JP6464944B2 - Cyclic azine compound, method for producing the same, and use thereof - Google Patents

Description

  The present invention relates to a cyclic azine compound useful as a component of an organic electroluminescent device, a production method thereof, and an application thereof. More specifically, the present invention relates to a cyclic azine compound having a phenylene group substituted with a condensed ring group in the molecule, a production method thereof, and an application thereof.

  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 excitons that are generated are deactivated, and is applied not only to small displays but also to large televisions and lighting. The hole transport layer is divided into a hole transport layer and a hole injection layer, the light emitting layer is divided into an electron blocking layer, a light emitting layer and a hole blocking layer, and the electron transport layer is divided into an electron transport layer and an electron injection layer. May be configured. In some cases, a co-deposited film doped with a metal, an organometallic compound, or another organic compound may be used as the carrier transport layer (electron transport layer or hole transport layer) of the organic electroluminescence device.

  Conventional organic electroluminescent elements have higher driving voltage than inorganic light-emitting diodes, low luminance and luminous efficiency, and extremely low element lifetime, so that they have not been put to practical use in a wide range of fields. Although recent organic electroluminescence devices are gradually improved in the above-mentioned drawbacks, excellent materials are demanded for the purpose of further improving the luminous efficiency characteristics, driving voltage characteristics, and long life characteristics. Among them, improvement of element lifetime is an urgent need for widespread use in a wide range of fields, and material development for that is required.

  As an electron transport material excellent in long-life property for organic electroluminescent elements, the triazine compound disclosed in Patent Document 1 can be mentioned. However, further improvements have been demanded in terms of the lifetime, voltage and luminous efficiency of the organic electroluminescent device.

JP 2011-063584 A

  An object of the present invention is to provide a specific cyclic azine compound that achieves an improvement in performance of an organic electroluminescent device as compared with a conventionally known cyclic azine compound.

As a result of intensive studies to solve the above problems, the present inventors have obtained a cyclic azine compound represented by the following general formula (1) (an azine ring skeleton and a condensed aromatic hydrocarbon represented by Ar ² ). The organic electroluminescence device using an electron transport material having a biphenylene group, a terphenylene group, or a quaterphenylene group between the groups is longer than when a conventionally known material is used. The inventors have found that the lifetime is reduced, the voltage is lowered, or the emission efficiency is improved, and the present invention has been completed.

  That is, the present invention relates to a cyclic azine compound represented by the following general formula (1) (hereinafter also referred to as azine compound (1)), a method for producing the azine compound (1), and uses thereof.

（一般式（１）中、Ａｒ^１は、お互い同じであって、炭素数１〜４のアルキル基、フッ素原子、フェニル基、又はピリジル基で置換されていてもよい炭素数６〜１０の芳香族炭素水素基を表す。Ａｒ^２は、炭素数１〜４のアルキル基、又はフッ素原子で置換されていてもよい炭素数１０〜１７の縮環芳香族炭化水素基を表す。Ａｒ^３は、炭素数１〜４のアルキル基、又はフッ素で置換されていてもよい炭素数６〜１７の芳香族炭化水素基、又は炭素数１〜４のアルキル基、又はフッ素原子で置換されていてもよい炭素数４〜９の６環のみで構成される複素芳香族基を表す。Ｘは、炭素数１〜４のアルキル基、又はフッ素原子で置換されていてもよいフェニレン基、アザフェニレン基、又はジアザフェニレン基を表す。Ｙは、ＣＨ、又は窒素原子を表す。ｐは、１〜３の整数を表す。ｑは、０〜３の整数を表す。）

(In General Formula (1), Ar ¹ is the same as each other, and the aromatic having 6 to 10 carbon atoms which may be substituted with an alkyl group having 1 to 4 carbon atoms, a fluorine atom, a phenyl group, or a pyridyl group. .Ar ² representing a family of carbon hydrogen group, .Ar ³ representing a condensed aromatic hydrocarbon group of the alkyl group, or fluorine atoms may be substituted with atoms 10 to 17 1 to 4 carbon atoms, An alkyl group having 1 to 4 carbon atoms, an aromatic hydrocarbon group having 6 to 17 carbon atoms which may be substituted with fluorine, an alkyl group having 1 to 4 carbon atoms, or a fluorine atom. Represents a heteroaromatic group composed only of 6 rings having 4 to 9 carbon atoms, X is an alkyl group having 1 to 4 carbon atoms, a phenylene group optionally substituted with a fluorine atom, an azaphenylene group, or Represents a diazaphenylene group, Y represents CH or nitrogen; .p representing the child, .q representing the integer of 1 to 3 represents an integer of 0 to 3.)

  The cyclic azine compound of the present invention can provide an organic electroluminescent device that is superior in lifetime, voltage or luminous efficiency as compared with conventionally known cyclic azine compounds.

  Hereinafter, the present invention will be described in detail.

  The azine compound (1) of the present invention is represented by the following general formula (1).

（一般式（１）中、Ａｒ^１は、お互い同じであって、炭素数１〜４のアルキル基、フッ素原子、フェニル基、又はピリジル基で置換されていてもよい炭素数６〜１０の芳香族炭素水素基を表す。Ａｒ^２は、炭素数１〜４のアルキル基、又はフッ素原子で置換されていてもよい炭素数１０〜１８の縮環芳香族炭化水素基を表す。Ａｒ^３は、炭素数１〜４のアルキル基、又はフッ素で置換されていてもよい炭素数６〜１８の芳香族炭化水素基、又は炭素数１〜４のアルキル基、又はフッ素原子で置換されていてもよい炭素数４〜９の６環のみで構成される複素芳香族基を表す。Ｘは、炭素数１〜４のアルキル基、又はフッ素原子で置換されていてもよいフェニレン基、アザフェニレン基、又はジアザフェニレン基を表す。Ｙは、ＣＨ、又は窒素原子を表す。ｐは、１〜３の整数を表す。ｑは、０〜３の整数を表す。）
なお、一般式（１）の各置換基については、有機ＥＬ素子の素子寿命の点で、下記の場合が好ましい。
（一般式（１）中、Ａｒ^１は、お互い同じであって、炭素数１〜４のアルキル基、フッ素原子、フェニル基、又はピリジル基で置換されていてもよい炭素数６〜１０の芳香族炭素水素基を表す。Ａｒ^２は、炭素数１〜４のアルキル基、又はフッ素原子で置換されていてもよい炭素数１０〜１７の縮環芳香族炭化水素基を表す。Ａｒ^３は、炭素数１〜４のアルキル基、又はフッ素で置換されていてもよい炭素数６〜１７の芳香族炭化水素基、又は炭素数１〜４のアルキル基、又はフッ素原子で置換されていてもよい炭素数４〜９の６環のみで構成される複素芳香族基を表す。Ｘは、炭素数１〜４のアルキル基、又はフッ素原子で置換されていてもよいフェニレン基、アザフェニレン基、又はジアザフェニレン基を表す。Ｙは、ＣＨ、又は窒素原子を表す。ｐは、１〜３の整数を表す。ｑは、０〜３の整数を表す。）
以下、一般式（１）で表される化合物について説明する。

(In General Formula (1), Ar ¹ is the same as each other, and the aromatic having 6 to 10 carbon atoms which may be substituted with an alkyl group having 1 to 4 carbon atoms, a fluorine atom, a phenyl group, or a pyridyl group. .Ar ² representing a family of carbon hydrogen group, .Ar ³ representing a condensed aromatic hydrocarbon group of the alkyl group, or fluorine atoms may be substituted with atoms 10 to 18 1 to 4 carbon atoms, An alkyl group having 1 to 4 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms which may be substituted with fluorine, an alkyl group having 1 to 4 carbon atoms, or a fluorine atom. Represents a heteroaromatic group composed only of 6 rings having 4 to 9 carbon atoms, X is an alkyl group having 1 to 4 carbon atoms, a phenylene group optionally substituted with a fluorine atom, an azaphenylene group, or Represents a diazaphenylene group, Y represents CH or nitrogen; .p representing the child, .q representing the integer of 1 to 3 represents an integer of 0 to 3.)
In addition, about each substituent of General formula (1), the following case is preferable at the point of the element lifetime of an organic EL element.
(In General Formula (1), Ar ¹ is the same as each other, and the aromatic having 6 to 10 carbon atoms which may be substituted with an alkyl group having 1 to 4 carbon atoms, a fluorine atom, a phenyl group, or a pyridyl group. .Ar ² representing a family of carbon hydrogen group, .Ar ³ representing a condensed aromatic hydrocarbon group of the alkyl group, or fluorine atoms may be substituted with atoms 10 to 17 1 to 4 carbon atoms, An alkyl group having 1 to 4 carbon atoms, an aromatic hydrocarbon group having 6 to 17 carbon atoms which may be substituted with fluorine, an alkyl group having 1 to 4 carbon atoms, or a fluorine atom. Represents a heteroaromatic group composed only of 6 rings having 4 to 9 carbon atoms, X is an alkyl group having 1 to 4 carbon atoms, a phenylene group optionally substituted with a fluorine atom, an azaphenylene group, or Represents a diazaphenylene group, Y represents CH or nitrogen; .p representing the child, .q representing the integer of 1 to 3 represents an integer of 0 to 3.)
Hereinafter, the compound represented by the general formula (1) will be described.

In General Formula (1), two Ar ¹ represent the same substituent.

