KR101968353B1 - 1, 2, 4, 5-substituted phenyl derivative, production method for same, and organic electroluminescent element - Google Patents

Abstract

식 중, Ar¹은 질소 함유 헤테로방향족기, 페닐기 또는 2 내지 4환의 탄화수소기이며, 이들 기는 페닐기 혹은 알킬기로 치환되어 있어도 된다. X는, 단결합, 페닐렌기, 나프틸렌기 또는 2가의 질소 함유 헤테로방향족기로서, 이들 기는, 알킬기로 치환되어 있어도 된다. Ar², Ar³ 및 Ar⁴ 중 적어도 1개는 알킬기로 치환되어 있어도 되는 질소 함유 헤테로방향족기이며, 나머지는 수소 원자이다. X가 1,3-페닐렌기일 때, Ar¹은 Ar² 및 Ar⁴와 동일하지 않고, 또한, X가 1,4-페닐렌기일 때, Ar¹은 Ar³과 동일하지 않다. 일반식 1 중의 수소 원자는 각각 독립적으로 중수소 원자이어도 된다. 이 1,2,4,5-치환 페닐 유도체는 유기 전계 발광 소자의 구성 성분, 특히 전자 수송층으로서 바람직하다.1,2,4,5-substituted phenyl derivatives represented by the following general formula 1:
[Formula 1]

In the formulas, Ar ¹ represents a nitrogen-containing heteroaromatic group, a phenyl group or a hydrocarbon group of 2 to 4 rings, and these groups may be substituted with a phenyl group or an alkyl group. X is a single bond, a phenylene group, a naphthylene group or a divalent nitrogen-containing heteroaromatic group, and these groups may be substituted with an alkyl group. 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, and the remainder is a hydrogen atom. When X 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 . The hydrogen atoms in the general formula (1) may be independently a deuterium atom. This 1,2,4,5-substituted phenyl derivative is preferable as a constituent component of an organic electroluminescent device, particularly an electron transporting layer.

Description

1, 2, 4, 5-SUBSTITUTED PHENYL DERIVATIVE, PRODUCTION METHOD FOR SAME, AND ORGANIC ELECTROLUMINESCENT ELEMENT,

The present invention relates to a 1,2,4,5-substituted phenyl derivative and a process for producing the same. The 1,2,4,5-substituted phenyl derivative of the present invention is characterized by having a substituent having a nitrogen-containing heteroaromatic group in any one of positions 1,2, 4, and 5 of benzene. This 1,2,4,5-substituted phenyl derivative has good charge-transporting properties and forms a stable thin film, and thus is useful as a component of a fluorescent or phosphorescent organic electroluminescent device.

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

The organic electroluminescent device is a device in which a light emitting layer containing a light emitting material is sandwiched between a hole transporting layer and an electron transporting layer and an anode and a cathode are adhered to the outside of the hole transporting layer and the electron transporting layer to excite excitons generated by recombination of holes and electrons injected into the light emitting layer (Fluorescence or phosphorescence) at the time of use, and has been applied to displays and the like.

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

As a 1,2,4,5-substituted phenyl derivative, an example of using a compound having a bipyridyl group introduced therein in an organic electroluminescent device (see Patent Document 2) is disclosed. In this derivative, the substituent is limited to a pyridyl group , And the 1,2,4,5-substituted phenyl derivatives of the present invention are not included.

Discloses an example in which a 1,2,4,5-substituted phenyl derivative is used in an organic electroluminescent device (see Patent Document 3). In this example, however, the ratio of 1,1 ': 4' Quot; and " 5 " positions of the compound of the present invention are different from the 1,2,4,5-substituted phenyl derivatives of the present invention. And the low power consumption / long life time required for the organic electroluminescent device are not disclosed, and the effect of the above compound is limited.

Further, there are examples using a derivative in which a phenyl group and a pyridyl group are combined in an organic electroluminescent device (for example, see Patent Documents 4 to 8). However, this derivative is not limited to the 1,2,4,5- The skeleton is different from that of the derivative, and the performance of the organic electroluminescent device is not sufficiently improved.

JP 2010-90085 A WO 2009-151039 A WO 2009-081873 A JP 2008-63232 A JP 2003-336043 A JP 2007-015993 A JP 2005-255986 A JP 2008-127326 A

Although organic electroluminescent devices are used in various display devices, it is required to achieve lower power consumption for use of organic electroluminescent devices in portable devices with limited power supply. In addition, at the same time, when commercial use of the organic electroluminescent device is performed, how to increase the device lifetime in order to obtain stable performance becomes a problem.

Particularly, with regard to an electron transporting material, a material having excellent charge injection and transport properties for driving a device at a low voltage to reduce consumption output and durability capable of longevity of a device can not be found in conventional compounds, New materials are being demanded.

It is an object of the present invention 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 a process for producing the 1,2,4,5-substituted phenyl derivative which is industrially advantageous.

It is still another object of the present invention to provide an organic electroluminescent device with excellent luminescence efficiency and high luminous efficiency.

 DISCLOSURE OF THE INVENTION The inventors of the present invention have conducted intensive investigations to solve the above problems. As a result, the present inventors have found that 1,2,4,5-substitution having a substituent having a nitrogen-containing heteroaromatic group in any one of 1, 2, The phenyl derivative has a wide energy gap and a high triplet energy required for use as a blue fluorescent element or a phosphorescent element and an organic electroluminescent element using the 1,2,4,5-substituted phenyl derivative as an electron transport layer , Has excellent properties such as dynamic and luminescent properties and high luminous efficiency, and has completed the present invention.

Namely, the present invention provides, in one aspect, a 1,2,4,5-substituted phenyl derivative represented by the following general formula 1:

[Formula 1]

In the formulas, Ar ¹ represents a phenyl group or a nitrogen-containing heteroaromatic group which may be substituted with an alkyl group, a phenyl group which may be substituted with a phenyl group or an alkyl group, or a hydrocarbon group which may be substituted with 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 a divalent nitrogen-containing heteroaromatic group which may be substituted with an alkyl group. Ar ² , Ar ³ and Ar ⁴ each independently represent a nitrogen-containing heteroaromatic group or a hydrogen atom which may be substituted with an alkyl group. Provided that 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 should not be the same as Ar ² and Ar ⁴ . When X is a 1,4-phenylene group, Ar ¹ should not be the same as Ar ³ . Each hydrogen atom in the formula may be independently a deuterium atom.

