JP2001335516A - Organic electroluminescence device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel compound which emits blue light with excellent luminous efficiency, heat resistance, long life and good color purity, and an organic electroluminescence (EL) device using the same. provide. A general formula A having a diphenylanthracene structure at the center and an aryl group-substituted specific structure at a terminal,
For example, novel compounds of formula 15. An organic EL 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 contains the novel compound.

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 illuminator of a wall-mounted television or a backlight of a display, and emits a blue light with high luminous efficiency, excellent heat resistance, long life and good color purity. The present invention relates to a novel compound and an organic electroluminescence device using the same.

[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, JP-A-8-12600 discloses an organic EL device using a dimer or trimer compound of phenylanthracene. An organic EL device using this compound contains 2 or 3 anthracene. Because of the connection by a conjugate group, the energy gap was small, and the color purity of blue light emission was inferior. In addition, this compound has a problem in that it is easily oxidized, has impurities, and is easily purified. Therefore, an organic EL using a compound in which the 1,9-position of anthracene is substituted with naphthalene or a compound in which the phenyl group of diphenylanthracene is substituted with m-aryl.
Although devices have been tried, the luminous efficiency was low and it was not practical. Japanese Patent Application Laid-Open No. 11-3782 discloses an organic E using a monoanthracene derivative substituted with a naphthalene.
An L element is disclosed. However, the luminous efficiency is 1
As low as cd / A, it was not practical. Further, U.S. Pat. No. 5,972,247 discloses an organic EL device using a compound having a phenylanthracene structure. However, this compound has excellent heat resistance due to aryl substitution at the m-position, but has a low luminous efficiency of about 2 cd / A and is not practical.

[0003]

DISCLOSURE OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and has a novel luminous efficiency, high heat resistance, a long life, and a blue color with good color purity. An object of the present invention is to provide a compound and an organic electroluminescence device using the compound.

[0004]

The present inventors have conducted intensive studies to develop a novel compound having the above-mentioned preferable properties and an organic electroluminescence device (hereinafter, referred to as an organic EL device) using the same. It has been found that the object can be achieved by using a novel compound having a specific structure having a diphenylanthracene structure at the center and substituted with an aryl group at the terminal. The present invention has been completed based on such findings.

That is, the novel compounds of the present invention are compounds represented by the following general formulas [A], [1] to [5] and [3 '].

The general formula [A]

Embedded image [Wherein, R ^{1 to} R ⁸ each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted carbon atom 1 to 20 alkoxy groups, substituted or unsubstituted aryloxy groups having 6 to 30 carbon atoms, substituted or unsubstituted alkylthio groups having 1 to 20 carbon atoms, substituted or unsubstituted 6 to 30 carbon atoms An arylthio group, a substituted or unsubstituted arylalkyl group having 7 to 30 carbon atoms, an unsubstituted monocyclic group having 5 to 30 carbon atoms, a substituted or unsubstituted fused polycyclic group having 10 to 30 carbon atoms, or Substituted or unsubstituted 5 to 30 carbon atoms
Is a heterocyclic group. Ar ³ and Ar ⁴ are each independently a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, and the substituent is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, Unsubstituted alkoxy group having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, substituted or unsubstituted alkylthio group having 1 to 20 carbon atoms, substituted or unsubstituted carbon atom An arylthio group having 6 to 30 atoms, a substituted or unsubstituted arylalkyl group having 6 to 30 carbon atoms, an unsubstituted monocyclic group having 5 to 30 carbon atoms,
It is a substituted or unsubstituted fused polycyclic group having 10 to 30 carbon atoms, a substituted or unsubstituted heterocyclic group having 5 to 30 carbon atoms, or a substituted or unsubstituted alkenyl group having 4 to 40 carbon atoms. However, this excludes the case where Ar ³ and Ar ⁴ are unsubstituted phenyl groups. ]

The general formula [1]

Embedded image[Wherein, R¹~ R^TenAre each independently a hydrogen atom,
Logen atom, cyano group, nitro group, substituted or unsubstituted
An alkyl group having 1 to 20 carbon atoms, substituted or unsubstituted
A substituted alkoxy group having 1 to 20 carbon atoms,
Unsubstituted aryloxy group having 6 to 30 carbon atoms, substitution
Or unsubstituted alkylthio having 1 to 20 carbon atoms
Group, substituted or unsubstituted aryl having 6 to 30 carbon atoms
A luthio group, substituted or unsubstituted having 7 to 30 carbon atoms
Arylalkyl group, unsubstituted C 5 -C 30
Ring group, substituted or unsubstituted 10 to 30 carbon atoms
Polycyclic ring group or substituted or unsubstituted 5 to 30 carbon atoms
Is a heterocyclic group. Ar¹And Ar^TwoAre independent
Is a substituted or unsubstituted aryl having 6 to 30 carbon atoms.
And the substituent is a substituted or unsubstituted carbon
An alkyl group having 1 to 20 atoms, substituted or unsubstituted
C1-C20 alkoxy group, substituted or unsubstituted
A substituted aryloxy group having 6 to 30 carbon atoms,
Or an unsubstituted alkylthio group having 1 to 20 carbon atoms,
Substituted or unsubstituted arylthio having 6 to 30 carbon atoms
Aryl, substituted or unsubstituted aryl having 7 to 30 carbon atoms
Alkyl group, unsubstituted monocyclic group having 5 to 30 carbon atoms,
A substituted or unsubstituted fused polycyclic ring having 10 to 30 carbon atoms
A group or a substituted or unsubstituted C5-C30 complex
It is a ring group. Where R⁹And R^TenIs a hydrogen atom and Ar
¹And Ar^TwoIs an unsubstituted phenyl group;⁹
And R^TenIs an aryl group substituted at the meta position and Ar¹as well as
Ar ^TwoIs an aryl group substituted at the meta position
Good. ]

The general formula [2]

Embedded image [Wherein, R ^{1 to} R ¹⁰ each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted carbon atom 1 to 20 alkoxy groups, substituted or unsubstituted aryloxy groups having 6 to 30 carbon atoms, substituted or unsubstituted alkylthio groups having 1 to 20 carbon atoms, substituted or unsubstituted 6 to 30 carbon atoms An arylthio group, a substituted or unsubstituted arylalkyl group having 7 to 30 carbon atoms, an unsubstituted monocyclic group having 5 to 30 carbon atoms, a substituted or unsubstituted fused polycyclic group having 10 to 30 carbon atoms, or Substituted or unsubstituted 5 to 30 carbon atoms
Is a heterocyclic group. Ar ³ and Ar ⁴ are each independently a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, and the substituent is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, Unsubstituted alkoxy group having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, substituted or unsubstituted alkylthio group having 1 to 20 carbon atoms, substituted or unsubstituted carbon atom An arylthio group having 6 to 30 atoms, a substituted or unsubstituted arylalkyl group having 7 to 30 carbon atoms, an unsubstituted monocyclic group having 5 to 30 carbon atoms,
It is a substituted or unsubstituted fused polycyclic group having 10 to 30 carbon atoms, a substituted or unsubstituted heterocyclic group having 5 to 30 carbon atoms, or a substituted or unsubstituted alkenyl group having 4 to 40 carbon atoms. n is 1-3 and m is 1-3. ]

The general formula [3]

Embedded image [Wherein, R ^{1 to} R ⁸ each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted carbon atom 1 to 20 alkoxy groups, substituted or unsubstituted aryloxy groups having 6 to 30 carbon atoms, substituted or unsubstituted alkylthio groups having 1 to 20 carbon atoms, substituted or unsubstituted 6 to 30 carbon atoms An arylthio group, a substituted or unsubstituted arylalkyl group having 7 to 30 carbon atoms, an unsubstituted monocyclic group having 5 to 30 carbon atoms, a substituted or unsubstituted fused polycyclic group having 10 to 30 carbon atoms, or Substituted or unsubstituted 5 to 30 carbon atoms
Is a heterocyclic group. Ar ³ and Ar ⁴ are each independently a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, and the substituent is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, Unsubstituted alkoxy group having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, substituted or unsubstituted alkylthio group having 1 to 20 carbon atoms, substituted or unsubstituted carbon atom An arylthio group having 6 to 30 atoms, a substituted or unsubstituted arylalkyl group having 6 to 30 carbon atoms, an unsubstituted monocyclic group having 5 to 30 carbon atoms,
It is a substituted or unsubstituted fused polycyclic group having 10 to 30 carbon atoms, a substituted or unsubstituted heterocyclic group having 5 to 30 carbon atoms, or a substituted or unsubstituted alkenyl group having 4 to 40 carbon atoms. ]

The general formula [3 ']

Embedded image [Wherein, R ^{1 to} R ⁸ each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted carbon atom 1 to 20 alkoxy groups, substituted or unsubstituted aryloxy groups having 6 to 30 carbon atoms, substituted or unsubstituted alkylthio groups having 1 to 20 carbon atoms, substituted or unsubstituted 6 to 30 carbon atoms An arylthio group, a substituted or unsubstituted arylalkyl group having 7 to 30 carbon atoms, an unsubstituted monocyclic group having 5 to 30 carbon atoms, a substituted or unsubstituted fused polycyclic group having 10 to 30 carbon atoms, or Substituted or unsubstituted 5 to 30 carbon atoms
Is a heterocyclic group. ]

The general formula [4]

Embedded image [Wherein, R ^{1 to} R ⁸ each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted carbon atom 1 to 20 alkoxy groups, substituted or unsubstituted aryloxy groups having 6 to 30 carbon atoms, substituted or unsubstituted alkylthio groups having 1 to 20 carbon atoms, substituted or unsubstituted 6 to 30 carbon atoms An arylthio group, a substituted or unsubstituted arylalkyl group having 7 to 30 carbon atoms, an unsubstituted monocyclic group having 5 to 30 carbon atoms, a substituted or unsubstituted fused polycyclic group having 10 to 30 carbon atoms, or Substituted or unsubstituted 5 to 30 carbon atoms
Is a heterocyclic group. R ^{9 ′} and R ^{10 ′} are each independently a substituted or unsubstituted alkenyl group having 8 to 30 carbon atoms. Ar ¹ and Ar ² are each independently:
A substituted or unsubstituted aryl group having 6 to 30 carbon atoms, wherein the substituent is 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 group, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted alkylthio group having 1 to 20 carbon atoms, a substituted or unsubstituted arylthio group having 6 to 30 carbon atoms,
A substituted or unsubstituted arylalkyl group having 7 to 30 carbon atoms, an unsubstituted monocyclic group having 5 to 30 carbon atoms, a substituted or unsubstituted fused polycyclic group having 10 to 30 carbon atoms, or a substituted or unsubstituted It is a substituted heterocyclic group having 5 to 30 carbon atoms. ]