The aromatic hydrocarbon group having 6 to 10 carbon atoms that may be substituted with an alkyl group having 1 to 4 carbon atoms, fluorine, phenyl group, or pyridyl group in Ar ¹ is not particularly limited. , Phenyl group, m-biphenyl group, p-biphenyl group, o-biphenyl group, p-tolyl group, m-tolyl group, o-tolyl group, 1-naphthyl group, 2-naphthyl group, 2-phenyl-1- Naphthyl group, 3-phenyl-1-naphthyl group, 4-phenyl-1-naphthyl group, 5-phenyl-1-naphthyl group, 6-phenyl-1-naphthyl group, 7-phenyl-1-naphthyl group, 7- Phenyl-1-naphthyl group, 8-phenyl-1-naphthyl group, 1-phenyl-2-naphthyl group, 3-phenyl-2-naphthyl group, 4-phenyl-2-naphthyl group, 5-phenyl-2-naphthyl group Til group, 6-phenyl-2-naphthyl group, 7-phenyl-2-naphthyl group, 7-phenyl-2-naphthyl group, 8-phenyl-2-naphthyl group, 2- (2-pyridyl) phenyl group, 2 -(3-pyridyl) phenyl group, 2- (4-pyridyl) phenyl group, 3- (2-pyridyl) phenyl group, 3- (3-pyridyl) phenyl group, 3- (4-pyridyl) phenyl group, 4 -(2-pyridyl) phenyl group, 4- (3-pyridyl) phenyl group, 4- (4-pyridyl) phenyl group, 2- (2-pyridyl) -1-naphthyl group, 3- (2-pyridyl)- 1-naphthyl group, 4- (2-pyridyl) -1-naphthyl group, 5- (2-pyridyl) -1-naphthyl group, 6- (2-pyridyl) -1-naphthyl group, 7- (2-pyridyl group) ) -1-Naphtyl group, 7- (2-pyridyl)- -Naphtyl group, 8- (2-pyridyl) -1-naphthyl group, 1- (2-pyridyl) -2-naphthyl group, 3- (2-pyridyl) -2-naphthyl group, 4- (2-pyridyl) 2-naphthyl group, 5- (2-pyridyl) -2-naphthyl group, 6- (2-pyridyl) -2-naphthyl group, 7- (2-pyridyl) -2-naphthyl group, 7- (2- Pyridyl) -2-naphthyl group, 8- (2-pyridyl) -2-naphthyl group, 2- (3-pyridyl) -1-naphthyl group, 3- (3-pyridyl) -1-naphthyl group, 4- ( 3-pyridyl) -1-naphthyl group, 5- (3-pyridyl) -1-naphthyl group, 6- (3-pyridyl) -1-naphthyl group, 7- (3-pyridyl) -1-naphthyl group, 7 -(3-pyridyl) -1-naphthyl group, 8- (3-pyridyl) -1-naphthyl group, 1- 3-pyridyl) -2-naphthyl group, 3- (3-pyridyl) -2-naphthyl group, 4- (3-pyridyl) -2-naphthyl group, 5- (3-pyridyl) -2-naphthyl group, 6 -(3-pyridyl) -2-naphthyl group, 7- (3-pyridyl) -2-naphthyl group, 7- (3-pyridyl) -2-naphthyl group, 8- (3-pyridyl) -2-naphthyl group 2- (4-pyridyl) -1-naphthyl group, 3- (4-pyridyl) -1-naphthyl group, 4- (4-pyridyl) -1-naphthyl group, 5- (4-pyridyl) -1- Naphthyl group, 6- (4-pyridyl) -1-naphthyl group, 7- (4-pyridyl) -1-naphthyl group, 7- (4-pyridyl) -1-naphthyl group, 8- (4-pyridyl)- 1-naphthyl group, 1- (4-pyridyl) -2-naphthyl group, 3- (4-pyridyl) -2- Naphthyl group, 4- (4-pyridyl) -2-naphthyl group, 5- (4-pyridyl) -2-naphthyl group, 6- (4-pyridyl) -2-naphthyl group, 7- (4-pyridyl)- 2-naphthyl group, 7- (4-pyridyl) -2-naphthyl group, 8- (4-pyridyl) -2-naphthyl group, 2,4-dimethylphenyl group, 3,5-dimethylphenyl group, mesityl group, 2-ethylphenyl group, 3-ethylphenyl group, 4-ethylphenyl group, 2,4-diethylphenyl group, 3,5-diethylphenyl group, 2-propylphenyl group, 3-propylphenyl group, 4-propylphenyl Group, 2,4-dipropylphenyl group, 3,5-dipropylphenyl group, 2-isopropylphenyl group, 3-isopropylphenyl group, 4-isopropylphenyl group, 2,4-diisopropyl Phenyl group, 3,5-diisopropylphenyl group, 2-butylphenyl group, 3-butylphenyl group, 4-butylphenyl group, 2,4-dibutylphenyl group, 3,5-dibutylphenyl group, 2-tert-butyl Phenyl group, 3-tert-butylphenyl group, 4-tert-butylphenyl group, 2,4-di-tert-butylphenyl group, 3,5-di-tert-butylphenyl group, biphenyl-2-yl group, Biphenyl-3-yl group, biphenyl-4-yl group, 3-methylbiphenyl-4-yl group, 2'-methylbiphenyl-4-yl group, 4'-methylbiphenyl-4-yl group, 2,2 ' -Dimethylbiphenyl-4-yl group, 2 ', 4', 6'-trimethylbiphenyl-4-yl group, 6-methylbiphenyl-3-yl group, 5-methylbiphenyl- -Yl group, 2'-methylbiphenyl-3-yl group, 4'-methylbiphenyl-3-yl group, 6,2'-dimethylbiphenyl-3-yl group, 2 ', 4', 6'-trimethylbiphenyl -3-yl group, 5-methylbiphenyl-2-yl group, 6-methylbiphenyl-2-yl group, 2'-methylbiphenyl-2-yl group, 4'-methylbiphenyl-2-yl group, 6, 2′-dimethylbiphenyl-2-yl group, 2 ′, 4 ′, 6′-trimethylbiphenyl-2-yl group, 3-ethylbiphenyl-4-yl group, 4′-ethylbiphenyl-4-yl group, 2 ', 4', 6'-triethylbiphenyl-4-yl group, 6-ethylbiphenyl-3-yl group, 4'-ethylbiphenyl-3-yl group, 5-ethylbiphenyl-2-yl group, 4'- Ethylbiphenyl-2-yl group, 2 ′, 4 ′, 6′-tri Ethylbiphenyl-2-yl group, 3-propylbiphenyl-4-yl group, 4′-propylbiphenyl-4-yl group, 2 ′, 4 ′, 6′-tripropylbiphenyl-4-yl group, 6-propyl Biphenyl-3-yl group, 4′-propylbiphenyl-3-yl group, 5-propylbiphenyl-2-yl group, 4′-propylbiphenyl-2-yl group, 2 ′, 4 ′, 6′-tripropyl Biphenyl-2-yl group, 3-isopropylbiphenyl-4-yl group, 4′-isopropylbiphenyl-4-yl group, 2 ′, 4 ′, 6′-triisopropylbiphenyl-4-yl group, 6-isopropylbiphenyl -3-yl group, 4'-isopropylbiphenyl-3-yl group, 5-isopropylbiphenyl-2-yl group, 4'-isopropylbiphenyl-2-yl group, 2 ', 4', 6'-triiso Ropyrbiphenyl-2-yl group, 3-butylbiphenyl-4-yl group, 4′-butylbiphenyl-4-yl group, 2 ′, 4 ′, 6′-tributylbiphenyl-4-yl group, 6-butyl Biphenyl-3-yl group, 4′-butylbiphenyl-3-yl group, 5-butylbiphenyl-2-yl group, 4′-butylbiphenyl-2-yl group, 2 ′, 4 ′, 6′-tributylbiphenyl 2-yl group, 3-tert-butylbiphenyl-4-yl group, 4′-tert-butylbiphenyl-4-yl group, 2 ′, 4 ′, 6′-tritert-butylbiphenyl-4-yl group 6-tert-butylbiphenyl-3-yl group, 4′-tert-butylbiphenyl-3-yl group, 5-tert-butylbiphenyl-2-yl group, 4′-tert-butylbiphenyl-2-yl group Or 2 ', ', And a 6'-tert- butyl-2-yl group.

  Among these, a phenyl group, m-tolyl group, p-tolyl group, p-biphenyl, m-biphenyl group, 1-naphthyl group, or 2-naphthyl group is preferable because the lifetime of the organic electroluminescent element is long.

  Furthermore, a phenyl group, a p-biphenyl group, or an m-biphenyl group is more preferable in terms of easy synthesis.

Alkyl group having 1 to 4 carbon atoms in Ar ^2, or as a condensed aromatic hydrocarbon group having fluorine atoms may be substituted with atoms 10 to 18, it is not particularly limited, for example, a naphthyl group , Anthracenyl group, pyrenyl group, phenanthrenyl group, triphenylenyl group or fluoranthenyl group (these groups may be substituted with an alkyl group having 1 to 4 carbon atoms or a fluorine atom), More specifically, 1-naphthyl group, 2-naphthyl group, 1-phenanthrenyl group, 2-phenanthrenyl group, 3-phenanthrenyl group, 4-phenanthrenyl group, 9-phenanthrenyl group, 1-anthracenyl group, 2-anthracenyl group 9-anthracenyl group, 1-pyrenyl group, 4-pyrenyl group, 1-triphenylenyl group, or 3-furyl Examples include an oranthenyl group.