In another aspect, the present invention is characterized in that a compound represented by the following general formula 2 and a compound represented by the following general formula 3 are subjected to a coupling reaction in the presence or absence of a base in the presence of a metal catalyst Substituted phenyl derivatives represented by the following general formula (1): < EMI ID =

[Formula 2]

In the formulas, Z ¹ represents a leaving group. Ar ² , Ar ³ and Ar ⁴ each independently represent a nitrogen-containing heteroaromatic group or a hydrogen atom which may be substituted with an alkyl group. Provided that 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 in the following 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 Ar ³ . Each hydrogen atom in the formula may be independently a deuterium atom;

[Formula 3]

In the formulas, Ar ¹ represents a phenyl group or a nitrogen-containing heteroaromatic group which may be substituted with an alkyl group, a phenyl group which may be substituted with a phenyl group or an alkyl group, or a hydrocarbon group which may be substituted with 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 a divalent nitrogen-containing heteroaromatic group which may be substituted with an alkyl group. M ¹ represents a metal group or a heteroatom. Each hydrogen atom in the formula may be independently a deuterium atom;

[Formula 1]

In the formulas, Ar ¹ represents a phenyl group or a nitrogen-containing heteroaromatic group which may be substituted with an alkyl group, a phenyl group which may be substituted with a phenyl group or an alkyl group, or a hydrocarbon group which may be substituted with 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 a divalent nitrogen-containing heteroaromatic group which may be substituted with an alkyl group. Ar ² , Ar ³ and Ar ⁴ each independently represent a nitrogen-containing heteroaromatic group or a hydrogen atom which may be substituted with an alkyl group. Provided that 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 should not be the same as Ar ² and Ar ⁴ . When X is a 1,4-phenylene group, Ar ¹ should not be the same as Ar ³ . Each hydrogen atom in the formula may be independently a deuterium atom.

In another aspect, the present invention provides a compound represented by the following general formula (2), wherein the compound represented by the following general formula (4) and the compound represented by the following general formula (5) Substituted phenyl derivatives represented by the following general formula 1, wherein the 1,2,4,5-substituted phenyl derivatives are prepared by coupling reaction in the presence of a catalyst;

[Formula 2]

In the formulas, Z ¹ represents a leaving group. Ar ² , Ar ³ and Ar ⁴ each independently represent a nitrogen-containing heteroaromatic group or a hydrogen atom which may be substituted with an alkyl group. Provided that 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. Further, when the general formula X 3 is 1,3-phenylene of the date, Ar ¹ is not the same as Ar ² and Ar ^4, also, when X is 1,4-phenylene date, Ar ¹ is and Ar ³ It is not the same. Each hydrogen atom in the formula may be independently a deuterium atom;

[Formula 4]

In the formulas, Ar ² , Ar ³ and Ar ⁴ each independently represent a nitrogen-containing heteroaromatic group or a hydrogen atom which may be substituted with an alkyl group. Provided that 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. Further, when the general formula X 3 is 1,3-phenylene of the date, Ar ¹ is not the same as Ar ² and Ar ^4, also, when X is 1,4-phenylene date, Ar ¹ is and Ar ³ It is not the same. M ² represents a metal group or a heteroatom. Each hydrogen atom in the formula may be independently a deuterium atom;

[Formula 5]

Wherein Z ¹ and Z ² each independently represent a leaving group. Provided that Z < ¹ > and Z < ² >

[Formula 1]

In the formulas, Ar ¹ represents a phenyl group or a nitrogen-containing heteroaromatic group which may be substituted with an alkyl group, a phenyl group which may be substituted with a phenyl group or an alkyl group, or a hydrocarbon group which may be substituted with 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 a divalent nitrogen-containing heteroaromatic group which may be substituted with an alkyl group. Ar ² , Ar ³ and Ar ⁴ each independently represent a nitrogen-containing heteroaromatic group or a hydrogen atom which may be substituted with an alkyl group. Provided that 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 should not be the same as Ar ² and Ar ⁴ . When X is a 1,4-phenylene group, Ar ¹ should not be the same as Ar ³ . Each hydrogen atom in the formula may be independently a deuterium atom.

In still another aspect, the present invention provides an organic electroluminescent device comprising, as a constituent component, a 1,2,4,5-substituted phenyl derivative represented by the following general formula 1:

[Formula 1]

In the formulas, Ar ¹ represents a phenyl group or a nitrogen-containing heteroaromatic group which may be substituted with an alkyl group, a phenyl group which may be substituted with a phenyl group or an alkyl group, or a hydrocarbon group which may be substituted with 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 a divalent nitrogen-containing heteroaromatic group which may be substituted with an alkyl group. Ar ² , Ar ³ and Ar ⁴ each independently represent a nitrogen-containing heteroaromatic group or a hydrogen atom which may be substituted with an alkyl group. Provided that 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 should not be the same as Ar ² and Ar ⁴ . When X is a 1,4-phenylene group, Ar ¹ should not be the same as Ar ³ . Each hydrogen atom in the formula may be independently a deuterium atom.

The 1,2,4,5-substituted phenyl derivative represented by the general formula (1) of the present invention has good charge injection and transport properties, and thus is useful as a material for a fluorescent or phosphorescent organic electroluminescent device. Particularly, Transporting materials and the like.

The band gap of the 1,2,4,5-substituted phenyl derivative is 3.2 eV or more, and the energy of each color of the three primary colors (red: 1.9 eV, green: 2.4 eV, and blue: 2.8 eV) Lt; RTI ID = 0.0 > a < / RTI > wide bandgap material. Therefore, the present invention can be applied to various devices such as monochromatic display devices, three primary color display devices, and white devices for lighting applications. The triplet energy of the present compound is high, and it can be applied to phosphorescence applications sufficiently. Further, since the solubility can be controlled by changing the substituent, it can be applied not only to the evaporation element but also to the application element.

1 is a cross-sectional view of an organic electroluminescent device manufactured in Test Example-1 below.
[Description of Symbols]
1: Glass substrate with ITO transparent electrode 2: Hole injection layer
3: 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)"), the phenyl group or alkyl group represented by Ar ¹ is substituted Preferable examples of the nitrogen-containing heteroaromatic group which may be present, the phenyl group which may be substituted with a phenyl group or the alkyl group, or the hydrocarbon group which may be substituted with a phenyl group or an alkyl group include a pyridyl group which may be substituted with an alkyl group, And a fluorenyl group which may be substituted with an alkyl group.

Specific examples of Ar ¹ are further given below, but Ar ¹ is not limited thereto.

Examples of the nitrogen-containing heteroaromatic group which may be substituted with a phenyl group or an alkyl group include a 2-pyridyl group, a 3-pyridyl group, a 4-pyridyl group, a 2-methylpyridin- Methylpyridin-4-yl group, 3-methylpyridin-5-yl group, 3-methylpyridine-6-yl group, Yl group, a 2,6-dimethylpyridin-4-yl group, a 3,6-dimethylmethylpyridin-2-yl group, Yl group, a 2-phenylpyridin-4-yl group, a 2-phenylpyridin-4-yl group, 3-phenylpyridin-4-yl group, 3-phenylpyridin-5-yl group, 3-phenylpyridine-6-yl group, 3-phenylpyridin- Yl group, a 4-phenylpyridin-2-yl group, a 4-phenylpyridin-3-yl group, a 2,6-diphenylpyridin- Pyridin-2-yl group 4-yl group, 3,6-diphenylpyridin-5-yl group, 2-pyrimidyl group, Methylpyrimidin-2-yl group, 4-methylpyrimidin-6-yl group, 5-methylpyrimidin-2-yl group, Yl group, 2-phenylpyrimidin-4-yl group, 2-phenylpyrimidin-4-yl group, 4-phenylpyrimidin-6-yl group, 5-phenylpyrimidin-2-yl group, 5-phenylpyrimidin-5-yl group, 2-pyridazin-2-yl group, a 2-pyridazinyl group, a 2-pyridazinyl group, Yl group, a 2-phenylpyrazin-5-yl group, a 2-methylpyrazine-6-yl group, a 2,6- And a phenylpyrazin-6-yl group.

