JP2001131541A - Material for organic electroluminescent element and electroluminescent element using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a material for organic electroluminescent(EL) elements that has high luminous efficiency, high heat resistance and long durability and the organic EL elements using the same. SOLUTION: The objective material for organic EL elements are represented by general formula 1 [A is a substituted or unsubstituted 22-60C arylene; X1 to X4 are independently a substituted or unsubstituted 6-30C arylene where X1 and X2 or X3 and X4 may link to each other, respectively; Y1 to Y4 independently represent general formula 2; a to d are each an integer of 0-2 where a+b+c+d>0 in the case of A<=26 and the number of anthracene nucleus is 1 or 0; (In general formula 2, R1 to R4 are independently H, a substituted or unsubstituted 1-20C alkyl, a substituted or unsubstituted 6-20C aryl, cyano, or R1 and R2 or R3 and R4 bond to form a triple bond; Z is a substituted or unsubstituted 6-20C aryl; n represents 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, a high heat resistance and a long life, and a material for an organic electroluminescent element. The present invention relates to an organic electroluminescence device used.

[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. Also, JP-A-8-199162 discloses that
An EL device in which a light emitting layer contains a fluorescent dopant composed of an amine or diamine derivative is disclosed. 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. Furthermore, Japanese Patent Application Laid-Open No. 9-268284 discloses a material for an EL device having a phenylanthracene group. However, when used at a high temperature for a long time, the emission luminance is greatly reduced and the heat resistance is insufficient. These devices do not emit orange to red light, and red light is indispensable for full color EL devices.
A device that emits red light has been desired.

[0003]

DISCLOSURE OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and it is an object of the present invention to provide a material for an organic electroluminescence device having high luminous efficiency, long life and high heat resistance. It is an object of the present invention to provide an organic electroluminescence device using the same.

[0004]

Means for Solving the Problems The present inventors have conducted intensive studies to develop a material for an organic electroluminescent device having the above-mentioned preferable properties and an organic electroluminescent device using the same. It has been found that the object can be achieved by using the compound represented by [1]. The present invention has been completed based on such findings.

That is, the material for an organic electroluminescent device of the present invention (hereinafter referred to as a material for an organic EL device) comprises:
It is a compound represented by the following general formula [1]. General formula [1]

Embedded image [In the formula, A is a substituted or unsubstituted carbon atom having 22 to 6 carbon atoms.
Represents an arylene group of 0. X ^{1 to} X ⁴ each independently represent a substituted or unsubstituted arylene group having 6 to 30 carbon atoms. 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, when A has 26 or less carbon atoms, a + b + c + d> 0, and A does not include two or more anthracene nuclei. 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. )]

[0006] The material for an organic EL device of the present invention may be a compound represented by the following general formula [3]. General formula [3]

Embedded image [Wherein B 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. 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, at least one of B, X ¹ , X ² , X ³ and X ⁴ contains a chrysene nucleus. ]

The above general formula [3] is represented by the following general formula [4],
[5] or [6] is preferable. General formula [4]

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

The general formula [5]

Embedded image [Wherein, B, X ¹ -X ² , Y ¹ -Y ² and a-b are each independently the same as in the above general formula [3]. ]

The general formula [6]

Embedded image [Wherein, B, X ¹ -X ² , Y ¹ -Y ² and a-b are each independently the same as in the above general formula [3]. ]

The material for an organic EL device of the present invention may be a compound represented by the following general formula [7]. General formula [7]

Embedded image[Wherein D contains a tetracene nucleus or a pentacene nucleus
Represents a divalent group. X ¹~ X^FourAre, independently of each other,
Substituted or unsubstituted arylene having 6 to 30 carbon atoms
X represents a group¹And X^Two, X^FourAnd X^ThreeAre connected to each other
You may. Y¹~ Y^FourIs, independently of each other,
Represents an organic group represented by [2]. ad is an integer of 0 to 2
Represents ]

The above general formula [7] is preferably the following general formula [8].

Embedded image In the formula, X ^{1 to} X ⁴ , Y ^{1 to} Y ⁴ and a to d are each independently the same as in the above general formula [7]. R ^{51 to} R ⁶⁰
Each independently represents 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 linked to each other to form a saturated or unsaturated carbon ring. ]

The material for an organic EL device of the present invention has the following general formula:

The compound represented by [9] may be used. General formula

[9]

Embedded image [In the formula, E represents a divalent group comprising an aryl group-substituted or unsubstituted anthracene nucleus. X ^{5 to} X ⁸ each independently represent a substituted or unsubstituted arylene group having 6 to 20 carbon atoms, and X ⁵ and X ⁶ , and X ⁷ and X ⁸ may be connected to each other. Y ^{1 to} Y ⁴ are each independently:
Represents an organic group represented by the general formula [2]. ad is 0
Represents an integer of ２2. However, E is unsubstituted

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

Embedded image including. ]

The material for an organic EL device of the present invention has the following general formula:

The compound represented by [9] may be used. General formula [10]

Embedded image [Wherein, Ar ¹ and Ar ³ each independently represent a substituted or unsubstituted phenylene, a substituted or unsubstituted 1,3
Naphthalene, substituted or unsubstituted 1,8 naphthalene,
Represents a divalent group consisting of a substituted or unsubstituted fluorene or a 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, 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. X ^{5 to} X ⁸ each independently represent a substituted or unsubstituted arylene group having 6 to 20 carbon atoms, and X ⁵ and X ⁶ , and X ⁷ and X ⁸ may be connected to each other. Y ^{1 to} Y ⁴ are each independently represented by the above general formula [2]
Represents an organic group represented by a to d represent integers of 0 to 2, and a + b + c + d ≦ 2. e is 0 or 1, f
Represents 1 or 2. However, when Ar ² is an anthracene nucleus, a = b = c = d and the case where both Ar ¹ and Ar ³ are p-phenylene groups is excluded. ]

The materials for organic EL devices represented by the general formulas [1] and [3] to [10] can also be used as light emitting materials for organic electroluminescence devices. An organic electroluminescence device (hereinafter, referred to as an organic EL device) of the present invention is 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 at least one of the organic electroluminescence devices has the general structure described above. This is a layer containing the organic EL element materials represented by the formulas [1] and [3] to [10]. The above-mentioned organic EL element is obtained by converting the material for an organic EL element represented by the general formulas [1] and [3] to [10] into at least one kind 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 above-mentioned organic EL device is prepared by using the above general formulas [1], [3] to [10]
The organic EL device material represented by
It is preferable that the content be contained by weight. The organic EL element is
The organic EL element materials represented by the general formulas [1], [3] to [10] are independently added to at least one kind of material selected from a hole injection material, a hole transport material, and a doping material. Is preferably 0.1 to 20% by weight. The light emitting layer is preferably a layer containing a stilbene derivative and a material for an organic EL device represented by the general formulas [1], [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.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, A of the compound represented by the general formula [1] represents a substituted or unsubstituted arylene group having 22 to 60 carbon atoms, and specific examples thereof include biphenyl, terphenyl, naphthalene, Examples include a divalent group formed from anthracene, phenanthrene, pyrene, fluorene, thiophene, coronene, fluoranthene, or the like, or a plurality of these linked to each other. X ^{1 to} X of the compound represented by the general formula [1]
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 skeleton. And a monovalent or divalent group containing X ¹ and X ² , and X ³ and X ⁴ may be connected to each other. The groups to be substituted on 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, and a carbon atom having 6 carbon atoms.
To 20 aryl groups, but excluding an aryloxy group, an arylthio group, an arylalkyl group, an arylketone group and the like as substituents. Compounds containing these excluded substituents are liable to be thermally decomposed at the time of vapor deposition, and the life of the light-emitting element is also inferior. In the general formula [1], a to
d represents an integer of 0 to 2. However, A has 26 carbon atoms.
In the following cases, a + b + c + d> 0, and A does not include two or more anthracene nuclei.

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] is a substituted or unsubstituted carbon atom having 6 to 20 carbon atoms.
Represents an aryl group. Specific examples of Z include a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a fluorenyl group, a pyrenyl group,
An aryl group such as a thiophene group, and the aryl group may have a substituent. Specific examples of the substituent include R ¹ to
In addition to the alkyl and aryl groups described for R ⁴ ,
Examples include an alkoxy group, an amino group, a cyano group, a hydroxyl group, a carboxylic acid group, an ether group, and an ester group. General formula [2]
N represents 0 or 1. As described above, since 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 terminal, the ionization energy becomes 5.6 eV or less, and holes are 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 becomes 2.5 eV or more due to the polyphenyl structure at the center, and electrons are easily injected. further,
Since the structure A has 22 or more carbon atoms, an amorphous thin film can be easily formed, and the glass transition temperature is 100 ° C. or more, which is excellent in heat resistance. When the structure A contains two or more anthracene nuclei, the compound [1] may be thermally decomposed. 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.

The compounds represented by the general formulas [3] to [6] in the present invention.
B of the compound to be prepared is the number of substituted or unsubstituted carbon atoms
Represents an arylene group of 6 to 60;
, Terphenyl, naphthalene, anthracene, phena
Nthrene, pyrene, fluorene, thiophene, corone
Or fluoranthene, etc.
And a divalent group formed by connecting a plurality of groups to each other.
You. Also, X¹~ X^Four, Y ¹~ Y^FourAnd ad are above
The same as in the general formula [1]. However, B, X¹, X ^Two,
X^ThreeOr X^FourOne contains a chrysene nucleus.

As described above, the general formula [3] of the present invention is used.
Compounds represented by (6) to (6) have a diamine structure at the center.
Having a styrylamine structure at the terminal
Energy becomes 5.6 eV or less and holes are injected.
Quick, hole mobility is 10^-Fourm ^Two/ V · s or more and holes
Excellent as injection material and hole transport material. Also, B,
X¹, X^Two, X^ThreeOr X^FourKu included in any one of
The licene nucleus improves durability and heat resistance. This
And can be driven for a long time.
A movable organic EL element is obtained. In addition, the general formula
Uses the compounds of [3] to [6] as doping materials
Then, the life of the organic EL element is extended, and
When used, the luminous efficiency is improved.