Ar ² is preferably an alkyl group having 1 to 4 carbon atoms, or a condensed aromatic hydrocarbon group having 10 to 17 carbon atoms which may be substituted with a fluorine atom, and is not particularly limited. Although not exemplified, for example, naphthyl group, anthracenyl group, pyrenyl group, phenanthrenyl group, or fluoranthenyl group (these groups may be substituted with an alkyl group having 1 to 4 carbon atoms or a fluorine atom) More specifically, 1-naphthyl group, 2-naphthyl group, 1-phenanthrenyl group, 2-phenanthrenyl group, 3-phenanthrenyl group, 4-phenanthrenyl group, 9-phenanthrenyl group, 1-anthracenyl group 2-anthracenyl group, 9-anthracenyl group, 1-pyrenyl group, 4-pyrenyl group, 3-fluoranthenyl group, etc. I can get lost.

  Of these, a naphthyl group, anthracenyl group, pyrenyl group, or phenanthrenyl group (these groups are substituted with an alkyl group having 1 to 4 carbon atoms or a fluorine atom in terms of the lifetime or efficiency of the organic electroluminescence device. More specifically, a 1-naphthyl group, a 2-naphthyl group, a 9-anthracenyl group, a 1-pyrenyl group, or a 9-phenanthrenyl group is preferable, and a 1-naphthyl group, 2- A naphthyl group, 9-anthracenyl group, 1-pyrenyl group, or 9-phenanthrenyl group is more preferable.

  Furthermore, a 9-phenanthrenyl group is more preferable in terms of easy synthesis.

Alkyl group having 1 to 4 carbon atoms in Ar ^3, or as a condensed aromatic hydrocarbon group having fluorine atoms may be substituted with atoms 10 to 18, it is not particularly limited, for example, a phenyl group , Naphthyl group, anthracenyl group, pyrenyl group, phenanthrenyl group, triphenylenyl group, or fluoranthenyl group (these groups may be substituted with an alkyl group having 1 to 4 carbon atoms or a fluorine atom) More specifically, 1-naphthyl group, 2-naphthyl group, 1-phenanthrenyl group, 2-phenanthrenyl group, 3-phenanthrenyl group, 4-phenanthrenyl group, 9-phenanthrenyl group, 1-anthracenyl group, 2 -Anthracenyl group, 9-anthracenyl group, 1-pyrenyl group, 4-pyrenyl group, 1-triphenylenyl group, Or 3-fluoranthenyl group etc. are mentioned.

Ar ³ is preferably an alkyl group having 1 to 4 carbon atoms, or a condensed aromatic hydrocarbon group having 10 to 17 carbon atoms which may be substituted with a fluorine atom, and is not particularly limited. However, for example, a phenyl group, a naphthyl group, an anthracenyl group, a pyrenyl group, a phenanthrenyl group, or a fluoranthenyl group (these groups may be substituted with an alkyl group having 1 to 4 carbon atoms or a fluorine atom) And more specifically, 1-naphthyl group, 2-naphthyl group, 1-phenanthrenyl group, 2-phenanthrenyl group, 3-phenanthrenyl group, 4-phenanthrenyl group, 9-phenanthrenyl group, 1-naphthyl group, Anthracenyl group, 2-anthracenyl group, 9-anthracenyl group, 1-pyrenyl group, 4-pyrenyl group, or 3-fluorantheni And the like.

  Of these, 1-naphthyl group, 2-naphthyl group, 9-anthracenyl group, 1-pyrenyl group, 9-phenanthrenyl group, 1-triphenylenyl group, or 3 in terms of the lifetime or efficiency of the organic electroluminescent device. A -fluoranthenyl group is preferred, and a 1-naphthyl group, 2-naphthyl group, 9-anthracenyl group, 1-pyrenyl group, 9-phenanthrenyl group, or 3-fluoranthenyl group is more preferred.

  Furthermore, a 9-phenanthrenyl group is more preferable in terms of easy synthesis.

Alkyl group having 1 to 4 carbon atoms represented by Ar ^3, or a heteroaromatic group which carbon atoms and optionally 4-9 substituted with a fluorine atom is not particularly limited, for example, a pyridyl group , Pyrimidyl group, pyrazyl group, quinolyl group, or isoquinolyl group (these groups may be substituted with an alkyl group having 1 to 4 carbon atoms or a fluorine atom), and more specifically 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 2-pyrimidyl group, 4-pyrimidyl group, 5-pyrimidyl group, 2-pyrazyl group, 2-quinolyl group, 3-quinolyl group, 4-quinolyl group 5-quinolyl group, 6-quinolyl group, 7-quinolyl group, 8-quinolyl group, 1-isoquinolyl group, 3-isoquinolyl group, 4-isoquinolyl group, 5-isoquinolyl group, 6-isoquinolyl group, 7 -An isoquinolyl group, an 8-isoquinolyl group, etc. are mentioned.

As described above, Ar ³ is a phenyl group, a tolyl group, a dimethylphenyl group, a naphthyl group, an anthracenyl group, a pyrenyl group, a phenanthrenyl group, a fluoranthenyl group, in terms of the lifetime or efficiency of the organic electroluminescence device. A pyridyl group, a pyrimidyl group, a pyrazyl group, a quinolyl group, or an isoquinolyl group is preferable. Examples of these groups include an o-tolyl group, an m-tolyl group, a p-tolyl group, and a 3,5-dimethylphenyl group. 1-naphthyl group, 2-naphthyl group, 9-anthracenyl group, 1-pyrenyl group, 9-phenanthrenyl group, fluoranthenyl group, 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 2-quinolyl group , 3-isoquinolyl group, or 4-isoquinolyl group.

Further, Ar ³ is preferably a phenyl group, a tolyl group, a dimethylphenyl group, a pyridyl group, a pyrimidyl group, or a pyrazyl group, and examples of these groups include an o-tolyl group, an m-tolyl group, p -Tolyl group, 3,5-dimethylphenyl group, 2-pyridyl group, 3-pyridyl group, 4-pyridyl group and the like can be mentioned.

  Furthermore, a phenyl group, a 3,5-dimethylphenyl group, a 9-phenanthryl group, a 2-pyridyl group, or a 3-pyridyl group is more preferable in terms of easy synthesis.

  The alkyl group having 1 to 4 carbon atoms represented by X or the phenylene group which may be substituted with fluorine is not particularly limited, and examples thereof include 1,2-phenylene group and 1,3-phenylene group. Group or a 1,4-phenylene group. Among these, a 1,3-phenylene group or a 1,4-phenylene group is preferable in terms of good lifetime or efficiency of the organic electroluminescent element.

  Although it does not specifically limit as a C1-C4 alkyl group represented by X, or the azaphenylene group which may be substituted by fluorine, For example, 2,3-pyridylene group, 2,4- Examples include a pyridylene group, a 2,5-pyridylene group, a 2,6-pyridylene group, a 3,4-pyridylene group, and a 3,5-pyridylene group.

  Although it does not specifically limit as a C1-C4 alkyl group represented by X, or the diazaphenylene group which may be substituted by fluorine, For example, a 2, 4- pyrimidylene group, 2, 5 -Pyrimidylene group, 4,5-pyrimidylene group, 4,6-pyrimidylene group, 2,3-pyrazylene group, 2,5-pyrazylene group, 2,6-pyrazylene group and the like.

  Y represents CH or a nitrogen atom, and a nitrogen atom is preferable in that the lifetime of the organic electroluminescent element is good.

  p is 1, 2, or 3, and q is 0, 1, 2, or 3.

  In view of the long lifetime of the organic electroluminescent element, p is preferably 1 or 2, and q is preferably 0, 1, or 2. Furthermore, in terms of easy synthesis, p is preferably 1, and q is preferably 0 or 1.

  The azine compound (1) of the present invention is not particularly limited, and examples thereof include the following A-1 to A-542.

次に、本発明のアジン化合物（１）の製造方法について説明する。

Next, the manufacturing method of the azine compound (1) of this invention is demonstrated.

（式中、Ａｒ^１、Ａｒ^２、Ａｒ^３、Ｘ、Ｙ、ｐ、及びｑは、一般式（１）と同じ定義である。Ｚは、脱離基を表し、Ｍは、ボロン酸化合物、又は金属含有基を表す。）
反応式（１）〜（４）中、Ｚは、脱離基を表し、特に限定するものではないが、例えば、塩素原子、臭素原子、トリフルオロメタンスルホニル基（トリフラート基）、又はヨウ素原子が挙げられる。このうち、反応収率がよい点で、臭素原子、又は塩素原子が好ましく、選択性が良い点で、塩素原子がより好ましい。

(In the formula, Ar ¹ , Ar ² , Ar ³ , X, Y, p, and q have the same definition as in general formula (1). Z represents a leaving group, M represents a boronic acid compound, Or represents a metal-containing group.)
In the reaction formulas (1) to (4), Z represents a leaving group and is not particularly limited, and examples thereof include a chlorine atom, a bromine atom, a trifluoromethanesulfonyl group (triflate group), or an iodine atom. It is done. Among these, a bromine atom or a chlorine atom is preferable in terms of good reaction yield, and a chlorine atom is more preferable in terms of good selectivity.

In the reaction formulas (1) to (4), M represents a boronic acid compound or a metal-containing group, and is not particularly limited. For example, Li, Na, MgCl, MgBr, MgI, CuCl, CuBr, CuI _{, AlCl 2, AlBr 2, Al} (Me) 2, Al (Et) 2, Al (i Bu) 2, Sn (Me) 3, Sn (Bu) 3, SnF 3, ZnCl, ZnBr, BF 3 K, B (OR ⁵ ) ₂ , B (OR ⁶ ) ₃ , Si (R ⁷ ) _{3 and the} like can be mentioned.

