JP2016141633A - Triazine compound, production method thereof, and organic electroluminescent element using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a triazine compound which can be used as an electron transport material in an organic electroluminescent element and realizes improved luminous efficacy and a long life.SOLUTION: The invention provides a triazine compound represented by the general formula (1), and an organic electroluminescent element using the compound. In the figure, number 1 represents a glass substrate with ITO transparent electrodes, number 2 represents a hole injection layer, number 3 represents a charge generation layer, number 4 represents a hole transport layer, number 5 represents a luminous layer, number 6 represents an electron transport layer, and number 7 represents a negative electrode layer.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a triazine compound having the same aromatic hydrocarbon group at the 3-position of two phenyl groups among the three phenyl groups of triphenyltriazine, a method for producing the triazine compound, and a method using the same. The present invention relates to an organic electroluminescent device having high efficiency, low voltage, and high durability.

  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. In addition, although recent organic electroluminescence devices have been improved gradually, excellent materials are required for the purpose of further improving 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 improvement in voltage, lifetime and luminous efficiency. In addition, it is generally known that anthracene derivatives such as anthracene-type triazine compounds disclosed in Patent Document 2 have photoreactivity such as photodimerization reaction and photooxidation, and the structure of anthracene derivatives than other condensed ring compounds Changes are likely to occur, which in turn can have a significant impact on device performance.

JP 2011-063584 A JP 2011-093864 A

  The present invention solves the above-described problems, and an object of the present invention is to provide a specific triazine compound that significantly improves the lifetime of an organic electroluminescent device as compared with a conventionally known triazine compound.

  Another object of the present invention is to provide a method for producing a triazine compound.

  Another object of the present invention is to provide a production intermediate necessary for producing a triazine compound.

  As a result of intensive studies to solve the above-mentioned problems, the inventors of the present invention have condensed ring aromatic hydrocarbons having at least three or more phenanthrenes or fluorenes as partial or whole skeletons, which are not higher in photoreactivity than anthracene. An organic electroluminescent device using a triazine compound represented by the following general formula (1) (hereinafter, also referred to as “triazine compound (1)”), which has a group, as an electron transport material is a conventionally known material As compared with the case where is used, it has been found that the lifetime characteristic is remarkably exhibited, and the present invention has been completed.

  That is, the present invention relates to the general formula (1)

（一般式（１）中、
２つのＡｒ^１は同一の置換基を表す。
Ａｒ^１は、部分又は全体骨格としてフェナントレン又はフルオレンを有する炭素数１４〜１８の縮環芳香族炭化水素基（該基は、炭素数１〜４のアルキル基で置換されていてもよい）を表す。
Ａｒ^２は、水素原子、炭素数１〜４のアルキル基で置換されていてもよい炭素数６〜１０の芳香族炭化水素基、又は炭素数１〜４のアルキル基で置換されていてもよい炭素数３〜９の含窒素ヘテロ芳香族基を表す。
Ｘは、各々独立して、炭素数１〜４のアルキル基で置換されていてもよい炭素数６〜１０の２価芳香族炭化水素基、又は炭素数１〜４のアルキル基で置換されていてもよい炭素数４〜５の２価含窒素ヘテロ芳香族基を表す。
ｐは０、１又は２の整数を示す。ｐが２の時、Ｘは同一または相異なっていてもよい。）
で示されるトリアジン化合物、その製造方法、及びそれを用いた有機電界発光素子に関するものである。

(In general formula (1),
Two Ar ¹ represent the same substituent.
Ar ¹ represents a condensed aromatic hydrocarbon group having 14 to 18 carbon atoms having phenanthrene or fluorene as a partial or entire skeleton (this group may be substituted with an alkyl group having 1 to 4 carbon atoms). .
Ar ² may be substituted with a hydrogen atom, an aromatic hydrocarbon group having 6 to 10 carbon atoms which may be substituted with an alkyl group having 1 to 4 carbon atoms, or an alkyl group having 1 to 4 carbon atoms. A nitrogen-containing heteroaromatic group having 3 to 9 carbon atoms is represented.
Each X is independently substituted with a C6-C10 divalent aromatic hydrocarbon group which may be substituted with a C1-C4 alkyl group or a C1-C4 alkyl group. And a C 4-5 divalent nitrogen-containing heteroaromatic group.
p represents an integer of 0, 1 or 2. When p is 2, X may be the same or different. )
And a method for producing the triazine compound, and an organic electroluminescent device using the triazine compound.

  The triazine compound of the present invention can significantly extend the lifetime of an organic electroluminescent device as compared with conventionally known compounds, and has the effect of significantly improving the product life and durability of the final product. In addition, the triazine compound of the present invention can also be used as an electron transport material excellent in driving voltage and power efficiency of an organic electroluminescence device. That is, according to the present invention, it is possible to provide an organic electroluminescence device having low power consumption and excellent device life.

  Hereinafter, the present invention will be described in detail.

  The present invention relates to the above triazine compound (1), a method for producing the same, and an organic electroluminescent device containing the same.

  The substituents in the triazine compound (1) are defined as follows.

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

As a condensed ring aromatic hydrocarbon group having 14 to 18 carbon atoms having phenanthrene or fluorene as a partial or whole skeleton in Ar ¹ (this group may be substituted with an alkyl group having 1 to 4 carbon atoms) Although not particularly limited, for example, a phenanthryl group, a fluoranthenyl group, a chrycenyl group, a triphenylenyl group, or a pyrenyl group (these groups may be substituted with an alkyl group having 1 to 4 carbon atoms) Is mentioned.

The alkyl group having 1 to 4 carbon atoms in Ar ^1, is not particularly limited, and methyl group, an ethyl group, a propyl group, an isopropyl group, preferred examples n- butyl group, or t- butyl group and the like It is done. Among these, a methyl group is more preferable in terms of excellent electron transport material characteristics.

As a condensed ring aromatic hydrocarbon group having 14 to 18 carbon atoms having phenanthrene or fluorene as a partial or whole skeleton in Ar ¹ (this group may be substituted with an alkyl group having 1 to 4 carbon atoms) Although not particularly limited, methylphenanthryl group, methylpyrenyl group, methyltriphenylenyl group, methylchrycenyl group, methylfluoranthenyl group, methylpyrenyl group, dimethylphenanthryl group, dimethylpyrenyl group, dimethyltriphenylenyl group Preferred examples include a ruthenium group, a dimethylchrysenyl group, a dimethylfluoranthenyl group, or a dimethylpyrenyl group.

Ar ¹ is a phenanthryl group, a fluoranthenyl group, a chrycenyl group, a triphenylenyl group, or a pyrenyl group (these groups are substituted with an alkyl group having 1 to 4 carbon atoms in terms of excellent electron transporting material properties). The phenanthryl group or the fluoranthenyl group (these substituents may have an alkyl group having 1 to 4 carbon atoms as a substituent), and the phenanthryl group (methyl group). Is more preferable as a substituent.

