JP2005320286A - Imido group-containing fluoranthene-based compound, light-emitting material given by using the same, and organic electroluminescent element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an imido group-containing fluoranthene-based compound having high light-emitting intensity, having high light-emitting efficiency, and capable of emitting bluish light or reddish light, to provide a light-emitting material given by using the same, and to provide an organic electroluminescent element given by utilizing the same. <P>SOLUTION: This imido group-containing fluoranthene compound is, for example, expressed by formula (1). The light-emitting material and the organic electroluminescent element are given by using the compound, respectively. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an imide group-containing fluoranthene compound and an organic electroluminescence device (organic EL device) using the imide group-containing fluoranthene compound, and particularly has high emission luminance and light emission efficiency and emits blue and red light. And an organic EL element using the same.

で示されるｔＢｕ−ＰＴＣが赤色系の発光材料として知られている非特許文献１が、素子発光のピーク波長が６１０ｎｍ付近であり、赤色としての色純度が不足しており、最大発光輝度も５００ｃｄ／ｍ^２レベルに留まっていて満足できるものではない。さらに、特許文献１には、ナフタール酸イミド誘導体をトリス（８−キノリノラート）アルミニウムにドープして電子注入輸送層とした有機ＥＬ素子の発光波長は５１０ｎｍで、緑色の発光を示すことが記されている。しかし、直流印加電圧６Ｖでの発光輝度は１ｃｄ／ｍ^２、発光効率は０．５３７ｌｍ／Ｗと低いものである。また、この誘導体では青色や赤色系の発光は得られていない。一方、有機ＥＬディスプレイの実用化は既に始まっており、フルカラー表示素子用の発光材料は不可欠のものである。とくに、青色や赤色系の色純度、発光効率が高い有機ＥＬ素子及びそのための発光材料のニーズは極めて高いものである。 Many compounds used as a light emitting material of a light emitting layer of an organic EL element are known. Particularly, as a compound having an imide group in a molecule, a perylene diimide derivative represented by the following formula

Non-patent document 1 in which tBu-PTC represented by the above formula is known as a red light-emitting material has a peak wavelength of element emission near 610 nm, lacks color purity as red, and has a maximum light emission luminance of 500 cd. It is not satisfactory to stay at the / m ² level. Further, Patent Document 1 describes that an organic EL device having an electron injecting and transporting layer doped with tris (8-quinolinolato) aluminum with a naphthalic acid imide derivative has an emission wavelength of 510 nm and emits green light. Yes. However, the light emission luminance at a DC applied voltage of 6 V is as low as 1 cd / m ² and the light emission efficiency is as low as 0.537 lm / W. In addition, no blue or red light emission is obtained with this derivative. On the other hand, the practical application of organic EL displays has already begun, and light emitting materials for full-color display elements are indispensable. In particular, the needs for organic EL elements having high blue and red color purity and high luminous efficiency and light emitting materials therefor are extremely high.

JP-A-4-320486 The Institute of Television Engineers, 44 (5) 578 (1990).

  An object of the present invention was made to solve the above-described problems, and is an imide group-containing fluoranthene-based compound that emits blue or red light with high emission luminance and light emission efficiency, and a light-emitting material using the same. It is in the point which provides the organic electroluminescent element using this.

  As a result of intensive studies to solve the above problems, the present inventors have solved the above problems by using an imide group-containing fluoranthene compound as an organic thin film layer of an organic EL device, particularly as a material for a light emitting layer. As a result, the present invention has been completed.

〔式中、Ａｒ^１は置換基を有することもある下記式

で示される基群から選ばれたものであり、Ａｒ^２は置換基を有することもある下記式

で示される基群から選ばれたものであり、式中、Ｒ^０は、水素、置換もしくは無置換の炭素数１〜３０のアルキル基、置換もしくは無置換の炭素数６〜４０のアリール基および置換もしくは無置換の炭素数７〜４０のアリールアルキル基よりなる群から選ばれた基であり、Ｒ^１〜Ｒ^１２は、水素、置換もしくは無置換の炭素数１〜３０のアルキル基、置換もしくは無置換の炭素数１〜３０のアルコキシ基、置換もしくは無置換の炭素数６〜４０のアリール基、置換もしくは無置換の炭素数７〜４０のアリールアルキル基、置換もしくは無置換の炭素数４〜３０のアルケニル基、置換もしくは無置換の炭素数３〜２０のトリアルキルシリル基、置換もしくは無置換の炭素数６〜４０のアリールオキシ基、シアノ基、ニトロ基、ハロゲン基および下記一般式

で示される基よりなる群からそれぞれ独立して選ばれた基であり、前記Ａｒ^３およびＡｒ^４は水素、置換もしくは無置換の炭素数１〜３０のアルキル基、置換もしくは無置換の炭素数６〜４０のアリール基および置換もしくは無置換の炭素数７〜４０のアリールアルキル基よりなる群からそれぞれ独立して選ばれた基であり、また、Ａｒ^３とＡｒ^４は互いに連結して環状構造を形成していてもよく、また、Ｒ^１〜Ｒ^１２は互いに隣接する基で環構造を形成していてもよい。〕
で示されるイミド基含有フルオランテン系化合物に関する。
本発明の第２は、請求項１記載のイミド基含有フルオランテン系化合物よりなる有機エレクトロルミネッセンス素子用発光材料に関する。
本発明の第３は、陰極と陽極間に一層または複数層からなる有機薄膜層が挟持されている有機エレクトロルミネッセンス素子において、該有機薄膜層の少なくとも１層が請求項１記載のイミド基含有フルオランテン系化合物を含有することを特徴とする有機エレクトロルミネッセンス素子に関する。
本発明の第４は、陰極と陽極間に、少なくとも電子輸送層、発光層および正孔輸送層が挟持されている有機エレクトロルミネッセンス素子において、発光層が請求項１記載のイミド基含有フルオランテン系化合物を１種類以上を含有することを特徴とする有機エレクトロルミネッセンス素子に関する。 The first of the present invention is the following general formula (A) or (B)

[In the formula, Ar ¹ may have a substituent,

Selected from the group represented by the following formula: Ar ² may have a substituent

In which R ⁰ is hydrogen, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 40 carbon atoms, and R ⁰ is a group selected from the group consisting of R ^{1 to} R ¹² are groups selected from the group consisting of substituted or unsubstituted arylalkyl groups having 7 to 40 carbon atoms, wherein R ^{1 to} R ¹² are hydrogen, substituted or unsubstituted alkyl groups having 1 to 30 carbon atoms, substituted or An unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 40 carbon atoms, a substituted or unsubstituted arylalkyl group having 7 to 40 carbon atoms, a substituted or unsubstituted carbon atom having 4 to 30 alkenyl groups, substituted or unsubstituted trialkylsilyl groups having 3 to 20 carbon atoms, substituted or unsubstituted aryloxy groups having 6 to 40 carbon atoms, cyano groups, nitro groups, halogen groups, and And the following general formula

Wherein Ar ³ and Ar ⁴ are each independently hydrogen, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted carbon number 6 A group selected from the group consisting of an aryl group of ˜40 and a substituted or unsubstituted arylalkyl group of 7 to 40 carbon atoms, and Ar ³ and Ar ⁴ are linked to each other to form a cyclic structure. R ^{1 to} R ¹² may form a ring structure with groups adjacent to each other. ]
It is related with the imide group containing fluoranthene type compound shown by these.
2nd of this invention is related with the luminescent material for organic electroluminescent elements which consists of an imide group containing fluoranthene type compound of Claim 1.
According to a third aspect of the present invention, in the organic electroluminescence device in which one or more organic thin film layers are sandwiched between the cathode and the anode, at least one of the organic thin film layers is the imide group-containing fluoranthene according to claim 1. The present invention relates to an organic electroluminescence device characterized by containing a compound.
4th of this invention is an organic electroluminescent element by which at least an electron carrying layer, a light emitting layer, and a positive hole transport layer are pinched | interposed between a cathode and an anode, The light emitting layer is an imide group containing fluoranthene type compound of Claim 1 It is related with the organic electroluminescent element characterized by containing 1 or more types.

  As typical imide group-containing fluoranthene compounds of the present invention, compounds represented by the following general formulas (1) to (9) can be exemplified.

（式中、Ｒ^０は、水素、置換もしくは無置換の炭素数１〜３０のアルキル基、置換もしくは無置換の炭素数６〜４０のアリール基および置換もしくは無置換の炭素数７〜４０のアリールアルキル基よりなる群から選ばれた基であり、Ｒ^１〜Ｒ^１２は、水素、置換もしくは無置換の炭素数１〜３０のアルキル基、置換もしくは無置換の炭素数１〜３０のアルコキシ基、置換もしくは無置換の炭素数６〜４０のアリール基、置換もしくは無置換の炭素数７〜４０のアリールアルキル基、置換もしくは無置換の炭素数４〜３０のアルケニル基、置換もしくは無置換の炭素数３〜２０のトリアルキルシリル基、置換もしくは無置換の炭素数６〜４０のアリールオキシ基、シアノ基、ニトロ基、ハロゲン基および下記一般式

で示される基よりなる群からそれぞれ独立して選ばれた基であり、前記Ａｒ^３およびＡｒ^４は水素、置換もしくは無置換の炭素数１〜３０のアルキル基、置換もしくは無置換の炭素数６〜４０のアリール基および置換もしくは無置換の炭素数７〜４０のアリールアルキル基よりなる群からそれぞれ独立して選ばれた基であり、また、Ａｒ^３とＡｒ^４は互いに連結して環状構造を形成していてもよく、また、Ｒ^１〜Ｒ^１２は互いに隣接する基で環構造を形成していてもよい。〕

(In the formula, R ⁰ represents hydrogen, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 40 carbon atoms, and a substituted or unsubstituted aryl group having 7 to 40 carbon atoms. R ^{1 to} R ¹² are groups selected from the group consisting of alkyl groups, and R ^{1 to} R ¹² are hydrogen, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, A substituted or unsubstituted aryl group having 6 to 40 carbon atoms, a substituted or unsubstituted arylalkyl group having 7 to 40 carbon atoms, a substituted or unsubstituted alkenyl group having 4 to 30 carbon atoms, a substituted or unsubstituted carbon number 3 to 20 trialkylsilyl group, substituted or unsubstituted aryloxy group having 6 to 40 carbon atoms, cyano group, nitro group, halogen group and the following general formula

Wherein Ar ³ and Ar ⁴ are each independently hydrogen, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted carbon number 6 A group selected from the group consisting of an aryl group of ˜40 and a substituted or unsubstituted arylalkyl group of 7 to 40 carbon atoms, and Ar ³ and Ar ⁴ are linked to each other to form a cyclic structure. R ^{1 to} R ¹² may form a ring structure with groups adjacent to each other. ]

In R ⁰ , the substituted or unsubstituted alkyl group having 1 to 30 carbon atoms is methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, tert-butyl group, n -Pentyl group, isopentyl group, neopentyl group, tert-pentyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 3,3-dimethylpentyl group, cyclopentyl group, n-hexyl group, isohexyl Group, 2,3,5-trimethylhexyl group, cyclohexyl group, n-heptyl group, isoheptyl group, 4-ethyl-3,3-dimethylheptyl group, n-octyl group, 4-ethyl-5-methyloctyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group Group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, eicosyl group, henicosyl group, docosyl group, tricosyl group, tetracosyl group, pentacosyl group, hexacosyl group, heptacosyl group, octacosyl group, nonacosyl group, triaconyl group, 2,7,8-trimethyl-decyl group, 5-methyl-4-propylnonyl group, cyclopentyl group, cyclohexyl group, bicyclohexyl-4-yl group, 4'-methyl-bicyclohexyl-4-yl group, etc. It is done.

In R ⁰ , the substituted or unsubstituted aryl group having 6 to 40 carbon atoms includes a phenyl group, a mesityl group, a 3-methylphenyl group, a 2,3-dimethylphenyl group, a 4-cyanophenyl group, and a 1-naphthyl group. 2-naphthyl group, 1-anthryl group, 2-anthryl group, 9-anthryl group, 2-phenanthryl group, 1-naphthacenyl group, 2-naphthacenyl group, 5-naphthacenyl group, pyrenyl group, 9,9-dimethyl- 9H-fluoren-2-yl group, 7,9,9-trimethyl-9H-fluoren-2-yl group, biphenyl-4-yl group, 4'-methyl-biphenyl-4-yl group, [1,1 ' , 4 ', 1 "] terphenyl-4-yl group and the like.

