JP2001294851A - New azole-boron compound, light emitting element material, and light emitting element using the compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain both a compound emitting fluorescence having a high intensity and a narrow half value width, and a light emitting element using the same. SOLUTION: This light emitting element uses a compound of general formula (I) (R1 is hydrogen atom or a substituent group; X1. and X2 are each halogen atom, an aryl group, an aliphatic hydrocarbon group or the like; Q1 and Q2 are each an atomic group required to form a nitrogen-containing heterocycle but not pyrrole ring at the same time), or its tautomer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a dye for a filter,
The present invention relates to a color conversion filter, a photographic light-sensitive material dye, a sensitizing dye, a pulp dye, a laser dye, a medical diagnostic fluorescent agent, a compound suitable for use as a material for a light-emitting device, and a light-emitting device using them. More specifically, the present invention relates to a light-emitting element material and a high-luminance light-emitting element that can be suitably used in the fields of display elements, displays, backlights, electrophotography, illumination light sources, recording light sources, signs, signs, interiors, and the like.

[0002]

2. Description of the Related Art Light-emitting elements using organic substances are expected to be used as inexpensive large-area, full-color display elements of the solid-state light-emitting type, and many developments have been made. In general, a light emitting element includes a light emitting layer and a pair of opposed electrodes sandwiching the light emitting layer. Light emission occurs when an electric field is applied between both electrodes.
Electrons are injected from the cathode, and holes are injected from the anode.
Further, the electrons and holes are recombined in the light emitting layer, and the energy is emitted as light when the energy level returns from the conduction band to the valence band.

[0003] Conventional light-emitting elements have a high driving voltage and low light emission luminance and light emission efficiency. In addition, the characteristic deterioration was remarkable, and it had not been put to practical use. In recent years, a light emitting device in which a thin film containing an organic compound having high fluorescence quantum efficiency and emitting light at a low voltage of 10 V or less is laminated has been reported (Applied
Physics Letters, 51, 913, 1987
Years), has attracted interest. This method uses a metal chelate complex, a fluorescent band layer, and an amine compound for a hole injection layer,
High-luminance green light emission is obtained, and the luminance reaches several 1000 cd / m ² at a DC voltage of 6 to 7 V. However, in consideration of a practical device, development of a further higher luminance and higher efficiency light emitting device is desired. Further, in consideration of utilization as a full-color display and a light source, it is necessary to emit three primary colors or white in practical use. The above-described element uses an 8-quinolinol Al complex (Alq) as a light-emitting material, emits green light, and the development of light-emitting elements having other light-emitting colors is desired. Until now, various light emitting materials that emit light other than green light have been developed, but they have problems such as low light emission luminance, low light emission efficiency, and low durability, and have not been put to practical use.

On the other hand, a light emitting element which achieves high-luminance light emission is an element in which an organic substance is laminated by vacuum deposition. However, the light emitting element is coated from the viewpoint of simplification of a manufacturing process, workability, and a large area. It is desirable to produce the element by a method. However, a device manufactured by a conventional coating method is inferior to a device manufactured by a vapor deposition method in terms of luminous luminance and luminous efficiency, and high luminance and highly efficient luminescence have been major issues.
Further, in a device in which an organic low-molecular compound is dispersed and applied in an organic polymer medium, there is a problem that it is difficult to emit uniform planar light due to aggregation of the organic low-molecular compound when light is emitted for a long time.

[0005] In recent years, there have been various types of fluorescent materials such as filter dyes, color conversion filters, photographic light-sensitive material dyes, sensitizing dyes, pulp dyes, laser dyes, fluorescent materials for medical diagnosis, and materials for light-emitting devices. Although it is used and its demand is increasing, application of an organic light-emitting device to a full-color display is being actively studied. To develop high-performance full-color displays, blue,
It is necessary to increase the color purity of green and red light emission.
However, many light-emitting materials represented by Alq have broad light emission, and it has been desired to develop a material having a narrow half width of fluorescence and a high intensity.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a compound which emits fluorescence having a high intensity and a narrow half width. A second object of the present invention is to provide a light-emitting element material and a light-emitting element that emit fluorescence with high intensity and a narrow half-value width.

[0007]

This object has been achieved by the following means. (1) A light-emitting element material, which is a compound represented by the following general formula (I) or a tautomer thereof.

[0008]

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[0009] (In the formula, R ₁ .X ₁ and X ₂ are each a halogen atom represents a hydrogen atom or a substituent, a carboxylate group, an aliphatic hydrocarbon group, an .X ₁ representing an aryl group or a heterocyclic group X ₂ good .Q ₁ be linked represents an atomic group necessary for forming a nitrogen-containing heterocycle .Q ₂
Represents an atomic group necessary for forming a nitrogen-containing heterocyclic ring.
However, Q ₁ and Q ₂ are not pyrrole rings at the same time. (2) A light-emitting element material, which is a compound represented by the following general formula (II) or a tautomer thereof.

[0010]

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Wherein R ₁ , R ₂ , R ₃ , R ₄ and R
₅ represents a hydrogen atom or a substituent, and if possible, may combine with each other to form a ring. X ₁ and X ₂ each represent a halogen atom, a carboxylate group, an aliphatic hydrocarbon group, an aryl group or a heterocyclic group. X ₁ and X ₂ may be linked. Q ₂ represents an atom group necessary for forming a nitrogen-containing heterocyclic ring. (3) A compound represented by the following general formula (III) or a tautomer thereof.

