JPWO2012060374A1 - Electron transport material and organic electroluminescent device using the same - Google Patents

Abstract

The compound represented by the formula (1) of the present invention is useful as an electron transport material for an organic EL device, and contributes to extending the life of the organic EL device by using this electron transport material. In formula (1), Py is independently a group represented by formula (2), (3) or (4); m and n are 0 or 1, but m + n = 1; and At least one of hydrogen in the benzene ring, naphthalene ring and pyridine ring in the formula (1) is replaced with alkyl having 1 to 6 carbons or cycloalkyl having 3 to 6 carbons.

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 either 9- (2-naphthyl) -10-phenylanthracene naphthyl or phenyl has pyridyl, bipyridyl, or pyridylphenyl, and a benzene ring or naphthalene ring. And a compound in which at least one of hydrogen in the pyridine ring is substituted with alkyl having 1 to 6 carbon atoms or cycloalkyl having 3 to 6 carbon atoms in the electron transport layer of the organic EL device, the organic EL can be driven with a long lifetime It was found that an element was obtained, and the present invention was completed based on this finding.
Said subject is solved by each item shown below.

式（１）において、
Ｐｙは独立して、式（２）、（３）または（４）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；そして、
式（１）中のベンゼン環、ナフタレン環およびピリジン環の水素の少なくとも１つは炭素数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る。[1] A compound represented by the following formula (1).

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

m and n are 0 or 1, but m + n = 1; and
At least one of hydrogen in the benzene ring, naphthalene ring and pyridine ring in the formula (1) is replaced with alkyl having 1 to 6 carbons or cycloalkyl having 3 to 6 carbons.

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

そして、式（１−１）および（１−２）中のベンゼン環、ナフタレン環およびピリジン環の水素の少なくとも１つは炭素数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る。[2] The compound according to [1], which is represented by the following formula (1-1) or (1-2).

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

Then, at least one of hydrogen in the benzene ring, naphthalene ring and pyridine ring in the formulas (1-1) and (1-2) is replaced with alkyl having 1 to 6 carbons or cycloalkyl having 3 to 6 carbons. ing.

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

そして、式（１−３）〜（１−６）中のベンゼン環、ナフタレン環およびピリジン環の水素の少なくとも１つは炭素数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る。[3] The compound according to [1], which is represented by the following formula (1-3), (1-4), (1-5), or (1-6).

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

Then, at least one of hydrogen in the benzene ring, naphthalene ring and pyridine ring in formulas (1-3) to (1-6) is replaced with alkyl having 1 to 6 carbons or cycloalkyl having 3 to 6 carbons. ing.

式（１−７）および（１−８）において、
Ｐｙは式（２）、（３）または（４）で表される基であり；

Ｒは炭素数１〜６のアルキルまたは炭素数３〜６のシクロアルキルであり；そして、
ｐは１〜５の整数である。[4] The compound according to [1], which is represented by the following formula (1-7) or (1-8).

In formulas (1-7) and (1-8),
Py is a group represented by the formula (2), (3) or (4);

R is alkyl having 1 to 6 carbons or cycloalkyl having 3 to 6 carbons; and
p is an integer of 1-5.

式（１−９）および（１−１０）において、
Ｐｙは式（２）、（３）または（４）で表される基であり；

Ｒは炭素数１〜６のアルキルまたは炭素数３〜６のシクロアルキルであり；そして、
ｑは１〜５の整数である。[5] The compound according to item [1], represented by the following formula (1-9) or (1-10):

In formulas (1-9) and (1-10),
Py is a group represented by the formula (2), (3) or (4);

R is alkyl having 1 to 6 carbons or cycloalkyl having 3 to 6 carbons; and
q is an integer of 1-5.

式（１−１１）および（１−１２）において、
Ｐｙ^１は式（２’）、（３’）または（４’）で表される基であり；

式（２’）、（３’）および（４’）において、Ｒは炭素数１〜６のアルキルまたは炭素数３〜６のシクロアルキルであり；そして、ｓは１〜４の整数である。[6] The compound according to [1], which is represented by the following formula (1-11) or (1-12).

In formulas (1-11) and (1-12),
Py ¹ is a group represented by the formula (2 ′), (3 ′) or (4 ′);

In the formulas (2 ′), (3 ′) and (4 ′), R is alkyl having 1 to 6 carbons or cycloalkyl having 3 to 6 carbons; and s is an integer of 1 to 4.

式（１−１３）および（１−１４）において、
Ｐｙ^１は式（２’）、（３’）または（４’）で表される基であり；

式（２’）、（３’）または（４’）において、Ｒは炭素数１〜６のアルキルまたは炭素数３〜６のシクロアルキルであり；そして、ｓは１〜４の整数である。[7] The compound according to item [1], represented by the following formula (1-13) or (1-14):

In formulas (1-13) and (1-14),
Py ¹ is a group represented by the formula (2 ′), (3 ′) or (4 ′);

In the formula (2 ′), (3 ′) or (4 ′), R is alkyl having 1 to 6 carbons or cycloalkyl having 3 to 6 carbons; and s is an integer of 1 to 4.

式（１−１５）および（１−１６）において、
Ｐｙは式（２）、（３）または（４）で表される基であり；

Ｒは炭素数１〜６のアルキルまたは炭素数３〜６のシクロアルキルであり；そして、ｔは１〜４の整数である。[8] The compound according to [1], which is represented by the following formula (1-15) or (1-16).

In formulas (1-15) and (1-16),
Py is a group represented by the formula (2), (3) or (4);

R is alkyl having 1 to 6 carbons or cycloalkyl having 3 to 6 carbons; and t is an integer of 1 to 4.

［１０］ 下記式（１−７−７４）で表される、前記［１］項に記載の化合物。

［１１］ 下記式（１−７−９８）で表される、前記［１］項に記載の化合物。

［１２］ 下記式（１−７−９６）で表される、前記［１］項に記載の化合物。

［１３］ 下記式（１−１４−１４）で表される、前記［１］項に記載の化合物。

[9] The compound according to [1], which is represented by the following formula (1-7-26).

[10] The compound according to [1], which is represented by the following formula (1-7-74).

[11] The compound according to [1], which is represented by the following formula (1-7-98).

[12] The compound according to [1], which is represented by the following formula (1-7-96).

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

[14] The following formulas (1-11-1), (1-11-2), (1-11-3), (1-11-4), (1-11-1-5), (1-11-1) 6), (1-11-1-8), (1-11-1-18), (1-11-139), (1-14-2), (1-14-3), (1-14-11) , (1-14-12), (1-14-13), (1-14-15), (1-14-16), (1-14-17), (1-14-18), and The compound according to [1], which is represented by any one of (1-14-20).

[15] An electron transport material containing the compound according to any one of [1] to [14].

[16] The electron transport material according to item [15], which is disposed between a pair of electrodes including an anode and a cathode, a light emitting layer disposed between the pair of electrodes, and the cathode and the light emitting layer. An organic electroluminescent device having an electron transport layer and / or an electron injection layer containing
[17] 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, [16] The organic electroluminescent element described in the item.
[18] 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 above [16] or [17].

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 the present invention for an electron transport layer and / or an electron injection layer of an organic EL device, an organic EL device having 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.

Hereinafter, the present invention will be described in more detail. In the present specification, for example, the “compound represented by the formula (1-7-26)” may be referred to as “compound (1-7-26)”. The “compound represented by the formula (1-7-74)” may be referred to as “compound (1-7-74)”. Other formula symbols and formula numbers are handled in the same manner.

式（１）において、Ｐｙは独立して、式（２）、（３）または（４）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。そして、式（１）中のベンゼン環、ナフタレン環およびピリジン環の水素の少なくとも１つが炭素数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ることが、本化合物の特徴である。<Description of compound>
The first invention of the present application is a compound having pyridyl, bipyridyl or pyridylphenyl represented by the following formula (1).

In the formula (1), Py is independently a group represented by the formula (2), (3) or (4), and m and n are 0 or 1, but m + n = 1. The feature of the present compound is that at least one of hydrogen in the benzene ring, naphthalene ring and pyridine ring in the formula (1) is replaced by alkyl having 1 to 6 carbons or cycloalkyl having 3 to 6 carbons. It is.

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.

Specific examples of pyridylphenyl represented by the formula (4) include 4- (2-pyridyl) phenyl, 4- (3-pyridyl) phenyl, 4- (4-pyridyl) phenyl, and 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.

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.

Examples of the alkyl having 1 to 6 carbon atoms substituted on the benzene ring, naphthalene ring and pyridine ring in the formula (1) are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, n- Pentyl, isopentyl, 2,2-dimethylpropyl, n-hexyl, and isohexyl. Of these, preferred alkyls are methyl, ethyl, isopropyl, and t-butyl, with methyl and t-butyl being more preferred. Examples of cycloalkyl having 3 to 6 carbon atoms are cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl. Among these, a preferred cycloalkyl is cyclohexyl in consideration of availability of raw materials and ease of synthesis.

式（１−１）および（１−２）におけるＰｙの定義は前記と同じである。The compound represented by the formula (1) is specifically a compound represented by the following formula (1-1) or (1-2).

The definition of Py in the formulas (1-1) and (1-2) is the same as described above.

式（１−３）〜（１−６）におけるＰｙの定義は前記と同じである。More specifically, the compound represented by the formula (1) is a compound represented by any one of the following formulas (1-3) to (1-6).

The definition of Py in formulas (1-3) to (1-6) is the same as described above.

式（１−７）〜（１−１０）におけるＰｙおよびＲの定義は前記と同じである。式（１−７）および（１−８）におけるｐは１〜５の整数であり、１〜２の整数であることが好ましく、１であることがより好ましい。Ｒが置換するフェニルの位置に制約はないが、３位または４位であることが好ましい。式（１−９）および（１−１０）におけるｑは１〜５の整数であり、１〜２の整数であることが好ましく、１であることがより好ましい。Ｒが置換するナフチルの位置に制約はないが、６位または７位であることが好ましい。More specifically, the compound represented by the formula (1) is a compound represented by any one of the following formulas (1-7) to (1-10).

In the formulas (1-7) to (1-10), Py and R are as defined above. P in the formulas (1-7) and (1-8) is an integer of 1 to 5, preferably an integer of 1 to 2, and more preferably 1. The position of phenyl substituted by R is not limited, but the 3-position or 4-position is preferred. Q in the formulas (1-9) and (1-10) is an integer of 1 to 5, preferably an integer of 1 to 2, and more preferably 1. The position of naphthyl substituted by R is not limited, but is preferably 6-position or 7-position.

式（１−１１）〜（１−１４）におけるＰｙ^１の定義は前記と同じである。前記の式（２’）、（３’）または（４’）におけるＲの定義は前記と同じである。ｓは１〜４の整数であり、１または２であることが好ましく、１であることがより好ましい。Ｒが置換するピリジルの位置には特に制約はない。The compound represented by the formula (1) is more specifically a compound represented by any of the following formulas (1-11) to (1-14).

The definition of Py ^{1 in} the formulas (1-11) to (1-14) is the same as described above. The definition of R in the above formula (2 ′), (3 ′) or (4 ′) is the same as described above. s is an integer of 1 to 4, preferably 1 or 2, and more preferably 1. The position of pyridyl substituted by R is not particularly limited.

式（１−１５）および（１−１６）におけるＰｙおよびＲの定義は前記と同じである。ｔは１〜４の整数であり、１または２であることが好ましく、１であることがより好ましい。Ｒが置換するフェニレンの位置に制約はないが、合成の容易さを考慮すると、１，４−フェニレンの場合はアントラセンに連結している炭素を基準にして３位が好ましい。１，３−フェニレンの場合は、アントラセンに連結している炭素を基準にして４位が好ましい。The compound represented by the formula (1) is more specifically a compound represented by the following formula (1-15) or (1-16).

The definitions of Py and R in the formulas (1-15) and (1-16) are the same as described above. t is an integer of 1 to 4, preferably 1 or 2, and more preferably 1. There is no restriction on the position of phenylene substituted by R, but considering the ease of synthesis, in the case of 1,4-phenylene, the 3-position is preferred based on the carbon linked to anthracene. In the case of 1,3-phenylene, the 4-position is preferred based on the carbon linked to the anthracene.

Specifically, the compounds represented by the formula (1) as described above are roughly classified into compounds represented by the formulas (1-7) to (1-16). Among these, preferred structures are formulas (1-7), formulas (1-9) to (1-11), and formulas (1-13) to (1-16), and more preferred structures are formulas (1- 7).