B (OR ⁵ ) ₂ is not particularly limited. For example, B (OH) ₂ , B (OMe) ₂ , B (O ⁱ Pr) ₂ , B (OBu) ₂ , or B (OPh) ₂ etc. can be mentioned. Examples of B (OR ⁵ ) ₂ in the case where two R ⁵ are combined to form a ring containing an oxygen atom and a boron atom include the following substituents.

これらの置換基のうち、反応の選択性がよい点で（ＩＩ）、又は（ＶＩＩ）で示されるものが好ましく、反応収率が良い点で、（ＩＩ）がより好ましい。

Among these substituents, those represented by (II) or (VII) are preferable from the viewpoint of good reaction selectivity, and (II) is more preferable from the viewpoint of good reaction yield.

Examples of B (OR ⁶ ) ₃ include the substituents shown below.

Ｓｉ（Ｒ^７）_３としては、特に限定するものではないが、例えば、ＳｉＭｅ_３、ＳｉＰｈ_３、ＳｉＭｅＰｈ_２、ＳｉＣｌ_３、ＳｉＦ_３、Ｓｉ（ＯＭｅ）_３、Ｓｉ（ＯＥｔ）_３、Ｓｉ（ＯＭｅ）_２ＯＨ等を挙げることができる。

Si The ^(R _{7) 3,} but are not particularly limited to, for _{example, SiMe 3, SiPh 3, SiMePh} 2, SiCl 3, SiF 3, Si (OMe) 3, Si (OEt) 3, Si (OMe) ₂ OH and the like.

  As shown in the reaction formulas (1) to (4), the azine compound (1) can be synthesized by performing a coupling reaction as described in each reaction formula in the presence of a palladium catalyst and a base. I can do it.

  Although it does not specifically limit as a palladium catalyst which can be used for reaction of Reaction formula (1)-(4), For example, salts, such as palladium chloride, palladium acetate, palladium trifluoroacetate, or palladium nitrate, are mentioned. be able to. Further, π-allyl palladium chloride dimer, palladium acetylacetonate, bis (dibenzylideneacetone) palladium, tris (dibenzylideneacetone) dipalladium, dichlorobis (triphenylphosphine) palladium, tetrakis (triphenylphosphine) palladium, tri (tert -Butyl) phosphine palladium, dichloro (1,1'-bis (diphenylphosphino) ferrocene) palladium and the like. Among them, a palladium complex having a tertiary phosphine such as dichlorobis (triphenylphosphine) palladium, tetrakis (triphenylphosphine) palladium, or tri (tert-butyl) phosphinepalladium as a ligand is preferable in terms of good yield. In terms of easy availability, tris (dibenzylideneacetone) dipalladium, tetrakis (triphenylphosphine) palladium, or tri (tert-butyl) phosphinepalladium is more preferable. The palladium complex having the tertiary phosphine as a ligand can also be prepared in a reaction system by adding a tertiary phosphine to a palladium salt or a complex compound.

  The tertiary phosphine is not particularly limited, and examples thereof include triphenylphosphine, trimethylphosphine, tributylphosphine, tri (tert-butyl) phosphine, tricyclohexylphosphine, tert-butyldiphenylphosphine, and 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 (diphenyl Sufino) ferrocene, 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, etc. can be illustrated. Of these, triphenylphosphine, (tert-butyl) phosphine, or 2-dicyclohexylphosphino-2 ', 4', 6'-triisopropylbiphenyl is preferable because it is easily available and yields are good.

  When adding tertiary phosphine to a palladium salt or a complex compound, the addition amount of the tertiary phosphine is 0.1 to 10 times mol with respect to 1 mol (in terms of palladium atom) of the palladium salt or complex compound. It is preferable that it is 0.3 to 5 times mol in terms of a good yield.

  In the reaction formulas (1) to (4), the base that can be used is not particularly limited. For example, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate, cesium carbonate, acetic acid Examples include potassium, sodium acetate, potassium phosphate, sodium phosphate, sodium fluoride, potassium fluoride, or cesium fluoride. Among these, potassium carbonate, potassium phosphate, or sodium hydroxide is preferable in terms of a good yield.

  It is preferable to implement reaction of Reaction formula (1)-(4) in a solvent. Examples of the solvent include, but are not limited to, water, dimethyl sulfoxide, dimethylformamide, tetrahydrofuran, toluene, benzene, diethyl ether, 1,4-dioxane, ethanol, butanol, and xylene. May be used in appropriate combination. Among these, tetrahydrofuran, 1,4-dioxane, or a toluene-butanol mixed solvent is preferable in terms of a good yield.

  The reactions of the reaction formulas (1) to (4) can be carried out at a temperature appropriately selected from 0 ° C. to 150 ° C., and more preferably from 50 ° C. to 100 ° C. in terms of good yield.

  An azine compound (1) is obtained by carrying out a normal process after completion | finish of Reaction formula (1)-(4). You may refine | purify by recrystallization, column chromatography, sublimation, etc. as needed.

  Hereinafter, the reaction formula (1) will be described.

  Compound (2) is, for example, Hiroshi Yamanaka, “New edition of heterocyclic compounds, basic edition”, Kodansha, 2004, Hiroshi Yamanaka, “New edition of heterocyclic compounds,” Kodansha, 2004, The Journal of Organic Chemistry, 1951, 16, 461-465, Macromolecules, 2001, 6, 477-480, or the method disclosed in Science and Technology Research Institute, Vol. 81, 441, 1986, etc. it can.

  Compound (2) can also be produced by the following reaction formula (1 ′).

（式中のＡｒ^１、Ａｒ^２，ｐ、Ｍ、又はＺは、前述したＡｒ^１、Ａｒ^２，ｐ、Ｍ、又はＺと同義である。Ｚ’は、Ｚと同義である。ＺとＺ’は、同一でもよいが、選択性が良い点で、異なる方が好ましい。）
反応式（１’）の反応に使用できるパラジウム触媒、ホスフィン配位子、塩基、又は溶媒は、前述した反応式（１）〜（４）と同様のものが挙げられる。

(In the formula, Ar ¹ , Ar ² , p, M, or Z has the same meaning as Ar ¹ , Ar ² , p, M, or Z described above. Z ′ has the same meaning as Z. Z and Z 'May be the same, but different ones are preferable in terms of good selectivity.)
Examples of the palladium catalyst, phosphine ligand, base, or solvent that can be used in the reaction of the reaction formula (1 ′) include the same as those in the reaction formulas (1) to (4) described above.

  The amount of the palladium catalyst used in the reaction formula (1 ′) is not particularly limited as long as it is a so-called catalyst amount. However, in terms of a good yield, it is 0.1 to 0.00 with respect to 1 mol of the compound (10). It is preferably 01 times mole (in terms of palladium atom).

  Although there is no restriction | limiting in particular in molar ratio with the compound (10) used by Reaction Formula (1 '), or a compound (3), Compound (10) is 0.2-5 with respect to 1 mol of compound (10). It is preferably a double mole.

  Although there is no restriction | limiting in particular as the usage-amount of a base, 0.5-10 times mole is preferable with respect to 1 mol of a compound (10), and 1-5 times mole is more preferable at the point with a sufficient yield.

  The compound (2) obtained by the reaction formula (1 ') may be purified after being isolated or may proceed to the next step without isolation. Compound (2) can be obtained by carrying out a usual treatment after completion of reaction formula (1 '). You may refine | purify by recrystallization, column chromatography, sublimation, etc. as needed.

  Although it does not specifically limit as a compound (2), For example, the following 2-1 to 2-75 etc. can be mentioned.

（式中、Ｒは、メチル基、エチル基、プロピル基、ブチル基、イソプロピル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、又はフッ素原子を表し、Ｚは、前述したＺと同義である。）
化合物（３）は、例えば、特開２００８−２８０３３０号公報［００６１］〜［００７６］又は特開２００１−３３５５１６号公報［００４７］〜［００８２］に開示されている方法を用いて製造することができる。

(Wherein R represents a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, a sec-butyl group, a tert-butyl group, or a fluorine atom, and Z has the same meaning as Z described above.)
Compound (3) can be produced, for example, using the method disclosed in JP 2008-280330 A [0061] to [0076] or JP 2001-335516 A [0047] to [0082]. it can.

  Although it does not specifically limit as a compound (3), For example, 3-1 to 3-56 shown below etc. can be mentioned.

（式中、Ｍは前記と同じ定義を表わす。）
反応式（１）で用いるパラジウム触媒の量は、いわゆる触媒量であれば特に制限はないが、収率がよい点で、化合物（２）の１モルに対して、０．１〜０．０１倍モル（パラジウム原子換算）であることが好ましい。

(In the formula, M represents the same definition as described above.)
The amount of the palladium catalyst used in the reaction formula (1) is not particularly limited as long as it is a so-called catalyst amount, but is 0.1 to 0.01 with respect to 1 mol of the compound (2) in terms of a good yield. It is preferably a double mole (in terms of palladium atom).

  Although there is no restriction | limiting in particular in the molar ratio with the compound (2) or compound (3) used by Reaction formula (1), Compound (2) is 0.2-5 times with respect to 1 mol of compound (2). Mole is preferred.

  Although there is no restriction | limiting in particular as the usage-amount of a base, 0.5-10 times mole is preferable with respect to 1 mol of a compound (2), and 1-5 times mole is more preferable at the point with a sufficient yield.

  Hereinafter, the reaction formula (2) will be described.

  The compound (4) can be prepared by, for example, Hiroshi Yamanaka, “New edition of heterocyclic compounds basic”, Kodansha, 2004, Hiroshi Yamanaka, “New edition of heterocyclic compounds,” Kodansha, 2004, or Chem. Rev. 95, 2457-2483, 1995, and the like.

  As the compound (4), the compound (2) described above may be used as a raw material.

