JPH06107648A - New oxadiazole compound - Google Patents
New oxadiazole compoundInfo
- Publication number
- JPH06107648A JPH06107648A JP4284041A JP28404192A JPH06107648A JP H06107648 A JPH06107648 A JP H06107648A JP 4284041 A JP4284041 A JP 4284041A JP 28404192 A JP28404192 A JP 28404192A JP H06107648 A JPH06107648 A JP H06107648A
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- Prior art keywords
- compound
- formula
- electroluminescent device
- general formula
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- Prior art date
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Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、製膜性に優れ且つ充分
な輝度を発揮しうる、電界発光素子構成材料である発光
材料及び電子輸送材料等として有用な新規オキサジアゾ
ール化合物及びその製造方法に関する。FIELD OF THE INVENTION The present invention relates to a novel oxadiazole compound having excellent film-forming properties and capable of exhibiting sufficient brightness, which is useful as a light-emitting material and an electron-transporting material, which is a constituent material of an electroluminescent device, and its production. Regarding the method.
【０００２】[0002]
【従来の技術】近年、情報機器の多様化に伴って、ＣＲ
Ｔより低消費電力で空間占有容積が少ない平面表示素子
のニーズが高まっている。このような平面表示素子とし
ては、液晶、プラズマディスプレイ等があるが、特に最
近は、発光型で表示が鮮明な電界発光素子（ＥＬ素子）
が注目されている。2. Description of the Related Art In recent years, with the diversification of information equipment, CR
There is an increasing need for a flat panel display device that consumes less power and occupies less space than T. Liquid crystal, plasma display, and the like are available as such flat display elements. Recently, electroluminescent elements (EL elements), which are luminescent type and have a clear display, have recently been developed.
Is attracting attention.
【０００３】ここで、上記ＥＬ素子は構成する材料によ
り、無機ＥＬ素子と有機ＥＬ素子とに大別することがで
き、無機ＥＬ素子は既に実用化されている。しかしなが
ら、上記無機ＥＬの駆動方式は、高電界の印加によって
加速された電子が、発光中心を衝突励起して発光させる
という所謂衝突励起型発光であるため、高電圧で駆動す
る必要がある。このため、周辺機器の高コスト化を招来
するという課題を有していた。Here, the above EL elements can be roughly classified into inorganic EL elements and organic EL elements depending on the constituent materials, and the inorganic EL elements have already been put to practical use. However, the driving method of the above-mentioned inorganic EL is so-called collision excitation type light emission in which electrons accelerated by application of a high electric field collide and excite light emission centers to emit light, and therefore, it is necessary to drive at a high voltage. Therefore, there is a problem that the cost of the peripheral device is increased.
【０００４】これに対し、上記有機ＥＬ素子は、有機発
光層を挾んで仕事関数の異なる対向電極が配置された構
造であり、陽極から注入されたホールと陰極から注入さ
れた電子とが発光層中で再結合して、発光層のケイ光と
同一波長の光を発するという所謂注入型発光である。し
たがって、低電圧で駆動することができ、且つ発光層の
材料を変更することにより任意の発光色を得ることが可
能である。On the other hand, the above-mentioned organic EL device has a structure in which opposing electrodes having different work functions are arranged across the organic light emitting layer, and holes injected from the anode and electrons injected from the cathode are the light emitting layer. This is so-called injection type light emission in which light having the same wavelength as the fluorescent light of the light emitting layer is recombined in the inside. Therefore, it is possible to drive at a low voltage, and it is possible to obtain an arbitrary emission color by changing the material of the light emitting layer.
【０００５】加えて、上記有機ＥＬ素子に用いる有機化
合物は、置換基を変える等によってその性質が異なるた
め、無機化合物よりも材料設計の自由度が大きい。した
がって、分子の電子状態を考慮しつつ有機化合物の分子
構造を変更することによって、任意の発光材料を得るこ
とができるものと考えられる。したがって、理論上は、
青色から赤色までの全ての色を発光させることが可能で
あり、実際に、緑色、黄色、橙色を発光させる安定な発
光材料は種々提案されている。In addition, since the organic compound used in the organic EL element has different properties by changing the substituents, the degree of freedom in material design is higher than that of the inorganic compound. Therefore, it is considered that an arbitrary light emitting material can be obtained by changing the molecular structure of the organic compound while considering the electronic state of the molecule. Therefore, in theory,
It is possible to emit all colors from blue to red, and in fact, various stable light emitting materials that emit green, yellow and orange have been proposed.
【０００６】しかしながら、青色を安定且つ高輝度で発
光させる構成材料は、無機ＥＬ素子、有機ＥＬ素子を問
わず、未だ開発されていない現状にある。例えば、有機
ＥＬ素子における青色の発光材料としては、１，１，
４，４−テトラフェニル−１，３−ブタジエン誘導体や
スチリルベンゼン誘導体が提案されているが、何れも製
膜性に劣り、満足な輝度と安定性とを得られるには至ら
ない。また電子輸送材料としては、２−（４−ｔｅｒｔ
−ブチルフェニル）−５−（ｐ−ビフェニル）−１，
３，４−オキサジアゾールが知られているが（特開平２
−２５０２９２号）、結晶化しやすく、満足な安定性に
欠くものである。更に前記一般式（Ｉ）においてＡｒが
フェニル基、４−ｔｅｒｔ−ブチルフェニル基のオキサ
ジアゾール化合物も知られているが（特公昭４５−２４
６７号）、スチルベン誘導体の製造中間体として記載さ
れているにすぎない。However, a constituent material for emitting blue light stably and with high brightness is not yet developed, regardless of whether it is an inorganic EL element or an organic EL element. For example, as a blue light emitting material in an organic EL element, 1,1,
Although a 4,4-tetraphenyl-1,3-butadiene derivative and a styrylbenzene derivative have been proposed, none of them has a poor film-forming property, so that satisfactory brightness and stability cannot be obtained. Further, as the electron transport material, 2- (4-tert)
-Butylphenyl) -5- (p-biphenyl) -1,
3,4-Oxadiazole is known (Japanese Patent Application Laid-Open No. HEI-2)
-250292), which easily crystallizes and lacks satisfactory stability. Further, an oxadiazole compound in which Ar is a phenyl group or a 4-tert-butylphenyl group in the general formula (I) is also known (Japanese Patent Publication No. 45-24).
