JPH0899941A - Amine compound - Google Patents
Amine compoundInfo
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- JPH0899941A JPH0899941A JP25968894A JP25968894A JPH0899941A JP H0899941 A JPH0899941 A JP H0899941A JP 25968894 A JP25968894 A JP 25968894A JP 25968894 A JP25968894 A JP 25968894A JP H0899941 A JPH0899941 A JP H0899941A
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Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、有機電界発光素子など
に用いられる電荷輸送材料として有用な新規アミン化合
物に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel amine compound useful as a charge transport material used in organic electroluminescent devices and the like.
【０００２】[0002]
【従来の技術】有機化合物を構成要素とする電界発光素
子は、従来より検討されていたが、充分な発光特性が得
られていなかった。しかし、近年数種の有機材料を積層
した構造とすることにより、その特性が著しく向上し、
以来、有機物を用いた電界発光素子に関する検討が活発
に行われている。この積層構造とした電界発光素子はコ
ダック社のＣ．Ｗ．Ｔａｎｇらにより最初に報告された
が〔Appl.Phys.Lett.51(1987)913〕、この中では１０Ｖ
以下の電圧で１０００ｃｄ／ｍ2以上の発光が得られて
おり、従来より実用化されている無機電界発光素子が２
００Ｖ以上の高電圧を必要とするのに比べ、格段に高い
特性を有することが示された。2. Description of the Related Art Electroluminescent devices containing organic compounds as constituent elements have been studied in the past, but sufficient luminous characteristics have not been obtained. However, recently, by adopting a structure in which several kinds of organic materials are laminated, the characteristics are significantly improved,
Since then, studies on electroluminescent devices using organic substances have been actively conducted. This electroluminescent device having a laminated structure is manufactured by Kodak C.I. W. It was first reported by Tang et al. [Appl. Phys. Lett. 51 (1987) 913], in which 10 V
Light emission of 1000 cd / m 2 or more was obtained at the following voltage, and the inorganic electroluminescence device that has been practically used in the past is 2
It has been shown that it has significantly higher characteristics as compared with requiring a high voltage of 00 V or higher.
【０００３】これら積層構造の電界発光素子は、有機蛍
光体と電荷輸送性の有機物（電荷輸送材）及び電極を積
層した構造となっており、それぞれの電極より注入され
た電荷（正孔及び電子）が電荷輸送材中を移動して、そ
れらが再結合することによって発光する。有機蛍光体と
しては、８−キノリノ−ルアルミニウム錯体やクマリリ
ンなど蛍光を発する有機色素などが用いられている。ま
た、電荷輸送材としては電子写真感光体用有機材料とし
て良く知られた種々の化合物を用いて検討されており、
例えばＮ，Ｎ’−ジ（ｍ−トリル）−Ｎ，Ｎ’−ジフェ
ニルベンジジンや１，１−ビス〔Ｎ，Ｎ−ジ（ｐ−トリ
ル）アミノフェニル〕シクロヘキサンといったジアミン
化合物や４−（Ｎ，Ｎ，−ジフェニルアミノ）ベンズア
ルデヒド−Ｎ，Ｎ−ジフェニルヒドラゾンなどのヒドラ
ゾン化合物が挙げられる。更に、銅フタロシアニンのよ
うなポルフィリン化合物も用いられている。These laminated electroluminescent devices have a structure in which an organic phosphor, a charge-transporting organic material (charge-transporting material), and electrodes are stacked, and charges (holes and electrons) injected from the respective electrodes are stacked. ) Migrate in the charge transport material, and they recombine to emit light. As the organic phosphor, an 8-quinolinol aluminum complex, an organic dye that fluoresces such as coumarin, or the like is used. Further, as the charge transport material, various compounds well known as organic materials for electrophotographic photoreceptors have been studied,
For example, diamine compounds such as N, N'-di (m-tolyl) -N, N'-diphenylbenzidine and 1,1-bis [N, N-di (p-tolyl) aminophenyl] cyclohexane and 4- (N, And hydrazone compounds such as N, -diphenylamino) benzaldehyde-N, N-diphenylhydrazone. Furthermore, porphyrin compounds such as copper phthalocyanine have also been used.
【０００４】ところで、有機電界発光素子は、高い発光
特性を有しているが、発光時の安定性や保存安定性の点
で充分ではなく、実用化には至っていない。素子の発光
時の安定性、保存安定性における問題点の一つとして、
電荷輸送材の安定性が指摘されている。電界発光素子の
有機物で形成されている層は百〜数百ｎｍと非常に薄
く、単位厚さあたりに加えられる電圧は非常に高い。ま
た、発光や通電による発熱もあり、従って電荷輸送材に
は電気的、熱的あるいは化学的な安定性が要求される。
更に、一般的に素子中の電荷輸送層は、非晶質の状態に
あるが、発光または保存による経時により、結晶化を起
こし、これによって発光が阻害されたり、素子破壊を起
こすといった現象が見られている。よって電荷輸送材に
は非晶質すなわちガラス状態を容易に形成し、かつ安定
に保持する性能が要求される。By the way, although the organic electroluminescence device has high light emission characteristics, it is not sufficient in terms of stability during light emission and storage stability and has not been put into practical use. As one of the problems in the stability of the device when emitting light and the storage stability,
The stability of charge transport materials has been pointed out. The layer formed of an organic material of the electroluminescent device is very thin, which is 100 to several hundreds nm, and the voltage applied per unit thickness is very high. Further, there is also heat generation due to light emission and electric conduction, so that the charge transport material is required to have electrical, thermal or chemical stability.