In R ⁰ , the substituted or unsubstituted arylalkyl group having 7 to 40 carbon atoms includes benzyl group, α-methylbenzyl group, cinnamyl group, α-ethylbenzyl group, α, α-dimethylbenzyl group, 4-methyl Examples include benzyl group, 4-ethylbenzyl group, 2-tert-butylbenzyl group, 4-n-octylbenzyl group, naphthylmethyl group, diphenylmethyl group and the like.

In R ^{1 to} R ¹² , the substituted or unsubstituted alkyl group having 1 to 30 carbon atoms is methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, tert-butyl. Group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 3,3-dimethylpentyl group, cyclopentyl group, n-hexyl Group, isohexyl group, 2,3,5-trimethylhexyl group, cyclohexyl group, n-heptyl group, isoheptyl group, 4-ethyl-3,3-dimethylheptyl group, n-octyl group, 4-ethyl-5-methyl Octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-te Ladecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, eicosyl group, henicosyl group, docosyl group, tricosyl group, tetracosyl group, pentacosyl group, hexacosyl group, heptacosyl group, octacosyl group, nonacosyl group, triaconyl group 2,7,8-trimethyl-decyl group, 5-methyl-4-propylnonyl group, cyclopentyl group, cyclohexyl group, bicyclohexyl-4-yl group, 4'-methyl-bicyclohexyl-4-yl group, hydroxy Methyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 2-hydroxyisobutyl group, 1,2-dihydroxyethyl group, 1,3-dihydroxyisopropyl group, chloromethyl group, 1-chloroethyl group, 2-chloroethyl group , 2-chloroi Butyl group, 1,2-dichloroethyl group, 1,3-dichloroisopropyl group, 2,3-dichloro-t-butyl group, bromomethyl group, 1-bromoethyl group, 2-bromoethyl group, 2-bromoisobutyl group, 1 , 2-dibromoethyl group, 1,3-dibromoisopropyl group, 1,2,3-tribromopropyl group, iodomethyl group, 1-iodoethyl group, 2-iodoethyl group, 2-iodoisobutyl group, 2,3-diiodo -T-butyl group, cyanomethyl group, 1-cyanomethyl group, 2-cyanomethyl group, 2,3-dicyano-t-butyl group, nitromethyl group, 1-nitromethyl group, 1,2-dinitroethyl group, 1,3- Examples thereof include a dinitroisopropyl group.

In R ^{1 to} R ¹² , the substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms is a group represented by —OY, and examples of Y include a methyl group, an ethyl group, a propyl group, and an isopropyl group. , N-butyl, s-butyl, isobutyl, t-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, hydroxyl, 1-hydroxyethyl, 2- Hydroxyethyl group, 1,2-dihydroxyethyl group, 2,3-dihydroxy-t-butyl group, chloromethyl group, 1-chloroethyl group, 2-chloroethyl group, 2-chloroisobutyl group 1,2-dichloroethyl group, 1,3-dichloroisopropyl group, 2,3-dichloro-t-butyl group, bromomethyl group, 1-bromoethyl group, 2-bromoethyl group, 2-bromoisobutyl 1,2-dibromoethyl group, 1,3-dibromoisopropyl group, 1,2,3-tribromopropyl group, iodomethyl group, 1-iodoethyl group, 2-iodoethyl group, 2-iodoisobutyl group, 2,3 -Diiodo-t-butyl group, cyanomethyl group, 1-cyanomethyl group, 2-cyanomethyl group, 2-cyanomethyl group, 2,3-dicyano-t-butyl group, nitromethyl group, 1-nitromethyl group, 1,2-dinitro Examples thereof include an ethyl group and a 1,3-dinitroisopropyl group.

In R ^{1 to} R ¹² , the substituted or unsubstituted aryl group having 6 to 40 carbon atoms is phenyl group, naphthyl group, anthryl group, phenanthryl group, naphthacenyl group, pyrenyl group, fluorenyl group, biphenyl group, terphenyl group And a stilbene group. Examples of the substituted or unsubstituted arylalkyl group having 7 to 40 carbon atoms in R ^{1 to} R ¹² include benzyl group, α-methylbenzyl group, cinnamyl group, α-ethylbenzyl group, α, α-dimethylbenzyl group, 4 -Methylbenzyl group, 4-ethylbenzyl group, 2-tert-butylbenzyl group, 4-n-octylbenzyl group, naphthylmethyl group, diphenylmethyl group and the like can be mentioned. Examples of the substituted or unsubstituted alkenyl group having 4 to 30 carbon atoms include vinyl group, allyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1,3-butanedienyl group, 1-methylvinyl group, Styryl group, 2,2-diphenylvinyl group, 2,2-ditolylvinyl group, 1,2-ditolylvinyl group, 1-methylallyl group, 2-methylallyl group, 1,2-dimethylallyl group, 1-phenylallyl group, 2 -Phenylallyl group, 3-phenylallyl group, 3,3-diphenylallyl group, 1-phenyl-1-butenyl group, 3-phenyl-1-butenyl group and the like can be mentioned.

Examples of the substituted or unsubstituted trialkylsilyl group having 3 to 20 carbon atoms in R ^{1 to} R ¹² include a trimethylsilyl group, a triethylsilyl group, a tripropylsilyl group, a tributylsilyl group, a tripentylsilyl group, a trihexylsilyl group, Examples include t-butyldimethylsilyl group.

  Examples of the substituted or unsubstituted aryloxy group having 6 to 40 carbon atoms include a phenoxy group, a naphthyloxy group, an ankle oxy group, a pyrenyloxy group, a biphenyloxy group, a fluoranthenyloxy group, a chrysenyloxy group, and a pyrenyloxy group. It is done.

  Examples of the substituent in the alkyl group and the alkoxy group include a halogen, a hydroxyl group, and a substituted or unsubstituted amino group (the substituent includes a halogen, a hydroxyl group, an alkyl group, an alkoxy group, and these substituents. It can be an aryl group.

  Examples of the substituent of the aryl group and alkenyl group include halogen, hydroxyl group, nitro group, cyano group, substituted or unsubstituted amino group (substituents include halogen, hydroxyl group, alkyl group, alkoxy group, and An aryl group having these substituents), a substituted or unsubstituted alkyl group (which is a halogen or a hydroxyl group), a substituted or unsubstituted alkenyl group (as this substituent) Is a halogen or a hydroxyl group), a substituted or unsubstituted cycloalkyl group (the substituent can be a halogen, a hydroxyl group, an alkyl group, an alkoxy group, and an aryl group having these substituents) Substituted or unsubstituted alkoxy group (this substituent includes halogen Or a hydroxyl group), a substituted or unsubstituted aralkyl group (the substituent can be a halogen, a hydroxyl group, an alkyl group, an alkoxy group, and an aryl group having these substituents), a substituted or unsubstituted Substituted aryloxy groups (substituents can be halogens, hydroxyl groups, alkyl groups, alkoxy groups, and aryl groups having these substituents).

In the general formulas (A) and (B), Ar ³ and Ar ⁴ are each independently hydrogen, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms (this substituent is the same as the substituent for the alkyl group) ), A substituted or unsubstituted aryl group having 6 to 40 carbon atoms (this substituent is the same as the substituent for the aryl group), a substituted or unsubstituted arylalkyl group having 7 to 40 carbon atoms (as a substituent, A halogen, a hydroxyl group, an alkyl group, an alkoxy group, and an aryl group having these substituents), and Ar ³ and Ar ⁴ may be linked to each other to form a cyclic structure.

  Specific examples of the compound of the present invention represented by the general formulas (1) to (9) are shown below, but the compound of the present invention is not limited thereto. In the formula, Me is a methyl group, Et is an ethyl group, t-Bu is a t-butyl group, n-Bu is an n-butyl group, i-Pr is an isopropyl group, n-Pr is an n-propyl group, OMe Represents a methoxy group.

The compounds represented by the general formulas (1) to (9) can be synthesized by the following methods, respectively. In the following reaction formulas, R ⁰ and R ^{1 to} R ¹² are as defined in the claims.

溶媒のテトラリンに、化合物（１−ａ）及び２倍当量のマレイミド誘導体を加え、１７０〜１８０℃で２時間加熱する。反応溶媒を減圧留去して得られる（１−ｂ）を含む粗生成物に、化合物（１−ａ）に対して当量の２，３−ジクロロ−５，６−ジシアノ−ベンゾキノン（ＤＤＱ）及びトルエンを加えて１００℃で５時間加熱する。反応液を濃縮して得られる固体を少量のアセトンで洗浄し、シリカゲルカラムクロマトグラフィーで精製して高純度の化合物（１）の固体を得る。

Compound (1-a) and 2-fold equivalent of maleimide derivative are added to tetralin as a solvent, and heated at 170 to 180 ° C. for 2 hours. To the crude product containing (1-b) obtained by distilling off the reaction solvent under reduced pressure, 2,3-dichloro-5,6-dicyano-benzoquinone (DDQ) equivalent to compound (1-a) and Add toluene and heat at 100 ° C. for 5 hours. The solid obtained by concentrating the reaction solution is washed with a small amount of acetone and purified by silica gel column chromatography to obtain a solid of compound (1) having a high purity.

キシレンと塩化メチレンの混合溶媒に、化合物（２−ａ）と２倍当量のマレイミド誘導体を加え、４〜５時間還流加熱する。得られた化合物（２−ｂ）を単離することなく、反応液を−６０℃に冷却し、化合物（２−ａ）に対して当量の３臭化ホウ素の塩化メチレン溶液を加えた後、５〜６時間還流加熱する。反応液を後処理した後、シリカゲルカラムクロマトグラフィーで精製し、高純度の化合物（２）を得る。

To a mixed solvent of xylene and methylene chloride, the compound (2-a) and 2-fold equivalent of a maleimide derivative are added, and heated at reflux for 4 to 5 hours. Without isolating the obtained compound (2-b), the reaction solution was cooled to −60 ° C., and an equivalent amount of boron tribromide in methylene chloride was added to the compound (2-a). Heat at reflux for 5-6 hours. The reaction solution is post-treated and then purified by silica gel column chromatography to obtain a highly pure compound (2).

溶媒のキシレンに、化合物（３−ａ）及び２倍当量のマレイミド誘導体を加え、１０時間還流加熱する。得られた化合物（３−ｂ）を単離することなく、化合物（３−ａ）に対して当量の２，３−ジクロロ−５，６−ジシアノ−ベンゾキノン（ＤＤＱ）を加えて１００℃で５時間加熱する。反応液を濃縮して得られる固体を少量のアセトンで洗浄し、シリカゲルカラムクロマトグラフィーで精製して高純度の化合物（３）の固体を得る。

The compound (3-a) and 2-fold equivalent maleimide derivative are added to xylene as a solvent, and heated at reflux for 10 hours. Without isolating the obtained compound (3-b), an equivalent amount of 2,3-dichloro-5,6-dicyano-benzoquinone (DDQ) was added to the compound (3-a), Heat for hours. The solid obtained by concentrating the reaction solution is washed with a small amount of acetone, and purified by silica gel column chromatography to obtain a highly pure compound (3) solid.

キシレンと塩化メチレンの混合溶媒に、化合物（４−ａ）及び２倍当量のマレイミド誘導体を加え、４〜５時間還流加熱する。得られた化合物（４−ｂ）を単離することなく、反応液を−６０℃に冷却し、化合物（４−ａ）に対して当量の３臭化ホウ素の塩化メチレン溶液を加えた後、５〜６時間還流加熱する。反応液を後処理した後、シリカゲルカラムクロマトグラフィーで精製し、高純度の化合物（４）を得る。

To a mixed solvent of xylene and methylene chloride, the compound (4-a) and a double equivalent of a maleimide derivative are added and heated to reflux for 4 to 5 hours. Without isolating the obtained compound (4-b), the reaction solution was cooled to −60 ° C., and an equivalent amount of boron tribromide in methylene chloride was added to the compound (4-a). Heat at reflux for 5-6 hours. The reaction solution is post-treated and then purified by silica gel column chromatography to obtain a highly pure compound (4).

溶媒のテトラリンに、化合物（５−ａ）及び２倍当量のマレイミド誘導体を加え、１７０〜１８０℃で５時間加熱する。反応液の溶媒を減圧留去して得られる（５−ｂ）を含む粗生成物に、化合物（５−ａ）に対して当量の２，３−ジクロロ−５，６−ジシアノ−ベンゾキノン（ＤＤＱ）及びトルエンを加えて１００℃で５時間加熱する。反応液を濃縮して得られる固体を少量のアセトンで洗浄し、シリカゲルカラムクロマトグラフィーで精製して高純度の化合物（５）の固体を得る。

Compound (5-a) and 2-fold equivalent maleimide derivative are added to tetralin as a solvent and heated at 170 to 180 ° C. for 5 hours. The crude product containing (5-b) obtained by distilling off the solvent of the reaction solution under reduced pressure was added to 2,3-dichloro-5,6-dicyano-benzoquinone (DDQ) equivalent to the compound (5-a). ) And toluene, and heated at 100 ° C. for 5 hours. The solid obtained by concentrating the reaction solution is washed with a small amount of acetone, and purified by silica gel column chromatography to obtain a high-purity compound (5) solid.

