WO2012081541A1 - 1, 2, 4, 5-substituted phenyl derivative, production method for same, and organic electroluminescent element - Google Patents

Abstract

Provided is a 1, 2, 4, 5-substituted phenyl derivative indicated by formula (1). (In the formula, Ar¹ is a nitrogen-containing heteroaromatic group, a phenyl group, or a 2- to 4-ring hydrocarbon group and said groups can be substituted with a phenyl group or an alkyl group. X is a single bond phenylene group or naphthylene group, or a bivalent nitrogen-containing heteroaromatic group, and said groups can be substituted with an alkyl group. At least one of Ar², Ar³, and Ar⁴ is a nitrogen-containing heteroaromatic group that can be substituted by an alkyl group and the remainder are hydrogen atoms. When X is a 1,3-phenylene group, Ar¹ is not the same as Ar² and Ar⁴, and when X is a 1,4-phenylene group, Ar¹ is not the same as Ar³.) The hydrogen atoms in formula (1) can each independently be a deuterium atom. The 1, 2, 4, 5-substituted phenyl derivative is suitable for use as a constituent component of an organic electroluminescent element, especially an electron transport layer.

Description

1,2,4,5-Substituted phenyl derivative, method for producing the same, and organic electroluminescent device

The present invention relates to a 1,2,4,5-substituted phenyl derivative and a production method thereof. The 1,2,4,5-substituted phenyl derivative of the present invention is characterized by having a substituent having a nitrogen-containing heteroaromatic group at any of 1,2,4,5 positions of benzene. This 1,2,4,5-substituted phenyl derivative is useful as a component of a fluorescent or phosphorescent organic electroluminescent device because it has good charge transport properties and forms a stable thin film.

The present invention further relates to an organic electroluminescent device having at least one organic compound layer composed of a 1,2,4,5-substituted phenyl derivative and having excellent driving performance and light emitting property and high luminous efficiency. .

An organic electroluminescent element is formed by sandwiching a light-emitting layer containing a light-emitting material between a hole transport layer and an electron transport layer, and further attaching an anode and a cathode to the outside, and recombination of holes and electrons injected into the light-emitting layer. It is an element that utilizes light emission (fluorescence or phosphorescence) when the generated excitons are deactivated, and is applied to displays and the like.

An example in which a 1,2,4,5-substituted phenyl derivative is used for an organic electroluminescent device (see Patent Document 1) is disclosed. In this example, the substituents at the 1,2,4,5-positions of benzene are limited to metaphenylene groups, and the 1,2,4,5-substituted phenyl derivatives of the present invention are not included.

As an example of a 1,2,4,5-substituted phenyl derivative, a compound in which a bipyridyl group-introduced compound is used in an organic electroluminescent device is disclosed (see Patent Document 2). It is limited and does not include the 1,2,4,5-substituted phenyl derivatives of the present invention.

An example in which a 1,2,4,5-substituted phenyl derivative is used in an organic electroluminescent device (see Patent Document 3) is disclosed. In this example, 1,1 ′: 4 ′, 1 ″ tellurium is disclosed. Only the compounds substituted at the 2 ′ and 5 ′ positions of the phenyl are defined and are different from the 1,2,4,5-substituted phenyl derivatives of the present invention. Further, this patent document only discusses that the above compound has high luminous efficiency, and does not describe low power consumption and long life desired for an organic electroluminescent device. Limited.

Further, there is an example in which a derivative in which a phenyl group and a pyridyl group are combined is used in an organic electroluminescence device (see, for example, Patent Documents 4 to 8). The skeleton is different from the phenyl derivative, and the performance of the organic electroluminescent device is not sufficiently improved.

JP 2010-90085 A WO2009-151039 WO2009-081873 JP 2008-63232 A JP 2003-336043 A JP 2007-015993 A JP 2005-255986 A JP 2008-127326 A

Organic electroluminescent elements are used in various display devices, but the use of organic electroluminescent elements in portable devices with limited power supply is required to achieve lower power consumption. At the same time, when the organic electroluminescence device is used commercially, how to extend the device lifetime in order to obtain stable performance becomes a problem.

Especially for electron transport materials, materials that combine excellent charge injection and transport characteristics to drive devices at low voltage and reduce power consumption, and durability that enables longer device lifetimes, are the conventional compounds. New materials are desired because they cannot be found in any of the above.

An object of the present invention is to provide a 1,2,4,5-substituted phenyl derivative having a novel structure having good charge injection and transport properties when used as a constituent material of an organic electroluminescent device.

Another object of the present invention is to provide an industrially advantageous method for producing the 1,2,4,5-substituted phenyl derivative.
Still another object of the present invention is to provide an organic electroluminescent device having excellent driving performance and light emitting property and high luminous efficiency.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have 1,2,2,5 having a substituent having a nitrogen-containing heteroaromatic group at any of the 1,2,4,5 positions of benzene. The 4,5-substituted phenyl derivative has a wide energy gap and a high triplet energy necessary for use as a blue fluorescent device or a phosphorescent device, and the 1,2,4,5-substituted phenyl derivative has an electron transport property. The organic electroluminescence device used as the layer was found to be excellent in driveability and luminescent properties and have high emission efficiency, and completed the present invention.

That is, the present invention provides, in one aspect, the following general formula (1)

(In the formula, Ar ¹ is substituted with a nitrogen-containing heteroaromatic group which may be substituted with a phenyl group or an alkyl group, a phenyl group which may be substituted with a phenyl group or an alkyl group, or a phenyl group or an alkyl group. X represents a single bond, a phenylene group which may be substituted with an alkyl group, a naphthylene group which may be substituted with an alkyl group, or an alkyl group. Ar ² , Ar ³ and Ar ⁴ each independently represent a nitrogen-containing heteroaromatic group which may be substituted with an alkyl group or a hydrogen atom. ^However, Ar 2, Ar ³ and of the Ar ⁴ at least one .X representing the substituents on these nitrogen-containing heterocyclic aromatic group with an alkyl group is 1,3-phenylene Weight of time, when Ar ¹ does not become the same as Ar ² and Ar ⁴ .X is 1,4-phenylene group, Ar ¹ is not the same as Ar ^3. Further, each of the hydrogen atom in the formula are each independently And a 1,2,4,5-substituted phenyl derivative represented by formula (1).

In another aspect of the present invention, the following general formula (2)

(In the formula, Z ¹ represents a leaving group. Ar ² , Ar ³ and Ar ⁴ each independently represents a nitrogen-containing heteroaromatic group which may be substituted with an alkyl group, or a hydrogen atom, provided that Ar ² , Ar ³ and Ar ⁴ represent a nitrogen-containing heteroaromatic group which may be substituted with an alkyl group, and X in the following general formula (3) is a 1,3-phenylene group In this case, Ar ¹ is not the same as Ar ² and Ar ^4, and when X is a 1,4-phenylene group, Ar ¹ is not the same as Ar ^3. Each hydrogen atom in the formula is independently A hydrogen atom)), and

The following general formula (3)

(In the formula, Ar ¹ is substituted with a nitrogen-containing heteroaromatic group which may be substituted with a phenyl group or an alkyl group, a phenyl group which may be substituted with a phenyl group or an alkyl group, or a phenyl group or an alkyl group. X represents a single bond, a phenylene group which may be substituted with an alkyl group, a naphthylene group which may be substituted with an alkyl group, or an alkyl group. Represents a divalent nitrogen-containing heteroaromatic group that may be substituted, M ¹ represents a metal group or a heteroatom group, and each hydrogen atom in the formula may independently be a deuterium atom. And a compound represented by (1) in the presence or absence of a base in the presence of a metal catalyst.

The following general formula (1)

(In the formula, Ar ¹ is substituted with a nitrogen-containing heteroaromatic group which may be substituted with a phenyl group or an alkyl group, a phenyl group which may be substituted with a phenyl group or an alkyl group, or a phenyl group or an alkyl group. X represents a single bond, a phenylene group which may be substituted with an alkyl group, a naphthylene group which may be substituted with an alkyl group, or an alkyl group. Ar ² , Ar ³ and Ar ⁴ each independently represent a nitrogen-containing heteroaromatic group which may be substituted with an alkyl group or a hydrogen atom. ^However, Ar 2, Ar ³ and of the Ar ⁴ at least one .X representing the substituents on these nitrogen-containing heterocyclic aromatic group with an alkyl group is 1,3-phenylene Weight of time, when Ar ¹ does not become the same as Ar ² and Ar ⁴ .X is 1,4-phenylene group, Ar ¹ is not the same as Ar ^3. Further, each of the hydrogen atom in the formula are each independently It may be a hydrogen atom.) And a method for producing a 1,2,4,5-substituted phenyl derivative represented by the following formula:

In another aspect of the present invention, the following general formula (2)

(In the formula, Z ¹ represents a leaving group. Ar ² , Ar ³ and Ar ⁴ each independently represents a nitrogen-containing heteroaromatic group which may be substituted with an alkyl group, or a hydrogen atom, provided that Ar ² , Ar ³ and Ar ⁴ represent a nitrogen-containing heteroaromatic group which may be substituted with an alkyl group, and X in the general formula (3) is a 1,3-phenylene group And Ar ¹ is not the same as Ar ² and Ar ⁴ and when X is a 1,4-phenylene group, Ar ¹ is not the same as Ar ^3. Each hydrogen atom in the formula is independently deuterium A compound represented by

The following general formula (4)

