JP5533863B2 - Electron transport material and organic electroluminescent device using the same - Google Patents

Description

The present invention relates to a novel electron transport material having a pyridyl group, an organic electroluminescence device using the electron transport material (hereinafter, sometimes abbreviated as an organic EL device or simply a device), and the like.

In recent years, organic EL elements have attracted attention as next-generation full-color flat panel displays, and active research has been conducted. In order to promote the practical use of organic EL elements, it is indispensable to reduce the drive voltage and extend the life of the elements, and new electron transport materials have been developed to achieve these. In particular, it is essential to lower the driving voltage and extend the life of the blue element. Patent Document 1 (Japanese Patent Laid-Open No. 2003-123983) discloses that an organic EL device can be driven at a low voltage by using a 2,2′-bipyridyl compound that is a phenanthroline derivative or an analog thereof as an electron transport material. It is stated that it can be done. However, the element characteristics (driving voltage, light emission efficiency, etc.) reported in the examples of this document are only relative values based on comparative examples, and no actual measurement values that can be judged as practical values are described. Alternatively, example of using 2,2'-bipyridyl compound to the electron transport material, non-patent document ^{1 (Proceedings of the 10 th International} Workshop on Inorganic and Organic Electroluminescence), Patent Document 2 (JP 2002-158093 JP ) And Patent Document 3 (International Publication No. 2007/86552 pamphlet). The compound described in Non-Patent Document 1 has a low Tg and is not practical. Although the compounds described in Patent Documents 2 and 3 can drive an organic EL device at a relatively low voltage, longer life is desired for practical use.

JP 2003-123983 A JP 2002-158093 A International Publication 2007/86552 Pamphlet

Proceedings of the 10th International Workshop on Inorganic and Organic Electroluminescence (2000)

The present invention has been made in view of the problems of such conventional techniques. It is an object of the present invention to provide an electron transport material that contributes to extending the lifetime of an organic EL element. Furthermore, this invention makes it a subject to provide the organic EL element using this electron transport material.

As a result of intensive studies, the present inventors have found that a compound having pyridyl, bipyridyl, phenylpyridyl, or pyridylphenyl on either naphthyl or phenyl of 9- (2-naphthyl) -10-phenylanthracene is an organic EL device. It has been found that an organic EL element that can be driven with a long lifetime can be obtained by using it in the electron transport layer, and the present invention has been completed based on this finding.
Said subject is solved by each item shown below.

式（１）中、
Ｐｙは独立して、式（２）、（３）、（４）、または（５）で表される基であり；

ｍおよびｎは０または１であるが、ｍ＋ｎ＝１であり；
式中のベンゼン環、ナフタレン環、およびピリジン環の−Ｈは独立して炭素数１〜６のアルキルまたは炭素数３〜６のシクロアルキルで置き換えられていてもよい。[1] A compound represented by the following formula (1).

In formula (1),
Py is independently a group represented by formula (2), (3), (4), or (5);

m and n are 0 or 1, but m + n = 1;
In the formula, -H in the benzene ring, naphthalene ring, and pyridine ring may be independently substituted with alkyl having 1 to 6 carbon atoms or cycloalkyl having 3 to 6 carbon atoms.

式（１−１）または（１−２）中、
Ｐｙは、式（２）、（３）、（４）、または（５）で表される基であり；

式中のベンゼン環、ナフタレン環、およびピリジン環の−Ｈは独立して炭素数１〜６のアルキルまたは炭素数３〜６のシクロアルキルで置き換えられていてもよい。[2] The compound according to [1], which is represented by the following formula (1-1) or (1-2).

In formula (1-1) or (1-2),
Py is a group represented by formula (2), (3), (4), or (5);

In the formula, -H in the benzene ring, naphthalene ring, and pyridine ring may be independently substituted with alkyl having 1 to 6 carbon atoms or cycloalkyl having 3 to 6 carbon atoms.

式（１−３）〜（１−６）のそれぞれにおいて、
Ｐｙは、式（２）、（３）、（４）または（５）で表される基であり；

式中のベンゼン環、ナフタレン環、およびピリジン環の−Ｈは独立して炭素数１〜６のアルキルまたは炭素数３〜６のシクロアルキルで置き換えられていてもよい。[3] The compound according to [1], which is represented by the following formula (1-3), (1-4), (1-5), or (1-6).

In each of the formulas (1-3) to (1-6),
Py is a group represented by the formula (2), (3), (4) or (5);

In the formula, -H in the benzene ring, naphthalene ring, and pyridine ring may be independently substituted with alkyl having 1 to 6 carbon atoms or cycloalkyl having 3 to 6 carbon atoms.

式（１−３）および（１−４）において、
Ｐｙは、式（２）、（３）、（４）または（５）で表される基であり；

式中のベンゼン環、ナフタレン環、およびピリジン環の−Ｈは独立して炭素数１〜６のアルキルまたは炭素数３〜６のシクロアルキルで置き換えられていてもよい。[4] The compound according to [1], which is represented by the following formula (1-3) or (1-4).

In formulas (1-3) and (1-4),
Py is a group represented by the formula (2), (3), (4) or (5);

In the formula, -H in the benzene ring, naphthalene ring, and pyridine ring may be independently substituted with alkyl having 1 to 6 carbon atoms or cycloalkyl having 3 to 6 carbon atoms.

式（１−５）および（１−６）において、
Ｐｙは、式（２）、（３）、（４）または（５）で表される基であり；

式中のベンゼン環、ナフタレン環、およびピリジン環の−Ｈは独立して炭素数１〜６のアルキルまたは炭素数３〜６のシクロアルキルで置き換えられていてもよい。[5] The compound according to [1], which is represented by the following formula (1-5) or (1-6).

In formulas (1-5) and (1-6),
Py is a group represented by the formula (2), (3), (4) or (5);

In the formula, -H in the benzene ring, naphthalene ring, and pyridine ring may be independently substituted with alkyl having 1 to 6 carbon atoms or cycloalkyl having 3 to 6 carbon atoms.

[6] The compound according to item [1], represented by the following formula (1-3-1).

[7] The compound according to [1], which is represented by the following formula (1-3-2).

[8] The compound according to [1], which is represented by the following formula (1-3-3).

[9] The compound according to [1], which is represented by the following formula (1-3-5).

[10] The compound according to item [1], represented by the following formula (1-3-12):

[11] The compound according to [1], which is represented by the following formula (1-3-21).

[12] The compound according to [1], which is represented by the following formula (1-3-22).

[13] The compound according to [1], which is represented by the following formula (1-3-24).

[14] The compound according to [1], which is represented by the following formula (1-3-25).

[15] The compound according to [1], which is represented by the following formula (1-3-27).

[16] The compound according to [1], which is represented by the following formula (1-4-2).

[17] The compound according to [1], which is represented by the following formula (1-5-11).

[18] The compound according to [1], which is represented by the following formula (1-5-24).

[19] The compound according to [1], which is represented by the following formula (1-6-1).

[20] The compound according to [1], which is represented by the following formula (1-6-2).

[21] The compound according to item [1], represented by the following formula (1-6-4):

[22] The compound according to [1], which is represented by the following formula (1-6-5).

[23] An electron transport material containing the compound according to any one of [1] to [22].

[24] The electron transport material according to item [23], wherein the electron transport material is disposed between a pair of electrodes including an anode and a cathode, a light emitting layer disposed between the pair of electrodes, the cathode and the light emitting layer. An organic electroluminescent device having an electron transport layer and / or an electron injection layer containing

[25] The item [24], wherein at least one of the electron transport layer and the electron injection layer further contains at least one selected from the group consisting of a quinolinol-based metal complex, a bipyridine derivative, a phenanthroline derivative, and a borane derivative. The organic electroluminescent element of description.

[26] At least one of the electron transport layer and the electron injection layer further includes an alkali metal, an alkaline earth metal, a rare earth metal, an alkali metal oxide, an alkali metal halide, an alkaline earth metal oxide, or an alkaline earth. Containing at least one selected from the group consisting of metal halides, rare earth metal oxides, rare earth metal halides, alkali metal organic complexes, alkaline earth metal organic complexes and rare earth metal organic complexes The organic electroluminescent element according to the item [24] or [25].

The compound of the present invention is stable even when a voltage is applied in a thin film state and has a feature of high charge transport capability. The compound of the present invention is suitable as a charge transport material in an organic EL device. By using the compound of this invention for the electron carrying layer of an organic EL element, the organic EL element which has a long lifetime can be obtained. By using the organic EL element of the present invention, a high-performance display device such as full-color display can be created.

式（１）中、Ｐｙは独立して、式（２）、（３）、（４）、または（５）で表される基であり、ｍおよびｎは０または１であるが、ｍ＋ｎ＝１である。Hereinafter, the present invention will be described in more detail. In the present specification, for example, the “compound represented by the formula (1-3-1)” may be referred to as “compound (1-3-1)”. The “compound represented by formula (1-3-2)” may be referred to as “compound (1-3-2)”. Other formula symbols and formula numbers are handled in the same manner.
<Description of compound>
The first invention of the present application is a compound having pyridyl, bipyridyl, phenylpyridyl, or pyridylphenyl represented by the following formula (1).

In formula (1), Py is independently a group represented by formula (2), (3), (4), or (5), and m and n are 0 or 1, but m + n = 1.

The pyridyl represented by the formula (2) is specifically 2-pyridyl, 3-pyridyl or 4-pyridyl.

Specifically, bipyridyl represented by the formula (3) is 2,2′-bipyridin-5-yl, 2,2′-bipyridin-6-yl, 2,2′-bipyridin-4-yl, 2, 3'-bipyridin-5-yl, 2,3'-bipyridin-6-yl, 2,3'-bipyridin-4-yl, 2,4'-bipyridin-5-yl, 2,4'-bipyridine-6 -Yl, 2,4'-bipyridin-4-yl, 3,2'-bipyridin-6-yl, 3,2'-bipyridin-5-yl, 3,3'-bipyridin-6-yl, 3,3 '-Bipyridin-5-yl, 3,4'-bipyridin-6-yl, 3,4'-bipyridin-5-yl, 4,2'-bipyridin-3-yl, 4,3'-bipyridin-3- Or 4,4′-bipyridin-3-yl. Among them, 2,2′-bipyridin-5-yl, 2,2′-bipyridin-6-yl, 2,3′-bipyridin-5-yl, 2,3′-bipyridin-6-yl, 2, 4'-bipyridin-5-yl, 2,4'-bipyridin-6-yl, 3,2'-bipyridin-6-yl, 3,2'-bipyridin-5-yl, 3,3'-bipyridine-6 -Yl, 3,3'-bipyridin-5-yl, 3,4'-bipyridin-6-yl, 3,4'-bipyridin-5-yl, 4,2'-bipyridin-3-yl, 4,3 '-Bipyridin-3-yl and 4,4'-bipyridin-3-yl are preferred. And 2,2′-bipyridin-5-yl, 2,2′-bipyridin-6-yl, 2,3′-bipyridin-5-yl, 2,3′-bipyridin-6-yl, 2,4 ′ -Bipyridin-5-yl, 2,4'-bipyridin-6-yl, 3,2'-bipyridin-5-yl, 3,2'-bipyridin-6-yl, 3,4'-bipyridin-6-yl And 3,4'-bipyridin-5-yl are more preferred.

