JP2001052868A - Organic electroluminescent element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve the light emitting efficiency and lifetime by including a specified quantity of the organic EL element material composed of a special compound as the center of the emission in a light emitting layer. SOLUTION: A light emitting layer includes 0.1-20 wt.% of an element material made of a compound expressed by formula I as the emission center. In formula I, A means a substituent or non-substituent allylene group having 6-21 carbon atoms, X1-X4 mean each a separate substituent or non-substituent allylene group having 6-30 carbon atoms (X1 and X2, X3 and X4 can be connected to each other), Y1-Y4 respectively means a group expressed with formula II, (a)-(d) is an integer 0-2, and (a)+(b)+(c)+(d)>0. In formula II, R1-R4 separately means a hydrogen atom, a substituent or non-substituent alkyl group and cyano group having 1-20 carbon atoms, or triple bond of R1 and R2, R3 and R4, and Z means a substituent or non-substituent aryl group having 6-20 carbon atoms, and (n) is 0 or 1.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is used as a light source for a flat light-emitting body of a wall-mounted television or a backlight of a display, and has a high luminous efficiency and a long life. It concerns compounds.

[0002]

2. Description of the Related Art Organic electroluminescence (EL) devices using organic substances are expected to be used as inexpensive, large-area, full-color display devices of the solid-state emission type, and many developments have been made. Generally, an EL element includes a light-emitting layer and a pair of opposed electrodes sandwiching the light-emitting 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. Further, the electrons recombine with holes in the light emitting layer to generate an excited state, and emit energy 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. In addition, the characteristic deterioration was remarkable, and it had not been put to practical use. Although recent organic EL devices have been gradually improved, they have not yet had sufficient luminous efficiency, heat resistance, and life. For example, Japanese Patent Application Laid-Open No. 8-12600 discloses a phenylanthracene derivative that can be used in an EL device. An organic EL device using this compound has a luminous efficiency of only about 2 to 4 cd / A, and a higher efficiency is obtained. Was required. JP-A-8-199162 discloses an EL device in which a light emitting layer contains a fluorescent dopant composed of an amine or diamine derivative. However, this EL element has a luminous efficiency of 4 to 6 cd / A, but has a lifetime of only 700 hours at an initial luminance of 300 cd / m ² , and a longer lifetime is required. JP-A-9-268284
Discloses a material for an EL device having a phenylanthracene group, and this material is used as a host material,
When other compounds were used as doping materials, a long life was not obtained. Practically, the initial luminance is 10,000 cd /
Although m ² or more is demanded not been obtained. JP 11
JP-152253 discloses an organic E having a binaphthalene structure.
An example is disclosed in which an L element material is added to an electron transporting light emitting layer such as an Al complex. However, in this example, the energy gap of the light emitting layer such as an Al complex is
Since it is smaller than the energy gap of the material for L element, A
The complex 1 and the like emitted light, and the material for an organic EL device did not function as a luminescent center. On the other hand, synthesis of arylamines used as materials for organic EL devices has been conventionally carried out by Ullmann reaction using amines and benzene iodides. For example, Chem. Lett. Pp. 1
145-1148, 1989, U.S. Pat. No. 4,764,
No. 625, JP-A-8-48974 and the like correspond to an inert hydrocarbon solvent such as decalin at 150 ° C. or higher in the presence of one equivalent or more of copper powder and a base typified by potassium hydroxide. It is described that a triarylamine is produced by reacting an iodobenzene with a diarylamine. However, in the method based on the Ullmann reaction, an expensive iodide had to be used as a reactant, and the applicability was poor and the reaction yield was not sufficient. 150 ° C
Since the above-mentioned high temperature and long reaction time are required and a large amount of copper powder is used, a waste liquid containing a large amount of copper is generated, and there is also an environmental problem.

[0003]

DISCLOSURE OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and has been developed to provide an organic electroluminescent device having a high luminous efficiency and a long life, and a novel material which can be used for a material for an organic electroluminescent device. An object of the present invention is to provide a method for producing a compound and a material for an organic device with high activity.

[0004]

Means for Solving the Problems The present inventors have developed an organic electroluminescent element (hereinafter, referred to as an organic EL element) and a material for an organic electroluminescent element (hereinafter, referred to as an organic EL element) having the above-mentioned preferable properties. As a result of intensive studies, it has been found that the object can be achieved by using a compound represented by the following general formula [1] or [1 '] as a doping material or a luminescent center. In addition, the present inventors, in the presence of a catalyst and a base consisting of a phosphine compound and a palladium compound,
By reacting an amine with an aryl halide, 3
It has been found that a material for an organic EL device of a class arylamine can be synthesized with high activity. The present invention has been completed based on such findings.

That is, an organic EL device according to the present invention is an organic EL 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. Organic EL comprising a compound represented by the formula:
An organic electroluminescent device comprising 0.1 to 20% by weight of a material for the device as a luminescent center. General formula [1]

Embedded image [In the formula, A is a substituted or unsubstituted carbon atom having 6 to 21 carbon atoms.
Represents an arylene group. X ^{1 to} X ⁴ each independently represent a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, and X ¹ and X ² , and X ³ and X ⁴ may be connected to each other. Y ^{1 to} Y ⁴ each independently represent an organic group represented by the following general formula [2]. a to d represent an integer of 0 to 2. However, a + b + c + d> 0. General formula [2]

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

The organic EL device of the present invention is an organic electroluminescent 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. Even if the organic EL device contains 0.1 to 20% by weight of the material for the organic EL device represented by the general formula [1] independently of at least one material selected from the electron transporting materials. Alternatively, the light emitting layer may be an organic EL device that is a layer containing a stilbene derivative and the material for an organic EL device represented by the general formula [1].

The organic EL device of the present invention may be an organic EL device in which a layer containing an aromatic tertiary amine derivative and / or a phthalocyanine derivative is formed between a light emitting layer and an anode.

A in the general formula [1] is preferably a group represented by the following general formula [3], [4] or [5].

The general formula [3]

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The general formula [4]

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The general formula [5]

Embedded image (Wherein, R ^{5 to} R ³⁴ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms,
Represents a substituted or unsubstituted aryl group or cyano group having 6 to 20 carbon atoms, and adjacent groups may be bonded to each other to form a saturated or unsaturated carbon ring. )

The energy gap of the material for an organic EL device represented by the general formula [1] is preferably smaller than the energy gap of the host material by 0.07 eV or more, and more preferably 0.15 eV or more.

The present invention also provides a novel compound wherein A in the following general formula [1 '] is the above general formula [5]. General formula [1 ']

Embedded image [In the formula, A represents a group represented by the general formula [5]. X
^{1 to} X ⁴ each independently represent 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. Y ^{1 to} Y
⁴ independently represents an organic group represented by the general formula [2]. a to d represent an integer of 0 to 2. Where a
+ B + c + d> 0. ]

Further, the method for producing a material for an organic EL device according to the present invention comprises the following formula [6] R (NR′H) _k [6] (6) in the presence of a catalyst comprising a phosphine compound and a palladium compound and a base. In the formula, k represents an integer of 1 to 3, and when k is 1, R and R ′ represent a hydrogen atom, an alkyl group, a substituted or unsubstituted aryl group, and when k is 2 or more, R represents an alkylene group or A substituted or unsubstituted arylene group, R ′ represents a hydrogen atom, an alkyl group, or a substituted or unsubstituted aryl group.) And a primary or secondary amine represented by the following general formula [7] Ar (X) _m [7] (wherein, Ar represents a substituted or unsubstituted aryl group;
Represents F, Cl, Br or I, and m represents an integer of 1 to 3. However, at least one of R, R 'and Ar contains a styryl group, and when k is 2, the R' substituted with N may be different. This is a method for producing a material for an organic device comprising an arylamine compound by reacting with an aryl halide represented by the formula (1).