(Ar ² , Ar ³ and Ar ⁴ each independently represent a nitrogen-containing heteroaromatic group which may be substituted with an alkyl group or a hydrogen atom, provided that at least one of Ar ² , Ar ³ and Ar ⁴ is Represents a nitrogen-containing heteroaromatic group which may be substituted with an alkyl group, and when X in the general formula (3) is a 1,3-phenylene group, Ar ¹ is the same as Ar ² and Ar ⁴ And when X is a 1,4-phenylene group, Ar ¹ is not the same as Ar ^3. M ² represents a metal group or a heteroatom group, and each hydrogen atom in the formula is independently May be a deuterium atom)),

The following general formula (5)

(In the formula, Z ¹ and Z ² each independently represent a leaving group, provided that Z ¹ and Z ² are not the same.) In the presence or absence of a base, the compound represented by The coupling reaction is carried out in the presence of

The following general formula (1)

(In the formula, Ar ¹ is substituted with a nitrogen-containing heteroaromatic group which may be substituted with a phenyl group or an alkyl group, a phenyl group which may be substituted with a phenyl group or an alkyl group, or a phenyl group or an alkyl group. X represents a single bond, a phenylene group which may be substituted with an alkyl group, a naphthylene group which may be substituted with an alkyl group, or an alkyl group. Ar ² , Ar ³ and Ar ⁴ each independently represent a nitrogen-containing heteroaromatic group which may be substituted with an alkyl group or a hydrogen atom. ^However, Ar 2, Ar ³ and of the Ar ⁴ at least one .X representing the substituents on these nitrogen-containing heterocyclic aromatic group with an alkyl group is 1,3-phenylene Weight of time, when Ar ¹ does not become the same as Ar ² and Ar ⁴ .X is 1,4-phenylene group, Ar ¹ is not the same as Ar ^3. Further, each of the hydrogen atom in the formula are each independently It may be a hydrogen atom.) And a method for producing a 1,2,4,5-substituted phenyl derivative represented by the following formula:

Furthermore, in another aspect of the present invention, the following general formula (1)

(In the formula, Ar ¹ is substituted with a nitrogen-containing heteroaromatic group which may be substituted with a phenyl group or an alkyl group, a phenyl group which may be substituted with a phenyl group or an alkyl group, or a phenyl group or an alkyl group. X represents a single bond, a phenylene group which may be substituted with an alkyl group, a naphthylene group which may be substituted with an alkyl group, or an alkyl group. Ar ² , Ar ³ and Ar ⁴ each independently represent a nitrogen-containing heteroaromatic group which may be substituted with an alkyl group or a hydrogen atom. ^however, Ar 2, Ar ³ and of the Ar ⁴ at least one .X representing the substituents on these nitrogen-containing heterocyclic aromatic group with an alkyl group is 1,3-phenylene Weight of time, when Ar ¹ does not become the same as Ar ² and Ar ⁴ .X is 1,4-phenylene group, Ar ¹ is not the same as Ar ^3. Further, each of the hydrogen atom in the formula are each independently And an organic electroluminescent device comprising the 1,2,4,5-substituted phenyl derivative represented by formula (1) as a constituent component.

The 1,2,4,5-substituted phenyl derivative represented by the general formula (1) of the present invention is useful as a material for a fluorescent or phosphorescent organic electroluminescent device because it has good charge injection and transport properties. In particular, it is suitable as a host material or an electron transport material.

The band gap of the 1,2,4,5-substituted phenyl derivative is 3.2 eV or more, and the three primary colors constituting the panel (red: 1.9 eV, green: 2.4 eV, blue: 2.8 eV) It is a wide band gap material sufficient to confine the energy of each color. Therefore, it can be applied to various elements such as a single color display element, a three primary color display element, and a white element for illumination use. The triplet energy of this compound is also high, and it can be sufficiently applied to phosphorescence. Furthermore, since the solubility can be controlled by changing the substituent, it can be applied not only to a vapor deposition element but also to a coating element.

FIG. 3 is a cross-sectional view of an organic electroluminescent element produced in Test Example 1 described later.

1. 1. Glass substrate with ITO transparent electrode 2. hole injection layer Hole transport layer 4. Light emitting layer 5. Electron transport layer 6. Cathode layer

Hereinafter, the present invention will be described in detail.
In the 1,2,4,5-substituted phenyl derivative represented by the general formula (1) of the present invention (hereinafter sometimes referred to as “compound (1)”), a phenyl group or an alkyl group represented by Ar ¹ Of a nitrogen-containing heteroaromatic group which may be substituted with, a phenyl group which may be substituted with a phenyl group or an alkyl group, or a 2- to 4-ring hydrocarbon group which may be substituted with a phenyl group or an alkyl group Preferable examples include a pyridyl group optionally substituted with an alkyl group, a phenyl group optionally substituted with an alkyl group, and a fluorenyl group optionally substituted with an alkyl group.

Hereinafter, more specific examples of Ar ¹ are, Ar ¹ is not intended to be limited thereto.
Examples of the nitrogen-containing heteroaromatic group which may be substituted with a phenyl group or an alkyl group include 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 2-methylpyridin-3-yl group, 2-methylpyridine -4-yl group, 2-methylpyridin-5-yl group, 2-methylpyridin-6-yl group, 3-methylpyridin-2-yl group, 3-methylpyridin-4-yl group, 3-methylpyridine -5-yl group, 3-methylpyridin-6-yl group, 4-methylpyridin-2-yl group, 4-methylpyridin-3-yl group, 2,6-dimethylpyridin-3-yl group, 2, 6-dimethylpyridin-4-yl group, 3,6-dimethylpyridin-2-yl group, 3,6-dimethylpyridin-4-yl group, 3,6-dimethylpyridin-5-yl group, 2-phenylpyridine -3-Ile 2-phenylpyridin-4-yl group, 2-phenylpyridin-5-yl group, 2-phenylpyridin-6-yl group, 3-phenylpyridin-2-yl group, 3-phenylpyridin-4-yl group 3-phenylpyridin-5-yl group, 3-phenylpyridin-6-yl group, 4-phenylpyridin-2-yl group, 4-phenylpyridin-3-yl group, 2,6-diphenylpyridin-3- Yl group, 2,6-diphenylpyridin-4-yl group, 3,6-diphenylpyridin-2-yl group, 3,6-diphenylpyridin-4-yl group, 3,6-diphenylpyridin-5-yl group 2-pyrimidyl group, 4-pyrimidyl group, 5-pyrimidyl group, 2-methylpyrimidin-4-yl group, 2-methylpyrimidin-5-yl group, 4-methylpyrimidin-2-yl group, -Methylpyrimidin-5-yl group, 4-methylpyrimidin-6-yl group, 5-methylpyrimidin-2-yl group, 5-methylpyrimidin-4-yl group, 2,4-dimethylpyrimidin-6-yl group 4,6-dimethylpyrimidin-2-yl group, 2-phenylpyrimidin-4-yl group, 2-phenylpyrimidin-5-yl group, 4-phenylpyrimidin-2-yl group, 4-phenylpyrimidin-5- Yl group, 4-phenylpyrimidin-6-yl group, 5-phenylpyrimidin-2-yl group, 5-phenylpyrimidin-4-yl group, 2,4-diphenylpyrimidin-6-yl group, 4,6-diphenyl Pyrimidin-2-yl group, 2-pyrazyl group, 2-methylpyrazin-3-yl group, 2-methylpyrazin-5-yl group, 2-methylpyrazin-6-yl group, 2, Examples include a 6-dimethylpyrazin-3-yl group, a 2-phenylpyrazin-3-yl group, a 2-phenylpyrazin-5-yl group, and a 2-phenylpyrazin-6-yl group.

2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 3-methylpyridin-6-yl group, 2-methylpyridin-5-yl group, 3-phenyl in terms of performance as an organic electroluminescent device material Pyridin-6-yl group, 2-phenylpyridin-5-yl group, 2-pyrimidyl group, 4-pyrimidyl group, 5-pyrimidyl group and 5-phenylpyrimidin-2-yl group are preferable. From the viewpoint of easy synthesis, 2-pyridyl group, 3-pyridyl group, 2-phenylpyridin-5-yl group and 5-phenylpyrimidin-2-yl group are more preferable.

Examples of the phenyl group which may be substituted with a phenyl group or an alkyl group include a phenyl group, p-tolyl group, m-tolyl group, 1,3,5-trimethylphenyl group, 2-biphenyl group, 3-biphenyl group, 4-biphenyl group, 1,1 ′: 3 ′, 1 ″ -terphenyl-2′-yl group, 1,1 ′: 3 ′, 1 ″ -terphenyl-4′-yl group, 1,1 ': 3', 1 ″ -terphenyl-5′-yl group, 1,1 ′: 3 ′, 1 ″ -terphenyl-6′-yl group, 1,1 ′: 2 ′, 1 ″ Terphenyl-3′-yl group, 1,1 ′: 2 ′, 1 ″ -terphenyl-4′-yl group, 1,1 ′: 4 ′, 1 ″ -terphenyl-2′-yl Groups and the like.

A phenyl group, a p-tolyl group, a 4-biphenyl group, and a 1,1 ′: 3 ′, 1 ″ -terphenyl-5′-yl group are preferable in terms of good performance as an organic electroluminescent element material. From the viewpoint of ease, a phenyl group, a p-tolyl group, and a 4-biphenyl group are more preferable.