Specifically, phenylpyridyl represented by the formula (4) is 3-phenylpyridin-2-yl, 4-phenylpyridin-2-yl, 5-phenylpyridin-2-yl, 6-phenylpyridin-2- Yl, 2-phenylpyridin-3-yl, 4-phenylpyridin-3-yl, 5-phenylpyridin-3-yl, 6-phenylpyridin-3-yl, 2-phenylpyridin-4-yl, or 3- Phenylpyridin-4-yl. Of these, 5-phenylpyridin-2-yl, 6-phenylpyridin-2-yl, 5-phenylpyridin-3-yl, and 6-phenylpyridin-3-yl are preferable.

Specifically, pyridylphenyl represented by the formula (5) is 4- (2-pyridyl) phenyl, 4- (3-pyridyl) phenyl, 4- (4-pyridyl) phenyl, 3- (2-pyridyl) It is phenyl, 3- (3-pyridyl) phenyl, 3- (4-pyridyl) phenyl, 2- (2-pyridyl) phenyl, 2- (3-pyridyl) phenyl or 2- (4-pyridyl) phenyl. Among these, 4- (2-pyridyl) phenyl, 4- (3-pyridyl) phenyl, 4- (4-pyridyl) phenyl, 3- (2-pyridyl) phenyl, 3- (3-pyridyl) phenyl, and 3- (4-pyridyl) is preferred.

In Formula (1), Py may be linked at any position in phenyl or 2-naphthyl, but 4-position and 3-position are preferred in phenyl, and 6-position and 7-position are preferred in 2-naphthyl. . In particular, the 3-position of phenyl is preferable in that the conjugated system cannot be expanded and the LUMO level is not lowered. Further, the 6-position of 2-naphthyl is particularly preferable in that the raw material is easily available.

-H of the benzene ring, naphthalene ring, and pyridine ring in the formula (1) may be independently substituted with alkyl having 1 to 6 carbon atoms or cycloalkyl having 3 to 6 carbon atoms. Examples of alkyl having 1 to 6 carbon atoms are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-pentyl, isopentyl, 2,2-dimethylpropyl, n-hexyl, isohexyl. . Examples of cycloalkyl having 3 to 6 carbon atoms are cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.

<Specific examples of compounds>
Specific examples of the compounds of the present invention are shown by the formulas listed below, but the present invention is not limited by the disclosure of these specific structures.

<Specific Example of Compound Represented by Formula (1-3)>
Specific examples of the compound represented by the formula (1-3) are represented by the following formulas (1-3-1) to (1-3-30). Among these, preferable compounds are represented by formulas (1-3-1) to (1-3-6), formulas (1-3-10) to (1-3-12), and formulas (1-3-16) to (1-3-27). Further preferred compounds are those represented by formulas (1-3-1) to (1-3-3), (1-3-5), (1-3-10) to (1-3-12), (1-3- 21), (1-3-22), (1-3-24), (1-3-25), and (1-3-27).

<Specific Example of Compound Represented by Formula (1-4)>
Specific examples of the compound represented by the formula (1-4) are represented by the following formulas (1-4-1) to (1-4-27). Among these, preferred compounds are those represented by formulas (1-4-1) to (1-4-6), (1-4-10) to (1-4-12), and (1-4-16) to (1 -4-21).

<Specific Example of Compound Represented by Formula (1-5)>
Specific examples of the compound represented by the formula (1-5) are represented by the following formulas (1-5-1) to (1-5-30). Among these, preferred compounds are those represented by formulas (1-5-1) to (1-5-6), (1-5-10) to (1-5-12) and (1-5-16) to (1 -5-24). Further preferred compounds are the formulas (1-5-1) to (1-5-3), (1-5-10) to (1-5-12) and (1-5-24).

<Specific Example of Compound Represented by Formula (1-6)>
Specific examples of the compound represented by the formula (1-6) are represented by the following formulas (1-6-1) to (1-6-30). Among these, preferred compounds are those represented by formulas (1-6-1) to (1-6-6), (1-6-10) to (1-6-12) and (1-6-16) to (1 -6-21). More preferable compounds are the formulas (1-6-1) to (1-6-6) and (1-6-10) to (1-6-12).

<Method of synthesizing compounds>
The compounds of the present invention can be synthesized using known synthesis methods. The method for synthesizing the compound of the present invention will be described with reference to the compound of formula (1-3-1).

先ず、反応１で９−フェニルアントラセンを合成する。ブロモベンゼンをＴＨＦ中で金属マグネシウムと反応させグリニャール試薬とし、これに触媒の存在下９−ブロモアントラセンを反応させて９−フェニルアントラセンとする。ベンゼン環とアントラセン環をカップリングするには上記の方法に限らず、根岸カップリング反応、鈴木カップリング反応などによっても可能であり、状況に応じてこれらの常法が適宜使用できる。また、９−フェニルアントラセンは市販品を用いることもできる。

First, 9-phenylanthracene is synthesized in Reaction 1. Bromobenzene is reacted with magnesium metal in THF to give a Grignard reagent, which is reacted with 9-bromoanthracene in the presence of a catalyst to give 9-phenylanthracene. The coupling of the benzene ring and the anthracene ring is not limited to the above-described method, and it can be performed by the Negishi coupling reaction, the Suzuki coupling reaction, or the like, and these conventional methods can be appropriately used depending on the situation. Moreover, 9-phenylanthracene can also use a commercial item.

反応２ではＮ−ブロモスクシンイミドを用いて９−フェニルアントラセンの１０位を臭素化する。ここでもＮ−ブロモスクシンイミド以外の常用される臭素化剤を使用することができる。

In reaction 2, the 10-position of 9-phenylanthracene is brominated using N-bromosuccinimide. Here too, a commonly used brominating agent other than N-bromosuccinimide can be used.

反応３ではアントラセン環とナフタレン環をカップリングする。先ず２−ブロモ−６−メトキシナフタレンを常法に従ってグリニャール試薬とし、これに触媒の存在下９−ブロモ−１０−フェニルアントラセンを反応させて９−（６−メトキシナフタレン−２−イル）−１０−フェニルアントラセンを合成する。

In reaction 3, the anthracene ring and the naphthalene ring are coupled. First, 2-bromo-6-methoxynaphthalene is used as a Grignard reagent according to a conventional method, and this is reacted with 9-bromo-10-phenylanthracene in the presence of a catalyst to give 9- (6-methoxynaphthalen-2-yl) -10-. Synthesize phenylanthracene.

反応４では９−（６−メトキシナフタレン−２−イル）−１０−フェニルアントラセンのメトキシ基を脱メチルしてナフトールにする。ここでも脱メチル化反応に常用される試薬が適宜使用できる。

In reaction 4, the methoxy group of 9- (6-methoxynaphthalen-2-yl) -10-phenylanthracene is demethylated to naphthol. Again, reagents commonly used in demethylation reactions can be used as appropriate.

反応５でナフトールの−ＯＨをトリフルオロメチルスルホネート（トリフラート）にする。反応式中の−ＯＴｆは−ＯＳＯ_２ＣＦ_３の略である。

In Reaction 5, naphthol —OH is converted to trifluoromethylsulfonate (triflate). -OTf in the reaction formula stands for -OSO ₂ CF _3.

反応６で根岸カップリング反応によってナフタレン環にピリジン環を結合させる。先ず４−ブロモピリジンをグリニャール試薬とする。ここでは原料に安定な４−ブロモピリジン塩酸塩を用いているためイソプロピルマグネシウムクロリドを２倍モル使用しているが、塩酸塩を用いる必要がない原料については等モルで差し支えない。グリニャール試薬に塩化亜鉛テトラメチルエチレンジアミン錯体を加えてピリジンの塩化亜鉛錯体を合成し、これにパラジウム触媒の存在下反応５で得たトリフラートを反応させて目的物を合成する。

In Reaction 6, a pyridine ring is bonded to the naphthalene ring by Negishi coupling reaction. First, 4-bromopyridine is used as a Grignard reagent. Here, since stable 4-bromopyridine hydrochloride is used as a raw material, isopropylmagnesium chloride is used in an amount twice as much, but a raw material which does not need to use hydrochloride may be used in an equimolar amount. A zinc chloride tetramethylethylenediamine complex is added to a Grignard reagent to synthesize a zinc chloride complex of pyridine, and this is reacted with the triflate obtained in the reaction 5 in the presence of a palladium catalyst to synthesize a target product.

Specific examples of the palladium catalyst used in the Negishi coupling reaction include Pd (PPh ₃ ) ₄ , PdCl ₂ (PPh ₃ ) ₂ , Pd (OAc) ₂ , tris (dibenzylideneacetone) dipalladium (0), tris ( Dibenzylideneacetone) dipalladium (0) chloroform complex, bis (dibenzylideneacetone) palladium (0), bis (tri-t-butylphosphino) palladium (0), or (1,1′-bis (diphenylphosphino) Ferrocene) dichloropalladium (II).

In this stage, in addition to the Negishi coupling reaction, a commonly used coupling reaction such as a Suzuki coupling reaction can be appropriately used. The Negishi coupling reaction and the Suzuki coupling reaction are described in, for example, “Metal-Catalyzed Cross-Coupling Reactions—Second, Completely Revised and Enlarged Edition”.

Compounds other than those represented by formula (1-3-1) can also be synthesized according to the above synthesis method by appropriately using raw materials according to the target product. For example, the compound of formula (1-3-4) will be described as an example.

反応７に従って合成したピリジンの塩化亜鉛錯体を、反応８によってジブロモピリジンとカップリングしてビピリジンの臭化物を得る。この臭化物を反応６に準じて再度塩化亜鉛錯体として、反応５で得たトリフラートと反応させることにより式（１−３−４）の化合物を合成することができる。

The zinc chloride complex of pyridine synthesized according to reaction 7 is coupled with dibromopyridine according to reaction 8 to give the bromide of bipyridine. The compound of formula (1-3-4) can be synthesized by reacting this bromide again with the triflate obtained in Reaction 5 as a zinc chloride complex according to Reaction 6.

Further, in the case of the compound of formula (1-3-16), 4- (2-pyridyl) bromobenzene was synthesized by using paradibromobenzene in place of dibromopyridine in the reaction 8, and this was synthesized in the same manner as described above. The zinc chloride complex can then be synthesized by reacting with the triflate obtained in Reaction 5.

In the case of the compounds of formulas (1-4-1) to (1-4-27), 2-bromo-7-methoxynaphthalene is used in place of 2-bromo-6-methoxynaphthalene in the above reaction 3. Good.

In the case of compounds of formulas (1-5-1) to (1-5-30) or formulas (1-6-1) to (1-6-30), the raw material benzene used in the above reactions 1 to 3 If the skeleton and the naphthalene skeleton are replaced, they can be synthesized in the same manner. That is, the Grignard reagent of 2-bromoanthracene and 9-bromoanthracene were coupled, brominated at position 10 of anthracene according to Reaction 2, and then this bromide was reacted with a Grignard reagent of paramethoxybromobenzene or metamethoxybromobenzene. To give 9- (4- or 3-methoxyphenyl) -10- (2-naphthyl) anthracene. The procedure after the demethylation reaction of the methoxy group for this compound may be performed according to the above. Furthermore, it goes without saying that compounds other than those specifically exemplified can be synthesized according to the above synthesis method by appropriately using raw materials in accordance with the target product.

When the compound of the present invention is used for an electron injection layer or an electron transport layer in an organic EL device, it is stable when an electric field is applied. These represent that the compound of the present invention is excellent as an electron injecting material or an electron transporting material for an electroluminescent device. The electron injection layer mentioned here is a layer for receiving electrons from the cathode to the organic layer, and the electron transport layer is a layer for transporting the injected electrons to the light emitting layer. The electron transport layer can also serve as the electron injection layer. The material used for each layer is referred to as an electron injection material and an electron transport material.