Specific examples of Ar ¹ include 1-phenanthryl group, 2-phenanthryl group, 3-phenanthryl group, 4-phenanthryl group, 9-phenanthryl group, 1-methylphenanthren-2-yl group, 1-methylphenanthrene-3- Yl group, 1-methylphenanthren-4-yl group, 1-methylphenanthrene-5-yl group, 1-methylphenanthrene-6-yl group, 1-methylphenanthren-7-yl group, 1-methylphenanthrene-8- Yl group, 1-methylphenanthren-9-yl group, 1-methylphenanthrene-10-yl group, 2-methylphenanthren-1-yl group, 2-methylphenanthren-3-yl group, 2-methylphenanthrene-4- Yl group, 2-methylphenanthren-5-yl group, 2-methylphenanthren-6-yl group 2-methylphenanthren-7-yl group, 2-methylphenanthren-8-yl group, 2-methylphenanthren-9-yl group, 2-methylphenanthren-10-yl group, 3-methylphenanthren-1-yl group 3-methylphenanthren-2-yl group, 3-methylphenanthren-4-yl group, 3-methylphenanthren-5-yl group, 3-methylphenanthren-6-yl group, 3-methylphenanthren-7-yl group 3-methylphenanthren-8-yl group, 3-methylphenanthren-9-yl group, 3-methylphenanthren-10-yl group, 4-methylphenanthren-1-yl group, 4-methylphenanthren-2-yl group 4-methylphenanthren-3-yl group, 4-methylphenanthren-5-yl group, 4-methylphenanthrene Entomen-6-yl group, 4-methylphenanthren-7-yl group, 4-methylphenanthren-8-yl group, 4-methylphenanthren-9-yl group, 4-methylphenanthren-10-yl group, 1-pyrenyl Group, 2-pyrenyl group, 4-pyrenyl group, 1-methylpyren-2-yl group, 1-methylpyren-3-yl group, 1-methylpyren-4-yl group, 1-methylpyren-5-yl group, 1- Methylpyren-6-yl group, 1-methylpyren-7-yl group, 1-methylpyren-8-yl group, 1-methylpyren-9-yl group, 1-methylpyren-10-yl group, 2-methylpyren-1-yl Group, 2-methylpyren-3-yl group, 2-methylpyren-4-yl group, 2-methylpyren-5-yl group, 2-methylpyren-6-yl group, 2-methylpyrene- -Yl group, 2-methylpyren-8-yl group, 2-methylpyren-9-yl group, 2-methylpyren-10-yl group, 9-methylpyren-1-yl group, 9-methylpyren-2-yl group, 9 -Methylpyrene-3-yl group, 9-methylpyren-4-yl group, 9-methylpyren-5-yl group, 9-methylpyren-6-yl group, 9-methylpyren-7-yl group, 9-methylpyrene-8- Yl group, 9-methylpyren-10-yl group, fluoranthen-1-yl group, fluoranthen-1-yl group, fluoranthen-2-yl group, fluoranthen-3-yl group, fluoranthen-4-yl group, fluoranthene-5 -Yl group, fluoranthen-6-yl group, fluoranthen-7-yl group, fluoranthen-8-yl group, fluoranthen-9-yl group, fluoranthe N-10-yl group, triphenylene-1-yl group, triphenylene-2-yl group, chrysen-1-yl group, chrysen-2-yl group, chrysen-5-yl group, or chrysen-6-yl group Is a preferred example. Among these substituents, 1-phenanthryl group, 2-phenanthryl group, 3-phenanthryl group, 4-phenanthryl group, 9-phenanthryl group, 1-methylphenanthren-2-yl group are excellent in electron transporting material characteristics. Group, 1-methylphenanthren-3-yl group, 1-methylphenanthren-4-yl group, 1-methylphenanthren-5-yl group, 1-methylphenanthren-6-yl group, 1-methylphenanthren-7-yl group Group, 1-methylphenanthren-8-yl group, 1-methylphenanthren-9-yl group, 1-methylphenanthren-10-yl group, 2-methylphenanthren-1-yl group, 2-methylphenanthren-3-yl Group, 2-methylphenanthren-4-yl group, 2-methylphenanthren-5-yl group, 2-methyl Ruphenanthren-6-yl group, 2-methylphenanthren-7-yl group, 2-methylphenanthren-8-yl group, 2-methylphenanthren-9-yl group, 2-methylphenanthren-10-yl group, 3- Methylphenanthren-1-yl group, 3-methylphenanthren-2-yl group, 3-methylphenanthren-4-yl group, 3-methylphenanthren-5-yl group, 3-methylphenanthren-6-yl group, 3- Methylphenanthren-7-yl group, 3-methylphenanthren-8-yl group, 3-methylphenanthren-9-yl group, 3-methylphenanthren-10-yl group, 4-methylphenanthren-1-yl group, 4- Methylphenanthren-2-yl group, 4-methylphenanthren-3-yl group, 4-methylphenanthre -5-yl group, 4-methylphenanthren-6-yl group, 4-methylphenanthren-7-yl group, 4-methylphenanthren-8-yl group, 4-methylphenanthren-9-yl group, or 4-methyl More preferred is a phenanthrene-10-yl group.

Ar ² may be substituted with a hydrogen atom, an aromatic hydrocarbon group having 6 to 10 carbon atoms which may be substituted with an alkyl group having 1 to 4 carbon atoms, or an alkyl group having 1 to 4 carbon atoms. A nitrogen-containing heteroaromatic group having 3 to 9 carbon atoms is represented.

The alkyl group having 1 to 4 carbon atoms in Ar ^2, is not particularly limited, and methyl group, an ethyl group, a propyl group, an isopropyl group, preferred examples n- butyl group, or t- butyl group and the like It is done. Among these, a methyl group is more preferable in terms of excellent electron transport material characteristics.

The aromatic hydrocarbon group having 6 to 10 carbon atoms in Ar ^2, is not particularly limited, for example, phenyl or naphthyl.

The nitrogen-containing heteroaromatic group having 3 to 9 carbon atoms in Ar ² is not particularly limited. For example, pyridyl group, pyrazyl group, pyrimidyl group, pyridazyl group, triazyl group, quinolyl group, isoquinolyl group, naphthyridyl group Preferred examples include a group, a quinazolyl group, a quinoxalyl group, and the like.

Specific examples of Ar ² include, but are not limited to, hydrogen atom, 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 2-methylpyridin-3-yl group, 2-methylpyridine-4. -Yl group, 2-methylpyridin-5-yl group, 2-methylpyridin-6-yl group, 3-methylpyridin-2-yl group, 3-methylpyridin-4-yl group, 3-methylpyridin-5 -Yl group, 3-methylpyridin-6-yl group, 4-methylpyridin-2-yl group, 4-methylpyridin-3-yl group, 2,6-dimethylpyridin-3-yl group, 2,6- Dimethylpyridin-4-yl group, 3,6-dimethylpyridin-2-yl group, 3,6-dimethylpyridin-4-yl group, 3,6-dimethylpyridin-5-yl group, pyridin-6-yl group 2-pyrimidyl group, 4-pi Limidyl group, 5-pyrimidyl group, 4,6-dimethylpyrimidin-2-yl group, quinolin-2-yl group, quinolin-3-yl group, quinolin-4-yl group, quinolin-5-yl group, quinolin- 6-yl group, quinolin-7-yl group, quinolin-8-yl group, quinolin-9-yl group, 2-methylquinolin-3-yl group, 2-methylquinolin-4-yl group, 2-methylquinoline -5-yl group, 2-methylquinolin-6-yl group, 2-methylquinolin-7-yl group, 2-methylquinolin-8-yl group, isoquinolin-1-yl group, isoquinolin-3-yl group, Isoquinolin-4-yl group, isoquinolin-5-yl group, isoquinolin-6-yl group, isoquinolin-7-yl group, isoquinolin-8-yl group, pyrazyl group, 2-methylpyrazin-5-yl group, 2 Methylpyrazin-6-yl group, pyridazin-3-yl group, pyridazin-4-yl group, 3-methylpyridazin-5-yl group, 3-methylpyridazin-6-yl group, 4-methylpyridazin-3-yl Group, 4-methylpyridazin-5-yl group, 4-methylpyridazin-6-yl group, 5-methylpyridazin-3-yl group, 5-methylpyridazin-3-yl group, 5-methylpyridazin-4-yl Group, 5-methylpyridazin-6-yl group, 6-methylpyridazin-3-yl group, 6-methylpyridazin-4-yl group, 6-methylpyridazin-5-yl group, triazyl group, 2,4-dimethyl Triazin-6-yl group, naphthyridin-2-yl group, naphthyridin-3-yl group, naphthyridin-4-yl group, quinoxalin-2-yl group, quinoxalin-5-yl Quinoxalin-6-yl group, 2,3-dimethylquinoxalin-5-yl group, 2,3-dimethylquinoxalin-6-yl group, quinazolin-2-yl group, quinazolin-4-yl group, quinazoline-5 Yl, quinazolin-6-yl, quinazolin-7-yl, quinazolin-8-yl, phenyl, p-tolyl, m-tolyl, o-tolyl, 2,4-dimethylphenyl, 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-i Sopropylphenyl group, 4-isopropylphenyl group, 2,4-diisopropylphenyl group, 3,5-diisopropylphenyl group, 2-butylphenyl group, 3-butylphenyl group, 4-butylphenyl group, 2,4-dibutyl Phenyl group, 3,5-dibutylphenyl group, 2-tert-butylphenyl group, 3-tert-butylphenyl group, 4-tert-butylphenyl group, 2,4-di-tert-butylphenyl group, 3,5 -Di-tert-butylphenyl group, 1-naphthyl group, 2-naphthyl group, 1-methylnaphthalen-4-yl group, 1-methylnaphthalen-5-yl group, 1-methylnaphthalen-6-yl group, 1 -Methylnaphthalen-7-yl group, 1-methylnaphthalen-8-yl group, 2-methylnaphthalen-1-yl group, 2-methylnaphth Len-3-yl group, 2-methylnaphthalen-4-yl group, 2-methylnaphthalen-5-yl group, 2-methylnaphthalen-6-yl group, 2-methylnaphthalen-7-yl group, or 2- Examples thereof include a methylnaphthalen-8-yl group.