  Although it does not specifically limit as a compound (4), For example, the frame | skeleton which replaced Z of the compound (2) mentioned above with M can be illustrated.

  Compound (5) can be prepared according to, for example, The Journal of Organic Chemistry, 2001, 66, 4333-4339, or Chem. Rev. 95, 2457-2483, 1995, and the method disclosed in 1995.

  Although it does not specifically limit as a compound (5), For example, the frame | skeleton which replaced M of the compound (3) mentioned above with Z can be illustrated.

  The amount of the palladium catalyst used in the reaction formula (2) is not particularly limited as long as it is a so-called catalyst amount, but is 0.1 to 0.01 with respect to 1 mol of the compound (4) in terms of good yield. It is preferably a double mole (in terms of palladium atom).

  Although there is no restriction | limiting in particular in the molar ratio with the compound (4) or compound (5) used by Reaction formula (2), Compound (5) is 0.2-5 times with respect to 1 mol of compound (4). Mole is preferred.

  Although there is no restriction | limiting in particular as the usage-amount of a base, 0.5-10 times mole is preferable with respect to 1 mol of a compound (4), and 1-5 times mole is more preferable at the point with a sufficient yield.

  Hereinafter, the reaction formula (3) will be described.

  Compound (6) can be produced in the same manner as compound (2) described above.

  Compound (6) can also be produced by the following reaction formula (3 ′).

（式中のＡｒ^１、Ａｒ^３，ｐ、Ｍ、又はＺは、前述したＡｒ^１、Ａｒ^３，ｐ、Ｍ、又はＺと同義である。Ｚ’は、Ｚと同義である。ＺとＺ’は、同一でもよいが、選択性が良い点で、異なる方が好ましい。）
反応式（３’）で得られた化合物（６）は、単離した後に精製を行っても、単離をせずに次工程に進んでもよい。化合物（６）は、反応式（３’）の終了後に通常の処理をすることで得られる。必要に応じて、再結晶、カラムクロマトグラフィー、又は昇華等で精製してもよい。

(In the formula, Ar ¹ , Ar ³ , p, M, or Z has the same meaning as Ar ¹ , Ar ³ , p, M, or Z described above. Z ′ has the same meaning as Z. Z and Z 'May be the same, but different ones are preferable in terms of good selectivity.)
The compound (6) obtained by the reaction formula (3 ′) may be purified after isolation, or may proceed to the next step without isolation. Compound (6) can be obtained by carrying out a usual treatment after completion of reaction formula (3 ′). You may refine | purify by recrystallization, column chromatography, sublimation, etc. as needed.

  Although it does not specifically limit as a compound (6), 2-1-2-75 mentioned above etc. can be mentioned. Further, the compound (6) is not particularly limited, and examples thereof include 6-1 to 6-20 shown below.

化合物（７）は、上述した化合物（３）と同様の方法で製造することができる。

Compound (7) can be produced in the same manner as compound (3) described above.

  Although it does not specifically limit as a compound (7), 3-34 to 3-36, 3-38 to 3-40, 3-42 to 3-44, 3-46 to 3-48 mentioned above, 3- Examples thereof include 50 to 3-52 and 3-54 to 3-56.

  The amount of the palladium catalyst used in the reaction formula (3) is not particularly limited as long as it is a so-called catalyst amount, but is 0.1 to 0.01 with respect to 1 mol of the compound (6) in terms of good yield. It is preferably a double mole (in terms of palladium atom).

  Although there is no restriction | limiting in particular in the molar ratio with the compound (6) used in Reaction Formula (3), or a compound (7), Compound (7) is 0.2-5 times with respect to 1 mol of a compound (6). Mole is preferred.

  Although there is no restriction | limiting in particular as the usage-amount of a base, 0.5-10 times mole is preferable with respect to 1 mol of a compound (6), and 1-5 times mole is more preferable at the point with a sufficient yield.

  Hereinafter, the reaction formula (4) will be described.

  Compound (8) can be produced in the same manner as Compound (4) described above.

  Although it does not specifically limit as a compound (8), For example, the frame | skeleton which replaced Z of the compound (6) mentioned above with M can be illustrated.

  Compound (9) can be produced in the same manner as compound (5) described above.

  Although it does not specifically limit as a compound (9), For example, the frame | skeleton which replaced M of the compound (7) mentioned above with Z can be illustrated.

  The amount of the palladium catalyst used in the reaction formula (4) is not particularly limited as long as it is a so-called catalyst amount, but is 0.1 to 0.01 with respect to 1 mol of the compound (8) in terms of good yield. It is preferably a double mole (in terms of palladium atom).

  Although there is no restriction | limiting in particular in the molar ratio with the compound (8) or compound (9) used by Reaction formula (4), Compound (9) is 0.2-5 times with respect to 1 mol of compound (8). Mole is preferred.

  Although there is no restriction | limiting in particular as the usage-amount of a base, 0.5-10 times mole is preferable with respect to 1 mol of a compound (8), and 1-5 times mole is more preferable at the point with a sufficient yield.

  The cyclic azine compound (1) of the present invention is suitably used as a material for an organic electroluminescence device.

  Furthermore, the cyclic azine compound (1) of the present invention is suitably used as an electron transport material or an electron injection material for an organic electroluminescence device.

  Hereinafter, the organic electroluminescent element of the present invention will be described.

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

The organic electroluminescent device of the present invention has a hole transport layer, an electron transport layer, an anode buffer layer, a cathode buffer layer, etc. in addition to the light emitting layer as required, and has a structure sandwiched between a cathode and an anode. Specific examples include the structures shown below.
(I) Anode / light emitting layer / cathode (ii) Anode / hole transport layer / light emitting layer / cathode (iii) Anode / light emitting layer / electron transport layer / cathode (iv) anode / hole transport layer / light emitting layer / electron Transport layer / cathode (v) anode / anode buffer layer / hole transport layer / light emitting layer / electron transport layer / cathode buffer layer / cathode For the light emitting layer in the organic electroluminescent device of the present invention, a conventionally known light emitting material is used. be able to. As a method for forming the light emitting layer, for example, there is a method of forming a thin film by a known method such as a vapor deposition method, a spin coating method, a casting method, or an LB method.

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

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

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

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

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

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

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

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

  In the organic electroluminescent element of the present invention, the electron transport layer contains a triazine compound represented by the general formula (1).

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

  In the present invention, the light emitting material is not limited to the light emitting layer, but may be contained in the hole transport layer or the electron transport layer adjacent to the light emitting layer. The luminous efficiency can be increased.

  The substrate that is preferably used in the organic electroluminescence device of the present invention is not particularly limited in the type of glass, plastic, and the like, and is not particularly limited as long as it is transparent. Examples of the substrate preferably used in the organic electroluminescence device of the present invention include glass, quartz, and a light transmissive plastic film.

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

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

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

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

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

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

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

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

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

  The organic electroluminescence device of the present invention may be used as a kind of lamp for illumination or exposure light source, a projection device for projecting an image, or a display for directly viewing a still image or a moving image. It may be used as a device (display). When used as a display device for reproducing moving images, the driving method may be either a simple matrix (passive matrix) method or an active matrix method. Moreover, it is possible to produce a full-color display device by using two or more organic electroluminescent elements of the present invention having different emission colors.

It is a cross-sectional schematic diagram of the organic electroluminescent element produced in the Example.

1. 1. Glass substrate with ITO transparent electrode 2. hole injection layer Charge generation layer 4. 4. Hole transport layer Light emitting layer 6. 6. Electron transport layer Electron injection layer 8. Cathode layer

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

¹ H-NMR measurement was performed using Gemini 200 (manufactured by Varian).

  The light emission characteristics of the organic electroluminescence device were evaluated by applying a direct current to the fabricated device at room temperature and using a luminance meter of LUMINANCEMETER (BM-9) (manufactured by TOPCON).

  Synthesis reference example-1

アルゴン気流下、２−（３−ブロモ−５−クロロフェニル）−４，６−ジフェニル−１，３，５−トリアジン（３０．０ｇ，７１ｍｍｏｌ）、４−（２−ピリジル）フェニルボロン酸（２１．２ｇ，１１０ｍｍｏｌ）、テトラキス（トリフェニルホスフィン）パラジウム（４．１０ｇ，３．６ｍｍｏｌ）を、トルエン（７１０ｍＬ）に懸濁し、１．０Ｍ−炭酸ナトリウム水溶液（２１０ｍＬ）を滴下し、８５℃で時間撹拌した。放冷後、メタノールと水を加え、析出した固体を濾別し、水、メタノール、ヘキサンで固体を洗浄した。さらに再結晶（トルエン）で精製することで目的の２−［５−クロロ−４’−（２−ピリジル）ビフェニル−３−イル］−４，６−ジフェニル−１，３，５−トリアジンの白色固体（収量２１．０ｇ，収率６０％）を得た。

Under an argon stream, 2- (3-bromo-5-chlorophenyl) -4,6-diphenyl-1,3,5-triazine (30.0 g, 71 mmol), 4- (2-pyridyl) phenylboronic acid (21. 2 g, 110 mmol), tetrakis (triphenylphosphine) palladium (4.10 g, 3.6 mmol) are suspended in toluene (710 mL), 1.0 M aqueous sodium carbonate solution (210 mL) is added dropwise, and the mixture is stirred at 85 ° C. for an hour. did. After allowing to cool, methanol and water were added, the precipitated solid was filtered off, and the solid was washed with water, methanol and hexane. Furthermore, the desired 2- [5-chloro-4 ′-(2-pyridyl) biphenyl-3-yl] -4,6-diphenyl-1,3,5-triazine is purified by recrystallization (toluene). A solid (yield 21.0 g, yield 60%) was obtained.