The arylamine compound is preferably a compound represented by the following formula [8]. General formula [8]

Embedded image [Wherein A is a substituted or unsubstituted carbon atom having 6 to 60 carbon atoms.
Represents an arylene group. X ^{1 to} X ⁴ each independently represent a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, and X ¹ and X ² , and X ³ and X ⁴ may be connected to each other. Y ^{1 to} Y ⁴ each independently represent an organic group represented by the general formula [2]. a to d represent an integer of 0 to 2. However, a + b + c + d> 0. It is preferable that the phosphine compound is a trialkyl phosphine compound, a triallyl phosphine compound, or a diphosphine compound.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION The general formulas [1] and [1 '] for materials and novel compounds used in the organic EL device of the present invention
A in the compound represented by represents a substituted or unsubstituted arylene group having 6 to 21 carbon atoms, and is formed from biphenyl, terphenyl, naphthalene, anthracene, phenanthrene, pyrene, fluorene, thiophene, fluoranthene, or the like as a specific example. Or a divalent group. X ¹ to X ^{1 of the} compound represented by the general formula [1]
X ⁴ independently represents a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, and specific examples thereof include phenylene, biphenyl, terphenyl, naphthalene, anthracene, phenanthrene, pyrene, fluorene, thiophene, coronene, and chrysene. Monovalent or 2 containing skeleton
Valence groups. X ¹ and X ² , and X ³ and X ⁴ may be connected to each other. General formulas [1] and [1 ']
In the formula, ad represents an integer of 0 to 2. However, a +
b + c + d> 0.

In the present invention, R ^{1 to} R ⁴ of the organic group represented by the general formula [2] each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkyl group. Represents an aryl group or a cyano group having 6 to 20 carbon atoms. Specific examples of R ^{1 to} R ⁴ include, as a substituted or unsubstituted alkyl group, a methyl group, an ethyl group, a propyl group, a butyl group, a sec-butyl group,
t-butyl group, pentyl group, hexyl group, heptyl 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,
α-ditrifluoromethylbenzyl group, triphenylmethyl group, α-benzyloxybenzyl group and the like. Examples of the substituted or unsubstituted aryl group include a phenyl group, 2
-Methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 4-ethylphenyl group, biphenyl group,
4-methylbiphenyl group, 4-ethylbiphenyl group, 4
-Cyclohexylbiphenyl group, terphenyl group, 3,
Examples include a 5-dichlorophenyl group, a naphthyl group, a 5-methylnaphthyl group, an anthryl group, and a pyrenyl group.

In the present invention, Z of the organic group represented by the general formula [2] independently represents a substituted or unsubstituted aryl group having 6 to 20 carbon atoms. Specific examples of Z include phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, fluorenyl, pyrenyl, thiophene, phenylethenyl,
An aryl group such as a diphenylethenyl group and a triphenylethenyl group, and the aryl group may have a substituent. 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, in addition to the alkyl group and the aryl group described in R ^{1 to} R ⁴ .
There are ester groups and the like. N in the general formula [2] is 0 or 1
Represents As described above, the compounds represented by the general formulas [1] and [1 '] 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 the light emission is reduced. When added to the layer, the hole injection property to the light emitting layer is improved, and by capturing holes, the balance (quantity ratio) of electrons and holes in the light emitting layer is improved. Service life is improved. The luminous efficiency and the lifetime are improved as compared with the case where the compound [1] or [1 ′] is used alone as a light emitting layer as a single material for an organic EL device. A compound in which X ¹ and X ² and X ³ and X ⁴ are linked by a single bond or a carbon ring bond has an improved glass transition temperature and excellent heat resistance.

In the present invention, R ^{5 to} R ^{34 in the} groups represented by the general formulas [3] to [5] each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, Alternatively, it represents an unsubstituted aryl group or cyano group having 6 to 20 carbon atoms, and adjacent groups may be bonded to each other to form a saturated or unsaturated carbon ring.
Specific examples of R ^{5 to} R ³⁴ include, as a substituted or unsubstituted alkyl group, 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, a heptyl group Octyl group, stearyl group, 2-phenylisopropyl group, trichloromethyl group, trifluoromethyl group, benzyl group, α-phenoxybenzyl group, α, α-dimethylbenzyl group, α, α-
Examples include a methylphenylbenzyl group, an α, α-ditrifluoromethylbenzyl group, a triphenylmethyl group, and an α-benzyloxybenzyl group. As a substituted or unsubstituted aryl group, a phenyl group, a 2-methylphenyl group,
3-methylphenyl group, 4-methylphenyl group, 4-ethylphenyl group, biphenyl group, 4-methylbiphenyl group, 4-ethylbiphenyl group, 4-cyclohexylbiphenyl group, terphenyl group, 3,5-dichlorophenyl group, Examples include a naphthyl group, a 5-methylnaphthyl group, an anthryl group, and a pyrenyl group.

The typical examples (1) to (15) of the compounds of the general formulas [1] and [1 '] of the present invention are shown below, but the present invention is not limited to these typical examples.

[0021]

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[0022]

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[0023]

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[0024]

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The organic EL device of the present invention is a device in which one or more organic thin films are formed between an anode and a cathode. In the case of a single layer type, a light emitting layer is provided between an anode and a cathode.
The light-emitting layer contains a light-emitting material and may further contain a hole-injection material or an electron-injection material for transporting holes injected from an anode or electrons injected from a cathode to the light-emitting material. However, it is preferable that the light emitting material has extremely high fluorescence quantum efficiency, high hole transport ability and electron transport ability, and forms a uniform thin film. The multilayer organic EL device includes (anode / hole injection layer / light-emitting layer / cathode), (anode / light-emitting layer / electron injection layer / cathode),
Some of them are stacked in a multilayer structure of (anode / hole injection layer / light emitting layer / electron injection layer / cathode). General formula [1], [1 ']
And the compound of [8] have high light-emitting properties and excellent hole-injecting and hole-trapping properties, and are added to the light-emitting layer by adding 0.1 to 20% by weight as a light-emitting center. be able to.

In the light emitting layer, if necessary, in addition to the compound of the general formula [1] or [1 '] of the present invention, a further known light emitting material, doping material, hole injection material or electron injection material is used. You can also. When the organic EL element has a multilayer structure, it is possible to prevent a decrease in luminance and life due to quenching. If necessary, a combination of a light emitting material, another doping material, a hole injection material and an electron injection material can be used. Further, with other doping materials, emission luminance and emission efficiency can be improved, and red and white light can be obtained. Further, each of the hole injection layer, the light emitting layer, and the electron injection layer may be formed in a layer structure of two or more layers. In this case, in the case of a hole injection layer, a layer for injecting holes from the electrode is a hole injection layer, and a layer for receiving holes from the hole injection layer and transporting 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 the electrode is called an electron injection layer, and a layer that receives electrons from the electron injection layer and transports electrons to the light emitting layer is called an electron transport layer. Each of these layers is selected and used depending on factors such as the energy level of the material, heat resistance, and adhesion to the organic layer or the metal electrode.

The light-emitting material or host material which can be used in the light-emitting layer together with the compound of the general formula [1] or [1 '] includes 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 chelated oxinoid compounds, quinacridone, rubrene, stilbene derivatives, fluorescent dyes, and the like, but are not limited thereto. The content of the host material in the light emitting layer is essential to be larger than the compound of the general formula [1] or [1 '], and is preferably 80 to 99.9% by weight.