In the present invention, the compound represented by the general formula [7]
D in the compound is a substituted or unsubstituted tetracene nucleus or
Represents a divalent group containing a pentacene nucleus.
Biphenyl, naphthalene, anthracene, phenanthate
Selected from among len, fluorene and thiophene
At least one species and a tetracene or pentacene nucleus
And a divalent group formed by several linkages. Also,
X¹~ X^Four, Y¹~ Y ^FourAnd ad are the above general formulas
Same as [1]. Where X¹And X^Two, X^FourAnd X^Three
May be connected to each other.

X ^{1 to} X ⁴ , Y ^{1 to} Y ⁴ and a to d of the compound represented by the general formula [8] in the present invention are each independently the same as in the above general formula [1]. R ^{51 to} R
⁶⁰ is 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 alkoxy group having 6 to 20 carbon atoms. 20 represents an aryl group or a cyano group. Adjacent R ^{51 to} R ⁶⁰ may be linked to each other to form a saturated or unsaturated, substituted or unsubstituted carbon ring. The groups used for the above substitution in the general formula [7] or [8] each independently have 1 to 2 carbon atoms.
An alkyl group of 0, an alkoxy group having 1 to 20 carbon atoms,
An aryl group having 6 to 20 carbon atoms is shown, but an aryloxy group, an arylthio group, an arylalkyl group, an aryl ketone group, or the like is excluded as a substituent. Compounds containing these substituents are liable to be thermally decomposed at the time of vapor deposition, and the life of the light-emitting element is inferior.

As described above, the general formula [7] in the present invention is used.
Has strong fluorescence in the orange to red region by having a tetracene or pentacene structure. Further, by having a diamine structure, holes are easily injected, and when this compound is contained in the light emitting layer,
Holes are easily captured, and electrons and holes are easily recombined.
Therefore, a highly efficient yellow, orange, or red light-emitting element can be obtained. In particular, when the compound represented by the general formula [7] is used as a doping material, the light-emitting element has a long life and unprecedented stability can be obtained.

General formula in the present invention

Chemical represented by [9]
E of the compound is an aryl-substituted or unsubstituted anthra
Represents a divalent group comprising a sen nucleus. X^Five~ X⁸Each
Independently of each other, substituted or unsubstituted C 6-20
Represents an arylene group, specific examples of which include phenylene and biphenyl
Nil, terphenyl, naphthalene, anthracene,
1 containing nanthrene, fluorene, thiophene skeleton
And divalent or divalent groups. Also, X^FiveAnd X⁶, X⁷
And X⁸May be connected to each other. Y¹~ Y ^FourAnd a
To d are the same as those in the general formula [1]. Where E is
Unsubstituted

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

Embedded image including.

Thus, the general formula of the present invention

[9]
The compound represented by has a diamine structure, has an ionization energy of 5.6 eV or less, easily injects holes, and has a hole mobility of 10 ^-4 m ² / V · s or more.
Excellent as a hole injection material and a hole transport material. Also,
By having a substituted or unsubstituted anthracene nucleus at the center, electrons can be easily injected. Further, when the central anthracene nucleus E is unsubstituted, the glass transition temperature becomes as low as 100 ° C. or lower, and thus the glass is obtained by performing at least two aryl group substitutions, preferably 2 to 4 substitutions as described above. The transition temperature is improved. Also, such a specific biphenyl structure has the general formula

The solubility of the compound represented by [9] is increased to facilitate purification. When there is a phenyl group at the para-position other than the above structure, purification is difficult, impurities increase, and the characteristics of the obtained organic EL device deteriorate. Further, by such aryl group substitution, formation of association pairs between molecules is suppressed, the fluorescence quantum efficiency is improved, and the luminous efficiency of the organic EL device is improved.

In the present invention, Ar ¹ and Ar ^{3 in the} compound represented by the general formula [10] each independently represent a substituted or unsubstituted phenylene, a substituted or unsubstituted 1,3
Naphthalene, substituted or unsubstituted 1,8 naphthalene,
Represents a divalent group consisting of a substituted or unsubstituted fluorene or a 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, 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,

[0026]

Embedded image

[0027]

Embedded image Is mentioned.

X ^{5 to} X ⁸ and Y ^{1 to} Y ⁴ are each independently the above-mentioned general formula

Same as [9]. a to d represent integers of 0 to 2, and a + b + c + d ≦ 2. e represents 0 or 1, and f represents 1 or 2. Where Ar
^{When 2} is an anthracene nucleus, a = b = c = d and the case where both Ar ¹ and Ar ³ are p-phenylene groups is excluded.

As described above, the general formula [1]
The compound represented by formula [0] has a diamine structure, so that the ionization energy is 5.6 eV or less, holes are easily injected, the hole mobility is 10 ^-4 m ² / V · s or more, and the hole injection material It is excellent as a hole transport material, particularly as a light emitting material. In addition, the polyphenyl structure containing a condensed ring at the center facilitates injection of electrons. Further, by having both a polyphenyl structure and a diamine structure, a stable amorphous thin film can be formed, and the glass transition temperature is 100 ° C. or higher, and the heat resistance is excellent. Further, the structure of the general formula [2] is
If more than one is included, it is necessary to satisfy a + b + c + d ≦ 2 because it is thermally decomposed by vapor deposition when forming a thin film. Ar
^{When 2} is an anthracene nucleus, by making Ar ¹ and Ar ³ have the specific structure as described above, thermal decomposition of the compound and oxidation during vapor deposition can be avoided.

Hereinafter, typical examples (1) to (28) of the compounds of the general formula [1] and typical examples (29) to (56) of the compounds of the general formulas [3] to [6] of the present invention will be described. Representative examples (57) to (74) of the compound of the formula [7], representative examples (75) to (86) of the compound of the general formula [8], a general formula

Representative examples (87) to (104) of the compound of [9] and representative examples (105) to (126) of the compound of the general formula [10] are shown, but the present invention is not limited to these representative examples. Absent.

[0031]

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The general formulas [1], [3] to [10] of the present invention
The compound represented by has strong fluorescence in the solid state due to the connection between the polyphenyl structure of the center A or B and the amine structure, has excellent electroluminescence, and has a fluorescence quantum efficiency of 0.3 or more. is there. In addition, the compounds represented by the general formulas [7] and [8] have yellow,
In the orange or red fluorescent region, it has strong fluorescence in a solid state or a dispersed state, and also has excellent electroluminescence. Further, the compounds represented by the general formulas [1] and [3] to [10] of the present invention have excellent hole injecting property and hole transporting property from a metal electrode or an organic thin film layer, and a metal electrode or an organic thin film layer. Since it has excellent electron injecting and electron transporting properties, it can be used effectively as a light emitting material.Furthermore, using a hole transporting material, an electron transporting material or a doping material I can't wait.
In particular, when the compounds represented by the general formulas [7] and [8] are used as a doping material, they serve as recombination centers of electrons and holes, so that red-type highly efficient light emission 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 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, since the light emitting material of the present invention has extremely high fluorescence quantum efficiency, high hole transporting ability and electron transporting ability and can form a uniform thin film, a light emitting layer is formed only with the light emitting material of the present invention. It is also possible. The multilayer type organic EL device includes (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 / (Cathode). Since the compounds of the general formulas [1] and [3] to [8] have high light-emitting properties and excellent hole-injecting properties, hole-transporting properties, electron-injecting properties and electron-transporting properties, It can be used for the light emitting layer as a material.

In the light emitting layer, 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, electron injection materials, etc. Materials can also be used. Organic EL elements
With a multi-layer structure, a decrease in luminance and life due to quenching can be prevented. If necessary, a combination of a light emitting material, a doping material, a hole injection material, and an electron injection material can be used. Further, with the use of the doping material, emission luminance and emission efficiency can be improved, and red and blue light emission 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 doping material which can be used in the light emitting layer together with the compounds of the general formulas [1] and [3] to [10] includes anthracene, naphthalene, phenanthrene, pyrene, tetracene, coronene, chrysene, fluorescein, perylene, Phthaloperylene, 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, diamino Examples include, but are not limited to, carbazole, pyran, thiopyran, polymethine, merocyanine, imidazole chelated oxinoid compounds, quinacridone, rubrene, stilbene derivatives, and fluorescent dyes. In particular, luminescent materials or doping materials that can be used in the luminescent layer together with the compounds [7] and [8] include quinoline metal complexes and stilbene derivatives.

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 injection materials that can be used in the organic EL device of the present invention, more effective hole injection 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, and has an excellent effect of injecting electrons into the light emitting layer or the light emitting material. 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 injecting 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 five-membered nitrogen-containing 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 compounds of the general formulas [1] and [3] to [8], a light emitting material, a doping material, a hole injection material and an electron injection material are provided in the light emitting layer. 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 element, a material having a work function of more than 4 eV is suitable, and carbon, aluminum, vanadium, iron, cobalt, nickel, tungsten, silver, gold, 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. As the transparent resin film, 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-perfluoroalkylvinyl ether copolymer, polyvinyl fluoride, tetrafluoroethylene-ethylene copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, polychlorotrifluoroethylene, Polyvinylidene fluoride, polyester, polycarbonate, polyurethane, polyimide, polyetherimide,
Examples include polyimide and polypropylene.

The layers 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 an 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 deteriorated. 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 light-emitting body 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.

[0083]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in more detail with reference to embodiments. Example 1 The above compound (2), 2,5-bis (1-naphthyl)-as a luminescent material was placed on a washed glass plate with an ITO electrode.
1,3,4-oxadiazole and a polycarbonate resin (Teijin Kasei: Panlite K-1300) were dissolved in tetrahydrofuran at a weight ratio of 5: 3: 2, and a 100 nm-thick light emitting layer was obtained by spin coating. . An electrode having a thickness of 150 nm was formed thereon using an alloy obtained by mixing aluminum and lithium at a ratio of 3% by weight of lithium to obtain an organic EL device. The light-emitting characteristics of this element are as follows: DC voltage 5 V
Emission luminance 200 (cd / m ² ) at the applied voltage of 1 and maximum luminance 1
Light emission of 4000 (cd / m ² ) and luminous efficiency of 2.1 (lm / W) was obtained.