<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 (1-7)>
Specific examples of the compound represented by the formula (1-7) are represented by the following formulas (1-7-1) to (1-7-144). Among these, preferable compounds are represented by formulas (1-7-1) to (1-7-6), formulas (1-7-10) to (1-7-12), and formulas (1-7-16) to (1-7-30), Formulas (1-7-34) to (1-7-36), Formulas (1-7-40) to (1-7-48), Formula (1-7-73) To (1-7-78), formula (1-7-82) to (1-7-84), formula (1-7-88) to (1-7-102), formula (1-7-106) ) To (1-7-108) and formulas (1-7-112) to (1-7-120).

<Specific Example of Compound Represented by Formula (1-8)>
Specific examples of the compound represented by the formula (1-8) are represented by the following formulas (1-8-1) to (1-8-105).

<Specific Example of Compound Represented by Formula (1-9)>
Specific examples of the compound represented by the formula (1-9) are represented by the following formulas (1-9-1) to (1-9-48). Among these, preferred compounds are those represented by formulas (1-9-10) to (1-9-12), (1-9-16) to (1-9-18), and formulas (1-9-34) to ( 1-9-36) and formulas (1-9-40) to (1-9-42).

<Specific Example of Compound Represented by Formula (1-10)>
Specific examples of the compound represented by the formula (1-10) are represented by the following formulas (1-10-1) to (1-10-48). Among these, preferred compounds are those represented by formulas (1-10-1) to (1-10-6), (1-10-10) to (1-10-12) and (1-10-16) to (1 -10-21).

<Specific Example of Compound Represented by Formula (1-11)>
Specific examples of the compound represented by the formula (1-11) are represented by the following formulas (1-11-1) to (1-111-60). Among these, preferred compounds are those represented by formulas (1-11-3) to (1-11-1-10), (1-11-1-25) to (1-11-128) and (1-11-151) to (1 -11-60).

<Specific Example of Compound Represented by Formula (1-12)>
Specific examples of the compound represented by the formula (1-12) are represented by the following formulas (1-12-1) to (1-12-60).

<Specific Example of Compound Represented by Formula (1-13)>
Specific examples of the compound represented by the formula (1-13) are represented by the following formulas (1-13-1) to (1-13-60). Among these, preferred compounds are the formulas (1-13-31) to (1-13-28) and the formulas (1-13-31) to (1-31-40).

<Specific Example of Compound Represented by Formula (1-14)>
Specific examples of the compound represented by the formula (1-14) are represented by the following formulas (1-14-1) to (1-14-60). Among these, preferred compounds are formulas (1-14-1) to (1-14-18).

<Specific Example of Compound Represented by Formula (1-15)>
Specific examples of the compound represented by the formula (1-15) are represented by the following formulas (1-15-1) to (1-15-48). Among these, preferred compounds are those represented by formulas (1-15-10) to (1-15-12), (1-15-16) to (1-15-18), and formulas (1-15-34) to ( 1-15-36) and (1-15-40) to (1-15-42).

<Specific Example of Compound Represented by Formula (1-16)>
Specific examples of the compound represented by the formula (1-16) are represented by the following formulas (1-16-1) to (1-16-24). Among these, preferred compounds are formulas (1-16-1) to (1-16-5).

<Method of synthesizing compounds>
The synthesis method of the compound of the present invention will be described below. The compound of the present invention can be synthesized by appropriately combining known synthesis methods that are widely used.

先ず、反応１でフェニルがアルキル基（シクロアルキル基）で置換された９−フェニルアントラセンを合成する。アルキル置換されたブロモベンゼンを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フェニルがアルキル基（シクロアルキル基）で置換された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、例えば亜鉛錯体を用いた根岸カップリング反応、ボロン酸またはボロン酸エステルを用いた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。<Synthesis Method of Compounds Represented by Formula (1-7-1) to Formula (1-7-144)>

First, 9-phenylanthracene in which phenyl is substituted with an alkyl group (cycloalkyl group) in Reaction 1 is synthesized. 9-Phenylanthracene in which phenyl is substituted with an alkyl group (cycloalkyl group) by reacting alkyl-substituted bromobenzene with metal magnesium in THF to form a Grignard reagent, which is reacted with 9-bromoanthracene in the presence of a catalyst. And The coupling of the benzene ring and the anthracene ring is not limited to the above method, and for example, the Negishi coupling reaction using a zinc complex, the Suzuki coupling reaction using a boronic acid or a boronic acid ester, and the like are also possible. These conventional methods can be appropriately used depending on the case.

反応２ではＮ−ブロモスクシンイミドを用いてフェニルがアルキル基（シクロアルキル基）で置換された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, N-bromosuccinimide is used to bromine the 10-position of 9-phenylanthracene in which phenyl is substituted with an alkyl group (cycloalkyl group). 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反応２で合成した９−ブロモアントラセン誘導体を反応させて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誘導体を合成する。反応１と同様に、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、例えば亜鉛錯体を用いた根岸カップリング反応、ボロン酸またはボロン酸エステルを用いた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。

In reaction 3, the anthracene ring and the naphthalene ring are coupled. First, 2-bromo-6-methoxynaphthalene was converted into a Grignard reagent according to a conventional method, and this was reacted with the 9-bromoanthracene derivative synthesized in Reaction 2 in the presence of a catalyst to give 9- (6-methoxynaphthalen-2-yl)- A 10-phenylanthracene derivative is synthesized. As in Reaction 1, coupling of the benzene ring and the anthracene ring is not limited to the above method. For example, Negishi coupling reaction using a zinc complex, Suzuki coupling reaction using a boronic acid or a boronic acid ester, and the like. These conventional methods can be appropriately used depending on the situation.

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誘導体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 the 9- (6-methoxynaphthalen-2-yl) -10-phenylanthracene derivative 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.

In Reaction 6, in addition to the Negishi coupling reaction, a commonly used coupling reaction such as a Suzuki coupling reaction can be appropriately used. When the Suzuki coupling reaction is used, an optimal boronic acid or boronic acid ester may be prepared according to the target product. For example, the target product can be obtained using a boronic acid ester as shown in the following reaction 7. .

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

In order to accelerate the reaction, a phosphine compound may be added to these palladium compounds in some cases. Specific examples of the phosphine compound include tri (t-butyl) phosphine, tricyclohexylphosphine, 1- (N, N-dimethylaminomethyl) -2- (di-t-butylphosphino) ferrocene, 1- (N, N-dibutylaminomethyl) -2- (di-t-butylphosphino) ferrocene, 1- (methoxymethyl) -2- (di-t-butylphosphino) ferrocene, 1,1′-bis (di-t-butylphos Fino) ferrocene, 2,2′-bis (di-t-butylphosphino) -1,1′-binaphthyl, 2-methoxy-2 ′-(di-t-butylphosphino) -1,1′-binaphthyl, or An example is 2-dicyclohexylphosphino-2 ′, 6′-dimethoxybiphenyl.

Specific examples of the base used in the reaction include sodium carbonate, potassium carbonate, cesium carbonate, sodium bicarbonate, sodium hydroxide, potassium hydroxide, barium hydroxide, sodium ethoxide, sodium t-butoxide, sodium acetate, phosphoric acid. Examples include tripotassium or potassium fluoride.

Specific examples of the solvent used in the reaction include benzene, toluene, xylene, 1,2,4-trimethylbenzene, N, N-dimethylformamide, tetrahydrofuran, diethyl ether, t-butyl methyl ether, 1,4- Examples include dioxane, methanol, ethanol, cyclopentyl methyl ether, and isopropyl alcohol. These solvents can be appropriately selected and may be used alone or as a mixed solvent.

<Synthesis Method of Compounds Represented by Formula (1-8-1) to Formula (1-8-105)>
In the above reaction 3, if 2-bromo-7-methoxynaphthalene is used instead of 2-bromo-6-methoxynaphthalene, the compound can be synthesized in the same manner.

<Synthesis Method of Compounds Represented by Formula (1-9-1) to Formula (1-9-48) and Formula (1-10-1) to Formula (1-10-48)>
It can synthesize | combine similarly to the above by using the raw material which replaced those benzene frame | skeletons and naphthalene frame | skeleton instead of the raw material used in said reaction 1-3. That is, the Grignard reagent of 2-bromoanthracene and 9-bromoanthracene are coupled, brominated at the 10th position of anthracene according to Reaction 2, and then this bromide is 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.

<Formula (1-11-1) to Formula (1-111-60), Formula (1-12-1) to Formula (1-12-60), Formula (1-13-1) to Formula (1- 13-60) and methods for synthesizing compounds represented by formula (1-14-1) to formula (1-10-60)>
By using a pyridine derivative substituted with an alkyl group or a cycloalkyl group as a raw material instead of the raw material pyridine derivative used in the reaction 6 or 7, the same synthesis as described above can be performed.

A pyridine derivative substituted with an alkyl group or a cycloalkyl group can be synthesized as shown in the following reactions 8 to 9. Here, the method for synthesizing the pyridine moiety in the compounds represented by formula (1-11-11), formula (1-12-11), formula (1-13-111) and formula (1-14-11) is illustrated. However, pyridine derivatives substituted with various alkyl groups or cycloalkyl groups can be synthesized by appropriately changing the raw materials.

式中のＲの定義は前記と同じである。０は１〜４の整数である。Ｒは目的とする化合物に応じてベンゼン環の任意の位置に、所望の数だけ連結してよい。<Synthesis Method of Compounds Represented by Formula (1-15-1) to Formula (1-15-48) and Formula (1-16-1) to Formula (1-16-24)>
Phenyl group in the above-mentioned "Method for synthesizing compounds represented by formula (1-9-1) to formula (1-9-48) and formula (1-10-1) to formula (1-10-48)" In the introduction step, a phenyl group substituted with an alkyl group or a cycloalkyl group may be used. For example, a synthesis method that can be represented by the following reaction 10 can be used.

The definition of R in the formula is the same as described above. 0 is an integer of 1 to 4. R may be linked in any desired number to any position of the benzene ring depending on the target compound.

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.

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 (1-7-74) <Synthesis of 9- (4-t-butylphenyl) anthracene>
Under a nitrogen atmosphere, reflux a flask containing 31 g of 9-bromoanthracene, 25 g of 4-t-butylphenylboronic acid, 1.3 g of Pd (PPh ₃ ) ₄ , 51 g of potassium phosphate and 150 ml of 1,2,4-trimethylbenzene. Stir at temperature for 21 hours. After the reaction solution was cooled to room temperature, water and toluene were added for liquid separation. The solid precipitated by distilling off the solvent under reduced pressure was collected by suction filtration and washed with methanol and then with ethyl acetate to obtain 28 g of 9- (4-t-butylphenyl) anthracene.

<Synthesis of 9-bromo-10- (4-t-butylphenyl) anthracene>
19 g of N-bromosuccinimide was added to a flask containing 27 g of 9- (4-tert-butylphenyl) anthracene, 0.1 g of iodine and 300 ml of THF under a nitrogen atmosphere. The mixture was stirred at room temperature for 18 hours, and an aqueous sodium thiosulfate solution was added to stop the reaction. This solution was transferred to a separatory funnel and extracted with chloroform. The solid precipitated by removing the solvent under reduced pressure was collected by suction filtration, and then recrystallized from chlorobenzene to obtain 29 g of 9-bromo-10- (4-t-butylphenyl) anthracene.

<Synthesis of 3- (6-bromonaphthalen-2-yl) pyridine>
A flask containing 10 g of 3-bromopyridine and 60 ml of THF was cooled in an ice bath, and 35 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 once raised to room temperature, cooled with ice water, and 17 g of zinc chloride tetramethylethylenediamine complex was added with stirring. Thereafter, after stirring at room temperature for 1 hour, 6 g of 6-bromonaphthalen-2-yl trifluoromethanesulfonate and 1.6 g of PdCl ₂ (dppp) were added, and the mixture was stirred at reflux temperature for 3 hours. After cooling the reaction solution to room temperature, a solution of ethylenediaminetetraacetic acid / tetrasodium salt dihydrate corresponding to about 3 moles of the target compound in an appropriate amount of water to remove the metal ions of the catalyst. (Hereinafter abbreviated as EDTA · 4Na aqueous solution) and toluene were added to separate the layers. After the solvent was distilled off under reduced pressure, the residue was purified by silica gel column chromatography (toluene / ethyl acetate = 7/3 (volume ratio)) to obtain 12 g of 3- (6-bromonaphthalen-2-yl) pyridine.

