JP5799772B2 - Electron transport material and organic electroluminescent device using the same - Google Patents
Electron transport material and organic electroluminescent device using the same Download PDFInfo
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- JP5799772B2 JP5799772B2 JP2011257116A JP2011257116A JP5799772B2 JP 5799772 B2 JP5799772 B2 JP 5799772B2 JP 2011257116 A JP2011257116 A JP 2011257116A JP 2011257116 A JP2011257116 A JP 2011257116A JP 5799772 B2 JP5799772 B2 JP 5799772B2
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- YNHIGQDRGKUECZ-UHFFFAOYSA-N dichloropalladium;triphenylphosphanium Chemical compound Cl[Pd]Cl.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 YNHIGQDRGKUECZ-UHFFFAOYSA-N 0.000 description 1
- NNNFHIWKVLLMKH-UHFFFAOYSA-N ditert-butyl-[1-(2-ditert-butylphosphanylnaphthalen-1-yl)naphthalen-2-yl]phosphane Chemical group C1=CC=C2C(C3=C4C=CC=CC4=CC=C3P(C(C)(C)C)C(C)(C)C)=C(P(C(C)(C)C)C(C)(C)C)C=CC2=C1 NNNFHIWKVLLMKH-UHFFFAOYSA-N 0.000 description 1
- MUPGNOONALUUNP-UHFFFAOYSA-N ditert-butyl-[1-(2-methoxynaphthalen-1-yl)naphthalen-2-yl]phosphane Chemical group C1=CC=C2C(C3=C4C=CC=CC4=CC=C3OC)=C(P(C(C)(C)C)C(C)(C)C)C=CC2=C1 MUPGNOONALUUNP-UHFFFAOYSA-N 0.000 description 1
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 125000005678 ethenylene group Chemical class [H]C([*:1])=C([H])[*:2] 0.000 description 1
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 150000002220 fluorenes Chemical class 0.000 description 1
- 150000002258 gallium Chemical class 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 150000004795 grignard reagents Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000004857 imidazopyridinyl group Chemical class N1C(=NC2=C1C=CC=N2)* 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000000990 laser dye Substances 0.000 description 1
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 description 1
- MESMXXUBQDBBSR-UHFFFAOYSA-N n,9-diphenyl-n-[4-[4-(n-(9-phenylcarbazol-3-yl)anilino)phenyl]phenyl]carbazol-3-amine Chemical compound C1=CC=CC=C1N(C=1C=C2C3=CC=CC=C3N(C=3C=CC=CC=3)C2=CC=1)C1=CC=C(C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C=C3C4=CC=CC=C4N(C=4C=CC=CC=4)C3=CC=2)C=C1 MESMXXUBQDBBSR-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 150000004893 oxazines Chemical class 0.000 description 1
- 150000002941 palladium compounds Chemical class 0.000 description 1
- JCDAUYWOHOLVMH-UHFFFAOYSA-N phenanthren-9-ylboronic acid Chemical compound C1=CC=C2C(B(O)O)=CC3=CC=CC=C3C2=C1 JCDAUYWOHOLVMH-UHFFFAOYSA-N 0.000 description 1
- 150000002987 phenanthrenes Chemical class 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical class N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 description 1
- 229920000548 poly(silane) polymer Polymers 0.000 description 1
- 229920002098 polyfluorene Polymers 0.000 description 1
- 229920000123 polythiophene Chemical class 0.000 description 1
- 150000004033 porphyrin derivatives Chemical class 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000011698 potassium fluoride Substances 0.000 description 1
- 235000003270 potassium fluoride Nutrition 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000003216 pyrazines Chemical class 0.000 description 1
- 150000003217 pyrazoles Chemical class 0.000 description 1
- 150000003220 pyrenes Chemical class 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- 150000004322 quinolinols Chemical class 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- YYMBJDOZVAITBP-UHFFFAOYSA-N rubrene Chemical class C1=CC=CC=C1C(C1=C(C=2C=CC=CC=2)C2=CC=CC=C2C(C=2C=CC=CC=2)=C11)=C(C=CC=C2)C2=C1C1=CC=CC=C1 YYMBJDOZVAITBP-UHFFFAOYSA-N 0.000 description 1
- 150000003967 siloles Chemical class 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 125000003003 spiro group Chemical group 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229940042055 systemic antimycotics triazole derivative Drugs 0.000 description 1
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 1
- 150000003518 tetracenes Chemical class 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 125000005259 triarylamine group Chemical group 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- PXFBSZZEOWJJNL-UHFFFAOYSA-N triphenylen-2-ylboronic acid Chemical compound C1=CC=C2C3=CC(B(O)O)=CC=C3C3=CC=CC=C3C2=C1 PXFBSZZEOWJJNL-UHFFFAOYSA-N 0.000 description 1
- BWHDROKFUHTORW-UHFFFAOYSA-N tritert-butylphosphane Chemical compound CC(C)(C)P(C(C)(C)C)C(C)(C)C BWHDROKFUHTORW-UHFFFAOYSA-N 0.000 description 1
- 125000001834 xanthenyl group Chemical class C1=CC=CC=2OC3=CC=CC=C3C(C12)* 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Electroluminescent Light Sources (AREA)
- Pyridine Compounds (AREA)
Description
本発明は、ビピリジル基を有する新規な電子輸送材料、この電子輸送材料を用いた有機電界発光素子（以下、有機ＥＬ素子または単に素子と略記することがある。）等に関する。 The present invention relates to a novel electron transport material having a bipyridyl group, an organic electroluminescence device using the electron transport material (hereinafter, may be simply referred to as an organic EL device or simply a device), and the like.
近年、次世代のフルカラーフラットパネルディスプレイとして有機ＥＬ素子が注目され、活発な研究がなされている。有機ＥＬ素子の実用化を促進するには、素子の駆動電圧の低減、長寿命化が不可欠な要素であり、これらを達成するために新しい電子輸送材料の開発がなされてきた。特に、青色素子の駆動電圧低下、長寿命化は必須である。特許文献１（特開２００３−１２３９８３号公報）には、フェナントロリン誘導体またはその類似体である２，２’−ビピリジル化合物を電子輸送材料に使用することで有機ＥＬ素子を低電圧で駆動させることができると記載されている。しかしながらこの文献の実施例に報告されている素子の特性（駆動電圧、発光効率など）は比較例を基準にした相対値のみであり、実用的な値と判断できる実測値は記載されていない。他に、２，２’−ビピリジル化合物を電子輸送材料に使用した例が、非特許文献１（Proceedings of the 10th International Workshop on Inorganic and Organic Electroluminescence）、特許文献２（特開２００２−１５８０９３号公報）および特許文献３（国際公開２００７／８６５５２パンフレット）に開示されている。非特許文献１に記載されている化合物はＴｇが低く、実用的ではなかった。特許文献２および３に記載の化合物は比較的低電圧で有機ＥＬ素子を駆動させることができるが、素子寿命が十分ではなかった。更には、３，２’−ビピリジル、３，３’−ビピリジルまたは３，４’−ビピリジルを分子中に２つ以上有する化合物を電子輸送材料に使用した例が、特許文献４〜６（特開２００７−２９１０９２、特開２００８−１５６２６６および特開２００８−２４７８９５）に開示されており、比較的長寿命の有機ＥＬ素子が得られているが、実用化には至っていない。 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, the device lifetime is not sufficient. Further, Patent Documents 4 to 6 (Patent Documents 4 to 6) disclose examples in which a compound having two or more 3,2′-bipyridyl, 3,3′-bipyridyl, or 3,4′-bipyridyl in a molecule is used as an electron transport material. 2007-291092, Japanese Patent Application Laid-Open No. 2008-156266, and Japanese Patent Application Laid-Open No. 2008-247895), and a relatively long-life organic EL element has been obtained, but has not yet been put into practical use.
本発明は、このような従来技術が有する課題に鑑みてなされたものである。本発明は、有機ＥＬ素子の長寿命化等に寄与する電子輸送材料を提供することを課題とする。さらに本発明は、この電子輸送材料を用いた有機ＥＬ素子を提供することを課題とする。 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.
本発明者らは鋭意検討した結果、３，２’−ビピリジル、３，３’−ビピリジルまたは３，４’−ビピリジルで置換されたベンゼン環が、１０位がアリールで置換されたアントリル基で置換されている化合物を有機ＥＬ素子の電子輸送層に用いることにより、長寿命で駆動できる有機ＥＬ素子が得られることを見出し、この知見に基づいて本発明を完成した。
上記の課題は以下に示す各項によって解決される。
As a result of intensive studies, the present inventors have found that a benzene ring substituted with 3,2′-bipyridyl, 3,3′-bipyridyl, or 3,4′-bipyridyl is substituted with an anthryl group substituted with aryl at the 10-position. The present inventors have found that an organic EL device that can be driven with a long lifetime can be obtained by using the compound used in the electron transport layer of the organic EL device, and the present invention has been completed based on this finding.
Said subject is solved by each item shown below.
［１］ 下記式（１）で表される化合物。
［２］ 下記式（１−１）または（１−２）で表される、前記［１］項に記載の化合物。
［３］ Ａｒが下記の１価の基の群から選ばれる１つである、前記［１］項または［２］項に記載の化合物。
各々の基の任意の水素は炭素数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てもよい。
[3] The compound according to [1] or [2], wherein Ar is one selected from the following monovalent group.
Any hydrogen in each group may be replaced with alkyl having 1 to 6 carbons or cycloalkyl having 3 to 6 carbons.
［４］ Ａｒが下記の群から選ばれる１価の基である、前記［１］項または［２］項に記載の化合物。
［５］ 下記式（１−１−２）、（１−１−３６）、（１−１−７０）、（１−２−６８）、（１−２−７４）、（１−２−７７）、（１−２−７９）、および（１−２−９５）で表される化合物の群から選ばれる１つである、前記［１］項または［２］項に記載の化合物。
［６］ 前記［１］〜［５］のいずれか１項に記載の化合物を含有する電子輸送材料。 [6] An electron transport material containing the compound according to any one of [1] to [5].
［７］ 陽極および陰極からなる一対の電極と、該一対の電極間に配置される発光層と、前記陰極と該発光層との間に配置され、前記［６］項に記載の電子輸送材料を含有する電子輸送層および／または電子注入層とを有する有機電界発光素子。 [7] A pair of electrodes including an anode and a cathode, a light emitting layer disposed between the pair of electrodes, an electron transport material according to the item [6], disposed between the cathode and the light emitting layer. An organic electroluminescent device having an electron transport layer and / or an electron injection layer containing
［８］ 前記電子輸送層および電子注入層の少なくとも１つは、さらに、キノリノール系金属錯体、ビピリジン誘導体、フェナントロリン誘導体およびボラン誘導体からなる群から選択される少なくとも１つを含有する、前記［７］項に記載する有機電界発光素子。 [8] 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, [7] The organic electroluminescent element described in the item.
［９］ 電子輸送層および電子注入層の少なくとも１つが、さらに、アルカリ金属、アルカリ土類金属、希土類金属、アルカリ金属の酸化物、アルカリ金属のハロゲン化物、アルカリ土類金属の酸化物、アルカリ土類金属のハロゲン化物、希土類金属の酸化物、希土類金属のハロゲン化物、アルカリ金属の有機錯体、アルカリ土類金属の有機錯体および希土類金属の有機錯体からなる群から選択される少なくとも１つを含有する、前記［７］項または［８］項に記載の有機電界発光素子。 [9] 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 device according to the item [7] or [8].
本発明の化合物は薄膜状態で電圧を印加しても安定であり、また、電荷の輸送能力が高いという特徴を持つ。本発明の化合物は有機ＥＬ素子における電荷輸送材料として適している。本発明の化合物を有機ＥＬ素子の電子輸送層および／または電子注入層に用いることで、長い寿命を有する有機ＥＬ素子を得ることができる。本発明の有機ＥＬ素子を用いることにより、フルカラー表示等の高性能のディスプレイ装置を作成できる。 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.
以下、本発明をさらに詳細に説明する。なお、本明細書においては、例えば「式（１−１−１）で表される化合物」のことを「化合物（１−１−１）」と称することがある。「式（１−１−２）で表される化合物」のことを「化合物（１−１−２）」と称することがある。その他の式記号、式番号についても同様に扱われる。 Hereinafter, the present invention will be described in more detail. In the present specification, for example, the “compound represented by the formula (1-1-1)” may be referred to as “compound (1-1-1)”. The “compound represented by the formula (1-1-2)” may be referred to as “compound (1-1-2)”. Other formula symbols and formula numbers are handled in the same manner.
化合物の定義において用いる用語「任意の」は「位置だけでなく数においても自由に選択できること」を意味する。例えば、「フェニルの任意の水素は炭素数１〜６のアルキルで置き換えられていてもよい」という表現は、「１つの水素がアルキルで置き換えられてもよい」のみならず、「複数の水素が同一のアルキル、または各々異なるアルキルで置き換えられていてもよい」ことをも意味する。
本明細書の構造式、化学反応式等で用いられる記号Ｍｅおよびｔ−Ｂｕは、それぞれメチルおよびターシャリーブチルを表す。
The term “arbitrary” used in the definition of compounds means “can be freely selected not only by position but also by number”. For example, the expression “any hydrogen of phenyl may be substituted with alkyl having 1 to 6 carbon atoms” is not limited to “a single hydrogen may be substituted with alkyl”, It may also mean “same alkyl, or each may be replaced by a different alkyl”.
The symbols Me and t-Bu used in the structural formulas, chemical reaction formulas and the like of this specification represent methyl and tertiary butyl, respectively.
＜化合物の説明＞
本願の第１の発明は、下記の式（１）で表される３，２’−ビピリジル、３，３’−ビピリジルまたは３，４’−ビピリジルを有する化合物である。
The first invention of the present application is a compound having 3,2′-bipyridyl, 3,3′-bipyridyl or 3,4′-bipyridyl represented by the following formula (1).
本発明の化合物は分子中にビピリジルを１つ有すること、およびビピリジルのフェニルに連結している２価のピリジン環が３，５−ピリジンジイルであることを最大の特徴としている。 The compound of the present invention is characterized by having one bipyridyl in the molecule and that the divalent pyridine ring linked to the phenyl of bipyridyl is 3,5-pyridinediyl.
式（１）において、３，２’−ビピリジル、３，３’−ビピリジルまたは３，４’−ビピリジルが連結するフェニルの位置は任意でよいが、４位および３位が好ましい。すなわち、式（１）の化合物の好ましい態様は、下記の式（１−１）または（１−２）で表すことができる。
式（１）中のベンゼン環およびピリジン環に置換する炭素数１〜６のアルキルの例はメチル、エチル、ｎ−プロピル、イソプロピル、ｎ−ブチル、イソブチル、ｔ−ブチル、ｎ−ペンチル、イソペンチル、２，２−ジメチルプロピル、ｎ−ヘキシル、およびイソヘキシルである。この中で好ましいアルキルはメチル、エチル、イソプロピル、およびｔ−ブチルであり、メチルおよびｔ−ブチルがより好ましい。炭素数３〜６のシクロアルキルの例はシクロプロピル、シクロブチル、シクロペンチル、シクロヘキシルである。この中で好ましいシクロアルキルは原料の入手、合成の容易さを考慮するとシクロヘキシルである。 Examples of the alkyl having 1 to 6 carbon atoms substituted on the benzene ring and the 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. Of these, cycloalkyl is preferably cyclohexyl in view of availability of raw materials and ease of synthesis.