Example 2 The above compound (9) was vacuum-deposited as a luminescent material on a washed glass plate with an ITO electrode to form a luminescent layer having a thickness of 100 nm. An electrode having a thickness of 100 nm was formed from an alloy mixed at a ratio of 100% to obtain an organic EL device. Emitting layer is 10 ^-6 T
Vapor deposition was performed at a substrate temperature of room temperature in a vacuum of orr. The light emission characteristics of this element are such that a light emission luminance of 110 (cd / m ² ) and a maximum luminance of 20,000 (c) are obtained by applying a DC voltage of 5 V.
d / m ² ) and luminescence efficiency of 2.1 (lm / W) was obtained.

Example 3 The above compound (2) as a luminescent material was vacuum-deposited on a washed glass plate with an ITO electrode to form a luminescent layer having a thickness of 50 nm. Then, the following compound (Alq)

Embedded image Was vacuum-deposited to form an electron injection layer having a thickness of 10 nm, and an electrode having a thickness of 100 nm was formed thereon by 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 are 10 ^-6
Vapor deposition was performed in a Torr vacuum at a substrate temperature of room temperature. The light emission characteristics of this element are such that a light emission luminance of about 600 (cd / m ² ) and a maximum luminance of 30000 are obtained at an applied voltage of 5 V DC.
(Cd / m ² ) and blue-green light emission with a luminous efficiency of 3.0 (lm / W) were obtained. Furthermore, initial light emission luminance 600 (cd / m ² )
The half-life was as long as 2000 hours when driven at a constant current.

Examples 4 to 16 The luminescent materials shown in Table 1 were vacuum-deposited on the cleaned glass plate with ITO electrodes to obtain a luminescent layer having a thickness of 80 nm. Further, the above compound (Alq) was 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 were mixed at a ratio of 3% by weight of lithium was formed thereon. An electrode having a film thickness was formed to obtain an organic EL device. Each layer was deposited at a substrate temperature of room temperature in a vacuum of 10 ^-6 Torr. Table 1 shows the emission characteristics of this device. Further, the organic EL element of this embodiment
All had high luminance characteristics of 10000 (cd / m ² ) or higher.

[0087]

[Table 1]

Example 17 The following compound (TPD74) as a hole injecting material was vacuum-deposited to a thickness of 60 nm on a washed glass plate with ITO electrodes.

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

Comparative Example 1 An organic EL device was produced in the same manner as in Example 1, except that the following compound (Comparative Example 1) was used as a light emitting material.

Embedded imageThe light emission characteristics of the obtained device were measured by applying a DC voltage of 5 V.
Light emission luminance 60 (cd / m ^Two), Luminous efficiency 0.34 (lm /
W) and sufficient performance could not be obtained.

Comparative Example 2 An organic EL device was produced in the same manner as in Example 3 except that the following compound (Comparative Example 2) was used as a light emitting material.

Embedded imageThe light emission characteristics of the obtained device were measured by applying a DC voltage of 5 V.
Luminance 200 (cd / m^Two), Luminous efficiency 1.2 (lm /
W), but the initial emission luminance was 400 (cd / m ^Two)
Is half life reduced to 600 hours when driven by current?
Was.

Heat Resistance Test The organic EL devices produced in Examples 2, 3, Comparative Example 1 and Comparative Example 2 were measured for light emission luminance and then placed in a thermostat at 100 ° C., at a constant current value. After the elapse of 500 hours, the emission luminance was measured again, and the luminance retention was calculated by comparing with the emission luminance before being put into the tank. As a result, the luminance retention rates of the organic EL devices of Example 2, Example 3, Comparative Example 1, and Comparative Example 2 were 85%, 90%, 25%, and 30%, respectively. As described above, the compounds of the light emitting materials used in Comparative Examples 1 and 2 were unable to maintain luminance because the glass transition temperature was 100 ° C. or less. On the other hand, since the compounds of the light emitting materials used in Examples 2 and 3 have a glass transition temperature of 110 ° C. or higher, they have high heat resistance and can maintain sufficient luminance for a long time.

Synthesis Example 1 (Compound (2)) Synthesis of Intermediate A In a 200 ml round bottom flask, 0.38 g (2.04 mmol) of 4-bromobenzaldehyde and 0.98 g (4.29 m) of ethyl benzylphosphonate were added.
mol), 40 ml of DMSO, and tBu
0.5 g (4.49 mmol) of OK was added little by little at room temperature and reacted. 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. In a 100 ml round bottom flask, 2.00 g of the above crude crystals, KI (12.
0 mmol), 1.14 g (6.0 mmol) of CuI.
l), 10 ml of HMPA was added, and the mixture was heated and stirred at 150 ° C. for 6 hours. After the reaction, 1N aqueous hydrochloric acid 10
Milliliter 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 of the following intermediate A (yield: 45%).

Embedded image

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 aqueous hydrochloric acid and cooled. At an internal temperature of 4 ° C., 1.25 g (18.1 mmol) of sodium sulfite / 5.3 ml of water were slowly added dropwise, followed by stirring at the same temperature for 1 hour to obtain a diazonium aqueous solution. Separately, 0.3 g of anthracene (1.7 mm) was placed in a 100 ml round bottom flask.
ol) was dissolved in 5 ml of acetone, and 0.46 g of cupric chloride dihydrate / 5.7 ml of water were added thereto, and the mixture was cooled to 4 ° C. After cooling, the above diazonium aqueous solution was added at the same temperature, and reacted at room temperature overnight. 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%).

Embedded image

Synthesis of Compound (2) In a 100 ml round bottom flask, aniline 0.0
18 g (0.2 mmol) was dissolved in 5 ml of methylene chloride, and 0.05 g (0.5 mmol) of acetic anhydride was dissolved.
l) was added and reacted at room temperature for 1 hour. 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 2 g of nitrobenzene 2
After adding 0 ml, the mixture was heated and stirred at 210 ° C. for 2 days. After that, 10 ml of diethylene glycol and 3 g of potassium hydroxide /
10 ml of water was added and reacted at 110 ° C. overnight. After the completion of the reaction, ethyl acetate / water was added to carry out liquid separation, and after distilling off the solvent, crude crystals were obtained. Subsequently, 0.05 g of the above crude crystals, Intermediate B (0.
1 mmol), 5 g of potassium carbonate, 0.3 g of copper powder and 20 ml of nitrobenzene.
For 2 days. After the reaction, the precipitated crystals were collected by filtration, washed with methanol and 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 NMR, IR and FD-MS (field desorption mass spectrum) measurements (yield 2).
0%).

Synthesis Example 2 (Compound (9)) Synthesis of Intermediate C In a 200 ml round bottom flask, 51.2 g (0.3 mol) of diphenylamine, 71.4 g (0.3 mol) of 1,4-dibromobenzene, tBuOK34 .
6 g (0.36 mol), PdCl ₂ (PPh ₃ ) ₂ 4.2
g (5.9 mmol) and 1.2 l 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 subjected to column chromatography (silica gel, hexane / toluene = 10
/ 1), 28 g of the following intermediate C (29% yield)
I got

Embedded image

Synthesis of Compound (9) Intermediate B 0.4 in a 100 ml round bottom flask
10 ml of diethyl ether was added to 8 g (1 mmol), and the mixture was cooled to -78 ° C. 2 ml (1.5 M, 3 mmol) of n-butyllithium was added thereto, and the mixture was stirred for 1 hour. Next, 0.3 g of trimethyl borate
(3 mmol) / 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 aqueous hydrochloric acid was added at room temperature. After separating the organic layer, the solvent was distilled off to obtain a crude crystal. In a 100 ml round bottom flask, the above crude crystals, Intermediate C 0.
97 g (3 mmol), 12 mg of Pd (PPh ₃ ) ₄ , 0.32 g (1.5 mmol) of potassium phosphate and DM
F 10 ml was added, and the mixture was stirred at 100 ° C. for 4 hours. After separating the organic layer, the solvent was distilled off to obtain a crude crystal. The crude crystals were purified by column chromatography (silica gel, benzene / ethyl acetate = 50/1) to give a yellow powder of 0.1%.
3 g were obtained. This powder was obtained by NMR, IR and FD-MS
Was identified as compound (9) (yield 14
%).

Synthesis Example 3 (Compound (18)) Synthesis of Intermediate D 0.48 g (2.0 mmol) of 1,4-dibromobenzene
l), Mg and diethyl ether were added to
ard reagent was prepared. Separately, in a 100 ml round bottom flask, 5.7 g of 1,4-dibromonaphthalene was added.
(20.0 mmol), NiCl ₂ (dppp) 10
mg and 20 ml of diethyl ether,
Cooled with greed. The above Grignard reagent was added thereto, and the mixture was heated under reflux for 6 hours. After completion of the reaction, 1N hydrochloric acid aqueous solution
10 milliliters were added. After liquid separation of the organic layer, the solvent was distilled off to obtain the following intermediate D 0.30 (yield 30%).

Embedded image

Synthesis of Compound (18) In a 100 ml round bottom flask, aniline 0.0
9 g (1.0 mmol) was dissolved in 5 ml of methylene chloride, and 0.25 g (2.5 mmol) of acetic anhydride was dissolved.
Was added and reacted at room temperature for 1 hour. Thereafter, the reaction solvent was distilled off to obtain an oily compound. To this compound, 0.4 g (4.5 mmol) of intermediate A, potassium carbonate
5 g, copper powder 0.3 g and nitrobenzene 20 ml were added, and the mixture was heated and stirred at 210 ° C. for 2 days. Thereafter, the solvent was distilled off, and the residue obtained was mixed with 10 ml of diethylene glycol and 3 g of potassium hydroxide in 10 g of water.
Milliliter was added and reacted at 110 ° C. overnight. After completion of the reaction, ethyl acetate / water was added for liquid separation, and the solvent was distilled off.
Crude crystals were obtained. Subsequently, in a 100 ml round bottom flask, 0.5 g of the above crude crystal, Intermediate D (1.0 mmol
l), 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 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 give a yellow powder 0.1
g was obtained. This powder was identified as compound (18) by NMR, IR and FD-MS measurements (yield 10
%).

