JP4410291B2 - Material for organic electroluminescence device and organic electroluminescence device using the same - Google Patents

Description

  The present invention relates to a material for an organic electroluminescence device that is used as a light source for a flat light emitter of a wall-mounted television or a backlight of a display, has high luminous efficiency, high heat resistance, and a long lifetime, and an organic electroluminescence device using the same. Is.

An organic electroluminescence (EL) element using an organic substance is expected to be used as an inexpensive large-area full-color display element of a solid light emitting type and has been developed in many ways. In general, an EL element is composed of a light emitting layer and a pair of counter electrodes sandwiching the layer. In light emission, when an electric field is applied between both electrodes, electrons are injected from the cathode side and holes are injected from the anode side. Furthermore, this is a phenomenon in which electrons recombine with holes in the light emitting layer to generate an excited state, and energy is emitted as light when the excited state returns to the ground state.
Conventional organic EL elements have a higher driving voltage and lower light emission luminance and light emission efficiency than inorganic light-emitting diodes. Further, the characteristic deterioration has been remarkably not put into practical use. Although recent organic EL devices have been gradually improved, they still do not have sufficient luminous efficiency, heat resistance and lifetime. For example, Patent Document 1 discloses a phenylanthracene derivative that can be used in an EL element, but an organic EL element using this compound has a luminous efficiency of only about 2 to 4 cd / A, and higher efficiency is required. It was. Patent Document 2 discloses an EL element containing a fluorescent dopant made of an amine or a diamine derivative in a light emitting layer. However, although this EL device has a luminous efficiency of 4 to 6 cd / A, the lifetime is only 700 hours at an initial luminance of 300 cd / m ² , and a longer lifetime is required. Furthermore, Patent Document 3 discloses a material for an EL element having a phenylanthracene group. However, when used for a long time at a high temperature, the emission luminance is greatly reduced and the heat resistance is insufficient. These elements do not emit orange to red light, and red light emission is indispensable for full colorization of EL elements. Therefore, an element emitting orange to red light has been desired.
JP-A-8-12600 Japanese Patent Application Laid-Open No. 8-1991162 JP-A-9-268284

  The present invention has been made to solve the above-mentioned problems, and provides a material for an organic electroluminescence device that has not only high luminous efficiency, long life but also high heat resistance, and an organic electroluminescence device using the same. It is intended to do.

  As a result of intensive studies to develop an organic electroluminescence device material having the above-mentioned preferable properties and an organic electroluminescence device using the same, the present inventors have used a compound represented by the following general formula [1]. It has been found that the purpose can be achieved. The present invention has been completed based on such findings.

〔式中、Ａは置換もしくは未置換の炭素原子数２２〜６０のアリーレン基を表す。Ｘ¹〜Ｘ⁴は、それぞれ独立に、置換もしくは未置換の炭素原子数６〜３０のアリーレン基を表す。Ｙ¹〜Ｙ⁴は、それぞれ独立に、下記一般式〔２〕で示される有機基を表す。ａ〜ｄは０〜２の整数を表す。ただし、Ａの炭素原子数２６以下の場合にはａ＋ｂ＋ｃ＋ｄ＞０であり、Ａ中に２以上のアントラセン核は含まれない。
一般式〔２〕

（式中、Ｒ¹〜Ｒ⁴は、それぞれ独立に、水素原子、置換もしくは未置換の炭素原子数１〜２０のアルキル基、置換もしくは未置換の炭素原子数６〜２０のアリール基、シアノ基を表すか、Ｒ¹とＲ²またはＲ³とＲ⁴が結合した三重結合を表す。Ｚは置換もしくは未置換の炭素原子数６〜２０のアリール基を表す。ｎは０もしくは１を表す。）〕 That is, the organic electroluminescent element material (hereinafter referred to as organic EL element material) of the present invention is a compound represented by the following general formula [1].
General formula [1]

[Wherein, A represents a substituted or unsubstituted arylene group having 22 to 60 carbon atoms. X ^{1 to} X ⁴ each independently represents a substituted or unsubstituted arylene group having 6 to 30 carbon atoms. Y ^{1 to} Y ⁴ each independently represents an organic group represented by the following general formula [2]. a to d represent an integer of 0 to 2; However, when A has 26 or less carbon atoms, a + b + c + d> 0, and A does not contain two or more anthracene nuclei.
General formula [2]

Wherein R ^{1 to} R ⁴ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or a cyano group. Or a triple bond in which R ¹ and R ² or R ³ and R ⁴ are bonded together, Z represents a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, and n represents 0 or 1. )]

〔式中、Ｂは置換もしくは未置換の炭素原子数６〜６０のアリーレン基を表す。Ｘ¹〜Ｘ⁴は、それぞれ独立に、置換もしくは未置換の炭素原子数６〜３０のアリーレン基を表す。Ｙ¹〜Ｙ⁴は、それぞれ独立に、上記一般式〔２〕で示される有機基を表す。ａ〜ｄは０〜２の整数を表す。ただし、Ｂ、Ｘ¹、Ｘ²、Ｘ³及びＸ⁴の中の少なくとも１つはクリセン核を含有する。〕 The organic EL device material of the present invention may be a compound represented by the following general formula [3].
General formula [3]

[Wherein, B represents a substituted or unsubstituted arylene group having 6 to 60 carbon atoms. X ^{1 to} X ⁴ each independently represents a substituted or unsubstituted arylene group having 6 to 30 carbon atoms. Y ^{1 to} Y ⁴ each independently represents an organic group represented by the general formula [2]. a to d represent an integer of 0 to 2; However, at least one of B, X ¹ , X ² , X ³ and X ⁴ contains a chrysene nucleus. ]

〔式中、Ｘ¹〜Ｘ⁴、Ｙ¹〜Ｙ⁴及びａ〜ｄは、それぞれ独立に、上記一般式〔３〕と同一である。〕 The general formula [3] is preferably the following general formula [4], [5] or [6].
General formula [4]

[Wherein, X ^{1 to} X ⁴ , Y ^{1 to} Y ⁴ and a to d are independently the same as those in the general formula [3]. ]

〔式中、Ｂ、Ｘ¹〜Ｘ²、Ｙ¹〜Ｙ²及びａ〜ｂは、それぞれ独立に、上記一般式〔３〕と同一である。〕 General formula [5]

[Wherein, B, X ^{1 to} X ² , Y ^{1 to} Y ^2, and a to b are independently the same as the above general formula [3]. ]

〔式中、Ｂ、Ｘ¹〜Ｘ²、Ｙ¹〜Ｙ²及びａ〜ｂは、それぞれ独立に、上記一般式〔３〕と同一である。〕 General formula [6]

[Wherein, B, X ^{1 to} X ² , Y ^{1 to} Y ^2, and a to b are independently the same as the above general formula [3]. ]

〔式中、Ｄはテトラセン核もしくはペンタセン核を含有する２価の基を表す。Ｘ¹〜Ｘ⁴は、それぞれ独立に、置換もしくは未置換の炭素原子数６〜３０のアリーレン基を表し、Ｘ¹とＸ²、Ｘ⁴とＸ³は互いに連結していてもよい。Ｙ¹〜Ｙ⁴は、それぞれ独立に、上記一般式〔２〕で示される有機基を表す。ａ〜ｄは０〜２の整数を表す。〕 The organic EL device material of the present invention may be a compound represented by the following general formula [7].
General formula [7]

[Wherein, D represents a divalent group containing a tetracene nucleus or a pentacene nucleus. X ^{1 to} X ⁴ each independently represents a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, and X ¹ and X ² , X ⁴ and X ³ may be linked to each other. Y ^{1 to} Y ⁴ each independently represents an organic group represented by the general formula [2]. a to d represent an integer of 0 to 2; ]

一般式〔８〕
〔式中、Ｘ¹〜Ｘ⁴、Ｙ¹〜Ｙ⁴及びａ〜ｄは、それぞれ独立に、上記一般式〔７〕と同一である。Ｒ⁵¹〜Ｒ⁶⁰は、それぞれ独立に、水素原子、置換もしくは未置換の炭素原子数１〜２０のアルキル基、置換もしくは未置換の炭素原子数６〜２０のアリール基、シアノ基を表す。隣接するＲ⁵¹〜Ｒ⁶⁰は、互いに連結して飽和もしくは不飽和の炭素環を形成していても良い。〕 The general formula [7] is preferably the following general formula [8].

General formula [8]
[Wherein, X ^{1 to} X ⁴ , Y ^{1 to} Y ^4, and a to d are independently the same as those in the general formula [7]. R ^{51 to} R ⁶⁰ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or a cyano group. Adjacent R ^{51 to} R ⁶⁰ may be connected to each other to form a saturated or unsaturated carbocycle. ]

〔式中、Ｅはアリール基置換もしくは未置換のアントラセン核からなる２価の基を表す。Ｘ⁵〜Ｘ⁸は、それぞれ独立に、置換もしくは未置換の炭素原子数６〜２０のアリーレン基を表し、Ｘ⁵とＸ⁶、Ｘ⁷とＸ⁸は互いに連結していても良い。Ｙ¹〜Ｙ⁴は、それぞれ独立に、上記一般式〔２〕で示される有機基を表す。ａ〜ｄは０〜２の整数を表す。ただし、Ｅが未置換の

である時は、Ｘ⁵〜Ｘ⁸の少なくとも２つは置換もしくは未置換の

を含む。〕 The organic EL device material of the present invention may be a compound represented by the following general formula [9].
General formula [9]

[Wherein, E represents a divalent group consisting of an aryl group-substituted or unsubstituted anthracene nucleus. X ^{5 to} X ⁸ each independently represents a substituted or unsubstituted arylene group having 6 to 20 carbon atoms, and X ⁵ and X ⁶ , X ⁷ and X ⁸ may be linked to each other. Y ^{1 to} Y ⁴ each independently represents an organic group represented by the general formula [2]. a to d represent an integer of 0 to 2; However, E is not substituted

When at least two of X ^{5 to} X ⁸ are substituted or unsubstituted

including. ]

〔式中、Ａｒ¹とＡｒ³は、それぞれ独立に、置換もしくは未置換のフェニレン、置換もしくは未置換の１，３ナフタレン、置換もしくは未置換の１，８ナフタレン、置換もしくは未置換のフルオレン又は置換もしくは未置換のビフェニルからなる２価の基を表し、Ａｒ²は、置換もしくは未置換のアントラセン核、置換もしくは未置換のピレン核、置換もしくは未置換のフェナントレン核、置換もしくは未置換のクリセン核、置換もしくは未置換のペンタセン核、置換もしくは未置換のナフタセン核又は置換もしくは未置換のフルオレン核からなる２価の基を表す。Ｘ⁵〜Ｘ⁸は、それぞれ独立に、置換もしくは未置換の炭素原子数６〜２０のアリーレン基を表し、Ｘ⁵とＸ⁶、Ｘ⁷とＸ⁸は互いに連結していても良い。Ｙ¹〜Ｙ⁴は、それぞれ独立に、上記一般式〔２〕で示される有機基を表す。ａ〜ｄは０〜２の整数を表し、ａ＋ｂ＋ｃ＋ｄ≦２である。ｅは０もしくは１、ｆは１もしくは２を表す。ただし、Ａｒ²がアントラセン核の場合は、ａ＝ｂ＝ｃ＝ｄで、かつＡｒ¹とＡｒ³が共にｐ−フェニレン基の場合を除く。〕 The organic EL device material of the present invention may be a compound represented by the following general formula [10].
General formula [10]

[Wherein Ar ¹ and Ar ³ are each independently substituted or unsubstituted phenylene, substituted or unsubstituted 1,3 naphthalene, substituted or unsubstituted 1,8 naphthalene, substituted or unsubstituted fluorene or substituted Alternatively, it represents a divalent group consisting of unsubstituted biphenyl, and Ar ² represents a substituted or unsubstituted anthracene nucleus, a substituted or unsubstituted pyrene nucleus, a substituted or unsubstituted phenanthrene nucleus, a substituted or unsubstituted chrysene nucleus, It represents a divalent group consisting of a substituted or unsubstituted pentacene nucleus, a substituted or unsubstituted naphthacene nucleus or a substituted or unsubstituted fluorene nucleus. X ^{5 to} X ⁸ each independently represents a substituted or unsubstituted arylene group having 6 to 20 carbon atoms, and X ⁵ and X ⁶ , X ⁷ and X ⁸ may be linked to each other. Y ^{1 to} Y ⁴ each independently represents an organic group represented by the general formula [2]. a to d represent an integer of 0 to 2, and a + b + c + d ≦ 2. e represents 0 or 1, and f represents 1 or 2. However, when Ar ² is an anthracene nucleus, a = b = c = d, and Ar ¹ and Ar ³ are both p-phenylene groups. ]

The organic EL device material represented by the general formulas [1] and [3] to [10] can be used as a light emitting material for an organic electroluminescence device.
The organic electroluminescence device of the present invention (hereinafter referred to as organic EL device) is an organic electroluminescence device in which a light emitting layer or a plurality of organic compound thin films including a light emitting layer is formed between a pair of electrodes. It is a layer containing a material for an organic EL device represented by the formulas [1] and [3] to [10].
The organic EL element includes at least one kind of organic EL element material represented by the general formulas [1] and [3] to [10] selected from a hole injection material, a hole transport material, and a doping material. It is preferable that a layer contained as a material is formed between the electrodes.
The organic EL element preferably contains 0.1 to 20% by weight of the organic EL element material represented by the general formulas [1] and [3] to [10] in the light emitting layer.
The organic EL element is an organic EL element represented by the above general formulas [1] and [3] to [10] in at least one material selected from a hole injection material, a hole transport material, and a doping material. It is preferable to contain 0.1 to 20% by weight of the materials for use independently.
The light emitting layer is preferably a layer containing a stilbene derivative and an organic EL device material represented by the general formulas [1] and [3] to [10].
In the organic EL device, a layer containing an aromatic tertiary amine derivative and / or a phthalocyanine derivative may be formed between the light emitting layer and the anode.