式（１）、（１−１）および（１−２）におけるＡｒは具体的には下記の１価の基の群から選ばれる１つである。
上記の基の中では下記に示す基が好ましい。
＜化合物の具体例＞
本発明の化合物の具体例は以下に列記する式によって示されるが、本発明はこれらの具体的な構造の開示によって限定されることはない。
<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.
＜式（１−１）で表される化合物の具体例＞
式（１−１）で表される化合物の具体例は下記の式（１−１−１）〜（１−１−９８）で示される。これらの中で好ましい化合物は式（１−１−１）、（１−１−２）、（１−１−４）、（１−１−６）〜（１−１−９）、（１−１−１１）、（１−１−１３）、（１−１−１８）〜（１−１−３６）、（１−１−３８）、（１−１−４０）〜（１−１−４３）、（１−１−４５）、（１−１−４７）、（１−１−５２）〜（１−１−７０）、（１−１−７２）、（１−１−７４）〜（１−１−７７）、（１−１−７９）、（１−１−８１）、および（１−１−８６）〜（１−１−９８）である。中でも特に好ましい化合物は式（１−１−１）、（１−１−２）、（１−１−４）、（１−１−６）〜（１−１−９）、（１−１−１１）、（１−１−１３）、（１−１−３５）、（１−１−３６）、（１−１−３８）、（１−１−４０）〜（１−１−４３）、（１−１−４５）、（１−１−４７）、（１−１−６９）、（１−１−７０）、（１−１−７２）〜（１−１−７４）、（１−１−７７）、（１−１−７９）、（１−１−８１）および（１−１−９８）である。
<Specific Example of Compound Represented by Formula (1-1)>
Specific examples of the compound represented by the formula (1-1) are represented by the following formulas (1-1-1) to (1-1-98). Among these, preferred compounds are those represented by formulas (1-1-1), (1-1-2), (1-1-4), (1-1-6) to (1-1-9), (1 (1-1-11), (1-1-13), (1-1-18) to (1-1-36), (1-1-38), (1-1-40) to (1-1 -43), (1-1-45), (1-1-47), (1-1-52) to (1-1-70), (1-1-72), (1-1-74 ) To (1-1-77), (1-1-79), (1-1-81), and (1-1-86) to (1-1-98). Among them, particularly preferred compounds are the formulas (1-1-1), (1-1-2), (1-1-4), (1-1-6) to (1-1-9), (1-1 -11), (1-1-13), (1-1-35), (1-1-36), (1-1-38), (1-1-40) to (1-1-43) ), (1-1-45), (1-1-47), (1-1-69), (1-1-70), (1-1-72) to (1-1-74), (1-1-77), (1-1-79), (1-1-81) and (1-1-98).
＜式（１−２）で表される化合物の具体例＞
式（１−２）で表される化合物の具体例は下記の式（１−２−１）〜（１−２−９５）で示される。これらの中で好ましい化合物は式（１−２−１）、（１−２−２）、（１−２−４）、（１−２−６）〜（１−２−９）、（１−２−１１）、（１−２−１３）、（１−２−１８）〜（１−２−３５）、（１−２−３７）、（１−２−３９）〜（１−２−４２）、（１−２−４４）、（１−２−４６）、（１−２−５１）〜（１−２−６８）、（１−２−７０）、（１−２−７２）〜（１−２−７５）、（１−２−７７）、（１−２−７９）、および（１−２−８４）〜（１−２−９５）である。中でも特に好ましい化合物は式（１−２−１）、（１−２−２）、（１−２−４）、（１−２−６）〜（１−２−９）、（１−２−１１）、（１−２−１３）、（１−２−３４）、（１−２−３５）、（１−２−３７）、（１−２−３９）〜（１−２−４２）、（１−２−４４）、（１−２−４６）、（１−２−６７）、（１−２−６８）、（１−２−７０）、（１−２−７２）〜（１−２−７５）（１−２−７７）、（１−２−７９）および（１−２−９５）である。
<Specific Example of Compound Represented by Formula (1-2)>
Specific examples of the compound represented by the formula (1-2) are represented by the following formulas (1-2-1) to (1-295). Among these, preferred compounds are those represented by formulas (1-2-1), (1-2-2), (1-2-4), (1-2-6) to (1-2-9), (1 -2-11), (1-2-13), (1-2-18) to (1-235), (1-237), (1-239) to (1-2) -42), (1-244), (1-246), (1-251) to (1-268), (1-270), (1-272) ) To (1-275), (1-277), (1-279), and (1-284) to (1-295). Among them, particularly preferred compounds are the formulas (1-2-1), (1-2-2), (1-2-4), (1-2-6) to (1-2-9), (1-2 -11), (1-2-13), (1-234), (1-235), (1-237), (1-239) to (1-242) ), (1-244), (1-246), (1-2-67), (1-268), (1-2-70), (1-2-72) to (1-2-75) (1-2-77), (1-2-79) and (1-2-95).
＜化合物の合成法＞
以下に本発明の化合物の合成法について説明する。本発明の化合物は、汎用される既知の合成法を適宜組み合わせて利用することにより合成することができる。
<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.
＜式（１−１−１）〜式（１−１−９８）で表される化合物の合成法１＞
＜式（１−１−１）〜式（１−１−９８）で表される化合物の合成法２＞
＜式（１−１−１）〜式（１−１−９８）で表される化合物の合成法３＞
下記反応１３に示したように、上記反応３〜７において、出発原料を９−ブロモアントラセンとし、５−（４−（アントラセン−９−イル）フェニル）−ビピリジン誘導体を合成した後、上記反応２で示した方法で臭素化、次いで種々のアリールボロン酸とカップリングさせることによっても、目的物を合成することができる。上記に例示した反応と同様に、カップリング反応には根岸カップリング反応などの常法が適宜使用できる。また、ここではボロン酸を使用した例を示したが、アリールボロン酸エステルを使用することもできる。
As shown in the following reaction 13, in the above reactions 3 to 7, the starting material was 9-bromoanthracene and a 5- (4- (anthracen-9-yl) phenyl) -bipyridine derivative was synthesized, and then the reaction 2 The desired product can also be synthesized by bromination by the method shown in the above and then coupling with various aryl boronic acids. As in the reactions exemplified above, conventional methods such as Negishi coupling reaction can be used as appropriate for the coupling reaction. Moreover, although the example which used boronic acid was shown here, aryl boronic acid ester can also be used.
カップリング反応で用いられるパラジウム触媒の具体例としては、テトラキス（トリフェニルホスフィン）パラジウム（０）：Ｐｄ（ＰＰｈ３）４、ビス（トリフェニルホスフィン）ジクロロパラジウム（II）：ＰｄＣｌ２（ＰＰｈ３）２、酢酸パラジウム（II）：Ｐｄ（ＯＡｃ）２、トリス（ジベンジリデンアセトン）二パラジウム（０）：Ｐｄ２（ｄｂａ）３、トリス（ジベンジリデンアセトン）二パラジウム（０）クロロホルム錯体：Ｐｄ２（ｄｂａ）３・ＣＨＣｌ３、ビス（ジベンジリデンアセトン）パラジウム（０）：Ｐｄ（ｄｂａ）２、ビス（トリｔ−ブチルホスフィノ）パラジウム（０）：Ｐｄ（Ｐ（ｔ−Ｂｕ）３）２、または［１，１’−ビス（ジフェニルホスフィノ）フェロセン］ジクロロパラジウム（II）：ＰｄＣｌ２（ｄｐｐｆ）があげられる。 Specific examples of the palladium catalyst used in the coupling reaction include tetrakis (triphenylphosphine) palladium (0): Pd (PPh 3 ) 4 , bis (triphenylphosphine) dichloropalladium (II): PdCl 2 (PPh 3 ). 2 , palladium acetate (II): Pd (OAc) 2 , tris (dibenzylideneacetone) dipalladium (0): Pd 2 (dba) 3 , tris (dibenzylideneacetone) dipalladium (0) chloroform complex: Pd 2 ( dba) 3 · CHCl 3 , bis (dibenzylideneacetone) palladium (0): Pd (dba) 2 , bis (tri-t-butylphosphino) palladium (0): Pd (P (t-Bu) 3 ) 2 , Or [1,1′-bis (diphenylphosphino) ferrocene] dichloropalladium (II ): PdCl 2 (dppf).
また、反応を促進させるため、場合によりこれらのパラジウム化合物にホスフィン化合物を加えてもよい。そのホスフィン化合物の具体例としては、トリ（ｔ−ブチル）ホスフィン、トリシクロヘキシルホスフィン、１−（Ｎ，Ｎ−ジメチルアミノメチル）−２−（ジｔ−ブチルホスフィノ）フェロセン、１−（Ｎ，Ｎ−ジブチルアミノメチル）−２−（ジｔ−ブチルホスフィノ）フェロセン、１−（メトキシメチル）−２−（ジｔ−ブチルホスフィノ）フェロセン、１，１’−ビス（ジｔ−ブチルホスフィノ）フェロセン、２，２’−ビス（ジｔ−ブチルホスフィノ）−１，１’−ビナフチル、２−メトキシ−２’−（ジｔ−ブチルホスフィノ）−１，１’−ビナフチル、または２−ジシクロヘキシルホスフィノ−２’，６’−ジメトキシビフェニルがあげられる。 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.
反応で用いられる塩基の具体例としては、炭酸ナトリウム、炭酸カリウム、炭酸セシウム、炭酸水素ナトリウム、水酸化ナトリウム、水酸化カリウム、水酸化バリウム、ナトリウムエトキシド、ナトリウムｔ−ブトキシド、酢酸ナトリウム、リン酸三カリウム、またはフッ化カリウムがあげられる。 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.
また、反応で用いられる溶媒の具体例としては、ベンゼン、トルエン、キシレン、１，２，４−トリメチルベンゼン、Ｎ，Ｎ−ジメチルホルムアミド、テトラヒドロフラン、ジエチルエーテル、ｔ−ブチルメチルエーテル、１，４−ジオキサン、メタノール、エタノール、シクロペンチルメチルエーテルまたはイソプロピルアルコールがあげられる。これらの溶媒は適宜選択でき、単独で用いてもよく、混合溶媒として用いてもよい。 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.
＜式（１−２−１）〜式（１−２−９５）で表される化合物の合成法＞
前記の反応３または反応１０において、４−メトキシフェニルボロン酸の代わりに３−メトキシフェニルボロン酸を使用すれば、同様に合成することができる。
<Synthesis Method of Compounds Represented by Formula (1-2-1) to Formula (1-295)>
In the above reaction 3 or reaction 10, if 3-methoxyphenylboronic acid is used in place of 4-methoxyphenylboronic acid, it can be synthesized in the same manner.
本発明の化合物を、有機ＥＬ素子における、電子注入層または電子輸送層に用いた場合、電界印加時において安定である。これらは、本発明の化合物が、電界発光型素子の電子注入材料、または電子輸送材料として優れていることを表す。ここで言う電子注入層とは陰極から有機層へ電子を受け取る層であり、電子輸送層とは注入された電子を発光層へ輸送するための層である。また、電子輸送層が電子注入層を兼ねることも可能である。それぞれの層に用いる材料を、電子注入材料および電子輸送材料という。 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.
＜有機ＥＬ素子の説明＞
本願の第２の発明は、電子注入層、または電子輸送層に、本発明の式（１）で表される化合物を含有する有機ＥＬ素子である。本発明の有機ＥＬ素子は駆動時の耐久性が高いという特徴を有する。
<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 is characterized by high durability during driving.
本発明の有機ＥＬ素子の構造は各種の態様があるが、基本的には陽極と陰極との間に少なくとも正孔輸送層、発光層、電子輸送層を挟持した多層構造である。素子の具体的な構成の例は、（１）陽極／正孔輸送層／発光層／電子輸送層／陰極、（２）陽極／正孔注入層／正孔輸送層／発光層／電子輸送層／陰極、（３）陽極／正孔注入層／正孔輸送層／発光層／電子輸送層／電子注入層／陰極、等である。 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.
本発明の化合物は、高い電子注入性および電子輸送性を持っているので、単体又は他の材料と併用して電子注入層、または電子輸送層に使用できる。本発明の有機ＥＬ素子は、本発明の電子輸送材料に他の材料を用いた正孔注入層、正孔輸送層、発光層、などを組み合わせることで、青色、緑色、赤色や白色の発光を得ることもできる。 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.
本発明の有機ＥＬ素子に使用できる発光材料または発光性ドーパントは、高分子学会編、高分子機能材料シリーズ“光機能材料”、共同出版(１９９１)、Ｐ２３６に記載されているような昼光蛍光材料、蛍光増白剤、レーザー色素、有機シンチレータ、各種の蛍光分析試薬等の発光材料、城戸淳二監修、“有機ＥＬ材料とディスプレイ”シーエムシー社出版（２００１）Ｐ１５５〜１５６に記載されているようなドーパント材料、Ｐ１７０〜１７２に記載されているような３重項材料の発光材料等である。 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.
発光材料または発光性ドーパントとして使用できる化合物は、多環芳香族化合物、ヘテロ芳香族化合物、有機金属錯体、色素、高分子系発光材料、スチリル誘導体、芳香族アミン誘導体、クマリン誘導体、ボラン誘導体、オキサジン誘導体、スピロ環を有する化合物、オキサジアゾール誘導体、フルオレン誘導体等である。多環芳香族化合物の例は、アントラセン誘導体、フェナントレン誘導体、ナフタセン誘導体、ピレン誘導体、クリセン誘導体、ペリレン誘導体、コロネン誘導体、ルブレン誘導体等である。ヘテロ芳香族化合物の例は、ジアルキルアミノ基またはジアリールアミノ基を有するオキサジアゾール誘導体、ピラゾロキノリン誘導体、ピリジン誘導体、ピラン誘導体、フェナントロリン誘導体、シロール誘導体、トリフェニルアミノ基を有するチオフェン誘導体、キナクリドン誘導体等である。有機金属錯体の例は、亜鉛、アルミニウム、ベリリウム、ユーロピウム、テルビウム、ジスプロシウム、イリジウム、白金、オスミウム、金、等と、キノリノール誘導体、ベンゾキサゾ−ル誘導体、ベンゾチアゾール誘導体、オキサジアゾール誘導体、チアジアゾール誘導体、ベンゾイミダゾール誘導体、ピロール誘導体、ピリジン誘導体、フェナントロリン誘導体等との錯体である。色素の例は、キサンテン誘導体、ポリメチン誘導体、ポルフィリン誘導体、クマリン誘導体、ジシアノメチレンピラン誘導体、ジシアノメチレンチオピラン誘導体、オキソベンズアントラセン誘導体、カルボスチリル誘導体、ペリレン誘導体、ベンゾオキサゾール誘導体、ベンゾチアゾール誘導体、ベンゾイミダゾール誘導体等の色素が挙げられる。高分子系発光材料の例は、ポリパラフェニルビニレン誘導体、ポリチオフェン誘導体、ポリビニルカルバゾ−ル誘導体、ポリシラン誘導体、ポリフルオレン誘導体、ポリパラフェニレン誘導体等である。スチリル誘導体の例は、アミン含有スチリル誘導体、スチリルアリーレン誘導体等である。 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.
