WO2018155275A1

WO2018155275A1 - Oxygen-bridged triarylamine compound, precursor thereof and light-emitting material

Info

Publication number: WO2018155275A1
Application number: PCT/JP2018/005028
Authority: WO
Inventors: 小野洋平; 松本直樹
Original assignee: 東ソー株式会社
Priority date: 2017-02-21
Filing date: 2018-02-14
Publication date: 2018-08-30

Abstract

Provided is an oxygen-bridged triphenylamine compound that is suitable for a light-emitting material of an organic electroluminescent element. The compound is represented by formula (1) [wherein ring A, ring B and ring C independently represent each an aryl ring having 6-18 carbon atoms or a heteroaryl ring having 3-13 carbon atoms, each ring having a definite substitute].

Description

Oxygen-bridged triarylamine compound, precursor thereof, and luminescent material

The present invention relates to an oxygen-bridged triarylamine compound, a precursor thereof, and a light emitting material.

A material used for a light-emitting layer of an organic electroluminescence element (organic EL element, Organic Light-Emitting Diode) needs to have a bipolar property capable of receiving both electrons and holes.
Patent Documents 1 and 2 have both a skeleton excellent in hole transport ability such as carbazole, diarylamine, or a bridged triarylamine, and a skeleton excellent in electron transport ability such as triazine and pyrimidine. Compounds are disclosed.

International Publication No. 2008/123189 Pamphlet International Publication No. 2010/050778 Pamphlet

However, even with the compounds according to Patent Documents 1 and 2, an organic EL element that satisfies the excellent light emission efficiency and sufficient long life of the organic EL element cannot be obtained, and further improvements are required.
As a result of further studies on the bipolar property by the present inventors, the following findings were obtained.
In an organic EL device using a light emitting layer that cannot transport electrons and holes in a well-balanced manner, extra holes or electrons that do not contribute to light emission are generated, and the light emission efficiency is lowered.

One embodiment of the present invention provides an oxygen-bridged triarylamine compound that has favorable bipolar properties, contributes to the formation of an organic electroluminescent device with low voltage and high luminous efficiency, and a precursor and a light-emitting material thereof. For the purpose.

[1]: A first embodiment of the present invention is a compound represented by the formula (1):

In formula (1),
Ring A, Ring B and Ring C are each independently
An aryl ring having 6 to 18 carbon atoms, or
A heteroaryl ring having 3 to 13 carbon atoms;
The aryl ring or the heteroaryl ring includes a deuterium atom, a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, a phenyl group, a naphthyl group, a biphenylyl group, a 9-phenylcarbazolyl group, a dibenzofuranyl group. Optionally substituted with at least one selected from the group consisting of a group, a dibenzothionyl group, and a substituent Z represented by formula (2);
However, the compound represented by the formula (1) has at least one substituent Z;

In formula (2),
L is independently
A divalent group selected from the group consisting of a phenylene group, a biphenyldiyl group, a naphthalenediyl group, a fluorenediyl group, a spirobifluorenediyl group, a dibenzothiophenediyl group, a dibenzofurandiyl group, and a 9-phenylcarbazole diyl group. Group of
Represents a single bond;
The divalent group is composed of a deuterium atom, a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 25 carbon atoms, and a heteroaryl group having 3 to 20 carbon atoms. Optionally substituted with at least one selected from the group;
Hy is independently a carbon number composed of at least one atom selected from the group consisting of a carbon atom, a hydrogen atom, an oxygen atom, a sulfur atom, and a nitrogen atom, and a nitrogen atom that forms a multiple bond. Represents 3 to 12 nitrogen-containing heteroaromatic groups;
The nitrogen-containing heteroaromatic group includes a deuterium atom, a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 25 carbon atoms, and a heteroaryl group having 3 to 20 carbon atoms, It may be substituted with at least one selected from the group consisting of

[2]: The second aspect of the present invention is
A ring, B ring and C ring are each independently one ring selected from the group consisting of benzene ring, naphthalene ring, phenanthrene ring, triphenylene ring, anthracene ring and chrysene ring,
The ring includes a deuterium atom, a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, phenyl group, naphthyl group, biphenylyl group, 9-phenylcarbazolyl group, dibenzofuranyl group, dibenzothionyl group, And the compound according to the first aspect, which may be substituted with at least one selected from the group consisting of the substituent Z.

[3]: The third aspect of the present invention is
A ring, B ring and C ring are each independently one ring selected from a benzene ring and a naphthalene ring;
The ring includes a deuterium atom, a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, phenyl group, naphthyl group, biphenylyl group, 9-phenylcarbazolyl group, dibenzofuranyl group, dibenzothionyl group, And the compound according to the first or second aspect, which may be substituted with at least one selected from the group consisting of the substituent Z.

[4]: The fourth aspect of the present invention is
The compound according to the first aspect, which is a compound represented by any one of formulas (1-1) to (1-26):

In formulas (1-1) to (1-26),
R is each independently a hydrogen atom, a deuterium atom, a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, a phenyl group, a naphthyl group, a biphenylyl group, a 9-phenylcarbazolyl group, a dibenzofuran group. Represents a nyl group or a dibenzothionyl group;
Z is synonymous with the formula (2).

[5]: The fifth aspect of the present invention is
L is independently
Single bond or
The compound according to any one of the first to fourth aspects, which is a group represented by any one of formulas (L-1) to (L-11):

In formulas (L-1) to (L-11), each R ¹ independently represents a hydrogen atom, a deuterium atom, a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, or 6 to 6 carbon atoms. Represents a 25 aryl group or a heteroaryl group having 3 to 20 carbon atoms.

[6]: The sixth aspect of the present invention is
Hy is each independently a pyridyl group, pyrimidinyl group, pyrazinyl group, triazinyl group, carbolinyl group, quinolinyl group, isoquinolinyl group, naphthyridinyl group, quinoxalinyl group, quinazolinyl group, benzoquinoxalinyl group, benzoquinazolinyl group , A benzothienopyrimidinyl group, and a benzofuroprimidinyl group, one group selected from the group consisting of
The group is selected from the group consisting of a deuterium atom, a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 25 carbon atoms, and a heteroaryl group having 3 to 20 carbon atoms. The compound according to any one of the first to fifth aspects, which may be substituted with at least one selected from the above.

[7]: The seventh aspect of the present invention is
The compound according to any one of the first to sixth aspects, wherein Hy is each independently a group represented by any one of formulas (Hy-1) to (Hy-9) Is:

In formulas (Hy-1) to (Hy-9), each R ² independently represents a hydrogen atom, a deuterium atom, a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, or 6 to 6 carbon atoms. Represents a 25 aryl group or a heteroaryl group having 3 to 20 carbon atoms.

[8]: The eighth aspect of the present invention is
A luminescent material comprising the compound according to any one of the first to seventh aspects.

[9]: The ninth aspect of the present invention is
A chlorine compound represented by the formula (1-a):

In formula (1-a),
Ring A, Ring B and Ring C are each independently
An aryl ring having 6 to 18 carbon atoms, or
A heteroaryl ring having 3 to 13 carbon atoms;
The aryl ring or the heteroaryl ring includes a deuterium atom, a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, a phenyl group, a naphthyl group, a biphenylyl group, a 9-phenylcarbazolyl group, a dibenzofuranyl group. Optionally substituted with at least one selected from the group consisting of a group, a dibenzothionyl group, and a chlorine atom;
However, the compound represented by the formula (1-a) has at least one chlorine atom.

[10]: The tenth aspect of the present invention is
A ring, B ring and C ring are each independently one ring selected from the group consisting of benzene ring, naphthalene ring, phenanthrene ring, triphenylene ring, anthracene ring and chrysene ring,
The ring includes a deuterium atom, a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, phenyl group, naphthyl group, biphenylyl group, 9-phenylcarbazolyl group, dibenzofuranyl group, dibenzothionyl group, And the chlorine compound according to the ninth aspect, which may be substituted with at least one selected from the group consisting of chlorine atoms.

[11]: The eleventh aspect of the present invention is
A ring, B ring and C ring are each independently one ring selected from a benzene ring and a naphthalene ring;
The ring includes a deuterium atom, a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, phenyl group, naphthyl group, biphenylyl group, 9-phenylcarbazolyl group, dibenzofuranyl group, dibenzothionyl group, And the chlorine compound according to the ninth or tenth aspect, which may be substituted with at least one selected from the group consisting of chlorine atoms.

[12]: The twelfth aspect of the present invention is
The chlorine compound according to the ninth aspect, which is a chlorine compound represented by any one of formulas (1-a1) to (1-a23):

In formulas (1-a1) to (1-a23), each R independently represents a hydrogen atom, a deuterium atom, a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, a phenyl group, or a naphthyl group. Represents a biphenylyl group, a 9-phenylcarbazolyl group, a dibenzofuranyl group, or a dibenzothionyl group.

According to one embodiment of the present invention, an oxygen-bridged triarylamine compound that has favorable bipolar properties, contributes to the formation of an organic electroluminescence device having low voltage and high luminous efficiency, a precursor thereof, and a light emitting material are provided. can do.

Exemplary embodiments for carrying out the present invention will be described in detail.
Hereinafter, the oxygen-bridged triarylamine compound according to one embodiment of the present invention, a precursor thereof (hereinafter also referred to as a chlorine compound), and a light-emitting material will be described in detail.

[Oxygen-bridged triarylamine compound (compound)]
The oxygen-bridged triarylamine compound is a compound represented by the formula (1):

The A ring, the B ring and the C ring are each independently an aryl ring having 6 to 18 carbon atoms or a heteroaryl ring having 3 to 13 carbon atoms. These aryl rings or heteroaryl rings may be substituted with at least one substituent X1. Here, at least one substituent X1 is a deuterium atom, a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, phenyl group, naphthyl group, biphenylyl group, 9-phenylcarbazolyl group, dibenzo It is at least one selected from the group consisting of a furanyl group, a dibenzothionyl group, and a substituent Z represented by the formula (2).

The aryl ring having 6 to 18 carbon atoms can be expressed as a monocyclic or condensed aryl ring having 6 to 18 carbon atoms, or a monocyclic or condensed aromatic ring having 6 to 18 carbon atoms. The aryl ring having 6 to 18 carbon atoms is not particularly limited, and examples thereof include a benzene ring, naphthalene ring, phenanthrene ring, triphenylene ring, anthracene ring, and chrysene ring.