The hole injecting material has the ability to transport holes, has the effect of injecting holes from the anode, and has an excellent hole injecting effect on the light emitting layer or the light emitting material. A compound that prevents excitons from migrating to the electron injection layer or the electron injection material and has 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, acylhydrazone, polyaryl Alkanes, stilbene, butadiene, benzidine-type triphenylamine, styrylamine-type triphenylamine,
Diamine-type triphenylamine and the like, derivatives thereof,
And polymer materials such as polyvinyl carbazole, polysilane, and conductive polymers, but are not limited thereto.

Among the hole injecting materials that can be used in the organic EL device of the present invention, more effective hole injecting materials are
It is an aromatic tertiary amine derivative or a phthalocyanine derivative. Specific examples of the aromatic tertiary amine derivative include triphenylamine, tolylamine, tolylphenylamine, 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, and the like, or oligomers or polymers having an aromatic tertiary amine skeleton. However, the present invention is not limited to this. Specific examples of the phthalocyanine (Pc) derivative include H ₂ Pc, CuPc, CoPc, NiPc, Zn
Pc, PdPc, FePc, MnPc, ClAlPc,
ClGaPc, ClInPc, ClSnPc, Cl ₂ S
iPc, (HO) AlPc, (HO) GaPc, VOP
c, TiOPc, MoOPc, GaPc-O-GaPc
Phthalocyanine derivatives and naphthalocyanine derivatives, but are not limited thereto.

The electron injecting material has the ability to transport electrons, has the effect of injecting electrons from the cathode, has an excellent electron injecting effect on the light emitting layer or the light emitting material, and has the positive effect of excitons generated in the light emitting layer. Compounds that prevent migration to the hole injection layer and have excellent thin film forming ability are preferred. Specifically, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole,
Triazole, imidazole, perylenetetracarboxylic acid, fluorenylidenemethane, anthraquinodimethane,
Examples include, but are not limited to, anthrones and their derivatives. The electron injecting property can be improved by adding an electron accepting substance to the hole injecting material and an electron donating substance 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. A specific example of the metal complex compound is 8-
Lithium hydroxyquinolinato, 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-quinolinato) (2-naphtholate) gallium, and the like,
It is not limited to these.

The nitrogen-containing five-membered derivative is preferably an oxazole, thiazole, oxadiazole, thiadiazole or triazole derivative. In particular,
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-phenyloxadiazolyl) -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) -1,3,4-triazole, 1,4-bis [2- (5-phenyltriazolyl)
], But not limited thereto.

In the organic EL device of the present invention, in addition to the compound of the general formula [1] or [1 '], at least one of a light emitting material, a doping material, a hole injection material and an electron injection material is contained in the light emitting layer. Species may be contained in the same layer. In order to improve the stability of the organic EL device obtained according to the present invention with respect to temperature, humidity, atmosphere, and the like, a protective layer may be provided on the surface of the device, or the entire device may be protected with silicon oil, resin, or the like. Is also possible.

As the conductive material used for the anode of the organic EL device, those having a work function of more than 4 eV are suitable, and include carbon, aluminum, vanadium, iron, cobalt, nickel, tungsten, silver, gold, and platinum. , Palladium and their alloys, tin oxide used for ITO substrate, NESA substrate, metal oxide such as indium oxide,
Further, an organic conductive resin such as polythiophene or polypyrrole is 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 the like and alloys thereof are used, but not limited thereto. Representative examples of the alloy include magnesium / silver, magnesium / indium, and lithium / aluminum, but are not limited thereto. The ratio of the alloy is controlled by the temperature, atmosphere, degree of vacuum, and the like of the evaporation source, and is selected to be an appropriate ratio. The anode and the cathode may be formed by two or more layers if necessary.

In the organic EL device, it is desirable that at least one surface is sufficiently transparent in the emission wavelength region of the device in order to emit light efficiently. Further, it is desirable that the substrate is also transparent. The transparent electrode is set using the above-described conductive material so as to secure a predetermined translucency by a method such as vapor deposition or sputtering. The electrode on the light emitting surface desirably has a light transmittance of 10% or more. The substrate is not limited as long as it has mechanical and thermal strengths and is transparent, 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, and polyetheretherketone. , Polysulfone, polyethersulfone, tetrafluoroethylene-perfluoroalkylvinyl ether copolymer, polyvinyl fluoride, tetrafluoroethylene-ethylene copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, polychlorotrifluoroethylene, Polyvinylidene fluoride, polyester, polycarbonate, polyurethane, polyimide, polyetherimide,
Examples include polyimide and polypropylene.

Each layer of the organic EL device according to the present invention can be formed by any of dry film forming methods such as vacuum deposition, sputtering, plasma, and ion plating, and wet film forming methods such as spin coating, dipping and flow coating. Can be applied. The film thickness is not particularly limited, but needs to be set to an appropriate film thickness. If the film thickness is too large, a large applied voltage is required to obtain a constant light output, resulting in poor efficiency. If the film thickness is too small, 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 is more preferably in the range of 10 nm to 0.2 μm.

In the case of the wet film forming method, the material forming each layer is made of ethanol, chloroform, tetrahydrofuran,
The thin film is formed by dissolving or dispersing in a suitable solvent such as dioxane, and any solvent may be used. In any of the organic thin film layers, a suitable resin or additive may be used for improving film forming properties, preventing pinholes in the film, and the like. Examples of usable resins include insulating resins such as polystyrene, polycarbonate, polyarylate, polyester, polyamide, polyurethane, polysulfone, polymethyl methacrylate, polymethyl acrylate, and cellulose, and copolymers thereof, and poly-N-vinyl. Examples thereof include photoconductive resins such as carbazole and polysilane, and conductive resins such as polythiophene and polypyrrole.
In addition, 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 device, a practically sufficient light-emitting luminance can be obtained at a low applied voltage, the light-emitting efficiency is high, and the life is hardly caused by deterioration. It is possible to obtain an organic EL element which is long and has excellent heat resistance.

The organic EL device of the present invention can be used for a flat illuminator such as a flat panel display of a wall-mounted television, a copying machine,
It can be used for a light source such as a printer, a backlight of a liquid crystal display or instruments, a display board, a sign lamp, and the like. The material of the present invention can be used not only in organic EL devices but also in the fields of electrophotographic photoreceptors, photoelectric conversion devices, solar cells, image sensors and the like.

The primary amine represented by the general formula [6] used in the method for producing a material for an organic device of the present invention includes methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, and the like.
sec-butylamine, tert-butylamine, n-
Amylamine, isoamylamine, tert-amylamine, cyclohexylamine, n-hexylamine, heptylamine, 2-aminoheptane, 3-aminoheptane, octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine,
Primary alkylamines such as 1-tetradecylamine, pentadecylamine, 1-hexadecylamine and octadecylamine; ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane and 1,4-diaminobutane Primary alkyl diamines; aniline, o-fluoroaniline, m-fluoroaniline, p-fluoroaniline, o-toluidine, m-toluidine, p-toluidine, o-anisidine, m-anisidine, p-anisidine, 1-naphthylamine , 2-naphthylamine, 1-aminoanthracene, 2-aminoanthracene, 2-aminobiphenyl, 4-aminobiphenyl, 9-aminophenanthrene, 2-trifluoromethyltoluidine, 3-
Arylamines such as trifluoromethyltoluidine and 4-trifluoromethyltoluidine; aryldiamines such as o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, fluorenediamine and 1,8-naphthalenediamine;

[0041]

Embedded image And the like.