[0012]

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(Wherein, R ₁ , R ₂ and R ₃ each represent a hydrogen atom or a substituent, and if possible, may be linked to each other to form a ring. X ₁ and X ₂ each represent a halogen Represents an atom, a carboxylate group, an aliphatic hydrocarbon group, an aryl group or a heterocyclic group; X ₁ and X ₂ may be linked; Y represents a carbonyl group, a sulfo group, a sulfonyl group or a phosphonyl group) (4) A light emitting device material characterized by being a compound represented by the above general formula (III) or a tautomer thereof. (5) In a light-emitting element in which a light-emitting layer or a plurality of organic compound thin layers including a light-emitting layer is formed between a pair of electrodes, at least one of the light-emitting elements has the general formula (I) described in (1) to (4),
A light-emitting element comprising a layer containing at least one compound represented by (II) or (III) or a tautomer thereof. (6) In a light-emitting element in which a light-emitting layer or a plurality of organic compound thin layers including a light-emitting layer is formed between a pair of electrodes, at least one of the light-emitting elements has the general formula (I) described in (1) to (4),
A light-emitting element comprising a layer in which at least one compound represented by (II) or (III) or a tautomer thereof is dispersed in a polymer.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION First, the compound represented by formula (I) of the present invention will be described in detail. R ₁ represents a hydrogen atom or a substituent. As the substituent represented by R ₁ ,
For example, an alkyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, and particularly preferably 1 to 8 carbon atoms)
For example, methyl, ethyl, iso-propyl, t
tert-butyl, n-octyl, n-decyl, n-hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl and the like. ), An alkenyl group (preferably having 2 to 20 carbon atoms, more preferably having 2 to 12 carbon atoms, particularly preferably having 2 to 8 carbon atoms, and examples thereof include vinyl, allyl, 2-butenyl, and 3-pentenyl. ), An alkynyl group (preferably having 2 to 20 carbon atoms, more preferably having 2 to 12 carbon atoms, and particularly preferably having 2 carbon atoms.
To 8, for example, propargyl, 3-pentynyl and the like. ), An aryl group (preferably having 6 to 6 carbon atoms)
30, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, for example, phenyl, p-methylphenyl, naphthyl and the like. ), An amino group (preferably having 0 to 20 carbon atoms, more preferably having 0 to 1 carbon atoms)
0, particularly preferably 0 to 6 carbon atoms, such as amino, methylamino, dimethylamino, diethylamino,
Examples include diphenylamino and dibenzylamino. ), An alkoxy group (preferably having 1 to 20 carbon atoms, more preferably having 1 to 12 carbon atoms, and particularly preferably having 1 carbon atoms.
To 8, for example, methoxy, ethoxy, butoxy and the like. ), An aryloxy group (preferably having 6 to 20 carbon atoms, more preferably having 6 to 16 carbon atoms, particularly preferably having 6 to 12 carbon atoms, for example, phenyloxy,
2-naphthyloxy and the like. ), An acyl group (preferably having 1 to 20 carbon atoms, more preferably having 1 carbon atom)
To 16, particularly preferably 1 to 12 carbon atoms, for example, acetyl, benzoyl, formyl, pivaloyl and the like. ), An alkoxycarbonyl group (preferably having 2 to 20 carbon atoms, more preferably having 2 to 16 carbon atoms, particularly preferably having 2 to 12 carbon atoms, for example, methoxycarbonyl, ethoxycarbonyl and the like.), Aryloxycarbonyl Group (preferably having 7 to 20 carbon atoms,
More preferably 7 to 16 carbon atoms, particularly preferably 7 to 10 carbon atoms,

For example, phenyloxycarbonyl and the like can be mentioned. ), An acyloxy group (preferably having 2 to 2 carbon atoms)
20, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 10 carbon atoms, such as acetoxy and benzoyloxy. ), An acylamino group (preferably having 2 to 20 carbon atoms, more preferably having 2 to 16 carbon atoms,
Particularly preferably, it has 2 to 10 carbon atoms, for example, acetylamino, benzoylamino and the like. ), An alkoxycarbonylamino group (preferably having 2 to 2 carbon atoms)
It has 0, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 12 carbon atoms, such as methoxycarbonylamino. ), An aryloxycarbonylamino group (preferably having 7 to 20 carbon atoms, more preferably having 7 to 16 carbon atoms, particularly preferably having 7 to 12 carbon atoms, for example, phenyloxycarbonylamino and the like), and sulfonylamino Group (preferably having 1 to 2 carbon atoms)
0, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, for example, methanesulfonylamino,
Benzenesulfonylamino and the like. ), A sulfamoyl group (preferably having 0 to 20, more preferably 0 to 16, and particularly preferably 0 to 12 carbon atoms, for example, sulfamoyl, methylsulfamoyl,
Dimethylsulfamoyl, phenylsulfamoyl and the like can be mentioned. ),

A carbamoyl group (preferably having 1 to 2 carbon atoms)
It has 0, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include carbamoyl, methylcarbamoyl, diethylcarbamoyl, and phenylcarbamoyl. ), An alkylthio group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, for example, methylthio,
Ethylthio and the like. ), An arylthio group (preferably having 6 to 20 carbon atoms, more preferably having 6 to 1 carbon atoms)
6, particularly preferably 6 to 12 carbon atoms, such as phenylthio. ), A sulfonyl group (preferably having 1 to 20 carbon atoms, more preferably having 1 to 16 carbon atoms,
Particularly preferably, it has 1 to 12 carbon atoms, for example, mesyl,
And tosyl. ), A sulfinyl group (preferably having 1 to 20 carbon atoms, more preferably having 1 to 16 carbon atoms,
Particularly preferably, it has 1 to 12 carbon atoms, and examples thereof include methanesulfinyl and benzenesulfinyl. ), Ureido group (preferably 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 1 carbon atoms)
12, for example, ureide, methylureide, phenylureide and the like. ), A phosphoric amide group (preferably having 1 to 20 carbon atoms, more preferably having 1 to 1 carbon atoms)
6, particularly preferably 1 to 12 carbon atoms, for example, diethylphosphoramide, phenylphosphoramide and the like. ), Hydroxy, mercapto, halogen (eg, fluorine, chlorine, bromine, iodine), cyano, sulfo, carboxyl, nitro, hydroxamic acid, sulfino, hydrazino,
An imino group, a heterocyclic group (preferably having 1 to 30 carbon atoms, more preferably having 1 to 12 carbon atoms, and examples of the hetero atom include a nitrogen atom, an oxygen atom, and a sulfur atom, specifically, for example, imidazolyl, pyridyl, Examples include quinolyl, furyl, thienyl, piperidyl, morpholino, benzoxazolyl, benzimidazolyl, benzothiazolyl, carbazolyl, and azepinyl.
30, particularly preferably 3 to 24 carbon atoms, for example, trimethylsilyl, triphenylsilyl and the like. ). These substituents may be further substituted. When there are two or more substituents,
They may be the same or different. When possible, they may be connected to each other to form a ring.

