JP4587703B2 - Novel quarter phenylene derivative and organic EL device using the same - Google Patents

Description

The present invention relates to novel Quarter-phenylene derivatives, Contact and an organic EL device using the same.

Conventional studies on organic EL have been performed using fluorescent materials. The pioneer was 1987, Kodak's C.I. W. Tang et al., Appl. Phys. It is an element using tris (8-hydroxyquinolinato) aluminum (Alq ₃ ) announced at Lett, which shows a brightness of about 1000 cd / m ² or more with a direct current of 1.0 V or less at that time. Organic EL was a major technological innovation that attracted attention.
Since then, many research institutions and companies have participated in the research, and research on high efficiency such as reduction in drive voltage, brightness, and improvement in service life has been actively conducted.
Regarding the light emission of the fluorescent material, singlet excitons generated by recombination of holes and electrons injected from the electrodes are involved, and the generation rate is estimated to be 25%. Considering the light extraction efficiency, the ratio is 20%, so the external quantum efficiency is 5% at the maximum, and there is a limit to increasing the efficiency.
In contrast, in 1999, Princeton University S. R. Forrest et al. First discovered and reported that phosphorescent materials can be used for organic EL in Non-Patent Document 1. According to this, in the case of phosphorescent materials, in addition to singlet excitons generated by recombination, triplet excitons generated at the same time contribute to light emission, thereby creating a device with higher efficiency than fluorescent materials. Is possible. That is, since excitons generated by recombination are related to 100% emission, the external quantum efficiency is 20% at the maximum even considering the extraction efficiency, and the merit of organic EL can be maximized. Actually, the device at this time gave green light emission showing an external quantum efficiency of 8% at a power efficiency of 311 m / W.
The element is characterized by combining a phosphorescent substance as a guest material and a host material that gives energy thereto. The host material used at this time was 4,4'-N, N'-dicarbazole-biphenyl (CBP), an amine-based material. Since then, many phosphorescent materials have been developed using this material as a host material. What is important for the host material is whether it has the ability to give sufficient energy to the phosphorescent material. To estimate this ratio, the band gap value between the HOMO and LUMO of the host material is used as a guide. .
According to this value, 4,4′-N, N′-dicarbazole-biphenyl (CBP) functions satisfactorily from green to red having a relatively long wavelength, but a blue phosphorescent material having a high energy level. For this, it did not have enough energy to make it function, and it was important to have a wide (band) gap in the host material. In order to achieve full color with a phosphorescent material, it is important to develop a host material that can cope with this.
However, conventionally, host materials having a large energy gap used for phosphorescent materials are hardly known, and it is a fact that provision of such host materials is strongly demanded.
Accordingly, the present inventors have developed the compound of claim 1 in consideration of the possibility that a compound having a twisted structure in the chemical structural formula can serve as the above-mentioned purpose. Chemical abstract search was performed on the following two compounds, but no literature on the compound was found.

Appl. Phys. Lett. , 75 (1) 4 (1999)

An object of the present invention, to achieve high efficiency in phosphorescent devices, developed a wood fees that have a wide energy gap, in that it provides a high performance organic EL element using the same.

〔式中、Ｒ ^１ 〜Ｒ ^５ のいずれか１つは下記〔化２〕で表される基であり、それ以外のＲ ^１ 〜Ｒ ^５ およびＲ ^６ 〜Ｒ^１３は水素、炭素数１〜４のアルキル基、アルコキシ基（アルキル部分の炭素数１〜４）、炭素数６〜２０のアリール基、アリーロキシ基（アリール部分の炭素数６〜２０）、ヘテロアリーロキシ基（ヘテロアリール部分は５〜１９個の炭素および窒素からなる）、アルコキシカルボニル基（アルキル部分の炭素数１〜４）、アリーロキシカルボニル基（アリール部分の炭素数６〜２０）、ヘテロアリーロキシカルボニル基（ヘテロアリール部分は５〜１９個の炭素および窒素からなる）、およびフッ素よりなる群からそれぞれ独立して選ばれた基である。〕

（式中、Ａｒ^１とＡｒ^２はそれぞれ独立に、炭素数６〜２０のアリール基、または５〜１９個の炭素および窒素からなるヘテロアリール基である。）
本発明の第２は、３．０ｅＶよりも広いエネルギーギャップを有するものである請求項１記載のクオーターフェニレン誘導体に関する。
本発明の第３は、請求項１または２記載のクオーターフェニレン誘導体を用いたことを特徴とする有機ＥＬ素子に関する。
本発明の第４は、発光材料として燐光材料を用いた請求項３記載の有機ＥＬ素子に関する。
本発明の第５は、その発光ピーク波長が４８０ｎｍよりも短波長の青色発光を示す燐光材料を発光材料として用いた請求項４記載の有機ＥＬ素子に関する。 The first of the present invention relates to a quarter phenylene derivative represented by the following general formula (1) .

