ represent the same group and are a substituted or unsubstituted phenyl group, naphthyl group, or pyridyl group;
When Ar ¹ has a substituent, the substituent is the cyclic azine compound according to the first or second aspect, which is a fluorine atom, a methyl group, or a phenyl group.

The cyclic azine compound according to the fourth aspect of the present invention is:
Two Ar ¹ are cyclic azine compounds as described in any one of the said 1st-3rd aspect whose all are phenyl groups.

The cyclic azine compound according to the fifth aspect of the present invention is:
Ar ² is
A hydrogen atom, or
Substituted or unsubstituted phenyl, naphthyl, fluorenyl, anthryl, phenanthryl, benzofluorenyl, pyrenyl, perylenyl, fluoranthenyl, triphenylenyl, pyrimidyl, pyridyl, pyridyl, Quinolyl group, isoquinolyl group, benzofuranyl group, benzothienyl group, dibenzofuranyl group, dibenzothienyl group,
When Ar ² has a substituent, the substituent is a phenyl group, a tolyl group, a pyridyl group, a methylpyridyl group, a dimethylpyridyl group, a fluorine atom, an alkyl group having 1 to 4 carbon atoms, or an alkyl group having 1 to 4 carbon atoms. It is a cyclic azine compound as described in any one of the said 1st-4th aspect which is an alkoxy group.

The cyclic azine compound according to the sixth aspect of the present invention is:
Ar ² is a substituted or unsubstituted fluorenyl group, benzofluorenyl group, pyridyl group, quinolyl group, isoquinolyl group, benzofuranyl group, benzothienyl group, dibenzofuranyl group, or dibenzothienyl group,
When Ar ² has a substituent, the substituent is a phenyl group, a tolyl group, a pyridyl group, a methylpyridyl group, a dimethylpyridyl group, a fluorine atom, an alkyl group having 1 to 4 carbon atoms, or an alkyl group having 1 to 4 carbon atoms. It is a cyclic azine compound as described in any one of the said 1st-5th aspect which is an alkoxy group.

The cyclic azine compound according to the seventh aspect of the present invention is:
Ar ³ and Ar ⁴ are each independently
Hydrogen atom;
Unsubstituted phenyl group, naphthyl group, pyridyl group; or
The cyclic azine compound according to any one of the first to sixth aspects, which is a single bond that binds to X ² .

The cyclic azine compound according to the eighth aspect of the present invention is:
X ¹ and X ² are each independently
Single bond;
The cyclic azine compound according to any one of the first to seventh aspects, which is an unsubstituted phenylene group, naphthylene group, biphenylene group, or pyridylene group.

The cyclic azine compound according to the ninth aspect of the present invention is:
Y ¹ , Y ² , Y ³ , and Y ⁴ are all groups represented by C—R;
Each R is independently
Hydrogen atom;
The alkyl group having 1 to 4 carbon atoms, the alkenyl group having 1 to 4 carbon atoms, the phenyl group, the naphthyl group, or the pyridyl group, which is unsubstituted; It is a cyclic azine compound.

The cyclic azine compound according to the tenth aspect of the present invention is:
The cyclic azine compound according to any one of the first to ninth aspects, in which W ¹ , W ² , and W ³ are all C—H.

The cyclic azine compound according to the eleventh aspect of the present invention is:
The organic electroluminescent element material containing the cyclic azine compound shown by Formula (1) as described in any one of the said 1st-10th aspect.

The cyclic azine compound according to the twelfth aspect of the present invention is:
The electron transport material for organic electroluminescent elements containing the cyclic azine compound shown by Formula (1) as described in any one of the said 1st-10th aspect.

  According to each aspect of the present invention, there are provided a cyclic azine compound having excellent heat resistance of film quality and a high triplet excitation level, an organic electroluminescent device material containing the same, and an electron transport material for an organic electroluminescent device Therefore, it contributes to the provision of an organic electroluminescent device that is excellent in low driving voltage, high luminous efficiency, high heat resistance, or long life.

It is sectional drawing of the single layer element produced in the Example.

  Hereinafter, exemplary embodiments for carrying out the present invention will be described in detail.

Each aspect of the present invention relates to a cyclic azine compound represented by the formula (1) (cyclic azine compound (1)), a method for producing the same, and a material for an organic electroluminescent element including the material.
The cyclic azine compound according to one embodiment of the present invention is a cyclic azine compound represented by the formula (1):

In formula (1),
Ar ¹ each independently represents a substituted or unsubstituted phenyl group, naphthyl group, or pyridyl group;
Ar ² is
A substituted or unsubstituted monocyclic or condensed aromatic hydrocarbon group having 6 to 24 carbon atoms,
A monocyclic or condensed nitrogen-containing heteroaromatic group having 4 to 25 carbon atoms consisting of only a substituted or unsubstituted 6-membered ring,
Represents a monocyclic or condensed heteroaromatic group having 3 to 25 carbon atoms or a hydrogen atom composed of an atom selected from the group consisting of substituted, unsubstituted H, C, O, and S;
Ar ³ and Ar ⁴ are each independently
Substituted or unsubstituted phenyl, naphthyl, pyridyl,
Hydrogen atom,
An unsubstituted alkyl group having 1 to 4 carbon atoms, or
Represents a single bond bonded to X ² ;
Ar ⁵ and Ar ⁶ are each independently
Substituted or unsubstituted phenyl, naphthyl, pyridyl,
Hydrogen atom,
An unsubstituted alkyl group having 1 to 4 carbon atoms, or
Represents a single bond bonded to X ² ;
W ¹ , W ² , and W ³ are
Each independently represents C—H or a nitrogen atom;
At least two represent C—H;
X ¹ and X ² are each independently
Substituted or unsubstituted phenylene group, naphthylene group, biphenylene group, pyridylene group, or
Represents a single bond;
Y ¹ , Y ² , Y ³ , and Y ⁴ are each independently
A group represented by C—R, or
Represents a nitrogen atom;
Each R is independently
Substituted or unsubstituted phenyl, naphthyl, pyridyl,
Hydrogen atom,
An unsubstituted alkyl group having 1 to 4 carbon atoms, or
Represents an unsubstituted alkenyl group having 1 to 4 carbon atoms;
R may be bonded to each other to form an aromatic ring;
Z represents a nitrogen atom or C—H;
When Ar ¹ , Ar ^{3 to} Ar ⁶ , X ^{1 to} X ² , or R has a substituent, the substituent is a fluorine atom, a methyl group, or a phenyl group;
When Ar ² has a substituent, the substituent is a phenyl group, a tolyl group, a pyridyl group, a methylpyridyl group, a dimethylpyridyl group, a fluorine atom, an alkyl group having 1 to 4 carbon atoms, or an alkyl group having 1 to 4 carbon atoms. An alkoxy group;

  The substituents in the cyclic azine compound (1) according to one embodiment of the present invention are defined as follows.

In formula (1), Ar ¹ each independently represents a phenyl group, a naphthyl group, or a pyridyl group (these groups may be substituted with a fluorine atom, a methyl group, or a phenyl group).
The phenyl group, naphthyl group, or pyridyl group substituted with a fluorine atom in Ar ¹ is not particularly limited, and examples thereof include a fluorophenyl group, a pentafluorophenyl group, a difluorophenyl group, a fluoronaphthyl group, and a difluoro group. Preferred examples include a naphthyl group, a fluoropyridyl group, a difluoropyridyl group, and the like.
The phenyl group, naphthyl group, or pyridyl group substituted with a methyl group in Ar ¹ is not particularly limited, and examples thereof include a tolyl group, a methylnaphthyl group, a dimethylphenyl group, a dimethylnaphthyl group, and a methylpyridyl group. Or a dimethylpyridyl group etc. are mentioned as a preferable example.
The phenyl group, naphthyl group, or pyridyl group substituted with a phenyl group in Ar ¹ is not particularly limited, and examples thereof include a biphenyl group, a phenylnaphthyl group, a terphenyl group, a diphenylnaphthyl group, and a phenylpyridyl group. A group etc. are mentioned as a preferable example.

When two Ar ¹ represent the same group and are substituted or unsubstituted phenyl group, naphthyl group, or pyridyl group, and Ar ¹ has a substituent, the substituent is a fluorine atom, a methyl group Or a phenyl group.

Ar ¹ is more preferably independently a phenyl group, a tolyl group, a naphthyl group, or a biphenyl group in terms of excellent electron transport material properties, and two Ar ¹ are the same, It is more preferable that they are a group, a tolyl group, a naphthyl group, or a biphenyl group, and it is further more preferable that both two Ar < ¹ > is a phenyl group at the point which is easy to synthesize | combine.

Ar ¹ preferably represents the same group in terms of easy synthesis.

Specific examples of Ar ¹ are not particularly limited, but for example, each independently a phenyl group, p-tolyl group, m-tolyl group, o-tolyl group, 2,4-dimethylphenyl group, 3, 5-dimethylphenyl group, mesityl group, 2-fluorophenyl group, 3-fluorophenyl group, 4-fluorophenyl group, 2,4-difluorophenyl group, 3,5-difluorophenyl group, biphenyl-2-yl group, Biphenyl-3-yl group, biphenyl-4-yl group, 1-naphthyl group, 2-naphthyl group, 1-phenylnaphthalen-2-yl group, 1-phenylnaphthalen-3-yl group, 1-phenylnaphthalene-4 -Yl group, 1-phenylnaphthalen-5-yl group, 1-phenylnaphthalen-6-yl group, 1-phenylnaphthalen-7-yl group, 1-phenylnaphthalene N-8-yl group, 2-phenylnaphthalen-1-yl group, 2-phenylnaphthalen-3-yl group, 2-phenylnaphthalen-4-yl group, 2-phenylnaphthalen-5-yl group, 2-phenyl Naphthalen-6-yl group, 2-phenylnaphthalen-7-yl group, 2-phenylnaphthalen-8-yl group, 1-methylnaphthalen-4-yl group, 1-methylnaphthalen-5-yl group, 1-methyl Naphthalen-6-yl group, 1-methylnaphthalen-7-yl group, 1-methylnaphthalen-8-yl group, 2-methylnaphthalen-1-yl group, 2-methylnaphthalen-3-yl group, 2-methyl Naphthalen-4-yl group, 2-methylnaphthalen-5-yl group, 2-methylnaphthalen-6-yl group, 2-methylnaphthalen-7-yl group, 2-methylnaphthalene-8 Yl group, 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 2-methylpyridin-3-yl group, 2-methylpyridin-4-yl group, 2-methylpyridin-5-yl group, 2- Methylpyridin-6-yl group, 3-methylpyridin-2-yl group, 3-methylpyridin-4-yl group, 3-methylpyridin-5-yl group, 3-methylpyridin-6-yl group, 4- Methylpyridin-2-yl group, 4-methylpyridin-3-yl group, 2,6-dimethylpyridin-3-yl group, 2,6-dimethylpyridin-4-yl group, 3,6-dimethylpyridin-2 -Yl group, 3,6-dimethylpyridin-4-yl group, 3,6-dimethylpyridin-5-yl group, 2-phenylpyridin-6-yl group, 3-phenylpyridin-6-yl group, 4- Phenylpyridin-6-yl 5-phenylpyridin-6-yl group, 2-phenylpyridin-3-yl group, 2-phenylpyridin-5-yl group, 3-phenylpyridin-5-yl group, 4-phenylpyridin-3-yl group Preferred examples include 3-phenylpyridin-4-yl group and 2-phenylpyridin-4-yl group. Of these substituents, a phenyl group, a p-tolyl group, a biphenyl-3-yl group, a biphenyl-4-yl group, a 1-naphthyl group, or -A naphthyl group is preferable, and each independently 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. The group is particularly preferred.

Ar ² is a monocyclic or condensed aromatic hydrocarbon group having 6 to 24 carbon atoms, a monocyclic or condensed nitrogen-containing heteroaromatic group having 4 to 25 carbon atoms consisting of only a 6-membered ring, or H, C, A monocyclic or condensed heteroaromatic group having 3 to 25 carbon atoms composed of an atom selected from an atomic group consisting of O and S (these groups include a phenyl group, a tolyl group, a pyridyl group, a methylpyridyl group, A dimethylpyridyl group, a fluorine atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms), or a hydrogen atom;

The Ar ² monocyclic or condensed aromatic hydrocarbon group having 6 to 24 carbon atoms is not particularly limited, and examples thereof include a phenyl group, a naphthyl group, a phenanthryl group, an anthryl group, a pyrenyl group, and a triphenylenyl group. Preferred examples include a chrysenyl group, a fluoranthenyl group, an acenaphthyl group, a fluorenyl group, or a benzofluorenyl group. In addition, as above-mentioned, these substituents are a phenyl group, a tolyl group, a pyridyl group, a methyl pyridyl group, a dimethyl pyridyl group, a fluorine atom, a C1-C4 alkyl group, or a C1-C4 alkoxy group. May be substituted.

In Ar ^2, The monocyclic or condensed nitrogen-containing heterocyclic aromatic group having a carbon number of 4 to 25 comprising only 6-membered ring, is not particularly limited, for example, a pyridyl group, pyrazyl group, pyrimidyl group, pyridazyl Preferred examples include a group, a quinolyl group, an isoquinolyl group, a phenanthridyl group, a benzoquinolyl group, and an acridinyl group. Note that the carbazolyl group is a heteroaromatic group containing a 5-membered ring, and the monocyclic or condensed nitrogen-containing heteroaromatic group having 4 to 25 carbon atoms consisting of only the 6-membered ring according to one embodiment of the present invention includes Not included. In addition, as described above, these substituents are phenyl group, tolyl group, pyridyl group, methylpyridyl group, dimethylpyridyl group, fluorine atom, alkyl group having 1 to 4 carbon atoms, or alkoxy group having 1 to 4 carbon atoms. May be substituted.

In Ar ^2, H, C, O, and The monocyclic or condensed heteroaromatic group having the number of atoms of carbon composed of atoms selected from the group 3 to 25 consisting of S, is not particularly limited, For example, a thienyl group, a furyl group, a bithienyl group, a bifuryl group, a benzothienyl group, a benzofuryl group, a dibenzothienyl group, a dibenzofuryl group, and the like are preferable examples. In addition, as above-mentioned, these substituents are a phenyl group, a tolyl group, a pyridyl group, a methyl pyridyl group, a dimethyl pyridyl group, a fluorine atom, a C1-C4 alkyl group, or a C1-C4 alkoxy group. May be substituted.

In Ar ^2, as the alkyl group having 1 to 4 carbon atoms is not particularly limited, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, n- butyl group, or t- butyl group and the like Take as an example.

The alkoxy group having 1 to 4 carbon atoms in Ar ² is not particularly limited, and examples thereof include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, and a t-butoxy group. A preferred example is given.

Ar ² is a hydrogen atom, a monocyclic or condensed aromatic hydrocarbon group having 6 to 24 carbon atoms, a monocyclic or condensed nitrogen-containing heteroaromatic group having 4 to 25 carbon atoms consisting of only a 6-membered ring, or H 2 It is preferable that it is a C3-C25 monocyclic or condensed heteroaromatic group comprised by the atom chosen from the atomic group which consists of C, O, and S. In addition, Ar ² is a monocyclic or condensed aromatic hydrocarbon group having 6 to 24 carbon atoms, or a monocyclic or condensed ring containing nitrogen having 4 to 25 carbon atoms consisting of only a 6-membered ring in that the glass transition temperature is high. A heteroaromatic group or a monocyclic or condensed heteroaromatic group having 3 to 25 carbon atoms composed of an atom selected from an atomic group consisting of H, C, O, and S is preferable.