Ar ² is a carbon atom that may be substituted with a hydrogen atom, an aromatic hydrocarbon group having 6 to 10 carbon atoms that may be substituted with a methyl group, or a methyl group in terms of excellent electron transporting material characteristics. It is preferably a nitrogen-containing heteroaromatic group of 3 to 9 and is not particularly limited. For example, a hydrogen atom, 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 2-methylpyridine- 6-yl group, 3-methylpyridin-6-yl group, 4-methylpyridin-6-yl group, 2-methylpyridin-5-yl 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-isoquinolyl group, 8-isoquinolyl group, 2-pyrimidyl group, 4,6-dimethylpyrimidyl group, pyrazyl group, phenyl group, p-tolyl group , 1-naphthyl group, or 2-naphthyl group.

Ar ² is a hydrogen atom, an unsubstituted aromatic hydrocarbon group having 6 to 10 carbon atoms, or an unsubstituted nitrogen-containing heteroaromatic group having 3 to 9 carbon atoms in terms of excellent electron transporting material characteristics. More preferably, although not particularly limited, for example, a hydrogen atom, 2-pyridyl group, 3-pyridyl group, 2-quinolyl group, 3-quinolyl group, 8-quinolyl group, 1-isoquinolyl group, 3 -Isoquinolyl group, 4-isoquinolyl group, phenyl group, 1-naphthyl group, 2-naphthyl group, etc. are mentioned.

Ar ² is a 3-pyridyl group, a 2-pyridyl group, a 3-quinolyl group, a 4-isoquinolyl group, a phenyl group, a 1-naphthyl group, or a 2-naphthyl group in terms of excellent electron transporting material characteristics. More preferably.

  Each X is independently substituted with a C6-C10 divalent aromatic hydrocarbon group which may be substituted with a C1-C4 alkyl group or a C1-C4 alkyl group. And a C 4-5 divalent nitrogen-containing heteroaromatic group.

  Although it does not specifically limit as a C1-C4 alkyl group in X, A methyl group, an ethyl group, a propyl group, an isopropyl group, n-butyl group, or t-butyl group etc. are mentioned as a preferable example. . Among these, a methyl group is more preferable in terms of excellent electron transport material characteristics.

  The divalent aromatic hydrocarbon group having 6 to 10 carbon atoms or the divalent nitrogen-containing heteroaromatic group having 4 to 5 carbon atoms in X is not particularly limited, but for example, a phenylene group or a naphthylene group , Etc.

  The divalent nitrogen-containing heteroaromatic group having 4 to 5 carbon atoms in X is not particularly limited, and examples thereof include a pyridylene group, a pyrazylene group, a pyrimidylene group, and a pyridazylene group.

  X is independently substituted with a methyl group, a divalent aromatic hydrocarbon group having 6 to 10 carbon atoms, which may be substituted with a methyl group, in terms of excellent electron transport material properties. It is preferably a divalent nitrogen-containing heteroaromatic group having 4 to 5 carbon atoms, and is not particularly limited. For example, a phenylene group, a methylphenylene group, a naphthylene group, a methylnaphthylene group, a pyridylene group, Examples thereof include a methylpyridylene group, a pyrazylene group, a methylpyrazylene group, a pyrimidylene group, a methylpyrimidylene group, a pyridazylene group, and a methylpyridazilen group.

  With respect to X, each is independently a phenylene group (for example, 1,2-phenylene group, 1,3-phenylene group, 1,4-phenylene group), naphthylene group, Pyridylene group (for example, 2,5-pyridylene group, 3,6-pyridylene group, etc.), methylpyridylene group (for example, 6-methyl-2,5-pyridylene group, 2-methyl-3,6-pyridylene group, etc.), A dimethylpyridylene group, a pyrazylene group, a methylpyrazylene group, a dimethylpyrazylene group, a pyrimidylene group, a methylpyrimidylene group, or a dimethylpyrimidylene group (for example, a 4,6-dimethyl-2,4-pyrimidylene group). It is more preferable.

  X is independently a phenylene group (1,2-phenylene group, 1,3-phenylene group, 1,4-phenylene group, etc.) or pyridylene group (for example, 2,5-pyridylene group and the like are more preferable.

  p represents 0, 1 or 2. In view of excellent sublimation purification operability, p is preferably 0 or 1.

In addition,-(X) _p -represents that p groups represented by -X- are connected. That is, when p = 2,-(X) _p -means "-X-X-". In this case, two Xs may be the same or different.

  Specific preferred specific examples of the triazine compound represented by the general formula (1) include the following (A-1) to (A-205), but the present invention is not limited thereto.

次に、本発明の製造方法について説明する。

Next, the manufacturing method of this invention is demonstrated.

  The triazine compound (1) of the present invention may be reacted with the following reaction formula (1) in the presence of a base and in the presence of a palladium catalyst.

（反応式（１）中、Ａｒ^１、Ａｒ^２、Ｘ、及びｐは、前記と同じ置換基を表す。Ｙ^１、Ｙ^２は、各々独立して、後述する置換基を表す。Ｍ^１及びＭ^２は、各々独立して、後述する置換基を表す。）
、又は反応式（２）

(In Reaction Formula (1), Ar ¹ , Ar ² , X, and p represent the same substituents as described above. Y ¹ and Y ² each independently represent a substituent described later. M ¹ and M ² represents each independently a substituent described later.)
Or reaction formula (2)

（反応式（２）中、Ａｒ^１、Ａｒ^２、Ｘ、及びｐは、前記と同じ置換基を表す。Ｙ^１、Ｙ^２は、各々独立して、後述する置換基を表す。Ｍ^１及びＭ^２は、各々独立して、後述する置換基を表す。）
で示される方法により製造することができる。

(In the reaction formula (2), Ar ¹ , Ar ² , X, and p represent the same substituents as described above. Y ¹ and Y ² each independently represent a substituent described later. M ¹ and M ² represents each independently a substituent described later.)
It can manufacture by the method shown by these.

  Hereinafter, the compound represented by the general formula (2) is referred to as a compound (2). In addition, it is synonymous also about a compound (3)-a compound (7).

