JP3220950B2 - Benzidine compound - Google Patents
Benzidine compoundInfo
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- JP3220950B2 JP3220950B2 JP29380193A JP29380193A JP3220950B2 JP 3220950 B2 JP3220950 B2 JP 3220950B2 JP 29380193 A JP29380193 A JP 29380193A JP 29380193 A JP29380193 A JP 29380193A JP 3220950 B2 JP3220950 B2 JP 3220950B2
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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ベンジジン
化合物及びその中間体に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel benzidine compound useful as a charge transporting material for use in an organic electroluminescent device and the like and an intermediate thereof.
【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 comprising an organic compound as a component have been conventionally studied, but have not been able to obtain sufficient light-emitting characteristics. However, in recent years, by adopting a structure in which several kinds of organic materials are laminated, the characteristics are remarkably improved,
Since then, studies on electroluminescent devices using organic substances have been actively conducted. The electroluminescent device having such a laminated structure is manufactured by Kodak Corporation. W. 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.
It has been shown that it has much higher characteristics than requiring a high voltage of 00 V or more.
【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−キノリノールアルミニウム錯体やクマリン
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。[0003] These stacked electroluminescent devices have a structure in which an organic phosphor, a charge-transporting organic substance (charge-transporting material), and electrodes are laminated, and charges (holes and electrons) injected from the respective electrodes. ) Move through the charge transport material and emit light when they recombine. The organic phosphors, such as an organic dye which emits fluorescence, such as 8-quinolinol aluminum complex or click Mari emission is used. Further, as a charge transport material, various compounds well known as an organic material for an electrophotographic photoreceptor 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-diphenyl) aminobenzaldehyde-N, N-diphenylhydrazone. Further, porphyrin compounds such as copper phthalocyanine have 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〜数百ナノメーターと非
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。この点、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。[0004] Although organic electroluminescent devices have high light-emitting characteristics, they are not sufficient in terms of stability during light emission and storage stability, and have not been put to practical use. As one of the problems in the stability during light emission and storage stability of the device,
The stability of the charge transport material has been pointed out. A layer formed of an organic material of an electroluminescent device is very thin, one hundred to several hundred nanometers, and a voltage applied per unit thickness is very high. In addition, heat is generated by light emission and energization. Therefore, the charge transporting material is required to have electrical, thermal or chemical stability. Further, the charge transport layer in the device is generally in an amorphous state, but with the lapse of time due to light emission or storage, crystallization occurs, thereby observing a phenomenon that light emission is inhibited or device breakdown occurs. Have been. In this regard, the charge transport material easily forms an amorphous state, that is, a glass state,
In addition, stable holding performance is required.
【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。[0005] Regarding the stability of the light emitting device caused by such a charge transport material, for example, many diamine compounds and porphyrin compounds are electrically and thermally stable, and high light emission characteristics are obtained. However, degradation of the element due to crystallization has not been solved. In addition, hydrazone compounds are not preferable materials because of insufficient 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、かつ新規なベンジジン化合物を提供することにあ
る。SUMMARY OF THE INVENTION An object of the present invention is to provide a novel charge-transporting material which can realize an organic electroluminescent device which is excellent not only in light-emitting characteristics but also in light-emitting stability and storage stability. To provide a novel benzidine 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）で表されるベンジジン化合物が提供される。According to the present invention, there is provided a benzidine compound represented by the following general formula (1).
【０００８】[0008]
【化９】 （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、Ａは下記式Embedded image (Wherein, R 1 , R 2 and R 3 may be the same or different and represent a hydrogen atom, a lower alkyl group or a lower alkoxy group, and R 4 represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, or a chlorine atom) And A represents the following formula:
【０００９】[0009]
【化１０】 Embedded image
【００１０】[0010]
【化１１】 Embedded image
【００１１】[0011]
【化１２】 Embedded image
【００１２】[0012]
【化１３】 で表され、Ｒ5は 水素原子、低級アルキル基、低級アル
コキシ基、塩素原子を表す。）Embedded image And R 5 represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, or a chlorine atom. )
【００１３】本発明の一般式（１）で表されるベンジジ
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ールと縮合反応する
ことにより合成することができる。The benzidine compound represented by the general formula (1) of the present invention is a novel compound, which is a condensation reaction of the corresponding triphenylbenzidine compound with a dihalide or the N, N of the corresponding diamino compound. The compound 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 aryl halide.
【００１４】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。These condensation reactions are methods known as the Ullmann reaction.