General formula [5]

Embedded image [Wherein, R ^{1 to} R ¹⁰ each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted carbon atom 1 to 20 alkoxy groups, substituted or unsubstituted aryloxy groups having 6 to 30 carbon atoms, substituted or unsubstituted alkylthio groups having 1 to 20 carbon atoms, substituted or unsubstituted 6 to 30 carbon atoms An arylthio group, a substituted or unsubstituted arylalkyl group having 7 to 30 carbon atoms, an unsubstituted monocyclic group having 5 to 30 carbon atoms, a substituted or unsubstituted fused polycyclic group having 10 to 30 carbon atoms, or Substituted or unsubstituted 5 to 30 carbon atoms
Is a heterocyclic group. Provided that at least one of R ^{1 to} R ⁸ is an alkyl group, an alkoxy group, an aryloxy group,
It is an alkylthio group, an arylthio group, an arylalkyl group, a monocyclic group, a condensed polycyclic group or a heterocyclic group. Ar ^{3 ′} and Ar ^{4 ′} are each independently a substituted or unsubstituted alkenyl group having 8 to 30 carbon atoms. n is 1-2,
m is 1-2. ]

The organic EL device of the present invention is an organic electroluminescent device comprising a light-emitting layer or a plurality of organic compound thin films including a light-emitting layer formed between a pair of electrodes. It contains any of the novel compounds represented by the general formulas [A], [1] to [5] and [3 '].

The light-emitting layer is formed of the general formulas [A] and [1].
It is preferable to contain any of the novel compounds represented by-[5] and [3 ']. The light emitting layer may contain any of the novel compounds represented by the general formulas [A], [1] to [5], and [3 ′] and a fluorescent dopant. The organic EL device of the present invention has a peak wavelength of 460.
It is preferable that the light emission is not more than nm. The fluorescent dopant is preferably an amine compound.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The novel compounds useful for the organic EL device emitting blue light of the present invention are represented by the above general formulas [A] and [1]-
It is represented by either [5] or [3 ']. R ^{1 to} R ⁸ in the general formula [A] each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted An alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted alkylthio group having 1 to 20 carbon atoms, a substituted or unsubstituted 6 carbon atom ~ 30 arylthio groups, substituted or unsubstituted 7 to 7 carbon atoms
30 arylalkyl groups, unsubstituted 5 to 3 carbon atoms
0 monocyclic group, substituted or unsubstituted 10 to 3 carbon atoms
0 fused polycyclic group or 5 substituted or unsubstituted carbon atoms
To 30 heterocyclic groups. A in the general formula [A]
r ³ and Ar ⁴ are each independently a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, and the substituent is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, Unsubstituted alkoxy group having 1 to 20 carbon atoms, substituted or unsubstituted 6 to 3 carbon atoms
0 aryloxy group, substituted or unsubstituted alkylthio group having 1 to 20 carbon atoms, substituted or unsubstituted arylthio group having 6 to 30 carbon atoms, substituted or unsubstituted arylalkyl having 6 to 30 carbon atoms Group, unsubstituted monocyclic group having 5 to 30 carbon atoms, substituted or unsubstituted fused polycyclic group having 10 to 30 carbon atoms, substituted or unsubstituted heterocyclic group having 5 to 30 carbon atoms or substituted Alternatively, it is an unsubstituted alkenyl group having 4 to 40 carbon atoms. However, this excludes the case where Ar ³ and Ar ⁴ are unsubstituted phenyl groups. When Ar ³ and / or Ar ⁴ is an aryl group, it is preferable that the number of carbon atoms be 10 or more, since the glass transition temperature is high.

R ^{1 to} R ¹⁰ in the general formula [1] are:
The same as R ^{1 to} R ⁸ in the general formula [A]. Ar ¹ and Ar ² in the above general formula [1] are each independently a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, and the substituent is a substituted or unsubstituted carbon atom having 1 to 30 carbon atoms. 20 alkyl groups, substituted or unsubstituted alkoxy groups having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy groups having 6 to 30 carbon atoms, substituted or unsubstituted alkylthio groups having 1 to 20 carbon atoms A substituted or unsubstituted arylthio group having 6 to 30 carbon atoms, a substituted or unsubstituted arylalkyl group having 7 to 30 carbon atoms, an unsubstituted monocyclic group having 5 to 30 carbon atoms,
It is a substituted or unsubstituted fused polycyclic group having 10 to 30 carbon atoms or a substituted or unsubstituted heterocyclic group having 5 to 30 carbon atoms. However, in the general formula [1], R
^{When 9} and R ¹⁰ are a hydrogen atom and Ar ¹ and Ar ² are unsubstituted phenyl groups, an aryl group where R ⁹ and R ¹⁰ are substituted at the meta position and an aryl group where Ar ¹ and Ar ² are substituted at the meta position Except when it is a group.

R ^{1 to} R ¹⁰ in the general formula [2] are:
The same as R ^{1 to} R ⁸ in the general formula [A]. Ar ³ and Ar ⁴ in the general formula [2] are represented by the general formula [A]
Are the same as Ar ³ and Ar ⁴ . In the general formula [2], n is 1 to 3 and m is 1 to 3.

R ^{1 to} R ⁸ in the general formula [3] are:
The same as R ^{1 to} R ⁸ in the general formula [A]. Ar ³ and Ar ⁴ in the general formula [3] are represented by the general formula [A]
Are the same as Ar ³ and Ar ⁴ . R ¹ to R in the general formula [3 '] ⁸ is the same as R ¹ to R ⁸ in the general formula (A).

As the above Ar ^{1 to} Ar ⁴ , for example,

Embedded image And alkyl-, alkoxy- or aryl-substituted products thereof.

R ^{1 to} R ⁸ in the general formula [4] are:
It is the same as R ^{1 to} R ⁸ in the general formula [A], and R ^{9 ′} and R ^{10 ′} are each independently a substituted or unsubstituted alkenyl group having 8 to 30 carbon atoms. Ar ¹ and Ar ² in formula (4) are the same as those for Ar ¹ and Ar ² in the general formula (1). The above general formula [4]
Since R ^{9 ′} and R ^{10 ′} are alkenyl groups, the compound has high fluorescence when used in an organic EL device,
Luminous efficiency is improved.

R ^{1 to} R ¹⁰ in the general formula [5] are:
The same as R ^{1 to} R ⁸ in the general formula [A]. However, at least one of R ^{1 to} R ⁸ is an alkyl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an arylalkyl group, a monocyclic group, a condensed polycyclic group or a heterocyclic group. Ar ^{3 ′} and Ar ^{4 ′} in the general formula [5] are each independently a substituted or unsubstituted alkenyl group having 8 to 30 carbon atoms. In the compound of the general formula [5], at least one of R ^{1 to} R ⁸ is an alkyl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an arylalkyl group, a monocyclic group, a condensed polycyclic group or a heterocyclic group. Organic EL
When used in an element, the uniformity of light emission on the light emitting surface is increased, and defects are less likely to occur.

The organic EL device of the present invention is, as described above, an organic electroluminescent device comprising a light emitting layer or a plurality of organic compound thin films including a light emitting layer formed between a pair of electrodes. At least one layer has the general formula [A], [1] to [5] and [3 ′]
Which contains any of the novel compounds. In the organic compound thin film, any one of the novel compounds represented by the general formulas [A], [1] to [5] and [3 '] is 1 to 1
It is preferably contained in an amount of 10 mol
More preferably, the content is 8 mol%. The organic EL device of the present invention emits blue light.

The general formulas [A] and [1] of the present invention will be described below.
Representative examples (1) to (40) of the compounds of [5] and [3 ']
However, the present invention is not limited to this representative example.

[0024]

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[0025]

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[0026]

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[0027]

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[0028]

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[0029]

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[0030]

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[0031]

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[0032]

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The organic EL device of the present invention is a device in which one or more organic layers are formed between an anode and a cathode. In the case of a single layer type, a light emitting layer is provided between an anode and a cathode. The light-emitting layer contains a light-emitting material and may further contain a hole-injection material or an electron-injection material for transporting holes injected from an anode or electrons injected from a cathode to the light-emitting material. However, it is preferable that the light emitting material has extremely high fluorescence quantum efficiency, high hole transport ability and electron transport ability, and forms a uniform thin film. The multilayer organic EL device includes (anode / hole injection layer / light-emitting layer / cathode), (anode / light-emitting layer / electron injection layer / cathode),
Some of them are stacked in a multilayer structure (anode / hole injection layer / light emitting layer / electron injection layer / cathode).

In the light emitting layer, if necessary, in addition to any of the compounds represented by the general formulas [A], [1] to [5] and [3 '] of the present invention, further known light emitting materials and doping materials Alternatively, a hole injection material or an electron injection material may be used. When the organic EL element has a multilayer structure, it is possible to prevent a decrease in luminance and life due to quenching.
If necessary, light emitting materials, other doping materials, hole injection materials and electron injection materials can be used in combination. Further, with other doping materials, emission luminance and emission efficiency can be improved, and red or white light emission can be obtained.
Further, each of the hole injection layer, the light emitting layer, and the electron injection layer may be formed with two or more layers. In that case,
In the case of a hole injection layer, a layer that injects holes from the electrode is called a hole injection layer, and a layer that receives holes from the hole injection layer and transports holes to the light emitting layer is called a hole transport layer. Similarly, in the case of an electron injection layer, a layer that 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. These layers are selected and used depending on factors such as the energy level of the material, heat resistance, and adhesion to the organic layer or the metal electrode.