Specifically, Ar ² is a hydrogen atom; phenyl group, naphthyl group, biphenyl group, fluorenyl group, anthryl group, phenanthryl group, benzofluorenyl group, pyrenyl group, perylenyl group, fluoranthenyl group, triphenylenyl group, Pyrimidyl group, pyrazyl group, pyridyl group, quinolyl group, isoquinolyl group, benzofuranyl group, benzothienyl group, dibenzofuranyl group, or dibenzothienyl group (these groups are phenyl group, tolyl group, pyridyl group, methylpyridyl group, It may preferably have a dimethylpyridyl group, a fluorine atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms. Ar ² is phenyl group, naphthyl group, biphenyl group, fluorenyl group, anthryl group, phenanthryl group, benzofluorenyl group, pyrenyl group, perylenyl group, fluoranthenyl group, triphenylenyl group, pyrimidyl group, pyrazyl group, pyridyl group Quinolyl group, isoquinolyl group, benzofuranyl group, benzothienyl group, dibenzofuranyl group, or dibenzothienyl group (these groups are phenyl group, tolyl group, pyridyl group, methylpyridyl group, dimethylpyridyl group, fluorine atom, carbon More preferably an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms). Ar ² is a phenyl group, naphthyl group, fluorenyl group, anthryl group, phenanthryl group, benzofluorenyl group, pyrenyl group, perylenyl group, fluoranthenyl group, triphenylenyl group, pyrimidyl group, pyrazyl group, pyridyl group, quinolyl group And more preferably an isoquinolyl group, a benzofuranyl group, a benzothienyl group, a dibenzofuranyl group, a dibenzothienyl group, a biphenyl group, a pyridylphenyl group, or a terphenyl group.

In addition, Ar ² is excellent in electron transporting material characteristics, and is a fluorenyl group, benzofluorenyl group, pyridyl group, quinolyl group, isoquinolyl group, benzofuranyl group, benzothienyl group, dibenzofuranyl group, or dibenzothienyl. A group (these groups may have a phenyl group, a tolyl group, a pyridyl group, a methylpyridyl group, a fluorine atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms); Preferably there is. More preferably, Ar ² is a pyridyl group.