In addition, the charge transport layer in the device is generally in an amorphous state, but there is a phenomenon that luminescence occurs or crystallization occurs with time due to storage, which causes light emission to be hindered or device damage. Has been. Therefore, the charge transport material is required to have a property of easily forming an amorphous state, that is, a glass state, and stably maintaining it.
【０００５】このような電荷輸送材に起因する発光素子
の安定性に関し、例えば、ジアミン化合物やポルフィリ
ン化合物においては、電気的、熱的に安定なものが多
く、高い発光特性が得られているが、結晶化による素子
の劣化は解決されていない。また、ヒドラゾン化合物
は、電気的、熱的安定性において充分ではないため、好
ましい材料ではない。Regarding the stability of the light emitting device due to such a charge transport material, for example, many diamine compounds and porphyrin compounds are electrically and thermally stable, and high light emitting characteristics are obtained. The deterioration of the element due to crystallization has not been solved. Further, the hydrazone compound is not a preferable material because it is insufficient in electrical and thermal stability.
【０００６】[0006]
【発明が解決しようとする課題】本発明の目的は、発光
特性のみならず、発光時の安定性、保存安定性に優れた
有機電界発光素子を実現し得る電荷輸送材として有用
で、かつ新規なアミン化合物を提供することにある。DISCLOSURE OF THE INVENTION The object of the present invention is to be useful as a charge transporting material which can realize an organic electroluminescent device which is excellent not only in light emission characteristics but also in stability during light emission and storage stability, and is novel. To provide a simple amine compound.
【０００７】[0007]
【課題を解決するための手段】本発明によれば、下記一
般式（１）で表されるアミン化合物が提供される。According to the present invention, an amine compound represented by the following general formula (1) is provided.
【０００８】[0008]
【化１２】 [Chemical 12]
【０００９】（式中、Ｒ1、Ｒ2、Ｒ3は同一でも異なっ
ていても良く、水素原子、低級アルキル基、低級アルコ
キシ基、置換または無置換のアリール基を表し、Ｒ4は
水素原子 、低級アルキル基、低級アルコキシ基、また
は塩素原子を表す。また、Ａ1は下記式(In the formula, R1, R2 and R3 may be the same or different and each represents a hydrogen atom, a lower alkyl group, a lower alkoxy group or a substituted or unsubstituted aryl group, and R4 is a hydrogen atom or a lower alkyl group. , A lower alkoxy group, or a chlorine atom, and A1 is represented by the following formula:
【００１０】[0010]
【化１３】 [Chemical 13]
【００１１】[0011]
【化１４】 [Chemical 14]
【００１２】[0012]
【化１５】 [Chemical 15]
【００１３】[0013]
【化１６】 [Chemical 16]
【００１４】[0014]
【化１７】 [Chemical 17]
【００１５】で表される。） 又、本発明によれば、下記一般式（２）で表されるアミ
ン化合物が提供される。It is represented by The present invention also provides an amine compound represented by the following general formula (2).
【００１６】[0016]
【化１８】 [Chemical 18]
【００１７】（式中、Ｒ5、Ｒ6は同一でも異なっていて
も良く、水素原子、低級アルキル基、低級アルコキシ
基、置換または無置換のアリール基を表し、Ｒ7は水素
原子、低級アルキル基、低級アルコキシ基、または塩素
原子を表す。また、Ａ2は下記式(In the formula, R5 and R6 may be the same or different and each represents a hydrogen atom, a lower alkyl group, a lower alkoxy group or a substituted or unsubstituted aryl group, and R7 is a hydrogen atom, a lower alkyl group or a lower group. Represents an alkoxy group or a chlorine atom, and A2 represents the following formula
【００１８】[0018]
【化１９】 [Chemical 19]
【００１９】[0019]
【化２０】 Embedded image
【００２０】[0020]
【化２１】 [Chemical 21]
【００２１】[0021]
【化２２】 [Chemical formula 22]
【００２２】で表される。） 本発明の一般式（１）で表されるアミン化合物は新規化
合物であり、これらは、相当するトリフェニルベンジジ
ン化合物とジハロゲン化物との縮合反応、あるいは、相
当するジアミノ化合物のＮ，Ｎ’−ジアセチル体と相当
する４’−ハロゲン化ビフェニリルアセトアニリド化合
物との縮合反応による生成物を加水分解した後、相当す
るハロゲン化アリ−ルと縮合反応することにより合成す
ることができる。これら縮合反応はウルマン反応として
知られる方法である。例えば、下記式It is represented by ) The amine compound represented by the general formula (1) of the present invention is a novel compound, which is a condensation reaction between a corresponding triphenylbenzidine compound and a dihalide, or a corresponding diamino compound N, N′-. It can be synthesized by hydrolyzing a product obtained by a condensation reaction between a diacetyl compound and a corresponding 4'-halogenated biphenylylacetanilide compound, and then subjecting the product to a condensation reaction with a corresponding halogenated aryl. These condensation reactions are methods known as the Ullmann reaction. For example, the following formula
【００２３】[0023]
【化２３】 [Chemical formula 23]
【００２４】（式中、Ｒ4は上で定義した通りであり、
Ｘは塩素原子、臭素原子または沃素原子を表す。但し、
Ｒ4とＸが同時に塩素原子ではない。）で表される４，
４’−ジハロゲン化ビフェニル化合物を下記式Where R4 is as defined above,
X represents a chlorine atom, a bromine atom or an iodine atom. However,
R4 and X are not chlorine atoms at the same time. ) Represented by 4,
A 4′-dihalogenated biphenyl compound is represented by the following formula
【００２５】[0025]
【化２４】 [Chemical formula 24]
【００２６】（式中、Ｒ1は上で定義した通りであ
る。）で表されるアニリド化合物と等量で縮合させ、下
記式(Wherein R 1 is as defined above) is condensed with an anilide compound represented by the formula:
【００２７】[0027]
【化２５】 [Chemical 25]
【００２８】（式中、Ｒ1、Ｒ4、Ｘは上で定義した通り
である。但し、Ｒ4とＸが同時に塩素原子ではない。）
で表される４’−ハロゲン化ビフェニリルアセトアニリ
ド化合物が得られる。この４’−ハロゲン化ビフェニリ
ルアセトアニリド化合物は、更に下記式(In the formula, R1, R4 and X are as defined above, provided that R4 and X are not chlorine atoms at the same time.)