67), only as an intermediate for the production of stilbene derivatives.
【０００７】[0007]
【発明が解決しようとする課題】本発明はかかる現状に
鑑みて成されたものであり、青色発光において充分な輝
度と安定性とを得ることができる発光材料、及びそれ自
身が製膜性に優れ、経時的に安定であり且つ高輝度発光
を可能とする電子輸送材料として有用な新規なオキサジ
アゾール化合物、及びその製造方法を提供することを目
的とする。SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and it is a light-emitting material capable of obtaining sufficient brightness and stability in blue light emission, and its own film-forming property. It is an object of the present invention to provide a novel oxadiazole compound which is excellent as an electron transport material which is stable with time and which enables high-luminance emission, and a method for producing the same.
【０００８】[0008]
【課題を解決するための手段】本発明によると、下記一
般式（Ｉ）（化１）で表わされる新規なオキサジアゾー
ル化合物が提供され、According to the present invention, there is provided a novel oxadiazole compound represented by the following general formula (I) (Formula 1),
【化１】 更に、下記一般式（ＩＩ）（化２）で表わされる５，
５′−（４，４′−ジベンジル）ジテトラゾールと、[Chemical 1] Further, 5, represented by the following general formula (II)
5 '-(4,4'-dibenzyl) ditetrazole,
【化２】 下記一般式（III）（化３）で表わされるカルボン酸ク
ロライド[Chemical 2] Carboxylic acid chloride represented by the following general formula (III)
【化３】 （式中、Ａｒは置換又は未置換のアリール基を示す。但
し、フェニル基、４−ｔｅｒｔ−ブチルフェニル基を除
く。）とを反応させることを特徴とする下記一般式
（Ｉ）（化１）で表わされる新規なオキサジアゾール化
合物の製造方法が提供される。[Chemical 3] (In the formula, Ar represents a substituted or unsubstituted aryl group. However, a phenyl group and a 4-tert-butylphenyl group are excluded.) The following general formula (I) The manufacturing method of the novel oxadiazole compound represented by these is provided.
【化１】 [Chemical 1]
【０００９】本発明者らは、上記課題を解決するための
発光層の構成要素について鋭意検討した結果、陽極およ
び陰極と、これらの間に挾持された一層または複数層の
有機化合物層より構成される電界発光素子において、前
記有機化合物層のうち少なくとも一層を構成する発光材
料として前記特定の複数のアリールオキサジアゾール骨
格を有するオキサジアゾール系化合物が、上記課題に対
し、有効であることを見い出し、本発明を完成するに至
った。The inventors of the present invention have made extensive studies as to the constituent elements of the light emitting layer for solving the above-mentioned problems, and as a result, are constituted by an anode and a cathode and one or a plurality of organic compound layers sandwiched between them. In an electroluminescent device according to the above, it was found that an oxadiazole-based compound having a specific plurality of aryl oxadiazole skeletons as a light emitting material constituting at least one of the organic compound layers is effective for the above problems. The present invention has been completed.
【００１０】本発明の、前記一般式（Ｉ）（化１）で表
わされるオキサジアゾール化合物は、新規であり、電界
発光素子構成材料の発光材料及び電子輸送材料として有
用であり、又、これらの化合物は前記公知化合物に比べ
て成膜性がさらに良いという特徴を有しており、電界発
光素子中の構成成分として使用した場合に、より経時的
劣化の少ない素子を作製することができる。特にこれら
の化合物は青色発光素子中の電子輸送層中の構成成分と
して有用であり、陽極および陰極の間に有機化合物層が
有機ホール輸送性発光層と有機電子輸送層とが陽極側か
ら順に形成された電界発光素子あるいは有機化合物層が
有機ホール輸送層、有機発光層及び有機電子輸送層とが
陽極側から順に形成された電界発光素子において、該有
機電子輸送層の構成成分として使用することにより、も
う一つの目的であるそれ自身が製膜性に優れ、経時的に
安定であり且つ高輝度発光を可能とする電子輸送性化合
物を有する電界発光素子を提供することができる。また
本発明の化合物は蛍光性を有しており、蛍光色素として
電界発光素子以外の用途、例えば蛍光増白材やレーザー
色素などとしても有用である。又、これらの化合物は電
子輸送性を有しており有機感光体等にも使用できる。The oxadiazole compound represented by the above general formula (I) (Formula 1) of the present invention is novel, and is useful as a light emitting material and an electron transporting material for an electroluminescent device. The compound (1) has a feature that the film forming property is better than that of the above-mentioned known compounds, and when used as a constituent component in an electroluminescent device, a device with less deterioration over time can be manufactured. In particular, these compounds are useful as constituent components in the electron transport layer in the blue light emitting device, and an organic compound layer is formed between the anode and the cathode to form an organic hole transporting light emitting layer and an organic electron transport layer in order from the anode side. In the electroluminescent device in which the electroluminescent device or the organic compound layer is formed by sequentially forming the organic hole transport layer, the organic luminescent layer, and the organic electron transport layer from the anode side, by using it as a constituent component of the organic electron transport layer. Another object of the present invention is to provide an electroluminescent device having an electron-transporting compound, which itself has excellent film-forming properties, is stable over time, and enables high-luminance light emission. Further, the compound of the present invention has fluorescence, and is useful as a fluorescent dye in applications other than electroluminescence devices, for example, as a fluorescent whitening material and a laser dye. Further, these compounds have an electron-transporting property and can be used for organic photoconductors and the like.
【００１１】本発明の下記一般式（Ｉ）（化１）で表わ
されるオキサジアゾール化合物The oxadiazole compound represented by the following general formula (I) (Formula 1) of the present invention
【化１】 において、Ａｒとしては置換もしくは無置換のフェニ
ル、ナフチル、アントリル、ピロジル、フェナントリル
等のアリール基が挙げられる（但し、フェニル基及び４
−ｔｅｒｔ−ブチルフェニル基を除く）。これらアリー
ル基の置換基としては、炭素数１〜６好ましくは炭素数
１〜４の直鎖状あるいは分岐状のアルキル基、前記アル
キル基を含むアルコキシ基、塩素、臭素等のハロゲン原
子、トリフルオロメチル基、シアノ基、ニトロ基、フェ
ニル、ナフチル、アントリル等のアリール基、前記アル
キル又はアリール基を含むアルコキシカルボニル基等が
挙げられる。Ａｒの具体例を次の表１に示す。[Chemical 1] Examples of Ar include substituted or unsubstituted aryl groups such as phenyl, naphthyl, anthryl, pyrrolyl and phenanthryl (provided that phenyl and 4
Excluding the -tert-butylphenyl group). As the substituent of these aryl groups, a linear or branched alkyl group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, an alkoxy group containing the alkyl group, a halogen atom such as chlorine or bromine, trifluoro Examples thereof include a methyl group, a cyano group, a nitro group, an aryl group such as phenyl, naphthyl and anthryl, and an alkoxycarbonyl group containing the above alkyl or aryl group. Specific examples of Ar are shown in Table 1 below.