Ar ² Specific examples of these include, but are not limited to, hydrogen atom, phenyl group, p-tolyl group, m-tolyl group, o-tolyl group, 2,4-dimethylphenyl group, 3,5-dimethylphenyl group. Mesityl group, 2-ethylphenyl group, 3-ethylphenyl group, 4-ethylphenyl group, 2,4-diethylphenyl group, 3,5-diethylphenyl group, 2-propylphenyl group, 3-propylphenyl group, 4-propylphenyl group, 2,4-dipropylphenyl group, 3,5-dipropylphenyl group, 2-isopropylphenyl group, 3-isopropylphenyl group, 4-isopropylphenyl group, 2,4-diisopropylphenyl group, 3,5-diisopropylphenyl group, 2-butylphenyl group, 3-butylphenyl group, 4-butylphenyl group, 2,4-dibutyl Phenyl group, 3,5-dibutylphenyl group, 2-tert-butylphenyl group, 3-tert-butylphenyl group, 4-tert-butylphenyl group, 2,4-di-tert-butylphenyl group, 3,5 -Di-tert-butylphenyl group, biphenyl-2-yl group, biphenyl-3-yl group, biphenyl-4-yl group, 3-methylbiphenyl-4-yl group, 2'-methylbiphenyl-4-yl group 4'-methylbiphenyl-4-yl group, 2,2'-dimethylbiphenyl-4-yl group, 6-methylbiphenyl-3-yl group, 5-methylbiphenyl-3-yl group, 2'-methylbiphenyl -3-yl group, 4'-methylbiphenyl-3-yl group, 6,2'-dimethylbiphenyl-3-yl group, 5-methylbiphenyl-2-yl group, 6-methylbiphenyl- -Yl group, 2'-methylbiphenyl-2-yl group, 4'-methylbiphenyl-2-yl group, 6,2'-dimethylbiphenyl-2-yl group, 3-ethylbiphenyl-4-yl group, 6 -Ethylbiphenyl-3-yl group, 5-ethylbiphenyl-2-yl group, 3-propylbiphenyl-4-yl group, 6-propylbiphenyl-3-yl group, 5-propylbiphenyl-2-yl group, 3 -Isopropylbiphenyl-4-yl group, 6-isopropylbiphenyl-3-yl group, 5-isopropylbiphenyl-2-yl group, 3-butylbiphenyl-4-yl group, 6-butylbiphenyl-3-yl group, 5 -Butylbiphenyl-2-yl group, 3-tert-butylbiphenyl-4-yl group, 4'-tert-butylbiphenyl-4-yl group, 6-tert-butylbiph Nyl-3-yl group, 5-tert-butylbiphenyl-2-yl group, 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 2-methylpyridin-3-yl group, 2-methylpyridine-4 -Yl group, 2-methylpyridin-5-yl group, 2-methylpyridin-6-yl group, 3-methylpyridin-2-yl group, 3-methylpyridin-4-yl group, 3-methylpyridin-5 -Yl group, 3-methylpyridin-6-yl group, 4-methylpyridin-2-yl group, 4-methylpyridin-3-yl group, 2,6-dimethylpyridin-3-yl group, 2,6- Dimethylpyridin-4-yl group, 3,6-dimethylpyridin-2-yl group, 3,6-dimethylpyridin-4-yl group, 3,6-dimethylpyridin-5-yl group, 2-phenylpyridin-6 -Yl group, 3-phenyl Pyridin-6-yl group, 4-phenylpyridin-6-yl group, 5-phenylpyridin-6-yl group, 2-phenylpyridin-3-yl group, 2-phenylpyridin-5-yl group, 3-phenyl Pyridin-5-yl group, 4-phenylpyridin-3-yl group, 3-phenylpyridin-4-yl group, 2-phenylpyridin-4-yl group, 2- (2-pyridyl) phenyl group, 3- ( 2-pyridyl) phenyl group,
4- (2-pyridyl) phenyl group, 2- (3-pyridyl) phenyl group, 3- (3-pyridyl) phenyl group, 4- (3-pyridyl) phenyl group, 2- (4-pyridyl) phenyl group, 3- (4-pyridyl) phenyl group, 4- (4-pyridyl) phenyl group, 2- (3-methyl-2-pyridyl) phenyl group, 3- (3-methyl-2-pyridyl) phenyl group, 4- (3-methyl-2-pyridyl) phenyl group, 2- (4-methyl-2-pyridyl) phenyl group, 3- (4-methyl-2-pyridyl) phenyl group, 4- (4-methyl-2-pyridyl) ) Phenyl group, 2- (5-methyl-2-pyridyl) phenyl group, 3- (5-methyl-2-pyridyl) phenyl group, 4- (5-methyl-2-pyridyl) phenyl group, 2- (6 -Methyl-2-pyridyl) phenyl group, 3 (6-methyl-2-pyridyl) phenyl group, 4- (6-methyl-2-pyridyl) phenyl group, 2- (2-methyl-3-pyridyl) phenyl group, 3- (2-methyl-3-pyridyl) ) Phenyl group, 4- (2-methyl-3-pyridyl) phenyl group, 2- (4-methyl-3-pyridyl) phenyl group, 3- (4-methyl-3-pyridyl) phenyl group, 4- (4 -Methyl-3-pyridyl) phenyl group, 2- (5-methyl-3-pyridyl) phenyl group, 3- (5-methyl-3-pyridyl) phenyl group, 4- (5-methyl-3-pyridyl) phenyl Group, 2- (6-methyl-3-pyridyl) phenyl group, 3- (6-methyl-3-pyridyl) phenyl group, 4- (6-methyl-3-pyridyl) phenyl group, 2- (2-methyl) -4-pyridyl) phenyl group, 3- (2 Methyl-4-pyridyl) phenyl group, 4- (2-methyl-4-pyridyl) phenyl group, 2- (3-methyl-4-pyridyl) phenyl group, 3- (3-methyl-4-pyridyl) phenyl group 4- (3-methyl-4-pyridyl) phenyl group, 2,6-diphenylpyridin-3-yl group, 2,6-diphenylpyridin-4-yl group, 4,6-diphenylpyridin-2-yl group 3,6-diphenylpyridin-4-yl group, 3,6-diphenylpyridin-5-yl group, 1-naphthyl group, 2-naphthyl group, 1-phenylnaphthalen-2-yl group, 1-phenylnaphthalene- 3-yl group, 1-phenylnaphthalen-4-yl group, 1-phenylnaphthalen-5-yl group, 1-phenylnaphthalen-6-yl group, 1-phenylnaphthalen-7-yl group, 1-phenyl group Nylnaphthalen-8-yl group, 2-phenylnaphthalen-1-yl group, 2-phenylnaphthalen-3-yl group, 2-phenylnaphthalen-4-yl group, 2-phenylnaphthalen-5-yl group, 2- Phenylnaphthalen-6-yl group, 2-phenylnaphthalen-7-yl group, 2-phenylnaphthalen-8-yl group, 1-methylnaphthalen-4-yl group, 1-methylnaphthalen-5-yl group, 1- Methylnaphthalen-6-yl group, 1-methylnaphthalen-7-yl group, 1-methylnaphthalen-8-yl group, 2-methylnaphthalen-1-yl group, 2-methylnaphthalen-3-yl group, 2- Methylnaphthalen-4-yl group, 2-methylnaphthalen-5-yl group, 2-methylnaphthalen-6-yl group, 2-methylnaphthalen-7-yl group, 2-methylnaphthalene The array type 8-yl group, 1-phenanthryl group, 2-phenanthryl group, 3-phenanthryl group, 4-phenanthryl group, 9-phenanthryl group,
1-phenylphenanthren-2-yl group, 1-phenylphenanthren-3-yl group, 1-phenylphenanthren-4-yl group, 1-phenylphenanthren-5-yl group, 1-phenylphenanthren-6-yl group, 1-phenylphenanthren-7-yl group, 1-phenylphenanthren-8-yl group, 1-phenylphenanthren-9-yl group, 1-phenylphenanthren-10-yl group, 2-phenylphenanthren-1-yl group, 2-phenylphenanthren-3-yl group, 2-phenylphenanthren-4-yl group, 2-phenylphenanthren-5-yl group, 2-phenylphenanthren-6-yl group, 2-phenylphenanthren-7-yl group, 2-phenylphenanthrene-8-yl group, 2-phenylphenanthre -9-yl group, 2-phenylphenanthren-10-yl group, 3-phenylphenanthren-1-yl group, 3-phenylphenanthren-2-yl group, 3-phenylphenanthren-4-yl group, 3-phenylphenanthrene -5-yl group, 3-phenylphenanthrene-6-yl group, 3-phenylphenanthrene-7-yl group, 3-phenylphenanthren-8-yl group, 3-phenylphenanthren-9-yl group, 3-phenylphenanthrene -10-yl group, 4-phenylphenanthren-1-yl group, 4-phenylphenanthren-2-yl group, 4-phenylphenanthren-3-yl group, 4-phenylphenanthren-5-yl group, 4-phenylphenanthrene -6-yl group, 4-phenylphenanthrene-7-yl group, 4-phenyl group Nylphenanthren-8-yl group, 4-phenylphenanthren-9-yl group, 4-phenylphenanthren-10-yl group, 1-methylphenanthren-2-yl group, 1-methylphenanthren-3-yl group, 1- Methylphenanthren-4-yl group, 1-methylphenanthren-5-yl group, 1-methylphenanthrene-6-yl group, 1-methylphenanthren-7-yl group, 1-methylphenanthren-8-yl group, 1- Methylphenanthren-9-yl group, 1-methylphenanthren-10-yl group, 2-methylphenanthren-1-yl group, 2-methylphenanthren-3-yl group, 2-methylphenanthren-4-yl group, 2- Methylphenanthren-5-yl group, 2-methylphenanthren-6-yl group, 2-methylphenane Tren-7-yl group, 2-methylphenanthren-8-yl group, 2-methylphenanthren-9-yl group, 2-methylphenanthren-10-yl group, 3-methylphenanthren-1-yl group, 3-methyl Phenanthren-2-yl group, 3-methylphenanthren-4-yl group, 3-methylphenanthren-5-yl group, 3-methylphenanthren-6-yl group, 3-methylphenanthren-7-yl group, 3-methyl Phenanthren-8-yl group, 3-methylphenanthren-9-yl group, 3-methylphenanthren-10-yl group, 4-methylphenanthren-1-yl group, 4-methylphenanthren-2-yl group, 4-methyl Phenanthren-3-yl group, 4-methylphenanthren-5-yl group, 4-methylphenanthren-6-yl 4-methylphenanthren-7-yl group, 4-methylphenanthren-8-yl group, 4-methylphenanthren-9-yl group, 4-methylphenanthren-10-yl group, 1-anthryl group, 2-anthryl group , 9-anthryl group,
1-phenylanthracen-2-yl group, 1-phenylanthracen-3-yl group, 1-phenylanthracen-4-yl group, 1-phenylanthracen-5-yl group, 1-phenylanthracen-6-yl group, 1-phenylanthracen-7-yl group, 1-phenylanthracen-8-yl group, 1-phenylanthracen-9-yl group, 1-phenylanthracen-10-yl group, 2-phenylanthracen-1-yl group, 2-phenylanthracen-3-yl group, 2-phenylanthracen-4-yl group, 2-phenylanthracen-5-yl group, 2-phenylanthracen-6-yl group, 2-phenylanthracen-7-yl group, 2-phenylanthracen-8-yl group, 2-phenylanthracen-9-yl group, 2-phenylanthant Sen-10-yl group, 9-phenylanthracen-1-yl group, 9-phenylanthracen-2-yl group, 9-phenylanthracen-3-yl group, 9-phenylanthracen-4-yl group, 9-phenyl Anthracen-5-yl group, 1-pyrenyl group, 2-pyrenyl group, 4-pyrenyl group, 1-phenylpyren-2-yl group, 1-phenylpyren-3-yl group, 1-phenylpyren-4-yl Group, 1-phenylpyren-5-yl group, 1-phenylpyren-6-yl group, 1-phenylpyren-7-yl group, 1-phenylpyren-8-yl group, 1-phenylpyren-9-yl Group, 1-phenylpyren-10-yl group, 2-phenylpyren-1-yl group, 2-phenylpyren-3-yl group, 2-phenylpyren-4-yl group, 2-phenylpyrene- -Yl group, 2-phenylpyren-6-yl group, 2-phenylpyren-7-yl group, 2-phenylpyren-8-yl group, 2-phenylpyren-9-yl group, 2-phenylpyrene-10 -Yl group, 9-phenylpyren-1-yl group, 9-phenylpyren-2-yl group, 9-phenylpyren-3-yl group, 9-phenylpyren-4-yl group, 9-phenylpyrene-5 -Yl group, 9-phenylpyren-6-yl group, 9-phenylpyren-7-yl group, 9-phenylpyren-8-yl group, 9-phenylpyren-10-yl group, 1-methylpyrene-2- Yl group, 1-methylpyren-3-yl group, 1-methylpyren-4-yl group, 1-methylpyren-5-yl group, 1-methylpyren-6-yl group, 1-methylpyren-7-yl group, 1- Methylpyrene-8-i Group, 1-methylpyren-9-yl group, 1-methylpyren-10-yl group, 2-methylpyren-1-yl group, 2-methylpyren-3-yl group, 2-methylpyren-4-yl group, 2- Methylpyren-5-yl group, 2-methylpyren-6-yl group, 2-methylpyren-7-yl group, 2-methylpyren-8-yl group, 2-methylpyren-9-yl group, 2-methylpyren-10-yl Group, 9-methylpyren-1-yl group, 9-methylpyren-2-yl group, 9-methylpyren-3-yl group, 9-methylpyren-4-yl group, 9-methylpyren-5-yl group, 9-methylpyrene -6-yl group, 9-methylpyren-7-yl group, 9-methylpyren-8-yl group, 9-methylpyren-10-yl group, fluoranthen-1-yl group, fluoranthen-1-yl group Fluoranthen-2-yl group, fluoranthen-3-yl group, fluoranthen-4-yl group, fluoranthen-5-yl group, fluoranthen-6-yl group, fluoranthen-7-yl group, fluoranthen-8-yl group, fluoranthene -9-yl group, fluoranthen-10-yl group, triphenylene-1-yl group, triphenylene-2-yl group, acenaphthylene-1-yl group, acenaphthylene-3-yl group, acenaphthylene-4-yl group, acenaphthylene- 5-yl group, chrysen-1-yl group, chrysen-2-yl group, chrysen-5-yl group, chrysen-6-yl group,
2-quinolyl group, 3-quinolyl group, 4-quinolyl group, 5-quinolyl group, 6-quinolyl group, 7-quinolyl group, 8-quinolyl group, 1-isoquinolyl group, 3-isoquinolyl group, 4-isoquinolyl group, 5-isoquinolyl group, 6-isoquinolyl group, 7-isoquinolyl group, 8-isoquinolyl group, quinoxalin-2-yl group, quinoxalin-5-yl group, quinoxalin-6-yl group, quinazolin-2-yl group, quinazoline- 4-yl group, quinazolin-5-yl group, quinazolin-6-yl group, quinazolin-7-yl group, quinazolin-8-yl group, pyrazin-2-yl group, 5-methylpyrazin-2-yl group, 5,6-diphenylpyrazin-2-yl group, pyrimidin-2-yl group, pyrimidin-4-yl group, pyrimidin-5-yl group, 2,4-diphenylpyrimidi -6-yl group, 4,6-diphenylpyrimidin-2-yl group, acridine-1-yl group, acridine-1-yl group, acridin-2-yl group, acridine-3-yl group, acridine-4- Yl group, acridine-9-yl group, phenanthridin-1-yl group, phenanthridin-1-yl group, phenanthridin-2-yl group, phenanthridin-3-yl group, phenanthridine- 4-yl group, phenanthridin-6-yl group, phenanthridin-7-yl group, phenanthridin-8-yl group, phenanthridin-9-yl group, phenanthridin-10-yl group, Phenazin-1-yl group, phenazin-2-yl group, benzo [h] quinolin-2-yl group, benzo [h] quinolin-3-yl group, benzo [h] quinolin-4-yl group, benzo [h ] Norin-5-yl group, benzo [h] quinolin-6-yl group, benzo [h] quinolin-7-yl group, benzo [h] quinolin-8-yl group, benzo [h] quinolin-9-yl group Benzo [h] quinolin-10-yl group, 2-thienyl group, 3-thienyl group, 2-furyl group, 3-furyl group, benzothiophen-2-yl group, benzothiophen-3-yl group, benzothiophene -4-yl group, benzothiophen-5-yl group, benzothiophen-6-yl group, benzothiophen-7-yl group, benzofuran-2-yl group, benzofuran-3-yl group, benzofuran-4-yl group Benzofuran-5-yl group, benzofuran-6-yl group, benzofuran-7-yl group, dibenzothiophen-1-yl group, dibenzothiophen-2-yl group, dibenzothiol Nen-3-yl group, dibenzofuran-1-yl group, dibenzofuran-2-yl group, dibenzofuran-3-yl group, 3-methylthiophen-2-yl group, 4-methylthiophen-2-yl group, 5 -Methylthiophen-2-yl group, 2-methylthiophen-3-yl group, 4-methylthiophen-3-yl group, 5-methylthiophen-3-yl group, 3-methylfuran-2-yl group, 4 -Methylfuran-2-yl group, 5-methylfuran-2-yl group, 2-methylfuran-3-yl group, 4-methylfuran-3-yl group, 5-methylfuran-3-yl group,
3-methylbenzothiophen-2-yl group, 4-methylbenzothiophen-2-yl group, 5-methylbenzothiophen-2-yl group, 6-methylbenzothiophen-2-yl group, 7-methylbenzothiophene- 2-yl group, 2-methylbenzothiophen-3-yl group, 4-methylbenzothiophen-3-yl group, 5-methylbenzothiophen-3-yl group, 6-methylbenzothiophen-3-yl group, 7 -Methylbenzothiophen-3-yl group, 2-methylbenzothiophen-4-yl group, 3-methylbenzothiophen-4-yl group, 5-methylbenzothiophen-4-yl group, 6-methylbenzothiophene-4 -Yl group, 7-methylbenzothiophen-4-yl group, 2-methylbenzothiophen-5-yl group, 3-methylbenzothiophene 5-yl group, 4-methylbenzothiophen-5-yl group, 6-methylbenzothiophen-5-yl group, 7-methylbenzothiophen-5-yl group, 2-methylbenzothiophen-6-yl group, 3 -Methylbenzothiophen-6-yl group, 4-methylbenzothiophen-6-yl group, 5-methylbenzothiophen-6-yl group, 7-methylbenzothiophen-6-yl group, 2-methylbenzothiophene-7 -Yl group, 3-methylbenzothiophen-7-yl group, 4-methylbenzothiophen-7-yl group, 5-methylbenzothiophen-7-yl group, 6-methylbenzothiophen-7-yl group, 3- Methylbenzofuran-2-yl group, 4-methylbenzofuran-2-yl group, 5-methylbenzofuran-2-yl group, 6-methylbenzofuran- -Yl group, 7-methylbenzofuran-2-yl group, 2-methylbenzofuran-3-yl group, 4-methylbenzofuran-3-yl group, 5-methylbenzofuran-3-yl group, 6-methylbenzofuran-3 -Yl group, 7-methylbenzofuran-3-yl group, 2-methylbenzofuran-4-yl group, 3-methylbenzofuran-4-yl group, 5-methylbenzofuran-4-yl group, 6-methylbenzofuran-4 -Yl group, 7-methylbenzofuran-4-yl group, 2-methylbenzofuran-5-yl group, 3-methylbenzofuran-5-yl group, 4-methylbenzofuran-5-yl group, 6-methylbenzofuran-5 -Yl group, 7-methylbenzofuran-5-yl group, 2-methylbenzofuran-6-yl group, 3-methylbenzofuran-6-yl group, 4-methyl Rubenzofuran-6-yl group, 5-methylbenzofuran-6-yl group, 7-methylbenzofuran-6-yl group, 2-methylbenzofuran-7-yl group, 3-methylbenzofuran-7-yl group, 4- Methylbenzofuran-7-yl group, 5-methylbenzofuran-7-yl group, 6-methylbenzofuran-7-yl group, 2-methyldibenzothiophen-1-yl group, 3-methyldibenzothiophen-1-yl group, 4-methyldibenzothiophen-1-yl group, 6-methyldibenzothiophen-1-yl group, 7-methyldibenzothiophen-1-yl group, 8-methyldibenzothiophen-1-yl group, 9-methyldibenzothiophene- 1-yl group, 1-methyldibenzothiophen-2-yl group, 3-methyldibenzothiophen-2-yl group, 4-methyl Dibenzothiophen-2-yl group, 6-methyldibenzothiophen-2-yl group, 7-methyldibenzothiophen-2-yl group, 8-methyldibenzothiophen-2-yl group, 9-methyldibenzothiophen-2-yl group Group, 1-methyldibenzothiophen-3-yl group, 2-methyldibenzothiophen-3-yl group, 4-methyldibenzothiophen-3-yl group, 6-methyldibenzothiophen-3-yl group, 7-methyldibenzo A thiophen-3-yl group, an 8-methyldibenzothiophen-3-yl group,
9-methyldibenzothiophen-3-yl group, 2-methyldibenzofuran-1-yl group, 3-methyldibenzofuran-1-yl group, 4-methyldibenzofuran-1-yl group, 6-methyldibenzofuran-1-yl group 7-methyldibenzofuran-1-yl group, 8-methyldibenzofuran-1-yl group, 9-methyldibenzofuran-1-yl group, 1-methyldibenzofuran-2-yl group, 3-methyldibenzofuran-2-yl group 4-methyldibenzofuran-2-yl group, 6-methyldibenzofuran-2-yl group, 7-methyldibenzofuran-2-yl group, 8-methyldibenzofuran-2-yl group, 9-methyldibenzofuran-2-yl group 1-methyldibenzofuran-3-yl group, 2-methyldibenzofuran-3-yl group, 4-methyldiben Furan-3-yl group, 6-methyldibenzofuran-3-yl group, 7-methyldibenzofuran-3-yl group, 8-methyldibenzofuran-3-yl group, 9-methyldibenzofuran-3-yl group, 3-phenyl Thiophen-2-yl group, 4-phenylthiophen-2-yl group, 5-phenylthiophen-2-yl group, 2-phenylthiophen-3-yl group, 4-phenylthiophen-3-yl group, 5-phenyl Thiophen-3-yl group, 3-phenylfuran-2-yl group, 4-phenylfuran-2-yl group, 5-phenylfuran-2-yl group, 2-phenylfuran-3-yl group, 4-phenyl Furan-3-yl group, 5-phenylfuran-3-yl group, 3-phenylbenzothiophen-2-yl group, 4-phenylbenzothiophen-2-yl group, -Phenylbenzothiophen-2-yl group, 6-phenylbenzothiophen-2-yl group, 7-phenylbenzothiophen-2-yl group, 2-phenylbenzothiophen-3-yl group, 4-phenylbenzothiophene-3 -Yl group, 5-phenylbenzothiophen-3-yl group, 6-phenylbenzothiophen-3-yl group, 7-phenylbenzothiophen-3-yl group, 2-phenylbenzothiophen-4-yl group, 3- Phenylbenzothiophen-4-yl group, 5-phenylbenzothiophen-4-yl group, 6-phenylbenzothiophen-4-yl group, 7-phenylbenzothiophen-4-yl group, 2-phenylbenzothiophen-5- Yl group, 3-phenylbenzothiophen-5-yl group, 4-phenylbenzothiophen-5-yl Group, 6-phenylbenzothiophen-5-yl group, 7-phenylbenzothiophen-5-yl group, 2-phenylbenzothiophen-6-yl group, 3-phenylbenzothiophen-6-yl group, 4-phenylbenzo Thiophen-6-yl group, 5-phenylbenzothiophen-6-yl group, 7-phenylbenzothiophen-6-yl group, 2-phenylbenzothiophen-7-yl group, 3-phenylbenzothiophen-7-yl group 4-phenylbenzothiophen-7-yl group, 5-phenylbenzothiophen-7-yl group, 6-phenylbenzothiophen-7-yl group, 3-phenylbenzofuran-2-yl group, 4-phenylbenzofuran-2 -Yl group, 5-phenylbenzofuran-2-yl group, 6-phenylbenzofuran-2-yl group, 7-fur Nylbenzofuran-2-yl group, 2-phenylbenzofuran-3-yl group, 4-phenylbenzofuran-3-yl group, 5-phenylbenzofuran-3-yl group, 6-phenylbenzofuran-3-yl group, 7- Phenylbenzofuran-3-yl group, 2-phenylbenzofuran-4-yl group, 3-phenylbenzofuran-4-yl group,