The substituent is preferably an alkyl group, an alkenyl group, an aralkyl group, an aryl group, an amino group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbonylamino group, a sulfonylamino group,
A sulfamoyl group, a carbamoyl group, a hydroxy group, a cyano group, a heterocyclic group or a substituent connected to form a condensed ring, more preferably an alkyl group, an alkenyl group, an aralkyl group, an aryl group, an amino group, a carbonyl An amino group, a sulfonylamino group, a hydroxy group, a cyano group, a heterocyclic group, a substituent connected to form a benzene ring, more preferably an alkyl group, an aralkyl group, an aryl group, an amino group, a carbonylamino group ,
It is one in which a sulfonylamino group, a hydroxy group, a cyano group, a heterocyclic group, and a substituent are linked to form a benzene ring.

R ₁ is preferably a hydrogen atom, an alkyl group, an aryl group, a cyano group, a heterocyclic group or a group linked to Q ₁ to form a ring, more preferably a hydrogen atom,
An alkyl group having 1 to 8 carbon atoms, which is linked to Q ₁ to form a ring, more preferably a hydrogen atom, a methyl group,
It is a compound which is linked to ₁ to form a ring, particularly preferably a compound which is linked to a hydrogen atom and Q ₁ to form a 5- or 6-membered ring.

The halogen atom represented by X ₁ and X ₂ includes, for example, a chlorine atom, a bromine atom and a fluorine atom, preferably a chlorine atom and a fluorine atom, and more preferably a fluorine atom. The carboxylate group represented by X ₁ and X ₂ is, for example, an alkyl carboxylate (preferably having 2 to 20 carbon atoms, more preferably having 2 to 16 carbon atoms, still more preferably having 2 to 12 carbon atoms, and And aryl carboxylates (preferably having 7 to 20 carbon atoms, more preferably having 7 to 16 carbon atoms, still more preferably having 7 to 12 carbon atoms, for example, phenyl carboxylate, naphthyl). Carboxylate, etc.), heterocyclic carboxylate (preferably having 1 to 20 carbon atoms, more preferably having 1 to 12 carbon atoms, and examples of the hetero atom include a nitrogen atom, an oxygen atom, a sulfur atom, and a specific example. Include, for example, pyridylcarboxylate, quinolylcarboxylate and the like.) , X ₁ and X ₂ are dicarboxylate linked (preferably having from 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, more preferably 2 to 12 carbon atoms, like for example oxalate, malonate, such as succinate is And the like, and preferably alkyl carboxylate or X ₁
And X ₂ are linked dicarboxylates, more preferably X ₁ and X ₂ are linked dicarboxylates, even more preferably oxalate.

The aliphatic hydrocarbon group represented by X ₁ or X ₂ is a linear, branched or cyclic alkyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and still more preferably Formulas 1 to 12, for example, methyl, ethyl, iso-propyl, tert-butyl, n-octyl, n-decyl, n-hexadecyl, cyclopropyl,
Cyclopentyl, cyclohexyl and the like can be mentioned. ), An alkenyl group (preferably having 2 to 30 carbon atoms, more preferably having 2 to 20 carbon atoms, and still more preferably having 2 carbon atoms).
-12, for example, vinyl, allyl, 2-butenyl,
3-pentenyl and the like. ), An alkynyl group (preferably having 2 to 30 carbon atoms, more preferably having 2 carbon atoms)
-20, more preferably 2-12 carbon atoms, such as propargyl and 3-pentynyl. ), Preferably an alkyl group or an alkenyl group, more preferably a methyl group, an ethyl group, a propyl group, a butyl group, or an allyl group.

The aryl group represented by X ₁ and X ₂ is preferably a monocyclic or bicyclic aryl group having 6 to 30 carbon atoms (for example, phenyl, naphthyl, etc.), and more preferably. A phenyl group having 6 to 20 carbon atoms, more preferably a phenyl group having 6 to 12 carbon atoms.

The heterocycle represented by X ₁ and X ₂ is N, O
Or a 3- to 10-membered saturated or unsaturated heterocyclic ring containing at least one S atom, which may be a single ring or may form a condensed ring with another ring. The heterocycle is preferably a 5- or 6-membered aromatic heterocycle, more preferably a 5- or 6-membered aromatic heterocycle containing a nitrogen atom, and even more preferably a 5- or 6-membered aromatic heterocycle containing 1 or 2 nitrogen atoms. It is a 6-membered aromatic heterocycle. Specific examples of the heterocycle include, for example, pyrrolidine, piperidine, piperazine, morpholine, thiophene, furan, pyrrole, imidazole, pyrazole, pyridine, pyrazine, pyridazine, triazole, triazine, indole, indazole, purine, thiazoline, thiazole, thiadiazole, Oxazoline, oxazole, oxadiazole, quinoline, isoquinoline, phthalazine, naphthyridine, quinoxaline, quinazoline, cinnoline, pteridine, acridine phenanthroline, phenazine, tetrazole, benzimidazole, benzoxazole, benzothiazole, benzotriazole, tetrazaindene, and the like. . Preferably as a heterocycle, pyrrole, imidazole, pyrazole, pyridine, pyrazine, pyridazine, triazole, triazine, indole, indazole, thiadiazole, oxadiazole, quinoline, phthalazine,
Quinoxaline, quinazoline, cinnoline, tetrazole, thiazole, oxazole benzimidazole, benzoxazole, benzothiazole, benzotriazole, more preferably imidazole, pyridine,
Quinoline, thiazole, oxazole, benzimidazole, benzoxazole, benzothiazole and benzotriazole, more preferably pyridine and quinoline.

X₁, X_TwoA halogen atom represented by
Boxylate group, aliphatic hydrocarbon group, aryl group or
The heterocyclic groups may be the same or different from each other. Also,
Where possible, it may further have a substituent.
In the general formula (I) ₁You can apply the ones listed in
You.

X ₁ and X ₂ are preferably a halogen atom, an aryl group or an aliphatic hydrocarbon group, more preferably a chlorine atom, a fluorine atom, an aryl group having 6 to 20 carbon atoms, or an alkyl group having 1 to 12 carbon atoms. Group, more preferably a fluorine atom, a phenyl group, a p-fluorophenyl group,
A methyl group and an ethyl group, particularly preferably a fluorine atom.