【００１２】[0012]
【表１】 [Table 1]
【００１３】前記一般式（Ｉ）（化１）で表わされる本
発明のオキサジアゾール化合物は、以下の方法により製
造することができる。 本発明の製造方法（表２に示す反応による） 式（ＩＶ）で表わされる４−シアノベンズアルデヒドと
式（Ｖ）で表わされる４−シアノベンジルジエチルホス
ホネートとを反応させて、式（ＶＩ）で表わされる４，
４′−ジシアノスチルベンを得る。次いでこれを水素還
元して式（ＶII）で表わされる４，４′−ジシアノジベ
ンジルを得る。更にこれを塩化リチウムの存在下でアジ
化ソーダと反応させて式ＩＩ（前記化２）で表わされる
５，５′−（４，４′−ジベンジル）ジテトラゾールを
得る。つぎに、これと一般式III（前記化３）で表わさ
れるカルボン酸クロライドとを反応させて、一般式
（Ｉ）（前記化１）で表わされる目的化合物オキサジア
ゾール化合物を得ることができる。The oxadiazole compound of the present invention represented by the general formula (I) (Formula 1) can be produced by the following method. Production method of the present invention (according to the reaction shown in Table 2) 4-cyanobenzaldehyde represented by the formula (IV) is reacted with 4-cyanobenzyldiethylphosphonate represented by the formula (V) to give the compound represented by the formula (VI). 4,
4'-Dicyanostilbene is obtained. Then, this is reduced with hydrogen to obtain 4,4'-dicyanodibenzyl represented by the formula (VII). Further, this is reacted with sodium azide in the presence of lithium chloride to obtain 5,5 '-(4,4'-dibenzyl) ditetrazole represented by the formula II (formula 2). Next, this can be reacted with the carboxylic acid chloride represented by the general formula III (Formula 3) to obtain the oxadiazole compound of the target compound represented by the general formula (I) (Formula 1).
【００１４】本発明の製造方法は、各合成過程の中間体
の精製が容易であり、最終的にも高純度の目的化合物を
製造することができ、優れた製造方法である。The production method of the present invention is an excellent production method because the intermediate in each synthetic process can be easily purified and the highly pure target compound can be finally produced.
【００１５】[0015]
【表２】 [Table 2]
【００１６】公知の方法を利用した製造方法（表３に示
す反応による） （ＶIII）で表わされるジベンジル−４，４′−ジカル
ボン酸クロライドを下記一般式（ＩＸ）で表わされるカ
ルボン酸モノヒドラジドと反応させて、一般式（Ｘ）で
表わされるアシルヒドラジン誘導体を得、更に脱水剤
（例えば、五塩化リン、ホスホン酸、塩化チオニル等）
を用いて環化することにより、一般式（Ｉ）（前記化
１）で表わされる目的化合物オキサジアゾール化合物を
得ることができる。また（ＸＩ）で表わされるジベンジ
ル４，４′−ジカルボン酸ジヒドラシドと一般式（II
I）（前記化３）で表わされるカルボン酸クロライドと
反応させて一般式（Ｘ）で表わされるアシルヒドラジン
誘導体を得、前記同様に脱水環化して目的化合物を得る
こともできる。Production method using known method (according to reaction shown in Table 3) Dibenzyl-4,4'-dicarboxylic acid chloride represented by (VIII) is converted to carboxylic acid monohydrazide represented by the following general formula (IX). The reaction is performed to obtain an acylhydrazine derivative represented by the general formula (X), and a dehydrating agent (eg, phosphorus pentachloride, phosphonic acid, thionyl chloride, etc.)
The oxadiazole compound of interest represented by the general formula (I) (Formula 1 above) can be obtained by cyclizing with. Further, dibenzyl 4,4'-dicarboxylic acid dihydrside represented by (XI) and the general formula (II
It is also possible to obtain the target compound by reacting I) with the carboxylic acid chloride represented by the above Chemical Formula 3 to obtain the acylhydrazine derivative represented by the general formula (X) and subjecting it to dehydration cyclization in the same manner as described above.
【００１７】この製造方法は、中間体である一般式
（Ｘ）で表わされるアシルヒドラジン誘導体の溶媒溶解
性が悪く、精製が困難であり、しかもそれに続く脱水環
化工程で着色性不純物が微量生成し、高純度の目的化合
物を得にくいという欠点がある。In this production method, the acylhydrazine derivative represented by the general formula (X), which is an intermediate, has poor solvent solubility and is difficult to purify, and a trace amount of a coloring impurity is produced in the subsequent dehydration cyclization step. However, there is a drawback that it is difficult to obtain a highly pure target compound.
【００１８】[0018]
【表３】 [Table 3]
【００１９】本発明における電界発光素子は以上で説明
した化合物を真空蒸着法、溶液塗布法等により薄膜化
し、陽極及び陰極で挟持することにより構成される。そ
の際、化合物中に添加物として他の物質を複数種添加す
ることもできる。また、電極からの電荷注入効率を向上
させるために電荷注入輸送層を電極との間に別に設ける
ことも可能である。The electroluminescent device in the present invention is constituted by thinning the compound described above by a vacuum vapor deposition method, a solution coating method or the like and sandwiching it with an anode and a cathode. At that time, plural kinds of other substances may be added to the compound as additives. Further, a charge injection / transport layer may be separately provided between the electrode and the electrode in order to improve the efficiency of charge injection from the electrode.