5-phenylbenzofuran-4-yl group, 6-phenylbenzofuran-4-yl group, 7-phenylbenzofuran-4-yl group, 2-phenylbenzofuran-5-yl group, 3-phenylbenzofuran-5-yl group, 4-phenylbenzofuran-5-yl group, 6-phenylbenzofuran-5-yl group, 7-phenylbenzofuran-5-yl group, 2-phenylbenzofuran-6-yl group, 3-phenylbenzofuran-6-yl group, 4-phenylbenzofuran-6-yl group, 5-phenylbenzofuran-6-yl group, 7-phenylbenzofuran-6-yl group, 2-phenylbenzofuran-7-yl group, 3-phenylbenzofuran-7-yl group, 4-phenylbenzofuran-7-yl group, 5-phenylbenzofuran-7-yl group, 6-phenylbenzoph N-7-yl group, 2-phenyldibenzothiophen-1-yl group, 3-phenyldibenzothiophen-1-yl group, 4-phenyldibenzothiophen-1-yl group, 6-phenyldibenzothiophen-1-yl group 7-phenyldibenzothiophen-1-yl group, 8-phenyldibenzothiophen-1-yl group, 9-phenyldibenzothiophen-1-yl group, 1-phenyldibenzothiophen-2-yl group, 3-phenyldibenzothiophene 2-yl group, 4-phenyldibenzothiophen-2-yl group, 6-phenyldibenzothiophen-2-yl group, 7-phenyldibenzothiophen-2-yl group, 8-phenyldibenzothiophen-2-yl group, 9-phenyldibenzothiophen-2-yl group, 1-phenyldibenzothiophene- -Yl group, 2-phenyldibenzothiophen-3-yl group, 4-phenyldibenzothiophen-3-yl group, 6-phenyldibenzothiophen-3-yl group, 7-phenyldibenzothiophen-3-yl group, 8- Phenyldibenzothiophen-3-yl group, 9-phenyldibenzothiophen-3-yl group, 2-phenyldibenzofuran-1-yl group, 3-phenyldibenzofuran-1-yl group, 4-phenyldibenzofuran-1-yl group, 6-phenyldibenzofuran-1-yl group, 7-phenyldibenzofuran-1-yl group, 8-phenyldibenzofuran-1-yl group, 9-phenyldibenzofuran-1-yl group, 1-phenyldibenzofuran-2-yl group, 3-phenyldibenzofuran-2-yl group, 4-phenyldibenzofuran-2-yl group Yl group, 6-phenyldibenzofuran-2-yl group, 7-phenyldibenzofuran-2-yl group, 8-phenyldibenzofuran-2-yl group, 9-phenyldibenzofuran-2-yl group, 1-phenyldibenzofuran-3-yl Yl group, 2-phenyldibenzofuran-3-yl group, 4-phenyldibenzofuran-3-yl group, 6-phenyldibenzofuran-3-yl group, 7-phenyldibenzofuran-3-yl group, 8-phenyldibenzofuran-3-yl group Yl group, 9-phenyldibenzofuran-3-yl group,
3- (2-pyridyl) thiophen-2-yl group, 4- (2-pyridyl) thiophen-2-yl group, 5- (2-pyridyl) thiophen-2-yl group, 2- (2-pyridyl) thiophene -3-yl group, 4- (2-pyridyl) thiophen-3-yl group, 5- (2-pyridyl) thiophen-3-yl group, 3- (2-pyridyl) furan-2-yl group, 4- (2-pyridyl) furan-2-yl group, 5- (2-pyridyl) furan-2-yl group, 2- (2-pyridyl) furan-3-yl group, 4- (2-pyridyl) furan-3 -Yl group, 5- (2-pyridyl) furan-3-yl group, 3- (2-pyridyl) benzothiophen-2-yl group, 4- (2-pyridyl) benzothiophen-2-yl group, 5- (2-pyridyl) benzothiophen-2-yl group, 6- (2-pi Dil) benzothiophen-2-yl group, 7- (2-pyridyl) benzothiophen-2-yl group, 2- (2-pyridyl) benzothiophen-3-yl group, 4- (2-pyridyl) benzothiophene- 3-yl group, 5- (2-pyridyl) benzothiophen-3-yl group, 6- (2-pyridyl) benzothiophen-3-yl group, 7- (2-pyridyl) benzothiophen-3-yl group, 2- (2-pyridyl) benzothiophen-4-yl group, 3- (2-pyridyl) benzothiophen-4-yl group, 5- (2-pyridyl) benzothiophen-4-yl group, 6- (2- Pyridyl) benzothiophen-4-yl group, 7- (2-pyridyl) benzothiophen-4-yl group, 2- (2-pyridyl) benzothiophen-5-yl group, 3- (2-pyridyl) benzothi Phen-5-yl group, 4- (2-pyridyl) benzothiophen-5-yl group, 6- (2-pyridyl) benzothiophen-5-yl group, 7- (2-pyridyl) benzothiophen-5-yl Group, 2- (2-pyridyl) benzothiophen-6-yl group, 3- (2-pyridyl) benzothiophen-6-yl group, 4- (2-pyridyl) benzothiophen-6-yl group, 5- ( 2-pyridyl) benzothiophen-6-yl group, 7- (2-pyridyl) benzothiophen-6-yl group, 2- (2-pyridyl) benzothiophen-7-yl group, 3- (2-pyridyl) benzo Thiophen-7-yl group, 4- (2-pyridyl) benzothiophen-7-yl group, 5- (2-pyridyl) benzothiophen-7-yl group, 6- (2-pyridyl) benzothiophen-7-yl Group, 3- (2-pyridyl) benzofuran-2-yl group, 4- (2-pyridyl) benzofuran-2-yl group, 5- (2-pyridyl) benzofuran-2-yl group, 6- (2-pyridyl) ) Benzofuran-2-yl group, 7- (2-pyridyl) benzofuran-2-yl group, 2- (2-pyridyl) benzofuran-3-yl group, 4- (2-pyridyl) benzofuran-3-yl group, 5- (2-pyridyl) benzofuran-3-yl group, 6- (2-pyridyl) benzofuran-3-yl group, 7- (2-pyridyl) benzofuran-3-yl group, 2- (2-pyridyl) benzofuran -4-yl group, 3- (2-pyridyl) benzofuran-4-yl group, 5- (2-pyridyl) benzofuran-4-yl group, 6- (2-pyridyl) benzofuran-4-yl group, 7- (2-pyridyl Benzofuran-4-yl group, 2- (2-pyridyl) benzofuran-5-yl group, 3- (2-pyridyl) benzofuran-5-yl group, 4- (2-pyridyl) benzofuran-5-yl group, 6 -(2-pyridyl) benzofuran-5-yl group, 7- (2-pyridyl) benzofuran-5-yl group, 2- (2-pyridyl) benzofuran-6-yl group, 3- (2-pyridyl) benzofuran- 6-yl group, 4- (2-pyridyl) benzofuran-6-yl group, 5- (2-pyridyl) benzofuran-6-yl group, 7- (2-pyridyl) benzofuran-6-yl group, 2- ( 2-pyridyl) benzofuran-7-yl group,
3- (2-pyridyl) benzofuran-7-yl group, 4- (2-pyridyl) benzofuran-7-yl group, 5- (2-pyridyl) benzofuran-7-yl group, 6- (2-pyridyl) benzofuran -7-yl group, 2- (2-pyridyl) dibenzothiophen-1-yl group, 3- (2-pyridyl) dibenzothiophen-1-yl group, 4- (2-pyridyl) dibenzothiophen-1-yl group 6- (2-pyridyl) dibenzothiophen-1-yl group, 7- (2-pyridyl) dibenzothiophen-1-yl group, 8- (2-pyridyl) dibenzothiophen-1-yl group, 9- (2 -Pyridyl) dibenzothiophen-1-yl group, 1- (2-pyridyl) dibenzothiophen-2-yl group, 3- (2-pyridyl) dibenzothiophen-2-yl group, 4- (2-pyridyl) L) Dibenzothiophen-2-yl group, 6- (2-pyridyl) dibenzothiophen-2-yl group, 7- (2-pyridyl) dibenzothiophen-2-yl group, 8- (2-pyridyl) dibenzothiophene- 2-yl group, 9- (2-pyridyl) dibenzothiophen-2-yl group, 1- (2-pyridyl) dibenzothiophen-3-yl group, 2- (2-pyridyl) dibenzothiophen-3-yl group, 4- (2-pyridyl) dibenzothiophen-3-yl group, 6- (2-pyridyl) dibenzothiophen-3-yl group, 7- (2-pyridyl) dibenzothiophen-3-yl group, 8- (2- Pyridyl) dibenzothiophen-3-yl group, 9- (2-pyridyl) dibenzothiophen-3-yl group, 2- (2-pyridyl) dibenzofuran-1-yl group, 3- (2 Pyridyl) dibenzofuran-1-yl group, 4- (2-pyridyl) dibenzofuran-1-yl group, 6- (2-pyridyl) dibenzofuran-1-yl group, 7- (2-pyridyl) dibenzofuran-1-yl group , 8- (2-pyridyl) dibenzofuran-1-yl group, 9- (2-pyridyl) dibenzofuran-1-yl group, 1- (2-pyridyl) dibenzofuran-2-yl group, 3- (2-pyridyl) Dibenzofuran-2-yl group, 4- (2-pyridyl) dibenzofuran-2-yl group, 6- (2-pyridyl) dibenzofuran-2-yl group, 7- (2-pyridyl) dibenzofuran-2-yl group, 8 -(2-pyridyl) dibenzofuran-2-yl group, 9- (2-pyridyl) dibenzofuran-2-yl group, 1- (2-pyridyl) dibenzofuran-3-yl group, 2- (2-pyridyl) dibenzofuran-3-yl group, 4- (2-pyridyl) dibenzofuran-3-yl group, 6- (2-pyridyl) dibenzofuran-3-yl group, 7- (2-pyridyl) dibenzofuran-3 -Yl group, 8- (2-pyridyl) dibenzofuran-3-yl group, 9- (2-pyridyl) dibenzofuran-3-yl group, 3- (3-pyridyl) thiophen-2-yl group, 4- (3 -Pyridyl) thiophen-2-yl group, 5- (3-pyridyl) thiophen-2-yl group, 2- (3-pyridyl) thiophen-3-yl group, 4- (3-pyridyl) thiophen-3-yl Group, 5- (3-pyridyl) thiophen-3-yl group, 3- (3-pyridyl) furan-2-yl group, 4- (3-pyridyl) furan-2-yl group, 5- (3-pyridyl) ) Furan-2-yl group 2- (3-pyridyl) furan-3-yl group, 4- (3-pyridyl) furan-3-yl group, 5- (3-pyridyl) furan-3-yl group,
3- (3-pyridyl) benzothiophen-2-yl group, 4- (3-pyridyl) benzothiophen-2-yl group, 5- (3-pyridyl) benzothiophen-2-yl group, 6- (3- Pyridyl) benzothiophen-2-yl group, 7- (3-pyridyl) benzothiophen-2-yl group, 2- (3-pyridyl) benzothiophen-3-yl group, 4- (3-pyridyl) benzothiophene- 3-yl group, 5- (3-pyridyl) benzothiophen-3-yl group, 6- (3-pyridyl) benzothiophen-3-yl group, 7- (3-pyridyl) benzothiophen-3-yl group, 2- (3-pyridyl) benzothiophen-4-yl group, 3- (3-pyridyl) benzothiophen-4-yl group, 5- (3-pyridyl) benzothiophen-4-yl group, 6- (3- Pilisi ) Benzothiophen-4-yl group, 7- (3-pyridyl) benzothiophen-4-yl group, 2- (3-pyridyl) benzothiophen-5-yl group, 3- (3-pyridyl) benzothiophene-5 -Yl group, 4- (3-pyridyl) benzothiophen-5-yl group, 6- (3-pyridyl) benzothiophen-5-yl group, 7- (3-pyridyl) benzothiophen-5-yl group, 2 -(3-pyridyl) benzothiophen-6-yl group, 3- (3-pyridyl) benzothiophen-6-yl group, 4- (3-pyridyl) benzothiophen-6-yl group, 5- (3-pyridyl) ) Benzothiophen-6-yl group, 7- (3-pyridyl) benzothiophen-6-yl group, 2- (3-pyridyl) benzothiophen-7-yl group, 3- (3-pyridyl) benzothiol N-7-yl group, 4- (3-pyridyl) benzothiophen-7-yl group, 5- (3-pyridyl) benzothiophen-7-yl group, 6- (3-pyridyl) benzothiophen-7-yl Group, 3- (3-pyridyl) benzofuran-2-yl group, 4- (3-pyridyl) benzofuran-2-yl group, 5- (3-pyridyl) benzofuran-2-yl group, 6- (3-pyridyl) ) Benzofuran-2-yl group, 7- (3-pyridyl) benzofuran-2-yl group, 2- (3-pyridyl) benzofuran-3-yl group, 4- (3-pyridyl) benzofuran-3-yl group, 5- (3-pyridyl) benzofuran-3-yl group, 6- (3-pyridyl) benzofuran-3-yl group, 7- (3-pyridyl) benzofuran-3-yl group, 2- (3-pyridyl) benzofuran -4-I Group, 3- (3-pyridyl) benzofuran-4-yl group, 5- (3-pyridyl) benzofuran-4-yl group, 6- (3-pyridyl) benzofuran-4-yl group, 7- (3- Pyridyl) benzofuran-4-yl group, 2- (3-pyridyl) benzofuran-5-yl group, 3- (3-pyridyl) benzofuran-5-yl group, 4- (3-pyridyl) benzofuran-5-yl group 6- (3-pyridyl) benzofuran-5-yl group, 7- (3-pyridyl) benzofuran-5-yl group, 2- (3-pyridyl) benzofuran-6-yl group, 3- (3-pyridyl) Benzofuran-6-yl group, 4- (3-pyridyl) benzofuran-6-yl group, 5- (3-pyridyl) benzofuran-6-yl group, 7- (3-pyridyl) benzofuran-6-yl group, 2 -(3-Pyridi ) Benzofuran-7-yl group, 3- (3-pyridyl) benzofuran-7-yl group, 4- (3-pyridyl) benzofuran-7-yl group, 5- (3-pyridyl) benzofuran-7-yl group, 6- (3-pyridyl) benzofuran-7-yl group,
2- (3-pyridyl) dibenzothiophen-1-yl group, 3- (3-pyridyl) dibenzothiophen-1-yl group, 4- (3-pyridyl) dibenzothiophen-1-yl group, 6- (3- Pyridyl) dibenzothiophen-1-yl group, 7- (3-pyridyl) dibenzothiophen-1-yl group, 8- (3-pyridyl) dibenzothiophen-1-yl group, 9- (3-pyridyl) dibenzothiophene- 1-yl group, 1- (3-pyridyl) dibenzothiophen-2-yl group, 3- (3-pyridyl) dibenzothiophen-2-yl group, 4- (3-pyridyl) dibenzothiophen-2-yl group, 6- (3-pyridyl) dibenzothiophen-2-yl group, 7- (3-pyridyl) dibenzothiophen-2-yl group, 8- (3-pyridyl) dibenzothiophene-2 Yl group, 9- (3-pyridyl) dibenzothiophen-2-yl group, 1- (3-pyridyl) dibenzothiophen-3-yl group, 2- (3-pyridyl) dibenzothiophen-3-yl group, 4- (3-pyridyl) dibenzothiophen-3-yl group, 6- (3-pyridyl) dibenzothiophen-3-yl group, 7- (3-pyridyl) dibenzothiophen-3-yl group, 8- (3-pyridyl) Dibenzothiophen-3-yl group, 9- (3-pyridyl) dibenzothiophen-3-yl group, 2- (3-pyridyl) dibenzofuran-1-yl group, 3- (3-pyridyl) dibenzofuran-1-yl group 4- (3-pyridyl) dibenzofuran-1-yl group, 6- (3-pyridyl) dibenzofuran-1-yl group, 7- (3-pyridyl) dibenzofuran-1-yl group, -(3-pyridyl) dibenzofuran-1-yl group, 9- (3-pyridyl) dibenzofuran-1-yl group, 1- (3-pyridyl) dibenzofuran-2-yl group, 3- (3-pyridyl) dibenzofuran- 2-yl group, 4- (3-pyridyl) dibenzofuran-2-yl group, 6- (3-pyridyl) dibenzofuran-2-yl group, 7- (3-pyridyl) dibenzofuran-2-yl group, 8- ( 3-pyridyl) dibenzofuran-2-yl group, 9- (3-pyridyl) dibenzofuran-2-yl group, 1- (3-pyridyl) dibenzofuran-3-yl group, 2- (3-pyridyl) dibenzofuran-3- Yl group, 4- (3-pyridyl) dibenzofuran-3-yl group, 6- (3-pyridyl) dibenzofuran-3-yl group, 7- (3-pyridyl) dibenzofuran-3-yl Group, 8- (3-pyridyl) dibenzofuran-3-yl group, 9- (3-pyridyl) dibenzofuran-3-yl group, 3- (4-pyridyl) thiophen-2-yl group, 4- (4-pyridyl) ) Thiophen-2-yl group, 5- (4-pyridyl) thiophen-2-yl group, 2- (4-pyridyl) thiophen-3-yl group, 4- (4-pyridyl) thiophen-3-yl group, 5- (4-pyridyl) thiophen-3-yl group, 3- (4-pyridyl) furan-2-yl group, 4- (4-pyridyl) furan-2-yl group, 5- (4-pyridyl) furan 2-yl group, 2- (4-pyridyl) furan-3-yl group, 4- (4-pyridyl) furan-3-yl group, 5- (4-pyridyl) furan-3-yl group, 3- (4-pyridyl) benzothiophen-2-yl group, 4- (4-pi Dil) benzothiophen-2-yl group, 5- (4-pyridyl) benzothiophen-2-yl group, 6- (4-pyridyl) benzothiophen-2-yl group, 7- (4-pyridyl) benzothiophene- 2-yl group, 2- (4-pyridyl) benzothiophen-3-yl group, 4- (4-pyridyl) benzothiophen-3-yl group,
5- (4-pyridyl) benzothiophen-3-yl group, 6- (4-pyridyl) benzothiophen-3-yl group, 7- (4-pyridyl) benzothiophen-3-yl group, 2- (4- Pyridyl) benzothiophen-4-yl group, 3- (4-pyridyl) benzothiophen-4-yl group, 5- (4-pyridyl) benzothiophen-4-yl group, 6- (4-pyridyl) benzothiophene- 4-yl group, 7- (4-pyridyl) benzothiophen-4-yl group, 2- (4-pyridyl) benzothiophen-5-yl group, 3- (4-pyridyl) benzothiophen-5-yl group, 4- (4-pyridyl) benzothiophen-5-yl group, 6- (4-pyridyl) benzothiophen-5-yl group, 7- (4-pyridyl) benzothiophen-5-yl group, 2- (4- Pilisi ) Benzothiophen-6-yl group, 3- (4-pyridyl) benzothiophen-6-yl group, 4- (4-pyridyl) benzothiophen-6-yl group, 5- (4-pyridyl) benzothiophene-6 -Yl group, 7- (4-pyridyl) benzothiophen-6-yl group, 2- (4-pyridyl) benzothiophen-7-yl group, 3- (4-pyridyl) benzothiophen-7-yl group, 4 -(4-pyridyl) benzothiophen-7-yl group, 5- (4-pyridyl) benzothiophen-7-yl group, 6- (4-pyridyl) benzothiophen-7-yl group, 3- (4-pyridyl) ) Benzofuran-2-yl group, 4- (4-pyridyl) benzofuran-2-yl group, 5- (4-pyridyl) benzofuran-2-yl group, 6- (4-pyridyl) benzofuran-2-yl group 7- (4-pyridyl) benzofuran-2-yl group, 2- (4-pyridyl) benzofuran-3-yl group, 4- (4-pyridyl) benzofuran-3-yl group, 5- (4-pyridyl) benzofuran -3-yl group, 6- (4-pyridyl) benzofuran-3-yl group, 7- (4-pyridyl) benzofuran-3-yl group, 2- (4-pyridyl) benzofuran-4-yl group, 3- (4-pyridyl) benzofuran-4-yl group, 5- (4-pyridyl) benzofuran-4-yl group, 6- (4-pyridyl) benzofuran-4-yl group, 7- (4-pyridyl) benzofuran-4 -Yl group, 2- (4-pyridyl) benzofuran-5-yl group, 3- (4-pyridyl) benzofuran-5-yl group, 4- (4-pyridyl) benzofuran-5-yl group, 6- (4 -Pyridyl) Nzofuran-5-yl group, 7- (4-pyridyl) benzofuran-5-yl group, 2- (4-pyridyl) benzofuran-6-yl group, 3- (4-pyridyl) benzofuran-6-yl group, 4 -(4-pyridyl) benzofuran-6-yl group, 5- (4-pyridyl) benzofuran-6-yl group, 7- (4-pyridyl) benzofuran-6-yl group, 2- (4-pyridyl) benzofuran- 7-yl group, 3- (4-pyridyl) benzofuran-7-yl group, 4- (4-pyridyl) benzofuran-7-yl group, 5- (4-pyridyl) benzofuran-7-yl group, 6- ( 4-pyridyl) benzofuran-7-yl group, 2- (4-pyridyl) dibenzothiophen-1-yl group, 3- (4-pyridyl) dibenzothiophen-1-yl group, 4- (4-pyridyl) dibenzothio E emission-1-yl group, 6- (4-pyridyl) dibenzothiophene-1-yl group, 7- (4-pyridyl) dibenzothiophene-1-yl group,
8- (4-pyridyl) dibenzothiophen-1-yl group, 9- (4-pyridyl) dibenzothiophen-1-yl group, 1- (4-pyridyl) dibenzothiophen-2-yl group, 3- (4- Pyridyl) dibenzothiophen-2-yl group, 4- (4-pyridyl) dibenzothiophen-2-yl group, 6- (4-pyridyl) dibenzothiophen-2-yl group, 7- (4-pyridyl) dibenzothiophene- 2-yl group, 8- (4-pyridyl) dibenzothiophen-2-yl group, 9- (4-pyridyl) dibenzothiophen-2-yl group, 1- (4-pyridyl) dibenzothiophen-3-yl group, 2- (4-pyridyl) dibenzothiophen-3-yl group, 4- (4-pyridyl) dibenzothiophen-3-yl group, 6- (4-pyridyl) dibenzothiophene-3 Yl group, 7- (4-pyridyl) dibenzothiophen-3-yl group, 8- (4-pyridyl) dibenzothiophen-3-yl group, 9- (4-pyridyl) dibenzothiophen-3-yl group, 2- (4-pyridyl) dibenzofuran-1-yl group, 3- (4-pyridyl) dibenzofuran-1-yl group, 4- (4-pyridyl) dibenzofuran-1-yl group, 6- (4-pyridyl) dibenzofuran-1 -Yl group, 7- (4-pyridyl) dibenzofuran-1-yl group, 8- (4-pyridyl) dibenzofuran-1-yl group, 9- (4-pyridyl) dibenzofuran-1-yl group, 1- (4 -Pyridyl) dibenzofuran-2-yl group, 3- (4-pyridyl) dibenzofuran-2-yl group, 4- (4-pyridyl) dibenzofuran-2-yl group, 6- (4-pyridyl) Benzofuran-2-yl group, 7- (4-pyridyl) dibenzofuran-2-yl group, 8- (4-pyridyl) dibenzofuran-2-yl group, 9- (4-pyridyl) dibenzofuran-2-yl group, 1 -(4-pyridyl) dibenzofuran-3-yl group, 2- (4-pyridyl) dibenzofuran-3-yl group, 4- (4-pyridyl) dibenzofuran-3-yl group, 6- (4-pyridyl) dibenzofuran- A 3-yl group, a 7- (4-pyridyl) dibenzofuran-3-yl group, an 8- (4-pyridyl) dibenzofuran-3-yl group, or a 9- (4-pyridyl) dibenzofuran-3-yl group is preferable. Take as an example. Of these substituents, hydrogen atoms, phenyl groups, p-tolyl groups, biphenyl-2-yl groups, biphenyl-3-yl groups, biphenyl-4-yl groups, 3 -(2-pyridyl) phenyl group, 4- (2-pyridyl) phenyl group, 3- (3-pyridyl) phenyl group, 4- (3-pyridyl) phenyl group, 2-pyridyl group, 3-pyridyl group, 4 -Pyridyl group, 2-phenylpyridin-6-yl group, 2-phenylpyridin-5-yl group, 2-phenylpyridin-4-yl group, 3-phenylpyridin-5-yl group, 3-phenylpyridin-6 -Yl group, 2,6-diphenylpyridin-4-yl group, 4,6-diphenylpyridin-2-yl group, 2-pyrimidyl group, 2-pyrazyl group, 1-naphthyl group, 2-naphthyl group, 3- Quinolyl 4-quinolyl group, 3-isoquinolyl group, 2-benzothienyl group, 2-benzofuryl group, 2-fluorenyl group, 9,9-dimethylfluoren-2-yl group, 9,9-diphenylfluorene-2- Yl, 9-anthranyl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 9-phenanthryl, 2-dibenzothienyl, 2-dibenzofuryl, 4-dibenzothienyl, 4-dibenzofuryl Group, 3-fluoranthenyl group, 1-pyrenyl group, 2-triphenylenyl group and the like are preferable. Ar ² Among these substituents, phenyl group, p-tolyl group, biphenyl-2-yl group, biphenyl-3-yl group, biphenyl-4-yl group, 3- (2-pyridyl) phenyl group, 4- (2-pyridyl) phenyl group, 3- (3-pyridyl) phenyl group, 4- (3-pyridyl) phenyl group, 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 2-phenylpyridine-6- Yl group, 2-phenylpyridin-5-yl group, 2-phenylpyridin-4-yl group, 3-phenylpyridin-5-yl group, 3-phenylpyridin-6-yl group, 2,6-diphenylpyridine- 4-yl group, 4,6-diphenylpyridin-2-yl group, 2-pyrimidyl group, 2-pyrazyl group, 1-naphthyl group, 2-naphthyl group, 3-quinolyl group, 4-quinolyl group, 3-isoquinolyl Base 2-benzothienyl group, 2-benzofuryl group, 2-fluorenyl group, 9,9-dimethylfluoren-2-yl group, 9,9-diphenylfluoren-2-yl group, 9-anthranyl group, 1-phenanthryl Group, 2-phenanthryl group, 3-phenanthryl group, 9-phenanthryl group, 2-dibenzothienyl group, 2-dibenzofuryl group, 4-dibenzothienyl group, 4-dibenzofuryl group, 3-fluoranthenyl group, 1- A pyrenyl group, a 2-triphenylenyl group, or the like is preferable. Furthermore, 3- (2-pyridyl) phenyl group, 4- (2-pyridyl) phenyl group, 3- (3-pyridyl) phenyl group, 4- (3-pyridyl) phenyl group, 2-pyridyl group, 3-pyridyl Group, 4-pyridyl group, 2-phenylpyridin-6-yl group, 2-phenylpyridin-5-yl group, 2-phenylpyridin-4-yl group, 3-phenylpyridin-5-yl group, 3-phenyl Pyridin-6-yl group, 3-quinolyl group, 4-quinolyl group, 3-isoquinolyl group, 2-benzothienyl group, 2-benzofuryl group, 2-fluorenyl group, 9,9-dimethylfluoren-2-yl group 9,9-diphenylfluoren-2-yl group, 2-dibenzothienyl group, 2-dibenzofuryl group, 4-dibenzothienyl group, 4-dibenzofuryl group and the like are particularly preferable.