The heteroaryl ring having 3 to 13 carbon atoms can be written as a monocyclic or condensed heteroaryl ring having 3 to 13 carbon atoms, or a monocyclic or condensed heteroaromatic ring having 3 to 13 carbon atoms. . The heteroaryl ring having 3 to 13 carbon atoms is not particularly limited, and examples thereof include a pyrrole ring, an imidazole ring, a triazine ring, a pyrazine ring, a pyrimidine ring, a pyridine ring, a quinoline ring, an isoquinoline ring, a phenazine ring, Examples include an acridine ring, furan ring, thiophene ring, pyrrole ring, thiazole ring, benzofuran ring, benzothiophene ring, dibenzofuran ring, and dibenzothiophene ring.

The linear, branched or cyclic alkyl group having 1 to 18 carbon atoms in the substituent X1 is not particularly limited, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, and an n-butyl group. , Sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, stearyl group, cyclopropyl group, cyclohexyl group and the like.

The A ring, B ring and C ring are preferably independently an aryl ring having 6 to 10 carbon atoms or a heteroaryl ring having 3 to 10 carbon atoms from the viewpoint of excellent bipolar properties. Note that the aryl ring having 6 to 10 carbon atoms or the heteroaryl ring having 3 to 10 carbon atoms may be substituted with at least one substituent X1. Here, the aryl ring having 6 to 10 carbon atoms is also referred to as a monocyclic or condensed aryl ring having 6 to 10 carbon atoms or a monocyclic or condensed aromatic hydrocarbon ring having 6 to 10 carbon atoms. The heteroaryl ring having 3 to 10 carbon atoms is also referred to as a monocyclic or condensed heteroaryl ring having 3 to 10 carbon atoms, or a monocyclic or condensed heteroaromatic ring having 3 to 10 carbon atoms.

A ring, B ring and C ring are each independently a benzene ring, naphthalene ring, phenanthrene ring, triphenylene ring, anthracene ring, chrysene ring, pyridine ring, pyrrole ring, thiophene ring, quinoline ring, and isoquinoline ring. It is preferably one ring selected from the group consisting of The ring may be substituted with at least one substituent X1.

More preferably, the A ring, the B ring, and the C ring are each independently one ring selected from the group consisting of a benzene ring, a naphthalene ring, a phenanthrene ring, a triphenylene ring, an anthracene ring, and a chrysene ring. . The ring may be substituted with at least one substituent X1.

It is particularly preferable that the A ring, the B ring, and the C ring are each independently one ring selected from the group consisting of a benzene ring and a naphthalene ring. The ring may be substituted with at least one substituent X1.

In addition, the compound represented by the formula (1) has at least one substituent Z.

Here, the substituent Z is preferably substituted with one, two, or three hydrogen atoms in the formula (1), and more preferably substituted with one or two hydrogen atoms. Preferably, it is more preferably substituted with one hydrogen atom.

The oxygen-bridged triarylamine compound represented by the formula (1) is not particularly limited. For example, the compound represented by any one of the formulas (1-1) to (1-26) Can be mentioned.

In formulas (1-1) to (1-26), each R independently represents a hydrogen atom, a deuterium atom, a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, a phenyl group, or a naphthyl group. , Biphenylyl group, 9-phenylcarbazolyl group, dibenzofuranyl group, and dibenzothionyl group. Z is synonymous with the formula (2). In addition, the linear, branched or cyclic alkyl group having 1 to 18 carbon atoms in the formulas (1-1) to (1-26) is a linear, branched or cyclic group having 1 to 18 carbon atoms in the substituent X1. It is synonymous with a cyclic alkyl group.

R is preferably a hydrogen atom, a deuterium atom, a phenyl group, a biphenyl group, or a naphthyl group independently from the viewpoint of not impairing the bipolar property of the compound.

In the substituent Z represented by the formula (2), each L independently represents a phenylene group, a biphenyldiyl group, a naphthalenediyl group, a fluorenediyl group, a spirobifluorenediyl group, a dibenzothiophenediyl group, a dibenzofuran. A divalent group selected from the group consisting of a diyl group and a 9-phenylcarbazolediyl group; or a single bond.

The divalent group may be substituted with at least one substituent X2. Here, at least one substituent X2 is a deuterium atom, a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 25 carbon atoms, and a heterogeneous group having 3 to 20 carbon atoms. It is at least one selected from the group consisting of an aryl group.
The linear, branched or cyclic alkyl group having 1 to 18 carbon atoms in the substituent X2 has the same meaning as the linear, branched or cyclic alkyl group having 1 to 18 carbon atoms in the substituent X1.

The aryl group having 6 to 25 carbon atoms in the substituent X2 is not particularly limited, and examples thereof include a phenyl group, a 2-biphenyl group, a 3-biphenyl group, a 4-biphenyl group, and a 1-naphthyl group. 2-naphthyl group, m-terphenyl-5′-yl group, triphenylene-1-yl group, triphenylene-2-yl group, 9,9-dimethylfluoren-1-yl group, 9,9-dimethylfluorene- 2-yl group, 9,9-dimethylfluoren-3-yl group, 9,9-dimethylfluoren-4-yl group, 9,9-diphenylfluoren-1-yl group, 9,9-diphenylfluorene-2- Yl group, 9,9-diphenylfluoren-3-yl group, 9,9-diphenylfluoren-4-yl group, 9,9′-spirobifluoren-1-yl group, 9,9′-spiro Fluoren-2-yl group, 9,9′-spirobifluoren-3-yl group, 9,9′-spirobifluoren-4-yl group, 1-phenanthryl group, 2-phenanthryl group, 3-phenanthryl group, Examples thereof include a 4-phenanthryl group and a 9-phenanthryl group.

The heteroaryl group having 3 to 20 carbon atoms in the substituent X2 is not particularly limited, and examples thereof include a benzothienyl group, a benzofuranyl group, a benzimidazolyl group, an indazolyl group, a benzothiazolyl group, and a benzoisothiazolyl group. 2,1,3-benzothiadiazolyl group, benzoxazolyl group, benzisoxazolyl group, 2,1,3-benzooxadiazolyl group, carbazolyl group, dibenzothienyl group, and dibenzofuranyl group Etc.

L is a divalent group independently selected from the group consisting of a phenylene group, a biphenyldiyl group, a naphthalenediyl group, a dibenzothiophenediyl group, and a dibenzofurandiyl group, in that L is excellent in the bipolar property of the compound; Or it is preferable that they are a single bond; The divalent group may be substituted with at least one substituent X2.

More preferably, each L is independently a single bond or a group represented by any one of formulas (L-1) to (L-11).

In formulas (L-1) to (L-11), each R ¹ independently represents a hydrogen atom, a deuterium atom, a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, or 6 to 6 carbon atoms. Represents a 25 aryl group or a C 3-20 heteroaryl group. In the formulas (L-1) to (L-11), a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 25 carbon atoms, and a heteroaryl group having 3 to 20 carbon atoms are These are synonymous with the linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, the aryl group having 6 to 25 carbon atoms, and the heteroaryl group having 3 to 20 carbon atoms, respectively, in the substituent X2.

L is a divalent group selected from the group consisting of a phenylene group, a biphenyldiyl group, a naphthalenediyl group, a dibenzothiophenediyl group, and a dibenzofurandiyl group, each of which is excellent in the bipolar property of the compound. Group; or preferably a single bond. The divalent group is a deuterium atom, methyl group, ethyl group, phenyl group, 2-biphenyl group, 3-biphenyl group, 4-biphenyl group, 1-naphthyl group, 2-naphthyl group, carbazolyl group, dibenzothienyl. It may be substituted with at least one selected from the group consisting of a group and a dibenzofuranyl group.

L is more preferably a single bond; or a group represented by any one of formulas (L-1) to (L-11), each having an excellent bipolar property. preferable.

In formulas (L-1) to (L-11), each R ¹ independently represents a hydrogen atom, a deuterium atom, a methyl group, an ethyl group, a phenyl group, a 2-biphenyl group, a 3-biphenyl group, 4 -Represents a biphenyl group, a 1-naphthyl group, a 2-naphthyl group, a carbazolyl group, a dibenzothienyl group, or a dibenzofuranyl group.

In the substituent Z represented by the formula (2), Hy each independently represents at least one atom selected from the group consisting of a carbon atom, a hydrogen atom, an oxygen atom, a sulfur atom, and a nitrogen atom, and It represents a nitrogen-containing heteroaromatic group having 3 to 12 carbon atoms, which is composed of nitrogen atoms forming multiple bonds. The nitrogen-containing heteroaromatic group may be substituted with at least one substituent X2.

The nitrogen-containing heteroaromatic group having 3 to 12 carbon atoms is not particularly limited, and examples thereof include pyridyl group, pyrimidinyl group, pyrazinyl group, triazinyl group, carbolinyl group, quinolinyl group, isoquinolinyl group, naphthyridinyl group. Group, quinoxalinyl group, quinazolinyl group, benzoquinoxalinyl group, benzoquinazolinyl group, benzothienopyrimidinyl group, benzofuropyrimidinyl group, phenazinyl group, benzothiazolyl group, and benzoimidazolyl group.

Hy is independently a pyridyl group, pyrimidinyl group, pyrazinyl group, triazinyl group, carbolinyl group, quinolinyl group, isoquinolinyl group, naphthyridinyl group, quinoxalinyl group, quinazolinyl group, benzoquinoxalinyl group, benzoquinazolinyl group It is preferably one group selected from the group consisting of benzothienopyrimidinyl group and benzofuroprimidinyl group. The group may be substituted with the substituent X2.

More preferably, each Hy is independently a group represented by any one of formulas (Hy-1) to (Hy-9).

In formulas (Hy-1) to (Hy-9), each R ² independently represents a hydrogen atom, a deuterium atom, a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, or 6 to 25 carbon atoms. And any one selected from a heteroaryl group having 3 to 20 carbon atoms. In formulas (Hy-1) to (Hy-9), a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 25 carbon atoms, and a heteroaryl group having 3 to 20 carbon atoms are These are synonymous with the linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, the aryl group having 6 to 25 carbon atoms, and the heteroaryl group having 3 to 20 carbon atoms, respectively, in the substituent X2. R ² is preferably any one selected from the group consisting of a hydrogen atom, a deuterium atom, a phenyl group, a biphenyl group, and a naphthyl group.