溶媒のテトラリンに、化合物（６−ａ）及び２倍当量のマレイミド誘導体を加え、１７０〜１８０℃で５時間加熱する。反応溶媒を減圧留去して得られる（６−ｂ）を含む粗生成物に化合物（６−ａ）に対して当量の２，３−ジクロロ−５，６−ジシアノ−ベンゾキノン（ＤＤＱ）及びトルエンを加えて１００℃で５時間加熱する。反応液を濃縮して得られる固体を少量のアセトンで洗浄し、シリカゲルカラムクロマトグラフィーで精製して高純度の化合物（６）の固体を得る。

Compound (6-a) and 2-fold equivalent maleimide derivative are added to tetralin as a solvent, and heated at 170 to 180 ° C. for 5 hours. The crude product containing (6-b) obtained by distilling off the reaction solvent under reduced pressure is equivalent to 2,3-dichloro-5,6-dicyano-benzoquinone (DDQ) and toluene with respect to compound (6-a). And heated at 100 ° C. for 5 hours. The solid obtained by concentrating the reaction solution is washed with a small amount of acetone, and purified by silica gel column chromatography to obtain a high-purity compound (6) solid.

溶媒のテトラリンに、化合物（７−ａ）及び４倍当量のマレイミド誘導体を加え、１７０〜１８０℃で５時間加熱する。反応溶媒を減圧留去して得られる（７−ｂ）を含む粗生成物に、化合物（７−ａ）に対して２倍当量の２，３−ジクロロ−５，６−ジシアノ−ベンゾキノン（ＤＤＱ）及びトルエンを加えて１００℃で５時間加熱する。反応液を濃縮して得られる固体を少量のアセトンで洗浄し、シリカゲルカラムクロマトグラフィーで精製して高純度の化合物（７）の固体を得る。

Compound (7-a) and 4-fold equivalent of maleimide derivative are added to tetralin as a solvent, and heated at 170 to 180 ° C. for 5 hours. The crude product containing (7-b) obtained by distilling off the reaction solvent under reduced pressure was added to 2-fold equivalent of 2,3-dichloro-5,6-dicyano-benzoquinone (DDQ) with respect to compound (7-a). ) And toluene, and heated at 100 ° C. for 5 hours. The solid obtained by concentrating the reaction solution is washed with a small amount of acetone, and purified by silica gel column chromatography to obtain a high-purity compound (7) solid.

溶媒のテトラリンに、化合物（８−ａ）及び４倍当量のマレイミド誘導体を加え、１７０〜１８０℃で５時間加熱する。反応溶媒を減圧留去して得られる（８−ｂ）粗生成物に、化合物（８−ａ）に対して２倍当量の２，３−ジクロロ−５，６−ジシアノ−ベンゾキノン（ＤＤＱ）及びトルエンを加えて１００℃で５時間加熱する。反応液を濃縮して得られる固体を少量のアセトンで洗浄し、シリカゲルカラムクロマトグラフィーで精製して高純度の化合物（８）の固体を得る。

Compound (8-a) and 4-fold equivalent of maleimide derivative are added to tetralin as a solvent, and heated at 170 to 180 ° C. for 5 hours. To the crude product (8-b) obtained by distilling off the reaction solvent under reduced pressure, 2,3-dichloro-5,6-dicyano-benzoquinone (DDQ) equivalent to twice the compound (8-a) and Add toluene and heat at 100 ° C. for 5 hours. The solid obtained by concentrating the reaction solution is washed with a small amount of acetone, and purified by silica gel column chromatography to obtain a high-purity compound (8) solid.

溶媒のテトラリンに、化合物（９−ａ）及び４倍当量のマレイミド誘導体を加え、１７０〜１８０℃で５時間加熱する。反応溶媒を減圧留去して得られる（９−ｂ）を含む粗生成物に、化合物（９−ａ）に対して２倍当量の２，３−ジクロロ−５，６−ジシアノ−ベンゾキノン（ＤＤＱ）及びトルエンを加えて１００℃で５時間加熱する。反応液を濃縮して得られる固体を少量のアセトンで洗浄し、シリカゲルカラムクロマトグラフィーで精製して高純度の化合物（９）の固体を得る。

Compound (9-a) and 4-fold equivalent of maleimide derivative are added to tetralin as a solvent, and heated at 170 to 180 ° C. for 5 hours. The crude product containing (9-b) obtained by distilling off the reaction solvent under reduced pressure was added to 2-fold equivalent of 2,3-dichloro-5,6-dicyano-benzoquinone (DDQ) with respect to compound (9-a). ) And toluene, and heated at 100 ° C. for 5 hours. The solid obtained by concentrating the reaction solution is washed with a small amount of acetone and purified by silica gel column chromatography to obtain a high-purity compound (9) solid.

  The imide group-containing fluoranthene compound of the present invention can be used as an organic compound for an organic EL device. In the organic EL device of the present invention, in which an organic thin film layer composed of one layer or a plurality of layers is sandwiched between a cathode and an anode, the light emitting layer preferably contains the imide group-containing fluoranthene compound of the present invention.

  The organic EL device of the present invention is a device in which one or more organic thin film layers are formed between the anode and the cathode as described above. In the case of the single layer type, a light emitting layer is provided between the anode and the cathode. The light emitting layer contains a light emitting material, and in addition, in order to transport holes injected from the anode or electrons injected from the cathode to the light emitting material, a hole injecting material, a hole transporting material or an electron injecting material, an electron It may contain a transport material. Further, the light emitting material of the present invention has extremely high fluorescence quantum efficiency, high hole transport ability and electron transport ability, and can form a uniform thin film. Multi-layer type organic EL devices include (anode / hole injection layer / light emitting layer / cathode), (anode / light emitting layer / electron injection layer / cathode), (anode / hole transport layer / light emitting layer / electron transport layer). / Cathode), (anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / cathode), etc.

  In addition to the compound of the present invention, further known host materials, light emitting materials, doping materials, hole injecting materials, and electron injecting materials can be used in combination in the light emitting layer as necessary. By making the organic EL element have a multilayer structure, it is possible to prevent a decrease in luminance and lifetime due to quenching, and by using other doping materials, it is possible to improve light emission luminance and light emission efficiency and to obtain red and white light emission. In addition, the hole injection layer, the hole transport layer, the light emitting layer, the electron transport layer, and the electron injection layer in the organic EL device of the present invention may be formed of two or more layers. At that time, in the case of a hole injection layer, the layer that injects holes from the anode is called a hole injection layer, and the layer that receives holes from the hole injection layer and transports holes to the light emitting layer is called a hole transport layer. . Similarly, in the case of an electron injection layer, a layer that plays the role of injecting electrons from the cathode is called an electron injection layer, and a layer that receives electrons from the electron injection layer and transports electrons to the light emitting layer is called an electron transport layer. Each of these layers is selected and used depending on factors such as the energy level of the material, heat resistance, adhesion with the organic thin film layer or the metal electrode.

As a hole injection material or a hole transport material, it has the ability to transport holes, and has a hole injection effect from the anode, and an excellent hole injection effect or hole transport effect for the light emitting layer or light emitting material. A compound that prevents the excitons generated in the light emitting layer from moving to the electron injection layer or the electron injection material and has an excellent thin film forming ability is preferable. Specifically, phthalocyanine derivatives, naphthalocyanine derivatives, porphyrin derivatives, oxazole, oxadiazole, triazole, imidazole, imidazolone, imidazolethione, pyrazoline, pyrazolone, tetrahydroimidazole, hydrazone, acylhydrazone, polyarylalkane, stilbene, benzidine type Examples include triphenylamine, styrylamine type triphenylamine, diamine type triphenylamine, and derivatives thereof, and polymer materials such as polyvinylcarbazole, polysilane, and conductive polymer.
It is not limited to these.

Among these hole injection materials or hole transport materials, more effective materials are aromatic tertiary amine derivatives or phthalocyanine derivatives. Specific examples of the aromatic tertiary amine derivative include triphenylamine, tolylamine, tridiphenylamine, N, N′-diphenyl-N, N ′-(3-methylphenyl) -1,1′-biphenyl-4, 4'-diamine, N, N, N ', N'-(4-methylphenyl) -1,1'-phenyl-4,4'-diamine, N, N, N ', N'-(4-methyl Phenyl) -1,1'-biphenyl-4,4'-diamine, N, N'-diphenyl-N, N'-dinaphthyl-1,1'-biphenyl-4,4'-diamine, N, N'- (Methylphenyl) -N, N ′-(4-n-butylphenyl) -phenanthrene-9,10-diamine, N, N-bis (4-di-4-tolylaminophenyl) -4-phenyl-cyclohexane, etc. Or these aromatic tertiary amino acids An oligomer or polymer having a backbone, but not limited thereto. Specific examples of the phthalocyanine (Pc) _{derivatives, PCH 2, PcCu, PcCo,} PcNi, PcZn, PcPd, PcFe, PcMn, PcClAl, PcClGa, PcClIn, PcClSn, PcCl 2 Si, Pc (HO) Al, Pc (HO) Ga Phthalocyanine derivatives such as PcVO, PcTiO, and PcMoO (see Sankyo Publishing Co., Ltd., Daigaku Dictionary, phthalocyanine complex salt) and naphthalocyanine derivatives. Examples of the conductive polymer include, but are not limited to, polyaniline derivatives (PAni) and polythiophene derivatives (PEDOT).

  The compound used as an electron injection material or an electron transport material has the ability to transport electrons, has an electron injection effect from the cathode, and has an excellent electron transport effect with respect to the light emitting layer or the light emitting material, and is generated in the light emitting layer. A compound that prevents exciton migration to the hole injection layer and is excellent in thin film formation is preferable. Examples include, but are not limited to, fluorenone, anthraquinodimethane, diphenoquinone, thiopyrandioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, fluorenylidenemethane, anthrone, and their derivatives. Is not to be done. Further, the charge injection property can be improved by adding an electron accepting substance to the hole transport material of the present invention and an electron donating substance to the electron injection material.

  In the organic EL device of the present invention, a more effective electron transport material is a metal complex compound, a nitrogen-containing five-membered ring derivative, or a nitrogen-containing aromatic compound. Specific examples of the metal complex compound include tris (8-quinolinato) lithium, tris (8-quinolinato) zinc, tris (8-quinolinato) copper, tris (8-quinolinato) manganese, tris (8-quinolinato) aluminum, tris. (2-Methyl-8-quinolinato) aluminum, tris (4-methyl-8-quinolinato) aluminum, tris (4-propyl-8-quinolinato) aluminum, tris (4-benzyl-8-quinolinato) aluminum, bis (2 -Methyl-8-quinolinato) (phenolate) aluminum, bis (2-methyl-8-quinolinato) (o-cresolate) aluminum, bis (2-methyl-8-quinolinato) (m-cresolate) aluminum, bis (2- Methyl-8-quinolinate) (p- Resoleate) aluminum, bis (2-methyl-8-quinolinato) (m-phenylphenolate) aluminum, bis (2-methyl-8-quinolinato) (p-phenylphenolate) aluminum, bis (2-methyl-8- Quinolinate) (3,5-dimethylphenolate) aluminum, bis (2-methyl-8-quinolinato) (1-naphtholato) aluminum, bis (2-methyl-8-quinolinato) (2-naphtholato) gallium, bis (2 -Methyl-8-quinolinato) (p-cresolate) gallium, bis (8-quinolinato) zinc, bis (8-quinolinato) copper, bis (8-quinolinato) manganese, and the like. Absent.