Q ₁ represents an atomic group necessary for forming a nitrogen-containing heterocyclic ring. The nitrogen-containing heterocyclic ring represented by Q ₁ is a 3- to 10-membered nitrogen-containing heterocyclic ring, which is a single ring. And a condensed ring may be formed with another ring.
The nitrogen-containing heterocycle is preferably a 5- or 6-membered nitrogen-containing aromatic heterocycle. Specific examples of the heterocycle include
For example, pyrrolidine, piperidine, piperazine, morpholine, pyrrole, imidazole, pyrazole, pyridine, pyrazine, pyridazine, triazole, triazine, indole, indazole, purine, thiazoline,
Thiazole, thiadiazole, oxazoline, oxazole, oxadiazole, quinoline, isoquinoline, phthalazine, naphthyridine, quinoxaline, quinazoline,
Cinnoline, pteridine, acridine phenanthroline, phenazine, tetrazole, benzimidazole,
Examples include benzoxazole, benzothiazole, benzotriazole, and tetrazaindene. Preferably as a heterocycle, pyrrole, imidazole, pyrazole, pyridine, pyrazine, pyridazine, triazole,
Triazine, indole, indazole, thiadiazole, oxadiazole, quinoline, phthalazine, quinoxaline, quinazoline, cinnoline, tetrazole, thiazole, oxazole, benzimidazole, benzoxazole, benzothiazole, benzotriazole, more preferably imidazole, pyridine, quinoline , Thiazole, oxazole, benzimidazole,
Benzoxazole, benzothiazole and benzotriazole are more preferable, and pyridine and quinoline are more preferable.

Q ₂ represents a group of atoms necessary for forming a nitrogen-containing heterocyclic ring. The ring formed by Q ₂ includes a saturated or unsaturated hetero ring. Or a condensed ring may be formed with another ring. Q ₂
Is preferably a 3- to 10-membered hetero ring, more preferably a 4- to 7-membered hetero ring, even more preferably a 5- to 6-membered hetero ring, particularly preferably a 5- to 6-membered ring. Is an aromatic heterocycle. Specific examples of the heterocycle include, for example, pyrrolidine, piperidine, piperazine, morpholine, pyrrole, imidazole, pyrazole, pyridine, pyrazine, pyridazine, triazole, triazine, indole, indazole,
Purine, thiazoline, thiazole, thiadiazole, oxazoline, oxazole, oxadiazole, quinoline, isoquinoline, phthalazine, naphthyridine, quinoxaline, quinazoline, cinnoline, pteridine, acridine phenanthroline, phenazine, tetrazole,
Examples include benzimidazole, benzoxazole, benzothiazole, benzotriazole, tetrazaindene, isoindolinone, and benzisothiazole dioxide. Preferably as a heterocycle, pyrrole, imidazole, pyrazole, pyridine, pyrazine, pyridazine, triazole, triazine, indole, indazole, thiadiazole, oxadiazole, quinoline, phthalazine, quinoxaline, quinazoline, cinnoline, tetrazole, thiazole, oxazole, benzimidazole , Benzoxazole, benzothiazole, benzotriazole, isoindolinone, benzisothiazole dioxide, more preferably imidazole, pyridine, quinoline, oxazole, benzimidazole, benzoxazole, benzothiazole,
Benzotriazole, isoindolinone, benzisothiazole dioxide, more preferably pyridine, quinoline, isoindolinone, benzisothiazole dioxide, particularly preferably isoindolinone, benzisothiazole dioxide .

Among the compounds represented by the general formula (I), the compound represented by the general formula (II) is preferred.

[0028]

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(Wherein, R ₁ , X ₁ , X ₂ and Q ₂ have the same meanings as those in formula (I), and their preferred ranges are also the same. R ₂ , R ₃ , R ₄ and R ₅₎ Each represents a hydrogen atom or a substituent, and if possible, may combine with each other to form a ring.)

As the substituent represented by R ₂ , R ₃ , R ₄ or R ₅ , those mentioned as the substituent of R ₁ in formula (I) can be applied. R ₂ is preferably a hydrogen atom, an alkyl group, an alkenyl group, an aralkyl group, an aryl group, an amino group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbonylamino group, a sulfonylamino group, a sulfamoyl group, a carbamoyl group, a hydroxy group. Group, a cyano group, a heterocyclic group, a halogen atom, a ring formed by linking to R ₁ , more preferably a hydrogen atom, an alkyl group, a halogen atom, linked to R ₁ to form a ring And more preferably a hydrogen atom,
It is linked to R ₁ to form a ring. R ₃ is preferably a hydrogen atom, an alkyl group, an alkenyl group, an aralkyl group, an aryl group, an amino group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbonylamino group, a sulfonylamino group, a sulfamoyl group, a carbamoyl group, A hydroxy group, a cyano group, a heterocyclic group, a halogen atom, more preferably a hydrogen atom,
An alkyl group and a halogen atom are preferred, and a hydrogen atom is more preferred. R ₄ and R ₅ are preferably a hydrogen atom,
Alkyl group, alkenyl group, aralkyl group, aryl group, amino group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbonylamino group, sulfonylamino group, sulfamoyl group, carbamoyl group,
Hydroxy group, cyano group, heterocyclic group, halogen atom,
R ₄ and R ₅ are condensed to form a benzene ring, more preferably a hydrogen atom, an alkyl group, a halogen atom, and R ₄ and R ₅ are condensed to form a benzene ring, more preferably Is a compound in which R ₄ and R ₅ are fused to form a benzene ring.

Among the compounds represented by the general formula (I), more preferred are the compounds represented by the general formula (III).

[0032]

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Wherein R ₁ , R ₂ , R ₃ , X ₁ and X
₂ has the same meaning as those in formula (II), and the preferred range is also the same. Y represents a carbonyl group, a sulfo group, a sulfonyl group or a phosphonyl group.
Q ₃ and Q ₄ each represent an atom group necessary for forming a ring. )

Y represents a carbonyl group, a sulfonyl group or a phosphonyl group, preferably a carbonyl group or a sulfonyl group.

Q ₃ represents an atom group necessary for forming a ring, and the ring formed by Q ₃ includes a hydrocarbon ring and a hetero ring. Further, these may be a single ring or may form a condensed ring with another ring.