【００１５】例えば、下記式For example, the following equation
【化１３】 （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Embedded image (Wherein, R 4 is as defined above, and X represents a chlorine atom, a bromine atom or an iodine atom, provided that R 4 and X are not chlorine atoms at the same time.) -A dihalogenated biphenyl compound represented by the following formula:
【００１６】[0016]
【化１４】 （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Embedded image (Wherein R 1 is as defined above) and is condensed in an equal amount with an anilide compound represented by the following formula:
【００１７】[0017]
【化１５】 （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Embedded image (Wherein R 1 , R 4 and X are as defined above, provided that R 4 and X are not chlorine atoms at the same time), whereby a 4′-halogenated biphenylyl acetanilide compound represented by the formula: . This 4'-halogenated biphenylyl acetanilide compound further has the following formula:
【００１８】[0018]
【化１６】 （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（２） Embedded image (Wherein R 2 and R 3 are as defined above), and after a condensation reaction with a diphenylamine compound represented by the following formula (2),
【００１９】[0019]
【化１７】 （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Embedded image (Wherein R 1 , R 2 , R 3 , and R 4 are as defined above), to give a triphenylbenzidine compound represented by the formula: Two equivalents of this triphenylbenzidine compound were added to 1
Equivalent equation below
【００２０】[0020]
【化１８】 （式中、Ｘ及びＡは上で定義した通りである。但し、Ｘ
とＲ5 は同時に塩素原子ではない。）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、本発明のベ
ンジジン化合物が得られる。Embedded image (Wherein X and A are as defined above, provided that X
And R 5 are not simultaneously chlorine atoms. By reacting and condensing the dihalide represented by the formula (1), the benzidine compound of the present invention can be obtained.
【００２１】一方、下記式On the other hand, the following equation
【化１９】 （式中、Ａ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Embedded image (In the formula, A is as defined above.) When a diamino compound represented by the following formula is used as a raw material, an amino group is acetylated to form a diacetyl form, and then the following formula:
【００２２】[0022]
【化２０】 （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ールと縮合し、加水分解して、下
記式Embedded image (Wherein R 1 and X are as defined above), are condensed and hydrolyzed to give the following formula
【００２３】[0023]
【化２１】 （式中、Ｒ1 及びＡは上で定義した通りである。）で表
される、ジアリー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Embedded image (Wherein R 1 and A are as defined above). In addition, a dihalogenated biphenyl compound and an anilide compound were synthesized in the same manner as above and the following formula
【００２４】[0024]
【化２２】 （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）Embedded image (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), condensing a 4′-halogenated biphenylylacetanilide compound represented by the formula: By hydrolysis, the following general formula ( 3 )
【００２５】[0025]
【化２３】 （式中、Ｒ1、Ｒ2、Ｒ4及びＡ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Embedded image (Wherein R 1 , R 2 , R 4 and A are as defined above) are obtained. Further, this tetraamine compound has the following formula
【００２６】[0026]
【化２４】 （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ー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。Embedded image (Wherein R 3 and X are as defined above). The compound of the present invention can also be obtained by condensing an aryl halide represented by the formula: In the condensation reaction between the 4,4'-dihalogenated biphenyl and the acetanilide compound, benzanilide may be used instead of the acetanilide compound.
【００２７】前述した、種々のハロゲン化アリール類と
種々のアミン化合物の縮合反応において、反応は無溶媒
下または溶媒の存在下で行うが、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１
６０〜２３０℃である。In the above-mentioned condensation reaction of various aryl halides with various amine compounds, the reaction is carried out without a solvent or in the presence of a solvent. As a solvent, nitrobenzene, dichlorobenzene or the like is used. As the basic compound as a deoxidizing agent, potassium carbonate, sodium carbonate, sodium hydrogen carbonate, potassium hydroxide, sodium hydroxide and the like are used. The reaction is usually performed using a catalyst such as copper powder or copper halide. The reaction temperature is usually 1
60-230 ° C.
【００２８】本発明により得られた新規なベンジジン化
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。The novel benzidine compound obtained by the present invention easily forms a glassy state, stably maintains the glassy state, is thermally and chemically stable, and is extremely useful as a charge transporting material in an organic electroluminescent device. Useful. In addition, it naturally has a high charge transporting ability, and it is needless to say that the material is effective for devices and systems utilizing charge transporting properties, such as electrophotographic photosensitive members.
【００２９】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。Specific compounds of the present invention thus obtained are shown below.
【００３０】[0030]
【化２５】 Embedded image
【００３１】[0031]
【化２６】 Embedded image
【００３２】[0032]
【化２７】 Embedded image
【００３３】[0033]
【化２８】 Embedded image
【００３４】[0034]
【化２９】 Embedded image
【００３５】[0035]
【化３０】 Embedded image
【００３６】[0036]
【化３１】 Embedded image
【００３７】[0037]
【化３２】 Embedded image
【００３８】[0038]
【化３３】 Embedded image
【００３９】[0039]
【化３４】 Embedded image
【００４０】[0040]
【化３５】 Embedded image
【００４１】[0041]
【化３６】 Embedded image
【００４２】[0042]
【化３７】 Embedded image
【００４３】[0043]
【化３８】 Embedded image
【００４４】[0044]
【化３９】 Embedded image
【００４５】[0045]
【化４０】 Embedded image
【００４６】[0046]
【化４１】 Embedded image
【００４７】[0047]
【化４２】 Embedded image
【００４８】[0048]
【化４３】 Embedded image
【００４９】[0049]
【化４４】 Embedded image
【００５０】以下、本発明を実施例により詳細に説明す
る。Hereinafter, the present invention will be described in detail with reference to examples.