The organic EL device material represented by the above general formulas [1], [3] to [6] and [9] to [10] of the present invention is used as a light emitting material, a hole injection material, a hole transport material or a doping material. The organic EL device used has practically sufficient emission brightness at a low applied voltage, has high luminous efficiency, has a long life that does not easily deteriorate even when used for a long time, has excellent heat resistance, and has a high temperature environment. Under performance does not deteriorate.
The organic EL device using the organic EL device material represented by the general formulas [7] and [8] as a light emitting material, a hole injecting material, a hole transporting material, or a doping material is yellow, orange to red. In a region, a practically sufficient light emission luminance can be obtained with a low applied voltage, the light emission efficiency is high, and the performance hardly deteriorates even when used for a long time, and the life is long.

A of the compound represented by the general formula [1] in the present invention represents a substituted or unsubstituted arylene group having 22 to 60 carbon atoms, and specific examples thereof include biphenyl, terphenyl, naphthalene, anthracene, phenanthrene, pyrene, and fluorene. , Divalent groups formed from thiophene, coronene, fluoranthene, or the like, or a plurality of these linked together. X ^{1 to} X ^{4 in the} compound represented by the general formula [1] each independently represents a substituted or unsubstituted arylene group having 6 to 30 carbon atoms. Specific examples include phenylene, biphenyl, terphenyl, and naphthalene. , Anthracene, phenanthrene, pyrene, fluorene, thiophene, coronene, and a monovalent or divalent group containing a chrysene skeleton. X ¹ and X ² , X ³ and X ⁴ may be connected to each other.
The groups substituted for X ^{1 to} X ⁴ are each independently an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms. As the group, an aryloxy group, an arylthio group, an arylalkyl group, an arylketone group and the like are excluded. This is because the compounds containing the substituents to be excluded are easily decomposed during vapor deposition, and the lifetime of the light-emitting element is also inferior.
In the general formula [1], a to d represent an integer of 0 to 2. However, when A has 26 or less carbon atoms, a + b + c + d> 0, and A does not contain two or more anthracene nuclei.

R ^{1 to} R ⁴ of the organic group represented by the general formula [2] in the present invention are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted carbon atom. The aryl group or cyano group of several 6-20 is represented. Specific examples of R ^{1 to} R ⁴ include a methyl group, an ethyl group, a propyl group, a butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, and a heptyl group as a substituted or unsubstituted alkyl group. Octyl group, stearyl group, 2-phenylisopropyl group, trichloromethyl group, trifluoromethyl group, benzyl group, α-phenoxybenzyl group, α, α-dimethylbenzyl group, α, α-methylphenylbenzyl group, α, There are α-ditrifluoromethylbenzyl group, triphenylmethyl group, α-benzyloxybenzyl group and the like. Examples of substituted or unsubstituted aryl groups include phenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 4-ethylphenyl, biphenyl, 4-methylbiphenyl, 4-ethylbiphenyl. Group, 4-cyclohexylbiphenyl group, terphenyl group, 3,5-dichlorophenyl group, naphthyl group, 5-methylnaphthyl group, anthryl group, pyrenyl group and the like.

Z in the organic group represented by the general formula [2] in the present invention represents a substituted or unsubstituted aryl group having 6 to 20 carbon atoms. Specific examples of Z are aryl groups such as a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a fluorenyl group, a pyrenyl group, and a thiophene group, and the aryl group has a substituent. May be. Specific examples of the substituent include an alkoxy group, an amino group, a cyano group, a hydroxyl group, a carboxylic acid group, an ether group, and an ester group in addition to the alkyl group and aryl group described in R ^{1 to} R ⁴ . In the general formula [2], n represents 0 or 1.
Thus, the compound represented by the general formula [1] in the present invention has a diamine structure at the center and a styrylamine structure at the end, so that the ionization energy becomes 5.6 eV or less and holes can be easily injected, The hole mobility is 10 ⁻⁴ m ² / V · s or more, which is excellent as a hole injection material and a hole transport material. Further, the electron affinity is 2.5 eV or more due to the polyphenyl structure at the center, and electrons are easily injected.
Furthermore, since the number of carbon atoms in the A structure is 22 or more, an amorphous thin film can be easily formed, and the glass transition temperature is 100 ° C. or more, which is excellent in heat resistance. If the A structure contains two or more anthracene nuclei, the compound [1] may be thermally decomposed.
A compound in which X ¹ and X ² , X ³ and X ⁴ are connected by a single bond or a carbocyclic bond has an improved glass transition temperature and excellent heat resistance.

B in the compounds represented by the general formulas [3] to [6] in the present invention represents a substituted or unsubstituted arylene group having 6 to 60 carbon atoms, and specific examples thereof include biphenyl, terphenyl, naphthalene, anthracene, and phenanthrene. , Pyrene, fluorene, thiophene, coronene, fluoranthene, and the like, or a divalent group formed by connecting a plurality of these together. X ^{1 to} X ⁴ , Y ^{1 to} Y ^4, and a to d are the same as those in the general formula [1]. However, any one of B, X ¹ , X ² , X ³ or X ⁴ contains a chrysene nucleus.

As described above, the compounds represented by the general formulas [3] to [6] in the present invention have a diamine structure at the center and a styrylamine structure at the terminal, so that the ionization energy is 5.6 eV or less and holes are not generated. It is easy to inject and has a hole mobility of 10 ⁻⁴ m ² / V · s or more, and is excellent as a hole injection material and a hole transport material. Further, durability and heat resistance are improved by the chrysene nucleus contained in any ^{one of} B, X ¹ , X ² , X ³ or X ⁴ . Thereby, the organic EL element which can be driven for a long time and can be stored or driven at a high temperature is obtained.
Furthermore, when the compounds of the general formulas [3] to [6] are used as the doping material, the lifetime of the organic EL element is extended, and when the compound is used as the material for the light emitting layer, the light emission efficiency is improved.

D of the compound represented by the general formula [7] in the present invention represents a divalent group containing a substituted or unsubstituted tetracene nucleus or pentacene nucleus, and specific examples include biphenyl, naphthalene, anthracene, phenanthrene, fluorene and thiophene. And a divalent group formed by linking at least one selected from among a plurality of tetracene nuclei or pentacene nuclei. X ^{1 to} X ⁴ , Y ^{1 to} Y ^4, and a to d are the same as those in the general formula [1]. However, X ¹ and X ² , X ⁴ and X ³ may be connected to each other.

In the present invention, X ^{1 to} X ⁴ , Y ^{1 to} Y ⁴ and a to d of the compound represented by the general formula [8] are each independently the same as the above general formula [1]. R ^{51 to} R ⁶⁰ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted carbon. An aryl group having 6 to 20 atoms and a cyano group are represented. Adjacent R ^{51 to} R ⁶⁰ may be linked to each other to form a saturated or unsaturated substituted or unsubstituted carbocycle.
As group used for the said substitution in general formula [7] or [8], it is each independently a C1-C20 alkyl group, a C1-C20 alkoxy group, and a C6-C20 aryl. A group, but an aryloxy group, an arylthio group, an arylalkyl group, an arylketone group and the like are excluded as a substituent. This is because the compounds containing these substituents are easily pyrolyzed during vapor deposition, and the lifetime of the light-emitting element is also inferior.

Thus, the compound represented by the general formula [7] in the present invention has a strong fluorescence in the orange to red region by having a tetracene or pentacene structure. Moreover, holes are easily injected by having a diamine structure, and when this compound is contained in the light emitting layer, holes are easily captured and electrons and holes are easily recombined. For this reason, a highly efficient yellow, orange, or red light emitting element is obtained.
In particular, when the compound represented by the general formula [7] is used as a doping material, the light emitting device has a long lifetime, and unprecedented stability can be obtained.

である時は、Ｘ⁵〜Ｘ⁸の少なくとも２つは置換もしくは未置換の

を含む。 E in the compound represented by the general formula [9] in the present invention represents a divalent group consisting of an aryl group-substituted or unsubstituted anthracene nucleus. X ^{5 to} X ⁸ each independently represents a substituted or unsubstituted arylene group having 6 to 20 carbon atoms, and specific examples include phenylene, biphenyl, terphenyl, naphthalene, anthracene, phenanthrene, fluorene, and thiophene skeleton. And monovalent or divalent groups. X ⁵ and X ⁶ , X ⁷ and X ⁸ may be connected to each other. Y ^{1 to} Y ⁴ and a to d are the same as those in the general formula [1].
However, E is not substituted

When at least two of X ^{5 to} X ⁸ are substituted or unsubstituted

including.

Thus, the compound represented by the general formula [9] in the present invention has a diamine structure, so that the ionization energy becomes 5.6 eV or less and holes are easily injected, and the hole mobility is 10 ⁻⁴ m ² /. V.s or more, which is excellent as a hole injection material and a hole transport material. Further, since it has a substituted or unsubstituted anthracene nucleus at the center, electrons are easily injected.
Further, when the central anthracene nucleus E is unsubstituted, the glass transition temperature is as low as 100 ° C. or lower, so that at least two aryl group substitutions, preferably 2 to 4 substitutions are performed as described above. The transition temperature is improved. Moreover, such a specific biphenyl structure increases the solubility of the compound represented by the general formula [9] and facilitates purification. When there is a phenyl group at a para position other than the above structure, purification is difficult and impurities increase, and the characteristics of the obtained organic EL device deteriorate. Moreover, such aryl group substitution suppresses the formation of association pairs between molecules, improves the fluorescence quantum efficiency, and improves the light emission efficiency of the organic EL element.

Ar ¹ and Ar ^{3 in the} compound represented by the general formula [10] in the present invention are each independently substituted or unsubstituted phenylene, substituted or unsubstituted 1,3 naphthalene, substituted or unsubstituted 1,8 naphthalene. Represents a divalent group consisting of substituted or unsubstituted fluorene or substituted or unsubstituted biphenyl, and Ar ² represents a substituted or unsubstituted anthracene nucleus, a substituted or unsubstituted pyrene nucleus, a substituted or unsubstituted phenanthrene nucleus Represents a divalent group consisting of a substituted or unsubstituted chrysene nucleus, a substituted or unsubstituted pentacene nucleus, a substituted or unsubstituted naphthacene nucleus or a substituted or unsubstituted fluorene nucleus. As a specific example,

が挙げられる。

Is mentioned.

X ^{5 to} X ⁸ and Y ^{1 to} Y ⁴ are each independently the same as in the general formula [9]. a to d represent an integer of 0 to 2, and a + b + c + d ≦ 2. e represents 0 or 1, and f represents 1 or 2. However, when Ar ² is an anthracene nucleus, a = b = c = d, and Ar ¹ and Ar ³ are both p-phenylene groups.

As described above, the compound represented by the general formula [10] in the present invention has a diamine structure, so that the ionization energy is 5.6 eV or less and holes are easily injected, and the hole mobility is 10 ⁻⁴ m ² /. V · s or more, which is excellent as a hole injection material, a hole transport material, particularly a light emitting material. Also, electrons are easily injected due to the polyphenyl structure containing a condensed ring at the center.
Further, by having both a polyphenyl structure and a diamine structure, an amorphous stable thin film can be formed, and the glass transition temperature is 100 ° C. or more, and the heat resistance is excellent. Furthermore, when two or more structures of the general formula [2] are included, a + b + c + d ≦ 2 needs to be satisfied because they are thermally decomposed by vapor deposition when forming a thin film. When Ar ² is an anthracene nucleus, Ar ¹ and Ar ³ have a specific structure as described above, so that thermal decomposition of the compound and oxidation during vapor deposition can be avoided.

   The following are representative examples (1) to (28) of the compound of the general formula [1] of the present invention, representative examples (29) to (56) of the compounds of the general formula [3] to [6], and the general formula [7]. ] Representative examples (57) to (74) of compounds of general formula (8), representative examples (75) to (86) of compounds of general formula [8], representative examples (87) to (104) of compounds of general formula [9], Representative examples (105) to (126) of the compound of the general formula [10] are illustrated, but the present invention is not limited to these representative examples.

The compounds represented by the general formulas [1] and [3] to [10] of the present invention have strong fluorescence in the solid state because the polyphenyl structure at the center A or B and the amine structure are linked. It is excellent in electroluminescence, and the fluorescence quantum efficiency is 0.3 or more. In addition, the compound represented by the general formulas [7] and [8] has a solid state or a dispersed state in a yellow, orange, or red fluorescent region by connecting a tetracene nucleus or pentacene nucleus containing structure and an amine structure. It has strong fluorescence and excellent electroluminescence.
The compounds represented by the general formulas [1] and [3] to [10] of the present invention are excellent in hole injecting and transporting properties from a metal electrode or an organic thin film layer, a metal electrode or an organic thin film layer. In combination with excellent electron injecting and electron transporting properties, it can be used effectively as a light-emitting material, and further using a hole transporting material, an electron transporting material or a doping material. No problem. In particular, when the compounds represented by the general formulas [7] and [8] are used as a doping material, they become recombination centers of electrons and holes, and thus red light emission with high efficiency can be obtained.
In particular, the compound represented by the general formula [8] has high performance because arylamine and tetracene are bonded at a specific bonding position.

  The organic EL device of the present invention is a device in which a single-layer or multilayer organic thin film is formed between an anode and a cathode. 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 may further contain a hole-injecting material or an electron-injecting material in order to transport holes injected from the anode or electrons injected from the cathode to the light-emitting material. However, since 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, the light emitting layer is formed only with the light emitting material of the present invention. It is also possible. Multi-layer type organic EL elements are (anode / hole injection layer / light emitting layer / cathode), (anode / light emitting layer / electron injection layer / cathode), (anode / hole injection layer / light emitting layer / electron injection layer / There is a laminated structure of a cathode). The compounds of the general formulas [1] and [3] to [8] have high emission characteristics and have excellent hole injection properties, hole transport properties, electron injection properties, and electron transport properties. It can be used for a light emitting layer as a material.