The secondary amine represented by the general formula [6] includes

Embedded image And the like.

The aryl halide represented by the general formula [7] is not particularly limited.
Usually, an alkyl group having 1 to 18 carbon atoms or a substituted or unsubstituted aryl group having 6 to 22 carbon atoms is used, and the aromatic ring may have a substituent. In the present invention, the aryl group includes a condensed cyclic hydrocarbon.

Specific examples of the aryl halide include bromobenzene, o-bromoanisole, m-bromoanisole, p-bromoanisole, o-bromotoluene and m-bromoanisole.
-Bromotoluene, p-bromotoluene, o-bromophenol, m-bromophenol, p-bromophenol, 2-bromobenzotrifluoride, 3-bromobenzotrilolide, 4-bromobenzotrifluoride, 1-bromo -2,4-dimethoxybenzene, 1-bromo-2,
5-dimethoxybenzene, 2-bromophenethyl alcohol, 3-bromophenethyl alcohol, 4-bromophenethyl alcohol, 5-bromo-1,2,4-trimethylbenzene, 2-bromo-m-xylene, 2-bromo-p- Xylene, 3-bromo-o-xylene, 4-bromo-o-xylene, 4-bromo-m-xylene, 5-bromo-m-xylene, 1-bromo-3- (trifluoromethoxy) benzene, 1-bromo -4- (trifluoromethoxy) benzene, 2-bromobiphenyl, 3-bromobiphenyl, 4-bromobiphenyl, 4-bromo-
Aryl bromides such as 1,2- (methylenedioxy) benzene, 1-bromonaphthalene, 2-bromonaphthalene, 1-bromo-2-methylnaphthalene, 1-bromo-4-methylnaphthalene; chlorobenzene, o-chloroanisole M-chloroanisole, p-chloroanisole, o-chlorotoluene, m-chlorotoluene, p-chlorotoluene, o-chlorophenol, m-chlorophenol, p-chlorophenol, 2-chlorobenzotrifluoride, 3 -Chlorobenzotrifluoride, 4-chlorobenzotrifluoride, 1-chloro-2,4-dimethoxybenzene, 1-chloro-2,5-dimethoxybenzene,
2-chlorophenethyl alcohol, 3-chlorophenethyl alcohol, 4-chlorophenethyl alcohol, 5-chlorophenethyl alcohol
Chloro-1,2,4-trimethylbenzene, 2-chloro-m-xylene, 2-chloro-p-xylene, 3-chloro-o-xylene, 4-chloro-o-xylene, 4-chloro-m-xylene , 5-chloro-m-xylene, 1-
Chloro-3- (trifluoromethoxy) benzene, 1-
Chloro-4- (trifluoromethoxy) benzene, 2-
Aryl chlorides such as chlorobiphenyl, 3-chlorobiphenyl, 4-chlorobiphenyl, 1-chloronaphthalene, 2-chloronaphthalene, 1-chloro-2-methylnaphthalene, 1-chloro-4-methylnaphthalene; iodobenzene, o -Iodoanisole, m-iodoanisole, p-iodoanisole, o-iodotoluene, m
-Iodotoluene, p-iodotoluene, o-iodophenol, m-iodophenol, p-iodophenol, 2-iodobenzotrifluoride, 3-iodobenzotrifluoride, 4-iodobenzotrifluoride, 1- Iodo-2,4-dimethoxybenzene, 1-iodo-2,
5-dimethoxybenzene, 2-iodophenethyl alcohol, 3-iodophenethyl alcohol, 4-iodophenethyl alcohol, 5-iodo-1,2,4-trimethylbenzene, 2-iodo-m-xylene, 2-iodo-p- Xylene, 3-iodo-o-xylene, 4-iodo-o-xylene, 4-iodo-m-xylene, 5-iodo-m-xylene, 1-iodo-3- (trifluoromethoxy) benzene, 1-iodo -4- (trifluoromethoxy) benzene, 2-iodobiphenyl, 3-iodobiphenyl, 4-iodobiphenyl, 1-iodonaphthalene, 2-iodonaphthalene, 1-iodo-2-methylnaphthalene, 1-iodo-4- Aryl iodides such as methylnaphthalene; fluorobenzene, o-fluoroanisole, -Fluoroanisole, p-fluoroanisole, o-fluorotoluene, m-fluorotoluene, p-fluorotoluene, o-fluorophenol, m-fluorophenol, p-fluorophenol, 2-fluorobenzotrifluoride, 3-fluoro Benzotrifluoride, 4-fluorobenzotrifluoride,
1-fluoro-2,4-dimethoxybenzene, 1-fluoro-2,5-dimethoxybenzene, 2-fluorophenethyl alcohol, 3-fluorophenethyl alcohol, 4-fluorophenethyl alcohol, 5-fluoro-1,2,4- Trimethylbenzene, 2-fluoro-m
-Xylene, 2-fluoro-p-xylene, 3-fluoro-o-xylene, 4-fluoro-o-xylene, 4-
Fluoro-m-xylene, 5-fluoro-m-xylene, 1-fluoro-3- (trifluoromethoxy) benzene, 1-fluoro-4- (trifluoromethoxy) benzene, 2-fluorobiphenyl, 3-fluorobiphenyl, 4-fluorobiphenyl, 4-fluoro-1,2
Aryl fluorides such as-(methylenedioxy) benzene, 1-fluoronaphthalene, 2-fluoronaphthalene, 1-fluoro-2-methylnaphthalene, 1-fluoro-4-methylnaphthalene, and the like;

[0045]

Embedded image Is mentioned.

In addition, unless departing from the object of the present invention, 1,2-dibromobenzene, 1,3-dibromobenzene, 1,4-dibromobenzene, 9,10-dibromoanthracene, 9,10-dichloroanthracene,
4,4'-dibromobiphenyl, 4,4'-dichlorodiphenyl, 4,4'-diiodobiphenyl, 1-bromo-2-fluorobenzene, 1-bromo-3-fluorobenzene, 1-bromo-4-fluoro Benzene, 2-bromochlorobenzene, 3-bromochlorobenzene, 4-bromochlorobenzene, 2-bromo-5-chlorotoluene, 3-bromo-4-chlorobenzotrifluoride, 5-
Bromo-2-chlorobenzotrifluoride, 1-bromo-
2,3-dichlorobenzene, 1-bromo-2,6-dichlorobenzene, 1-bromo-3,5-dichlorobenzene, 2-bromo-4-fluorotoluene, 2-bromo-
5-fluorotoluene, 3-bromo-4-fluorotoluene, 4-bromo-2-fluorotoluene, 4-bromo-3-fluorotoluene, tris (4-bromophenyl) amine, 1,3,5-tribromobenzene ,

[0047]

Embedded image And the like. An aryl halide having two or more, preferably two to three halogen atoms can also be used.

The method for adding an aryl halide in the method for producing a material for an organic device of the present invention is not particularly limited. For example, before starting the reaction, two different aryl halides are added simultaneously with the primary amine, and these are added. The primary amine may be reacted with one of the aryl halides, and then the other secondary halide may be added to the secondary amine to react. Since the tertiary arylamine can be produced more selectively, the latter method of sequentially adding different aryl halides is preferable.

The amount of the aryl halide to be added is not particularly limited. However, when two different aryl halides are added simultaneously with the primary amine, 0.5 mol is added to 1 mol of the primary amine. In order to facilitate post-treatment such as economical efficiency and separation of unreacted aryl halide, it is preferably 0.7 to 5 moles per 1 mole of primary amine. It is molar times. When different aryl halides are successively added, the aryl halide to be added first is added to the reaction system in a range of 0.5 to 1.5 times the mole of one amino group of the primary amine. From the viewpoint of improving the selectivity of the target tertiary arylamine, it is more preferable that the molar ratio be in the range of 0.9 mol to 1.1 mol per one amino group of the primary amine. What is necessary is just to add to a reaction system.