【００５１】実施例１ アセトアニリド２０．３ｇ（０．１５モル）と４，４′
−ジヨードビフェニル７３．１ｇ（０．１８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℃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′−ヨード−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℃であった。Example 1 20.3 g (0.15 mol) of acetanilide and 4,4 '
-73.1 g (0.18 mol) of diiodobiphenyl, 22.1 g (0.16 mol) of anhydrous potassium carbonate, 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 insolubles were 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 (64.8% yield). I got The melting point was 135.0-136.0 ° C.
【００５２】続いてＮ−（４′−ヨード−４−ビフェニ
リル）アセトアニリド１３．２ｇ（０．０３２モル）、
ジフェニルアミン６．６０ｇ（０．０３９モル）、無水
炭酸カリウム５．５３ｇ（０．０４０モル）及び銅粉
０．４５ｇ（０．００７モル）、ニトロベンゼン１０ｍ
ｌを混合し、２００〜２１２℃で１５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
ソアミルアルコール６０ｍｌに溶解し、水１ｍｌ、８５
％水酸化カリウム２．６４ｇ（０．０４０モル）を加
え、１３０℃で加水分解した。水蒸気蒸留でイソアミル
アルコールを留去後、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／ｎ−
ヘキサン＝１／２）、Ｎ，Ｎ，Ｎ′−トリフェニルベン
ジジン１０．５ｇ（収率７２．２％）を得た。融点は１
６７．５〜１６８．５℃であった。Subsequently, 13.2 g (0.032 mol) of N- (4'-iodo-4-biphenylyl) acetanilide was obtained,
6.60 g (0.039 mol) of diphenylamine, 5.53 g (0.040 mol) of anhydrous potassium carbonate, 0.45 g (0.007 mol) of copper powder, and 10 m of nitrobenzene
were mixed and reacted at 200 to 212 ° C. for 15 hours.
The reaction product was extracted with 100 ml of toluene, the insolubles were removed by filtration, and the mixture was concentrated to an oil. The oily substance is dissolved in 60 ml of isoamyl alcohol, and 1 ml of water, 85 ml
% Potassium hydroxide (2.64 g, 0.040 mol) was added, and the mixture was hydrolyzed at 130 ° C. After isoamyl alcohol was distilled off by steam distillation, the mixture was extracted with 250 ml of toluene, washed with water, dried and concentrated. The concentrate is purified by column chromatography (carrier; silica gel, eluent; toluene / n-
Hexane = 1/2), 10.5 g of N, N, N'-triphenylbenzidine (72.2% yield) was obtained. Melting point is 1
67.5-168.5 ° C.
【００５３】更に、Ｎ，Ｎ，Ｎ′−トリフェニルベンジ
ジン８．６６ｇ（０．０２１モル）、４，４′−ジヨー
ドビフェニル４．０６ｇ（０．０１モル）、無水炭酸カ
リウム２．９０ｇ（０．０２１モル）、銅粉０．３２ｇ
（０．００５モル）、ニトロベンゼン１０ｍｌを混合
し、１９５〜２１０℃で２０時間反応させた。反応生成
物をトルエン１４０ｍｌで抽出し、不溶分をろ別、濃縮
後、ｎ−ヘキサン１２０ｍｌを加えて粗結晶を取りだし
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＝１／
２）、Ｎ，Ｎ′−ビス（４′−ジフェニルアミノ−４−
ビフェニリル）−Ｎ，Ｎ′−ジフェニルベンジジン４．
７３ｇ（収率；４８．５％）を得た。融点は２４２．５
〜２４３．５℃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。Further, 8.66 g (0.021 mol) of N, N, N'-triphenylbenzidine, 4.06 g (0.01 mol) of 4,4'-diiodobiphenyl, 2.90 g of anhydrous potassium carbonate ( 0.021 mol), 0.32 g of copper powder
(0.005 mol) and 10 ml of nitrobenzene were mixed and reacted at 195 to 210 ° C for 20 hours. The reaction product was extracted with 140 ml of toluene, the insoluble matter was separated by filtration, and after concentration, 120 ml of n-hexane was added to take out crude crystals. The crude crystals are purified by column chromatography (carrier;
Silica gel, eluent; toluene / n-hexane = 1 /
2), N, N'-bis (4'-diphenylamino-4-
3. biphenylyl) -N, N'-diphenylbenzidine
73 g (yield; 48.5%) was obtained. Melting point 242.5
２４243.5 ° C. FIG. 1 shows an infrared absorption spectrum (measurement instrument; IR-700, manufactured by JASCO Corporation, measurement method; KBr tablet method).