A 2-methylpyridin-5-yl group, a 3-phenylpyridine-5-yl group, a 2-methylpyridine-5-yl group, Yl group, a 2-pyrimidyl group, a 4-pyrimidyl group, a 5-pyrimidyl group and a 5-phenylpyrimidin-2-yl group. More preferred are a 2-pyridyl group, a 3-pyridyl group, a 2-phenylpyridin-5-yl group and a 5-phenylpyrimidin-2-yl group in view of ease of synthesis.

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

A phenyl group, a p-tolyl group, a 4-biphenyl group and a 1,1 ': 3', 1 "-terphenyl-5'-yl group are preferable from the viewpoint of good performance as an organic electroluminescent material, , A phenyl group, a p-tolyl group, and a 4-biphenyl group are more preferable.

Examples of the 2- to 4-carbon hydrocarbon group which may be substituted with a phenyl group or an alkyl group include a 1-naphthyl group, 4-methylnaphthalen-1-yl group, 4-trifluoromethylnaphthalen- Methylnaphthalen-1-yl group, a 5-ethylnaphthalen-1-yl group, a 5-ethylnaphthalen-1-yl group, Propylnaphthalen-1-yl group, a 5-tert-butylnaphthalen-1-yl group, a 2-naphthyl group, a 6-methylnaphthalen- A 6-ethylnaphthalene-2-yl group, a 6-ethylnaphthalene-2-yl group, a 6-ethylnaphthalene- Methylnaphthalene-2-yl group, a 1-anthryl group, a 2-methyl anthracene-1-yl group, A methyl group, a 3-methyl anthracene-1-yl group, a 4-methyl anthracene- Phenanthracene-1-yl group, 4-phenylanthracene-1-yl group, 5-phenylanthracene-1-yl group, Phenanthracene-1-yl group, 10-phenylanthracene-1-yl group, 2-phenylanthracene-1-yl group, Anthryl group, 1-methyl anthracene-2-yl group, 3-methyl anthracene-2-yl group, 4-methyl anthracene- A phenanthracene-2-yl group, a 6-phenylanthracene-2-yl group, a 7-phenylanthracene- Anthryl group, 2-methylanthracene-9-yl group, 3-methyl anthracene-2-yl group, Anthracene-9-yl group, 2-phenylanthracene-9-yl group, 3- A phenanthracene-9-yl group, a 4-phenylanthracene-9-yl group, a 10-phenylanthracene- Phenylphenanthrene-2-yl group, 3-phenylphenanthrene-2-yl group, 4-phenylphenanthrene-1-yl group, A phenanthren-2-yl group, a 9-phenylphenanthrene-2-yl group, a 3-phenanthryl group, a 1-phenylphenanthrene- Phenanthren-3-yl group, a 4-phenanthryl group, a 1-phenylphenanthrene-4-yl group, a 2-phenyl- Phenylphenanthrene-9-yl group, 3-phenylphenanthrene-9-yl group, 4-phenylphenanthrene group, Yl group, an 8-phenylpyran-1-yl group, a 2-pyrenyl group, a 6-phenylpyran-2-yl group , A 7-phenylpyrylene-2-yl group, a 1-triphenylrenyl group, a 2-triphenyl A 9,9-dimethylfluorene-1-yl group, a 9,9-dimethylfluorene-2-yl group, a 9,9-dimethylfluorene- Yl group, a 9,9-diphenylfluorene-1-yl group, a 9,9-diphenylfluorene-2-yl group, a 9,9- Yl group, 9,9-dimethylbenzo [a] fluorene-3-yl group, 9,9-dimethylbenzo [a] fluoren- Yl group, 9,9-dimethylbenzo [a] fluorene-6-yl group, 9,9-dimethylbenzo [a] fluorene- yl group, 9,9-dimethylbenzo [b] fluorene-1-yl group, 9,9-dimethylbenzo [b] fluoren- yl group, 9,9-dimethylbenzo [b] fluoren-6-yl group, 9,9-dimethylbenzo [b] fluoren- Yl group, 9,9-dimethylbenzo [c] fluoren-1-yl group, 9,9-dimethylbenzo [c] fluoren- A methylbenzo [c] fluoren-5-yl group, a 9,9-dimethylbenzo [c] fluoren-6-yl group, a 9,9- 9,9-diphenylbenzo [a] fluoren-4-yl group, 9,9-diphenylbenzo [a] fluoren- 9,9-diphenylbenzo [a] fluoren-7-yl group, 9,9-diphenylbenzo [a] fluoren- , 9,9-diphenylbenzo [a] fluorene-8-yl group, 9,9-diphenylbenzo [b] fluorene- A 9,9-diphenylbenzo [b] fluoren-5-yl group, a 9,9-diphenylbenzo [b] fluoren-6-yl group, a 9,9-diphenylbenzo [b] Yl group, 9,9-diphenylbenzo [b] fluorene-8-yl group, 9,9-diphenylbenzo [c] fluorene- Dienes, 9,9-diphenylbenzo [c] fluoren-5-yl groups, 9,9-diphenylbenzo [c] -Work , 9,9-diphenyl-benzo [c], and the like fluorene-8-diary.

From the viewpoint of good performance of the organic electroluminescent device, it is preferable to use at least one selected from the group consisting of a 9,9-dimethylfluorene-2-yl group, a 1-naphthyl group, a 2-naphthyl group, a 1-pyrenyl group, a 2-phenanthrenyl group, , 9,9-dimethylbenzo [c] fluorene-2-yl group and 9-anthryl group are preferable, and 9,9-dimethylfluorene- More preferred is a 9-phenanthrenyl group.

In the compound (1), Ar ² , Ar ³ and Ar ⁴ each independently represent a nitrogen-containing heteroaromatic group or a hydrogen atom which may be substituted with an alkyl group. Provided that 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 , a pyridyl group optionally substituted with an alkyl group, or a hydrogen atom are preferable from the viewpoint of good performance as a material for an organic electroluminescent device. It is more preferable that Ar ³ is a pyridyl group, and Ar ² and Ar ⁴ are a hydrogen atom.

Specific examples of Ar ² , Ar ³ and Ar ⁴ are further exemplified below, but are not limited thereto.

Examples of the nitrogen-containing heteroaromatic group which may be substituted with an alkyl group include a 2-pyridyl group, a 3-pyridyl group, a 4-pyridyl group, a 2-methylpyridin- Yl group, 3-methylpyridin-5-yl group, 3-methylpyridin-6-yl group, 3-methylpyridin- Methylpyridin-3-yl group, 2,6-dimethylpyridin-4-yl group, 3,6-dimethylpyridine- 2-yl group, 3,6-dimethylpyridin-4-yl group, 3,6-dimethylpyridin-5-yl group, 2-pyrimidyl group, 4-pyrimidyl group, Methylpyrimidin-5-yl group, 4-methylpyrimidin-6-yl group, 5-methylpyridine group, Methylpyrimidin-4-yl group, 2,4-dimethylpyrimidin-6-yl group, 4,6-dimethylpyrimidin-2-yl group, 2- Methylpyrazin-3-yl group, 2- Pyrazin-5-naphthyl group, and the like can be mentioned 2-methyl-6-pyrazinyl group, a 2, 6-dimethyl-3-diary.