The aryl halide to be added after the production of the secondary amine may be added in an amount of 0.1 to 10 times the molar amount of one amino group of the primary amine used as a raw material. Since the operation of separating the aryl halide and the unreacted secondary amine becomes complicated, it is preferable to add 0.9 to 5 moles per one amino group of the primary amine.

The palladium compound used as a catalyst component in the present invention is not particularly limited as long as it is a palladium compound. For example, sodium hexachloropalladium (IV) tetrahydrate, potassium hexachloropalladium (IV), etc. Tetravalent palladium compounds; palladium (II) chloride, palladium (II) bromide, palladium (II) acetate, palladium acetylacetonate (II),
Dichlorobis (benzonitrile) palladium (II), dichlorobis (acetonitrile) palladium (II), dichloro (bis (diphenylphosphino) ethane) palladium (II), dichlorobis (triphenylphosphine) palladium (II), dichlorotetraamminepalladium (II) ), Dichloro (cycloocta-1,5-diene) palladium (II), palladium trifluoroacetate (II) and other divalent palladium compounds; tris (dibenzylideneacetone) dipalladium (0) (Pd ₂ (db
a) ₃ ), zero-valent palladium compounds such as tris (dibenzylideneacetone) dipalladium chloroform complex (0), tetrakis (triphenylphosphine) palladium (0), bis (bis (diphenylphosphino) ethane) palladium (0) And the like.

In the production method of the present invention, the amount of the palladium compound to be used is not particularly limited, but is 0.00001 to 0.1 mol in terms of palladium per mol of primary amine.
20.0 mol%. If palladium is within the above range, a tertiary arylamine can be synthesized with high selectivity,
Since an expensive palladium compound is used, it is more preferably 0.001 to 5.0 mol% in terms of palladium based on 1 mol of the primary amine.

In the production method of the present invention, the trialkylphosphine compound used as a catalyst component includes
There is no particular limitation, for example, triethylphosphine, tricyclohexylphosphine, triisopropylphosphine, tri-n-butylphosphine, triisobutylphosphine, tri-sec-butylphosphine, tri-tert-butylphosphine, and the like. Tri-tert-butylphosphine is preferred because of its activity. The triarylphosphine compound is not particularly limited, and examples thereof include triphenylphosphine, benzyldiphenylphosphine, tolylphosphine (P (Tol) ₃ ), tri-o-triylphosphine, tri-m-triylphosphine, Bird
Examples include p-triylphosphine, preferably triphenylphosphine and tri-o-triylphosphine. The diphosphine compound is not particularly limited. For example, bis (dimethylphosphino) methane, bis (dimethylphosphino) ethane, bis (dicyclohexylphosphino) methane, bis (dicyclohexylphosphino) ethane, bis (diphenylphosphino) ) Ethane, 1,3-bis (diphenylphosphino) propane,
1,4-bis (diphenylphosphino) butane, bis (diphenylphosphino) ferrocene, (R) -2,
2'-bis (diphenylphosphino) -1,1'-binaphthyl ((R) -BINAP), (S) -2,2'-bis (diphenylphosphino) -1,1'-binaphthyl ((S) -BINAP), 2,2'-bis (diphenylphosphino) -1,1'-binaphthyl ((±) -BIN
AP), 2S, 3S-bis (diphenylphosphino) butane ((S, S) -CHIRAPHOS), 2R, 3R
-Bis (diphenylphosphino) butane ((R, R)-
CHIRAPHOS), 2,3-bis (diphenylphosphino) butane ((±) -CHIRAPHOS),
(R) -2,2'-bis (di-p-triylphosphino) -1,1'-binaphthyl ((R) -Tol-BIN
AP), (S) -2,2'-bis (di-p-triylphosphino) -1,1'-binaphthyl ((S) -Tol-
BINAP), 2,2′-bis (di-p-triylphosphino) -1,1′-binaphthyl ((±) -Tol-B
INAP), 4R, 5R-bis (diphenylphosphinomethyl) -2,2-dimethyl-1,3-dioxolane ((R, R) -DIOP), 4S, 5S-bis (diphenylphosphinomethyl) -2, 2-dimethyl-1,3-
Dioxolane ((S, S) -DIOP), 4,5-bis (diphenylphosphinomethyl) -2,2-dimethyl-
1,3-dioxolane ((±) -DIOP), N, N ′
-Dimethyl- (S) -1-[(R) -1 ', 2-bis (diphenylphosphino) ferrocenyl] ethylamine ((S), (R) -BPPFA), N, N'-dimethyl- (R) -1-[(S) -1 ′, 2-bis (diphenylphosphino) ferrocenyl] ethylamine ((R),
(S) -BPPFA), N, N'-dimethyl-1-
[1 ′, 2-bis (diphenylphosphino) ferrocenyl] ethylamine ((±) -BPPFA);
Preferably bis (diphenylphosphino) ethane, 1,
3-bis (diphenylphosphino) propane, bis (diphenylphosphino) ferrocene, BINAP,
BINAP may be optically active or racemic.

The amount of the trialkylphosphine compound, triphenylphosphine compound or diphosphine compound used may be 0.01 to 10000 times the molar amount of the palladium compound. If the amount used is in this range, the selectivity of the arylamine does not change, but since an expensive phosphine compound is used, it is more preferably 0.1 to 10 times the mol of the palladium compound.

In the production method of the present invention, a palladium compound and a phosphine compound are essential as catalyst components, and both are combined and added to the reaction system as a catalyst. Regarding the method of addition, they may be added individually to the reaction system, or may be prepared in advance and added in the form of a complex.

The base that can be used in this reaction is sodium,
What is necessary is just to select from inorganic bases, such as potassium carbonate and alkali metal alkoxide, and organic bases, such as a tertiary amine,
Although not particularly limited, preferably, for example, sodium methoxide, sodium ethoxide, potassium methoxide, potassium ethoxide, lithium-tert-
Alkali metal alkoxides such as butoxide, sodium-tert-butoxide, potassium-tert-butoxide, and cesium cardinate (Cs ₂ CO ₃ ); It may be prepared in situ from an alkali metal and an alkali metal hydroxide and an alcohol and supplied to a reaction field.

The amount of the base to be used is not particularly limited, but it is preferable to use 0.5 times or more moles of the halogen atom of the two different aryl halides to be added to the reaction. If the amount of the base is less than 0.5 mol, the reaction activity is decreased, and the yield of the arylamine is decreased, which is not preferable. Even if the amount of the base is added in a large excess, the yield of the arylamine does not change, but the post-treatment operation after the completion of the reaction becomes complicated, so it is more preferably from 1.0 to 5%.
It is less than twice the molar.

The reaction in the production method of the present invention is usually carried out in an inert solvent, and any inert solvent may be used as long as it does not significantly inhibit the reaction, such as benzene, toluene, xylene and the like. Aromatic hydrocarbon solvents; ether solvents such as diethyl ether, tetrahydrofuran and dioxane; acetonitrile, dimethylformamide, dimethylsulfoxide, hexamethylphosphotriamide and the like. More preferably,
It is an aromatic hydrocarbon solvent such as benzene, toluene and xylene.

The production method of the present invention is preferably carried out under normal pressure and in an atmosphere of an inert gas such as nitrogen or argon, but can be carried out even under pressurized conditions.
In the production method of the present invention, the reaction temperature may be selected from the range of 20C to 300C, more preferably 50C to 200C, and the reaction time may be selected from the range of several minutes to 72 hours.