<Synthesis of Compound (1-7-74)>
6.2 g of 3- (6-bromonaphthalen-2-yl) pyridine, 5.9 g of bispinacholate diboron, 0.4 g of bis (dibenzylideneacetone) palladium (0), 0.5 g of tricyclohexylphosphine, potassium acetate 3 A flask containing 9.9 g and 50 ml of dimethoxyethane was stirred at reflux temperature for 4 hours under a nitrogen atmosphere. To this solution was added 8.6 g of 9-bromo-10- (4-t-butyl) phenyl) anthracene, 9.3 g of potassium phosphate and 50 ml of 1,2,4-trimethylbenzene, and dimethoxyethane was used using a Dean-Stark tube. The solvent was distilled off at room temperature. 5 ml of t-butyl alcohol, 5 ml of water, 0.4 g of bis (dibenzylideneacetone) palladium (0) and 0.5 g of tricyclohexylphosphine were added, and the mixture was further stirred at reflux temperature for 5 hours. The reaction solution was cooled to room temperature, washed with water to dissolve the salt, and a solid was collected by suction filtration. The obtained solid was washed with methanol and then with ethyl acetate, and then purified by silica gel column chromatography (toluene / ethyl acetate = 9/1 (volume ratio)) to obtain compound (1-7-74): 3- ( 1.0 g of 6- (10- (4-t-butyl) phenyl) anthracen-9-yl) naphthalen-2-yl) pyridine was obtained. The structure of the compound was confirmed by NMR measurement.
¹ H-NMR (CDCl ₃ ): δ = 9.07 (m, 1H), 8.68 (dd, 1H), 8.23 (m, 1H), 8.15 (d, 1H), 8.08 (M, 1H), 8.03 (m, 2H), 7.83 (dd, 1H), 7.78 (d, 2H), 7.72 (d, 2H), 7.68 (dd, 1H) 7.63 (d, 2H), 7.42-7.48 (m, 3H), 7.30-7.38 (m, 4H), 1.49 (s, 9H).

Synthesis Example 2 Synthesis of Compound (1-7-26) <Synthesis of 9- (3-Tolyl) anthracene>
Under a nitrogen atmosphere, a flask containing 36 g of 9-bromoanthracene, 21 g of 3-methylphenylboronic acid, 1.4 g of Pd (PPh ₃ ) ₄ , 59 g of potassium phosphate and 150 ml of 1,2,4-trimethylbenzene was refluxed. Stir for 2.5 hours. After the reaction solution was cooled to room temperature, water and toluene were added for liquid separation. After the obtained toluene solution was purified with a silica gel short column, the solvent was distilled off under reduced pressure. Heptane was added to the obtained oil, and the precipitated solid was collected by suction filtration to obtain 31 g of 9- (3-tolyl) anthracene.

<Synthesis of 9-bromo-10- (3-tolyl) anthracene>
A flask containing 30 g of 9- (3-tolyl) anthracene and 200 ml of THF was cooled in an ice bath under a nitrogen atmosphere, and 20 g of N-bromosuccinimide and 0.1 g of iodine were added. The mixture was stirred at room temperature for 15 hours, and an aqueous sodium thiosulfate solution was added to stop the reaction. This solution was transferred to a separatory funnel, extracted with toluene, and then subjected to a silica gel short column. The solvent was distilled off under reduced pressure, heptane was added to the resulting solution, and the precipitated solid was collected by suction filtration to obtain 30 g of 9-bromo-10- (3-tolyl) anthracene.

<Synthesis of 4,4,5,5-tetramethyl-2- (10- (3-tolyl) anthracen-9-yl) -1,3,2-dioxaborolane>
30 g of 9-bromo-10- (3-tolyl) anthracene, 26 g of bispinacholate diboron, 1.5 g of bis (dibenzylideneacetone) palladium (0), 1.4 g of tricyclohexylphosphine, 15 g of potassium acetate, 12 g of potassium carbonate and A flask containing 100 ml of cyclopentyl methyl ether was stirred at reflux temperature for 16 hours under a nitrogen atmosphere. After cooling the reaction solution to room temperature, water and toluene were added for liquid separation, and the resulting toluene solution was purified with a silica gel short column. The solvent was distilled off under reduced pressure, heptane was added to the obtained oil, and the precipitated solid was collected by suction filtration, and 4,4,5,5-tetramethyl-2- (10- (3-tolyl) anthracene- 24 g of 9-yl) -1,3,2-dioxaborolane were obtained.

<Synthesis of Compound (1-7-26)>
4,4,5,5-tetramethyl-2- (10- (3-tolyl) anthracen-9-yl) -1,3,2-dioxaborolane 12 g, 3- (6-bromonaphthalen-2-yl) pyridine A flask containing 10 g, Pd (PPh ₃ ) ₄ 1.0 g, potassium phosphate 13 g, 1,2,4-trimethylbenzene 50 ml, t-butyl alcohol 10 ml and water 10 ml was stirred at reflux temperature for 1 hour. After cooling the reaction solution to room temperature, water and toluene were added for liquid separation, and the solvent was distilled off under reduced pressure. The obtained crude product was purified by silica gel column chromatography (toluene / ethyl acetate = 20/1 (volume ratio)) and then recrystallized from a toluene / heptane mixed solution to give compound (1-7-26): 3 There was obtained 7.1 g of-(6- (10- (3-tolyl) anthracen-9-yl) naphthalen-2-yl) pyridine. The structure of the compound was confirmed by NMR measurement.
¹ H-NMR (CDCl ₃ ): δ = 9.06 (m, 1H), 8.67 (dd, 1H), 8.22 (m, 1H), 8.14 (d, 1H), 8.06 (M, 1H), 8.02 (m, 2H), 7.81 (m, 1H), 7.75 (d, 2H), 7.72 (d, 2H), 7.66 (dd, 1H) , 7.50 (t, 1H), 7.45 (m, 1H), 7.27-7.39 (m, 7H), 2.50 (s, 3H).

[Synthesis Example 3] Synthesis of Compound (1-7-98) <Synthesis of 9- (3-t-butylphenyl) anthracene>
Under a nitrogen atmosphere, 9-bromoanthracene 23 g, 2- (3-t-butylphenyl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane 25 g, Pd (PPh ₃ ) ₄ 3.1 g A flask containing 37 g of potassium phosphate, 250 ml of 1,2,4-trimethylbenzene, 50 ml of t-butyl alcohol and 30 ml of water was stirred at reflux temperature for 21 hours. After the reaction solution was cooled to room temperature, water and toluene were added for liquid separation. The obtained toluene solution was purified with a silica gel short column, the solvent was distilled off under reduced pressure, and the solid precipitated by adding methanol was collected by suction filtration to obtain 24 g of 9- (3-t-butylphenyl) anthracene. .

<Synthesis of 9-bromo-10- (3-tert-butylphenyl) anthracene>
To a flask containing 23 g of 9- (3-t-butylphenyl) anthracene, 0.1 g of iodine and 100 ml of THF, 13 g of N-bromosuccinimide was added under a nitrogen atmosphere. The mixture was stirred at room temperature for 1 hour, and an aqueous sodium thiosulfate solution was added to stop the reaction. This solution was transferred to a separatory funnel and extracted with toluene. The obtained toluene solution was purified with a silica gel short column, and the solvent was distilled off under reduced pressure. Then, toluene / methanol was reprecipitated to obtain 23 g of 9-bromo-10- (3-t-butylphenyl) anthracene.

<Synthesis of Compound (1-7-98)>
6.2 g of 3- (6-bromonaphthalen-2-yl) pyridine, 5.9 g of bispinacholate diboron, 0.4 g of bis (dibenzylideneacetone) palladium (0), 0.5 g of tricyclohexylphosphine, potassium acetate 3 A flask containing 9.9 g and 50 ml of dimethoxyethane was stirred at reflux temperature for 4 hours under a nitrogen atmosphere. To this solution, 8.6 g of 9-bromo-10- (3-t-butylphenyl) anthracene, 9.3 g of potassium phosphate and 50 ml of 1,2,4-trimethylbenzene were added, and dimethoxyethane was added using a Dean-Stark tube. Distilled with heating at room temperature. 5 ml of t-butyl alcohol, 5 ml of water, 0.4 g of bis (dibenzylideneacetone) palladium (0) and 0.5 g of tricyclohexylphosphine were added, and the mixture was further stirred at reflux temperature for 2 hours. The reaction solution was cooled to room temperature, washed with water to dissolve the salt, and a solid was collected by suction filtration. The obtained solid was purified by silica gel column chromatography (toluene / ethyl acetate = 9/1 (volume ratio)) and then recrystallized from toluene to give compound (1-7-98): 3- (6- (10 There was obtained 1.5 g of-(3-t-butylphenyl) anthracen-9-yl) naphthalen-2-yl) pyridine. The structure of the compound was confirmed by NMR measurement.
¹ H-NMR (CDCl ₃ ): δ = 9.07 (m, 1H), 8.68 (dd, 1H), 8.23 (s, 1H), 8.16 (d, 1H), 8.08 (M, 1H), 8.03 (m, 2H), 7.83 (m, 1H), 7.75 (d, 2H), 7.72 (d, 2H), 7.68 (m, 1H) 7.52-7.61 (m, 3H), 7.46 (m, 1H), 7.30-7.38 (m, 5H), 1.41 (s, 9H).

[Synthesis Example 4] Synthesis of Compound (1-7-96) <2- (10- (4-t-butylphenyl) anthracen-9-yl) -4,4,5,5-tetramethyl-1,3 Synthesis of 1,2-dioxaborolane>
7.8 g of 9-bromo-10- (4-t-butylphenyl) anthracene, 6.1 g of bispinacolatodiboron, 0.3 g of bis (dibenzylideneacetone) palladium (0), 0.3 g of tricyclohexylphosphine, acetic acid A flask containing 3.9 g of potassium, 2.8 g of potassium carbonate, and 40 ml of cyclopentyl methyl ether was stirred at reflux temperature for 6 and a half hours under a nitrogen atmosphere. After cooling the reaction solution to room temperature, water and toluene were added for liquid separation, and the solvent was distilled off under reduced pressure. The oil obtained by adding heptane to the obtained oil was collected by suction filtration, and 2- (10- (4-t-butylphenyl) anthracen-9-yl) -4,4,5,5-tetramethyl was collected. 6.9 g of -1,3,2-dioxaborolane was obtained.

<Synthesis of 4- (3- (6-bromonaphthalen-2-yl) phenyl) pyridine>
Under a nitrogen atmosphere, a flask containing 9.8 g of 4- (3-bromophenyl) pyridine and 20 ml of THF was cooled to −70 ° C. or lower in a dry ice / methanol bath, and 17 ml of 2.6 M normal butyl lithium was slowly added dropwise. After completion of dropping, the mixture was stirred at the same temperature for 0.5 hours, and 12 g of zinc chloride tetramethylethylenediamine complex was added. Then, after stirring at room temperature for 0.5 hour, 15 g of 6-bromonaphthalen-2-yl trifluoromethanesulfonate, bis (dibenzylideneacetone) palladium (0) and 1,2-bis (diphenylphosphino) propane 0 0.5 g was added and stirred at reflux temperature for 1 hour. After completion of the reaction, an EDTA · 4Na aqueous solution and ethyl acetate were added for liquid separation, the solvent was distilled off under reduced pressure, and the residue was purified by activated alumina column chromatography (toluene / ethyl acetate = 9/1 (volume ratio)). Subsequently, it was washed with methanol and recrystallized from a mixed solvent of ethyl acetate / methanol to obtain 5.3 g of 4- (3- (6-bromonaphthalen-2-yl) phenyl) pyridine.