The hydrocarbon ring formed by Q ₃ may be an aromatic hydrocarbon ring or a non-aromatic hydrocarbon ring, and is preferably an aromatic hydrocarbon ring (preferably having 6 to 30 carbon atoms, more preferably having 6 to 24, more preferably 6 carbon atoms
-20, particularly preferably a benzene ring and a naphthalene ring, and most preferably a benzene ring. ).

The heterocyclic ring formed by Q ₃ is preferably a 3- to 10-membered heterocyclic ring containing at least one N, O or S atom, and these may be a monocyclic ring or a ring with another ring. A condensed ring may be formed. The heterocyclic ring is preferably a 5- or 6-membered aromatic heterocyclic ring. Specific examples of the heterocyclic ring include, for example, thiophene, furan, pyrrole, imidazole, pyrazole, pyridine, pyrazine,
Pyridazine, triazole, triazine, indole,
Indazole, purine, thiazoline, thiazole, thiadiazole, oxazoline, oxazole, oxadiazole, quinoline, isoquinoline, phthalazine, naphthyridine, quinoxaline, quinazoline, cinnoline, pteridine, acridine phenanthroline, phenazine,
Examples include benzimidazole, benzoxazole, benzothiazole, benzotriazole, and tetrazaindene. Preferably as a heterocycle, pyrrole, imidazole, pyrazole, pyridine, pyrazine, pyridazine, triazole, triazine, indole, indazole, thiadiazole, oxadiazole, quinoline, phthalazine, quinoxaline, quinazoline, cinnoline, thiazole, oxazole, benzimidazole,
Benzoxazole, benzothiazole and benzotriazole, more preferably imidazole, pyridine, pyrazine, pyridazine, quinoline, thiazole and oxazole, and still more preferably pyridine and pyrazine.

Q ₃ is preferably an aromatic hydrocarbon ring,
An aromatic hetero ring, more preferably 6 to 20 carbon atoms
And more preferably an aromatic hydrocarbon ring having 6 to 20 carbon atoms, particularly preferably benzene and naphthalene.

Q ₄ represents a group of atoms necessary to form a ring. Examples of the ring formed by Q ₄ include a saturated or unsaturated hydrocarbon ring and a saturated or unsaturated hetero ring. A condensed ring may be formed with another ring.

The saturated or unsaturated hydrocarbon ring formed by Q ₄ may be an aliphatic hydrocarbon ring or an aromatic hydrocarbon ring, preferably an aromatic hydrocarbon ring (preferably having 6 carbon atoms).
To 30, more preferably 6 to 24 carbon atoms, still more preferably 6 to 20 carbon atoms, particularly preferably benzene and naphthalene, and most preferably benzene. ).

The heterocyclic ring formed by Q ₄ is preferably a 3- to 10-membered heterocyclic ring containing at least one N, O or S atom, and these may be a single ring or a heterocyclic ring. A condensed ring may be formed. The hetero ring is preferably an aromatic hetero ring, and more preferably a 5- or 6-membered aromatic hetero ring. Specific examples of the heterocycle include, for example, pyrrolidine, piperidine, piperazine, morpholine, thiophene, furan, pyrrole, imidazole, pyrazole, pyridine, pyrazine, pyridazine, triazole, triazine, indole, indazole,
Purine, thiazoline, thiazole, thiadiazole, oxazoline, oxazole, oxadiazole, quinoline, isoquinoline, phthalazine, naphthyridine, quinoxaline, quinazoline, cinnoline, pteridine, acridine phenanthroline, phenazine, benzimidazole, benzoxazole, benzothiazole, benzotriazole, tetra Seinden and the like. Preferably as a heterocycle, pyrrole, imidazole, pyrazole, pyridine, pyrazine, pyridazine, triazole, triazine, indole, indazole, thiadiazole, oxadiazole, quinoline, phthalazine,
Quinoxaline, quinazoline, cinnoline, thiazole,
Oxazole, benzimidazole, benzoxazole, benzothiazole, benzotriazole, more preferably pyridine, pyrazine, pyridazine,
More preferably, it is pyridine.

Q ₄ is preferably an aromatic hydrocarbon ring,
An aromatic hetero ring, more preferably 6 to 20 carbon atoms
Aromatic hydrocarbon ring, a nitrogen-containing aromatic heterocycle, more preferably benzene, naphthalene, pyridine, pyrazine, pyridazine, particularly preferably benzene,
Pyridine and pyrazine.

Among the compounds represented by formula (I), more preferred are compounds represented by formulas (III-a ₁ ) and (III-b ₁ ).

[0044]

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First, the compound represented by formula (III-a ₁ ) will be described in detail. In the general formula (III-a ₁ ), R ₁ ,
R ₂ , R ₃ , X ₁ , X ₂ , Q ₃ and Q ₄ have the same meanings as those in formula (III), and the preferred ranges are also the same. Among the compounds represented by the general formula (III-a ₁ ), a compound represented by the general formula (III-a ₂ ) is preferable.

[0046]

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Wherein R ₁ , R ₂ , R ₃ , X ₁ and X
₂ has the same meaning as those in formula (III), and the preferred range is also the same. R _10, R _11, R ₁₂ and R ₁₃ represents a hydrogen atom or a substituent, it can be applied those described as the substituent group R ₁ in the general formula (I) as a substituent, R _10, R _11, R Preferred as ₁₂ and R ₁₃ are a hydrogen atom, an alkyl group, an alkenyl group, an aralkyl group, an aryl group, an amino group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbonylamino group, a sulfonylamino group, a sulfamoyl group, and carbamoyl. Group, a hydroxy group, a cyano group, a hetero ring, and a halogen atom, more preferably a hydrogen atom, an alkyl group, and a halogen atom, and still more preferably a hydrogen atom. Q ₅ represents an aromatic hydrocarbon ring or an aromatic hetero ring, preferably an aromatic hydrocarbon ring having 6 to 20 carbon atoms, and a 5- to 6-membered aromatic hetero ring, more preferably benzene, naphthalene , Pyridine, pyrazine and pyridazine, and more preferably benzene, pyridine and pyrazine. )

Among the compounds represented by the general formula (III-a ₁ ), more preferred are the compounds represented by the general formula (III-a ₃ ).