[0060]

The present invention will be described below in more detail with reference to Synthesis Examples and Examples. Synthesis Example 1 (Compound a) Synthesis of Intermediate A In a 500 ml three-necked flask under a stream of argon,
50 g of p-bromobenzaldehyde (0.27 mo
l), benzylphosphonic acid diethyl ester 50 g
(0.22 mmol), dimethyl sulfoxide (DMS
O) 200 milliliters were charged. Next, 30 g (0.27 mol) of potassium t-butoxide was added little by little, and the mixture was stirred and reacted at room temperature overnight. After the completion of the reaction, the reaction solution was poured into 500 ml of water and extracted with ethyl acetate. After drying over magnesium sulfate, the mixture was concentrated under reduced pressure using a rotary evaporator. The obtained crude crystals were recrystallized from 100 ml of ethyl acetate to give Intermediate A 46
g (81% yield).

Synthesis of Intermediate B Under a stream of argon, 10 g (38 mmol) of Intermediate A, 14 g (150 mmol) of aniline, 0.53 g (1.5 mol) of dipalladium tris (dibenzylideneacetone) were placed in a 300 ml three-necked flask equipped with a condenser.
%), 0.35 g of tri-o-toluylphosphine (3%
mol%), 7.4 g of sodium t-butoxide (77 m
ol) and 100 ml of dry toluene were added, and the mixture was heated and stirred at 100 ° C. overnight to react. After completion of the reaction, the precipitated crystals were collected by filtration and washed with 100 ml of methanol. The obtained crude crystals were extracted with ethyl acetate 50.
The crystals were recrystallized in milliliters to obtain 7.7 g of intermediate B (73% yield).

Synthesis of Intermediate C In a 100 ml eggplant flask equipped with a cooling tube,
Bromobenzyl bromide 12.5 g (50 mmo
1) and 12.5 (75 mmol) of triethyl phosphite were added, and the mixture was heated and stirred at 100 ° C. for 7 hours to be reacted. After completion of the reaction, excess triethyl phosphite is distilled off under reduced pressure,
15.4 g of intermediate C were obtained. Intermediate C was used for the next reaction without further purification.

Synthesis of Intermediate D 9.2 g (50 mm) of p-bromobenzaldehyde was placed in a 300 ml three-necked flask under a stream of argon.
ol), 15.4 g (50 mmol) of intermediate C, DM
100 ml of SO was charged. Next, 6.7 g (60 mmol) of potassium t-butoxide was added little by little, and the mixture was stirred and reacted at room temperature overnight. After completion of the reaction, the reaction solution was poured into 200 ml of water and extracted with ethyl acetate. After drying over magnesium sulfate, the mixture was concentrated under reduced pressure using a rotary evaporator. The obtained crude crystals were washed with 100 ml of methanol, and 13 g of intermediate D was obtained.
(77% yield).

Synthesis of Compound a In a 200 ml three-necked flask equipped with a condenser under an argon stream, 4 g (15 mmol) of Intermediate B and Intermediate D
2 g (6 mmol), 0.16 g (3 mol%) of tris (dibenzylideneacetone) dipalladium, (S)
After adding 0.22 g (6 mol%) of BINAP, 1.4 g (15 mmol) of sodium t-butoxide and 50 ml of dry toluene, the mixture was heated and stirred at 100 ° C. overnight to react. After completion of the reaction, the precipitated crystals were collected by filtration, washed with methanol, and dried by heating at 60 ° C. overnight.
The obtained crude crystals are subjected to column chromatography (silica gel,
Hexane / toluene = 8/2), yellow powder
1.4 g were obtained. This powder has NMR, IR and FD-
The powder was identified as Compound a by the measurement of MS (field desorption mass spectrum) (yield 32%: ¹ H).
Δ at _NMR (90 MHz) 7.0-7.4 ppm (4
2H, m))). FIG. 1 shows an NMR chart of the compound a. The reaction formula of compound a is shown below.

[0065]

Embedded image

Synthesis Example 2 (Compound b) Synthesis of Intermediate E In a 300 ml three-necked flask, 6 g (50 mmol) of p-tolualdehyde, 15.4 g (50 mmol) of intermediate C, and 100 ml of DMSO were charged under a stream of argon. . Next, potassium t-butoxy6.
7 g (60 mmol) was added little by little, and the mixture was stirred and reacted at room temperature overnight. After completion of the reaction, the reaction solution was poured into 200 ml of water and extracted with ethyl acetate. After drying over magnesium sulfate, the mixture was concentrated under reduced pressure using a rotary evaporator. The obtained crude crystals were washed with 100 ml of methanol to obtain 9.2 g of intermediate E (yield 67%).

Synthesis of Compound b Under a stream of argon, in a 200 ml three-necked flask equipped with a condenser, 4 g (15 mmol) of intermediate E, N, N '
-Diphenylbenzidine 2 g (6 mmol), tris (dibenzylideneacetone) dipalladium 0.16 g
(3 mol%), 0.22 g of (S) -BINAP (6
mol%), 1.4 g of sodium t-butoxide (15 m
mol) and 50 ml of dry toluene, and the mixture was heated and stirred at 100 ° C. overnight to react. After completion of the reaction, the precipitated crystals were collected by filtration and washed with methanol,
It was dried by heating at ℃ overnight. The obtained crude crystals are subjected to column chromatography (silica gel, hexane / toluene = 8/2).
And 2.5 g of a yellow powder was obtained. This powder is NM
It was identified as Compound b by measurement of R, IR and FD-MS (yield 58%: δ by ¹ H _NMR (90 MHz)).
7.0-7.4 ppm (40H, m), δ 2.34p
pm (6H, s))). FIG. 2 shows an NMR chart of the compound b. The reaction formula of compound b is shown below.

[0068]

Embedded image

Synthesis Example 3 (Compound c) Synthesis of Compound c In a 200 ml three-necked flask equipped with a condenser under an argon stream, 4 g (15 mmol) of Intermediate B and 1,4-
1.7 g (6 mmol) of dipromonaphthalene, 0.16 g of tris (dibenzylideneacetone) dipalladium
(3 mol%), 0.22 g of (S) -BINAP (6
mol%), 1.4 g of sodium t-butoxide (15 m
mol) and 50 ml of dry toluene, and the mixture was heated and stirred at 100 ° C. overnight to react. After completion of the reaction, the precipitated crystals were collected by filtration and washed with methanol,
It was dried by heating at ℃ overnight. The obtained crude crystals are subjected to column chromatography (silica gel, hexane / toluene = 8/2).
Then, 2.0 g of a yellow powder was obtained. This powder is NM
It was identified as compound c by the measurement of R, IR and FD-MS (yield 50%: δ by ¹ H _NMR (90 MHz)).
7.0-7.4 ppm (68H, m)). The reaction formula of compound c is shown below.

[0070]

Embedded image

Synthesis Example 4 (Compound d) Synthesis of Compound d In a 200 ml three-necked flask equipped with a condenser under an argon stream, 4 g (15 mmol) of Intermediate B, 9,10
-2 g (6 mmol) of dipromoanthracene, 0.16 g of tris (dibenzylideneacetone) dipalladium
(3 mol%), tri-t-butylphosphine 0.0
7 g (6 mol%), sodium t-butoxide 1.4
g (15 mmol) and 50 ml of dry toluene were added, and the mixture was heated and stirred at 100 ° C. overnight to react. After completion of the reaction, the precipitated crystals were collected by filtration, washed with methanol, and dried by heating at 60 ° C. overnight. The obtained crude crystals were purified by column chromatography (silica gel, hexane / toluene = 8/2) to obtain 1.9 g of a yellow powder. This powder was measured by NMR, IR and FD-MS,
It was identified as Compound d (44% yield: ¹ H _NMR (90 M
Hz) δ 7.0-7.4 ppm (40H,
m))). The reaction formula of compound d is shown below.