【００５４】実施例２ アセトアニリド１６．２ｇ（０．１２モル）と３，３′
−ジメチル−４，４′−ジヨードビフェニル５６．４ｇ
（０．１３モル）、無水炭酸カリウム１８．０ｇ（０．
１３モル）、銅粉１．７１ｇ（０．０２７モル）、ニト
ロベンゼン３０ｍｌを混合し、１９２〜２０３℃で１３
時間反応させた。反応生成物をトルエン１６０ｍｌ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＝７／１）、Ｎ−（３，３′
−ジメチル−４′−ヨード−４−ビフェニリル）アセト
アニリド３６．７ｇ（収率６９．３％）を得た。Example 2 16.2 g (0.12 mol) of acetanilide and 3,3 '
-Dimethyl-4,4'-diiodobiphenyl 56.4 g
(0.13 mol), 18.0 g of anhydrous potassium carbonate (0.
13 mol), 1.71 g (0.027 mol) of copper powder, and 30 ml of nitrobenzene.
Allowed to react for hours. The reaction product was extracted with 160 ml of toluene, the insolubles were removed by filtration, and the mixture was concentrated to dryness. This was purified by column chromatography (carrier: silica gel, eluent: toluene / ethyl acetate = 7/1), and N- (3,3 ′) was purified.
-Dimethyl-4'-iodo-4-biphenylyl) acetanilide was obtained in an amount of 36.7 g (yield 69.3%).
【００５５】続いてＮ−（３，３′−ジメチル−４′−
ヨード−４−ビフェニリル）アセトアニリド１３．２ｇ
（０．０３０モル）、ジフェニルアミン６．０９ｇ
（０．０３６モル）、無水炭酸カリウム５．１１ｇ
（０．０３７モル）及び銅粉０．４４ｇ（０．００７モ
ル）、ニトロベンゼン１０ｍｌを混合し、１９８〜２１
１℃で１３時間反応させた。反応生成物をトルエン１０
０ｍｌ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ール５０ｍ
ｌに溶解し、水１ｍｌ、８５％水酸化カリウム２．３８
ｇ（０．０３６モル）を加え、１３０℃で加水分解し
た。水蒸気蒸留でイソアミルアルコールを留去後、トル
エン２００ｍｌ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／ｎ−ヘキサン＝１／３）、３，
３′−ジメチル−Ｎ，Ｎ，Ｎ′−トリフェニルベンジジ
ン９．２７ｇ（収率７０．１％）を得た。融点は１０
４．０〜１０５．０℃であった。Subsequently, N- (3,3'-dimethyl-4'-
13.2 g of iodo-4-biphenylyl) acetanilide
(0.030 mol), 6.09 g of diphenylamine
(0.036 mol), 5.11 g of anhydrous potassium carbonate
(0.037 mol), 0.44 g (0.007 mol) of copper powder and 10 ml of nitrobenzene were mixed.
The reaction was performed at 1 ° C. for 13 hours. The reaction product is toluene 10
The mixture was extracted with 0 ml, the insoluble matter was removed by filtration, and the mixture was concentrated to an oil. Oily substance is isoamyl alcohol 50m
1 ml of water, 85% potassium hydroxide 2.38
g (0.036 mol) was added and hydrolyzed at 130 ° C. After isoamyl alcohol was distilled off by steam distillation, the mixture was extracted with 200 ml of toluene, washed with water, dried and concentrated. The concentrate was purified by column chromatography (carrier; silica gel, eluent; toluene / n-hexane = 1/3).
9.27 g (yield 70.1%) of 3'-dimethyl-N, N, N'-triphenylbenzidine was obtained. Melting point is 10
4.0-105.0 ° C.
【００５６】更に、３，３′−ジメチル−Ｎ，Ｎ，Ｎ′
−トリフェニルベンジジン８．３７ｇ（０．０１９モ
ル）、４，４′−ジヨードビフェニル３．６５ｇ（０．
００９モル）、無水炭酸カリウム２．６３ｇ（０．０１
９モル）、銅粉０．２５ｇ（０．００４モル）、ニトロ
ベンゼン７ｍｌを混合し、１９７〜２１２℃で３６時間
反応させた。反応生成物をトルエン１３０ｍｌで抽出
し、不溶分をろ別、濃縮後、ｎ−ヘキサン１１０ｍｌ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＝１／２）、Ｎ，Ｎ′−ビス（３，
３′−ジメチル−４′−ジフェニルアミノ−４−ビフェ
ニリル）−Ｎ，Ｎ′−ジフェニルベンジジン４．８４ｇ
（収率；５２．１％）を得た。明瞭な融点は見られなか
った。図２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。Further, 3,3'-dimethyl-N, N, N '
8.37 g (0.019 mol) of triphenylbenzidine, 3.65 g of 4,4'-diiodobiphenyl (0.