Example 18 The above compound (30), 2,5-bis (1-naphthyl)-as a luminescent material was placed on a washed glass plate with an ITO electrode.
1,3,4-oxadiazole and a polycarbonate resin (Teijin Kasei: Panlite K-1300) were dissolved in tetrahydrofuran at a weight ratio of 5: 3: 2, and a 100 nm-thick light emitting layer was obtained by spin coating. . An electrode having a thickness of 150 nm was formed thereon using an alloy obtained by mixing aluminum and lithium at a ratio of 3% by weight of lithium to obtain an organic EL device. The light-emitting characteristics of this element are as follows: DC voltage 5 V
Emission luminance 320 (cd / m ² ), maximum luminance 1
Light emission of 4000 (cd / m ² ) and luminous efficiency of 2.5 (lm / W) was obtained.

Example 19 The above-mentioned compound (37) as a luminescent material was vacuum-deposited on a washed glass plate with an ITO electrode to form a 100 nm-thick luminescent layer, on which lithium fluoride was used to form a luminescent layer having a thickness of 0 nm. .3
After forming an inorganic electron injection layer having a thickness of 100 nm, an electrode having a thickness of 100 nm was formed with aluminum to obtain an organic EL device.
The light emitting layer was deposited in a vacuum of 10 ^-6 Torr at a substrate temperature of room temperature. The light-emitting characteristics of this element are as follows.
With an applied voltage of V, light emission luminance 110 (cd / m ² ), maximum luminance 20,000 (cd / m ² ), light emission efficiency 1.2 (lm / W)
Was obtained.

Example 20 A hole injection layer having a thickness of 40 nm was formed on a washed glass plate with ITO electrodes by vacuum-depositing CuPc as a hole injection material. Next, the above compound (47) was used as a hole transporting material in a hole transporting layer having a thickness of 20 nm.
q) Vacuum evaporation to form a 60 nm-thick light-emitting layer, an alloy in which rubrene is added to the light-emitting layer to a concentration of 4% by weight, and aluminum and lithium are mixed at a ratio of 3% by weight of lithium. To form an electrode having a thickness of 100 nm, thereby obtaining an organic EL device. Each layer is placed in a vacuum of 10 ^-6 Torr,
The deposition was performed at a substrate temperature of room temperature. The light emission characteristics of this element are such that a light emission luminance of about 700 (cd)
/ M ^2), the maximum luminance 80000 (cd / m ^2), green light emission efficiency 6.0 (lm / W) was 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 4000 hours.

Examples 21 to 33 A hole transporting layer having a thickness of 20 nm was obtained by vacuum-depositing the hole transporting materials shown in Table 2 on the cleaned glass plate with ITO electrodes. Further, the above compound (Alq) was vacuum-deposited as a light emitting material to form a light emitting layer having a thickness of 60 nm, rubrene was added to the light emitting layer so as to have a concentration of 4% by weight, and aluminum and lithium were further changed to lithium. 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 device. Each layer was deposited at a substrate temperature of room temperature in a vacuum of 10 ^-6 Torr. Table 2 shows the emission characteristics of this device. Further, the organic EL element of this embodiment
All had high luminance characteristics of 10000 (cd / m ² ) or higher.

[0103]

[Table 2]

Example 34 The above compound (TPD74) as a hole injecting material was vacuum-deposited to a thickness of 60 nm on a washed glass plate with ITO electrodes. Next, the compound (NPD) as a hole transporting material was vacuum-deposited to a thickness of 20 nm. Next, 4,4′-bis (2,2-diphenylvinyl) phenylanthracene (DPVDPAN) as a light-emitting material and the above compound (36) as a dopant were added at a ratio of the compound (36) of 2% by weight and a film thickness of 40 nm. Co-evaporation was carried out. next,
The above compound (Alq) is used as a charge injection material in a thickness of 20 nm.
Then, LiF is deposited in a thickness of 0.5 nm, and aluminum is deposited in a thickness of 100 nm to form an electrode.
An L element was obtained. Each layer was deposited at a substrate temperature of room temperature in a vacuum of 10 ^-6 Torr. The light emission characteristics of this element are:
Light emission luminance of 500 (cd / m ² ) at an applied voltage of DC voltage of 8 V
And blue light emission with high luminance and excellent color purity. Furthermore, when the device was driven at a constant current with an initial light emission luminance of 100 (cd / m ² ), the half life was 7000 hours, which was a long life. When the emission spectrum of this device was measured, DPVBi
Was identical to That is, the compound (36) has no effect on light emission, but has an effect of giving a long life to the device.

Comparative Example 3 An organic EL device was manufactured in the same manner as in Example 34 except that the compound (36) was not added as a dopant. For this element, an initial light emission luminance of 100 (cd / m
^{In (2} ), the half-life was 4000 hours, which was shorter than that of Example 34 when driven at a constant current.

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

Heat resistance test Organic E prepared in Examples 20, 27 and Comparative Example 4
After measuring the light emission luminance, the L element was placed in a constant temperature bath at 105 ° C., and after a lapse of 500 hours at a constant current value, the light emission luminance was measured again and compared with the light emission luminance before being put into the tank, the luminance retention ratio Was calculated. As a result, Example 20 and Example 2
7. The luminance retention rates of the organic EL elements of Comparative Example 4 were 87%, 90%, and 25%, respectively. Thus, the compound of the luminescent material used in Comparative Example 4 has a glass transition temperature of 10
Since the temperature was 5 ° C. or less, the luminance could not be maintained. On the other hand, since the compounds of the light emitting materials used in Examples 20 and 27 have a glass transition temperature of 110 ° C. or higher, they have high heat resistance and can maintain sufficient luminance for a long time.

Synthesis Example 4 (Compound (30)) Synthesis of Intermediate E (6,12-Diiodochrysene) 5 g of chrysene was placed in a 300 ml round bottom flask.
(22 mmol) and 100 ml of carbon tetrachloride, and 16 g of iodine / carbon tetrachloride (64 mmol / 1
(00 ml) was added dropwise little by little at room temperature to cause a reaction. After heating and stirring the reaction solution for 5 hours, the precipitated crystals were collected by filtration and washed with 100 ml of carbon tetrachloride. The obtained crude crystals were recrystallized from 200 ml of toluene to obtain 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, and 2.5 g (25 mmol) of acetic anhydride was dissolved.
l) 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 and 3 g of potassium carbonate were added to this compound.
(30 mmol), 0.06 g (1 mmol) of copper powder and 100 ml of nitrobenzene were added, and 220
The mixture was heated and stirred at ℃ for 2 days. 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 the completion of the reaction, ethyl acetate / water was added to carry out liquid separation, and after distilling off the solvent, crude crystals were obtained. Three
In a 00 ml two-neck flask, 2.4 g (5 mmol) of the obtained crude crystal and Intermediate E, potassium carbonate 3
g (20 mmol), copper powder 0.06 g (1 mmol)
And 100 ml of nitrobenzene and add 23
The mixture was heated and stirred at 0 ° C. for 2 days. After the reaction, the precipitated crystals were collected by filtration, washed with methanol and dried, and purified by column chromatography (silica gel, hexane / toluene = 1/1) to obtain 1.0 g of a yellow powder. This powder has NMR, IR and F
The powder was identified as Compound (30) by D-MS measurement (yield: 25%).

Synthesis Example 5 (Compound (36)) Synthesis of Compound (36) In a 100 ml round bottom flask, 3.4 g (20 mmol) of diphenylamine and 4.8 g of intermediate E (1
0 mmol), 3 g (30 mmol) of potassium carbonate,
Copper powder 0.06 g (1 mmol) and nitrobenzene
100 ml was added, and the mixture was heated and stirred at 210 ° C. for 2 days. After the reaction, the precipitated crystals were collected by filtration, washed with methanol and 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 the measurement of NMR, IR and FD-MS (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 a stream of argon. 9.7 g (30 mmol) of phenylamine / THF 10
0 ml is added dropwise little by little at room temperature.
The mixture was heated and stirred at 0 ° C. for 1 hour to prepare a Grignard reagent. In a 300 ml four-necked flask under a stream of argon, 4.8 g (10 mmol) of Intermediate E, THF 5
0 ml, PdCl ₂ (PPh ₃ ) ₂ 0.28 g
(0.4 mmol) and AlH (iso-Bu) ₂ /
1.0M toluene solution 1.0ml (1mmo
l) was added thereto, and the above-mentioned Grignard reagent was added dropwise at room temperature, and then heated 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 from 100 ml of acetone to obtain 4.3 g of a yellow powder. This powder is NM
The compound (38) was measured by R, IR and FD-MS.
(60% yield).

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 added to methylene chloride.
Dissolve in milliliter and add 2.5g of acetic anhydride (25mm
ol) 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 and 3 g of potassium carbonate were added to this compound.
(30 mmol), 0.06 g (1 mmol) of copper powder and 100 ml of nitrobenzene were added, and 220
The mixture was heated and stirred at ℃ for 2 days. 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 the completion of the reaction, ethyl acetate / water was added to carry out liquid separation, and after distilling off the solvent, crude crystals were obtained. Three
In a 00 ml two-necked flask, 2 g (5 mmol) of the obtained crude crystal and 4,4′-diiodobiphenyl,
Potassium carbonate 3g (30mmol), copper powder 0.06g
(1 mmol) and 100 ml of nitrobenzene were added, and the mixture was heated and stirred at 230 ° C. for 2 days. After the reaction, the precipitated crystals were collected by filtration, washed with methanol, and dried, and then subjected to column chromatography (silica gel, hexane / toluene = 1/3).
And 0.8 g of a yellow powder was obtained. This powder is N
According to the measurement of MR, IR and FD-MS, the compound (4
7) (30% yield).

Example 35 The above compound (58), 2,5-bis (1-naphthyl)-as a luminescent material was placed on a washed glass plate with an ITO electrode.
1,3,4-oxadiazole and a polycarbonate resin (Teijin Chemical: Panlite K-1300) were dissolved in tetrahydrofuran at a weight ratio of 5: 2: 2, and a 100 nm-thick light emitting layer was obtained by spin coating. . An electrode having a thickness of 150 nm was formed thereon using an alloy obtained by mixing aluminum and lithium at a ratio of 3% by weight of lithium to obtain an organic EL device. The light-emitting characteristics of this element are as follows: DC voltage 5 V
At an applied voltage of 130 (cd / m ² ) and a maximum luminance of 1
Yellow-orange light emission of 4000 (cd / m ² ) and luminous efficiency of 1.2 (lm / W) was obtained.