[0072]

Embedded image

Synthesis Example 5 (Compound e) Synthesis of Intermediate E Trans-4-stilbenaldehyde 10.4 was placed in a 300 ml three-necked flask under a stream of argon.
g (50 mmol), 15.4 g of intermediate C (50 mm
ol) and 100 ml of DMSO. Next, 6.7 g (60 mmol) of potassium t-butoxide was added little by little, and the mixture was stirred and reacted at room temperature overnight. After completion of the reaction, the reaction solution was poured into 200 ml of water and extracted with ethyl acetate. After drying over magnesium sulfate, the mixture was concentrated under reduced pressure using a rotary evaporator. The obtained crude crystals were washed with 100 ml of methanol to obtain an intermediate F
12.5 g (69% yield) was obtained.

Synthesis of Compound e In a 200 ml three-necked flask equipped with a condenser under an argon stream, 5.4 g (15 mmol) of intermediate F, N,
N′-diphenylbenzidine 2 g (6 mmol), tris (dibenzylideneacetone) dipalladium 0.1
6 g (3 mol%), tri-o-toluylphosphine
0.11 g (6 mol%), sodium t-butoxide
After adding 1.4 g (15 mmol) and 50 ml of dry toluene, the mixture was heated and stirred at 100 ° C. overnight to react. After completion of the reaction, the precipitated crystals were collected by filtration, washed with methanol, and dried by heating at 60 ° C. overnight. The obtained crude crystals were purified by column chromatography (silica gel, hexane / toluene = 6/4) to obtain 1.0 g of a yellow powder. This powder was identified as Compound e by NMR, IR and FD-MS measurements (yield 19%: ¹ H).
Δ 7.0-7.5 ppm (52 at _NMR (90 MHz)).
H, m)). FIG. 3 shows an NMR chart of the compound e.
The reaction formula of compound e is shown below.

[0075]

Embedded image

Synthesis of Compound f Under a stream of argon, 7.8 g (30 mmol) of intermediate A was placed in a 200 ml three-necked flask equipped with a condenser.
1.7 g of 4'-diaminostilbene carbon dioxide (6
mmol), 0.16 g (3 mol%) of tris (dibenzylideneacetone) dipalladium, (S) -BINA
0.22 g (6 mol%) of P, 9.6 g (0.1 mol) of sodium t-butoxide and 50 parts of dry toluene
After adding milliliter, the mixture was heated and stirred at 100 ° C. overnight to react. After completion of the reaction, the precipitated crystals were collected by filtration, washed with methanol, and dried by heating at 60 ° C. overnight. The obtained crude crystals were purified by column chromatography (silica gel, hexane / toluene = 6/4) to obtain 2.0 g of a yellow powder. This powder was identified as compound f by NMR, IR and FD-MS measurements (36% yield: ¹ H _NMR).
(90 MHz) δ 7.0 to 7.5 ppm (54
H, m)). The reaction formula of compound f is shown below.

[0077]

Embedded image

Example 1 The following compound (TPD74) as a hole injection material was vacuum-deposited to a thickness of 60 nm on a washed glass plate with an ITO electrode.

Embedded image Next, the following compound (NPD) was used as a hole transport material to a thickness of 2
Vacuum deposited to 0 nm.

Embedded image Next, a stilbene derivative 4,4′-bis (2,2-diphenylvinyl) biphenyl (DPVB) was used as a light emitting material.
i) and the above compound (a), when the ratio of the compound (a) is 2
Co-evaporation was performed so that the weight% and the film thickness became 40 nm. still,
Compound (a) functions as a fluorescent dopant or luminescent center. Next, the following compound (Al
q)

Embedded image Is deposited in a thickness of 20 nm, and LiF is further deposited in a thickness of 0.5 n.
After depositing with m, aluminum was deposited to a thickness of 100 nm to form an electrode to obtain an organic EL device. Each layer was deposited at a substrate temperature of room temperature in a vacuum of 10 ^-6 Torr. The luminous characteristics of this device are such that a luminous luminance of 10 at a DC voltage of 6 V is applied.
0 (cd / m ² ), and the luminous efficiency was 2.1 (lm / W). The chromaticity coordinates were (0.146, 0.140), and blue light emission with high purity was possible. In addition, initial light emission luminance 200
(Cd / m ² ), the half life was 20 when driven at a constant current.
The life was as long as 00 hours. Table 1 shows these light emission characteristics. The energy gap of compound a is 2.78 e.
V and DPVBi were 3.0 eV.

Example 2 An organic EL device was produced in the same manner as in Example 1 except that the above compound b was used as a dopant or a luminescent center. The light-emitting characteristics of this device were such that a light-emitting luminance of 110 (cd / m ² ) and a light-emitting efficiency of 1.3 (lm) were obtained by applying a DC voltage of 6 V.
/ W). The chromaticity coordinates are (0.152, 0.16
3) and high-purity blue light emission became possible. In addition, the half-life was 1500 hours when the device was driven at a constant current at an initial luminance of 200 (cd / m ² ). Table 1 shows these light emission characteristics. In addition, the energy gap of compound b was 2.90 eV, and DPVBi was 3.0 eV.

Example 3 An organic EL device was produced in the same manner as in Example 1 except that the above compound c was used as a dopant or a luminescent center. The light-emitting characteristics of this device are such that a light-emitting luminance is 130 (cd / m ² ) and a light-emitting efficiency is 2.1 (lm) when a DC voltage of 6 V is applied.
/ W). The chromaticity coordinates are (0.162, 0.18
1) Blue light emission with high purity was made possible. In addition, when the device was driven at a constant current at an initial luminance of 200 (cd / m ² ), the half-life was 2800 hours, which was a long life. Table 1 shows these light emission characteristics. In addition, the energy gap of compound c was 2.83 eV, and DPVBi was 3.0 eV.

Example 4 An organic EL device was produced in the same manner as in Example 1 except that the above compound d was used as a dopant or a luminescent center. The light-emitting characteristics of this device are such that a light-emitting luminance is 300 (cd / m ² ) at a DC voltage of 6 V and a light-emitting efficiency is 4.6 (lm).
/ W), high-efficiency green light emission became possible. In addition, when driven at a constant current at an initial luminance of 200 (cd / m ² ), the half life was 3400 hours, which was a long life. Table 1 shows these light emission characteristics. In addition, the energy gap of compound d was 2.78 eV, and DPVBi was 3.0 eV.

Comparative Example 1 An organic EL device was prepared in the same manner as in Example 1, except that the following compound (TPD) was used as a dopant or a luminescent center.

Embedded image Regarding the light emission characteristics of this element, sufficient performance such as a light emission luminance of 60 (cd / m ² ) and a light emission efficiency of 0.7 (lm / W) at an applied voltage of DC voltage of 5 V could not be obtained. TPD did not function as a light emission center, and thus light emission from DPVTP was obtained.
When driven at a constant current with an initial light emission luminance of 200 (cd / m ² ), the half-life was as short as 100 hours. Table 1 shows these light emission characteristics. The energy gap of TPD was 3.10 eV, and DPVBi was 3.0 eV.