009 mol), 2.63 g (0.01
9 mol), 0.25 g (0.004 mol) of copper powder and 7 ml of nitrobenzene were mixed and reacted at 197 to 212 ° C. for 36 hours. The reaction product was extracted with 130 ml of toluene, the insolubles were filtered off, concentrated, and 110 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 = 1/2) to give N, N'-bis (3,
3.84 g of 3'-dimethyl-4'-diphenylamino-4-biphenylyl) -N, N'-diphenylbenzidine
(Yield; 52.1%) was obtained. No clear melting point was found. FIG. 2 shows an infrared absorption spectrum (measurement instrument; IR-700, manufactured by JASCO Corporation, measurement method: KBr tablet method).
【００５７】実施例３ １，１−ビス（４−アミノフェニル）シクロヘキサン１
６．０ｇ（０．０６モル）を氷酢酸５０ｍｌに溶解し、
４０℃で無水酢酸１３．３ｇ（０．１３モル）を滴下し
た。滴下後６０℃で２時間反応し、反応液を氷水３００
ｍｌ中へ注加して、析出した結晶をろ過、水洗、乾燥し
た。この結晶を酢酸エチル４０ｍｌとメタノ−ル１５０
ｍｌの混合溶媒で再結晶し、１，１−ビス（４−アセト
アミドフェニル）シクロヘキサン１３．５ｇ（収率；６
４．３％）を得た。融点は２７０．０〜２７１．０℃で
あった。Example 3 1,1-bis (4-aminophenyl) cyclohexane 1
6.0 g (0.06 mol) was dissolved in 50 ml of glacial acetic acid,
At 40 ° C., 13.3 g (0.13 mol) of acetic anhydride was added dropwise. After the dropwise addition, the reaction was carried out at 60 ° C. for 2 hours.
The solution was poured into the resulting solution, and the precipitated crystals were filtered, washed with water, and dried. The crystals were combined with 40 ml of ethyl acetate and 150 ml of methanol.
The mixture was recrystallized with 1 ml of a mixed solvent to obtain 13.5 g of 1,1-bis (4-acetamidophenyl) cyclohexane (yield: 6).
4.3%). Melting point was 270.0-271.0 ° C.
【００５８】得られた１，１−ビス（４−アセトアミド
フェニル）シクロヘキサン１０．５ｇ（０．０３モ
ル）、ブロモベンゼン１０．４ｇ（０．０６６モル）、
無水炭酸カリウム８．７１ｇ（０．０６３モル）、銅粉
０．９５ｇ（０．０１５モル）を混合し、１７０〜２０
０℃で１６時間反応させた。反応生成物をトルエン１５
０ｍｌ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ール５０ｍ
ｌに溶解し、水１ｍｌ、８５％水酸化カリウム４．１６
ｇ（０．０６３モル）を加え、１３０℃で加水分解し
た。水蒸気蒸留でイソアミルアルコールを留去後、トル
エン２００ｍｌ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／ｎ−ヘキサン＝３／２）、１，
１−ビス（４−アニリノフェニル）シクロヘキサン９．
３１ｇ（収率７４．１％）を得た。The obtained 1,1-bis (4-acetamidophenyl) cyclohexane (10.5 g, 0.03 mol), bromobenzene 10.4 g (0.066 mol),
A mixture of 8.71 g (0.063 mol) of anhydrous potassium carbonate and 0.95 g (0.015 mol) of copper powder was mixed.
The reaction was carried out at 0 ° C. for 16 hours. The reaction product was converted to toluene 15
The mixture was extracted with 0 ml, the insoluble matter was removed by filtration, and the mixture was concentrated to an oil. Oily substance is isoamyl alcohol 50m
1 ml of water, 85% potassium hydroxide 4.16
g (0.063 mol) was added and hydrolyzed at 130 ° C. After isoamyl alcohol was distilled off by steam distillation, the mixture was extracted with 200 ml of toluene, washed with water, dried and concentrated. The concentrate was purified by column chromatography (carrier: silica gel, eluent: toluene / n-hexane = 3/2),
1-bis (4-anilinophenyl) cyclohexane9.
31 g (74.1% yield) was obtained.