The light emitting material or host material which can be used in the organic layer together with any of the compounds of the general formulas [A], [1] to [5] and [3 '] 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, amino Quinoline metal complex, benzoquinoline metal complex, imine,
Diphenylethylene, vinylanthracene, diaminocarbazole, pyran, thiopyran, polymethine, merocyanine, imidazole chelated oxinoid compound,
Examples include, but are not limited to, quinacridone, rubrene, stilbene derivatives, and fluorescent dyes.

The hole injecting material has the ability to transport holes, has the effect of injecting holes from the anode, has an excellent hole injecting effect on the light emitting layer or the light emitting material, and is produced in the light emitting layer. 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. Further, the charge 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 nitrogen-containing five-membered derivative is preferably an oxazole, thiazole, oxadiazole, thiadiazole or triazole derivative. In particular,
2,5-bis (1-phenyl) -1,3,4-oxazole, dimethyl POPOP, 2,5-bis (1-phenyl) -1,3,4-thiazole, 2,5-bis (1-phenyl) ) -1,3,4-oxadiazole, 2- (4 ′
-Tert-butylphenyl) -5- (4 "-biphenyl) 1,3,4-oxadiazole, 2,5-bis (1
-Naphthyl) -1,3,4-oxadiazole, 1,4
-Bis [2- (5-phenyloxadiazolyl)] benzene, 1,4-bis [2- (5-phenyloxadiazolyl) -4-tert-butylbenzene], 2- (4 '
-Tert-butylphenyl) -5- (4 "-biphenyl) -1,3,4-thiadiazole, 2,5-bis (1
-Naphthyl) -1,3,4-thiadiazole, 1,4-
Bis [2- (5-phenylthiadiazolyl)] benzene, 2- (4'-tert-butylphenyl) -5- (
4 "-biphenyl) -1,3,4-triazole, 2,
5-bis (1-naphthyl) -1,3,4-triazole, 1,4-bis [2- (5-phenyltriazolyl)
Benzene and the like, but are not limited thereto.

In the organic EL device of the present invention, in addition to the compounds of the general formulas [A], [1] to [5] and [3 '], a light emitting material, a doping material and a hole injection At least one of the material and the electron injection material may be contained in the same layer. Further, in order to improve the stability of the organic EL device obtained according to the present invention with respect to temperature, humidity, atmosphere, etc., a protective layer may be provided on the surface of the device, or silicone oil,
It is also possible to protect the entire element with a resin or the like.

As the conductive material used for the anode of the organic EL device, those having a work function of more than 4 eV are suitable, and include carbon, aluminum, vanadium, iron, cobalt, nickel, tungsten, silver, gold, and platinum. , Palladium and their alloys, metal oxides such as tin oxide and indium oxide used for ITO substrates and NESA substrates,
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 has transparency, 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.

Each layer of the organic EL device according to the present invention can be formed by any of dry film forming methods such as vacuum evaporation, 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 novel compound of the present invention for the organic layer of the organic EL device, an organic EL device which emits blue light with high luminous efficiency, excellent heat resistance, long life and good color purity can be obtained. An element can be obtained. The organic EL element 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 copier, a printer, a light source such as a backlight or a meter of a liquid crystal display, a display board, a sign lamp and the like.

[0047]

The present invention will be described below in more detail with reference to Synthesis Examples and Examples. Synthesis Example 1 (Compound 14) (1) Synthesis of 2,2′-dibromobiphenyl Under an argon atmosphere, 1,2-dibromobenzene (25 g, 0.1 g) was used.
11mol) was dissolved in anhydrous THF (240ml) and cooled to -67 ° C in a dry ice / methanol bath. An n-butyllithium / hexane solution (1.50 mol / l, 35 ml, 53 mmol, 0.5 eq) was added thereto.
It was dropped slowly over a period of minutes. After stirring at -67 ° C for 1 hour, the mixture was stirred at room temperature for 3 hours. To the reaction mixture was added a saturated aqueous ammonium chloride solution (100 ml), and the organic layer was separated.
(50 ml), dried over anhydrous magnesium sulfate, and evaporated to give a brown liquid (ca. 19 g). This was purified by column chromatography (silica gel / hexane) to give white needles.
(9.5 g, 57%). ¹ H-NMR (CDCl ₃ , TMS) δ 7.2-7.4 (6H, m), 7.6-7.7 (2H,
m)

(2) Synthesis of 2-phenyl-2'-bromobiphenyl 2,2'-dibromobiphenyl (9.5
g, 30 mmol), phenylboronic acid (3.7 g, 30 mmol), tetrakis (triphenylphosphine) palladium (0) (1.0 g,
0.87 mmol, 3% Pd) was dissolved in toluene (75 ml), an aqueous sodium carbonate solution (9.7 g, 92 mmol, 3 eq / 46 ml) was added, the mixture was refluxed for 10 hours, and left overnight. The organic layer was separated, and saturated saline (5
0ml), dried over anhydrous magnesium sulfate, and evaporated to give a dark yellow oil. This was purified by column chromatography (silica gel / hexane, then hexane + 3% dichloromethane, and finally hexane + 5% dichloromethane) to obtain a colorless oil (6.5 g, 70%). ¹ H-NMR (CDCl ₃ , TMS) δ 6.6-6.7 (1H, m), 7.0-7.6 (12
H, m)

(3) 9,10-bis (2- (2-phenylphenyl) phenyl) -9,10-dihydroxy-
Synthesis of 9,10-dihydroanthracene Under an argon atmosphere, 2-phenyl-2'-bromobiphenyl (6.5 g, 21 mmol, 2.5 eq) was dissolved in a mixed solvent of anhydrous toluene (25 ml) and anhydrous THF (25 ml), and dried on ice. / Methanol bath to -30 ° C. An n-butyllithium / hexane solution (1.50 mol / l, 15 ml, 23 mmol, 1.1 eq) was added thereto, and the mixture was stirred at -20 ° C for 1 hour. Anthraquinone (1.7 g, 8.2 mmol) was added thereto, and the mixture was added at -20 ° C for 1 hour and at room temperature for 2 hours.
Stirred for hours and left overnight. A saturated ammonium chloride aqueous solution (20 ml) was added to the reaction mixture, and the resulting solid was filtered off.
After washing with water, methanol and acetone, a white solid (2.9 g, 5
3%). ¹ H-NMR (CDCl ₃ , TMS) δ 0.47 (2H, s), 5.7-5.8 (2H,
m), 6.3-7.4 (30H, m), 8.3-8.4 (2H, m)

(4) Synthesis of 9,10-bis (2- (2-phenylphenyl) phenyl) anthracene (Compound 14) 9,10-bis (2- (2-phenylphenyl) phenyl) -9,10- Dihydroxy-9,10-dihydroanthracene (2.9 g, 4.3 mmol) was suspended in acetic acid (45 ml).
% Hydroiodic acid (6 ml, 45 mmol, 10 eq) was added, and the mixture was stirred at 100 ° C. for 6 hours. Add 50% aqueous hypophosphorous acid solution (3
0 ml), and the solid was filtered off and washed with water, methanol and acetone to give a pale yellow solid (2.4 g, 88%). ¹ H-NMR (CDCl ₃ , TMS) δ 6.7-7.5 (34H, m).

Synthesis Example 2 (Compound 15) (1) Synthesis of 1- (2-bromophenyl) naphthalene 2-bromoiodobenzene (7.0 g, 2
5 mmol), naphthaleneboronic acid (4.0 g, 23 mmol), tetrakis (triphenylphosphine) palladium (0) (0.5 g, 0.1 g).
43 mmol, 1.7% Pd) was dissolved in toluene (50 ml), an aqueous sodium carbonate solution (7.3 g, 69 mmol, 3 eq / 35 ml) was added, the mixture was refluxed for 10 hours, and left overnight. The organic layer was separated, and saturated saline (5
0ml), dried over anhydrous magnesium sulfate and evaporated to give a yellow oil. This was purified by column chromatography (silica gel / hexane, then hexane + 3% dichloromethane, and finally hexane + 10% dichloromethane) to obtain white needles (5.4 g, 83%). ¹ H-NMR (CDCl ₃ , TMS) δ 7.3-7.8 (9H, m), 7.90 (2H, d
d, J = 8Hz, 2Hz)

(2) 9,10-bis (2- (1-naphthyl) phenyl) -9,10-dihydroxy-9,10-
Synthesis of dihydroanthracene Under an argon atmosphere, 1- (2-bromophenyl) naphthalene (5.4 g, 19 mmol, 2.8 eq) was dissolved in a mixed solvent of anhydrous toluene (25 ml) and anhydrous THF (25 ml), and dried in a dry ice / methanol bath. Cooled to -40 ° C. To this was added an n-butyllithium / hexane solution (1.50 mol / l, 14 ml, 21 mmol, 1.1 eq), and the mixture was stirred at -20 ° C for 1 hour. Anthraquinone (1.4 g, 6.7 mmol) was added thereto, and the mixture was added at -20 ° C for 1 hour and at room temperature for 3 hours.
Stirred for hours and left overnight. A saturated ammonium chloride aqueous solution (20 ml) was added to the reaction mixture, and the resulting solid was filtered off.
After washing with water, methanol and acetone, a white solid (3.5 g, 8
5%). ¹ H-NMR (CDCl ₃ , TMS) δ -0.20 (2H, s), 5.76 (2H, dd,
J = 13Hz, 7Hz), 6.2-7.7 (26H, m), 8.43 (2H, d, J = 8H
z)

(3) Synthesis of 9,10-bis (2- (1-naphthyl) phenyl) anthracene (compound 15) 9,10-bis (2- (1-naphthyl) phenyl)-
9,10-Dihydroxy-9,10-dihydroanthracene (3.5 g, 5.7 mmol) is suspended in acetic acid (80 ml), 57% hydroiodic acid (15 ml, 0.11 mol, 20 eq) is added, and the mixture is added at 100 ° C. for 7 hours. Stirred. A 50% aqueous solution of hypophosphorous acid is added to the reaction mixture (30 ml)
Was added, and the solid was filtered off and washed with water, methanol and acetone to give a white solid (3.2 g, 96%). ¹ H-NMR (CDCl ₃ , TMS) δ 6.7-7.5 (30H, m) .all-H

