JP2021066689A - Triazine compound having group 14 element - Google Patents

Abstract

To provide a triazine compound that contributes to formation of an organic electroluminescent element that achieves high luminous efficiency and a method for producing the triazine compound, and an organic electroluminescent element that achieves high luminous efficiency and has excellent heat resistance.SOLUTION: A triazine compound has a specific structure represented by formula (1).SELECTED DRAWING: Figure 2

Description

The present disclosure relates to a triazine compound having a Group 14 element, a method for producing the same, and an organic electroluminescent device.

Practical use of organic electroluminescent devices has begun, mainly for small mobile applications. However, performance improvement is indispensable for further popularization and expansion of applications, and in particular, a material having high luminous efficiency characteristics is required in order to reduce power consumption.

Here, Patent Document 1 discloses a triazine compound which is a material for an organic electroluminescent device capable of reducing a driving voltage with high efficiency.

Japanese Patent No. 5812583

The market demand for expanding the applications of organic electroluminescent devices is very strong. Therefore, a material having a particularly high luminous efficiency is required.
Here, the triazine compound according to Patent Document 1 sufficiently satisfies the above-mentioned characteristics at a predetermined level, but development of a material having a higher luminous efficiency is required.

Therefore, one aspect of the present disclosure is directed to providing a triazine compound and a method for producing the triazine compound, which contributes to the formation of an organic electroluminescent device exhibiting high luminous efficiency.
Another aspect of the present disclosure is directed to providing an organic electroluminescent device having high luminous efficiency using the triazine compound.

The triazine compound according to one aspect of the present disclosure is represented by the formula (1):

During the ceremony
Ar ¹ and Ar ² independently represent a phenyl group, a biphenylyl group or a naphthyl group;
Ar ³ is
Hydrogen atom,
Aromatic hydrocarbon groups of monocyclic, linked or fused rings with 6 to 20 carbon atoms, or
Represents a nitrogen-containing aromatic group consisting of only a 6-membered ring and having 4 to 14 carbon atoms;
Ar ¹ , Ar ² and Ar ³ may each be independently substituted with one or more groups selected from the group consisting of a fluorine atom, an alkyl group having 1 to 4 carbon atoms, and a phenyl group;
R is the same or different,
Alkyl groups with 1 to 6 carbon atoms,
An aromatic hydrocarbon group having 6 to 20 carbon atoms, a monocyclic ring, a linking ring, or a condensed ring, which may be substituted with an alkyl group having 1 to 4 carbon atoms.
A nitrogen-containing aromatic group having 4 to 14 carbon atoms consisting of only a 6-membered ring which may be substituted with an alkyl group having 1 to 4 carbon atoms or a phenyl group, or a nitrogen-containing aromatic group having 4 to 14 carbon atoms.
Heteroatoms that may be substituted with alkyl or phenyl groups of 1 to 4 carbons represent group 16 elements, heterocyclic groups of 4 to 14 carbons;
Two adjacent Rs may be integrated to form a 5- or 6-membered ring containing a Z to which the two Rs are bonded;
L represents a phenylene group;
Z represents a carbon atom, a silicon atom, a germanium atom, or a tin atom;
p represents 0, 1 or 2.

In the method for producing a triazine compound represented by the formula (1a) according to another aspect of the present disclosure, the compound represented by the formula (2) and the compound represented by the formula (3) are coupled by a coupling reaction. Including:

During the ceremony
Ar ¹ and Ar ² independently represent a phenyl group, a biphenylyl group or a naphthyl group;
Ar ³ is
Hydrogen atom,
Aromatic hydrocarbon groups of monocyclic, linked or fused rings with 6 to 20 carbon atoms, or
Represents a nitrogen-containing aromatic group consisting of only a 6-membered ring and having 4 to 14 carbon atoms;
Ar ¹ , Ar ² and Ar ³ may each be independently substituted with one or more groups selected from the group consisting of a fluorine atom, an alkyl group having 1 to 4 carbon atoms, and a phenyl group;
R is the same or different,
Alkyl groups with 1 to 6 carbon atoms,
An aromatic hydrocarbon group having 6 to 20 carbon atoms, a monocyclic ring, a linking ring, or a condensed ring, which may be substituted with an alkyl group having 1 to 4 carbon atoms.
A nitrogen-containing aromatic group having 4 to 14 carbon atoms consisting of only a 6-membered ring which may be substituted with an alkyl group having 1 to 4 carbon atoms or a phenyl group, or a nitrogen-containing aromatic group having 4 to 14 carbon atoms.
Heteroatoms that may be substituted with alkyl or phenyl groups of 1 to 4 carbons represent group 16 elements, heterocyclic groups of 4 to 14 carbons;
Two adjacent Rs may be integrated to form a 5- or 6-membered ring containing a Z to which the two Rs are bonded;
L represents a phenylene group;
Z represents a carbon atom, a silicon atom, a germanium atom, or a tin atom;
p'represents 1 or 2;
M ¹ represents ZnY ¹ , MgY ² , Sn (Y ³ ) ₃ , or B (OY ⁴ ) ₂ ;
Y ¹ and Y ² independently represent a chlorine atom, a bromine atom or an iodine atom;
Y ³ are the same or different and each represents an alkyl group or a phenyl group having 1 to 4 carbon atoms;
Y ⁴ are the same or different and each represents a hydrogen atom, an alkyl group or a phenyl group having 1 to 4 carbon atoms;
The two (OY ⁴ ) groups may be united to form a ring with the boron atom to which the ^{two (OY 4) groups are attached;}
X ¹ represents a chlorine atom, a bromine atom, a trifluoromethanesulfonyloxy group or an iodine atom.

In the method for producing a triazine compound represented by the formula (1b) according to another aspect of the present disclosure, the compound represented by the formula (4) and the compound represented by the formula (5) are coupled by a coupling reaction. Including:

During the ceremony
Ar ¹ and Ar ² independently represent a phenyl group, a biphenylyl group or a naphthyl group;
Ar ³ is
Hydrogen atom,
Aromatic hydrocarbon groups of monocyclic, linked or fused rings with 6 to 20 carbon atoms, or
Represents a nitrogen-containing aromatic group consisting of only a 6-membered ring and having 4 to 14 carbon atoms;
Ar ¹ , Ar ² and Ar ³ may each be independently substituted with one or more groups selected from the group consisting of a fluorine atom, an alkyl group having 1 to 4 carbon atoms, and a phenyl group;
R is the same or different,
Alkyl groups with 1 to 6 carbon atoms,
An aromatic hydrocarbon group having 6 to 20 carbon atoms, a monocyclic ring, a linking ring, or a condensed ring, which may be substituted with an alkyl group having 1 to 4 carbon atoms.
A nitrogen-containing aromatic group having 4 to 14 carbon atoms consisting of only a 6-membered ring which may be substituted with an alkyl group having 1 to 4 carbon atoms or a phenyl group, or a nitrogen-containing aromatic group having 4 to 14 carbon atoms.
Heteroatoms that may be substituted with alkyl or phenyl groups of 1 to 4 carbons represent group 16 elements, heterocyclic groups of 4 to 14 carbons;
Two adjacent Rs may be integrated to form a 5- or 6-membered ring containing a Z to which the two Rs are bonded;
L represents a phenylene group;
Z represents a carbon atom, a silicon atom, a germanium atom, or a tin atom;
p'' represents 1 or 2;
X ² represents a chlorine atom, a bromine atom, a trifluoromethanesulfonyloxy group or an iodine atom;
M ² represents ZnY ¹ , MgY ² , Sn (Y ³ ) ₃ , or B (OY ⁴ ) ₂ ;
Y ¹ and Y ² independently represent a chlorine atom, a bromine atom or an iodine atom;
Y ³ are the same or different and each represents an alkyl group or a phenyl group having 1 to 4 carbon atoms;
Y ⁴ are the same or different and each represents a hydrogen atom, an alkyl group or a phenyl group having 1 to 4 carbon atoms;
The two (OY ⁴ ) groups may be integrated to form a ring together with the boron atom to which the two (OY ^{4) groups are bonded.}

The organic electroluminescent device according to another aspect of the present disclosure contains the above triazine compound.

According to one aspect of the present disclosure, it is possible to provide a triazine compound that contributes to the production of an organic electroluminescent device exhibiting high luminous efficiency, and a method for producing the triazine compound.
According to another aspect of the present disclosure, it is possible to provide an organic electroluminescent device having high luminous efficiency.

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

Hereinafter, the triazine compound according to one aspect of the present disclosure will be described in detail.
The triazine compound according to one aspect of the present disclosure is represented by the formula (1):

During the ceremony
Ar ¹ and Ar ² independently represent a phenyl group, a biphenylyl group or a naphthyl group;
Ar ³ is
Hydrogen atom,
Aromatic hydrocarbon groups of monocyclic, linked or fused rings with 6 to 20 carbon atoms, or
Represents a nitrogen-containing aromatic group consisting of only a 6-membered ring and having 4 to 14 carbon atoms;
Ar ¹ , Ar ² and Ar ³ may each be independently substituted with one or more groups selected from the group consisting of a fluorine atom, an alkyl group having 1 to 4 carbon atoms, and a phenyl group;
R is the same or different,
Alkyl groups with 1 to 6 carbon atoms,
An aromatic hydrocarbon group having 6 to 20 carbon atoms, a monocyclic ring, a linking ring, or a condensed ring, which may be substituted with an alkyl group having 1 to 4 carbon atoms.
A nitrogen-containing aromatic group having 4 to 14 carbon atoms consisting of only a 6-membered ring which may be substituted with an alkyl group having 1 to 4 carbon atoms or a phenyl group, or a nitrogen-containing aromatic group having 4 to 14 carbon atoms.
Heteroatoms that may be substituted with alkyl or phenyl groups of 1 to 4 carbons represent group 16 elements, heterocyclic groups of 4 to 14 carbons;
Two adjacent Rs may be integrated to form a 5- or 6-membered ring containing a Z to which the two Rs are bonded;
L represents a phenylene group;
Z represents a carbon atom, a silicon atom, a germanium atom, or a tin atom;
p represents 0, 1 or 2.

In the triazine compound having the structure represented by the formula (1), the present inventors increase the molecular volume by introducing a Group 14 element having a substituent at an appropriate position in the molecule, and at the same time, a heavy atom. It is speculated that the above problems can be solved by the effect.

Hereinafter, the triazine compound according to one aspect of the present disclosure (hereinafter, also simply referred to as triazine compound (1)) will be described in more detail.
The triazine compound (1) is represented by the formulas (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i), or (1j). Will be done.

In the formula, Ar ¹ , Ar ² , Ar ³ , R, Z, L and p have the same definitions as the above formula (1).