A 4'-halogenated biphenylyl acetanilide compound represented by is obtained. This 4'-halogenated biphenylyl acetanilide compound has the following formula
【００２９】[0029]
【化２６】 [Chemical formula 26]
【００３０】（式中、Ｒ2、Ｒ3は上で定義した通りであ
る。）で表されるジフェニルアミン化合物と縮合反応し
た後、加水分解することにより、下記式After the condensation reaction with the diphenylamine compound represented by the formula (wherein R2 and R3 are as defined above), the compound is hydrolyzed to give the following formula.
【００３１】[0031]
【化２７】 [Chemical 27]
【００３２】（式中、Ｒ1、Ｒ2、Ｒ3、Ｒ4は上で定義し
た通りである。）で表されるトリフェニルベンジジン化
合物が得られる。このトリフェニルベンジジン化合物の
２当量を１当量の下記式A triphenylbenzidine compound represented by the formula (wherein R 1, R 2, R 3 and R 4 are as defined above) is obtained. 2 equivalents of this triphenylbenzidine compound are replaced by 1 equivalent of the following formula
【００３３】[0033]
【化２８】 [Chemical 28]
【００３４】（式中、Ｘ及びＡ1は上で定義した通りで
ある。）で表されるジハロゲン化物を作用させて縮合す
ることにより、本発明のアミン化合物が得られる。一
方、下記式By reacting the dihalide represented by the formula (wherein X and A1 are as defined above) to cause condensation, the amine compound of the present invention is obtained. On the other hand, the following formula
【００３５】[0035]
【化２９】 [Chemical 29]
【００３６】（式中、Ａ1は上で定義した通りであ
る。）で表されるジアミノ化合物を原料とする場合は、
アミノ基をアセチル化してジアセチル体とした後、下記
式When the raw material is a diamino compound represented by the formula (A1 is as defined above),
After acetylating the amino group to give the diacetyl derivative, the following formula
【００３７】[0037]
【化３０】 [Chemical 30]
【００３８】（式中、Ｒ1及びＸは上で定義した通りで
ある。）で表されるハロゲン化アリ−ルと縮合し、加水
分解して、下記式(Wherein R 1 and X are as defined above), condensed with a halogenated aryl and hydrolyzed to give the following formula:
【００３９】[0039]
【化３１】 [Chemical 31]
【００４０】（式中、Ｒ1及びＸは上で定義した通りで
ある。）で表されるジアリ−ルジアミノ化合物とする。
これに、ジハロゲン化ビフェニル化合物とアニリド化合
物より上と同様にして合成した下記式(In the formula, R 1 and X are as defined above.) A diaryldiamino compound represented by the formula
To this, the following formula synthesized in the same manner as above for the dihalogenated biphenyl compound and the anilide compound
【００４１】[0041]
【化３２】 [Chemical 32]
【００４２】（式中、Ｒ2、Ｒ4及びＸは上で定義した通
りである。但し、Ｒ4とＸは同時に塩素原子ではな
い。）で表される４’−ハロゲン化ビフェニリルアセト
アニリド化合物を縮合させ、加水分解することにより、
下記一般式（３）(Wherein R 2, R 4 and X are as defined above, provided that R 4 and X are not chlorine atoms at the same time) and the 4′-halogenated biphenylyl acetanilide compound is condensed. , By hydrolysis,
The following general formula (3)
【００４３】[0043]
【化３３】 [Chemical 33]
【００４４】（式中、Ｒ1、Ｒ2、Ｒ4及びＡ1は上で定義
した通りである。）で表されるテトラアミン化合物が得
られる。更にこのテトラアミン化合物に、下記式A tetraamine compound represented by the formula: wherein R1, R2, R4 and A1 are as defined above is obtained. Furthermore, this tetraamine compound has the following formula
【００４５】[0045]
【化３４】 Embedded image
【００４６】（式中、Ｒ3及びＸは上で定義した通りで
ある。）で表されるハロゲン化アリ−ルを縮合させるこ
とによっても本発明の化合物を得ることができる。ま
た、前記縮合反応のうち、４，４’−ジハロゲン化ビフ
ェニルとアセトアニリド化合物との反応においては、ア
セトアニリド化合物の代わりにベンズアニリドを用いて
も良い。The compound of the present invention can also be obtained by condensing a halogenated aryl represented by the formula (wherein R 3 and X are as defined above). Further, in the reaction of 4,4′-dihalogenated biphenyl with an acetanilide compound in the condensation reaction, benzanilide may be used instead of the acetanilide compound.