Ar ³ and Ar ⁴ are each independently a phenyl group, a naphthyl group, or a pyridyl group (these groups may be substituted with a fluorine atom, a methyl group, or a phenyl group), a hydrogen atom, and a carbon number. It represents a single bond to form 1-4 alkyl group, or ^{X 2} and.

The alkyl group having 1 to 4 carbon atoms in Ar ³ and Ar ⁴ is not particularly limited, but a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a t-butyl group, or the like Is a preferred example.
The phenyl group, naphthyl group, and pyridyl group substituted with a fluorine atom in Ar ³ and Ar ⁴ are not particularly limited, and examples thereof include the same groups as Ar ¹ .
The phenyl group, naphthyl group, and pyridyl group substituted with a methyl group in Ar ³ and Ar ⁴ are not particularly limited, and examples thereof include the same groups as Ar ¹ .
The phenyl group, naphthyl group, and pyridyl group substituted with a phenyl group in Ar ³ and Ar ⁴ are not particularly limited, and examples thereof include the same groups as Ar ¹ .

Ar ³ and Ar ⁴ are each preferably a single bond formed with a hydrogen atom, a phenyl group, a naphthyl group, a biphenyl group, a pyridyl group, or X ² independently from the viewpoint of excellent electron transporting material properties. Yes. Ar ³ and Ar ⁴ are each more preferably a hydrogen atom or a single bond formed with X ² independently from the viewpoint of easy synthesis.

Specific examples of the phenyl group, naphthyl group, or pyridyl group in Ar ³ and Ar ⁴ (these groups may be substituted with a fluorine atom, a methyl group, or a phenyl group) are particularly limited. Although it is not, the same group as Ar ¹ is mentioned. Of these substituents, phenyl group, biphenyl-3-yl group, biphenyl-4-yl group, 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 1 -A naphthyl group or a 2-naphthyl group is preferable, and a phenyl group is particularly preferable in terms of easy synthesis.

Ar ⁵ and Ar ⁶ are each independently a phenyl group, a naphthyl group, a pyridyl group (these groups may be substituted with a fluorine atom, a methyl group, or a phenyl group), a hydrogen atom, or a carbon atom. The alkyl group of number 1-4 is represented. Ar ⁵ or Ar ⁶ may be a single bond that binds to X ² .

Although it does not specifically limit as a C1-C4 alkyl group in Ar < ⁵ > and Ar < ⁶ >, A methyl group, an ethyl group, a propyl group, an isopropyl group, n-butyl group, or t-butyl group etc. Is a preferred example.
The phenyl group, naphthyl group, and pyridyl group substituted with a fluorine atom in Ar ⁵ and Ar ⁶ are not particularly limited, and examples thereof include the same groups as Ar ¹ .
The phenyl group, naphthyl group, and pyridyl group substituted with a methyl group in Ar ⁵ and Ar ⁶ are not particularly limited, and examples thereof include the same groups as Ar ¹ .
The phenyl group, naphthyl group, and pyridyl group substituted with a phenyl group in Ar ⁵ and Ar ⁶ are not particularly limited, and examples thereof include the same groups as Ar ¹ .

Ar ⁵ and Ar ⁶ are each independently a single bond bonded to a hydrogen atom, a phenyl group, a tolyl group, a naphthyl group, a biphenyl group, a pyridyl group, or X ^{2 in} terms of excellent electron transporting material properties. It is preferable that it is a single bond bonded to a hydrogen atom or X ^{2 in} terms of easy synthesis.

W ¹ , W ² , and W ³ each independently represent C—H or a nitrogen atom, and W ¹ , W ² , and W ³ all represent C—H, or W ¹ , W ² , W ³ represents a nitrogen atom, and the remaining two represent C—H. That is, W ¹ , W ² , and W ³ each independently represent C—H or a nitrogen atom, and at least two represent C—H.
W ¹ , W ² , and W ³ are all preferably C—H from the viewpoint of easy synthesis.

X ¹ and X ² are each independently a phenylene group, a naphthylene group, a biphenylene group, or a pyridylene group (these groups may be substituted with a fluorine atom, a methyl group, or a phenyl group), or a single group. Represents a bond.
X ¹ and X ² are each independently
Single bond;
It is preferably an unsubstituted phenylene group, naphthylene group, biphenylene group, or pyridylene group.
Of these groups, a single bond, a phenylene group, or a pyridylene group is more preferable independently from the viewpoint of easy availability of raw materials.

  Z represents a nitrogen atom or C—H. Among these, it is preferable that Z is a nitrogen atom at the point which is excellent in an electron transport material characteristic.

Y ¹ , Y ² , Y ³ , and Y ⁴ each independently represent a group represented by C—R or a nitrogen atom. R represents a phenyl group, a naphthyl group, or a pyridyl group (these groups may be substituted with a fluorine atom, a methyl group, or a phenyl group), a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and 1 carbon atom. Represents an alkenyl group of ˜4.

Further, when any of Y ¹ , Y ² , Y ³ , and Y ⁴ represents a nitrogen atom, only one of Y ¹ , Y ² , Y ³ , and Y ⁴ is a nitrogen atom, and the rest is C Groups represented by -R (R each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 1 to 4 carbon atoms, a phenyl group, a naphthyl group, or a pyridyl group. , A naphthyl group, or a pyridyl group may be substituted with a fluorine atom, a methyl group, or a phenyl group), from the viewpoint of easy synthesis.

Among these, Y ¹ , Y ² , Y ³ , and Y ⁴ are all groups represented by C—R (where each R is independently a hydrogen atom or a carbon atom having 1 to 4 carbon atoms) in that synthesis is easy. It is preferably an alkyl group, an alkenyl group having 1 to 4 carbon atoms, a phenyl group, a naphthyl group, or a pyridyl group. It is more preferable that Y ¹ , Y ² , Y ³ , and Y ⁴ are all groups represented by C—H.

  R may be bonded to each other to form an aromatic ring. In addition, although it does not specifically limit as a compound which R couple | bonded together and formed the aromatic ring, For example, Formula (1f) or (1g) etc. which are mentioned later are mentioned.

  The compound represented by the formula (1) is not particularly limited. For example, the following formula (1a), (1b), (1c), (1d), (1e), (1f), or (1g) and the like can be embodied.

(In the formulas (1a), (1b), (1c), (1d), (1e), (1f), and (1g), Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , Ar ⁵ , Ar ⁶ , X ¹ , X ² , Z, Y ¹ , Y ² , Y ³ , Y ⁴ , and R are as defined in the above formula (1).)

  In formula (1a), (1b), (1c), (1d), (1e), (1f), or (1g), the preferred range of each definition is the same as the preferred range shown in formula (1) It is.

  When the cyclic azine compound (1) according to one embodiment of the present invention is used as a part of the components of the organic electroluminescent device, effects such as high luminous efficiency, long life, and low voltage can be obtained. In particular, this effect is prominent when used as an electron transport layer or a hole blocking layer.

  Among the compounds represented by the formula (1), specific examples of particularly preferable compounds include the following (A-1) to (A-1356), but the present disclosure is not limited thereto.

Hereinafter, the use of the cyclic azine compound (1) will be described.
Although it does not specifically limit about the cyclic azine compound (1) concerning 1 aspect of this invention, For example, it can use as a material for organic electroluminescent elements.
Therefore, the organic electroluminescent element material according to one embodiment of the present invention includes the cyclic azine compound (1).

  In a broad sense, the light emitting layer in an organic electroluminescent element refers to a layer that emits light when a current is passed through an electrode composed of a cathode and an anode. Specifically, it refers to a layer containing a fluorescent compound that emits light when an electric current is passed through an electrode composed of a cathode and an anode. Usually, an organic electroluminescent element has a structure in which a light emitting layer is sandwiched between a pair of electrodes.

The organic electroluminescent device according to one embodiment of the present invention includes a hole transport layer, an electron transport layer, an anode buffer layer, a cathode buffer layer, and the like in addition to the light emitting layer as necessary, and is sandwiched between the cathode and the anode. Take the structure. Specific examples include the structures shown below.
(I) Anode / light emitting layer / cathode (ii) Anode / hole transport layer / light emitting layer / cathode (iii) Anode / light emitting layer / electron transport layer / cathode (iv) anode / hole transport layer / light emitting layer / electron Transport layer / cathode (v) anode / anode buffer layer / hole transport layer / light emitting layer / electron transport layer / cathode buffer layer / cathode

  A conventionally known light emitting material can be used for the light emitting layer. As a method for forming the light emitting layer, for example, there is a method of forming a thin film by a known method such as a vapor deposition method, a spin coating method, a casting method, or an LB method.

  The light emitting layer can be obtained by dissolving the light emitting material in a solvent together with a binder such as a resin to form a solution, and then applying the solution by a spin coating method or the like to form a thin film.

  There is no restriction | limiting in particular about the film thickness of the light emitting layer formed in this way, Although it can select suitably according to a condition, Usually, it is the range of 5 nm-5 micrometers.

  Next, other layers constituting the organic electroluminescence device in combination with the light emitting layer, such as a hole injection layer, a hole transport layer, an electron injection layer, and an electron transport layer, will be described.

  The hole injection layer and the hole transport layer have a function of transmitting the 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. Thus, many holes are injected into the light emitting layer with a lower electric field.

  In addition, electrons injected from the cathode and transported from the electron injection layer and / or the electron transport layer to the light-emitting layer are generated by the electron barrier existing at the interface between the light-emitting layer and the hole injection layer or the hole transport layer. It accumulates at the interface in the light emitting layer without leaking into the injection layer or the hole transport layer, resulting in an element with excellent light emitting performance such as improved luminous efficiency.

  The hole injection material and the hole transport material have any one of hole injection or transport and electron barrier properties, and may be either organic or inorganic. Examples of the hole injection material and hole transport material include triazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives and pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, oxazoles. Derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aniline copolymers, and conductive polymer oligomers, particularly thiophene oligomers. As the hole injecting material and the hole transporting material, those described above can be used, and porphyrin compounds, aromatic tertiary amine compounds, and styrylamine compounds, particularly aromatic tertiary amine compounds can be used. preferable.