The compound represented by the formula (1a), (1b), (1c), (1d), or (1e) in that the triazine compound (1) contributes to the formation of a higher-performance organic electroluminescent device. Is preferable, and the compound represented by the formula (1a), the formula (1b), or (1c) is particularly preferable.
Further, among the compounds represented by the formula (1a), the formula (1b), or (1c), the compound represented by the formula (11a), the formula (11b), or the formula (11c) is more likely to be used. preferable.

In the formula, Ar ¹ , Ar ² , Ar ³ , R, Z, and L have the same definitions as the above formula (1).
q represents 0 or 1.

^{The definitions of Ar 1} , Ar ² , Ar ³ , R, L, Z and p in the triazine compound (1) will be described.

[About Ar ¹ and Ar ² ]
Ar ¹ and Ar ² independently represent a phenyl group, a biphenylyl group or a naphthyl group, respectively. Ar ¹ and Ar ² may be independently substituted with one or more groups selected from the group consisting of a fluorine atom, an alkyl group having 1 to 4 carbon atoms and a phenyl group.

^{Further, it is preferable that Ar 1} and Ar ² are independently phenyl groups or biphenylyl groups, respectively, because the triazine compound (1) is excellent in electron transport characteristics.
^{Ar 1} and Ar ² are preferably the same group in that the triazine compound (1) can be easily synthesized.

[About ^{Ar 3]}
Ar ³ is
(I) Hydrogen atom,
(Ii) Aromatic hydrocarbon groups of monocyclic, linked or condensed rings having 6 to 20 carbon atoms, or
(Iii) Represents a nitrogen-containing heterocyclic group having 4 to 14 carbon atoms.
Ar ³ may be substituted with one or more groups selected from the group consisting of a fluorine atom, an alkyl group having 1 to 4 carbon atoms, and a phenyl group.

(Ii) Aromatic hydrocarbon groups Examples of the aromatic hydrocarbon groups include phenyl group, naphthyl group, biphenylyl group, phenanthryl group, anthryl group, pyrenyl group, fluorenyl group, benzofluorenyl group, triphenylenyl group and full. An oranthenyl group can be mentioned. These groups may be substituted with one or more groups selected from the group consisting of a fluorine atom, an alkyl group having 1 to 4 carbon atoms, and a phenyl group. The alkyl group having 1 to 4 carbon atoms may be a linear, branched or cyclic alkyl group, and specifically, a methyl group, an ethyl group, a propyl group, a 2-methylpropyl group, an isopropyl group or a cyclo. Examples thereof include propyl group, butyl group, 2-butyl group and tert-butyl group.

(Iii) Nitrogen-containing heterocyclic group Examples of the nitrogen-containing heterocycle include a pyridyl group, a piperidyl group, a benzo [b] quinolyl group, a phenylpyridyl group, a carbazolyl group and the like. These groups may be substituted with one or more groups selected from the group consisting of a fluorine atom, an alkyl group having 1 to 4 carbon atoms, and a phenyl group. The alkyl group having 1 to 4 carbon atoms may be a linear, branched or cyclic alkyl group, and specifically, a methyl group, an ethyl group, a propyl group, a 2-methylpropyl group, an isopropyl group or a cyclo. Examples thereof include propyl group, butyl group, 2-butyl group and tert-butyl group.

^{Ar 3} is described in that the triazine compound (1) contributes to the formation of a higher performance organic electroluminescent device.
Hydrogen atom or
Unsubstituted or substituted with a methyl group,
Aromatic hydrocarbon groups of monocyclic, linked or fused rings with 6 to 20 carbon atoms, or
It is preferably a nitrogen-containing aromatic group consisting of only a 6-membered ring and having 4 to 14 carbon atoms.
Further, ^{it is particularly preferable that Ar 3} is a hydrogen atom, a phenyl group, a biphenyl group, a naphthyl group, a phenanthrenyl group, a dimethylfluorenyl group, a pyridyl group, a dimethylpyridyl group, or a phenylpyridyl group.

[About R]
R is the same or different,
(I) Alkyl groups having 1 to 6 carbon atoms,
(Ii) An aromatic hydrocarbon group having 6 to 20 carbon atoms, a monocyclic ring, a connecting ring, or a condensed ring, which may be substituted with an alkyl group having 1 to 4 carbon atoms.
(Iii) A nitrogen-containing aromatic group having 4 to 14 carbon atoms or a nitrogen-containing aromatic group consisting of only a 6-membered ring which may be substituted with an alkyl group or a phenyl group having 1 to 4 carbon atoms.
(Iv) A heteroatom that may be substituted with an alkyl group or a phenyl group having 1 to 4 carbon atoms represents a heterocyclic group having 4 to 14 carbon atoms, which is a group 16 element.
Here, the two adjacent Rs may be integrated to form a 5- or 6-membered ring containing Z to which the two Rs are bonded.

(I) Alkyl group The alkyl group having 1 to 6 carbon atoms may be, for example, a linear, branched or cyclic alkyl group, and specifically, a methyl group, an ethyl group, a propyl group or a 2-methyl group. Examples thereof include propyl group, isopropyl group, cyclopropyl group, butyl group, 2-butyl group, tert-butyl group and cyclobutyl group. R is preferably a methyl group because the triazine compound (1) can be easily synthesized.

(Ii) Aromatic hydrocarbon groups Examples of the aromatic hydrocarbon groups include phenyl group, naphthyl group, biphenylyl group, phenanthryl group, anthryl group, pyrenyl group, fluorenyl group, benzofluorenyl group, triphenylenyl group and full. Examples thereof include an oranthenyl group. These groups may be substituted with alkyl groups having 1 to 4 carbon atoms. The alkyl group having 1 to 4 carbon atoms may be a linear, branched or cyclic alkyl group, and specifically, a methyl group, an ethyl group, a propyl group, a 2-methylpropyl group, an isopropyl group or a cyclo. Examples thereof include propyl group, butyl group, 2-butyl group and tert-butyl group. In that the triazine compound (1) can be easily synthesized, R is an unsubstituted aromatic hydrocarbon group having 6 to 14 carbon atoms or an aromatic hydrocarbon group having 6 to 14 carbon atoms substituted with a methyl group. It is preferable, and a phenyl group or a biphenylyl group is particularly preferable.

(Iii) Nitrogen-containing aromatic group Examples of the nitrogen-containing heterocycle include a pyridyl group, a piperidyl group, a benzo [b] quinolyl group, a phenylpyridyl group, a carbazolyl group and the like. These groups may be substituted with one or more groups selected from the group consisting of alkyl groups having 1 to 4 carbon atoms and phenyl groups. The alkyl group having 1 to 4 carbon atoms may be a linear, branched or cyclic alkyl group, and specifically, a methyl group, an ethyl group, a propyl group, a 2-methylpropyl group, an isopropyl group or a cyclo. Examples thereof include propyl group, butyl group, 2-butyl group and tert-butyl group. R is preferably a pyridyl group because the triazine compound (1) can be easily synthesized.

(Iv) Heterocyclic group in which the heteroatom is a Group 16 element Examples of the heterocycle include a dibenzothiophenyl group, a dibenzofuranyl group, a benzonaphthofuranyl group or a benzonaphthophenyl group. These groups may be substituted with one or more groups selected from the group consisting of alkyl groups having 1 to 4 carbon atoms and phenyl groups. The alkyl group having 1 to 4 carbon atoms may be a linear, branched or cyclic alkyl group, and specifically, a methyl group, an ethyl group, a propyl group, a 2-methylpropyl group, an isopropyl group or a cyclo. Examples thereof include propyl group, butyl group, 2-butyl group and tert-butyl group. R is preferably a dibenzofuranyl group or a dibenzothiophenyl group in that the triazine compound (1) contributes to the formation of a higher performance organic electroluminescent device.

Here, it is said that R is the same or different.
All three Rs may be different from each other
All three Rs may be the same
Two of the three Rs may be the same and the remaining one may be different from the other two.
Indicates that it is one of the following.

Also, R is the same or different,
Alkyl groups with 1 to 4 carbon atoms, or
Unsubstituted or substituted with a methyl group,
Aromatic hydrocarbon groups of monocyclic, linked or fused rings with 6 to 20 carbon atoms,
A nitrogen-containing aromatic group consisting of only a 6-membered ring and having 4 to 14 carbon atoms, or
It is more preferable that the hetero atom is a heterocyclic group having 4 to 14 carbon atoms, which is a group 16 element.

Furthermore, it is particularly preferred that R is the same or differently a methyl group, a phenyl group, a biphenylyl group, a naphthyl group, a fluorenyl group, a pyridyl group, a dibenzofuranyl group or a dibenzothiophenyl group.

[About L]
L represents a phenylene group. Examples of the phenylene group include an orthophenylene group (1,2-phenylene group), a meta-phenylene group (1,3-phenylene group), and a paraphenylene group (1,4-phenylene group). L is a metaphenylene group (1,3-phenylene group) or a paraphenylene group (1,4-phenylene group) in that the triazine compound (1) contributes to the formation of a higher-performance organic electric field light emitting element. Is preferable, and a metaphenylene group (1,3-phenylene group) is particularly preferable.

[About Z]
Z represents a carbon atom, a silicon atom, a germanium atom, or a tin atom. Z is preferably a carbon atom, a silicon atom, or a germanium atom, and is a silicon atom or a germanium atom, in that the triazine compound (1) contributes to the formation of a higher-performance organic electric field light emitting element. Is particularly preferable.

[About p]
p represents 0, 1 or 2. P is preferably 0 or 1 in that the triazine compound (1) contributes to the formation of a higher performance organic electroluminescent device.

[Specific example of triazine compound (1)]
Specific examples of the triazine compound (1) are not particularly limited, but examples thereof include compounds having the structures shown in 1-1 to 1-192 below. The triazine compound (1) is 1-1, 1-2, 1-28, 1-40, 1-41, 1-66, 1-74 in that it has good performance as an electron transporting material in an organic electroluminescent device. , 1-133, 1-148, 1-165, 1-178, or 1-179 are preferred.

Next, a method for producing a triazine compound according to another aspect of the present disclosure (hereinafter, referred to as a method for producing a triazine compound (1)) will be described.
The triazine compounds (1a) and (1b) contained in the triazine compound (1) can be produced by step 1 or 2 shown in the following reaction formula.
That is, the method for producing the triazine compound (1a) includes a coupling reaction between the compound represented by the formula (2) and the compound represented by the formula (3).
The method for producing the triazine compound (1b) includes a coupling reaction between the compound represented by the formula (4) and the compound represented by the formula (5).