  If necessary, in addition to the compounds of the general formulas [1] and [3] to [10] of the present invention, further known light emitting materials, doping materials, hole injection materials and electron injection materials are used for the light emitting layer. You can also By making the organic EL element have a multi-layer structure, it is possible to prevent a decrease in luminance and lifetime due to quenching. If necessary, a light emitting material, a doping material, a hole injection material, and an electron injection material can be used in combination. Further, by using a doping material, it is possible to improve light emission luminance and light emission efficiency and to obtain red and blue light emission. Further, the hole injection layer, the light emitting layer, and the electron injection layer may each be formed with a layer configuration of two or more layers. In that case, in the case of a hole injection layer, the layer that injects holes from the electrode is a hole injection layer, and the layer that receives holes from the hole injection layer and transports holes to the light emitting layer is a hole transport layer. Call. Similarly, in the case of an electron injection layer, a layer that injects electrons from an electrode is referred to as an electron injection layer, and a layer that receives electrons from the electron injection layer and transports electrons to a light emitting layer is referred to as 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, and adhesion to the organic layer or metal electrode.

Examples of the light emitting material or doping material that can be used in the light emitting layer together with the compounds of the general formulas [1] and [3] to [10] include anthracene, naphthalene, phenanthrene, pyrene, tetracene, coronene, chrysene, fluorescein, perylene, phthaloperylene, and naphthaloperylene. , Perinone, phthaloperinone, naphthaloperinone, diphenylbutadiene, tetraphenylbutadiene, coumarin, oxadiazole, aldazine, bisbenzoxazoline, bisstyryl, pyrazine, cyclopentadiene, quinoline metal complex, aminoquinoline metal complex, benzoquinoline metal complex, imine, Diphenylethylene, vinylanthracene, diaminocarbazole, pyran, thiopyran, polymethine, merocyanine, imidazole chelating oxinoid compounds, Nakuridon, rubrene, but stilbene derivatives and fluorescent dyes, and the like, but is not limited thereto.
In particular, luminescent materials or doping materials that can be used in the light emitting layer together with the compounds [7] and [8] are quinoline metal complexes and stilbene derivatives.

  As a hole injection material, it has the ability to transport holes, has a hole injection effect from the anode, an excellent hole injection effect for the light emitting layer or the light emitting material, and excitons generated in the light emitting layer. A compound that prevents movement 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, oxazole, oxadiazole, hydrazone, acyl hydrazone, polyaryl Examples include alkane, stilbene, butadiene, benzidine type triphenylamine, styrylamine type triphenylamine, diamine type triphenylamine, and their derivatives, and polymer materials such as polyvinylcarbazole, polysilane, and conductive polymers. However, it is not limited to these.

Among the hole injection materials that can be used in the organic EL device of the present invention, a more effective hole injection material is an aromatic tertiary amine derivative or a phthalocyanine derivative.
Specific examples of the aromatic tertiary amine derivative are triphenylamine, tolylamine, tolyldiphenylamine, 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-methylphenyl) ) -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 oligomers having an aromatic tertiary amine skeleton Properly is a polymer, but is not limited thereto.
Specific examples of phthalocyanine (Pc) derivatives are H ₂ Pc, CuPc, CoPc, NiPc, ZnPc, PdPc, FePc, MnPc, ClAlPc, ClGaPc, ClInPc, ClSnPc, Cl2SiPc, (HO) AlPc, (HO) GaPc, VOPc , Phthalocyanine derivatives such as TiOPc, MoOPc, GaPc-O-GaPc, and naphthalocyanine derivatives, but are not limited thereto.

  As an electron injection material, it has the ability to transport electrons, has an electron injection effect from the cathode, an excellent electron injection effect for the light emitting layer or light emitting material, and a hole injection layer of excitons generated in the light emitting layer The compound which prevents the movement to and is excellent in thin film forming ability is preferable. Specifically, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, fluorenylidenemethane, anthraquinodimethane, anthrone and their derivatives However, it is not limited to these. Further, the electron injecting property can be improved by adding an electron accepting material to the hole injecting material and an electron donating material to the electron injecting material.

In the organic EL device of the present invention, a more effective electron injection material is a metal complex compound or a nitrogen-containing five-membered ring derivative.
Specific examples of the metal complex compound include 8-hydroxyquinolinate lithium, bis (8-hydroxyquinolinato) zinc, bis (8-hydroxyquinolinato) copper, bis (8-hydroxyquinolinato) manganese, tris ( 8-hydroxyquinolinato) aluminum, tris (2-methyl-8-hydroxyquinolinato) aluminum, tris (8-hydroxyquinolinato) gallium, bis (10-hydroxybenzo [h] quinolinato) beryllium, bis ( 10-hydroxybenzo [h] quinolinato) zinc, bis (2-methyl-8-quinolinato) chlorogallium, bis (2-methyl-8-quinolinato) (o-cresolate) gallium, bis (2-methyl-8-quinolinato) ) (1-Naphtholate) aluminum, bis (2-methyl-8-) Norinato) (2-naphtholato) gallium and the like, but not limited thereto.

  The nitrogen-containing five-membered derivative is preferably an oxazole, thiazole, oxadiazole, thiadiazole or triazole derivative. Specifically, 2,5-bis (1-phenyl) -1,3,4-oxazole, dimethyl POPOP, 2,5-bis (1-phenyl) -1,3,4-thiazole, 2,5- Bis (1-phenyl) -1,3,4-oxadiazole, 2- (4′-tert-butylphenyl) -5- (4 ″ -biphenyl) 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-phenyloxa) Diazolyl) -4-tert-butylbenzene], 2- (4′-tert-butylphenyl) -5- (4 ″ -biphenyl) -1,3,4-thiadiazole, 2,5-bis (1-naphthyl) ) -1,3,4-thiadiazole, 1,4-bis [2- (5-phenylthiadiazolyl)] benzene, 2- (4′-tert-butylphenyl) -5- (4 ″ -biphenyl) -1,3,4-triazole, 2,5-bis (1-naphthyl) Examples include, but are not limited to, -1,3,4-triazole, 1,4-bis [2- (5-phenyltriazolyl)] benzene and the like.

  In the organic EL device of the present invention, in the light emitting layer, in addition to the compounds of the general formulas [1] and [3] to [8], at least one of a light emitting material, a doping material, a hole injecting material, and an electron injecting material. The seed may be contained in the same layer. In order to improve the stability of the organic EL device obtained by the present invention with respect to temperature, humidity, atmosphere, etc., a protective layer is provided on the surface of the device, or the entire device is protected by silicon oil, resin, etc. Is also possible.

  As a conductive material used for an anode of an organic EL 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, etc. Further, metal oxides such as tin oxide and indium oxide used for alloys thereof, ITO substrates and NESA substrates, and organic conductive resins such as polythiophene and polypyrrole are used. As the conductive material used for the cathode, those having a work function smaller than 4 eV are suitable, and magnesium, calcium, tin, lead, titanium, yttrium, lithium, ruthenium, manganese, aluminum, and alloys thereof are used. However, 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 is controlled by the temperature of the vapor deposition source, the atmosphere, the degree of vacuum, etc., and is selected to an appropriate ratio. If necessary, the anode and the cathode may be formed of two or more layers.

  In an organic EL element, in order to emit light efficiently, it is desirable that at least one surface is sufficiently transparent in the light emission wavelength region of the element. The substrate is also preferably transparent. The transparent electrode is set using the above-described conductive material so as to ensure a predetermined translucency 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 includes a glass substrate and a transparent resin film. Transparent resin films include polyethylene, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, polypropylene, polystyrene, polymethyl methacrylate, polyvinyl chloride, polyvinyl alcohol, polyvinyl butyral, nylon, polyether ether ketone. , Polysulfone, polyethersulfone, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, polyvinyl fluoride, tetrafluoroethylene-ethylene copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, polychlorotrifluoroethylene, Polyvinylidene fluoride, polyester, polycarbonate, polyurethane, polyimide, polyetherimide, polyimide, polypropylene, etc. It is.

  For the formation of each layer of the organic EL device according to the present invention, any of dry film forming methods such as vacuum deposition, sputtering, plasma, ion plating, etc. and wet film forming methods such as spin coating, dipping, and flow coating is applied. be able to. The film thickness is not particularly limited, but must be set to an appropriate film thickness. If the film thickness is too thick, a large applied voltage is required to obtain a constant light output, resulting in poor efficiency. If the film thickness is too thin, pinholes and the like are generated, and sufficient light emission luminance cannot be obtained even when an electric field is applied. The normal film thickness is suitably in the range of 5 nm to 10 μm, but more preferably in the range of 10 nm to 0.2 μm.

  In the case of the wet film-forming method, the material for forming each layer is dissolved or dispersed in an appropriate solvent such as ethanol, chloroform, tetrahydrofuran, dioxane or the like to form a thin film, and any solvent may be used. In any organic thin film layer, an appropriate resin or additive may be used for improving film formability and preventing pinholes in the film. Usable resins include insulating resins such as polystyrene, polycarbonate, polyarylate, polyester, polyamide, polyurethane, polysulfone, polymethyl methacrylate, polymethyl acrylate, and cellulose, and copolymers thereof, poly-N-vinyl. Examples thereof include photoconductive resins such as carbazole and polysilane, and conductive resins such as polythiophene and polypyrrole. Examples of the additive include an antioxidant, an ultraviolet absorber, and a plasticizer.

  As described above, by using the compound of the present invention in the light emitting layer of the organic EL element, a practically sufficient light emission luminance can be obtained with a low applied voltage, so that the light emission efficiency is high and the life is long because it is difficult to deteriorate. Can obtain an organic EL device having excellent heat resistance.

The organic EL device of the present invention can be used for a flat light emitter such as a flat panel display of a wall-mounted television, a light source such as a copying machine, a printer, a backlight of a liquid crystal display or instruments, a display board, a marker lamp, and the like.
The material of the present invention can be used not only in an organic EL device but also in fields such as an electrophotographic photosensitive member, a photoelectric conversion device, a solar cell, and an image sensor.

Hereinafter, the present invention will be described in more detail based on examples.
Reference example 1
On the washed glass plate with ITO electrode, the above compound (2), 2,5-bis (1-naphthyl) -1,3,4-oxadiazole, polycarbonate resin (Teijin Chemicals: Panlite K-) 1300) was dissolved in tetrahydrofuran at a weight ratio of 5: 3: 2, and a light emitting layer having a thickness of 100 nm was obtained by a spin coating method. On top of that, an electrode having a thickness of 150 nm was formed from an alloy in which aluminum and lithium were mixed at a ratio of 3% by weight of lithium to obtain an organic EL device. As for the light emission characteristics of this device, light emission with an emission luminance of 200 (cd / m ² ), a maximum luminance of 14000 (cd / m ² ), and an emission efficiency of 2.1 (lm / W) was obtained at an applied voltage of DC voltage 5V. .

Reference example 2
On the washed glass plate with an ITO electrode, the above compound (9) was vacuum deposited as a light emitting material to form a light emitting layer having a film thickness of 100 nm, and aluminum and lithium were mixed at a ratio of 3% by weight of lithium thereon. An electrode having a film thickness of 100 nm was formed from an alloy to obtain an organic EL device. The light emitting layer was deposited in a vacuum of 10 ⁻⁶ Torr and the substrate temperature was room temperature. With respect to the light emission characteristics of this device, light emission with an emission luminance of 110 (cd / m ² ), a maximum luminance of 20000 (cd / m ² ), and an emission efficiency of 2.1 (lm / W) was obtained at an applied voltage of DC voltage 5V. .

を真空蒸着して膜厚１０ｎｍの電子注入層を作成し、その上に、アルミニウムとリチウムをリチウム３重量％の割合で混合した合金で膜厚１００ｎｍの電極を形成して有機ＥＬ素子を得た。発光層および電子注入層は１０^-6Ｔｏｒｒの真空中で、基板温度室温の条件下で蒸着した。この素子の発光特性は、直流電圧５Ｖの印加電圧で発光輝度約６００（ｃｄ／ｍ²)、最高輝度３００００（ｃｄ／ｍ²)、発光効率３．０（ｌｍ／Ｗ）の青緑色発光が得られた。さらに初期発光輝度６００（ｃｄ／ｍ²)で、定電流駆動したところ半減寿命は２０００時間と長かった。 Reference example 3
On the washed glass plate with an ITO electrode, the compound (2) as a light emitting material was vacuum-deposited to form a light emitting layer having a thickness of 50 nm. Next, the following compound (Alq)

Was deposited by vacuum evaporation to form an electron injection layer having a thickness of 10 nm, and an electrode having a thickness of 100 nm was formed thereon using an alloy in which aluminum and lithium were mixed at a ratio of 3% by weight of lithium to obtain an organic EL device. . The light emitting layer and the electron injection layer were deposited in a vacuum of 10 ⁻⁶ Torr at a substrate temperature of room temperature. The light emission characteristics of this element are blue-green light emission with a light emission luminance of about 600 (cd / m ² ), a maximum luminance of 30000 (cd / m ² ), and a light emission efficiency of 3.0 (lm / W) at an applied voltage of DC voltage 5V. Obtained. Furthermore, when the device was driven at a constant current at an initial light emission luminance of 600 (cd / m ² ), the half life was as long as 2000 hours.

Reference Examples 4-16
On the washed glass plate with an ITO electrode, the light emitting material shown in Table 1 was vacuum deposited to obtain a light emitting layer having a thickness of 80 nm. Further, the compound (Alq) is vacuum-deposited as an electron injecting material to form an electron injecting layer having a thickness of 20 nm, and an alloy in which aluminum and lithium are mixed at a ratio of 3% by weight of aluminum is formed thereon with a thickness of 150 nm. An electrode having a film thickness was formed to obtain an organic EL element. Each layer was deposited in a vacuum of 10 ⁻⁶ Torr at a substrate temperature of room temperature. The light emission characteristics of this device are shown in Table 1. The organic EL elements of this reference example all had high luminance characteristics with a maximum luminance of 10,000 (cd / m ² ) or more.