In addition, Hy is each independently a pyridyl group, pyrimidinyl group, pyrazinyl group, triazinyl group, carbolinyl group, quinolinyl group, isoquinolinyl group, naphthyridinyl group, quinoxalinyl group, quinazolinyl group, benzoquinoxalinyl group, benzoquinazolinyl group. A group selected from a nyl group, a benzothienopyrimidinyl group, and a benzofuroprimidinyl group is preferable. The group is a deuterium atom, methyl group, ethyl group, phenyl group, biphenyl group, naphthyl group, terphenyl group, triphenylenyl group, 9,9-dimethylfluorenyl group, 9,9-diphenylfluorenyl group, It may be substituted with at least one selected from the group consisting of 9,9′-spirobifluorenyl group, phenanthryl group, carbazolyl group, dibenzothienyl group, and dibenzofuranyl group.

Specific examples of these include groups represented by any one of formulas (Hy-1) to (Hy-9).

R ² in the formulas (Hy-1) to (Hy-9) each independently represents a hydrogen atom, a deuterium atom, a methyl group, an ethyl group, a phenyl group, a biphenyl group, a naphthyl group, a terphenyl group, or a triphenylenyl group. , 9,9-dimethylfluorenyl group, 9,9-diphenylfluorenyl group, 9,9'-spirobifluorenyl group, phenanthryl group, carbazolyl group, dibenzothienyl group, and dibenzofuranyl group Any one selected from the group is preferable, and any one selected from the group consisting of a hydrogen atom, a deuterium atom, a phenyl group, a biphenyl group, and a naphthyl group is more preferable.

In addition, Hy is each independently a pyridyl group, pyrimidinyl group, pyrazinyl group, triazinyl group, carbolinyl group, quinolinyl group, isoquinolinyl group, naphthyridinyl group, quinoxalinyl group, quinazolinyl group, benzoquinoxalinyl group, benzoquinazolinyl group. It is preferably one group selected from the group consisting of a nyl group, a benzothienopyrimidinyl group, and a benzofuroprimidinyl group. The group includes deuterium atom, methyl group, ethyl group, phenyl group, 2-biphenyl group, 3-biphenyl group, 4-biphenyl group, 1-naphthyl group, 2-naphthyl group, m-terphenyl-5′-. Yl group, triphenylene-1-yl group, triphenylene-2-yl group, 9,9-dimethylfluoren-1-yl group, 9,9-dimethylfluoren-2-yl group, 9,9-dimethylfluorene-3- Yl group, 9,9-dimethylfluoren-4-yl group, 9,9-diphenylfluoren-1-yl group, 9,9-diphenylfluoren-2-yl group, 9,9-diphenylfluoren-3-yl group 9,9-diphenylfluoren-4-yl group, 9,9′-spirobifluoren-1-yl group, 9,9′-spirobifluoren-2-yl group, 9,9′-spirobifluorene 3-yl group, 9,9′-spirobifluoren-4-yl group, 1-phenanthryl group, 2-phenanthryl group, 3-phenanthryl group, 4-phenanthryl group, 9-phenanthryl group, carbazolyl group, dibenzothienyl group Or may be substituted with a dibenzofuranyl group.

In the formulas (Hy-1) to (Hy-9), each R ² is independently a hydrogen atom, deuterium atom, methyl group, ethyl group, phenyl group, 2-biphenyl group, 3-biphenyl group, 4 -Biphenyl group, 1-naphthyl group, 2-naphthyl group, m-terphenyl-5'-yl group, triphenylene-1-yl group, triphenylene-2-yl group, 9,9-dimethylfluoren-1-yl group 9,9-dimethylfluoren-2-yl group, 9,9-dimethylfluoren-3-yl group, 9,9-dimethylfluoren-4-yl group, 9,9-diphenylfluoren-1-yl group, 9 , 9-diphenylfluoren-2-yl group, 9,9-diphenylfluoren-3-yl group, 9,9-diphenylfluoren-4-yl group, 9,9′-spirobifluoren-1-yl group, 9 , 9'-Spi Robifluoren-2-yl group, 9,9′-spirobifluoren-3-yl group, 9,9′-spirobifluoren-4-yl group, 1-phenanthryl group, 2-phenanthryl group, 3-phenanthryl group , 4-phenanthryl group, 9-phenanthryl group, carbazolyl group, dibenzothienyl group, and dibenzofuranyl group, and are preferably any one selected from the group consisting of a hydrogen atom, a deuterium atom, a phenyl group, More preferably, it is any one selected from the group consisting of a biphenyl group and a naphthyl group.

Preferred compounds are exemplified below, but the oxygen-bridged triarylamine compound is not limited to these compounds.

The oxygen-bridged triarylamine compound represented by the formula (1) can be synthesized, for example, by the following route.

In the formula, Ak each independently represents a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms. Ak is preferably a methyl group or an ethyl group in terms of easy availability of raw materials.

Here, an example in which the hydrogen atom of the ring C is substituted with the substituent Z is shown. However, based on the common knowledge of those skilled in the art, it is possible to introduce Z into a desired ring and substitution position by appropriately changing the raw material. Is possible.

Step (1) Aryl halide having ortho groups on both sides substituted with fluorine is subjected to a coupling reaction of an aryl halide having an alkoxy group at the ortho position such as 2-iodoanisole using a palladium catalyst or a copper catalyst, A secondary amine is obtained.
Step (2) The secondary amine obtained in step (1) is further reacted with an aryl halide having an alkoxy group at the ortho position to obtain a tertiary amine.
Step (3) After cleaving the alkyl of the alkoxy group by a conventional method, an oxygen-bridged triarylamine compound having a coupling reactive group such as a chloro group is obtained by a nucleophilic substitution reaction.
Step (4) From the Suzuki coupling reaction of the oxygen-bridged triarylamine compound having a coupling reactive group and the boronic acid compound or boronic ester compound of the substituent Z, the oxygen represented by the formula (1) A crosslinked triarylamine compound can be obtained.

Here, an example using the boronic acid compound or boronic acid ester compound of the substituent Z is shown. However, the oxygen-bridged triarylamine compound is used as a boronic acid compound or a boronic acid ester compound, , And may be reacted with a halide of substituent Z.

Also, Negishi coupling reaction or Kumada / Tamao coupling reaction can be used instead of Suzuki coupling reaction.

Even when the raw material primary amine is changed to a B ring or C ring instead of the A ring, an oxygen-bridged triarylamine compound can be synthesized by appropriately changing the substituent of each ring. Similarly, an oxygen-bridged triarylamine compound can be synthesized using the B ring and C ring alkoxy groups as the A ring and the fluorinated aryl as the B ring and C ring.

The substituent Z is defined by the formula (2), but the boronic acid compound or boronic ester compound of the substituent Z can be synthesized based on a known method.

[Chlorine compound (precursor)]
The chlorine compound obtained from the above step (3) is represented by the formula (1-a):

In the A ring, B ring and C ring in the formula (1-a), an aryl ring having 6 to 18 carbon atoms, a heteroaryl ring having 3 to 13 carbon atoms, and a linear, branched or cyclic group having 1 to 18 carbon atoms The definition of the alkyl group is as follows. The aryl ring having 6 to 18 carbon atoms, the heteroaryl ring having 3 to 13 carbon atoms, and the 1 to 18 carbon atoms in the A ring, the B ring, and the C ring in the formula (1) These are the same as the definition of the linear, branched or cyclic alkyl group, and the preferred range is also the same.

In the formula (1-a), A ring, B ring and C ring are each independently selected from the group consisting of benzene ring, naphthalene ring, phenanthrene ring, triphenylene ring, anthracene ring and chrysene ring. One ring is preferred. The ring includes a deuterium atom, a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, phenyl group, naphthyl group, biphenylyl group, 9-phenylcarbazolyl group, dibenzofuranyl group, dibenzothionyl group, And may be substituted with at least one selected from the group consisting of chlorine atoms.

More preferably, the A ring, B ring and C ring in the general formula (1-a) are each independently one ring selected from a benzene ring and a naphthalene ring. The ring includes a deuterium atom, a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, phenyl group, naphthyl group, biphenylyl group, 9-phenylcarbazolyl group, dibenzofuranyl group, dibenzothionyl group, And may be substituted with at least one selected from the group consisting of chlorine atoms.

However, the chlorine compound represented by the formula (1-a) has at least one chlorine atom.

Thus, the chlorine compound represented by the formula (1-a) is preferably a chlorine compound represented by any one of the formulas (1-a1) to (1-a23).

The linear, branched or cyclic alkyl group having 1 to 18 carbon atoms in R in the formulas (1-a1) to (1-a23) is a linear, branched or cyclic group having 1 to 18 carbon atoms in the formula (1). The same applies to the preferred range.

In the general formulas (1-a1) to (1-a23), each R is independently a hydrogen atom, a deuterium atom, a phenyl group, or biphenyl from the viewpoint that the bipolar property of the compound is not impaired. Or a naphthyl group.

[Luminescent material]
A light-emitting material according to one embodiment of the present invention includes the above-described compound (oxygen-bridged triarylamine compound).

[Organic electroluminescence device]
The oxygen-bridged triarylamine compound represented by the formula (1) can be used in each layer of an organic electroluminescence element (organic EL element), but can be preferably used as a light-emitting host material or a light-emitting dopant material. . The oxygen-bridged triarylamine compound represented by the formula (1) has bipolar properties, can transport holes and electrons stably, and has excellent light emission characteristics. When used as a material for the light emitting layer, it is possible to achieve high efficiency and long life of the organic EL element.

When the oxygen-bridged triarylamine compound represented by the formula (1) is used as a material for the light emitting layer of the organic EL device, the oxygen-bridged triarylamine compound may be used alone, The light emitting host material may be doped and used, or a known light emitting dopant may be doped.

As a method for forming the light emitting layer containing the oxygen-bridged triarylamine compound represented by the formula (1), for example, a known method such as a vacuum deposition method, a spin coating method, or a casting method can be applied. .

As a basic structure of an organic EL device that can achieve a desired effect, a substrate, an anode, a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, and a cathode are preferable. May be omitted or may be added conversely.