【００４７】又、本発明の一般式（２）で表されるアミ
ン化合物は新規化合物であり、これらは、相当するハロ
ゲン化ビフェニリルジフェニルアミン化合物と相当する
ジアミン化合物とを縮合させることにより合成すること
ができる。あるいはまた相当するハロゲン化ビフェニリ
ルジフェニルアミン化合物とアミド化合物との縮合反応
による生成物を加水分解して得られるトリアミン化合物
を相当するジハロゲン化物と縮合させることによっても
合成することができる。これら縮合反応はウルマン反応
として知られる方法である。例えば、下記式The amine compound represented by the general formula (2) of the present invention is a novel compound, and these are synthesized by condensing the corresponding halogenated biphenylyldiphenylamine compound and the corresponding diamine compound. You can Alternatively, it can also be synthesized by condensing a triamine compound obtained by hydrolyzing a product obtained by the condensation reaction of a corresponding halogenated biphenylyldiphenylamine compound and an amide compound with a corresponding dihalide. These condensation reactions are methods known as the Ullmann reaction. For example, the following formula
【００４８】[0048]
【化３５】 Embedded image
【００４９】（式中、Ｒ7及びＸは上で定義した通りで
ある。但し、Ｒ7とＸは同時に塩素原子ではない。）で
表される４，４’−ジハロゲン化ビフェニル化合物を下
記式(Wherein R7 and X are as defined above, provided that R7 and X are not chlorine atoms at the same time), and a 4,4'-dihalogenated biphenyl compound represented by the following formula:
【００５０】[0050]
【化３６】 Embedded image
【００５１】（式中、Ｒ5、Ｒ6は上で定義した通りであ
る。）で表されるジフェニルアミン化合物と等量で縮合
させ、下記式(Wherein R5 and R6 are as defined above) and condensed with a diphenylamine compound represented by the following formula:
【００５２】[0052]
【化３７】 Embedded image
【００５３】（式中、Ｒ5、Ｒ6、Ｒ7、Ｘは上で定義し
た通りである。但し、Ｒ7とＸが同時に塩素原子ではな
い。）で表される４’−ハロゲン化ビフェニリルジフェ
ニルアミン化合物が得られる。この４’−ハロゲン化ビ
フェニリルジフェニルアミン化合物４当量を下記式(Wherein R5, R6, R7, and X are as defined above, provided that R7 and X are not chlorine atoms at the same time), and the 4'-halogenated biphenylyldiphenylamine compound is can get. 4 equivalents of this 4'-halogenated biphenylyldiphenylamine compound are represented by the following formula:
【００５４】[0054]
【化３８】 [Chemical 38]
【００５５】（式中、Ａ2は上で定義した通りであ
る。）で表されるジアミン化合物１当量に作用させて縮
合することにより、本発明のアミン化合物が得られる。By reacting 1 equivalent of the diamine compound represented by the formula (wherein A 2 is as defined above) and condensing, the amine compound of the present invention is obtained.
【００５６】一方、ジハロゲン化ビフェニル化合物とジ
フェニルアミン化合物より上と同様にして合成した下記
式On the other hand, the following formula synthesized from the dihalogenated biphenyl compound and the diphenylamine compound in the same manner as above
【００５７】[0057]
【化３９】 [Chemical Formula 39]
【００５８】（式中、Ｒ5、Ｒ6、Ｒ7、及びＸは上で定
義した通りである。但し、Ｒ7とＸは同時に塩素原子で
はない。）で表される４’−ハロゲン化ビフェニリルジ
フェニルアミン化合物２当量をアセトアミド１当量に縮
合させ、加水分解することにより、下記式(Wherein R5, R6, R7, and X are as defined above, provided that R7 and X are not chlorine atoms at the same time). By condensing 2 equivalents to 1 equivalent of acetamide and hydrolyzing, the following formula
【００５９】[0059]
【化４０】 [Chemical 40]
【００６０】（式中、Ｒ5、Ｒ6、Ｒ7は上で定義した通
りである。）で表されるトリアミン化合物が得られる。
更にこのトリアミン化合物２当量を下記式A triamine compound represented by the formula: wherein R5, R6 and R7 are as defined above is obtained.
Further, 2 equivalents of this triamine compound are represented by the following formula
【００６１】[0061]
【化４１】 Embedded image
【００６２】（式中、Ｘ及びＡ2は上で定義した通りで
ある。）で表されるジハロゲン化物１当量に作用させ縮
合することによっても本発明の化合物を得ることができ
る。また、前記縮合反応のうち、４’−ハロゲン化ビフ
ェニリルジフェニルアミン化合物２当量とアセトアミド
１当量との縮合反応においては、アセトアミドの代わり
にベンズアミドを用いても良い。The compound of the present invention can also be obtained by allowing 1 equivalent of the dihalide represented by the formula (wherein X and A2 are as defined above) to be condensed. In addition, in the condensation reaction of 2 ′ of the 4′-halogenated biphenylyldiphenylamine compound and 1 equivalent of acetamide in the condensation reaction, benzamide may be used instead of acetamide.