During the ceremony
Ar ¹ and Ar ² independently represent a phenyl group, a biphenylyl group or a naphthyl group;
Ar ³ is
Hydrogen atom,
Aromatic hydrocarbon groups of monocyclic, linked or fused rings with 6 to 20 carbon atoms, or
Represents a nitrogen-containing aromatic group consisting of only a 6-membered ring and having 4 to 14 carbon atoms;
Ar ¹ , Ar ² and Ar ³ may each be independently substituted with one or more groups selected from the group consisting of a fluorine atom, an alkyl group having 1 to 4 carbon atoms, and a phenyl group;
R is the same or different,
Alkyl groups with 1 to 6 carbon atoms,
An aromatic hydrocarbon group having 6 to 20 carbon atoms, a monocyclic ring, a linking ring, or a condensed ring, which may be substituted with an alkyl group having 1 to 4 carbon atoms.
A nitrogen-containing aromatic group having 4 to 14 carbon atoms consisting of only a 6-membered ring which may be substituted with an alkyl group having 1 to 4 carbon atoms or a phenyl group, or a nitrogen-containing aromatic group having 4 to 14 carbon atoms.
Heteroatoms that may be substituted with alkyl or phenyl groups of 1 to 4 carbons represent group 16 elements, heterocyclic groups of 4 to 14 carbons;
Two adjacent Rs may be integrated to form a 5- or 6-membered ring containing a Z to which the two Rs are bonded;
L represents a phenylene group;
Z represents a carbon atom, a silicon atom, a germanium atom, or a tin atom;
p'and p'independently represent 1 or 2;
M ¹ represents ZnY ¹ , MgY ² , Sn (Y ³ ) ₃ , or B (OY ⁴ ) ₂ ;
M ² represents ZnY ¹ , MgY ² , Sn (Y ³ ) ₃ , or B (OY ⁴ ) ₂ ;
Y ¹ and Y ² independently represent a chlorine atom, a bromine atom or an iodine atom;
Y ³ are the same or different and each represents an alkyl group or a phenyl group having 1 to 4 carbon atoms;
Y ⁴ are the same or different and each represents a hydrogen atom, an alkyl group or a phenyl group having 1 to 4 carbon atoms;
The two (OY ⁴ ) groups may be united to form a ring with the boron atom to which the ^{two (OY 4) groups are attached;}
X ¹ represents a chlorine atom, a bromine atom, a trifluoromethanesulfonyloxy group or an iodine atom;
X ² represents a chlorine atom, a bromine atom, a trifluoromethanesulfonyloxy group or an iodine atom.

Step 1 is a step of producing the triazine compound (1a) by subjecting the triazine compound (2) and the compound (3) to a coupling reaction. Here, the coupling reaction is preferably carried out in the presence of a catalyst. In step 1, the desired product is obtained in good yield by applying the reaction conditions of general coupling reactions such as Suzuki-Miyaura reaction, Negishi reaction, Tamao-Kumada reaction, Stille-Kosugi-Stille reaction. Can be done. When the reaction conditions of the Suzuki-Miyaura reaction are applied to step 1, it is preferable to carry out the reaction in the presence of a base. Further, as the catalyst, a palladium catalyst is preferable.

The compound represented by the formula (2) used in the step 1 is, for example, a method disclosed in Japanese Patent No. 531824, or a general organometallic compound is synthesized from the compound represented by the formula (4). It can be synthesized using a reaction (see, eg, Angew. Chem. Int. Ed. 2007, 46, 5359-5363).

Examples of the compound represented by the formula (2) include compounds having the structures shown in 2-1 to 2-48 below, but the present invention is not limited thereto. In equations (2-1) to (2-48), M ¹ has the same definition as equation (2).

The ^{group represented by M 1} is not particularly limited, and examples thereof include ZnY ¹ , MgY ² , Sn (Y ³ ) ₃ , B (OY ⁴ ) _{2, and the} like. Among these, B (OY ⁴ ) ₂ is preferable.

The ZnY ¹ and MgY ² are not particularly limited, and examples thereof include ZnCl, ZnBr, ZnI, MgCl, MgBr, and MgI.
The Sn (Y ³ ) ₃ is not particularly limited, and examples thereof include Sn (Me) ₃ and Sn (Bu) ₃ .
The B (OY ⁴ ) ₂ is not particularly limited, but for example, B (OH) ₂ , B (OMe) ₂ , B (O ⁱ Pr) ₂ , B (OBu) ₂ , B (OPh). ₂ etc. can be exemplified. Me is a methyl group, ⁱ Pr is an isopropyl group, Bu is a butyl group, and Ph is a phenyl group.

^{Further, the example of B (OY 4} ) _{2 in} the case where two (OY ⁴ ) groups are integrally formed with a boron atom is not particularly limited, but for example, the following ( The groups represented by (I) to (VI) can be exemplified, and the group represented by (II) is preferable in terms of good yield.

Compound (3) used in step 1 can be produced, for example, according to Japanese Patent Application Laid-Open No. 2013-93332. Moreover, you may use a commercially available product.
Examples of the compound (3) include the following 3-1 to 3-60, but the present disclosure is not limited thereto. In equations (3-1) to (3-60), X ¹ has the same definition as equation (3).

The ^{leaving group represented by X 1} is a chlorine atom, a bromine atom, a trifluoromethanesulfonyloxy group or an iodine atom. A chlorine atom or a bromine atom is preferable because the yield of the triazine compound (1a) is good. However, it may be preferable to use a trifluoromethanesulfonyloxy group from the viewpoint of availability of raw materials.

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

A palladium complex having a tertiary phosphine as a ligand can also be prepared in a reaction system by adding a tertiary phosphine to a palladium salt or a complex compound. Examples of the tertiary phosphine that can be used at this time include triphenylphosphine, trimethylphosphine, tributylphosphine, tri (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-kisilyl) phosphine, (±) -2,2'-bis (diphenylphosphine) ) -1,1'-binaphthyl, 2-dicyclohexylphosphino-2', 4', 6'-triisopropylbiphenyl and the like can be exemplified.

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

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

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

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

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

Next, step 2 will be described.
Step 2 is a step of producing a triazine compound (1b) by subjecting the compound represented by the formula (4) and the compound represented by the formula (5) to a coupling reaction. Here, the coupling reaction is preferably carried out in the presence of a catalyst. In step 2, the desired product is obtained in good yield by applying the reaction conditions of general coupling reactions such as Suzuki-Miyaura reaction, Negishi reaction, Tamao-Kumada reaction, Stille-Kosugi-Stille reaction. Can be done. When the reaction conditions of the Suzuki-Miyaura reaction are applied to step 2, it is preferable to carry out the reaction in the presence of a base. Further, as the catalyst, a palladium catalyst is preferable.

The triazine compound represented by the formula (4) used in the step 2 can be produced, for example, according to the method disclosed in JP-A-2018-115151.
^{The triazine compound represented by the formula (4) is a compound in which M 1} in the formulas (2-1) to (2-36), which is a specific example of the compound represented by the formula (2), is replaced with X ^2. It can be exemplified. Here, X ² has the same definition as in equation (4).

The ^{desorbing group represented by X 2} is not particularly limited, but a chlorine atom, a bromine atom, a trifluoromethanesulfonyloxy group or an iodine atom can be exemplified, and the yield of the triazine compound (1) can be exemplified. However, a chlorine atom or a bromine atom is preferable.

The compound represented by the formula (5) used in the step 2 can be produced according to, for example, Days and Pigments, Vol. 134, p. 266, 2016. Further, it can be synthesized from the compound represented by the formula (3) by using a reaction for synthesizing a general organometallic compound (for example, Angew. Chem. Int. Ed. 2007, 46, 5359-5363). Commercially available products may be used.

The compound represented by the formula (5) can exemplify a skeleton in which ^{X 1} is replaced with M ² in the compounds represented by the formulas (3-1) to (3-60). M ² has the same definition as equation (5).

As the palladium catalyst, base, solvent, reaction temperature, and post-treatment (purification) that can be used in step 2, the same ones as those exemplified in step 1 can be exemplified, and the same applies to the preferable configurations thereof. is there.

Further, the triazine compound (1c) contained in the triazine compound (1) can be produced according to the method shown in the next step 3.

In the formula, Ar ¹ , Ar ² , Ar ³ , R and Z have the same meanings as described above;
X ³ represents a chlorine atom, a bromine atom, a trifluoromethanesulfonyloxy group or an iodine atom;
M ³ represents ZnY ¹ , MgY ² , Sn (Y ³ ) ₃ , or B (OY ⁴ ) ₂ ;
Y ³ are the same or different and each represents an alkyl group or a phenyl group having 1 to 4 carbon atoms;
Y ⁴ are the same or different and each represents a hydrogen atom, an alkyl group or a phenyl group having 1 to 4 carbon atoms. Further, a ring may be formed together with a boron atom in which ^{two (OY 4) groups are integrally bonded.}

Next, step 3 will be described.
Step 3 is a step of producing a triazine compound (1c) by subjecting the compound represented by the formula (6) and the compound represented by the formula (7) to a coupling reaction, for example, Synthesis Example-. A good yield can be obtained by applying the conditions shown in 6. Here, the coupling reaction is preferably carried out in the presence of a catalyst. As the catalyst, a palladium catalyst is preferable.

The triazine compound represented by the formula (6) used in the step 3 can be produced, for example, according to the method disclosed in Days and Pigments, Vol. 157, p. 377, 2018.

The ^{leaving group represented by X 3} is not particularly limited, but a chlorine atom, a bromine atom, a trifluoromethanesulfonyloxy group or an iodine atom can be exemplified, and the yield of the triazine compound (1c) can be exemplified. Chlorine atom is preferable in that

The compound represented by the formula (7) used in the step 3 can be obtained in good yield by applying, for example, the conditions shown in Synthesis Example-6 described later. Further, it can be synthesized from the compound represented by the formula (3) by using a reaction for synthesizing a general organometallic compound (for example, Angew. Chem. Int. Ed. 2007, 46, 5359-5363). Commercially available products may be used.

As the palladium catalyst, base, solvent, reaction temperature, and post-treatment (purification) that can be used in step 3, the same ones as those exemplified in step 1 can be exemplified, and the same applies to the preferable configurations thereof. is there.
As a preferable example of the triazine compound (1c) obtained in step 3, compounds having a structure of 1-28 to 1-39 can be exemplified.

The triazine compound (1) can be used, for example, in organic electronic device applications such as organic electroluminescent devices and photoelectric devices. Among these, the triazine compound (1) is preferably used as a material for an organic electroluminescent device.

<Material for organic electroluminescent device>
The material for an organic electroluminescent device according to one aspect of the present disclosure contains the above-mentioned triazine compound (1).
The triazine compound (1) can be used, for example, as an electron transport material for an organic electroluminescent device. The material for an organic electroluminescent device containing the triazine compound (1) achieves a high level of drive voltage, luminous efficiency and life, and contributes to the production of an organic electroluminescent device that can be used in various applications and in various environments. Is.

<Organic electroluminescent device>
The material for an organic electroluminescent device according to one aspect of the present disclosure contains the above-mentioned triazine compound (1).