  Representative examples of the aromatic tertiary amine compound and 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- Tolylaminophenyl) -4-phenylcyclohexane, bis (4-dimethylamino-2-methylphenyl) phenylmethane, bis (4-di-p-tolylaminophenyl) phenylmethane, N, N′-diphenyl-N, N -Di (4-methoxyphenyl) -4,4'-diaminobiphenyl, N, N, N ', N'-tetraphenyl-4,4'-diaminodiphenyl ether, 4,4'-bis (diphenylamino) quadri Phenyl, N, N, N-tri (p-tolyl) amine, 4- (di-p-tolylamino) -4 ′-[4- (di-p-tolylamino) styryl] stilbene, 4-N, N-diphenyl Amino- (2-diphenylvinyl) benzene, 3-methoxy-4′-N, N-diphenylaminostilbenzene, N-phenylcarbazole, 4,4′-bis [N- (1-naphthyl) -N-phenylamino ] Biphenyl (NPD), 4,4 ′, 4 ″ -tris [N- (3-methylphenyl) -N-phenylamino] triphenylamine (MTDATA) and the like. That.

  In addition, inorganic compounds such as p-type-Si and p-type-SiC can also be used as the hole injection material and the hole transport material. The hole injection layer and the hole transport layer are formed by thinning the hole injection material and the hole transport material by a known method such as a vacuum deposition method, a spin coating method, a casting method, or an LB method. Can be formed. Although there is no restriction | limiting in particular about the film thickness of a positive hole injection layer and a positive hole transport layer, Usually, it is about 5 nm-5 micrometers. The hole injection layer and hole transport layer may have a single layer structure composed of one or more of the above materials, or may have a multilayer structure composed of a plurality of layers having the same composition or different compositions.

  In the organic electroluminescence device according to one embodiment of the present invention, the electron transport layer preferably includes a cyclic azine compound represented by the above formula (1). Therefore, the electron transport material for organic electroluminescent elements according to one embodiment of the present invention includes the cyclic azine compound (1). In addition, about the cyclic azine compound (1) concerning 1 aspect of this invention, it can also be used other than the electron carrying layer of an organic electroluminescent element.

  The electron transport layer may be formed by forming a cyclic azine compound represented by the above formula (1) by a known thin film forming method such as a vacuum deposition method, a spin coating method, a casting method, or an LB method. it can. The thickness of the electron transport layer is not particularly limited, but is usually selected in the range of 5 nm to 5 μm. In addition, the electron transport layer preferably includes a cyclic azine compound represented by the formula (1), may include a conventionally known electron transport material, and has a single-layer structure composed of one kind or two or more kinds. Alternatively, a laminated structure composed of a plurality of layers having the same composition or different compositions may be used.

  In addition, the light emitting material is not limited to the light emitting layer, and one kind may be contained in the hole transport layer or the electron transport layer adjacent to the light emitting layer, thereby further increasing the light emission efficiency of the organic electroluminescent device. be able to.

  There are no particular limitations on the type of glass, plastic, etc. The substrate is not particularly limited as long as it is transparent. Examples of the substrate preferably used in the organic electroluminescent device according to one embodiment of the present invention include glass, quartz, and a light-transmitting plastic film.

  Examples of the light transmissive plastic film include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyethersulfone (PES), polyetherimide, polyetheretherketone, polyphenylene sulfide, polyarylate, polyimide, and polycarbonate (PC). And a film made of cellulose triacetate (TAC), cellulose acetate propionate (CAP), or the like.

  A suitable example for producing an organic electroluminescent element will be described. As an example, a method for producing an organic electroluminescent element composed of the anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode will be described.

  First, a thin film made of a desired electrode material, for example, an anode material, is formed on a suitable substrate by a method such as vapor deposition or sputtering so as to have a film thickness of 1 μm or less, preferably 10 to 200 nm. An anode is produced. Next, a thin film comprising a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer / electron injection layer, which is a device material, is formed thereon.

  A buffer layer (electrode interface layer) may exist between the anode and the light emitting layer or the hole injection layer and between the cathode and the light emitting layer or the electron injection layer.

  Furthermore, in addition to the basic constituent layer, a layer having other functions may be laminated as necessary. For example, a functional layer such as a hole blocking layer or an electron blocking layer may be provided.

Next, an electrode of the organic electroluminescent element according to one embodiment of the present invention will be described. As the anode in the organic electroluminescence device, an electrode material made of a metal, an alloy, an electrically conductive compound, or a mixture thereof having a high work function (4 eV or more) is preferably used. Specific examples of such an electrode substance include a conductive transparent material such as a metal such as Au, CuI, indium-tin oxide (ITO), SnO ₂ , and ZnO.

  The anode may be formed by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering, and a pattern having a desired shape may be formed by photolithography, or the pattern may be formed through a mask having a desired shape at the time of vapor deposition or sputtering. May be formed.

On the other hand, as the cathode, those using an electrode substance of a metal having a small work function (4 eV or less) (referred to as an electron injecting metal), an alloy, an electrically conductive compound and a mixture thereof are preferably used. Specific examples of such electrode materials 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 ) Mixtures, indium, lithium / aluminum mixtures, rare earth metals and the like. Among these, a mixture of an electron injecting metal and a second metal which is a stable metal having a larger work function value than this from the viewpoint of durability against electron injecting and oxidation, for example, a magnesium / silver mixture, magnesium An aluminum / aluminum mixture, a magnesium / indium mixture, an aluminum / aluminum oxide (Al ₂ O ₃ ) mixture, a lithium / aluminum mixture, and the like are preferable. The cathode can be produced by forming a thin film from these electrode materials by a method such as vapor deposition or sputtering.

  As described above, a thin film made of a desired electrode material, for example, an anode material, is formed on a suitable substrate by a method such as vapor deposition or sputtering so as to have a film thickness of 1 μm or less, preferably 10 to 200 nm. After preparing the anode, after forming each layer thin film consisting of the hole injection layer, the hole transport layer, the light emitting layer, the electron transport layer / electron injection layer on the anode as described above, for the cathode A thin film made of a substance is formed by a method such as vapor deposition or sputtering so as to have a film thickness of 1 μm or less, preferably in a range of 50 to 200 nm, and a desired organic electroluminescent device is obtained.

  The organic electroluminescence device according to one embodiment of the present invention may be used as a kind of lamp for illumination or an exposure light source, or may be a projection device that projects an image, or directly recognizes a still image or a moving image. It may be used as a type of display device (display). When used as a display device for reproducing moving images, the driving method may be either a simple matrix (passive matrix) method or an active matrix method. A full-color display device can be manufactured by using two or more organic electroluminescent elements according to one embodiment of the present invention having different emission colors.

Next, a manufacturing method according to one embodiment of the present invention will be described.
The cyclic azine compound (1) according to one embodiment of the present invention is not particularly limited. For example, in the presence or absence of a base, in the presence of a palladium catalyst, the following reaction formulas (1) to (1) (4) It can manufacture by the method shown by either.

(In the reaction formula (1), Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , Ar ⁵ , Ar ⁶ , X ¹ , X ² , Z, W ¹ , W ² , W ³ , Y ¹ , Y ² , Y ³ and Y ⁴ represent the same substituent as in the formula (1), A ¹ and A ² represent a leaving group described later, and M ³ and M ⁴ represent a substituent described later. )

(In the reaction formula (2), Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , Ar ⁵ , Ar ⁶ , X ¹ , X ² , Z, W ¹ , W ² , W ³ , Y ¹ , Y ² , Y ³ and Y ⁴ represent the same substituent as in the formula (1), A ² and A ³ represent a leaving group described later, and M ¹ and M ⁴ represent a substituent described later. )

(In Reaction Formula (3), Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , Ar ⁵ , Ar ⁶ , X ¹ , X ² , Z, W ¹ , W ² , W ³ , Y ¹ , Y ² , Y ³ and Y ⁴ represent the same substituent as in formula (1), A ⁴ represents a leaving group described later, and M ² represents a substituent described later.

(In the reaction formula (4), Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , Ar ⁵ , Ar ⁶ , X ¹ , X ² , Z, W ¹ , W ² , W ³ , Y ¹ , Y ² , Y ³ and Y ⁴ represent the same substituent as in the formula (1), A ² represents a leaving group described later, and M ⁴ represents a substituent described later.

  Hereinafter, the compound represented by formula (2a) is referred to as compound (2a). The same applies to compound (3a), compound (4a), compound (5a), compound (3b), compound (4b), compound (5b), compound (4c), compound (1g) and the like. Hereinafter, the definition of these compounds will be described.

A ¹ , A ² , A ³ , and A ⁴ represent a leaving group and are not particularly limited, and examples thereof include a chlorine atom, a bromine atom, an iodine atom, or a triflate independently. Of these, a bromine atom or a chlorine atom is preferable independently from the viewpoint of good reaction yield. However, it may be preferable to use triflate because of the availability of raw materials.

M ¹ , M ² , M ³ , and M ⁴ each represent a leaving group and are not particularly limited. For example, each independently, ZnR ¹ , MgR ² , Sn (R ³ ) ₃ or B ( OR ⁴⁾ ₂ and the like. However, said R < ¹ > and R < ² > respectively independently represents a chlorine atom, a bromine atom, or an iodine atom, said R < ³ > represents a C1-C4 alkyl group or a phenyl group, and said R < ⁴ > is hydrogen atom, an alkyl group or a phenyl group having a carbon number of 1 to ^4, B (oR 4) 2 two R ⁴ ₂ may be the same or different. Further, two R ⁴ may form a ring containing an oxygen atom and a boron atom together.

The ZnR ^1, MgR ^2, is not particularly limited, for example, ZnCl, ZnBr, ZnI, MgCl , MgBr, MgI like.

The Sn ^(R ₃₎ 3, is not particularly limited, for _{example, Sn (Me) 3, Sn} (Bu) 3 and the like.

B (OR ⁴ ) ₂ is not particularly limited, and examples thereof include B (OH) ₂ , B (OMe) ₂ , B (O ⁱ Pr) ₂ , and B (OBu) ₂ . Examples of B (OR ⁴ ) ₂ in the case where two R ⁴ are united to form a ring containing an oxygen atom and a boron atom include the following (C-1) to (C-6): The group shown can be illustrated, and the group shown by (C-2) is desirable in that the yield is good.

  The compound (5a) used in the reaction formula (1) is, for example, J. Am. Chem. Soc. , 1963, 85 (10), 1549, paragraphs [0091] to [0103] of WO2010 / 082621, or paragraphs [0045] to [0067] of JP2013-223458A Can be manufactured in combination.

  Then, Reaction formula (1) is demonstrated. Reaction formula (1) is a method for obtaining the cyclic azine compound (1) according to one embodiment of the present invention by performing “Step 2” after “Step 1”. “Step 1” is a method in which compound (2a) is reacted with compound (3a) in the presence or absence of a base and in the presence of a palladium catalyst to obtain compound (4a). Suzuki-Miyaura reaction By applying reaction conditions for general coupling reactions such as Negishi reaction, Tamao-Kumada reaction, Stille reaction, etc., the target product can be obtained in high yield.

The palladium catalyst that can be used in “Step 1” is not particularly limited, and examples thereof include salts of palladium chloride, palladium acetate, palladium trifluoroacetate, palladium nitrate, and the like. In addition, π-allyl palladium chloride dimer, palladium acetylacetonate, tris (dibenzylideneacetone) dipalladium, dichlorobis (triphenylphosphine) palladium, tetrakis (triphenylphosphine) palladium and dichloro (1,1′-bis (diphenylphosphine). Examples include complex compounds such as fino) ferrocene) palladium. Among these, a palladium complex having a tertiary phosphine as a ligand is more preferable in terms of a good reaction yield, is easily available, and a palladium complex having triphenylphosphine as a ligand is preferable in terms of a good reaction yield. Particularly preferred.
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. The tertiary phosphine that can be used in this case is not particularly limited. For example, triphenylphosphine, trimethylphosphine, tributylphosphine, tri (tert-butyl) phosphine, tricyclohexylphosphine, tert-butyldiphenylphosphine. 9,9-dimethyl-4,5-bis (diphenylphosphino) xanthene, 2- (diphenylphosphino) -2 ′-(N, N-dimethylamino) biphenyl, 2- (di-tert-butylphosphino) ) Biphenyl, 2- (dicyclohexylphosphino) biphenyl, bis (diphenylphosphino) methane, 1,2-bis (diphenylphosphino) ethane, 1,3-bis (diphenylphosphino) propane, 1,4-bis ( Diphenylphosphino) butane, 1, 1′-bis (diphenylphosphino) ferrocene, tri (2-furyl) phosphine, tri (o-tolyl) phosphine, tris (2,5-xylyl) phosphine, (±) -2,2′-bis (diphenylphosphine) (Fino) -1,1′-binaphthyl, 2-dicyclohexylphosphino-2 ′, 4 ′, 6′-triisopropylbiphenyl and the like. 2-dicyclohexylphosphino-2 ′, 4 ′, 6′-triisopropylbiphenyl or triphenylphosphine is preferable because it is easily available and the reaction yield is good. The molar ratio between the tertiary phosphine and the palladium salt or complex compound is preferably 1:10 to 10: 1, and more preferably 1: 2 to 5: 1 in terms of good reaction yield.

  The base that can be used in “Step 1” is not particularly limited. For example, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate, cesium carbonate, potassium phosphate, sodium phosphate Sodium fluoride, potassium fluoride, cesium fluoride, and the like can be exemplified, and potassium carbonate is preferable in terms of a good yield. The molar ratio of base to compound (3a) is preferably 1: 2 to 10: 1, and more preferably 1: 1 to 3: 1 in terms of good yield.

  The molar ratio of the compound (2a) to the compound (3a) used in “Step 1” is not particularly limited, but for example, 1: 2 to 5: 1 is desirable, and 1: 2 in terms of good yield. To 2: 1 is more desirable.

  The solvent that can be used in “Step 1” is not particularly limited, and examples thereof include water, dimethyl sulfoxide, dimethylformamide, tetrahydrofuran, 1,4-dioxane, dimethoxyethane, toluene, benzene, diethyl ether, ethanol, Examples thereof include methanol or xylene, and these may be used in appropriate combination. It is desirable to use a mixed solvent of dioxane or tetrahydrofuran and water in terms of a good yield.

  “Step 1” is not particularly limited, but can be performed at a temperature appropriately selected from 0 ° C. to 150 ° C., for example, and is preferably performed at 50 ° C. to 100 ° C. in terms of good yield. desirable.

  Compound (4a) can be obtained by carrying out a normal treatment after completion of “Step 1”. If necessary, it may be purified by recrystallization, column chromatography or sublimation.

"Step 2" is a reaction of compound (4a) obtained in "Step 1" with compound (5a) in the presence or absence of a base and in the presence of a palladium catalyst. This is a method for obtaining such a cyclic azine compound (1). By applying reaction conditions of general coupling reactions such as Suzuki-Miyaura reaction, Negishi reaction, Tamao-Kumada reaction, Stille reaction, etc., the yield is improved. The object can be obtained. Of the conditions listed in “Step 1”, “Step 2” can be applied by replacing Compound (2a) with Compound (5a) and Compound (3a) with Compound (4a). However, the reaction conditions are not necessarily the same as those in “Step 1”. After completion of “Step 2”, it may be purified by recrystallization, column chromatography, sublimation or the like, if necessary.
The reaction conditions in reaction formula (2) are the same as those in reaction formula (1). That is, “Step 3” in the reaction formula (2) is the same as the conditions listed in “Step 1” except that the compound (2a) is replaced with the compound (3b) and the compound (3a) is replaced with the compound (2b). Can be applied. The same reaction conditions as those mentioned in “Step 1” can be applied to “Step 4” in the reaction formula (2). After completion of “Step 4”, it may be purified by recrystallization, column chromatography, sublimation or the like, if necessary.
The reaction conditions in Reaction Formula (3) are the same as those in Reaction Formula (1). That is, in “Step 5” in the reaction formula (3), compound (2a) was replaced with compound (5b) and compound (3a) was replaced with compound (4b) among the conditions listed in “Step 1”. Conditions can be applied. However, the reaction conditions are not necessarily the same as those in “Step 1”. After completion of “Step 5”, it may be purified by recrystallization, column chromatography, sublimation or the like, if necessary.