The anode and cathode of the organic EL element are connected to a power source through an electrical conductor. The organic EL element operates by applying a potential between the anode and the cathode.

Holes are injected into the organic EL element from the anode, and electrons are injected into the organic EL element at the cathode.
The organic EL element is typically placed on a substrate, and the anode or cathode can be in contact with the substrate. The electrode in contact with the substrate is called the lower electrode for convenience. Generally, the lower electrode is an anode, but the organic EL element according to one embodiment of the present disclosure is not limited to such a form.

The substrate may be light transmissive or opaque depending on the intended emission direction. The light transmission characteristics can be confirmed by electroluminescence emission through the substrate. Generally, transparent glass or plastic is used as the substrate in such a case. The substrate may be a composite structure including multiple material layers.
When the electroluminescent emission is confirmed through the anode, the anode is formed by passing or substantially passing through the emission.

The transparent material used for the anode is not particularly limited. For example, indium-tin oxide (ITO), indium-zinc oxide (IZO), tin oxide, aluminum -Metal oxides such as doped tin oxide, magnesium-indium oxide, nickel-tungsten oxide; metal nitrides such as gallium nitride; metal selenides such as zinc selenide; metal sulfides such as zinc sulfide; Can be mentioned. The anode can be modified with plasma deposited fluorocarbon.

When electroluminescence emission is confirmed only through the cathode, the transmission characteristic of the anode is not important, and any transparent, opaque or reflective conductive material can be used as the anode material. Examples of materials used for the anode in this case include gold, iridium, molybdenum, palladium, platinum, and the like.

A plurality of hole transporting layers such as a hole injection layer and a hole transport layer can be provided between the anode and the light emitting layer. The hole injection layer and the hole transport layer have a function of transmitting holes injected from the anode to the light emitting layer. By interposing these layers between the anode and the light emitting layer, the hole injection layer and the hole transport layer are often used in a lower electric field. Holes can be injected into the light emitting layer.

As the hole transport layer and / or hole injection layer, known hole injection materials and hole transport materials can be used. Examples of hole injection materials and hole transport materials include triazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives and pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, oxazole derivatives. , A styryl anthracene derivative, a fluorenone derivative, a hydrazone derivative, a stilbene derivative, a silazane derivative, an aniline copolymer, and a conductive polymer oligomer, particularly a thiophene oligomer. As the hole injecting material and the hole transporting material, those described above can be used, but it is preferable to use a porphyrin compound, an aromatic tertiary amine compound, or a styrylamine compound, and an aromatic tertiary amine compound. It is particularly preferable to use

Representative examples of the aromatic tertiary amine compounds and styrylamine compounds include N, N, N ′, N′-tetraphenyl-4,4′-diaminophenyl, N, N′-diphenyl-N, N ′. -Bis (3-methylphenyl)-[1,1'-biphenyl] -4,4'-diamine (TPD), 2,2-bis (4-di-p-tolylaminophenyl) propane, 1,1- Bis (4-di-p-tolylaminophenyl) cyclohexane, N, N, N ′, N′-tetra-p-tolyl-4,4′-diaminobiphenyl, 1,1-bis (4-di-p- Tolylaminophenyl) -4-phenylcyclohexane, bis (4-dimethylamino-2-methylphenyl) phenylmethane, bis (4-di-p-tolylaminophenyl) phenylmethane, N, N′-diphenyl-N, '-Di (4-methoxyphenyl) -4,4'-diaminobiphenyl, N, N, N', N'-tetraphenyl-4,4'-diaminodiphenyl ether, 4,4'-bis (diphenylamino) c Audriphenyl, N, N, N-tri (p-tolyl) amine, 4- (di-p-tolylamino) -4 ′-[4- (di-p-tolylamino) styryl] stilbene, 4-N, N— Diphenylamino- (2-diphenylvinyl) benzene, 3-methoxy-4'-N, N-diphenylaminostilbenzene, N-phenylcarbazole, 4,4'-bis [N- (1-naphthyl) -N-phenyl Amino] biphenyl (NPD), 4,4 ′, 4 ″ -tris [N- (3-methylphenyl) -N-phenylamino] triphenylamine (MTDATA) It is.

Inorganic compounds such as p-type-Si and p-type-SiC can also be used as a hole injection material and a hole transport material.

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

The light emitting layer contains the above-described oxygen-bridged triarylamine compound. For the light-emitting layer, a known light-emitting material (light-emitting host material, fluorescent dopant, phosphorescent dopant) can be selected and combined with the oxygen-bridged triarylamine compound.

Examples of the luminescent host material include compounds having a biphenyl group, a fluorenyl group, a triphenylsilyl group, a carbazole group, a pyrenyl group, and an anthranyl group. For example, DPVBi (4,4′-bis (2,2-diphenylvinyl) -1,1′-biphenyl), BCzVBi (4,4′-bis (9-ethyl-3-carbazovinylene) 1,1′-biphenyl ), TBADN (2-tert-butyl-9,10-di (2-naphthyl) anthracene), ADN (9,10-di (2-naphthyl) anthracene), CBP (4,4′-bis (carbazole-9) -Yl) biphenyl), CDBP (4,4′-bis (carbazol-9-yl) -2,2′-dimethylbiphenyl), 9,10-bis (biphenyl) anthracene and the like.

Examples of fluorescent dopants include anthracene, tetracene, xanthene, perylene, rubrene, coumarin, rhodamine, quinacridone, dicyanomethylenepyran compound, thiopyran compound, polymethine compound, pyrylium or thiapyrylium compound, fluorene derivative, perifuranthene derivative, indenoperylene derivative, Examples thereof include bis (azinyl) amine boron compounds, bis (azinyl) methane compounds, and carbostyryl compounds.

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

Examples of dopants include Ir (PPy) 3 (tris (2-phenylpyridine) iridium (III), FirPic (bis (3,5-difluoro-2- (2-pyridyl) phenyl- (2-carboxypyridyl) iridium ( III), Ir (piq) 2 (acac) bis (1-phenylisoquinoline) (acetylacetonato) iridium (III), Ir (piq) 3tris (1-phenylisoquinoline) iridium (III) and the like.

Between the cathode and the light emitting layer, a single layer or a plurality of electron transport layers are provided.
Examples of the electron transporting material contained in the electron transporting layer 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-hydroxyquinolinato) zinc, and bis (8-hydroxyquinolinato) copper. Bis (8-hydroxyquinolinato) manganese, tris (8-hydroxyquinolinato) aluminum, tris (2-methyl-8-hydroxyquinolinato) aluminum, tris (8-hydroxyquinolinato) gallium, bis (10-hydroxybenzo [h] quinolinato) beryllium, bis (10-hydroxybenzo [h] quinolinato) zinc, bis (2-methyl-8-quinolinato) chlorogallium, bis (2-methyl-8-quinolinato) (o -Crezolate) gallium, bis (2-methyl-8-quinolinato)- - naphthoquinone Trat aluminum, bis (2-methyl-8-quinolinato) -2-naphthoquinone Trad gallium, and the like.

A hole blocking layer may be provided between the light emitting layer and the electron transport layer for the purpose of improving carrier balance. Desirable compounds as a material for the hole blocking layer include BCP (2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline), Bphen (4,7-diphenyl-1,10-phenanthroline), BAlq (bis (2-methyl-8-quinolinolato) -4- (phenylphenolato) aluminum), bis (10-hydroxybenzo [h] quinolinato) beryllium) and the like.

In the organic EL device, an electron injection layer may be provided for the purpose of improving electron injection properties and improving device characteristics (for example, light emission efficiency, constant voltage driving, high durability).
Preferred compounds for the electron injection layer include fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, fluorenylidenemethane, anthraquinodimethane, anthrone, etc. Is mentioned. In addition, the above metal complexes, alkali metal oxides, alkaline earth oxides, rare earth oxides, alkali metal halides, alkaline earth halides, rare earth halides, SiO ₂ , AlO, SiN, SiON, AlON, GeO, Various oxides such as LiO, LiON, TiO, TiON, TaO, TaON, TaN, and C, and inorganic compounds such as nitrides and oxynitrides can also be used.

The cathode can be formed from any conductive material if light emission is only confirmed through the anode. Desirable 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 ) mixture, indium , Lithium / aluminum mixtures, rare earth metals and the like.

Another object of one embodiment of the present disclosure is to provide an organic electroluminescence device having a low voltage, high luminous efficiency, and long life using the above-described specific oxygen-bridged triarylamine compound.
An organic EL device having at least one light emitting layer containing an oxygen-bridged triarylamine compound facilitates both electron injection and hole injection into the light emitting layer, and recombines electrons and holes in the light emitting layer. Efficiency is improved. Therefore, according to one embodiment of the present disclosure, it is possible to provide an organic EL element that has high luminance and high efficiency and excellent lifetime.
In addition, the chlorine compound has an effect that the reaction selectivity is high and the generation of impurities is less than that of a conventionally known oxygen-bridged triarylamine halogen compound, and for organic EL devices that require extremely high purity. Industrially important as a material production intermediate.

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

¹ H-NMR was performed using Gemini 200 manufactured by Varian.
The FDMS measurement was performed using Hitachi M-80B.

Synthesis Example 1 (Synthesis of 5-chloro-N- (2,6-difluorophenyl) -2-methoxy-N- (2-methoxyphenyl) aniline)

Under a nitrogen stream, 5.0 g (21.3 mmol) of 2,6-difluoro-N- (2-methoxyphenyl) aniline synthesized by the method disclosed in International Publication No. 2012/118164 in a 200 mL three-necked flask, 4-Chloro-2-iodoanisole 8.6 g (31.9 mmol), copper powder 7.2 g (31.9 mmol), potassium carbonate 6.1 g (63.8 mmol), 18-crown-6 1.1 g (4. 3 mmol) and 30 mL of o-dichlorobenzene were added and stirred at 180 ° C. for 9 hours. After cooling to room temperature and removing inorganic salts by suction filtration, the solvent was distilled off under reduced pressure using a rotary pump. The precipitated solid was washed with hexane, and 7.1 g (18.9 mmol) of a white solid of 5-chloro-N- (2,6-difluorophenyl) -2-methoxy-N- (2-methoxyphenyl) aniline was obtained. Released. (Yield 89%).