  Further, specific examples of the nitrogen-containing five-membered ring derivative are preferably an oxazole derivative, a thiazole derivative, an oxadiazole derivative, a thiadiazole derivative, or a triazole derivative. Specifically, 2,5-bis (1-phenyl) -1,3,4-oxazole, 2,5-bis (1-phenyl) -1,3,4-thiazole, 2,5-bis (1 -Phenyl) -1,3,4-oxadiazole, 2,5-bis (1-naphthyl) -1,3,4-oxadiazole, 1,4-bis [2- (5-phenyloxadiazolyl) )] Benzene, 1,4-bis [2- (5-phenyloxadiazolyl) -4-tert-butylbenzene], 2- (4'-tert-butylphenyl) -5- (4 "-biphenyl)- 1,3,4-oxadiazole, 2- (4′-tert-butylphenyl) -5- (4 ″ -biphenyl) -1,3,4-thiazole, 2,5-bis (1-naphthyl)- 1,3,4-thiazole, 1,4-bis [2- (5-phenylthiadi Zolyl)] benzene, 2- (4′-tert-butylphenyl) -5- (4 ″ -biphenyl) -1,3,4-triazole, 2,5-bis (1-naphthyl) -1,3,4 -Triazole, 4-bis [2- (5-phenyltriazolyl)] benzene and the like may be mentioned, but are not limited thereto.

  Furthermore, a specific example of the nitrogen-containing aromatic compound is preferably a phenanthroline derivative. Specifically, 4,7-diphenyl-1,10-phenanthroline, 4,7-di-m-tolyl-1,10-phenanthroline, 4,7-di-p-tolyl-1,10-phenanthroline, , 9-dimethyl-4,7-diphenyl-1,10-phenanthroline, 2,9-dimethyl-4,7-di-p-tolyl-1,10-phenanthroline, 2,9-dimethyl-4,7-di -M-tolyl-1,10-phenanthroline, 2,9-diethyl-4,7-diphenyl-1,10-phenanthroline, 2,9-diethyl-4,7-di-p-tolyl-1,10-phenanthroline 2,9-diethyl-4,7-di-m-tolyl-1,10-phenanthroline, 2,9-dimethyl-4,7-bis (naphthalen-1-yl) -1,10-phenanthroline, 2, 9 Dimethyl-4,7-bis (naphthalen-2-yl) -1,10-phenanthroline, 2,9-diphenyl-4,7-diphenyl-1,10-phenanthroline, 2,9-dimethyl-4,7-bis (Biphenylene-4-yl) -1,10-phenanthroline, 3,8-di (α-naphthyl) -1,10-phenanthroline, 3,8-di (β-naphthyl) -1,10-phenanthroline, 1, 4-di (1,10-phenanthrolin-2-yl) benzene, 4,4'-di (1,10-phenanthroline-2-yl) biphenyl, 1,5-di (1,10-phenanthrolin-2-yl) ) Anthracene, 1,3,5-tri (1,10-phenanthrolin-2-yl) benzene and the like, but are not limited thereto.

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

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

The formation of each layer of the organic electroluminescence element in the present invention may be performed by a dry film forming method such as vacuum deposition, sputtering, plasma, ion plating, spin coating,
Any method of wet film formation such as dipping and flow coating can be used.
The thickness of each layer of the organic thin film layer sandwiched between the anode and the cathode is not particularly limited, but must be set to an appropriate thickness. The normal film thickness is preferably selected as appropriate in the range of 0.5 nm to 500 nm.

  When the compound of the present invention is formed into a film, either a vacuum deposition method or a wet film formation method can be used. In the wet film forming method, the solvent used for preparing the solution used to form these organic thin films is dichloromethane, 1,2-dichloroethane, chloroform, tetrahydrofuran, dioxane, 1,2-dimethoxymethane, 1,2- Examples include diethoxymethane, acetone, and toluene, but are not particularly limited.

  In the organic electroluminescence device of the present invention, in addition to the compound of the present invention, at least one of a light emitting material, a doping material, a hole injection material, a hole transport material, an electron injection material and an electron transport material is contained in the same layer. May be. In addition, in order to improve the stability of the organic electroluminescent device obtained by the present invention with respect to temperature, humidity, atmosphere, etc., it is possible to provide a protective layer on the surface of the device or to protect the entire device with a resin or the like It is.

  When the imide group-containing fluoranthene compound of the present invention is used as a light-emitting material, an organic EL device that emits light in blue, yellow-orange, red-orange, red, or the like with high emission luminance and emission efficiency and high color purity can be obtained. For this reason, the organic EL element of the present invention is extremely useful as a light source for flat-panel illuminators of flat-screen televisions and flat panel displays, light sources for copiers and printers, liquid crystal displays and instruments, lighting fixtures, display boards, and indicator lights. Useful.

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

２００ｍｌの３つ口フラスコにアセサイクロン（ａ−１）３．５６ｇ（１０．０ｍｍｏｌ）、N−メチルマレイミド１．６６ｇ（２５．０ｍｍｏｌ）、テトラリン１００ｍｌを加えて、１８０℃で２時間撹拌した。反応終了後、テトラリンを加熱減圧留去して得られた固体を少量のメタノールで洗浄、乾燥し、黄色固体の化合物（ａ−２）３．８３ｇ（８．７ｍｍｏｌ）を得た。次に、この化合物３．７０ｇ（８．４ｍｍｏｌ）と２，３−ジクロロ−５，６−ジシアノ−ベンゾキノン（ＤＤＱ）２．２７ｇ（１０．０ｍｍｏｌ）をトルエン１００ｍｌに加えて、５時間１００℃で撹拌した。反応液を濾過、濃縮後、得られた黄色固体をアセトンでリンスし、さらに、シリカゲルカラムクロマトグラフィーで目的物を分離した。溶媒を留去して乾燥し、黄白色固体の化合物（１−１）３．３４ｇを得た（収率８８％）。さらに、高真空下で昇華精製を行なった。同定は^１H−ＮＭＲ、ＦＤ−ＭＡＳＳスペクトル：ｍ／ｚ ４３７（Ｍ^＋，１００）で行なった。なお、前記ＤＤＱは脱水素剤（酸化剤）として機能し、（ａ−２）に示した水素原子を引抜き、ハイドロキノンとなる。以下の実施例２〜４、６、８、１１、１２、１５、１７においても同様である。 Example 1 Synthesis of (Compound 1-1)

To a 200 ml three-necked flask, 3.56 g (10.0 mmol) of acecyclone (a-1), 1.66 g (25.0 mmol) of N-methylmaleimide and 100 ml of tetralin were added and stirred at 180 ° C. for 2 hours. After completion of the reaction, tetralin was heated and distilled off under reduced pressure, and the resulting solid was washed with a small amount of methanol and dried to obtain 3.83 g (8.7 mmol) of a yellow solid compound (a-2). Next, 3.70 g (8.4 mmol) of this compound and 2.27 g (10.0 mmol) of 2,3-dichloro-5,6-dicyano-benzoquinone (DDQ) were added to 100 ml of toluene, and the mixture was heated at 100 ° C. for 5 hours. Stir. After filtering and concentrating the reaction solution, the resulting yellow solid was rinsed with acetone, and further the target product was separated by silica gel column chromatography. The solvent was distilled off and the residue was dried to obtain 3.34 g of a yellowish white solid compound (1-1) (yield 88%). Furthermore, sublimation purification was performed under high vacuum. Identification was performed by ¹ H-NMR, FD-MASS spectrum: m / z 437 (M ⁺ , 100). The DDQ functions as a dehydrogenating agent (oxidizing agent), and draws out the hydrogen atom shown in (a-2) to become hydroquinone. The same applies to Examples 2 to 4, 6, 8, 11, 12, 15, and 17 below.

２００ｍｌの３つ口フラスコに化合物（ｂ−１）４．３５ｇ（１０．０ｍｍｏｌ）、Ｎ−ｔ−ブチルマレイミド３．８３ｇ（２５．０ｍｍｏｌ）、テトラリン１００ｍｌを加えて、１８０℃で２時間撹拌した。反応終了後、テトラリンを加熱減圧留去して得られた固体を少量のメタノールで洗浄、乾燥し、黄色固体の化合物（ｂ−２）５．００ｇ（８．９ｍｍｏｌ）を得た。さらに、この化合物全量とＤＤＱ２．２７ｇ（１０．０ｍｍｏｌ）をトルエン１００ｍｌに加えて、５時間１００℃で撹拌した。反応液を濾過、濃縮後、得られた黄色固体をアセトンでリンスし、さらに、シリカゲルカラムクロマトグラフィーで目的物を分離した。溶媒を留去して乾燥し、黄色固体の化合物（ｂ−３）４．６０ｇを得た。さらに、１００ｍｌの３つ口フラスコに、この化合物２．２３ｇ（４．０ｍｍｏｌ）、１−ナフチル−ボロン酸０．８８ｇ（５．１ｍｍｏｌ）、トルエン４０ｍｌを入れて窒素ガス雰囲気下、テトラキス（トリフェニルホスフィン）パラジウム１７７ｍｇ、２M−炭酸ソーダ水溶液８ｍｌを加えて、７時間９５℃で撹拌した。反応液をクロロホルムで抽出し、シリカゲルカラムクロマトグラフィーで目的物を分離した。溶媒を留去して乾燥させて薄緑色固体の化合物（６−２）を２．１５ｇ得た（収率８９％）。さらに、高真空下で昇華精製を行なった。同定は^１H−ＮＭＲ、ＦＤ−ＭＡＳＳスペクトル：ｍ／ｚ ６０５（Ｍ^＋，１００）により行なった。 Example 2 Synthesis of (Compound 6-2)

To a 200 ml three-necked flask, 4.35 g (10.0 mmol) of compound (b-1), 3.83 g (25.0 mmol) of Nt-butylmaleimide and 100 ml of tetralin were added and stirred at 180 ° C. for 2 hours. . After completion of the reaction, tetralin was heated and distilled off under reduced pressure, and the resulting solid was washed with a small amount of methanol and dried to obtain 5.00 g (8.9 mmol) of a yellow solid compound (b-2). Further, the total amount of this compound and 2.27 g (10.0 mmol) of DDQ were added to 100 ml of toluene, and the mixture was stirred at 100 ° C. for 5 hours. After filtering and concentrating the reaction solution, the resulting yellow solid was rinsed with acetone, and further the target product was separated by silica gel column chromatography. The solvent was distilled off and the residue was dried to obtain 4.60 g of a yellow solid compound (b-3). Further, 2.23 g (4.0 mmol) of this compound, 0.88 g (5.1 mmol) of 1-naphthyl-boronic acid and 40 ml of toluene were placed in a 100 ml three-necked flask, and tetrakis (triphenyl) was added under a nitrogen gas atmosphere. Phosphine) palladium (177 mg) and 2M aqueous sodium carbonate solution (8 ml) were added and the mixture was stirred at 95 ° C. for 7 hours. The reaction solution was extracted with chloroform, and the target product was separated by silica gel column chromatography. The solvent was distilled off and dried to obtain 2.15 g of light green solid compound (6-2) (yield 89%). Furthermore, sublimation purification was performed under high vacuum. Identification was performed by ¹ H-NMR, FD-MASS spectrum: m / z 605 (M ⁺ , 100).

２００ｍｌの３つ口フラスコに、化合物（ｃ−１）４．３５ｇ（１０．０ｍｍｏｌ）、Ｎ−メチルマレイミド２．７８ｇ（２５．０ｍｍｏｌ）、テトラリン１００ｍｌを加えて、１８０℃で２時間撹拌した。反応終了後、テトラリンを加熱減圧留去して得られた固体を少量のメタノールで洗浄、乾燥し、黄色固体の化合物（ｃ−２）４．５０ｇ（８．７ｍｍｏｌ）を得た。さらに、この化合物全量とＤＤＱ２．２７ｇ（１０．０ｍｍｏｌ）をトルエン１００ｍｌに加えて、５時間１００℃で撹拌した。反応液を濾過、濃縮後、得られた黄色固体をアセトンでリンスし、さらに、シリカゲルカラムクロマトグラフィーで目的物を分離した。溶媒を留去して乾燥し、黄色固体の化合物（ｃ−３）４．７０ｇを得た。さらに、１００ｍｌの３つ口フラスコに、この化合物２．０６ｇ（４．０ｍｍｏｌ）、１−ナフチル−ボロン酸０．８８ｇ（５．１ｍｍｏｌ）、トルエン４０ｍｌを入れて窒素ガス雰囲気下、テトラキス（トリフェニルホスフィン）パラジウム１７７ｍｇ、２M−炭酸ソーダ水溶液８ｍｌを加えて、５時間９５℃で撹拌した。反応液をクロロホルムで抽出し、シリカゲルカラムクロマトグラフィーで目的物を分離した。溶媒を留去して乾燥させて黄白色固体の化合物（８−１）１．８４ｇを得た（収率８２％）。さらに、高真空下で昇華精製を行なった。同定は^１H−ＮＭＲ、ＦＤ−ＭＡＳＳスペクトル：ｍ／ｚ ５６３（Ｍ^＋，１００）により行なった。 Example 3 Synthesis of (Compound 8-1)

To a 200 ml three-necked flask, 4.35 g (10.0 mmol) of compound (c-1), 2.78 g (25.0 mmol) of N-methylmaleimide and 100 ml of tetralin were added and stirred at 180 ° C. for 2 hours. After completion of the reaction, tetralin was heated and distilled off under reduced pressure, and the resulting solid was washed with a small amount of methanol and dried to obtain 4.50 g (8.7 mmol) of a yellow solid compound (c-2). Further, the total amount of this compound and 2.27 g (10.0 mmol) of DDQ were added to 100 ml of toluene, and the mixture was stirred at 100 ° C. for 5 hours. After filtering and concentrating the reaction solution, the resulting yellow solid was rinsed with acetone, and further the target product was separated by silica gel column chromatography. The solvent was distilled off and the residue was dried to obtain 4.70 g of a yellow solid compound (c-3). Further, in a 100 ml three-necked flask, 2.06 g (4.0 mmol) of this compound, 0.88 g (5.1 mmol) of 1-naphthyl-boronic acid and 40 ml of toluene were placed, and tetrakis (triphenyl) was added in a nitrogen gas atmosphere. Phosphine) palladium (177 mg) and 2M aqueous sodium carbonate solution (8 ml) were added, and the mixture was stirred at 95 ° C. for 5 hours. The reaction solution was extracted with chloroform, and the target product was separated by silica gel column chromatography. The solvent was distilled off and dried to obtain 1.84 g of a yellowish white solid compound (8-1) (yield 82%). Furthermore, sublimation purification was performed under high vacuum. Identification was performed by ¹ H-NMR, FD-MASS spectrum: m / z 563 (M ⁺ , 100).