<Organic electroluminescent device>
Hereinafter, an organic electroluminescent device containing the triazine compound (1) (hereinafter, may be simply referred to as an organic electroluminescent device) will be described.
The organic electroluminescent device according to one aspect of the present disclosure contains a triazine compound (1).
The configuration of the organic electroluminescent device is not particularly limited, and examples thereof include the configurations (i) to (v) 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 / hole injection layer / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode

The triazine compound (1) may be contained in any of the above layers, but is superior to the group consisting of the light emitting layer and the layer between the light emitting layer and the cathode in that it is excellent in the light emitting characteristics of the organic electroluminescent device. It is preferably contained in one or more selected layers. Therefore, in the case of the configurations shown in (i) to (v) above, it is preferable that the triazine compound (1) is contained in one or more layers selected from the group consisting of a light emitting layer, an electron transporting layer and an electron injecting layer. ..

Hereinafter, the organic electroluminescent device according to one aspect of the present disclosure will be described in more detail with reference to FIG. 1 by taking the configuration of the above (v) as an example.
The organic electroluminescent device shown in FIG. 1 has a so-called bottom emission type element configuration, but the organic electroluminescent device according to one aspect of the present disclosure is not limited to the bottom emission type element configuration. Absent. That is, the organic electroluminescent device according to one aspect of the present disclosure may have another known device configuration such as a top emission type.

FIG. 1 is a schematic cross-sectional view showing an example of a laminated structure of an organic electroluminescent device containing a triazine compound according to one aspect of the present disclosure.

The organic electroluminescent device 100 includes a substrate 1, an anode 2, a hole injection layer 3, a hole transport layer 4, a light emitting layer 5, an electron transport layer 6, an electron injection layer 7, and a cathode 8 in this order. However, some of these layers may be omitted, and conversely, other layers may be added. For example, a hole blocking layer may be provided between the light emitting layer 5 and the electron transporting layer 6, the hole injection layer 3 is omitted, and the hole transporting layer 4 is directly provided on the anode 2. May be good. Further, for example, a single layer having a function of a plurality of layers, such as an electron injection / transport layer having a function of an electron injection layer and a function of an electron transport layer in a single layer, is formed into the plurality of layers. It may be a configuration provided instead of. Further, for example, the single-layer hole transport layer 4 and the single-layer electron transport layer 6 may each be composed of a plurality of layers.

<< Layer containing triazine compound (1) >>
In the configuration example shown in FIG. 1, the organic electroluminescent device 100 contains the triazine compound (1) in one or more layers selected from the group consisting of the light emitting layer 5, the electron transport layer 6, and the electron injection layer 7. In particular, it is preferable that the electron transport layer 6 contains the triazine compound (1). The triazine compound (1) may be contained in a plurality of layers included in the organic electroluminescent device.
In the following, the organic electroluminescent device 100 in which the electron transport layer 6 contains the triazine compound (1) will be described.

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

[Anode 2]
An anode 2 is provided on the substrate 1 (on the hole injection layer 3 side).
Examples of the material of the anode include metals, alloys, electrically conductive compounds and mixtures thereof having a large work function (for example, 4 eV or more). Specific examples of the material of the anode include metals such as Au; conductive transparent materials such as _{CuI, indium tin oxide (ITO), SnO 2, and ZnO.}
In the case of an organic electroluminescent device in which light emission is taken out through an anode, the anode is formed of a conductive transparent material that allows or substantially passes the light emission.

[Hole injection layer 3, hole transport layer 4]
A hole injection layer 3 and a hole transport layer 4 are provided in this order between the anode 2 and the light emitting layer 5 described later from the anode 2 side.

The hole injection layer and the hole transport layer have a function of transmitting holes injected from the anode to the light emitting layer, and the hole injection layer and the hole transport layer are interposed between the anode and the light emitting layer. Injects more holes into the light emitting layer with a lower electric field.

The hole injection layer and the hole transport layer also function as electron barrier layers. That is, the electrons injected from the cathode and transported from the electron 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 and / or the hole transport layer. , Leakage into the hole injection layer and / or the hole transport layer is suppressed. As a result, the electrons are accumulated at the interface in the light emitting layer to bring about effects such as improvement of luminous efficiency, and an organic electroluminescent device having excellent light emitting performance can be obtained.

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

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

Specific examples of the aromatic tertiary amine compound and the styrylamine compound include N, N, N', N'-tetraphenyl-4,4'-diaminophenyl, N, N'-diphenyl-N, N'-. Bis (m-trill)-[1,1'-biphenyl] -4,4'-diamine (TPD), 2,2-bis (4-di-p-tolylaminophenyl) propane, 1,1-bis ( 4-di-p-trillaminophenyl) cyclohexane, N, N, N', N'-tetra-p-tolyl-4,4'-diaminobiphenyl, 1,1-bis (4-di-p-tolylaminophenyl) Phenyl) -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) quadriphenyl , N, N, N-tri (p-tolyl) amine, 4- (di-p-tolylamino) -4'-[4- (di-p-tolylamino) styryl] stillben, 4-N, N-diphenylamino -(2-Diphenylvinyl) benzene, 3-methoxy-4'-N, N-diphenylaminostillbenzene, N-phenylcarbazole, 4,4'-bis [N- (1-naphthyl) -N-phenylamino] Examples thereof include biphenyl (NPD), 4,4', 4''-tris [N- (m-tolyl) -N-phenylamino] triphenylamine (MTDATA) and the like.

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

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

[Light emitting layer 5]
A light emitting layer 5 is provided between the hole transport layer 4 and the electron transport layer 6 described later.
Examples of the material of the light emitting layer include a phosphorescent light emitting material, a fluorescent light emitting material, and a thermal activated delayed fluorescent light emitting material. In the light emitting layer, electron-hole pairs are recombined, resulting in light emission.

The light emitting layer may consist of a single low molecular weight material or a single polymer material, but more generally it consists of a host material doped with a guest compound. The luminescence comes primarily from the dopant and can have any color.

Examples of the host material include compounds having a biphenylyl group, a fluorenyl group, a triphenylsilyl group, a carbazole group, a pyrenyl group, and an anthryl group. More specifically, DPVBi (4,4'-bis (2,2-diphenylvinyl) -1,1'-biphenyl), BCzVBi (4,4'-bis (9-ethyl-3-carbazobinylene) 1, 1'-biphenyl), TBADN (2-talshalbutyl-9,10-di (2-naphthyl) anthracene), ADN (9,10-di (2-naphthyl) anthracene), CBP (4,4'-bis) (Carbazole-9-yl) biphenyl), CDBP (4,4'-bis (carbazole-9-yl) -2,2'-dimethylbiphenyl), 2- (9-phenylcarbazole-3-yl) -9- [Examples include 4- (4-phenylphenylquinazoline-2-yl) carbazole, 9,10-bis (biphenyl) anthracene and the like.

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

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

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

Further, the light emitting material is not limited to being contained only in the light emitting layer. For example, the light emitting material may contain a layer (hole transport layer 4 or electron transport layer 6) adjacent to the light emitting layer. This makes it possible to further increase the current efficiency of the organic electroluminescent device.

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

[Electron transport layer 6]
An electron transport layer 6 is provided between the light emitting layer 5 and the electron injection layer 7 described later.
The electron transport layer has a function of transferring electrons injected from the cathode to the light emitting layer. By interposing the electron transport layer between the cathode and the light emitting layer, electrons are injected into the light emitting layer with a lower electric field.

As described above, the electron transport layer preferably contains the triazine compound (1). Further, the electron transport layer may further contain one or more selected from conventionally known electron transport materials in addition to the triazine compound (1).
When the triazine compound (1) is not contained in the electron transport layer but is contained in another layer, one or more selected from conventionally known electron transport materials should be used as the electron transport material constituting the electron transport layer. Can be done.

Examples of conventionally known electron-transporting materials include alkali metal complexes, alkaline earth metal complexes, and earth metal complexes. Examples of the alkali metal complex, alkaline earth metal complex, and earth metal complex include 8-hydroxyquinolinate lithium (Liq), bis (8-hydroxyquinolinate) zinc, and bis (8-hydroxyquinolinate) copper. , Bis (8-hydroxyquinolinate) manganese, tris (8-hydroxyquinolinate) aluminum, tris (2-methyl-8-hydroxyquinolinate) aluminum, tris (8-hydroxyquinolinate) gallium, bis (10-Hydroxybenzo [h] quinolinate) berylium, bis (10-hydroxybenzo [h] quinolinate) zinc, bis (2-methyl-8-quinolinate) chlorogallium, bis (2-methyl-8-quinolinate) (o -Crezolate) gallium, bis (2-methyl-8-quinolinate) -1-naphtholate aluminum, bis (2-methyl-8-quinolinate) -2-naphtholate gallium and the like can be mentioned.

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

In the organic electroluminescent device according to this embodiment, an electron injection layer may be provided for the purpose of improving the electron injection property and the device characteristics (for example, luminous efficiency, constant voltage drive, or high durability).

[Electron injection layer 7]
An electron injection layer 7 is provided between the electron transport layer 6 and the cathode 8 described later.
The electron injection layer has a function of transferring electrons injected from the cathode to the light emitting layer. By interposing the electron injection layer between the cathode and the light emitting layer, electrons are injected into the light emitting layer with a lower electric field.

Materials for the electron injection layer include fluorenone, anthraquinodimethane, diphenoquinone, thiopyrandioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, fleolenilidenemethane, anthraquinodimethane, and antron. Examples include organic compounds. Further, as the material of the electron injection layer, _{various oxides, nitrides, oxide nitrides such as SiO 2} , AlO, SiN, SiON, AlON, Geo, LiO, LiON, TiO, TiON, TaO, TaON, TaN, C and the like are used. Inorganic compounds such as, etc. are also mentioned.

[Cathode 8]
A cathode 8 is provided on the electron injection layer 7.
In the case of an organic electroluminescence device having a configuration in which only light emitted through the anode is extracted, the cathode can be formed from any conductive material.
Examples of the material of the cathode include metals having a small work function (hereinafter, also referred to as electron-injectable metals), alloys, electrically conductive compounds, and mixtures thereof. Here, the metal having a small work function is, for example, a metal having a work function of 4 eV or less.
Specific examples of cathode 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 ). Examples include mixtures, indium, lithium / aluminum mixtures, rare earth metals and the like.
Among these, from the viewpoint of electron injectability and durability against oxidation, a mixture of an electron injectable metal and a second metal which is a stable metal having a larger work function value than this, for example, magnesium / silver mixture, magnesium / Aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al ₂ O ₃ ) mixture, lithium / aluminum mixture and the like are preferable.