[In the formula, any one of R ^{1 to} R ⁵ is a group represented by the following [Chemical Formula 2], and the other R ^{1 to} R ⁵ and R ^{6 to} R ¹³ are hydrogen and have 1 to 4 carbon atoms. alkyl group, an alkoxy group (having 1 to 4 carbon atoms in the alkyl moiety), an aryl group having 6 to 20 carbon atoms, an aryloxy group (having 6 to 20 carbon atoms in the aryl moiety), a hetero aryloxy group (the heteroaryl moiety is 5 to 19 carbons and nitrogen) , alkoxycarbonyl group (C1-C4 of alkyl part) , aryloxycarbonyl group (C6-C20 of aryl part) , heteroaryloxycarbonyl group (heteroaryl part is 5) It consists to 19 carbons and nitrogen), and Oh Ru are independently a group selected from the group consisting of fluorine. ]

(Wherein each Ar ¹ and Ar ² are independently a heteroaryl group comprising an aryl group having 6 to 20 carbon atoms or 5 to 19 carbon and nitrogen,.)
The second invention relates quarter phenylene derivative according to claim 1 Symbol placement and has a wider energy gap than 3.0 eV.
The third invention relates to an organic EL element characterized in use be had a quarter phenylene derivative according to claim 1 or 2 wherein.
A fourth aspect of the present invention relates to the organic EL element according to claim 3 , wherein a phosphorescent material is used as the light emitting material.
A fifth aspect of the present invention relates to the organic EL device according to claim 4, wherein a phosphorescent material exhibiting blue light emission whose emission peak wavelength is shorter than 480 nm is used as a light emitting material.

^Wherein, the aryl group definitive in ^{Ar 1, Ar 2, R 1} ~R 13, may be of either 1 or polycyclic structure which may have a substituent. Specific examples include phenyl, biphenyl, terphenyl, quarterphenyl, quinckphenyl, sesquiphenyl, septiphenyl, octiphenyl, nobiphenyl, decylphenyl, naphthyl, azulenyl, anthranyl, phenanthrenyl, naphthacenyl, chrysenyl, pentarenyl, indenyl, azulenyl, Heptadenyl, biphenylyl, as-indacenyl, s-indacenyl, acenaphthylenyl, fluorenyl, phenalenyl, fluoracenyl, acephenanthrarenyl, aceanthrylenyl, triphenylyl, pyrenyl, preadenyl, picenyl, perylenyl, pentaphenyl, pentaphenyl, tetraphenylenyl Nyl, hexaphenyl, hexaacenyl, ruvicenyl, coronyl, trinaphthylenyl, hexaphenyl, hex It Aseniru, rubicenyl, coronenyl, Torinafutereniru, heptaphenyl, heptacenyl, Piranseniru, and ovalenyl.

Wherein, as the heteroaryl group definitive in ^{Ar 1, Ar 2, R 1} ~R 13, is also located heteroaryl group various which may be substituted, it may be of either 1 or polycyclic structure . Specific examples include furanyl, pyrrolonyl, 3-pyrrolonyl, pyrazolyl, imidazolyl, oxazolyl, thiazolyl, 1,2,3-oxadiazolyl, triazolyl, pyranyl, pyridinyl, pyridazinyl, pyrimidinyl, pyrazinyl, 1,3,5-triazinyl, Examples thereof include benzofuranyl, indolyl, benzo [b] thiophenyl, benzimidazolyl, benzothiazolyl, purinyl, quinolinyl, isoquinolinyl, cinnolinyl, quinoxalinyl, carbazolyl, acridinyl, 1,10-fentrenyl and the like.

The alkyl group definitive in ^R 1 ^{to R 13,} methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl And eicosyl. These may be linear or branched.

The alkoxy group definitive in the ^R 1 ^{to R 13,} methoxy, ethoxy, propoxy, butoxy, pentoxy, hexyloxy, heptyloxy, octyloxy, Nonirokishi, decyloxy, Fundeshiroshikishi, dodecyloxy, Torideshirokishi, tetradecyloxy, Pentadeshirokishi, hexadecyloxy Heptadecyloxy, octadecyloxy, nonadecyloxy, eicosyloxy and the like. These may be linear or branched. The alkoxy moiety in the alkoxycarbonyl group is the same as the alkoxy group.
The halogen definitive in the ^R 1 ^{to R 13,} may be any halogen.

The aryloxy group and the aryl moiety in the aryloxycarbonyl group are the same as the aryl group, the heteroaryloxy group and the heteroaryl moiety in the heteroaryloxycarbonyl group are the same as the heteroaryl group, the aryl group, the aryloxy group, Examples of the substituent in the heteroaryl group, heteroaryloxy group, aryloxycarbonyl group, and heteroaryloxycarbonyl group include an alkyl group, an alkoxyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, and a halogen. Examples of the alkoxy group include those described above, and the same applies to the alkyl group attached to the alkoxycarbonyl group and the aryl group attached to the aryloxycarbonyl group. .
In addition, examples of the substituent in the alkyl group or alkoxy group include an ester group and a halogen.