【００５９】続いて、実施例１と同様にして、アセトア
ニリドと４，４′−ジヨードビフェニルとの縮合反応に
より得られたＮ−（４′−ヨード−４−ビフェニリル）
アセトアニリド１８．４ｇ（０．０４２モル）と前記
１，１−ビス（４−アニリノフェニル）シクロヘキサン
８．３７ｇ（０．０２モル）及び無水炭酸カリウム５．
８０ｇ（０．０４２モル）、銅粉０．５７ｇ（０．００
９モル）、ニトロベンゼン２０ｍｌを混合し、１９８〜
２１５℃で２１時間反応させた。反応生成物をトルエン
１５０ｍｌ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ール８
０ｍｌに溶解し、水１ｍｌ、８５％水酸化カリウム２．
７７ｇ（０．０４２モル）を加え、１３０℃で加水分解
した。水蒸気蒸留でイソアミルアルコールを留去後、ト
ルエン１８０ｍｌ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／ｎ−ヘキサン＝１／１）、
１，１−ビス［ｐ−［Ｎ−（４′−アニリノ−４−ビフ
ェニリル）アニリノ］フェニル］シクロヘキサン１０．
４ｇ（収率５７．３％）を得た。Subsequently, N- (4'-iodo-4-biphenylyl) obtained by the condensation reaction of acetanilide with 4,4'-diiodobiphenyl in the same manner as in Example 1.
18.4 g (0.042 mol) of acetanilide, 8.37 g (0.02 mol) of 1,1-bis (4-anilinophenyl) cyclohexane and anhydrous potassium carbonate 5.
80 g (0.042 mol), copper powder 0.57 g (0.00
9 mol), 20 ml of nitrobenzene,
The reaction was performed at 215 ° C. for 21 hours. The reaction product was extracted with 150 ml of toluene, the insolubles were removed by filtration, and the mixture was concentrated to an oil. The oily substance is isoamyl alcohol 8
0 ml, water 1 ml, 85% potassium hydroxide 2.
77 g (0.042 mol) was added, and the mixture was hydrolyzed at 130 ° C. After isoamyl alcohol was distilled off by steam distillation, the mixture was extracted with 180 ml of toluene, washed with water, dried and concentrated.
The concentrate was purified by column chromatography (carrier: silica gel, eluent: toluene / n-hexane = 1/1),
1,1-bis [p- [N- (4'-anilino-4-biphenylyl) anilino] phenyl] cyclohexane
4 g (57.3% yield) were obtained.
【００６０】更に、１，１−ビス［ｐ−［Ｎ−（４′−
アニリノ−４−ビフェニリル）アニリノ］フェニル］シ
クロヘキサン９．０５ｇ（０．０１モル）、ヨードベン
ゼン４．４９ｇ（０．０２２モル）、無水炭酸カリウム
２．９０ｇ（０．０２１モル）、銅粉０．３２ｇ（０．
００５モル）、ニトロベンゼン１５ｍｌを混合し、１９
８〜２１３℃で１９時間反応させた。反応生成物をトル
エン１５０ｍｌで抽出し、不溶分をろ別除去後、濃縮し
た。濃縮物にｎ−ヘキサン１１０ｍｌ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＝２／３）、１，１−ビス［ｐ−［Ｎ−（４′−ジフ
ェニルアミノ−４−ビフェニリル）アニリノ］フェニ
ル］シクロヘキサン５．１７ｇ（収率；４８．９％）を
得た。明瞭な融点は見られなかった。図３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。Further, 1,1-bis [p- [N- (4'-
Anilino-4-biphenylyl) anilino] phenyl] cyclohexane 9.05 g (0.01 mol), iodobenzene 4.49 g (0.022 mol), anhydrous potassium carbonate 2.90 g (0.021 mol), copper powder 0. 32 g (0.
005 mol) and 15 ml of nitrobenzene.
The reaction was performed at 8 to 213 ° C for 19 hours. The reaction product was extracted with 150 ml of toluene, and the insoluble matter was removed by filtration and then concentrated. 110 ml of n-hexane was added to the concentrate, and crude crystals were taken out. The crude crystals were purified by column chromatography (carrier; silica gel, eluent: toluene / n-hexane = 2/3) to give 1,1-bis [p- [N- (4'-diphenylamino-4-biphenylyl). ) Anilino] phenyl] cyclohexane 5.17 g (yield; 48.9%) was obtained. No clear melting point was found. FIG. 3 shows an infrared absorption spectrum (measurement device; IR-IR manufactured by JASCO Corporation).
700, measurement method; KBr tablet method).