Synthesis Example 3 (Compound 17) (1) Synthesis of 9-phenanthrene boronic acid Under an argon atmosphere, 9-bromophenanthrene (15 g, 58
(mmol) in anhydrous ether (150 ml) and cooled to -35 ° C in a dry ice / methanol bath. An n-butyllithium / hexane solution (1.50 mol / l, 43 ml, 65 mmol) was added dropwise thereto, and the mixture was stirred at -20 ° C for 1 hour. The reaction mixture is -67 ° C
And triisopropoxyborane (37 ml, 0.16 mol,
2.8 eq) of anhydrous ether solution (30 ml) and add
The mixture was stirred for 2 hours at room temperature and left overnight. A 10% aqueous hydrochloric acid solution (150 ml) was added to the reaction mixture, and the mixture was stirred at room temperature for 1 hour. The organic layer was separated, washed with saturated brine (50 ml), dried over anhydrous magnesium sulfate, and evaporated to give a solid. Was washed with hexane to give a white solid (10 g, 78%). ¹ H-NMR (CDCl ₃ , TMS) δ 7.6-7.9 (5H, m), 8.17 (1H,
s), 8.5-8.8 (3H, m)

(2) Synthesis of 9- (3-bromophenyl) phenanthrene 3-bromoiodobenzene (7.0 g, 2
5 mmol), phenanthreneboronic acid (5.0 g, 23 mmol), tetrakis (triphenylphosphine) palladium (0) (0.5
g, 0.43 mmol, 1.7% Pd) in toluene (100 ml),
An aqueous sodium carbonate solution (7.3 g, 69 mmol, 3 eq / 35 ml) was added, the mixture was refluxed for 10 hours, and left overnight. The organic layer was separated, washed with saturated saline (50 ml), dried over anhydrous magnesium sulfate, and evaporated to give a yellow oil. This was purified by column chromatography (silica gel / hexane, then hexane + 3% dichloromethane, and finally hexane + 5% dichloromethane) to obtain white needles (6.5 g, 85%). ¹ H-NMR (CDCl ₃ , TMS) δ 7.3-8.7 (11H, m), 8.76 (2H,
d, J = 7Hz)

(3) 9,10-bis (3- (9-phenanthryl) phenyl) -9,10-dihydroxy-9,
Synthesis of 10-dihydroanthracene Under an argon atmosphere, 1- (3-bromophenyl) phenanthrene (6.5 g, 20 mmol, 2.8 eq) was added to anhydrous toluene (25 ml).
And dry THF (25 ml) in a mixed solvent.
Cooled to −25 ° C. in a methanol bath. To this was added an n-butyllithium / hexane solution (1.50 mol / l, 15 ml, 23 mmol, 1.1e
q) was added and the mixture was stirred at -20 ° C for 1 hour. Anthraquinone (1.5 g, 7.2 mmol) was added thereto, and the mixture was stirred at −20 ° C. for 1 hour, at room temperature for 3 hours, and left overnight. A saturated ammonium chloride aqueous solution (20 ml) was added to the reaction mixture, and the resulting solid was filtered off, washed with water, methanol and acetone to give a white solid (5.9
g, quant). ¹ H-NMR (CDCl ₃ , TMS) δ -0.16 (2H, s), 6.06 (2H, s),
6.4-7.0 (12H, m), 7.1-7.7 (12H, m), 8.20 (2H, dd,
J = 8Hz, 2Hz), 8.4-8.6 (6H, m)

(4) Synthesis of 9,10-bis (3- (9-phenanthryl) phenyl) anthracene (compound 17) 9,10-bis (3- (9-phenanthryl) phenyl) -9,10-dihydroxy- 9,10-dihydroanthracene (5.2 g, 7.3 mmol) was suspended in acetic acid (120 ml),
Add 57% hydroiodic acid (10ml, 77mmol, 10eq) and add to 100 ℃
For 6 hours. Add 50% aqueous solution of hypophosphorous acid to the reaction mixture
(40 ml) was added, and the solid was separated by filtration and washed with water, methanol and acetone to obtain a white solid (5.0 g, quant). ¹ H-NMR (CDCl ₃ , TMS) δ 7.0-8.5 (34H, m).

Synthesis Example 4 (Compound 20) (1) Synthesis of 1- (4-bromophenyl) pyrene 4-bromoiodobenzene (7.0 g, 2
5 mmol), 1-pyreneboronic acid (5.7 g, 23 mmol), tetrakis (triphenylphosphine) palladium (0) (0.5 g, 0.
43 mmol, 1.7% Pd) was dissolved in toluene (50 ml), an aqueous sodium carbonate solution (7.3 g, 69 mmol, 3 eq / 35 ml) was added, the mixture was refluxed for 10 hours, and left overnight. The organic layer was separated, and saturated saline (5
0ml), dried over anhydrous magnesium sulfate and evaporated to give a yellow oil. This was purified by column chromatography (silica gel / hexane, then hexane + 3% dichloromethane, and finally hexane + 10% dichloromethane) to obtain white needles (6.6 g, 80%). ¹ H-NMR (CDCl ₃ , TMS) δ 7.3-7.8 (11H, m), 7.90 (2H,
d, J = 8Hz)

(2) 9,10-bis (4- (1-pyrenyl) phenyl) -9,10-dihydroxy-9,10-
Synthesis of dihydroanthracene 1- (2-bromophenyl) pyrene under argon atmosphere
(6.6 g, 18 mmol, 2.8 eq) in anhydrous toluene (25 ml) and anhydrous TH
It was dissolved in a mixed solvent of F (25 ml) and cooled to -40 ° C in a dry ice / methanol bath. The n-butyl lithium /
A hexane solution (1.50 mol / l, 14 ml, 21 mmol, 1.1 eq) was added, and the mixture was stirred at -20 ° C for 1 hour. To this anthraquinone
(1.4 g, 6.7 mmol) was added, and the mixture was stirred at -20 ° C for 1 hour and at room temperature for 3 hours, and left overnight. A saturated ammonium chloride aqueous solution (20 ml) was added to the reaction mixture, and the resulting solid was filtered off.
Wash with methanol and acetone to give a white solid (4.5g, 88%)
I got ¹ H-NMR (CDCl ₃ , TMS) δ -0.20 (2H, s), 5.76 (2H, dd,
J = 13Hz, 7Hz), 6.2-7.7 (30H, m), 8.43 (2H, d, J = 8H
z)

(3) Synthesis of 9,10-bis (4- (1-pyrenyl) phenyl) anthracene (compound 20) 9,10-bis (4- (1-pyrenyl) phenyl)-
9,10-Dihydroxy-9,10-dihydroanthracene (4.5 g, 5.9 mmol) is suspended in acetic acid (80 ml), 57% hydroiodic acid (15 ml, 0.11 mol, 20 eq) is added, and the mixture is added at 100 ° C. for 7 hours. Stirred. A 50% aqueous solution of hypophosphorous acid is added to the reaction mixture (30 ml)
Was added, and the solid was filtered off and washed with water, methanol and acetone to give a white solid (3.9 g, 90%). ¹ H-NMR (CDCl ₃ , TMS) δ 6.7-7.5 (30H, m) .all-H

Synthesis Example 5 (Compound 22) (1) Synthesis of 2-biphenylboronic acid Under an argon atmosphere, 2-bromobiphenyl (20 g, 86 mmo) was used.
l) in anhydrous ether (200 ml) and dry ice /
Cooled to −35 ° C. in a methanol bath. An n-butyllithium / hexane solution (1.50 mol / l, 63 ml, 95 mmol) was added dropwise thereto, and the mixture was stirred at -20 ° C for 1 hour. The reaction mixture was cooled to -67 ° C and triisopropoxyborane (50 ml, 0.22 mol, 2.5
eq) in anhydrous ether (50 ml) was added, and the mixture was stirred at -65 ° C for 1 hour, at room temperature for 2 hours, and left overnight. To the reaction mixture
After adding 10% hydrochloric acid aqueous solution (200 ml) and stirring at room temperature for 1 hour,
The organic layer was separated, washed with saturated saline (50 ml), dried over anhydrous magnesium sulfate, and the solvent obtained by evaporating the solvent was washed with hexane to obtain a white solid (11 g, 62%). ¹ H-NMR (CDCl ₃ , TMS) δ 6.74 (1H, d, J = 7Hz), 7.1-7.4
(8H, m)

(2) Synthesis of 2- (4-bromophenyl) biphenyl 2-bromoiodobenzene (7.9 g, 2
5 mmol), biphenylboronic acid (5.0 g, 25 mmol), tetrakis (triphenylphosphine) palladium (0) (0.5 g, 0.1 g).
43 mmol, 1.7% Pd) was dissolved in toluene (60 ml), an aqueous sodium carbonate solution (8.0 g, 75 mmol, 3 eq / 40 ml) was added, the mixture was refluxed for 10 hours, and left overnight. The organic layer was separated, and saturated saline (5
0ml), dried over anhydrous magnesium sulfate and evaporated to give a yellow oil. This was purified by column chromatography (silica gel / hexane, then hexane + 3% dichloromethane, and finally hexane + 5% dichloromethane) to obtain white needles (6.8 g, 88%). ¹ H-NMR (CDCl ₃ , TMS) δ 7.3-8.7 (11H, m), 8.76 (2H,
d, J = 7Hz)

(3) 9,10-bis (4- (2-phenylphenyl) phenyl) -9,10-dihydroxy-
Synthesis of 9,10-dihydroanthracene Under an argon atmosphere, 2- (4-bromophenyl) biphenyl (6.8 g, 22 mmol, 2.5 eq) was dissolved in a mixed solvent of anhydrous toluene (25 ml) and anhydrous THF (25 ml), and dried on dry ice. / Methanol bath to -30 ° C. An n-butyllithium / hexane solution (1.50 mol / l, 15 ml, 23 mmol, 1.1 eq) was added thereto, and the mixture was stirred at -20 ° C for 1 hour. Anthraquinone (1.7 g, 8.2 mmol) was added thereto, and the mixture was added at -20 ° C for 1 hour and at room temperature for 2 hours.
Stirred for hours and left overnight. A saturated ammonium chloride aqueous solution (20 ml) was added to the reaction mixture, and the resulting solid was filtered off.
After washing with water, methanol and acetone, a white solid (4.9 g, 8
9%). ¹ H-NMR (CDCl ₃ , TMS) δ 5.7-5.8 (2H, m), 6.3-7.4 (30
H, m), 8.3-8.4 (2H, m)

(4) Synthesis of 9,10-bis (4- (2-phenylphenyl) phenyl) anthracene (Compound 22) 9,10-bis (4- (2-phenylphenyl) phenyl) -9,10- Dihydroxy-9,10-dihydroanthracene (4.9 g, 7.3 mmol) was suspended in acetic acid (70 ml).
% Hydroiodic acid (10 ml, 77 mmol, 10 eq) was added, and the mixture was stirred at 100 ° C. for 6 hours. Add 50% aqueous hypophosphorous acid solution (5
0 ml), and the solid was filtered off and washed with water, methanol and acetone to give a pale yellow solid (4.6 g, 88%). ¹ H-NMR (CDCl ₃ , TMS) δ 6.7-7.5 (34H, m).