【００２０】陽極材料としてはニッケル、金、白金、パ
ラジウムやこれらの合金或いは酸化錫（ＳｎＯ2）、酸
化錫インジウム（ＩＴＯ）、沃化銅などの仕事関数の大
きな金属やそれらの合金、化合物、更にはポリ（３−メ
チルチオフェン）、ポリピロール等の導電性ポリマーな
どを用いることができる。As the anode material, nickel, gold, platinum, palladium, alloys thereof, or metals having a large work function such as tin oxide (SnO 2 ), indium tin oxide (ITO) and copper iodide, alloys and compounds thereof, Further, conductive polymers such as poly (3-methylthiophene) and polypyrrole can be used.
【００２１】一方、陰極材料としては、仕事関数の小さ
な銀、錫、鉛、マグネシウム、マンガン、アルミニウ
ム、或いはこれらの合金が用いられる。陽極及び陰極と
して用いる材料のうち少なくとも一方は、素子の発光波
長領域において十分透明であることが望ましい。具体的
には８０％以上の光透過率を有することが望ましい。On the other hand, as the cathode material, silver, tin, lead, magnesium, manganese, aluminum, or an alloy thereof having a small work function is used. At least one of the materials used as the anode and the cathode is preferably sufficiently transparent in the emission wavelength region of the device. Specifically, it is desirable to have a light transmittance of 80% or more.
【００２２】図１に本発明に係る電界発光素子の代表的
な構成例を示す。図１において、１は基板、２，４は電
極、３ａは発光層、３ｂは電子輸送層、３ｃは正孔輸送
層である。図１は、基板１上に電極２を設け、電極２上
に発光層３ａを単独で設け、その上に電極を設けた構成
のものである。図２は、図１において電極２と発光層３
ａの間に正孔輸送層３ｃを設けたものであり、図３は、
図１において発光層３ａと電極４の間に電子輸送層３ｂ
を設けたものである。図４は、図３において電極２と発
光層３ａとの間に正孔輸送層３ｃを設けた構成ものであ
る。FIG. 1 shows a typical configuration example of the electroluminescent device according to the present invention. In FIG. 1, 1 is a substrate, 2 and 4 are electrodes, 3a is a light emitting layer, 3b is an electron transport layer, and 3c is a hole transport layer. FIG. 1 shows a structure in which an electrode 2 is provided on a substrate 1, a light emitting layer 3a is independently provided on the electrode 2, and an electrode is provided thereon. 2 shows an electrode 2 and a light emitting layer 3 in FIG.
The hole transport layer 3c is provided between a and
In FIG. 1, the electron transport layer 3b is provided between the light emitting layer 3a and the electrode 4.
Is provided. FIG. 4 shows a structure in which the hole transport layer 3c is provided between the electrode 2 and the light emitting layer 3a in FIG.
【００２３】本発明の電界発光素子は以上の各層をガラ
ス等の透明基板上に順次積層されて素子として構成され
るわけであるが、素子の安定性の向上、特に大気中の水
分に対する保護のために、別に保護層を設けたり、素子
全体をセル中に入れ、シリコンオイル等を封入するよう
にしてもよい。The electroluminescent device of the present invention is constructed as a device by sequentially laminating the above layers on a transparent substrate such as glass. However, the stability of the device is improved, and in particular, protection against moisture in the atmosphere is provided. Therefore, a protective layer may be separately provided, or the entire device may be put in a cell and silicon oil or the like may be sealed therein.
【００２４】図３、図４に示す構成において一般式
（Ｉ）（化１）で表わされるオキサジアゾール化合物を
電子輸送層の構成成分として使用する場合に、発光層及
び正孔輸送層に使用される材料としては以下の物があ
る。正孔輸送性発光層に使用される有機化合物として
は、固体状態において強い蛍光を示し、かつ、正孔輸送
能に優れた化合物であればいずれのものも使用される。
このような物質としては、たとえばトリフェニルアミン
類、スチルベン誘導体類、ピラゾリン誘導体類等が挙げ
られ、その具体例としては、たとえば以下の表４に示す
ような物が例示される。特に青色発光のためには下記
、、、のものが好ましい。これらの化合物は図
４に示す構成における発光層にも使用される。When the oxadiazole compound represented by the general formula (I) (Formula 1) is used as a constituent component of the electron transport layer in the constitution shown in FIGS. 3 and 4, it is used for the light emitting layer and the hole transport layer. The following materials are available. As the organic compound used in the hole-transporting light-emitting layer, any compound can be used as long as it exhibits strong fluorescence in the solid state and has an excellent hole-transporting ability.
Examples of such substances include triphenylamines, stilbene derivatives, pyrazoline derivatives, and the like, and specific examples thereof include those shown in Table 4 below. In particular, the following ones are preferable for blue light emission. These compounds are also used for the light emitting layer in the structure shown in FIG.