  Synthesis Reference Example-2

アルゴン気流下、９−ブロモフェナントレン（１０．０ｇ，３９ｍｍｏｌ）、４−クロロフェニルボロン酸（６．０８ｇ，３９ｍｍｏｌ）、テトラキス（トリフェニルホスフィン）パラジウム（０．８９９ｇ，０．７８ｍｍｏｌ）をトルエン（３９０ｍＬ）に懸濁し、２．０Ｍ−炭酸ナトリウム水溶液（５８ｍＬ）を滴下し、８５℃で２４時間撹拌した。放冷後、反応液を濃縮し、カラムクロマトグラフィー（ヘキサン：クロロホルム＝１：０〜１：１）で精製することで目的の９−（４−クロロフェニル）フェナントレンの白色固体（収量８．７１ｇ，収率７８％）を得た。

Under an argon stream, 9-bromophenanthrene (10.0 g, 39 mmol), 4-chlorophenylboronic acid (6.08 g, 39 mmol), tetrakis (triphenylphosphine) palladium (0.899 g, 0.78 mmol) in toluene (390 mL) 2.0M-aqueous sodium carbonate solution (58 mL) was added dropwise, and the mixture was stirred at 85 ° C. for 24 hours. After allowing to cool, the reaction mixture was concentrated and purified by column chromatography (hexane: chloroform = 1: 0 to 1: 1) to give the desired 9- (4-chlorophenyl) phenanthrene as a white solid (yield 8.71 g, Yield 78%) was obtained.

  Synthesis Reference Example-3

アルゴン気流下、９−（４−クロロフェニル）フェナントレン（２．７１ｇ，９．４ｍｍｏｌ）、４，４，４’，４’，５，５，５’，５’−オクタメチル−２，２’−ビ−１，３，２−ジオキサボロラン（３．５７ｇ，１４ｍｍｏｌ）、酢酸パラジウム（６３．２ｍｇ，０．２８ｍｍｏｌ）、酢酸カリウム（２．７６ｇ，２８ｍｍｏｌ）を１，４−ジオキサン（４７ｍＬ）に懸濁し、１００℃で１４時間撹拌した。放冷後、反応液を濃縮し、カラムクロマトグラフィー（ヘキサン：クロロホルム＝４：１〜１：１）で精製することで目的の９−［４−（４，４，５，５−テトラメチル−１，３，２−ジオキサボラン−２−イル）フェニル］フェナントレンの白色固体（収量８．７１ｇ，収率７８％）を得た。

Under an argon stream, 9- (4-chlorophenyl) phenanthrene (2.71 g, 9.4 mmol), 4,4,4 ′, 4 ′, 5,5,5 ′, 5′-octamethyl-2,2′-bi -1,3,2-dioxaborolane (3.57 g, 14 mmol), palladium acetate (63.2 mg, 0.28 mmol), potassium acetate (2.76 g, 28 mmol) were suspended in 1,4-dioxane (47 mL), Stir at 100 ° C. for 14 hours. After allowing to cool, the reaction mixture is concentrated and purified by column chromatography (hexane: chloroform = 4: 1 to 1: 1) to give the desired 9- [4- (4,4,5,5-tetramethyl- A white solid (yield 8.71 g, 78% yield) of 1,3,2-dioxaboran-2-yl) phenyl] phenanthrene was obtained.

  Synthesis Reference Example-4

合成参考例−２において、９−ブロモフェナントレンの代わりに１−ブロモ−３−クロロベンゼンを、４−クロロフェニルボロン酸の代わりに９−アントラセンボロン酸を用いた以外は、合成参考例−２と同じ方法で反応を行い、目的の９−（３−クロロフェニル）アントラセンを得た。

In Synthesis Reference Example-2, the same method as in Synthesis Reference Example-2, except that 1-bromo-3-chlorobenzene was used instead of 9-bromophenanthrene and 9-anthraceneboronic acid was used instead of 4-chlorophenylboronic acid The desired 9- (3-chlorophenyl) anthracene was obtained.

  Synthesis Reference Example-5

合成参考例−２において、４−クロロフェニルボロン酸の代わりに３−クロロフェニルボロン酸を、９−ブロモフェナントレンの代わりに１−ブロモピレンを用いた以外は、合成参考例−２と同じ方法で反応を行い、目的の１−（３−クロロフェニル）ピレンを得た。

In Synthesis Reference Example-2, the reaction was performed in the same manner as in Synthesis Reference Example-2 except that 3-chlorophenylboronic acid was used instead of 4-chlorophenylboronic acid and 1-bromopyrene was used instead of 9-bromophenanthrene. The desired 1- (3-chlorophenyl) pyrene was obtained.

  Synthesis Reference Example-6

合成参考例−２において、４−クロロフェニルボロン酸の代わりに２−クロロフェニルボロン酸を、９−ブロモフェナントレンの代わりに２−ブロモナフタレンを用いた以外は、合成参考例−２と同じ方法で反応を行い、目的の２−（２−クロロフェニル）ナフタレンを得た。

In Synthesis Reference Example-2, the reaction was performed in the same manner as in Synthesis Reference Example-2 except that 2-chlorophenylboronic acid was used instead of 4-chlorophenylboronic acid and 2-bromonaphthalene was used instead of 9-bromophenanthrene. The target 2- (2-chlorophenyl) naphthalene was obtained.

  Synthesis Reference Example-7

合成参考例−３において、９−（４−クロロフェニル）フェナントレンの代わりに（３−クロロ−３’，５’−ジメチル−１，１’−ビフェニル−５−イル）−４，６−ジフェニル−１，３，５−トリアジンを用いた以外は、合成参考例−３と同じ方法で反応を行い、目的の［３’，５’−ジメチル−（４，４，５，５−テトラメチル−１，３，２−ジオキサボラン−２−イル）−１，１’−ビフェニル−５−イル］−４，６−ジフェニル−１，３，５−トリアジンを得た。

In Synthesis Reference Example-3, (3-chloro-3 ′, 5′-dimethyl-1,1′-biphenyl-5-yl) -4,6-diphenyl-1 instead of 9- (4-chlorophenyl) phenanthrene The reaction is carried out in the same manner as in Synthesis Reference Example 3 except that 3,3,5-triazine is used and the desired [3 ′, 5′-dimethyl- (4,4,5,5-tetramethyl-1, 3,2-Dioxaboran-2-yl) -1,1′-biphenyl-5-yl] -4,6-diphenyl-1,3,5-triazine was obtained.

  Synthesis Example-1

アルゴン気流下、合成例−１で得られた２−［５−クロロ−４’−（２−ピリジル）ビフェニル−３−イル］−４，６−ジフェニル−１，３，５−トリアジン（１．００ｇ，２．０ｍｍｏｌ）、９−［４−（４，４，５，５−テトラメチル−１，３，２−ジオキサボラン−２−イル）フェニル］フェナントレン（１．１５ｇ，３．０ｍｍｏｌ）、トリス（ジベンジリデンアセトン）ジパラジウム（３６．９ｍｇ，０．０４０ｍｍｏｌ）、２−ジシクロヘキシルホスフィノ−２’，４’，６’−トリイソプロピルビフェニル（７６．７ｍｇ，０．１６ｍｍｏｌ）を、１，４−ジオキサン（４０ｍＬ）に懸濁し、２．０Ｍ−リン酸三カリウム水溶液（２０ｍＬ）を滴下し、９５℃で１６時間撹拌した。放冷後、メタノールと水を加え、析出した固体を濾別し、水、メタノール、ヘキサンで固体を洗浄した。さらに再結晶（トルエン）で精製することで目的の４，６−ジフェニル−２−［４’’−（９−フェナントレニル）−４−（２−ピリジル）−１，１’；３’，１’’−テルフェニル−５’−イル］−１，３，５−トリアジン（化合物Ａ−１０）の白色固体（収量１．１２ｇ，収率７８％）を得た。

Under an argon stream, 2- [5-chloro-4 ′-(2-pyridyl) biphenyl-3-yl] -4,6-diphenyl-1,3,5-triazine (1. 00 g, 2.0 mmol), 9- [4- (4,4,5,5-tetramethyl-1,3,2-dioxaboran-2-yl) phenyl] phenanthrene (1.15 g, 3.0 mmol), tris (Dibenzylideneacetone) dipalladium (36.9 mg, 0.040 mmol), 2-dicyclohexylphosphino-2 ′, 4 ′, 6′-triisopropylbiphenyl (76.7 mg, 0.16 mmol), 1,4- The mixture was suspended in dioxane (40 mL), 2.0 M tribasic potassium phosphate aqueous solution (20 mL) was added dropwise, and the mixture was stirred at 95 ° C. for 16 hours. After allowing to cool, methanol and water were added, the precipitated solid was filtered off, and the solid was washed with water, methanol and hexane. Further, the desired 4,6-diphenyl-2- [4 ″-(9-phenanthrenyl) -4- (2-pyridyl) -1,1 ′; 3 ′, 1 ′ is purified by recrystallization (toluene). A white solid (yield 1.12 g, yield 78%) of '-terphenyl-5'-yl] -1,3,5-triazine (Compound A-10) was obtained.

¹ H-NMR (CDCl ₃ ) δ (ppm): 7.31 (t, J = 5.8 Hz, 1H), 7.59-7.67 (m, 8H), 7.69-7.74 (m , 2H), 7.76 (d, J = 8.2 Hz, 2H), 7.80 (s, 1H), 7.84-7.88 (m, 2H), 7.96 (d, J = 8 .2 Hz, 1H), 7.98 (d, J = 7.8 Hz, 4H), 8.06 (d, J = 8.2 Hz, 1H), 8.20-8.25 (m, 3H), 8 .76-8.86 (m, 7H), 9.09 (t, J = 1.6 Hz, 1H), 9.12 (t, J = 1.6 Hz, 1H)
The structural formulas and abbreviations of the compounds used for device evaluation are shown below.