Synthesis Example 6 (Synthesis of Compound 1) (1) 9,10-bis (4- (3-phenylphenyl)
Synthesis of phenyl) -9,10-dihydroxy-9,10-dihydroanthracene Under an argon atmosphere, 3- (4-bromophenyl) biphenyl (6.8 g, 22 mmol, 2.5 eq) was added to anhydrous toluene (25 ml) and anhydrous THF (25 ml). ) And cooled to −30 ° C. in a dry ice / methanol bath. An n-butyllithium / hexane solution (1.50 mol / l, 15 ml, 23 mmol, 1.1 eq) was added thereto, and the mixture was stirred at -20 ° C for 1 hour. Anthraquinone (1.7 g, 8.2 mmol) was added thereto, and the mixture was added at -20 ° C for 1 hour and at room temperature for 2 hours.
Stirred for hours and left overnight. A saturated ammonium chloride aqueous solution (20 ml) was added to the reaction mixture, and the resulting solid was filtered off.
Wash with water, methanol and acetone to obtain a white solid (5.0 g, 9
1%). ¹ H-NMR (CDCl ₃ , TMS) δ 5.7-5.8 (2H, m), 6.3-7.4 (30
H, m), 8.3-8.4 (2H, m)

(2) Synthesis of 9,10-bis (4-3-phenylphenyl) phenyl) anthracene (Compound 1) 9,10-bis (4- (3-phenylphenyl) phenyl) -9,10-dihydroxy -9,10-Dihydroanthracene (4.9 g, 7.3 mmol) was suspended in acetic acid (70 ml) and
% Hydroiodic acid (10 ml, 77 mmol, 10 eq) was added, and the mixture was stirred at 100 ° C. for 6 hours. Add 50% aqueous hypophosphorous acid solution (5
0 ml), and the solid was filtered off and washed with water, methanol and acetone to give a pale yellow solid (4.1 g, 79%). ¹ H-NMR (CDCl ₃ , TMS) δ 6.7-7.5 (34H, m).

Synthesis Example 7 (Synthesis of Compound 2) (1) 9,10-bis (4- (3,5-diphenylphenyl) phenyl) -9,10-dihydroxy-9,10
Synthesis of -dihydroanthracene Under an argon atmosphere, 1,3-diphenyl-5- (4-bromophenyl) benzene (8.5 g, 22 mmol, 2.5 eq) was dissolved in a mixed solvent of anhydrous toluene (25 ml) and anhydrous THF (25 ml). ,
Cool to −30 ° C. in a dry ice / methanol bath. Add n-butyllithium / hexane solution (1.50mol / l, 15m
l, 23 mmol, 1.1 eq) and stirred at -20 ° C for 1 hour. Anthraquinone (1.7 g, 8.2 mmol) is added to this
The mixture was stirred at 20 ° C. for 1 hour and at room temperature for 2 hours, and left overnight. A saturated ammonium chloride aqueous solution (20 ml) was added to the reaction mixture, and the resulting solid was filtered off and washed with water, methanol and acetone to obtain a white solid (16 g, 90%). ¹ H-NMR (CDCl ₃ , TMS) δ 5.7-5.8 (2H, m), 6.3-7.4 (30
H, m), 8.3-8.4 (2H, m)

(2) Synthesis of 9,10-bis (4- (3,5-diphenylphenyl) phenyl) anthracene (Compound 2) 9,10-bis (4- (3,5-diphenylphenyl)
Phenyl) -9,10-dihydroxy-9,10-dihydroanthracene (6.0 g, 7.3 mmol) was suspended in acetic acid (70 ml), and 57% hydroiodic acid (10 ml, 77 mmol, 10 eq) was added.
Stirred at 0 ° C. for 6 hours. A 50% aqueous solution of hypophosphorous acid (50 ml) was added to the reaction mixture, and the solid was separated by filtration and washed with water, methanol and acetone to obtain a pale yellow solid (5.3 g, 93%). ¹ H-NMR (CDCl ₃ , TMS) δ 6.7-7.5 (34H, m).

Synthesis Example 8 (Synthesis of Compound 3) (1) Synthesis of 9,10-bis (4- (2-naphthyl) phenyl) -9,10-dihydroxy-9,10-dihydroanthracene -(4-Bromophenyl) naphthalene (5.4 g, 19 mmol, 2.8 eq) was dissolved in a mixed solvent of anhydrous toluene (25 ml) and anhydrous THF (25 ml) and cooled to -40 ° C in a dry ice / methanol bath. To this was added an n-butyllithium / hexane solution (1.50 mol / l, 14 ml, 21 mmol, 1.1 eq), and the mixture was stirred at -20 ° C for 1 hour. Anthraquinone (1.4 g, 6.7 mmol) was added thereto, and the mixture was added at -20 ° C for 1 hour and at room temperature for 3 hours.
Stirred for hours and left overnight. A saturated ammonium chloride aqueous solution (20 ml) was added to the reaction mixture, and the resulting solid was filtered off.
After washing with water, methanol and acetone, a white solid (3.7 g, 9
1%). ¹ H-NMR (CDCl ₃ , TMS) δ -0.20 (2H, s), 5.76 (2H, dd,
J = 13Hz, 7Hz), 6.2-7.7 (26H, m), 8.43 (2H, d, J = 8H
z)

(2) Synthesis of 9,10-bis (4- (2-naphthyl) phenyl) anthracene (compound 3) 9,10-bis (4- (2-naphthyl) phenyl)-
9,10-Dihydroxy-9,10-dihydroanthracene (3.5 g, 5.7 mmol) is suspended in acetic acid (80 ml), 57% hydroiodic acid (15 ml, 0.11 mol, 20 eq) is added, and the mixture is added at 100 ° C. for 7 hours. Stirred. A 50% aqueous solution of hypophosphorous acid is added to the reaction mixture (30 ml)
Was added, and the solid was filtered off and washed with water, methanol and acetone to give a white solid (3.3 g, 98%). ¹ H-NMR (CDCl ₃ , TMS) δ 6.7-7.5 (30H, m) .all-H

Synthesis Example 9 (Compound 25) (1) Synthesis of 1- (2,2-diphenylvinyl) -3,5-dibromobenzene 3,5-dibromobenzaldehyde under an argon atmosphere
(12.1 g, 46 mmol), diethyl diphenylmethylphosphonate
(15 g, 49 mmol, 1.1 eq) was dissolved in DMSO (60 ml), potassium t-butoxide (6.2 g, 55 mmol, 1.2 eq) was added little by little, and the mixture was stirred at room temperature for 9 hours and left overnight. Water (60 ml) was added to the reaction mixture, and the mixture was extracted with ethyl acetate (250 ml). Was. This was subjected to column chromatography (silica gel / hexane,
Hexane + 3% dichloromethane)
(14.0 g, 74%). ¹ H-NMR (CDCl ₃ , TMS) δ 6.80 (1 H, s), 7.03 (2 H, d, J = 2 Hz), 7.
3-7.4 (11H, m)

(2) 1- (2,2-diphenylvinyl)
Synthesis of -3-phenyl-5-bromobenzene 1- (2,2-diphenylvinyl) under argon atmosphere
-3,5-dibromobenzene (7.0 g, 17 mmol), phenylboronic acid (2.1 g, 17 mmol), tetrakis (triphenylphosphine) palladium (0) (0.4 g, 0.35 mmol, 2% Pd) in toluene (40 ml) And 2M aqueous sodium carbonate solution (25m
l, 51 mmol, 3 eq), and the mixture was refluxed for 10 hours and left overnight. The organic layer was separated, washed with saturated saline (30 ml), dried over magnesium sulfate, and evaporated to give a yellow oil. This was subjected to column chromatography (silica gel / hexane,
Next, hexane + 3% dichloromethane, and finally hexane + 10
% Dichloromethane) (3.9 g, 56%)
I got ¹ H-NMR (CDCl ₃ , TMS) δ 6.94 (1H, s), 7.1-7.5 (18H, m)

(3) 9,10-bis (3- (2,2-diphenylvinyl) phenyl-5-phenyl) -9,10
Synthesis of -dihydroxy-9,10-dihydroanthracene 1- (2,2-diphenylvinyl) under an argon atmosphere
-3-phenyl-5-bromobenzene (3.9 g, 9.5 mmol,
2.7 eq) was dissolved in a mixed solvent of anhydrous toluene (20 ml) and anhydrous THF (20 ml), and cooled to −40 ° C. in a dry ice / methanol bath. To this was added an n-butyllithium / hexane solution (1.6
0 mol / l, 6 ml, 9.6 mmol, 1.0 eq) and stirred at -20 ° C for 1 hour. Anthraquinone (0.7 g, 3.4 mmol) was added thereto, and the mixture was stirred at −20 ° C. for 1 hour, at room temperature for 7 hours, and left overnight. A saturated ammonium chloride aqueous solution (50 ml) was added to the reaction mixture.
The organic layer was collected by filtration, and saturated saline (30 ml).
, Dried over magnesium sulfate and evaporated to give a yellow oil. This was purified by column chromatography (silica gel / hexane + 50% dichloromethane, then dichloromethane, and finally dichloromethane + 3% methanol) to obtain a pale yellow amorphous solid (2.0 g, 67%). ¹ H-NMR (CDCl ₃ , TMS) δ 2.56 (2H, s), 6.5-6.6 (4H,
m), 6.8-7.4 (34H, m), 7.41 (4H, dd, J = 6Hz, 3Hz), 7.71 (4
(H, dd, J = 6Hz, 3Hz)