次に、正孔輸送材として下記化合物（ＮＰＤ）を膜厚２０ｎｍに真空蒸着した。

次に、発光材料として４，４’−ビス（２，２−ジフェニルビニル）ビフェニル（ＤＰＶＢｉ）および上記化合物（３）を、化合物（３）の割合が５重量％、膜厚４０ｎｍとなるように同時蒸着した。尚、化合物（３）は蛍光性のドーパントとして機能する。次に、電荷注入材として上記化合物（Ａｌｑ）を膜厚２０ｎｍで蒸着し、さらにＬｉＦを膜厚０．５ｎｍで蒸着後アルミニウムを膜厚１００ｎｍ蒸着し電極を形成して有機ＥＬ素子を得た。各層は１０^-6Ｔｏｒｒの真空中で、基板温度室温の条件下で蒸着した。この素子の発光特性は、直流電圧５Ｖの印加電圧で発光輝度７５０（ｃｄ／ｍ²)と高輝度であった。さらに初期発光輝度４００（ｃｄ／ｍ²)で、定電流駆動したところ半減寿命は３０００時間と長寿命であった。 Reference Example 17
On the washed glass plate with an ITO electrode, the following compound (TPD74) as a hole injecting material was vacuum deposited to a film thickness of 60 nm.

Next, the following compound (NPD) was vacuum deposited as a hole transporting material to a film thickness of 20 nm.

Next, 4,4′-bis (2,2-diphenylvinyl) biphenyl (DPVBi) and the above compound (3) are used as the light emitting material so that the ratio of the compound (3) is 5% by weight and the film thickness is 40 nm. Co-deposited. The compound (3) functions as a fluorescent dopant. Next, the compound (Alq) was deposited as a charge injection material in a thickness of 20 nm, LiF was deposited in a thickness of 0.5 nm, and then aluminum was deposited in a thickness of 100 nm to form an electrode to obtain an organic EL device. Each layer was deposited in a vacuum of 10 ⁻⁶ Torr at a substrate temperature of room temperature. The light emission characteristic of this device was as high as 750 (cd / m ² ) in luminance with an applied voltage of 5 V DC. Further, when the device was driven at a constant current at an initial light emission luminance of 400 (cd / m ² ), the half life was as long as 3000 hours.

得られた素子の発光特性は、直流電圧５Ｖの印加電圧で発光輝度６０（ｃｄ／ｍ²)、発光効率０．３４（ｌｍ／Ｗ）と充分な性能が得られなかった。 Comparative Example 1
An organic EL device was produced in the same manner as in Reference Example 1 except that the following compound (Comparative Example 1) was used as the light emitting material.

With respect to the light emission characteristics of the obtained device, sufficient performance was not obtained with a light emission luminance of 60 (cd / m ² ) and a light emission efficiency of 0.34 (lm / W) at an applied voltage of DC voltage of 5V.

得られた素子の発光特性は、直流電圧５Ｖの印加電圧で発光輝度２００（ｃｄ／ｍ²)、発光効率１．２（ｌｍ／Ｗ）であったが、初期発光輝度４００（ｃｄ／ｍ²)で定電流駆動したところ半減寿命は６００時間と寿命が短かった。 Comparative Example 2
An organic EL device was produced in the same manner as in Reference Example 3 except that the following compound (Comparative Example 2) was used as the light emitting material.

The light emitting characteristics of the obtained device were an emission luminance of 200 (cd / m ² ) and an emission efficiency of 1.2 (lm / W) at an applied voltage of DC voltage of 5 V, but an initial emission luminance of 400 (cd / m ^2). ) Was driven at a constant current, the half-life was 600 hours, which was short.

Heat resistance test
The organic EL devices produced in Reference Example 2, Reference Example 3 , Comparative Example 1 and Comparative Example 2 were measured for emission luminance and then placed in a thermostatic chamber at 100 ° C., and light was emitted again after a lapse of 500 hours at a constant current value. Luminance retention was calculated by measuring the luminance and comparing it with the emission luminance before being placed in the tank.
As a result, the luminance retentions of the organic EL elements of Reference Example 2, Reference Example 3 , Comparative Example 1, and Comparative Example 2 were 85%, 90%, 25%, and 30%, respectively. Thus, since the compound of the luminescent material used in Comparative Example 1 and Comparative Example 2 had a glass transition temperature of 100 ° C. or lower, the luminance could not be maintained. On the other hand, the compounds of the light emitting materials used in Reference Example 2 and Reference Example 3 have high heat resistance because they have a glass transition temperature of 110 ° C. or higher, and can maintain sufficient luminance for a long time.

Synthesis Example 1 (Compound (2))
Synthesis of Intermediate A A 200 ml round bottom flask was charged with 0.38 g (2.04 mmol) of 4-bromobenzaldehyde, 0.98 g (4.29 mmol) of benzylphosphonic acid ethyl ester and 40 ml of DMSO, and 0.5 g of tBuOK (4. 49 mmol) was added little by little at room temperature to react. The reaction solution obtained by reacting for 18 hours was poured into 500 ml of water, and 0.5 g of precipitated crude crystals were collected by filtration.
The crude crystal, KI 2.00 g (12.0 mmol), CuI 1.14 g (6.0 mmol), and HMPA 10 ml were placed in a 100 ml round bottom flask, and the mixture was heated and stirred at 150 ° C. for 6 hours. After completion of the reaction, 10 ml of 1N hydrochloric acid water was added, and the organic layer was extracted with toluene. After concentration, the residue was purified by recrystallization from diethyl ether / methanol to obtain 0.28 g (45% yield) of the following intermediate A.

Synthesis of Intermediate B In a 50 ml round bottom flask, 3 g (17.4 mmol) of p-bromoaniline was suspended in 10 ml of 6N hydrochloric acid and cooled. Sodium sulfite (1.25 g, 18.1 mmol) / water (5.3 ml) was slowly added dropwise at an internal temperature of 4 ° C., and stirred at the same temperature for 1 hour to obtain a diazonium aqueous solution.
Separately, 0.3 g (1.7 mmol) of anthracene was dissolved in 5 ml of acetone in a 100 ml round bottom flask, and then 0.46 g of cupric chloride dihydrate / 5.7 ml of water was added up to 4 ° C. Cooled down. After cooling, the diazonium aqueous solution was added at the same temperature and allowed to react overnight at room temperature. After the reaction, the precipitated crystals were collected by filtration, washed with methanol and dried to obtain 0.2 g of the following intermediate B (yield 24%).

Synthesis of Compound (2) 0.018 g (0.2 mmol) of aniline was dissolved in 5 ml of methylene chloride in a 100 ml round bottom flask, 0.05 g (0.5 mmol) of acetic anhydride was added, and the reaction was performed at room temperature for 1 hour. I let you. Thereafter, the reaction solvent was distilled off to obtain an oily compound. To this compound, 0.56 g (1.8 mmol) of intermediate A, 5 g of potassium carbonate, 0.3 g of copper powder and 20 ml of nitrobenzene were added, and the mixture was heated and stirred at 210 ° C. for 2 days. Thereafter, 10 ml of diethylene glycol and 3 g of potassium hydroxide / 10 ml of water were added to the residue obtained by distilling off the solvent, and the mixture was reacted at 110 ° C. overnight. After completion of the reaction, ethyl acetate / water was added for liquid separation, and the solvent was distilled off to obtain crude crystals.
Subsequently, the above crude crystal, 0.05 g (0.1 mmol) of the intermediate B, 5 g of potassium carbonate, 0.3 g of copper powder and 20 ml of nitrobenzene were added in a 100 ml round bottom flask, and the mixture was heated and stirred at 220 ° C. for 2 days. After the reaction, the precipitated crystals were collected by filtration, washed with methanol, dried, and purified by column chromatography (silica gel, hexane / toluene = 1/1) to obtain 0.017 g of a yellow powder. This powder was identified as compound (2) by measurement of NMR, IR and FD-MS (field desorption mass spectrum) (yield 20%).

Synthesis Example 2 (Compound (9))
Synthesis of Intermediate C 51.2 g (0.3 mol) of diphenylamine, 71.4 g (0.3 mol) of 1,4-dibromobenzene, 34.6 g (0.36 mol) of tBuOK, PdCl ₂ (PPh) in a 200 ml round bottom flask. ₃ ) 4.2 g (5.9 mmol) of ₂ and 1.2 liters of xylene were mixed and stirred at 130 ° C. overnight.
After completion of the reaction, the organic layer was concentrated to obtain about 100 g of brown crystals. The crystals were purified by column chromatography (silica gel, hexane / toluene = 10/1) to obtain 28 g of the following intermediate C (yield 29%).

Synthesis of Compound (9) In a 100 ml round bottom flask, 10 ml of diethyl ether was added to 0.48 g (1 mmol) of Intermediate B and cooled to -78 ° C. Thereto was added 2 ml (1.5 M, 3 mmol) of n-butyllithium, followed by stirring for 1 hour. Next, 0.3 g (3 mmol) of trimethyl borate / 5 ml of diethyl ether was added dropwise. After completion of the dropwise addition, the mixture was stirred at -78 ° C for 1 hour, and 10 ml of 1N hydrochloric acid water was added at room temperature. After separating the organic layer, the solvent was distilled off to obtain crude crystals. In a 100 ml round bottom flask, add the above crude crystals, intermediate C 0.97 g (3 mmol), Pd (PPh ₃ ) ₄ 12 mg, potassium phosphate 0.32 g (1.5 mmol) and DMF 10 ml, at 100 ° C. Stir for 4 hours. After separating the organic layer, the solvent was distilled off to obtain crude crystals. The crude crystals were purified by column chromatography (silica gel, benzene / ethyl acetate = 50/1) to obtain 0.13 g of a yellow powder. This powder was identified as Compound (9) by NMR, IR and FD-MS measurements (yield 14%).

Synthesis Example 3 (Compound (18))
Synthesis of Intermediate D Grignard reagent was prepared by adding Mg and diethyl ether to 0.48 g (2.0 mmol) of 1,4-dibromobenzene. Separately, 5.7 g (20.0 mmol) of 1,4-dibromonaphthalene, 10 mg of NiCl 2 (dppp) and 20 ml of diethyl ether were added to a 100 ml round bottom flask and cooled with ice greed. The said Grignard reagent was added there, and it heated and refluxed for 6 hours. After completion of the reaction, 10 ml of 1N hydrochloric acid water was added. After separating the organic layer, the solvent was distilled off to obtain the following intermediate D0.30 (yield 30%).

Synthesis of Compound (18) 0.09 g (1.0 mmol) of aniline was dissolved in 5 ml of methylene chloride in a 100 ml round bottom flask, and 0.25 g (2.5 mmol) of acetic anhydride was added and reacted at room temperature for 1 hour. I let you. Thereafter, the reaction solvent was distilled off to obtain an oily compound. To this compound, 0.4 g (4.5 mmol) of Intermediate A, 5 g of potassium carbonate, 0.3 g of copper powder, and 20 ml of nitrobenzene were added and heated and stirred at 210 ° C. for 2 days. Thereafter, 10 ml of diethylene glycol and 3 g of potassium hydroxide / 10 ml of water were added to the residue obtained by distilling off the solvent, and the mixture was reacted at 110 ° C. overnight. After completion of the reaction, ethyl acetate / water was added for liquid separation, and the solvent was distilled off to obtain crude crystals.
Subsequently, in the 100 ml round bottom flask, the above crude crystals, intermediate D 0.5 g (1.0 mmol), potassium carbonate 5 g, copper powder 0.3 g and nitrobenzene 20 ml were added, and the mixture was heated and stirred at 220 ° C. for 2 days. After the reaction, the precipitated crystals were collected by filtration, washed with methanol, dried, and purified by column chromatography (silica gel, hexane / toluene = 1/1) to obtain 0.1 g of a yellow powder. This powder was identified as the compound (18) by NMR, IR and FD-MS measurements (yield 10%).

Reference Example 18
On the washed glass plate with the ITO electrode, the above compound (30), 2,5-bis (1-naphthyl) -1,3,4-oxadiazole, polycarbonate resin (Teijin Chemicals: Panlite K-) as the luminescent material. 1300) was dissolved in tetrahydrofuran at a weight ratio of 5: 3: 2, and a light emitting layer having a thickness of 100 nm was obtained by a spin coating method. On top of that, an electrode having a thickness of 150 nm was formed from an alloy in which aluminum and lithium were mixed at a ratio of 3% by weight of lithium to obtain an organic EL device. As for the light emission characteristics of this device, light emission with an emission luminance of 320 (cd / m ² ), a maximum luminance of 14000 (cd / m ² ), and an emission efficiency of 2.5 (lm / W) was obtained at an applied voltage of DC voltage 5V. .

Reference Example 19
The compound (37) is vacuum-deposited as a luminescent material on a cleaned glass plate with an ITO electrode to form a luminescent layer with a film thickness of 100 nm, and an inorganic electron injection with a film thickness of 0.3 nm is formed thereon with lithium fluoride. A layer was formed, and an electrode having a film thickness of 100 nm was further formed from aluminum to obtain an organic EL element. The light emitting layer was deposited in a vacuum of 10 ⁻⁶ Torr and the substrate temperature was room temperature. With respect to the light emission characteristics of this device, light emission with an emission luminance of 110 (cd / m ² ), a maximum luminance of 20000 (cd / m ² ), and an emission efficiency of 1.2 (lm / W) was obtained at an applied voltage of DC voltage 5V. .