Examples of the 2- to 4-ring hydrocarbon group which may be substituted with a phenyl group or an alkyl group include a 1-naphthyl group, a 4-methylnaphthalen-1-yl group, a 4-trifluoromethylnaphthalen-1-yl group, 4-ethylnaphthalen-1-yl group, 4-propylnaphthalen-1-yl group, 4-butylnaphthalen-1-yl group, 4-tert-butylnaphthalen-1-yl group, 5-methylnaphthalen-1-yl Group, 5-ethylnaphthalen-1-yl group, 5-propylnaphthalen-1-yl group, 5-butylnaphthalen-1-yl group, 5-tert-butylnaphthalen-1-yl group, 2-naphthyl group, 6 -Methylnaphthalen-2-yl group, 6-trifluoromethylnaphthalen-2-yl group, 6-ethylnaphthalen-2-yl group, 6-propylnaphthalen-2-y group Group, 6-butylnaphthalen-2-yl group, 6-tert-butylnaphthalen-2-yl group, 7-methylnaphthalen-2-yl group, 7-ethylnaphthalen-2-yl group, 7-propylnaphthalene-2 -Yl group, 7-butylnaphthalen-2-yl group, 7-tert-butylnaphthalen-2-yl group, 1-anthryl group, 2-methylanthracen-1-yl group, 3-methylanthracen-1-yl group 4-methylanthracen-1-yl group, 9-methylanthracen-1-yl group, 10-methylanthracen-1-yl group, 2-phenylanthracen-1-yl group, 3-phenylanthracen-1-yl group 4-phenylanthracen-1-yl group, 5-phenylanthracen-1-yl group, 6-phenylanthracen-1-yl group, 7-pheny Anthracen-1-yl group, 8-phenylanthracen-1-yl group, 9-phenylanthracen-1-yl group, 10-phenylanthracen-1-yl group, 2-anthryl group, 1-methylanthracen-2-yl Group, 3-methylanthracen-2-yl group, 4-methylanthracen-2-yl group, 9-methylanthracen-2-yl group, 10-methylanthracen-2-yl group, 1-phenylanthracen-2-yl group Group, 3-phenylanthracen-2-yl group, 4-phenylanthracen-2-yl group, 5-phenylanthracen-2-yl group, 6-phenylanthracen-2-yl group, 7-phenylanthracen-2-yl group Group, 8-phenylanthracen-2-yl group, 9-phenylanthracen-2-yl group, 10-phenylant Rasen-2-yl, 9-anthryl, 2-methylanthracen-9-yl, 3-methylanthracen-9-yl, 4-methylanthracen-9-yl, 10-methylanthracen-9-yl Group, 1-phenylanthracen-9-yl group, 2-phenylanthracen-9-yl group, 3-phenylanthracen-9-yl group, 4-phenylanthracen-9-yl group, 10-phenylanthracen-9-yl group Group, 1-phenanthryl group, 2-phenylphenanthren-1-yl group, 3-phenylphenanthren-1-yl group, 4-phenylphenanthren-1-yl group, 9-phenylphenanthren-1-yl group, 2-fentolyl 1-phenylphenanthren-2-yl group, 3-phenylphenanthren-2-yl group, 4-phenyl Ruphenanthren-2-yl group, 9-phenylphenanthren-2-yl group, 3-phenanthryl group, 1-phenylphenanthren-3-yl group, 2-phenylphenanthren-3-yl group, 4-phenylphenanthrene-3- Yl group, 9-phenylphenanthrene-3-yl group, 4-phenanthryl group, 1-phenylphenanthrene-4-yl group, 2-phenyl-4-phenanthryl group, 3-phenyl-4-phenanthryl group, 9-phenylphenanthrene -4-yl group, 9-phenanthryl group, 1-phenylphenanthren-9-yl group, 2-phenylphenanthren-9-yl group, 3-phenylphenanthren-9-yl group, 4-phenylphenanthren-9-yl group 1-pyrenyl group, 6-phenylpyren-1-yl group, 7-phenyl group Rupyren-1-yl group, 8-phenylpyren-1-yl group, 2-pyrenyl group, 6-phenylpyren-2-yl group, 7-phenylpyren-2-yl group, 1-triphenylenyl group, 2-triphenylenyl 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-dimethylbenzo [a] fluoren-3-yl group, 9,9-dimethylbenzo [a] fluoren-4-yl group, 9,9-dimethylbenzo [a] fluoren-5-yl group, 9,9-dimethylbenzo [a] fluoren-6-yl group, 9,9-dimethylbenzo [a] fluoren-7-yl group, 9,9-dimethylbenzo [a] fluoren-8-yl group, 9-dimethylbenzo [b] fluoren-1-yl group, 9,9-dimethylbenzo [b] fluoren-4-yl group, 9,9-dimethylbenzo [b] fluoren-5-yl group, 9,9- Dimethylbenzo [b] fluoren-6-yl group, 9,9-dimethylbenzo [b] fluoren-7-yl group, 9,9-dimethylbenzo [b] fluoren-8-yl group, 9,9-dimethylbenzo [C] fluoren-1-yl group, 9,9-dimethylbenzo [c] fluoren-2-yl group, 9,9-dimethylbenzo [c] fluoren-5-yl group, 9,9-dimethylbenzo [c ] Fluorene-6 Yl group, 9,9-dimethylbenzo [c] fluoren-7-yl group, 9,9-dimethylbenzo [c] fluoren-8-yl group, 9,9-diphenylbenzo [a] fluoren-3-yl group 9,9-diphenylbenzo [a] fluoren-4-yl group, 9,9-diphenylbenzo [a] fluoren-5-yl group, 9,9-diphenylbenzo [a] fluoren-6-yl group, 9 , 9-diphenylbenzo [a] fluoren-7-yl group, 9,9-diphenylbenzo [a] fluoren-8-yl group, 9,9-diphenylbenzo [b] fluoren-1-yl group, 9,9 -Diphenylbenzo [b] fluoren-4-yl group, 9,9-diphenylbenzo [b] fluoren-5-yl group, 9,9-diphenylbenzo [b] fluoren-6-yl group, 9,9-diph Nylbenzo [b] fluoren-7-yl group, 9,9-diphenylbenzo [b] fluoren-8-yl group, 9,9-diphenylbenzo [c] fluoren-1-yl group, 9,9-diphenylbenzo [ c] Fluoren-2-yl group, 9,9-diphenylbenzo [c] fluoren-5-yl group, 9,9-diphenylbenzo [c] fluoren-6-yl group, 9,9-diphenylbenzo [c] Examples thereof include a fluoren-7-yl group and a 9,9-diphenylbenzo [c] fluoren-8-yl group.

In view of good performance of the organic electroluminescence device, 9,9-dimethylfluoren-2-yl group, 1-naphthyl group, 2-naphthyl group, 1-pyrenyl group, 2-phenanthrenyl group, 9-phenanthrenyl group, 9, A 9-dimethylbenzo [c] fluoren-2-yl group and a 9-anthryl group are preferable, and a 9,9-dimethylfluoren-2-yl group, a 1-naphthyl group, and a 9-phenanthrenyl group are more preferable in terms of easy synthesis. preferable.

In the compound (1), Ar ² , Ar ³ and Ar ⁴ each independently represent a nitrogen-containing heteroaromatic group which may be substituted with an alkyl group or a hydrogen atom. However, at least one of Ar ² , Ar ³ and Ar ⁴ is a nitrogen-containing heteroaromatic group which may be substituted with an alkyl group. Ar ² , Ar ³ and Ar ⁴ are preferably a pyridyl group or a hydrogen atom which may be substituted with an alkyl group, from the viewpoint of good performance as a material for an organic electroluminescence device. More preferably, Ar ³ is a pyridyl group, and Ar ² and Ar ⁴ are hydrogen atoms.

Specific examples of Ar ² , Ar ^3, and Ar ⁴ will be given below, but are not limited thereto.
Examples of the nitrogen-containing heteroaromatic group which may be substituted with an alkyl group include 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 2-methylpyridin-3-yl group, 2-methylpyridine-4- Yl group, 2-methylpyridin-5-yl group, 2-methylpyridin-6-yl group, 3-methylpyridin-2-yl group, 3-methylpyridin-4-yl group, 3-methylpyridin-5- Yl group, 3-methylpyridin-6-yl group, 4-methylpyridin-2-yl group, 4-methylpyridin-3-yl group, 2,6-dimethylpyridin-3-yl group, 2,6-dimethyl group Pyridin-4-yl group, 3,6-dimethylpyridin-2-yl group, 3,6-dimethylpyridin-4-yl group, 3,6-dimethylpyridin-5-yl group, 2-pyrimidyl group, 4- Pyrimidyl group, 5-pyrimid Group, 2-methylpyrimidin-4-yl group, 2-methylpyrimidin-5-yl group, 4-methylpyrimidin-2-yl group, 4-methylpyrimidin-5-yl group, 4-methylpyrimidin-6- Yl group, 5-methylpyrimidin-2-yl group, 5-methylpyrimidin-4-yl group, 2,4-dimethylpyrimidin-6-yl group, 4,6-dimethylpyrimidin-2-yl group, 2-pyrazyl Group, 2-methylpyrazin-3-yl group, 2-methylpyrazin-5-yl group, 2-methylpyrazin-6-yl group, 2,6-dimethylpyrazin-3-yl group and the like.

2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 3-methylpyridin-6-yl group, 2-methylpyridin-5-yl group, 2-pyrimidyl group because of its good performance as an organic electroluminescent device material Group, 5-pyrimidyl group and 2-pyrazyl group are preferred. From the viewpoint of easy synthesis, 2-pyridyl group, 3-pyridyl group, 3-methylpyridin-6-yl group and 2-methylpyridin-5-yl group are more preferable.