<Description of organic EL element>
2nd invention of this application is an organic EL element containing the compound represented by Formula (1) of this invention in an electron injection layer or an electron carrying layer. The organic EL element of the present invention has a low driving voltage and high durability during driving.

Although the structure of the organic EL device of the present invention has various modes, it is basically a multilayer structure in which at least a hole transport layer, a light emitting layer, and an electron transport layer are sandwiched between an anode and a cathode. Examples of the specific configuration of the device are (1) anode / hole transport layer / light emitting layer / electron transport layer / cathode, (2) anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer. / Cathode, (3) anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode, etc.

Since the compound of the present invention has high electron injecting property and electron transporting property, it can be used for an electron injecting layer or an electron transporting layer alone or in combination with other materials. The organic EL device of the present invention emits blue, green, red and white light by combining a hole injection layer, a hole transport layer, a light emitting layer, etc. using other materials with the electron transport material of the present invention. It can also be obtained.

The light-emitting material or light-emitting dopant that can be used in the organic EL device of the present invention is daylight fluorescence as described in the Polymer Society of Japan, Polymer Functional Materials Series “Optical Functional Materials”, Joint Publication (1991), P236. Materials, fluorescent brighteners, laser dyes, organic scintillators, various fluorescent analysis reagents and other luminescent materials, supervised by Koji Koji, “Organic EL materials and displays” published by CMC Publishing Co., Ltd. (2001) P155-156 And a light emitting material of a triplet material as described in P170 to 172.

The compounds that can be used as the light emitting material or the light emitting dopant are polycyclic aromatic compounds, heteroaromatic compounds, organometallic complexes, dyes, polymer light emitting materials, styryl derivatives, aromatic amine derivatives, coumarin derivatives, borane derivatives, oxazines. Derivatives, compounds having a spiro ring, oxadiazole derivatives, fluorene derivatives and the like. Examples of the polycyclic aromatic compound are anthracene derivatives, phenanthrene derivatives, naphthacene derivatives, pyrene derivatives, chrysene derivatives, perylene derivatives, coronene derivatives, rubrene derivatives, and the like. Examples of heteroaromatic compounds are oxadiazole derivatives having a dialkylamino group or diarylamino group, pyrazoloquinoline derivatives, pyridine derivatives, pyran derivatives, phenanthroline derivatives, silole derivatives, thiophene derivatives having a triphenylamino group, quinacridone derivatives Etc. Examples of organometallic complexes are zinc, aluminum, beryllium, europium, terbium, dysprosium, iridium, platinum, osmium, gold, etc., quinolinol derivatives, benzoxazole derivatives, benzothiazole derivatives, oxadiazole derivatives, thiadiazole derivatives, A complex with a benzimidazole derivative, a pyrrole derivative, a pyridine derivative, a phenanthroline derivative, or the like. Examples of dyes are xanthene derivatives, polymethine derivatives, porphyrin derivatives, coumarin derivatives, dicyanomethylenepyran derivatives, dicyanomethylenethiopyran derivatives, oxobenzanthracene derivatives, carbostyril derivatives, perylene derivatives, benzoxazole derivatives, benzothiazole derivatives, benzimidazoles And pigments such as derivatives. Examples of the polymer light-emitting material include polyparaphenyl vinylene derivatives, polythiophene derivatives, polyvinyl carbazole derivatives, polysilane derivatives, polyfluorene derivatives, polyparaphenylene derivatives, and the like. Examples of styryl derivatives are amine-containing styryl derivatives, styrylarylene derivatives, and the like.

Other electron transport materials used in the organic EL device of the present invention are arbitrarily selected from compounds that can be used as electron transport compounds in photoconductive materials and compounds that can be used in the electron transport layer and electron injection layer of organic EL devices. Can be used.

Specific examples of such electron transport materials include quinolinol metal complexes, 2,2′-bipyridyl derivatives, phenanthroline derivatives, diphenylquinone derivatives, perylene derivatives, oxadiazole derivatives, thiophene derivatives, triazole derivatives, thiadiazole derivatives, oxine derivatives. Metal complexes, quinoxaline derivatives, polymers of quinoxaline derivatives, benzazole compounds, gallium complexes, pyrazole derivatives, perfluorinated phenylene derivatives, triazine derivatives, pyrazine derivatives, benzoquinoline derivatives, imidazopyridine derivatives, borane derivatives, and the like.

Regarding the hole injection material and the hole transport material used in the organic EL device of the present invention, in a photoconductive material, a compound conventionally used as a charge transport material for holes or a hole injection of an organic EL device is used. Any known material used for the layer and the hole transport layer can be selected and used. Specific examples thereof are carbazole derivatives, triarylamine derivatives, phthalocyanine derivatives and the like.

Each layer constituting the organic EL element of the present invention can be formed by forming a material to constitute each layer into a thin film by a method such as a vapor deposition method, a spin coating method, or a casting method. The thickness of each layer formed in this way is not particularly limited and can be appropriately set according to the properties of the material, but is usually in the range of 2 nm to 5000 nm. Note that it is preferable to employ a vapor deposition method as a method of thinning the light emitting material from the standpoint that a homogeneous film can be easily obtained and pinholes are hardly generated. When thinning using the vapor deposition method, the vapor deposition conditions differ depending on the type of the light emitting material of the present invention. Deposition conditions generally include a boat heating temperature of 50 to 400 ° C., a degree of vacuum of 10 ⁻⁶ to 10 ⁻³ Pa, a deposition rate of 0.01 to 50 nm / second, a substrate temperature of −150 to + 300 ° C., and a film thickness of 5 nm to 5 μm. It is preferable to set appropriately within the range.

The organic EL device of the present invention is preferably supported by a substrate in any of the structures described above. The substrate only needs to have mechanical strength, thermal stability, and transparency, and glass, a transparent plastic film, and the like can be used. As the anode material, metals, alloys, electrically conductive compounds and mixtures thereof having a work function larger than 4 eV can be used. Specific examples thereof include metals such as Au, CuI, indium tin oxide (hereinafter abbreviated as ITO), SnO ₂ , ZnO, and the like.

Cathode materials can use metals, alloys, electrically conductive compounds, and mixtures thereof with work functions of less than 4 eV. Specific examples thereof are aluminum, calcium, magnesium, lithium, magnesium alloy, aluminum alloy and the like. Specific examples of the alloy include aluminum / lithium fluoride, aluminum / lithium, magnesium / silver, and magnesium / indium. In order to efficiently extract light emitted from the organic EL element, it is desirable that at least one of the electrodes has a light transmittance of 10% or more. The sheet resistance as the electrode is preferably several hundred Ω / □ or less. Although the film thickness depends on the properties of the electrode material, it is usually set in the range of 10 nm to 1 μm, preferably 10 to 400 nm. Such an electrode can be produced by forming a thin film by a method such as vapor deposition or sputtering using the electrode material described above.

Next, as an example of a method for producing an organic EL device using the light emitting material of the present invention, an organic material comprising the above-mentioned anode / hole injection layer / hole transport layer / light emitting layer / electron transport material of the present invention / cathode is used. A method for creating an EL element will be described. A thin film of an anode material is formed on a suitable substrate by vapor deposition to produce an anode, and then a thin film of a hole injection layer and a hole transport layer is formed on the anode. A light emitting layer thin film is formed thereon. On this light emitting layer, the electron transport material of this invention is vacuum-deposited, a thin film is formed and it is set as an electron carrying layer. Furthermore, the target organic EL element is obtained by forming the thin film which consists of a substance for cathodes by a vapor deposition method, and making it a cathode. In the production of the organic EL element described above, the production order can be reversed, and the cathode, the electron transport layer, the light emitting layer, the hole transport layer, the hole injection layer, and the anode can be produced in this order.

When a DC voltage is applied to the organic EL device thus obtained, the anode may be applied with a positive polarity and the cathode with a negative polarity. When a voltage of about 2 to 40 V is applied, a transparent or translucent electrode is applied. Luminescence can be observed from the side (anode or cathode and both). The organic EL element also emits light when an alternating voltage is applied. The alternating current waveform to be applied may be arbitrary.

[Example]
Hereinafter, the present invention will be described in more detail based on examples. First, synthesis examples of the compounds used in the examples are described below.

[Synthesis Example 1] Synthesis of Compound (1-3-1) <Synthesis of 9-bromo-10-phenylanthracene>
Under a nitrogen atmosphere, 10 ml of a chloroform solution containing 0.2 g of iodine was added dropwise to 580 ml of a chloroform solution containing 104 g of 9-phenylanthracene and 80 g of N-bromosuccinimide with stirring at room temperature. After completion of dropping, the mixture was stirred at reflux temperature for 3 hours. After cooling the reaction solution to room temperature, the precipitate was removed by suction filtration, and 500 ml of toluene was added for liquid separation. The organic layer was washed with water, the solvent was distilled off under reduced pressure, and the resulting solid was washed with 250 ml of methanol to obtain 135 g of 9-bromo-10-phenylanthracene.

<Synthesis of 9- (6-methoxynaphthalen-2-yl) -10-phenylanthracene>
Under a nitrogen atmosphere, a THF solution containing 70 g of 2-bromo-6-methoxynaphthalene was dropped into a flask containing 10.7 g of magnesium and a small amount of iodine to prepare a Grignard reagent. Under a nitrogen atmosphere, this Grignard reagent was added dropwise to a flask containing 67 g of 9-bromo-10-phenylanthracene, 0.5 g of nickel chloride and 140 ml of THF while stirring at room temperature. After completion of dropping, the mixture was further stirred for 30 minutes, and toluene was added to separate the layers. The organic layer was washed with water, the solvent was distilled off under reduced pressure, and the resulting solid was vacuum-dried to obtain 80 g of 9- (6-methoxynaphthalen-2-yl) -10-phenylanthracene.

<Synthesis of 6- (10-phenylanthracen-9-yl) naphthalen-2-ol>
To 400 ml of a dichloromethane solution containing 50 g of 9- (6-methoxynaphthalen-2-yl) -10-phenylanthracene, 120 ml of a dichloromethane solution containing 39 g of boron tribromide was added dropwise with stirring at a salt ice temperature. After completion of the dropwise addition, the mixture was further stirred at room temperature for 14 hours, and then 300 ml of water was added while cooling with ice water. The reaction mixture was extracted with 1 l of ethyl acetate, and the organic layer was washed with water. The solid obtained by distilling off the solvent under reduced pressure was vacuum-dried to obtain 51 g of 6- (10-phenylanthracen-9-yl) naphthalen-2-ol.

<Synthesis of 6- (10-phenylanthracen-9-yl) naphthalen-2-yl trifluoromethanesulfonate>
In a flask containing 51 g of 6- (10-phenylanthracen-9-yl) naphthalen-2-ol, 12.3 g of pyridine, and 600 ml of toluene, a solution of 40 g of trifluoromethanesulfonic anhydride in 100 ml of toluene was added. The solution was added dropwise with stirring at an ice bath temperature. After completion of dropping, the mixture was further stirred at room temperature for 19 hours. The reaction mixture was extracted with 700 ml of toluene, and the organic layer was washed with water. The solvent was once distilled off under reduced pressure, dissolved again in toluene, and passed through an alumina short column (toluene). The solid obtained by distilling off the solvent under reduced pressure was washed three times with heptane (250 ml) to obtain 50 g of 6- (10-phenylanthracen-9-yl) naphthalen-2-yl trifluoromethanesulfonate.