Reference Example 20
On the cleaned glass plate with an ITO electrode, CuPc was vacuum deposited as a hole injecting material to form a 40 nm thick hole injecting layer. Next, as a hole transporting material, the compound (47) is vapor-deposited with a 20 nm-thick hole transport layer and the compound (Alq) is vacuum-deposited to form a 60-nm-thick light-emitting layer. An electrode having a thickness of 100 nm was formed from an alloy in which aluminum and lithium were mixed at a ratio of 3% by weight of lithium to obtain an organic EL device. Each layer was deposited in a vacuum of 10 ⁻⁶ Torr at a substrate temperature of room temperature. The light emission characteristics of this element are green light emission with an emission voltage of about 700 (cd / m ² ), a maximum luminance of 80000 (cd / m ² ), and a light emission efficiency of 6.0 (lm / W) at an applied voltage of DC 5V. It was. Further, when the device was driven at a constant current at an initial light emission luminance of 600 (cd / m ² ), the half life was as long as 4000 hours.

Examples 1-3 and Reference Examples 21-30
On the washed glass plate with an ITO electrode, the hole transport material shown in Table 2 was vacuum-deposited to obtain a 20 nm-thick hole transport layer. Further, the above compound (Alq) is vacuum-deposited as a light emitting material to prepare a light emitting layer having a film thickness of 60 nm, and rubrene is added to the light emitting layer so as to have a concentration of 4% by weight. An electrode having a thickness of 150 nm was formed from an alloy mixed at a ratio of 3% by weight to obtain an organic EL element. Each layer was deposited in a vacuum of 10 ⁻⁶ Torr at a substrate temperature of room temperature. The light emission characteristics of this device are shown in Table 2. In addition, all the organic EL elements of this example had high luminance characteristics with a maximum luminance of 10,000 (cd / m ² ) or more.

Example 4
On the cleaned glass plate with an ITO electrode, the above compound (TPD74) was vacuum deposited as a hole injecting material to a film thickness of 60 nm. Next, the compound (NPD) was vacuum-deposited to a thickness of 20 nm as a hole transport material.
Next, 4,4′-bis (2,2-diphenylvinyl) phenylanthracene (DPVDPAN) as a light emitting material and the compound (36) as a dopant, the ratio of the compound (36) is 2% by weight, and the film thickness is 40 nm. Co-deposited so that Next, the compound (Alq) was deposited as a charge injection material in a thickness of 20 nm, LiF was deposited in a thickness of 0.5 nm, and then aluminum was deposited in a thickness of 100 nm to form an electrode to obtain an organic EL device. Each layer was deposited in a vacuum of 10 ⁻⁶ Torr at a substrate temperature of room temperature. The light emission characteristics of this device were blue light emission with an emission luminance of 500 (cd / m ² ) and a high luminance with an applied voltage of DC voltage of 8 V and excellent color purity. Further, when the device was driven at a constant current at an initial light emission luminance of 100 (cd / m ² ), the half-life was 7000 hours, which was a long life.
The emission spectrum of this device was measured and found to be the same as DPVBi. That is, the compound (36) does not affect the light emission, but has an effect of giving the device a long life.

Comparative Example 3
An organic EL device was produced in the same manner as in Example 4 except that the compound (36) was not added as a dopant. When this element was driven at a constant current at an initial light emission luminance of 100 (cd / m ² ), the half-life was 4000 hours, which was shorter than that of Example 4 .

Comparative Example 4
An organic EL device was produced in the same manner as in Reference Example 20 , except that the above compound (Comparative Example 2) was used as the hole transport material.
The light emission characteristics of the obtained device were a light emission luminance of 300 (cd / m ² ) and a light emission efficiency of 4.2 (lm / W) at an applied voltage of DC voltage 5 V, but an initial light emission luminance of 400 (cd / m ^2). ) Was driven at a constant current, the half-life was 300 hours, which was short.

Heat resistance test
The organic EL elements prepared in Reference Example 20, Reference Example 24 and Comparative Example 4 were measured for emission luminance and then placed in a thermostatic chamber at 105 ° C., and the emission luminance was measured again after 500 hours at a constant current value. The luminance retention was calculated by comparison with the emission luminance before entering the tank.
As a result, the luminance retentions of the organic EL elements of Reference Example 20, Reference Example 24 , and Comparative Example 4 were 87%, 90%, and 25%, respectively. Thus, since the compound of the luminescent material used in Comparative Example 4 has a glass transition temperature of 105 ° C. or lower, the luminance could not be maintained. On the other hand, the compounds of the light emitting materials used in Reference Example 20 and Reference Example 24 have high heat resistance because the glass transition temperature is 110 ° C. or higher, and can maintain sufficient luminance for a long time.

Synthesis Example 4 (Compound (30))
Synthesis of Intermediate E (6,12-diiodochrysene) In a 300 ml round bottom flask, 5 g (22 mmol) of chrysene and 100 ml of carbon tetrachloride were placed, and 16 g of iodine / carbon tetrachloride (64 mmol / 100 ml) was added at room temperature. The reaction was carried out dropwise. After the reaction solution was heated and stirred for 5 hours, the precipitated crystals were collected by filtration and washed with 100 ml of carbon tetrachloride. The obtained crude crystals were recrystallized with 200 ml of toluene to obtain an intermediate E (yield 35%).

Synthesis of Compound (30) In a 100 ml two-necked flask, 2 g (10 mmol) of 4-aminostilbene was dissolved in 20 ml of methylene chloride, 2.5 g (25 mmol) of acetic anhydride was added and reacted at room temperature for 1 hour. . Thereafter, the reaction solvent was distilled off to obtain an oily compound. In a 300 ml two-necked flask, 4.1 g (20 mmol) of iodobenzene, 3 g (30 mmol) of potassium carbonate, 0.06 g (1 mmol) of copper powder and 100 ml of nitrobenzene were added to this compound, and the mixture was heated and stirred at 220 ° C. for 2 days. did. Thereafter, 10 ml of diethylene glycol and 30 g of potassium hydroxide / 100 ml of water were added to the residue obtained by distilling off the solvent, and the mixture was reacted at 110 ° C. overnight. After completion of the reaction, ethyl acetate / water was added for liquid separation, and the solvent was distilled off to obtain crude crystals.
In a 300 ml two-necked flask, 2.4 g (5 mmol) of the obtained crude crystal, intermediate E 3 g (20 mmol), potassium carbonate 3 g (20 mmol), copper powder 0.06 g (1 mmol) and nitrobenzene 100 ml were added, and 230 ° C. for 2 days. Stir with heating. After the reaction, the precipitated crystals were collected by filtration, washed with methanol, dried, and purified by column chromatography (silica gel, hexane / toluene = 1/1) to obtain 1.0 g of a yellow powder. This powder was identified as Compound (30) by NMR, IR, and FD-MS measurements (yield 25%).

Synthesis Example 5 (Compound (36))
Synthesis of Compound (36) In a 100 ml round bottom flask was added 3.4 g (20 mmol) of diphenylamine, 4.8 g (10 mmol) of intermediate E, 3 g (30 mmol) of potassium carbonate, 0.06 g (1 mmol) of copper powder and 100 ml of nitrobenzene. In addition, the mixture was stirred at 210 ° C. for 2 days. After the reaction, the precipitated crystals were collected by filtration, washed with methanol, dried, and purified by column chromatography (silica gel, hexane / toluene = 1/1) to obtain 2.8 g of a yellow powder. This powder was identified as Compound (36) by NMR, IR, and FD-MS measurements (yield 50%).

Synthesis Example 6 (Compound (38))
Synthesis of Compound (38) 1.0 g (41 mmol) of magnesium, 1 ml of THF, and a small piece of iodine were placed in a 100 ml four-necked flask under an argon stream, and 9.7 g (30 mmol) of 4-bromotriphenylamine / 100 ml of THF was added at room temperature. After the dropwise addition, the mixture was heated and stirred at 60 ° C. for 1 hour to prepare a Grignard reagent.
In a 300 ml four-necked flask under an argon stream, Intermediate E 4.8 g (10 mmol), THF 50 ml, PdCl ₂ (PPh ₃ ) ₂ 0.28 g (0.4 mmol) and AlH (iso-Bu) ₂ /1.0 M toluene 1.0 ml (1 mmol) of the solution was added, and the above Grignard reagent was added dropwise at room temperature, followed by heating to reflux overnight. After completion of the reaction, the reaction solution was cooled with ice water, and the precipitated crystals were collected by filtration and washed with acetone. The obtained crude crystals were recrystallized with 100 ml of acetone to obtain 4.3 g of yellow powder. This powder was identified as Compound (38) by NMR, IR and FD-MS measurements (yield 60%).

Synthesis Example 7 (Compound (47))
Synthesis of Compound (47) In a 100 ml two-necked flask, 2.4 g (10 mmol) of 6-aminochrysene was dissolved in 20 ml of methylene chloride, 2.5 g (25 mmol) of acetic anhydride was added, and the reaction was performed at room temperature for 1 hour. I let you. Thereafter, the reaction solvent was distilled off to obtain an oily compound. In a 300 ml two-necked flask, 4.1 g (20 mmol) of iodobenzene, 3 g (30 mmol) of potassium carbonate, 0.06 g (1 mmol) of copper powder and 100 ml of nitrobenzene were added to this compound, and the mixture was heated and stirred at 220 ° C. for 2 days. did. Thereafter, 10 ml of diethylene glycol and 30 ml of potassium hydroxide / 100 ml of water were added to the residue obtained by distilling off the solvent, and the mixture was reacted at 110 ° C. overnight. After completion of the reaction, ethyl acetate / water was added for liquid separation, and the solvent was distilled off to obtain crude crystals.
In a 300 ml two-necked flask, the obtained crude crystals, 2,4′-diiodobiphenyl 2 g (5 mmol), potassium carbonate 3 g (30 mmol), copper powder 0.06 g (1 mmol) and nitrobenzene 100 ml were added. The mixture was stirred at 2 ° C. for 2 days. After the reaction, the precipitated crystals were collected by filtration, washed with methanol, dried, and purified by column chromatography (silica gel, hexane / toluene = 1/3) to obtain 0.8 g of a yellow powder. This powder was identified as Compound (47) by NMR, IR and FD-MS measurements (yield 30%).

Reference Example 31
On the washed glass plate with an ITO electrode, the above compound (58), 2,5-bis (1-naphthyl) -1,3,4-oxadiazole, polycarbonate resin (Teijin Chemicals: Panlite K-) 1300) was dissolved in tetrahydrofuran at a weight ratio of 5: 2: 2, and a light emitting layer having a thickness of 100 nm was obtained by a spin coating method. On top of that, an electrode having a thickness of 150 nm was formed from an alloy in which aluminum and lithium were mixed at a ratio of 3% by weight of lithium to obtain an organic EL device. The light emission characteristics of this element are yellow-orange light emission with a light emission luminance of 130 (cd / m ² ), a maximum luminance of 14000 (cd / m ² ), and a light emission efficiency of 1.2 (lm / W) at a DC voltage of 5V. It was.

Reference Example 32
On the washed glass plate with an ITO electrode, the compound (71) as a luminescent material was vacuum-deposited to form a luminescent layer having a thickness of 100 nm, and aluminum and lithium were mixed at a ratio of 3% by weight of lithium thereon. An electrode having a film thickness of 100 nm was formed from an alloy to obtain an organic EL device. The light emitting layer was deposited in a vacuum of 10 ⁻⁶ Torr and the substrate temperature was room temperature. The light emission characteristic of this element is that an orange light emission having an emission luminance of 120 (cd / m ² ), a maximum luminance of 1800 (cd / m ² ), and an emission efficiency of 0.3 (lm / W) can be obtained at an applied voltage of DC voltage of 5V. It was.

Reference Example 33
On the washed glass plate with an ITO electrode, the compound (71) as a luminescent material was vacuum-deposited to form a luminescent layer having a thickness of 50 nm. Next, the compound (Alq) is vacuum-deposited to form an electron injection layer having a thickness of 10 nm, and an electrode having a thickness of 100 nm is formed thereon using an alloy in which aluminum and lithium are mixed at a ratio of 3% by weight of lithium. Thus, an organic EL element was obtained. The light emitting layer and the electron injection layer were deposited in a vacuum of 10 ⁻⁶ Torr at a substrate temperature of room temperature. The light emission characteristics of this element are orange light emission with an emission voltage of about 200 (cd / m ² ), a maximum luminance of 12000 (cd / m ² ), and a light emission efficiency of 1.0 (lm / W) at a DC voltage of 5V. It was.

Reference Examples 34-42
On the washed glass plate with an ITO electrode, the light emitting material shown in Table 3 was vacuum-deposited to obtain a light emitting layer having a thickness of 80 nm. Further, the compound (Alq) is vacuum-deposited as an electron injecting material to form an electron injecting layer having a thickness of 20 nm, and an alloy in which aluminum and lithium are mixed at a ratio of 3% by weight of aluminum is formed thereon with a thickness of 150 nm. An electrode having a film thickness was formed to obtain an organic EL element. Each layer was deposited in a vacuum of 10 ⁻⁶ Torr at a substrate temperature of room temperature. The light emission characteristics of this device are shown in Table 3. The organic EL elements of this reference example all had high luminance characteristics with a maximum luminance of 5000 (cd / m ² ) or more.

Reference Example 43
On the cleaned glass plate with an ITO electrode, the above compound (TPD74) was vacuum deposited as a hole injecting material to a film thickness of 60 nm. Next, the following compound (NPD) was vacuum deposited as a hole transporting material to a film thickness of 20 nm.