Example 36 The above-mentioned compound (71) was vacuum-deposited as a luminescent material on a washed glass plate with an ITO electrode to form a 100-nm-thick luminescent layer, on which aluminum and lithium were weighed with 3 weight percent of lithium. % Alloy with a thickness of 100 nm
Was formed to obtain an organic EL device. The light emitting layer is 10 ^-6
Vapor deposition was performed in a Torr vacuum at a substrate temperature of room temperature. The light-emitting characteristics of this device are such that a light-emitting luminance of 120 (cd / m ² ) and a maximum luminance of 1800 (cd) are obtained by applying a DC voltage of 5 V.
/ M ^2), orange light emission efficiency 0.3 (lm / W) was obtained.

Example 37 The above-mentioned compound (71) as a luminescent material was vacuum-deposited on a washed glass plate with an ITO electrode to form a 50-nm-thick luminescent layer. Next, the compound (Alq) is vacuum-deposited to form an electron injection layer having a thickness of 10 nm.
An electrode having a thickness of 100 nm is formed of an alloy in which aluminum and lithium are mixed at a ratio of 3% by weight of lithium to form an organic EL.
An element was obtained. The light emitting layer and the electron injection layer are 10 ^-6 Torr
Vacuum was deposited in a vacuum at a substrate temperature of room temperature. The light emission characteristics of this device are such that a light emission luminance of about 200 (cd / m ² ) and a maximum luminance of 12000 (cd /
m ² ), and orange luminescence with a luminous efficiency of 1.0 (lm / W) was obtained.

Examples 38 to 46 The luminescent materials shown in Table 3 were vacuum-deposited on the cleaned glass plate with ITO electrodes to obtain a luminescent layer having a thickness of 80 nm. Further, the above compound (Alq) was 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 were mixed at a ratio of 3% by weight of lithium was formed thereon. An electrode having a film thickness was formed to obtain an organic EL device. Each layer was deposited at a substrate temperature of room temperature in a vacuum of 10 ^-6 Torr. Table 3 shows the emission characteristics of this device. Further, the organic EL element of this embodiment
All had high luminance characteristics of the maximum luminance of 5000 (cd / m ² ) or more.

[0117]

[Table 3]

Example 47 The above compound (TPD74) as a hole injecting material was vacuum-deposited to a thickness of 60 nm on a washed glass plate with ITO electrodes. Next, the following compound (NPD) was vacuum-deposited as a hole-transporting material to a thickness of 20 nm.

Next, 4,4′-bis (2,2-diphenylvinyl) biphenyl (DPVB) was used as a light emitting material.
i) and the compound (58) were co-evaporated so that the ratio of the compound (58) was 5% by weight and the film thickness was 40 nm. Note that the compound (58) functions as a fluorescent dopant. Next, the above compound (Alq) is used as a charge injection material.
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 light emission characteristics of this element were as high as yellow light emission luminance of 600 (cd / m ² ) when a DC voltage of 5 V was applied. Further, when the device was driven at a constant current at an initial luminance of 400 (cd / m ² ), the half life was 2800 hours, which was a long life.

Example 48 Except that the above-mentioned compound (Alq) as a luminescent material and the above-mentioned compound (61) as a dopant were co-deposited so that the ratio of the compound (61) was 5% by weight to form a luminescent layer. An organic EL device was produced in the same manner as in Example 47. With respect to the light emission characteristics of this element, red light emission having a light emission luminance of 240 (cd / m ² ) was obtained with an applied voltage of 5 V DC. Further, when the device was driven at a constant current with 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 Example 35, except that the above compound (Comparative Example 1) was used as a light emitting material. The light-emitting characteristics of the obtained device were such that the light-emitting luminance was 60 (cd / m ² ) and the light-emitting efficiency was 0.34 (l
m / W), sufficient performance could not be obtained. The emission color was blue.

Comparative Example 6 An organic EL device was produced in the same manner as in Example 37, except that the above compound (Comparative Example 2) was used as a light emitting material. The light emitting characteristics of the obtained device were as follows: light emission luminance 200 (cd / m ² ) and light emission efficiency 1.2 (l
m / W), but the initial emission luminance was 400 (cd / m ² ).
And 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 Example 47, except that the compound (Comparative Example 1) was used instead of the compound (58) as the light emitting material. The light emission characteristics of the obtained device were such that a light emission luminance of 200 (cd) was obtained by applying a DC voltage of 5 V.
/ M ² ), and when driven at a constant current with an initial luminance of 400 (cd / m ² ), the half life was short, 700 hours, 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 and stannic chloride 108
g (0.57 mmol), 500 ml of acetic acid,
200 ml of concentrated hydrochloric acid was added, and the mixture was heated and stirred for 2 hours to react. After completion of the reaction, the precipitated crystals were collected by filtration, washed with water, and dried overnight in a vacuum drier to obtain 48 g of crude crystals. In a 2-liter four-necked flask, 50 g of the obtained crude crystal and triphenylphosphine (0.
19 mmol), 300 ml of DMF,
At room temperature, 64 g (0.4 mmol) of bromine / 200 ml of DMF was added dropwise at room temperature to react. After the addition, the mixture was heated and stirred at 200 ° C. overnight. After completion of the reaction, DMF was distilled off 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 then 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 a yellow powder. This powder has NMR, IR and FD-
The powder was identified as Intermediate F by MS measurement (yield: 40
%).

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, and 2.5 g (25 mmol) of acetic anhydride was dissolved.
l) 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 and 3 g of potassium carbonate were added to this compound.
(30 mmol), 0.06 g (1 mmol) of copper powder and 100 ml of nitrobenzene were added, and 220
The mixture was heated and stirred at ℃ for 2 days. 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 the completion of the reaction, ethyl acetate / water was added to carry out liquid separation, and after distilling off the solvent, crude crystals were obtained. In a 100 ml two-necked flask under a stream of argon, the obtained crude crystals, 1.9 g (5 mmol) of intermediate F, t
1.3 g (12 mmol) of BuOK, PdCl ₂ (PP
40 mg (5 mol%) of h ₃ ) ₂ and 30 ml of xylene were mixed and stirred at 130 ° C. overnight for reaction.
After the 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 measured by NMR, IR and FD-MS,
It was identified as compound (58) (yield 25%).

Synthesis Example 9 (Compound (59)) Synthesis of compound (59)
-Hydroxystilbene 2 g (10 mmol), triphenylphosphine 5.2 g (20 mmol), D
Add 50 ml of MF and 5 g of iodine (20 m
(mol) / DMF 50 ml little by little at room temperature for reaction. After the addition, the mixture was stirred at 200 ° C. overnight. After completion of the reaction, DMF was distilled off 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 then concentrated under reduced pressure using a rotary evaporator to obtain an oily compound. Column chromatography (silica gel, hexane / toluene = 1
/ 1) to obtain 2.5 g of a yellow powder. Separately, 10
In a 0 ml two-necked flask, 2 g (10 mmol) of 4-aminostilbene was dissolved in 20 ml of methylene chloride, and 2.5 g (25 mmol) of acetic anhydride was dissolved.
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, the yellow powder was added to this compound.
2.5 g, potassium carbonate 3 g (30 mmol), copper powder 0.06 g (1 mmol) and nitrobenzene 10
0 ml was added, and the mixture was heated and stirred at 220 ° C. for 2 days. After that, 10 ml of diethylene glycol and 30 ml of potassium hydroxide were added to the residue obtained by distilling off the solvent.
g / water (100 ml) was added and reacted at 110 ° C. overnight. After the completion of the reaction, ethyl acetate / water was added to carry out liquid separation, and after distilling off the solvent, crude crystals were obtained. In a 300 ml two-necked flask, 2.4 g of the above crude crystal, Intermediate F (5
mmol), 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 reacted by stirring at 130 ° C. 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 a yellow powder. This powder has NMR, IR and FD
The powder was identified as Compound (59) by -MS measurement (yield: 5%).

Synthesis Example 10 (Compound (61)) Synthesis of Compound (61)
-Bromotriphenylamine 9.7 g (30 mmo
l), toluene (50 ml) and diethyl ether (50 ml) were added, cooled with ice water, and n-butyllithium / hexane (22 ml) (1.52 m
ol / liter, 33 mmol) / 100 ml of THF was added dropwise little by little at room temperature and reacted. After the addition, the mixture was stirred overnight at the same temperature. After completion of the reaction, 50 ml of water was added, the organic layer was extracted with diethyl ether, dried over magnesium sulfate, and concentrated under reduced pressure by a rotary evaporator to obtain 7.4 g of an oily compound. 300
The above compound, 6.6 g (40 mmol) of potassium iodide and 100 ml of acetic acid were placed in a milliliter four-necked flask, and the mixture was heated under reflux for 1 hour. After the reaction,
After cooling to room temperature, 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. The orange solid was analyzed by NMR, IR and FD-MS to determine
It was identified as compound (61) (yield 35%).

Synthesis Example 11 (Compound (62)) Synthesis of Intermediate G (5,11-diiodonaphthacene) In a 500 ml round bottom flask, naphthacene 50 was added.
g (0.22 mmol), tetrachloroethane 200
Add milliliter and add 160g of iodine / carbon tetrachloride
(0.64 mol / 200 ml) was added dropwise little by little at room temperature to cause a reaction. After heating and stirring the reaction solution for 5 hours, the precipitated crystals were collected by filtration and washed with 500 ml of methanol. The obtained crude crystals were recrystallized from 200 ml of toluene to obtain 34 g of an 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 a stream of argon, and 9.7 g (30 mmol) of 4-bromotriphenylamine was added. THF 10
0 ml is added dropwise little by little at room temperature.
The mixture was heated and stirred at 0 ° C. for 1 hour to prepare a Grignard reagent. In a 300 ml four-necked flask, 4.8 g (10 mmol) of Intermediate G and THF
0 ml, PdCl ₂ (PPh ₃ ) ₂ 0.28 g
(0.4 mmol) and AlH (iso-Bu) ₂ /
1.0M toluene solution 1.0ml (1mmo
l) was added thereto, and the above-mentioned Grignard reagent was added dropwise at room temperature, and then heated 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 from 100 ml of acetone to obtain 3.6 g of a yellow powder. This powder is NM
The compound (62) was measured by R, IR and FD-MS.
(50% yield).