[0049]

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(Wherein R ₁ , R ₂ , R ₃ , R ₁₀ , R ₁₁ ,
R ₁₂ , R ₁₃ and Q ₅ have the same meanings as those in formula (III-a ₂ ), respectively, and their preferred ranges are also the same. )

The compound represented by formula (III-b ₁ ) will be described below in detail. In the general formula (III-b ₁ ), R ₁ ,
R ₂ , R ₃ , X ₁ , X ₂ , Q ₃ and Q ₄ have the same meanings as those in formula (III), and the preferred ranges are also the same. Of the compounds represented by the general formula (III-b ₁ ), a compound represented by the general formula (III-b ₂ ) is preferable.

[0052]

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(Wherein R ₁ , R ₂ , R ₃ , R ₁₀ , R ₁₁ ,
R ₁₂ , R ₁₃ , X ₁ , X ₂ and Q ₅ are each represented by the general formula (II
It has the same meanings as those defined in I-a _2), and preferred ranges are also the same. )

Among the compounds represented by the general formula (III-b ₁ ), more preferred are the compounds represented by the general formula (III-b ₃ ).

[0055]

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(Wherein R ₁ , R ₂ , R ₃ , R ₁₀ , R ₁₁ ,
R ₁₂ , R ₁₃ , and Q ₅ have the same meanings as those in formula (III-a ₂ ), and the preferred ranges are also the same. )

The compounds of the general formulas (I), (II), (III) and (I
_{II-a 1), (III} -a 2), (III-a 3), (III-b 1), (III
The compound represented by -b ₂ ) or (III-b ₃ ) may be a low molecular weight compound or a high molecular weight compound having a residue in which a polymer main chain is connected (preferably, a mass average molecular weight of 1,000 to 500).
0000, more preferably 5000 to 2,000,000,
More preferably, it may be 10,000 to 1,000,000) or a high molecular weight compound having the main chain of the compound of the present invention (preferably, a mass average molecular weight of 1,000 to 5,000,000, more preferably 5,000 to 2,000,000, and still more preferably 10,000 to 1,000,000). In the case of a high molecular weight compound, it may be a homopolymer, or may be a copolymer with another polymer.If it is a copolymer, it may be a random copolymer or a block copolymer. There may be. The compound used in the present invention is preferably a low molecular weight compound. Further, in the above general formula, the compound is represented by an extreme structure for convenience, but may be a tautomer thereof.

Specific examples of the compound represented by formula (I) of the present invention are shown below, but the present invention is not limited to these. For convenience, the compounds shown below are represented by the ultimate structure, but may be tautomers thereof.

[0059]

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[0060]

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[0061]

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[0062]

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The compound represented by the general formula (I) is, for example,
Z. Chem., 28, 23 (1988);
It can be synthesized by the method described in US Pat. In addition, an example of a method for synthesizing the compound represented by the general formula (I) of the present invention is shown in Scheme 1.

[0064]

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(Wherein Q ₁ , Q ₂ , R ₁ , X ₁ and X
₂ has the same meaning as those in formula (I), and the preferred range is also the same. )

Compound (B) is specifically prepared in the presence of a base,
(A) and BF_ThreeCan be synthesized by reacting
You. As the base, an organic base (for example, organic amines, a
Sols, etc.), inorganic bases (eg, potassium salt, sodium
Um salt). Equivalent amounts of bases correspond to (A)
1 to 10 equivalents, more preferably 1 to 5 equivalents.
And more preferably 1 to 2 equivalents. BF_ThreeAs a complex
BF_ThreeDialkyl ether complexes (eg BF_ThreeJime
Tyl ether complex, BF_ThreeDiethyl ether complex, BF
_Threetert-butyl methyl ether complex), BF_ThreeArco
Complex (for example, BF_ThreeMethanol complex, BF_Threen-p
Lopanol complex), BF_ThreeAmine complexes (eg BF_Three
Ethylamine complex, BF _ThreePiperidine complex etc.), BF_Three
Carboxylic acid complexes (eg BF_ThreeAcetic acid complex), BF_ThreeS
Sulfide complexes (eg BF_ThreeDimethyl sulfide complex
And the like, and preferably a BF3 dialkyl ether complex
Body, more preferably BF_ThreeDiethyl ether complex
It is. As the solvent, hydrocarbons (for example, hexa
Benzene, toluene, xylene and the like. ), Nito
Rils (for example, acetonitrile and the like), ether
(Eg, tetrahydrofuran, 1,4-dioxa
And diethyl ether. ) Is preferred and the reaction temperature
The temperature is not particularly limited, but is preferably 0 to 150 ° C.
More preferably, it is 0-100 degreeC. Compound
(C) is specifically for the reaction between compound (B) and an organometallic.
Thus obtained. Lithium salt as organic metal, Grignard
There are reagents and the like, and the equivalent is preferably 2 to 50 equivalents.
And more preferably 2 to 20 equivalents, even more preferably
Or 2 to 10 equivalents. As solvents, hydrocarbons
(For example, benzene, toluene, xylene, etc.
Ethers (eg, tetrahydrofuran, 1,4-di
Oxane, diethyl ether and the like. ) Is preferred,
The reaction temperature is not particularly limited, but is preferably 0 to 150 ° C.
And more preferably 0 to 100 ° C.

The light-emitting device of the present invention is a device in which a light-emitting layer or a plurality of organic compound thin layers including the light-emitting layer are formed between a pair of anode and cathode electrodes. It may have a layer, an electron injection layer, an electron transport layer, a protective layer, and the like, and each of these layers may have another function. Various materials can be used for forming each layer.

The anode supplies holes to the hole injection layer, the hole transport layer, the light emitting layer, etc., and may be made of a metal, an alloy, a metal oxide, an electrically conductive compound, or a mixture thereof. It is possible to use a material having a work function of 4 eV or more. Specific examples include conductive metal oxides such as tin oxide, zinc oxide, indium oxide, and indium tin oxide (ITO), or metals such as gold, silver, chromium, and nickel, and furthermore, these metals and conductive metal oxides. Mixtures or laminates, inorganic conductive substances such as copper iodide and copper sulfide, organic conductive materials such as polyaniline, polythiophene, and polypyrrole, and laminates of these with ITO, and the like. Oxides,
In particular, ITO is preferable in terms of productivity, high conductivity, transparency, and the like. The thickness of the anode can be appropriately selected depending on the material, but is usually preferably in the range of 10 nm to 5 μm, more preferably 50 nm to 1 μm, and still more preferably 100 nm to 500 nm.