<Synthesis of Compound (1-3-1)>
A flask containing 9.3 g of 4-bromopyridine hydrochloride and 45 ml of THF was cooled in a dry ice / methanol bath, and 25 ml of 2M isopropylmagnesium chloride THF solution was added dropwise with stirring under a nitrogen atmosphere. After completion of the dropwise addition, the temperature was raised to 0 ° C. and then cooled with ice water, and 25 ml of 2M isopropylmagnesium chloride THF solution was added dropwise with stirring. After completion of the dropwise addition, the mixture was further stirred at room temperature for 1 hour and a half. After confirming that 4-bromopyridine had been consumed, the flask was cooled with ice water, and zinc chloride tetramethylethylenediamine complex (12.6 g) was added with stirring. It was. Thereafter, the mixture was stirred at room temperature for 14 hours, 19 g of 6- (10-phenylanthracen-9-yl) naphthalen-2-yl trifluoromethanesulfonate, 1.7 g of Pd (PPh ₃ ) ₄ and 50 ml of THF were added, and the mixture was heated at reflux temperature for 9 hours. Stir. The reaction solution was cooled to room temperature, washed with water to remove salts, and the separated organic layer was purified by alumina column chromatography (toluene / ethyl acetate = 10/1 (volume ratio)). The solid obtained by distilling off the solvent under reduced pressure was recrystallized from anisole to give compound (1-3-1): 4- (6- (10-phenylanthracen-9-yl) naphthalen-2-yl) pyridine. 3.2 g was obtained. The structure of the compound was confirmed by NMR measurement.
¹ H-NMR (CDCl ₃ ): 8.75 (d, 2H), 8.3 (m, 1H), 8.15 (dd, 1H), 8.05 (m, 2H), 7.85 (d , 1H), 7.65-7.75 (m, 7H), 7.6 (t, 2H), 7.55-7.6 (m, 1H), 7.5 (m, 2H), 7. 35 (m, 4H).

Synthesis Example 2 Synthesis of Compound (1-3-2) Into a flask, 2.8 g of 3-pyridineboronic acid, 10.0 g of 6- (10-phenylanthracen-9-yl) naphthalen-2-yl trifluoromethanesulfonate, 0.7 g of Pd (PPh ₃ ) ₄ , 8.0 g of potassium phosphate, 40 ml of 1,2,4-trimethylbenzene, 4 ml of 2-propanol, and 4 ml of water were added and stirred at reflux temperature for 6 hours. The reaction solution was cooled to room temperature, washed with water to remove salts, and the separated organic layer was purified by silica gel column chromatography (toluene / ethyl acetate = 95/5 (volume ratio)). The solid obtained by distilling off the solvent under reduced pressure was washed with methanol, and then compound (1-3-2): 3- (6- (10-phenylanthracen-9-yl) naphthalen-2-yl) pyridine. 1 g was obtained. The structure of the compound was confirmed by NMR measurement.
¹ H-NMR (CDCl ₃ ): 9.1 (dd, 1H), 8.7 (dd, 1H), 8.2 (d, 1H), 8.2 to 8.1 (d, 1H), 8 .1 to 8.0 (m, 1H), 8.0 (m, 2H), 7.8 (dd, 1H), 7.7 (m, 4H), 7.7 to 7.6 (dd, 1H) ), 7.6 (m, 2H), 7.6 to 7.5 (m, 1H), 7.5 (m, 2H), 7.5 to 7.4 (m, 1H), 7.4 to 7.3 (m, 4H).

[Synthesis Example 3] Synthesis of Compound (1-3-3) In a flask containing 4.1 g of 2-bromopyridine and 20 ml of THF, 14.3 ml of a 2M isopropylmagnesium chloride THF solution was stirred at room temperature in a nitrogen atmosphere. It was dripped. After completion of dropping, the mixture was cooled with ice water, and 7.2 g of zinc chloride tetramethylethylenediamine complex was added with stirring. Thereafter, the mixture was stirred at room temperature for 0.5 hours, and then 12.4 g of 6- (10-phenylanthracen-9-yl) naphthalen-2-yl trifluoromethanesulfonate and 0.3 g of Pd (PPh ₃ ) ₄ were added at the reflux temperature. Stir for 0.5 hour. After cooling the reaction solution to room temperature, a solution in which ethylenediaminetetraacetic acid / tetrasodium salt dihydrate equivalent to about twice the amount of the target compound is dissolved in an appropriate amount of water to remove the metal ions of the catalyst. (Hereafter, abbreviated as EDTA · 4Na aqueous solution) was added and stirred. The solid in the liquid was collected by suction filtration, washed with methanol and then ethyl acetate, dissolved in toluene, and purified by silica gel column chromatography (toluene / ethyl acetate = 95/5 (volume ratio)). The solid obtained by distilling off the solvent under reduced pressure was recrystallized from chlorobenzene to give compound (1-3-3): 2- (6- (10-phenylanthracen-9-yl) naphthalen-2-yl) pyridine. 5.6 g was obtained. The structure of the compound was confirmed by NMR measurement.
¹ H-NMR (CDCL3): 8.8 (m, 1H), 8.7 (m, 1H), 8.25 (dd, 1H), 8.2 (d, 1H), 8.0 (m, 2H), 7.95 (d, 1H), 7.8 (td, 1H), 7.75 (m, 4H), 7.65 to 7.5 (m, 6H), 7.35 to 7.25. (M, 5H).

[Synthesis Example 4] Synthesis of Compound (1-3-5) <4,4,5,5-tetramethyl-2- (6- (10-phenylanthracen-9-yl) naphthalen-2-yl) -1 Of 2,3,2-dioxaborolane>
Under an argon atmosphere, the flask was charged with 6- (10-phenylanthracen-9-yl) naphthalen-2-yl trifluoromethanesulfonate 180.9 g, bispinacolatodiboron 129.5 g, bis (dibenzylideneacetone) palladium (0) 19 .6 g, tricyclohexylphosphine 19.1 g, potassium acetate 66.7 g, potassium carbonate 47.0 g, and anisole 300 ml were added and stirred at reflux temperature for 3 hours. After cooling the reaction solution to room temperature, toluene was added and stirred to dissolve the organic matter, and then the inorganic solid was separated by suction filtration using a Kiriyama funnel with celite. Heptane was added to the obtained filtrate, the precipitated solid was washed with heptane, and 4,4,5,5-tetramethyl-2- (6- (10-phenylanthracen-9-yl) naphthalen-2-yl ) -1,3,2-dioxaborolane (109.0 g) was obtained.

<Synthesis of Compound (1-3-5)>
The flask was charged with 4,4,5,5-tetramethyl-2- (6- (10-phenylanthracen-9-yl) naphthalen-2-yl) -1,3,2-dioxaborolane 15.0 g, 5-bromo- Add 8.3 g of 2,3′-bipyridine, 1.0 g of Pd (PPh ₃ ) ₄ , 12.6 g of potassium phosphate, 60 ml of 1,2,4-trimethylbenzene, 12 ml of 2-propanol, and 2.4 ml of water. And stirred at reflux temperature for 5 hours. After cooling the reaction solution to room temperature, the solid in the solution was collected by suction filtration and washed with EDTA · 4Na water and then ethanol. This solid was put into chlorobenzene and dissolved at reflux temperature, and then the insoluble matter was separated by suction filtration. The solution was concentrated and recrystallized from chlorobenzene to give compound (1-3-5): 5- (6- (10-phenylanthracen-9-yl) naphthalen-2-yl) -2,3′-bipyridine 5 0.7 g was obtained. The structure of the compound was confirmed by NMR measurement.
¹ H-NMR (CDCl ₃ ): 9.3 (s, 1H), 9.2 (s, 1H), 8.7 (m, 1H), 8.45 (d, 1H), 8.3 (s , 1H), 8.2 (m, 2H), 8.05 (m, 2H), 7.95 (d, 1H), 7.9 (dd, 1H), 7.4-7.8 (m, 11H), 7.35 (m, 4H).

[Synthesis Example 5] Synthesis of compound (1-3-12) 4,4,5,5-tetramethyl-2- (6- (10-phenylanthracen-9-yl) naphthalen-2-yl)- 1,3,2-dioxaborolane 5.0 g, 6-bromo-2,4′-bipyridine 2.3 g, Pd (PPh ₃ ) ₄ 0.3 g, potassium phosphate 4.2 g, 1,2,4-trimethylbenzene 20 ml, 2-propanol 4 ml, and water 1 ml were added and stirred at reflux temperature for 3 hours. The reaction solution was cooled to room temperature, water and methanol were added, and the precipitated solid was collected by suction filtration. This solid was washed with water and then with methanol, dissolved in toluene, and purified by silica gel chromatography (toluene / ethyl acetate = 60/40 (volume ratio)). After the solvent was distilled off under reduced pressure, recrystallization from chlorobenzene gave compound (1-3-12): 6- (6- (10-phenylanthracen-9-yl) naphthalen-2-yl) -2,4 ′. -1.3 g of bipyridine was obtained. The structure of the compound was confirmed by NMR measurement.
¹ H-NMR (CDCl ₃ ): 8.8 (dd, 2H), 8.75 (m, 1H), 8.45 (dd, 1H), 8.2 (d, 1H), 8.1 (dd , 2H), 8.05 (m, 3H), 8.0 (t, 1H), 7.85 (d, 1H), 7.75 (m, 4H), 7.7 (dd, 1H)), 7.6 (m, 2H), 7.55 (m, 1H), 7.5 (m, 2H), 7.35 (m, 4H).

Synthesis Example 6 Synthesis of Compound (1-3-21) 4,4,5,5-tetramethyl-2- (6- (10-phenylanthracen-9-yl) naphthalen-2-yl)- 1,3,2-dioxaborolane 15.0 g, 4- (3-bromophenyl) pyridine 6.9 g, Pd (PPh ₃ ) ₄ 1.0 g, potassium phosphate 12.6 g, 1,2,4-trimethylbenzene 60 ml Then, 12 ml of 2-propanol and 3 ml of water were added and stirred at reflux temperature for 4 hours. After the reaction solution was cooled to room temperature, water and chlorobenzene were added to separate the layers. After the solvent was distilled off under reduced pressure, the residue was dissolved again in toluene and purified by silica gel chromatography (toluene / ethyl acetate = 80/20 (volume ratio)). The solid obtained by distilling off the solvent under reduced pressure was recrystallized from chlorobenzene to give compound (1-3-21): 4- (3- (6- (10-phenylanthracen-9-yl) naphthalene-2- 9.7 g of yl) phenyl) pyridine was obtained. The structure of the compound was confirmed by NMR measurement.
¹ H-NMR (CDCl ₃ ): 8.7 (dd, 2H), 8.3 (m, 1H), 8.15 (d, 1H), 8.0 (m, 3H), 7.9 (m , 2H), 7.50-7.75 (m, 14H), 7.3 (m, 4H).

Synthesis Example 7 Synthesis of Compound (1-3-22) <Synthesis of 5-bromo-3,2′-bipyridine>
To a flask containing 52.1 g of 3,5-dibromopyridine and 300 ml of THF, 121 ml of 2M isopropylmagnesium chloride THF solution was added dropwise with stirring at room temperature. After completion of dropping, the mixture was cooled with ice water, and 81.0 g of zinc chloride tetramethylethylenediamine complex was added with stirring. Thereafter, the mixture was further stirred at room temperature for 1 hour, 45.1 g of 2-iodopyridine and 2.5 g of Pd (PPh ₃ ) ₄ were added, and the mixture was stirred for 3 hours while cooling in a water bath. To the reaction solution, EDTA · 4Na water and toluene were added for liquid separation. The solvent of the organic layer was once distilled off under reduced pressure, and the solid was dissolved in toluene and purified by silica gel column chromatography (toluene / ethyl acetate = 90/10 (volume ratio)). The solid obtained by distilling off the solvent under reduced pressure was recrystallized from heptane to obtain 39.0 g of 5-bromo-3,2′-bipyridine.