Synthesis Example 2 (Synthesis of 5-chloro-N- (2,6-difluorophenyl) -2-hydroxy-N- (2-hydroxyphenyl) aniline)

In a 500 mL three-necked flask under a nitrogen stream, 9.0 g (23. 5) of 5-chloro-N- (2,6-difluorophenyl) -2-methoxy-N- (2-methoxyphenyl) aniline obtained in Synthesis Example 1 was obtained. 9 mmol), 99.6 g (862.1 mmol) of pyridine hydrochloride, and 10 mL of N-methylpyrrolidone were added and stirred at 190 ° C. for 12 hours. After cooling to 100 ° C. or lower, 30 mL of pure water was added and stirred overnight at room temperature. After extracting the organic layer with toluene, the solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography (mixed solvent of toluene and ethyl acetate), and white powder of 5-chloro-N- (2,6-difluorophenyl) -2-hydroxy-N- (2-hydroxyphenyl) aniline 4.1 g (11.8 mmol) was isolated (49% yield).

Example 1 (Synthesis of 2-chloro- [1,4] benzoxazino [2,3,4-kl] phenoxazine)

In a 500 mL three-necked flask under a nitrogen stream, 4.0 g (11. 5) of 5-chloro-N- (2,6-difluorophenyl) -2-hydroxy-N- (2-hydroxyphenyl) aniline obtained in Synthesis Example 2 was obtained. 5 mmol), 4.8 g (34.5 mmol) of potassium carbonate, and 160 mL of N, N-dimethylformamide were added and stirred at 100 ° C. for 6 hours. After cooling to room temperature, the solvent was distilled off under reduced pressure, 300 mL of pure water was added and stirred, and the precipitated solid was collected by suction filtration. The obtained solid was dissolved in toluene, passed through a silica gel pass column, and then toluene was distilled off under reduced pressure. The residue was reprecipitated by adding hexane, and 3.1 g (10.1 mmol) of 2-chloro- [1,4] benzoxazino [2,3,4-kl] phenoxazine white solid was isolated by suction filtration. (Yield 78%).

The compound was identified by FDMS and ¹ H-NMR measurement.
FDMS (m / z); 307 (M +)
¹ H-NMR (CDCl 3) δ (ppm); 7.29-7.34 (m, 2H), 6.88-7.01 (m, 3H), 6.75-6.88 (m, 3H) 6.50 (m, 2H)

Example 2 (Synthesis of Compound (1-3-1))

In a 200 mL three-necked flask under a nitrogen stream, 2.5 g (8.1 mmol) of 2-chloro- [1,4] benzoxazino [2,3,4-kl] phenoxazine obtained in Example 1 and 2,3- Diphenyl-6- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) quinoxaline 4.3 g (10.6 mmol), palladium acetate 55 mg (0.25 mmol), X-phos 230 mg (0.49 mmol), 85 mL of tetrahydrofuran, and 12.2 mL of 2M tripotassium phosphate aqueous solution were added and stirred at reflux temperature for 2.5 hours. After cooling to room temperature, 50 mL of pure water and 100 mL of toluene were added to separate the organic layer. The organic layer was washed with water and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (toluene), the solvent was distilled off under reduced pressure, 20 mL of ethyl acetate was added to the resulting oily component for reprecipitation, and the compound (1-3-1) orange powder was filtered by suction filtration 3.8 g (6.9 mmol) was isolated (84% yield).

The compound was identified by FDMS and ¹ H-NMR measurement.
FDMS (m / z); 554 (M +)
¹ H-NMR (CDCl 3) δ (ppm); 8.29 (s, 1 H), 8.21 (d, 1 H), 7.96 (d, 1 H), 7.76 (s, 1 H), 7. 20-7.58 (m, 12H), 6.68-7.08 (m, 4H), 6.80 (t, 1H), 6.55 (d, 2H)

Synthesis Example 3 (Synthesis of 2,6-difluoro-N- (2-methoxynaphthalen-3-yl) aniline)

In a 500 mL three-necked flask under a nitrogen stream, 1-5.0 g (63.3 mmol) of 2-bromo-3-methoxynaphthalene, 9.8 g (75.9 mmol) of 2,6-difluoroaniline, 7.3 g of sodium-tert-butoxide (75.9 mmol), 170 mL of o-xylene, 142 mg (0.6 mmol) of palladium acetate, and 384 mg (1.9 mmol) of tri (tert-butyl) phosphine were added and stirred at 140 ° C. for 2 hours. After cooling to room temperature, 100 mL of pure water was added to separate the organic layer. The organic layer was washed with water and saturated brine, dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure. The residue was purified by silica gel column chromatography (mixed solvent of toluene and hexane), the solvent was distilled off under reduced pressure, and the resulting solid was washed with hexane to give 2,6-difluoro-N- (2-methoxynaphthalene- 15.4 g (54.0 mmol) of a light purple powder of 3-yl) aniline was isolated (yield 87%).

Synthesis Example 4 (Synthesis of 5-chloro-N- (2,6-difluorophenyl) -2-methoxy-N- (2-methoxynaphthalen-3-yl) aniline)

In a 200 mL three-necked flask under a nitrogen stream, 15.0 g (52.6 mmol) of 2,6-difluoro-N- (2-methoxynaphthalen-3-yl) aniline obtained in Synthesis Example 3 and 4-chloro-2- Iodoanisole 25.0 g (93.1 mmol), copper powder 17.7 g (78.9 mmol), potassium carbonate 15.2 g (157.7 mmol), 18-crown-6 2.8 g (10.5 mmol), and o- 90 mL of dichlorobenzene was added and stirred at 180 ° C. for 25 hours. After cooling to room temperature and removing inorganic salts by suction filtration, the solvent was distilled off under reduced pressure using a rotary pump. The residue was purified by silica gel column chromatography (mixed solvent of toluene and hexane), the solvent was distilled off under reduced pressure, and the resulting solid was washed with hexane to give 5-chloro-N- (2,6-difluorophenyl)- 19.4 g (45.6 mmol) of a light purple solid of 2-methoxy-N- (2-methoxynaphthalen-3-yl) aniline was isolated. (Yield 87%).

Synthesis Example 5 (Synthesis of 5-chloro-N- (2,6-difluorophenyl) -2-hydroxy-N- (2-hydroxynaphthalen-3-yl) aniline)

In a 500 mL three-necked flask under a nitrogen stream, 5-chloro-N- (2,6-difluorophenyl) -2-methoxy-N- (2-methoxynaphthalen-3-yl) aniline obtained in Synthesis Example 4 19. 0 g (44.6 mmol), 154.7 g (1338.5 mmol) of pyridine hydrochloride, and 100 mL of N-methylpyrrolidone were added and stirred at 190 ° C. for 4 hours and a half. After cooling to 100 ° C. or lower, 300 mL of pure water was added to stop the reaction. Sufficient toluene was added to dissolve the precipitated solid, followed by liquid separation, and the solvent of the organic layer was distilled off under reduced pressure. The residue was purified by silica gel column chromatography (a mixed solvent of toluene and ethyl acetate), and (5-chloro-N- (2,6-difluorophenyl) -2-hydroxy-N- (2-hydroxynaphthalen-3-yl) was obtained. ) 7.8 g (19.6 mmol) of aniline pale yellow powder was isolated (44% yield).

Example 3 (Synthesis of 2-chloro-benzo [b] [1,4] benzoxazino [2,3,4-kl] phenoxazine)

(5-Chloro-N- (2,6-difluorophenyl) -2-hydroxy-N- (2-hydroxynaphthalen-3-yl) aniline obtained in Synthesis Example 5 was placed in a 500 mL three-necked flask under a nitrogen stream. 0.8 g (19.6 mmol), potassium carbonate 8.1 g (58.8 mmol), and N, N-dimethylformamide 120 mL were added and stirred for 15 hours at 100 ° C. The reaction solution was cooled to 70 ° C. and then purified water. After adding 100 mL and stirring, the precipitated solid was collected by suction filtration, and the resulting solid was washed with hexane, and 2-chloro-benzo [b] [1,4] benzoxazino [2,3,4- The white solid of kl] phenoxazine was isolated (6.7 g, 18.7 mmol) (yield 96%).

The compound was identified by FDMS and ¹ H-NMR measurement.
FDMS (m / z); 357 (M +)
¹ H-NMR (CDCl 3) δ (ppm); 7.60-7.68 (m, 3H), 7.53 (m, 1H), 7.28-7.40 (m, 3H), 6.77 -6.95 (m, 3H), 6.03 (d, 1H), 6.52 (d, 1H)

Example 4 (Synthesis of Compound (1-9-1))

In a 200 mL three-necked flask under a nitrogen stream, 2.5 g (7.0 mmol) of 2-chloro-benzo [b] [1,4] benzoxazino [2,3,4-kl] phenoxazine obtained in Example 3; 2,3-diphenyl-6- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) quinoxaline 3.7 g (9.1 mmol), palladium acetate 47 mg (0.2 mmol) X-phos (200 mg, 0.4 mmol), tetrahydrofuran (85 mL), and 2M tripotassium phosphate aqueous solution (10.5 mL) were added, and the mixture was stirred at reflux temperature for 1.5 hours. After cooling to room temperature, 100 mL of pure water and 100 mL of toluene were added to separate the organic layer. The organic layer was washed with water and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was dissolved in chloroform, passed through a silica gel short pass column, the solvent was distilled off under reduced pressure, and 20 mL of hexane was added to the obtained oily component for reprecipitation. The precipitate was collected by suction filtration, washed with ethyl acetate and then with tetrahydrofuran, and 2.6 g (4.3 mmol) of an orange powder of compound (1-9-1) was isolated (yield 62%).