An example of a typical method for synthesizing the compound of the present invention is shown below. R ^{1 to} R ¹³ and Ar ¹ and Ar ² are as described above.

Specific compounds of the present invention are listed below.

Quarter-phenylene derivatives of the present invention, have preferably be used as the organic compound for the organic EL element.

  Each of the hole injection layer, the hole transport layer, the light emitting layer, the electron transport layer, and the electron injection layer in the organic EL device of the present invention may be formed of two or more layers. At that time, in the case of a hole injection layer, the layer that injects holes from the anode is called a hole injection layer, and the layer that receives holes from the hole injection layer and transports holes to the light emitting layer is called a hole transport layer. . Similarly, in the case of an electron injection layer, a layer that injects electrons from the cathode is called an electron injection layer, and a layer that receives electrons from the electron injection layer and transports electrons to the light emitting layer is called an electron transport layer. Each of these layers is selected and used depending on factors such as the energy level of the material, heat resistance, adhesion with the organic thin film layer or the metal electrode.

  The organic EL device of the present invention is a device in which one or more organic thin film layers are formed between an anode and a cathode as described above. In the case of a single layer type, it contains a light emitting layer containing the quarter phenylene derivative of the present invention, and in addition to transporting holes injected from the anode or electrons injected from the cathode to the light emitting material containing the quarter phenylene derivative of the present invention. In addition, hole injection or electron injection materials may be included. Moreover, it is preferable that the light emitting material used for the guest exhibits extremely high quantum efficiency and forms a uniform thin film. As a multi-layer type organic EL device, (anode / hole transport layer / light emitting layer / electron transport layer / cathode), (anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / cathode) , (Anode / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode), (anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode), etc. And those laminated in a multi-layer structure.

As the light emitting material for the guest in the organic EL device of the present invention, a known compound that emits phosphorescence can be used. These are not particularly limited and can be selected from known compounds. For example, FIrpic in blue, tris (2-phenylpyridine) iridium [tris (2-phenylpyridine) iridium], iridium (III) Bis (2-phenylpyridinato-N, C ² ) acetylacetone [Iridium (III) bis (2-phenylpyridinato-N, C ² ) (acetylacetone)] and the like are tris {2- (2 -Benzo [b] thiophenylpyridine)} iridium [tris {2- (2-benzo [b] thiophenylpyridine)} iridium], (2,3,7,8,12,13,17,18-octethylporphyrin) Platinium Such as (2,3,7,8,12,13,17,18-Octethylporphyrin) platinum] iridium complexes and platinum complexes such as can be used.

  As a hole injection material or a hole transport material, it has the ability to transport holes, has a hole injection effect from the anode, and has an excellent hole transport effect for the light emitting layer or light emitting material. A compound that prevents the generated excitons from moving to the electron transport layer or the electron transport material and has an excellent thin film forming ability is preferable. Specifically, phthalocyanine derivatives, naphthalocyanine derivatives, porphyrin derivatives, oxazole, oxadiazole, triazole, imidazole, imidazolone, imidazolethione, pyrazoline, pyrazolone, tetrahydroimidazole, hydrazone, acylhydrazone, polyarylalkane, stilbene, benzidine type Triphenylamine, styrylamine-type triphenylamine, diamine-type triphenylamine, etc., and those combined with a Lewis acid, and polymer materials such as conductive polymers such as polyvinyl carbazole, polysilane, or polyaniline, and Lewis Although what combined the acid is mentioned, it is not limited to these.

Among these hole injection materials or hole transport materials, more effective hole injection materials or hole transport materials are aromatic tertiary amine derivatives or phthalocyanine derivatives. Specific examples of the aromatic tertiary amine derivative include triphenylamine, tolylamine, tridiphenylamine, N, N′-diphenyl-N, N ′-(3-methylphenyl) -1,1′-biphenyl-4, 4'-diamine, N, N, N ', N'-(4-methylphenyl) -1,1'-phenyl-4,4'-diamine, N, N, N ', N'-(4-methyl Phenyl) -1,1'-biphenyl-4,4'-diamine, N, N'-diphenyl-N, N'-dinaphthyl-1,1'-biphenyl-4,4'-diamine, N, N'- (Methylphenyl) -N, N ′-(4-n-butylphenyl) -phenanthrene-9,10-diamine, N, N-bis (4-di-4-tolylaminophenyl) -4-phenyl-cyclohexane, etc. Or these aromatic tertiary amino acids An oligomer or polymer having a backbone, but not limited thereto. Specific examples of phthalocyanine (Pc) derivatives are H ₂ PC, CuPc, CoPc, NiPc, ZnPc, PdPc, FePc, MnPc, ClAlPc, ClGaPc, ClInPc, ClSnPc, Cl ₂ SiPc, (HO) AlPc, (HO) GaPc, Phthalocyanine derivatives and naphthalocyanine derivatives such as VOPc, TiOPc, and MoOPc. Examples of the conductive polymer include, but are not limited to, polyaniline derivatives and polythiophene derivatives.