  The compound (3) used in the reaction formula (1) or the reaction formula (2) is manufactured using, for example, a method disclosed in JP 2008-280330 A or JP 2001-335516 A. Can do. Examples of the compound (3) include the following (B-1) to (B-5), but the present invention is not limited to these.

Ｍ^１は、ＺｎＲ^１、ＭｇＲ^２、Ｓｎ（Ｒ^３）_３、又はＢ（ＯＲ^４）_２で表される置換基である。

M ¹ is a substituent represented by ZnR ¹ , MgR ² , Sn (R ³ ) ₃ , or B (OR ⁴ ) ₂ .

The substituents represented by ZnR ¹ and MgR ² are not particularly limited, and examples thereof include ZnCl, ZnBr, ZnI, MgCl, MgBr, and MgI. Examples of the substituent represented by Sn ^(R ₃₎ 3, is not particularly limited, for _{example, Sn (Me) 3, Sn} (Bu) 3 and the like.

The substituent represented by B (OR ⁴ ) ₂ is not particularly limited. For example, B (OH) ₂ , B (OMe) ₂ , B (O ⁱ Pr) ₂ , B (OBu) ₂ The following groups (C-1) to (C-6) can be exemplified. Of these, the group represented by (C-2) is preferable in that the reaction yield is good.

反応式（１）又は反応式（２）で用いられる、化合物（４）は、例えば、特開２００８−２８０３３０号公報に開示されている方法又は特開２００１−３３５５１６号公報に開示されている方法を用いて製造することができる。化合物（４）中のＭ^２は前記Ｍ^１と同様の置換基を例示することができる。化合物（４）としては、特に限定するものではないが、次の（Ｄ−１）から（Ｄ−３７）等を例示できる。

The compound (4) used in the reaction formula (1) or the reaction formula (2) is, for example, a method disclosed in JP 2008-280330 A or a method disclosed in JP 2001-335516 A. Can be used. M ² in the compound (4) can exemplify the same substituent as M ¹ . Although it does not specifically limit as a compound (4), The following (D-1) to (D-37) etc. can be illustrated.

化合物（２）、化合物（５）又は化合物（７）におけるＹ^１は、塩素原子、臭素原子、又はヨウ素原子表す。Ｙ^２は、水素原子、塩素原子、臭素原子、又はヨウ素原子表す。２つのＹ^１は同一の置換基を表し、Ｙ^１とＹ^２はまた、反応の選択性を向上させる為にＹ^１及びＹ^２は異なる置換基を有す。

Y ¹ in the compound (2), the compound (5) or the compound (7) represents a chlorine atom, a bromine atom or an iodine atom. Y ² represents a hydrogen atom, a chlorine atom, a bromine atom, or an iodine atom. Two Y ¹ represents the same substituent, Y ¹ and Y ² may also, Y ¹ and Y ² in order to improve the selectivity of the reaction having a different substituent.

  Then, Reaction formula (1) is demonstrated. “Step 1” is a method in which compound (2) is reacted with compound (3) in the presence of a palladium catalyst in the presence of a palladium catalyst to obtain compound (5) as a synthetic intermediate, Suzuki -By applying reaction conditions for general coupling reactions such as Miyaura reaction, Negishi reaction, Tamao-Kumada reaction, Stille reaction, etc., the desired product can be obtained in good yield.

  The palladium catalyst that can be used in “Step 1” is not particularly limited, and examples thereof include salts of palladium chloride, palladium acetate, palladium trifluoroacetate, palladium nitrate, and the like. In addition, π-allyl palladium chloride dimer, palladium acetylacetonate, tris (dibenzylideneacetone) dipalladium, dichlorobis (triphenylphosphine) palladium, tetrakis (triphenylphosphine) palladium and dichloro (1,1′-bis (diphenylphosphine). Complex compounds such as fino) ferrocene) palladium can also be exemplified. Among these, a palladium complex having a tertiary phosphine as a ligand is more preferable in terms of a good reaction yield, is easily available, and a palladium complex having triphenylphosphine as a ligand is preferable in terms of a good reaction yield. Particularly preferred.

  A palladium complex having a tertiary phosphine as a ligand can also be prepared in a reaction system by adding a tertiary phosphine to a palladium salt or a complex compound. The tertiary phosphine that can be used at this time is triphenylphosphine, trimethylphosphine, tributylphosphine, tri (tert-butyl) phosphine, tricyclohexylphosphine, tert-butyldiphenylphosphine, 9,9-dimethyl-4,5. -Bis (diphenylphosphino) xanthene, 2- (diphenylphosphino) -2 '-(N, N-dimethylamino) biphenyl, 2- (di-tert-butylphosphino) biphenyl, 2- (dicyclohexylphosphino) Biphenyl, bis (diphenylphosphino) methane, 1,2-bis (diphenylphosphino) ethane, 1,3-bis (diphenylphosphino) propane, 1,4-bis (diphenylphosphino) butane, 1,1 ′ -Bis (diphenylphosphino) Erocene, tri (2-furyl) phosphine, tri (o-tolyl) phosphine, tris (2,5-xylyl) phosphine, (plus-minus) -2,2'-bis (diphenylphosphino) -1,1'- Binaphthyl, 2-dicyclohexylphosphino-2 ′, 4 ′, 6′-triisopropylbiphenyl and the like can be exemplified. 2-dicyclohexylphosphino-2 ', 4', 6'-triisopropylbiphenyl or triphenylphosphine is preferable because it is easily available and the reaction yield is good. The molar ratio between the tertiary phosphine and the palladium salt or complex compound is preferably 1:10 to 10: 1, and more preferably 1: 2 to 5: 1 in terms of good reaction yield.

  Bases that can be used in “Step 1” include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate, cesium carbonate, potassium phosphate, sodium phosphate, sodium fluoride, potassium fluoride, fluorine. Examples thereof include cesium chloride, and potassium carbonate is preferable in terms of a good yield. The molar ratio of base to compound (3) is preferably 1: 2 to 10: 1, and more preferably 1: 1 to 3: 1 in terms of good yield.

  The molar ratio of the compound (2) and the compound (3) used in “Step 1” is preferably 1: 4 to 5: 1, and more preferably 1: 3 to 2: 1 in terms of a good yield.

  Examples of the solvent that can be used in “Step 1” include water, dimethyl sulfoxide, dimethylformamide, tetrahydrofuran, 1,4-dioxane, dimethoxyethane, toluene, benzene, diethyl ether, ethanol, methanol, and xylene. You may use it combining suitably. It is preferable to use dioxane or a mixed solvent of THF and water in terms of good yield.

  “Step 1” can be performed at a temperature appropriately selected from 0 ° C. to 150 ° C., and is more preferably performed at 50 ° C. to 100 ° C. in terms of a good yield.

  Compound (5) can be obtained by carrying out a normal treatment after completion of “Step 1”. If necessary, it may be purified by recrystallization, column chromatography or sublimation. “Step 2” is a method in which compound (5) is reacted with compound (4) in the presence of a palladium catalyst to obtain triazine compound (1) of the present invention. Suzuki-Miyaura reaction, Negishi reaction, Tamao- By applying reaction conditions for general coupling reactions such as Kumada reaction and Stille reaction, the target product can be obtained in high yield. In “Step 2”, the same reaction conditions as those mentioned in “Step 1” can be selected. However, the reaction conditions are not necessarily the same as those in “Step 1”. Further, the triazine compound (1) can be synthesized by adding the compound (4) to the reaction system of “Step 1” without isolating the compound (5) which is a synthetic intermediate. After completion of “Step 2”, it may be purified by recrystallization, column chromatography, sublimation or the like, if necessary.

  In addition, the compound (5) is an excellent material for industrially supplying a compound such as the compound (1) that is remarkably excellent in the low driving voltage property, the high light emission efficiency, and the long life of the organic electroluminescence device. And industrially very valuable.