Next, 4,4′-bis (2,2-diphenylvinyl) biphenyl (DPVBi) and the above compound (58) are used as the light emitting material so that the ratio of the compound (58) is 5% by weight and the film thickness is 40 nm. Co-deposited. Compound (58) functions as a fluorescent dopant. Next, the compound (Alq) was deposited as a charge injection material in a thickness of 20 nm, LiF was deposited in a thickness of 0.5 nm, and then aluminum was deposited in a thickness of 100 nm to form an electrode to obtain an organic EL device. Each layer was deposited in a vacuum of 10 ⁻⁶ Torr at a substrate temperature of room temperature. The light emission characteristics of this device were as high as yellow light emission luminance 600 (cd / m ² ) at an applied voltage of DC voltage 5V. Further, when the device was driven at a constant current at an initial light emission luminance of 400 (cd / m ² ), the half life was as long as 2800 hours.

Reference Example 44
The same as Reference Example 43 , except that the above compound (Alq) as a luminescent material and the above compound (61) as a dopant were co-evaporated so that the proportion of the compound (61) was 5% by weight to form a luminescent layer. Thus, an organic EL element was produced. The light emission characteristic of this element is that red light emission having a light emission luminance of 240 (cd / m ² ) can be obtained at an applied voltage of DC voltage 5V. Further, when the device was driven at a constant current at an initial light emission luminance of 400 (cd / m ² ), the half life was as long as 3200 hours.

Comparative Example 5
An organic EL device was produced in the same manner as in Reference Example 31 except that the above compound (Comparative Example 1) was used as the light emitting material.
With respect to the light emission characteristics of the obtained device, sufficient performance was not obtained with a light emission luminance of 60 (cd / m ² ) and a light emission efficiency of 0.34 (lm / W) at an applied voltage of DC voltage of 5V. The emission color was blue.

Comparative Example 6
An organic EL device was produced in the same manner as in Reference Example 33 except that the above compound (Comparative Example 2) was used as the light emitting material.
The light emitting characteristics of the obtained device were an emission luminance of 200 (cd / m ² ) and an emission efficiency of 1.2 (lm / W) at an applied voltage of DC voltage of 5 V, but an initial emission luminance of 400 (cd / m ^2). ) Was driven at a constant current, the half-life was 600 hours, which was short. The emission color was blue.

Comparative Example 7
An organic EL device was produced in the same manner as in Reference Example 43 except that the above compound (Comparative Example 1) was used instead of the above compound (58) of the light emitting material.
The light emitting characteristics of the obtained device were a light emission luminance of 200 (cd / m ² ) at an applied voltage of DC voltage of 5V, but when driven at a constant current with an initial light emission luminance of 400 (cd / m ² ), the half life was 700. The time and life were short and the emission color was blue.

Synthesis Example 8 (Compound (58))
Synthesis of intermediate F (5,11-dibromonaphthacene) In a 2 liter round bottom flask, 50 g (0.19 mmol) of 5,12-naphthacenequinone, 108 g (0.57 mmol) of stannic chloride, 500 ml of acetic acid, concentrated hydrochloric acid 200 milliliters was added, and the reaction was conducted by heating and stirring for 2 hours. After completion of the reaction, the precipitated crystals were collected by filtration, washed with water, and dried overnight in a vacuum dryer to obtain 48 g of crude crystals.
The obtained crude crystals, 50 g (0.19 mmol) of triphenylphosphine and 300 ml of DMF were placed in a 2 liter four-necked flask under an argon stream, and 64 g (0.4 mmol) of bromine / 200 ml of DMF were added dropwise at room temperature. I let you. After completion of dropping, the mixture was stirred with heating at 200 ° C. overnight. After completion of the reaction, DMF was removed by distillation under reduced pressure, and 200 ml of water was added to the residue. The organic layer was extracted with toluene, dried over magnesium sulfate, and concentrated under reduced pressure using a rotary evaporator to obtain an oily compound. Purification by column chromatography (silica gel, hexane / toluene = 1/1) gave 30 g of yellow powder. This powder was identified as Intermediate F (yield 40%) by NMR, IR and FD-MS measurements.

Synthesis of Compound (58) In a 100 ml two-necked flask, 2 g (10 mmol) of 4-aminostilbene was dissolved in 20 ml of methylene chloride, 2.5 g (25 mmol) of acetic anhydride was added and reacted at room temperature for 1 hour. . Thereafter, the reaction solvent was distilled off to obtain an oily compound. In a 300 ml two-necked flask, 4.1 g (20 mmol) of iodobenzene, 3 g (30 mmol) of potassium carbonate, 0.06 g (1 mmol) of copper powder and 100 ml of nitrobenzene were added to this compound, and the mixture was heated and stirred at 220 ° C. for 2 days. did. Thereafter, 10 ml of diethylene glycol and 30 ml of potassium hydroxide / 100 ml of water were added to the residue obtained by distilling off the solvent, and the mixture was reacted at 110 ° C. overnight. After completion of the reaction, ethyl acetate / water was added for liquid separation, and the solvent was distilled off to obtain crude crystals.
In a 100 ml two-necked flask under an argon stream, the obtained crude crystals, intermediate F 1.9 g (5 mmol), tBuOK 1.3 g (12 mmol), PdCl ₂ (PPh ₃ ) ₂ 40 mg (5 mol%) and xylene 30 ml were added. The mixture was stirred and reacted at 130 ° C. overnight. After completion of the reaction, the precipitated crystals were collected by filtration and washed with methanol. Purification by column chromatography (silica gel, hexane / toluene = 1/1) gave 0.9 g of a yellow powder. This powder was identified as the compound (58) by NMR, IR and FD-MS measurements (yield 25%).

Synthesis Example 9 (Compound (59))
Synthesis of Compound (59) 4-hydroxystilbene 2 g (10 mmol), triphenylphosphine 5.2 g (20 mmol), and DMF 50 ml were placed in a 300 ml four-necked flask under an argon stream, and iodine 5 g (20 mmol) / DMF 50 ml was added. The reaction was carried out dropwise at room temperature. After completion of dropping, the mixture was stirred overnight at 200 ° C. After completion of the reaction, DMF was removed by distillation under reduced pressure, and 200 ml of water was added to the residue. The organic layer was extracted with toluene, dried over magnesium sulfate, and concentrated under reduced pressure using a rotary evaporator to obtain an oily compound. Purification by column chromatography (silica gel, hexane / toluene = 1/1) gave 2.5 g of yellow powder.
Separately, in a 100 ml two-necked flask, 2 g (10 mmol) of 4-aminostilbene was dissolved in 20 ml of methylene chloride, 2.5 g (25 mmol) of acetic anhydride was added, and reacted at room temperature for 1 hour. Thereafter, the reaction solvent was distilled off to obtain an oily compound.
In a 300 ml two-necked flask, 2.5 g of the above yellow powder, 3 g (30 mmol) of potassium carbonate, 0.06 g (1 mmol) of copper powder and 100 ml of nitrobenzene were added to this compound, and the mixture was heated and stirred at 220 ° C. for 2 days. Thereafter, 10 ml of diethylene glycol and 30 ml of potassium hydroxide / 100 ml of water were added to the residue obtained by distilling off the solvent, and the mixture was reacted at 110 ° C. overnight. After completion of the reaction, ethyl acetate / water was added for liquid separation, and the solvent was distilled off to obtain crude crystals.
In a 300 ml two-necked flask, the above crude crystals, 2.4 g (5 mmol) of intermediate F, 1.3 g (12 mmol) of tBuOK, 40 mg (5 mol%) of PdCl ₂ (PPh ₃ ) ₂ and 30 ml of xylene were mixed, and 130 ° C. And reacted overnight. After completion of the reaction, the precipitated crystals were collected by filtration, washed with methanol and dried. Purification by column chromatography (silica gel, hexane / toluene = 1/1) gave 0.2 g of yellow powder. This powder was identified as Compound (59) by NMR, IR, and FD-MS measurements (yield 5%).

Synthesis Example 10 (Compound (61))
Synthesis of Compound (61) In a 300 ml four-necked flask under an argon stream, 9.7 g (30 mmol) of 4-bromotriphenylamine, 50 ml of toluene, and 50 ml of diethyl ether were cooled with ice water, and n-butyllithium / Hexane 22 ml (1.52 mol / liter, 33 mmol) / THF 100 ml was added dropwise at room temperature to cause the reaction. After completion of dropping, the mixture was stirred overnight at the same temperature. After completion of the reaction, 50 ml of water was added, and the organic layer was extracted with diethyl ether, dried over magnesium sulfate, and concentrated under reduced pressure using a rotary evaporator to obtain 7.4 g of an oily compound.
In a 300 ml four-necked flask, the above compound, 6.6 g (40 mmol) of potassium iodide and 100 ml of acetic acid were placed and heated to reflux for 1 hour. After completion of the reaction, the mixture was cooled to room temperature and the precipitated crystals were collected by filtration. The obtained crystals were washed with water and acetone to obtain 2.7 g of an orange solid. This orange solid was identified as Compound (61) by NMR, IR and FD-MS measurements (yield 35%).

Synthesis Example 11 (Compound (62))
Synthesis of Intermediate G (5,11-diiodonaphthacene) A 500 ml round bottom flask was charged with 50 g (0.22 mmol) of naphthacene and 200 ml of tetrachloroethane, and 160 g of iodine / carbon tetrachloride (0.64 mol / 200 ml). ) Was added dropwise little by little at room temperature. After the reaction solution was heated and stirred for 5 hours, the precipitated crystals were collected by filtration and washed with 500 ml of methanol. The obtained crude crystals were recrystallized with 200 ml of toluene to obtain 34 g of intermediate G (yield 40%).

Synthesis of Compound (62) 1.0 g (41 mmol) of magnesium, 1 ml of THF and a small piece of iodine were placed in a 100 ml four-necked flask under an argon stream, and 9.7 g (30 mmol) of 4-bromotriphenylamine / 100 ml of THF was added at room temperature. After the dropwise addition, the mixture was heated and stirred at 60 ° C. for 1 hour to prepare a Grignard reagent.
In a 300 ml four-necked flask under an argon stream, intermediate G 4.8 g (10 mmol), THF 50 ml, PdCl ₂ (PPh ₃ ) ₂ 0.28 g (0.4 mmol) and AlH (iso-Bu) ₂ /1.0 M toluene 1.0 ml (1 mmol) of the solution was added, and the above Grignard reagent was added dropwise at room temperature, followed by heating to reflux overnight. After completion of the reaction, the reaction solution was cooled with ice water, and the precipitated crystals were collected by filtration and washed with acetone. The obtained crude crystals were recrystallized with 100 ml of acetone to obtain 3.6 g of yellow powder. This powder was identified as Compound (62) by NMR, IR, and FD-MS measurements (yield 50%).

Reference Example 45
On the cleaned glass plate with an ITO electrode, the above compound (TPD74) was vacuum deposited as a hole injecting material to a film thickness of 60 nm. Next, the compound (NPD) was vacuum-deposited to a thickness of 20 nm as a hole transport material.
Next, the compound (Alq) as a light emitting material and the compound (75) as a dopant were co-evaporated so that the ratio of the compound (75) was 2 wt% and the film thickness was 40 nm. Next, the compound (Alq) as an electron injecting material was vapor-deposited with a thickness of 20 nm, LiF was vapor-deposited with a thickness of 0.5 nm, and aluminum was vapor-deposited with a thickness of 100 nm to form an electrode to obtain an organic EL device. Each layer was deposited in a vacuum of 10 ⁻⁶ Torr at a substrate temperature of room temperature. The light emission characteristics of this device were as follows: an emission luminance of 500 (cd / m ² ) and an orange emission at an applied voltage of DC voltage of 8V. Furthermore, when the device was driven at a constant current at an initial light emission luminance of 500 (cd / m ² ), the half-life exceeded 2000 hours and was particularly long.

Reference Example 46
An organic EL device was produced in the same manner as in Reference Example 45 except that the compound (86) was added instead of the compound (75) as a dopant. When this element was driven at a constant current at an initial light emission luminance of 500 (cd / m ² ), the half-life was 2000 hours and a long life. The emission color was vermilion.

Reference Example 47
An organic EL device was produced in the same manner as in Reference Example 45 except that the compound (82) was added instead of the compound (75) as a dopant. When this element was driven at a constant current at an initial light emission luminance of 500 (cd / m ² ), the half-life was as long as 2800 hours or longer. The emission color was red.

Synthesis Example 12 (Compound (75))
Synthesis of Compound (75) In a 200 ml three-necked flask under an argon stream, 6,12-dibromonaphthacene (40577-78-4 2.16 g (5.6 mmol), Pd (OAc) ₂ 0.06 g (0.3 mmol) ), 0.23 g (1.1 mmol) of P (tBu) ₃ , 1.51 g (15.7 mmol) of NaOtBu, 1.89 g (11.2 mmol) of Ph ₂ NH and 25 ml of toluene, and the mixture is heated and stirred at 120 ° C. for 7 hours. After completion of the reaction, the reaction mixture was allowed to cool, and red crystals were collected by filtration, washed with toluene and water, and dried under reduced pressure to obtain 3.02 g of a red powder, which was measured by NMR, IR, and FD-MS. Was identified as Compound (75) (yield 96%).
In NMR (CDC13, TMS), 6.8-7.0 (m, 2H), 7.0-7.4 (m, 10H), 7.8-7.9 (m, 1H), 8.0 -8.1 (m, 1H), 8.85 (s, 1H).