In the compound (1), X represents a single bond, a phenylene group that may be substituted with an alkyl group, a naphthylene group that may be substituted with an alkyl group, or a divalent nitrogen-containing group that may be substituted with an alkyl group. Represents a heteroaromatic substituent. Examples of the divalent nitrogen-containing heteroaromatic group include, but are not limited to, a pyridylene group, a pyrimidylene group, a pyrazylene group, and a pyridazylene group. Among these, X is preferably a single bond, a phenylene group, a pyridylene group or a pyrimidylene group from the viewpoint of good performance as a material for an organic electroluminescent element.

The alkyl group as a substituent is preferably an alkyl group having 1 to 6 carbon atoms, specifically, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, 1-methylpropyl group, tert-butyl. Group, pentan-1-yl group, 3-methylbutyl, 2,2-dimethylpropyl group, hexane-1-yl group and the like, but are not limited thereto.

When X is a 1,3-phenylene group, Ar ¹ is not the same as either Ar ² or Ar ⁴ . When X is a 1,4-phenylene group, Ar ¹ is not the same as Ar ³ .
In the compound (1), each hydrogen atom may be independently a deuterium atom.

Examples of the compound (1) include the following (A1) to (A88), but the present invention is not limited to these.

The compound represented by the general formula (3) (hereinafter sometimes referred to as “compound (3)”) is prepared using, for example, the method disclosed in JP-A-2008-280330 [0061] to [0076]. Can be manufactured.
Examples of compound (3) include (B1) to (B96) below, but are not limited thereto. Here, M ¹ represents a metal group or a heteroatom group.

The compound represented by the general formula (4) (hereinafter sometimes referred to as “compound (4)”) is prepared using, for example, the method disclosed in JP-A-2008-280330 [0061] to [0076]. Can be manufactured.
Examples of the compound (4) include (C1) to (C27) below, but are not limited thereto. Incidentally, M ² here represents a metal group or a hetero atom group.

Next, a method for producing the 1,2,4,5-substituted phenyl derivative of the present invention will be described.
The 1,2,4,5-substituted phenyl derivative (1) can be produced by “Step 1” shown by the following reaction formula.

In the general formulas (1), (2), and (3), Ar ¹ may be substituted with a nitrogen-containing heteroaromatic group that may be substituted with a phenyl group or an alkyl group, a phenyl group, or an alkyl group. It represents a phenyl group, or a 2- to 4-ring hydrocarbon group which may be substituted with a phenyl group or an alkyl group. X represents a single bond, a phenylene group that may be substituted with an alkyl group, a naphthylene group that may be substituted with an alkyl group, or a divalent nitrogen-containing heteroaromatic group that may be substituted with an alkyl group. . Ar ² , Ar ³ and Ar ⁴ each independently represent a nitrogen-containing heteroaromatic group which may be substituted with an alkyl group or a hydrogen atom. However, at least one of Ar ² , Ar ³ and Ar ⁴ represents a nitrogen-containing heteroaromatic group which may be substituted with an alkyl group. When X is a 1,3-phenylene group, Ar ¹ is not the same as Ar ² and Ar ⁴ . When X is a 1,4-phenylene group, Ar ¹ is not the same as Ar ³ . Z ¹ represents a leaving group. M ¹ represents a metal group or a hetero atom group.

In “Step 1”, the compound represented by the general formula (2) (hereinafter sometimes referred to as the compound (2)) is reacted with the compound (3) in the presence of a metal catalyst in the presence of a base. This is a method for obtaining the 1,2,4,5-substituted phenyl derivative of the present invention. In this reaction, the target product can be obtained in high yield by applying reaction conditions of general coupling reactions such as Suzuki-Miyaura reaction, Negishi reaction, Tamao-Kumada reaction, Stille reaction and the like.

The leaving group represented by Z ¹ in the compound (2) includes a chlorine group, a bromine group, an iodine group, a trifluoromethylsulfonyloxy group, a methanesulfonyloxy group, a chloromethanesulfonyloxy group, and a p-toluenesulfonyloxy group. Etc.

Examples of the metal group or heteroatom group represented by M ¹ in the compound (3) include ZnR ¹ , MgR ² , Sn (R ³ ) ₃ , B (OR ⁴ ) _{2 and the} like. However, R < ¹ > and R < ² > represents a chlorine atom, a bromine atom, or an iodine atom each independently, R < ³ > represents a C1-C4 alkyl group or a phenyl group, R < ⁴ > is a hydrogen atom, carbon number 1 It represents an alkyl group or a phenyl group 4, B ^(oR ₄₎ 2 two ^{R 4} ₂ may be the same or different. Further, two R ⁴ may form a ring containing an oxygen atom and a boron atom together.

Examples of B (OR ⁴ ) ₂ in the compound (3) include B (OH) ₂ , B (OMe) ₂ , B (O ⁱ Pr) ₂ , B (OBu) ₂ , B (OPh) _{2 and the} like. In addition, as an example of B (OR ⁴ ) ₂ in the case where two R ⁴ are united to form a ring containing an oxygen atom and a boron atom, groups represented by the following (D1) to (D6) are: The group represented by (D2) is preferable because it can be exemplified and the yield is good.

Examples of the metal catalyst that can be used in “Step 1” include a palladium catalyst and a nickel catalyst.
Examples of the palladium catalyst that can be used in “Step 1” include salts of palladium chloride, palladium acetate, palladium trifluoroacetate, palladium nitrate, and the like. Furthermore, π-allyl palladium chloride dimer, palladium acetylacetonate, tris (dibenzylideneacetone) dipalladium, dichlorobis (triphenylphosphine) palladium, tetrakis (triphenylphosphine) palladium and dichloro (1,1′-bis (diphenylphosphine). Examples include complex compounds such as fino) ferrocene) palladium. Among these, a palladium complex having a tertiary phosphine as a ligand is preferable in terms of a good reaction yield.

A palladium complex having tertiary phosphine as a ligand can also be prepared in a reaction system by adding tertiary phosphine to a palladium salt or complex compound. The tertiary phosphine that can be used at this time is 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) Erocene, tri (2-furyl) phosphine, tri (o-tolyl) phosphine, tris (2,5-xylyl) phosphine, (±) -2,2′-bis (diphenylphosphino) -1,1′-binaphthyl 2-dicyclohexylphosphino-2 ′, 4 ′, 6′-triisopropylbiphenyl, 2-dicyclohexylphosphino-2 ′, 6′-dimethoxybiphenyl and the like. 2-dicyclohexylphosphino-2 ', 4', 6'-triisopropylbiphenyl is preferred because it is readily available and the reaction yield is good.

The molar ratio of the tertiary phosphine to the palladium salt or complex compound is preferably 1:10 to 10: 1, and more preferably 1: 2 to 5: 1 from the viewpoint of good reaction yield.

Specific examples of nickel catalysts that can be used in “Step 1” include [1,1′bis (diphenylphosphino) ferrocene] nickel (II) dichloride, [1,2-bis (diphenylphosphino) ethane]. Nickel (II) dichloride, [1,3-bis (diphenylphosphino) propane] nickel (II) dichloride, [1,1′bis (diphenylphosphino) propane] nickel (II) dichloride, 1,2-bis ( Diphenylphosphino) ethane] nickel (II) dichloride, [1,3-bis (diphenylphosphino) propane] nickel (II) dichloride, and the like.

Examples of the base that can be used in “Step 1” include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate, cesium carbonate, tripotassium phosphate, sodium phosphate, sodium fluoride, potassium fluoride, Cesium fluoride and the like can be exemplified, and tripotassium phosphate is desirable in terms of a good yield.
The molar ratio of base to compound (3) is preferably from 1: 2 to 10: 1, and more preferably from 1: 1 to 3: 1 in terms of good yield.

The molar ratio of the compound (2) and the compound (3) used in “Step 1” is preferably 1: 2 to 1:10, and more preferably 1: 2 to 1: 4 in terms of a good yield.

Examples of the solvent that can be used in “Step 1” include water, dimethyl sulfoxide, dimethylformamide, tetrahydrofuran, dioxane, toluene, benzene, diethyl ether, ethanol, methanol, and xylene, and these may be used in appropriate combination. . It is desirable to use a mixed solvent of dioxane and water in terms of good yield.

“Step 1” can be performed at a temperature appropriately selected from 0 ° C. to 150 ° C., and is more preferably performed at 80 ° C. to 100 ° C. in terms of a good yield.
Compound (1) can be obtained by carrying out a normal treatment after completion of “Step 1”. If necessary, it may be purified by recrystallization, column chromatography or sublimation.

Next, in the production method of the 1,2,4,5-substituted phenyl derivative (1), the production method of the compound (2) used as the raw material of “Step 1” will be described.
Compound (2) can be produced by “Step 2” shown in the following reaction formula.

In the general formulas (2), (4), and (5), Z ¹ and Z ² each independently represent a leaving group. However, ^{Z 1} and ^{Z 2} are not the same. M ² represents a metal group or a hetero atom group. Ar ² , Ar ³ and Ar ⁴ each independently represent a nitrogen-containing heteroaromatic group which may be substituted with an alkyl group or a hydrogen atom. However, at least one of Ar ² , Ar ³ and Ar ⁴ represents a nitrogen-containing heteroaromatic group which may be substituted with an alkyl group.

“Step 2” is a reaction of a compound represented by the general formula (5) (hereinafter sometimes referred to as “compound (5)”) with a compound (4) in the presence of a metal catalyst in the presence of a base. This is a method for obtaining the compound (2) used in the production of the compound (1), and applies reaction conditions of general coupling reactions such as Suzuki-Miyaura reaction, Negishi reaction, Tamao-Kumada reaction, Stille reaction, etc. As a result, the target product can be obtained with good yield.