  Then, Reaction formula (2) is demonstrated. “Step 3” is a method in which compound (2) is reacted with compound (4) in the presence of a palladium catalyst to obtain compound (7) as a synthetic intermediate. Suzuki-Miyaura reaction, Negishi reaction, Tamao -By applying reaction conditions of general coupling reactions such as Kumada reaction and Stille reaction, the target product can be obtained in high yield. In “Step 3”, the same reaction conditions as those mentioned in “Step 1” can be selected. However, the reaction conditions are not necessarily the same as those in “Step 1”. After completion of “Step 3”, it may be purified by recrystallization, column chromatography, sublimation or the like, if necessary. “Step 4” is a method in which the compound (7) is reacted with the compound (3) in the presence of a palladium catalyst in the presence of a palladium catalyst to obtain the triazine compound (1) of the present invention. By applying reaction conditions for general coupling reactions such as Miyaura reaction, Negishi reaction, Tamao-Kumada reaction, Stille reaction, etc., the target product can be obtained in good yield. In “Step 4”, reaction conditions similar to those mentioned in “Step 1” can be selected. However, the reaction conditions are not necessarily the same as those in “Step 1”. Further, the triazine compound (1) can be synthesized by adding the compound (3) to the reaction system of “Step 3” without isolating the compound (7) which is a synthetic intermediate. After completion of “Step 4”, it may be purified by recrystallization, column chromatography, sublimation or the like, if necessary.

  The compound (7) is an excellent material for industrially supplying a compound such as the compound (1) that is remarkably excellent in the low driving voltage property, the high light emission efficiency, and the long life of the organic electroluminescence device. And industrially very valuable.

  Next, the synthesis method of a compound (2) is demonstrated.

  Compound (2) has the following reaction formula (3)

（反応式（３）中、Ｙ^１、及びＹ^２は、各々独立して、前述した置換基を表す。Ｚは陰イオンを示す。）
で示される方法により製造することができる。

(In Reaction Formula (3), Y ¹ and Y ² each independently represent the substituent described above. Z represents an anion.)
It can manufacture by the method shown by these.

  Z is not particularly limited, for example, tetrafluoroborate ion, chlorotrifluoroborate ion, tetrachloroaluminate ion, tetrachloroiron (III) acid ion, pentachlorotin (IV) acid ion or Hexachloroantimonate (V) ion can be exemplified.

  Hereinafter, the compound represented by the general formula (8) is referred to as a compound (8). In addition, it is synonymous also about a compound (8)-a compound (10).

  The compound (2) used in the reaction formula (1), the reaction formula (2), or the reaction formula (3) can be produced using, for example, a method disclosed in JP 2008-280330 A. it can.

Y ¹ in the compound (2), the compound (8), the compound (9), or the compound (10) represents a chlorine atom, a bromine atom, or an iodine atom. Y ² represents a hydrogen atom, a chlorine atom, a bromine atom, or an iodine atom. Two Y ¹ represents the same substituent, Y ¹ and Y ² may also, reaction formula (1), Y ¹ and Y ² in order to improve the reaction selectivity of the reaction formula (2) is different substituents Have Examples of the compound (2) include the following (E-1) to (E-6).

これらのうち、化合物（２）としては反応式（１）、反応式（２）での反応収率がよい点で（Ｅ−１）、又は（Ｅ−３）が好ましい。

Among these, (E-1) or (E-3) is preferable as the compound (2) in that the reaction yield in the reaction formula (1) and the reaction formula (2) is good.

Then, Reaction formula (2) is demonstrated. In “Step 5”, the compound (8) and the compound (9) are reacted in the presence of a Lewis acid to obtain a salt represented by the synthetic intermediate compound (10), which is treated with aqueous ammonia. Can be manufactured.
Although a high yield is obtained in a wide range of 1:10 to 10: 1 molar ratio with the compounds (8) and (9) used in “Step 5”, the reaction proceeds sufficiently even in a stoichiometric amount.

  Examples of the solvent that can be used in “Step 5” include chloroform, dichloromethane, 1,2-dichloroethane, carbon tetrachloride, chlorobenzene, 1,2-dichlorobenzene, and the like. From the viewpoint of good yield, dichloromethane or chloroform is preferable.

  Examples of the Lewis acid that can be used in “Step 5” include boron trifluoride, aluminum trichloride, iron trichloride, tin tetrachloride, and antimony pentachloride. Antimony pentachloride is preferred because of its good yield. Although the salt (10) can be isolated, it may be subjected to the next reaction operation as a solution. In the case of isolation, Z of the salt (10) is not particularly limited as long as it is an anion, but tetrafluoroborate ion, chlorotrifluoro ion, which is a fluoride ion or chloride ion bonded to the Lewis acid mentioned above. When a borate ion, tetrachloroaluminate ion, tetrachloroiron (III) acid ion, pentachlorotin (IV) acid ion or hexachloroantimonate (V) ion is obtained as a counter anion, the yield is good.

  Although there is no restriction | limiting in particular in the density | concentration of the ammonia water which can be used at "the process 5," 5 to 50% is preferable and reaction advances fully even if it is 28% on the market.

  In “Step 5”, the reaction temperature is not particularly limited, but the reaction is preferably performed at a temperature appropriately selected from −50 ° C. to the solvent reflux temperature. Moreover, although reaction time is based on balance with reaction temperature, it is preferable that it is 30 minutes-24 hours.

  Compound (2) is obtained by distilling off the solvent after completion of “Step 5”. If necessary, it may be purified by recrystallization, column or sublimation.

  The compound (2) is an excellent material for industrially supplying a compound such as the compound (1) which is remarkably excellent in the low driving voltage property, the high light emission efficiency and the long life of the organic electroluminescence device. And industrially very valuable.

  The triazine compound (1) of the present invention is effective when used as a part of the components of the organic electroluminescence device. In particular, when used as an electron transport layer, effects such as longer life, higher efficiency, and lower voltage can be obtained than conventional devices. Moreover, when using the triazine compound (1) of this invention as an organic electroluminescent element material, it is also possible to use it as a co-deposition film | membrane with arbitrary organometallic seeds, an organic compound, or an inorganic compound.

  Since the triazine compound (1) of the present invention exhibits good electron transport properties, it is preferably used as a material for an organic thin film layer having electron transport properties such as a light emitting layer, an electron transport layer, and an electron injection layer in an organic electroluminescence device. be able to.

Although there is no restriction | limiting in particular in the manufacturing method of the thin film for organic electroluminescent elements containing the triazine compound (1) of this invention, The film-forming by a vacuum evaporation method is possible. Film formation by the vacuum evaporation method can be performed by using a general-purpose vacuum evaporation apparatus. The vacuum degree of the vacuum chamber when forming a film by the vacuum evaporation method is determined by taking into account the manufacturing tact time and manufacturing cost of manufacturing the organic electroluminescence device, and commonly used diffusion pumps, turbo molecular pumps, cryopumps, etc. 1 × 10 ⁻² to 1 × 10 ⁻⁵ Pa which can be reached by the above is desirable. The deposition rate is preferably 0.005 to 1.0 nm / second, depending on the thickness of the film to be formed. In addition, since the triazine compound (1) of the present invention has high solubility in chloroform, dichloromethane, 1,2-dichloroethane, chlorobenzene, toluene, ethyl acetate, tetrahydrofuran or the like, a spin coating method using a general-purpose apparatus, inkjet Film formation by a method, a casting method, a dip method or the like is also possible.

It is a cross-sectional schematic diagram of the organic electroluminescent element produced by embodiment (element evaluation).

  EXAMPLES Hereinafter, although a synthesis example, a synthesis example, a device example, a reference example, etc. are given and this invention is demonstrated further in detail, this invention is limited to these and is not interpreted.