【００２５】[0025]
【表４】 [Table 4]
【００２６】図２、図４に示す構成における正孔輸送層
に使用される正孔輸送物質としては従来公知のものが使
用される。例えば(1)米国特許第３１１２１９７号明細
書等に記載されているトリアゾール誘導体、(2)米国特
許第３１８９４４７号明細書等に記載されているオキサ
ジアゾール誘導体、(3)特公昭３７−１６０９６号公報
等に記載されているイミダゾール誘導体、(4)米国特許
第３６１５４０２号、同３８２０９８９号、同３５４２
５４４号明細書や特公昭４５−５５５８号、同５１−１
０９８３号公報さらには特開昭５１−９３２２４号、同
５５−１７１０５号、同５６−４１４８号、同５５−１
０８６６７号、同５５−１５６９５３号、同５６−３６
６５６号公報等に記載されているポリアリールアルカン
誘導体、(5)米国特許第３１８０７２９号、同４２７８
７４６号明細書や特開昭５５−８８０６４６号、同５５
−８８０６５号、同４９−１０５５３７号、同５５−５
１０８６号、同５６−８００５１号、同５６−８８１４
１号、同５７−４５５４５号、同５４−１１２６３７
号、同５５−７４５４６号公報等に記載されているピラ
ゾリン誘導体およびピラゾロン誘導体、(6)米国特許第
３６１５４０４号や特公昭５１−１０１０５号、同４６
−３７１２号、同４７−２５３３６号公報さらには特開
昭５４−５３４３５号、同５４−１１０５３６号、同５
４−１１９９２５号公報等に記載されているフェニレン
ジアミン誘導体、(7)米国特許第３５６７４５０号、同
３１８０７０３号、同３２４０５９７号、同３６５８５
２０号、同４２３２１０３号、同４１７５９６１号、同
４０１２３７６号明細書や特公昭４９−３５７０２号、
同３９−２７５７７号公報さらには特開昭５５−１４４
２５０号、同５６−１１９１３２号、同５６−２２４３
７号公報、***特許第１１１０５１８号明細書等に記載
されているアリールアミン誘導体、(8)米国特許第３５
２６５０１号明細書等に記載されているアミノ置換カル
コン誘導体、(9)米国特許第３２５７２０３号明細書等
に記載されているオキサジアゾール誘導体、(10)特開昭
５６−４６２３４号公報等に記載されているスチリルア
ントラセン誘導体、(11)特開昭５４−１１０８３７号公
報等に記載されているフルオレノン誘導体(12)米国特許
第３７１７４６２号明細書や特開昭５４−５９１４３
号、同５５−５２０６３号、同５５−５２０６４号、同
５５−４６７６０号、同５５−８５４９５号、同５７−
１１３５０号、同５７−１４８７４９号公報等に記載さ
れているヒドラゾン誘導体、(13)特開昭６１−２１０３
６３号、同６１−２２８４５１号、同６１−１４６４２
号、同６１−７２２５５号、同６２−４７６４６号、同
６２−３６６７４号、同６２−１０６５２号、同６２−
３０２５５号、同６０−９３４４５号、同６０−９４４
６２号、同６０−１７４７４９号、同６０−１７５０５
２号公報等に記載されているスチルベン誘導体などを列
記することができる。さらに特に好ましい例としては、
特開昭６３−２９５６９５号公報に開示されているホー
ル輸送層としての化合物（芳香族三級アミン）や正孔注
入帯としての化合物（ポルフィリン化合物）をあげるこ
とができる。さらに特に正孔伝達化合物として好ましい
例は、特開昭５３−２７０３３号公報、同５４−５８４
４５号公報、同５４−１４９６３４号公報、同５４−６
４２９９号公報、同５５−７９４５０号公報、同５５−
１４４２５０号公報、同５６−１１９１３２号公報、同
６１−２９５５５８号公報、同６１−９８３５３号公報
及び米国特許第４１２７４１２号明細書等に開示されて
いるものである。それらの例を示せば次の表５の如くで
ある。As the hole transport material used in the hole transport layer in the structure shown in FIGS. 2 and 4, conventionally known substances are used. For example, (1) triazole derivatives described in U.S. Pat. No. 3,121,197, etc., (2) oxadiazole derivatives described in U.S. Pat. No. 3,189,447, etc., (3) JP-B-37-16096. (4) U.S. Pat. Nos. 3,615,402, 3,820,989, and 3,542, which are described in the gazettes and the like.
No. 544 and Japanese Patent Publication Nos. 45-5558 and 51-1
Further, JP-A No. 0983 and JP-A Nos. 51-93224, 55-17105, 56-4148, and 55-1.
08667, 55-156953, 56-36
Polyarylalkane derivatives described in Japanese Patent No. 656, etc., (5) US Pat. Nos. 3,180,729 and 4,278.
746 and JP-A-55-880646, 55
-88065, 49-105537, 55-5
No. 1086, No. 56-80051, No. 56-8814
No. 1, No. 57-45545, No. 54-112637.
Nos. 55-74546 and the like, and pyrazoline derivatives and pyrazolone derivatives described in (6) U.S. Pat. No. 3,615,404 and Japanese Patent Publication Nos. 51-10105 and 46.
No. 3712, No. 47-25336, and JP-A Nos. 54-53435, 54-110536 and 5
Phenylenediamine derivatives described in JP-A 4-119925, (7) U.S. Pat. Nos. 3,567,450, 3,180,703, 3,240,597, and 36,585.
No. 20, No. 4232103, No. 4175961, No. 4012376 and Japanese Patent Publication No. 49-35702.
JP-A-39-27577 and JP-A-55-144.
250, 56-119132, 56-2243.
Arylamine derivatives described in Japanese Patent No. 7 and West German Patent No. 1110518, and (8) US Patent No. 35
26501 and the like, amino substituted chalcone derivatives, (9) US Pat. No. 3,257,203 and the like, oxadiazole derivatives, (10) JP-A-56-46234, etc. (11) Fluorenone derivatives described in JP-A-54-110837 and (12) US Pat. No. 3,717,462 and JP-A-54-59143.
No. 55, No. 55-52063, No. 55-52064, No. 55-46760, No. 55-85495, No. 57-.
Hydrazone derivatives described in JP 11350, JP 57-148749, and the like, (13) JP-A-61-2103
63, 61-228451, 61-14642.
No. 61-72255, No. 62-47646, No. 62-36674, No. 62-10652, No. 62-1.
No. 30255, No. 60-93445, No. 60-944
No. 62, No. 60-174749, No. 60-17505.
The stilbene derivatives and the like described in Japanese Patent Publication No. 2 can be listed. More particularly preferred examples include
Examples thereof include a compound (aromatic tertiary amine) as a hole transport layer and a compound (porphyrin compound) as a hole injection zone disclosed in JP-A-63-295695. More preferable examples of the hole transfer compound are disclosed in JP-A-53-27033 and JP-A-54-584.
No. 45, No. 54-149634, No. 54-6.
4299, 55-79450, 55-
No. 144250, No. 56-119132, No. 61-295558, No. 61-98353, and U.S. Pat. No. 4,127,412. The examples are shown in Table 5 below.
【００２７】[0027]
【表５】 [Table 5]
【００２８】これらの正孔輸送物質から正孔注入輸送層
を形成するが、この正孔注入輸送層は一層からなっても
よく、あるいは上記一層と別種の化合物を用いた正孔注
入輸送層を積層してもよい。The hole injecting and transporting layer is formed from these hole transporting substances, and the hole injecting and transporting layer may be composed of one layer, or a hole injecting and transporting layer using a compound different from the above one layer. You may laminate.
【００２９】以下実施例に基づいて、本発明をより具体
的に説明する。The present invention will be described more specifically based on the following examples.