The compound was identified by FDMS and ¹ H-NMR measurement.
FDMS (m / z); 604 (M +)
¹ H-NMR (CDCl 3) δ (ppm); 8.31 (s, 1 H), 8.21 (d, 1 H), 7.95 (m, 2 H), 7.79 (s, 1 H), 7. 48-7.70 (m, 6H), 7.28-7.43 (m, 10H), 7.08 (d, 1H), 6.83 (t, 1H), 6.63 (d, 1H) , 6.59 (d, 1H)

Example 5 (Device Evaluation of Compound (1-3-1))
The glass substrate on which the ITO transparent electrode (anode) having a thickness of 200 nm was laminated was subjected to ultrasonic cleaning with acetone and pure water and boiling cleaning with isopropyl alcohol. Further, ultraviolet ozone cleaning was carried out, and after evacuation with a vacuum pump until it was 1 × 10 ⁻⁴ Pa after installation in a vacuum deposition apparatus. First, 4,4′-bis [N- (9-phenylcarbazol-3-yl) -N-phenyl] biphenyl was vapor-deposited at a vapor deposition rate of 0.3 nm / sec on an ITO transparent electrode to form a 65 nm hole injection layer. It was. Subsequently, 4,4′-bis [N- (1-naphthyl) -N-phenyl] biphenyl (NPD) was deposited to a thickness of 10 nm at a deposition rate of 0.3 nm / second to form a hole transport layer. Subsequently, bis- (1-phenylisoquinolyl) iridium (III) acetylacetonate ((piq) 2Ir (acac)) as a light-emitting dopant material and compound (1-3-1) as a host material in a weight ratio of 8 Was co-deposited at a deposition rate of 0.25 nm / second to obtain a light emitting layer of 40 nm. Next, the weight ratio of 9,10-di (naphthalen-2-yl) -2- [4- (1-phenyl-1H-benzimidazol-2-yl) phenyl] anthracene and lithium quinolinol is 50:50. Thus, co-evaporation was performed at a deposition rate of 0.15 nm / second to obtain a 30 nm electron transport layer. Furthermore, silver and magnesium were co-deposited at a deposition rate of 0.5 nm / second to a weight ratio of 1:10 to form a cathode. In a nitrogen atmosphere, a sealing glass plate was bonded with a UV curable resin to obtain an organic EL element for evaluation. A current of 20 mA / cm ² was applied to the device thus fabricated, and driving voltage, current efficiency, and luminance reduction time of 20% were measured. The results are shown in Table 1.

Comparative Examples 1 to 3
The same organic as in Example 5 except that the compound (1-3-1) was changed to 4,4′-bis (carbazol-9-yl) biphenyl (CBP), comparative compound (a) or comparative compound (b) An EL element was produced. Table 1 shows the driving voltage, current efficiency, and luminance reduction time of 20% when a current of 20 mA / cm ² was applied.

Synthesis Example 6 (Synthesis of 3-chloro-2,6-difluoro-N, N-bis (2-methoxyphenyl) aniline)

In a 1 L three-necked flask under a nitrogen stream, 3-chloro-2,6-difluoroaniline 19.0 g (116.2 mmol), 2-iodoanisole 82.0 g (348.5 mmol), copper powder 78.2 g (348. 5 mmol), potassium carbonate 67.0 g (697.0 mmol), 18-crown-6 6.1 g (23.2 mmol), and o-dichlorobenzene 290 mL were added and stirred at 180 ° C. for 20 hours. After cooling to room temperature and removing inorganic salts by suction filtration, the solvent was distilled off under reduced pressure using a rotary pump. The residue was passed through a silica gel short path column (toluene), the solvent was distilled off under reduced pressure, and hexane was added to the resulting oily component for reprecipitation. The precipitate was collected by suction filtration and washed with hexane to give 35.5 g (99.2 mmol) of a white solid of 3-chloro-2,6-difluoro-N, N-bis (2-methoxyphenyl) aniline. Isolated. (Yield 81%).

Synthesis Example 7 (Synthesis of 3-chloro-2,6-difluoro-N, N-bis (2-hydroxyphenyl) aniline)

In a 500 mL three-necked flask under a nitrogen stream, 35.5 g (94.5 mmol) of 3-chloro-2,6-difluoro-N, N-bis (2-methoxyphenyl) aniline obtained in Synthesis Example 6 and dodecylmethyl sulfide 102.2 g (472.3 mmol) and 190 mL of toluene were added, and the mixture was cooled and stirred in an ice bath. After adding 63.0 g (472.3 mmol) of anhydrous aluminum chloride to this solution, the ice bath was removed and the mixture was stirred at room temperature for 20 hours. The mixture was cooled again in an ice bath, water was added to stop the reaction, and organic substances were extracted with ethyl acetate. The extract was dried over anhydrous magnesium sulfate, concentrated under reduced pressure, re-precipitated by adding hexane, and the precipitate was collected by suction filtration. By washing the obtained precipitate with 200 ml of hexane, 27.2 g (78.2 mmol) of a white solid of 3-chloro-2,6-difluoro-N, N-bis (2-hydroxyphenyl) aniline was isolated. . (Yield 83%).

Example 6 (Synthesis of 6-chloro- [1,4] benzoxazino [2,3,4-kl] phenoxazine)

In a 1 L three-necked flask under a nitrogen stream, 27.2 g (78.2 mmol) of 3-chloro-2,6-difluoro-N, N-bis (2-hydroxyphenyl) aniline obtained in Synthesis Example 7 and potassium carbonate 32 .4 g (234.7 mmol) and 380 mL of N, N-dimethylformamide were added and stirred at 100 ° C. for 15.5 hours. The solution was cooled to 80 ° C., and 300 mL of pure water was added for reprecipitation. The precipitated solid was collected by suction filtration and washed with water and then with methanol to give 23.0 g (74. 7) of a white solid of 6-chloro- [1,4] benzoxazino [2,3,4-kl] phenoxazine. 7 mmol) was isolated (95% yield).

Example 7 (Synthesis of Compound (1-2-1))

In a 200 mL three-necked flask under a nitrogen stream, 2.3 g (7.3 mmol) of 6,6-chloro- [1,4] benzoxazino [2,3,4-kl] phenoxazine obtained in Example 6 was used. Diphenyl-6- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) quinoxaline 3.6 g (8.8 mmol), palladium acetate 50 mg (0.22 mmol), X-phos 210 mg (0.44 mmol), 27 mL of tetrahydrofuran, and 5.5 mL of 2M tripotassium phosphate aqueous solution were added, and the mixture was stirred at reflux temperature for 3.5 hours. After cooling to room temperature, 50 mL of pure water and 100 mL of toluene were added to separate the organic layer. The organic layer was washed with water and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (toluene), and the solvent was evaporated under reduced pressure to give an oily component. Then, 20 mL of ethyl acetate was added for reprecipitation, and 3.5 g (6.3 mmol) of an orange powder of the compound (1-2-1) was isolated by suction filtration (yield 88%).

The compound was identified by FDMS and ¹ H-NMR measurement.
FDMS (m / z); 554 (M +)
¹ H-NMR (CDCl 3) δ (ppm); 8.31 (s, 1 H), 8.21 (d, 1 H), 7.97 (d, 1 H), 7.54 (m, 4 H), 7. 30-7.40 (m, 8H), 6.84-7.06 (m, 7H), 6.65 (d, 1H)

Synthesis Example 8 Synthesis of (2- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-[1,4] benzoxazino [2,3,4-kl] phenoxazine )

In a 200 mL three-necked flask under a nitrogen stream, 13.0 g (42.2 mmol) of 2-chloro- [1,4] benzoxazino [2,3,4-kl] phenoxazine obtained in Example 1 and bis (pinacolato) Diboron 14.0 g (54.9 mmol), palladium acetate 95 mg (0.42 mmol), X-phos 400 mg (0.85 mmol), potassium acetate 12.4 g (126.7 mmol), and tetrahydrofuran 150 mL were added at reflux temperature. Stir for 5 hours. After cooling to room temperature, the inorganic salt was removed by suction filtration, and the filtrate was concentrated under reduced pressure. The residue was dissolved in toluene and passed through an activated carbon short pass column, and then the solvent was concentrated under reduced pressure. Hexane is added to the residue for reprecipitation, and 2- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-[1,4] benzoxazino [2] is filtered by suction filtration. , 3,4-kl] phenoxazine, 15.4 g (38.6 mmol) of a white solid was isolated (yield 90%)

Example 8 (Synthesis of Compound (1-3-15))

In a 200 mL three-necked flask under a nitrogen stream, 2- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-[1,4] benzooxazino [ 2,3,4-kl] phenoxazine 3.5 g (8.8 mmol), 2-chloro-4-phenylquinazoline 2.7 g (11.4 mmol), palladium acetate 180 mg (0.79 mmol), X-phos 750 mg ( 1.6 mmol), 60 mL of tetrahydrofuran, and 6.6 mL of 2M tripotassium phosphate aqueous solution were added and stirred at reflux temperature for 17 hours. After cooling to room temperature, 50 mL of pure water was added for reprecipitation, and the precipitated solid was collected by suction filtration. The obtained solid was washed with methanol, dissolved in 500 ml of heated chlorobenzene, and passed through a silica gel short pass column. The filtrate was concentrated under reduced pressure to cause reprecipitation, and 1.9 g (4.0 mmol) of a pale yellow powder of compound (1-3-15) was isolated by suction filtration (yield 45%).

The compound was identified by FDMS and ¹ H-NMR measurement.
FDMS (m / z); 478 (M +)
¹ H-NMR (CDCl 3) δ (ppm); 8.73 (s, 1 H), 8.26 (d, 1 H), 8.11 (t, 2 H), 7.87 (m, 3 H), 7. 59 (m, 5H), 6.90-7.08 (m, 4H), 6.77 (t, 1H), 6.53 (d, 2H)

Example 9 (Synthesis of Compound (1-3-24))

In a 200 mL three-necked flask under a nitrogen stream, 2- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-[1,4] benzooxazino [ 2,3,4-kl] phenoxazine 3.5 g (8.8 mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine 2.8 g (10.5 mmol), Pd (PPh ₃ ) ₄ 51 mg (0.44 mmol), tetrahydrofuran 44 mL, and 2M potassium carbonate aqueous solution 8.8 mL were added, and the mixture was stirred at reflux temperature for 15 hours. After cooling to room temperature, 50 mL of pure water was added for reprecipitation, and the precipitated solid was collected by suction filtration. The obtained solid was washed with methanol, dissolved in 600 ml of heated chlorobenzene, and passed through a silica gel short pass column. The filtrate was concentrated under reduced pressure to cause reprecipitation, and 1.9 g (8.3 mmol) of a yellow powder of compound (1-3-24) was isolated by suction filtration (yield 96%).