From the viewpoint of good performance as an organic electroluminescent material, it is preferable to use a 2-pyridyl group, a 3-pyridyl group, a 4-pyridyl group, a 3-methylpyridin-6-yl group, , A 5-pyrimidyl group, and a 2-pyrazinyl group. More preferred are a 2-pyridyl group, a 3-pyridyl group, a 3-methylpyridin-6-yl group and a 2-methylpyridin-5-yl group from the viewpoint of easy synthesis.

In the compound (1), 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 a divalent nitrogen-containing heteroaromatic substituent which may be substituted with an alkyl group. Examples of the divalent nitrogen-containing heteroaromatic group include a pyridylene group, a pyrimidylene group, a pyrazylene group and a pyridazylene group, but are not limited thereto. X is preferably a single bond, a phenylene group, a pyridylene group or a pyrimidylene group, among the above-mentioned ones, from the viewpoint of good performance as a material for an organic electroluminescence device.

The alkyl group as a substituent is preferably an alkyl group having 1 to 6 carbon atoms, and specific examples thereof include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, -Yl group, 3-methylbutyl group, 2,2-dimethylpropyl group, hexan-1-yl group, and the like.

When X is a 1,3-phenylene group, Ar ¹ should not be the same as Ar ² or Ar ⁴ . When X is a 1,4-phenylene group, Ar ¹ should not be the same as Ar ³ .

In the compound (1), each hydrogen atom may be independently a deuterium atom.

As the compound (1), the following (A1) to (A88) are exemplified, but the present invention is not limited thereto:

The compound represented by the general formula 3 (hereinafter sometimes referred to as "compound (3)") is disclosed in, for example, JP-A-2008-280330 [0061] to [0076] Can be produced by using the method as described above.

Examples of the compound (3) include, but are not limited to, the following (B1) to (B96). Here, M ¹ represents a metal group or a heteroatom.

The compound represented by the general formula 4 (hereinafter sometimes referred to as "compound (4)") is disclosed in, for example, JP-A 2008-280330 [0061] to [0076] Can be produced by using the method as described above.

Examples of the compound (4) include, but are not limited to, the following (C1) to (C27). Here, M ² represents a metal group or a hetero atomic group.

Next, the 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" represented by the following reaction formula.

In the general formulas (1), (2) and (3), Ar ¹ represents 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 hydrocarbon group of 2 to 4 carbon atoms which may be substituted. 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 a divalent nitrogen-containing heteroaromatic group which may be substituted with an alkyl group. Ar ² , Ar ³ and Ar ⁴ each independently represent a nitrogen-containing heteroaromatic group or a hydrogen atom which may be substituted with an alkyl group. Provided that 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 should not be the same as Ar ² and Ar ⁴ . When X is a 1,4-phenylene group, Ar ¹ should not be the same as Ar ³ . Z ¹ represents a leaving group. M ¹ represents a metal group or a heteroatom.

Is a step of reacting a compound represented by the general formula (2) (hereinafter sometimes referred to as a compound (2)) with a compound (3) optionally in the presence of a base in the presence of a metal catalyst, To obtain a 1,2,4,5-substituted phenyl derivative of the present invention. In this reaction, a general coupling reaction such as a Suzuki-Miyaura reaction, a Negishi reaction, a Tamao-Kumada reaction, and a Stille reaction can be used. , The desired product can be obtained in a satisfactory yield.

Examples of the leaving group represented by Z ¹ in the compound (2) include a chlorine group, a bromine group, an iodine group, a trifluoromethylsulfonyloxy group, a methanesulfonyloxy group, a chloromethanesulfonyloxy group and a p-toluenesulfonyloxy group And the like.

Examples of the metal group represented by M ¹ or the hetero atom of the compound (3) include ZnR ¹ , MgR ² , Sn (R ³ ) ₃ and B (OR ⁴ ) ₂ . R ¹ and R ² each independently represent a chlorine atom, a bromine atom or an iodine atom, R ³ represents an alkyl group having 1 to 4 carbon atoms or a phenyl group, R ⁴ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms Or a phenyl group, and two R ⁴ in B (OR ⁴ ) ₂ may be the same or different. The two R ⁴ may be monosubstituted to form a ring including an oxygen atom and a boron atom.

B (OH) ₂ , B (OMe) ₂ , B (O ⁱ Pr) ₂ , B (OBu) ₂ and B (OPh) ₂ are exemplified as B (OR ⁴ ) ₂ in the compound (3) . Examples of B (OR ⁴ ) _{2 in} the case where two R ⁴ are combined to form a ring including an oxygen atom and a boron atom include the groups represented by the following formulas (D1) to (D6) , And a group represented by (D2) in view of good yield.

Examples of the metal catalyst that can be used in " Process 1 " include a palladium catalyst and a nickel catalyst.

Examples of the palladium catalyst that can be used in "Step 1" include palladium chloride, palladium acetate, palladium trifluoroacetate, and palladium nitrate. In addition, it is also possible to use palladium complexes such as π-allylpalladium chloride dimer, palladium acetylacetonate, tris (dibenzylideneacetone) dipalladium, dichlorobis (triphenylphosphine) palladium, tetrakis (triphenylphosphine) palladium and dichloro , 1'-bis (diphenylphosphino) ferrocene) palladium, and the like. Among them, a palladium complex having a tertiary phosphine as a ligand is preferable in that the reaction yield is good.

The palladium complex having a tertiary phosphine as a ligand can also be prepared by adding tertiary phosphine to the palladium salt or the complex compound in the reaction system. Examples of the tertiary phosphine that can be used at this time include triphenylphosphine, trimethylphosphine, tributylphosphine, tri (tert-butyl) phosphine, tricyclohexylphosphine, tert-butyldiphenylphosphine, (Diphenylphosphino) -2'- (N, N-dimethylamino) biphenyl, 2- (di-tert- Bis (diphenylphosphino) ethane, 1,3-bis (diphenylphosphino) biphenyl, bis (diphenylphosphino) Bis (diphenylphosphino) ferrocene, tri (2-furyl) phosphine, tri (o-tolyl) phosphine, tris (2,5-xylyl) phosphine, (±) -2,2'-bis (diphenylphosphino) -1,1'-binaphthyl, 2-dicyclohexylphosphino- , 6'-triisopropylbiphenyl and 2-dicyclohexylphosphine -2 and the like can be given ', 6'-dimethoxy-biphenyl. 2-dicyclohexylphosphino-2 ', 4', 6'-triisopropylbiphenyl is preferred because it is readily available and has a good reaction yield.

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

Specific examples of the nickel catalyst that can be used in "Process 1" include [1,1 'bis (diphenylphosphino) ferrocene] nickel (II) dichloride, [1,2- bis (diphenylphosphino) ethane] (II) dichloride, [1, 1 'bis (diphenylphosphino) propane] nickel (II) dichloride, (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 "Process 1" include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate, cesium carbonate, tripotassium phosphate, sodium phosphate, sodium fluoride, potassium fluoride, cesium fluoride, Dipotassium phosphate is preferred because of its good yield. The molar ratio of the base to the 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) to the compound (3) used in the " process 1 " is preferably 1: 2 to 1:10 and more preferably 1: 2 to 1: 4 in view of good yield.