【００６１】実施例４ 実施例３と同様にして得た、１，１−ビス（４−アニリ
ノフェニル）シクロヘキサン１０．５ｇ（０．０２５モ
ル）と実施例２と同様にして得た、Ｎ−（３，３′−ジ
メチル−４′−ヨード−４−ビフェニリル）アセトアニ
リド２２．９ｇ（０．０５２モル）、及び無水炭酸カリ
ウム７．１９ｇ（０．０５２モル）、銅粉０．７６ｇ
（０．０１２モル）、ニトロベンゼン２０ｍｌを混合
し、２００〜２０８℃で１８時間反応させた。反応生成
物をトルエン１８０ｍｌ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
ルアルコール８０ｍｌに溶解し、水１ｍｌ、８５％水酸
化カリウム２．７７ｇ（０．０４２モル）を加え、１３
０℃で加水分解した。水蒸気蒸留でイソアミルアルコー
ルを留去後、トルエン１８０ｍｌ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／ｎ−ヘキサン
＝１／１）、１，１−ビス［ｐ−［Ｎ−（４′−アニリ
ノ−３，３′−ジメチル−４−ビフェニリル）アニリ
ノ］フェニル］シクロヘキサン１３．３ｇ（収率５５．
１％）を得た。Example 4 10.5 g (0.025 mol) of 1,1-bis (4-anilinophenyl) cyclohexane obtained in the same manner as in Example 3 and N -(3,3'-dimethyl-4'-iodo-4-biphenylyl) acetanilide 22.9 g (0.052 mol), and anhydrous potassium carbonate 7.19 g (0.052 mol), copper powder 0.76 g
(0.012 mol) and 20 ml of nitrobenzene were mixed and reacted at 200 to 208 ° C. for 18 hours. The reaction product was extracted with 180 ml of toluene, the insolubles were removed by filtration, and the mixture was concentrated to an oil. The oily substance was dissolved in 80 ml of isoamyl alcohol, and 1 ml of water and 2.77 g (0.042 mol) of 85% potassium hydroxide were added thereto.
Hydrolyzed at 0 ° C. After isoamyl alcohol was distilled off by steam distillation, the mixture was extracted with 180 ml of toluene, washed with water, dried and concentrated. The concentrate was purified by column chromatography (carrier; silica gel, eluent; toluene / n-hexane = 1/1) to give 1,1-bis [p- [N- (4'-anilino-3,3'-). 13.3 g of dimethyl-4-biphenylyl) anilino] phenyl] cyclohexane (yield 55.
1%).
【００６２】この１，１−ビス［ｐ−［Ｎ−（４′−ア
ニリノ−３，３′−ジメチル−４−ビフェニリル）アニ
リノ］フェニル］シクロヘキサン１１．５ｇ（０．０１
２モル）を、ヨードベンゼン５．３０ｇ（０．０２６モ
ル）、無水炭酸カリウム３．４６ｇ（０．０２５モ
ル）、銅粉０．３８ｇ（０．００６モル）、ニトロベン
ゼン１５ｍｌと混合し、１９８〜２１３℃で１９時間反
応させた。反応生成物をトルエン１５０ｍｌで抽出し、
不溶分をろ別除去後、濃縮した。濃縮物にｎ−ヘキサン
１２０ｍｌ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＝１／３）、１，１−ビ
ス［ｐ−［Ｎ−（４′−ジフェニルアミノ−３，３′−
ジメチル−４−ビフェニリル）アニリノ］フェニル］シ
クロヘキサン５．５７ｇ（収率；４１．７％）を得た。
明瞭な融点は見られなかった。表１に実施例１から４で
得られた化合物の元素分析結果を示す。また、図４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。The 1,1-bis [p- [N- (4'-anilino-3,3'-dimethyl-4-biphenylyl) anilino] phenyl] cyclohexane 11.5 g (0.01
2 mol) was mixed with 5.30 g (0.026 mol) of iodobenzene, 3.46 g (0.025 mol) of anhydrous potassium carbonate, 0.38 g (0.006 mol) of copper powder, and 15 ml of nitrobenzene. The reaction was performed at 213 ° C. for 19 hours. The reaction product was extracted with 150 ml of toluene,
After insoluble matter was removed by filtration, the mixture was concentrated. 120 ml of n-hexane was added to the concentrate, and a crude crystal was taken out. The crude crystal is
Purification by column chromatography (carrier: silica gel, eluent: toluene / n-hexane = 1/3), 1,1-bis [p- [N- (4'-diphenylamino-3,3'-
5.57 g (yield: 41.7%) of dimethyl-4-biphenylyl) anilino] phenyl] cyclohexane was obtained.
No clear melting point was found. Table 1 shows the results of elemental analysis of the compounds obtained in Examples 1 to 4. FIG. 4 shows an infrared absorption spectrum (measurement instrument; JASCO Corporation)
IR-700, KBr tablet method).
【００６３】[0063]
【表１】 [Table 1]
【００６４】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。Further, the usefulness of the compounds found according to the present invention will be described with reference to specific application examples.
【００６５】応用例１ 十分に洗浄したＩＴＯ電極に、前記実施例１で得られた
化合物（一般式（１）；Ｒ1 ＝Ｈ、Ｒ2 ＝Ｈ、Ｒ3 ＝
Ｈ、Ｒ4 ＝Ｈ、Ａ＝ビフェニレン基）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−キノリノール）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、５
０ｎｍ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
よってモニターした。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１００ｍＡ／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１００ｃ
ｄ／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／ｃｍ
2 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３４００
ｃｄ／ｍ2 、発光の寿命は６６０時間、保存安定性は１
９００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、２２００ｃｄ／ｍ2 、２２０時間、４６０時
間であった。Application Example 1 The compound (general formula (1); R 1 = H, R 2 = H, R 3 =
(H, R 4 = H, A = biphenylene group) were used as the charge transporting material, and vacuum-deposited at a rate of 0.1 nm / sec to a thickness of 50 nm. On the deposited film, as a luminescent material,
The purified tris (8-quinolinol) aluminum complex was vacuum-deposited at a rate of 0.1 nm / sec.