(4) Synthesis of 9,10-bis (3- (2,2-diphenylvinyl) phenyl-5-phenyl) anthracene (Compound 25) 9,10-bis (3- (2,2-diphenylvinyl) ) Phenyl-5-phenyl) -9,10-dihydroxy-
9,10-Dihydroanthracene (2.0 g, 2.3 mmol) was dissolved in acetic acid (25 ml), and potassium iodide (1.5 g, 90 mmol, 4e) was dissolved.
q) was added and the mixture was stirred for 3 hours. The reaction mixture was quenched with a 50% aqueous phosphinic acid solution, and the solid was filtered off and washed with water, methanol and acetone to give a white solid (1.4 g, 73%). ¹ H-NMR (CDCl ₃ , TMS) δ 7.2-7.4 (42H, m), 7.65 (4H, dd, J
= 7 Hz, 3 Hz) The solid (1.4 g) was purified by sublimation at 380 ° C./10 ⁻⁶ Torr for 1 hour to obtain a pale yellow solid (0.8 g). _{FDMS, ca1cd for C 66 H 46} = 838, found m / z = 838 (M +,
4) λmax, 398,358,306nm (PhMe) Fmax, 416,435nm (PhMe, λex = 395nm) Eg = 3.00eV Ip = 5.87eV (51Y / eV, 100nW) Tg = 130 ℃

Synthesis Example 10 (Compound 26) (1) 1- (2,2-diphenylvinyl) -3- (1-
Synthesis of naphthyl) -5-bromobenzene 1- (2,2-diphenylvinyl) under argon atmosphere
-3,5-dibromobenzene (8.3 g, 20 mmol), 1-naphthaleneboronic acid (3.4 g, 20 mmol), tetrakis (triphenylphosphine) palladium (0) (0.46 g, 0.4 mmol, 2% P
d) was dissolved in toluene (50 ml), a 2M aqueous sodium carbonate solution (30 ml, 60 mmol, 3 eq) was added, the mixture was refluxed for 10 hours, and left overnight. The organic layer was separated and washed with saturated saline (50 ml),
Drying over magnesium sulfate and evaporation of the solvent gave a yellow oil. This was purified by column chromatography (silica gel / hexane, then hexane + 3% dichloromethane, and finally hexane + 10% dichloromethane) to give a white glassy solid.
(5.5 g, 60%). ¹ H-NMR (CDCl ₃ , TMS) δ 6.96 (1H, s), 7.1-7.6 (18H,
m), 7.8-7.9 (2H, m)

(2) 9,10-bis (3- (2,2-diphenylvinyl) phenyl-5- (1-naphthyl))-
Synthesis of 9,10-dihydroxy-9,10-dihydroanthracene 1- (2,2-diphenylvinyl) under an argon atmosphere
-3- (1-Naphthyl) -5-bromobenzene (5.5 g, 1
2mmol, 2.7eq) in anhydrous toluene (30ml) and anhydrous THF (30ml)
In a mixed solvent of dry ice / methanol bath-
Cooled to 30 ° C. An n-butyllithium / hexane solution (1.60 mol / l, 8 ml, 13 mmol, 1.0 eq) was added thereto, and
Stirred at C for 1 hour. Add anthraquinone (0.9g, 4.4
mmol) and stirred at -20 ° C for 1 hour and at room temperature for 7 hours.
Left overnight. The reaction mixture was quenched by the addition of a saturated aqueous ammonium chloride solution (50 ml), the organic layer was collected by filtration, washed with brine (30 ml), dried over magnesium sulfate, and evaporated to give a yellow oil. This was purified by column chromatography (silica gel / hexane + 50% dichloromethane, then dichloromethane) to give a white amorphous solid (2.7 g,
63%). ¹ H-NMR (CDCl ₃ , TMS) δ 2.56 (2H, s), 6.5-6.8 (6H,
m), 6.9-7.5 (36H, m), 7.6-7.8 (8H, m)

(3) Synthesis of 9,10-bis (3- (2,2-diphenylvinyl) phenyl-5- (1-naphthyl)) anthracene (Compound 26) 9,10-bis (3- (2,2) 2-diphenylvinyl) phenyl-5- (1-naphthyl))-9,10-dihydroxy-9,10-dihydroanthracene (2.7 g, 2.8 mmol)
Was dissolved in acetic acid (30 ml) and potassium iodide (1.8 g, 11 mmo
l, 4 eq) and stirred for 3 hours. The reaction mixture was quenched by adding a 50% aqueous solution of phosphinic acid (40 ml), and the solid was separated by filtration, washed with water, methanol, and acetone to give a white solid (2.0%).
g, 78%). ¹ H-NMR (CDCl ₃ , TMS) δ 7.2-7.5 (40H, m), 7.7-7.9 (10H,
m) The solid (2.0 g) was purified by sublimation at 400 ° C./10 ⁻⁶ Torr for 1 hour to obtain a pale yellow solid (1.2 g). _{FDMS, ca1cd for C 74 H 50} = 938, found m / z = 938 (M +,
100), 469 (M ²⁺ , 6) λmax, 398,377,358nm (PhMe) Fmax, 418,436nm (PhMe, λex = 395nm) Eg = 3.00eV Ip = 5.86eV (34Y / eV, 100nW) Tg = 132 ℃

Synthesis Example 11 (Compound 33) (1) 2-t-butyl-9,10-bis (4- (2,2
-Diphenylvinyl) Synthesis of phenyl) -9,10-dihydroxy-9,10-dihydroanthracene 4- (2,2-diphenylvinyl) under an argon atmosphere
Bromobenzene (5.0 g, 15 mmol, 2.6 eq) in anhydrous toluene
(25 ml) and anhydrous THF (25 ml) in a mixed solvent, and cooled to -40 ° C in a dry ice / methanol bath. Add butyllithium / hexane solution (1.60mol / l, 10ml, 16mmol, 1.
1 eq) and stirred at -20 ° C for 1 hour. To this 2-
(T-Butyl) anthraquinone (1.5 g, 5.7 mmol) was added, and the mixture was stirred at −20 ° C. for 1 hour, at room temperature for 7 hours, and left overnight. The reaction mixture was quenched by the addition of a saturated aqueous ammonium chloride solution (50 ml), the organic layer was collected by filtration, washed with brine (30 ml), dried over magnesium sulfate, and evaporated to give a yellow oil. This was purified by column chromatography (silica gel / hexane + 50% dichloromethane, then dichloromethane, and finally dichloromethane + 1% methanol) to obtain a white amorphous solid (3.3 g, 75%). ¹ H-NMR (CDCl ₃ , TMS) δ 1.29 (9H, s), 2.65 (1H, s), 2.71
(1H, s), 6.68 (9H, s), 6.84 (2H, s), 7.1-7.4 (23H, m),
7.5-7.7 (4H, m)

(2) Synthesis of 3-tert-butyl-9,10-bis (4- (2,2-diphenylvinyl) phenyl) anthracene (Compound 33) 2-tert-butyl-9,10-bis (4 -(2,2-diphenylvinyl) phenyl) -9,10-dihydroxy-
9,10-Dihydroanthracene (3.3 g, 4.3 mmol) was dissolved in acetic acid (30 ml), and potassium iodide (1.9 g, 11 mmol, 2.7 mmol) was dissolved.
eq) Sodium phosphinate monohydrate (0.6g, 5.7mmol)
Was added and stirred for 2 hours. The reaction mixture was separated by filtration and washed with water, methanol and acetone to obtain a pale yellow solid (2.8 g, 88%). ¹ H-NMR (CDCl ₃ , TMS) δ 1.28 (9H, s), 7.14 (2H, s), 7.2-
7.5 (30H, m), 7.6-7.7 (5H, m) The solid (2.8 g) was purified by sublimation at 360 ° C./10 ^-6 Torr for 1 hour to obtain a pale yellow solid (2.2 g). _{FDMS, ca1cd for C 58 H 46} = 742, found m / z = 742 (M +,
100), 371 (M2 ⁺ , 4) λmax, 397, 379, 360, 310nm (PhMe) Fmax, 450nm (PhMe, λex = 397nm) Eg = 2.92eV Ip = 5.71eV (39Y / eV, 100nW) Tg = 105 ℃

Synthesis Example 12 (Compound 34) (1) Synthesis of 2-phenylanthraquinone 2-chloroanthraquinone (5.0 g, 21 g) was prepared under an argon atmosphere.
mmol), phenylboronic acid (2.8 g, 23 mmol, 1.1 eq), tris (dibedylideneacetone) dipalladium (0) (0.2 g, 0.
22mmol, 2% Pd), potassium fluoride (4.4g, 76mmol, 3.3e
q) was suspended in anhydrous dioxane (30 ml) and tri-t-butylphosphine / toluene solution (66%, 0.13 ml, 0.42 mmol,
1 eq) and stirred at 80 ° C. for 3 hours. The reaction mixture was separated by filtration and washed with toluene (100 ml). The filtrate was saturated with saline
(30 ml), dried over magnesium sulfate, and evaporated to give a yellow solid. This was washed with boiling ethanol (50 ml) to give a yellow solid (5.2 g, 87%). ¹ H-NMR (CDCl ₃ , TMS) δ 7.4-7.6 (3H, m), 7.6-7.9 (4H,
m), 7.98 (1H, dd, J = 8Hz, 2Hz), 8.2-8.4 (3H, m), 8.50 (1H
(H, d, J = 2Hz)