Examples of the solvent that can be used in the " Process 1 " include water, dimethylsulfoxide, dimethylformamide, tetrahydrofuran, dioxane, toluene, benzene, diethylether, ethanol, methanol or xylene , And these may be appropriately combined and used. It is preferable to use a mixed solvent of dioxane and water in view of good yield.

&Quot; Process 1 " can be conducted at a temperature appropriately selected from 0 deg. C to 150 deg. C, and more preferably from 80 deg. C to 100 deg. C from the viewpoint of good yield. The compound (1) can be obtained by a usual treatment after the completion of the " Step 1 ". If necessary, it may be purified by recrystallization, column chromatography or sublimation.

Next, the production method of the compound (2) used as a raw material of the " process 1 " in the process for producing the 1,2,4,5-substituted phenyl derivative (1) will be described.

Compound (2) can be prepared 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 should not be the same. M ² represents a metal group or a heteroatom. Ar ² , Ar ³ and Ar ⁴ each independently represent a nitrogen-containing heteroaromatic group or a hydrogen atom which may be substituted with an alkyl group. Provided that 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.

Is a step of reacting a compound represented by the general formula (5) (hereinafter sometimes referred to as a compound (5)) with a compound (4) optionally in the presence of a base in the presence of a metal catalyst, (2) to be used in the production of the compound (1), and the reaction conditions of a typical coupling reaction such as a Suzuki-Miyaura reaction, a Negishi reaction, a Tamao-Kumar reaction, The object can be preferably obtained.

Examples of the metal group represented by M ² or the hetero atom of the compound (4) include ZnR ¹ , MgR ² , Sn (R ³ ) ₃ and B (OR ⁴ ) ₂ . R ⁴ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group having 1 to 4 carbon atoms or a phenyl group; R ¹ and R ² each independently represents a chlorine atom, a bromine atom or an iodine atom; R ³ represents an alkyl group having 1 to 4 carbon atoms or a phenyl group; , And two R ⁴ in B (OR ⁴ ) ₂ may be the same or different. The two R ⁴ may be monosubstituted to form a ring including an oxygen atom and a boron atom.

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

Examples of the leaving group represented by Z ¹ and Z ² in the compound (5) include a chlorine group, a fluorine group, an iodine group, a trifluoromethylsulfonyloxy group, a methanesulfonyloxy group, a chloromethanesulfonyloxy group and p- Sulfonyloxy group and the like. As the compound (5), the following (E1) to (E5) are exemplified, but the present invention is not limited thereto:

.

.

The metal catalyst that can be used in " Process 2 " is the same as the palladium or nickel catalyst exemplified in " Process 1 ". Among them, a palladium complex having triphenylphosphine as a ligand is particularly preferable because it is easy to obtain and the reaction yield is good.

The palladium complex having a tertiary phosphine as a ligand may be prepared by adding a tertiary phosphine to the palladium salt or the complex and adjusting the reaction system. As the tertiary phosphine which can be used at this time, those similar to the tertiary phosphine exemplified in " process 1 " can be mentioned. Triphenylphosphine is preferred because it is readily available and has good reaction yield. The molar ratio of the tertiary phosphine to the palladium salt or complex is preferably 1:10 to 10: 1, and more preferably 1: 2 to 5: 1 in terms of good reaction yield.

As the base which can be used in " Process 2 ", those similar to the bases exemplified in " Step 1 " can be mentioned, and sodium carbonate is preferable from the viewpoint of good yield. The molar ratio of the base to the compound (4) is preferably 1: 1 to 10: 1, and is preferably 2: 1 to 5: 1 in terms of good yield.

As the solvent which can be used in "Process 2", water, dimethyl sulfoxide, dimethylformamide, tetrahydrofuran, dioxane, toluene, benzene, diethyl ether, ethanol, methanol or xylene can be exemplified , And these may be appropriately combined and used. It is preferable to use a mixed solvent of tetrahydrofuran and water in view of good yield.

&Quot; Step 2 " can be conducted at a temperature appropriately selected from 0 deg. C to 150 deg. C, and more preferably from 50 deg. C to 60 deg. C from the viewpoint of good yield.

Compound (2) is obtained by carrying out usual treatment after the termination of " process 1 ". If necessary, it may be purified by recrystallization, column chromatography or sublimation, but may be provided in " Step 1 " without isolation.

The method for producing the organic electroluminescent device comprising the 1,2,4,5-substituted phenyl derivative (1) of the present invention as a component is not particularly limited, but it is possible to form a film by a vacuum evaporation method. The film formation by the vacuum vapor deposition method can be performed by using a general-purpose vacuum vapor deposition apparatus. Considering the manufacturing tact time and manufacturing cost of the organic electroluminescent device, the degree of vacuum of the vacuum chamber at the time of forming the film by the vacuum vapor deposition method can be set to 1, which can be reached by a commonly used diffusion pump, turbo molecular pump, cryo pump, X 10 < ^-2 > to 1 x 10 < ^-5 > Pa. The deposition rate depends on the thickness of the film to be formed, but is preferably 0.005 to 1.0 nm / second.

The 1,2,4,5-substituted phenyl derivative of the present invention can also be formed by a spin coating method, an inkjet method, a casting method, a dipping method, or the like using a general-purpose apparatus.

Example

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

(11.2 mmol) of 4,6-dichloro-1,3-dihydroxybenzene and 3.53 g (44.7 mmol) of pyridine were dissolved in 11.2 ml of dichloromethane under an argon stream, . Then, 26.8 ml (26.8 mmol) of a solution of trifluoromethanesulfonic anhydride diluted with 1 M of dichloromethane was added dropwise over 20 minutes, and the mixture was stirred at room temperature for 3 hours. Diethyl ether was added to the reaction solution to dilute, and the mixture was washed with 1M hydrochloric acid, saturated aqueous sodium hydrogencarbonate solution and saturated brine. The obtained organic layer was concentrated to dryness to obtain an orange liquid (yield: 4.2 g, yield 85%) of the desired 1,3-dichloro-4,6-bis (trifluoromethanesulfonyloxy) benzene.

¹ H-NMR (CDCl ₃ ):? 7.73 (s, 1 H), 7.39 (s, 1 H).

Example-2

Under a stream of argon, 5.69 g (12.8 mmol) of 1,3-dichloro-4,6-bis (trifluoromethanesulfonyloxy) benzene and 5.11 g (0.38 mmol) of dichlo- rovistriphenylphosphine palladium was dissolved in 193 ml of tetrahydrofuran, 38.5 ml (77.0 mmol) of 2M sodium carbonate aqueous solution was added, and the mixture was stirred under reflux for 29 hours Respectively. After cooling to room temperature, the aqueous layer was removed and the organic layer was concentrated to give a crude reaction product. The resulting crude reaction product was purified by silica gel column chromatography (developing solvent: a mixed solvent of chloroform and hexane) to obtain the desired 4 ', 6'-dichloro-4,4'-di (2- (Yield: 3.59 g, yield 62%) of 1,1 ': 3', 1 " -terphenyl.