【００６３】前述した、種々のハロゲン化アリ−ル類と
種々のアミン化合物の縮合反応において、反応は無溶媒
下または溶媒存在下で行うが、溶媒としてはニトロベン
ゼンやジクロロベンゼンなどが用いられる。脱酸剤とし
ての塩基性化合物には炭酸カリウム、炭酸ナトリウム、
炭酸水素ナトリウム、水酸化カリウム、水酸化ナトリウ
ムなどが用いられる。また、通常、銅粉やハロゲン化銅
などの触媒を用いて反応させる。反応温度は通常１６０
〜２３０゜Ｃである。In the above-mentioned condensation reaction of various halogenated aryls with various amine compounds, the reaction is carried out without solvent or in the presence of a solvent, and nitrobenzene, dichlorobenzene or the like is used as the solvent. Basic compounds as deoxidizers include potassium carbonate, sodium carbonate,
Sodium hydrogen carbonate, potassium hydroxide, sodium hydroxide and the like are used. Further, usually, the reaction is carried out using a catalyst such as copper powder or copper halide. Reaction temperature is usually 160
~ 230 ° C.
【００６４】本発明により得られた新規なアミン化合物
は、容易にガラス状態を形成しかつ安定に保持すると共
に、熱的、化学的にも安定であり、有機電界発光素子に
おける電荷輸送材料として極めて有用である。また、基
本的に高い電荷輸送能を有しており、電子写真感光体を
はじめとする電荷輸送性を利用する素子、システムに有
効な材料であることはいうまでもない。このようにして
得られた本発明の具体的な化合物を以下に示す。The novel amine compound obtained by the present invention easily forms a glass state and stably maintains it, and is also thermally and chemically stable, and is extremely useful as a charge transport material in an organic electroluminescence device. It is useful. Needless to say, it is a material that has a basically high charge transporting ability and is effective for an element and a system that utilize the charge transporting ability such as an electrophotographic photoreceptor. The specific compounds of the present invention thus obtained are shown below.
【００６５】[0065]
【化４２】 [Chemical 42]
【００６６】[0066]
【化４３】 [Chemical 43]
【００６７】[0067]
【化４４】 [Chemical 44]
【００６８】[0068]
【化４５】 [Chemical formula 45]
【００６９】[0069]
【化４６】 [Chemical formula 46]
【００７０】[0070]
【化４７】 [Chemical 47]
【００７１】[0071]
【化４８】 [Chemical 48]
【００７２】[0072]
【化４９】 [Chemical 49]
【００７３】[0073]
【化５０】 [Chemical 50]
【００７４】[0074]
【化５１】 [Chemical 51]
【００７５】[0075]
【化５２】 [Chemical 52]
【００７６】[0076]
【化５３】 Embedded image
【００７７】[0077]
【化５４】 [Chemical 54]
【００７８】[0078]
【化５５】 [Chemical 55]
【００７９】[0079]
【化５６】 [Chemical 56]
【００８０】[0080]
【化５７】 [Chemical 57]
【００８１】[0081]
【化５８】 [Chemical 58]
【００８２】[0082]
【化５９】 Embedded image
【００８３】[0083]
【化６０】 [Chemical 60]
【００８４】[0084]
【化６１】 [Chemical formula 61]
【００８５】[0085]
【化６２】 [Chemical formula 62]
【００８６】[0086]
【化６３】 [Chemical formula 63]
【００８７】[0087]
【化６４】 [Chemical 64]
【００８８】[0088]
【化６５】 [Chemical 65]
【００８９】[0089]
【化６６】 [Chemical formula 66]
【００９０】[0090]
【化６７】 Embedded image
【００９１】以下、本発明を実施例により詳細に説明す
る。The present invention will be described in detail below with reference to examples.
【実施例】以下に本発明を実施例によって具体的に示す
が、本発明は以下の実施例によって限定されるものでは
ない。EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to the following examples.
【００９２】実施例１ アセトアニリド２０．０ｇ（０．１５モル）と４，４’
−ジヨ−ドビフェニル６５．０ｇ（０．１６モル）、無
水炭酸カリウム２２．１ｇ（０．１６モル）、銅粉２．
１６ｇ（０．０３４モル）、ニトロベンゼン３５ｍｌを
混合し、１９０〜２０５゜Ｃで１０時間反応させた。反
応生成物をトルエン２００ｍｌで抽出し、不溶分をろ別
除去後、濃縮乾固した。これをカラムクロマトにより精
製して（担体；シリカゲル、溶離液；トルエン／酢酸エ
チル＝６／１）、Ｎ−（４’−ヨ−ド−４−ビフェニリ
ル）アセトアニリド４０．２ｇ（収率６４．８％）を得
た。融点は、１３５．０〜１３６．０゜Ｃであった。Example 1 20.0 g (0.15 mol) of acetanilide and 4,4 '
-Diyodobiphenyl 65.0 g (0.16 mol), anhydrous potassium carbonate 22.1 g (0.16 mol), copper powder 2.