本発明の有機ＥＬ素子に使用される他の電子輸送材料は、光導電材料において電子伝達化合物として使用できる化合物、有機ＥＬ素子の電子輸送層および電子注入層に使用できる化合物の中から任意に選択して用いることができる。 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.
このような電子輸送材料の具体例は、キノリノール系金属錯体、２，２’−ビピリジル誘導体、フェナントロリン誘導体、ジフェニルキノン誘導体、ペリレン誘導体、オキサジアゾール誘導体、チオフェン誘導体、トリアゾール誘導体、チアジアゾール誘導体、オキシン誘導体の金属錯体、キノキサリン誘導体、キノキサリン誘導体のポリマー、ベンザゾール類化合物、ガリウム錯体、ピラゾール誘導体、パ−フルオロ化フェニレン誘導体、トリアジン誘導体、ピラジン誘導体、ベンゾキノリン誘導体、イミダゾピリジン誘導体、ボラン誘導体等である。 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.
本発明の有機ＥＬ素子に使用される正孔注入材料および正孔輸送材料については、光導電材料において、正孔の電荷輸送材料として従来から慣用されている化合物や、有機ＥＬ素子の正孔注入層および正孔輸送層に使用されている公知のものの中から任意のものを選択して用いることができる。それらの具体例は、カルバゾ−ル誘導体、トリアリールアミン誘導体、フタロシアニン誘導体等である。 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.
本発明の有機ＥＬ素子を構成する各層は、各層を構成すべき材料を蒸着法、スピンコート法またはキャスト法等の方法で薄膜とすることにより、形成することができる。このようにして形成された各層の膜厚については特に限定はなく、材料の性質に応じて適宜設定することができるが、通常２ｎｍ〜５０００ｎｍの範囲である。なお、発光材料を薄膜化する方法は、均質な膜が得やすく、かつピンホールが生成しにくい等の点から蒸着法を採用するのが好ましい。蒸着法を用いて薄膜化する場合、その蒸着条件は、本発明の発光材料の種類により異なる。蒸着条件は一般的に、ボート加熱温度５０〜４００℃、真空度１０−６〜１０−３Ｐａ、蒸着速度０．０１〜５０ｎｍ／秒、基板温度−１５０〜＋３００℃、膜厚５ｎｍ〜５μｍの範囲で適宜設定することが好ましい。 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.
本発明の有機ＥＬ素子は、前記のいずれの構造であっても、基板に支持されていることが好ましい。基板は機械的強度、熱安定性および透明性を有するものであればよく、ガラス、透明プラスチックフィルム等を用いることができる。陽極物質は４ｅＶより大きな仕事関数を有する金属、合金、電気伝導性化合物およびこれらの混合物を用いることができる。その具体例は、Ａｕ等の金属、ＣｕＩ、インジウムチンオキシド（以下、ＩＴＯと略記する）、ＳｎＯ２、ＺｎＯ等である。 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.
陰極物質は４ｅＶより小さな仕事関数の金属、合金、電気伝導性化合物、およびこれらの混合物を使用できる。その具体例は、アルミニウム、カルシウム、マグネシウム、リチウム、マグネシウム合金、アルミニウム合金等である。合金の具体例は、アルミニウム／弗化リチウム、アルミニウム／リチウム、マグネシウム／銀、マグネシウム／インジウム等である。有機ＥＬ素子の発光を効率よく取り出すために、電極の少なくとも一方は光透過率を１０％以上にすることが望ましい。電極としてのシート抵抗は数百Ω／□以下にすることが好ましい。なお、膜厚は電極材料の性質にもよるが、通常１０ｎｍ〜１μｍ、好ましくは１０〜４００ｎｍの範囲に設定される。このような電極は、上述の電極物質を使用して、蒸着やスパッタリング等の方法で薄膜を形成させることにより作製することができる。 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.
次に、本発明の発光材料を用いて有機ＥＬ素子を作成する方法の一例として、前述の陽極／正孔注入層／正孔輸送層／発光層／本発明の電子輸送材料／陰極からなる有機ＥＬ素子の作成法について説明する。適当な基板上に、陽極材料の薄膜を蒸着法により形成させて陽極を作製した後、この陽極上に正孔注入層および正孔輸送層の薄膜を形成させる。この上に発光層の薄膜を形成させる。この発光層の上に本発明の電子輸送材料を真空蒸着し、薄膜を形成させ、電子輸送層とする。さらに陰極用物質からなる薄膜を蒸着法により形成させて陰極とすることにより、目的の有機ＥＬ素子が得られる。なお、上述の有機ＥＬ素子の作製においては、作製順序を逆にして、陰極、電子輸送層、発光層、正孔輸送層、正孔注入層、陽極の順に作製することも可能である。 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.
このようにして得られた有機ＥＬ素子に直流電圧を印加する場合には、陽極を＋、陰極を−の極性として印加すればよく、電圧２〜４０Ｖ程度を印加すると、透明又は半透明の電極側（陽極又は陰極、および両方）より発光が観測できる。また、この有機ＥＬ素子は、交流電圧を印加した場合にも発光する。なお、印加する交流の波形は任意でよい。 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.
以下に、本発明を実施例に基づいて更に詳しく説明する。まず、実施例で用いた化合物の合成例について、以下に説明する。 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.
［合成例１］化合物（１−１−７０）の合成
＜５−（４−（メトキシフェニル）−３，４’−ビピリジンの合成＞
窒素雰囲気下、５−ブロモ−３，４’−ビピリジン（５．９ｇ）、パラメトキシフェニルボロン酸（４．２ｇ）、Ｐｄ（ＰＰｈ３）４（０．９ｇ）、リン酸カリウム（１０．６ｇ）、１，２，４−トリメチルベンゼン（５０ｍｌ）、ｔ−ブチルアルコール（５ｍｌ）および水（１ｍｌ）の入ったフラスコを還流温度で１時間撹拌した。反応液を室温まで冷却した後、水およびトルエンを加え分液した。溶媒を減圧留去した後、シリカゲルカラムクロマトグラフィー（トルエン／酢酸エチル＝１／１（容積比））で精製し、５−（４−（メトキシフェニル）−３，４’−ビピリジン（２．８ｇ）を得た。
[Synthesis Example 1] Synthesis of Compound (1-1-70) <Synthesis of 5- (4- (methoxyphenyl) -3,4'-bipyridine>
Under a nitrogen atmosphere, 5-bromo-3,4'-bipyridine (5.9 g), paramethoxyphenylboronic acid (4.2 g), Pd (PPh 3 ) 4 (0.9 g), potassium phosphate (10.6 g) ), 1,2,4-trimethylbenzene (50 ml), t-butyl alcohol (5 ml) and water (1 ml) were stirred at reflux temperature for 1 hour. After the reaction solution was cooled to room temperature, water and toluene were added for liquid separation. After distilling off the solvent under reduced pressure, the residue was purified by silica gel column chromatography (toluene / ethyl acetate = 1/1 (volume ratio)) to give 5- (4- (methoxyphenyl) -3,4'-bipyridine (2.8 g). )
＜４−（［３，４’−ビピリジン］−５−イル）フェノールの合成＞
５−（４−（メトキシフェニル）−３，４’−ビピリジン（２．８ｇ）およびピリジン塩酸塩（６．３ｇ）の入ったフラスコを、窒素雰囲気下、１９０℃で４時間撹拌した。反応液を室温まで冷却した後、炭酸水素ナトリウム水溶液で中和して析出した沈殿を吸引濾過にて採取した。この沈殿を水、次いでメタノールで洗浄し、４−（［３，４’−ビピリジン］−５−イル）フェノール（１．２ｇ）を得た。
<Synthesis of 4-([3,4'-bipyridin] -5-yl) phenol>
A flask containing 5- (4- (methoxyphenyl) -3,4'-bipyridine (2.8 g) and pyridine hydrochloride (6.3 g) was stirred under a nitrogen atmosphere at 190 ° C. for 4 hours. Was cooled to room temperature, neutralized with an aqueous sodium hydrogen carbonate solution, and the deposited precipitate was collected by suction filtration, washed with water and then with methanol, and 4-([3,4'-bipyridine]- 5-yl) phenol (1.2 g) was obtained.
＜４−（［３，４’−ビピリジン］−５−イル）フェニル トリフルオロメタンスルホネートの合成＞
４−（［３，４’−ビピリジン］−５−イル）フェノール（１．２ｇ）およびピリジン（１０ｍｌ）を入れたフラスコを氷浴で冷却し、窒素雰囲気下、トリフルオロメタンスルホン酸無水物（１．７ｇ）を滴下した。滴下終了後、室温で３０分撹拌した後、水を加え反応を停止した。析出した沈殿を吸引濾過にて採取した後、得られた沈殿をメタノール／水混合溶媒にて再沈殿を行い、４−（［３，４’−ビピリジン］−５−イル）フェニルトリフルオロメタンスルホネート（１．７ｇ）を得た。
<Synthesis of 4-([3,4'-bipyridin] -5-yl) phenyl trifluoromethanesulfonate>
A flask containing 4-([3,4'-bipyridin] -5-yl) phenol (1.2 g) and pyridine (10 ml) was cooled in an ice bath and trifluoromethanesulfonic anhydride (1 0.7 g) was added dropwise. After completion of the dropwise addition, the mixture was stirred at room temperature for 30 minutes, and water was added to stop the reaction. After collecting the deposited precipitate by suction filtration, the obtained precipitate was reprecipitated with a methanol / water mixed solvent, and 4-([3,4'-bipyridin] -5-yl) phenyl trifluoromethanesulfonate ( 1.7 g) was obtained.
＜化合物（１−１−７０）の合成＞
市販品である（１０−（ナフタレン−１−イル）アントラセン−９−イル）ボロン酸（２．９ｇ）、４−（［３，４’−ビピリジン］−５−イル）フェニルトリフルオロメタンスルホネート（１．７ｇ）、Ｐｄ（ＰＰｈ３）４（０．２ｇ）、リン酸カリウム（２．０ｇ）、１，２，４−トリメチルベンゼン（１２ｍｌ）、ｔ−ブチルアルコール（３ｍｌ）および水（１ｍｌ）の入ったフラスコを還流温度で６．５時間撹拌した。反応液を室温まで冷却した後、水およびトルエンを加え分液した。溶媒を減圧留去した後、シリカゲルカラムクロマトグラフィー（トルエン／酢酸エチル＝１／１（容積比））で精製し、溶媒を減圧留去した。更にクロロベンゼンから再結晶し、式（１−１−７０）で表される化合物：５−（４−（１０−（ナフタレン−１−イル）アントラセン−９−イル）フェニル）−３，４’−ビピリジン（０．７ｇ）を得た。ＮＭＲ測定により化合物の構造を確認した。
１Ｈ−ＮＭＲ（ＣＤＣｌ３）： δ＝９．１２（ｍ，１Ｈ）， ８．９６（ｍ，１Ｈ）， ８．７９（ｄｄ，２Ｈ）， ８．３０（ｍ，１Ｈ）， ８．０８（ｄ，１Ｈ）， ８．０３（ｄ，１Ｈ）， ７．９３（ｔ，２Ｈ）， ７．８０（ｄ，２Ｈ）， ７．６９−７．７６（ｍ，３Ｈ）， ７．６６（ｄｄ，２Ｈ）， ７．５９（ｄｄ，１Ｈ）， ７．４５−７．５２（ｍ，３Ｈ）， ７．３７（ｍ，２Ｈ）， ７．１７−７．２６（ｍ，４Ｈ）．
<Synthesis of Compound (1-1-70)>
Commercially available (10- (naphthalen-1-yl) anthracen-9-yl) boronic acid (2.9 g), 4-([3,4′-bipyridin] -5-yl) phenyl trifluoromethanesulfonate (1 0.7 g), Pd (PPh 3 ) 4 (0.2 g), potassium phosphate (2.0 g), 1,2,4-trimethylbenzene (12 ml), t-butyl alcohol (3 ml) and water (1 ml). The flask in was stirred at reflux temperature for 6.5 hours. After the reaction solution was cooled to room temperature, water and toluene were added for liquid separation. After the solvent was distilled off under reduced pressure, the residue was purified by silica gel column chromatography (toluene / ethyl acetate = 1/1 (volume ratio)), and the solvent was distilled off under reduced pressure. Further, recrystallization from chlorobenzene gave a compound represented by the formula (1-1-70): 5- (4- (10- (naphthalen-1-yl) anthracen-9-yl) phenyl) -3,4'- Bipyridine (0.7 g) was obtained. The structure of the compound was confirmed by NMR measurement.
1 H-NMR (CDCl 3 ): δ = 9.12 (m, 1H), 8.96 (m, 1H), 8.79 (dd, 2H), 8.30 (m, 1H), 8.08 (D, 1H), 8.03 (d, 1H), 7.93 (t, 2H), 7.80 (d, 2H), 7.69-7.76 (m, 3H), 7.66 ( dd, 2H), 7.59 (dd, 1H), 7.45-7.52 (m, 3H), 7.37 (m, 2H), 7.17-7.26 (m, 4H).
［合成例２］化合物（１−１−２）の合成
＜９−（４−メトキシフェニル）−１０−（ナフタレン−１−イル）アントラセンの合成＞
市販品である９−ブロモ−１０−（ナフタレン−１−イル）アントラセン（４６．０ｇ）、（４−メトキシフェニル）ボロン酸（２０．１ｇ）、Ｐｄ（ＰＰｈ３）４（１．４ｇ）、リン酸カリウム（５０．９ｇ）、１，２，４−トリメチルベンゼン（３００ｍｌ）、ｔ−ブチルアルコール（６０ｍｌ）および水（１２ｍｌ）をフラスコに入れ、窒素雰囲気下、還流温度で８時間攪拌した。反応の進行が遅かった為、更にＰｄ（ＰＰｈ３）４（１．３９ｇ）を追加し９時間攪拌した。反応液を室温まで冷却し水を加え、吸引濾過にて固体を採取し、次いでシリカゲルショートカラム（展開液：トルエン）で精製し、溶出液を濃縮して、９−（４−メトキシフェニル）−１０−（ナフタレン−１−イル）アントラセン（４６．５ｇ）を得た。
Synthesis Example 2 Synthesis of Compound (1-1-2) <Synthesis of 9- (4-methoxyphenyl) -10- (naphthalen-1-yl) anthracene>
Commercially available 9-bromo-10- (naphthalen-1-yl) anthracene (46.0 g), (4-methoxyphenyl) boronic acid (20.1 g), Pd (PPh 3 ) 4 (1.4 g), Potassium phosphate (50.9 g), 1,2,4-trimethylbenzene (300 ml), t-butyl alcohol (60 ml) and water (12 ml) were placed in a flask and stirred at reflux temperature for 8 hours under a nitrogen atmosphere. Since the progress of the reaction was slow, Pd (PPh 3 ) 4 (1.39 g) was further added and stirred for 9 hours. The reaction solution was cooled to room temperature, water was added, and the solid was collected by suction filtration, then purified with a silica gel short column (developing solution: toluene), the eluate was concentrated, and 9- (4-methoxyphenyl)- 10- (Naphthalen-1-yl) anthracene (46.5 g) was obtained.