<Synthesis of Compound (1-7-96)>
2- (10- (4-t-butylphenyl) anthracen-9-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane 6.1 g, 4- (3- (6- Bromonaphthalen-2-yl) phenyl) pyridine (5.0 g), Pd (PPh ₃ ) ₄ 0.5 g, potassium phosphate 3.0 g, 1,2,4-trimethylbenzene 25 ml, t-butyl alcohol 5 ml and water 5 ml The filled flask was stirred at reflux temperature for 6 hours. After the reaction solution was cooled to room temperature, EDTA / Na water and toluene were added for liquid separation, and the solvent was distilled off under reduced pressure. The obtained crude product was purified by activated alumina column chromatography (toluene / ethyl acetate = 9/1 (volume ratio)). The solid obtained by distilling off the solvent under reduced pressure was washed with ethyl acetate, and then recrystallized from toluene to give compound (1-7-96): 4 (3- (6- (10- (4-t-butyl). Phenyl) anthracen-9-yl) naphthalen-2-yl) phenyl) pyridine 3.3 g was obtained. The structure of the compound was confirmed by NMR measurement.
¹ H-NMR (CDCl ₃ ): 8.73 (dd, 2H), 8.27 (m, 1H), 8.15 (d, 1H), 8.03 (m, 3H), 7.9 (m , 2H), 7.78 (d, 2H), 7.73 (d, 2H), 7.61-7.70 (m, 7H), 7.44 (m, 2H), 7.30-7. 38 (m, 4H), 1.49 (s, 9H).

Synthesis Example 5 Synthesis of Compound (1-14-14) <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 a flask, 90.3 g of 3- (10- (naphthalen-2-yl) anthracen-9-yl) phenyl trifluoromethanesulfonate, 52.1 g of bispinacolatodiboron, 7.4 g of bis (dibenzylideneacetone) palladium (0) Then, 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 the mixture was 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 (1-14-14)>
In a flask, 8.6 g of 4,4,5,5-tetramethyl-2- (3- (10- (naphthalen-2-yl) anthracen-9-yl) phenyl) -1,3,2-dioxaborolane, JP, 5.1 g of 5′-bromo-3-methyl-2,2′-bipyridine synthesized by the method described in 2009-124114, 0.6 g of Pd (PPh ₃ ) ₄ , 7.2 g of potassium phosphate, 1, 25 ml of 2,4-trimethylbenzene, 5 ml of t-butyl alcohol and 1 ml of water were added, and the mixture was stirred at reflux temperature for 2.5 hours. After cooling the reaction solution to room temperature, water was added, and the solid in the solution was collected by suction filtration and washed with methanol. This solid was purified by silica gel column chromatography (toluene / ethyl acetate = 9/1 (volume ratio)) and then further purified by activated carbon column chromatography. The solution is concentrated and recrystallized from chlorobenzene to give compound (1-14-14): 3-methyl-5 ′-(3- (10- (naphthalen-2-yl) anthracen-9-yl) phenyl)- 2.3 g of 2,2′-bipyridine was obtained. The structure of the compound was confirmed by NMR measurement.
¹ H-NMR (CDCl ₃ ): δ = 9.05 (m, 1H), 8.55 (d, 1H), 8.11 (dd, 1H), 8.09 (d, 1H), 8.02 (M, 1H), 8.00 (s, 1H), 7.73-7.95 (m, 9H), 7.60 (m, 5H), 7.30-7.40 (m, 4H), 7.23 (m, 1H), 2.56 (s, 3H).

Synthesis Example 6 Synthesis of Compound (1-11-1) <Synthesis of 2-methyl-4- (6- (10-phenylanthracen-9-yl) naphthalen-2-yl) pyridine>
4,4,5,5-tetramethyl-2- (6- (10-phenylanthracen-9-yl) naphthalen-2-yl) -1,3,2-dioxaborolane (2.0 g), 4-bromo- 2-methylpyridine (0.8 g), Pd (PPh ₃ ) ₄ (0.3 g), potassium phosphate (1.7 g), 1,2,4-trimethylbenzene (20 ml), t-butyl alcohol (5 ml) And water (1 ml) were placed in a flask and stirred at reflux temperature for 7 and a half hours under a nitrogen atmosphere. After completion of the heating, the reaction solution was cooled to room temperature, and water and toluene were added for liquid separation. The solvent was distilled off under reduced pressure, and the resulting solid was purified by silica gel column chromatography (developing solution: toluene / ethyl acetate = 95/5). Subsequently, the obtained eluate was passed through an activated carbon short column to remove colored components. Crystals precipitated during the distillation of the obtained filtrate under reduced pressure were collected, and the compound 2-methyl-4- (6- (10-phenylanthracen-9-yl) represented by (1-11-1) was collected. ) Naphthalen-2-yl) pyridine (0.7 g) was obtained.
The structure of the compound was confirmed by NMR measurement.
¹ H-NMR (CDCl ₃ ): δ = 8.66 (d, 1H), 8.30 (s, 1H), 8.17 (d, 1H), 8.03 (m, 2H), 7.87 (D, 1H), 7.72-7.78 (m, 4H), 7.70 (d, 1H), 7.65 (m, 2H), 7.58 (m, 2H), 7.56 ( m, 3H), 7.31-7.39 (m, 4H), 2.73 (s, 3H).

Synthesis Example 7 Synthesis of Compound (1-11-2) <Synthesis of 3-methyl-4- (6- (10-phenylanthracen-9-yl) naphthalen-2-yl) pyridine>
4,4,5,5-tetramethyl-2- (6- (10-phenylanthracen-9-yl) naphthalen-2-yl) -1,3,2-dioxaborolane (2.0 g), 4-bromo- 3-methylpyridine hydrochloride (1.0 g), Pd (PPh ₃ ) ₄ (0.3 g), potassium phosphate (1.7 g), 1,2,4-trimethylbenzene (20 ml), t-butyl alcohol ( 5 ml) and water (1 ml) were placed in a flask and stirred at reflux temperature for 24 hours and a half under a nitrogen atmosphere. After completion of the heating, the reaction solution was cooled to room temperature, and water and toluene were added for liquid separation. The solvent was distilled off under reduced pressure, and the resulting solid was purified by silica gel column chromatography (developing solution: toluene / ethyl acetate = 95/5). Subsequently, the obtained eluate was passed through an activated carbon short column to remove colored components. Crystals deposited while the filtrate was distilled off under reduced pressure were collected, recrystallized from toluene, and compound 3-methyl-4- (6- (10) represented by (1-11-2). -Phenylanthracen-9-yl) naphthalen-2-yl) pyridine (0.5 g) was obtained.
The structure of the compound was confirmed by NMR measurement.
¹ H-NMR (CDCl ₃ ): δ = 8.62 (s, 1H), 8.58 (d, 1H), 8.13 (d, 1H), 8.06 (s, 1H), 8.02 (D, 1H), 7.99 (s, 1H), 7.75 (d, 4H), 7.70 (dd, 1H), 7.65 (t, 2H), 7.59 (t, 2H) 7.53 (m, 2H), 7.33-7.39 (m, 5H), 2.44 (s, 3H).

Synthesis Example 8 Synthesis of Compound (1-11-3) <Synthesis of 2-methyl-5- (6- (10-phenylanthracen-9-yl) naphthalen-2-yl) pyridine>
4,4,5,5-tetramethyl-2- (6- (10-phenylanthracen-9-yl) naphthalen-2-yl) -1,3,2-dioxaborolane (2.0 g), 5-bromo- 2-methylpyridine (0.8 g), Pd (PPh ₃ ) ₄ (0.15 g), potassium phosphate (1.7 g), 1,2,4-trimethylbenzene (20 ml), t-butanol (5 ml) and Water (1 ml) was placed in the flask and stirred at reflux temperature for 5 hours under a nitrogen atmosphere. After completion of the heating, the reaction solution was cooled to room temperature, and water and toluene were added for liquid separation. The solvent was distilled off under reduced pressure, and the resulting solid was purified by silica gel column chromatography (developing solution: toluene / ethyl acetate = 95/5). The solid obtained by distilling off the solvent under reduced pressure was recrystallized from toluene, and the compound 2-methyl-5- (6- (10-phenylanthracen-9-yl) naphthalene represented by (1-11-3) -2-yl) pyridine (1.2 g) was obtained.
The structure of the compound was confirmed by NMR measurement.
¹ H-NMR (CDCl ₃ ): δ = 8.95 (m, 1H), 8.20 (s, 1H), 8.14 (d, 1H), 8.01 (m, 2H), 7.96 (Dd, 1H), 7.81 (dd, 1H), 7.74 (m, 4H), 7.67 (dd, 1H), 7.63 (t, 2H), 7.57 (t, 1H) 7.52 (m, 2H), 7.30-7.37 (m, 5H), 2.67 (s, 3H).

[Synthesis Example 9] Synthesis of Compound (1-11-4) <Synthesis of 3-methyl-5- (6- (10-phenylanthracen-9-yl) naphthalen-2-yl) pyridine>
4,4,5,5-tetramethyl-2- (6- (10-phenylanthracen-9-yl) naphthalen-2-yl) -1,3,2-dioxaborolane (2.0 g), 3-bromo- 5-methylpyridine (0.8 g), Pd (PPh ₃ ) ₄ (0.3 g), potassium phosphate (1.7 g), 1,2,4-trimethylbenzene (20 ml), t-butanol (5 ml) and Water (1 ml) was placed in the flask and stirred at reflux temperature for 7 hours and a half under a nitrogen atmosphere. After completion of the heating, the reaction solution was cooled to room temperature, and water and toluene were added for liquid separation. The solvent was distilled off under reduced pressure, and the resulting solid was purified by silica gel column chromatography (developing solution: toluene / ethyl acetate = 95/5). Subsequently, the obtained eluate was passed through an activated carbon short column to remove colored components. The solvent was distilled off under reduced pressure, heptane was added for reprecipitation, and the compound 3-methyl-5- (6- (10-phenylanthracen-9-yl) naphthalen-2-yl represented by (1-11-4) ) Pyridine (1.3 g) was obtained.
The structure of the compound was confirmed by NMR measurement.
¹ H-NMR (CDCl ₃ ): δ = 8.87 (m, 1H), 8.51 (m, 1H), 8.22 (s, 1H), 8.15 (d, 1H), 8.03 (M, 2H), 7.89 (m, 1H), 7.83 (dd, 1H), 7.73 (m, 4H), 7.67 (dd, 1H), 7.63 (m, 2H) , 7.57 (t, 1H), 7.52 (m, 2H), 7.30-7.37 (m, 4H), 2.49 (s, 3H).

[Synthesis Example 10] Synthesis of Compound (1-11-1) <Synthesis of 4-methyl-3- (6- (10-phenylanthracen-9-yl) naphthalen-2-yl) pyridine>
4,4,5,5-tetramethyl-2- (6- (10-phenylanthracen-9-yl) naphthalen-2-yl) -1,3,2-dioxaborolane (2.0 g), 3-bromo- 4-methylpyridine hydrochloride (1.0 g), Pd (PPh ₃ ) ₄ (0.3 g), potassium phosphate (1.7 g), 1,2,4-trimethylbenzene (20 ml), t-butyl alcohol ( 5 ml) and water (1 ml) were placed in a flask and stirred at reflux temperature for 7 hours under a nitrogen atmosphere. After completion of the heating, the reaction solution was cooled to room temperature, and water and toluene were added for liquid separation. The solvent was distilled off under reduced pressure, and the resulting solid was purified by silica gel column chromatography (developing solution: toluene / ethyl acetate = 95/5). Subsequently, the obtained eluate was passed through an activated carbon short column to remove colored components. The solvent was distilled off under reduced pressure, and the resulting solid was recrystallized from toluene to give a compound 4-methyl-3- (6- (10-phenylanthracen-9-yl) naphthalene represented by (1-1-11) -2-yl) pyridine (0.6 g) was obtained.
The structure of the compound was confirmed by NMR measurement.
¹ H-NMR (CDCl ₃ ): δ = 8.64 (s, 1H), 8.55 (d, 1H), 8.14 (d, 1H), 8.06 (s, 1H), 8.02 (D, 1H), 7.99 (s, 1H), 7.76 (m, 4H), 7.70 (dd, 1H), 7.63 (m, 2H), 7.59 (t, 2H) 7.53 (m, 2H), 7.32-7.39 (m, 4H), 7.30 (d, 1H), 2.45 (s, 3H).