２００ｍｌの３つ口フラスコに、化合物（ｄ−１）４．３５ｇ（１０．０ｍｍｏｌ）、Ｎ−メチルマレイミド２．７８ｇ（２５．０ｍｍｏｌ）、テトラリン１００ｍｌを加えて、１８０℃で２時間撹拌した。反応終了後、テトラリンを加熱減圧留去して得られた固体を少量のメタノールで洗浄、乾燥し、黄色固体の化合物（ｄ−２）５．２５ｇ（８．８ｍｍｏｌ）を得た。さらに、この化合物全量とＤＤＱ２．２７ｇ（１０．０ｍｍｏｌ）をトルエン１００ｍｌに加えて、５時間１００℃で撹拌した。反応液を濾過、濃縮後、得られた黄色固体をアセトンでリンスし、さらに、シリカゲルカラムクロマトグラフィーで目的物を分離した。溶媒を留去して乾燥し、黄色固体の化合物（ｄ−３）４．７０ｇを得た。次に、１００ｍｌの３つ口フラスコに、この化合物２．３８ｇ（４．０ｍｍｏｌ）を用いて実施例２と同様にして反応、精製を行ない、黄白色固体の化合物（９−１）２．０ｇを得た（収率７３％）。さらに、高真空下で昇華精製を行なった。同定は^１H−ＮＭＲ、ＦＤ−ＭＡＳＳスペクトル：ｍ／ｚ ６８９（Ｍ^＋，１００）により行なった。 Example 4 Synthesis of (Compound 9-1)

To a 200 ml three-necked flask, 4.35 g (10.0 mmol) of the compound (d-1), 2.78 g (25.0 mmol) of N-methylmaleimide and 100 ml of tetralin were added and stirred at 180 ° C. for 2 hours. After completion of the reaction, tetralin was heated and distilled off under reduced pressure, and the resulting solid was washed with a small amount of methanol and dried to obtain 5.25 g (8.8 mmol) of a yellow solid compound (d-2). Further, the total amount of this compound and 2.27 g (10.0 mmol) of DDQ were added to 100 ml of toluene, and the mixture was stirred at 100 ° C. for 5 hours. After filtering and concentrating the reaction solution, the resulting yellow solid was rinsed with acetone, and further the target product was separated by silica gel column chromatography. The solvent was distilled off and the residue was dried to obtain 4.70 g of a yellow solid compound (d-3). Next, reaction and purification were carried out in the same manner as in Example 2 using 2.38 g (4.0 mmol) of this compound in a 100 ml three-necked flask to obtain 2.0 g of compound (9-1) as a pale yellow solid. Was obtained (yield 73%). Furthermore, sublimation purification was performed under high vacuum. Identification was performed by ¹ H-NMR, FD-MASS spectrum: m / z 689 (M ⁺ , 100).

５００ｍｌの３つ口フラスコに、化合物（ｅ−１）４．１０ｇ（１０．４ｍｍｏｌ），Ｎ−メチルマレイミド２．３６ｇ（２１．２ｍｍｏｌ）、キシレン４００ｍｌ、塩化メチレン６００ｍｌを入れて、窒素ガス雰囲気下に４時間６０℃で加熱した。中間体（ｅ−２）は単離せずに、この反応液を−６０℃に冷却し、３臭化ほう素の１Ｍ−塩化メチレン溶液２４ｍｌを滴下して３０分後に６時間６０℃で加熱した。反応液を１Ｎ−ＮａＯＨ水溶液及び水で洗浄後、有機層を分離、濃縮し、シリカゲルカラムクロマトグラフィーで目的物を分離した。溶媒を留去して乾燥し、黄褐色固体の化合物（１２−１）４．１２ｇを得た（収率８４％）。さらに、高真空下で昇華精製を行なった。同定は^１H−ＮＭＲ、ＦＤ−ＭＡＳＳスペクトル：ｍ／ｚ ４８７（Ｍ^＋，１００）で行なった。なお、前記３臭化ほう素は（ｅ−２）に示す水素原子を引抜く脱水素剤として機能している。実施例７、１３、１６も同様である。（ｅ−２）は不安定なため単離せずに３臭化ほう素を加えている。 Example 5 Synthesis of (Compound 12-1)

In a 500 ml three-necked flask, 4.10 g (10.4 mmol) of compound (e-1), 2.36 g (21.2 mmol) of N-methylmaleimide, 400 ml of xylene, and 600 ml of methylene chloride were placed under a nitrogen gas atmosphere. For 4 hours at 60 ° C. Without isolating the intermediate (e-2), this reaction solution was cooled to −60 ° C., 24 ml of a 1M solution of boron tribromide in methylene chloride was added dropwise, and 30 minutes later, the mixture was heated at 60 ° C. for 6 hours. . The reaction solution was washed with 1N-NaOH aqueous solution and water, the organic layer was separated and concentrated, and the target product was separated by silica gel column chromatography. The solvent was distilled off and the residue was dried to obtain 4.12 g of a tan solid compound (12-1) (yield 84%). Furthermore, sublimation purification was performed under high vacuum. Identification was performed by ¹ H-NMR, FD-MASS spectrum: m / z 487 (M ⁺ , 100). The boron tribromide functions as a dehydrogenating agent for extracting a hydrogen atom shown in (e-2). The same applies to Examples 7, 13, and 16. Since (e-2) is unstable, boron tribromide is added without isolation.

３つ口フラスコに化合物（ｆ−１）４．００ｇ（９．８ｍｍｏｌ）、Ｎ−メチルマレイミド２．２２ｇ（２０．０ｍｍｏｌ）、キシレン１６０ｍｌを入れて１３０℃で１０時間攪拌した後、中間体（ｆ−２）を単離せずに１００℃でＤＤＱ２．５０ｇ（１１．０ｍｍｏｌ）を加えて５時間攪拌した。反応液を実施例１と同様に処理、精製し、橙色固体の化合物（１３−１）４．２２ｇを得た（収率８８％）。同定は^１Ｈ−ＮＭＲ、ＦＤ−ＭＡＳＳスペクトル：ｍ／ｚ ４８７（Ｍ^＋，１００）で行なった。さらに、高真空下で昇華精製を行なった。 Example 6 Synthesis of (Compound 13-1)

In a three-necked flask, 4.00 g (9.8 mmol) of compound (f-1), 2.22 g (20.0 mmol) of N-methylmaleimide and 160 ml of xylene were added and stirred at 130 ° C. for 10 hours. Without isolating f-2), DDQ 2.50 g (11.0 mmol) was added at 100 ° C. and stirred for 5 hours. The reaction solution was treated and purified in the same manner as in Example 1 to obtain 4.22 g of orange solid compound (13-1) (yield 88%). Identification was performed by ¹ H-NMR, FD-MASS spectrum: m / z 487 (M ⁺ , 100). Furthermore, sublimation purification was performed under high vacuum.

５００ｍｌの３つ口フラスコに、化合物（ｇ−１）４．７２ｇ（１０．０ｍｍｏｌ）、Ｎ−ｎ−プロピルマレイミド２．７８ｇ（２０ｍｍｏｌ）、キシレン４００ｍｌ、塩化メチレン６００ｍｌを入れて、窒素ガス雰囲気下に４時間６０℃で加熱した。中間体（ｇ−２）は単離せずに、この反応液を−６０℃に冷却し、３臭化ほう素の１Ｍ−塩化メチレン溶液２４ｍｌを滴下して３０分後に６時間６０℃で加熱した。反応液を１Ｎ−ＮａＯＨ水溶液及び水で洗浄後、有機層を分離、濃縮し、シリカゲルカラムクロマトグラフィーで目的物を分離した。溶媒を留去して乾燥し、赤橙色固体の化合物（１４−３）４．６２ｇを得た（収率７８％）。同定は^１Ｈ−ＮＭＲ、ＦＤ−ＭＡＳＳスペクトル：ｍ／ｚ ５９３（Ｍ^＋，１００）で行なった。さらに、高真空下で昇華精製を行なった。 Example 7 Synthesis of (Compound 14-3)

In a 500 ml three-necked flask, 4.72 g (10.0 mmol) of the compound (g-1), 2.78 g (20 mmol) of Nn-propylmaleimide, 400 ml of xylene, and 600 ml of methylene chloride were placed under a nitrogen gas atmosphere. For 4 hours at 60 ° C. Without isolating the intermediate (g-2), this reaction solution was cooled to −60 ° C., 24 ml of a 1M boron tribromide solution in methylene chloride was added dropwise, and 30 minutes later, the mixture was heated at 60 ° C. for 6 hours. . The reaction solution was washed with 1N-NaOH aqueous solution and water, the organic layer was separated and concentrated, and the target product was separated by silica gel column chromatography. The solvent was distilled off and the residue was dried to obtain 4.62 g of red-orange solid compound (14-3) (yield 78%). Identification was performed by ¹ H-NMR, FD-MASS spectrum: m / z 593 (M ⁺ , 100). Furthermore, sublimation purification was performed under high vacuum.

２００ｍｌの３つ口フラスコに、化合物（ｈ−１）４．３５ｇ（１０．０ｍｍｏｌ）、Ｎ−メチルマレイミド１．６６ｇ（２５．０ｍｍｏｌ）、テトラリン１００ｍｌを加えて、１８０℃で２時間撹拌した。反応終了後、テトラリンを加熱減圧留去して得られた固体を少量のメタノールで洗浄、乾燥し、黄色固体の化合物（ｈ−２）４．４５ｇ（８．６ｍｍｏｌ）を得た。さらに、この化合物全量とＤＤＱ２．２７ｇ（１０．０ｍｍｏｌ）をトルエン１００ｍｌに加えて、５時間１００℃で撹拌した。反応液を濾過、濃縮後、得られた黄色固体をアセトンでリンスし、さらに、シリカゲルカラムクロマトグラフィーで目的物を分離した。溶媒を留去して乾燥し、黄色固体の化合物（ｈ−３）３．９４ｇを得た。さらに、３００ｍｌの３つ口フラスコに、この化合物２．００ｇ（３．９ｍｍｏｌ）、４，４′−ジトリルアミン０．８８ｇ（４．３ｍｍｏｌ）、トルエン１２０ｍｌを入れ、窒素ガス雰囲気下、室温で酢酸パラジウム２０ｍｇ（０．０８８ｍｍｏｌ）、ソジウム−ｔ−ブトキサイド５．２ｇ（５．０ｍｍｏｌ）、トリ（ｔ−ブチル）ホスフィン１００ｍｇ（０．４９ｍｍｏｌ）を加えた後、１１０℃で４時間撹拌した。反応液を濾過した後、濃縮し、シリカゲルカラムクロマトグラフィーで目的物を分離した。溶媒を減圧留去し、乾燥させて赤紫色固体の化合物（１５−２）を２．０ｇ得た（収率８２％）。さらに、高真空下で昇華精製を行なった。同定は^１Ｈ−ＮＭＲ、ＦＤ−ＭＡＳＳスペクトル：ｍ／ｚ ６３２（Ｍ^＋，１００）により行なった。なお、（ｈ−３）から（１５−２）の化合物への反応は、Ｂｒ化合物とアミノ化合物との一般的な反応手段によるアミノ化反応である。この反応には、パラジウム系錯体、ソジウム−ｔ−ブトキシドなどのアルコキシド、トリ（ｔ−ブチル）ホスフィンなどのホスフィンよりなる触媒を用いる。 Example 8 Synthesis of (Compound 15-2)