  Reaction formula (4) is a method for obtaining the cyclic azine compound (1 g) according to one embodiment of the present invention by carrying out “Step 6”. The reaction conditions in Reaction Formula (4) are the same as those in Reaction Formula (1). That is, in “Step 6” in the reaction formula (4), compound (2a) was replaced with compound (5a) and compound (3a) was replaced with compound (4c) among the conditions listed in “Step 1”. Conditions can be applied. However, the reaction conditions are not necessarily the same as those in “Step 1”. After completion of “Step 5”, it may be purified by recrystallization, column chromatography, sublimation or the like, if necessary.

  Hereinafter, although each aspect of this invention is demonstrated in detail based on an Example, each aspect of this invention is limited and is not interpreted at all by these Examples.

¹ H-NMR measurement was performed using Gemini 200 (manufactured by Varian).
The glass transition temperature was measured using DSC7020 (manufactured by Hitachi High-Tech Science).
Triplet excitation level measurement was performed using FP-6500 (manufactured by JASCO Corporation). The conversion formula of the triplet excited level is as follows.
Triplet excited level (eV) = 1241.6 / λonset
“Λonset” represents a wavelength value at the intersection of the tangent line and the horizontal axis by drawing a tangent line to the rising edge on the short wavelength side in the phosphorescence spectrum, where the vertical axis indicates the phosphorescence intensity and the horizontal axis indicates the wavelength.
The calculation of the triplet excited level by molecular orbital calculation was performed using Gaussian 09 (manufactured by Gaussian).
The light emission characteristics of the organic electroluminescence device were evaluated by applying a direct current to the fabricated device at room temperature and using a luminance meter of LUMINANCEMETER (BM-9) (manufactured by TOPCON).

  Synthesis Example-1

  Under an argon stream, 2- [3-chloro-5- (3-pyridyl) phenyl] -4,6-diphenyl-1,3,5-triazine (5.01 g, 11.9 mmol), bis (pinacolato) diboron ( 3.32 g, 13.1 mmol), potassium acetate (3.50 g, 35.6 mmol), palladium acetate (26.7 mg, 0.119 mmol), and 2-dicyclohexylphosphino-2 ′, 4 ′, 6′-tri Isopropyl biphenyl (113.7 mg, 0.238 mmol) was suspended in tetrahydrofuran (70 mL) and stirred at 75 ° C. for 22 hours. After cooling to room temperature, the reaction solution was concentrated under reduced pressure. Toluene (100 mL) was added to the resulting slurry, stirred at 100 ° C., and the solid was filtered off. The obtained filtrate was concentrated under reduced pressure, and the solid obtained by drying the concentrated solution was purified by recrystallization (toluene) to obtain the desired 4,6-diphenyl-2- [3- (3-pyridyl). ) -5- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl] -1,3,5-triazine (yield 5.01 g, yield 82) %).

  Synthesis Example-1

  Under a stream of argon, 4,6-diphenyl-2- [3- (3-pyridyl) -5- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl]- 1,3,5-triazine (1.10 g, 2.15 mmol), 2-bromo-9,10-dihydro-9,10- [1,2] benzenoanthracene (0.84 g, 2.53 mmol), and Tetrakis (triphenylphosphine) palladium (90.3 mg, 0.078 mmol) was suspended in tetrahydrofuran (60 mL). To this was added 2M aqueous potassium carbonate (4.2 mL, 8.4 mmol), and the mixture was stirred at 75 ° C. for 72 hours. After cooling to room temperature, the reaction solution was concentrated under reduced pressure. Water (100 mL) was added to the obtained concentrated liquid, the mixture was stirred at 78 ° C., and the precipitated solid was separated by filtration. The obtained solid was washed with water (30 mL), methanol (30 mL), and hexane (30 mL). This solid was dissolved in chloroform (100 mL), silica gel was added, and the mixture was filtered through Celite, and the filtrate was concentrated under reduced pressure. The solid obtained by drying this concentrated liquid was purified twice by recrystallization (toluene), whereby the desired 2- [3- (9,10-dihydro-9,10- [1,2] benze was obtained. Noanthracen-2-yl) -5- (3-pyridyl) phenyl] -4,6-diphenyl-1,3,5-triazine (Compound A-257) (Yield 0.81 g, 59% yield) )

¹ H-NMR (CDCl ₃ ) δ (ppm): 5.50 (d, J = 19.8 Hz, 2H), 6.95-7.00 (m, 4H), 7.34 (d, J = 7 .6 Hz, 1H), 7.36-7.42 (m, 4H), 7.49-7.59 (m, 8H), 7.72 (s, 1H), 7.85 (s, 1H), 8.18 (s, 1H), 8.63 (d, J = 5.1 Hz, 1H), 8.71 (d, J = 5.1 Hz, 4H), 8.85 (s, 1H), 8. 89 (s, 1H), 9.00 (s, 1H).
Compound A-257 had a glass transition temperature of 158 ° C.
The triplet excited level of Compound A-257 was 2.9 eV.

  Synthesis Example-2

  4,6-diphenyl-2- [3- (3-pyridyl) -5- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl] -1,3 5-Triazine as 4,6-diphenyl-2- [3- (4-pyridyl) -5- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl]- 2- [3- (9,10-dihydro-9,10- [1,2] benzenoanthracene was prepared in the same manner as in Synthesis Example 1 except that 1,3,5-triazine was used. 2-yl) -5- (4-pyridyl) phenyl] -4,6-diphenyl-1,3,5-triazine (Compound A-337) as a white solid (yield 0.83 g, 67% yield). Obtained.

¹ H-NMR (CDCl ₃ ) δ (ppm): 5.50 (d, J = 19.8 Hz, 2H), 6.96-7.00 (m, 4H), 7.33 (d, J = 7 .6 Hz, 1H), 7.37-7.41 (m, 4H), 7.51-7.61 (m, 7H), 7.70 (s, 1H), 7.93 (s, 1H), 7.97 (d, J = 6.1 Hz, 2H), 8.70 (d, J = 7.5 Hz, 4H), 8.75 (d, J = 5.1 Hz, 2H), 8.96 (d , J = 11.9 Hz, 2H).
Compound A-337 had a glass transition temperature of 167 ° C.
The triplet excitation level of Compound A-337 was 2.9 eV.

Synthesis Example-3

  4,6-diphenyl-2- [3- (3-pyridyl) -5- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl] -1,3 5-Triazine as 4,6-diphenyl-2- [3- (3-quinolyl) -5- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl]- 2- [3- (9,10-dihydro-9,10- [1,2] benzenoanthracene was prepared in the same manner as in Synthesis Example 1 except that 1,3,5-triazine was used. 2-yl) -5- (3-quinolyl) phenyl] -4,6-diphenyl-1,3,5-triazine (Compound A-705) as a white solid (4.44 g, 73% yield) Obtained.

¹ H-NMR (CDCl ₃ ) δ (ppm): 5.50 (d, J = 19.9 Hz, 2H), 6.95-6.99 (m, 4H), 7.36-7.41 (m , 5H), 7.50-7.58 (m, 8H), 7.71 (t, J = 7.6 Hz, 1H), 7.76 (s, 1H), 7.90 (d, J = 8 .1 Hz, 1 H), 7.98 (s, 1 H), 8.12 (d, J = 8.0 Hz, 1 H), 8.41 (s, 1 H), 8.72 (d, J = 6.5 Hz) , 4H), 8.88 (s, 1H), 8.98 (s, 1H), 9.30 (s, 1H).
Compound A-705 had a glass transition temperature of 163 ° C.

Synthesis Example 4

４，６−ジフェニル−２−［３−（３−ピリジル）−５−（４，４，５，５−テトラメチル−１，３，２−ジオキサボロラン−２−イル）フェニル］−１，３，５−トリアジンを４，６−ジフェニル−２−［３−（４−イソキノリル）−５−（４，４，５，５−テトラメチル−１，３，２−ジオキサボロラン−２−イル）フェニル］−１，３，５−トリアジンに変更した以外は合成実施例−１と同様の実験操作を行って、２−［３−（９，１０−ジヒドロ−９，１０−［１，２］ベンゼノアントラセン−２−イル）−５−（４−イソキノリル）フェニル］−４，６−ジフェニル−１，３，５−トリアジン（化合物Ａ−７６９）の白色固体（収量４．１１ｇ，収率７３％）を得た。
^１Ｈ−ＮＭＲ（ＣＤＣｌ_３）δ（ｐｐｍ）：５．４６（ｄ，Ｊ＝１５．３Ｈｚ，２Ｈ），６．９３−６．９８（ｍ，４Ｈ），７．３４−７．３８（ｍ，５Ｈ），７．４８−７．５６（ｍ，７Ｈ），７．７２−７．８４（ｍ，４Ｈ），８．０３（ｄ，Ｊ＝８．２Ｈｚ，１Ｈ），８．１７（ｄ，Ｊ＝７．９Ｈｚ，１Ｈ），８．５９（ｓ，１Ｈ），８．６８（ｄ，Ｊ＝６．６Ｈｚ，４Ｈ），８．７６（ｓ，１Ｈ），８．９９（ｓ，１Ｈ），９．３６（ｓ，１Ｈ）．
化合物Ａ−７６９のガラス転移温度は１７１℃であった。

4,6-diphenyl-2- [3- (3-pyridyl) -5- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl] -1,3 5-Triazine as 4,6-diphenyl-2- [3- (4-isoquinolyl) -5- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl]- 2- [3- (9,10-dihydro-9,10- [1,2] benzenoanthracene was prepared in the same manner as in Synthesis Example 1 except that 1,3,5-triazine was used. -2-yl) -5- (4-isoquinolyl) phenyl] -4,6-diphenyl-1,3,5-triazine (Compound A-769) as a white solid (Yield 4.11 g, 73%) Obtained.
¹ H-NMR (CDCl ₃ ) δ (ppm): 5.46 (d, J = 15.3 Hz, 2H), 6.93-6.98 (m, 4H), 7.34-7.38 (m , 5H), 7.48-7.56 (m, 7H), 7.72-7.84 (m, 4H), 8.03 (d, J = 8.2 Hz, 1H), 8.17 (d , J = 7.9 Hz, 1H), 8.59 (s, 1H), 8.68 (d, J = 6.6 Hz, 4H), 8.76 (s, 1H), 8.99 (s, 1H) ), 9.36 (s, 1H).
Compound A-769 had a glass transition temperature of 171 ° C.

Synthesis Example-5

  Under an argon stream, 2- [3-chloro-1,1′-biphenyl-5-yl] -4,6-diphenyl-1,3,5-triazine (4.00 g, 9.53 mmol), 2- (9 , 10-dihydro-9,10- [1,2] benzenoanthracene) boronic acid (3.12 g, 10.48 mmol), palladium acetate (22.2 mg, 0.099 mmol), and 2-dicyclohexylphosphino-2 ', 4', 6'-Triisopropylbiphenyl (92.8 mg, 0.195 mmol) was suspended in tetrahydrofuran (190 mL) and stirred at 75 ° C. for 6 hours. After cooling to room temperature, the reaction solution was concentrated under reduced pressure. Water (100 mL) was added to the resulting slurry, stirred at room temperature, and the solid was filtered off. The obtained solid was washed with water (50 mL), methanol (50 mL), and hexane (50 mL). This solid was dissolved in o-xylene (200 mL), silica gel was added, and the mixture was filtered through Celite, and the filtrate was concentrated under reduced pressure. The solid obtained by drying this concentrated solution was purified by recrystallization (toluene) to give 2- [5- (9,10-dihydro-9,10- [1,2] benzenoanthracene-2. -Il) -1,1'-biphenyl-3-yl] -4,6-diphenyl-1,3,5-triazine (Compound A-97) as a white solid (Yield 5.58 g, 92% yield) Obtained.

¹ H-NMR (CDCl ₃ ) δ (ppm): 5.46 (d, J = 15.7 Hz, 2H), 6.92-6.97 (m, 4H), 7.31-7.38 (m , 6H), 7.43-7.56 (m, 9H), 7.66-7.71 (m, 3H), 7.85 (s, 1H), 8.70 (d, J = 6.7 Hz). , 4H), 8.77 (s, 1H), 8.83 (s, 1H).
Compound A-97 had a glass transition temperature of 155 ° C.
The triplet excited level of Compound A-97 was 2.9 eV.

Synthesis Example-6

  2- [3-Chloro-1,1′-biphenyl-5-yl] -4,6-diphenyl-1,3,5-triazine as 2- (2-biphenyl) -4- (4-biphenyl) -6 -[3-Chloro-1,1'-biphenyl-5-yl] -1,3,5-triazine, 2- (9,10-dihydro-9,10- [1,2] benzenoanthracene) boronic acid Except that is changed to 2- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -9,10-dihydro-9,10- [1,2] benzenoanthracene Were subjected to the same experimental procedure as in Synthesis Example-5 to give 2- (2-biphenyl) -4- (4-biphenyl) -6- [5- (9,10-dihydro-9,10- [1, 2] Benzenoanthracen-2-yl) -1,1'-biphenyl-3-yl] -1,3,5- A white solid (yield 0.55 g, yield 79%) of triazine (compound A-1354) was obtained.

¹ H-NMR (CDCl ₃ ) δ (ppm): 5.55 (d, J = 14.9 Hz, 2H), 7.01-7.06 (m, 4H), 7.11 (t, J = 7) .3 Hz, 1H), 7.24 (t, J = 7.9 Hz, 2H), 7.32-7.36 (m, 3H), 7.39-7.70 (m, 20H), 7.73 (S, 1H), 7.86 (s, 1H), 8.33 (d, J = 7.6 Hz, 1H), 8.42 (d, J = 8.4 Hz, 2H), 8.49 (s , 2H).
Compound A-1354 had a glass transition temperature of 159 ° C.

Synthesis Example-7

  2- (2-biphenyl) -4- (4-biphenyl) -6- [3-chloro-1,1′-biphenyl-5-yl] -1,3,5-triazine is converted to 4,6-diphenyl-2 -[3- (4-Chloro-3-pyridyl)] phenyl-1,3,5-triazine, 2- (9,10-dihydro-9,10- [1,2] benzanthanthracene) boronic acid -(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -9,10-dihydro-9,10- [1,2] benzenoanthracene The same experimental procedure as in Example 5 was performed, and 2- {3- [4- (9,10-dihydro-9,10- [1,2] benzenoanthracen-2-yl) -3-pyridyl] Phenyl} -4,6-diphenyl-1,3,5-triazine (Compound A-8) Was obtained color solid (yield 3.28 g, 62% yield).

¹ H-NMR (CDCl ₃ ) δ (ppm): 5.47 (d, J = 24.1 Hz, 2H), 6.93-6.97 (m, 4H), 7.34-7.38 (m 4H), 7.45 (d, J = 7.9 Hz, 1H), 7.50-7.65 (m, 8H), 7.75 (d, J = 8.3 Hz, 1H), 7.80. (D, J = 8.1 Hz, 1H), 8.00 (d, J = 8.1 Hz, 1H), 8.13 (s, 1H), 8.72-8.76 (m, 5H), 8 .98 (s, 1H), 9.00 (s, 1H).
Compound A-8 had a glass transition temperature of 148 ° C.

Synthesis Example-8

  2- (2-biphenyl) -4- (4-biphenyl) -6- [3-chloro-1,1′-biphenyl-5-yl] -1,3,5-triazine is converted to 4,6-diphenyl-2 -[3- (3-Chloro-4-pyridyl)] phenyl-1,3,5-triazine, 2- (9,10-dihydro-9,10- [1,2] benzanthanthracene) boronic acid -(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -9,10-dihydro-9,10- [1,2] benzenoanthracene The same experimental procedure as in Example 5 was performed, and 2- {3- [3- (9,10-dihydro-9,10- [1,2] benzenoanthracen-2-yl) -4-pyridyl] Phenyl} -4,6-diphenyl-1,3,5-triazine (Compound A-11) White solid (Yield 3.28 g, 62% yield).