  The compound used as the electron transport material has the ability to transport electrons, has an electron injection effect from the cathode, and has an excellent electron transport effect with respect to the light emitting layer or the light emitting material. A compound that prevents movement to the hole injection layer and is excellent in thin film formation is preferable. As electron transport materials, metal complex compounds, nitrogen-containing compounds and the like are known. Examples of the metal complex compound include tris (8-quinolinato) lithium, tris (8-quinolinato) zinc, tris (8-quinolinato) copper, tris (8-quinolinato) manganese, tris (8-quinolinato) aluminum, tris (2-methyl). -8-quinolinato) aluminum, tris (4-methyl-8-quinolinato) aluminum, tris (4-propyl-8-quinolinato) aluminum and the like. Known nitrogen-containing compounds include oxazole derivatives, thiazole derivatives, oxadiazole derivatives, thiadiazole derivatives, and phenanthroline derivatives. In particular, phenanthroline derivatives include 4,7-diphenyl-1,10-phenanthroline, 4,7-di-m-tolyl-1,10-phenanthroline, 4,7-di-p-tolyl-1,10-phenanthroline. 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline, 2,9-dimethyl-4,7-di-p-tolyl-1,10-phenanthroline, 2,9-dimethyl-4,7 -Di-m-tolyl-1,10-phenanthroline, 2,9-diethyl-4,7-diphenyl-1,10-phenanthroline and the like.

  In the present invention, as an electron transport material, alkali metal halides such as lithium fluoride, alkali metal complexes of 8-hydroxyquinoline derivatives, alkaline earth metal complexes of phenanthroline derivatives, alkaline metal complexes of alkaline earth metals, and alkaline earth metal complexes However, it is not limited to these.

  As a conductive material used for an anode of an organic electroluminescence element, a material having a work function larger than 4 eV is suitable, and carbon, aluminum, vanadium, iron, cobalt, nickel, tungsten, silver, gold, platinum, palladium And their alloys, metal oxides such as tin oxide and indium oxide used for ITO substrates and NESA substrates, and organic conductive resins such as polythiophene and polypyrrole. As the conductive material used for the cathode, a material having a work function smaller than 4 eV is suitable, and magnesium, calcium, tin, lead, titanium, yttrium, lithium, ruthenium, manganese, and alloys thereof are used. It is not limited to these. Examples of alloys include magnesium / silver, magnesium / indium, lithium / aluminum, and the like, but are not limited thereto. The ratio of the alloy can be appropriately controlled by the temperature of the vapor deposition source, the atmosphere, the degree of vacuum, and the like. The anode and the cathode may be composed of two or more layers as necessary.

  The transparent electrode support substrate used in the organic EL device of the present invention is desirably sufficiently transparent in order to efficiently emit light. The transparent electrode is set using the above-described conductive material so that predetermined translucency can be ensured by a method such as vapor deposition or sputtering. The electrode on the light emitting surface preferably has a light transmittance of 10% or more. The substrate is not limited as long as it has mechanical and thermal strength and is transparent, and examples thereof include a glass substrate and a transparent resin film and sheet. Transparent resins used for films and sheets include polyethylene, polyethylene copolymer, polypropylene, polypropylene copolymer, polystyrene, polystyrene copolymer, syndiotactic polystyrene, polymethyl methacrylate, nylon, polyethersulfone, and polysulfone. , Polycarbonate, polycarbonate copolymer, polyarylate, polyetherimide, tetrafluoroethylene-ethylene copolymer, polyvinylidene fluoride, polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate and the like.

  The formation of each layer of the organic electroluminescence element in the present invention uses any of dry deposition methods such as vacuum deposition, sputtering, plasma, and ion plating, and wet deposition methods such as spin coating, dipping, and flow coating. be able to. The thickness of each layer of the organic thin film layer sandwiched between the anode and the cathode is not particularly limited, but must be set to an appropriate thickness. The normal film thickness is preferably selected as appropriate in the range of 0.2 nm to 500 nm.

When creating including organic EL elements Quarter phenylene derivatives of the present invention, a dry film forming method, all of which can be used for wet film formation method vacuum deposition to create a high-performance devices, sputtering etc. It is desirable to use a dry film forming method.