The compound was identified by FDMS and ¹ H-NMR measurement.
FDMS (m / z); 505 (M +)
¹ H-NMR (CDCl 3) δ (ppm); 8.82 (s, 1 H), 8.73 (d, 4 H), 8.34 (d, 1 H), 7.59 (m, 7 H), 6. 90-7.10 (m, 4H), 6.80 (t, 1H), 6.55 (d, 2H)

Example 10 (Synthesis of Compound (1-3-42))

In a 200 mL three-necked flask under a nitrogen stream, 2- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-[1,4] benzooxazino [ 2,3,4-kl] phenoxazine 2.5 g (6.3 mmol), 2- (4′-bromophenyl) -4,6-diphenyl-1,3,5-triazine 3.2 g (8.1 mmol) Then, 40 mg (0.19 mmol) of palladium acetate, 180 mg (0.38 mmol) of X-phos, 47 mL of tetrahydrofuran, and 4.7 mL of 2M tripotassium phosphate aqueous solution were added and stirred at reflux temperature for 18 hours. After cooling to room temperature, 50 mL of pure water was added for reprecipitation, and the precipitated solid was collected by suction filtration. The obtained solid was washed with methanol, dissolved in 350 ml of heated chlorobenzene, and passed through a silica gel short pass column. The filtrate was concentrated under reduced pressure and reprecipitated, and 2.8 g (4.8 mmol) of a yellow powder of compound (1-3-42) was isolated by suction filtration (yield 78%).

The compound was identified by FDMS and ¹ H-NMR measurement.
FDMS (m / z); 581 (M +)
¹ H-NMR (CDCl 3) δ (ppm); 8.81 (m, 6H), 7.53-7.76 (m, 10H), 7.45 (d, 1H), 6.90-7.05 (M, 4H), 6.79 (t, 1H), 6.54 (d, 2H)

Synthesis Example 9 (Synthesis of 2,6-difluoro-N- (2-chloro-6-methoxyphenyl) aniline)

In a 1 L three-necked flask under a nitrogen stream, 2,6-difluoroiodobenzene 40.0 g (166.6 mmol), 2-chloro-6-methoxyaniline 23.6 g (150.0 mmol), palladium acetate 374 mg (1.7 mmol) ), Sodium tert-butoxide (19.2 g, 200.0 mmol), 25% tri-tert-butylphosphine / o-xylene solution (4.6 ml), and o-xylene (460 mL) were added, and the mixture was stirred at reflux temperature for 9 and a half hours. The reaction solution was cooled to room temperature, inorganic salts were removed by suction filtration, and then passed through a silica gel short pass column. The solvent was concentrated under reduced pressure, and the residue was purified by silica gel column chromatography (mixed solvent of toluene and hexane), and a white solid of 2,6-difluoro-N- (2-chloro-6-methoxyphenyl) aniline was obtained as 32. Isolated 0.0 g (118.7 mmol). (Yield 79%).

Synthesis Example 10 (Synthesis of 2-chloro-N- (2,6-difluorophenyl) -6-methoxy-N- (2-methoxyphenyl) aniline)

In a 500 mL three-necked flask under a nitrogen stream, 30.0 g (111.3 mmol) of 2,6-difluoro-N- (2-chloro-6-methoxyphenyl) aniline obtained in Synthesis Example 9 and 2-iodoanisole 39. 0 g (166.8 mmol), copper powder 37.5 g (166.8 mmol), potassium carbonate 32.1 g (333.6 mmol), 18-crown-6 6.0 g (22.2 mmol), and o-dichlorobenzene 180 mL The mixture was added and stirred at 180 ° C. for 15 and a half hours. After cooling to room temperature and removing inorganic salts by suction filtration, the solvent was distilled off under reduced pressure using a rotary pump. The precipitated solid was washed with hexane to obtain 19.5 g of a white solid containing 2-chloro-N- (2,6-difluorophenyl) -6-methoxy-N- (2-methoxyphenyl) aniline. The resulting mixture was used in the next step without purification.

Synthesis Example 11 (Synthesis of 2-chloro-N- (2,6-difluorophenyl) -6-hydroxy-N- (2-hydroxyphenyl) aniline)

In a 500 mL three-necked flask under a nitrogen stream, 19.5 g of the 2-chloro-N- (2,6-difluorophenyl) -6-methoxy-N- (2-methoxyphenyl) aniline mixture obtained in Synthesis Example 10 was added to dodecyl. Methyl sulfide (54.7 g, 252.8 mmol) and toluene (101 mL) were added, and the mixture was cooled and stirred in an ice bath. After adding 33.7 g (252.8 mmol) of anhydrous aluminum chloride to this solution, the ice bath was removed and the mixture was stirred at room temperature for 20 hours. The mixture was cooled again in an ice bath, water was added to stop the reaction, and organic substances were extracted with ethyl acetate. The extract was dried over anhydrous magnesium sulfate, concentrated under reduced pressure, re-precipitated by adding hexane, and the precipitate was collected by suction filtration. The obtained precipitate was washed with 200 ml of hexane to obtain 17.5 g of a white solid containing 2-chloro-N- (2,6-difluorophenyl) -6-hydroxy-N- (2-hydroxyphenyl) aniline. did. (Yield 57%).

Example 11 (Synthesis of 4-chloro- [1,4] benzoxazino [2,3,4-kl] phenoxazine)

In a 500 mL three-necked flask under a nitrogen stream, 17.5 g of the mixture of 2-chloro-N- (2,6-difluorophenyl) -6-hydroxy-N- (2-hydroxyphenyl) aniline obtained in Synthesis Example 11 and carbonic acid 20.9 g (151.0 mmol) of potassium and 250 mL of N, N-dimethylformamide were added and stirred at 100 ° C. for 15 hours. After cooling to room temperature, the solvent was distilled off under reduced pressure, 200 mL of pure water was added and stirred, and then the precipitated solid was collected by suction filtration. The obtained solid was purified by silica gel column chromatography (mixed solvent of toluene and hexane), and 10.5 g of 4-chloro- [1,4] benzoxazino [2,3,4-kl] phenoxazine white solid (34 -1 mmol) was isolated.

The compound was identified by FDMS and ¹ H-NMR measurement.
FDMS (m / z); 307 (M +)
¹ H-NMR (CDCl 3) δ (ppm); 7.28 (d, 1 H), 7.22 (d, 1 H), 6.90-6.98 (m, 4 H), 6.86 (t, 1 H ), 6.79 (t, 1H), 6.61 (d, 1H), 6.53 (d, 1H)

Example 12 (Synthesis of Compound (1-5-1))

In a 200 mL three-necked flask under a nitrogen stream, 2.0 g (5.6 mmol) of 4-chloro- [1,4] benzoxazino [2,3,4-kl] phenoxazine obtained in Example 11 was used. Diphenyl-6- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) quinoxaline 3.0 g (7.3 mmol), palladium acetate 40 mg (0.17 mmol), X-phos 160 mg (0.34 mmol), 40 mL of tetrahydrofuran, and 4.0 mL of 2M tripotassium phosphate aqueous solution were added and stirred at reflux temperature for 6 and a half hours. After cooling to room temperature, 50 mL of pure water was added and the precipitated solid was collected by suction filtration. The obtained solid was dissolved in toluene and passed through a silica gel short pass column, and then the solvent was concentrated under reduced pressure to cause reprecipitation, and the orange powder of compound (1-5-1) was obtained by suction filtration. 1 g (3.8 mmol) was isolated (68% yield).

The compound was identified by FDMS and ¹ H-NMR measurement.
FDMS (m / z); 554 (M +)
¹ H-NMR (CDCl 3) δ (ppm); 8.35 (s, 1 H), 8.24 (d, 1 H), 8.00 (d, 1 H), 7.54 (m, 5 H), 7. 32-7.42 (m, 8H), 7.11 (m, 2H), 6.96 (m, 3H), 6.4-6.54 (m, 2H)

Synthesis Example 12 (Synthesis of 6- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -2,4-diphenylquinazoline)
Under a nitrogen stream, 6.0 g (18.9 mmol) of 6-chloro-2,4-diphenylquinazoline obtained by the synthesis method described in European Journal of Chemistry 3 (2) (2012) 252-257 in a 200 mL three-necked flask , Bis (pinacolato) diboron 6.3 g (24.6 mmol), palladium acetate 43 mg (0.19 mmol), X-phos 180 mg (0.38 mmol), potassium acetate 5.6 g (56.8 mmol), and tetrahydrofuran 70 mL are added. The mixture was stirred at reflux temperature for 3.5 hours. After cooling to room temperature, the inorganic salt was removed by suction filtration, and the filtrate was concentrated under reduced pressure. The residue was dissolved in toluene and passed through an activated carbon short pass column, and then the solvent was concentrated under reduced pressure. Hexane is added to the residue for reprecipitation, and 6- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -2,4-diphenylquinazoline is white by suction filtration. 5.0 g (12.2 mmol) of solid was isolated (yield 65%)

Example 13 (Synthesis of Compound (1-5-39))

In a 200 mL three-necked flask under a nitrogen stream, 2.0 g (5.6 mmol) of 4-chloro- [1,4] benzoxazino [2,3,4-kl] phenoxazine obtained in Example 11 was used. The obtained 6- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -2,4-diphenylquinazoline 3.0 g (7.3 mmol), palladium acetate 40 mg (0. 17 mmol), 160 mg (0.34 mmol) of X-phos, 40 mL of tetrahydrofuran, and 4.0 mL of 2M tripotassium phosphate aqueous solution were added, and the mixture was stirred at reflux temperature for 3 hours. After cooling to room temperature, 50 mL of pure water was added and the precipitated solid was collected by suction filtration. The obtained solid was dissolved in chlorobenzene and passed through a silica gel short pass column. Then, the solvent was concentrated under reduced pressure to cause reprecipitation, and the precipitate was collected by suction filtration. Further, 2.7 g (6.6 mmol) of a pale yellow powder of the compound (1-5-39) was isolated by recrystallization from chlorobenzene 65 (yield 64%).