As the anode, a layer formed on a soda lime glass, a non-alkali glass, a transparent resin substrate or the like is usually used. When glass is used, it is preferable to use non-alkali glass in order to reduce ions eluted from the glass. Further, when soda lime glass is used, it is preferable to use a glass coated with a barrier coat such as silica. The thickness of the substrate is not particularly limited as long as it is sufficient to maintain the mechanical strength. When glass is used, the thickness is usually 0.2 mm or more, preferably 0.7 mm or more. Various methods are used for producing the anode depending on the material. For example, in the case of ITO, an electron beam method, a sputtering method, a resistance heating evaporation method, a chemical reaction method (such as a sol-gel method), and a coating of a dispersion of indium tin oxide are used. The film is formed by the method described above. The anode can be cleaned or otherwise treated to lower the device's drive voltage,
It is also possible to increase the luminous efficiency. For example, in the case of ITO, UV-ozone treatment, oxygen plasma treatment and the like are effective.

The cathode supplies electrons to the electron injecting layer, the electron transporting layer, the light emitting layer, etc., and provides the adhesion between the negative electrode such as the electron injecting layer, the electron transporting layer, the light emitting layer, the ionization potential, and the like. It is selected in consideration of stability and the like. As a material of the cathode, a metal, an alloy, a metal oxide, an electrically conductive compound, or a mixture thereof can be used. Specific examples thereof include alkali metals (eg, Li, Na, K, Cs
Or its fluorides, oxides, alkaline earth metals (eg, Mg, Ca, etc.) or its fluorides, oxides,
Gold, silver, lead, aluminum, sodium-potassium alloy or a mixed metal thereof, lithium-aluminum alloy or a mixed metal thereof, magnesium-silver alloy or a mixed metal thereof, indium, rare earth metals such as ytterbium, and the like, Preferably, the material has a work function of 4 eV or less, and more preferably, aluminum, a lithium-aluminum alloy or a mixed metal thereof, a magnesium-silver alloy or a mixed metal thereof, or the like. The thickness of the cathode can be appropriately selected depending on the material, but is usually 10 n
m to 5 μm, more preferably 5 to 5 μm.
0 nm to 1 μm, more preferably 100 nm to 1 μm.
μm. A method such as an electron beam method, a sputtering method, a resistance heating evaporation method, or a coating method is used for manufacturing the cathode, and a metal can be evaporated alone or two or more components can be simultaneously evaporated. Further, an alloy electrode can be formed by depositing a plurality of metals at the same time, or an alloy prepared in advance may be deposited. The sheet resistance of the anode and the cathode is preferably low, and is preferably several hundred Ω / □ or less.

The material of the light emitting layer is capable of injecting holes from an anode, a hole injection layer, or a hole transport layer and applying electrons from a cathode, an electron injection layer, or an electron transport layer when an electric field is applied. Any material can be used as long as it can form a layer having a function, a function of transferring injected charges, and a function of providing a field of recombination of holes and electrons to emit light. Preferably, the light-emitting layer contains the compound of the present invention, but other light-emitting materials of the compound of the present invention can also be used. For example, benzoxazole derivatives,
Benzimidazole derivatives, benzothiazole derivatives,
Styrylbenzene derivatives, polyphenyl derivatives, diphenylbutadiene derivatives, tetraphenylbutadiene derivatives, naphthalimide derivatives, coumarin derivatives, perylene derivatives, perinone derivatives, oxadiazole derivatives, aldazine derivatives, cyclopentadiene derivatives, bisstyrylanthracene derivatives, quinacridone derivatives, Metal complexes and transition metal complexes of pyrrolopyridine derivatives, thiadiazolopyridine derivatives, cyclopentadiene derivatives, styrylamine derivatives, aromatic dimethylidin compounds, and 8-quinolinol derivatives (for example, ortho metal such as tris (2-phenylpyridine) iridium (III) Metalated complexes),
Examples include various metal complexes represented by rare earth complexes, and polymer compounds such as polythiophene, polyphenylene, and polyphenylenevinylene. The thickness of the light emitting layer is not particularly limited, but is usually preferably in the range of 1 nm to 5 μm, more preferably 5 nm to 1 μm, and still more preferably 10 nm to 500 nm. The method of forming the light-emitting layer is not particularly limited, but includes resistance heating evaporation, electron beam, sputtering, molecular lamination, coating (spin coating, casting, dip coating, etc.), LB, and ink jet. , A printing method, and the like, and preferably a resistance heating evaporation and a coating method.

The material of the hole injection layer and the hole transport layer has one of a function of injecting holes from the anode, a function of transporting holes, and a function of blocking electrons injected from the cathode. Anything should do. Specific examples thereof include carbazole derivatives, triazole derivatives, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, and styryl anthracene derivatives , Fluorenone derivative, hydrazone derivative, stilbene derivative, silazane derivative, aromatic tertiary amine compound, styrylamine compound, aromatic dimethylidin compound, porphyrin compound, polysilane compound,
Examples thereof include poly (N-vinylcarbazole) derivatives, aniline-based copolymers, thiophene oligomers, and conductive polymer oligomers such as polythiophene. The thicknesses of the hole injection layer and the hole transport layer are not particularly limited, but are usually preferably in the range of 1 nm to 5 μm, more preferably 5 nm to 1 μm, and still more preferably 10 nm to 5 μm.
00 nm. The hole injection layer and the hole transport layer may have a single-layer structure composed of one or more of the above-described materials, or may have a multilayer structure composed of a plurality of layers having the same composition or different compositions. Examples of the method for forming the hole injection layer and the hole transport layer include a vacuum deposition method, an LB method, and a method in which the hole injection / transport agent is dissolved or dispersed in a solvent and coated (spin coating method, casting method, dip coating method). Such),
An ink jet method and a printing method are used. In the case of the coating method, it can be dissolved or decomposed together with the resin component. Examples of the resin component include polyvinyl chloride, polycarbonate, polystyrene, polymethyl methacrylate, polybutyl methacrylate, polyester, polysulfone, polyphenylene oxide, polybutadiene, and poly (N -Vinyl carbazole), hydrocarbon resins, ketone resins, phenoxy resins, polyamides, ethyl cellulose, vinyl acetate, ABS resins, polyurethanes, melamine resins, unsaturated polyester resins, alkyd resins, epoxy resins, silicone resins, and the like.