【００３０】〔公知方法による−実施例１〜１０〕 実施例１（中間体の合成） ジベンジル−４，４′ジカルボン酸ジヒドラジド（Ｘ
Ｉ）２．９８ｇｒとピリジン９０ｍｌを反応フラスコ中
で撹拌しながらｐ−フェニル安息香酸クロライド(III−
１）４．７７ｇｒを添加した。その後７時間加熱還流し
た後放冷した反応液を水１．５ｌ中に加え、濾過、水洗
した後乳白色の粗収物５．５４ｇｒ（収率８４％）を得
た。これをさらにＮ，Ｎ−ジメチルホルムアミド（ＤＭ
Ｆ）６００ｍｌで再結晶し下式一般式（Ｘ−１）（化
４）で示されるアシルビドラジン化合物の純品４．９３
ｇｒ（収率７５％）を得た。[By Known Method-Examples 1 to 10] Example 1 (Synthesis of Intermediate) Dibenzyl-4,4'-dicarboxylic acid dihydrazide (X
I) 2.98 gr and 90 ml of pyridine were stirred in a reaction flask while p-phenylbenzoyl chloride (III-
1) 4.77 gr was added. Then, the reaction solution was heated and refluxed for 7 hours and then allowed to cool, added to 1.5 l of water, filtered, and washed with water to obtain 5.54 gr (yield 84%) of a milky white crude product. This is further added to N, N-dimethylformamide (DM
F) A pure product of an acyl vidazine compound represented by the following general formula (X-1)
gr (75% yield) was obtained.
【化４】 融点：＞３００℃ 赤外線吸収スペクトル（ＫＢｒ錠剤法）３２５０ｃ
ｍ-1、１６９０ｃｍ-1、１６６０ｃｍ-1カルボキシアミ
ノ基に帰属。[Chemical 4] Melting point:> 300 ° C. infrared absorption spectrum (KBr tablet method) 3250c
Attributable to m -1 , 1690 cm -1 , 1660 cm -1 carboxyamino group.
【表６】 [Table 6]
【００３１】実施例２〜５（中間体の合成） カルボン酸クロライド（III）を下記表７に示したもの
に変えた以外は実施例１と同様に操作して、下記表８に
示す目的の中間体化合物（Ｘ−２）〜（Ｘ−５）を得
た。Examples 2 to 5 (Synthesis of Intermediate) The same operation as in Example 1 was carried out except that the carboxylic acid chloride (III) was changed to that shown in Table 7 below. Intermediate compounds (X-2) to (X-5) were obtained.
【表７】 [Table 7]
【００３２】[0032]
【表８】 [Table 8]
【００３３】[0033]
【実施例６】実施例１で得られたアシルヒドラジン化合
物（Ｘ−１）２．０ｇｒを脱水剤オキシ塩化リン２０ｍ
ｌ中で１７時間加熱撹拌した。反応液を放冷後水中にあ
け、沈殿物を水洗して粗収物１．６９ｇｒ（収率９０
％）を得た。これをＮ，Ｎ−ジメチルホルムアミドで２
回再結晶し、シリカゲルカラム（展開溶媒：クロロホル
ム−酢酸エチル混合溶媒）で精製した。さらに１，２，
４−トリクロロベンゼンで再結晶し、目的のオキサジア
ゾール化合物（表１Ｎｏ．１）０．１９ｇｒ（収率１０
％）を得た。[Example 6] 2.0 g of the acylhydrazine compound (X-1) obtained in Example 1 was added to 20 m of a dehydrating agent, phosphorus oxychloride.
The mixture was heated and stirred in 1 for 17 hours. The reaction solution was allowed to cool and then poured into water, and the precipitate was washed with water to obtain 1.69 gr of a crude product (yield 90
%) Was obtained. 2 with N, N-dimethylformamide
The crystals were recrystallized twice and purified with a silica gel column (developing solvent: chloroform-ethyl acetate mixed solvent). 1, 2,
Recrystallized from 4-trichlorobenzene to give the desired oxadiazole compound (No. 1 in Table 1) 0.19 gr (yield 10
%) Was obtained.
【００３４】[0034]
【実施例７】実施例２で得られたアシルヒドラジン化合
物（Ｘ−２）を使用する以外は実施例６と同様にして目
的のオキサジアゾール化合物（表１Ｎｏ２）０．９ｇｒ
（収率４８％）を得た。Example 7 In the same manner as in Example 6 except that the acylhydrazine compound (X-2) obtained in Example 2 was used, the desired oxadiazole compound (No. 2 in Table 1) 0.9 gr
(Yield 48%) was obtained.
【００３５】[0035]
【実施例８】実施例３で得られたアシルヒドラジン化合
物（Ｘ−３）を使用する以外は実施例６と同様にして目
的のオキサジアゾール化合物（表１Ｎｏ．３）０．４３
ｇｒ（収率２２％）を得た。Example 8 The target oxadiazole compound (No. 3 in Table 1) 0.43 was prepared in the same manner as in Example 6 except that the acylhydrazine compound (X-3) obtained in Example 3 was used.
gr (yield 22%) was obtained.
【００３６】[0036]
【実施例９】実施例４で得られたアシルヒドラジン化合
物（Ｘ−４）を使用し、脱水剤としてポリリン酸を使用
する以外は実施例６と同様に合成し、昇華精製により目
的のオキサジアゾール化合物（表１Ｎｏ．４）０．３１
ｇｒ（収率１７％）を得た。[Example 9] The acylhydrazine compound (X-4) obtained in Example 4 was used and synthesized in the same manner as in Example 6 except that polyphosphoric acid was used as a dehydrating agent, and the target oxazine was purified by sublimation. Azole compound (No. 4 in Table 1) 0.31
gr (17% yield) was obtained.
【００３７】[0037]
【実施例１０】実施例５で得られたアシルヒドラジン化
合物（Ｘ−５）２．４７ｇを脱水剤塩化チオニル４０ｍ
ｌ中で６時間加熱還流した。その後、塩化チオニルを蒸
留により除き、水洗して粗収物２．２５ｇｒ（収率９７
％）を得た。その後、Ｎ，Ｎ−ジメチルホルムアミドで
再結晶し、さらに昇華精製して目的のオキサジアゾール
化合物（表１Ｎｏ．５）０．２３ｇ（収率１０％）を得
た。実施例６から１０で得られたオキサジアゾール化合
物の物性値を下記表９に示す。Example 10 2.47 g of the acylhydrazine compound (X-5) obtained in Example 5 was used as a dehydrating agent thionyl chloride (40 m).