(1) According to the present invention, a novel quarter phenylene derivative could be provided.
(2) The present invention could provide a novel wood charge having a wide energy gap (for example, 3.5 eV).
(3) By using the compound of the present invention for an organic EL device, a blue phosphorescent device and a green phosphorescent device can be provided.

  Hereinafter, the present invention will be described with reference to synthesis examples and examples, but the present invention is not limited thereto.

３００ｍｌ四つ口フラスコに窒素気流下、ｎ−ＢｕＬｉヘキサン溶液（１．６Ｍ） １８０ｍｌ（２９６ｍｍｏｌ）を入れ、Ｎ，Ｎ，Ｎ′，Ｎ′−テトラメチルエチレンジアミン（ＴＭＥＤＡ）（テトラエチルエチレンジアミンのようなテトラアルキルエチレンジアミン類を溶媒として用いてもよい）４４ｍｌ（２９６ｍｍｏｌ）を加えた。しばらく室温で撹拌した後、ビフェニル １８．８ｇ（１２２ｍｍｏｌ）を加え、４日間撹拌した。得られた赤褐色の溶液をアセトン／ドライアイスバスにて−２０℃に冷却し、析出した黄色結晶をデカンテーションにより単離し、ジエチルエーテル２００ｍｌを加えて懸濁液とした。これを−４０℃に冷却し、トリメトキシボラン（トリエトキシボランなどの他のアルコキシボランでもよい）５０ｍｌ（４４０ｍｍｏｌ）をゆっくりと加えた。その後徐々に室温に戻して一晩撹拌後、スラリー状の析出物をテトラヒドロフラン（ＴＨＦ）２００ｍｌを加えて溶解させ、１時間撹拌した。反応液を５％塩酸４００ｍｌに加え６時間撹拌後、有機溶媒を濃縮し、ジクロロメタンで抽出（２００ｍｌ×３）、乾燥、溶媒留去してトルエン／リグロインで再結晶し白色固体の目的物を得た〔収量１．５０ｇ（６．２０ｍｍｏｌ）、収率５．１％〕。 Synthesis Example 1 [Synthesis Example 1 of 2,2′-biphenyldiboric acid (2BPDBA)]

In a 300 ml four-necked flask, 180 ml (296 mmol) of n-BuLi hexane solution (1.6 M) is placed under a nitrogen stream, and N, N, N ′, N′-tetramethylethylenediamine (TMEDA) (tetraethylethylenediamine-like tetra 44 ml (296 mmol) was added) (alkylethylenediamines may be used as solvents). After stirring at room temperature for a while, 18.8 g (122 mmol) of biphenyl was added and stirred for 4 days. The obtained reddish brown solution was cooled to −20 ° C. with an acetone / dry ice bath, and the precipitated yellow crystals were isolated by decantation, and 200 ml of diethyl ether was added to form a suspension. This was cooled to −40 ° C. and 50 ml (440 mmol) of trimethoxyborane (which may be other alkoxyboranes such as triethoxyborane) was slowly added. After gradually returning to room temperature and stirring overnight, 200 ml of tetrahydrofuran (THF) was dissolved in the slurry-like precipitate and stirred for 1 hour. The reaction solution was added to 400 ml of 5% hydrochloric acid and stirred for 6 hours. The organic solvent was concentrated, extracted with dichloromethane (200 ml × 3), dried, evaporated and recrystallized with toluene / ligroin to give the desired product as a white solid. [Yield 1.50 g (6.20 mmol), Yield 5.1%].

Synthesis Example 2 [Synthesis Example 2 of 2,2′-biphenyldiboric acid (2BPDBA)]
Under a nitrogen stream, 45 ml (74 mmol) of n-BuLi hexane solution (1.6 M) was placed in a 300 ml four-necked flask, and 11 ml (74 mmol) of N, N, N ′, N′-tetramethylethylenediamine (TMEDA) was added. . After stirring at room temperature for a while, 4.7 g (30.5 mmol) of biphenyl was added, and the mixture was stirred at room temperature for 1 hour and at 60 ° C. for 2 hours. The resulting reddish brown solution was cooled to −40 ° C. in a methanol / dry ice bath, and 30 ml of diethyl ether was added to form a suspension. Further, 18 ml (141 mmol) of trimethoxyborane was slowly added at −40 ° C. After gradually returning to room temperature and stirring overnight, the slurry-like precipitate was dissolved in 60 ml of THF and stirred for 1 hour. The reaction solution was added to 80 ml of 5% hydrochloric acid and stirred for 4 hours. The organic solvent was concentrated, extracted with dichloromethane (100 ml × 3), dried, evaporated and reprecipitated with n-hexane to give a white solid. The target product was obtained [yield 2.80 g (11.7 mmol), yield 38%].