Examples of the metal group or heteroatom group represented by M ² in the compound (4) include ZnR ¹ , MgR ² , Sn (R ³ ) ₃ , B (OR ⁴ ) _{2 and the} like. However, R < ¹ > and R < ² > represents a chlorine atom, a bromine atom, or an iodine atom each independently, R < ³ > represents a C1-C4 alkyl group or a phenyl group, R < ⁴ > is a hydrogen atom, carbon number 1 represents an alkyl group or phenyl group having 4, B ^(oR ₄₎ 2 two ^{R 4} ₂ may be the same or different from each other. Further, two R ⁴ may form a ring containing an oxygen atom and a boron atom together.

B (OR ⁴ ) ₂ in the compound (4) is preferably a group represented by the above (D2) in terms of a good yield.

Examples of the leaving group represented by Z ¹ and Z ² in the compound (5) include a chlorine group, a bromine group, an iodine group, a trifluoromethylsulfonyloxy group, a methanesulfonyloxy group, a chloromethanesulfonyloxy group, and p-toluene. A sulfonyloxy group etc. can be mentioned. Examples of compound (5) include the following (E1) to (E5), but the present invention is not limited thereto.

As the metal catalyst that can be used in “Step 2”, the same palladium catalyst or nickel catalyst as exemplified in “Step 1” can be exemplified. Among them, a palladium complex having triphenylphosphine as a ligand is particularly preferable because it is easily available and the reaction yield is good.

The palladium complex having tertiary phosphine as a ligand can be prepared in a reaction system by adding tertiary phosphine to a palladium salt or complex compound. Examples of the tertiary phosphine that can be used at this time include the same tertiary phosphines as exemplified in “Step 1”. Triphenylphosphine is preferable because it is easily available and the reaction yield is good. The molar ratio of the tertiary phosphine to the palladium salt or complex compound is preferably 1:10 to 10: 1, and more preferably 1: 2 to 5: 1 in terms of good reaction yield.

As the base that can be used in “Step 2”, the same bases as those exemplified in “Step 1” can be exemplified, and sodium carbonate is desirable in terms of good yield. The molar ratio of base to compound (4) is preferably from 1: 1 to 10: 1, and preferably from 2: 1 to 5: 1 in terms of good yield.

Examples of the solvent that can be used in “Step 2” include water, dimethyl sulfoxide, dimethylformamide, tetrahydrofuran, dioxane, toluene, benzene, diethyl ether, ethanol, methanol, and xylene, and these may be used in appropriate combination. . It is desirable to use a mixed solvent of tetrahydrofuran and water in terms of a good yield.

“Step 2” can be performed at a temperature appropriately selected from 0 ° C. to 150 ° C., and is more preferably performed at 50 ° C. to 60 ° C. in terms of a good yield.

Compound (2) is obtained by performing a normal treatment after completion of “Step 1”. If necessary, it may be purified by recrystallization, column chromatography, sublimation or the like, but it can also be subjected to “Step 1” without isolation.

Although there is no particular limitation on the method for producing an organic electroluminescent device containing the 1,2,4,5-substituted phenyl derivative (1) of the present invention as a constituent component, film formation by vacuum vapor deposition is possible. Film formation by the vacuum evaporation method can be performed by using a general-purpose vacuum evaporation apparatus. The vacuum degree of the vacuum chamber when forming a film by the vacuum evaporation method is reached by a diffusion pump, a turbo molecular pump, a cryopump, etc. that are generally used in consideration of the manufacturing tact time and manufacturing cost of manufacturing the organic electroluminescence device. It is preferably about 1 × 10 ⁻² to 1 × 10 ⁻⁵ Pa. The deposition rate is preferably 0.005 to 1.0 nm / sec depending on the thickness of the film to be formed.

In addition, the 1,2,4,5-substituted phenyl derivative of the present invention can be formed by a spin coat method, an ink jet method, a cast method, a dip method or the like using a general-purpose apparatus.

Hereinafter, the present invention will be described in more detail with reference to experimental examples and test examples, but the present invention is not limited thereto.

Example-1

Tf: trifluoromethanesulfonyl

Under an argon stream, 4,6-dichloro-1,3-dihydroxybenzene (2.00 g, 11.2 mmol) and pyridine (3.53 g, 44.7 mmol) were dissolved in 11.2 mL of dichloromethane and cooled to 0 ° C. Thereafter, 26.8 mL (26.8 mmol) of a solution obtained by diluting trifluoromethanesulfonic anhydride to 1M with dichloromethane was added dropwise over 20 minutes, followed by stirring at room temperature for 3 hours. Diethyl ether was added to the resulting reaction solution for dilution, and the mixture was washed with 1M hydrochloric acid, saturated aqueous sodium hydrogen carbonate solution, and saturated brine. The obtained organic layer was concentrated and dried to obtain the target 1,3-dichloro-4,6-bis (trifluoromethanesulfonyloxy) benzene amber liquid (yield 4.2 g, yield 85%).
¹ H-NMR (CDCl ₃ ): δ. 7.73 (s, 1H), 7.39 (s, 1H).

Example-2

Under an argon stream, 5.69 g (12.8 mmol) of 1,3-dichloro-4,6-bis (trifluoromethanesulfonyloxy) benzene, 5.11 g (25.7 mmol) of 4- (2-pyridyl) phenylboronic acid, 270 mg (0.38 mmol) of dichlorobistriphenylphosphine palladium was dissolved in 193 mL of tetrahydrofuran, 38.5 mL (77.0 mmol) of 2M aqueous sodium carbonate solution was added, and the mixture was stirred for 29 hours with heating under reflux. After cooling to room temperature, the aqueous layer was removed, and the organic layer was concentrated to obtain a reaction crude. The resulting reaction crude product was purified by silica gel column chromatography (developing solvent: mixed solvent of chloroform and hexane) to obtain the desired 4 ′, 6′-dichloro-4,4 ″ -di (2-pyridyl) -1 , 1 ′: 3 ′, 1 ″ -Terphenyl yellowish white solid (yield 3.59 g, yield 62%) was obtained.

¹ H-NMR (CDCl ₃ ): δ. 7.25 (dd, J = 8.7, 4.7 Hz, 2H), 7.42 (s, 1H), 7.58 (d, J = 8.6 Hz, 4H), 7.64 (s, 1H) ), 7.77 (d, J = 3.5 Hz, 4H), 8.07 (d, J = 8.6 Hz, 4H), 8.71 (d, J = 4.7 Hz, 2H).

Example-3

Under an argon stream, 4 ', 6'-dichloro-4,4 "-di (2-pyridyl) -1,1': 3 ', 1" -terphenyl 3.00 g (6.62 mmol), 4, 4,4 ′, 4 ′, 5,5,5′5′-octamethyl-2,2-bi-1,3,2-dioxaborolane 6.72 g (26.5 mmol), trisdibenzylideneacetone palladium 121.2 mg ( 0.13 mmol), 2-dicyclohexylphosphino-2 ′, 4 ′, 6′-triisopropylbiphenyl 125.8 mg (0.26 mmol), potassium acetate 2.60 g (26.5 mmol), 150 mL of 1,4-dioxane And it melt | dissolved in the mixed solvent of 30 mL of water, and it stirred under heating-refluxing for 2 hours. After the reaction solution was concentrated, chloroform was added, and the organic layer and the aqueous layer were separated. The obtained organic layer was concentrated, and the resulting crude product was purified by silica gel chromatography (developing solvent: mixed solvent of chloroform and methanol) to obtain the desired 4′6′-bis (4, 4, 5, 5- Tetramethyl-1,3,2-dioxaborolan-2-yl) -4,4 ″ -di (2-pyridyl) -1,1 ′: 3 ′, 1 ″ -terphenyl (yield 1.60 g, yield) The rate was 38%).

¹ H-NMR (CDCl ₃ ): δ. 1.25 (s, 24H), 7.21 (ddd, J = 6.7, 5.0, 1.8 Hz, 2H), 7.47 (s, 1H), 7.54 (d, J = 8 .6 Hz, 4H), 7.72-7.78 (m, 4H), 8.01 (d, J = 8.4 Hz, 4H), 8.10 (s, 1H), 8.70 (d, J = 4.7 Hz, 2H).

Example-4

Under argon flow, 4 ′, 6′-dichloro-4,4 ″ -di (2-pyridyl) -1,1 ′: 0.7 ′ g (1.54 mmol) of 3 ′, 1 ″ -terphenyl, phenylboron 0.75 g (6.18 mmol) of acid, 10.4 mg (0.046 mmol) of palladium acetate, 44.1 mg (0.092 mmol) of 2-dicyclohexylphosphino-2 ′, 4 ′, 6′-triisopropylbiphenyl, cesium carbonate 4.02 (12.4 mmol) was dissolved in 30 mL of tetrahydrofuran, and the mixture was stirred for 26 minutes while heating under reflux. After cooling to room temperature, the reaction system was diluted with chloroform, and then the inorganic residue was removed by filtration. The obtained organic layer was concentrated and then purified by silica gel column chromatography (developing solvent: mixed solvent of chloroform and hexane) to obtain the target 4′-phenyl-4- (2-pyridyl) -5 ′-[4- A white solid (yield 0.69 g, yield 83%) of (2-pyridyl) phenyl] -1,1 ′: 2 ′, 1 ″ -terphenyl was obtained.

¹ H-NMR (CDCl ₃ ): δ. 7.20-7.27 (m, 12H), 7.35 (d, J = 8.4 Hz, 4H), 7.55 (s, 1H), 7.61 (s, 1H), 7.69- 7.75 (m, 4H), 7.89 (d, J = 8.5 Hz, 4H), 8.67 (d, J = 4.6 Hz, 2H).