<Synthesis of Compound (1-3-22)>
To the flask was added 4,4,5,5-tetramethyl-2- (6- (10-phenylanthracen-9-yl) naphthalen-2-yl) -1,3,2-dioxaborolane, 11.1 g, 5-bromo- 5.6 g of 3,2′-bipyridine, 0.8 g of Pd (PPh ₃ ) ₄ , 9.3 g of potassium phosphate, 50 ml of 1,2,4-trimethylbenzene, 5 ml of t-butyl alcohol, and 5 ml of water were added. Stir at reflux for 3 hours. After the reaction solution was cooled to room temperature, water and toluene were added for liquid separation. The solvent of the organic layer was once distilled off under reduced pressure, and the solid was dissolved in toluene and purified by silica gel chromatography (toluene / ethyl acetate = 80/20 (volume ratio)). The solid obtained by distilling off the solvent under reduced pressure was recrystallized from toluene to give compound (1-3-22): 5- (6- (10-phenylanthracen-9-yl) naphthalen-2-yl) -3. Thus, 7.6 g of 2′-bipyridine was obtained. The structure of the compound was confirmed by NMR measurement.
¹ H-NMR (CDCL3): 9.25 (m, 1H), 9.1 (m, 1H), 8.8 (m, 1H), 8.75 (t, 1H), 8.35 (m, 1H), 8.15 (d, 1H), 8.05 (m, 2H), 7.85 to 7.95 (m, 3H), 7.75 (dd, 4H), 7.7 (dd, 1H) ), 7.6 (m, 2H), 7.55 (m, 1H), 7.5 (m, 2H), 7.3-7.4 (m, 5H).

[Synthesis Example 8] Synthesis of compound (1-3-24) 4,4,5,5-tetramethyl-2- (6- (10-phenylanthracen-9-yl) naphthalen-2-yl)- 1,3,2-dioxaborolane 15.0 g, 5-bromo-3,4'-bipyridine (8.3 g), Pd (PPh ₃ ) ₄ 1.0 g, potassium phosphate 12.6 g, 1,2,4- 60 ml of trimethylbenzene, 12 ml of 2-propanol, and 2.4 ml of water were added and stirred at reflux temperature for 3 hours. After cooling the reaction solution to room temperature, the solid in the solution was collected by suction filtration. This solid was washed with EDTA · 4Na water and then ethanol, dissolved in toluene, and purified with an activated carbon short column (toluene). The solid obtained by distilling off the solvent under reduced pressure was recrystallized from chlorobenzene to give compound (1-3-24): 5- (6- (10-phenylanthracen-9-yl) naphthalen-2-yl) -3. , 4'-bipyridine 6.2g was obtained. The structure of the compound was confirmed by NMR measurement.
¹ H-NMR (CDCL3): 9.15 (m, 1H), 8.95 (m, 1H), 8.8 (dd, 2H), 8.3 (m, 2H), 8.2 (d, 1H), 8.05 (m, 2H), 7.9 (dd, 1H), 7.5 to 7.75 (m, 12H), 7.4 to 7.3 (m, 4H).

Synthesis Example 9 Synthesis of Compound (1-3-25) <Synthesis of 3-bromo-5-phenylpyridine>
To a flask containing 33.2 g of 3,5-dibromopyridine and 150 ml of THF, 77 ml of 2M isopropylmagnesium chloride THF solution was added dropwise with stirring at room temperature. After completion of the dropwise addition, the mixture was further stirred for 1 hour at room temperature, then cooled with ice water, and 34.3 g of zinc chloride tetramethylethylenediamine complex was gradually added with stirring. After stirring at room temperature for 1 hour, 57.1 g of iodobenzene and Pd (PPh ₃ ) ₄ (1.6 g) were added, and the mixture was stirred at room temperature for 43 hours. EDTA · 4Na water and toluene were added to the reaction solution to separate the layers. The solvent of the organic layer was once distilled off under reduced pressure, and the solid was dissolved in toluene and purified by silica gel column chromatography (toluene / ethyl acetate = 90/10 (volume ratio)). The solvent was distilled off under reduced pressure to obtain 25.0 g of solid 3-bromo-5-phenylpyridine.

<Synthesis of Compound (1-3-25)>
The flask was charged with 4,4,5,5-tetramethyl-2- (6- (10-phenylanthracen-9-yl) naphthalen-2-yl) -1,3,2-dioxaborolane 10.1 g, 3-bromo- A mixture of 5.2 g of 5-phenylpyridine, 0.7 g of Pd (PPh ₃ ) ₄ , 8.5 g of potassium phosphate, 50 ml of 1,2,4-trimethylbenzene, 5 ml of t-butyl alcohol, and 5 ml of water was added to the reflux temperature. For 3 hours. After cooling the reaction solution to room temperature, the solid in the solution was collected by suction filtration. This solid was washed with water and then with methanol, dissolved in toluene, and purified by silica gel chromatography (toluene / ethyl acetate = 90/10 (volume ratio)). The solvent was distilled off under reduced pressure to obtain 6.4 g of compound (1-3-25): 3-phenyl-5- (6- (10-phenylanthracen-9-yl) naphthalen-2-yl) pyridine. The structure of the compound was confirmed by NMR measurement.
¹ H-NMR (CDCL3): 9.05 (m, 1H), 8.9 (m, 1H), 8.3 (s, 1H), 8.25 (m, 1H), 8.15 (d, 1H), 8.05 (m, 2H), 7.9 (dd, 1H), 7.45 to 7.75 (m, 15H), 7.4 to 7.3 (m, 4H).

Synthesis Example 10 Synthesis of Compound (1-3-27) <Synthesis of 5-bromo-2-phenylpyridine>
A solution of 23.4 g of phenylboronic acid, 50 g of 2,5-dibromopyridine, 4.4 g of Pd (PPh ₃ ) ₄ , 40.3 g of sodium carbonate in 150 ml of water and 500 ml of toluene was placed in a flask under an argon atmosphere. Stir at reflux for 3 and a half hours. The reaction solution was cooled to room temperature, the solvent of the separated organic layer was once distilled off under reduced pressure, the solid was dissolved in toluene, and purified with a silica gel short column (toluene). The solid obtained by distilling off the solvent under reduced pressure was recrystallized from heptane to obtain 28.8 g of 5-bromo-2-phenylpyridine.

<Synthesis of Compound (1-3-27)>
To a flask containing 5.2 g of 5-bromo-2-phenylpyridine and 20 ml of THF, 12.1 ml of 2M isopropylmagnesium chloride THF solution was added dropwise with stirring at room temperature. After completion of dropping, the mixture was further stirred at room temperature for 7 hours. The flask was cooled with ice water, and 6.1 g of zinc chloride tetramethylethylenediamine complex was added with stirring. Thereafter, the mixture was stirred at room temperature for 0.5 hours, and 10.5 g of 6- (10-phenylanthracen-9-yl) naphthalen-2-yl trifluoromethanesulfonate and 0.3 g of Pd (PPh ₃ ) ₄ were added thereto at the reflux temperature. Stir for 2 hours. The reaction solution was cooled to room temperature, EDTA · 4Na water was added, and the solid in the solution was collected by suction filtration. This solid was washed with methanol and then with ethyl acetate, dissolved in toluene, and purified by silica gel column chromatography (toluene). The solid obtained by distilling off the solvent under reduced pressure was recrystallized from chlorobenzene to give compound (1-3-27): 2-phenyl-5- (6- (10-phenylanthracen-9-yl) naphthalene-2- Yl) 2.2 g of pyridine was obtained. The structure of the compound was confirmed by NMR measurement.
¹ H-NMR (CDCL3): 9.15 (m, 1H), 8.3 (s, 1H), 8.2 (m, 2H), 8.1 (m, 2H), 8.05 (m, 2H), 7.9 (m, 2H), 7.75 (dd, 4H), 7.7 (dd, 1H), 7.65 (m, 2H), 7.5 to 7.6 (m, 5H) ), 7.45 (m, 1H), 7.3-7.4 (m, 4H).

[Synthesis Example 11] Synthesis of Compound (1-4-2) <Synthesis of Naphthalene-2,7-diylbis (trifluoromethanesulfonate)>
A flask containing 22.7 g of 2,7-dihydroxynaphthalene and 200 ml of pyridine was cooled in an ice bath, and 100 g of trifluoromethanesulfonic anhydride was added dropwise with stirring under a nitrogen atmosphere. After completion of the dropwise addition, the mixture was further stirred at room temperature for 3 hours, water was added, and the mixture was extracted with ethyl acetate. The solvent of the organic layer was once distilled off under reduced pressure, and the solid was dissolved in toluene and purified by silica gel chromatography (heptane / toluene = 80/20 (volume ratio)). The solvent was distilled off under reduced pressure to obtain 42.8 g of naphthalene-2,7-diylbis (trifluoromethanesulfonate).

<Synthesis of 7- (pyridin-3-yl) naphthalen-2-yl trifluoromethanesulfonate>
A flask containing 14.0 g of 3-bromopyridine and 50 ml of THF was cooled in an ice bath, and 48.7 ml of 2M isopropylmagnesium chloride THF solution was added dropwise with stirring under a nitrogen atmosphere. After completion of the dropwise addition, the mixture was further stirred at room temperature, and after confirming that 3-bromopyridine was consumed, the mixture was cooled again in an ice bath, and 24.6 g of zinc chloride tetramethylethylenediamine complex was added with stirring. Thereafter, the mixture was stirred at room temperature for 0.5 hours, 41.4 g of naphthalene-2,7-diylbis (trifluoromethanesulfonate) and 0.5 g of Pd (PPh ₃ ) ₄ were added, and the mixture was stirred at reflux temperature for 0.5 hours. The reaction mixture was cooled to room temperature, EDTA · 4Na water was added, and the mixture was extracted with ethyl acetate. The solvent of the organic layer was once distilled off under reduced pressure, and the solid was dissolved in toluene and purified by silica gel column chromatography (toluene / ethyl acetate = 80/20 (volume ratio)). The solvent was distilled off under reduced pressure to obtain 11.4 g of 7- (pyridin-3-yl) naphthalen-2-yl trifluoromethanesulfonate.

<Synthesis of Compound (1-4-2)>
In the flask, (10-phenylanthracen-9-yl) boronic acid 8.0 g, 7- (pyridin-3-yl) naphthalen-2-yl trifluoromethanesulfonate 11.4 g, Pd (PPh ₃ ) ₄ 0.9 g, phosphorus Potassium acid 11.4 g, 1,2,4-trimethylbenzene 54 ml, 2-propanol 11 ml, and water 2.2 ml were added and stirred at reflux temperature for 4 hours. After cooling the reaction solution to room temperature, the solid in the solution was collected by suction filtration. This solid was washed with water and then with EDTA · 4Na water, dissolved in toluene, and purified by activated alumina chromatography (toluene / ethyl acetate = 60/40 (volume ratio)). The solvent was distilled off under reduced pressure to obtain 6.3 g of compound (1-4-2): 3- (7- (10-phenylanthracen-9-yl) naphthalen-2-yl) pyridine. The structure of the compound was confirmed by NMR measurement.
¹ H-NMR (CDCL3): 9.05 (m, 1H), 8.65 (m, 1H), 8.1-8.15 (m, 3H), 8.05 (m, 2H), 7. 85 (d, 1H), 7.7 to 7.75 (m, 4H), 7.6 to 7.7 (m, 3H), 7.55 (m, 1H), 7.5 (m, 2H) 7.45 (m, 1H), 7.3-7.4 (m, 4H).