The mixture was heated to reflux in 1 for 6 hours. Then, thionyl chloride was removed by distillation and washed with water to obtain 2.25 gr of a crude product (yield 97
%) Was obtained. Then, it was recrystallized from N, N-dimethylformamide and further purified by sublimation to obtain 0.23 g (yield 10%) of the desired oxadiazole compound (No. 5 in Table 1). The physical properties of the oxadiazole compounds obtained in Examples 6 to 10 are shown in Table 9 below.
【００３８】[0038]
【表９】 [Table 9]
【００３９】[0039]
【本発明の製造方法による−実施例１１〜１２】 実施例１１（中間体の合成） ４，４′−ジシアノジベンジル（ＶIII）１．６７ｇ
ｒ、アジ化ソーダ１．４ｇｒ、塩化リチウム０．９８ｇ
ｒを２−メトキシエタノール５０ｍｌ中で１０５時間加
熱還流した。その後、放冷し氷水１５０ｍｌ中へあけ不
溶物を濾別した後、濾液に濃塩酸約３ｍｌを添加した。
生じた無色の沈殿物を濾過、水洗して、５，５′−
（４，４′ジベンジル）ジテトラゾール（ＩＩ）の粗収
物２．０７ｇｒ（収率９０．４％）を得た。さらにジオ
キサン−Ｎ，Ｎ−ジメチルホルムアミド混合溶媒で再結
晶し、純品１．７８ｇｒ（収率７７．７％）を得た。融
点２８６．０〜２８７．０℃（発泡分解）、ＩＲ（ＫＢ
ｒ錠剤法）２８００−２６００ｃｍ-1：νN-H帰属。According to the production method of the present invention-Examples 11 to 12 Example 11 (Synthesis of intermediate) 1.67 g of 4,4'-dicyanodibenzyl (VIII)
r, sodium azide 1.4gr, lithium chloride 0.98g
r was heated under reflux in 50 ml of 2-methoxyethanol for 105 hours. Then, the mixture was allowed to cool, poured into 150 ml of ice water to separate insoluble matter by filtration, and then about 3 ml of concentrated hydrochloric acid was added to the filtrate.
The resulting colorless precipitate was filtered and washed with water to give 5,5'-
2.07 gr (yield 90.4%) of a crude product of (4,4′dibenzyl) ditetrazole (II) was obtained. Further, it was recrystallized with a mixed solvent of dioxane-N, N-dimethylformamide to obtain 1.78 gr of pure product (yield: 77.7%). Melting point 286.0-287.0 ° C (foaming decomposition), IR (KB
r tablet method) 2800-2600 cm −1 : νN-H attribute.
【００４０】実施例１２ 実施例１１で得られた５，５′−（４，４′ジベンジ
ル）ジテトラゾール（ＩＩ）０．５ｇｒ、Ｐ−フェニル
安息香酸クロライド（III−１）１．０２ｇｒをピリジ
ン中で１３時間加熱還流した。放冷後、水１５０ｍｌ中
へあけ、得られた沈殿物を濾過、水洗して目的物（表１
Ｎｏ．１）の粗収物０．９ｇｒ（収率９２％）を得た。
本法で得られた目的物は実施例６の合成法と比較して粗
収物の段階から微量の着色性不純物を含んでおらず、ほ
とんど精製を必要としなかった。Example 12 0.5g of 5,5 '-(4,4'dibenzyl) ditetrazole (II) obtained in Example 11 and 1.02gr of P-phenylbenzoic acid chloride (III-1) were added to pyridine. Heated to reflux for 13 hours. After allowing to cool, it is poured into 150 ml of water, and the resulting precipitate is filtered and washed with water to obtain the desired product (Table 1
No. The crude product of 1) 0.9 gr (yield 92%) was obtained.
Compared to the synthesis method of Example 6, the target product obtained by this method did not contain a trace amount of coloring impurities from the stage of the crude product, and required almost no purification.
【００４１】応用例１ 表面抵抗２０Ω／□のＩＴＯ陽極を有するガラス基板上
に表４Ｎｏ．５の化合物であるスチルベン誘導体より成
る厚さ５００Åの発光層、下記式（Ｉ−１）（化５）で
示される。オキサジアゾール化合物より成る厚さ５００
Åの電子輸送層、原子比１０：１のＭｇＡｇ合金より成
る厚さ２０００Åの陰極を順次真空蒸着により積層して
図３に示す様な電界発光素子を作製した。この様にして
得られた素子は２０Ｖ以下の駆動電圧において明瞭な青
色の発光を示し、経時的な劣化の少ない素子であった。Application Example 1 No. 4 in Table 4 was formed on a glass substrate having an ITO anode having a surface resistance of 20 Ω / □. A light emitting layer having a thickness of 500 Å made of a stilbene derivative which is a compound of formula 5, and represented by the following formula (I-1) (formula 5). Thickness consisting of oxadiazole compound 500
An Å electron transport layer and a 2000 Å thick cathode made of a MgAg alloy having an atomic ratio of 10: 1 were sequentially laminated by vacuum vapor deposition to fabricate an electroluminescent device as shown in FIG. The device thus obtained showed clear blue light emission at a drive voltage of 20 V or less, and was a device with little deterioration over time.
【化５】 [Chemical 5]
【００４２】応用例２〜５ 電子輸送層に表１Ｎｏ．１〜Ｎｏ．４のオキサジアゾー
ル化合物を使用する以外は応用例１と同様にして電界発
光素子を作製した。これらの素子は２０Ｖ以下の駆動電
圧において明瞭な青色の発光を示し、応用例１と同様に
経時的劣化の少ない安定した素子であった。Application Examples 2 to 5 Table 1 No. 1-No. An electroluminescent device was produced in the same manner as in Application Example 1 except that the oxadiazole compound of Example 4 was used. These devices showed clear blue light emission at a driving voltage of 20 V or less, and were stable devices with little deterioration with time as in Application Example 1.