Example-5

Under an argon stream, 4 ′, 6′-dichloro-4,4 ″ -di (2-pyridyl) -1,1 ′: 0.7 ′ g (1.54 mmol) of 3 ′, 1 ″ -terphenyl, 4- 1.22 g (6.18 mmol) of biphenylboronic acid, 10.4 mg (0.046 mmol) of palladium acetate, 44.1 mg (0.093 mmol) of 2-dicyclohexylphosphino-2 ′, 4 ′, 6′-triisopropylbiphenyl, Cesium carbonate 4.02g (12.4mmol) was melt | dissolved in 30 mL tetrahydrofuran, and it stirred for 24 hours under heating-refluxing. Subsequently, 5 mL of water was added, and the mixture was stirred for 24 hours with heating under reflux. After cooling to room temperature, the aqueous layer was removed and the organic layer was concentrated. The obtained crude product was purified by silica gel column chromatography (developing solvent: mixed solvent of chloroform and hexane) to obtain the desired 4 ″, 6 ″ -bis [4- (2-pyridyl) phenyl] -1, 1 ′: 4 ′, 1 ″: 3 ″, 1 ′ ″: 4 ′ ″, 1 ″ ″-kinkphenyl white solid (yield 0.62 g, yield 58%) was obtained.

¹ H-NMR (CDCl ₃ ): δ. 7.18-7.22 (m, 2H), 7.30 (t, J = 7.3 Hz, 2H), 7.35 (d, J = 8.5 Hz, 4H), 7.39 (t, J = 7.9 Hz, 4H), 7.40 (d, J = 8.6 Hz, 4H), 7.49 (d, J = 8.5 Hz, 4H), 7.58 (d, J = 7.0 Hz, 4H), 7.65 (s, 2H), 7.70-7.74 (m, 4H), 7.91 (d, J = 8.5 Hz, 4H), 8.66 (d, J = 4. 6Hz, 2H).

Example-6

Under argon flow, 4 ′, 6′-dichloro-4,4 ″ -di (2-pyridyl) -1,1 ′: 3 ′, 1 ″ -terphenyl 0.80 g (1.76 mmol), 9, 0.66 g (3.31 mmol) of 9-dimethylfluorene-2-boronic acid, 19.8 mg (0.088 mmol) of palladium acetate, 84.1 mg of 2-dicyclohexylphosphino-2 ′, 4 ′, 6′-triisopropylbiphenyl (0.18 mmol) and 1.94 g (9.17 mmol) of tripotassium phosphate were dissolved in a mixed solvent of 100 mL of dioxane and 15 mL of water and stirred for 26 hours under heating to reflux. After cooling to room temperature, the aqueous layer was removed and the organic layer was concentrated. The resulting crude product was purified by silica gel column chromatography (developing solvent: mixed solvent of chloroform and hexane) to obtain the desired 4 ′, 6′-bis (9,9-dimethylfluoren-2-yl) -4. , 4 ″ -di (2-pyridyl) -1,1 ′: 3 ′, 1 ″ -terphenyl was obtained as a white solid (yield 0.45 g, yield 33%).

¹ H-NMR (CDCl ₃ ): δ. 1.24 (s, 12H), 7.19 (t, J = 6.2 Hz, 4H), 7.25-7.38 (m, 12H), 7.62-7.70 (m, 9H), 7.77 (s, 1H), 7.87 (d, J = 8.5 Hz, 4H), 8.65 (d, J = 4.4 Hz, 2H).

Example-7

Under a stream of argon, 4 ′, 6′-dichloro-4,4 ″ -di (2-pyridyl) -1,1 ′: 1.00 g (2.21 mmol) of 3 ′, 1 ″ -terphenyl, 3- 1.08 g (8.82 mmol) of pyridineboronic acid, 24.8 mg (0.11 mmol) of palladium acetate, 105 mg (0.22 mmol) of 2-dicyclohexylphosphino-2 ′, 4 ′, 6′-triisopropylbiphenyl, phosphoric acid 3.74 g (17.6 mmol) of tripotassium was dissolved in a mixed solvent of 100 mL of toluene, 10 mL of ethanol and 10 mL of water, and the mixture was stirred for 24 hours while heating under reflux. After cooling to room temperature, the aqueous layer was removed and the organic layer was concentrated. The obtained crude product was purified by silica gel column chromatography (developing solvent: mixed solvent of chloroform and methanol) to obtain the desired 4,4 ″ -di (2-pyridyl) -4 ′, 6′-di (3 A white solid (yield 0.25 g, yield 21%) of -pyridyl) -1,1 ′: 3 ′, 1 ″ -terphenyl was obtained.

¹ H-NMR (CDCl ₃ ): δ. 7.20-7.27 (m, 4H), 7.33 (d, J = 8.5 Hz, 4H), 7.52 (s, 1H), 7.56 (d, J = 8.3 Hz, 2H) ), 7.68 (s, 1H), 7.72 (d, J = 7.8 Hz, 2H), 7.77 (t, J = 7.5 Hz, 2H), 7.93 (d, J = 8) .5 Hz, 4H), 8.49 (d, J = 5.0 Hz, 2H), 8.60 (s, 2H), 8.68 (d, J = 5.0 Hz, 2H).

Example-8

Under an argon stream, 4 ′, 6′-dichloro-4,4 ″ -di (2-pyridyl) -1,1 ′: 0.5 ′ g (1.10 mmol) of 3 ′, 1 ″ -terphenyl, 4- (3-Pyridyl) phenylboronic acid 0.66 g (3.31 mmol), palladium acetate 12.4 mg (0.055 mmol), 2-dicyclohexylphosphino-2 ′, 4 ′, 6′-triisopropylbiphenyl 52.6 mg ( 0.11 mmol) and 2.34 g (11.0 mmol) of tripotassium phosphate were dissolved in a mixed solvent of 30 mL of dioxane and 20 mL of water, and the mixture was stirred for 75 minutes while heating under reflux. After cooling to room temperature, the aqueous layer was removed and the organic layer was concentrated. The obtained crude product was recrystallized twice with toluene twice to obtain the desired 4- (2-pyridyl) -4 ″-(3-pyridyl) -4 ′-[4- (3-pyridyl) phenyl]- A brown solid of 5 ′-[4- (2-pyridyl) phenyl] -1,1 ′: 2 ′, 1 ″ -terphenyl was obtained (yield 0.27 g, yield 35%).

¹ H-NMR (CDCl ₃ ): δ. 7.18-7.22 (m, 2H), 7.32 (d, J = 7.9 Hz, 1H), 7.34 (d, J = 7.9 Hz, 1H), 7.39 (d, J = 8.5 Hz, 4H), 7.40 (d, J = 8.5 Hz, 4H), 7.49 (d, J = 8.5 Hz, 4H), 7.62 (s, 1H), 7.66. (S, 1H), 7.70-7.72 (m, 4H), 7.86 (d, J = 8.1 Hz, 2H), 7.92 (d, J = 8.5 Hz, 4H), 8 .55 (d, J = 4.9 Hz, 2H), 8.66 (d, J = 4.6 Hz, 2H), 8.84 (s, 2H).

Example-9

Under an argon stream, 4 ′, 6′-dichloro-4,4 ″ -di (2-pyridyl) -1,1 ′: 0.5 ′ g (1.10 mmol) of 3 ′, 1 ″ -terphenyl, 2- Phenylpyridin-5-ylboronic acid 0.66 g (3.31 mmol), palladium acetate 12.4 mg (0.055 mmol), 2-dicyclohexylphosphino-2 ′, 4 ′, 6′-triisopropylbiphenyl 52.6 mg (0 .11 mmol) and 2.34 g (11.0 mmol) of tripotassium phosphate were dissolved in a mixed solvent of 15 mL of dioxane and 10 mL of water, and the mixture was stirred for 91 minutes while heating under reflux. After cooling to room temperature, the aqueous layer was removed and the organic layer was concentrated. The obtained crude product was recrystallized twice with toluene twice to obtain the desired 4 ′, 6′-bis (2-phenylpyridin-5-yl) -4,4 ″ -di (2-pyridyl) -1 , 1 ′: 3 ′, 1 ″ -terphenyl gray solid (yield 0.22 g, 29% yield).

¹ H-NMR (CDCl ₃ ): δ. 7.21 (t, J = 5.6 Hz, 2H), 7.36-7.46 (m, 10H), 7.57-7.63 (m, 5H), 7.69-7.75 (m 5H), 7.93 (d, J = 8.3 Hz, 4H), 7.98 (d, J = 7.0 Hz, 4H), 8.66 (d, J = 4.6 Hz, 2H), 8 .68 (d, J = 1.4 Hz, 2H).

Example-10

Under a stream of argon, 4 ′, 6′-dichloro-4,4 ″ -di (2-pyridyl) -1,1 ′: 0.10 g (0.22 mmol) of 3 ′, 1 ″ -terphenyl, 2- [3,5-di (2-pyridyl) phenyl] -4,4,5,5-tetramethyl-1,3,2-dioxaborolane 0.24 g (0.66 mmol), palladium acetate 2.5 mg (0.011 mmol) ), 2-dicyclohexylphosphino-2 ′, 4 ′, 6′-triisopropylbiphenyl 11.0 mg (0.023 mmol), tripotassium phosphate 421 mg (1.99 mmol) in 11 mL of 1,4-dioxane and 2. It melt | dissolved in the mixed solvent of 5 mL of water, and stirred for 40 minutes under heating recirculation | reflux. After cooling to room temperature, the aqueous layer and the organic layer were separated, and the organic layer was concentrated. The obtained crude product was purified by silica gel column chromatography (developing solvent: chloroform) to obtain the desired 3,5-di (2-pyridyl) -5 ′-{3,5-di (2-pyridyl) phenyl}. -4 ″-(2-pyridyl) -4 ′-{4- (2-pyridyl) phenyl} -1,1 ′: 2 ′, 1 ″ -terphenyl gray solid (yield 0.030 g, yield) 16%).