  Synthesis Example-1

アルゴン気流下、３−ブロモベンゾニトリル（２９．１ｇ，１６０．０ｍｍｏｌ）と３−クロロ安息香酸クロリド（１４．０ｇ，８０.０ｍｍｏｌ）を１３０ｍＬのクロロホルムで溶解した。得られた溶液に、５塩化アンチモン（２６．３ｇ，８８．０ｍｍｏｌ）を０℃で滴下した。混合物を室温で１時間攪拌後、７０℃に加熱して２時間撹拌させて反応させた。室温まで冷却後、減圧下で低沸点成分を除去し、黄色固体を得た。得られた黄色固体をアルゴン気流中で粉砕し、これを０℃で２８％アンモニア水溶液にゆっくりと加えた。得られた懸濁液を室温でさらに１時間攪拌した。析出した固体をろ取し、水，メタノ−ルで順次洗浄した。固体を乾燥後、固体中のアンチモン塩を除去すべく、３００ｍＬのクロロホルム中で７０℃まで加熱し、目的物を含んだ液を抽出した。抽出液を放冷後、３００ｍＬのメタノールを加え、析出した固体をろ取した。得られた析出物をトルエンによる再結晶によって精製し、目的物である２，４−ビス（３−ブロモフェニル）−６−（３−クロロフェニル）−１，３，５−トリアジンの白色粉末（収量１８．５ｇ、収率４６．０％）を得た。
^１Ｈ−ＮＭＲ（ＣＤＣｌ_３）δ（ｐｐｍ），７．４７（ｔ，Ｊ＝７．８Ｈｚ，２Ｈ），７．５４（ｔ，Ｊ＝７．７Ｈｚ，１Ｈ），７．６１（ｄｑ，Ｊ＝７．９Ｈｚ，Ｊ＝１．２Ｈｚ，１Ｈ），７．７６（ｄｑ，Ｊ＝８．０Ｈｚ，Ｊ＝１．０Ｈｚ，２Ｈ），８．６５（ｄｔ，Ｊ＝７．８Ｈｚ，Ｊ＝１．２Ｈｚ，１Ｈ），８．６８（ｔ，Ｊ＝１．２Ｈｚ，１Ｈ），８．７０−８．７１（ｍ，２Ｈ），８．８６（ｔ，Ｊ＝１．７Ｈｚ，２Ｈ）
合成例−２

Under an argon stream, 3-bromobenzonitrile (29.1 g, 160.0 mmol) and 3-chlorobenzoic acid chloride (14.0 g, 80.0 mmol) were dissolved in 130 mL of chloroform. To the resulting solution, antimony pentachloride (26.3 g, 88.0 mmol) was added dropwise at 0 ° C. The mixture was stirred at room temperature for 1 hour, then heated to 70 ° C. and allowed to react for 2 hours. After cooling to room temperature, low-boiling components were removed under reduced pressure to obtain a yellow solid. The resulting yellow solid was pulverized in a stream of argon and slowly added to a 28% aqueous ammonia solution at 0 ° C. The resulting suspension was stirred for an additional hour at room temperature. The precipitated solid was collected by filtration and washed successively with water and methanol. After drying the solid, in order to remove the antimony salt in the solid, it was heated to 70 ° C. in 300 mL of chloroform, and a liquid containing the target product was extracted. The extract was allowed to cool, 300 mL of methanol was added, and the precipitated solid was collected by filtration. The resulting precipitate was purified by recrystallization from toluene, and the desired product, 2,4-bis (3-bromophenyl) -6- (3-chlorophenyl) -1,3,5-triazine, was obtained as a white powder (yield) 18.5 g, yield 46.0%).
¹ H-NMR (CDCl ₃ ) δ (ppm), 7.47 (t, J = 7.8 Hz, 2H), 7.54 (t, J = 7.7 Hz, 1H), 7.61 (dq, J = 7.9 Hz, J = 1.2 Hz, 1H), 7.76 (dq, J = 8.0 Hz, J = 1.0 Hz, 2H), 8.65 (dt, J = 7.8 Hz, J = 1) .2 Hz, 1H), 8.68 (t, J = 1.2 Hz, 1H), 8.70-8.71 (m, 2H), 8.86 (t, J = 1.7 Hz, 2H)
Synthesis Example-2

アルゴン気流下、２，４−ビス（３−ブロモフェニル）−６−（３−クロロフェニル）−１，３，５−トリアジン（３．００ｇ，５．９８ｍｍｏｌ）、９−フェンナントレンボロン酸（３．１９ｇ，１４．３５ｍｍｏｌ）及びテトラキストリフェニルホスフィンパラジウム（２０６．９ｍｇ，０．１７９ｍｍｏｌ）をテトラヒドロフラン（１４０ｍＬ）に懸濁し、７０℃に加熱した。これに１Ｍ−Ｋ_２ＣＯ_３水溶液（１７．９４ｍＬ，１７．９４ｍｍｏｌ）をゆっくりと滴下した後、６時間撹拌した。室温まで放冷後、反応混合物に水（１４０ｍＬ）を加え、析出物をろ取した。得られた析出物をトルエンによる再結晶により精製し、目的物である２−（３−クロロフェニル）−４，６−ビス［３−（フェナントレン−９−イル）フェニル］−１，３，５−トリアジンの白色固体（収量２．６ｇ，収率６２．４％）を得た。
^１Ｈ−ＮＭＲ（ＣＤＣｌ_３）δ（ｐｐｍ）：７．４５（ｔ，Ｊ＝７．７Ｈｚ，１Ｈ），７．５０−７．５５（ｍ，３Ｈ），７．６２−７．７３（ｍ，８Ｈ），７．７６−７．７９（ｍ，４Ｈ），７．９１（ｄｄ，Ｊ＝４．３Ｈｚ，１．２Ｈｚ，２Ｈ），７．９３（ｄｄ，Ｊ＝３．８Ｈｚ，１．０Ｈｚ，２Ｈ），８．６２（ｄｔ，Ｊ＝７．８Ｈｚ，１．５Ｈｚ，１Ｈ），８．７０（ｔ，Ｊ＝１．８Ｈｚ．１Ｈ），８．７５（ｂｒｄ，Ｊ＝８．３Ｈｚ，２Ｈ），８．８０（ｂｒｄ，Ｊ＝４．３Ｈｚ，２Ｈ），８．８４（ｂｒｄ，Ｊ＝７．６Ｈｚ，２Ｈ），８．９１（ｔ，Ｊ＝１．５Ｈｚ，２Ｈ）．
合成実施例−１

Under an argon stream, 2,4-bis (3-bromophenyl) -6- (3-chlorophenyl) -1,3,5-triazine (3.00 g, 5.98 mmol), 9-phenanthreneboronic acid (3 .19 g, 14.35 mmol) and tetrakistriphenylphosphine palladium (206.9 mg, 0.179 mmol) were suspended in tetrahydrofuran (140 mL) and heated to 70 ° C. A 1M-K ₂ CO ₃ aqueous solution (17.94 mL, 17.94 mmol) was slowly added dropwise thereto, followed by stirring for 6 hours. After allowing to cool to room temperature, water (140 mL) was added to the reaction mixture, and the precipitate was collected by filtration. The obtained precipitate was purified by recrystallization from toluene, and the target product, 2- (3-chlorophenyl) -4,6-bis [3- (phenanthrene-9-yl) phenyl] -1,3,5- A white solid of triazine (yield 2.6 g, yield 62.4%) was obtained.
¹ H-NMR (CDCl ₃ ) δ (ppm): 7.45 (t, J = 7.7 Hz, 1H), 7.50-7.55 (m, 3H), 7.62-7.73 (m 8H), 7.76-7.79 (m, 4H), 7.91 (dd, J = 4.3 Hz, 1.2 Hz, 2H), 7.93 (dd, J = 3.8 Hz, 1.). 0 Hz, 2H), 8.62 (dt, J = 7.8 Hz, 1.5 Hz, 1H), 8.70 (t, J = 1.8 Hz. 1H), 8.75 (brd, J = 8.3 Hz) , 2H), 8.80 (brd, J = 4.3 Hz, 2H), 8.84 (brd, J = 7.6 Hz, 2H), 8.91 (t, J = 1.5 Hz, 2H).
Synthesis Example-1