To a 200 ml three-necked flask, 4.35 g (10.0 mmol) of compound (h-1), 1.66 g (25.0 mmol) of N-methylmaleimide and 100 ml of tetralin were added and stirred at 180 ° C. for 2 hours. After completion of the reaction, tetralin was heated and distilled off under reduced pressure, and the resulting solid was washed with a small amount of methanol and dried to obtain 4.45 g (8.6 mmol) of a yellow solid compound (h-2). Further, the total amount of this compound and 2.27 g (10.0 mmol) of DDQ were added to 100 ml of toluene, and the mixture was stirred at 100 ° C. for 5 hours. After filtering and concentrating the reaction solution, the resulting yellow solid was rinsed with acetone, and further the target product was separated by silica gel column chromatography. The solvent was distilled off and the residue was dried to obtain 3.94 g of a yellow solid compound (h-3). Further, 2.00 g (3.9 mmol) of this compound, 0.88 g (4.3 mmol) of 4,4′-ditolylamine and 120 ml of toluene were placed in a 300 ml three-necked flask, and palladium acetate was added at room temperature under a nitrogen gas atmosphere. After adding 20 mg (0.088 mmol), sodium-t-butoxide 5.2 g (5.0 mmol) and tri (t-butyl) phosphine 100 mg (0.49 mmol), the mixture was stirred at 110 ° C. for 4 hours. The reaction solution was filtered, concentrated, and the target product was separated by silica gel column chromatography. The solvent was distilled off under reduced pressure and dried to obtain 2.0 g of red purple solid compound (15-2) (yield 82%). Furthermore, sublimation purification was performed under high vacuum. Identification was performed by ¹ H-NMR, FD-MASS spectrum: m / z 632 (M ⁺ , 100). The reaction from (h-3) to the compound of (15-2) is an amination reaction by a general reaction means between a Br compound and an amino compound. In this reaction, a catalyst comprising a palladium complex, an alkoxide such as sodium-t-butoxide, or a phosphine such as tri (t-butyl) phosphine is used.

３００ｍｌの３つ口フラスコに、化合物（ｈ−３）２．０１ｇ（３．９ｍｍｏｌ）、４，４′−ジメトキシジフェニルアミン０．９６ｇ（４．２ｍｍｏｌ）、トルエン１２０ｍｌを入れ、窒素ガス雰囲気下、室温で酢酸パラジウム２０ｍｇ（０．０８８ｍｍｏｌ）、ソジウム−ｔ−ブトキサイド５．２ｇ（５．０ｍｍｏｌ）、トリ（ｔ−ブチル）ホスフィン１００ｍｇ（０．４９ｍｍｏｌ）を加えた後、１１０℃で４時間撹拌した。反応液を濾過した後、濃縮し、シリカゲルカラムクロマトグラフィーで目的物を分離した。溶媒を減圧留去し、乾燥させて紫色固体の化合物（１５−３）１．８９ｇを得た（収率７３％）。さらに、高真空下で昇華精製を行なった。同定は^１Ｈ−ＮＭＲ、ＭＡＳＳスペクトル：ｍ／ｚ ６６４（Ｍ^＋，１００））により行なった。 Example 9 Synthesis of (Compound 15-3)

A 300 ml three-necked flask was charged with 2.01 g (3.9 mmol) of compound (h-3), 0.96 g (4.2 mmol) of 4,4′-dimethoxydiphenylamine, and 120 ml of toluene. After adding 20 mg (0.088 mmol) of palladium acetate, 5.2 g (5.0 mmol) of sodium-t-butoxide and 100 mg (0.49 mmol) of tri (t-butyl) phosphine, the mixture was stirred at 110 ° C. for 4 hours. The reaction solution was filtered, concentrated, and the target product was separated by silica gel column chromatography. The solvent was distilled off under reduced pressure and dried to obtain 1.89 g of a purple solid compound (15-3) (yield 73%). Furthermore, sublimation purification was performed under high vacuum. Identification was performed by ¹ H-NMR, MASS spectrum: m / z 664 (M ⁺ , 100)).

３００ｍｌの３つ口フラスコに、化合物（ｈ−３）２．０１ｇ（３．９ｍｍｏｌ）、Ｎ，Ｎ−（１−ナフチル）−フェニルアミン０．９３ｇ（４．２ｍｍｏｌ）、トルエン１２０ｍｌを入れ、窒素ガス雰囲気下、室温で酢酸パラジウム２０ｍｇ（０．０８８ｍｍｏｌ）、ソジウム−ｔ−ブトキサイド５．２ｇ（５．０ｍｍｏｌ）、トリ（ｔ−ブチル）ホスフィン１００ｍｇ（０．４９ｍｍｏｌ）を加えた後、１１０℃で４時間撹拌した。反応液を濾過した後、濃縮し、シリカゲルカラムクロマトグラフィーで目的物を分離した。溶媒を減圧留去し、乾燥させて橙色固体の化合物（１５−７）１．７８ｇを得た（収率７０％）。さらに、高真空下で昇華精製を行なった。同定は^１Ｈ−ＮＭＲ、ＦＤ−ＭＡＳＳスペクトル：ｍ／ｚ ６５４（Ｍ^＋，１００）により行なった。 Example 10 Synthesis of (Compound 15-7)

A 300 ml three-necked flask was charged with 2.01 g (3.9 mmol) of compound (h-3), 0.93 g (4.2 mmol) of N, N- (1-naphthyl) -phenylamine and 120 ml of toluene, and nitrogen was added. Under a gas atmosphere, 20 mg (0.088 mmol) of palladium acetate, 5.2 g (5.0 mmol) of sodium-t-butoxide, and 100 mg (0.49 mmol) of tri (t-butyl) phosphine were added at 110 ° C. at room temperature. Stir for 4 hours. The reaction solution was filtered, concentrated, and the target product was separated by silica gel column chromatography. The solvent was distilled off under reduced pressure and dried to obtain 1.78 g of an orange solid compound (15-7) (yield 70%). Furthermore, sublimation purification was performed under high vacuum. Identification was performed by ¹ H-NMR, FD-MASS spectrum: m / z 654 (M ⁺ , 100).

２００ｍｌの３つ口フラスコに、化合物（ｉ−１）１０．７１ｇ（２０．８ｍｍｏｌ）、Ｎ−メチルマレイミド４．４４ｇ（４０．０ｍｍｏｌ）、テトラリン１５０ｍｌを加えて１８０℃で２時間撹拌した。反応終了後、テトラリンを加熱減圧留去して得られた固体を少量のメタノールで洗浄、乾燥し、黄色固体の化合物（ｉ−２）１０．５６ｇ（１７．６ｍｍｏｌ）を得た。さらに、この化合物１０．０ｇ（１６．７ｍｍｏｌ）、ＤＤＱ４．５４ｇ（２０．０ｍｍｏｌ）をトルエン２００ｍｌに加えて、５時間１００℃で撹拌した。反応液を濾過、濃縮後、得られた黄色固体をアセトンでリンスし、さらに、シリカゲルカラムクロマトグラフィーで目的物を分離した。溶媒を留去して乾燥し、黄色固体の化合物（ｉ−３）８．９０ｇを得た。次に、３００ｍｌの３つ口フラスコに、化合物（ｉ−３）３．５６ｇ（６．０ｍｍｏｌ）、Ｎ，Ｎ−（１−ナフチル）フェニルアミン２．８８ｇ（１３．２ｍｍｏｌ）、トルエン２００ｍｌを入れ、窒素雰囲気下にトリス（ジベンジリデンアセトン）ジパラジウム１４０ｍｇ（０．１５ｍｍｏｌ）、ソジウム−ｔ−ブトキサイド１．６８ｇ（１７．４ｍｍｏｌ）、トリ−ｔ−ブチル−ホスフィン１００ｍｇ（０．４９ｍｍｏｌ）を加えて、１１０℃で６時間攪拌した。反応液を濾過、濃縮し、シリカゲルカラムクロマトグラフィーで目的物を分離した。溶媒を留去して乾燥し、淡褐色固体の化合物（１５−１０）３．５２ｇを得た（収率６８％）。さらに、この化合物を高真空下に脱気した。同定は^１Ｈ−ＮＭＲ、ＦＤ−ＭＡＳＳスペクトル：ｍ／ｚ ８７２（Ｍ^＋，１００）により行なった。 Example 11 Synthesis of (Compound 15-10)

To a 200 ml three-necked flask, 10.71 g (20.8 mmol) of compound (i-1), 4.44 g (40.0 mmol) of N-methylmaleimide and 150 ml of tetralin were added and stirred at 180 ° C. for 2 hours. After completion of the reaction, tetralin was heated and distilled off under reduced pressure, and the resulting solid was washed with a small amount of methanol and dried to obtain 10.56 g (17.6 mmol) of yellow solid compound (i-2). Further, 10.0 g (16.7 mmol) of this compound and 4.54 g (20.0 mmol) of DDQ were added to 200 ml of toluene, followed by stirring at 100 ° C. for 5 hours. After filtering and concentrating the reaction solution, the resulting yellow solid was rinsed with acetone, and further the target product was separated by silica gel column chromatography. The solvent was distilled off and the residue was dried to obtain 8.90 g of yellow solid compound (i-3). Next, in a 300 ml three-necked flask, 3.56 g (6.0 mmol) of compound (i-3), 2.88 g (13.2 mmol) of N, N- (1-naphthyl) phenylamine and 200 ml of toluene were placed. Under a nitrogen atmosphere, tris (dibenzylideneacetone) dipalladium 140 mg (0.15 mmol), sodium-t-butoxide 1.68 g (17.4 mmol), and tri-t-butyl-phosphine 100 mg (0.49 mmol) were added. , And stirred at 110 ° C. for 6 hours. The reaction solution was filtered and concentrated, and the target product was separated by silica gel column chromatography. The solvent was distilled off and the residue was dried to obtain 3.52 g of light brown solid compound (15-10) (yield 68%). In addition, the compound was degassed under high vacuum. Identification was performed by ¹ H-NMR, FD-MASS spectrum: m / z 872 (M ⁺ , 100).

３００ｍｌの３つ口フラスコに、化合物（ｊ−１）５．９７ｇ（１０．０ｍｍｏｌ）、Ｎ−ｔ−ブチルマレイミド２．８６ｇ（２０．０ｍｍｏｌ）、キシレン２００ｍｌを入れ、１１０℃で１０時間攪拌した後、中間体（ｊ−２）を単離せずに、１００℃でＤＤＱ２．５０ｇ（１１．０ｍｍｏｌ）を加えて５時間攪拌した。反応液を濾過、濃縮後、得られた黄色固体をアセトンでリンスし、さらに、シリカゲルカラムクロマトグラフィーで目的物を分離した。溶媒を留去して乾燥し、黄色固体の化合物（ｊ−３）６．１０ｇを得た。次に、３つ口フラスコに、この化合物３．５８ｇ（５．０ｍｍｏｌ）、Ｎ，Ｎ−（２−ナフチル）アミン３．９３ｇ（１７．９ｍｍｏｌ）、トルエン２００ｍｌを入れ、窒素ガス雰囲気下にトリス（ジベンジリデンアセトン）ジパラジウム２１０ｍｇ（０．２３ｍｍｏｌ）、ソジウム−ｔ−ブトキサイド２．５２ｇ（２６．２ｍｍｏｌ）、トリ−ｔ−ブチル−ホスフィン１５０ｍｇ（０．７４ｍｍｏｌ）を加えて、１１０℃で６時間攪拌した。反応液を濾過、濃縮し、シリカゲルカラムクロマトグラフィーで目的物を分離した。溶媒を留去して乾燥し、赤橙色固体の化合物（１５−１１）３．９５ｇを得た（収率７０％）。さらに、この化合物を高真空下に加熱、脱気した。同定は^１Ｈ−ＮＭＲ、ＦＤ−ＭＡＳＳスペクトル：ｍ／ｚ １１３０（Ｍ^＋，１００）により行なった。 Example 12 Synthesis of (Compound 15-11)

A 300 ml three-necked flask was charged with 5.97 g (10.0 mmol) of compound (j-1), 2.86 g (20.0 mmol) of Nt-butylmaleimide and 200 ml of xylene, and stirred at 110 ° C. for 10 hours. After that, without isolating the intermediate (j-2), DDQ2.50 g (11.0 mmol) was added at 100 ° C. and stirred for 5 hours. After filtering and concentrating the reaction solution, the resulting yellow solid was rinsed with acetone, and further the target product was separated by silica gel column chromatography. The solvent was distilled off and the residue was dried to obtain 6.10 g of yellow solid compound (j-3). Next, 3.58 g (5.0 mmol) of this compound, 3.93 g (17.9 mmol) of N, N- (2-naphthyl) amine, and 200 ml of toluene are placed in a three-necked flask, and Tris is added under a nitrogen gas atmosphere. (Dibenzylideneacetone) dipalladium (210 mg, 0.23 mmol), sodium-tert-butoxide (2.52 g, 26.2 mmol), tri-tert-butyl-phosphine (150 mg, 0.74 mmol) was added, and the mixture was heated at 110 ° C. for 6 hours. Stir. The reaction solution was filtered and concentrated, and the target product was separated by silica gel column chromatography. The solvent was distilled off and the residue was dried to obtain 3.95 g of red-orange solid compound (15-11) (yield 70%). Furthermore, this compound was heated and degassed under high vacuum. Identification was performed by ¹ H-NMR, FD-MASS spectrum: m / z 1130 (M ⁺ , 100).