16 g (0.034 mol) and 35 ml of nitrobenzene were mixed and reacted at 190 to 205 ° C for 10 hours. The reaction product was extracted with 200 ml of toluene, the insoluble matter was removed by filtration, and the mixture was concentrated to dryness. This was purified by column chromatography (carrier; silica gel, eluent: toluene / ethyl acetate = 6/1), and 40.2 g of N- (4'-iodo-4-biphenylyl) acetanilide (yield 64.8). %) Was obtained. The melting point was 135.0 to 136.0 ° C.
【００９３】次に４，４’−ジアミノ−１，１’−ジフ
ェニルエーテル１２．０ｇ（０．０６モル）を氷酢酸１
００ｍｌに溶解し、４０゜Ｃで無水酢酸１３．５ｇ
（０．１３モル）を滴下した。滴下後４５゜Ｃで２時間
反応し、反応液を氷水７００ｍｌ中へ注加して、析出し
た結晶をろ過、水洗、乾燥した。この結晶をメタノ−ル
１６０ｍｌで再結晶し、４，４’−ジアセトアミド−
１，１’−ジフェニルエーテル１３．４ｇ（収率；７
８．３％）を得た。融点は２３１．０〜２３１．５゜Ｃ
であった。Next, 12.0 g (0.06 mol) of 4,4'-diamino-1,1'-diphenyl ether was added to 1 part of glacial acetic acid.
Dissolve in 00 ml and acetic anhydride 13.5 g at 40 ° C
(0.13 mol) was added dropwise. After the dropwise addition, the mixture was reacted at 45 ° C for 2 hours, poured into 700 ml of ice water, and the precipitated crystals were filtered, washed with water, and dried. The crystals were recrystallized from 160 ml of methanol to give 4,4'-diacetamide-
1,1'-diphenyl ether 13.4 g (yield; 7
8.3%). Melting point is 231.0-231.5 ° C
Met.
【００９４】続いて４，４’−ジアセトアミド−１，
１’−ジフェニルエーテル７．１１ｇ（０．０２５モ
ル）、Ｎ−（４’−ヨード−４−ビフェニリル）アセト
アニリド２２．７ｇ（０．０５５モル）、無水炭酸カリ
ウム７．６０ｇ（０．０５５モル）及び銅粉０．７０ｇ
（０．０１１モル）、ニトロベンゼン１０ｍｌを混合
し、１８５〜１９５゜Ｃで８時間反応させた。反応生成
物をトルエン５００ｍｌで抽出し、不溶分をろ別除去
後、濃縮してオイル状物とした。オイル状物はイソアミ
ルアルコ−ル６０ｍｌに溶解し、水１ｍｌ、８５％水酸
化カリウム１．８ｇ（０．０２７モル）を加え、１３０
゜Ｃで加水分解した。水蒸気蒸留でイソアミルアルコ−
ルを留去後、トルエン２５０ｍｌで抽出し、水洗、乾燥
して濃縮した。濃縮物はカラムクロマトにより精製して
（担体；シリカゲル、溶離液；トルエン／酢酸エチル＝
１／１）、４，４’−ビス（４’−ジアニリノ−４−ビ
フェニリルアミノ）−１，１’−ジフェニルエーテル
８．９３ｇ（収率５２．０％）を得た。融点は２８５．
５〜２８６．５゜Ｃであった。Subsequently, 4,4'-diacetamide-1,
7.11 g (0.025 mol) of 1'-diphenyl ether, 22.7 g (0.055 mol) of N- (4'-iodo-4-biphenylyl) acetanilide, 7.60 g (0.055 mol) of anhydrous potassium carbonate and Copper powder 0.70g
(0.011 mol) and 10 ml of nitrobenzene were mixed and reacted at 185 to 195 ° C for 8 hours. The reaction product was extracted with 500 ml of toluene, the insoluble matter was removed by filtration, and the mixture was concentrated to give an oily substance. The oily substance was dissolved in 60 ml of isoamyl alcohol, added with 1 ml of water and 1.8 g (0.027 mol) of 85% potassium hydroxide, and added to 130 ml.
Hydrolyzed at ° C. Isoamyl alcohol by steam distillation
After distilling off the solvent, it was extracted with 250 ml of toluene, washed with water, dried and concentrated. The concentrate was purified by column chromatography (carrier; silica gel, eluent; toluene / ethyl acetate =
1/1), 4,4'-bis (4'-dianilino-4-biphenylylamino) -1,1'-diphenyl ether (8.93 g, yield 52.0%) was obtained. The melting point is 285.
It was 5 to 286.5 ° C.