The compound was identified by FDMS and ¹ H-NMR measurement.
FDMS (m / z); 554 (M +)
¹ H-NMR (CDCl 3) δ (ppm); 8.73 (d, 2 H), 8.33 (s, 1 H), 8.25 (d, 1 H), 8.09 (d, 1 H), 7. 95 (m, 2H), 7.50-7.62 (m, 6H), 7.30-7.40 (m, 2H), 6.90-7.10 (m, 5H), 6.72 ( t, 1H), 6.52 (d, 1H), 6.26 (d, 1H)

Example 14 (Device evaluation of compound (1-2-1))
The structural formulas and abbreviations of the compounds used for device evaluation are shown below.

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

(Preparation for vacuum deposition)
Each layer was vacuum-deposited by a vacuum deposition method on the substrate that had been subjected to the surface treatment after the cleaning, and each layer was laminated.
First, the glass substrate was introduced into a vacuum evaporation tank, and the pressure was reduced to 1.0 × 10 ⁻⁴ Pa. And each layer was produced according to the film-forming conditions of each layer in the following order.

(Production of organic EL element)
First, HIL was deposited to a thickness of 55 nm on the ITO transparent electrode at a rate of 0.15 nm / second to produce a hole injection layer. Subsequently, HAT was deposited to a thickness of 5 nm at a rate of 0.05 nm / second to produce a charge generation layer. On the HAT layer, HTL-1 was deposited to a thickness of 15 nm at a rate of 0.15 nm / second to produce a first hole transport layer. Further thereon, HTL-2 was deposited to a thickness of 50 nm at a rate of 0.15 nm / second to produce a second hole transport layer. Subsequently, bis- (1-phenylisoquinolyl) iridium (III) acetylacetonate ((piq) 2Ir (acac)) as a light-emitting dopant material and compound (1-2-1) as a host material have a weight ratio of 5 Was co-evaporated at a deposition rate of 0.18 nm / second so as to obtain a light emitting layer of 35 nm. Next, ETL and Liq were deposited in a thickness of 30 nm at a ratio of 50:50 (mass ratio) to produce an electron transport layer. The deposition rate was 0.15 nm / second. Finally, a metal mask was arranged so as to be orthogonal to the ITO stripe on the substrate, and a cathode was formed. 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 / second, and the film formation rate of silver was 0.2 nm / second.

As described above, an organic electroluminescence device having a light emission area of 4 mm ² was produced. Each film thickness was measured with a stylus type film thickness meter (DEKTAK, manufactured by Bruker).

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

Table 2 shows the drive voltage and current efficiency when a current of 10 mA / cm ² was applied to the organic electroluminescent device produced as described above.

Example 15 Device Evaluation of (Compound 1-342) The same method as in Example 14, except that the compound (1-3-42) was used instead of the compound (1-2-1) in Example 14. An organic electroluminescent device was prepared and evaluated. The obtained measurement results are shown in Table 2.

Example 16 Device evaluation of (Compound 1-5-1) In Example 14, the same method as in Example 14 except that Compound (1-5-1) was used instead of Compound (1-2-1). An organic electroluminescent device was prepared and evaluated. The obtained measurement results are shown in Table 2.

Example 17 Device evaluation of (Compound 1-5-39) In Example 14, the same method as in Example 14 except that Compound (1-5-39) was used instead of Compound (1-2-1). An organic electroluminescent device was prepared and evaluated. The obtained measurement results are shown in Table 2.

Comparative Example 4 Device Evaluation of Comparative Compound (c) An organic electroluminescent device was prepared in the same manner as in Example 14 except that Comparative Compound (c) was used instead of Compound (1-2-1) in Example 14. Prepared and evaluated. The obtained measurement results are shown in Table 2.

The organic EL device containing the oxygen-bridged triarylamine compound according to one embodiment of the present invention having good bipolar properties can be expected to improve the recombination efficiency of electrons and holes in the light emitting layer. . Therefore, the oxygen-bridged triarylamine compound according to one embodiment of the present invention can provide an organic EL element with high luminance and efficiency and excellent lifetime.

Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.

The entire contents of the specification, claims, drawings and abstract of Japanese Patent Application No. 2017-030382, filed on February 21, 2017, Japanese Patent Application filed on October 20, 2017 Description of application 2017-203571, claims, entire contents of drawings and abstract, as well as specification and claims of Japanese Patent Application No. 2018-023489 filed on Feb. 13, 2018 The entire contents of the drawings and abstract are hereby incorporated by reference as the disclosure of the specification of the present invention.

Claims

Compound represented by formula (1):

In formula (1),
Ring A, Ring B and Ring C are each independently
An aryl ring having 6 to 18 carbon atoms, or
A heteroaryl ring having 3 to 13 carbon atoms;
The aryl ring or the heteroaryl ring includes a deuterium atom, a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, a phenyl group, a naphthyl group, a biphenylyl group, a 9-phenylcarbazolyl group, a dibenzofuranyl group. Optionally substituted with at least one selected from the group consisting of a group, a dibenzothionyl group, and a substituent Z represented by formula (2);
However, the compound represented by the formula (1) has at least one substituent Z;

In formula (2),
L is independently
A divalent group selected from the group consisting of a phenylene group, a biphenyldiyl group, a naphthalenediyl group, a fluorenediyl group, a spirobifluorenediyl group, a dibenzothiophenediyl group, a dibenzofurandiyl group, and a 9-phenylcarbazole diyl group. Group of
Represents a single bond;
The divalent group is composed of a deuterium atom, a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 25 carbon atoms, and a heteroaryl group having 3 to 20 carbon atoms. Optionally substituted with at least one selected from the group;
Hy is independently a carbon number composed of at least one atom selected from the group consisting of a carbon atom, a hydrogen atom, an oxygen atom, a sulfur atom, and a nitrogen atom, and a nitrogen atom that forms a multiple bond. Represents 3 to 12 nitrogen-containing heteroaromatic groups;
The nitrogen-containing heteroaromatic group includes a deuterium atom, a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 25 carbon atoms, and a heteroaryl group having 3 to 20 carbon atoms, It may be substituted with at least one selected from the group consisting of
A ring, B ring and C ring are each independently one ring selected from the group consisting of benzene ring, naphthalene ring, phenanthrene ring, triphenylene ring, anthracene ring and chrysene ring,
The ring includes a deuterium atom, a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, phenyl group, naphthyl group, biphenylyl group, 9-phenylcarbazolyl group, dibenzofuranyl group, dibenzothionyl group, The compound according to claim 1, which may be substituted with at least one selected from the group consisting of the substituent Z.
A ring, B ring and C ring are each independently one ring selected from a benzene ring and a naphthalene ring;
The ring includes a deuterium atom, a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, phenyl group, naphthyl group, biphenylyl group, 9-phenylcarbazolyl group, dibenzofuranyl group, dibenzothionyl group, The compound according to claim 1, wherein the compound is optionally substituted with at least one selected from the group consisting of the substituent Z.
The compound according to claim 1, which is a compound represented by any one of formulas (1-1) to (1-26):

In formulas (1-1) to (1-26),
R is each independently a hydrogen atom, a deuterium atom, a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, a phenyl group, a naphthyl group, a biphenylyl group, a 9-phenylcarbazolyl group, a dibenzofuran group. Represents a nyl group or a dibenzothionyl group;
Z is synonymous with the formula (2).
L is independently
Single bond or
The compound according to any one of claims 1 to 4, which is a group represented by any one of formulas (L-1) to (L-11):

In formulas (L-1) to (L-11), each R 1 independently represents a hydrogen atom, a deuterium atom, a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, or 6 to 6 carbon atoms. Represents a 25 aryl group or a heteroaryl group having 3 to 20 carbon atoms.
Hy is each independently a pyridyl group, pyrimidinyl group, pyrazinyl group, triazinyl group, carbolinyl group, quinolinyl group, isoquinolinyl group, naphthyridinyl group, quinoxalinyl group, quinazolinyl group, benzoquinoxalinyl group, benzoquinazolinyl group , A benzothienopyrimidinyl group, and a benzofuroprimidinyl group, one group selected from the group consisting of
The group is selected from the group consisting of a deuterium atom, a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 25 carbon atoms, and a heteroaryl group having 3 to 20 carbon atoms. 6. The compound according to any one of claims 1 to 5, which may be substituted with at least one of the following.
The compound according to any one of claims 1 to 6, wherein Hy is each independently a group represented by any one of formulas (Hy-1) to (Hy-9):

In formulas (Hy-1) to (Hy-9), each R 2 independently represents a hydrogen atom, a deuterium atom, a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, or 6 to 6 carbon atoms. Represents a 25 aryl group or a heteroaryl group having 3 to 20 carbon atoms.
A light emitting material comprising the compound according to any one of claims 1 to 7.
Chlorine compound represented by formula (1-a):

In formula (1-a),
Ring A, Ring B and Ring C are each independently
An aryl ring having 6 to 18 carbon atoms, or
A heteroaryl ring having 3 to 13 carbon atoms;
The aryl ring or the heteroaryl ring includes a deuterium atom, a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, a phenyl group, a naphthyl group, a biphenylyl group, a 9-phenylcarbazolyl group, a dibenzofuranyl group. Optionally substituted with at least one selected from the group consisting of a group, a dibenzothionyl group, and a chlorine atom;
However, the compound represented by the formula (1-a) has at least one chlorine atom.
A ring, B ring and C ring are each independently one ring selected from the group consisting of benzene ring, naphthalene ring, phenanthrene ring, triphenylene ring, anthracene ring and chrysene ring,
The ring includes a deuterium atom, a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, phenyl group, naphthyl group, biphenylyl group, 9-phenylcarbazolyl group, dibenzofuranyl group, dibenzothionyl group, The chlorine compound according to claim 9, which may be substituted with at least one selected from the group consisting of chlorine atoms.
A ring, B ring and C ring are each independently one ring selected from a benzene ring and a naphthalene ring;
The ring includes a deuterium atom, a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, phenyl group, naphthyl group, biphenylyl group, 9-phenylcarbazolyl group, dibenzofuranyl group, dibenzothionyl group, The chlorine compound according to claim 9 or 10, which may be substituted with at least one selected from the group consisting of chlorine atoms.
The chlorine compound according to claim 9, which is a chlorine compound represented by any one of formulas (1-a1) to (1-a23):

In formulas (1-a1) to (1-a23), each R independently represents a hydrogen atom, a deuterium atom, a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, a phenyl group, or a naphthyl group. Represents a biphenylyl group, a 9-phenylcarbazolyl group, a dibenzofuranyl group, or a dibenzothionyl group.