３つ口フラスコに、化合物（ｋ−１）２．８４ｇ（６．０ｍｍｏｌ）Ｎ−メチルマレイミド１．３５ｇ（１２ｍｍｏｌ）、塩化メチレン１８０ｍｌ、キシレン２００ｍｌを入れ、窒素雰囲気下に６０℃で１０時間攪拌した。中間体（ｋ−２）を単離せずに、反応液を−２０℃に冷却し、３臭化ほう素の１Ｍ−塩化メチレン溶液６ｍｌを加えた後、６０℃で５時間攪拌した。反応液を実施例５と同様にして精製し、黄色固体の化合物（ｋ−３）１．６０ｇを得た。次に、２００ｍｌの３つ口フラスコに、この化合物１．２９ｇ（２．３ｍｍｏｌ）、４，４′−ジトリルアミン０．５０ｇ（２．５ｍｍｏｌ）、トルエン１００ｍｌを入れ、窒素ガス雰囲気下にトリス（ジベンジリデンアセトン）ジパラジウム２７．７ｍｇ（０．０２９ｍｍｏｌ）、ソジウム−ｔ−ブトキサイド０．４９ｇ（５．１ｍｍｏｌ）、トリ−ｔ−ブチル−ホスフィン２７ｍｇ（０．１３ｍｍｏｌ）を加えて、１１０℃で６時間攪拌した。反応液を濾過、濃縮した後、シリカゲルカラムクロマトグラフィーで目的物を分離した。溶媒を減圧留去して乾燥し、橙色固体の化合物（１６−２）１．１０ｇを得た（収率７０％）。さらに、この化合物を高真空下に昇華精製した。同定は^１Ｈ−ＮＭＲ、ＦＤ−ＭＡＳＳスペクトル：ｍ／ｚ ６８２（Ｍ^＋，１００）により行なった。 Example 13 Synthesis of (Compound 16-2)

A compound (k-1) 2.84 g (6.0 mmol) N-methylmaleimide 1.35 g (12 mmol), methylene chloride 180 ml, and xylene 200 ml are placed in a three-necked flask, and the mixture is stirred at 60 ° C. for 10 hours in a nitrogen atmosphere. did. Without isolating the intermediate (k-2), the reaction solution was cooled to −20 ° C., 6 ml of a 1M boron tribromide methylene chloride solution was added, and the mixture was stirred at 60 ° C. for 5 hours. The reaction solution was purified in the same manner as in Example 5 to obtain 1.60 g of a yellow solid compound (k-3). Next, 1.29 g (2.3 mmol) of this compound, 0.50 g (2.5 mmol) of 4,4′-ditolylamine and 100 ml of toluene were placed in a 200 ml three-necked flask, and tris (di- Benzylideneacetone) dipalladium (27.7 mg, 0.029 mmol), sodium-tert-butoxide (0.49 g, 5.1 mmol), tri-tert-butyl-phosphine (27 mg, 0.13 mmol) was added, and the mixture was heated at 110 ° C. for 6 hours. Stir. The reaction solution was filtered and concentrated, and the target product was separated by silica gel column chromatography. The solvent was distilled off under reduced pressure and dried to obtain 1.10 g of an orange solid compound (16-2) (yield 70%). Further, this compound was purified by sublimation under high vacuum. Identification was performed by ¹ H-NMR, FD-MASS spectrum: m / z 682 (M ⁺ , 100).

２００ｍｌの３つ口フラスコに、化合物（ｋ−３）１．２９ｇ（２．３ｍｍｏｌ）、４，４′−ジメトキシジフェニルアミン０．５７ｇ（２．５ｍｍｏｌ）、トルエン１００ｍｌを入れ、窒素ガス雰囲気下にトリス（ジベンジリデンアセトン）ジパラジウム２７．７ｍｇ（０．０２９ｍｍｏｌ）、ソジウム−ｔ−ブトキサイド０．４９ｇ（５．１ｍｍｏｌ）、トリ−ｔ−ブチル−ホスフィン２７ｍｇ（０．１３ｍｍｏｌ）を加えて、１１０℃で６時間攪拌した。反応液を濾過、濃縮した後、シリカゲルカラムクロマトグラフィーで目的物を分離した。溶媒を減圧留去して乾燥し、紫色固体の化合物（１６−４）１．２６ｇを得た（収率７７％）。さらに、高真空下に昇華精製した。同定は^１Ｈ−ＮＭＲ、ＦＤ−ＭＡＳＳスペクトル：ｍ／ｚ ７１４（Ｍ^＋，１００）により行なった。 Example 14 Synthesis of (Compound 16-4)

A 200 ml three-necked flask is charged with 1.29 g (2.3 mmol) of the compound (k-3), 0.57 g (2.5 mmol) of 4,4′-dimethoxydiphenylamine and 100 ml of toluene, and tris under a nitrogen gas atmosphere. (Dibenzylideneacetone) dipalladium (27.7 mg, 0.029 mmol), sodium-t-butoxide (0.49 g, 5.1 mmol), tri-t-butyl-phosphine (27 mg, 0.13 mmol) was added at 110 ° C. Stir for 6 hours. The reaction solution was filtered and concentrated, and the target product was separated by silica gel column chromatography. The solvent was distilled off under reduced pressure and dried to obtain 1.26 g of a purple solid compound (16-4) (yield 77%). Furthermore, it was purified by sublimation under high vacuum. Identification was performed by ¹ H-NMR, FD-MASS spectrum: m / z 714 (M ⁺ , 100).

３００ｍｌの２口フラスコに、化合物（ｌ−１）５．９２ｇ（１２．２ｍｍｏｌ）、Ｎ−エチルマレイミド２．５０ｇ（２０ｍｍｏｌ）、テトラリン１５０ｍｌを入れて、２３時間１８０℃で加熱攪拌した。反応液を減圧加熱して溶媒を留去し、粗生成物の中間体（ｌ−２）６．００ｇを得た。この化合物全量に、塩化メチレン３００ｍｌ、ＤＤＱ３．３２ｇ（１４．６ｍｍｏｌ）を加えて、４０℃で２３時間攪拌した。反応液を濾過、濃縮後、得られた黄色固体をアセトンでリンスし、さらに、シリカゲルカラムクロマトグラフィーで目的物を分離した。溶媒を留去して乾燥し、橙色固体の化合物（ｌ−３）４．８０ｇを得た。次に、５００ｍｌの３つ口フラスコに、この化合物２．８３ｇ（５．０ｍｍｏｌ）、４，４′−ジトリルアミン１．０８ｇ（５．５ｍｍｏｌ）、トルエン２００ｍｌを入れ、窒素ガス雰囲気下にトリス（ジベンジリデンアセトン）ジパラジウム５９ｍｇ（０．０６４ｍｍｏｌ）、ソジウム−ｔ−ブトキサイド１．０８ｇ（１１．２ｍｍｏｌ）、トリ−ｔ−ブチル−ホスフィン６０ｍｇ（０．３０ｍｍｏｌ）を加えて、１１０℃で６時間攪拌した。反応液を濾過、濃縮した後、シリカゲルカラムクロマトグラフィーで目的物を分離した。溶媒を減圧留去して乾燥し、橙色固体の化合物（１７−２）２．１０ｇを得た（収率６１％）。さらに、この化合物を高真空下に昇華精製した。同定は^１Ｈ−ＮＭＲ、ＦＤ−ＭＡＳＳスペクトル：ｍ／ｚ ６９６（Ｍ^＋，１００）により行なった。 Example 15 Synthesis of (Compound 17-2)

In a 300 ml two-necked flask, 5.92 g (12.2 mmol) of compound (l-1), 2.50 g (20 mmol) of N-ethylmaleimide, and 150 ml of tetralin were added and stirred with heating at 180 ° C. for 23 hours. The reaction solution was heated under reduced pressure to distill off the solvent, thereby obtaining 6.00 g of a crude product intermediate (1-2). To this total amount of compound, 300 ml of methylene chloride and 3.32 g (14.6 mmol) of DDQ were added, and the mixture was stirred at 40 ° C. for 23 hours. After filtering and concentrating the reaction solution, the resulting yellow solid was rinsed with acetone, and further the target product was separated by silica gel column chromatography. The solvent was distilled off and the residue was dried to obtain 4.80 g of orange solid compound (l-3). Next, 2.83 g (5.0 mmol) of this compound, 1.08 g (5.5 mmol) of 4,4′-ditolylamine, and 200 ml of toluene were placed in a 500 ml three-necked flask, and tris (di- Benzylideneacetone) dipalladium 59 mg (0.064 mmol), sodium-t-butoxide 1.08 g (11.2 mmol), tri-t-butyl-phosphine 60 mg (0.30 mmol) were added, and the mixture was stirred at 110 ° C. for 6 hours. . The reaction solution was filtered and concentrated, and the target product was separated by silica gel column chromatography. The solvent was distilled off under reduced pressure and dried to obtain 2.10 g of orange solid compound (17-2) (yield 61%). Further, this compound was purified by sublimation under high vacuum. Identification was performed by ¹ H-NMR, FD-MASS spectrum: m / z 696 (M ⁺ , 100).

１０００ｍｌの３つ口フラスコに、化合物（ｍ−１）５．２３ｇ（１０．０ｍｍｏｌ）Ｎ−シクロヘキシルマレイミド３．５４ｇ（２０ｍｍｏｌ）、塩化メチレン３００ｍｌ、キシレン３００ｍｌを入れ、窒素ガス雰囲気下に６０℃で１０時間攪拌した。中間体（ｍ−２）は単離せずに、反応液を−２０℃に冷却し、３臭化ほう素の１Ｍ−塩化メチレン溶液１０ｍｌを加えた後、６０℃で５時間攪拌した。反応液を実施例５と同様にして精製し、橙色固体の化合物（ｍ−３）４．３４ｇを得た。次に、５００ｍｌの３つ口フラスコに、この化合物３．４２ｇ（５．０ｍｍｏｌ）、４，４′−ジトリルアミン１．２０ｇ（６．０ｍｍｏｌ）、トルエン２５０ｍｌを入れ、窒素ガス雰囲気下にトリス（ジベンジリデンアセトン）ジパラジウム６０ｍｇ（０．０６５ｍｍｏｌ）、ソジウム−ｔ−ブトキサイド１．０８ｇ（１１．２ｍｍｏｌ）、トリ−ｔ−ブチル−ホスフィン６０ｍｇ（０．３０ｍｍｏｌ）を加えて、１１０℃で６時間攪拌した。反応液を濾過、濃縮した後、シリカゲルカラムクロマトグラフィーで目的物を分離した。溶媒を減圧留去して乾燥し、紫色固体の化合物（１８−７）２．９６ｇを得た（収率７４％）。さらに、この化合物を高真空下に昇華精製した。同定は^１Ｈ−ＮＭＲ、ＦＤ−ＭＡＳＳスペクトル：ｍ／ｚ ８００（Ｍ^＋，１００）により行なった。 Example 16 Synthesis of (Compound 18-7)

In a 1000 ml three-necked flask, 5.23 g (10.0 mmol) of compound (m-1) 3.54 g (20 mmol) of N-cyclohexylmaleimide, 300 ml of methylene chloride, and 300 ml of xylene are placed, and the nitrogen gas atmosphere is used at 60 ° C. Stir for 10 hours. Without isolating the intermediate (m-2), the reaction solution was cooled to −20 ° C., 10 ml of 1M boron tribromide methylene chloride solution was added, and the mixture was stirred at 60 ° C. for 5 hours. The reaction solution was purified in the same manner as in Example 5 to obtain 4.34 g of an orange solid compound (m-3). Next, 3.42 g (5.0 mmol) of this compound, 1.20 g (6.0 mmol) of 4,4′-ditolylamine and 250 ml of toluene are placed in a 500 ml three-necked flask, and tris (di- Benzylideneacetone) dipalladium 60 mg (0.065 mmol), sodium-t-butoxide 1.08 g (11.2 mmol), tri-t-butyl-phosphine 60 mg (0.30 mmol) were added, and the mixture was stirred at 110 ° C. for 6 hours. . The reaction solution was filtered and concentrated, and the target product was separated by silica gel column chromatography. The solvent was distilled off under reduced pressure and dried to obtain 2.96 g of a purple solid compound (18-7) (yield 74%). Further, this compound was purified by sublimation under high vacuum. Identification was performed by ¹ H-NMR, FD-MASS spectrum: m / z 800 (M ⁺ , 100).