【００９５】更に、４，４’−ビス（４’−アニリノ−
４−ビフェニリルアミノ）−１，１’−ジフェニルエー
テル６．８７ｇ（０．０１モル）、ヨ−ドベンゼン２
４．５ｇ（０．１２モル）、無水炭酸カリウム６．０８
ｇ（０．０４４モル）、銅粉０ ．５１ｇ（０．００８
モル）を混合し、１９５〜２１０゜Ｃで１６．５時間反
応させた。反応生成物をトルエン１００ｍｌで抽出し、
不溶分をろ別除去、濃縮後、ｎ−ヘキサン３５０ｍｌを
加えて、粗結晶を取り出した。粗結晶は、カラムクロマ
トにより精製して（担体；シリカゲル、溶離液；トルエ
ン／ｎ−ヘキサン＝３／４）、４，４’−ビス（４’−
ジフェニルアミノ−４−ビフェニリルアニリノ）−１，
１’−ジフェニルエーテル４．０６ｇ（収率；４１．０
％）を得た 。融点は１７５．０〜１７６．５゜Ｃであ
った。図１には赤外線吸収スペクトル（測定機器；日本
分光工業（株）製ＩＲ−７００、測定法；ＫＢｒ錠剤
法）を示す。更に、本発明より見いだされた化合物が有
用であることを、具体的な応用例によって説明する。Furthermore, 4,4'-bis (4'-anilino-
4-biphenylylamino) -1,1'-diphenyl ether 6.87 g (0.01 mol), iodobenzene 2
4.5 g (0.12 mol), anhydrous potassium carbonate 6.08
g (0.044 mol), copper powder 0. 51 g (0.008
Mol) and mixed and reacted at 195 to 210 ° C for 16.5 hours. The reaction product is extracted with 100 ml of toluene,
After removing insolubles by filtration and concentrating, 350 ml of n-hexane was added to take out crude crystals. The crude crystals were purified by column chromatography (carrier; silica gel, eluent: toluene / n-hexane = 3/4), and 4,4'-bis (4'-
Diphenylamino-4-biphenylylanilino) -1,
4.06 g of 1'-diphenyl ether (yield; 41.0
%). The melting point was 175.0 to 176.5 ° C. FIG. 1 shows an infrared absorption spectrum (measuring instrument; IR-700 manufactured by JASCO Corporation, measuring method; KBr tablet method). Further, the usefulness of the compounds found from the present invention will be explained by specific application examples.
【００９６】応用例１ 十分に洗浄したガラス基板（ＩＴＯ電極は成膜済み）
に、前記実施例１で得られた化合物〔一般式（１）；Ｒ
1＝Ｈ、Ｒ2＝Ｈ、Ｒ3＝Ｈ、Ｒ4＝Ｈ及びＡ1は下記式で
表される。〕Application Example 1 A glass substrate that has been thoroughly washed (ITO electrodes have already been formed)
And the compound obtained in Example 1 [general formula (1); R
1 = H, R2 = H, R3 = H, R4 = H and A1 are represented by the following formulas. ]
【００９７】[0097]
【化６８】 [Chemical 68]
【００９８】を電荷輸送材として、０．１ｎｍ／秒の速
度で真空蒸着により５０ｎｍの厚さまで蒸着した。蒸着
した膜の上に、発光材として、精製したトリス（８−キ
ノリノ−ル）アルミニウム錯体を真空蒸着により、同じ
く０．１ｎｍ／秒の速度で、５０ｎｍの厚さまで蒸着し
た。更に、この膜の上に、真空蒸着によりＭｇ／Ａｇ電
極を１００ｎｍの厚さで形成して、ＥＬ素子を作製し
た。これらの蒸着は、途中で真空を破らずに連続して行
った。また、膜厚は水晶振動子によってモニタ−した。
素子作製後、直ちに乾燥窒素中で電極の取り出しを行
い、引続き特性の測定を行った。素子の発光特性は １
００ｍＡ／ｃｍ2の電流を印加した場合の発光輝度で定
義し、発光の寿命は ２００ｃｄ／ｍ2の発光が得られる
電流を連続で印加し、輝度が １００ｃｄ／ｃｍ2になる
までの時間とした。また、保存安定性は室温、乾燥空気
中に一定時間放置後、２０ｍＡ／ｃｍ2 の電流を印加
し、輝度が初期発光特性の半分になるまでの時間で定義
した。測定の結果、発光特性は３１００ｃｄ／ｍ2、発
光の寿命は５８０時間、保存安定性は２１００時間であ
った。比較のために、電荷輸送材として、Ｎ，Ｎ’−ジ
（ｍ−トリル）−Ｎ，Ｎ’−ジフェニルベンジジンを用
い、同様の条件でＥＬ素子を作製しその特性を調べた。
発光特性、発光の寿命、保存安定性はそれぞれ、２２０
０ｃｄ／ｍ2、２２０時間、４６０時間であった。Using as a charge transport material, vacuum deposition was performed at a rate of 0.1 nm / sec. To a thickness of 50 nm. On the vapor-deposited film, purified tris (8-quinolinol) aluminum complex as a luminescent material was vapor-deposited by vacuum vapor deposition at a rate of 0.1 nm / sec to a thickness of 50 nm. Further, a Mg / Ag electrode having a thickness of 100 nm was formed on this film by vacuum vapor deposition to fabricate an EL device. These vapor depositions were continuously performed without breaking the vacuum on the way. The film thickness was monitored by a crystal oscillator.
Immediately after the device was manufactured, the electrode was taken out in dry nitrogen, and the characteristics were continuously measured. The emission characteristics of the device are 1
It is defined as the emission brightness when a current of 00 mA / cm 2 is applied, and the life of emission is the time until the brightness reaches 100 cd / cm 2 by continuously applying a current that gives an emission of 200 cd / m 2 . . Further, the storage stability was defined as the time until the luminance became half of the initial light emission characteristics after applying a current of 20 mA / cm 2 after leaving it in the dry air at room temperature for a certain time. As a result of the measurement, the light emission property was 3100 cd / m 2 , the light emission life was 580 hours, and the storage stability was 2100 hours. For comparison, N, N′-di (m-tolyl) -N, N′-diphenylbenzidine was used as a charge transport material, an EL device was prepared under the same conditions, and its characteristics were examined.