Example 49 The above compound (TPD74) as a hole injecting material was vacuum-deposited to a thickness of 60 nm on a washed glass plate with an ITO electrode. Next, the compound (NPD) as a hole transporting material was vacuum-deposited to a thickness of 20 nm. Next, the above compound (Alq) as a light emitting material and the above compound (75) as a dopant were used at a ratio of 2% by weight of the compound (75) and a film thickness of 4%.
Co-evaporation was performed to a thickness of 0 nm. Next, the above-mentioned compound (Alq) was deposited as an electron injecting material in a thickness of 20 nm, LiF was deposited in a thickness of 0.5 nm, and aluminum was deposited in a thickness of 100 nm to form an electrode to obtain an organic EL element. Each layer was deposited at a substrate temperature of room temperature in a vacuum of 10 ^-6 Torr. The light emission characteristics of this element are as follows: DC voltage 8
With an applied voltage of V, the light emission luminance was 500 (cd / m ² ), high luminance, and orange light emission. Furthermore, initial light emission luminance 500 (c
d / m ² ), the half life is 2000 when driven at a constant current.
It was particularly long life over time.

Example 50 An organic EL device was produced in the same manner as in Example 49, except that the compound (86) was added instead of the compound (75) as a dopant. When the device was driven at a constant current with an initial light emission luminance of 500 (cd / m ² ), the half life was as long as 2000 hours. The emission color was vermilion.

Example 51 An organic EL device was fabricated in the same manner as in Example 49, except that the compound (82) was added instead of the compound (75) as a dopant. When the device 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 more. The emission color was red.

Synthesis Example 12 (Compound (75)) Synthesis of Compound (75) In a 200 ml three-necked flask under a stream of argon,
6,12-dibromonaphthacene (40577-78-
4) 2.16 g (5.6 mmol), Pd (OAc)
₂ 0.06 g (0.3 mmol), P (tBu) ₃₀ .
23 g (1.1 mmol), NaOtBu 1.51 g
(15.7 mmol), 1.89 g of Ph ₂ NH (1
1.2 mmol) and 25 ml of toluene.
The mixture was heated and stirred at 0 ° C. for 7 hours to be reacted. After completion of the reaction, the reaction solution 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 red powder. This powder is N
According to the measurement of MR, IR and FD-MS, the compound (7
5) (96% yield). NMR (CDC1
3, TMS), 6.8 to 7.0 (m, 2H),
7.0 to 7.4 (m, 10H), 7.8 to 7.9 (m,
1H), 8.0 to 8.1 (m, 1H), 8.85 (s,
1H).

Example 52 A transparent anode of a 100 nm-thick indium-tin oxide film was provided on a glass substrate having a size of 25 mm × 75 mm × 1.1 mm, and washed with ultraviolet light and ozone for 10 minutes. This glass substrate was put in a vacuum tea-coating apparatus (Japan Vacuum Engineering Co., Ltd.) and the pressure was reduced to about 10 ⁻⁴ Pa. afterwards,
The TPD 74 is deposited at a deposition rate of 0.2 nm / sec at 60 nm.
Deposited to a thickness of Next, a TPD 78 having the following structure is
Deposition was performed to a thickness of 20 nm at a deposition rate of 0.2 nm / sec.
Next, the 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 / sec, and the deposition rate of compound (100) was 0.0
It was 1 nm / sec. Further, Alq was vapor-deposited at a vapor deposition rate of 0.2 nm / sec, and finally aluminum and lithium were simultaneously vapor-deposited to form a cathode with a thickness of 150 nm, thereby obtaining an organic EL device. At this time, the deposition rate of aluminum was 1 nm / sec, and the deposition rate of lithium was 0.004 nm / sec.

Embedded image The performance of the obtained organic EL device was evaluated. The emission luminance at the voltage shown in Table 4 was measured, the emission efficiency was calculated, and the emission color was observed. Further, a constant current drive was performed at an initial light emission luminance of 500 (cd / m ² ) under a nitrogen gas flow, and the light emission luminance was 25
The half-life which became 0 (cd / m ² ) was measured. Table 4 shows the results.

Examples 53 to 62 Organic EL devices were prepared and evaluated in the same manner as in Example 52 except that the compounds shown in Table 4 were used as the luminescent materials instead of the compound (100). Table 4 shows the results.

Comparative Example 8 In Example 52, the following diamine compound was used as a luminescent material instead of the compound (100).

Embedded image An organic EL device was prepared and evaluated in the same manner except that was used. Table 4 shows the results.

[0137]

[Table 4]

As shown in Table 4, the general formula of the present invention

The organic EL devices of Examples 52 to 62 using the compounds of [9] and [10] as a light emitting material or a hole transport material,
Compared with the organic EL device using the diamine compound of Comparative Example 8, the luminous brightness, the luminous efficiency and the life were excellent.

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

Synthesis of Intermediate I In a 500 ml eggplant flask equipped with a condenser, 23.7 g (98 mmol) of Intermediate H and 200 ml of acetic anhydride were added.
Milliliter was added, and the mixture was stirred at 80 ° C for 3 hours. After completion of the reaction, excess acetic anhydride was distilled off to obtain the desired intermediate I
22 g (10% yield) were obtained. Synthesis of Intermediate J Under a stream of argon, 7.7 g (50 mmol) of biphenyl was placed in a 500 ml three-necked flask equipped with a condenser.
13.4 g (0.1 mol) of anhydrous aluminum chloride,
Add 200 ml of 1,2-dichloroethane,
Cooled to 0 ° C. Next, 22 g of Intermediate I (98 mmo
1) was added slowly and stirred at 40 ° C. for 2 hours. After the reaction was completed, ice water was added, and the mixture was separated and extracted with chloroform. After drying over magnesium sulfate, the mixture was concentrated under reduced pressure using a rotary evaporator to obtain 19.0 g of the desired intermediate J (yield: 10%).
0%).

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 Intermediate J was added little by little, and the mixture was stirred at the same temperature for 3 hours. After the reaction was completed, ice water was added, and the mixture was separated and extracted with chloroform. After drying over magnesium sulfate, the mixture was concentrated under reduced pressure using a rotary evaporator. The obtained crude crystals were purified by column chromatography (silica gel, chloroform / methanol = 99/1) to obtain 19 g of the desired intermediate K (yield 55%). Synthesis of Intermediate L Under a stream of argon, 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 to a 500 mL eggplant flask equipped with a cooling tube 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 (yield 100%) of the desired intermediate L.

Synthesis of Intermediate M In a 500 ml three-necked flask equipped with a condenser under an argon stream, 19.0 g (28 mmol) of intermediate L, 16 g (60 mmol) of triphenylphosphine, DM
200 ml of F were added. Subsequently, bromine 9.
After 6 g (60 mmol) / 50 mL of DMF was gradually added dropwise, 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 (yield: 50%) of a target intermediate M. Synthesis of Compound (100) Under a stream of argon, in a 200 ml three-necked flask equipped with a condenser, 4.9 g (10 mmol) of Intermediate M, 5.1 g (30 mmol) of diphenylamine, 0.14 g of tris (dibenzylidesiacetone) divaladium.
(1.5 mol%), tri-o-toluylphosphine
0.91 g (3 mol%), sodium t-butoxide
After adding 2.9 g (30 mmol) and 50 ml of dry toluene, the mixture was heated and stirred at 100 ° C. overnight. After completion of the reaction, the precipitated crystals were collected by filtration, and methanol 100
After washing with milliliters, 4.0 g of a yellow powder was obtained.
This powder was identified as compound (100) by NMR, IR and FD-MS measurements (60% yield).

Structural formula of the above intermediate and compound (100)
Is shown below.

Embedded image

Synthesis Example 14 (Compound (101)) Synthesis of Intermediate N Under a stream of argon, in a 500 ml eggplant flask equipped with a condenser, 12 g (50 mmol) of 2,6-dihydroxy-anthraquinone and 42.5 g of methyl iodide
(0.3 mol), 17 g of potassium hydroxide (0.3 m
ol) and 200 ml of DMSO, and
Stirred for 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 of the desired intermediate N (yield: 80%). Synthesis of Intermediate O Under an argon stream. In a 500 ml three-necked flask, intermediate N 10.7 (40 mmol), dry THF
After adding 200 ml and cooling to −40 ° C., 1.5
53 ml (80 mmol) of a M phenyllithium / hexane solution was gradually added dropwise. After the addition, the mixture was stirred at room temperature overnight. After completion of the reaction, the precipitated crystals were collected by filtration, and then 100 ml of methanol followed by acetone
Washed with 100 ml. The resulting crude crystals of the diol were used in the next reaction without further purification. The above crude crystals, 100 ml of 57% aqueous hydrogen iodide, and acetic acid 2 were placed in a 500 ml eggplant flask equipped with a cooling tube.
After adding 00 ml, the mixture was heated under 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 of the desired intermediate O (yield 70%).・

Synthesis of Intermediate P Under a stream of argon, in a 500 ml three-necked flask equipped with a condenser, 10.1 g (28 mmol) of intermediate O, 7.9 g (30 mmol) of triphenylphosphine, D
200 ml of MF was added. Then bromine
After 4.8 g (30 mmol) / 50 ml of DMF was gradually added dropwise, 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.
Wash with water and methanol 8.2 g of the desired intermediate P
(60% yield). Synthesis of Compound (101) In a 200 ml three-necked flask equipped with a cooling tube under an argon stream, 4.9 g (30 mmol) of intermediate P, 5.1 g (30 mmol) of diphenylamine, 0.14 g of tris (dibenzylidesiacetone) divalazium
(1.5 mol%), tri-o-toluylphosphine
0.91 g (3 mol%), sodium t-butoxide
After adding 2.9 g (30 mmol) and 50 ml of dry toluene, the mixture was heated and stirred at 100 ° C. overnight. After the completion of the reaction, the precipitated crystals were collected by filtration and washed with 100 ml of methanol to obtain 4.0 g of a yellow powder. This powder was measured by NMR, IR and FD-MS,
It was identified as compound (101) (yield 60%).

Structural formula of the above intermediate and compound (101)
Is shown below.