[Formation method of each layer]
Each layer excluding the electrodes (anode, cathode) described above is formed by thinning by a known method such as a vacuum deposition method, a spin coating method, a casting method, or an LB (Langmuir-Blodgett method) method. be able to. The material of each layer may be used alone, or may be used together with a material such as a binder resin and a solvent, if necessary.
The film thickness of each layer thus formed is not particularly limited and may be appropriately selected depending on the situation, but is usually in the range of 5 nm to 5 μm.

The anode and cathode can be formed by thinning the electrode material by a method such as thin film deposition or sputtering. A pattern may be formed through a mask having a desired shape during vapor deposition or sputtering, or a thin film may be formed by vapor deposition or sputtering, and then a pattern having a desired shape may be formed by photolithography.

The film thickness of the anode and the cathode is preferably 1 μm or less, and more preferably 10 nm or more and 200 nm or less.

The layer containing the triazine compound (1) may be formed in combination with the above-mentioned conventionally known electron-transporting material. Therefore, for example, the triazine compound (1) and the conventionally known electron-transporting material may be co-deposited, or a layer of the conventionally known electron-transporting material may be laminated on the layer of the triazine compound (1).

The organic electroluminescent element may be used as a kind of lamp such as an illumination or an exposure light source, a projection device of a type that projects an image on a screen or the like, or a display of a type that directly visually recognizes a still image or a moving image. It may be used as a device (display). When an organic electroluminescent element is used as a display device for video reproduction, the drive method may be a simple matrix (passive matrix) method or an active matrix method. Further, a full-color display device can be manufactured by using two or more kinds of organic electroluminescent elements having different emission colors.

The triazine compound (1) can provide an organic electroluminescent device having superior luminous efficiency as compared with a conventionally known triazine compound when used as an electron transport layer. Further, the triazine compound (1) is highly amorphous due to its steric hindrance skeleton and has high film quality stability. Therefore, effects such as improvement of driving stability of the organic electroluminescent element and improvement of luminous efficiency can be obtained.

By using the triazine compound (1) as an electron transport layer of an organic electroluminescent device, both low voltage drive and high efficiency of the device can be achieved at a high level. Further, the organic electroluminescent device using the triazine compound (1) can exhibit low voltage drive and high efficiency.

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

[ ^{1 1} H-NMR measurement]
¹ Bruker ASCEND 400 (400 MHz; manufactured by BRUKER) was used for 1 H-NMR measurement. ^{1 1} H-NMR was _{measured using deuterated chloroform (CDCl 3} ) as a measurement solvent and tetramethylsilane (TMS) as an internal standard substance.

[DSC measurement (glass transition temperature)]
The glass transition temperature was measured in a nitrogen atmosphere (flow rate 50 ml / min) using a DSC (Differential scanning calorimetry) device DSC6220 (product name, manufactured by Hitachi High-Tech Science Co., Ltd.). _{Aluminum oxide (Al 2} O ₃ ) was used as a reference in the DSC measurement, and the sample was measured at 10 mg.
As a pretreatment for the measurement, the sample was melted by raising the temperature from 50 ° C. to a temperature above the melting point at a rate of 10 ° C./min, and then rapidly cooled with liquid nitrogen. Subsequently, the temperature of the pretreated sample was raised at a rate of 50 ° C. to 10 ° C./min, and the glass transition temperature, crystallization temperature and melting point were measured.

[Measurement of light emission characteristics]
The light emitting characteristics of the organic electroluminescent device are evaluated using a luminance meter BM-9 (product name, manufactured by Topcon Techno House) in an environment of 25 ° C. by applying a direct current to the devices manufactured in each example (described later). did.
In addition, commercially available reagents were used.

Synthesis Example-1

Under an argon atmosphere, 2,4-diphenyl-6- [3- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -1,1': 2', 1''-Terphenyl-3-yl] -1,3,5-triazine (2.74 g, 4.7 mmol), 3-bromo-1-triphenylsilylbenzene (2.18 g, 5.1 mmol), palladium acetate (2.74 g, 4.7 mmol) 60 mg, 0.29 mmol), and 2-dicyclohexylphosphino-2', 4', 6'-triisopropylbiphenyl (252 mg, 0.58 mmol) were suspended in THF (60 mL). After adding a 2M-potassium carbonate aqueous solution (8 mL) to this suspension, the mixture was heated under reflux for 24 hours. After allowing to cool, water and methanol were added to the reaction mixture, and the resulting solid was collected by filtration. By washing the obtained solid with toluene, the desired 2,4-diphenyl-6- [3-triphenylsilyl-1,1': 5', 1'': 2'', 1'''- Quaterphenyl-3'-yl] -1,3,5-triazine (1-41) was obtained (3.09 g, 3.88 mmol, 83%).
^{1 1} H-NMR (CDCl ₃ ) δ (ppm): 6.84 (tt, J = 7.4, 1.2 Hz, 1H), 7.02 (ddd, J = 8.0, 7.6, 1. 4Hz, 2H), 7.18 (dd, J = 8.0, 1.0Hz, 2H), 7.38-7.67 (m, 30H), 8.68 (dd, J = 1.6Hz, 1H) ), 8.73 (ddd, 6.8, 1.6, 1.6Hz, 4H), 8.76 (dd, J = 1.6Hz, 1H)

The obtained 2,4-diphenyl-6- [3-triphenylsilyl-1,1': 5', 1'': 2'', 1'''-quaterphenyl-3'-yl] -1 The glass transition temperature of 3,5-triazine was 110 ° C.

Synthesis Example-2

Under an argon atmosphere, 2,4-diphenyl-6- [3- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -biphenyl-5-yl] -1,3 , 5-Triazine (2.69 g, 5.3 mmol), 3-Bromo-1-triphenylsilylbenzene (2.40 g, 5.8 mmol), Palladium acetate (60 mg, 0.29 mmol), 2-Dicyclohexylphosphino- 2', 4', 6'-triisopropylbiphenyl (252 mg, 0.58 mmol) was suspended in THF (60 mL). After adding a 2M-potassium carbonate aqueous solution (8 mL) to this suspension, the mixture was heated under reflux for 24 hours. After allowing to cool, water and methanol were added to the reaction mixture. The precipitated solid was collected by filtration and washed with toluene to obtain the desired 2,4-diphenyl-6- [3-triphenylsilyl-1,1': 5', 1 "-terphenyl-3'-. Ill] -1,3,5-triazine (1-40) was obtained (2.66 g, 3.7 mmol, 70%).
^{1 1} H-NMR (CDCl ₃ ) δ (ppm): 7.38-7.47 (m, 9H), 7.51-7.68 (m, 16H), 7.18 (dd, J = 8.0) , 1.0Hz, 2H), 7.75 (dd, J = 7.1, 1.4Hz, 1H), 7.86 (ddd, 7.7, 1.8, 1.3Hz, 1H), 7. 94 (dd, J = 1.8, 1.8Hz, 1H), 8.00 (s, 1H), 8.77 (ddd, J = 6.7, 1.5, 1.4Hz, 4H), 8 .90 (dd, 1.6, 1.6Hz, 1H), 8.95 (dd, 1.6, 1.6Hz, 1H).

Synthesis Example-3

Under an argon atmosphere, 2,4-diphenyl-6- [3- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -1,1': 2', 1''-Terphenyl-3-yl] -1,3,5-triazine (3.14 g, 5.3 mmol), 4-bromo-1-triphenylsilylbenzene (2.23 g, 5.9 mmol), palladium acetate (2.23 g, 5.9 mmol) 60 mg, 0.29 mmol), 2-dicyclohexylphosphino-2', 4', 6'-triisopropylbiphenyl (254 mg, 0.58 mmol) was suspended in THF (60 mL). After adding a 2M-potassium carbonate aqueous solution (8 mL) to this suspension, the mixture was heated under reflux for 24 hours. After allowing to cool, water and methanol were added to the reaction mixture. The precipitated solid is collected by filtration and washed with toluene to obtain the desired 2,4-diphenyl-6- [4-triphenylsilyl-1,1': 5', 1'': 2'', 1'. ''-Quaterphenyl-3'-yl] -1,3,5-triazine (1-2) was obtained (3.09 g, 3.9 mmol, 84%).
^{1 1} H-NMR (CDCl ₃ ) δ (ppm): 7.13-7.24 (m, 2H), 7.26-7.30 (m, 4H), 7.39 (dd, J = 1.6) , 1.4Hz, 1H), 7.40-7.59 (m, 16H), 7.60-7.64 (m, 10H), 7.65-7.66 (m, 2H), 8.68 (Dd, J = 1.6, 1.6Hz, 1H), 8.74 (ddd, 6.8, 1.7, 1.4Hz, 4H), 8.85 (dd, J = 1.7,1) .6Hz, 1H).

Synthesis Example-4

Under an argon atmosphere, 2,4-diphenyl-6- [3- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -biphenyl-5-yl] -1,3 , 5-Triazine (2.76 g, 5.4 mmol), 4-Bromo-1-triphenylsilylbenzene (2.37 g, 5.8 mmol), Palladium acetate (60 mg, 0.29 mmol), 2-Dicyclohexylphosphino- 2', 4', 6'-triisopropylbiphenyl (252 mg, 0.58 mmol) was suspended in THF (60 mL). A 2.0 M-potassium carbonate aqueous solution (8 mL) was added to this suspension, and the mixture was heated under reflux for 24 hours. After allowing to cool, water and methanol were added to the reaction mixture. The resulting solid was collected by filtration and washed with toluene to obtain the desired 2,4-diphenyl-6- [4-triphenylsilyl-1,1': 5', 1''-terphenyl-3'-. Il] -1,3,5-triazine (1-1) was obtained (2.68 g, 3.8 mmol, 70%).
^{1 1} H-NMR (CDCl ₃ ) δ (ppm): 7.39-7.50 (m, 10H), 7.51-7.67 (m, 14H), 7.75 (dd, J = 8.2) , 1.8Hz, 2H), 7.81 (ddd, J = 8.3, 8.2, 1.1, 4H), 8.07 (dd, J = 1.8, 1.8Hz, 1H), 8.80 (ddd, J = 6.4,2.0, 1.4Hz, 4H), 8.98-9.01 (m, 2H).

Glass transition temperature of the obtained 2,4-diphenyl-6- [4-triphenylsilyl-1,1': 5', 1''-terphenyl-3'-yl] -1,3,5-triazine Was 119 ° C.