Evaporated to a thickness of 0 nm. Further, an Mg / Ag electrode having a thickness of 100 nm was formed on this film by vacuum evaporation to produce an EL element. These depositions were performed continuously without breaking the vacuum on the way. The film thickness was monitored by a quartz oscillator. Immediately after the production of the device, the electrode was taken out in dry nitrogen, and the characteristics were subsequently measured. The light emission characteristics of the device are defined by the light emission luminance when a current of 100 mA / cm 2 is applied, and the light emission lifetime is 200 cd / m 2.
Is applied continuously to obtain a light emission of 100 c.
d / cm 2 . The storage stability is 20 mA / cm 2 after leaving in a dry air for a certain time at room temperature.
The current was defined as the time until the luminance became half of the initial light emission characteristic when the current of 2 was applied. As a result of the measurement, the light emission characteristic was 3400.
cd / m 2 , luminescence lifetime is 660 hours, storage stability is 1
900 hours. For comparison, N, N'-di (m-tolyl) -N, N'-diphenylbenzidine was used as a charge transporting material, and an EL device was manufactured under the same conditions and its characteristics were examined. The emission characteristics, emission lifetime, and storage stability were 2200 cd / m 2 , 220 hours, and 460 hours, respectively.
【００６６】[0066]
【発明の効果】本発明により見いだされた新規ベンジジ
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。The novel benzidine compound found by the present invention functions effectively as a charge-transporting material, easily forms a glass state and stably maintains the glass state, and is thermally and chemically stable. Is also a substance useful as a charge transporting material in an organic electroluminescent device.
【図１】実施例１により得られた化合物のＩＲスペクト
ルである。FIG. 1 is an IR spectrum of a compound obtained in Example 1.
【図２】実施例２により得られた化合物のＩＲスペクト
ルである。FIG. 2 is an IR spectrum of the compound obtained in Example 2.
【図３】実施例３により得られた化合物のＩＲスペクト
ルである。FIG. 3 is an IR spectrum of the compound obtained in Example 3.
【図４】実施例４により得られた化合物のＩＲスペクト
ルである。FIG. 4 is an IR spectrum of the compound obtained in Example 4.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 平１−136159（ＪＰ，Ａ) 特開 平７−165683（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C07C 211/00 C07C 217/00 C09K 11/00 ＣＡ（ＳＴＮ) ＲＥＧＩＳＴＲＹ（ＳＴＮ)────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-1-136159 (JP, A) JP-A-7-165683 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) C07C 211/00 C07C 217/00 C09K 11/00 CA (STN) REGISTRY (STN)
Claims (2)
化合物。 【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、Ａは下記式 【化２】 【化３】 【化４】 【化５】 【化６】 で表され、Ｒ5は水素原子、低級アルキル基、低級アル
コキシ基、塩素原子を表す。）1. A benzidine compound represented by the following general formula (1). Embedded image (Wherein, R 1 , R 2 and R 3 may be the same or different and represent a hydrogen atom, a lower alkyl group or a lower alkoxy group, and R 4 represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, or a chlorine atom) And A represents the following formula: Embedded image Embedded image Embedded image Embedded image And R 5 represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, or a chlorine atom. )
ン化合物。 【化７】 （式中、Ｒ1、Ｒ 2 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
は塩素原子を表し、Ａは請求項１で定義した通りであ
る。）2. Tetraamido represented by the following general formula ( 3 ) :
Down compound. Embedded image (Wherein, R 1, R 2 may be the same or different, represent a hydrogen atom, a lower alkyl group, a lower alkoxy group, R 4
Represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, or a chlorine atom, and A is as defined in claim 1
You . )
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29380193A JP3220950B2 (en) | 1993-11-01 | 1993-11-01 | Benzidine compound |
| 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 |
|---|---|---|---|
| JP29380193A JP3220950B2 (en) | 1993-11-01 | 1993-11-01 | Benzidine compound |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000332663A Division JP3567323B2 (en) | 2000-10-31 | 2000-10-31 | Method for producing benzidine compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07126226A JPH07126226A (en) | 1995-05-16 |
| JP3220950B2 true JP3220950B2 (en) | 2001-10-22 |
Family
ID=17799332
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP29380193A Expired - Lifetime JP3220950B2 (en) | 1993-11-01 | 1993-11-01 | Benzidine compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3220950B2 (en) |
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|---|---|
| JPH07126226A (en) | 1995-05-16 |
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