５００ｍｌの３つ口フラスコに、１，２，５，６−テトラケトピラセン２．３６ｇ（１０．０ｍｍｏｌ）、１，３−ジフェニル−２−プロパノン７．１５ｇ（３０．０ｍｍｏｌ）、メタノール３００ｍｌ、トリエチルアミン３０ｍｌを入れ、７０℃で１５時間攪拌した。
析出した黒色結晶を濾別してメタノールで洗浄し、化合物（ｎ−１）５．０ｇを得た。次に、３００ｍｌの３つ口フラスコに、化合物（ｎ−１）４．０１ｇ（５．０ｍｍｏｌ）、Ｎ−イソプロピルマレイミド２．８０ｇ（２０．０ｍｍｏｌ）、テトラリン１５０ｍｌを入れ、１７０℃で１０時間攪拌した。反応終了後、テトラリンを加熱減圧留去して得られた固体を少量のメタノールで洗浄、乾燥し、黄色固体の化合物（ｎ−２）３．２３ｇを得た。さらに、３００ｍｌの２口フラスコに化合物（ｎ−２）３．２０ｇ（４．０ｍｍｏｌ）、ＤＤＱ２．２７ｇ（１０．０ｍｍｏｌ）、ｏ−ジクロロベンゼン１５０ｍｌを入れ、１００℃で５時間攪拌した。反応液を濾過、濃縮後、得られた黄色固体をアセトンでリンスし、さらに、シリカゲルカラムクロマトグラフィーで目的物を分離した。溶媒を留去して乾燥し、黄色固体の化合物（ｎ−２）３．３４ｇを得、実施例１と同様にして反応、処理、精製を行ない、黄色固体の化合物（２７−２）２．８９ｇ（収率７２％）を得た。さらに、この化合物を高真空下に昇華精製した。同定は^１Ｈ−ＮＭＲ、ＦＤ−ＭＡＳＳスペクトル：ｍ／ｚ ８０２（Ｍ^＋，１００）により行なった。 Example 17 Synthesis of Compound (27-2)

In a 500 ml three-necked flask, 2.36 g (10.0 mmol) of 1,2,5,6-tetraketopyracene, 7.15 g (30.0 mmol) of 1,3-diphenyl-2-propanone, 300 ml of methanol, 30 ml of triethylamine was added and stirred at 70 ° C. for 15 hours.
The precipitated black crystals were separated by filtration and washed with methanol to obtain 5.0 g of compound (n-1). Next, 4.01 g (5.0 mmol) of compound (n-1), 2.80 g (20.0 mmol) of N-isopropylmaleimide and 150 ml of tetralin are placed in a 300 ml three-necked flask and stirred at 170 ° C. for 10 hours. did. After completion of the reaction, tetralin was heated and distilled off under reduced pressure, and the resulting solid was washed with a small amount of methanol and dried to obtain 3.23 g of yellow solid compound (n-2). Further, 3.20 g (4.0 mmol) of compound (n-2), 2.27 g (10.0 mmol) of DDQ and 150 ml of o-dichlorobenzene were placed in a 300 ml two-necked flask and stirred at 100 ° C. for 5 hours. After filtering and concentrating the reaction solution, the resulting yellow solid was rinsed with acetone, and further the target product was separated by silica gel column chromatography. The solvent was distilled off and drying was performed to obtain 3.34 g of yellow solid compound (n-2). Reaction, treatment and purification were carried out in the same manner as in Example 1 to obtain yellow solid compound (27-2) 2. 89 g (yield 72%) was obtained. Further, this compound was purified by sublimation under high vacuum. Identification was performed by ¹ H-NMR, FD-MASS spectrum: m / z 802 (M ⁺ , 100).

Application example 1
A 25 mm × 25 mm ITO glass substrate having an ITO transparent electrode with a thickness of 150 nm was subjected to ultrasonic cleaning using acetone, a cleaning agent (trade name: Semicoclean 56), and isopropanol. Furthermore, after boiling in isopropanol, UV / ozone cleaned was used as a transparent conductive support substrate. This glass substrate was placed in a vacuum deposition apparatus. First, the following DNTPD was deposited as a hole injection layer to a thickness of 60 nm, and then the following α-NPD was deposited as a hole transport layer to a thickness of 20 nm. did. Furthermore, the following α-NPD as a light emitting medium and the compound (6-2) as a light emitting material were simultaneously vapor-deposited at a weight ratio of 10: 1 to form a light emitting layer having a thickness of 20 nm. On top of this, tris (8-quinolinato) aluminum (Alq ₃ ) was deposited as an electron transport layer to a film thickness of 60 nm. Next, LiF was vapor-deposited to a thickness of 0.2 nm as an electron injection layer, and aluminum was vapor-deposited thereon to a thickness of 150 nm to produce an organic EL device. When a DC voltage of 6.0 V is applied to the device, the current density is 4.5 mA / cm ² , the light emission luminance (applied voltage 6.0 V) 110 cd / m ² , the light emission efficiency 2.4 cd / A [light emission efficiency = (light emission luminance Blue light emission was obtained.

Application examples 2-14
In Application Example 1, an organic EL device was produced in the same manner as in Application Example 1 except that the compound described in Table 1 was used instead of the compound (6-2) as the light emitting material. Table 1 shows the current density, light emission luminance, light emission efficiency, and light emission color at a DC applied voltage of 6.0 V of this device.

Application examples 15-27
In Application Example 1, an organic EL device was produced in the same manner as in Application Example 1 except that α-Phen was used instead of Alq ₃ as the electron transport layer and the compounds described in Table 2 were used as the light emitting material. . Table 2 shows the current density, light emission luminance, light emission efficiency, and light emission color at a DC applied voltage of 6.0 V of this device.

Application Example 28
In Application Example 1, Alq ₃ was used instead of α-NPD used as the light emitting medium of the light emitting layer. That is, as in Application Example 1, the α-NPD was deposited as a hole transport layer to a thickness of 20 nm on a DNTPD thin film having a thickness of 60 nm deposited as a hole injection layer. Further, Alq ₃ as a luminescent medium and compound (15-1) as a luminescent material were simultaneously vapor-deposited at a weight ratio of 50: 2 to form a 50 nm-thick luminescent layer. Further, an organic EL device was produced in the same manner as in Application Example 1 except that Alq ₃ was deposited as an electron transport layer on the film to a thickness of 60 nm. When a DC voltage of 6.0 V was applied to the device, yellow-orange light emission with a current density of 3.9 mA / cm ² , an emission luminance of 97 cd / m ² , and an emission efficiency of 2.4 cd / A was obtained.

Application Example 29
The following water-soluble PEDOT (which is a polymer, n is about 50 to 100) filtered through a microfilter having a pore size of 0.2 μm on a transparent conductive support substrate washed in the same manner as in Application Example 1. 1 ml of the solution was dropped and spin-coated (3,000 rpm, 180 seconds), and then dried by heating to form a hole injection and hole transport layer having a film thickness of 65 nm. After standing to cool, 0.1 ml of a 1,2-dichloroethane solution (0.011 g / ml) of compound (15-10) was added dropwise, spin-coated (3,500 rpm, 5 seconds), and dried by heating under reduced pressure. Thus, a light emitting layer having a thickness of 20 nm was obtained. Next, this substrate was set in a vacuum deposition apparatus, and the α-Phen was deposited to a thickness of 60 nm as an electron transport layer instead of Alq ₃ in Application Example 1. Next, LiF was vapor-deposited to a thickness of 0.2 nm as an electron injection layer, and then aluminum was vapor-deposited to a thickness of 150 nm to produce an organic EL device. When a DC voltage of 6.0 V was applied to the device, yellow light emission with a current density of 15.0 mA / cm ² , 309 cd / m ² and a light emission efficiency of 2.0 cd / A was obtained.

Application Example 30
An organic EL device was produced in the same manner as in Application Example 29, except that in Application Example 29, Compound (15-11) was used instead of Compound (15-10). When a DC voltage of 6.0 V was applied to the device, orange light emission with a current density of 8.9 mA / cm ² , 268 cd / m ² and a light emission efficiency of 3.0 cd / A was obtained.

Comparative Example 1
In Application Example 1, an organic EL device was produced in the same manner as Application Example 1 except that the following compound was used instead of the compound (6-2) as the light emitting material. This device emitted blue light with a DC applied voltage of 6.0 V, a current density of 1.2 mA / cm ² , a light emission luminance of 15 cd / m ² , and a light emission efficiency of 1.2 cd / A, but the light emission luminance was extremely low and slightly It's about to shine.

Comparative Example 2
In Application Example 9, an organic EL device was produced in the same manner as Application Example 1 except that the following compound was used instead of the compound (15-2) as the light emitting material. This device emitted yellowish green light with a DC applied voltage of 9.0 V, a current density of 2.2 mA / cm ² , an emission luminance of 25 cd / m ² , and an emission efficiency of 1.1 cd / A, but the emission luminance was extremely low.

Comparative Example 3
In Application Example 15, an organic EL device was produced in the same manner as Application Example 1 except that the following compound was used instead of the compound (6-2) as the light emitting material. This device produced blue light with a DC applied voltage of 7.0 V, a current density of 2.9 mA / cm ² , a light emission luminance of 19 cd / m ² , and a light emission efficiency of 0.6 cd / A, but the light emission luminance was extremely low.

It is the schematic which shows the basic composition of the organic EL element of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Cathode 2 Electron transport layer 3 Light emitting layer 4 Hole transport layer 5 Hole injection layer 6 Anode 7 Substrate

Claims (4)

The following general formula (A) or (B)

[In the formula, Ar ¹ may have a substituent,

Selected from the group represented by the following formula: Ar ² may have a substituent

In which R ⁰ is hydrogen, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 40 carbon atoms, and R ⁰ is a group selected from the group consisting of R ^{1 to} R ¹² are groups selected from the group consisting of substituted or unsubstituted arylalkyl groups having 7 to 40 carbon atoms, wherein R ^{1 to} R ¹² are hydrogen, substituted or unsubstituted alkyl groups having 1 to 30 carbon atoms, substituted or An unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 40 carbon atoms, a substituted or unsubstituted arylalkyl group having 7 to 40 carbon atoms, a substituted or unsubstituted carbon atom having 4 to 30 alkenyl groups, substituted or unsubstituted trialkylsilyl groups having 3 to 20 carbon atoms, substituted or unsubstituted aryloxy groups having 6 to 40 carbon atoms, cyano groups, nitro groups, halogen groups, and And the following general formula

Wherein Ar ³ and Ar ⁴ are each independently hydrogen, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted carbon number 6 A group selected from the group consisting of an aryl group of ˜40 and a substituted or unsubstituted arylalkyl group of 7 to 40 carbon atoms, and Ar ³ and Ar ⁴ are linked to each other to form a cyclic structure. R ^{1 to} R ¹² may form a ring structure with groups adjacent to each other. ]
An imide group-containing fluoranthene compound represented by the formula:   A light emitting material for an organic electroluminescence device comprising the imide group-containing fluoranthene compound according to claim 1.   In the organic electroluminescent device in which one or more organic thin film layers are sandwiched between a cathode and an anode, at least one of the organic thin film layers contains the imide group-containing fluoranthene compound according to claim 1. An organic electroluminescence device characterized. In the organic electroluminescence device in which at least an electron transport layer, a light emitting layer and a hole transport layer are sandwiched between a cathode and an anode, the light emitting layer contains one or more imide group-containing fluoranthene compounds according to claim 1. An organic electroluminescence device characterized by that.

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