Luminous properties, luminescence life, and storage stability are 220
It was 0 cd / m 2 , 220 hours and 460 hours.
【００９９】[0099]
【発明の効果】本発明により見いだされた新規アミン化
合物は、電荷輸送性材料として有効に機能し、また、容
易にガラス状態を形成しかつ安定にガラス状態を保持
し、熱的、化学的にも安定なため、特に有機電界発光素
子における電荷輸送材料として有用な物質である。INDUSTRIAL APPLICABILITY The novel amine compound found by the present invention effectively functions as a charge-transporting material, easily forms a glass state and stably retains the glass state, and thermally and chemically. Since it is also stable, it is particularly useful as a charge transport material in organic electroluminescent devices.
【図１】実施例１により得られた化合物の赤外線吸収ス
ペクトルを示す図面。FIG. 1 is a drawing showing an infrared absorption spectrum of the compound obtained in Example 1.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｇ０３Ｇ 5/06 ３１９ ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification code Office reference number FI technical display location G03G 5/06 319
Claims (2)
物。 【化１】 （式中、Ｒ1、Ｒ2、Ｒ3は同一でも異なっていても良
く、水素原子、低級アルキル基、低級アルコキシ基、置
換または無置換のアリール基を表し、Ｒ4は水素原子
、低級アルキル基、低級アルコキシ基、または塩素原
子を表す。また、Ａ1は下記式 【化２】 【化３】 【化４】 【化５】 【化６】 で表される。）1. An amine compound represented by the following general formula (1): [Chemical 1] (In the formula, R1, R2 and R3 may be the same or different and each represents a hydrogen atom, a lower alkyl group, a lower alkoxy group or a substituted or unsubstituted aryl group, and R4 represents a hydrogen atom, a lower alkyl group or a lower alkoxy group. Represents a group or a chlorine atom, and A1 represents the following formula: [Chemical 3] [Chemical 4] [Chemical 5] [Chemical 6] It is represented by. )
物。 【化７】 （式中、Ｒ5、Ｒ6は同一でも異なっていても良く、水素
原子、低級アルキル基、低級アルコキシ基、置換または
無置換のアリール基を表し、Ｒ7は水素原子、低級アル
キル基、低級アルコキシ基、または塩素原子を表す。ま
た、Ａ2は下記式 【化８】 【化９】 【化１０】 【化１１】 で表される。）2. An amine compound represented by the following general formula (2). [Chemical 7] (In the formula, R5 and R6 may be the same or different and each represents a hydrogen atom, a lower alkyl group, a lower alkoxy group or a substituted or unsubstituted aryl group, and R7 is a hydrogen atom, a lower alkyl group, a lower alkoxy group, Or represents a chlorine atom, and A2 is represented by the following formula: [Chemical 9] [Chemical 10] [Chemical 11] It is represented by. )
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25968894A JP3714980B2 (en) | 1994-09-30 | 1994-09-30 | Amine compounds |
| EP19940117206 EP0650955B1 (en) | 1993-11-01 | 1994-10-31 | Amine compound and electro-luminescence device comprising same |
| DE1994612567 DE69412567T2 (en) | 1993-11-01 | 1994-10-31 | Amine compound and electroluminescent device containing it |
| US08/332,726 US5639914A (en) | 1993-11-01 | 1994-11-01 | Tetraaryl benzidines |
| US08/738,326 US5707747A (en) | 1993-11-01 | 1996-10-25 | Amine compound and electro-luminescence device comprising same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25968894A JP3714980B2 (en) | 1994-09-30 | 1994-09-30 | Amine compounds |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0899941A true JPH0899941A (en) | 1996-04-16 |
| JP3714980B2 JP3714980B2 (en) | 2005-11-09 |
Family
ID=17337543
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP25968894A Expired - Fee Related JP3714980B2 (en) | 1993-11-01 | 1994-09-30 | Amine compounds |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3714980B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009522273A (en) * | 2005-12-29 | 2009-06-11 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | Compositions containing novel compounds and electronic devices made using such compositions |
| EP2292583A3 (en) * | 2004-03-31 | 2011-08-31 | E. I. du Pont de Nemours and Company | Triarylamine compounds for use as charge transport materials |
| WO2015137384A1 (en) * | 2014-03-14 | 2015-09-17 | 日産化学工業株式会社 | Aniline derivative and use thereof |
-
1994
- 1994-09-30 JP JP25968894A patent/JP3714980B2/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2292583A3 (en) * | 2004-03-31 | 2011-08-31 | E. I. du Pont de Nemours and Company | Triarylamine compounds for use as charge transport materials |
| JP2009522273A (en) * | 2005-12-29 | 2009-06-11 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | Compositions containing novel compounds and electronic devices made using such compositions |
| WO2015137384A1 (en) * | 2014-03-14 | 2015-09-17 | 日産化学工業株式会社 | Aniline derivative and use thereof |
| JPWO2015137384A1 (en) * | 2014-03-14 | 2017-04-06 | 日産化学工業株式会社 | Aniline derivatives and uses thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3714980B2 (en) | 2005-11-09 |
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