  Synthesis Example-2

合成実施例−１において、２−［５−クロロ−４’−（２−ピリジル）ビフェニル−３−イル］−４，６−ジフェニル−１，３，５−トリアジンの代わりに２−［３−クロロ−５−（３−ピリジル）フェニル］−４，６−ジフェニル−１，３，５−トリアジンを用いた以外は、合成実施例−１と同じ方法で反応を行い、目的の４，６−ジフェニル−２−［４’−（９−フェナントレニル）−３−（３−ピリジル）ビフェニル−５−イル］−１，３，５−トリアジン（化合物Ａ−３）の白色固体を得た。

In Synthesis Example-1, instead of 2- [5-chloro-4 ′-(2-pyridyl) biphenyl-3-yl] -4,6-diphenyl-1,3,5-triazine, 2- [3- The reaction was carried out in the same manner as in Synthesis Example 1 except that chloro-5- (3-pyridyl) phenyl] -4,6-diphenyl-1,3,5-triazine was used. A white solid of diphenyl-2- [4 ′-(9-phenanthrenyl) -3- (3-pyridyl) biphenyl-5-yl] -1,3,5-triazine (Compound A-3) was obtained.

¹ H-NMR (CDCl ₃ ) δ (ppm): 7.52 to 7.86 (m, 14H), 7.96 to 8.04 (m, 3H), 8.09 (d, J = 7.5 Hz) , 1H), 8.19 (brs, 2H), 8.76 (d, J = 4.5 Hz, 1H), 8.80 (d, J = 7.8 Hz, 1H), 8.87 (m, 5H) ), 9.07 (s, 1H), 9.16 (s, 1H), 9.20 (s, 1H)
Synthesis Example-3

合成実施例−１において、２−［５−クロロ−４’−（２−ピリジル）ビフェニル−３−イル］−４，６−ジフェニル−１，３，５−トリアジンの代わりに２−［５−クロロ−４’−（３−ピリジル）ビフェニル−３−イル］−４，６−ジフェニル−１，３，５−トリアジンを用いた以外は、合成実施例−１と同じ方法で反応を行い、目的の４，６−ジフェニル−２−［４’’−（９−フェナントレニル）−４−（３−ピリジル）−１，１’；３’，１’’−テルフェニル−５’−イル］−１，３，５−トリアジン（化合物Ａ−７）を得た。

In Synthesis Example-1, instead of 2- [5-chloro-4 ′-(2-pyridyl) biphenyl-3-yl] -4,6-diphenyl-1,3,5-triazine, 2- [5- Chloro-4 ′-(3-pyridyl) biphenyl-3-yl] -4,6-diphenyl-1,3,5-triazine was used in the same manner as in Synthesis Example-1, except that Of 4,6-diphenyl-2- [4 ″-(9-phenanthrenyl) -4- (3-pyridyl) -1,1 ′; 3 ′, 1 ″ -terphenyl-5′-yl] -1 , 3,5-triazine (Compound A-7) was obtained.

¹ H-NMR (CDCl ₃ ) δ (ppm): 7.46 (dd, J = 4.8, 7.8 Hz, 1H), 7.57-8.17 (m, 24H), 8.68 (d , J = 4.5 Hz, 1H), 8.77-8.91 (m, 5H), 9.01 (s, 1H), 9.09 (s, 1H), 9.13 (s, 1H)
Synthesis Example 4

合成実施例−１において、２−［５−クロロ−４’−（２−ピリジル）ビフェニル−３−イル］−４，６−ジフェニル−１，３，５−トリアジンの代わりに９−（３−クロロフェニル）アントラセンを、９−［４−（４，４，５，５−テトラメチル−１，３，２−ジオキサボラン−２−イル）フェニル］フェナントレンの代わりに４，６−ジフェニル−２−［５−（４，４，５，５−テトラメチル−１，３，２−ジオキサボラン−２−イル）ビフェニル−３−イル］−１，３，５−トリアジンを用いた以外は、合成実施例−１と同じ方法で反応を行い、目的化合物（化合物Ａ−４８８）を得た。

In Synthesis Example-1, instead of 2- [5-chloro-4 ′-(2-pyridyl) biphenyl-3-yl] -4,6-diphenyl-1,3,5-triazine, 9- (3- Chlorophenyl) anthracene is replaced by 4,6-diphenyl-2- [5 instead of 9- [4- (4,4,5,5-tetramethyl-1,3,2-dioxaboran-2-yl) phenyl] phenanthrene. Synthesis Example 1 except that-(4,4,5,5-tetramethyl-1,3,2-dioxaboran-2-yl) biphenyl-3-yl] -1,3,5-triazine was used The target compound (Compound A-488) was obtained by performing the reaction in the same manner as in Example 1.

¹ H-NMR (CDCl ₃ ) δ (ppm): 7.39-7.74 (m, 13H), 7.78-7.95 (m, 6H), 8.01-8.09 (m, 2H) ), 8.13 (d, J = 8.4 Hz, 2H), 8.57 (d, J = 9.6 Hz, 1H), 8.79-8.89 (m, 5H), 9.03 (s) , 1H), 9.12 (s, 1H)
Synthesis experiment example-5

合成実施例−１において、２−［５−クロロ−４’−（２−ピリジル）ビフェニル−３−イル］−４，６−ジフェニル−１，３，５−トリアジンの代わりに１−（３−クロロフェニル）ピレンを、９−［４−（４，４，５，５−テトラメチル−１，３，２−ジオキサボラン−２−イル）フェニル］フェナントレンの代わりに４，６−ジフェニル−２−［３−（９−フェナントレニル）−５−（４，４，５，５−テトラメチル−１，３，２−ジオキサボラン−２−イル）フェニル］−１，３，５−トリアジンを用いた以外は、合成実施例−１と同じ方法で反応を行い、目的の４，６−ジフェニル−２−（９’−ピレニル−１，１’；３’，１’’−テルフェニル−５’−イル）−１，３，５−トリアジン（化合物Ａ−５０４）を得た。

In Synthesis Example-1, instead of 2- [5-chloro-4 ′-(2-pyridyl) biphenyl-3-yl] -4,6-diphenyl-1,3,5-triazine, 1- (3- Chlorophenyl) pyrene is replaced with 4,6-diphenyl-2- [3 instead of 9- [4- (4,4,5,5-tetramethyl-1,3,2-dioxaboran-2-yl) phenyl] phenanthrene. Synthesis except that-(9-phenanthrenyl) -5- (4,4,5,5-tetramethyl-1,3,2-dioxaboran-2-yl) phenyl] -1,3,5-triazine was used The reaction was carried out in the same manner as in Example 1 to obtain the desired 4,6-diphenyl-2- (9′-pyrenyl-1,1 ′; 3 ′, 1 ″ -terphenyl-5′-yl) -1 , 3,5-triazine (Compound A-504) was obtained.

¹ H-NMR (CDCl ₃ ) δ (ppm): 7.45-8.40 (m, 24H), 8.71-8.90 (m, 5H), 9.03 (s, 1H), 9. 12 (s, 1H)
Synthesis Example-6

合成実施例−１において、２−［５−クロロ−４’−（２−ピリジル）ビフェニル−３−イル］−４，６−ジフェニル−１，３，５−トリアジンの代わりに２−（２−クロロフェニル）ナフタレンを、９−［４−（４，４，５，５−テトラメチル−１，３，２−ジオキサボラン−２−イル）フェニル］フェナントレンの代わりに［３’，５’−ジメチル−（４，４，５，５−テトラメチル−１，３，２−ジオキサボラン−２−イル）−１，１’−ビフェニル−５−イル］−４，６−ジフェニル−１，３，５−トリアジンを用いた以外は、合成実施例−１と同じ方法で反応を行い、目的化合物（化合物Ａ−４８６）を得た。

In Synthesis Example-1, instead of 2- [5-chloro-4 ′-(2-pyridyl) biphenyl-3-yl] -4,6-diphenyl-1,3,5-triazine, 2- (2- Chlorophenyl) naphthalene is replaced with [3 ′, 5′-dimethyl- (9) instead of 9- [4- (4,4,5,5-tetramethyl-1,3,2-dioxaboran-2-yl) phenyl] phenanthrene. 4,4,5,5-tetramethyl-1,3,2-dioxaboran-2-yl) -1,1′-biphenyl-5-yl] -4,6-diphenyl-1,3,5-triazine The reaction was conducted in the same manner as in Synthesis Example 1 except that the target compound (Compound A-486) was obtained.

¹ H-NMR (CDCl ₃ ) δ (ppm): 2.63 (s, 6H), 7.45-8.40 (m, 20H), 8.65-8.73 (m, 5H), 9. 01 (s, 1H), 9.07 (s, 1H)

素子実施例−１
基板には、２ｍｍ幅の酸化インジウム−スズ（ＩＴＯ）膜がストライプ状にパターンされたＩＴＯ透明電極付きガラス基板を用いた。この基板をイソプロピルアルコールで洗浄した後、オゾン紫外線洗浄にて表面処理を行った。洗浄後の基板に、真空蒸着法で各層の真空蒸着を行い、断面図を図１に示すような発光面積４ｍｍ^２有機電界発光素子を作製した。

Element Example-1
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 as shown in FIG.