Synthesis Example-5

Under an argon atmosphere, 2,4-diphenyl-6- [3- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -1,1': 2', 1''-Terphenyl-3-yl] -1,3,5-triazine (5.00 g, 8.5 mmol), 1-trifluoromethylsulfonyloxy-4-triphenylmethylbenzene (4.31 g, 9.3 mmol) , Palladium acetate (96 mg, 0.43 mmol), 2-dicyclohexylphosphino-2', 4', 6'-triisopropylbiphenyl (409 mg, 0.86 mmol) was suspended in THF (80 mL). After adding a 2M-potassium carbonate aqueous solution (14 mL) to this suspension, the mixture was heated under reflux for 24 hours. After allowing to cool, water and methanol were added to the reaction mixture. The precipitated solid is collected by filtration and washed with toluene to obtain the desired 2,4-diphenyl-6- [4-triphenylmethyl-1,1': 5', 1'': 2'', 1'. ''-Quaterphenyl-3'-yl] -1,3,5-triazine (1-66) was obtained (2.08 g, 3.4 mmol, 40%).
^{1 1} H-NMR (CDCl ₃ ) δ (ppm): 7.15-7.25 (m, 8H), 7.25-7.32 (m, 15H), 7.36 (ddd, J = 8.6) , 2.2, 1.2Hz, 2H), 7.48-7.66 (m, 11H), 8.62 (dd, J = 1.6, 1.6Hz, 1H), 8.73 (ddd, J = 6.5, 1.6, 1.4Hz, 4H), 8.82 (dd, J = 1.6Hz, 1H).

Synthesis Example-6

To 3-chloro-5-triphenylsilyl biphenylyl (3.61 g, 8.1 mmol), bis (pinacolato) diboron (2.46 g, 9.7 mmol), palladium acetate (54 mg, 0.24 mmol), 2-dicyclo Xylphosphino-2', 4', 6'-triisopropylbiphenyl (231 mg, 0.48 mmol) and potassium acetate (2.37 g, 24 mmol) were suspended in THF (81 mL) and refluxed by heating for 18 hours. After allowing to cool to room temperature, water and methanol were added to the reaction mixture, and the resulting solid was collected by filtration. The obtained solid was dissolved in chloroform, activated carbon was added, and the mixture was stirred for a while. After stirring, Celite filtration was performed to obtain the desired 3- (4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -5-triphenylsilylbiphenylyl (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -5-triphenylsilylbiphenylyl. Yield 3.87 g, yield 89%).
^{1 1} HNMR (CDCl ₃ ) δ1.31 (s, 12H), 7.30 (td, J = 7.4, 2.5Hz, 1H), 7.35-7.41 (m, 8H), 7.41 -7.46 (m, 3H), 7.51-7.54 (m, 2H), 7.60 (td, J = 6.5, 2.5Hz, 6H), 7.87 (dd, J = 1.1, 0.8Hz, 1H), 8.07 (t, J = 1.1Hz, 1H), 8.12 (dd, J = 1.1, 0.8Hz, 1H).

Synthesis Example-A

3- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -5-triphenylsilylbiphenylyl (3.00 g, 5.57 mmol), 2- Chloro-4,6-diphenyl-1,3,5-triazine (1.49 g, 5.57 mmol) and tetrakis (triphenylphosphine) palladium (322 mg, 0.28 mmol) were suspended in THF (56 mL). A 2.0 M-potassium phosphate aqueous solution (8.4 mL) was added to this suspension, and the mixture was heated under reflux for 14 hours. After allowing to cool, water and methanol were added to the reaction mixture. The resulting solid was collected by filtration. By purifying the obtained solid by silica gel column chromatography (hexane / chloroform), the desired 2,4-diphenyl-6-[(5-phenyl-3-triphenylsilyl) phenyl] -1,3,5 -Triazine (1-28) was obtained (yield 3.21 g, yield 90%).
^{1 1} H-NMR (CDCl ₃ ) δ (ppm): 7.40 (tt, J = 7.6, 1.3 Hz, 1H), 7.43-7.59 (m, 15H), 7.62 (tt) , J = 7.6,0.7Hz, 2H), 7.68-7.73 (m, 8H), 8.10 (dd, J = 1.8, 0.5Hz, 1H), 8.68 ( dt, J = 6.9, 1.5Hz, 4H), 9.01 (dd, J = 5.9, 1.8Hz, 1H).

Synthesis Example-7

2- [5-Phenyl-3- (4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl] -4,6-diphenyl-1,3, under an argon atmosphere 5-Triazine (2.04 g, 4.00 mmol), 3-chloro-1-triphenylgelmilbenzene (1.96 g, 4.60 mmol), palladium acetate (45 mg, 0.20 mmol) and 2-dicyclohexylphosphine- 2', 4', 6'-triisopropylbiphenyl (191 mg, 0.40 mmol) was suspended in THF (40 mL). A 2M aqueous potassium phosphate solution (6.0 mL) was added to this suspension, and the mixture was heated under reflux for 18 hours. After allowing to cool, water and methanol were added to the reaction mixture. The resulting solid was collected by filtration. By purifying the obtained solid by silica gel column chromatography (hexane / chloroform), the desired 2,4-diphenyl-6-[(5-phenyl-3-triphenyl gelmil) phenyl] -1,3 5-Triazine (1-74) was obtained (yield 1.81 g, yield 59%).
^{1 1} H-NMR (CDCl ₃ ) δ (ppm): 9.04 (dt, J = 9.0, 1.7 Hz, 2H), 8.81 (dt, J = 6.8, 1.7 Hz, 4H) , 8.24 (td, J = 7.0, 1.5Hz, 4H), 8.13 (t, J = 1.7Hz, 1H), 8.10 (t, J = 1.8Hz, 1H), 8.00 (s, 2H), 7.91 (td, J = 7.7, 1.4Hz, 1H), 7.84 (d, J = 1.2Hz, 1H), 7.82 (t, J) = 1.3Hz, 1H), 7.72 (t, J = 7.7Hz, 1H), 7.50-7.63 (m, 15H), 7.42-7.49 (m, 4H).

Synthesis Example-8

Under an argon atmosphere, 2,4-diphenyl-6- [3-chloro-4- (4-pyridyl) phenyl] -1,3,5-triazine (147 mg, 0.35 mmol), 4,4,5,5- Tetramethyl-2- [3- (trimethylsilyl) phenyl] -1,3,2-dioxaborolane (125 mg, 0.45 mmol), palladium acetate (2.4 mg, 0.01 mmol), 2-dicyclohexylphosphino-2', 4', 6'-triisopropylbiphenyl (10 mg, 21 μmol) was dissolved in tetrahydrofuran (3.5 mL). A 2M-potassium carbonate aqueous solution (0.5 mL) was added thereto, and the mixture was stirred at 80 ° C. for 24 hours. After allowing to cool to room temperature, the low boiling point was distilled off under reduced pressure, chloroform and water were added to the obtained solid, and the organic layer was extracted. The organic layer was dried over sodium sulfate, and the low boiling point was distilled off under reduced pressure. By purifying the obtained crude product by column chromatography, 2,4-diphenyl-6- [2- (4-pyridyl) -3'-trimethylsilylbiphenyl-5-yl] -1,3,5-triazine The white solid of (1-94) was obtained (yield 182 mg, yield 98%).
^{1 1} H-NMR (CDCl ₃ ) δ (ppm): 0.14 (s, 9H), 7.12-7.14 (m, 2H), 7.24 (s, 1H), 7.38-7. 48 (m, 3H), 7.56-7.65 (m, 7H), 8.49-8.51 (m, 2H), 8.78-8.81 (m, 4H), 8.85 ( dd, J = 8.0, 1.8Hz, 1H), 8.90 (d, J = 1.6Hz, 1H)

Synthesis Example-9

2- [4-Chloro-2- (9-phenanthrenyl) phenyl] -4,6-diphenyl-1,3,5-triazine (104 mg, 0.20 mmol), 4,4,5,5- under an argon atmosphere Tetramethyl-2- [3- (triphenylsilyl) phenyl] -1,3,2-dioxaborolane (120 mg, 0.26 mmol), palladium acetate (1.3 mg, 6 μmol), 2-dicyclohexylphosphino-2', 4', 6'-triisopropylbiphenyl (5.7 mg, 12 μmol) was dissolved in tetrahydrofuran (2 mL). A 2M-potassium carbonate aqueous solution (0.6 mL) was added thereto, and the mixture was stirred at 80 ° C. for 24 hours. After allowing to cool to room temperature, the low boiling point was distilled off under reduced pressure, and the residue was washed with water and methanol to obtain a crude product. By purifying the obtained crude product by column chromatography, 2,4-diphenyl-6- [2- (9-phenanthrenyl) -3'-triphenylsilyl (biphenyl-4-yl)] -1, A white solid of 3,5-triazine (1-95) was obtained (yield 122 mg, 74%).
^{1 1} H-NMR (CDCl ₃ ) δ (ppm): 7.18 (t, J = 8.0 Hz, 4H), 7.36-7.51 (m, 13H), 7.55-7.72 (m) , 12H), 7.76 (d, J = 1.8Hz, 1H), 7.78-7.82 (m, 2H), 7.87 (d, J = 7.8Hz, 1H), 7.95 -7.99 (m, 5H), 8.70-8.73 (m, 3H)

Synthesis Example-10

2- [5-Phenyl-3- (4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl] -4,6-diphenyl-1,3, under an argon atmosphere 5-Triazine (1.27 g, 2.5 mmol), 3-bromo-1-diphenylmethylsilylbenzene (1.06 g, 3.0 mmol), palladium acetate (28 mg, 0.13 mmol), 2-dicyclohexylphosphino-2 ', 4', 6'-triisopropylbiphenyl (119 mg, 0.25 mmol) was suspended in tetrahydrofuran (25 mL). A 2M-potassium carbonate aqueous solution (7.5 mL) was added to this suspension, and the mixture was stirred at 80 ° C. for 20 hours. After allowing to cool to room temperature, the low boiling point was distilled off under reduced pressure, and the residue was washed with water and methanol to obtain a crude product. By purifying the obtained crude product by column chromatography, 2,4-diphenyl-6- [3- (diphenylmethylsilyl) -1,1': 5', 1''-terphenyl-3' -Il] -1,3,5-triazine (1-164) was obtained as a white solid (yield 1.42 g, yield 87%).
^{1 1} H-NMR (CDCl ₃ ) δ (ppm): 0.94 (s, 3H), 7.37-7.47 (m, 7H), 7.52-7.66 (m, 14H), 7. 94 (brs, 1H), 7.96 (t, J = 1.7Hz, 1H), 8.79 (dt, J = 6.8, 1.7Hz, 4H), 8.93 (t, J = 1) .7Hz, 1H), 8.95 (t, J = 1.7Hz, 1H).