＜４−（１０−（ナフタレン−１−イル）アントラセン−９−イル）フェノールの合成＞
窒素雰囲気下、９−（４−メトキシフェニル）−１０−（ナフタレン−１−イル）アントラセン（４５．２ｇ）、ピリジン塩酸塩（６３．８ｇ）、Ｎ−メチルピロリドン（５０ｍｌ）をフラスコに入れ、還流温度で５時間攪拌した。反応液を室温まで冷却し水を加え、不溶性の固体を採取した。得られた固体を温水で洗浄し、更にメタノールで洗浄して、４−（１０−（ナフタレン−１−イル）アントラセン−９−イル）フェノール（４２．０ｇ）を得た。
<Synthesis of 4- (10- (naphthalen-1-yl) anthracen-9-yl) phenol>
Under a nitrogen atmosphere, 9- (4-methoxyphenyl) -10- (naphthalen-1-yl) anthracene (45.2 g), pyridine hydrochloride (63.8 g), N-methylpyrrolidone (50 ml) was placed in the flask. Stir at reflux for 5 hours. The reaction solution was cooled to room temperature, water was added, and an insoluble solid was collected. The obtained solid was washed with warm water and further washed with methanol to obtain 4- (10- (naphthalen-1-yl) anthracen-9-yl) phenol (42.0 g).
＜４−（１０−（ナフタレン−１−イル）アントラセン−９−イル）フェニル トリフルオロメタンスルホナートの合成＞
窒素雰囲気下、４−（１０−ナフタレン−１−イル）アントラセン−９−イル）フェノール（１８．０ｇ）、ピリジン（脱水）（１３０ｍｌ）の入ったフラスコを、氷浴で冷却した。次いで、トリフルオロメタンスルホン酸無水物（１１．２ｍｌ）をこの溶液に滴下した。滴下終了後氷浴を外し、室温で８時間撹拌し、水を加え反応を停止した。生成した固体を吸引濾過にて採取し、水、次いで２−プロパノールで洗浄した。得られた固体をシリカゲルカラムクロマトグラフィー（トルエン）で精製した後、トルエン／ヘプタン混合溶媒にて再沈殿を行い、４−（１０−（ナフタレン−１−イル）アントラセン−９−イル）フェニル トリフルオロメタンスルホナート（１５．０ｇ）を得た。
<Synthesis of 4- (10- (naphthalen-1-yl) anthracen-9-yl) phenyl trifluoromethanesulfonate>
Under a nitrogen atmosphere, a flask containing 4- (10-naphthalen-1-yl) anthracen-9-yl) phenol (18.0 g) and pyridine (dehydrated) (130 ml) was cooled in an ice bath. Then trifluoromethanesulfonic anhydride (11.2 ml) was added dropwise to this solution. After completion of the dropwise addition, the ice bath was removed, the mixture was stirred at room temperature for 8 hours, and water was added to stop the reaction. The produced solid was collected by suction filtration and washed with water and then 2-propanol. The obtained solid was purified by silica gel column chromatography (toluene), and then reprecipitated with a toluene / heptane mixed solvent to give 4- (10- (naphthalen-1-yl) anthracen-9-yl) phenyl trifluoromethane. Sulfonate (15.0 g) was obtained.
＜４，４，５，５−テトラメチル−２−（４−（１０−（ナフタレン−１−イル）アントラセン−９−イル−）フェニル）−１，３，２−ジオキサボロランの合成＞
窒素雰囲気下、４−（１０−（ナフタレン−１−イル）アントラセン−９−イル）フェニル トリフルオロメタンスルホナート（１５．０ｇ）、ビスピナコラートジボロン（８．６ｇ）、酢酸カリウム（５．６ｇ）、ＰｄＣｌ２（ｄｐｐｆ）（０．７ｇ）およびシクロペンチルメチルエーテル（１３０ｍｌ）の入ったフラスコを還流温度で７時間撹拌した。反応液を室温まで冷却した後、水およびトルエンを加え分液し、溶媒を減圧留去した。得られた固体をシリカゲルショートカラム（トルエン）で精製し、４，４，５，５−テトラメチル−２−（４−（１０−（ナフタレン−１−イル）アントラセン−９−イル−）フェニル）−１，３，２−ジオキサボロラン（１１．２ｇ）を得た。
<Synthesis of 4,4,5,5-tetramethyl-2- (4- (10- (naphthalen-1-yl) anthracen-9-yl-) phenyl) -1,3,2-dioxaborolane>
Under a nitrogen atmosphere, 4- (10- (naphthalen-1-yl) anthracen-9-yl) phenyl trifluoromethanesulfonate (15.0 g), bispinacolato diboron (8.6 g), potassium acetate (5.6 g) ), PdCl 2 (dppf) (0.7 g) and cyclopentyl methyl ether (130 ml) were stirred at reflux temperature for 7 hours. 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 solid was purified with a silica gel short column (toluene) and 4,4,5,5-tetramethyl-2- (4- (10- (naphthalen-1-yl) anthracen-9-yl-) phenyl). -1,3,2-dioxaborolane (11.2 g) was obtained.
＜化合物（１−１−２）の合成＞
４，４，５，５−テトラメチル−２−（４−（１０−（ナフタレン−１−イル）アントラセン−９−イル−）フェニル）−１，３，２−ジオキサボロラン（１．５ｇ）、５’−ブロモ−２，３’−ビピリジン（０．８ｇ）、Ｐｄ（ＰＰｈ３）４（０．２ｇ）、リン酸カリウム（１．３ｇ）、１，２，４−トリメチルベンゼン（１０ｍｌ）、ｔ−ブチルアルコール（１ｍｌ）および水（１ｍｌ）の入ったフラスコを還流温度で１０時間撹拌した。反応液を室温まで冷却した後、水およびトルエンを加え分液した。溶媒を減圧留去した後、シリカゲルカラムクロマトグラフィー（トルエン／酢酸エチル）で精製した。この際、「有機化学実験のてびき（１）−物質取扱法と分離精製法−」株式会社化学同人出版、９４頁に記載の方法を参考にして、展開液中の酢酸エチルの比率を徐々に増加させて目的物を溶出させた。溶出液の溶媒を減圧留去し、トルエンから再結晶して、式（１−１−２）で表される化合物：５’−（４−（１０−（ナフタレン−１−イル）アントラセン−９−イル）フェニル）−２，３’−ビピリジン（０．８ｇ）を得た。ＮＭＲ測定により化合物の構造を確認した。
１Ｈ−ＮＭＲ（ＣＤＣｌ３）： δ＝９．２４（ｍ，１Ｈ）， ９．１０（ｍ，１Ｈ）， ８．８０（ｄ，１Ｈ）， ８．７６（ｍ，１Ｈ）， ８．０８（ｄ，１Ｈ）， ８．０３（ｄ，１Ｈ）， ７．９７（ｔ，２Ｈ）， ７．９１（ｍ，１Ｈ）， ７．８７（ｔ，１Ｈ）， ７．８１（ｄ，２Ｈ）， ７．７３（ｄ，２Ｈ）， ７．６９（ｔ，１Ｈ）， ７．５９（ｄ，１Ｈ）， ７．５０（ｔ，１Ｈ）， ７．４７（ｄ，２Ｈ）， ７．３６（ｍ，３Ｈ）， ７．１３−７．２７（ｍ，４Ｈ）．
<Synthesis of Compound (1-1-2)>
4,4,5,5-tetramethyl-2- (4- (10- (naphthalen-1-yl) anthracen-9-yl-) phenyl) -1,3,2-dioxaborolane (1.5 g), 5 '-Bromo-2,3'-bipyridine (0.8 g), Pd (PPh 3 ) 4 (0.2 g), potassium phosphate (1.3 g), 1,2,4-trimethylbenzene (10 ml), t A flask containing butyl alcohol (1 ml) and water (1 ml) was stirred at reflux temperature for 10 hours. After the reaction solution was cooled to room temperature, water and toluene were added for liquid separation. After the solvent was distilled off under reduced pressure, the residue was purified by silica gel column chromatography (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. The solvent of the eluate was distilled off under reduced pressure, recrystallized from toluene, and the compound represented by the formula (1-1-2): 5 ′-(4- (10- (naphthalen-1-yl) anthracene-9 -Il) 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 = 9.24 (m, 1H), 9.10 (m, 1H), 8.80 (d, 1H), 8.76 (m, 1H), 8.08 (D, 1H), 8.03 (d, 1H), 7.97 (t, 2H), 7.91 (m, 1H), 7.87 (t, 1H), 7.81 (d, 2H) , 7.73 (d, 2H), 7.69 (t, 1H), 7.59 (d, 1H), 7.50 (t, 1H), 7.47 (d, 2H), 7.36 ( m, 3H), 7.13-7.27 (m, 4H).
［合成例３］化合物（１−１−３６）の合成
＜化合物（１−１−３６）の合成＞
４，４，５，５−テトラメチル−２−（４−（１０−（ナフタレン−１−イル）アントラセン−９−イル−）フェニル）−１，３，２−ジオキサボロラン（１．５ｇ）、５−ブロモ−３，３’−ビピリジン（０．８ｇ）、Ｐｄ（ＰＰｈ３）４（０．２ｇ）、リン酸カリウム（１．３ｇ）、１，２，４−トリメチルベンゼン（１０ｍｌ）、ｔ−ブチルアルコール（１ｍｌ）および水（１ｍｌ）の入ったフラスコを還流温度で３時間半撹拌した。反応液を室温まで冷却した後、水およびトルエンを加え分液した。溶媒を減圧留去した後、シリカゲルカラムクロマトグラフィー（トルエン／酢酸エチル）で精製した。この際、展開液中の酢酸エチルの比率を徐々に増加させて目的物を溶出させた。溶出液の溶媒を減圧留去し、トルエンから再結晶して、式（１−１−３６）で表される化合物：５−（４−（１０−（ナフタレン−１−イル）アントラセン−９−イル）フェニル）−３，３’−ビピリジン（０．５ｇ）を得た。ＮＭＲ測定により化合物の構造を確認した。
１Ｈ−ＮＭＲ（ＣＤＣｌ３）： δ＝９．１０（ｍ，１Ｈ）， ９．００（ｍ，１Ｈ）， ８．９１（ｍ，１Ｈ）， ８．７２（ｄｄ，１Ｈ）， ８．２６（ｍ，１Ｈ）， ８．０８（ｄ，１Ｈ）， ８．０３（ｄ，２Ｈ）， ７．９４（ｔ，２Ｈ）， ７．８１（ｄ，２Ｈ）， ７．６７−７．７６（ｍ，３Ｈ）， ７．５８（ｄ，１Ｈ）， ７．４５−７．５２（ｍ，４Ｈ）， ７．３７（ｍ，２Ｈ）， ７．２０−７．３０（ｍ，３Ｈ）， ７．１８（ｍ，１Ｈ）．
[Synthesis Example 3] Synthesis of Compound (1-1-36) <Synthesis of Compound (1-1-36)>
4,4,5,5-tetramethyl-2- (4- (10- (naphthalen-1-yl) anthracen-9-yl-) phenyl) -1,3,2-dioxaborolane (1.5 g), 5 -Bromo-3,3'-bipyridine (0.8 g), Pd (PPh 3 ) 4 (0.2 g), potassium phosphate (1.3 g), 1,2,4-trimethylbenzene (10 ml), t- A flask containing butyl alcohol (1 ml) and water (1 ml) was stirred at reflux temperature for 3.5 hours. After the reaction solution was cooled to room temperature, water and toluene were added for liquid separation. After the solvent was distilled off under reduced pressure, the residue was purified by silica gel column chromatography (toluene / ethyl acetate). At this time, the target product was eluted by gradually increasing the ratio of ethyl acetate in the developing solution. The solvent of the eluate was distilled off under reduced pressure, recrystallized from toluene, and the compound represented by the formula (1-1-36): 5- (4- (10- (naphthalen-1-yl) anthracene-9- Yl) phenyl) -3,3′-bipyridine (0.5 g) was obtained. The structure of the compound was confirmed by NMR measurement.
1 H-NMR (CDCl 3 ): δ = 9.10 (m, 1H), 9.00 (m, 1H), 8.91 (m, 1H), 8.72 (dd, 1H), 8.26 (M, 1H), 8.08 (d, 1H), 8.03 (d, 2H), 7.94 (t, 2H), 7.81 (d, 2H), 7.67-7.76 ( m, 3H), 7.58 (d, 1H), 7.45-7.52 (m, 4H), 7.37 (m, 2H), 7.20-7.30 (m, 3H), 7 .18 (m, 1H).
［合成例４］化合物（１−２−６８）の合成
＜９−（３−メトキシフェニル）−１０−（ナフタレン−１−イル）アントラセンの合成＞
窒素雰囲気下、市販品である９−ブロモ−１０−（ナフタレン−１−イル）アントラセン（３０．０ｇ）、（３−メトキシ）フェニルボロン酸（１３．１ｇ）、Ｐｄ（ＰＰｈ３）４（２．７ｇ）、リン酸カリウム（３３．３ｇ）、１，２，４−トリメチルベンゼン（２００ｍｌ）、ｔ−ブチルアルコール（２０ｍｌ）および水（２０ｍｌ）の入ったフラスコを還流温度で４時間撹拌した。反応液を室温まで冷却し、水を加え生成した固体を吸引濾過にて採取し、シリカゲルショートカラム（トルエン）で精製した。溶出液を減圧留去し、ヘプタンを加えて再沈殿を行い、９−（３−メトキシフェニル）−１０−（ナフタレン−１−イル）アントラセン（３２．０ｇ）を得た。
Synthesis Example 4 Synthesis of Compound (1-268) <Synthesis of 9- (3-methoxyphenyl) -10- (naphthalen-1-yl) anthracene>
9-Bromo-10- (naphthalen-1-yl) anthracene (30.0 g), (3-methoxy) phenylboronic acid (13.1 g), Pd (PPh 3 ) 4 (2 0.7 g), potassium phosphate (33.3 g), 1,2,4-trimethylbenzene (200 ml), t-butyl alcohol (20 ml) and water (20 ml) were stirred at reflux temperature for 4 hours. The reaction solution was cooled to room temperature, water was added and the resulting solid was collected by suction filtration and purified with a silica gel short column (toluene). The eluate was distilled off under reduced pressure, and heptane was added for reprecipitation to obtain 9- (3-methoxyphenyl) -10- (naphthalen-1-yl) anthracene (32.0 g).
＜３−（１０−（ナフタレン−１−イル）アントラセン−９−イル）フェノールの合成＞
窒素雰囲気下、９−（３−メトキシフェニル）−１０−（ナフタレン−１−イル）アントラセン（３２．０ｇ）、ピリジン塩酸塩（４５．０ｇ）および１−メチル−２−ピロリドン（ＮＭＰ）（３０ｍｌ）の入ったフラスコを２００℃で７時間加熱撹拌した。反応液を室温まで冷却し、水を加え生成した固体を、吸引濾過にて採取した。得られた固体を更に温水で洗浄した後、トルエンから再結晶し、３−（１０−（ナフタレン−１−イル）アントラセン−９−イル）フェノール（３３．５ｇ）を得た。ここで得られた３−（１０−（ナフタレン−１−イル）アントラセン−９−イル）フェノールはＮＭＰを僅かに含んでいたが、次工程にそのまま使用した。
<Synthesis of 3- (10- (naphthalen-1-yl) anthracen-9-yl) phenol>
9- (3-methoxyphenyl) -10- (naphthalen-1-yl) anthracene (32.0 g), pyridine hydrochloride (45.0 g) and 1-methyl-2-pyrrolidone (NMP) (30 ml) under nitrogen atmosphere ) Was stirred with heating at 200 ° C. for 7 hours. The reaction solution was cooled to room temperature, water was added, and the resulting solid was collected by suction filtration. The obtained solid was further washed with warm water and then recrystallized from toluene to obtain 3- (10- (naphthalen-1-yl) anthracen-9-yl) phenol (33.5 g). The 3- (10- (naphthalen-1-yl) anthracen-9-yl) phenol obtained here contained a little NMP, but was used as it was in the next step.