Embedded image

Synthesis Example 15 (Compound (102)) Synthesis of Intermediate Q Under a stream of argon, 11.7 g (50 g) of 2-bromobiphenyl was placed in a 300 ml three-necked flask equipped with a condenser.
mmol), aniline 19 g (0.2 mol), tris (dibenzylidesiacetone) dibaradium 0.69
g (1.5 mol%), 0.46 g (3 mol%) of tri-o-toluylphosphine, 7.2 g (75 mmol) of sodium t-butoxy, and 100 ml of dry toluene, and then heated and stirred at 100 ° C. overnight. did. After completion of the reaction, the precipitated crystals were collected by filtration, and methanol
The crude crystals obtained by washing with 100 ml were recrystallized with 50 ml of ethyl acetate to obtain 9.8 g of the desired intermediate Q (yield 80%). Synthesis of Compound (102) 9,10-Dibromoanthracene 2.4 in a 200 ml three-necked flask equipped with a condenser under a stream of argon.
g (10 mmol), 7.4 g of intermediate Q (30 mmol)
l), 0.14 g (1.5 mol%) of tris (dibenzylidesiacetone) divaladium, 0.91 g (3 mol%) of tri-o-toluylphosphine, 2.9 g (30 mmol) of sodium t-butoxy, dry toluene 50 After adding milliliter, 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 yellow powdered.
3 g were obtained. This powder was obtained by NMR, IR and FD-MS
Was identified as compound (102) (yield 6
5%).

Structural formula of the above intermediate and compound (102)
Is shown below.

Embedded image

Synthesis Example 16 (Compound (103)) Synthesis of Intermediate R In a 1-liter three-necked flask equipped with a condenser under a stream of argon, 34 g (0.2 mol) of 3-phenylphenol was added.
l), 58 g of triphenylphosphine (0.22 mm
ol) and 300 ml of DMF. Subsequently, 35 g (0.22 mmol) of bromine / DMF 10
After 0 ml was gradually added dropwise, 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 37 g of the desired intermediate R (yield: 80%). Synthesis of Intermediate S 19 g (0.2 mmol) of aniline and 0.69 g of tris (dibenzylidesiacetone) dibaradium were placed in a 300 ml three-necked flask equipped with a condenser under an argon stream.
(1.5 mol%), tri-o-toluylphosphine
0.46 g (3 mol%), sodium t-butoxide
After adding 7.2 g (75 mmol) and 100 ml of dry toluene, the mixture was heated and stirred at 100 ° C. overnight.
After completion of the reaction, the precipitated crystals were collected by filtration, and methanol 10
The crude crystals obtained by washing with 0 ml were recrystallized with 50 ml of ethyl acetate to obtain 9.8 g of the desired intermediate Q (yield: 80%). Synthesis of Compound (103) 9,10-Dibromoanthracene 2.4 in a 200 ml three-necked flask equipped with a condenser under a stream of argon.
g (10 mmol), 7.4 g of intermediate S (30 mmol)
l), 0.14 g (1.5 mol%) of tris (dibenzylidesiacetone) divaladium, 0.91 g (3 mol%) of tri-o-toluylphosphine, 2.9 g (30 mmol) of sodium t-butoxy, dry toluene 50 After adding milliliter, 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 yellow powdered.
2 g were obtained. This powder was obtained by NMR, IR and FD-MS
Was identified as compound (103) (yield 7
0%).

Structural formula of the above intermediate and compound (103)
Is shown below.

Embedded image

Synthesis Example 17 (Compound (104)) Synthesis of Intermediate T Under a stream of argon, 23 g of 4-bromobiphenyl (0.1 m
ol), 9.8 g of aminostilbene (50 mmo
l), Tris (dibenzylidesiacetone) 0.69 g (1.5 mol%) of divalazim, 0.46 g (3 mol%) of tri-o-toluylphosphine, 7.2 g (75 mmol) of sodium t-butoxy, dry toluene 100 After adding milliliter, 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 the obtained crude crystals were recrystallized with 50 ml of ethyl acetate to obtain 13.9 g of the desired intermediate T (80% yield). ) Got. Synthesis of Compound (104) 9,10-Dibromoanthracene 2.4 in a 200 ml three-necked flask equipped with a condenser under a stream of argon.
g (10 mmol), 7.4 g of intermediate T (30 mmol)
l), 0.14 g (1.5 mol%) of tris (dibenzylidesiacetone) divaladium, 0.91 g (3 mol%) of tri-o-toluylphosphine, 2.9 g (30 mmol) of sodium t-butoxy, dry toluene 50 After adding milliliter, 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 yellow powdered.
5 g were obtained. This powder was obtained by NMR, IR and FD-MS
Was identified as compound (104) (yield 7
0%).

The structural formula of the above intermediate and compound (104)
Is shown below.

Embedded image

Synthesis Example 18 (Compound (121)) Synthesis of Intermediate U Under a stream of argon, 25 g (0.1 mol) of triphenylamine was placed in a 500 ml three-necked flask equipped with a condenser.
l), N-bromosuccinimide 18 g (0.1 mol
l), 2,2'-azobisisobutyronitrile 0.8
2 g (5 mol%) and 200 ml of DMF 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 obtained crude crystals were purified by column chromatography (silica gel, methylene chloride) to obtain 19 g of the desired intermediate U (yield: 60%). Synthesis of Intermediate V 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 condenser under a stream of argon, and the mixture was heated at room temperature for 3 hours.
After stirring for 0 minutes, Intermediate U 19 g (60 mol) / TH
F 300 ml solution was added dropwise. After dropping,
The mixture was heated and stirred at 60 ° C. for 1 hour to prepare a Grignard reagent. Under a stream of argon, 42 g of 1,3 dibromobenzene (0.18
mmol), dichlorobis (triphenylphosphine)
Palladium 2.1 (5 mol%), diisobutylaluminum hydride / toluene solution 6 ml (1
M, 6 mmol) and 200 ml of THF. The Grignard reagent was added dropwise at room temperature, and the temperature was raised 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 desired intermediate V (yield: 60%).

Synthesis of Compound (121) 0.8 g (33 mmol) of magnesium was placed in a 500 ml three-necked flask equipped with a condenser under a stream of argon.
l), a small piece of iodine and 50 ml of THF were added, and the mixture was stirred at room temperature for 30 minutes.
mol) / THF 100 ml solution was added dropwise. After dropping, the mixture was stirred at 60 ° C. for 1 hour and
d reagent was prepared. Under a stream of argon, with cooling tube 500
In a milliliter three-necked flask, 3.4 g (10 mmol) of 9,10-dibromoanthracene and 0.4 g (5 mmol) of dichlorobis (triphenylphosphine) palladium were added.
mol%), diisobutylaluminum hydride / toluene solution 1 ml (1 M, 1 mmol), TH
100 ml of F was added. Here the above-mentioned Grign
After dropping the ard reagent at room temperature, 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 4.1 g of a yellow powder.
This powder was identified as compound (121) by NMR, IR and FD-MS measurements (yield 50%).

Structural formula of the above intermediate and compound (121)
Is shown below.

Embedded image

Synthesis Example 19 (Compound (122)) Synthesis of Intermediate W In a 300-liter three-necked flask equipped with a condenser under a stream of argon, 19 g of 1,3-dibromobenzene (80 mm
ol), 6.5 g (20 mmol) of diphenylamine
l), 0.27 g (1.5 mol%) of tris (dibenzylidesiacetone) divaladium, 0.18 g (3 mol%) of tri-o-toluylphosphine, 2.9 g (30 mmol) of sodium t-butoxy, 100 parts of dry toluene After adding milliliter, 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 the obtained crude crystals were recrystallized with 50 ml of ethyl acetate to obtain 4.9 g of the desired intermediate W (yield 75%). ) Got. Synthesis of Compound (122) 0.5 g (20 mmol) of magnesium was placed in a 300 ml three-necked flask equipped with a condenser under a stream of argon.
l), a small piece of iodine and 50 ml of THF were added thereto, and the mixture was stirred at room temperature for 30 minutes.
(mmol) / 100 ml of THF was added dropwise. After dropping, the mixture was stirred at 60 ° C. for 1 hour and
d reagent was prepared. Under a stream of argon, with cooling tube 500
In a milliliter three-necked flask, 1.7 g (5 mmol) of 9-10 dibromoanthracene and 0.2 g (5 mo) of dichlorobis (triphenylphosphine) palladium
1%), 0.5 ml of diisobutylaluminum hydride / toluene solution (1 M, 0.5 mmol),
100 ml of THF was added. Here, the Gr
After the dropwise addition of an Igard reagent at room temperature, the temperature was raised 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.
Washing was performed in the order of 50 ml 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
%).

Structural formula of the above intermediate and compound (122)
Is shown below.

Embedded image

Synthesis Example 20 (Compound (123)) Synthesis of Intermediate X 16 g (0.1 mol) of bromobenzene, 9.8 g (50 mmol) of aminostilbene, tris (Dibenzylidesiacetone) 0.69 g of divalazium
(1.5 mol%), tri-o-toluylphosphine
0.46 g (3 mol%), sodium t-butoxide
After adding 7.2 g (75 mmol) and 100 ml of dry toluene, the mixture was heated and stirred at 100 ° C. overnight.
After completion of the reaction, the precipitated crystals were collected by filtration, and methanol 10
After washing with 0 ml, the resulting crude crystals were recrystallized with 50 ml of ethyl acetate to obtain the desired intermediate X
11 g (80% yield) were obtained. Synthesis of Intermediate Y 38 g (0.16 mol) of bromobenzene was placed in a 500-liter three-necked flask equipped with a condenser under an argon stream.
Intermediate X 11 g (40 mmol), tris (dibenzylidesiacetone) divaladium 0.55 g (1.5 m
ol%), 0.37 g of tri-o-toluylphosphine
(3 mol%), t-butoxy sodium 5.8 g
(60 mmol) and 300 ml of dry toluene were added, and the mixture was heated and stirred at 120 ° C. overnight. After completion of the reaction, the precipitated crystals were collected by filtration, washed with 100 ml of methanol, and the obtained crude crystals were washed with 50 ml of ethyl acetate.
Recrystallize in milliliters to obtain the desired intermediate Y13
g (75% yield).