¹ H-NMR (CDCl ₃ ): δ. 7.14-7.20 (m, 6H), 7.49 (d, J = 8.5 Hz, 4H), 7.50 (d, J = 8.0 Hz, 4H), 7.59-7.71 (M, 8H), 7.72 (s, 1H), 7.92 (d, J = 7.5 Hz, 4H), 7.93 (s, 1H), 7.95 (d, J = 2.0 Hz) , 4H), 8.54 (t, J = 1.6 Hz, 2H), 8.63-8.66 (m, 6H).

Example-11

Under a stream of argon, 4′6′-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -4,4 ″ -di (2-pyridyl) -1, 1 ′: 3 ′, 1 ″ -terphenyl 0.30 g (0.47 mmol), palladium acetate 5.3 mg (0.024 mmol), 2-dicyclohexylphosphino-2 ′, 4 ′, 6′-triisopropylbiphenyl 22.5 mg (0.047 mmol), 2-chloro-5-phenylpyridine 0.21 g (1.13 mmol), tripotassium phosphate 0.48 (2.26 mmol) in 15 mL 1,4-dioxane and 4.5 mL After being dissolved in a mixed solvent of water, the mixture was stirred at 60 ° C. for 24 hours and at 95 ° C. for 3 hours. After cooling to 0 ° C., the precipitated solid is collected by filtration, and the obtained crude product is purified by recrystallization from toluene to obtain the desired 4 ′, 6′-bis (3-phenylpyridin-6-yl)- A gray solid of 4,4 ″ -di (2-pyridyl) -1,1 ′: 3 ′, 1 ″ -terphenyl was obtained (yield 0.069 g, yield 21%).

¹ H-NMR (CDCl ₃ ): δ. 7.11 (dd, J = 8.2, 0.9 Hz, 2H), 7.21 (t, J = 5.1 Hz, 2H), 7.36 (t, J = 7.3 Hz, 2H), 7 .42-7.46 (m, 8H), 7.58 (dd, J = 8.5, 1.4 Hz, 4H), 7.63 (dd, J = 8.3, 2.4 Hz, 2H), 7.66 (s, 1H), 7.72 (d, J = 4.2 Hz, 4H), 7.94 (d, J = 8.5 Hz, 4H), 8.21 (s, 1H), 8. 67 (d, J = 4.6 Hz, 2H), 8.89 (dd, J = 2.4, 0.8 Hz, 2H).

Example-12

Under a stream of argon, 4′6′-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -4,4 ″ -di (2-pyridyl) -1, 1 ′: 3 ′, 1 ″ -terphenyl 0.39 g (0.61 mmol), tetrakis (triphenylphosphine) palladium 2.8 mg (0.024 mmol), 2-chloro-5-phenylpyrimidine 0.35 g (1 .82 mmol) was dissolved in 8 mL of N, N-dimethylformamide, and 1.82 mL (3.64 mmol) of a tripotassium phosphate aqueous solution adjusted to 2 M was added. The resulting mixture was heated to 100 ° C. and stirred for 12 hours. After cooling to room temperature, 15 mL of water and 15 mL of methanol were added and cooled to 0 ° C. The precipitated solid was collected by filtration, and the obtained crude product was purified by recrystallization from toluene to obtain the desired 4′6′-bis (5-phenylpyrimidin-2-yl) -4,4 ″ -di A gray solid (yield 0.28 g, 67% yield) of (2-pyridyl) -1,1 ′: 3 ′, 1 ″ -terphenyl was obtained.

¹ H-NMR (CDCl ₃ ): δ. 7.18-7.22 (m, 2H), 7.40-7.44 (m, 6H), 7.48 (t, J = 7.4 Hz, 4H), 7.57 (d, J = 7 0 Hz, 4H), 7.72-7.74 (m, 5H), 7.94 (d, J = 8.6 Hz, 4H), 8.57 (s, 1H), 8.66 (d, J = 4.6 Hz, 2H), 8.88 (s, 4H).

Test example-1
The organic material used for device fabrication was used after sublimation purification. As the substrate, a glass substrate with an ITO transparent electrode in which an indium-tin oxide (ITO) film having a width of 2 mm was patterned in a stripe shape was used. The substrate was cleaned with isopropyl alcohol and then surface treated by ozone ultraviolet cleaning. Each layer was vacuum-deposited on the cleaned substrate by a vacuum deposition method, and an organic electroluminescence device having a light-emitting area of 4 mm ² having a multilayer structure shown in FIG. 1 was produced.

First, the glass substrate was introduced into a vacuum evaporation tank, and the pressure was reduced to 1.0 × 10 ⁻⁴ Pa. Thereafter, a hole injection layer 2, a hole transport layer 3, a light emitting layer 4 and an electron transport layer 5 are sequentially formed on the glass substrate as an organic compound layer shown in FIG. A film was formed. As the hole injection layer 2, sublimation-purified phthalocyanine copper (II) was vacuum-deposited with a film thickness of 25 nm. As the hole transport layer 3, N, N′-di (1-naphthyl) -N, N′-diphenylbenzidine (NPD) was vacuum-deposited with a film thickness of 45 nm. As the light emitting layer 4, 2-tert-butyl-9,10-di (2-naphthyl) anthracene (TBADN) and 4,4′-bis [4- (di-p-tolylamino) phenylethen-1-yl] Biphenyl (DPAVBi) was vacuum-deposited at a film thickness of 40 nm at a ratio of 97: 3 (% by mass). As the electron transport layer 5, 4′-phenyl-4- (2-pyridyl) -5 ′-[4- (2-pyridyl) phenyl] -1,1 ′: 2 ′, 1 synthesized in Example-4 was used. '' -Terphenyl was vacuum deposited with a film thickness of 20 nm.

Each organic material was formed into a film by a resistance heating method, and the heated compound was vacuum-deposited at a film formation rate of 0.3 to 0.5 nm / second. Finally, a metal mask is disposed so as to be orthogonal to the ITO stripe, and the cathode layer 6 is formed. The cathode layer 6 was made into a two-layer structure by vacuum deposition of lithium fluoride and aluminum with a thickness of 1.0 nm and 100 nm, respectively. Each film thickness was measured with a stylus type film thickness meter (DEKTAK).
Furthermore, this element was sealed in a nitrogen atmosphere glove box having an oxygen and moisture concentration of 1 ppm or less. For the sealing, a glass sealing cap and the above-described film-forming substrate epoxy type ultraviolet curable resin (manufactured by Nagase ChemteX Corporation) were used.

A direct current was applied to the produced organic electroluminescence device, and the light emission characteristics were evaluated using a luminance meter of LUMINANCE METER (BM-9) manufactured by TOPCON. As light emission characteristics, voltage (V), luminance (cd / m ² ), current efficiency (cd / A), and power efficiency (lm / W) when a current density of 20 mA / cm ² was passed were measured.
The measured values of the manufactured element were 6.15 V, 1792 cd / m ² , 8.96 cd / A, and 4.58 lm / W.

Comparative Example-1
Instead of the electron transport layer 5 of Test Example 1, it was prepared in the same manner as Test Example 1 except that the existing material Tris (8-quinolinolato) aluminum (III) (Alq) was vacuum-deposited with a film thickness of 20 nm. .
The measured values of the manufactured element were 6.44 V, 1664 cd / m ² , 8.32 cd / A, and 4.06 lm / W.

Test Example-2
Instead of the electron transport layer 5 of Test Example-1, 4 ″, 6 ″ -bis [4- (2-pyridyl) phenyl] -1,1 ′ synthesized in Example-5, 4 ′, 1 ′ ': 3 ″, 1 ′ ″: 4 ′ ″, 1 ″ ″ — Kink phenyl was prepared in the same manner as in Test Example 1 except that the film was vacuum-deposited with a thickness of 20 nm.
The measured values of the fabricated element were 5.76 V, 1818 cd / m ² , 9.09 cd / A, and 4.96 lm / W.

Test Example-3
Instead of the light-emitting layer 4 of Test Example 1, 2-tert-butyl-9,10-di (2-naphthyl) anthracene (TBADN) and 4,4′-bis [4- (di-p-tolylamino) phenyl Ethene-1-yl] biphenyl (DPAVBi) in a ratio of 93: 7 (mass%) to a thickness of 40 nm was used instead of the electron transport layer 5 of Test Example 1, and synthesized in Example 7 ″ -Di (2-pyridyl) -4 ′, 6′-di (3-pyridyl) -1,1 ′: tested except that 3 ′, 1 ″ -terphenyl was vacuum deposited to a thickness of 20 nm Prepared in the same manner as in Example-1.
The measured values of the fabricated element were 4.3 V, 2040 cd / m ² , 10.2 cd / A, and 7.49 lm / W. The luminance half time of this device was 192 hours.

Comparative Example-2
Instead of the electron transport layer 5 of Test Example 3, it was prepared in the same manner as Test Example 1 except that the existing material Tris (8-quinolinolato) aluminum (III) (Alq) was vacuum-deposited to a thickness of 20 nm. .
The measured values of the fabricated element were 5.7 V, 1985 cd / m ² , 9.93 cd / A, 5.48 lm / W. The luminance half time of this device was 578 hours.