＜３−（１０−（ナフタレン−１−イル）アントラセン−９−イル）フェニル トリフルオロメタンスルホナートの合成＞
窒素雰囲気下、３−（１０−ナフタレン−１−イル）アントラセン−９−イル）フェノール（３３．０ｇ）、ピリジン（脱水）（２４０ｍｌ）の入ったフラスコを、氷浴で冷却した。次いで、トリフルオロメタンスルホン酸無水物（３１．０ｍｌ）をこの溶液に滴下した。滴下終了後氷浴を外し、室温で８時間撹拌し、水を加え反応を停止した。生成した固体を吸引濾過にて採取し、水、次いでメタノールで洗浄した。得られた固体をシリカゲルカラムクロマトグラフィー（トルエン）で精製し、溶出液の溶媒を減圧留去して、３−（１０−（ナフタレン−１−イル）アントラセン−９−イル）フェニル トリフルオロメタンスルホナート（２８．０ｇ）を得た。
<Synthesis of 3- (10- (naphthalen-1-yl) anthracen-9-yl) phenyl trifluoromethanesulfonate>
Under a nitrogen atmosphere, a flask containing 3- (10-naphthalen-1-yl) anthracen-9-yl) phenol (33.0 g) and pyridine (dehydrated) (240 ml) was cooled in an ice bath. Then trifluoromethanesulfonic anhydride (31.0 ml) was added dropwise to this solution. After completion of the dropwise addition, the ice bath was removed, the mixture was stirred at room temperature for 8 hours, and water was added to stop the reaction. The produced solid was collected by suction filtration and washed with water and then methanol. The obtained solid was purified by silica gel column chromatography (toluene), the solvent of the eluate was distilled off under reduced pressure, and 3- (10- (naphthalen-1-yl) anthracen-9-yl) phenyl trifluoromethanesulfonate was obtained. (28.0 g) was obtained.
＜４，４，５，５−テトラメチル−２−（３−（１０−（ナフタレン−１−イル）アントラセン−９−イル−）フェニル）−１，３，２−ジオキサボロランの合成＞
窒素雰囲気下、３−（１０−（ナフタレン−１−イル）アントラセン−９−イル）フェニル トリフルオロメタンスルホナート（２８．０ｇ）、ビスピナコラートジボロン（１６．２ｇ）、酢酸カリウム（１０．４ｇ）、ＰｄＣｌ２（ｄｐｐｆ）（１．３ｇ）およびシクロペンチルメチルエーテル（１８０ｍｌ）の入ったフラスコを還流温度で３時間撹拌した。反応液を室温まで冷却した後、水およびトルエンを加え分液し、溶媒を減圧留去した。得られた固体を活性炭ショートカラム（トルエン）で精製し、更にトルエン／ヘプタンで再沈殿し、４，４，５，５−テトラメチル−２−（３−（１０−（ナフタレン−１−イル）アントラセン−９−イル−）フェニル）−１，３，２−ジオキサボロラン（２０．０ｇ）を得た。
<Synthesis of 4,4,5,5-tetramethyl-2- (3- (10- (naphthalen-1-yl) anthracen-9-yl-) phenyl) -1,3,2-dioxaborolane>
Under a nitrogen atmosphere, 3- (10- (naphthalen-1-yl) anthracen-9-yl) phenyl trifluoromethanesulfonate (28.0 g), bispinacolatodiboron (16.2 g), potassium acetate (10.4 g) ), PdCl 2 (dppf) (1.3 g) and cyclopentyl methyl ether (180 ml) were stirred at reflux temperature for 3 hours. 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 solid was purified with an activated carbon short column (toluene) and reprecipitated with toluene / heptane, and 4,4,5,5-tetramethyl-2- (3- (10- (naphthalen-1-yl) was obtained. Anthracen-9-yl-) phenyl) -1,3,2-dioxaborolane (20.0 g) was obtained.
＜化合物（１−２−６８）の合成＞
４，４，５，５−テトラメチル−２−（３−（１０−（ナフタレン−１−イル）アントラセン−９−イル−）フェニル）−１，３，２−ジオキサボロラン（２．０ｇ）、５−ブロモ−３，４’−ビピリジン（１．１ｇ）、Ｐｄ（ＰＰｈ３）４（０．２ｇ）、リン酸カリウム（２．０ｇ）、１，２，４−トリメチルベンゼン（１０ｍｌ）、ｔ−ブチルアルコール（１ｍｌ）および水（１ｍｌ）の入ったフラスコを還流温度で４時間撹拌した。反応液を室温まで冷却した後、水およびトルエンを加え分液した。溶媒を減圧留去した後、シリカゲルカラムクロマトグラフィー（トルエン／酢酸エチル）で精製した。この際、展開液中の酢酸エチルの比率を徐々に増加させて目的物を溶出させた。更にトルエンから再結晶し、式（１−２−６８）で表される化合物：５−（３−（１０−（ナフタレン−１−イル）アントラセン−９−イル）フェニル）−３，４’−ビピリジン（１．７ｇ）を得た。ＮＭＲ測定により化合物の構造を確認した。
１Ｈ−ＮＭＲ（ＣＤＣｌ３）： δ＝９．０６（ｄｄ，１Ｈ）， ８．８８（ｍ，１Ｈ） ，８．７０（ｔ，２Ｈ）， ８．１９（ｄ，１Ｈ）， ８．０８（ｄ，１Ｈ）， ８．０３（ｄ，１Ｈ）， ７．８８（ｍ，２Ｈ）， ７．８０（ｍ，４Ｈ）， ７．６２−７．７５（ｍ，２Ｈ）， ７．５７（ｍ，３Ｈ）， ７．４８（ｍ，３Ｈ）， ７．３５（ｔ，２Ｈ）, ７．１５−７．２８（ｍ，３Ｈ）．
<Synthesis of Compound (1-268)>
4,4,5,5-tetramethyl-2- (3- (10- (naphthalen-1-yl) anthracen-9-yl-) phenyl) -1,3,2-dioxaborolane (2.0 g), 5 -Bromo-3,4'-bipyridine (1.1 g), Pd (PPh 3 ) 4 (0.2 g), potassium phosphate (2.0 g), 1,2,4-trimethylbenzene (10 ml), t- A flask containing butyl alcohol (1 ml) and water (1 ml) was stirred at reflux temperature for 4 hours. After the reaction solution was cooled to room temperature, water and toluene were added for liquid separation. After the solvent was distilled off under reduced pressure, the residue was purified by silica gel column chromatography (toluene / ethyl acetate). At this time, the target product was eluted by gradually increasing the ratio of ethyl acetate in the developing solution. Further, recrystallization from toluene gave a compound represented by the formula (1-2-68): 5- (3- (10- (naphthalen-1-yl) anthracen-9-yl) phenyl) -3,4'- Bipyridine (1.7 g) was obtained. The structure of the compound was confirmed by NMR measurement.
1 H-NMR (CDCl 3 ): δ = 9.06 (dd, 1H), 8.88 (m, 1H), 8.70 (t, 2H), 8.19 (d, 1H), 8.08 (D, 1H), 8.03 (d, 1H), 7.88 (m, 2H), 7.80 (m, 4H), 7.62-7.75 (m, 2H), 7.57 ( m, 3H), 7.48 (m, 3H), 7.35 (t, 2H), 7.15-7.28 (m, 3H).
［合成例５］化合物（１−２−７４）の合成
＜９−（３−メトキシフェニル）アントラセンの合成＞
窒素雰囲気下、９−ブロモアントラセン（３０．０ｇ）、（３−メトキシ）フェニルボロン酸（１９．５ｇ）、Ｐｄ（ＰＰｈ３）４（４．１ｇ）、リン酸カリウム（４９．５ｇ）、１，２，４−トリメチルベンゼン（２５０ｍｌ）、ｔ−ブチルアルコール（２０ｍｌ）および水（２０ｍｌ）の入ったフラスコを還流温度で６時間撹拌した。反応液を室温まで冷却し、トルエンを加え、不溶分をセライトを敷いた桐山ロートで濾別した。この溶液に水を加え分液し、溶媒を減圧留去し得られた固体をシリカゲルカラムクロマトグラフィー（トルエン／ヘプタン＝１／３（容量比））にて精製し、溶出液の溶媒を減圧留去して９−（３−メトキシフェニル）アントラセン（３２．０ｇ）を得た。
Synthesis Example 5 Synthesis of Compound (1-274) <Synthesis of 9- (3-methoxyphenyl) anthracene>
Under a nitrogen atmosphere, 9-bromoanthracene (30.0 g), (3-methoxy) phenylboronic acid (19.5 g), Pd (PPh 3 ) 4 (4.1 g), potassium phosphate (49.5 g), 1 , 2,4-Trimethylbenzene (250 ml), t-butyl alcohol (20 ml) and water (20 ml) were stirred at reflux temperature for 6 hours. The reaction solution was cooled to room temperature, toluene was added, and the insoluble matter was filtered off with a Kiriyama funnel with celite. Water was added to the solution for liquid separation, the solvent was distilled off under reduced pressure, and the resulting solid was purified by silica gel column chromatography (toluene / heptane = 1/3 (volume ratio)), and the solvent of the eluate was distilled under reduced pressure. This gave 9- (3-methoxyphenyl) anthracene (32.0 g).
＜３−（アントラセン−９−イル）フェノールの合成＞
窒素雰囲気下、９−（３−メトキシフェニル）アントラセン（３２．０ｇ）、ピリジン塩酸塩（７５．０ｇ）およびＮＭＰ（２０ｍｌ）の入ったフラスコを２００℃で６時間加熱撹拌した。反応液を室温まで冷却し、水およびトルエンを加え分液した。溶媒を減圧留去した後、シリカゲルカラムクロマトグラフィー（トルエン／酢酸エチル）で精製し、溶出液の溶媒を減圧留去して３−（アントラセン−９−イル）フェノール（２７．２ｇ）を得た。この際、展開液中の酢酸エチルの比率を徐々に増加させて目的物を溶出させた。
<Synthesis of 3- (anthracen-9-yl) phenol>
Under a nitrogen atmosphere, a flask containing 9- (3-methoxyphenyl) anthracene (32.0 g), pyridine hydrochloride (75.0 g) and NMP (20 ml) was heated and stirred at 200 ° C. for 6 hours. The reaction solution was cooled to room temperature, and water and toluene were added for liquid separation. After the solvent was distilled off under reduced pressure, the residue was purified by silica gel column chromatography (toluene / ethyl acetate), and the solvent of the eluate was distilled off under reduced pressure to obtain 3- (anthracen-9-yl) phenol (27.2 g). . At this time, the target product was eluted by gradually increasing the ratio of ethyl acetate in the developing solution.
＜３−（アントラセン−９−イル）フェニル トリフルオロメタンスルホナートの合成＞
窒素雰囲気下、３−（アントラセン−９−イル）フェノール（２７．０ｇ）、ピリジン（脱水）（２５０ｍｌ）の入ったフラスコを、氷浴で冷却した。次いで、トリフルオロメタンスルホン酸無水物（３３．０ｍｌ）をこの溶液に滴下した。滴下終了後氷浴を外して、室温で終夜撹拌し、水を加え反応を停止した。トルエンを加えて分液し、溶媒を減圧留去して得られた油状物質をシリカゲルカラムクロマトグラフィー（トルエン／ヘプタン＝１／１（容量比））で精製し、溶出液の溶媒を減圧留去して３−（アントラセン−９−イル）フェニル トリフルオロメタンスルホナート（４０．０ｇ）を得た。
<Synthesis of 3- (anthracen-9-yl) phenyl trifluoromethanesulfonate>
Under a nitrogen atmosphere, a flask containing 3- (anthracen-9-yl) phenol (27.0 g) and pyridine (dehydrated) (250 ml) was cooled in an ice bath. Then trifluoromethanesulfonic anhydride (33.0 ml) was added dropwise to this solution. After completion of the dropwise addition, the ice bath was removed, the mixture was stirred at room temperature overnight, and water was added to stop the reaction. Toluene was added for liquid separation, and the solvent was distilled off under reduced pressure. The oily substance obtained was purified by silica gel column chromatography (toluene / heptane = 1/1 (volume ratio)), and the solvent of the eluent was distilled off under reduced pressure. Thus, 3- (anthracen-9-yl) phenyl trifluoromethanesulfonate (40.0 g) was obtained.
＜２−（３−（アントラセン−９−イル−）フェニル）−４，４，５，５−テトラメチル−１，３，２−ジオキサボロランの合成＞
窒素雰囲気下、３−（アントラセン−９−イル）フェニル トリフルオロメタンスルホナート（４０．０ｇ）、ビスピナコラートジボロン（３０．３ｇ）、酢酸カリウム（１９．５ｇ）、ＰｄＣｌ２（ｄｐｐｆ）（２．４ｇ）およびシクロペンチルメチルエーテル（２５０ｍｌ）の入ったフラスコを還流温度で３時間撹拌した。反応液を室温まで冷却した後、水およびトルエンを加え分液し、溶媒を減圧留去した。得られた固体を活性炭ショートカラム（トルエン）で精製し、溶出液の溶媒を減圧留去して２−（３−（アントラセン−９−イル−）フェニル）−４，４，５，５−テトラメチル−１，３，２−ジオキサボロラン（３７．３ｇ）を得た。
<Synthesis of 2- (3- (anthracen-9-yl-) phenyl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane>
Under nitrogen atmosphere, 3- (anthracen-9-yl) phenyl trifluoromethanesulfonate (40.0 g), bispinacolato diboron (30.3 g), potassium acetate (19.5 g), PdCl 2 (dppf) (2 .4g) and cyclopentyl methyl ether (250 ml) were stirred at reflux for 3 hours. 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 solid was purified with an activated carbon short column (toluene), and the solvent of the eluate was distilled off under reduced pressure to give 2- (3- (anthracen-9-yl-) phenyl) -4,4,5,5-tetra. Methyl-1,3,2-dioxaborolane (37.3 g) was obtained.