Synthesis of Compound (123) 0.97 g (40 mmol) of magnesium was placed in a 300 ml three-necked flask equipped with a condenser under a stream of argon.
l), a small piece of iodine and 50 ml of THF were added, and the mixture was stirred at room temperature for 30 minutes.
mol) / 100 ml of THF was added dropwise.
After completion of the dropwise addition, the mixture was stirred at 60 ° C. for 1 hour to prepare a Grignard reagent. Under a stream of argon, 3.4 g (10 mmol) of 9,10-dibromoanthracene and 0.4 g of dichlorobis (triphenylphosphine) palladium were placed in a 500 ml three-necked flask equipped with a condenser.
1%), diisobutylaluminum hydride / toluene solution 1 ml (1 M, 1 mmol), THF1
00 ml was added. Here the above Grinar
After the reagent d was added dropwise at room temperature, the temperature was raised 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 5.4 g of a yellow powder.
This powder was identified as compound (122) by the measurement of NMR, IR and FD-MS (yield: 50%).

Structural formula of the above intermediate and compound (123)
Is shown below.

Embedded image

Synthesis Example 21 (Compound (124)) Synthesis of Compound (124) 2.5 g (5 mmol) of 10,10′-dibromo-9,9′-bianthril in a 500 ml three-necked flask equipped with a condenser under a stream of argon. ), Dichlorobis (triphenylphosphine) palladium 0.2 g (5 mo
1%), 0.5 ml of diisobutylaluminum hydride / toluene solution (1 M, 0.5 mmol),
100 ml of THF was added. The Grignard reagent prepared in Synthesis Example (19) 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 2.0 g of a yellow powder. This powder is NMR,
The powder was identified as Compound (124) by the measurement of IR and FD-MS (yield: 60%).

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

Embedded image

Synthesis Example 22 (Compound (125)) Synthesis of Compound (125) 1.9 g (5,12) of dibromochrysene was placed in a 500 ml three-necked flask equipped with a condenser under a stream of argon.
mmol), dichlorobis (triphenylphosphine)
0.2 g (5 mol%) of palladium, 0.5 ml (1 M, 0.5 mmol) of a diisobutylaluminum hydride / toluene solution, and 100 ml of THF were added. Here, Grig prepared in Synthesis Example (19)
After the nard reagent was added dropwise at room temperature, the temperature was raised 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.
Washing in the order of milliliters gave 2.1 g of a yellow powder. This powder was identified as Compound (125) by NMR, IR and FD-MS measurements (60% yield).

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

Embedded image

Synthesis Example 23 (Compound (126)) Synthesis of Compound (126) 1.9 g of 5,12-dibromonaphthacene was placed in a 500 ml three-necked flask equipped with a condenser under a stream of argon.
(5 mmol), 0.2 g (5 mol%) of dichlorobis (triphenylphosphine) palladium, 0.5 ml (1 M, 0.5 mmol) of a diisobutylaluminum hydride / toluene solution, and 100 ml of THF were added. Here, G prepared in Synthesis Example (19)
After the dropwise addition of the reagent, 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, washed with 50 ml of methanol and 50 ml of acetone 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
%).

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

Embedded image

[0167]

The above general formulas [1] and [3] of the present invention
[6] and

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

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Hidetoshi Koga 1280 Kamiizumi, Sodegaura-shi, Chiba Prefecture (72) Inventor Hidetsugu Ikeda 1280, Kamiizumi, Sodegaura-shi, Chiba F term (reference) 3K007 AB00 AB02 AB03 AB06 AB14 CA01 CB01 DA00 DB03 EB00 FA01

Claims (16)

[Claims] An organic electro-chemical compound represented by the following general formula [1]:
Materials for troll luminescence elements. General formula [1][In the formula, A is a substituted or unsubstituted carbon atom having 22 to 6 carbon atoms.
Represents an arylene group of 0. X¹~ X^FourAre independent
Is a substituted or unsubstituted aryl having 6 to 30 carbon atoms.
X represents a len group¹And X^Two, X^ThreeAnd X^FourAre connected to each other
May be. Y ¹~ Y^FourIs, independently of each other,
Represents an organic group represented by the general formula [2]. ad is 0-2
Represents an integer. However, when A has 26 or less carbon atoms,
Is a + b + c + d> 0, and two or more anthra
Does not include Sen nuclei. General formula [2](Where R¹~ R^FourAre each independently a hydrogen atom,
A substituted or unsubstituted alkyl group having 1 to 20 carbon atoms,
Substituted or unsubstituted aryl having 6 to 20 carbon atoms
Group, a cyano group, or R¹And R^TwoOr R^ThreeAnd R^FourBut
Represents a bound triple bond. Z is a substituted or unsubstituted charcoal
Represents an aryl group having 6 to 20 elementary atoms. n is 0 or
Represents 1. )] 2. A material for an organic electroluminescence device represented by the following general formula [3]. General formula [3] [Wherein B 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, at least one of B, 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,
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. )] 3. The material for an organic electroluminescent device according to claim 2, wherein the general formula [3] is represented by the following general formula [4]. General formula [4] [Wherein, X ^{1 to} X ⁴ , Y ^{1 to} Y ⁴ and a to d are the same as described above. ] 4. The material for an organic electroluminescence device according to claim 2, wherein the general formula [3] is represented by the following general formula [5]. General formula [5] [Wherein, B, X ¹ -X ² , Y ¹ -Y ² and a-b are the same as above. ] 5. The material for an organic electroluminescence device according to claim 2, wherein the general formula [3] is represented by the following general formula [6]. General formula [6] [Wherein, B, X ¹ -X ² , Y ¹ -Y ² and a-b are the same as above. ] 6. An organic element represented by the following general formula [7]:
Materials for troll luminescence elements. General formula [7][Wherein D contains a tetracene nucleus or a pentacene nucleus
Represents a divalent group. X ¹~ X^FourAre, independently of each other,
Substituted or unsubstituted arylene having 6 to 30 carbon atoms
X represents a group¹And X^Two, X^FourAnd X^ThreeAre connected to each other
May be. Y¹~ Y^FourIs, independently of each other,
Represents an organic group represented by [2]. ad is an integer of 0 to 2
Represents General formula [2](Where R¹~ R^FourAre each independently a hydrogen atom,
A substituted or unsubstituted alkyl group having 1 to 20 carbon atoms,
Substituted or unsubstituted aryl having 6 to 20 carbon atoms
Group, a cyano group, or R¹And R^TwoOr R^ThreeAnd R^FourBut
Represents a bound triple bond. Z is a substituted or unsubstituted charcoal
Represents an aryl group having 6 to 20 elementary atoms. n is 0 or
Represents 1. )] 7. The material for an organic electroluminescence device according to claim 6, wherein the general formula [7] is represented by the following general formula [8]. General formula [8] Wherein X ^{1 to} X ⁴ , Y ^{1 to} Y ⁴ and a to d are each independently the same as described above. R ^{51 to} R ⁶⁰ each independently represent a hydrogen atom, a substituted or unsubstituted carbon atom
A substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, and a cyano group. Adjacent R ^{51 to} R ⁶⁰ may be linked to each other to form a saturated or unsaturated, substituted or unsubstituted carbon ring. ] 8. A material for an organic electroluminescence device represented by the following general formula [9]. General formula [9] [In the formula, E represents a divalent group comprising an aryl group-substituted or unsubstituted anthracene nucleus. X ^{5 to} X ⁸ each independently represent a substituted or unsubstituted arylene group having 6 to 20 carbon atoms, and X ⁵ and X ⁶ , and X ⁷ and X ⁸ may be connected to each other. Y ^{1 to} Y ⁴ are each independently:
It represents an organic group represented by the following general formula [2]. ad is 0
Represents an integer of ２2. Provided that E is unsubstituted. When at least two of X ^{5 to} X ⁸ are substituted or unsubstituted including. 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. A material for an organic electroluminescence device represented by the following general formula [10]. General formula [10] [Wherein, Ar ¹ and Ar ³ each independently represent a substituted or unsubstituted phenylene, a substituted or unsubstituted 1,3
Naphthalene, substituted or unsubstituted 1,8 naphthalene,
Represents a divalent group consisting of a substituted or unsubstituted fluorene or a 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, 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. X ^{5 to} X ⁸ each independently represent a substituted or unsubstituted arylene group having 6 to 20 carbon atoms, and X ⁵ and X ⁶ , and X ⁷ and X ⁸ may be connected to each other. Y ^{1 to} Y ⁴ are each independently represented by the following general formula [2]
Represents an organic group represented by a to d represent integers of 0 to 2, and a + b + c + d ≦ 2. e is 0 or 1, f
Represents 1 or 2. However, when Ar ² is an anthracene nucleus, a = b = c = d and the case where both Ar ¹ and Ar ³ are p-phenylene groups is excluded. 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. )] 10. The material for an organic electroluminescence device according to claim 1, which is a light emitting material for an organic electroluminescence device. 11. 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 at least one of the organic compound thin films is any one of claims 1 to 9. 3. An organic electroluminescent device, comprising a layer containing the material for an organic electroluminescent device according to item 1. 12. 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 organic electroluminescent device according to claim 1 is used. An organic electroluminescence device comprising a layer containing at least one material selected from a hole injection material, a hole transport material, and a doping material, between the electrodes. 13. An organic electroluminescence device in which a light emitting layer or a plurality of organic compound thin films including the light emitting layer is formed between a pair of electrodes, wherein the light emitting layer is formed.
An organic electroluminescent device comprising 0.1 to 20% by weight of the material for an organic electroluminescent device according to any one of items 1 to 9. 14. 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, selected from a hole injection material, a hole transport material, and a doping material. An organic electroluminescent device, characterized in that the organic electroluminescent device material according to any one of claims 1 to 9 is independently contained in the at least one type of material in an amount of 0.1 to 20% by weight. 15. An organic electroluminescence device in which a light emitting layer or a plurality of organic compound thin films including the light emitting layer is formed between a pair of electrodes, wherein the light emitting layer is a stilbene derivative and any one of claims 1 to 9. An organic electroluminescence device, which is a layer containing the device material described in the above. 16. The method according to claim 11, wherein a layer containing an aromatic tertiary amine derivative and / or a phthalocyanine derivative is formed between the light emitting layer and the anode.
5. The organic electroluminescent device according to any one of 5.