(2) 2-phenyl-9,10-bis (4
-(2,2-diphenylvinyl) phenyl) -9,10
Synthesis of -dihydroxy-9,10-dihydroanthracene 4- (2,2-diphenylvinyl) under an argon atmosphere
Bromobenzene (5.0 g, 15 mmol, 2.6 eq) in anhydrous toluene
(25 ml) and anhydrous THF (25 ml) in a mixed solvent, and cooled to -40 ° C in a dry ice / methanol bath. Add butyllithium / hexane solution (1.60mol / l, 10ml, 16mmol, 1.
1 eq) and stirred at -20 ° C for 1 hour. To this was added 2-phenylanthraquinone (1.6 g, 5.6 mmol),
For 1 hour and at room temperature for 7 hours and left overnight. The reaction mixture was quenched by the addition of a saturated aqueous ammonium chloride solution (50 ml), the organic layer was collected by filtration, washed with brine (30 ml), dried over magnesium sulfate, and evaporated to give a yellow oil.
This was purified by column chromatography (silica gel / hexane + 50% dichloromethane, then dichloromethane, and finally hexane + 1% methanol) to obtain a white amorphous solid (2.3 g, 52%). ¹ H-NMR (CDCl ₃ , TMS) δ 2.75 (1H, s), 2.78 (1H, s),
6.68 (8H, s), 6.83 (2H, s), 7.1-7.7 (31H, m), 7.90
(1H, d, J = 2Hz)

(3) Synthesis of 3-phenyl-9,10-bis ((4- (2,2-diphenylvinyl) phenyl) anthracene (compound 34) 2-phenyl-9,10-bis (4- (2 , 2-diphenylvinyl) phenyl) -9,10-dihydroxy-
9,10-Dihydroanthracene (2.3 g, 2.9 mmol) was dissolved in acetic acid (20 ml), and potassium iodide (1.4 g, 8.4 mmol, 3e
q), sodium phosphinate monohydrate (0.4 g, 3.8 mmol)
Was added and stirred for 1 hour. The reaction mixture was separated by filtration and washed with water, methanol and acetone to obtain a pale yellow solid (2.1 g, 95%). ¹ H-NMR (CDCl ₃ , TMS) δ 7.14 (2H, s), 7.2-7.5 (39H, m),
7.87 (1H, s) The solid (2.1 g) was purified by sublimation at 370 ° C./10 ^-6 Torr for 1 hour to obtain a pale yellow solid (0.9 g). FDMS, ca1cd for C ₆₀ H ₄₂ = 762, found m / z = 762 (M ⁺ ,
100) λmax, 409,388,370nm (PhMe) Fmax, 453nm (PhMe, λex = 409nm) Eg = 2.85eV Ip = 5.70eV (14Y / eV, 100nW) Tg = 114 ℃

Example 1 A 25 mm × 75 mm × 1.1 mm thick glass substrate with an ITO transparent electrode (manufactured by Geomatic) was subjected to ultrasonic cleaning in isopropyl alcohol for 5 minutes, and then to UV / ozone cleaning for 30 minutes. The glass substrate with the transparent electrode lines after cleaning is mounted on a substrate holder of a vacuum evaporation apparatus, and first, a 60 nm-thick N, N '-Bis (N, N'-diphenyl-4-aminophenyl) -N, N-diphenyl-
4,4′-diamino-1,1′-biphenyl film (hereinafter, referred to as “4,4′-diamino-1,1′-biphenyl film”)
TPD232 film). This TPD232 film is
It functions as a first hole injection layer (hole transport layer). Next, on the TPD232 film, 4,4′-bis [N
-(1-Naphthyl) -N-phenylamino] biphenyl film (hereinafter referred to as NPD film) was formed. This NPD film is the second
Functions as a hole injection layer (hole transport layer). further,
Compound (15) having a thickness of 40 nm was deposited and deposited on the NPD film. This film functions as a light emitting layer. The film thickness on this film
A 20 nm-thick tris (8-quinolinol) aluminum film (hereinafter, Alq film) was formed. This Alq film functions as an electron injection layer. Thereafter, Li (Li source: manufactured by Saes Getter Co.) and Alq are binary deposited to form an electron injection layer (cathode).
An Alq: Li film was formed. Metallic Al was vapor-deposited on this Alq: Li film to form a metal cathode to produce an organic EL device. This element emits light at 80 cd / m at DC voltage of 6V.
^2. Blue light with a maximum emission luminance of 23000 cd / m ² and a luminous efficiency of 2.0 cd / A was obtained. FIG. 1 shows the spectrum of the organic EL device. As shown in the figure, the spectrum of this organic EL device was near the peak wavelength of 450 nm, and it was excellent in color purity. Compound (15) has a glass transition temperature of 118 ° C. and high heat resistance, and the obtained organic EL device is stored at a high temperature (85 ° C.).
(° C., 500 hours), it was confirmed that there was no change in the performance and the heat resistance was excellent. In addition, the initial emission luminance is 80 cd / m ²
The half life was as long as 13000 hours when driven at a constant current.

Examples 2 to 13 Organic EL devices were prepared in the same manner as in Example 1 except that the compounds shown in Table 1 were used instead of the compound (15). The luminous efficiency was measured, and the luminescent color was observed. Table 1 shows the results.

[Table 1]

Examples 14 to 23 and Comparative Examples 1 and 2 Novel compounds of the present invention shown in Table 2 and the following compound (C1)
(Comparative Example 1) and (C2) (Comparative Example 2)

Embedded image , The glass transition temperature was measured by DSC measurement. Table 2 shows the results.

[0086]

[Table 2] As shown in Table 2, the compounds of Comparative Examples had low glass transition temperatures of 100 ° C. or lower and low heat resistance.
Compound 23 is a heat-resistant compound having a glass transition temperature of 100 ° C. or higher.

Example 24 In Example 1, instead of vapor-depositing compound (15), compound (15) and the following compound PAVB (functioning as a fluorescent dopant)

Embedded image Was produced in the same manner except that the film was formed by vapor deposition at a vapor deposition rate ratio of 40: 1, and at a DC voltage of 5.5 V,
The light emission luminance, light emission efficiency and maximum light emission luminance were measured, and the light emission color was observed. Table 3 shows the results.

Example 25 In Example 1, instead of depositing compound (15), compound (17) and compound PAVB were used in a ratio of 40: 1.
An organic EL device was prepared in the same manner except that a film was formed by vapor deposition at a vapor deposition rate ratio of 5.5.
The luminous efficiency and the maximum luminous brightness were measured, and the luminescent color was observed. Table 3 shows the results. Example 26 Instead of depositing compound (15) in Example 1, compound (18) and compound PAVB were used in a ratio of 40: 1.
An organic EL device was prepared in the same manner except that a film was formed by vapor deposition at a vapor deposition rate ratio of 5.5.
The luminous efficiency and the maximum luminous brightness were measured, and the luminescent color was observed. Table 3 shows the results.

[0089]

[Table 3] As shown in Table 3, the addition of a fluorescent dopant to the novel compound of the present invention increases the efficiency.

Comparative Example 3 In Example 1, instead of depositing the compound (15), the following compound (C3) was used.

Embedded image Was formed in the same manner as above except that a film was formed by vapor deposition. This device has a DC voltage of 6.5 V and a luminance of 92 cd.
/ m ² , blue-green light emission with a luminous efficiency of 1.22 cd / A, and the efficiency was low and not practical.

Example 27 An organic EL device was prepared in the same manner as in Example 1, except that Compound (25) was used instead of Compound (15). For this element, the initial emission luminance was 500 cd /
m ^{2, and} the constant current driving was at half life 840 hours (100c
In d / m ^2, about equivalent to 6000 hours) and long life, high temperature storage (85 ° C., 500 hours) were place performance without change, is excellent in heat resistance, uniform defects emission of the light emitting surface There was no. The luminous efficiency of this device was 2.8 cd / A, and blue light with high chromaticity coordinates (0.16, 0.08) and high purity was obtained. Example 28 An organic EL device was prepared in the same manner as in Example 1, except that the compound (33) was used instead of the compound (15). For this element, the initial emission luminance was 500 cd /
m ^{2, and} the constant current driving was at half life 1100 hours (100c
In d / m ^2, about equivalent to 8000 hours) and long life, high temperature storage (85 ° C., 500 hours) were place performance without change, is excellent in heat resistance, uniform defects emission of the light emitting surface There was no. The luminous efficiency of this device was as excellent as 3.6 cd / A.

Comparative Example 4 In Example 1, instead of depositing the compound (15), the following compound (C4) was used.

Embedded image Was formed in the same manner as above except that a film was formed by vapor deposition. For this element, the initial emission luminance is 500 cd / m
^{In 2} , the half-life was extremely short at 25 hours when driven with a constant current, which was not practical. The luminous efficiency is 1.7cd / A
Was low.

Comparative Example 5 In Example 1, instead of depositing the compound (15), the following compound (C5) was used.

Embedded image Was formed in the same manner as above except that a film was formed by vapor deposition. For this element, the initial emission luminance is 500 cd / m
^In Figure ² , the half-life was as short as 420 hours when driven at constant current, which was not practical. The luminous efficiency was as low as 2.1 cd / A.

Comparative Example 6 In Example 1, instead of depositing the compound (15), the following compound (C6) was used.

Embedded image Was formed in the same manner as above except that a film was formed by vapor deposition. For this element, the initial emission luminance is 500 cd / m
^In Example ² , the half-life was as long as 1000 hours when driven at a constant current, but after storage at high temperature (85 ° C, 500 hours), a defect occurred on a part of the light emitting surface, and the color of the defective portion changed.

As described above, the device using the compound of the present invention can emit blue light with a luminous efficiency of 2 cd / A or more.
Superior to the comparative example. Furthermore, it has a long life, high heat resistance, and can maintain uniform light emission even after storage at high temperatures.

[0096]

As described in detail above, the organic electroluminescent device of the present invention utilizing any of the novel compounds represented by the above [A], [1] to [5] and [3 '] It emits blue light with high luminous efficiency, excellent heat resistance, long life, and good color purity. For this reason,
The organic electroluminescence device of the present invention is useful as a light source such as a flat light emitter of a wall-mounted television or a backlight of a display.