Synthesis Example 11 Synthesis of Compound (1-11-1) <Synthesis of 2-methyl-3- (6- (10-phenylanthracen-9-yl) naphthalen-2-yl) pyridine>
4,4,5,5-tetramethyl-2- (6- (10-phenylanthracen-9-yl) naphthalen-2-yl) -1,3,2-dioxaborolane (2.0 g), 3-bromo- 2-methylpyridine (0.8 g), Pd (PPh ₃ ) ₄ (0.15 g), potassium phosphate (1.7 g), 1,2,4-trimethylbenzene (20 ml), t-butyl alcohol (5 ml) And water (1 ml) were placed in a flask and stirred at reflux temperature for 4 hours under a nitrogen atmosphere. After completion of the heating, the reaction solution was cooled to room temperature, and water and toluene were added for liquid separation. The solvent was distilled off under reduced pressure, and the resulting solid was purified by silica gel column chromatography (developing solution: toluene / ethyl acetate = 95/5). Subsequently, the obtained eluate was passed through an activated carbon short column to remove colored components. The solvent was distilled off under reduced pressure, heptane was added for reprecipitation, and the compound 2-methyl-3- (6- (10-phenylanthracen-9-yl) naphthalen-2-yl represented by (1-1-11-6) ) Pyridine (1.1 g) was obtained.
The structure of the compound was confirmed by NMR measurement.
¹ H-NMR (CDCl ₃ ): δ = 8.60 (m, 1H), 8.11 (d, 1H), 8.05 (s, 1H), 8.00 (d, 1H), 7.96 (S, 1H), 7.74 (m, 4H), 7.69 (m, 2H), 7.63 (m, 2H), 7.57 (m, 2H), 7.52 (m, 2H) 7.30-7.37 (m, 4H), 7.28 (m, 1H), 2.66 (s, 3H).

Synthesis Example 12 Synthesis of Compound (1-11-1) <Synthesis of 5-methyl-2- (6- (10-phenylanthracen-9-yl) naphthalen-2-yl) pyridine>
4,4,5,5-tetramethyl-2- (6- (10-phenylanthracen-9-yl) naphthalen-2-yl) -1,3,2-dioxaborolane (2.5 g), 3-bromo- 2-methylpyridine (1.0 g), Pd (PPh ₃ ) ₄ (0.15 g), potassium phosphate (2.1 g), 1,2,4-trimethylbenzene (20 ml), t-butyl alcohol (5 ml) And water (1 ml) were placed in a flask and stirred at reflux temperature for 18 hours under a nitrogen atmosphere. After heating, the reaction solution was cooled to room temperature, and the precipitated solid was collected by suction filtration. The obtained solid was purified by silica gel column chromatography (developing solution: toluene). Subsequently, the obtained eluate was passed through an activated carbon short column to remove colored components. The solvent was distilled off under reduced pressure, ethyl acetate was added for reprecipitation, and the compound represented by (1-1-11-8) 5-methyl-2- (6- (10-phenylanthracen-9-yl) naphthalene-2- Yl) pyridine (1.5 g) was obtained.
The structure of the compound was confirmed by NMR measurement.
¹ H-NMR (CDCl ₃ ): δ = 8.63 (m, 2H), 8.23 (dd, 1H), 8.16 (d, 1H), 8.00 (m, 2H), 7.86 (D, 1H), 7.73 (m, 4H), 7.60-7.67 (m, 4H), 7.56 (t, 1H), 7.51 (m, 2H), 7.30- 7.36 (m, 4H), 2.44 (s, 3H).

Synthesis Example 13 Synthesis of Compound (1-11-139) <Synthesis of 5-bromo-2′-methyl-3,4′-bipyridine>
A flask containing 4-bromo-2-methylpyridine (13.8 g) and toluene (150 ml) was cooled in an acetone / dry ice bath. To this solution, a 1.6 M normal butyl lithium hexane solution (55 ml) was added dropwise. After completion of dropping, the mixture was stirred for 1 hour while cooling in an acetone / dry ice bath, zinc chloride tetramethylethylenediamine (29.3 g) and THF (45 ml) were added, the acetone / dry ice bath was removed, and the temperature was raised. After raising the temperature to room temperature, toluene (20 ml), 3,5-dibromopyridine (19.0 g) and Pd (PPh ₃ ) ₄ (2.8 g) were added, and the mixture was stirred at reflux temperature for 2 hours. After cooling the reaction solution to room temperature, a solution of ethylenediaminetetraacetic acid / tetrasodium salt dihydrate corresponding to about 3 moles of the target compound in an appropriate amount of water to remove the metal ions of the catalyst. (Hereinafter abbreviated as EDTA · 4Na aqueous solution) and toluene were added to separate the layers. After the solvent was distilled off under reduced pressure, the obtained solid was purified by silica gel column chromatography (developing solution: toluene / ethyl acetate). At this time, referring to the method described in “Chemical Doujin Shuppan Co., Ltd., page 94”, the ratio of ethyl acetate in the developing solution was gradually increased. The target product was eluted by increasing the amount to 1. Subsequently, the solvent was distilled off under reduced pressure, and the obtained solid was recrystallized from heptane to obtain 5-bromo-2′-methyl-3,4′-bipyridine (5.3 g).

<Synthesis of 2'-methyl-5- (6- (10-phenylanthracen-9-yl) naphthalen-2-yl) 3,4'-bipyridine>
4,4,5,5-tetramethyl-2- (6- (10-phenylanthracen-9-yl) naphthalen-2-yl) -1,3,2-dioxaborolane (2.5 g), 5-bromo- 2′-methyl-3,4′-bipyridine (1.1 g), Pd (PPh ₃ ) ₄ (0.15 g), potassium phosphate (1.7 g), 1,2,4-trimethylbenzene (20 ml), t-Butyl alcohol (5 ml) and water (1 ml) were placed in a flask and stirred at reflux temperature for 3 hours under a nitrogen atmosphere. After completion of the heating, the reaction solution was cooled to room temperature, and water and toluene were added for liquid separation. The solvent was distilled off under reduced pressure, and the resulting solid was purified by silica gel column chromatography (developing solution: toluene / ethyl acetate = 1/1). The solvent was distilled off under reduced pressure, and the resulting solid was recrystallized from toluene to give the compound 2′-methyl-5- (6- (10-phenylanthracen-9-yl) represented by (1-11-139). Naphthalen-2-yl) 3,4'-bipyridine (0.3 g) was obtained.
The structure of the compound was confirmed by NMR measurement.
¹ H-NMR (CDCl ₃ ): δ = 9.11 (m, 1H), 8.92 (m, 1H), 8.65 (d, 1H), 8.28 (m, 2H), 8.17 (D, 1H), 8.05 (m, 2H), 7.87 (d, 1H), 7.68-7.75 (m, 5H), 7.61 (m, 2H), 7.56 ( t, 1H), 7.51 (m, 3H), 7.45 (m, 1H), 7.30-7.37 (m, 4H), 2.70 (s, 3H).

Synthesis Example 14 Synthesis of Compound (1-14-2) <Synthesis of 3-methyl-4- (3- (10- (naphthalen-2-yl) anthracen-9-yl) phenyl) pyridine>
4,4,5,5-tetramethyl-2- (3- (10- (naphthalen-2-yl) anthracen-9-yl) phenyl) -1,3,2-dioxaborolane (2.5 g), 4- Bromo-3-methylpyridine hydrochloride (1.3 g), Pd (PPh ₃ ) ₄ (0.35 g), potassium phosphate (3.2 g), 1,2,4-trimethylbenzene 20 ml, t-butyl alcohol 5 ml And 1 ml of water were added and stirred at reflux temperature for 11 and a half hours. After cooling the reaction solution to room temperature, toluene and water were added to separate the layers. The solvent was distilled off under reduced pressure, and the resulting solid was purified by silica gel column chromatography (developing solution: toluene / ethyl acetate = 95/5). Subsequently, the obtained eluate was passed through an activated carbon short column to remove colored components. The solvent was distilled off under reduced pressure, heptane was added for reprecipitation, and the compound 3-methyl-4- (3- (10- (naphthalen-2-yl) anthracen-9-yl) represented by (1-14-2) ) Phenyl) pyridine (1.4 g) was obtained.
The structure of the compound was confirmed by NMR measurement.
¹ H-NMR (CDCl ₃ ): δ = 8.53 (s, 1H), 8.50 (d, 1H), 8.08 (dd, 1H), 8.02 (m, 1H), 7.97 (D, 1H), 7.92 (m, 1H), 7.70-7.78 (m, 5H), 7.48-7.63 (m, 6H), 7.35-7.39 (m , 2H), 7.29-7.34 (m, 3H), 2.41 (s, 3H).

Synthesis Example 15 Synthesis of Compound (1-14-3) <Synthesis of 2-methyl-5- (3- (10- (naphthalen-2-yl) anthracen-9-yl) phenyl) pyridine>
4,4,5,5-tetramethyl-2- (3- (10- (naphthalen-2-yl) anthracen-9-yl) phenyl) -1,3,2-dioxaborolane (2.5 g), 5- Bromo-2-methylpyridine (1.0 g), Pd (PPh ₃ ) ₄ (0.35 g), potassium phosphate (3.2 g), 1,2,4-trimethylbenzene 20 ml, t-butyl alcohol 5 ml, and 1 ml of water was added and stirred at reflux temperature for 8 and a half hours. After cooling the reaction solution to room temperature, the precipitated solid was collected by suction filtration. The obtained solid was purified by silica gel column chromatography (developing solution: toluene / ethyl acetate = 95/5). Subsequently, the obtained eluate was passed through an activated carbon short column to remove colored components. The solvent was distilled off under reduced pressure, the obtained solid was washed with ethyl acetate, and the compound 2-methyl-5- (3- (10- (naphthalen-2-yl) anthracene represented by (1-14-3) was represented. -9-yl) phenyl) pyridine (1.5 g) was obtained.
The structure of the compound was confirmed by NMR measurement.
¹ H-NMR (CDCl ₃ ): δ = 8.45 (m, 1H), 8.08 (d, 1H), 8.03 (m, 1H), 7.99 (s, 1H), 7.93 (M, 1H), 7.87 (dd, 1H), 7.70-7.81 (m, 7H), 7.57-7.63 (m, 3H), 7.54 (m, 1H), 7.30-7.40 (m, 4H), 7.23 (d, 1H), 2.61 (s, 3H).

Synthesis Example 16 Synthesis of Compound (1-14-11) <Synthesis of 5-bromo-6′-methyl-2,2′-bipyridine>
A flask containing 2-bromo-6-methylpyridine (5.2 g) and cyclopentyl methyl ether (30 ml) was cooled in a methanol / dry ice bath. To this solution, a 1.6 M normal butyl lithium hexane solution (22 ml) was added dropwise. After completion of the dropwise addition, the mixture was stirred for 2 hours while cooling in a methanol / dry ice bath, zinc chloride tetramethylethylenediamine (8.3 g) was added, the methanol / dry ice bath was removed, and the temperature was raised. After raising the temperature to room temperature, 2,5-dibromopyridine (7.1 g) and Pd (PPh ₃ ) ₄ (1.0 g) were added, and the mixture was stirred at reflux temperature for 3.5 hours. After the reaction solution was cooled to room temperature, an EDTA · 4Na aqueous solution and toluene were added to separate the layers. After the solvent was distilled off under reduced pressure, the obtained solid was purified by silica gel column chromatography (developing solution: toluene / ethyl acetate). At this time, the target product was eluted by gradually increasing the ratio of ethyl acetate in the developing solution. Subsequently, the solvent was distilled off under reduced pressure, and the obtained solid was recrystallized from heptane to obtain 5-bromo-6′-methyl-2,2′-bipyridine (1.4 g).

<Synthesis of 6'-methyl-5- (3- (10- (naphthalen-2-yl) anthracen-9-yl) phenyl) -2,2'-bipyridine>
4,4,5,5-tetramethyl-2- (3- (10- (naphthalen-2-yl) anthracen-9-yl) phenyl) -1,3,2-dioxaborolane (2.0 g), 5- Bromo-6′-methyl-2,2′-bipyridine (1.0 g), Pd (PPh ₃ ) ₄ (0.15 g), potassium phosphate (1.7 g), 1,2,4-trimethylbenzene 20 ml, 5 ml of t-butyl alcohol and 1 ml of water were added and stirred at reflux temperature for 7 and a half hours. After cooling the reaction solution to room temperature, the precipitated solid was collected by suction filtration. The obtained solid was purified by silica gel column chromatography (developing solution: toluene / ethyl acetate = 95/5), and the obtained eluate was suction filtered using a Kiriyama funnel covered with activated carbon to remove the colored components. did. The solvent was distilled off under reduced pressure, ethyl acetate was added for reprecipitation, and the compound 6′-methyl-5- (3- (10- (naphthalen-2-yl) anthracene-9 represented by (1-14-11) was represented. -Yl) phenyl) -2,2'-bipyridine (1.2 g) was obtained.
The structure of the compound was confirmed by NMR measurement.
¹ H-NMR (CDCl ₃ ): δ = 9.03 (m, 1H), 8.49 (dd, 1H), 8.22 (d, 1H), 8.09 (m, 2H), 8.03 (M, 1H), 8.00 (s, 1H), 7.93 (m, 1H), 7.87 (d, 1H), 7.68-7.83 (m, 7H), 7.55- 7.64 (m, 4H), 7.30-7.40 (m, 4H), 7.17 (d, 1H), 2.65 (s, 3H).