得られた有機ＥＬ素子について性能を評価した。第４表に示す電圧における発光輝度を測定し、発光効率を算出し、発光色を観察した。さらに、窒素気流下で初期発光輝度５００（ｃｄ／ｍ²)で定電流駆動し、発光輝度２５０（ｃｄ／ｍ²)となる半減寿命を測定した。これらの結果を第４表に示す。 Reference Example 48
A transparent anode having an indium tin oxide film thickness of 100 nm was provided on a glass substrate having a size of 25 mm × 75 mm × 1.1 mm, and was washed for 10 minutes using both ultraviolet rays and ozone.
This glass substrate was put into a vacuum tea ceremony apparatus (Nippon Vacuum Technology Co., Ltd.) and decompressed to about 10 ⁻⁴ Pa. Thereafter, the TPD74 was deposited to a thickness of 60 nm at a deposition rate of 0.2 nm / second. Next, TPD78 having the following structure was deposited to a thickness of 20 nm at a deposition rate of 0.2 nm / second.
Next, DPVDPAN having the following structure and the compound (100) as a light emitting material were co-evaporated to form a light emitting layer having a thickness of 40 nm. At this time, the deposition rate of DPVDPAN was 0.4 nm / second, and the deposition rate of compound (100) was 0.01 nm / second. Furthermore, the Alq was vapor-deposited at a vapor deposition rate of 0.2 nm / second, and finally aluminum and lithium were vapor-deposited simultaneously to form a cathode with a thickness of 150 nm to obtain an organic EL device. At this time, the deposition rate of aluminum was 1 nm / second, and the deposition rate of lithium was 0.004 nm / second.

The performance was evaluated about the obtained organic EL element. The light emission luminance at the voltage shown in Table 4 was measured, the light emission efficiency was calculated, and the light emission color was observed. Further, a half-life at which the emission luminance was 250 (cd / m ² ) was measured by driving at a constant current with an initial emission luminance of 500 (cd / m ² ) under a nitrogen stream. These results are shown in Table 4.

Reference Examples 49-58
In Reference Example 48 , an organic EL device was prepared and evaluated in the same manner except that the compound shown in Table 4 was used as the light emitting material instead of the compound (100). The results are shown in Table 4.

を使用した以外は同様にして有機ＥＬ素子を作製し、評価した。それらの結果を第４表に示す。 Comparative Example 8
In Reference Example 48 , the following diamine compound was used as the light emitting material instead of the compound (100).

An organic EL device was prepared and evaluated in the same manner except that was used. The results are shown in Table 4.

As shown in Table 4, the organic EL devices of Reference Examples 48 to 58 using the compounds of the general formulas [9] and [10] of the present invention as the light emitting material or the hole transporting material are those of Comparative Example 8 described above. Compared with the organic EL device using a diamine compound, the light emission luminance, the light emission efficiency, and the lifetime were excellent.

Synthesis Example 13 (Compound (100))
Synthesis of Intermediate H Under a stream of argon, 22.7 g (0.1 mol) of 4-bromophthalic anhydride, 42.4 g (0.4 mol) of sodium carbonate, and 300 ml of water were added to a 1-liter three-necked flask with a condenser. , Heated to 60 ° C. to dissolve. After dissolution, the mixture was cooled to room temperature, 18.3 g (0.15 mol) of phenylboronic acid and 0.7 g (3 mol%) of palladium acetate were added, and the mixture was stirred overnight at room temperature. After completion of the reaction, water was added to dissolve the precipitated crystals, the catalyst was removed by filtration, acidified with concentrated hydrochloric acid, and the precipitated crystals were collected by filtration and washed with water. The obtained crystals were dissolved in ethyl acetate, and the organic layer was extracted. After drying with magnesium sulfate, the mixture was concentrated under reduced pressure using a rotary evaporator to obtain 23.7 g (yield 98%) of the target intermediate H.

Synthesis of Intermediate I Intermediate H 23.7 g (98 mmol) and acetic anhydride 200 ml were added to a 500 ml eggplant flask equipped with a condenser, and stirred at 80 ° C. for 3 hours. After completion of the reaction, excess acetic anhydride was distilled off to obtain 22 g of the intended intermediate I (yield 10%).
Synthesis of Intermediate J Under a stream of argon, 7.7 g (50 mmol) of biphenyl, 13.4 g (0.1 mol) of anhydrous aluminum chloride and 200 ml of 1,2-dichloroethane were added to a 500 ml three-necked flask equipped with a cooling tube. Cooled to ° C. Next, 22 g (98 mmol) of Intermediate I was gradually added and stirred at 40 ° C. for 2 hours. Ice water was added after completion | finish of reaction, and liquid separation extraction was carried out with chloroform. After drying over magnesium sulfate, the mixture was concentrated under reduced pressure using a rotary evaporator to obtain the desired intermediate J19.0 g (yield 100%).

Synthesis of Intermediate K 200 ml of polyphosphoric acid was placed in a 500 ml eggplant flask equipped with a cooling tube and heated to 150 ° C. Next, 19 g (50 mmol) of the intermediate J was added little by little and stirred at the same temperature for 3 hours. Ice water was added after completion | finish of reaction, and liquid separation extraction was carried out with chloroform. After drying over magnesium sulfate, the mixture was concentrated under reduced pressure using a rotary evaporator. The resulting crude crystals were purified by column chromatography (silica gel, chloroform / methanol = 99/1) to obtain 19 g of the intended intermediate K (yield 55%).
Synthesis of Intermediate L In a 500 ml eggplant flask with a condenser under an argon stream, 19.0 g (28 mmol) of intermediate K, 0.19 g (1 mmol) of tin chloride, 100 ml of acetic acid and 50 ml of concentrated hydrochloric acid were added for 2 hours. Heated to reflux. After completion of the reaction, the reaction solution was cooled with ice water, and the precipitated crystals were collected by filtration and washed with water to obtain 19 g of the intended intermediate L (yield 100%).

Synthesis of Intermediate M Under a stream of argon, 19.0 g (28 mmol) of intermediate L, 16 g (60 mmol) of triphenylphosphine, and 200 ml of DMF were added to a 500 ml three-necked flask with a condenser. Subsequently, 9.6 g (60 mmol) of bromine / 50 ml of DMF was gradually added dropwise, and the mixture was heated and stirred at 200 ° C. for 8 hours. After completion of the reaction, the reaction solution was cooled with ice water, and the precipitated crystals were collected by filtration and washed with water and methanol to obtain 6.7 g of the intended intermediate M (yield 50%).
Synthesis of Compound (100) In a 200 ml three-necked flask with a condenser tube under an argon stream, intermediate M4.9 g (10 mmol), diphenylamine 5.1 g (30 mmol), tris (dibenzylidacetone) divaladium 0.14 g ( 1.5 mol%), 0.91 g (3 mol%) of tri-o-toluylphosphine, 2.9 g (30 mmol) of t-butoxy sodium, and 50 ml of dry toluene were added, followed by heating and stirring at 100 ° C. overnight. After completion of the reaction, the precipitated crystals were collected by filtration and washed with 100 ml of methanol to obtain 4.0 g of yellow powder. This powder was identified as the compound (100) by NMR, IR and FD-MS measurements (yield 60%).

The structural formula of the above intermediate and the reaction route of the compound (100) are shown below.

Synthesis Example 14 (Compound (101))
Synthesis of Intermediate N Under argon flow, 2,6-dihydroxy-anthraquinone 12 g (50 mmol), methyl iodide 42.5 g (0.3 mol), potassium hydroxide 17 g (0 3 mol) and DMSO (200 ml) were added, and the mixture was stirred at room temperature for 2 hours. After completion of the reaction, the precipitated crystals were collected by filtration and washed with 100 ml of methanol to obtain 10.7 g (yield 80%) of the target intermediate N.
Synthesis of intermediate O Under argon stream. In a 500 ml three-necked flask, intermediate N10.7 (40 mmol) and dry THF 200 ml were added and cooled to −40 ° C., and then 1.5 ml phenyl lithium / hexane solution 53 ml (80 mmol). ) Was gradually added dropwise. After completion of dropping, the mixture was stirred overnight at room temperature. After completion of the reaction, the precipitated crystals were collected by filtration and washed with 100 ml of methanol followed by 100 ml of acetone. The obtained geol crude crystals were used for the next reaction without further purification.
The above-mentioned crude crystals, 100 ml of 57% hydrogen iodide water, and 200 ml of acetic acid were added to a 500 ml eggplant flask equipped with a cooling tube, and the mixture was heated to reflux for 3 hours. After cooling to room temperature, a small amount of hypophosphorous acid was added to quench excess hydrogen iodide. The precipitated crystals were collected by filtration and washed with 100 ml of water, 100 ml of methanol, and 100 ml of acetone in this order to obtain 10.1 g (yield 70%) of the desired intermediate O.・

Synthesis of Intermediate P Under a stream of argon, 10.1 g (28 mmol) of intermediate O, 7.9 g (30 mmol) of triphenylphosphine and 200 ml of DMF were added to a 500 ml three-necked flask with a condenser. Subsequently, 4.8 g (30 mmol) of bromine / 50 ml of DMF were gradually added dropwise, and the mixture was heated and stirred at 200 ° C. for 8 hours. After completion of the reaction, the reaction solution was cooled with ice water and the precipitated crystals were collected by filtration and washed with water and methanol to obtain 8.2 g of the intended intermediate P (yield 60%).
Synthesis of Compound (101) In a 200 ml three-necked flask equipped with a cooling tube under an argon stream, intermediate P4.9 g (30 mmol), diphenylamine 5.1 g (30 mmol), tris (dibenzylidacetone) divaladium 0.14 g ( 1.5 mol%), 0.91 g (3 mol%) of tri-o-toluylphosphine, 2.9 g (30 mmol) of t-butoxy sodium, and 50 ml of dry toluene were added, followed by heating and stirring at 100 ° C. overnight. After completion of the reaction, the precipitated crystals were collected by filtration and washed with 100 ml of methanol to obtain 4.0 g of yellow powder. This powder was identified as the compound (101) by NMR, IR and FD-MS measurements (yield 6%).

The structural formula of the above intermediate and the reaction route of the compound (101) are shown below.

Synthesis Example 15 (Compound (102))
Synthesis of Intermediate Q Under a stream of argon, in a 300 ml three-necked flask with a condenser tube, 11.7 g (50 mmol) of 2-bromobiphenyl, 19 g (0.2 mol) of aniline, 0.69 g of tris (dibenzylidacetone) dibaradium (1.5 mol%), 0.46 g (3 mol%) of tri-o-toluylphosphine, 7.2 g (75 mmol) of t-butoxy sodium, and 100 ml of dry toluene were added, followed by heating and stirring at 100 ° C. overnight. . After completion of the reaction, the precipitated crystals were collected by filtration, washed with 100 ml of methanol and recrystallized from 50 ml of ethyl acetate to obtain the desired intermediate Q9.8 g (yield 80%). Got.
Synthesis of Compound (102) Under a stream of argon, 2.4 g (10 mmol) of 9,10-dibromoanthracene, 7.4 g (30 mmol) of intermediate Q, tris (dibenzylidacetone) in a 200 ml three-necked flask with a condenser tube After adding 0.14 g (1.5 mol%) of divaladium, 0.91 g (3 mol%) of tri-o-toluylphosphine, 2.9 g (30 mmol) of t-butoxy sodium, and 50 ml of dry toluene, the mixture was added at 100 ° C. The mixture was stirred overnight. After completion of the reaction, the precipitated crystals were collected by filtration and washed with 100 ml of methanol to obtain 4.3 g of a yellow powder. This powder was identified as Compound (102) by NMR, IR, and FD-MS measurements (yield 65%).

The structural formula of the above intermediate and the reaction route of the compound (102) are shown below.

Synthesis Example 16 (Compound (103))
Synthesis of Intermediate R Under a stream of argon, 34 g (0.2 mol) of 3-phenylphenol, 58 g (0.22 mmol) of triphenylphosphine, and 300 ml of DMF were added to a 1-liter three-neck flask with a condenser. Subsequently, 35 g (0.22 mmol) of bromine / 100 ml of DMF were gradually added dropwise, and then the mixture was heated and stirred at 200 ° C. for 8 hours. After completion of the reaction, the reaction solution was cooled with ice water, and the precipitated crystals were collected by filtration and washed with water and methanol to obtain the desired intermediate R37g (yield 80%).
Synthesis of Intermediate S In a 300 ml three-necked flask with a condenser tube under an argon stream, 19 g (0.2 mmol) of aniline, 0.69 g (1.5 mol%) of tris (dibenzylidacetone) divaladium, tri-o- Toluylphosphine 0.46 g (3 mol%), t-butoxy sodium 7.2 g (75 mmol), and dry toluene 100 ml were added, and the mixture was heated and stirred at 100 ° C. overnight. After completion of the reaction, the precipitated crystals were collected by filtration, washed with 100 ml of methanol and recrystallized from 50 ml of ethyl acetate to obtain the desired intermediate Q9.8 g (yield 80%). Got.
Synthesis of Compound (103) In a 200 ml three-necked flask with a condenser tube under an argon stream, 2.4 g (10 mmol) of 9,10-dibromoanthracene, 7.4 g (30 mmol) of intermediate S, tris (dibenzylidacetone) After adding 0.14 g (1.5 mol%) of divaladium, 0.91 g (3 mol%) of tri-o-toluylphosphine, 2.9 g (30 mmol) of sodium t-butoxy, and 50 ml of dry toluene, the mixture was added at 100 ° C. The mixture was stirred overnight. After completion of the reaction, the precipitated crystals were collected by filtration and washed with 100 ml of methanol to obtain 4.2 g of a yellow powder. This powder was identified as Compound (103) by NMR, IR, and FD-MS measurements (yield 70%).

The structural formula of the above intermediate and the reaction route of the compound (103) are shown below.

Synthesis Example 17 (Compound (104))
Synthesis of Intermediate T In a 300 ml three-necked flask with a condenser tube under an argon stream, 23 g (0.1 mol) of 4-bromobiphenyl, 9.8 g (50 mmol) of aminostilbene, tris (dibenzylidacetone) dibaradium 69 g (1.5 mol%), tri-o-toluylphosphine 0.46 g (3 mol%), t-butoxy sodium 7.2 g (75 mmol), and dry toluene 100 ml were added, followed by heating and stirring at 100 ° C. overnight. did. After completion of the reaction, the precipitated crystals were collected by filtration, washed with 100 ml of methanol and recrystallized from 50 ml of ethyl acetate to obtain the desired intermediate T 13.9 g (yield 80%). Got.
Synthesis of Compound (104) In a 200 ml three-necked flask with a condenser tube under an argon stream, 2.4 g (10 mmol) of 9,10-dibromoanthracene, 7.4 g (30 mmol) of intermediate T, tris (dibenzylidacetone) After adding 0.14 g (1.5 mol%) of divaladium, 0.91 g (3 mol%) of tri-o-toluylphosphine, 2.9 g (30 mmol) of sodium t-butoxy, and 50 ml of dry toluene, the mixture was added at 100 ° C. The mixture was stirred overnight. After completion of the reaction, the precipitated crystals were collected by filtration and washed with 100 ml of methanol to obtain 4.5 g of a yellow powder. This powder was identified as Compound (104) by NMR, IR and FD-MS measurements (yield 70%).