２００ｍｌ四つ口フラスコに、１−ブロモ−４−アイオドベンゼン ７．２４ｇ（２５．６ｍｍｏｌ）、ｐ，ｐ′−ジ−ｐ−トルイルアミン５．０５ｇ（２５．６ｍｍｏｌ）、トリス（ジベンジリデンアセトン）ジパラジウム（０）２９２ｍｇ（０．３２ｍｍｏｌ）、２，２′−ビナフトール（ＢＩＮＡＰ）０．８０ｇ（１．２８ｍｍｏｌ）、ｔ−ブタン酸ナトリウム ４．９２ｇ（５１．２ｍｍｏｌ）、トルエン１００ｍｌを加え、窒素気流下、２４時間還流した。室温に冷却後、反応液を濃縮しクロロホルムに溶解させ不溶物を濾過、ろ液を脱イオン水、飽和食塩水で洗浄した。有機層を硫酸マグネシウムにて乾燥し、溶媒留去後、シリカゲルカラムクロマトグラフィー（展開溶媒：クロロホルム／ｎ−へキサン＝１：３）にて精製し、薄褐色固体の目的物を得た〔収量４．０８ｇ（１１．６ｍｍｏｌ）、収率４５％〕。 Synthesis Example 3 [Synthesis of 4-bromophenyl-di- (p-tolyl) -amine (4BPDTA)]

In a 200 ml four-necked flask, 7.24 g (25.6 mmol) of 1-bromo-4-iodobenzene, 5.05 g (25.6 mmol) of p, p′-di-p-toluylamine, tris (dibenzylideneacetone) ) Dipalladium (0) 292 mg (0.32 mmol), 2,2′-binaphthol (BINAP) 0.80 g (1.28 mmol), sodium t-butanoate 4.92 g (51.2 mmol), toluene 100 ml was added, The mixture was refluxed for 24 hours under a nitrogen stream. After cooling to room temperature, the reaction solution was concentrated and dissolved in chloroform, insoluble matters were filtered, and the filtrate was washed with deionized water and saturated brine. The organic layer was dried over magnesium sulfate, the solvent was distilled off, and the residue was purified by silica gel column chromatography (developing solvent: chloroform / n-hexane = 1: 3) to obtain the desired product as a light brown solid [yield 4.08 g (11.6 mmol), 45% yield].

２００ｍｌ四つ口フラスコに、１−ブロモ−３−アイオドベンゼン ８．００ｇ（２８．３ｍｍｏｌ）、ｐ，ｐ′−ジ−ｐ−トルイルアミン ７．２６ｇ（３６．８ｍｍｏｌ）、Ｃｕ粉末６．０ｇ（９．４ｍｍｏｌ）、炭酸カリウム１１．７ｇ（８４．９ｍｍｏｌ）、ｏ−ジクロロベンゼン３０ｍｌを加え、窒素気流下１８０℃で６時間撹拌した。反応液を濾過し、ろ液を濃縮後、シリカゲルカラムクロマトグラフィー（展開溶媒：ｎ−へキサン）にて精製し、無色固体の目的物を得た〔収量４．２１ｇ（１２．０ｍｍｏｌ）、収率４２％〕。 Synthesis Example 4 {Synthesis of p, p '-[N- (3-bromophenyl)] ditoluylamine (3BPDTA)}

In a 200 ml four-necked flask, 8.00 g (28.3 mmol) of 1-bromo-3-iodobenzene, 7.26 g (36.8 mmol) of p, p'-di-p-toluylamine, 6.0 g of Cu powder (9.4 mmol), potassium carbonate 11.7 g (84.9 mmol) and o-dichlorobenzene 30 ml were added, and the mixture was stirred at 180 ° C. for 6 hours under a nitrogen stream. The reaction solution was filtered, and the filtrate was concentrated and purified by silica gel column chromatography (developing solvent: n-hexane) to obtain the desired product as a colorless solid [yield 4.21 g (12.0 mmol), 42%].

１００ｍｌ四つ口フラスコに２，２′−ビフェニルジホウ酸（２ＢＰＤＢＡ）１．５０ｇ（６．２０ｍｍｏｌ）、４−ブロモフェニル−ジ−（ｐ−トリル）−アミン（４ＢＰＤＴＡ）４．００ｇ（１１．４ｍｍｏｌ）、テトラキス（トリフェニルホスフィン）パラジウム（０） ３４ｍｇ（０．０２９ｍｍｏｌ）、トルエン ３０ｍｌ、テトラブチルアンモニウムヒドロキシドのメタノール溶液（１．０Ｍ）１９ｍｌを加え、窒素気流下４８時間還流した。室温に冷却後、反応液を濃縮し、クロロホルムに溶解させ不溶物を濾過、ろ液を５％塩酸、飽和食塩水で洗浄した。有機層を硫酸マグネシウムにて乾燥し、溶媒留去後、シリカゲルカラムクロマトグラフィー（展開溶媒：クロロホルム／ｎ−へキサン＝１：３）にて精製し白色固体の目的物を得た〔収量０．９３ｇ（１．３３ｍｍｏｌ）、収率２２％〕。この熱特性および電気化学特性を表１に示す。 Example 1 {Synthesis of 2,2'-bis [4 "-(N, N'-ditoluylamino) phenyl] biphenyl (4DTAPBP))}