アルゴン気流下、合成例−２で得られた２−（３−クロロフェニル）−４，６−ビス［３−（フェナントレン−９−イル）フェニル］−１，３，５−トリアジン（１．５ｇ，２．１５ｍｍｏｌ）、３−ピリジルボロン酸（０．３２ｇ，２．５９ｍｍｏｌ）、酢酸パラジウム（９．６７ｍｇ，０．０４３ｍｍｏｌ）、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（４１．１ｍｇ，０．０８６ｍｍｏｌ）及びＫ_２ＣＯ_３水溶液（０．８９ｇ，６．４６ｍｍｏｌ）をＴＨＦ（３０ｍＬ）及び水（６ｍＬ）の混合溶媒に懸濁し、７０℃に加熱して１９時間撹拌させて反応させた。室温まで放冷後、反応混合物に水（３０ｍＬ）を加え、析出物をろ取した。得られた析出物をトルエンによる再結晶により精製し、目的物である４，６−ビス［３−（フェナントレン−９−イル）フェニル］−２−[３−（３−ピリジル）フェニル]−１，３，５−トリアジン（化合物Ａ−１）の白色固体（収量０．７９ｇ，収率４９．７５％）を得た。
^１Ｈ−ＮＭＲ（ＣＤＣｌ_３）δ（ｐｐｍ）：７．４７（ｔ，Ｊ＝７．２Ｈｚ，２Ｈ），７．５４−７．７３（ｍ，１２Ｈ），７.７３−７.８０（ｍ，３Ｈ），７．８６（ｄｄ，Ｊ＝１．３Ｈｚ，Ｊ＝７．７Ｈｚ，２Ｈ），７．８９（ｄ，Ｊ＝８．３Ｈｚ，２Ｈ），８．２２（ｄ，Ｊ＝８．１Ｈｚ，１Ｈ），８．６３（ｄｄ，Ｊ＝１．４Ｈｚ，Ｊ＝５．１Ｈｚ，１Ｈ），８．６９（ｄ，Ｊ＝８．０Ｈｚ，２Ｈ），８．７６（ｔ，Ｊ＝８．６Ｈｚ，５Ｈ），８．９１（ｄ，Ｊ＝６．８Ｈｚ，３Ｈ），８．９６（ｓ，１Ｈ）．
素子評価に用いた化合物の構造式及びその略称を以下に示す。

Under an argon stream, 2- (3-chlorophenyl) -4,6-bis [3- (phenanthren-9-yl) phenyl] -1,3,5-triazine (1.5 g, obtained in Synthesis Example-2) was obtained. 2.15 mmol), 3-pyridylboronic acid (0.32 g, 2.59 mmol), palladium acetate (9.67 mg, 0.043 mmol), 2-dicyclohexylphosphino-2 ′, 4 ′, 6′-triisopropylbiphenyl (41.1 mg, 0.086 mmol) and K ₂ CO ₃ aqueous solution (0.89 g, 6.46 mmol) were suspended in a mixed solvent of THF (30 mL) and water (6 mL), heated to 70 ° C. and stirred for 19 hours. Allowed to react. After allowing to cool to room temperature, water (30 mL) was added to the reaction mixture, and the precipitate was collected by filtration. The obtained precipitate was purified by recrystallization from toluene, and the desired product, 4,6-bis [3- (phenanthren-9-yl) phenyl] -2- [3- (3-pyridyl) phenyl] -1 , 3,5-triazine (Compound A-1) was obtained as a white solid (yield 0.79 g, yield 49.75%).
¹ H-NMR (CDCl ₃ ) δ (ppm): 7.47 (t, J = 7.2 Hz, 2H), 7.54-7.73 (m, 12H), 7.73-7.80 (m 3H), 7.86 (dd, J = 1.3 Hz, J = 7.7 Hz, 2H), 7.89 (d, J = 8.3 Hz, 2H), 8.22 (d, J = 8. 1 Hz, 1H), 8.63 (dd, J = 1.4 Hz, J = 5.1 Hz, 1H), 8.69 (d, J = 8.0 Hz, 2H), 8.76 (t, J = 8 .6 Hz, 5H), 8.91 (d, J = 6.8 Hz, 3H), 8.96 (s, 1H).
The structural formulas and abbreviations of the compounds used for device evaluation are shown below.

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。なお、各有機材料は抵抗加熱方式により成膜した。

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. Each organic material was formed by a resistance heating method.

First, the said glass substrate was introduce | transduced in the vacuum evaporation tank and it pressure-reduced to 1.0 * 10 <^-4> Pa.

  Then, as an organic compound layer on the glass substrate with an ITO transparent electrode shown by 1 in FIG. 1, 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 layer 7 and the cathode layer 8 were both deposited in this order, and were formed by vacuum deposition.

  As the hole injection layer 2, a sublimated HIL film having a thickness of 65 nm was formed at a rate of 0.15 nm / second.

  As the charge generation layer 3, sublimation-purified HAT was deposited to a thickness of 5 nm at a rate of 0.05 nm / second.

  As the hole transport layer 4, HTL was formed to a thickness of 10 nm at a rate of 0.15 nm / second.

  As the light emitting layer 5, EML-1 and EML-2 were formed to a thickness of 25 nm at a ratio of 95: 5 (weight ratio) (deposition rate of 0.18 nm / second).

  As the electron transport layer 6, 4,6-bis [3- (phenanthren-9-yl) phenyl] -2- [3- (3-pyridyl) phenyl] -1 synthesized in Synthesis Example 1 of the present invention was used. , 3,5-triazine (Compound A-1) and Liq were deposited at a ratio of 50:50 (weight ratio) to a thickness of 30 nm (co-evaporation, deposition rate of 0.15 nm / second).

  Finally, a metal mask was arranged so as to be orthogonal to the ITO stripe, and the cathode layer 7 was formed. The cathode layer 7 is formed of silver / magnesium (weight ratio 1/10) and silver in this order at 80 nm (film formation rate 0.5 nm / second) and 20 nm (film formation rate 0.2 nm / second), respectively. And it was set as the 2 layer structure.

  Each film thickness was measured with a stylus type film thickness meter (DEKTAK).

  Furthermore, this element was sealed in a nitrogen atmosphere glove box having an oxygen and moisture concentration of 1 ppm or less. Sealing was performed using a glass sealing cap and the above-described film-forming substrate epoxy type ultraviolet curable resin (manufactured by Nagase ChemteX Corporation).

Element Reference Example-1
In device example-1, 2- [5- (9-phenanthryl) -4 ′-(2-pyrimidyl) biphenyl-3-yl] -4, described in JP-A-2010-183145 is used for the electron transport layer 6. An organic electroluminescent element was produced in the same manner as in Example 1 except that 6-diphenyl-1,3,5-triazine (the above formula, represented by 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 800 cd / m ² was measured. The time when the luminance (cd / m ² ) is reduced by 25% is indicated as the element lifetime (h) below.

表１より、素子参考例に比べて、本発明のトリアジン化合物を用いた有機電界発光素子は、駆動電圧、電流効率及び素子寿命において上回る特性を示す事が分かる。

From Table 1, it can be seen that the organic electroluminescent device using the triazine compound of the present invention exhibits characteristics superior in driving voltage, current efficiency and device lifetime as compared with the device reference example.