Synthesis Example-11

Under an argon atmosphere, 4,6-diphenyl-2- [3- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -biphenyl-5'-yl] -1, 3,5-Triazine (2.76 g, 5.42 mmol), 3-bromo-1-triphenylsilylbenzene (2.37 g, 5.76 mmol), Palladium acetate (60 mg, 0.29 mmol), 2-dicyclohexylphosphino -2', 4', 6'-triisopropylbiphenyl (252 mg, 0.58 mmol) was suspended in THF (60 mL). After adding a 2M-potassium carbonate aqueous solution (8 mL) to this suspension, the mixture was heated under reflux for 24 hours. After allowing to cool, water and methanol were added to the reaction mixture. By filtering the resulting solid and recrystallizing it with toluene, 4,6-diphenyl-2- [3-triphenylsilyl- (1,1': 3', 1'') -terphenyl-3' A white solid of'-yl] -1,3,5-triazine (1-171) was obtained (2.68 g, 70%).
^{1 1} H-NMR (CDCl ₃ ) δ7.39-7.50 (m, 10H), 7.51-7.67 (m, 14H), 7.75 (dd, J = 8.2, 1.8Hz, 2H), 7.81 (ddd, J = 8.3,8.2,1.1Hz, 4H), 8.07 (dd, J = 1.8, 1.8Hz, 1H), 8.80 (dddd) , J = 6.4,2.0, 1.4Hz, 4H), 8.98-9.01 (m, 2H).

Reference example-1

Under a nitrogen atmosphere, 2- [3-chloro-5- (phenanthrene-9-yl) phenyl] -4,6-diphenyl-1,3,5-triazine (1.00 g, 1.9 mmol), phenylboronic acid ( 282 mg, 2.3 mmol), palladium acetate (13.0 mg, 0.06 mmol), 2-dicyclohexylphosphino-2', 4', 6'-triisopropylbiphenyl (XPhos, 55.0 mg, 0.12 mmol), 1 , 4-Dioxane (50 mL) and 2M-tripotassium phosphate aqueous solution (2.9 mL, 5.8 mmol) were added to a 300 mL four-necked flask, and the mixture was stirred at 95 ° C. for 6 hours. The obtained reaction solution was allowed to cool to room temperature, water (100 mL) was added to the reaction mixture, the precipitate was collected by filtration, and washed with water, methanol, and then hexane to obtain a gray powder. The obtained gray powder was purified by recrystallization with toluene, and the target compound, 2,4-diphenyl-6- [5- (phenanthrene-9-yl) -biphenyl-3-yl] -1,3, A gray powder (yield 700 mg, yield 65%) of 5-triazine (compound ETL-1) was obtained.

The obtained compound ETL-1 had a glass transition temperature of 108 ° C., a crystallization temperature of 207 ° C., and a melting point of 260 ° C.

^{1 1} H-NMR (CDCl ₃ ): δ7.45 (t, J = 7.3Hz, 1H), 7.52-7.63 (m, 9H), 7.67 (t, J = 7.2Hz, 1H) ), 7.73 (t, J = 7.8Hz, 1.3Hz, 2H), 7.84 (dd, J = 8.1Hz, 1.0Hz, 2H), 7.88 (s, 1H), 7 .98 (dd, J = 7.8Hz, 1.4Hz, 1H), 8.01-8.04 (m, 2H), 8.77-8.80 (m, 5H), 8.85 (d, J = 8.3Hz, 1H), 8.93 (t, J = 1.7Hz, 1H), 9.12 (t, J = 1.7Hz, 1H).

Then, the device evaluation was carried out using the obtained compound.

Device Example-1 (see FIG. 2)

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

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

(Preparation of hole injection layer 3)
Sublimated and purified N- [1,1'-biphenyl] -4-yl-9,9-dimethyl-N- [4- (9-phenyl-9H-carbazol-3-yl) phenyl] -9H-fluorene -2-Amine and 1,2,3-tris [(4-cyano-2,3,5,6-tetrafluorophenyl) methylene] cyclopropane were deposited at a ratio of 99: 1 (mass ratio) at 10 nm. , The hole injection layer 3 was prepared. The film forming rate was 0.1 nm / sec.

(Preparation of the first hole transport layer 41)
Sublimated and purified N- [1,1'-biphenyl] -4-yl-9,9-dimethyl-N- [4- (9-phenyl-9H-carbazole-3-yl) phenyl] -9H-fluorene-2 -Amine was formed into a film at 85 nm at a rate of 0.2 nm / sec to prepare a first hole transport layer 41.

(Preparation of second hole transport layer 42)
Sublimated and purified N-phenyl-N- (9,9-diphenylfluorene-2-yl) -N- (1,1'-biphenyl-4-yl) amine was formed into a 5 nm film at a rate of 0.15 nm / sec. , The second hole transport layer 42 was prepared.

(Preparation of light emitting layer 5)
Sublimated and purified 3- (10-phenyl-9-anthril) -dibenzofuran and 2,7-bis [N, N-di- (4-tertbutylphenyl)] amino-bisbenzofurano-9,9'-spirofluorene And 20 nm were formed at a ratio of 95: 5 (mass ratio) to prepare a light emitting layer 5. The film forming rate was 0.1 nm / sec.

(Preparation of hole blocking layer 6)
Synthesis Example-1, 2,4-diphenyl-6- [3-triphenylsilyl-1, 1': 5', 1'': 2'', 1'''-quaterphenyl-3'synthesized in Example-1 -Il] -1,3,5-triazine (1-41) was formed into a 6 nm film at a rate of 0.05 nm / sec to prepare a hole blocking layer 9.

(Preparation of electron transport layer 7)
Sublimated and purified 4,6-diphenyl-2- (4- {4- [4'-cyano- (1,1'-biphenyl) -4-yl] naphthalene-1-yl} phenyl) -1,3,5 -Triazine and 8-hydroxyquinolinolate lithium (hereinafter, Liq) were formed into a film at a ratio of 50:50 (mass ratio) at 25 nm to prepare an electron transport layer 6. The film forming rate was 0.15 nm / sec.

(Preparation of electron injection layer 8)
A 1 nm film was formed on Liq at a rate of 0.02 nm / sec to prepare an electron injection layer 7.

(Preparation of cathode 9)
Finally, a metal mask was arranged so as to be orthogonal to the ITO stripe (anode 2) on the substrate 1, and the cathode 8 was formed into a film. As the cathode, silver / magnesium (mass ratio 1/10) and silver were formed in this order at 80 nm and 20 nm, respectively, to form a two-layer structure. The film formation rate of silver / magnesium was 0.5 nm / sec, and the film formation rate of silver was 0.2 nm / sec.

^{As described above, the 2} organic electroluminescent device 100 having a light emitting area of 4 mm as shown in FIG. 2 was manufactured. Each film thickness was measured with a stylus type film thickness measuring meter (DEKTAK, manufactured by Bruker).
Further, this element was sealed in a nitrogen atmosphere glove box having an oxygen and water concentration of 1 ppm or less. Sealing was performed by using a glass sealing cap and a film-forming substrate (element) with a bisphenol F type epoxy resin (manufactured by Nagase ChemteX Corporation).

Element Example-2
In the element Example-1, instead of forming a 6 nm film of compound 1-41 on the hole blocking layer 6 (deposition rate of 0.05 nm / sec), 2,4-diphenyl- synthesized in Synthesis Example-2. 6- [3-Triphenylsilyl-1,1': 5', 1 "-terphenyl-3'-yl] -1,3,5-triazine (1-40) formed at 6 nm (deposition rate) An organic electric field light emitting device was produced in the same manner as in Device Example-1 except that the temperature was 0.05 nm / sec).

Element Example-3
In the element Example-1, instead of forming a 6 nm film of compound 1-41 on the hole blocking layer 6 (deposition rate of 0.05 nm / sec), 2,4-diphenyl- synthesized in Synthesis Example-3. 6- [4-Triphenylsilyl-1,1': 5', 1'': 2'', 1'''-quaterphenyl-3'-yl] -1,3,5-triazine (1- An organic electric field light emitting element was produced by the same method as in Element Example 1 except that 2) was formed into a 6 nm film (deposition rate: 0.05 nm / sec).

Element Example-4
In the element Example-1, instead of forming a 6 nm film of compound 1-41 on the hole blocking layer 6 (deposition rate of 0.05 nm / sec), 2,4-diphenyl- synthesized in Synthesis Example-4. 6- [4-Triphenylsilyl-1,1': 5', 1 "-terphenyl-3'-yl] -1,3,5-triazine (1-1) formed at 6 nm (deposition rate) An organic electric field light emitting device was produced in the same manner as in Device Example-1 except that the temperature was 0.05 nm / sec).

Element Example-5
In the element Example-1, instead of forming a 6 nm film of compound 1-41 on the hole blocking layer 6 (deposition rate of 0.05 nm / sec), 2,4-diphenyl- synthesized in Synthesis Example-5. 6- [4-Triphenylmethyl-1,1': 5', 1'': 2'', 1'''-quaterphenyl-3'-yl] -1,3,5-triazine (1- An organic electric field light emitting element was produced in the same manner as in Element Example 1 except that 66) was formed into a 6 nm film (deposition rate: 0.05 nm / sec).

Element Example-6
In the element Example-1, instead of forming the compound 1-41 on the hole blocking layer 6 at 6 nm (deposition rate of 0.05 nm / sec), the 2,4-diphenyl- synthesized in Synthesis Example-6 Example of the device except that 6-[(5-phenyl-3-triphenylsilyl) phenyl] -1,3,5-triazine (1-28) was deposited at 6 nm (deposition rate 0.05 nm / sec). An organic electroluminescent element was produced in the same manner as in -1.

Element Example-7
In the element Example-1, instead of forming compound 1-41 on the hole blocking layer 6 at 6 nm (deposition rate of 0.05 nm / sec), 2,4-diphenyl- synthesized in Synthesis Example-7. The device was implemented except that 6-[(5-phenyl-3-triphenyl gel mill) phenyl] -1,3,5-triazine (1-74) was deposited at 6 nm (deposition rate 0.05 nm / sec). An organic electric field light emitting element was produced by the same method as in Example-1.

Element Example-8
In the element Example-1, instead of forming a 6 nm film of compound 1-41 on the hole blocking layer 6 (deposition rate of 0.05 nm / sec), 4,6-diphenyl- synthesized in Synthesis Example-8. 2- [3-Triphenylsilyl- (1,1': 3', 1'') -terphenyl-3''-yl] -1,3,5-triazine (1-171) was formed in 6 nm. An organic electric field light emitting device was produced in the same manner as in Device Example-1 except that the film formation rate was 0.05 nm / sec).

Element reference example-1
In the element Example-1, instead of forming a 6 nm film of compound 1-41 on the hole blocking layer 6 (deposition rate of 0.05 nm / sec), 2,4-diphenyl-6 synthesized in Reference Example-1 -[5- (Phenanthrene-9-yl) -biphenyl-3-yl] -1,3,5-triazine (compound ETL-1) was deposited at 6 nm (deposition rate 0.05 nm / sec). An organic electroluminescent element was produced in the same manner as in Example-1 of the element.

A direct current was applied to the produced organic electroluminescent device, and the light emitting characteristics were evaluated according to the method described in the above light emitting characteristic measurement.