Synthesis Example 17 Synthesis of Compound (1-14-12) <Synthesis of 5-bromo-5′-methyl-2,2′-bipyridine>
A flask containing 2-bromo-5-methylpyridine (1.7 g) and THF (5 ml) was cooled in an ice bath, and 2 M isopropylmagnesium chloride THF solution (5.5 ml) was added dropwise to the solution. After completion of the dropwise addition, the ice bath was removed and the mixture was stirred at room temperature for 3 and a half hours, then cooled again in an ice bath, and zinc chloride tetramethylethylenediamine (2.8 g) was added. After removing the ice bath and raising the temperature to room temperature, 2,5-dibromopyridine (2.4 g) and Pd (PPh ₃ ) ₄ (0.35 g) were added, and the mixture was stirred at reflux temperature for 1.5 hours. After the reaction solution was cooled to room temperature, an EDTA · 4Na aqueous solution and toluene were added to separate the layers. After the solvent was distilled off under reduced pressure, the obtained solid was purified by silica gel column chromatography (developing solution: toluene / ethyl acetate = 9/1). The solvent was distilled off under reduced pressure, and heptane was added for reprecipitation to obtain 5-bromo-5′-methyl-2,2′-bipyridine (1.5 g).

<Synthesis of 5-methyl-5 '-(3- (10- (naphthalen-2-yl) anthracen-9-yl) phenyl) -2,2'-bipyridine>
4,4,5,5-tetramethyl-2- (3- (10- (naphthalen-2-yl) anthracen-9-yl) phenyl) -1,3,2-dioxaborolane (2.0 g), 5- Bromo-5′-methyl-2,2′-bipyridine (1.2 g), Pd (PPh ₃ ) ₄ (0.15 g), potassium phosphate (1.7 g), 1,2,4-trimethylbenzene 20 ml, 5 ml of t-butyl alcohol and 1 ml of water were added and stirred at reflux temperature for 6 hours. After cooling the reaction solution to room temperature, toluene and water were added to separate the layers. The solvent was distilled off under reduced pressure, and the resulting solid was purified by silica gel column chromatography (developing solution: toluene / ethyl acetate = 95/5), and the resulting eluate was passed through an activated carbon short column to remove colored components. did. The solvent was distilled off under reduced pressure, ethyl acetate was added for reprecipitation, and the resulting solid was further recrystallized from toluene to give the compound 5-methyl-5 ′-(3- (3- ( 10- (Naphthalen-2-yl) anthracen-9-yl) phenyl) -2,2′-bipyridine (1.2 g) was obtained.
The structure of the compound was confirmed by NMR measurement.
¹ H-NMR (CDCl ₃ ): δ = 9.03 (m, 1H), 8.52 (s, 1H), 8.44 (dd, 1H), 8.33 (d, 1H), 8.09 (M, 1H), 8.03 (m, 1H), 8.00 (s, 2H), 7.93 (m, 1H), 7.87 (m, 1H), 7.73-7.83 ( m, 6H), 7.56-7.66 (m, 5H), 7.31-7.39 (m, 4H), 2.41 (s, 3H).

[Synthesis Example 18] Synthesis of Compound (1-14-13) <Synthesis of 5'-bromo-4-methyl-2,2'-bipyridine>
A flask containing 2-bromo-4-methylpyridine (6.9 g) and THF (20 ml) was cooled in an ice bath, and 2M isopropylmagnesium chloride THF solution (24 ml) was added dropwise to the solution. After completion of the dropwise addition, the ice bath was removed and the mixture was stirred at room temperature for 1 hour, then cooled again in an ice bath, and zinc chloride tetramethylethylenediamine (12.1 g) was added. After removing the ice bath and raising the temperature to room temperature, 2,5-dibromopyridine (9.5 g) and Pd (PPh ₃ ) ₄ (1.4 g) were added, and the mixture was stirred at reflux temperature for 2.5 hours. After the reaction solution was cooled to room temperature, an EDTA · 4Na aqueous solution and toluene were added to separate the layers. After the solvent was distilled off under reduced pressure, the obtained solid was purified by silica gel column chromatography (developing solution: toluene / ethyl acetate = 9/1). The solvent was distilled off under reduced pressure, and the resulting solid was recrystallized from heptane to obtain 5'-bromo-4-methyl-2,2'-bipyridine (5.5 g).

<Synthesis of 4-methyl-5 '-(3- (10- (naphthalen-2-yl) anthracen-9-yl) phenyl) -2,2'-bipyridine>
4,4,5,5-tetramethyl-2- (3- (10- (naphthalen-2-yl) anthracen-9-yl) phenyl) -1,3,2-dioxaborolane (2.0 g), '- Bromo-4-methyl-2,2′-bipyridine (1.2 g), Pd (PPh ₃ ) ₄ (0.15 g), potassium phosphate (1.7 g), 1,2,4-trimethylbenzene 20 ml, t -5 ml of butyl alcohol and 1 ml of water were added and stirred at reflux temperature for 16 hours. After cooling the reaction solution to room temperature, toluene and water were added to separate the layers. The solvent was distilled off under reduced pressure, and the resulting solid was purified by silica gel column chromatography (developing solution: toluene / ethyl acetate = 95/5), and the resulting eluate was passed through an activated carbon short column to remove colored components. did. The solvent was distilled off under reduced pressure and washed with heptane, whereby the compound 4-methyl-5 ′-(3- (10- (naphthalen-2-yl) anthracene-9-) represented by (1-14-13) was obtained. Yl) phenyl) -2,2'-bipyridine (1.4 g) was obtained.
The structure of the compound was confirmed by NMR measurement.
¹ H-NMR (CDCl ₃ ): δ = 9.04 (m, 1H), 8.55 (d, 1H), 8.47 (dd, 1H), 8.28 (s, 1H), 8.11 (Dd, 1H), 8.09 (d, 1H), 8.03 (m, 1H), 8.00 (s, 1H), 7.93 (m, 1H), 7.88 (d, 1H) , 7.73-7.83 (m, 6H), 7.57-7.63 (m, 4H), 7.30-7.40 (m, 4H), 7.14 (d, 1H), 2 .45 (s, 3H).

Synthesis Example 19 Synthesis of Compound (1-14-15) <Synthesis of 5-Bromo-6′-methyl-2,3′-bipyridine>
A flask containing 5-bromo-2-methylpyridine (3.4 g) and THF (10 ml) was cooled in an ice bath, and 2M isopropylmagnesium chloride THF solution (11 ml) was added dropwise to the solution. After completion of the dropwise addition, the ice bath was removed and the mixture was stirred at room temperature for 3 hours, and then cooled again in an ice bath, and zinc chloride tetramethylethylenediamine (5.5 g) was added. After removing the ice bath and raising the temperature to room temperature, 2,5-dibromopyridine (4.7 g) and Pd (PPh ₃ ) ₄ (0.7 g) were added, and the mixture was stirred at reflux temperature for 5 hours. After the reaction solution is cooled to room temperature, it is abbreviated as EDTA · 4Na aqueous solution. ) And toluene were added to separate the layers. After the solvent was distilled off under reduced pressure, the obtained solid was purified by silica gel column chromatography (developing solution: toluene / ethyl acetate = 7/3), and 5-bromo-6′-methyl-2,3′-bipyridine ( 1.5 g) was obtained.

<Synthesis of 6'-methyl-5- (3- (10- (naphthalen-2-yl) anthracen-9-yl) phenyl) -2,3'-bipyridine>
4,4,5,5-tetramethyl-2- (3- (10- (naphthalen-2-yl) anthracen-9-yl) phenyl) -1,3,2-dioxaborolane (2.0 g), 5- Bromo-6′-methyl-2,3′-bipyridine (1.2 g), Pd (PPh ₃ ) ₄ (0.15 g), potassium phosphate (1.7 g), 1,2,4-trimethylbenzene 25 ml, 5 ml of t-butyl alcohol and 1 ml of water were added and stirred for 5 hours at reflux temperature. After cooling the reaction solution to room temperature, the precipitated solid was collected by suction filtration, washed with methanol and then ethyl acetate. Subsequently, the silica gel column chromatography (developing solution: toluene / ethyl acetate = 4/1) refine | purified, and the obtained eluate was passed through the activated carbon short column, and the coloring component was removed. The solvent was distilled off under reduced pressure, and the obtained solid was further recrystallized from chlorobenzene to give a compound 6′-methyl-5- (3- (10- (naphthalen-2-yl) represented by (1-14-15). ) Anthracen-9-yl) phenyl) -2,3'-bipyridine (1.3 g) was obtained.
The structure of the compound was confirmed by NMR measurement.
¹ H-NMR (CDCl ₃ ): δ = 9.13 (m, 1H), 9.07 (m, 1H), 8.28 (dd, 1H), 8.01-8.11 (m, 3H) , 8.00 (s, 1H), 7.93 (m, 1H), 7.86 (m, 1H), 7.73-7.83 (m, 7H), 7.57-7.64 (m , 4H), 7.31-7.39 (m, 4H), 7.28 (d, 1H), 2.63 (s, 3H).

Synthesis Example 20 Synthesis of Compound (1-14-16) <Synthesis of 5-bromo-5′-methyl-2,3′-bipyridine>
A flask containing 3-bromo-5-methylpyridine (3.4 g) and THF (10 ml) was cooled in an ice bath, and 2M isopropylmagnesium chloride THF solution (11 ml) was added dropwise to the solution. After completion of the dropwise addition, the ice bath was removed and the mixture was stirred at room temperature for 1 hour and a half, then cooled again in an ice bath, and zinc chloride tetramethylethylenediamine (5.5 g) was added. After removing the ice bath and raising the temperature to room temperature, 2,5-dibromopyridine (4.7 g) and Pd (PPh ₃ ) ₄ (0.7 g) were added, and the mixture was stirred at reflux temperature for 5 hours. After the reaction solution was cooled to room temperature, an EDTA · 4Na aqueous solution and toluene were added to separate the layers. After the solvent was distilled off under reduced pressure, the obtained solid was purified by silica gel column chromatography (developing solution: toluene / ethyl acetate = 7/3) to give 5-bromo-5′-methyl-2,3′-bipyridine ( 1.4 g) was obtained.

<Synthesis of 5'-methyl-5- (3- (10- (naphthalen-2-yl) anthracen-9-yl) phenyl) -2,3'-bipyridine>
4,4,5,5-tetramethyl-2- (3- (10- (naphthalen-2-yl) anthracen-9-yl) phenyl) -1,3,2-dioxaborolane (2.0 g), 5- Bromo-6′-methyl-2,3′-bipyridine (1.2 g), Pd (PPh ₃ ) ₄ (0.15 g), potassium phosphate (1.7 g), 1,2,4-trimethylbenzene 25 ml, 5 ml of t-butyl alcohol and 1 ml of water were added and stirred for 5 hours at reflux temperature. After cooling the reaction solution to room temperature, the precipitated solid was collected by suction filtration, washed with methanol and then ethyl acetate. Subsequently, the product was purified by silica gel column chromatography (developing solution: toluene / ethyl acetate = 4/1), and the resulting eluate was passed through an activated carbon short column to remove colored components. The solvent was distilled off under reduced pressure, and the resulting solid was further recrystallized from chlorobenzene to give a compound 5′-methyl-5- (3- (10- (naphthalen-2-yl) represented by (1-14-16). ) Anthracen-9-yl) phenyl) -2,3'-bipyridine (1.3 g) was obtained.
The structure of the compound was confirmed by NMR measurement.
¹ H-NMR (CDCl ₃ ): δ = 9.08 (m, 1H), 9.04 (s, 1H), 8.50 (s, 1H), 8.21 (s, 1H), 8.09 (M, 2H), 8.04 (m, 1H), 8.00 (s, 1H), 7.93 (m, 1H), 7.73-7.88 (m, 8H), 7.62 ( m, 4H), 7.31-7.40 (m, 4H), 2.45 (s, 3H).