¹ H-NMR (CDCl ₃ ):? (D, J = 8.7, 4.7 Hz, 2H), 7.42 (s, 1H), 7.58 (d, J = 8.6 Hz, 4H), 7.64 ), 8.07 (d, J = 8.6 Hz, 4H), 8.71 (d, J = 4.7 Hz, 2H).

Example-3

(6.62 mmol) of 4 ', 6'-dichloro-4,4'-di (2-pyridyl) -1,1': 3 ' , 6.72 g (26.5 mmol) of 4 ', 4', 5,5,5'5-octamethyl-2,2-di-1,3,2-dioxaborolane, trisdabenzylideneacetone palladium 121.2 , 125.8 mg (0.26 mmol) of 2-dicyclohexylphosphino-2 ', 4', 6'-triisopropylbiphenyl and 2.60 g (26.5 mmol) of potassium acetate, Dioxane and 30 ml of water, and the mixture was stirred under reflux for 2 hours. After the reaction solution was concentrated, chloroform was added to separate the organic layer and the aqueous layer. The obtained organic layer was concentrated and the resulting crude product was purified by silica gel chromatography (developing solvent: a mixed solvent of chloroform and methanol) to obtain the objective 4'6'-bis (4,4,5,5-tetramethyl 1, 3 ', 1 " -terphenyl (yield: 1.60 g, yield 38%) was obtained in the same manner as in Example 1, ).

¹ H-NMR (CDCl ₃ ):? 2H), 7.47 (s, 1H), 7.54 (d, J = 8.6Hz, 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

(1.54 mmol) of 4 ', 6'-dichloro-4,4'-di (2-pyridyl) -1,1': 3 ', 1 " (6.18 mmol) of palladium acetate, 10.4 mg (0.046 mmol) of palladium acetate, 44.1 mg (0.092 mmol) of 2-dicyclohexylphosphino-2 ', 4', 6'- triisopropylbiphenyl, 4.02 (12.4 mmol) was dissolved in 30 ml of tetrahydrofuran, and the mixture was stirred under reflux for 26 hours. After cooling to room temperature, chloroform was added to the reaction system to dilute it, and the inorganic residue was removed by filtration. The resulting organic layer was concentrated and then purified by silica gel column chromatography (developing solvent: chloroform) and a mixed solvent of hexane to obtain the objective 4'-phenyl-4- (2-pyridyl) -5 '- [ - (2-pyridyl) phenyl] -1,1 ': 2', 1 "-terphenyl as a white solid (yield 0.69 g, yield 83%).

¹ H-NMR (CDCl ₃ ):? 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

(1.54 mmol) of 4 ', 6' -dichloro-4,4'-di (2-pyridyl) -1,1 ': 3' (6.18 mmol) of phenylboronic acid, 10.4 mg (0.046 mmol) of palladium acetate and 44.1 mg (0.093 mmol) of 2-dicyclohexylphosphino-2 ', 4', 6'-triisopropylbiphenyl And 4.02 g (12.4 mmol) of cesium carbonate were dissolved in 30 ml of tetrahydrofuran, and the mixture was stirred under reflux for 24 hours. Subsequently, 5 ml of water was added, and the mixture was stirred for 24 hours under reflux. After cooling to room temperature, the aqueous layer was removed and the organic layer was concentrated. The crude product thus obtained was purified by silica gel column chromatography (developing solvent: chloroform) and hexane to obtain the objective 4 ", 6" -bis [4- (2-pyridyl) phenyl] 1 ': 4', 1 ": 3", 1 "': 4"', 1 "" -quinquiphenyl as a white solid (yield 0.62 g, yield 58%).

¹ H-NMR (CDCl ₃ ):? (D, J = 8.5 Hz, 4H), 7.39 (t, J = 7.9 Hz, 4H), 7.40 (t, J = 7.3 Hz, 2H), 7.18-7.22 = 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 , J = 8.5 Hz, 4H), 8.66 (d, J = 4.6 Hz, 2H).

Example-6

Under argon stream, 0.80 g (1.76 mmol) of 4 ', 6'-dichloro-4,4'-di (2-pyridyl) (3.31 mmol) of dimethylfluorene-2-boronic acid, 19.8 mg (0.088 mmol) of palladium acetate, 2-dicyclohexylphosphino-2 ', 4', 6'-triisopropylbiphenyl 84.1 mg (0.18 mmol) of tripotassium phosphate 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 the mixture was stirred under reflux for 26 hours. After cooling to room temperature, the aqueous layer was removed and the organic layer was concentrated. The crude product thus obtained was purified by silica gel column chromatography (developing solvent: chloroform) and a mixed solvent of hexane to obtain the target 4 ', 6'-bis (9,9-dimethylfluoren-2-yl ) -4,4 "-di (2-pyridyl) -1,1 ': 3', 1" -terphenyl as a white solid (0.45 g, yield 33%).

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

Example-7

Under argon stream, 1.00 g (2.21 mmol) of 4 ', 6'-dichloro-4,4'-di (2-pyridyl) (8.82 mmol) of boronic acid, 24.8 mg (0.11 mmol) of palladium acetate, 105 mg (0.22 mmol) of 2-dicyclohexylphosphino-2 ', 4', 6'- triisopropylbiphenyl, 3.74 g (17.6 mmol) of tripotassium phosphate 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 under reflux for 24 hours. 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: a mixed solvent of chloroform and methanol) to obtain the objective 4,4 "-di (2-pyridyl) -4 ', 6'- -Pyridyl) -1,1 ': 3', 1 "-terphenyl as a white solid (yield 0.25 g, yield 21%).

¹ H-NMR (CDCl ₃ ):? (D, J = 8.3 Hz, 2H), 7.68 (s, 1H), 7.72 (d, J = 8.5 Hz, 4H), 7.52 J = 7.8 Hz, 2H), 7.77 (t, J = 7.5 Hz, 2H), 7.93 (d, J = 8.5 Hz, 4H), 8.49 ), 8.68 (d, J = 5.0 Hz, 2H).

Example-8

(1.10 mmol) of 4 ', 6' -dichloro-4,4'-di (2-pyridyl) (3.31 mmol) of palladium acetate, 12.4 mg (0.055 mmol) of 2-dicyclohexylphosphino-2 ', 4', 6'-triisopropylbiphenyl (0.11 mmol) of tripotassium phosphate 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 under reflux for 75 hours. 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 to obtain the objective 4- (2-pyridyl) -4 "- (3-pyridyl) -4 '- [4- ] -5 '- [4- (2-pyridyl) phenyl] -1,1': 2 ', 1 "-terphenyl as a brown solid (yield 0.27 g, yield 35%).

¹ H-NMR (CDCl ₃ ):? 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 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

Example-9

(1.10 mmol) of 4 ', 6'-dichloro-4,4'-di (2-pyridyl) -1,1': 3 ' (3.31 mmol) of pyridine-5-ylboronic acid, 12.4 mg (0.055 mmol) of palladium acetate and 52.6 mg (0.11 mmol) of 2-dicyclohexylphosphino-2 ', 4', 6'-triisopropylbiphenyl 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 under reflux for 91 hours. 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 to obtain the objective 4 ', 6'-bis (2-phenylpyridin-5-yl) -4,4'-di , 1 ': 3', 1 "-terphenyl (yield 0.22 g, yield 29%).