【００４３】[0043]
【発明の効果】本発明の一般式（１）で示される新規な
オキサジアゾール化合物は、製膜性に優れ、蛍光性、電
子輸送性を持つ事から青色発光において充分な輝度と安
定性を備えた電界発光素子を提供する事ができる。特に
図３、４に示す構成よりなる電界発光素子において、そ
れらの電子輸送層構成成分に一般式（１）で示されるオ
キサジアゾール化合物を使用する事によって青色発光を
含む任意な色調を呈し、特に耐久性に優れた高輝度の電
界発光素子の提供ができる。更に、本発明の製造方法に
より、電界発光素子用構成材料として有用な一般式
（１）で示されるオキサジアゾール化合物を容易に高純
度で提供できる。INDUSTRIAL APPLICABILITY The novel oxadiazole compound represented by the general formula (1) of the present invention has excellent film-forming property, fluorescence property and electron transport property, and therefore has sufficient brightness and stability in blue light emission. It is possible to provide an electroluminescent device having the same. In particular, in the electroluminescent device having the configuration shown in FIGS. 3 and 4, by using the oxadiazole compound represented by the general formula (1) as the component of the electron transport layer, an arbitrary color tone including blue light emission is exhibited, In particular, it is possible to provide a high-brightness electroluminescent element having excellent durability. Furthermore, the oxadiazole compound represented by the general formula (1), which is useful as a constituent material for an electroluminescent device, can be easily provided in high purity by the production method of the present invention.
【図１】本発明のオキサジアゾール化合物を構成材料と
して用いた電界発光素子の模式断面図である。FIG. 1 is a schematic cross-sectional view of an electroluminescence device using an oxadiazole compound of the present invention as a constituent material.
【図２】本発明のオキサジアゾール化合物を構成材料と
して用いた他の電界発光素子の模式断面図である。FIG. 2 is a schematic cross-sectional view of another electroluminescent device using the oxadiazole compound of the present invention as a constituent material.
【図３】本発明のオキサジアゾール化合物を構成材料と
して用いた別の電界発光素子の模式断面図である。FIG. 3 is a schematic cross-sectional view of another electroluminescent device using the oxadiazole compound of the present invention as a constituent material.
【図４】本発明のオキサジアゾール化合物を構成材料と
して用いた更に別の電界発光素子の模式断面図である。FIG. 4 is a schematic cross-sectional view of still another electroluminescent device using the oxadiazole compound of the present invention as a constituent material.
【図５】本発明の表１中、Ｎｏ．１のオキサジアゾール
化合物のＩ．Ｒ．スペクトル（ＫＢｒ錠剤法）。FIG. 5 shows No. 1 in Table 1 of the present invention. Of the oxadiazole compound of I.I. R. Spectrum (KBr tablet method).
【図６】本発明の表１中、Ｎｏ．２のオキサジアゾール
化合物のＩ．Ｒ．スペクトル（ＫＢｒ錠剤法）。6 is a table showing No. 1 in Table 1 of the present invention. I. of the oxadiazole compound of 2. R. Spectrum (KBr tablet method).
【図７】本発明の表１中、Ｎｏ．３のオキサジアゾール
化合物のＩ．Ｒ．スペクトル（ＫＢｒ錠剤法）。FIG. 7 shows No. 1 in Table 1 of the present invention. Of the oxadiazole compound of 3 R. Spectrum (KBr tablet method).
【図８】本発明の表１中、Ｎｏ．４のオキサジアゾール
化合物のＩ．Ｒ．スペクトル（ＫＢｒ錠剤法）。FIG. 8: No. 1 in Table 1 of the present invention. 4 of the oxadiazole compound of I.4. R. Spectrum (KBr tablet method).
【図９】本発明の表１中、Ｎｏ．５のオキサジアゾール
化合物のＩ．Ｒ．スペクトル（ＫＢｒ錠剤法）。FIG. 9 shows No. 1 in Table 1 of the present invention. Of the oxadiazole compound of 5 R. Spectrum (KBr tablet method).
１…基板、２，４…電極、３ａ…発光層、３ｂ…電子輸
送層、３ｃ…正孔輸送層。1 ... Substrate, 2, 4 ... Electrode, 3a ... Light emitting layer, 3b ... Electron transport layer, 3c ... Hole transport layer.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 安達 千波矢 東京都大田区中馬込１丁目３番６号 株式 会社リコー内 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Chihaya Adachi 1-3-3 Nakamagome, Ota-ku, Tokyo Inside Ricoh Co., Ltd.
Claims (2)
新規なオキサジアゾール化合物。 【化１】 1. A novel oxadiazole compound represented by the following general formula (I) (Formula 1). [Chemical 1]
る５，５′−（４，４′−ジベンジル）ジテトラゾール
と、 【化２】 下記一般式（III）（化３）で表わされるカルボン酸ク
ロライド 【化３】 （式中、Ａｒは置換又は未置換のアリール基を示す。但
し、フェニル基、４−ｔｅｒｔ−ブチルフェニル基を除
く。）とを反応させることを特徴とする下記一般式
（Ｉ）（化１）で表わされる新規なオキサジアゾール化
合物の製造方法。 【化１】 2. A 5,5 ′-(4,4′-dibenzyl) ditetrazole represented by the following general formula (II) (Chemical Formula 2): Carboxylic acid chloride represented by the following general formula (III) (In the formula, Ar represents a substituted or unsubstituted aryl group. However, a phenyl group and a 4-tert-butylphenyl group are excluded.) The following general formula (I) ) A method for producing a novel oxadiazole compound represented by: [Chemical 1]
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4284041A JPH06107648A (en) | 1992-09-29 | 1992-09-29 | New oxadiazole compound |
| US08/051,070 US5420288A (en) | 1992-04-14 | 1993-04-14 | Electroluminescent device comprising oxadiazole compounds luminescent material, oxadiazole compounds for the device, and method of producing oxadiazole compounds |
| US08/321,765 US5656401A (en) | 1992-04-14 | 1994-10-12 | Electroluminescent device comprising oxadiazole compounds luminescent material, oxadiazole compounds for the device, and method of producing oxadiazole compounds |
| US08/476,681 US5597925A (en) | 1992-04-14 | 1995-06-07 | Method of producing oxadiazole compounds |
| US08/478,674 US5610309A (en) | 1992-04-14 | 1995-06-07 | Electroluminescent device comprising oxadiazole compounds luminescent material, oxadiazole compounds for the device, and method of producing oxadiazole compounds |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4284041A JPH06107648A (en) | 1992-09-29 | 1992-09-29 | New oxadiazole compound |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH06107648A true JPH06107648A (en) | 1994-04-19 |
Family
ID=17673533
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4284041A Pending JPH06107648A (en) | 1992-04-14 | 1992-09-29 | New oxadiazole compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH06107648A (en) |
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