＜５−（３−（アントラセン−９−イル）フェニル）−３，４’−ビピリジンの合成＞
２−（３−（アントラセン−９−イル−）フェニル）−４，４，５，５−テトラメチル−１，３，２−ジオキサボロラン（２０．０ｇ）、５−ブロモ−３，４’−ビピリジン（１４．８ｇ）、Ｐｄ（ＰＰｈ３）４（１．８ｇ）、リン酸カリウム（２２．３ｇ）、１，２，４−トリメチルベンゼン（１３０ｍｌ）、ｔ−ブチルアルコール（１３ｍｌ）および水（１３ｍｌ）の入ったフラスコを還流温度で２時間半撹拌した。反応液を室温まで冷却した後、水およびトルエンを加え分液した。溶媒を減圧留去した後、シリカゲルカラムクロマトグラフィー（トルエン／酢酸エチル）で精製した。この際、展開液中の酢酸エチルの比率を徐々に増加させて目的物を溶出させた。溶媒を減圧留去した後、ヘプタンから再結晶して、５−（３−（アントラセン−９−イル）フェニル）−３，４’−ビピリジン（１９．９ｇ）を得た。
<Synthesis of 5- (3- (anthracen-9-yl) phenyl) -3,4'-bipyridine>
2- (3- (Anthracen-9-yl-) phenyl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane (20.0 g), 5-bromo-3,4'-bipyridine (14.8 g), Pd (PPh 3 ) 4 (1.8 g), potassium phosphate (22.3 g), 1,2,4-trimethylbenzene (130 ml), t-butyl alcohol (13 ml) and water (13 ml) ) Was stirred at reflux temperature for 2.5 hours. After the reaction solution was cooled to room temperature, water and toluene were added for liquid separation. After the solvent was distilled off under reduced pressure, the residue was purified by silica gel column chromatography (toluene / ethyl acetate). At this time, the target product was eluted by gradually increasing the ratio of ethyl acetate in the developing solution. After distilling off the solvent under reduced pressure, recrystallization from heptane gave 5- (3- (anthracen-9-yl) phenyl) -3,4'-bipyridine (19.9 g).
＜５−（３−（１０−ブロモアントラセン−９−イル）フェニル）−３，４’−ビピリジン＞
５−（３−（アントラセン−９−イル）フェニル）−３，４’−ビピリジン（１０．０ｇ）、Ｎ−ブロモコハク酸イミド（５．２ｇ）、ヨウ素（０．１ｇ）およびテトラヒドロフラン（１００ｍｌ）の入ったフラスコを、室温で終夜攪拌した。チオ硫酸ナトリウム水溶液を加え反応を停止し、クロロベンゼンを加え分液した。溶媒を減圧留去し、シリカゲルカラムクロマトグラフィー（トルエン／酢酸エチル）で精製した。この際、展開液中の酢酸エチルの比率を徐々に増加させて目的物を溶出させた。溶出液の溶媒を減圧留去し、トルエンから再結晶して、５−（３−（１０−ブロモアントラセン−９−イル）フェニル）−３，４’−ビピリジン（８．２ｇ）を得た。
<5- (3- (10-Bromoanthracen-9-yl) phenyl) -3,4'-bipyridine>
Of 5- (3- (anthracen-9-yl) phenyl) -3,4'-bipyridine (10.0 g), N-bromosuccinimide (5.2 g), iodine (0.1 g) and tetrahydrofuran (100 ml) The flask in was stirred at room temperature overnight. A sodium thiosulfate aqueous solution was added to stop the reaction, and chlorobenzene was added to separate the layers. The solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography (toluene / ethyl acetate). At this time, the target product was eluted by gradually increasing the ratio of ethyl acetate in the developing solution. The solvent of the eluate was distilled off under reduced pressure, and recrystallized from toluene to obtain 5- (3- (10-bromoanthracen-9-yl) phenyl) -3,4'-bipyridine (8.2 g).
＜化合物（１−２−７４）の合成＞
５−（３−（１０−ブロモアントラセン−９−イル）フェニル）−３，４’−ビピリジン（２．０ｇ）、（４−（ナフタレン−１−イル）フェニル）ボロン酸（１．２ｇ）、Ｐｄ（ＰＰｈ３）４（０．１４ｇ）、リン酸カリウム（１．７ｇ）、１，２，４−トリメチルベンゼン（１２ｍｌ）、ｔ−ブチルアルコール（１ｍｌ）および水（１ｍｌ）の入ったフラスコを還流温度で６時間撹拌した。反応液を室温まで冷却し、水およびトルエンを加え分液した。溶媒を減圧留去して得られた固体をアミノ基修飾シリカゲル（ＮＨ ＤＭ１０２０：富士シリシア製）カラムクロマトグラフィー（展開液：トルエン）で精製した。溶媒を減圧留去した後、トルエン／ヘプタン混合溶媒で再沈殿し、式（１−２−７４）で表される化合物：５−（３−（１０−（４−（ナフタレン−１−イル）フェニル）アントラセン−９−イル）フェニル）−３，４’−ビピリジン（１．２ｇ）を得た。ＮＭＲ測定により化合物の構造を確認した。
１Ｈ−ＮＭＲ（ＣＤＣｌ３）： δ＝９．０５（ｍ，１Ｈ）， ８．８８（ｍ，１Ｈ），８．７２（ｍ，２Ｈ）， ８．１８（ｍ，２Ｈ）， ７．９７（ｍ，１Ｈ）， ７．８６−７．９５（ｍ，４Ｈ）， ７．７４−７．８３（ｍ，６Ｈ）， ７．５９−７．６６（ｍ，５Ｈ）， ７．５３−７．５９（ｍ，４Ｈ）， ７．３８−７．４６（ｍ，４Ｈ）．
<Synthesis of Compound (1-2-74)>
5- (3- (10-bromoanthracen-9-yl) phenyl) -3,4'-bipyridine (2.0 g), (4- (naphthalen-1-yl) phenyl) boronic acid (1.2 g), A flask containing Pd (PPh 3 ) 4 (0.14 g), potassium phosphate (1.7 g), 1,2,4-trimethylbenzene (12 ml), t-butyl alcohol (1 ml) and water (1 ml) was added. Stir at reflux for 6 hours. 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 amino group-modified silica gel (NH DM1020: manufactured by Fuji Silysia) column chromatography (developing solution: toluene). The solvent was distilled off under reduced pressure, and then reprecipitated with a toluene / heptane mixed solvent, and the compound represented by the formula (1-274): 5- (3- (10- (4- (naphthalen-1-yl)) Phenyl) anthracen-9-yl) phenyl) -3,4'-bipyridine (1.2 g) was obtained. The structure of the compound was confirmed by NMR measurement.
1 H-NMR (CDCl 3 ): δ = 9.05 (m, 1H), 8.88 (m, 1H), 8.72 (m, 2H), 8.18 (m, 2H), 7.97 (M, 1H), 7.86-7.95 (m, 4H), 7.74-7.83 (m, 6H), 7.59-7.66 (m, 5H), 7.53-7 .59 (m, 4H), 7.38-7.46 (m, 4H).
［合成例６］化合物（１−２−７７）の合成
＜化合物（１−２−７７）の合成＞
５−（３−（１０−ブロモアントラセン−９−イル）フェニル）−３，４’−ビピリジン（２．０ｇ）、フェナンスレン−９−イルボロン酸（１．１ｇ）、酢酸パラジウム（０．０３ｇ）、ＳＰｈｏｓ（アルドリッチ品）（０．１３ｇ）、リン酸カリウム（１．７ｇ）およびトルエン（１２ｍｌ）の入ったフラスコを還流温度で８時間撹拌した。反応液を室温まで冷却し、水を加えて生成した固体を吸引濾過にて採取した。得られた固体を水、次いでメタノールで洗浄した後、アミノ基修飾シリカゲルカラムクロマトグラフィー（展開液：トルエン）で精製した。溶媒を減圧留去した後、トルエンから再結晶し、式（１−２−７７）で表される化合物：５−（３−（１０−（フェナントレン−９−イル）アントラセン−９−イル）フェニル）−３，４’−ビピリジン（１．７ｇ）を得た。ＮＭＲ測定により化合物の構造を確認した。
１Ｈ−ＮＭＲ（ＣＤＣｌ３）： δ＝９．０７（ｄｄ，１Ｈ）， ８．８９（ｍ，３Ｈ）， ８．７２（ｍ，２Ｈ）， ８．２０（ｍ，１Ｈ）， ７．７６−７．９６（ｍ，８Ｈ）， ７．６３−７．７３（ｍ，３Ｈ）， ７．５６−７．６２（ｍ，４Ｈ）， ７．３０−７．４０（ｍ，３Ｈ）， ７．２０−７．２８（ｍ，３Ｈ）．
[Synthesis Example 6] Synthesis of Compound (1-2-77) <Synthesis of Compound (1-2-77)>
5- (3- (10-bromoanthracen-9-yl) phenyl) -3,4'-bipyridine (2.0 g), phenanthrene-9-ylboronic acid (1.1 g), palladium acetate (0.03 g), A flask containing SPhos (Aldrich product) (0.13 g), potassium phosphate (1.7 g) and toluene (12 ml) was stirred at reflux temperature for 8 hours. The reaction solution was cooled to room temperature, water was added, and the resulting solid was collected by suction filtration. The obtained solid was washed with water and then with methanol, and then purified by amino group-modified silica gel column chromatography (developing solution: toluene). The solvent was distilled off under reduced pressure, and then recrystallized from toluene, and the compound represented by the formula (1-2-77): 5- (3- (10- (phenanthren-9-yl) anthracen-9-yl) phenyl ) -3,4'-bipyridine (1.7 g) was obtained. The structure of the compound was confirmed by NMR measurement.
1 H-NMR (CDCl 3 ): δ = 9.07 (dd, 1H), 8.89 (m, 3H), 8.72 (m, 2H), 8.20 (m, 1H), 7.76 -7.96 (m, 8H), 7.63-7.73 (m, 3H), 7.56-7.62 (m, 4H), 7.30-7.40 (m, 3H), 7 20-7.28 (m, 3H).
［合成例７］化合物（１−２−７９）の合成
＜化合物（１−２−７９）の合成＞
５−（３−（１０−ブロモアントラセン−９−イル）フェニル）−３，４’−ビピリジン（１．５ｇ）、トリフェニレン−２−イルボロン酸（１．２ｇ）、Ｐｄ（ＰＰｈ３）４（０．１ｇ）、リン酸カリウム（１．３ｇ）、１，２，４−トリメチルベンゼン（１０ｍｌ）、ｔ−ブチルアルコール（１ｍｌ）および水（１ｍｌ）の入ったフラスコを還流温度で３時間撹拌した。反応液を室温まで冷却し、水を加えて生成した固体を吸引濾過にて採取した。得られた固体を水、次いでメタノールで洗浄した後、アミノ基修飾シリカゲルカラムクロマトグラフィー（トルエン／酢酸エチル）で精製し、溶出液の溶媒を減圧留去して、式（１−２−７９）で表される化合物：５−（３−（１０−（トリフェニレン−２−イル）アントラセン−９−イル）フェニル）−３，４’−ビピリジン（１．２ｇ）を得た。この際、展開液中の酢酸エチルの比率を徐々に増加させて目的物を溶出させた。ＮＭＲ測定により化合物の構造を確認した。
１Ｈ−ＮＭＲ（ＣＤＣｌ３）： δ＝９．０６（ｍ，１Ｈ）， ８．８８−８．９３（ｍ，２Ｈ）， ８．８１（ｍ，２Ｈ）， ８．７３（ｍ，４Ｈ）， ８．５８（ｔ，１Ｈ）， ８．１９（ｍ，１Ｈ）， ７．８９（ｄ，１Ｈ）， ７．６３−７．８６（ｍ，１１Ｈ）， ７．５６−７．６２（ｍ，３Ｈ）， ７．３３−７．４２（ｍ，４Ｈ）．
[Synthesis Example 7] Synthesis of Compound (1-2-79) <Synthesis of Compound (1-2-79)>
5- (3- (10-Bromoanthracen-9-yl) phenyl) -3,4'-bipyridine (1.5 g), triphenylene-2-ylboronic acid (1.2 g), Pd (PPh 3 ) 4 (0 0.1 g), potassium phosphate (1.3 g), 1,2,4-trimethylbenzene (10 ml), t-butyl alcohol (1 ml) and water (1 ml) were stirred at reflux temperature for 3 hours. The reaction solution was cooled to room temperature, water was added, and the resulting solid was collected by suction filtration. The obtained solid was washed with water and then with methanol, and then purified by amino group-modified silica gel column chromatography (toluene / ethyl acetate). The solvent of the eluate was distilled off under reduced pressure to obtain a compound of formula (1-2-79) Compound represented by: 5- (3- (10- (triphenylene-2-yl) anthracen-9-yl) phenyl) -3,4'-bipyridine (1.2 g) was obtained. At this time, the target product was eluted by gradually increasing the ratio of ethyl acetate in the developing solution. The structure of the compound was confirmed by NMR measurement.
1 H-NMR (CDCl 3 ): δ = 9.06 (m, 1H), 8.88-8.93 (m, 2H), 8.81 (m, 2H), 8.73 (m, 4H) , 8.58 (t, 1H), 8.19 (m, 1H), 7.89 (d, 1H), 7.63-7.86 (m, 11H), 7.56-7.62 (m) , 3H), 7.33-7.42 (m, 4H).
［合成例８］化合物（１−２−９５）の合成
＜２−メチル−４−（４，４，５，５−テトラメチル−１，３，２−ジオキサボロラン−２−イル）ピリジンの合成＞
窒素雰囲気下、４−ブロモ−２−メチルピリジン（２４．８ｇ）、ビスピナコラートジボロン（３６．８ｇ）、酢酸カリウム（４２．８ｇ）、ＰｄＣｌ２（ｄｐｐｆ）（２．５ｇ）およびシクロペンチルメチルエーテル（４００ｍｌ）の入ったフラスコを還流温度で５時間撹拌した。反応液を室温まで冷却した後、不溶分を吸引濾過にて濾別し、溶媒を減圧留去した。得られた固体を活性炭カラムクロマトグラフィー（トルエン）で精製し、溶出液の溶媒を減圧留去して、２−メチル−４−（４，４，５，５−テトラメチル−１，３，２−ジオキサボロラン−２−イル）ピリジン（３１．４ｇ）を得た。
Synthesis Example 8 Synthesis of Compound (1-295) <Synthesis of 2-methyl-4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) pyridine>
Under a nitrogen atmosphere, 4-bromo-2-methylpyridine (24.8 g), bispinacolatodiboron (36.8 g), potassium acetate (42.8 g), PdCl 2 (dppf) (2.5 g) and cyclopentylmethyl A flask containing ether (400 ml) was stirred at reflux for 5 hours. After cooling the reaction solution to room temperature, the insoluble matter was removed by suction filtration, and the solvent was distilled off under reduced pressure. The obtained solid was purified by activated carbon column chromatography (toluene), and the solvent of the eluate was distilled off under reduced pressure to give 2-methyl-4- (4,4,5,5-tetramethyl-1,3,2). -Dioxaborolan-2-yl) pyridine (31.4 g) was obtained.