¹ H-NMR (CDCl ₃ ):? (M, 5H), 7.69-7.75 (m, 5H), 7.93 (d, J = 8.3 Hz, 4H), 7.21 (t, J = 5.6 Hz, 2H), 7.36-7.46 , 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

(2-pyridyl) -1,1 ': 3', 1 "-terphenyl and 0.10 g (0.22 mmol) of 4 ', 6'- 0.24 g (0.66 mmol) of 3,5-di (2-pyridyl) phenyl] -4,4,5,5-tetramethyl-1,3,2-dioxaborolane, 2.5 mg 11.0 mg (0.023 mmol) of 2-dicyclohexylphosphino-2 ', 4', 6'-triisopropylbiphenyl and 421 mg (1.99 mmol) of tripotassium phosphate were added to 11 ml of 1,4- Dioxane and 2.5 ml of water, and the mixture was stirred under reflux for 40 hours. 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 '- { Phenyl} -4 "- (2-pyridyl) -4 '- {4- (2- pyridyl) phenyl} -1,1': 2 ', 1" 16%).

¹ H-NMR (CDCl ₃ ):? (M, 6H), 7.49 (d, J = 8.5 Hz, 4H), 7.50 (d, J = 8.0 Hz, 4H), 7.59-7.71 (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 .

Example-11

(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -4,4 "-di (2-pyridyl) (0.47 mmol) of 1,1 ': 3', 1 "-terphenyl, 5.3 mg (0.024 mmol) of palladium acetate, 2-dicyclohexylphosphino-2 ', 4' (1.13 mmol) of 2-chloro-5-phenylpyridine and 0.48 (2.26 mmol) of tripotassium phosphate were dissolved in 15 mL of 1,4-dioxane and 4.5 mL of water After dissolving in a mixed solvent, the mixture was stirred at 60 캜 for 24 hours and at 95 캜 for 3 hours. After cooling to 0 ° C, the precipitated solid was collected by filtration, and the obtained crude product was purified by recrystallization with toluene to obtain the objective 4 ', 6'-bis (3-phenylpyridin-6-yl) (Yield 0.069 g, yield 21%) of the title compound was obtained as an off-white solid.

¹ H-NMR (CDCl ₃ ):? (D, 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 J = 8.5, 1.4 Hz, 4H), 7.63 (dd, J = 8.3, 2.4 Hz, 2H), 7.66 (Dd, J = 2.4, 0.8 Hz, 2H), 8.21 (s, 1H), 8.67 (d, J = 4.6 Hz, 2H).

Example-12

(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -4,4 "-di (2-pyridyl) (0.41 g, 0.61 mmol) of tetrakis (triphenylphosphine) palladium and 2.8 mg (0.024 mmol) of tetrakis (triphenylphosphine) palladium 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 obtained mixed solution was heated to 100 DEG C and stirred for 12 hours. After cooling to room temperature, 15 ml of water and 15 ml of methanol were added and the mixture was cooled to 0 °. The precipitated solid was collected by filtration and the resulting crude product was purified by recrystallization with toluene to obtain the desired 4'6'-bis (5-phenylpyrimidin-2-yl) -4,4'- Pyridyl) -1,1 ': 3', 1 "-terphenyl (yield 0.28 g, yield 67%).

¹ H-NMR (CDCl ₃ ):? J = 7.0Hz, 4H), 7.72-7.74 (m, 5H), 7.18-7.22 (m, 2H), 7.40-7.44 , 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. An ITO transparent electrode-adhered glass substrate on which an indium oxide-tin oxide (ITO) film having a width of 2 mm was patterned in a stripe shape was used as a substrate. The substrate was washed with isopropyl alcohol, and then subjected to surface treatment by ozone ultraviolet cleaning. Vacuum evaporation of each layer was carried out on the cleaned substrate by the vacuum evaporation method to prepare an organic electroluminescent element having a light emitting area of 4 mm 2 having the multilayer structure shown in Fig.

First, the glass substrate was introduced into a vacuum vapor deposition vessel, and the pressure was reduced to 1.0 × 10 ^-4 Pa. Thereafter, a hole injecting layer 2, a hole transporting layer 3, a light emitting layer 4 and an electron transporting layer 5 are sequentially formed as an organic compound layer on the glass substrate shown in Fig. 1 (1) The cathode layer 6 was formed. As the hole injecting layer 2, phthalocyanine copper (II) sublimed and purified was vacuum-deposited to a thickness of 25 nm. As the hole transport layer 3, N, N'-di (1-naphthyl) -N, N'-diphenylbenzidine (NPD) was vacuum deposited at 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- -Propyl] biphenyl (DPAVBi) in a ratio of 97: 3 (mass%) at a film thickness of 40 nm. As the electron transporting layer 5, 4'-phenyl-4- (2-pyridyl) -5 '- [4- (2-pyridyl) phenyl] , 1 " -terphenyl was vacuum deposited to a film thickness of 20 nm.

Each of the organic materials was deposited by resistance heating and the heated compound was vacuum deposited at a deposition rate of 0.3 to 0.5 nm / sec. Finally, a metal mask was disposed so as to be orthogonal to the ITO stripe, and the cathode layer 6 was formed. The cathode layer 6 was formed by vacuum vapor deposition of lithium fluoride and aluminum at a film thickness of 1.0 nm and 100 nm, respectively, to form a two-layer structure.

Each film thickness was measured with a stylus type film thickness meter (DEKTAK). The device was sealed in a glove box with a nitrogen atmosphere at a concentration of 1 ppm or less in oxygen and moisture. As the sealing, a sealing cap made of glass and an epoxy type ultraviolet curing resin (manufactured by Nagase Chemtech Co., Ltd.) were used.

A direct current was applied to the fabricated organic electroluminescent device, and the luminescent characteristics were evaluated using a luminometer of LUMINANCE METER (BM-9) manufactured by Topcon Corporation. (Cd / m 2), current efficiency (cd / A), and power efficiency (㏐ / W) were measured when the current density was 20 mA / cm 2.

The measured values of the fabricated device were 6.15 V, 1792 cd / m 2, 8.96 cd / A, and 4.58 cd / W.

Comparative Example 1

(8-quinolinolato) aluminum (Alq) (Alq) of the existing material was vacuum-deposited in a thickness of 20 nm instead of the electron transport layer (5) in Test Example-1, Respectively.

The measured values of the manufactured device were 6.44 V, 1664 cd / m 2, 8.32 cd / A, and 4.06 cd / W.

Test Example 2

4 ', 6 "-bis [4- (2-pyridyl) phenyl] -1,1': 4 ', 1": 3 ", 1 " ': 4 "', 1 " " -quinquephenyl was vacuum deposited at a film thickness of 20 nm.

The measured values of the manufactured device were 5.76 V, 1818 cd / m 2, 9.09 cd / A, and 4.96 cd / W.