Synthesis Example 12 Synthesis Example of Compound (1-5-11) <Synthesis of 9- (4-ethoxyphenyl) -10- (naphthalen-2-yl) anthracene>
The flask was charged with 38.0 g of 4-ethoxyphenylboronic acid, 57.7 g of 9-bromo-10- (naphthalen-2-yl) anthracene, 1.7 g of Pd (PPh ₃ ) ₄ , 63.9 g of potassium phosphate, and 1, 350 ml of 2,4-trimethylbenzene was added and stirred at 100 ° C. for 4 hours under an argon atmosphere. After the reaction solution was cooled to room temperature, the solid in the solution was collected by suction filtration and washed with methanol and then with water. This solid was dissolved in chlorobenzene by heating, and insoluble matters were removed by suction filtration. The solution was concentrated and recrystallized from chlorobenzene to give 58.2 g of 9- (4-ethoxyphenyl) -10- (naphthalen-2-yl) anthracene.

<Synthesis of 4- (10- (naphthalen-2-yl) anthracen-9-yl) phenol>
A flask was charged with 45.1 g of 9- (4-ethoxyphenyl) -10- (naphthalen-2-yl) anthracene and 500.0 g of pyridine hydrochloride and stirred at reflux temperature for 10 hours under a nitrogen atmosphere. After cooling the reaction solution to room temperature, water was added and the precipitated solid was collected by suction filtration, washed with methanol, and 4- (10- (naphthalen-2-yl) anthracen-9-yl) phenol 42. 0.0 g was obtained.

<Synthesis of 4- (10- (naphthalen-2-yl) anthracen-9-yl) phenyl trifluoromethanesulfonate>
Into a flask containing 42.0 g of 4- (10- (naphthalen-2-yl) anthracen-9-yl) phenol and 500 ml of pyridine, 45.2 g of trifluoromethanesulfonic acid anhydride was cooled in an ice bath under a nitrogen atmosphere. Was dripped. After completion of dropping, the mixture was further stirred at room temperature for 15 hours. Water was added and the precipitated solid was collected by suction filtration. This solid was washed with methanol and recrystallized from chlorobenzene to obtain 38.3 g of 4- (10- (naphthalen-2-yl) anthracen-9-yl) phenyl trifluoromethanesulfonate.

<Synthesis of 4,4,5,5-tetramethyl-2- (4- (10- (naphthalen-2-yl) anthracen-9-yl) phenyl) -1,3,2-dioxaborolane>
In the flask, 35.0 g of 4- (10- (naphthalen-2-yl) anthracen-9-yl) phenyl trifluoromethanesulfonate, 25.2 g of bispinacolatodiborane, 2.2 g of bis (dibenzylideneacetone) palladium (0), 2.8 g of tricyclohexylphosphine, 13.0 g of potassium acetate, and 250 ml of cyclopentyl methyl ether were added and stirred at reflux temperature for 5.5 hours. After cooling the reaction solution to room temperature, insoluble matters were removed by suction filtration, and the solvent of the filtrate was distilled off under reduced pressure. The solid was dissolved in toluene and purified by silica gel column chromatography (toluene). The solvent was distilled off under reduced pressure to give 4,4,5,5-tetramethyl-2- (4- (10- (naphthalen-2-yl) anthracen-9-yl) phenyl) -1,3,2-dioxaborolane. 16.0 g was obtained.

<Synthesis of Compound (1-5-11)>
In a flask, 5.0 g of 4,4,5,5-tetramethyl-2- (4- (10- (naphthalen-2-yl) anthracen-9-yl) phenyl) -1,3,2-dioxaborolane, 6- Bromo-2,3′-bipyridine 2.8 g, Pd (PPh ₃ ) ₄ 0.7 g, potassium phosphate 4.2 g, 1,2,4-trimethylbenzene 20 ml, t-butyl alcohol 4 ml, and water 4.0 ml And stirred at reflux temperature for 9.5 hours. After the reaction solution was cooled to room temperature, the solid in the solution was collected by suction filtration and washed with methanol. This solid was dissolved in toluene by heating, and insoluble matters were removed by suction filtration. The solution was concentrated and recrystallized from toluene to give compound (1-5-11): 6- (4- (10- (naphthalen-2-yl) anthracen-9-yl) phenyl) -2,3′- Bipyridine 3.3g was obtained. The structure of the compound was confirmed by NMR measurement.
¹ H-NMR (CDCl ₃ ): 9.4 (m, 1H), 8.7 (d, 1H), 8.55 (dd, 1H), 8.4 (d, 2H), 8.1 (d , 1H), 8.05 (m, 1H), 7.9-8.0 (m, 4H), 7.8 (m, 3H), 7.75 (d, 2H), 7.65 (d, 2H), 7.6 (m, 3H), 7.45 (m, 1H), 7.35 (m, 4H).

Synthesis Example 13 Synthesis of Compound (1-5-24) 4,4,5,5-tetramethyl-2- (4- (10- (naphthalen-2-yl) anthracen-9-yl) phenyl was added to a flask. ) -1,3,2-dioxaborolane 5.0 g, 5-bromo-3,4'-bipyridine 2.8 g, Pd (PPh ₃ ) ₄ 0.4 g, potassium phosphate 4.2 g, 1,2,4- 20 ml of trimethylbenzene, 4 ml of t-butyl alcohol and 0.8 ml of water were added and stirred at reflux temperature for 4 hours. After the reaction solution was cooled to room temperature, the solid in the solution was collected by suction filtration and washed with methanol. This solid was dissolved in toluene by heating, and insoluble matters were removed by suction filtration. The solution was concentrated and recrystallized from toluene to give compound (1-5-24): 5- (4- (10- (naphthalen-2-yl) anthracen-9-yl) phenyl) -3,4'- 3.9 g of bipyridine was obtained. The structure of the compound was confirmed by NMR measurement.
¹ H-NMR (CDCl ₃ ): 9.1 (m, 1H), 8.95 (m, 1H), 8.8 (dd, 2H), 8.3 (m, 1H), 8.1 (d , 1H), 8.05 (m, 1H), 8.0 (s, 1H), 7.9-7.95 (m, 3H), 7.75-7.8 (m, 4H), 7. 6-7.7 (m, 7H), 7.3-7.4 (m, 4H).

Synthesis Example 14 Synthesis of Compound (1-6-1) <Synthesis of 9-bromo-10- (naphthalen-2-yl) anthracene>
A solution prepared by dissolving 39.7 g of 9- (naphthalen-2-yl) anthracene and 25.5 g of N-bromosuccinimide in 200 ml of chloroform was dissolved in 3 ml of chloroform under a nitrogen atmosphere. The solution was added dropwise with stirring at room temperature. After completion of the dropwise addition, the mixture was stirred at reflux temperature for 3 hours, and then the reaction solution was cooled to room temperature and the precipitate was removed by suction filtration. To this filtrate, 2000 ml of toluene was added and washed with water. The solvent of the organic layer was distilled off under reduced pressure, and the resulting solid was washed with 100 ml of methanol to obtain 45 g of 9-bromo-10- (naphthalen-2-yl) anthracene.

<Synthesis of 4,4,5,5-tetramethyl-2- (10- (naphthalen-2-yl) anthracen-9-yl) 1,3,2-dioxaborolane>
Under an argon atmosphere, in a flask, 20.0 g of 9-bromo-10- (naphthalen-2-yl) anthracene, 15.8 g of bispinacolatodiboron, 0.9 g of bis (dibenzylideneacetone) palladium (0), tricyclohexylphosphine 1.1 g, potassium acetate (10.2 g, and 100 ml of cyclopentyl methyl ether were added, and the mixture was stirred at reflux temperature for 14 hours. The reaction solution was cooled to room temperature, and 100 ml of toluene was added to dissolve organic substances, followed by suction filtration. The toluene solution was purified by silica gel column chromatography (heptane / toluene = 2/1 (volume ratio)) and the solvent was distilled off under reduced pressure to obtain a solid obtained by mixing THF / heptane mixed solvent (1 / 10 (volume ratio)), 4,4,5,5-tetramethyl-2- (10- ( Was obtained Futaren-2-yl) anthracene-9-yl) 1,3,2-dioxaborolane 17.9 g.

<Synthesis of 4- (3-bromophenyl) pyridine>
A flask containing 4-bromopyridine hydrochloride (200 g) and THF (800 ml) was cooled to −40 ° C., and 540 ml of 2M isopropylmagnesium chloride THF solution was added dropwise thereto with stirring under a nitrogen atmosphere. After completion of the dropwise addition, the temperature was raised to 0 ° C., and then 540 ml of 2M isopropyl magnesium chloride / THF solution was added dropwise while cooling with ice water and stirring. After completion of the dropwise addition, the mixture was stirred at room temperature for 1 hour, and after confirming that 4-bromopyridine was consumed, it was cooled with ice water, and 273 g of zinc chloride tetramethylethylenediamine complex was added with stirring. Thereafter, the mixture was stirred at room temperature for 0.5 hour, 485 g of 1,3-dibromobenzene and 1.2 g of Pd (PPh ₃ ) ₄ were added, and the mixture was stirred at reflux temperature for 3 hours. The reaction solution was cooled to room temperature, EDTA / Na water was added, and the mixture was separated, and the organic layer was washed with water. The solvent was distilled off under reduced pressure to obtain 165.7 g of 4- (3-bromophenyl) pyridine.

<Synthesis of Compound Represented by Formula (1-6-1)>
In a flask, 4,4,5,5-tetramethyl-2- (10- (naphthalen-2-yl) anthracen-9-yl) 1,3,2-dioxaborolane 4.0 g, 4- (3-bromophenyl) 2.6 g of pyridine, 0.3 g of Pd (PPh ₃ ) ₄ , 4.0 g of potassium phosphate, 20 ml of 1,2,4-trimethylbenzene, 4 ml of 2-propanol, and 1 ml of water were added at a reflux temperature of 6.5. Stir for hours. After the reaction solution was cooled to room temperature, the solid in the solution was collected by suction filtration and washed with methanol and then with water. The solid was further washed with methanol and ethyl acetate, recrystallized from toluene, and then recrystallized from chlorobenzene to give compound (1-6-1): 4- (3- (10- (naphthalen-2-yl). 2.1 g of anthracen-9-yl) phenyl) pyridine was obtained. The structure of the compound was confirmed by NMR measurement.
¹ H-NMR (CDCl ₃ ): 8.7 (m, 2H), 8.1 (d, 1H), 8.05 (m, 1H), 8.0 (m, 1H), 7.95 (m , 1H), 7.85 (m, 1H), 7.8 (m, 1H), 7.7-7.75 (m, 5H), 7.6 (m, 6H), 7.3-7. 4 (m, 4H).