In a 100 ml four-necked flask, 1.50 g (6.20 mmol) of 2,2′-biphenyldiboric acid (2BPDBA), 4.00 g (11.4 mmol) of 4-bromophenyl-di- (p-tolyl) -amine (4BPDTA) ), 34 mg (0.029 mmol) of tetrakis (triphenylphosphine) palladium (0), 30 ml of toluene, and 19 ml of a methanol solution of tetrabutylammonium hydroxide (1.0 M) were added and refluxed for 48 hours under a nitrogen stream. After cooling to room temperature, the reaction solution was concentrated, dissolved in chloroform, insoluble matter was filtered, and the filtrate was washed with 5% hydrochloric acid and saturated brine. The organic layer was dried over magnesium sulfate, the solvent was distilled off, and the residue was purified by silica gel column chromatography (developing solvent: chloroform / n-hexane = 1: 3) to obtain the desired product as a white solid [yield 0. 93 g (1.33 mmol), 22% yield]. The thermal and electrochemical characteristics are shown in Table 1 .

１００ｍｌ四つ口フラスコに２，２′−ビフェニルジホウ酸（２ＢＰＤＢＡ）２．００ｇ（８．３０ｍｍｏｌ）、３−ブロモフェニル−ジ−（ｐ−トリル）−アミン（３ＢＰＤＴＡ）５．３２ｇ（１５．１ｍｍｏｌ）、テトラキス（トリフェニルホスフィン）パラジウム（０） ４５ｍｇ（０．０４ｍｍｏｌ）、トルエン ３０ｍｌ、テトラブチルアンモニウムヒドロキシドのメタノール溶液（１．０Ｍ）２５ｍｌを加え、窒素気流下４８時間還流した。室温に冷却後、反応液を濃縮し、クロロホルムに溶解させ不溶物を濾過、ろ液を５％塩酸、飽和食塩水で洗浄した。有機層を硫酸マグネシウムにて乾燥し、溶媒留去後、シリカゲルカラムクロマトグラフィー（展開溶媒：クロロホルム／ｎ−へキサン＝１：３）にて精製し白色固体の目的物を得た〔収量１．４２ｇ（２．０４ｍｍｏｌ）、収率２５％〕。この熱特性および電気化学特性を表１に示す。 Example 2 {Synthesis of 2,2'-bis [3 "-(N, N'-ditoluylamino) phenyl] biphenyl (3DTAPBP))}

In a 100 ml four-necked flask, 2.00 g (8.30 mmol) of 2,2′-biphenyldiboric acid (2BPDBA), 5.32 g (15.1 mmol) of 3-bromophenyl-di- (p-tolyl) -amine (3BPDTA) ), 45 mg (0.04 mmol) of tetrakis (triphenylphosphine) palladium (0), 30 ml of toluene, and 25 ml of a solution of tetrabutylammonium hydroxide in methanol (1.0 M) were added and refluxed for 48 hours under a nitrogen stream. After cooling to room temperature, the reaction solution was concentrated, dissolved in chloroform, insoluble matter was filtered, and the filtrate was washed with 5% hydrochloric acid and saturated brine. The organic layer was dried over magnesium sulfate, the solvent was distilled off, and the residue was purified by silica gel column chromatography (developing solvent: chloroform / n-hexane = 1: 3) to obtain the desired product as a white solid [yield 1. 42 g (2.04 mmol), 25% yield]. The thermal and electrochemical characteristics are shown in Table 1 .

１００ｍｌ四つ口フラスコに２，２′−ビフェニルジホウ酸（２ＢＰＤＢＡ）２．００ｇ（８．３ｍｍｏｌ）、３−ブロモフェニル−ジフェニル−アミン（３ＢＴＰＡ）４．８９ｇ（１５．１ｍｍｏｌ）、テトラキス（トリフェニルホスフィン）パラジウム（０） ４５ｍｇ（０．０４ｍｍｏｌ）、トルエン ３０ｍｌ、テトラブチルアンモニウムヒドロキシドのメタノール溶液（１．０Ｍ）２５ｍｌを加え、窒素気流下４８時間還流した。室温に冷却後、反応液を濃縮し、クロロホルムに溶解させ不溶物を濾過、ろ液を５％塩酸、飽和食塩水で洗浄した。有機層を硫酸マグネシウムにて乾燥し、溶媒留去後、シリカゲルカラムクロマトグラフィー（展開溶媒：クロロホルム／ｎ−へキサン＝１：３）にて精製し白色固体の目的物を得た〔収量１．９７ｇ（３．０７ｍｍｏｌ）、収率３７％〕。この熱特性および電気化学特性を表１に示す。 Example 3 {Synthesis of 2,2'-bis [3 "-(N, N'-diphenylamino) phenyl] biphenyl (3DPAPBP))}