Synthesis Example 21 Synthesis of Compound (1-14-17) <Synthesis of 5-bromo-4′-methyl-2,3′-bipyridine>
A flask containing 3-bromo-4-methylpyridine (5.2 g) and THF (10 ml) was cooled in an ice bath, and 2M isopropylmagnesium chloride THF solution (17 ml) was added dropwise to the solution. After completion of the dropwise addition, the ice bath was removed and the mixture was stirred at room temperature for 9 hours, then cooled again in an ice bath and zinc chloride tetramethylethylenediamine (8.3 g) was added. After removing the ice bath and raising the temperature to room temperature, 2,5-dibromopyridine (7.1 g), Pd-137 (Johnson Massey) (0.4 g) and NMP (25 ml) were added and refluxed for 6 hours. Stir. After the reaction solution was cooled to room temperature, an EDTA · 4Na aqueous solution and toluene were added to separate the layers. After the solvent was distilled off under reduced pressure, the obtained solid was purified by silica gel column chromatography (developing solution: toluene / ethyl acetate = 7/3). The solvent was distilled off under reduced pressure, and the resulting solid was washed with heptane to obtain 5-bromo-4′-methyl-2,3′-bipyridine (2.4 g).

<Synthesis of 4'-methyl-5- (3- (10- (naphthalen-2-yl) anthracen-9-yl) phenyl) -2,3'-bipyridine>
4,4,5,5-tetramethyl-2- (3- (10- (naphthalen-2-yl) anthracen-9-yl) phenyl) -1,3,2-dioxaborolane (2.0 g), 5- Bromo-6′-methyl-2,3′-bipyridine (1.2 g), Pd (PPh ₃ ) ₄ (0.15 g), potassium phosphate (1.7 g), 1,2,4-trimethylbenzene 25 ml, 5 ml of t-butyl alcohol and 1 ml of water were added and stirred for 5 hours at reflux temperature. After cooling the reaction solution to room temperature, toluene and water were added to separate the layers. The solvent was distilled off under reduced pressure, and the resulting solid was purified by silica gel column chromatography (developing solution: toluene / ethyl acetate = 7/3), and the eluate obtained there was passed through an activated carbon short column to remove the colored components. Removed. The solvent was distilled off under reduced pressure, and the resulting solid was further recrystallized from toluene to give a compound 4′-methyl-5- (3- (10- (naphthalen-2-yl) represented by (1-14-17). ) Anthracen-9-yl) phenyl) -2,3'-bipyridine (0.7 g) was obtained.
The structure of the compound was confirmed by NMR measurement.
¹ H-NMR (CDCl ₃ ): δ = 9.09 (s, 1H), 8.67 (s, 1H), 8.51 (d, 1H), 8.09 (m, 2H), 8.03 (M, 1H), 8.00 (m, 1H), 7.93 (m, 1H), 7.88 (d, 1H), 7.73-7.84 (m, 6H), 7.61 ( m, 4H), 7.52 (d, 1H), 7.31-7.40 (m, 4H), 7.23 (d, 1H), 2.46 (s, 3H).

[Synthesis Example 22] Synthesis of Compound (1-14-18) <Synthesis of 5-bromo-2'-methyl-2,3'-bipyridine>
A flask containing 3-bromo-2-methylpyridine (5.2 g) and THF (10 ml) was cooled in an ice bath, and 2M isopropylmagnesium chloride THF solution (17 ml) was added dropwise to the solution. After completion of the dropwise addition, the ice bath was removed and the mixture was stirred at room temperature for 2 hours, then cooled again in an ice bath, and zinc chloride tetramethylethylenediamine (8.3 g) was added. After removing the ice bath and raising the temperature to room temperature, 2,5-dibromopyridine (7.1 g), Pd (PPh ₃ ) ₄ (1.0 g) and xylene (10 ml) were added, and the mixture was stirred at reflux temperature for 7 hours. After the reaction solution was cooled to room temperature, an EDTA · 4Na aqueous solution and toluene were added to separate the layers. After the solvent was distilled off under reduced pressure, the obtained solid was purified by silica gel column chromatography (developing solution: toluene / ethyl acetate = 4/1) to give 5-bromo-2′-methyl-2,3′-bipyridine ( 1.3 g) was obtained.

<Synthesis of 2'-methyl-5- (3- (10- (naphthalen-2-yl) anthracen-9-yl) phenyl) -2,3'-bipyridine>
4,4,5,5-tetramethyl-2- (3- (10- (naphthalen-2-yl) anthracen-9-yl) phenyl) -1,3,2-dioxaborolane (2.0 g), 5- Bromo-6′-methyl-2,3′-bipyridine (1.2 g), Pd (PPh ₃ ) ₄ (0.15 g), potassium phosphate (1.7 g), 1,2,4-trimethylbenzene 25 ml, 5 ml of t-butyl alcohol and 1 ml of water were added and stirred at reflux temperature for 12 hours. After cooling the reaction solution to room temperature, toluene and water were added to separate the layers. The solvent was distilled off under reduced pressure, and the resulting solid was purified by silica gel column chromatography (developing solution: toluene / ethyl acetate = 4/1), and the eluate thus obtained was passed through an activated carbon short column to remove the colored components. Removed. The solvent was distilled off under reduced pressure, and the precipitated solid was collected by suction filtration, and the compound represented by (1-14-18) 2′-methyl-5- (3- (10- (naphthalen-2-yl) Anthracen-9-yl) phenyl) -2,3′-bipyridine (0.8 g) was obtained.
The structure of the compound was confirmed by NMR measurement.
¹ H-NMR (CDCl ₃ ): δ = 9.08 (m, 1H), 8.57 (m, 1H), 7.99-8.10 (m, 4H), 7.92 (m, 1H) , 7.88 (d, 1H), 7.73-7.83 (m, 7H), 7.61 (m, 4H), 7.51 (dd, 1H), 7.30-7.40 (m , 4H), 7.25 (m, 1H), 2.66 (s, 3H).

Synthesis Example 23 Synthesis of Compound (1-14-20) <Synthesis of 5-bromo-3′-methyl-2,4′-bipyridine>
A flask containing 4-bromo-3-methylpyridine (5.0 g) and THF (30 ml) was cooled in a dry ice / methanol bath, and 2M isopropylmagnesium chloride THF solution (16 ml) was added dropwise thereto. After completion of the dropwise addition, the cooling bath was removed and the mixture was stirred at room temperature for 2.5 hours, cooled in an ice bath, and zinc chloride tetramethylethylenediamine (8.0 g) was added. After removing the ice bath and raising the temperature to room temperature, 2,5-dibromopyridine (7.6 g) and Pd (PPh ₃ ) ₄ (1.0 g) were added, and the mixture was stirred at reflux temperature for 2 hours. After cooling the reaction solution to room temperature, an EDTA · 4Na aqueous solution and ethyl acetate were added to separate the layers. After the solvent was distilled off under reduced pressure, the obtained solid was purified by silica gel column chromatography (developing solution: toluene / ethyl acetate = 5/1) to give 5-bromo-3′-methyl-2,4′-bipyridine ( 5.6 g) was obtained.

<Synthesis of 3'-methyl-5- (3- (10- (naphthalen-2-yl) anthracen-9-yl) phenyl) -2,4'-bipyridine>
4,4,5,5-tetramethyl-2- (3- (10- (naphthalen-2-yl) anthracen-9-yl) phenyl) -1,3,2-dioxaborolane (2.0 g), 5- Bromo-3′-methyl-2,4′-bipyridine (1.2 g), Pd (PPh ₃ ) ₄ (0.15 g), potassium phosphate (1.7 g), 1 ml of 1,2,4-trimethylbenzene, 1 ml of t-butyl alcohol and 1 ml of water were added and stirred at reflux temperature for 4 hours. The reaction solution was cooled to room temperature, water was added, and the precipitate was collected by suction filtration. The resulting solid was washed with water and methanol, and then purified by NH-modified silica gel (DM1020: manufactured by Fuji Silysia) column chromatography (developing solution: toluene), and compound 3 represented by (1-14-20) '-Methyl-5- (3- (10- (naphthalen-2-yl) anthracen-9-yl) phenyl) -2,4'-bipyridine (1.7 g) was obtained.
The structure of the compound was confirmed by NMR measurement.
¹ H-NMR (CDCl ₃ ): δ = 9.09 (m, 1H), 8.56 (s, 1H), 8.55 (d, 1H), 8.10 (m, 2H), 8.03 (M, 1H), 8.00 (d, 1H), 7.93 (d, 1H), 7.88 (d, 1H), 7.73-7.83 (m, 6H), 7.61 ( m, 4H), 7.53 (d, 1H), 7.31-7.41 (m, 5H), 2.44 (s, 3H).

Synthesis Example 24 Synthesis of Compound (1-11-1-18) <2′-Methyl-5- (6- (10-phenylanthracen-9-yl) naphthalen-2-yl) 2,3′-bipyridine >
4,4,5,5-tetramethyl-2- (6- (10-phenylanthracen-9-yl) naphthalen-2-yl) -1,3,2-dioxaborolane (2.0 g), 5-bromo- 2′-methyl-2,3′-bipyridine (1.2 g), Pd (PPh ₃ ) ₄ (0.15 g), potassium phosphate (1.7 g), 1,2,4-trimethylbenzene (20 ml), t-Butyl alcohol (5 ml) and water (1 ml) were placed in a flask and stirred at reflux temperature for 8 hours under a nitrogen atmosphere. After completion of the heating, the reaction solution was cooled to room temperature, and the precipitated solid was collected by suction filtration, and washed with methanol and ethyl acetate. Subsequently, it was purified by silica gel column chromatography (developing solution: toluene / ethyl acetate = 7/3), and the eluate thus obtained was passed through an activated carbon short column to remove colored components. The solvent was distilled off under reduced pressure, and the precipitated solid was collected by suction filtration, and the compound 2′-methyl-5- (6- (10-phenylanthracen-9-yl) represented by (1-1-11-18) Naphthalen-2-yl) 2,3′-bipyridine (1.1 g) was obtained.
The structure of the compound was confirmed by NMR measurement.
¹ H-NMR (CDCl ₃ ): δ = 9.17 (m, 1H), 8.60 (dd, 1H), 8.230 (s, 1H), 8.19 (m, 2H), 8.06 (M, 2H), 7.87 (dd, 1H), 7.85 (dd, 1H), 7.73 (m, 4H), 7.69 (dd, 1H), 7.55-7.65 ( m, 4H), 7.51 (m, 2H), 7.26-7.37 (m, 5H), 2.73 (s, 3H).

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 Examples 1 to 4 and Comparative Examples 1 to 2 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. went. Hereinafter, examples and comparative examples will be described in detail.

Table 1 below shows the material configuration of each layer in the devices according to Examples 1 to 4 and Comparative Examples 1 and 2 that were manufactured.

In Table 1, “HI” is N ⁴ , N ^{4 ′} -diphenyl-N ⁴ , N ^{4 ′} -bis (9-phenyl-9H-carbazol-3-yl)-[1,1′-biphenyl] -4, 4′-diamine, “NPD” is N ⁴ , N ^{4 ′} -di (naphthalen-1-yl) -N ⁴ , N ^{4 ′} -diphenyl- [1,1′-biphenyl] -4,4′-diamine, compound (A) is 9-phenyl-10- (4-phenyl-1-yl) anthracene, the compound (B) is ^{N 5, N 5, N 9} , N 9 -7,7- hexaphenyl -7H- benzo [C] Fluorene-5,9-diamine, Compound (C) is 9,10-di ([2,2′-bipyridin] -5-yl) anthracene, Compound (D) is 9,10-bis (4- (Pyridin-3-yl) naphthalen-1-yl) anthracene. The chemical structure is shown below together with “Liq” used for the layer formed between the electron transport layer and the cathode.

<Element Using Compound (1-7-74) 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 Showa Vacuum 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 (1-7-74), molybdenum vapor deposition boat containing Liq, 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 (1-7-74) 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 Liq was heated to deposit at a 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 thickness 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 a cathode was formed so that the deposition rate was 0.1 to 10 nm / second, thereby obtaining 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 7.33 V, and the luminance was 90% (1800 cd / m ² ) or more of the initial value. The holding time was 45 hours.