＜５−ブロモ−２’−メチル−３，４’−ビピリジンの合成＞
窒素雰囲気下、２−メチル−４−（４，４，５，５−テトラメチル−１，３，２−ジオキサボロラン−２−イル）ピリジン（１０．０ｇ）、３，５−ジブロモピリジン（１１．０ｇ）、Ｐｄ（ＰＰｈ３）４（１．０ｇ）、リン酸カリウム（１９．０ｇ）およびＮ，Ｎ−ジメチルアセトアミド（２００ｍｌ）の入ったフラスコを還流温度で６時間撹拌した。反応液を室温まで冷却した後、触媒の金属イオンを除去するため、目的の化合物に対しておよそ３倍モルに相当するエチレンジアミン四酢酸・四ナトリウム塩二水和物を適量の水に溶解した溶液および酢酸エチルを加え分液した。溶媒を減圧留去し、アミノ基修飾シリカゲルカラムクロマトグラフィー（トルエン／ヘプタン＝１／４（容量比））で精製し、５−ブロモ−２’−メチル−３，４’−ビピリジン（３．２ｇ）を得た。
<Synthesis of 5-bromo-2'-methyl-3,4'-bipyridine>
Under a nitrogen atmosphere, 2-methyl-4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) pyridine (10.0 g), 3,5-dibromopyridine (11. 0 g), Pd (PPh 3 ) 4 (1.0 g), potassium phosphate (19.0 g) and N, N-dimethylacetamide (200 ml) were stirred at reflux temperature for 6 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. And ethyl acetate were added to separate the layers. The solvent was distilled off under reduced pressure, and the residue was purified by amino group-modified silica gel column chromatography (toluene / heptane = 1/4 (volume ratio)) to give 5-bromo-2′-methyl-3,4′-bipyridine (3.2 g). )
＜化合物（１−２−９５）の合成＞
４，４，５，５−テトラメチル−２−（３−（１０−（ナフタレン−１−イル）アントラセン−９−イル−）フェニル）−１，３，２−ジオキサボロラン（２．０ｇ）、５−ブロモ−２’−メチル−３，４’−ビピリジン（１．２ｇ）、Ｐｄ（ＰＰｈ３）４（０．１４ｇ）、リン酸カリウム（１．７ｇ）、１，２，４−トリメチルベンゼン（１０ｍｌ）、ｔ−ブチルアルコール（１ｍｌ）および水（１ｍｌ）の入ったフラスコを還流温度で４時間撹拌した。反応液を室温まで冷却した後、水およびトルエンを加え分液した。溶媒を減圧留去した後、アミノ基修飾シリカゲルカラムクロマトグラフィー（トルエン）で精製し、溶出液の溶媒を減圧留去して、式（１−２−９５）で表される化合物：２’−メチル−５−（３−（１０−（ナフタレン−１−イル）アントラセン−９−イル）フェニル）−３，４’−ビピリジン（１．６ｇ）を得た。ＮＭＲ測定により化合物の構造を確認した。
１Ｈ−ＮＭＲ（ＣＤＣｌ３）： δ＝９．０５（ｄｄ，１Ｈ）， ８．８７（ｍ，１Ｈ）， ８．６０（ｔ，１Ｈ）， ８．１８（ｍ，１Ｈ）， ８．０９（ｄ，１Ｈ）， ８．０２（ｄ，１Ｈ）， ７．７７−７．９１（ｍ，５Ｈ）， ７．６２−７．７５（ｍ，２Ｈ）， ７．５８（ｔ，１Ｈ）， ７．４５−７．５２（ｍ，３Ｈ）， ７．４３（ｄ，１Ｈ）， ７．３８（ｍ，３Ｈ）， ７．１５−７．２６（ｍ，４Ｈ）， ２．６５（ｍ，３Ｈ）．
<Synthesis of Compound (1-295)>
4,4,5,5-tetramethyl-2- (3- (10- (naphthalen-1-yl) anthracen-9-yl-) phenyl) -1,3,2-dioxaborolane (2.0 g), 5 -Bromo-2'-methyl-3,4'-bipyridine (1.2 g), Pd (PPh 3 ) 4 (0.14 g), potassium phosphate (1.7 g), 1,2,4-trimethylbenzene ( 10 ml), t-butyl alcohol (1 ml) and water (1 ml) were stirred at reflux temperature for 4 hours. After the reaction solution was cooled to room temperature, water and toluene were added for liquid separation. After the solvent was distilled off under reduced pressure, the residue was purified by amino group-modified silica gel column chromatography (toluene), the solvent of the eluate was distilled off under reduced pressure, and the compound represented by the formula (1-295): 2′- Methyl-5- (3- (10- (naphthalen-1-yl) anthracen-9-yl) phenyl) -3,4'-bipyridine (1.6 g) was obtained. The structure of the compound was confirmed by NMR measurement.
1 H-NMR (CDCl 3 ): δ = 9.05 (dd, 1H), 8.87 (m, 1H), 8.60 (t, 1H), 8.18 (m, 1H), 8.09 (D, 1H), 8.02 (d, 1H), 7.77-7.91 (m, 5H), 7.62-7.75 (m, 2H), 7.58 (t, 1H), 7.45-7.52 (m, 3H), 7.43 (d, 1H), 7.38 (m, 3H), 7.15-7.26 (m, 4H), 2.65 (m, 3H).
原料の化合物を適宜変更することにより、上述した合成例に準じた方法で、本発明の他の誘導体化合物を合成することができる。 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.
以下、本発明をさらに詳細に説明するために、本発明の化合物を用いた有機ＥＬ素子の実施例を示すが、本発明はこれらに限定されるものではない。 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.
実施例１および比較例１に係る素子を作製し、それぞれ、定電流駆動試験における初期値の８０％以上の輝度を保持する時間（ｈｒ）の測定を行った。以下、実施例および比較例について詳細に説明する。 The elements according to Example 1 and Comparative Example 1 were manufactured, and the time (hr) during which the luminance was maintained at 80% or more of the initial value in the constant current driving test was measured. Hereinafter, examples and comparative examples will be described in detail.
作製した実施例１および比較例１に係る素子における、各層の材料構成を下記表１に示す。
表１において、「ＨＩ」はＮ４，Ｎ４’−ジフェニル−Ｎ４，Ｎ４’−ビス（９−フェニル−９Ｈ−カルバゾール−３−イル）−［１，１’−ビフェニル］−４，４’−ジアミン、「ＴＢＢ」はＮ４，Ｎ４，Ｎ４’，Ｎ４’−テトラ（［１，１’−ビフェニル］−４−イル）−［１，１’−ビフェニル］−４，４’−ジアミン、化合物（Ａ）は９−フェニル−１０−（４−フェニルナフタレン−１−イル）アントラセン、化合物（Ｂ）はＮ５，Ｎ５，Ｎ９，Ｎ９−７，７−ヘキサフェニル−７Ｈ−ベンゾ［ｃ］フルオレン−５，９−ジアミン、化合物（Ｃ）は９，１０−ジ（［２，２’−ビピリジン］−５−イル）アントラセンである。電子輸送層と陰極の中間に形成する層に用いた「Ｌｉｑ」と共に以下に化学構造を示す。 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, “TBB” is N 4 , N 4 , N 4 ′ , N 4 ′ -tetra ([1,1′-biphenyl] -4-yl)-[1,1′-biphenyl] -4, 4'-diamine, compound (A) 9-phenyl-10- (4-phenyl-1-yl) anthracene, the compound (B) is N 5, N 5, N 9 , N 9 -7,7- hexa Phenyl-7H-benzo [c] fluorene-5,9-diamine, compound (C) is 9,10-di ([2,2′-bipyridin] -5-yl) anthracene. The chemical structure is shown below together with “Liq” used for the layer formed between the electron transport layer and the cathode.
＜化合物（１−１−７０）を電子輸送層に用いた素子１＞
スパッタリングにより１８０ｎｍの厚さに製膜したＩＴＯを１５０ｎｍまで研磨した、２６ｍｍ×２８ｍｍ×０．７ｍｍのガラス基板（（株）オプトサイエンス製）を透明支持基板とした。この透明支持基板を市販の蒸着装置（昭和真空（株）製）の基板ホルダーに固定し、ＨＩを入れたモリブデン製蒸着用ボート、ＴＢＢを入れたモリブデン製蒸着用ボート、化合物（Ａ）を入れたモリブデン製蒸着用ボート、化合物（Ｂ）を入れたモリブデン製蒸着用ボート、化合物（１−１−７０）を入れたモリブデン製蒸着用ボート、Ｌｉｑを入れたモリブデン製蒸着用ボート、マグネシウムを入れたモリブデンボートおよび銀を入れたタングステン製蒸着用ボートを装着した。
<Element 1 using Compound (1-1-70) 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 TBB, and a compound (A) are placed therein. Molybdenum vapor deposition boat, molybdenum vapor deposition boat containing compound (B), molybdenum vapor deposition boat containing compound (1-1-70), molybdenum vapor deposition boat containing Liq, magnesium A molybdenum boat and a tungsten evaporation boat containing silver were installed.
透明支持基板のＩＴＯ膜の上に順次、下記各層を形成した。真空槽を５×１０−４Ｐａまで減圧し、まず、ＨＩが入った蒸着用ボートを加熱して膜厚４０ｎｍになるように蒸着して正孔注入層を形成し、ついで、ＴＢＢが入った蒸着用ボートを加熱して膜厚３０ｎｍになるように蒸着して正孔輸送層を形成した。次に、化合物（Ａ）が入った蒸着用ボートと化合物（Ｂ）の入った蒸着用ボートを同時に加熱して膜厚３５ｎｍになるように蒸着して発光層を形成した。化合物（Ａ）と化合物（Ｂ）の重量比がおよそ９５対５になるように蒸着速度を調節した。次に、化合物（１−１−７０）の入った蒸着用ボートを加熱して膜厚１５ｎｍになるように蒸着して電子輸送層を形成した。各層の蒸着速度は０．０１〜１ｎｍ／秒であった。 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 TBB was contained. The vapor deposition boat was heated and vapor-deposited so that it might become a film thickness of 30 nm, and the positive hole transport layer was formed. Next, the vapor deposition boat containing the compound (A) and the vapor deposition boat containing the compound (B) were heated at the same time to form a light emitting layer by vapor deposition to a film thickness of 35 nm. The deposition rate was adjusted so that the weight ratio of compound (A) to compound (B) was approximately 95 to 5. Next, the evaporation boat containing the compound (1-1-70) was heated and evaporated to a thickness of 15 nm to form an electron transport layer. The deposition rate of each layer was 0.01 to 1 nm / second.
その後、Ｌｉｑが入った蒸着用ボートを加熱して膜厚１ｎｍになるように０．０１〜０．１ｎｍ／秒の蒸着速度で蒸着した。次いで、マグネシウムの入ったボートと銀の入ったボートを同時に加熱して膜厚１００ｎｍになるように蒸着して陰極を形成した。この時、マグネシウムと銀の原子数比が１０対１となるように、蒸着速度を０．１〜１０ｎｍ／秒の間で調節した。 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 between 0.1 and 10 nm / second so that the atomic ratio of magnesium and silver was 10: 1.
このようにして作成した有機ＥＬ素子のＩＴＯ電極を陽極、マグネシウム／銀電極を陰極として、直流電圧を印加すると、波長約４６０ｎｍの青色発光が得られた。また、初期輝度２０００ｃｄ／ｍ２を得るための電流密度により、定電流駆動試験を実施したところ、初期値の８０％（１６００ｃｄ／ｍ２）以上の輝度を保持する時間は３１２時間であった。 When a direct current voltage was applied using the ITO electrode of the organic EL device thus prepared as the anode and the magnesium / silver electrode as the cathode, blue light emission having a wavelength of about 460 nm was obtained. Further, when a constant current driving test was performed at a current density for obtaining an initial luminance of 2000 cd / m 2 , the time for maintaining the luminance of 80% (1600 cd / m 2 ) or more of the initial value was 312 hours.
［比較例１］
化合物（１−１−７０）を化合物（Ｃ）に替えた以外は実施例１に準じた方法で有機ＥＬ素子を得た。ＩＴＯ電極を陽極、マグネシウム／銀電極を陰極として、初期輝度２０００ｃｄ／ｍ２を得るための電流密度により、定電流駆動試験を実施した。その結果、初期値の８０％以上の輝度を保持する時間は１９７時間であった。
[Comparative Example 1]
An organic EL device was obtained by the method according to Example 1 except that the compound (1-1-70) 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 time for maintaining the brightness of 80% or more of the initial value was 197 hours.
以上の結果を表２にまとめた。
実施例２〜９および比較例２〜４に係る素子を作製し、それぞれ、定電流駆動試験における初期値の９０％以上の輝度を保持する時間（ｈｒ）の測定を行った。以下、実施例および比較例について詳細に説明する。 The elements according to Examples 2 to 9 and Comparative Examples 2 to 4 were produced, and the time (hr) for maintaining the luminance of 90% or more of the initial value in the constant current driving test was measured. Hereinafter, examples and comparative examples will be described in detail.
作製した実施例２〜８および比較例２〜３に係る素子における、各層の材料構成を下記表３に示す。
表３において、ＨＴはＮ−（［１，１’−ビフェニル］−４−イル）−９，９−ジメチル−Ｎ−（４−（９−フェニル−９Ｈ−カルバゾール−３−イル）フェニル）−９Ｈ−フルオレン−２−アミン、化合物（Ｄ）は９−（４−（ナフタレン−１−イル）フェニル）−１０−フェニルアントラセン、化合物（Ｅ）は４，４’−（（７，７−ジフェニル−７Ｈ−ベンゾ［ｃ］フルオレン−５，９−ジイル）ビス（（フェニル）アミノ））ジベンゾニトリル、化合物（Ｆ）は４’−（４−（１０−（ナフタレン−２−イル）アントラセン−９−イル）フェニル）−２，２’：６’，２”−テルピリジン、化合物（Ｇ）は５−（４−（１０−（ナフタレン−１−イル）アントラセン−９−イル）フェニル）−２，４’−ビピリジン、化合物（Ｈ）は５，５”−（２−フェニルアントラセン−９，１０−ジイル）ジ−３，４’−ビピリジンである。 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 (D) is 9- (4- (naphthalen-1-yl) phenyl) -10-phenylanthracene, compound (E) is 4,4 ′-((7,7-diphenyl) -7H-benzo [c] fluorene-5,9-diyl) bis ((phenyl) amino)) dibenzonitrile, compound (F) is 4 '-(4- (10- (naphthalen-2-yl) anthracene-9 -Yl) phenyl) -2,2 ': 6', 2 "-terpyridine, compound (G) is 5- (4- (10- (naphthalen-1-yl) anthracen-9-yl) phenyl) -2, 4′-bipyridine, compound (H) is , 5 "- (2-phenyl-9,10-diyl) di-3,4'-bipyridine.
＜化合物（１−１−７０）を電子輸送層に用いた素子２＞
スパッタリングにより１８０ｎｍの厚さに製膜したＩＴＯを１５０ｎｍまで研磨した、２６ｍｍ×２８ｍｍ×０．７ｍｍのガラス基板（（株）オプトサイエンス製）を透明支持基板とした。この透明支持基板を市販の蒸着装置（昭和真空（株）製）の基板ホルダーに固定し、ＨＩを入れたモリブデン製蒸着用ボート、ＨＴを入れたモリブデン製蒸着用ボート、化合物（Ｄ）を入れたモリブデン製蒸着用ボート、化合物（Ｅ）を入れたモリブデン製蒸着用ボート、化合物（１−１−７０）を入れたモリブデン製蒸着用ボート、Ｌｉｑを入れたモリブデン製蒸着用ボート、マグネシウムを入れたモリブデンボートおよび銀を入れたタングステン製蒸着用ボートを装着した。
<Element 2 using Compound (1-1-70) 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 HT, and compound (D) are placed therein. Molybdenum vapor deposition boat, molybdenum vapor deposition boat containing compound (E), molybdenum vapor deposition boat containing compound (1-1-70), molybdenum vapor deposition boat containing Liq, magnesium A molybdenum boat and a tungsten evaporation boat containing silver were installed.