Comparative Example 2 The above compound a was used as a dopant or a luminescent material.
Except that the above compound (Alq) was used as a material,
An organic EL device was manufactured in the same manner as in Example 1. This element
The light emission characteristics of the element are as follows.
10 (cd / m ^Two) And luminous efficiency of 1.3 (lm / W).
However, only pink emission of Alq was obtained. Also, the first
Initial luminance 200 (cd / m^Two) With constant current drive
The half life was short, 200 hours. These luminescence
Table 1 shows the characteristics. Compound a functions as a luminescent center
did not exist. The energy gap of the compound a is 2.
95 eV and Alq were 2.7 eV.

Comparative Example 3 An organic EL device was manufactured in the same manner as in Example 1 except that the above compound c was used as a single light emitting material without using a dopant or a light emitting material. The light emission characteristics of this element were such that a light emission luminance of 40 (cd / m
² ) Sufficient performance with a luminous efficiency of 0.9 (lm / W) was not obtained. When the device was driven at a constant current with an initial light emission luminance of 200 (cd / m ² ), the half life was short, that is, 180 hours. Table 1 shows these light emission characteristics.

[0085]

[Table 1]

As shown in Table 1, Examples 1 to 5 in which a very small amount (1 to 20% by weight) of the compound represented by the above general formula [1] was added to the host material as a dopant or an emission center.
The organic EL device of No. 3 had higher luminous efficiency and a longer life than Comparative Examples 1 to 3.

[0087]

As described in detail above, a material for an organic electroluminescent device comprising the compound represented by the above general formula [1] of the present invention or a novel compound represented by the above [1 '] is used as a dopant or The organic electroluminescent element used as the luminescent center can obtain practically sufficient luminous brightness at a low applied voltage, has high luminous efficiency, has a long life, and its performance is not easily deteriorated even when used for a long time. In addition, when an organic element material is produced by the method of the present invention, a highly active organic electroluminescent element material having high luminous efficiency, long life, and high activity can be produced with a small amount of impurities and a high yield.

[Brief description of the drawings]

FIG. 1 shows ¹ H of compound a synthesized by the production method of the present invention.
_{It is an NMR} chart.

FIG. 2 shows ¹ H of compound b synthesized by the production method of the present invention.
_{It is an NMR} chart.

FIG. 3 shows ¹ H of compound e synthesized by the production method of the present invention.
_{It is an NMR} chart.

Claims (11)

[Claims] 1. An organic electroluminescent 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 made of a compound represented by the following general formula [1]. An organic electroluminescence device comprising 0.1 to 20% by weight of a material for an organic electroluminescence device based on a light emission center. General formula [1] [In the formula, A is a substituted or unsubstituted carbon atom having 6 to 21 carbon atoms.
Represents an arylene group. X ^{1 to} X ⁴ each independently represent a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, and X ¹ and X ² , and X ³ and X ⁴ may be connected to each other. Y ^{1 to} Y ⁴ each independently represent an organic group represented by the following general formula [2]. a to d represent an integer of 0 to 2. However, a + b + c + d> 0. 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,
It represents a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, a cyano group, or a triple bond in which R ¹ and R ² or R ³ and R ⁴ are bonded. Z represents a substituted or unsubstituted aryl group having 6 to 20 carbon atoms. n represents 0 or 1. )] 2. 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 material is selected from a hole injection material, a hole transport material, and an electron transport material. An organic electroluminescent device characterized in that each of the at least one selected material independently contains 0.1 to 20% by weight of the material for an organic electroluminescent device represented by the general formula [1] according to claim 1. Luminescent element. 3. An organic electroluminescence device comprising a light-emitting layer or a plurality of organic compound thin films including the light-emitting layer formed between a pair of electrodes, wherein the light-emitting layer is a stilbene derivative and a compound represented by the general formula [1] 1) An organic electroluminescence device comprising a layer containing the material for an organic electroluminescence device shown in 1). 4. The method according to claim 1, wherein a layer containing an aromatic tertiary amine derivative and / or a phthalocyanine derivative is formed between the light emitting layer and the anode. Organic electroluminescent element. 5. The organic compound according to claim 1, wherein A in the general formula [1] is a group represented by the following general formula [3] or [4]. Electroluminescence element. General formula [3] General formula [4] (Wherein, R ^{5 to} R ²⁴ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms,
Represents a substituted or unsubstituted aryl group or cyano group having 6 to 20 carbon atoms, and adjacent groups may be bonded to each other to form a saturated or unsaturated carbon ring. ) 6. The compound according to claim 1, wherein A in the general formula [1] is a group represented by the following general formula [5].
6. The organic electroluminescence device according to any one of items 1 to 5, General formula [5] (Wherein, R ^{25 to} R ³⁴ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms,
Represents a substituted or unsubstituted aryl group having 6 to 20 carbon atoms or a cyano group, and adjacent groups may be bonded to each other to form a saturated or unsaturated carbon ring. ) 7. The energy gap of the material for an organic electroluminescence device represented by the general formula [1] is 0.07 eV higher than the energy gap of the host material.
The organic electroluminescent device according to claim 1, wherein the organic electroluminescent device is small. 8. A novel compound represented by the following general formula [1 ′]. General formula [1 '] [In the formula, A represents a group represented by the following general formula [5]. X
^{1 to} X ⁴ each independently represent 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. 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. Where a
+ B + c + d> 0. General formula [5] (Wherein, R ^{25 to} R ³⁴ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms,
Represents a substituted or unsubstituted aryl group having 6 to 20 carbon atoms or a cyano group, and adjacent groups may be bonded to each other to form a saturated or unsaturated carbon ring. ) 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,
It represents a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, a cyano group, or a triple bond in which R ¹ and R ² or R ³ and R ⁴ are bonded. Z represents a substituted or unsubstituted aryl group having 6 to 20 carbon atoms. n represents 0 or 1. )] 9. In the presence of a catalyst comprising a phosphine compound and a palladium compound and a base, the following general formula [6] R (NR′H) _k [6] (where k represents an integer of 1 to 3, When k is 1, R and R ′ represent a hydrogen atom, an alkyl group or a substituted or unsubstituted aryl group, and when k is 2 or more, R is an alkylene group or a substituted or unsubstituted arylene group, and R ′ is a hydrogen atom , An alkyl group or a substituted or unsubstituted aryl group) and a primary or secondary amine represented by the following general formula [7] Ar (X) _m [7] (where Ar is substituted or unsubstituted) X represents an aryl group
Represents F, Cl, Br or I, and m represents an integer of 1 to 3. However, at least one of R, R 'and Ar contains a styryl group, and when k is 2, the R' substituted with N may be different. A) producing an organic device material comprising an arylamine compound by reacting the compound with an aryl halide represented by the formula (1). 10. The method for producing a material for an organic device according to claim 9, wherein the arylamine compound is a compound represented by the following formula [8]. General formula [8] [Wherein A is a substituted or unsubstituted carbon atom having 6 to 60 carbon atoms.
Represents an arylene group. X ^{1 to} X ⁴ each independently represent a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, and X ¹ and X ² , and X ³ and X ⁴ may be connected to each other. Y ^{1 to} Y ⁴ each independently represent an organic group represented by the following general formula [2]. a to d represent an integer of 0 to 2. However, a + b + c + d> 0. 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,
It represents a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, a cyano group, or a triple bond in which R ¹ and R ² or R ³ and R ⁴ are bonded. Z represents a substituted or unsubstituted aryl group having 6 to 20 carbon atoms. n represents 0 or 1. )] 11. The phosphine compound according to claim 9, wherein the compound is a trialkylphosphine compound, a triarylphosphine compound or a diphosphine compound.
3. The method for producing a material for an organic element according to item 1.