Synthesis Example 15 Synthesis of Compound (1-6-2) In a flask, 4,4,5,5-tetramethyl-2- (10- (naphthalen-2-yl) anthracen-9-yl) 1,3, 2-dioxaborolane 6.0 g, 3- (3-bromophenyl) pyridine 3.9 g, Pd (PPh ₃ ) ₄ 0.5 g, potassium phosphate 5.9 g, 1,2,4-trimethylbenzene 28 ml, 2-propanol 5.5 ml and 1 ml of water were added and stirred at reflux temperature for 9.5 hours. After the reaction solution was cooled to room temperature, the solid in the solution was collected by suction filtration and washed with methanol and then with water. This solid was further washed with methanol and ethyl acetate and then recrystallized from chlorobenzene to give compound (1-6-2): 3- (3- (10- (naphthalen-2-yl) anthracen-9-yl). 3.5 g of phenyl) pyridine was obtained. The structure of the compound was confirmed by NMR measurement.
¹ H-NMR (CDCl ₃ ): 9.0 (m, 1H), 8.6 (m, 1H), 8.1 (d, 1H), 8.05 (m, 1H), 8.0 (m , 2H), 7.9 (m, 1H), 7.7-7.8 (m, 7H), 7.55-7.65 (m, 4H), 7.3-7.4 (m, 5H) ).

Synthesis Example 16 Synthesis of Compound (1-6-4) <Synthesis of 1-bromo-3-ethoxybenzene>
A flask was charged with 100.0 g of 3-bromophenol, 69.4 g of bromoethane, 95.8 g of potassium carbonate, and 500 ml of DMF, and stirred at 55 ° C. for 6 hours under a nitrogen atmosphere. The reaction solution was cooled to room temperature, and extracted with water and heptane. The solvent of the organic layer was distilled off under reduced pressure to obtain 109.0 g of 1-bromo-3-ethoxybenzene.

<Synthesis of 9- (3-ethoxyphenyl) -10- (naphthalen-2-yl) anthracene>
In the flask, 72.4 g of 1-bromo-3-ethoxybenzene, 104.5 g of (10- (naphthalen-2-yl) anthracen-9-yl) boronic acid, 10.4 g of Pd (PPh ₃ ) ₄ , and potassium phosphate 127 .4 g, 1,2,4-trimethylbenzene (600 ml), 2-propanol (120 ml) and water (120 ml) were added, and the mixture was stirred at reflux temperature for 6 hours under a nitrogen atmosphere. After the reaction solution was cooled to room temperature, the solid in the solution was collected by suction filtration and washed with methanol to obtain 82 g of 9- (3-ethoxyphenyl) -10- (naphthalen-2-yl) anthracene. .

<Synthesis of 3- (10- (naphthalen-2-yl) anthracen-9-yl) phenol>
A flask was charged with 82 g of 9- (3-ethoxyphenyl) -10- (naphthalen-2-yl) anthracene and 446.0 g of pyridine hydrochloride and stirred at reflux temperature for 8 hours under a nitrogen atmosphere. After cooling the reaction solution to room temperature, water was added and the precipitated solid was collected by suction filtration, washed with methanol and then with toluene, and then 3- (10- (naphthalen-2-yl) anthracen-9-yl. ) 76.0 g of phenol was obtained.

<Synthesis of 3- (10- (naphthalen-2-yl) anthracen-9-yl) phenyl trifluoromethanesulfonate>
A flask containing 3- (10- (naphthalen-2-yl) anthracen-9-yl) phenol (76.0 g) and pyridine (1 L) was cooled in an ice bath, where trifluoromethanesulfonic acid was added under a nitrogen atmosphere. 65.0 g of anhydride was added dropwise. After completion of the dropwise addition, the mixture was further stirred at room temperature for 15 hours, and water was added, and the precipitated solid was collected by suction filtration. This solid was washed with methanol to obtain 90.3 g of 3- (10- (naphthalen-2-yl) anthracen-9-yl) phenyl trifluoromethanesulfonate.

<Synthesis of 4,4,5,5-tetramethyl-2- (3- (10- (naphthalen-2-yl) anthracen-9-yl) phenyl) -1,3,2-dioxaborolane>
In the flask, 90.3 g of 3- (10- (naphthalen-2-yl) anthracen-9-yl) phenyl trifluoromethanesulfonate, 52.1 g of bispinacolatodiborane, 7.4 g of bis (dibenzylideneacetone) palladium (0), 7.2 g of tricyclohexylphosphine, 33.6 g of potassium acetate, 23.6 g of potassium carbonate, and 500 ml of anisole were added and stirred at reflux temperature for 5 hours. The reaction solution was cooled to room temperature, filtered with suction through a Kiriyama funnel with celite to remove insoluble matters, and the filtrate was washed with EDTA · 4Na water. The solvent of the filtrate was distilled off under reduced pressure, and the resulting solid was washed with heptane, and 4,4,5,5-tetramethyl-2- (3- (10- (naphthalen-2-yl) anthracen-9-yl) was obtained. Phenyl) -1,3,2-dioxaborolane (52.0 g) was obtained.

<Synthesis of Compound (1-6-4)>
The flask was charged with 15.4 g of 4,4,5,5-tetramethyl-2- (3- (10- (naphthalen-2-yl) anthracen-9-yl) phenyl) -1,3,2-dioxaborolane, 5- Bromo-2,2′-bipyridine 8.5 g, Pd (PPh ₃ ) ₄ 1.0 g, potassium phosphate 12.7 g, 1,2,4-trimethylbenzene 120 ml, t-butyl alcohol 12.0 ml, and water 2 .4 ml was added and stirred at reflux temperature for 3 hours. After the reaction solution was cooled to room temperature, the solid in the solution was collected by suction filtration and washed with methanol. This solid was dissolved in toluene by heating, and insoluble matters were removed by suction filtration. The solution was concentrated and recrystallized from toluene to give compound (1-6-4): 5- (3- (10- (naphthalen-2-yl) anthracen-9-yl) phenyl) -2,2′- 8.3 g of bipyridine was obtained. The structure of the compound was confirmed by NMR measurement.
¹ H-NMR (CDCl ₃ ): 9.05 (m, 1H), 8.7 (m, 1H), 8.45-8.5 (m, 2H), 8.1-8.15 (m, 2H), 8.05 (m, 1H), 8.0 (s, 1H), 7.5-7.75 (m, 9H), 7.55-7.65 (m, 4H), 7.3 -7.4 (m, 5H).

Synthesis Example 17 Synthesis of Compound (1-6-5) 4,4,5,5-tetramethyl-2- (3- (10- (naphthalen-2-yl) anthracen-9-yl) phenyl was added to a flask. ) -1,3,2-dioxaborolane 9.6 g, 5-bromo-2,3′-bipyridine 5.3 g, Pd (PPh ₃ ) ₄ 0.7 g, potassium phosphate 8.1 g, 1,2,4- 40 ml of trimethylbenzene, 8.0 ml of 2-propanol, and 1.6 ml of water were added, and the mixture was stirred at reflux temperature for 4 hours. After the reaction solution was cooled to room temperature, the solid in the solution was collected by suction filtration and washed with methanol. This solid was dissolved in chlorobenzene by heating, and insoluble matters were removed by suction filtration. The solution was concentrated and recrystallized from chlorobenzene to give compound (1-6-5): 5- (3- (10- (naphthalen-2-yl) anthracen-9-yl) phenyl) -2,3′- 7.1 g of bipyridine was obtained. The structure of the compound was confirmed by NMR measurement.
¹ H-NMR (CDCl ₃ ): 9.25 (m, 1H), 9.1 (m, 1H), 8.65 (dd, 1H), 8.4 (m, 1H), 8.1 (d , 2H), 8.05 (m, 1H), 8.0 (s, 1H), 7.95 (m, 1H), 7.85 (t, 2H), 7.7-7.8 (m, 6H), 7.6 (m, 4H), 7.4 (m, 1H), 7.3-7.4 (m, 4H).

By appropriately changing the raw material compound, other derivative compounds of the present invention can be synthesized by a method according to the synthesis example described above.

Hereinafter, in order to describe the present invention in more detail, examples of the organic EL device using the compound of the present invention are shown, but the present invention is not limited thereto.

The elements according to Example 1 and Comparative Example 1 were manufactured, and the driving start voltage (V) in the constant current driving test and the time (hr) for maintaining the luminance of 90% or more of the initial value were measured. Hereinafter, examples and comparative examples will be described in detail.

Table 1 below shows the material structure of each layer in the fabricated element according to Example 1 and Comparative Example 1.

In Table 1, "CuPc" is copper phthalocyanine, and "NPD" is N4, N4'-di (naphthalen-1-yl) -N4, N4'-diphenyl- [1,1'-biphenyl] -4,4'- Diamine, compound (A) is 9-((6- [1,1 ′; 3,1 ″ terphenyl] -5′-yl) naphthalen-2-yl) -10-phenylanthracene, compound (B) is N ^{5, N 5, N 9,} N 9 -7,7- a hexaphenyl -7H- benzo [C] fluorene-5,9-diamine, compound (C) is 5,5 '- (2-phenyl-anthracene - 9,10-diyl) di-2,2′-bipyridine, each having the following chemical structure.

<Element (1) Using Compound (1-3-1) for Electron Transport Layer>
A 26 mm × 28 mm × 0.7 mm glass substrate (manufactured by Optoscience Co., Ltd.) obtained by polishing ITO deposited to a thickness of 180 nm by sputtering to 150 nm was used as a transparent support substrate. This transparent support substrate is fixed to a substrate holder of a commercially available vapor deposition apparatus (manufactured by Vacuum Kiko Co., Ltd.), and a molybdenum vapor deposition boat containing CuPc, a molybdenum vapor deposition boat containing NPD, and a compound (A) are placed therein. Molybdenum vapor deposition boat, molybdenum vapor deposition boat containing compound (B), molybdenum vapor deposition boat containing compound (1-3-1), molybdenum vapor deposition boat containing lithium fluoride, and A tungsten evaporation boat containing aluminum was installed.

The following layers were sequentially formed on the ITO film of the transparent support substrate. The vacuum chamber was depressurized to 5 × 10 ⁻⁴ Pa, and first, a vapor deposition boat containing CuPc was heated and vapor-deposited to a film thickness of 70 nm to form a hole injection layer, and then NPD was contained. The vapor deposition boat was heated and vapor-deposited so that it might become a film thickness of 30 nm, and the positive hole transport layer was formed. Next, the vapor deposition boat containing the compound (A) and the vapor deposition boat containing the compound (B) were heated at the same time to form a light emitting layer by vapor deposition to a film thickness of 35 nm. The deposition rate was adjusted so that the weight ratio of compound (A) to compound (B) was approximately 95 to 5. Next, the evaporation boat containing the compound (1-3-1) was heated and evaporated to a film thickness of 15 nm to form an electron transport layer. The deposition rate of each layer was 0.01 to 1 nm / second.

Thereafter, the evaporation boat containing lithium fluoride is heated to deposit at a deposition rate of 0.003 to 0.1 nm / second so that the film thickness becomes 0.5 nm, and then the evaporation boat containing aluminum is heated. The cathode was formed by vapor deposition at a deposition rate of 0.01 to 10 nm / second so as to obtain a film thickness of 100 nm to obtain an organic EL device.

When a DC voltage was applied using the ITO electrode as the anode and the lithium fluoride / aluminum electrode as the cathode, blue light emission with a wavelength of about 455 nm was obtained. When a constant current driving test was performed at a current density for obtaining an initial luminance of 2000 cd / m ² , the driving test start voltage was 5.65 V, and the time for maintaining the luminance of 90% (1800 cd / m ² ) or more of the initial value was maintained. Was 110 hours.