The structural formula of the above intermediate and the reaction route of the compound (104) are shown below.

Synthesis Example 18 (Compound (121))
Synthesis of Intermediate U In a 500 ml three-necked flask with a condenser tube under an argon stream, 25 g (0.1 mol) of triphenylamine, 18 g (0.1 mol) of N-bromosuccinimide, 2,2′-azobisisobutyro Nitrile 0.82 g (5 mol%) and DMF 200 ml were added and the mixture was heated and stirred at 110 ° C. for 4 hours. After completion of the reaction, impurities were filtered off, and the filtrate was concentrated under reduced pressure using a rotary evaporator. The resulting crude crystals were purified by column chromatography (silica gel, methylene chloride) to obtain 19 g of the intended intermediate U (yield 60%).
Synthesis of Intermediate V Under a stream of argon, 1.6 g (66 mmol) of magnesium, a small piece of iodine, and 100 ml of THF were placed in a 1-liter three-necked flask equipped with a cooling tube. After stirring for 30 minutes at room temperature, Intermediate U19 g (60 mol) / A 300 ml THF solution was added dropwise. After completion of dropping, the mixture was heated and stirred at 60 ° C. for 1 hour to prepare a Grignard reagent.
Under a stream of argon, in a 1-liter three-necked flask with a condenser tube, 42 g (0.18 mmol) of 1,3 dibromobenzene, 2.1 (5 mol%) of dichlorobis (triphenylphosphine) palladium, 6 ml of diisobutylaluminum hydride / toluene solution ( 1M, 6 mmol) and 200 milliliters of THF were added. The above Grignard reagent was added dropwise at room temperature, and the mixture was heated and stirred overnight. After completion of the reaction, the reaction solution was cooled with ice water and the precipitated crystals were collected by filtration and washed with acetone to obtain 14 g of the intended intermediate V (yield 60%).

Synthesis of Compound (121) In a 500 ml three-necked flask with a condenser tube under an argon stream, 0.8 g (33 mmol) of magnesium, a small piece of iodine, and 50 ml of THF were stirred at room temperature for 30 minutes, and then intermediate V12 g (30 mmol). / THF 100 ml solution was added dropwise. After completion of dropping, the mixture was stirred at 60 ° C. for 1 hour to prepare a Grignard reagent.
Under a stream of argon, in a 500 ml three-necked flask with a condenser tube, 3.4 g (10 mmol) of 9,10-dibromoanthracene, 0.4 g (5 mol%) of dichlorobis (triphenylphosphine) palladium, 1 ml of diisobutylaluminum hydride / toluene solution (1M, 1 mmol), 100 mL of THF was added. The above Grignard reagent was added dropwise at room temperature, and the mixture was heated and stirred overnight. After completion of the reaction, the reaction solution was cooled with ice water and the precipitated crystals were collected by filtration and washed with methanol (50 ml) and acetone (50 ml) in this order to obtain 4.1 g of a yellow powder. This powder was identified as the compound (121) by NMR, IR and FD-MS measurements (yield 50%).

The structural formula of the above intermediate and the reaction route of the compound (121) are shown below.

Synthesis Example 19 (Compound (122))
Synthesis of Intermediate W In a 300-liter three-necked flask with a condenser tube under an argon stream, 1,3-dibromobenzene 19 g (80 mmol), diphenylamine 6.5 g (20 mmol), tris (dibenzylidacetone) dibaradium 0.27 g (1.5 mol%), 0.18 g (3 mol%) of tri-o-toluylphosphine, 2.9 g (30 mmol) of t-butoxy sodium, and 100 ml of dry toluene were added, followed by heating and stirring at 100 ° C overnight. . After completion of the reaction, the precipitated crystals are collected by filtration, washed with 100 ml of methanol, and the obtained crude crystals are recrystallized with 50 ml of ethyl acetate to obtain 4.9 g of the desired intermediate W (yield 75%). Got.
Synthesis of Compound (122) In a 300 ml three-necked flask with a condenser tube under an argon stream, 0.5 g (20 mmol) of magnesium, a small piece of iodine, and 50 ml of THF were added and stirred for 30 minutes at room temperature. 15 mmol) / THF 100 ml solution was added dropwise. After completion of dropping, the mixture was stirred at 60 ° C. for 1 hour to prepare a Grignard reagent.
In a 500 ml three-necked flask equipped with a condenser tube under an argon stream, 1.7 g (5 mmol) of 9-10 dibromoanthracene, 0.2 g (5 mol%) of dichlorobis (triphenylphosphine) palladium, 0.5 of diisobutylaluminum hydride / toluene solution Milliliter (1M, 0.5 mmol) and 100 ml THF were added. The above Grignard reagent was added dropwise at room temperature, and the mixture was heated and stirred overnight. After completion of the reaction, the reaction solution was cooled with ice water and the precipitated crystals were collected by filtration and washed with 50 ml of methanol and 50 ml of acetone in this order to obtain 1.7 g of a yellow powder. This powder was identified as Compound (122) by NMR, IR and FD-MS measurements (yield 50%).

The structural formula of the above intermediate and the reaction route of the compound (122) are shown below.

Synthesis Example 20 (Compound (123))
Synthesis of Intermediate X In a 300-liter three-necked flask with a condenser tube under an argon stream, 16 g (0.1 mol) of bromobenzene, 9.8 g (50 mmol) of aminostilbene, 0.69 g of tris (dibenzylidacetone) dibaradium ( 1.5 mol%), 0.46 g (3 mol%) of tri-o-toluylphosphine, 7.2 g (75 mmol) of t-butoxy sodium, and 100 ml of dry toluene, and then heated and stirred at 100 ° C. overnight. After completion of the reaction, the precipitated crystals are collected by filtration, washed with 100 ml of methanol, and the resulting crude crystals are recrystallized with 50 ml of ethyl acetate to obtain 11 g of the intended intermediate X (yield 80%). It was.
Synthesis of Intermediate Y In a 500-liter three-necked flask with a condenser tube under an argon stream, 38 g (0.16 mol) of bromobenzene, 11 g (40 mmol) of intermediate X, 0.55 g of tris (dibenzylidacetone) dibaradium (1. 5 mol%), 0.37 g (3 mol%) of tri-o-toluylphosphine, 5.8 g (60 mmol) of t-butoxy sodium, and 300 ml of dry toluene, and then heated and stirred at 120 ° C. overnight. After completion of the reaction, the precipitated crystals are collected by filtration, washed with 100 ml of methanol, and the obtained crude crystals are recrystallized with 50 ml of ethyl acetate to obtain 13 g of the desired intermediate Y (yield 75%). It was.

Synthesis of Compound (123) 0.97 g (40 mmol) of magnesium, a small piece of iodine, and 50 ml of THF were placed in a 300 ml three-necked flask with a condenser tube under an argon stream, and stirred for 30 minutes at room temperature, and then intermediate Y12 g (30 mmol) / THF 100 ml solution was added dropwise. After completion of dropping, the mixture was stirred at 60 ° C. for 1 hour to prepare a Grignard reagent.
Under a stream of argon, in a 500 ml three-necked flask with a condenser tube, 3.4 g (10 mmol) of 9,10-dibromoanthracene, 0.4 g (5 mol%) of dichlorobis (triphenylphosphine) palladium, 1 ml of diisobutylaluminum hydride / toluene solution (1M, 1 mmol), 100 mL of THF was added. The above Grignard reagent was added dropwise at room temperature, and the mixture was heated and stirred overnight. After completion of the reaction, the reaction solution was cooled with ice water and the precipitated crystals were collected by filtration and washed with methanol (50 ml) and acetone (50 ml) in this order to obtain 5.4 g of a yellow powder. This powder was identified as Compound (122) by NMR, IR and FD-MS measurements (yield 50%).

The structural formula of the above intermediate and the reaction route of the compound (123) are shown below.

Synthesis Example 21 (Compound (124))
Synthesis of Compound (124) In a 500 ml three-necked flask with a condenser tube under an argon stream, 2.5 g (5 mmol) of 10,10′-dibromo-9,9′-bianthryl, 0.2 g of dichlorobis (triphenylphosphine) palladium (5 mol%), 0.5 ml (1M, 0.5 mmol) of diisobutylaluminum hydride / toluene solution and 100 ml of THF were added. The Grignard reagent prepared in Synthesis Example (19) was added dropwise thereto at room temperature, and the temperature was raised and stirred overnight. After completion of the reaction, the reaction solution was cooled with ice water, and the precipitated crystals were collected by filtration and washed with 50 ml of methanol and 50 ml of acetone in this order to obtain 2.0 g of a yellow powder. This powder was identified as Compound (124) by NMR, IR, and FD-MS measurements (yield 60%).

A reaction route of the compound (124) is shown below.

Synthesis Example 22 (Compound (125))
Synthesis of Compound (125) 1.9 g (5 mmol) of 6,12 dibromochrysene, 0.2 g (5 mol%) of dichlorobis (triphenylphosphine) palladium, diisobutylaluminum hydride in a 500 ml three-necked flask with a condenser tube under an argon stream / Toluene solution 0.5 ml (1M, 0.5 mmol) and THF 100 ml were added. The Grignard reagent prepared in Synthesis Example (19) was added dropwise thereto at room temperature, and the temperature was raised and stirred overnight. After completion of the reaction, the reaction solution was cooled with ice water and the precipitated crystals were collected by filtration and washed with methanol (50 ml) and acetone (50 ml) in this order to obtain 2.1 g of a yellow powder. This powder was identified as Compound (125) by NMR, IR and FD-MS measurements (yield 60%).

A reaction route of the compound (125) is shown below.

Synthesis Example 23 (Compound (126))
Synthesis of Compound (126) In a 500 ml three-necked flask with a condenser tube under an argon stream, 1.9 g (5 mmol) of 5,12-dibromonaphthacene, 0.2 g (5 mol%) of dichlorobis (triphenylphosphine) palladium, diisobutyl 0.5 ml (1M, 0.5 mmol) of an aluminum hydride / toluene solution and 100 ml of THF were added. The Grignard reagent prepared in Synthesis Example (19) was added dropwise thereto at room temperature, and the temperature was raised and stirred overnight. After completion of the reaction, the reaction solution was cooled with ice water and the precipitated crystals were collected by filtration and washed with methanol (50 ml) and acetone (50 ml) in this order to obtain 2.1 g of a yellow powder. This powder was identified as Compound (126) by NMR, IR, and FD-MS measurements (yield 60%).

A reaction route of the compound (126) is shown below.

Claims (9)

A material for an organic electroluminescence element represented by the following general formula [4].
General formula [4]

[Wherein, X ^{1 to} X ⁴ each independently represents a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, and X ¹ and X ² , X ³ and X ⁴ may be linked to each other. Good. Y ^{1 to} Y ⁴ each independently represents an organic group represented by the following general formula [2]. a to d represent an integer of 0 to 2; However, none of X ¹ , X ² , X ³ and X ⁴ contains a chrysene nucleus.
General formula [2]

Wherein R ^{1 to} R ⁴ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or a cyano group. Or a triple bond in which R ¹ and R ² or R ³ and R ⁴ are bonded together, Z represents a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, and n represents 0 or 1. )] The groups substituted for X ^{1 to} X ⁴ are each independently selected from an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms. The organic electroluminescent element material according to claim 1 . It is a light emitting material for organic electroluminescent elements, The material for organic electroluminescent elements of Claim 1 or 2 characterized by the above-mentioned. The organic electroluminescent element formed by forming a light emitting layer or a plurality of layers of organic compound thin films including a light emitting layer between a pair of electrodes, wherein at least one of the organic compound thin films is for the organic electroluminescent element according to claim 1 or 2 . An organic electroluminescence device characterized by being a layer containing a material. In the organic electroluminescent element formed by forming a light emitting layer or a plurality of layers of organic compound thin films including a light emitting layer between a pair of electrodes, the material for an organic electroluminescent element according to claim 1 or 2 is a positive hole injection material, a positive electrode. An organic electroluminescence device, wherein a layer containing at least one material selected from a hole transport material and a doping material is formed between the electrodes. In the organic electroluminescent element formed by forming a light emitting layer or a plurality of organic compound thin film including a light emitting layer between a pair of electrodes, the light emitting layer is made of the organic electroluminescent element material according to claim 1 or 2 in an amount of 0.0. 1 to 20 weight% of organic electroluminescent element characterized by the above-mentioned. In an organic electroluminescence device formed by forming a light emitting layer or a plurality of layers of organic compound thin films including a light emitting layer between a pair of electrodes, at least one kind selected from a hole injection material, a hole transport material or a doping material The organic electroluminescent element characterized by containing 0.1-20 weight% of materials for organic electroluminescent elements of Claim 1 or 2 each independently in material. 3. An organic electroluminescence device comprising a light emitting layer or a plurality of organic compound thin films including a light emitting layer formed between a pair of electrodes, wherein the light emitting layer is a stilbene derivative and the organic electroluminescent device material according to claim 1 or 2. An organic electroluminescence element characterized by being a layer containing. The organic electroluminescence according to any one of claims 4 to 8 , wherein a layer containing an aromatic tertiary amine derivative and / or a phthalocyanine derivative is formed between the light emitting layer and the anode. element.