  The triazine compound of the present invention is used as an electron transport material excellent in durability, driving voltage, and power efficiency. Furthermore, according to the present invention, an organic EL element with low power consumption and excellent element lifetime can be provided.

  Further, the thin film comprising the triazine compound (1) of the present invention or the thin film comprising the triazine compound (1) of the present invention has high surface smoothness, amorphousness, heat resistance, electron transport ability, hole blocking ability, Since it has oxidation-reduction resistance, water resistance, oxygen resistance, electron injection characteristics, etc., it is useful as a material for organic electroluminescence devices, and can be used as an electron transport material, a hole blocking material, a light emitting host material, and the like. Further, since it is a wide band gap compound, it can be applied not only to conventional fluorescent device applications but also to phosphorescent devices. Therefore, the thin film comprising the triazine compound (1) of the present invention or the thin film comprising the triazine compound (1) of the present invention is expected to be used as a component of the organic electroluminescence device.

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 Cathode layer

Claims (12)

General formula (1)

(In general formula (1),
Two Ar ¹ represent the same substituent.
Ar ¹ represents a condensed aromatic hydrocarbon group having 14 to 18 carbon atoms having phenanthrene or fluorene as a partial or entire skeleton (this group may be substituted with an alkyl group having 1 to 4 carbon atoms). .
Ar ² is substituted with a hydrogen atom, an aromatic hydrocarbon group having 6 to 10 carbon atoms which may be substituted with an alkyl group having 1 to 4 carbon atoms, or an alkyl group having 1 to 4 carbon atoms. And represents a nitrogen-containing heteroaromatic group having 3 to 9 carbon atoms.
Each X is independently substituted with a C6-C10 divalent aromatic hydrocarbon group which may be substituted with a C1-C4 alkyl group or a C1-C4 alkyl group. And a C 4-5 divalent nitrogen-containing heteroaromatic group.
p represents an integer of 0, 1 or 2. When p is 2, X may be the same or different. )
A triazine compound represented by: The triazine compound according to claim 1, wherein Ar ¹ is a phenanthryl group or a fluoranthenyl group (these substituents may have an alkyl group having 1 to 4 carbon atoms as a substituent). Ar ² is a hydrogen atom, an aromatic hydrocarbon group having 6 to 10 carbon atoms that may be substituted with a methyl group, or a nitrogen-containing heteroaromatic group having 3 to 9 carbon atoms that may be substituted with a methyl group The triazine compound according to claim 1 or 2.   X is each independently a bivalent aromatic hydrocarbon group having 6 to 10 carbon atoms that may be substituted with a methyl group, or a divalent group having 4 to 5 carbon atoms that may be substituted with a methyl group. The triazine compound according to any one of claims 1 to 3, wherein the triazine compound is a nitrogen heteroaromatic group. The compound represented by the general formula (2) and the compounds represented by the general formula (3) and the general formula (4) are subjected to a coupling reaction sequentially or simultaneously in the presence of a palladium catalyst. A method for producing the triazine compound according to 1.

(Where
Two Ar ¹ represent the same substituent.
Ar ¹ , Ar ² , X, and p are the same as defined in claim 1.
Y ¹ represents a chlorine atom, a bromine atom, or an iodine atom. Y ² represents a hydrogen atom, a chlorine atom, a bromine atom, or an iodine atom.
Two Y ¹ represent the same substituent, and Y ¹ and Y ² represent different substituents.
M ¹ represents ZnR ¹ , MgR ² , Sn (R ³ ) ₃ or B (OR ⁴ ) ₂ . However, R ¹ and R ² each independently represent a chlorine atom, a bromine atom or an iodine atom, R ³ represents an alkyl group or a phenyl group having 1 to 4 carbon atoms, R ⁴ is a hydrogen atom, a carbon number 1 It represents to 4 alkyl or a phenyl group, B ^(oR ₄₎ 2 two ^{R 4} ₂ may be the same or different. Further, two R ⁴ may form a ring containing an oxygen atom and a boron atom together.
M ² represents ZnR ¹ , MgR ² , Sn (R ³ ) ₃ or B (OR ⁴ ) ₂ . However, R < ¹ > and R < ² > represents a chlorine atom, a bromine atom, or an iodine atom each independently, R < ³ > represents a C1-C4 alkyl group or a phenyl group, R < ⁴ > is a hydrogen atom, carbon number 1 It represents an alkyl group or a phenyl group 4, B ^(oR ₄₎ 2 two ^{R 4} ₂ may be the same or different. Further, two R ⁴ may form a ring containing an oxygen atom and a boron atom together. ) The method for producing a triazine compound according to claim 1, wherein the compound represented by the general formula (5) and the compound represented by the general formula (4) are subjected to a coupling reaction in the presence of a palladium catalyst.

(Where
Two Ar ¹ represent the same substituent.
Ar ¹ , Ar ² , X, and p are the same as defined in claim 1.
Y ² represents a hydrogen atom, a chlorine atom, a bromine atom, or an iodine atom.
M ² represents the same ZnR ¹ , MgR ² , Sn (R ³ ) ₃ or B (OR ⁴ ) ₂ . However, R < ¹ > and R < ² > represents a chlorine atom, a bromine atom, or an iodine atom each independently, R < ³ > represents a C1-C4 alkyl group or a phenyl group, R < ⁴ > is a hydrogen atom, carbon number 1 It represents an alkyl group or a phenyl group 4, B ^(oR ₄₎ 2 two ^{R 4} ₂ may be the same or different. Further, two R ⁴ may form a ring containing an oxygen atom and a boron atom together. ) The method for producing a triazine compound according to claim 1, wherein the compound represented by the general formula (7) and the compound represented by the general formula (3) are subjected to a coupling reaction in the presence of a palladium catalyst.

(Where
Two Ar ¹ represent the same substituent.
Ar ¹ , Ar ² , X, and p are the same as defined in claim 1.
Y ¹ represents a chlorine atom, a bromine atom, or an iodine atom.
Two Y ¹ represent the same substituent.
M ¹ represents ZnR ¹ , MgR ² , Sn (R ³ ) ₃ or B (OR ⁴ ) ₂ . However, R < ¹ > and R < ² > represents a chlorine atom, a bromine atom, or an iodine atom each independently, R < ³ > represents a C1-C4 alkyl group or a phenyl group, R < ⁴ > is a hydrogen atom, carbon number 1 It represents an alkyl group or a phenyl group 4, B ^(oR ₄₎ 2 two ^{R 4} ₂ may be the same or different. Further, two R ⁴ may form a ring containing an oxygen atom and a boron atom together. )   The production method according to claim 5, 6 or 7, wherein the palladium catalyst is a palladium catalyst having tertiary phosphine as a ligand.   The palladium catalyst is a palladium catalyst having triphenylphosphine or 2-dicyclohexylphosphino-2 ', 4', 6'-triisopropylbiphenyl as a ligand. 9. The production method according to 8. The triazine compound of Claim 6 represented by General formula (5).

(Where
Two Ar ¹ represent the same substituent.
Ar ¹ represents the same definition as in claim 6.
Y ² represents a hydrogen atom, a chlorine atom, a bromine atom, or an iodine atom. ) The triazine compound of Claim 7 represented by General formula (7).

(Where
Ar ² , X, and p are as defined in claim 7.
Y ¹ represents a chlorine atom, a bromine atom, or an iodine atom.
Two Y ¹ represent the same substituent. ) The triazine compound of Claim 5 represented by General formula (10).

(Where
Y ¹ represents a chlorine atom, a bromine atom, or an iodine atom.
Y ² represents a hydrogen atom, a chlorine atom, a bromine atom, or an iodine atom.
Two Y ¹ represent the same substituent, and Y ¹ and Y ² represent different substituents. )

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