透明支持基板のＩＴＯ膜の上に順次、下記各層を形成した。真空槽を５×１０−４Ｐａまで減圧し、まず、ＨＩが入った蒸着用ボートを加熱して膜厚４０ｎｍになるように蒸着して正孔注入層を形成し、ついで、ＨＴが入った蒸着用ボートを加熱して膜厚３０ｎｍになるように蒸着して正孔輸送層を形成した。次に、化合物（Ｄ）が入った蒸着用ボートと化合物（Ｅ）の入った蒸着用ボートを同時に加熱して膜厚３５ｎｍになるように蒸着して発光層を形成した。化合物（Ｄ）と化合物（Ｅ）の重量比がおよそ９５対５になるように蒸着速度を調節した。次に、化合物（１−１−７０）の入った蒸着用ボートとＬｉｑの入った蒸着用ボートを同時に加熱して膜厚２５ｎｍになるように蒸着して電子輸送層を形成した。化合物（１−１−７０）とＬｉｑの重量比がおよそ１：１になるように蒸着速度を調節した。各層の蒸着速度は０．０１〜１ｎｍ／秒であった。 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 to a film thickness of 30 nm to form a hole transport layer. Next, the vapor deposition boat containing the compound (D) and the vapor deposition boat containing the compound (E) 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 (D) to compound (E) was approximately 95 to 5. Next, the vapor deposition boat containing the compound (1-1-70) 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 (1-1-70) and Liq was approximately 1: 1. The deposition rate of each layer was 0.01 to 1 nm / second.
その後、Ｌｉｑが入った蒸着用ボートを加熱して膜厚１ｎｍになるように０．０１〜０．１ｎｍ／秒の蒸着速度で蒸着した。次いで、マグネシウムの入ったボートと銀の入ったボートを同時に加熱して膜厚１００ｎｍになるように蒸着して陰極を形成した。この時、マグネシウムと銀の原子数比が１０対１となるように蒸着速度を調節し、蒸着速度が０．１〜１０ｎｍ／秒になるように陰極を形成し有機電界発光素子を得た。 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.
ＩＴＯ電極を陽極、マグネシウム／銀電極を陰極として、直流電圧を印加すると、波長約４５０ｎｍの青色発光が得られ、そのときの外部量子効率は４．８８％であった。また、初期輝度２０００ｃｄ／ｍ２を得るための電流密度により、定電流駆動試験を実施したところ、初期値の９０％（１８００ｃｄ／ｍ２）以上の輝度を保持する時間は１０３時間であった。 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, and the external quantum efficiency at that time was 4.88%. Further, when a constant current driving test was performed at a current density for obtaining an initial luminance of 2000 cd / m 2 , the time for maintaining the luminance of 90% (1800 cd / m 2 ) or more of the initial value was 103 hours.
＜化合物（１−１−２）を電子輸送層に用いた素子＞
化合物（１−１−７０）を化合物（１−１−２）に替えた以外は実施例２に準じた方法で有機ＥＬ素子を得た。ＩＴＯ電極を陽極、マグネシウム／銀電極を陰極として、直流電圧を印加して発光させたときの外部量子効率は５．０５％であった。また、初期輝度２０００ｃｄ／ｍ２を得るための電流密度により、定電流駆動試験を実施したところ、初期値の９０％以上の輝度を保持する時間は６０時間だった。
<Element Using Compound (1-1-2) for Electron Transport Layer>
An organic EL device was obtained by the method according to Example 2 except that the compound (1-1-70) was changed to the compound (1-1-2). When the ITO electrode was used as an anode and the magnesium / silver electrode was used as a cathode, the external quantum efficiency was 5.05% when light was emitted by applying a DC voltage. Further, when a constant current driving test was performed with a current density for obtaining an initial luminance of 2000 cd / m 2 , the time for maintaining a luminance of 90% or more of the initial value was 60 hours.
＜化合物（１−１−３６）を電子輸送層に用いた素子＞
化合物（１−１−７０）を化合物（１−１−３６）に替えた以外は実施例２に準じた方法で有機ＥＬ素子を得た。ＩＴＯ電極を陽極、マグネシウム／銀電極を陰極として、直流電圧を印加して発光させたときの外部量子効率は５．００％であった。また、初期輝度２０００ｃｄ／ｍ２を得るための電流密度により、定電流駆動試験を実施したところ、初期値の９０％以上の輝度を保持する時間は７０時間だった。
<Element Using Compound (1-1-36) for Electron Transport Layer>
An organic EL device was obtained by the method according to Example 2 except that the compound (1-1-70) was changed to the compound (1-1-36). When the ITO electrode was used as an anode and the magnesium / silver electrode was used as a cathode, the external quantum efficiency was 5.00% when light was emitted by applying a DC voltage. Further, when a constant current driving test was performed with a current density for obtaining an initial luminance of 2000 cd / m 2 , the time for maintaining a luminance of 90% or more of the initial value was 70 hours.
＜化合物（１−２−６８）を電子輸送層に用いた素子＞
化合物（１−１−７０）を化合物（１−２−６８）に替えた以外は実施例２に準じた方法で有機ＥＬ素子を得た。ＩＴＯ電極を陽極、マグネシウム／銀電極を陰極として、直流電圧を印加して発光させたときの外部量子効率は４．９９％であった。また、初期輝度２０００ｃｄ／ｍ２を得るための電流密度により、定電流駆動試験を実施したところ、初期値の９０％以上の輝度を保持する時間は５４時間だった。
<Device Using Compound (1-268) for Electron Transport Layer>
An organic EL device was obtained by the method according to Example 2 except that the compound (1-1-70) was changed to the compound (1-268). Using the ITO electrode as the anode and the magnesium / silver electrode as the cathode, the external quantum efficiency was 4.99% when light was emitted by applying a DC voltage. Further, when a constant current driving test was performed with a current density for obtaining an initial luminance of 2000 cd / m 2 , the time for maintaining the luminance of 90% or more of the initial value was 54 hours.
＜化合物（１−２−７４）を電子輸送層に用いた素子＞
化合物（１−１−７０）を化合物（１−２−７４）に替えた以外は実施例２に準じた方法で有機ＥＬ素子を得た。ＩＴＯ電極を陽極、マグネシウム／銀電極を陰極として、直流電圧を印加して発光させたときの外部量子効率は５．０７％であった。また、初期輝度２０００ｃｄ／ｍ２を得るための電流密度により、定電流駆動試験を実施したところ、初期値の９０％以上の輝度を保持する時間は６４時間だった。
<Element Using Compound (1-2-74) for Electron Transport Layer>
An organic EL device was obtained by the method according to Example 2 except that the compound (1-1-70) was changed to the compound (1-2-74). When the ITO electrode was used as an anode and the magnesium / silver electrode was used as a cathode, the external quantum efficiency was 5.07% when light was emitted by applying a DC voltage. Further, when a constant current driving test was performed with a current density for obtaining an initial luminance of 2000 cd / m 2 , the time for maintaining the luminance of 90% or more of the initial value was 64 hours.
＜化合物（１−２−７７）を電子輸送層に用いた素子＞
化合物（１−１−７０）を化合物（１−２−７７）に替えた以外は実施例２に準じた方法で有機ＥＬ素子を得た。ＩＴＯ電極を陽極、マグネシウム／銀電極を陰極として、直流電圧を印加して発光させたときの外部量子効率は５．３５％であった。また、初期輝度２０００ｃｄ／ｍ２を得るための電流密度により、定電流駆動試験を実施したところ、初期値の９０％以上の輝度を保持する時間は６９時間だった。
<Device Using Compound (1-2-77) for Electron Transport Layer>
An organic EL device was obtained by the method according to Example 2 except that the compound (1-1-70) was changed to the compound (1-2-77). When the ITO electrode was used as an anode and the magnesium / silver electrode was used as a cathode, the external quantum efficiency was 5.35% when light was emitted by applying a DC voltage. Further, when a constant current driving test was performed with a current density for obtaining an initial luminance of 2000 cd / m 2 , the time for maintaining a luminance of 90% or more of the initial value was 69 hours.
＜化合物（１−２−７９）を電子輸送層に用いた素子＞
化合物（１−１−７０）を化合物（１−２−７９）に替えた以外は実施例２に準じた方法で有機ＥＬ素子を得た。ＩＴＯ電極を陽極、マグネシウム／銀電極を陰極として、直流電圧を印加して発光させたときの外部量子効率は５．３８％であった。また、初期輝度２０００ｃｄ／ｍ２を得るための電流密度により、定電流駆動試験を実施したところ、初期値の９０％以上の輝度を保持する時間は７２時間だった。
<Device Using Compound (1-2-79) for Electron Transport Layer>
An organic EL device was obtained by the method according to Example 2 except that the compound (1-1-70) was changed to the compound (1-2-79). Using the ITO electrode as the anode and the magnesium / silver electrode as the cathode, the external quantum efficiency was 5.38% when light was emitted by applying a DC voltage. Further, when a constant current driving test was performed with a current density for obtaining an initial luminance of 2000 cd / m 2 , the time for maintaining the luminance of 90% or more of the initial value was 72 hours.
＜化合物（１−２−９５）を電子輸送層に用いた素子＞
化合物（１−１−７０）を化合物（１−２−９５）に替えた以外は実施例２に準じた方法で有機ＥＬ素子を得た。ＩＴＯ電極を陽極、マグネシウム／銀電極を陰極として、直流電圧を印加して発光させたときの外部量子効率は６．１５％であった。また、初期輝度２０００ｃｄ／ｍ２を得るための電流密度により、定電流駆動試験を実施したところ、初期値の９０％以上の輝度を保持する時間は７４時間だった。
<Device Using Compound (1-295) for Electron Transport Layer>
An organic EL device was obtained by the method according to Example 2 except that the compound (1-1-70) was changed to the compound (1-295). Using the ITO electrode as the anode and the magnesium / silver electrode as the cathode, the external quantum efficiency was 6.15% when light was emitted by applying a DC voltage. Further, when a constant current driving test was performed with a current density for obtaining an initial luminance of 2000 cd / m 2 , the time for maintaining the luminance of 90% or more of the initial value was 74 hours.
［比較例２］
化合物（１−１−７０）を化合物（Ｆ）に替えた以外は実施例２に準じた方法で有機ＥＬ素子を得た。ＩＴＯ電極を陽極、マグネシウム／銀電極を陰極として、直流電圧を印加して発光させたときの外部量子効率は４．６１％であった。また、初期輝度２０００ｃｄ／ｍ２を得るための電流密度により、定電流駆動試験を実施したところ、初期値の９０％以上の輝度を保持する時間は２時間だった。
[Comparative Example 2]
An organic EL device was obtained by the method according to Example 2 except that the compound (1-1-70) was changed to the compound (F). Using the ITO electrode as the anode and the magnesium / silver electrode as the cathode, the external quantum efficiency was 4.61% when light was emitted by applying a DC voltage. Further, when a constant current driving test was performed with a current density for obtaining an initial luminance of 2000 cd / m 2 , the time for maintaining the luminance of 90% or more of the initial value was 2 hours.
［比較例３］
化合物（１−１−７０）を化合物（Ｇ）に替えた以外は実施例２に準じた方法で有機ＥＬ素子を得た。ＩＴＯ電極を陽極、マグネシウム／銀電極を陰極として、直流電圧を印加して発光させたときの外部量子効率は４．３６％であった。また、初期輝度２０００ｃｄ／ｍ２を得るための電流密度により、定電流駆動試験を実施したところ、初期値の９０％以上の輝度を保持する時間は３０時間だった。
[Comparative Example 3]
An organic EL device was obtained by the method according to Example 2 except that the compound (1-1-70) was changed to the compound (G). Using the ITO electrode as the anode and the magnesium / silver electrode as the cathode, the external quantum efficiency was 4.36% when light was emitted by applying a DC voltage. Further, when a constant current driving test was performed with a current density for obtaining an initial luminance of 2000 cd / m 2 , the time for maintaining the luminance of 90% or more of the initial value was 30 hours.
［比較例４］
化合物（１−１−７０）を化合物（Ｈ）に替えた以外は実施例２に準じた方法で有機ＥＬ素子を得た。ＩＴＯ電極を陽極、マグネシウム／銀電極を陰極として、直流電圧を印加して発光させたときの外部量子効率は１．６８％であった。また、初期輝度２０００ｃｄ／ｍ２を得るための電流密度により、定電流駆動試験を実施したところ、初期値の９０％以上の輝度を保持する時間は２７時間だった。
[Comparative Example 4]
An organic EL device was obtained by the method according to Example 2 except that the compound (1-1-70) was changed to the compound (H). When the ITO electrode was used as an anode and the magnesium / silver electrode was used as a cathode, the external quantum efficiency was 1.68% when light was emitted by applying a DC voltage. Further, when a constant current driving test was performed with a current density for obtaining an initial luminance of 2000 cd / m 2 , the time for maintaining a luminance of 90% or more of the initial value was 27 hours.
以上の結果を表４にまとめた。
本発明の好ましい態様によれば、特に発光素子の寿命を向上させた有機電界発光素子、それを備えた表示装置およびそれを備えた照明装置などを提供することができる。 According to a preferred embodiment of the present invention, it is possible to provide an organic electroluminescent element having a particularly improved lifetime of the light emitting element, a display device provided with the organic electroluminescent device, a lighting device provided with the same.
Claims (9)
Ａｒは２−ナフチルを除く炭素数６〜３０のアリールであり；
Ｐｙは２−ピリジル、３−ピリジルまたは４−ピリジルであり；
式中のＡｒ、ベンゼン環およびピリジン環の任意の水素は炭素数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てもよく；また、
式（１）で表される化合物における少なくとも１つの水素が重水素で置き換えられていてもよい。 A compound represented by the following formula (1).
Ar is aryl having 6 to 30 carbon atoms excluding 2-naphthyl ;
Py is 2-pyridyl, 3-pyridyl or 4-pyridyl;
Ar in the formula, any hydrogen of the benzene ring and pyridine ring may be replaced by alkyl having 1 to 6 carbons or cycloalkyl having 3 to 6 carbons;
At least one hydrogen in the compound represented by the formula (1) may be replaced with deuterium.
Ａｒは２−ナフチルを除く炭素数６〜３０のアリールであり；
Ｐｙは２−ピリジル、３−ピリジルまたは４−ピリジルであり；
式中のＡｒ、ベンゼン環およびピリジン環の任意の水素は炭素数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てもよく；また、
式（１−１）または（１−２）で表される化合物における少なくとも１つの水素が重水素で置き換えられていてもよい。 The compound of Claim 1 represented by a following formula (1-1) or (1-2).
Ar is aryl having 6 to 30 carbon atoms excluding 2-naphthyl ;
Py is 2-pyridyl, 3-pyridyl or 4-pyridyl;
Ar in the formula, any hydrogen of the benzene ring and pyridine ring may be replaced by alkyl having 1 to 6 carbons or cycloalkyl having 3 to 6 carbons;
At least one hydrogen in the compound represented by formula (1-1) or (1-2) may be replaced with deuterium.
各々の基の任意の水素は炭素数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てもよい。 The compound according to claim 1 or 2, wherein Ar is one selected from the group of monovalent groups below.
Any hydrogen in each group may be replaced with alkyl having 1 to 6 carbons or cycloalkyl having 3 to 6 carbons.
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