[Brief description of the drawings]

FIG. 1 is a diagram showing a spectrum of an organic electroluminescence device according to Example 1 of the present invention.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09K 11/06 635 C09K 11/06 635 H05B 33/14 H05B 33/14 B F-term (reference) 3K007 AB03 AB04 AB11 CA01 CB01 DA01 DB03 DC00 EB00 4H006 AA01 AB64

Claims (12)

[Claims] 1. A novel compound represented by the following general formula [A]. General formula [A] [Wherein, R ^{1 to} R ⁸ each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted carbon atom 1 to 20 alkoxy groups, substituted or unsubstituted aryloxy groups having 6 to 30 carbon atoms, substituted or unsubstituted alkylthio groups having 1 to 20 carbon atoms, substituted or unsubstituted 6 to 30 carbon atoms An arylthio group, a substituted or unsubstituted arylalkyl group having 7 to 30 carbon atoms, an unsubstituted monocyclic group having 5 to 30 carbon atoms, a substituted or unsubstituted fused polycyclic group having 10 to 30 carbon atoms, or Substituted or unsubstituted 5 to 30 carbon atoms
Is a heterocyclic group. Ar ³ and Ar ⁴ are each independently a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, and the substituent is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, Unsubstituted alkoxy group having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, substituted or unsubstituted alkylthio group having 1 to 20 carbon atoms, substituted or unsubstituted carbon atom An arylthio group having 6 to 30 atoms, a substituted or unsubstituted arylalkyl group having 6 to 30 carbon atoms, an unsubstituted monocyclic group having 5 to 30 carbon atoms,
It is a substituted or unsubstituted fused polycyclic group having 10 to 30 carbon atoms, a substituted or unsubstituted heterocyclic group having 5 to 30 carbon atoms, or a substituted or unsubstituted alkenyl group having 4 to 40 carbon atoms. However, this excludes the case where Ar ³ and Ar ⁴ are unsubstituted phenyl groups. ] 2. A novel compound represented by the following general formula [1]:
object. General formula [1][Wherein, R¹~ R^TenAre each independently a hydrogen atom,
Logen atom, cyano group, nitro group, substituted or unsubstituted
An alkyl group having 1 to 20 carbon atoms, substituted or unsubstituted
A substituted alkoxy group having 1 to 20 carbon atoms,
Unsubstituted aryloxy group having 6 to 30 carbon atoms, substitution
Or unsubstituted alkylthio having 1 to 20 carbon atoms
Group, substituted or unsubstituted aryl having 6 to 30 carbon atoms
A luthio group, substituted or unsubstituted having 7 to 30 carbon atoms
Arylalkyl group, unsubstituted C 5 -C 30
Ring group, substituted or unsubstituted 10 to 30 carbon atoms
Polycyclic ring group or substituted or unsubstituted 5 to 30 carbon atoms
Is a heterocyclic group. Ar¹And Ar^TwoAre independent
Is a substituted or unsubstituted aryl having 6 to 30 carbon atoms.
And the substituent is a substituted or unsubstituted carbon
An alkyl group having 1 to 20 atoms, substituted or unsubstituted
C1-C20 alkoxy group, substituted or unsubstituted
A substituted aryloxy group having 6 to 30 carbon atoms,
Or an unsubstituted alkylthio group having 1 to 20 carbon atoms,
Substituted or unsubstituted arylthio having 6 to 30 carbon atoms
Aryl, substituted or unsubstituted aryl having 7 to 30 carbon atoms
Alkyl group, unsubstituted monocyclic group having 5 to 30 carbon atoms,
A substituted or unsubstituted fused polycyclic ring having 10 to 30 carbon atoms
A group or a substituted or unsubstituted C5-C30 complex
It is a ring group. Where R⁹And R^TenIs a hydrogen atom and Ar
¹And Ar^TwoIs an unsubstituted phenyl group;⁹
And R^TenIs an aryl group substituted at the meta position and Ar¹as well as
Ar ^TwoIs an aryl group substituted at the meta position
Good. ] 3. A novel compound represented by the following general formula [2]. General formula [2] [Wherein, R ^{1 to} R ¹⁰ each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted carbon atom 1 to 20 alkoxy groups, substituted or unsubstituted aryloxy groups having 6 to 30 carbon atoms, substituted or unsubstituted alkylthio groups having 1 to 20 carbon atoms, substituted or unsubstituted 6 to 30 carbon atoms An arylthio group, a substituted or unsubstituted arylalkyl group having 7 to 30 carbon atoms, an unsubstituted monocyclic group having 5 to 30 carbon atoms, a substituted or unsubstituted fused polycyclic group having 10 to 30 carbon atoms, or Substituted or unsubstituted 5 to 30 carbon atoms
Is a heterocyclic group. Ar ³ and Ar ⁴ are each independently a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, and the substituent is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, Unsubstituted alkoxy group having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, substituted or unsubstituted alkylthio group having 1 to 20 carbon atoms, substituted or unsubstituted carbon atom An arylthio group having 6 to 30 atoms, a substituted or unsubstituted arylalkyl group having 7 to 30 carbon atoms, an unsubstituted monocyclic group having 5 to 30 carbon atoms,
It is a substituted or unsubstituted fused polycyclic group having 10 to 30 carbon atoms, a substituted or unsubstituted heterocyclic group having 5 to 30 carbon atoms, or a substituted or unsubstituted alkenyl group having 4 to 40 carbon atoms. n is 1-3 and m is 1-3. ] 4. A novel compound represented by the following general formula [3]. General formula [3] [Wherein, R ^{1 to} R ⁸ each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted carbon atom 1 to 20 alkoxy groups, substituted or unsubstituted aryloxy groups having 6 to 30 carbon atoms, substituted or unsubstituted alkylthio groups having 1 to 20 carbon atoms, substituted or unsubstituted 6 to 30 carbon atoms An arylthio group, a substituted or unsubstituted arylalkyl group having 7 to 30 carbon atoms, an unsubstituted monocyclic group having 5 to 30 carbon atoms, a substituted or unsubstituted fused polycyclic group having 10 to 30 carbon atoms, or Substituted or unsubstituted 5 to 30 carbon atoms
Is a heterocyclic group. Ar ³ and Ar ⁴ are each independently a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, and the substituent is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, Unsubstituted alkoxy group having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, substituted or unsubstituted alkylthio group having 1 to 20 carbon atoms, substituted or unsubstituted carbon atom An arylthio group having 6 to 30 atoms, a substituted or unsubstituted arylalkyl group having 6 to 30 carbon atoms, an unsubstituted monocyclic group having 5 to 30 carbon atoms,
It is a substituted or unsubstituted fused polycyclic group having 10 to 30 carbon atoms, a substituted or unsubstituted heterocyclic group having 5 to 30 carbon atoms, or a substituted or unsubstituted alkenyl group having 4 to 40 carbon atoms. ] 5. A novel compound represented by the following general formula [3 ′]. General formula [3 '] [Wherein, R ^{1 to} R ⁸ each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted carbon atom 1 to 20 alkoxy groups, substituted or unsubstituted aryloxy groups having 6 to 30 carbon atoms, substituted or unsubstituted alkylthio groups having 1 to 20 carbon atoms, substituted or unsubstituted 6 to 30 carbon atoms An arylthio group, a substituted or unsubstituted arylalkyl group having 7 to 30 carbon atoms, an unsubstituted monocyclic group having 5 to 30 carbon atoms, a substituted or unsubstituted fused polycyclic group having 10 to 30 carbon atoms, or Substituted or unsubstituted 5 to 30 carbon atoms
Is a heterocyclic group. ] 6. A novel compound represented by the following general formula [4]. General formula [4] [Wherein, R ^{1 to} R ⁸ each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted carbon atom 1 to 20 alkoxy groups, substituted or unsubstituted aryloxy groups having 6 to 30 carbon atoms, substituted or unsubstituted alkylthio groups having 1 to 20 carbon atoms, substituted or unsubstituted 6 to 30 carbon atoms An arylthio group, a substituted or unsubstituted arylalkyl group having 7 to 30 carbon atoms, an unsubstituted monocyclic group having 5 to 30 carbon atoms, a substituted or unsubstituted fused polycyclic group having 10 to 30 carbon atoms, or Substituted or unsubstituted 5 to 30 carbon atoms
Is a heterocyclic group. R ^{9 ′} and R ^{10 ′} are each independently a substituted or unsubstituted alkenyl group having 8 to 30 carbon atoms. Ar ¹ and Ar ² are each independently:
A substituted or unsubstituted aryl group having 6 to 30 carbon atoms, wherein the substituent is 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 group, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted alkylthio group having 1 to 20 carbon atoms, a substituted or unsubstituted arylthio group having 6 to 30 carbon atoms,
A substituted or unsubstituted arylalkyl group having 7 to 30 carbon atoms, an unsubstituted monocyclic group having 5 to 30 carbon atoms, a substituted or unsubstituted fused polycyclic group having 10 to 30 carbon atoms, or a substituted or unsubstituted It is a substituted heterocyclic group having 5 to 30 carbon atoms. ] 7. A novel compound represented by the following general formula [5]. General formula [5] [Wherein, R ^{1 to} R ¹⁰ each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted carbon atom 1 to 20 alkoxy groups, substituted or unsubstituted aryloxy groups having 6 to 30 carbon atoms, substituted or unsubstituted alkylthio groups having 1 to 20 carbon atoms, substituted or unsubstituted 6 to 30 carbon atoms An arylthio group, a substituted or unsubstituted arylalkyl group having 7 to 30 carbon atoms, an unsubstituted monocyclic group having 5 to 30 carbon atoms, a substituted or unsubstituted fused polycyclic group having 10 to 30 carbon atoms, or Substituted or unsubstituted 5 to 30 carbon atoms
Is a heterocyclic group. Provided that at least one of R ^{1 to} R ⁸ is an alkyl group, an alkoxy group, an aryloxy group,
It is an alkylthio group, an arylthio group, an arylalkyl group, a monocyclic group, a condensed polycyclic group or a heterocyclic group. Ar ^{3 ′} and Ar ^{4 ′} are each independently a substituted or unsubstituted alkenyl group having 8 to 30 carbon atoms. n is 1-2,
m is 1-2. ] 8. 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, wherein at least one of the organic compound thin films is any one of claims 1 to 7. 9. An organic electroluminescent device, comprising a layer containing the novel compound described in 1. 9. 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.
7. An organic electroluminescence device, which is a layer containing the novel compound according to any one of 7. 10. 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 a layer containing the novel compound according to any one of Items 1 to 7 and a fluorescent dopant. 11. 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, wherein the light emitting layer is formed.
8. An organic electroluminescent device, comprising: a layer containing the novel compound according to any one of items 1 to 7, which emits light having a peak wavelength of 460 nm or less. 12. The organic electroluminescence device according to claim 10, wherein the fluorescent dopant is an amine compound.