In a 100 ml four-necked flask, 2.00 g (8.3 mmol) of 2,2′-biphenyldiboric acid (2BPDBA), 4.89 g (15.1 mmol) of 3-bromophenyl-diphenyl-amine (3BTPA), tetrakis (triphenyl) Phosphine) palladium (0) 45 mg (0.04 mmol), toluene 30 ml, tetrabutylammonium hydroxide in methanol (1.0 M) 25 ml were added and refluxed for 48 hours under a nitrogen stream. After cooling to room temperature, the reaction solution was concentrated, dissolved in chloroform, insoluble matter was filtered, and the filtrate was washed with 5% hydrochloric acid and saturated brine. The organic layer was dried over magnesium sulfate, the solvent was distilled off, and the residue was purified by silica gel column chromatography (developing solvent: chloroform / n-hexane = 1: 3) to obtain the desired product as a white solid [yield 1. 97 g (3.07 mmol), yield 37%]. The thermal and electrochemical characteristics are shown in Table 1 .

Reference Application Example [α-NPD is used as a hole transport material, and as a host material of FIrpic which is a phosphorescent material , 2,2′-bis (4-carbazolylphenyl) biphenyl represented by the following [Chemical Formula 16] Blue-white light-emitting EL element using 4CzPBP)
EL element configuration:
ITO / α-NPD (400 Å) / 7 wt% FIrpic doped 4CzPBP (300 Å) / t-BuTAZ (300 Ｌｉ) / LiF (5 Å) / Al (1000 Å)
Table 2 shows the characteristics of the device.

４ＣｚＰＢＰをホストとするリン光素子において、ホール輸送材料としてα−ＮＰＤを用いるよりも、本発明の４ＤＴＡＰＢＰを用いた方が一層、各データが向上していることが判る。 Application example (EL element using 4DTAPBP as the hole transport material and 4CzPBP as the host material of the phosphorescent material)
EL element configuration:
ITO / 4DTAPBP (400Å) / 7wt% FIrpic doped 4CzPBP (300Å) / t-BuTAZ (300Å) / LiF (5Å) / Al (1000Å)
The characteristics of the device are shown in Table 2 and FIGS .

It can be seen that in the phosphorescent device having 4 CzPBP as the host, each data is further improved by using 4DTAPBP of the present invention rather than using α-NPD as the hole transport material.

In applications in Reference applications is a graph showing the EL spectrum of shows to E L element. It is a graph which shows the current density-voltage characteristic of this invention EL element shown to an application example and a reference application example. Applications and brightness of shows to E L elements in Reference applications - is a graph showing the voltage characteristic. Applications and brightness of shows to E L elements in Reference applications - is a graph showing current density characteristics. Applications and luminous efficiency shown to E L elements in Reference applications - is a graph showing the voltage characteristic. Applications current efficiency indicates to E L elements in Reference applications - is a graph showing the voltage characteristic.

Claims (5)

Quarter phenylene derivative represented by the following general formula (1) .

[In the formula, any one of R ^{1 to} R ⁵ is a group represented by the following [Chemical Formula 2], and the other R ^{1 to} R ⁵ and R ^{6 to} R ¹³ are hydrogen and have 1 to 4 carbon atoms. alkyl group, an alkoxy group (having 1 to 4 carbon atoms in the alkyl moiety), an aryl group having 6 to 20 carbon atoms, an aryloxy group (having 6 to 20 carbon atoms in the aryl moiety), a hetero aryloxy group (the heteroaryl moiety is 5 to 19 carbons and nitrogen) , alkoxycarbonyl group (C1-C4 of alkyl part) , aryloxycarbonyl group (C6-C20 of aryl part) , heteroaryloxycarbonyl group (heteroaryl part is 5) It consists to 19 carbons and nitrogen), and Oh Ru are independently a group selected from the group consisting of fluorine. ]

(Wherein each Ar ¹ and Ar ² are independently a heteroaryl group comprising an aryl group having 6 to 20 carbon atoms or 5 to 19 carbon and nitrogen,.) Quarter phenylene derivative according to claim 1 Symbol placement and has a wider energy gap than 3.0 eV. The organic EL element characterized by using a claim 1 or 2 quarter phenylene derivative according. The organic EL device according to claim 3 , wherein a phosphorescent material is used as the light emitting material. The organic EL element according to claim 4, wherein a phosphorescent material exhibiting blue light emission whose emission peak wavelength is shorter than 480 nm is used as a light emitting material.

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