Test Example-4
Instead of the electron transport layer 5 in Test Example 3, 4- (2-pyridyl) -4 ″-(3-pyridyl) -4 ′-[4- (3-pyridyl) phenyl synthesized in Example-8 ] -5 ′-[4- (2-pyridyl) phenyl] -1,1 ′: produced in the same manner as in Test Example 1 except that 2 ′, 1 ″ -terphenyl was vacuum-deposited to a thickness of 20 nm. did.
The measured values of the manufactured element were 4.1 V, 1993 cd / m ² , 9.97 cd / A, and 7.67 lm / W. The luminance half time of this device was 243 hours.

Test example-5
Instead of the electron transport layer 5 of Test Example 3, 4 ′, 6′-bis (2-phenylpyridin-5-yl) -4,4 ″ -di (2-pyridyl) synthesized in Example-9 -1,1 ′: 3 ′, 1 ″ -terphenyl was prepared in the same manner as in Test Example 1 except that vacuum deposition was performed with a film thickness of 20 nm.
The measured values of the fabricated element were 4.2 V, 2060 cd / m ² , 10.3 cd / A, and 7.72 lm / W. The luminance half time of this device was 218 hours.

The thin film comprising the 1,2,4,5-substituted phenyl derivative of the present invention has an amorphous property, heat resistance, electron transport ability, hole blocking ability, water resistance, oxygen resistance, electron injection characteristics, etc. It is useful as a material for a light emitting element, and can be used as an electron transport material, a hole blocking material, a light emitting host material, and the like. Furthermore, since the 1,2,4,5-substituted phenyl derivative (1) of the present invention has a wide band gap, it can be used not only for fluorescent elements but also for phosphorescent elements, and for improving conductivity and improving element lifetime. Thus, the present invention can be applied to a doping element to which an n-dopant is added.

Also, in the example of the present invention, high luminous efficiency and low driving power can be realized as a vapor deposition element. Thus, it can be used for lighting other than the panel. Furthermore, since it has solubility in organic solvents and high electron transport properties, it can be used for application to coating elements, flexible elements, organic transistors, organic thin-film solar cells, and the like.

Claims (8)

1. The following general formula (1)
   

   

   (In the formula, Ar ¹ is substituted with a nitrogen-containing heteroaromatic group which may be substituted with a phenyl group or an alkyl group, a phenyl group which may be substituted with a phenyl group or an alkyl group, or a phenyl group or an alkyl group. X represents a single bond, a phenylene group which may be substituted with an alkyl group, a naphthylene group which may be substituted with an alkyl group, or an alkyl group. A divalent nitrogen-containing heteroaromatic group which may be optionally substituted, Ar ² , Ar ³ and Ar ⁴ each independently represent a nitrogen-containing heteroaromatic group which may be substituted with an alkyl group or a hydrogen atom; , ^Ar 2, Ar ³ and at least one .X represents an alkyl group which may be substituted nitrogen-containing heterocyclic aromatic groups are 1,3-phenylene group among Ar ⁴ When, when Ar ¹ is not the same as Ar ² and Ar ⁴ .X is 1,4-phenylene group, Ar ¹ is not the same as Ar ^3. Further, each of the hydrogen atom in the formula are each independently A 1,2,4,5-substituted phenyl derivative represented by the following formula:
2. The ^{1, 2 according} to claim ^{1, wherein} Ar ¹ is a pyridyl group which may be substituted with an alkyl group, a phenyl group which may be substituted with an alkyl group, or a fluorenyl group which may be substituted with an alkyl group. , 4,5-substituted phenyl derivatives.
3. The 1,2,4,5-substituted phenyl derivative according to claim 1 or 2, wherein X is a single bond, a phenylene group, a pyridylene group or a pyrimidylene group.
4. The 1,2,4,5-substituted phenyl derivative according to any one of claims 1 to 3, wherein Ar ² , Ar ³ and Ar ⁴ are each independently a pyridyl group or a hydrogen atom which may be substituted with an alkyl group. .
5. The 1,2,4,5-substituted phenyl derivative according to any one of claims 1 to 4, wherein Ar ³ is a pyridyl group, and Ar ² and Ar ⁴ are hydrogen atoms.
6. The following general formula (2)
   

   

   (In the formula, Z ¹ represents a leaving group. Ar ² , Ar ³ and Ar ⁴ each independently represents a nitrogen-containing heteroaromatic group which may be substituted with an alkyl group, or a hydrogen atom, provided that Ar ² , Ar ³ and Ar ⁴ represent a nitrogen-containing heteroaromatic group which may be substituted with an alkyl group, and X in the following general formula (3) is a 1,3-phenylene group And Ar ¹ is not the same as Ar ² and Ar ⁴ and when X is a 1,4-phenylene group, Ar ¹ is not the same as Ar ^3. Each hydrogen atom in the formula is independently deuterium And a compound represented by the following general formula (3):
   

   

   (In the formula, Ar ¹ is substituted with a nitrogen-containing heteroaromatic group which may be substituted with a phenyl group or an alkyl group, a phenyl group which may be substituted with a phenyl group or an alkyl group, or a phenyl group or an alkyl group. X represents a single bond, a phenylene group which may be substituted with an alkyl group, a naphthylene group which may be substituted with an alkyl group, or an alkyl group. Represents a divalent nitrogen-containing heteroaromatic group which may be substituted, M ¹ represents a metal group or a heteroatom group, and each hydrogen atom in the formula may independently be a deuterium atom. And a compound represented by the following general formula (1), wherein the compound is subjected to a coupling reaction in the presence or absence of a base in the presence of a metal catalyst.
   

   

   (In the formula, Ar ¹ is substituted with a nitrogen-containing heteroaromatic group which may be substituted with a phenyl group or an alkyl group, a phenyl group which may be substituted with a phenyl group or an alkyl group, or a phenyl group or an alkyl group. X represents a single bond, a phenylene group which may be substituted with an alkyl group, a naphthylene group which may be substituted with an alkyl group, or an alkyl group. A divalent nitrogen-containing heteroaromatic group which may be optionally substituted, Ar ² , Ar ³ and Ar ⁴ each independently represent a nitrogen-containing heteroaromatic group which may be substituted with an alkyl group or a hydrogen atom; , ^Ar 2, Ar ³ and at least one .X represents an alkyl group which may be substituted nitrogen-containing heterocyclic aromatic groups are 1,3-phenylene group among Ar ⁴ When, when Ar ¹ is not the same as Ar ² and Ar ⁴ .X is 1,4-phenylene group, Ar ¹ is not the same as Ar ^3. Further, each of the hydrogen atom in the formula are each independently A method of producing a 1,2,4,5-substituted phenyl derivative represented by the following formula:
7. The following general formula (2)
   

   

   (In the formula, Z ¹ represents a leaving group. Ar ² , Ar ³ and Ar ⁴ each independently represents a nitrogen-containing heteroaromatic group which may be substituted with an alkyl group, or a hydrogen atom, provided that Ar ² , Ar ³ and Ar ⁴ represent a nitrogen-containing heteroaromatic group which may be substituted with an alkyl group, and when X in the general formula (3) is a 1,3-phenylene group , Ar ¹ is not the same as Ar ² and Ar ^4, and when X is a 1,4-phenylene group, Ar ¹ is not the same as Ar ^3. Each hydrogen atom in the formula is independently a deuterium atom. Or a compound represented by the following general formula (4):
   

   

   (Ar ² , Ar ³ and Ar ⁴ each independently represent a nitrogen-containing heteroaromatic group which may be substituted with an alkyl group or a hydrogen atom, provided that at least one of Ar ² , Ar ³ and Ar ⁴ is Represents a nitrogen-containing heteroaromatic group which may be substituted with an alkyl group, and when X in the general formula (3) is a 1,3-phenylene group, Ar ¹ is the same as Ar ² and Ar ⁴ And when X is a 1,4-phenylene group, Ar ¹ is not the same as Ar ^3. M ² represents a metal group or a heteroatom group, and each hydrogen atom in the formula is independently A deuterium atom)) and the following general formula (5)
   

   

   (Wherein Z ¹ and Z ² each independently represent a leaving group, provided that Z ¹ and Z ² are not the same), a metal catalyst in the presence or absence of a base The method for producing a 1,2,4,5-substituted phenyl derivative according to claim 6, wherein the production is carried out by a coupling reaction in the presence of.
8. The following general formula (1)
   

   

   (In the formula, Ar ¹ is substituted with a nitrogen-containing heteroaromatic group which may be substituted with a phenyl group or an alkyl group, a phenyl group which may be substituted with a phenyl group or an alkyl group, or a phenyl group or an alkyl group. X represents a single bond, a phenylene group which may be substituted with an alkyl group, a naphthylene group which may be substituted with an alkyl group, or an alkyl group. A divalent nitrogen-containing heteroaromatic group which may be optionally substituted, Ar ² , Ar ³ and Ar ⁴ each independently represent a nitrogen-containing heteroaromatic group which may be substituted with an alkyl group or a hydrogen atom; , ^Ar 2, Ar ³ and at least one .X represents an alkyl group which may be substituted nitrogen-containing heterocyclic aromatic groups are 1,3-phenylene group among Ar ⁴ When, when Ar ¹ is not the same as Ar ² and Ar ⁴ .X is 1,4-phenylene group, Ar ¹ is not the same as Ar ^3. Further, each of the hydrogen atom in the formula are each independently An organic electroluminescent device comprising a 1,2,4,5-substituted phenyl derivative represented by the formula:

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