Test Example 3

(2-naphthyl) anthracene (TBADN) and 4,4'-bis [4- (di-p-tolylamino (DPAVBi) in a ratio of 93: 7 (mass%) to a thickness of 40 nm, instead of the electron transport layer 5 of Test Example-1, (3-pyridyl) -1,1 ': 3', 1 " -terphenyl synthesized in Synthesis Example 4 Except that vacuum deposition was carried out, the same procedure as in Test Example-1 was carried out.

The measured values of the fabricated device were 4.3 V, 2040 cd / m 2, 10.2 cd / A, and 7.49 cd / W. In addition, the luminance halftime of this device was 192 hours.

Comparative Example 2

As in Experimental Example-1, except that tris (8-quinolinolato) aluminum (Alq) (Alq) of a conventional material was vacuum-deposited in a thickness of 20 nm instead of the electron transport layer (5) Respectively.

The measured values of the fabricated device were 5.7 V, 1985 cd / m 2, 9.93 cd / A, and 5.48 cd / W. Further, the luminance half-life time of this device was 578 hours.

Test Example 4

(2-pyridyl) -4 "- (3-pyridyl) -4 '- [4- (3-pyridyl ) - phenyl] -5 '- [4- (2-pyridyl) phenyl] -1,1': 2 ', 1 " -terphenyl was vacuum deposited at a film thickness of 20 nm Respectively.

The measured values of the fabricated device were 4.1 V, 1993 cd / m 2, 9.97 cd / A, and 7.67 cd / W. Further, the luminance halftime of this device was 243 hours.

Test Example 5

(2-phenylpyridin-5-yl) -4,4 "-di (2-pyridyl) -4,4'-dicarboxylate synthesized in Example-9 was used in place of the electron- -1,1 ': 3', 1 "-terphenyl was vacuum-deposited at a film thickness of 20 nm.

The measured values of the fabricated device were 4.2 V, 2060 cd / m 2, 10.3 cd / A, and 7.72 cd / W. Further, the brightness half-life time of this device was 218 hours.

Since the thin film made of the 1,2,4,5-substituted phenyl derivative of the present invention has amorphous properties, heat resistance, electron transportation ability, hole blocking ability, water resistance, anaerobic oxidation and electron injection characteristics, It can be used as an electron transporting material, a hole blocking material, a light emitting host material and the like. Further, since the 1,2,4,5-substituted phenyl derivative (1) of the present invention has a wide band gap, for the purpose of being used not only for a fluorescent element but also for a phosphorescent element, the present invention is also applicable to a doping device for applying an n-dopant.

Further, in the embodiment of the present invention, high emission efficiency and low driving power can be realized as a vapor deposition device. This makes it possible to use for illumination other than the panel. In addition, since it has solubility in an organic solvent and high electron transportability, it can be used for application to a coating device, a flexible device, an organic transistor, and an organic thin film solar cell.

Claims (8)

1,2,4,5-substituted phenyl derivatives represented by the following general formula 1:
[Formula 1]

In the formulas, Ar ¹ represents a phenyl group or a phenyl group which may be substituted with an alkyl group, or a 2- to 4-carbon hydrocarbon group which may be substituted with a phenyl group or an alkyl group. X represents a single bond, a 1,4-phenylene group, or a pyridylene group. Ar ² , Ar ³ and Ar ⁴ each independently represents a 2-pyridyl group, a 3-pyridyl group, a 4-pyridyl group, a 3-methylpyridin-6-yl group, , A 5-pyrimidyl group, a 2-pyrazinyl group or a hydrogen atom. Provided that at least one of Ar ² , Ar ³ and Ar ⁴ is a 2-pyridyl group, a 3-pyridyl group, a 4-pyridyl group, a 3-methylpyridin-6-yl group, A pyrimidyl group, a 5-pyrimidyl group, or a 2-pyrazinyl group. Each hydrogen atom in the formula may be independently a deuterium atom. The 1,2,4,5-substituted phenyl derivative according to claim 1, wherein Ar < ^{1 >} is a phenyl group optionally substituted by an alkyl group, or a fluorenyl group optionally substituted by an alkyl group. According to claim 1 or 2, Ar ^2, Ar ³ and Ar ⁴ of the each independently a group-2-pyridyl, group-3-pyridyl, 4-pyridyl group or a hydrogen atom, Ar ^2, Ar ³ and Ar ⁴ And at least one is a 2-pyridyl group, a 3-pyridyl group or a 4-pyridyl group. ^3. The compound according to claim 1 or 2, wherein Ar ³ is a 2-pyridyl group, a 3-pyridyl group or a 4-pyridyl group, and Ar ² and Ar ⁴ are hydrogen atoms. derivative. A process for producing a compound represented by the general formula (1), comprising the step of coupling reaction of a compound represented by the following general formula (2) and a compound represented by the following general formula (3) in the presence or absence of a base in the presence of a metal catalyst , Preparation of 2,4,5-substituted phenyl derivatives:
[Formula 2]

In the formulas, Z ¹ represents a leaving group. Ar ² , Ar ³ and Ar ⁴ each independently represents a 2-pyridyl group, a 3-pyridyl group, a 4-pyridyl group, a 3-methylpyridin-6-yl group, , A 5-pyrimidyl group, a 2-pyrazinyl group or a hydrogen atom. Provided that at least one of Ar ² , Ar ³ and Ar ⁴ is a 2-pyridyl group, a 3-pyridyl group, a 4-pyridyl group, a 3-methylpyridin-6-yl group, A pyrimidyl group, a 5-pyrimidyl group, or a 2-pyrazinyl group. Each hydrogen atom in the formula may be independently a deuterium atom;
[Formula 3]

In the formulas, Ar ¹ represents a phenyl group or a phenyl group which may be substituted with an alkyl group, or a 2- to 4-carbon hydrocarbon group which may be substituted with a phenyl group or an alkyl group. X represents a single bond, a 1,4-phenylene group, or a pyridylene group. M ¹ represents a metal group or a heteroatom. Each hydrogen atom in the formula may be independently a deuterium atom. A process for producing a compound represented by the general formula 2 of claim 5, which comprises reacting a compound represented by the following general formula 4 with a compound represented by the following general formula 5 in the presence or absence of a base in the presence of a metal catalyst ≪ / RTI >:<
[Formula 4]

Wherein Ar ² , Ar ³ and Ar ⁴ each independently represents a 2-pyridyl group, a 3-pyridyl group, a 4-pyridyl group, a 3- methylpyridin- A pyrimidyl group, a 5-pyrimidyl group, a 2-pyrazinyl group or a hydrogen atom. Provided that at least one of Ar ² , Ar ³ and Ar ⁴ is a 2-pyridyl group, a 3-pyridyl group, a 4-pyridyl group, a 3-methylpyridin-6-yl group, A pyrimidyl group, a 5-pyrimidyl group, or a 2-pyrazinyl group. M ² represents a metal group or a heteroatom. Each hydrogen atom in the formula may be independently a deuterium atom;
[Formula 5]

Wherein Z ¹ and Z ² each independently represent a leaving group. However, Z ¹ and Z ² should not be the same. An organic electroluminescent device comprising the 1,2,4,5-substituted phenyl derivative of claim 1 as a constituent component. delete

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