¹ H-NMR (CDCl ₃ ) δ (ppm): 5.47 (d, J = 22.9 Hz, 2H), 6.92-6.97 (m, 4H), 7.32-7.37 (m , 4H), 7.46 (d, J = 7.3 Hz, 1H), 7.50-7.59 (m, 7H), 7.64-7.67 (m, 2H), 7.82 (d , J = 8.0 Hz, 1H), 7.92 (s, 1H), 8.12 (s, 1H), 8.71-8.74 (m, 5H), 8.81 (d, J = 8 .0Hz, 1H), 8.96 (s, 1H).
The glass transition temperature of Compound A-11 was 148 ° C.

  Table 1 shows the glass transition temperatures of the compounds obtained in Synthesis Example-1 to Synthesis Example-8 and Reference Example-1.

  2- [5- (9-phenanthryl) -3- (4-pyridyl) phenyl] -4,6-diphenyl-1,3,5-triazine (ETL-3) described in JP-A-2011-063584 Comparison shows that the cyclic azine compound to which a group having a triptycene structure according to one embodiment of the present invention is bonded has a very high glass transition temperature.

  Synthesis Examples-1, 2, 5, 8 and Reference Example-1, and Examples 9-14 (Compound A-1, Compound A-21, Compound A-33, Compound A-1185, Compound A-1305, Tables 2 and 3 show triplet excited levels of the compound obtained from Compound A-1333).

2- [5- (9-phenanthryl) -3- (4-pyridyl) phenyl] -4,6-diphenyl-1,3,5-triazine (ETL-3) described in JP-A-2011-063584 Comparison shows that the cyclic azine compound according to one embodiment of the present invention to which a group having a triptycene structure is bonded has a high triplet excitation level.
However, the triplet excitation level in Table 2 is an actual measurement value measured using the aforementioned FP-6500 (manufactured by JASCO Corporation).
The triplet excited level in Table 3 is a value obtained by DFT calculation (B3LYP / 6-31G (d)) performed using Gaussian 09 (manufactured by Gaussian).

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

Element Example-1
As the substrate, a glass substrate with an ITO transparent electrode on which a 2 mm wide indium-tin oxide (ITO) film (film thickness 110 nm) was patterned in a stripe shape was used. The substrate was cleaned with isopropyl alcohol and then surface treated by ozone ultraviolet cleaning. Each layer was vacuum-deposited on the cleaned substrate by a vacuum deposition method, and an organic electroluminescence device having a light-emitting area of 4 mm ² as shown in FIG. Each organic material was formed by a resistance heating method.
First, the said glass substrate was introduce | transduced in the vacuum evaporation tank and it pressure-reduced to 1.0 * 10 <^-4> Pa.
Thereafter, as an organic compound layer on the glass substrate with an ITO transparent electrode shown by 1 in FIG. 6. The first electron transport layer 7, the second electron transport layer 8, and the cathode layer 9 were all formed by vacuum deposition while being laminated in this order.

As the hole injection layer 2, a sublimated HIL film having a thickness of 55 nm was formed at a rate of 0.15 nm / second.
As the charge generation layer 3, sublimation-purified HAT was deposited to a thickness of 5 nm at a rate of 0.05 nm / second.
As the first hole transport layer 4, HTL-1 was formed to a thickness of 10 nm at a speed of 0.15 nm / second.
As the second hole transport layer 5, HTL-2 was formed to a thickness of 10 nm at a speed of 0.15 nm / second.
As the light emitting layer 6, EML-1 and EML-2 were deposited to a thickness of 25 nm at a ratio of 95: 5 (deposition rate of 0.18 nm / second).
As the first electron transport layer 7, ETL-1 was deposited to a thickness of 5 nm at a speed of 0.15 nm / second.
As the second electron transport layer 8, 2- [3- (9,10-dihydro-9,10- [1,2] benzenoanthracen-2-yl) -5- (synthesized in Synthesis Example-1) 3-pyridyl) phenyl] -4,6-diphenyl-1,3,5-triazine (Compound A-257) and Liq were deposited in a ratio of 50:50 (weight ratio) to a thickness of 25 nm (deposition rate of 0.15 nm) / Sec).

Finally, a metal mask was disposed so as to be orthogonal to the ITO stripe, and the cathode layer 9 was formed.
The cathode layer 9 is formed of silver / magnesium (weight ratio 1/10) and silver in this order at 80 nm (film formation rate 0.5 nm / second) and 20 nm (film formation rate 0.2 nm / second), respectively. And it was set as the 2 layer structure.
Each film thickness was measured with a stylus type film thickness meter (DEKTAK).

  Furthermore, this element was sealed in a nitrogen atmosphere glove box having an oxygen and moisture concentration of 1 ppm or less. For the sealing, a glass sealing cap and the above-described film-forming substrate epoxy type ultraviolet curable resin (manufactured by Nagase ChemteX Corporation) were used.

A direct current was applied to the organic electroluminescence device produced as described above, and the light emission characteristics were evaluated using a luminance meter of LUMINANCE METER (BM-9) manufactured by TOPCON. As light emission characteristics, voltage (V) and current efficiency (cd / A) when a current density of 10 mA / cm ² was passed were measured, and element lifetime (h) during continuous lighting was measured. Incidentally, the element lifetime of Table 4, the luminance was measured decay time at the time of continuous lighting when driving was prepared device at an initial luminance 1000 cd / m ^2, the luminance (cd / m ²⁾ is required until reduced 10% Time was measured. The voltage, current efficiency, and element lifetime were expressed as relative values based on the result in element reference example 1 described later as a reference value (100). The results are shown in Table 4.

Element Example-2
2- [3- (9,10-dihydro-9,10- [1,2] benzenoanthracen-2-yl) synthesized in Synthesis Example-2 in place of Compound A-257 in Device Example 1 The organic electroluminescent device was prepared in the same manner as in Device Example 1 except that −5- (4-pyridyl) phenyl] -4,6-diphenyl-1,3,5-triazine (Compound A-337) was used. Prepared and evaluated. The results are shown in Table 4. Note that the voltage, current efficiency, and element lifetime are shown as relative values with the result in element reference example-1 described later as the reference value (100).

Element Example-3
2- [3- (9,10-dihydro-9,10- [1,2] benzenoanthracen-2-yl) synthesized in Synthesis Example-3 in place of Compound A-257 in Device Example 1 An organic electroluminescent device was prepared in the same manner as in Device Example 1 except that −5- (3-quinolyl) phenyl] -4,6-diphenyl-1,3,5-triazine (Compound A-705) was used. Prepared and evaluated. The results are shown in Table 4. Note that the voltage, current efficiency, and element lifetime are shown as relative values with the result in element reference example-1 described later as the reference value (100).

Element Example 4
2- [3- (9,10-dihydro-9,10- [1,2] benzenoanthracen-2-yl) synthesized in Synthesis Example-4 instead of Compound A-257 in Device Example 1 An organic electroluminescent element was prepared in the same manner as in Example 1 except that −5- (4-isoquinolyl) phenyl] -4,6-diphenyl-1,3,5-triazine (Compound A-769) was used. Prepared and evaluated. The results are shown in Table 4. Note that the voltage, current efficiency, and element lifetime are shown as relative values with the result in element reference example-1 described later as the reference value (100).

Element Example-5
In Device Example 1, 2- (2-biphenyl) -4- (4-biphenyl) -6- [5- (9,10-dihydro-9) synthesized in Synthesis Example-6 instead of Compound A-257 , 10- [1,2] Benzenoanthracen-2-yl) -1,1′-biphenyl-3-yl] -1,3,5-triazine (Compound A-1354) An organic electroluminescent device was prepared and evaluated in the same manner as in Example-1. The results are shown in Table 4. Note that the voltage, current efficiency, and element lifetime are shown as relative values with the result in element reference example-1 described later as the reference value (100).

Element Example-6
2- {3- [4- (9,10-dihydro-9,10- [1,2] benzenoanthracene-2) synthesized in Synthesis Example-7 instead of Compound A-257 in Device Example 1 -Yl) -3-pyridyl] phenyl} -4,6-diphenyl-1,3,5-triazine (Compound A-8) was used, and the organic electroluminescence device was fabricated in the same manner as in Device Example-1. Prepared and evaluated. The results are shown in Table 4. Note that the voltage, current efficiency, and element lifetime are shown as relative values with the result in element reference example-1 described later as the reference value (100).

Element Example-7
In Device Example 1, 2- {3- [3- (9,10-dihydro-9,10- [1,2] benzenoanthracene-2) synthesized in Synthesis Example-8 instead of Compound A-257 -Yl) -4-pyridyl] phenyl} -4,6-diphenyl-1,3,5-triazine (Compound A-11) was used, and the organic electroluminescence device was fabricated in the same manner as in Device Example-1. Prepared and evaluated. The results are shown in Table 4. Note that the voltage, current efficiency, and element lifetime are shown as relative values with the result in element reference example-1 described later as the reference value (100).

Element Reference Example-1
In Device Example-1, instead of compound A-257, 2- [5- (9-phenanthryl) -4 ′-(2-pyrimidyl) biphenyl-3-yl]-described in JP2011-063584- An organic electroluminescence device was prepared and evaluated in the same manner as in Device Example 1 except that 4,6-diphenyl-1,3,5-triazine (ETL-2) was used. The results are shown in Table 4. In addition, about the voltage, the current efficiency, and the element lifetime, the result of this element reference example-1 was made into the reference value (100).

The cyclic azine compound (1) according to one embodiment of the present invention is extremely excellent in heat resistance of film quality, and by using the compound, an organic electroluminescent device excellent in long life and luminous efficiency can be provided.
Moreover, the cyclic azine compound (1) concerning 1 aspect of this invention is utilized as an electron transport material for organic electroluminescent elements which is excellent in a low drive voltage. Furthermore, according to one embodiment of the present invention, an organic electroluminescent element having excellent power consumption can be provided.
In addition, the cyclic azine compound according to one embodiment of the present invention is excellent in sublimation purification operability due to good thermal stability during sublimation purification, and provides a material with less impurities causing deterioration of the organic electroluminescence device. can do. In addition, since the cyclic azine compound according to one embodiment of the present invention is excellent in stability of a deposited film, an organic electroluminescent element having a long lifetime can be provided.
In addition, the thin film formed of the cyclic azine compound (1) according to one embodiment of the present invention is excellent in electron transport ability, hole blocking ability, redox resistance, water resistance, oxygen resistance, electron injection characteristics, etc. It is useful as an element material, and is useful as an electron transport material, a hole blocking material, a light emitting host material, and the like. It is particularly useful when used as an electron transport material.
In addition, since the cyclic azine compound (1) according to one embodiment of the present invention has a wide band gap and a high triplet excitation level, it can be used not only for conventional fluorescent devices but also for phosphorescent devices and thermally activated delayed fluorescence ( It can be suitably used for an organic electroluminescent device using TADF).

1. 1. Glass substrate with ITO transparent electrode 2. hole injection layer Charge generation layer 4. First hole transport layer 5. Second hole transport layer 6. Light emitting layer 7. First electron transport layer 8. Second electron transport layer 9. Cathode layer

Claims (12)

Cyclic azine compound represented by the formula (1):

In formula (1),
Ar ¹ each independently represents a substituted or unsubstituted phenyl group, naphthyl group, or pyridyl group;
Ar ² is
A substituted or unsubstituted monocyclic or condensed aromatic hydrocarbon group having 6 to 24 carbon atoms,
A monocyclic or condensed nitrogen-containing heteroaromatic group having 4 to 25 carbon atoms consisting of only a substituted or unsubstituted 6-membered ring,
Represents a monocyclic or condensed heteroaromatic group having 3 to 25 carbon atoms or a hydrogen atom composed of an atom selected from the group consisting of substituted, unsubstituted H, C, O, and S;
Ar ³ and Ar ⁴ are each independently
Substituted or unsubstituted phenyl, naphthyl, pyridyl,
Hydrogen atom,
An unsubstituted alkyl group having 1 to 4 carbon atoms, or
Represents a single bond bonded to X ² ;
Ar ⁵ and Ar ⁶ are each independently
Substituted or unsubstituted phenyl, naphthyl, pyridyl,
Hydrogen atom,
An unsubstituted alkyl group having 1 to 4 carbon atoms, or
Represents a single bond bonded to X ² ;
W ¹ , W ² , and W ³ are
Each independently represents C—H or a nitrogen atom;
At least two represent C—H;
X ¹ and X ² are each independently
Substituted or unsubstituted phenylene group, naphthylene group, biphenylene group, pyridylene group, or
Represents a single bond;
Y ¹ , Y ² , Y ³ , and Y ⁴ are each independently
A group represented by C—R, or
Represents a nitrogen atom;
Each R is independently
Substituted or unsubstituted phenyl, naphthyl, pyridyl,
Hydrogen atom,
An unsubstituted alkyl group having 1 to 4 carbon atoms, or
Represents an unsubstituted alkenyl group having 1 to 4 carbon atoms;
R may be bonded to each other to form an aromatic ring;
Z represents a nitrogen atom or C—H;
When Ar ¹ , Ar ^{3 to} Ar ⁶ , X ^{1 to} X ² , or R has a substituent, the substituent is a fluorine atom, a methyl group, or a phenyl group;
When Ar ² has a substituent, the substituent is a phenyl group, a tolyl group, a pyridyl group, a methylpyridyl group, a dimethylpyridyl group, a fluorine atom, an alkyl group having 1 to 4 carbon atoms, or an alkyl group having 1 to 4 carbon atoms. An alkoxy group;   The cyclic azine compound according to claim 1, wherein Z is a nitrogen atom. Two Ar ¹ represent the same group and are a substituted or unsubstituted phenyl group, naphthyl group, or pyridyl group;
The cyclic azine compound according to claim 1 or 2, wherein when Ar ¹ has a substituent, the substituent is a fluorine atom, a methyl group, or a phenyl group. The cyclic azine compound according to any one of claims 1 to 3, wherein both of Ar ¹ are phenyl groups. Ar ² is
A hydrogen atom, or
Substituted or unsubstituted phenyl, naphthyl, fluorenyl, anthryl, phenanthryl, benzofluorenyl, pyrenyl, perylenyl, fluoranthenyl, triphenylenyl, pyrimidyl, pyridyl, pyridyl, Quinolyl group, isoquinolyl group, benzofuranyl group, benzothienyl group, dibenzofuranyl group, dibenzothienyl group,
When Ar ² has a substituent, the substituent is a phenyl group, a tolyl group, a pyridyl group, a methylpyridyl group, a dimethylpyridyl group, a fluorine atom, an alkyl group having 1 to 4 carbon atoms, or an alkyl group having 1 to 4 carbon atoms. The cyclic azine compound according to any one of claims 1 to 4, which is an alkoxy group. Ar ² is a substituted or unsubstituted fluorenyl group, benzofluorenyl group, pyridyl group, quinolyl group, isoquinolyl group, benzofuranyl group, benzothienyl group, dibenzofuranyl group, or dibenzothienyl group,
When Ar ² has a substituent, the substituent is a phenyl group, a tolyl group, a pyridyl group, a methylpyridyl group, a dimethylpyridyl group, a fluorine atom, an alkyl group having 1 to 4 carbon atoms, or an alkyl group having 1 to 4 carbon atoms. The cyclic azine compound according to any one of claims 1 to 5, which is an alkoxy group. Ar ³ and Ar ⁴ are each independently
Hydrogen atom;
Unsubstituted phenyl group, naphthyl group, pyridyl group; or
Single bond to bond to X ^2; a, cyclic azine compound according to any one of claims 1-6. X ¹ and X ² are each independently
Single bond;
The cyclic azine compound according to claim 1, which is an unsubstituted phenylene group, naphthylene group, biphenylene group, or pyridylene group. Y ¹ , Y ² , Y ³ , and Y ⁴ are all groups represented by C—R;
Each R is independently
Hydrogen atom;
The cyclic azine compound according to any one of claims 1 to 8, which is an unsubstituted alkyl group having 1 to 4 carbon atoms, an alkenyl group having 1 to 4 carbon atoms, a phenyl group, a naphthyl group, or a pyridyl group. . The cyclic azine compound according to claim ¹ , wherein W ¹ , W ² , and W ³ are all C—H.   The organic electroluminescent element material containing the cyclic azine compound shown by Formula (1) of any one of Claims 1-10.   The electron transport material for organic electroluminescent elements containing the cyclic azine compound shown by Formula (1) of any one of Claims 1-10.

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