<Comparative Example 1>
An organic EL device was obtained by the method according to Example 1 except that the compound (1-3-1) was changed to the compound (C). A constant current driving test was performed using an ITO electrode as an anode and a lithium fluoride / aluminum electrode as a cathode at a current density for obtaining an initial luminance of 2000 cd / m ² . The driving test start voltage was 4.59 V, and the time for maintaining the luminance of 90% or more of the initial value was 39 hours.

The above results are summarized in Table 2.

The material used for the hole injection layer was changed from CuPc of Example 1 to HI, which is a compound having no emission peak in the red region, and the materials shown in Table 3 were used as materials for the electron transport layer. The elements according to 2 to 9 were manufactured, and the driving start voltage (V) in the constant current driving test and the time (hr) for maintaining the luminance of 90% or more of the initial value were measured. Hereinafter, examples and comparative examples will be described in detail. HI is N4, N4′-diphenyl-N4, N4′-bis (9-phenyl-9H-carbazol-3-yl)-[1,1′-biphenyl] -4,4′-diamine. It has the chemical structure of

Table 3 below shows the material structure of each layer in the manufactured devices according to Examples 2 to 9.

<Element (2) using Compound (1-3-1) for Electron Transport Layer>
A glass substrate of 26 mm × 28 mm × 0.7 mm (manufactured by Optoscience Co., Ltd.) obtained by polishing ITO deposited to a thickness of 180 nm by sputtering to 150 nm was used as a transparent support substrate. This transparent support substrate is fixed to a substrate holder of a commercially available vapor deposition apparatus (manufactured by Vacuum Kiko Co., Ltd.), and a molybdenum vapor deposition boat containing HI, a molybdenum vapor deposition boat containing NPD, and compound (A) are placed therein. Molybdenum vapor deposition boat, molybdenum vapor deposition boat containing compound (B), molybdenum vapor deposition boat containing compound (1-3-1), molybdenum vapor deposition boat containing lithium quinoline, magnesium A molybdenum boat and a tungsten evaporation boat containing silver were installed.

The following layers were sequentially formed on the ITO film of the transparent support substrate. The vacuum chamber was depressurized to 5 × 10 ⁻⁴ Pa, and first, a vapor deposition boat containing HI was heated and vapor-deposited to a film thickness of 40 nm to form a hole injection layer, and then NPD entered. The vapor deposition boat was heated and vapor-deposited so that it might become a film thickness of 30 nm, and the positive hole transport layer was formed. Next, the vapor deposition boat containing the compound (A) and the vapor deposition boat containing the compound (B) were heated at the same time to form a light emitting layer by vapor deposition to a film thickness of 35 nm. The deposition rate was adjusted so that the weight ratio of compound (A) to compound (B) was approximately 95 to 5. Next, the evaporation boat containing the compound (1-3-1) was heated and evaporated to a film thickness of 15 nm to form an electron transport layer. The deposition rate of each layer was 0.01 to 1 nm / second.

Then, the vapor deposition boat containing lithium quinoline was heated and vapor-deposited at a vapor deposition rate of 0.01 to 0.1 nm / second so as to have a film thickness of 1 nm. Next, a boat containing magnesium and a boat containing silver were heated at the same time and evaporated to a film pressure of 100 nm to form a cathode. At this time, the deposition rate was adjusted so that the atomic ratio of magnesium and silver was 10: 1, and the cathode was formed so that the deposition rate was from 0.1 nm to 10 nm to obtain an organic electroluminescent device.

When a direct current voltage was applied using the ITO electrode as the anode and the magnesium / silver electrode as the cathode, blue light emission with a wavelength of about 460 nm was obtained. Further, when a constant current driving test was performed with a current density for obtaining an initial luminance of 2000 cd / m ² , the driving test start voltage was 6.77 V, and the luminance was 90% (1800 cd / m ² ) or more of the initial value. The holding time was 108 hours.

<Element Using Compound (1-3-2) for Electron Transport Layer>
An organic EL device was obtained by the method according to Example 2 except that the compound (1-3-1) was changed to the compound (1-3-2). A constant current driving test was carried out using an ITO electrode as an anode and a magnesium / silver electrode as a cathode at a current density for obtaining an initial luminance of 2000 cd / m ² . The driving test start voltage was 5.71 V, and the time for maintaining the luminance of 90% or more of the initial value was 74 hours.

<Element Using Compound (1-3-5) for Electron Transport Layer>
An organic EL device was obtained by the method according to Example 2 except that the compound (1-3-1) was changed to the compound (1-3-5). A constant current driving test was carried out using an ITO electrode as an anode and a magnesium / silver electrode as a cathode at a current density for obtaining an initial luminance of 2000 cd / m ² . The driving test start voltage was 5.71 V, and the time for maintaining the luminance of 90% or more of the initial value was 88 hours.

<Element Using Compound (1-3-22) for Electron Transport Layer>
An organic EL device was obtained by the method according to Example 2 except that the compound (1-3-1) was changed to the compound (1-3-22). A constant current driving test was carried out using an ITO electrode as an anode and a magnesium / silver electrode as a cathode at a current density for obtaining an initial luminance of 2000 cd / m ² . The driving test starting voltage was 6.97 V, and the time for maintaining the luminance of 90% or more of the initial value was 98 hours.

<Element Using Compound (1-3-24) for Electron Transport Layer>
An organic EL device was obtained by the method according to Example 2 except that the compound (1-3-1) was changed to the compound (1-3-24). A constant current driving test was carried out using an ITO electrode as an anode and a magnesium / silver electrode as a cathode at a current density for obtaining an initial luminance of 2000 cd / m ² . The driving test starting voltage was 7.16 V, and the time for maintaining the luminance of 90% or more of the initial value was 143 hours.

<Element Using Compound (1-3-25) for Electron Transport Layer>
An organic EL device was obtained by the method according to Example 2 except that the compound (1-3-1) was changed to the compound (1-3-25). A constant current driving test was carried out using an ITO electrode as an anode and a magnesium / silver electrode as a cathode at a current density for obtaining an initial luminance of 2000 cd / m ² . The driving test starting voltage was 7.35 V, and the time for maintaining the luminance of 90% or more of the initial value was 165 hours.

<Element Using Compound (1-5-24) for Electron Transport Layer>
An organic EL device was obtained by the method according to Example 2 except that the compound (1-3-1) was changed to the compound (1-5-24). A constant current driving test was carried out using an ITO electrode as an anode and a magnesium / silver electrode as a cathode at a current density for obtaining an initial luminance of 2000 cd / m ² . The driving test start voltage was 6.36 V, and the time for maintaining the luminance of 90% or more of the initial value was 103 hours.

<Element Using Compound (1-6-4) for Electron Transport Layer>
An organic EL device was obtained by the method according to Example 2 except that the compound (1-3-1) was changed to the compound (1-6-4). A constant current driving test was carried out using an ITO electrode as an anode and a magnesium / silver electrode as a cathode at a current density for obtaining an initial luminance of 2000 cd / m ² . The driving test start voltage was 6.34 V, and the time for maintaining the luminance of 90% or more of the initial value was 120 hours.

The above results are summarized in Table 4.

According to a preferred aspect of the present invention, it is possible to provide an organic electroluminescent element that improves the lifetime of the light emitting element and has an excellent balance with the driving voltage, a display device including the organic electroluminescent element, and a lighting device including the organic electroluminescent element. it can.

Claims (26)

A compound represented by the following formula (1).

In formula (1),
Py is independently a group represented by formula (2), (3), (4), or (5);

m and n are 0 or 1, but m + n = 1;
In the formula, -H of the benzene ring, naphthalene ring, and pyridine ring may be independently substituted with alkyl having 1 to 6 carbons or cycloalkyl having 3 to 6 carbons ,
When m is 1 and Py is linked to the 4-position of phenyl, formula (3) is not 2,4′-bipyridin-6-yl . The compound of Claim 1 represented by a following formula (1-1) or (1-2).

In formula (1-1) or (1-2),
Py is a group represented by formula (2), (3), (4), or (5);

In the formula, -H of the benzene ring, naphthalene ring, and pyridine ring may be independently substituted with alkyl having 1 to 6 carbons or cycloalkyl having 3 to 6 carbons ,
In Formula (1-2), when Py is linked to the 4-position of phenyl, Formula (3) is not 2,4′-bipyridin-6-yl . The compound of Claim 1 represented by following formula (1-3), (1-4), (1-5), or (1-6).

In each of the formulas (1-3) to (1-6),
Py is a group represented by the formula (2), (3), (4) or (5);

In the formula, -H of the benzene ring, naphthalene ring, and pyridine ring may be independently substituted with alkyl having 1 to 6 carbons or cycloalkyl having 3 to 6 carbons ,
In the formula (1-5), the formula (3) is not 2,4′-bipyridin-6-yl . The compound of Claim 1 represented by a following formula (1-3) or (1-4).

In formulas (1-3) and (1-4),
Py is a group represented by the formula (2), (3), (4) or (5);

In the formula, -H in the benzene ring, naphthalene ring, and pyridine ring may be independently substituted with alkyl having 1 to 6 carbon atoms or cycloalkyl having 3 to 6 carbon atoms. The compound of Claim 1 represented by a following formula (1-5) or (1-6).

In formulas (1-5) and (1-6),
Py is a group represented by the formula (2), (3), (4) or (5);

In the formula, -H of the benzene ring, naphthalene ring, and pyridine ring may be independently substituted with alkyl having 1 to 6 carbons or cycloalkyl having 3 to 6 carbons ,
In the formula (1-5), the formula (3) is not 2,4′-bipyridin-6-yl . The compound of Claim 1 represented by a following formula (1-3-1).

The compound of Claim 1 represented by a following formula (1-3-2).

The compound of Claim 1 represented by a following formula (1-3-3).

The compound of Claim 1 represented by a following formula (1-3-5).

The compound of Claim 1 represented by a following formula (1-3-12).

The compound of Claim 1 represented by a following formula (1-3-21).

The compound of Claim 1 represented by a following formula (1-3-22).

The compound of Claim 1 represented by a following formula (1-3-24).

The compound of Claim 1 represented by a following formula (1-3-25).

The compound of Claim 1 represented by a following formula (1-3-27).

The compound of Claim 1 represented by a following formula (1-4-2).

The compound of Claim 1 represented by a following formula (1-5-11).

The compound of Claim 1 represented by a following formula (1-5-24).

The compound of Claim 1 represented by a following formula (1-6-1).

The compound of Claim 1 represented by a following formula (1-6-2).

The compound of Claim 1 represented by a following formula (1-6-4).

The compound of Claim 1 represented by a following formula (1-6-5).

The electron transport material containing the compound of any one of Claims 1-22. 24. Electron transport containing an electron transport material according to claim 23, comprising a pair of electrodes comprising an anode and a cathode, a light emitting layer disposed between the pair of electrodes, and disposed between the cathode and the light emitting layer. An organic electroluminescent device having a layer and / or an electron injection layer. The organic material according to claim 24, wherein at least one of the electron transport layer and the electron injection layer further contains at least one selected from the group consisting of a quinolinol-based metal complex, a bipyridine derivative, a phenanthroline derivative, and a borane derivative. Electroluminescent device. At least one of the electron transport layer and the electron injection layer is further made of an alkali metal, an alkaline earth metal, a rare earth metal, an alkali metal oxide, an alkali metal halide, an alkaline earth metal oxide, or an alkaline earth metal. The material contains at least one selected from the group consisting of halides, rare earth metal oxides, rare earth metal halides, alkali metal organic complexes, alkaline earth metal organic complexes and rare earth metal organic complexes. The organic electroluminescent device according to 24 or 25.