As the light emission characteristics, the voltage (V) and the current efficiency (cd / A) when a current density of 10 mA / cm ^{2 was passed were measured, and the element life during continuous lighting was measured.} The device lifetime was measured luminance decay time at the time of continuous lighting when driving the initial luminance 1000 cd / m ^2, to measure the time required until the luminance (cd / m ²⁾ is reduced 3%. The values of voltage (V), current efficiency (cd / A), and lifetime are expressed as relative values when the device reference example-1 is set to 100. The results are shown in Table 1.

From Table 1, it was found that the organic electroluminescent device using the triazine compound (1) can achieve a higher level of voltage and luminous efficiency than the reference example.

1 Substrate 2 Anode 3 Hole injection layer 41 First hole transport layer 42 Second hole transport layer 5 Light emitting layer 6 Hole blocking layer 7 Electron transport layer 8 Electron injection layer 9 Cathode 100 Organic electroluminescent element

Claims (21)

The triazine compound represented by the formula (1):

During the ceremony
Ar ¹ and Ar ² independently represent a phenyl group, a biphenylyl group or a naphthyl group;
Ar ³ is
Hydrogen atom;
Aromatic hydrocarbon groups of monocyclic, linked or fused rings with 6 to 20 carbon atoms, or
Represents a nitrogen-containing aromatic group consisting of only a 6-membered ring and having 4 to 14 carbon atoms;
Ar ¹ , Ar ² and Ar ³ may each be independently substituted with one or more groups selected from the group consisting of a fluorine atom, an alkyl group having 1 to 4 carbon atoms, and a phenyl group;
R is the same or different,
Alkyl groups with 1 to 6 carbon atoms,
An aromatic hydrocarbon group having 6 to 20 carbon atoms, a monocyclic ring, a linking ring, or a condensed ring, which may be substituted with an alkyl group having 1 to 4 carbon atoms.
A nitrogen-containing aromatic group having 4 to 14 carbon atoms consisting of only a 6-membered ring which may be substituted with an alkyl group having 1 to 4 carbon atoms or a phenyl group, or a nitrogen-containing aromatic group having 4 to 14 carbon atoms.
Heteroatoms that may be substituted with alkyl or phenyl groups of 1 to 4 carbons represent group 16 elements, heterocyclic groups of 4 to 14 carbons;
Two adjacent Rs may be integrated to form a 5- or 6-membered ring containing a Z to which the two Rs are bonded;
L represents a phenylene group;
Z represents a carbon atom, a silicon atom, a germanium atom, or a tin atom;
p represents 0, 1 or 2. The triazine compound according to claim 1, which is represented by the formula (1a), (1b), (1c), (1d), or (1e):

In the formula, Ar ¹ , Ar ² , Ar ³ , R, Z, L and p have the same definitions as the above formula (1). The triazine compound according to claim 1, which is represented by the formula (1a), the formula (1b), or (1c):

In the formula, Ar ¹ , Ar ² , Ar ³ , R, Z, L and p have the same definitions as the above formula (1). The triazine compound according to claim 1, which is represented by the formula (11a), the formula (11b), or (11c):

In the equation, Ar ¹ , Ar ² , Ar ³ , R, Z, and L have the same definition as the equation (1);
q represents 0 or 1. The triazine compound according to any one of claims 1 to 4, wherein Z is a carbon atom, a silicon atom, or a germanium atom. The triazine compound according to any one of claims 1 to 5, wherein Z is a silicon atom or a germanium atom. The triazine compound according to any one of claims 1 to 6, wherein Ar ¹ and Ar ^{2 are independently phenyl groups or biphenylyl groups.} The triazine compound according to any one of claims 1 to 7, wherein Ar ¹ and Ar ^{2 are the same group.} Ar ³
Hydrogen atom or
Unsubstituted or substituted with a methyl group,
Aromatic hydrocarbon groups of monocyclic, linked or fused rings with 6 to 20 carbon atoms, or
The triazine compound according to any one of claims 1 to 8, which is a nitrogen-containing aromatic group consisting of only a 6-membered ring and having 4 to 14 carbon atoms. The ^{invention according to any one of claims 1 to 9, wherein Ar 3} is a hydrogen atom, a phenyl group, a biphenyl group, a naphthyl group, a phenanthrenyl group, a dimethylfluorenyl group, a pyridyl group, a dimethylpyridyl group, or a phenylpyridyl group. Triazine compounds. R is the same or different,
Alkyl groups with 1 to 4 carbon atoms, or
Unsubstituted or substituted with a methyl group,
Aromatic hydrocarbon groups of monocyclic, linked or fused rings with 6 to 20 carbon atoms,
A nitrogen-containing aromatic group consisting of only a 6-membered ring and having 4 to 14 carbon atoms, or
The triazine compound according to any one of claims 1 to 10, wherein the heteroatom is a group 16 element and is a heterocyclic group having 4 to 14 carbon atoms. The invention according to any one of claims 1 to 11, wherein R is the same or differently a methyl group, a phenyl group, a biphenylyl group, a naphthyl group, a fluorenyl group, a pyridyl group, a dibenzofuranyl group or a dibenzothiophenyl group. Triazine compounds. The triazine compound according to any one of claims 1 to 12, wherein L is a metaphenylene group or a paraphenylene group. The triazine compound according to any one of claims 1 to 13, wherein L is a metaphenylene group. The triazine compound according to any one of claims 1 to 14, wherein p is 0 or 1. A method for producing a triazine compound represented by the formula (1a), which comprises a coupling reaction between a compound represented by the formula (2) and a compound represented by the formula (3).

During the ceremony
Ar ¹ and Ar ² independently represent a phenyl group, a biphenylyl group or a naphthyl group;
Ar ³ is
Hydrogen atom,
Aromatic hydrocarbon groups of monocyclic, linked or fused rings with 6 to 20 carbon atoms, or
Represents a nitrogen-containing aromatic group consisting of only a 6-membered ring and having 4 to 14 carbon atoms;
Ar ¹ , Ar ² and Ar ³ may each be independently substituted with one or more groups selected from the group consisting of a fluorine atom, an alkyl group having 1 to 4 carbon atoms, and a phenyl group;
R is the same or different,
Alkyl groups with 1 to 6 carbon atoms,
An aromatic hydrocarbon group having 6 to 20 carbon atoms, a monocyclic ring, a linking ring, or a condensed ring, which may be substituted with an alkyl group having 1 to 4 carbon atoms.
A nitrogen-containing aromatic group having 4 to 14 carbon atoms consisting of only a 6-membered ring which may be substituted with an alkyl group having 1 to 4 carbon atoms or a phenyl group, or a nitrogen-containing aromatic group having 4 to 14 carbon atoms.
Heteroatoms that may be substituted with alkyl or phenyl groups of 1 to 4 carbons represent group 16 elements, heterocyclic groups of 4 to 14 carbons;
Two adjacent Rs may be integrated to form a 5- or 6-membered ring containing a Z to which the two Rs are bonded;
L represents a phenylene group;
Z represents a carbon atom, a silicon atom, a germanium atom, or a tin atom;
p'represents 1 or 2;
M ¹ represents ZnY ¹ , MgY ² , Sn (Y ³ ) ₃ , or B (OY ⁴ ) ₂ ;
Y ¹ and Y ² independently represent a chlorine atom, a bromine atom or an iodine atom;
Y ³ are the same or different and each represents an alkyl group or a phenyl group having 1 to 4 carbon atoms;
Y ⁴ are the same or different and each represents a hydrogen atom, an alkyl group or a phenyl group having 1 to 4 carbon atoms;
The two (OY ⁴ ) groups may be united to form a ring with the boron atom to which the ^{two (OY 4) groups are attached;}
X ¹ represents a chlorine atom, a bromine atom, a trifluoromethanesulfonyloxy group or an iodine atom. A method for producing a triazine compound represented by the formula (1b), which comprises a coupling reaction between a compound represented by the formula (4) and a compound represented by the formula (5).

During the ceremony
Ar ¹ and Ar ² independently represent a phenyl group, a biphenylyl group or a naphthyl group;
Ar ³ is
Hydrogen atom,
Aromatic hydrocarbon groups of monocyclic, linked or fused rings with 6 to 20 carbon atoms, or
Represents a nitrogen-containing aromatic group consisting of only a 6-membered ring and having 4 to 14 carbon atoms;
Ar ¹ , Ar ² and Ar ³ may each be independently substituted with one or more groups selected from the group consisting of a fluorine atom, an alkyl group having 1 to 4 carbon atoms, and a phenyl group;
R is the same or different,
Alkyl groups with 1 to 6 carbon atoms,
An aromatic hydrocarbon group having 6 to 20 carbon atoms, a monocyclic ring, a linking ring, or a condensed ring, which may be substituted with an alkyl group having 1 to 4 carbon atoms.
A nitrogen-containing aromatic group having 4 to 14 carbon atoms consisting of only a 6-membered ring which may be substituted with an alkyl group having 1 to 4 carbon atoms or a phenyl group, or a nitrogen-containing aromatic group having 4 to 14 carbon atoms.
Heteroatoms that may be substituted with alkyl or phenyl groups of 1 to 4 carbons represent group 16 elements, heterocyclic groups of 4 to 14 carbons;
Two adjacent Rs may be integrated to form a 5- or 6-membered ring containing a Z to which the two Rs are bonded;
L represents a phenylene group;
Z represents a carbon atom, a silicon atom, a germanium atom, or a tin atom;
"p" represents 1 or 2;
X ² represents a chlorine atom, a bromine atom, a trifluoromethanesulfonyloxy group or an iodine atom;
M ² represents ZnY ¹ , MgY ² , Sn (Y ³ ) ₃ , or B (OY ⁴ ) ₂ ;
Y ¹ and Y ² independently represent a chlorine atom, a bromine atom or an iodine atom;
Y ³ are the same or different and each represents an alkyl group or a phenyl group having 1 to 4 carbon atoms;
Y ⁴ are the same or different and each represents a hydrogen atom, an alkyl group or a phenyl group having 1 to 4 carbon atoms;
The two (OY ⁴ ) groups may be integrated to form a ring together with the boron atom to which the ^{two (OY 4) groups are bonded.} The method for producing a triazine compound according to claim 16 or 17, wherein ^{M 1} or M ² is B (OY ⁴ ) _2. The production method according to any one of claims 16 to 18, wherein the coupling reaction is carried out in the presence of a palladium catalyst having a tertiary phosphine as a ligand. 16: The coupling reaction is carried out in the presence of a palladium catalyst having triphenylphosphine or 2--dicyclohexylphosphine-2-', 4', 6'-triisopropylbiphenyl as a ligand. The production method according to any one of 19. An organic electroluminescent device containing the triazine compound according to any one of claims 1 to 15.

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