First, the said glass substrate was introduce | transduced in the vacuum evaporation tank and it pressure-reduced to 1.0 * 10 <^-4> Pa. Thereafter, a hole injection layer 2, a charge generation layer 3, a hole transport layer 4, a light emitting layer 5, an electron transport layer 6, and an electron injection are formed as an organic compound layer on the glass substrate with an ITO transparent electrode shown by 1 in FIG. Layer 7 was sequentially formed, and then cathode layer 8 was formed. As the hole injection layer 2, sublimation-purified HIL was vacuum-deposited with a thickness of 20 nm. As the charge generation layer 3, sublimated and purified HAT was vacuum-deposited with a thickness of 5 nm. As the hole transport layer 4, HTL was vacuum-deposited with a film thickness of 25 nm. As the light emitting layer 5, EML-1 and EML-2 were vacuum-deposited by the film thickness of 35 nm in the ratio of 97: 3 (weight ratio). As the electron transport layer 6, 4,6-diphenyl-2- [4 ″-(9-phenanthrenyl) -4- (2-pyridyl) -1,1 ′ synthesized in Synthesis Example-1 of the present invention; 3 ′, 1 ″ -terphenyl-5′-yl] -1,3,5-triazine (Compound A-10) was vacuum-deposited with a film thickness of 45 nm. As the electron injection layer 7, sublimated and purified Liq was used. Each organic material was deposited by a resistance heating method, and the heated compound was vacuum deposited at a deposition rate of 0.3 to 0.5 nm / second. A metal mask is disposed so as to be orthogonal to the ITO stripe, and a cathode layer 8 is formed, and the cathode layer 8 is formed by vacuum deposition of silver magnesium and silver at a thickness of 80 nm and 20 nm, respectively, to form a two-layer structure. The film thickness is 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, and the sealing was made of a glass sealing cap and the above-mentioned film forming substrate epoxy type ultraviolet curable resin (manufactured by Nagase ChemteX Corporation). Was used.

Element Reference Example-1
In Device Example-1, 2- [5- (9-phenanthryl) -4 ′-(2-pyridyl) biphenyl-3-yl] -4,6-diphenyl-1,3, instead of compound A-10 An organic electroluminescent element was produced in the same manner as in Example 1 except that 5-triazine (ETL-1) was 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 the light emission characteristics, voltage (V) and current efficiency (cd / A) when a current density of 10 mA / cm ² was passed were measured, and a luminance half time during continuous lighting was measured. In addition, the luminance decay time during continuous lighting when the initial luminance was driven at 1200 cd / m ² was measured. Table 1 below shows the time when the luminance (cd / m ² ) is reduced by 50% as the element lifetime.

表１より、参考例に比べて、本発明のアジン化合物（１）を用いた有機電界発光素子は、素子寿命において優れることが見出された。また、本発明のアジン化合物（１）は、参考例にくらべて有機電界発光素子の駆動電圧及び電流効率においても上回る特性を示す事が見出された。

From Table 1, it was found that the organic electroluminescence device using the azine compound (1) of the present invention was superior in device life compared to the reference example. In addition, it was found that the azine compound (1) of the present invention exhibits characteristics exceeding the driving voltage and current efficiency of the organic electroluminescence device as compared with the reference example.

Element Example-2
In Device Example-1, HIL is 65 nm, HTL is 10 nm, EML-1 and EML-2 are 20 nm in a ratio of 95: 5 (weight ratio), and Synthesis Example-2 of the present invention is used instead of Compound A-10. 4,6-diphenyl-2- [4 ′-(9-phenanthrenyl) -3- (3-pyridyl) biphenyl-5-yl] -1,3,5-triazine (Compound A-3) An organic electroluminescent device was produced in the same manner as in Device Example 1 except that.

Element Reference Example-2
In the device example-2, an organic electroluminescence device was produced by the same method as the device example-2 except that ETL-2 was used instead of the compound A-3.

Element Reference Example-3
In the device example-2, an organic electroluminescence device was produced in the same manner as the device example-2 except that ETL-3 was used instead of the compound A-3.

The luminance decay time during continuous lighting when the initial luminance was driven at 1000 cd / m ² was measured. Table 2 below shows the time when the luminance (cd / m ² ) is reduced by 95% as the element lifetime.

  The present invention provides a cyclic azine compound having a novel structure that can be used as an electron transport layer of an organic electroluminescent device to enable low voltage driving, high efficiency, and long life of the device.

Claims (10)

The cyclic azine compound represented by General formula (1).

(In General Formula (1), Ar ¹ is the same as each other, and the aromatic having 6 to 10 carbon atoms which may be substituted with an alkyl group having 1 to 4 carbon atoms, a fluorine atom, a phenyl group, or a pyridyl group. .Ar ² representing a family of carbon hydrogen group, .Ar ³ representing a condensed aromatic hydrocarbon group of the alkyl group, or fluorine atoms may be substituted with atoms 10 to 17 1 to 4 carbon atoms, An alkyl group having 1 to 4 carbon atoms, an aromatic hydrocarbon group having 6 to 17 carbon atoms which may be substituted with fluorine, an alkyl group having 1 to 4 carbon atoms, or a fluorine atom. Represents a heteroaromatic group composed only of 6 rings having 4 to 9 carbon atoms, X is an alkyl group having 1 to 4 carbon atoms, a phenylene group optionally substituted with a fluorine atom, an azaphenylene group, or Represents a diazaphenylene group, Y represents CH or nitrogen; .p representing the child, .q representing the integer of 1 to 3 represents an integer of 0 to 3.) The cyclic azine compound according to claim 1, wherein Ar ¹ is a phenyl group, a p-tolyl group, an m-tolyl group, a p-biphenyl group, an m-biphenyl group, a 1-naphthyl group, or a 2-naphthyl group. The cyclic azine compound according to claim 1 or ² , wherein Ar ² is a naphthyl group, an anthracenyl group, a pyrenyl group, a phenanthrenyl group, or a fluoranthenyl group. The cyclic azine compound according to claim 1 or ² , wherein Ar ² is a naphthyl group, an anthracenyl group, a pyrenyl group, or a phenanthrenyl group. Ar ³ is a phenyl group, tolyl group, dimethylphenyl group, naphthyl group, anthracenyl group, pyrenyl group, phenanthrenyl group, fluoranthenyl group, pyridyl group, pyrimidyl group, pyrazyl group, quinolyl group, or isoquinolyl group The cyclic azine compound according to any one of claims 1 to 4. The cyclic azine compound according to any one of claims 1 to 5, wherein X is a phenylene group. The cyclic azine compound according to any one of claims 1 to 6, wherein Y is a nitrogen atom. The cyclic azine compound according to any one of claims 1 to 7, wherein the cyclic azine compound represented by the general formula (1) is any of the following compounds.

General formula (2)

(In General Formula (2), Ar ¹ is the same as each other, and is an aromatic group having 6 to 10 carbon atoms which may be substituted with an alkyl group having 1 to 4 carbon atoms, fluorine, phenyl group, or pyridyl group. Ar ² represents an alkyl group having 1 to 4 carbon atoms or a condensed aromatic hydrocarbon group having 10 to 17 carbon atoms which may be substituted with a fluorine atom, and Z represents a halogen atom. Y represents CH or a nitrogen atom, and p represents an integer of 1 to 3.)
And a compound represented by the general formula (3)

(In General Formula (3), Ar ³ is an alkyl group having 1 to 4 carbon atoms, an aromatic hydrocarbon group having 6 to 17 carbon atoms which may be substituted with fluorine, or an alkyl having 1 to 4 carbon atoms. Represents a heteroaromatic group composed of only a 6-ring having 4 to 9 carbon atoms which may be substituted with a group or a fluorine atom, and X is substituted with an alkyl group having 1 to 4 carbon atoms or a fluorine atom And represents a phenylene group, an azaphenylene group, or a diazaphenylene group that may be present, q represents an integer of 0 to 3, and M represents a leaving group.
The compound represented by formula (1) is subjected to a coupling reaction in the presence of a base and a palladium catalyst, or in the presence of a base, a palladium catalyst, and an alkali metal salt. )

(In the general formula (1), Ar ¹ , Ar ² , Ar ³ , X, Y, p, and q are the same as described above.)
The manufacturing method of the cyclic azine compound represented by these. General formula (4)

(In General Formula (2), Ar ¹ is the same as each other, and is an aromatic group having 6 to 10 carbon atoms which may be substituted with an alkyl group having 1 to 4 carbon atoms, fluorine, phenyl group, or pyridyl group. Ar ² represents an alkyl group having 1 to 4 carbon atoms or a condensed aromatic hydrocarbon group having 10 to 17 carbon atoms which may be substituted with a fluorine atom, Y represents CH, Or represents a nitrogen atom, p represents an integer of 1 to 3, and M represents a leaving group.)
And a compound represented by the general formula (5)

(In General Formula (3), Ar ³ is an alkyl group having 1 to 4 carbon atoms, an aromatic hydrocarbon group having 6 to 17 carbon atoms which may be substituted with fluorine, or an alkyl having 1 to 4 carbon atoms. Represents a heteroaromatic group composed of only 6 groups of 4 to 9 carbon atoms which may be substituted with a group or a fluorine atom, Z represents a halogen atom, Y represents CH or a nitrogen atom; Q represents an integer of 0 to 3.)
The compound represented by formula (1) is subjected to a coupling reaction in the presence of a base and a palladium catalyst, or in the presence of a base, a palladium catalyst, and an alkali metal salt. )

(In the general formula (1), Ar ¹ , Ar ² , Ar ³ , X, Y, p, and q are the same as described above.)
The manufacturing method of the cyclic azine compound represented by these.

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