<Element Using Compound (1-7-26) for Electron Transport Layer>
An organic EL device was obtained by the method according to Example 2 except that the compound (1-7-74) was changed to the compound (1-7-26). 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 151 hours.

<Element Using Compound (1-7-98) for Electron Transport Layer>
An organic EL device was obtained by the method according to Example 2 except that the compound (1-7-74) was changed to the compound (1-7-98). 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 7.34 V, and the time for maintaining the luminance of 90% or more of the initial value was 265 hours.

<Element Using Compound (1-7-96) for Electron Transport Layer>
An organic EL device was obtained by the method according to Example 2 except that the compound (1-7-74) was changed to the compound (1-7-96). 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 5.33 V, and the time for maintaining the luminance of 90% or more of the initial value was 103 hours.

[Comparative Example 1]
An organic EL device was obtained by the method according to Example 1 except that the compound (1-7-96) was changed to the compound (C). 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 . As a result, the drive test start voltage was 5.06 V, and the time for maintaining the luminance of 90% or more of the initial value was 6 hours.

[Comparative Example 2]
An organic EL device was obtained by the method according to Example 1 except that the compound (1-7-96) was changed to the compound (D). 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 . As a result, the drive test start voltage was 5.05 V, and the time for maintaining the luminance of 90% or more of the initial value was 10 hours.

The above results are summarized in Table 2.

The elements according to Examples 5 to 20 and Comparative Examples 3 to 5 were manufactured, and the measurement of 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 was performed. went. Hereinafter, examples and comparative examples will be described in detail.

Table 3 below shows the material structure of each layer in the devices according to Examples 5 to 20 and Comparative Examples 3 to 5.

In Table 3, HT is N-([1,1′-biphenyl] -4-yl) -9,9-dimethyl-N- (4- (9-phenyl-9H-carbazol-3-yl) phenyl)- 9H-fluoren-2-amine, compound (E) is 9- (4- (naphthalen-1-yl) phenyl) -10-phenylanthracene, compound (F) is 4,4 ′-((7,7-diphenyl) -7H-benzo [c] fluorene-5,9-diyl) bis ((phenyl) amino)) dibenzonitrile, compound (G) is 4 '-(4- (10- (naphthalen-2-yl) anthracene-9 -Yl) phenyl) -2,2 ': 6', 2 "-terpyridine, compound (H) is 3- (6- (10-phenylanthracen-9-yl) naphthalen-2-yl) pyridine, compound (I ) Is 6- (4- (10- Naphthalen-1-yl) anthracene-9-yl) phenyl) 2,4'-bipyridine.

<Element Using Compound (1-11-1) 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 Showa Vacuum Co., Ltd.), a molybdenum vapor deposition boat containing HI, a molybdenum vapor deposition boat containing HT, and a compound (E) Molybdenum vapor deposition boat, molybdenum vapor deposition boat containing compound (F), molybdenum vapor deposition boat containing compound (1-11-1), molybdenum vapor deposition boat containing Liq, 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 HT 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 (E) and the vapor deposition boat containing the compound (F) 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 (E) to compound (F) was approximately 95 to 5. Next, the vapor deposition boat containing the compound (1-11-1) and the vapor deposition boat containing Liq were heated at the same time to form a film having a thickness of 25 nm, thereby forming an electron transport layer. The deposition rate was adjusted so that the weight ratio of the compound (1-11-1) and Liq was approximately 1: 1. The deposition rate of each layer was 0.01 to 1 nm / second.

Thereafter, the evaporation boat containing Liq was heated to deposit at a 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 thickness 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 a cathode was formed so that the deposition rate was 0.1 to 10 nm / second, thereby obtaining 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 450 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 4.00 V, and the luminance was 90% (1800 cd / m ² ) or more of the initial value. The holding time was 87 hours.

<Element Using Compound (1-11-2) for Electron Transport Layer>
An organic EL device was obtained by the method according to Example 5 except that the compound (1-11-1) was changed to the compound (1-11-2). 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 starting voltage was 4.12 V, and the time for maintaining the luminance of 90% or more of the initial value was 85 hours.

<Element Using Compound (1-11-3) for Electron Transport Layer>
An organic EL device was obtained by the method according to Example 5 except that the compound (1-11-1) was changed to the compound (1-11-3). 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 drive test start voltage was 3.78 V, and the time for maintaining the luminance of 90% or more of the initial value was 97 hours.

<Element Using Compound (1-11-4) for Electron Transport Layer>
An organic EL device was obtained by the method according to Example 5 except that the compound (1-11-1) was changed to the compound (1-11-4). 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 starting voltage was 3.95 V, and the time for maintaining the luminance of 90% or more of the initial value was 83 hours.

<Device Using Compound (1-1-11-5) for Electron Transport Layer>
An organic EL device was obtained by the method according to Example 5 except that the compound (1-11-1) was replaced with the compound (1-11-1-5). 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 starting voltage was 3.88 V, and the time for maintaining the luminance of 90% or more of the initial value was 93 hours.

<Element Using Compound (1-11-139) for Electron Transport Layer>
An organic EL device was obtained by the method according to Example 5 except that the compound (1-11-1) was changed to the compound (1-11-139). 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 4.16 V, and the time for maintaining the luminance of 90% or more of the initial value was 74 hours.

<Element Using Compound (1-14-2) for Electron Transport Layer>
An organic EL device was obtained by the method according to Example 5 except that the compound (1-11-1) was changed to the compound (1-14-2). 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 3.61 V, and the time for maintaining the luminance of 90% or more of the initial value was 76 hours.

<Element Using Compound (1-14-3) for Electron Transport Layer>
An organic EL device was obtained by the method according to Example 5 except that the compound (1-11-1) was changed to the compound (1-14-3). 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 3.85 V, and the time for maintaining the luminance of 90% or more of the initial value was 141 hours.

<Element Using Compound (1-14-11) for Electron Transport Layer>
An organic EL device was obtained by the method according to Example 5 except that the compound (1-11-1) was changed to the compound (1-14-11). 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 4.16 V, and the time for maintaining the luminance of 90% or more of the initial value was 162 hours.

<Element Using Compound (1-14-12) for Electron Transport Layer>
An organic EL device was obtained by the method according to Example 5 except that the compound (1-11-1) was changed to the compound (1-14-12). 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 3.87 V, and the time for maintaining the luminance of 90% or more of the initial value was 75 hours.

<Element Using Compound (1-14-14) for Electron Transport Layer>
An organic EL device was obtained by the method according to Example 5 except that the compound (1-11-1) was changed to the compound (1-14-14). 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 3.82 V, and the time for maintaining the luminance of 90% or more of the initial value was 227 hours.

<Element Using Compound (1-14-15) for Electron Transport Layer>
An organic EL device was obtained by the method according to Example 5 except that the compound (1-11-1) was changed to the compound (1-14-15). 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 3.98 V, and the time for maintaining the luminance of 90% or more of the initial value was 101 hours.

<Element Using Compound (1-14-16) for Electron Transport Layer>
An organic EL device was obtained by the method according to Example 5 except that the compound (1-11-1) was changed to the compound (1-14-16). 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 4.25 V, and the time for maintaining the luminance of 90% or more of the initial value was 70 hours.

<Element Using Compound (1-14-18) for Electron Transport Layer>
An organic EL device was obtained by the method according to Example 5 except that the compound (1-11-1) was changed to the compound (1-14-18). 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 3.75 V, and the time for maintaining the luminance of 90% or more of the initial value was 125 hours.

<Element Using Compound (1-14-20) for Electron Transport Layer>
An organic EL device was obtained by the method according to Example 5 except that the compound (1-11-1) was changed to the compound (1-14-20). 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 4.19 V, and the time for maintaining the luminance of 90% or more of the initial value was 63 hours.

<Element Using Compound (1-11-1-18) for Electron Transport Layer>
An organic EL device was obtained by the method according to Example 5 except that the compound (1-11-1) was changed to the compound (1-11-1-18). 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 drive test start voltage was 4.29 V, and the time for maintaining the luminance of 90% or more of the initial value was 60 hours.

[Comparative Example 3]
An organic EL device was obtained by a method according to Example 5 except that the compound (1-11-1) was changed to the compound (G). 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 . As a result, the drive test start voltage was 5.36 V, and the time for maintaining the luminance of 90% or more of the initial value was 2 hours.

[Comparative Example 4]
An organic EL device was obtained by a method according to Example 5 except that the compound (1-11-1) was changed to the compound (H). 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 . As a result, the driving test start voltage was 4.12 V, and the time for maintaining the luminance of 90% or more of the initial value was 26 hours.

[Comparative Example 5]
An organic EL device was obtained by the method according to Example 5 except that the compound (1-11-1) was changed to the compound (I). 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 . As a result, the driving test start voltage was 4.15 V, and the time for maintaining the luminance of 90% or more of the initial value was 30 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 (18)

A compound represented by the following formula (1).

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

m and n are 0 or 1, but m + n = 1; and
At least one of hydrogen in the benzene ring, naphthalene ring and pyridine ring in the formula (1) is replaced with alkyl having 1 to 6 carbons or cycloalkyl having 3 to 6 carbons. The compound of Claim 1 represented by a following formula (1-1) or (1-2).

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

Then, at least one of hydrogen in the benzene ring, naphthalene ring and pyridine ring in the formulas (1-1) and (1-2) is replaced with alkyl having 1 to 6 carbons or cycloalkyl having 3 to 6 carbons. ing. The compound of Claim 1 represented by following formula (1-3), (1-4), (1-5), or (1-6).

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

Then, at least one of hydrogen in the benzene ring, naphthalene ring and pyridine ring in formulas (1-3) to (1-6) is replaced with alkyl having 1 to 6 carbons or cycloalkyl having 3 to 6 carbons. ing. The compound of Claim 1 represented by a following formula (1-7) or (1-8).

In formulas (1-7) and (1-8),
Py is a group represented by the formula (2), (3) or (4);

R is alkyl having 1 to 6 carbons or cycloalkyl having 3 to 6 carbons; and
p is an integer of 1-5. The compound of Claim 1 represented by a following formula (1-9) or (1-10).

In formulas (1-9) and (1-10),
Py is a group represented by the formula (2), (3) or (4);

R is alkyl having 1 to 6 carbons or cycloalkyl having 3 to 6 carbons; and
q is an integer of 1-5. The compound of Claim 1 represented by a following formula (1-11) or (1-12).

In formulas (1-11) and (1-12),
Py ¹ is a group represented by the formula (2 ′), (3 ′) or (4 ′);

In the formulas (2 ′), (3 ′) and (4 ′), R is alkyl having 1 to 6 carbons or cycloalkyl having 3 to 6 carbons; and s is an integer of 1 to 4. The compound of Claim 1 represented by a following formula (1-13) or (1-14).

In formulas (1-13) and (1-14),
Py ¹ is a group represented by the formula (2 ′), (3 ′) or (4 ′);

In the formula (2 ′), (3 ′) or (4 ′), R is alkyl having 1 to 6 carbons or cycloalkyl having 3 to 6 carbons; and s is an integer of 1 to 4. The compound of Claim 1 represented by a following formula (1-15) or (1-16).

In formulas (1-15) and (1-16),
Py is a group represented by the formula (2), (3) or (4);

R is alkyl having 1 to 6 carbons or cycloalkyl having 3 to 6 carbons; and t is an integer of 1 to 4. The compound of Claim 1 represented by a following formula (1-7-26).

The compound of Claim 1 represented by a following formula (1-7-74).

The compound of Claim 1 represented by a following formula (1-7-98).

The compound of Claim 1 represented by a following formula (1-7-96).

The compound of Claim 1 represented by a following formula (1-14-14).

The following formulas (1-11-1), (1-11-2), (1-11-3), (1-11-4), (1-11-1-5), (1-11-1), (1-11-1-8), (1-11-1-18), (1-11-139), (1-14-2), (1-14-3), (1-14-11), (1 -14-12), (1-14-13), (1-14-15), (1-14-16), (1-14-17), (1-14-18), and (1- The compound according to claim 1, which is represented by any one of 14-20).

The electron transport material containing the compound of any one of Claims 1-14. An electron transport containing the electron transport material according to claim 15, disposed between a pair of electrodes composed of an anode and a cathode, a light emitting layer disposed between the pair of electrodes, and 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 16, 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 16 or 17.