The material of the electron injecting layer and the electron transporting layer is not limited as long as it has a function of injecting electrons from the cathode, a function of transporting electrons, and a function of blocking holes injected from the anode. Good. Specific examples thereof include triazole derivatives, oxazole derivatives, oxadiazole derivatives,
Heterocyclic tetracarboxylic acid anhydrides such as fluorenone derivatives, antokyranodimethane derivatives, anthrone derivatives, diphenylquinone derivatives, thiopyrandioxide derivatives, carbodiimide derivatives, fluorenylidenemethane derivatives, distyrylpyrazine derivatives, naphthalene perylene, and phthalocyanine derivatives And various metal complexes typified by metal complexes of 8-quinolinol derivatives, metal phthalocyanines, and metal complexes having benzoxazole or benzothiazole as ligands. The thickness of the electron injection layer and the electron transport layer is not particularly limited, but is usually 1 nm to 5 μm.
m, more preferably 5 nm to 1
μm, and more preferably 10 nm to 500 nm. The electron injection layer and the electron transport layer may have a single layer structure composed of one or more of the above-mentioned materials, or may have a multilayer structure composed of a plurality of layers having the same composition or different compositions. Examples of the method for forming the electron injecting layer and the electron transporting layer include a vacuum evaporation method, an LB method, a method in which the electron injecting and transporting agent is dissolved or dispersed in a solvent and coated (spin coating, casting, dip coating, etc.), An ink jet method, a printing method, or the like is used. In the case of the coating method, it can be dissolved or dispersed together with the resin component. As the resin component, for example, those exemplified in the case of the hole injection transport layer can be applied.

As the material of the protective layer, any material may be used as long as it has a function of preventing a substance that promotes element deterioration such as moisture or oxygen from entering the element. As a specific example,
In, Sn, Pb, Au, Cu, Ag, Al, Ti, N
metal such as i, MgO, SiO, SiO ₂ , Al ₂ O ₃ ,
GeO, NiO, CaO, BaO, Fe 2 O 3, Y 2 O
_3, a metal oxide such as TiO _2, MgF _2, LiF, Al
F ₃ , metal fluoride such as CaF ₂ , polyethylene, polypropylene, polymethyl methacrylate, polyimide,
Polyurea, polytetrafluoroethylene, polychlorotrifluoroethylene, polydichlorodifluoroethylene, copolymer of chlorotrifluoroethylene and dichlorodifluoroethylene, copolymerizing a monomer mixture containing tetrafluoroethylene and at least one comonomer Copolymer obtained, a fluorine-containing copolymer having a cyclic structure in the copolymer main chain, a water-absorbing substance having a water absorption of 1% or more,
A moisture-proof substance having a water absorption of 0.1% or less can be used. There is no particular limitation on the method for forming the protective layer. For example, a vacuum deposition method, a sputtering method, a reactive sputtering method,
BE (molecular beam epitaxy) method, cluster ion beam method, ion plating method, plasma polymerization method (high frequency excitation ion plating method), plasma CVD method, laser CVD method, thermal CVD method, gas source CVD method, coating method, An inkjet method and a printing method can be applied.

[0075]

EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited thereto.

Example 1 Synthesis of Exemplified Compound 1

[0077]

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Method for synthesizing compound a 67.3 g (1.2 mol) of potassium hydroxide was added to 200 mL of water.
And 58.8 g (0.4 mol) of isatin was added little by little, followed by stirring at 50 ° C. for 3.5 hours. Then, slowly cyclopentanone 62.2 g (0.74 mol)
Was added and heated under reflux for 7 hours. After cooling the reaction solution to room temperature, the reaction solution is dropped into 120 mL of concentrated hydrochloric acid and 600 mL of water. The precipitated crystals were separated by filtration and dried to obtain 93.1 g of Compound a as a white solid. Method for synthesizing compound b 93.1 g of compound a is placed in a 500 mL three-necked flask, and vigorously stirred at an external temperature of 300 ° C. with a mantle heater.
As the reaction proceeded, the contents of the flask dissolved. About 2
After stirring for an hour, the mixture was cooled to room temperature, extracted with chloroform and a saturated aqueous solution of sodium hydrogen carbonate, the organic phase was collected, dried over sodium sulfate, filtered, the solvent was distilled off under reduced pressure, and silica gel column chromatography (hexane -Ethyl acetate, 9/1 to 6/4, vol / vol) to obtain 27.7 g of compound b as a brown liquid (yield 41% from isatin). Method for synthesizing compound c 6.2 g (36 mmol) of compound b, 5.3 of phthalimide
g (40 mmol), zinc chloride 11.4 g (84 mmol)
l), 90 mL of dimethylaniline was stirred at 150 ° C for 2 hours, and then stirred at 180 ° C for 4 hours. The reaction solution was cooled to room temperature, 500 mL of a 30% aqueous hydrochloric acid solution was added, and the mixture was heated at 90 ° C for 1 hour.
After stirring for an hour, the mixture was cooled to room temperature, and the precipitated solid was separated by filtration. The obtained solid was dissolved in chloroform, the organic layer was washed with an aqueous sodium hydroxide solution, the organic phase was collected, dried over sodium sulfate, and filtered. The solvent was distilled off under reduced pressure, and silica gel column chromatography (chloroform-methanol, (100/3, vol / vol) and recrystallization from chloroform and ethanol to obtain 4.9 g of compound c as yellow crystals (yield: 45%). Synthesis method of compound 1 Compound c 0.5 g (1.6 mmol), DBU (1,8-
Diazabicyclo [5,4,0] undec-7-ene)
BF in 50 mL of 0.24 mL (1.6 mmol) toluene
After 0.5 mL (3.5 mmol) of 3 diethyl ether complex was added dropwise at room temperature, the mixture was refluxed for 4 hours. After the reaction solution was cooled to room temperature, the precipitated crystals were separated by filtration. The compound was recrystallized twice with chloroform to give Compound 1 in an amount of 420 m.
g (yield 72%). Melting point 305 ° C (decomposition temperature)

Example 2 Synthesis of Compound 2

Method for synthesizing compound e Compound d was obtained by changing cyclopentanone to cyclohexanone in the same manner as for compound a. 500 mL of 22.7 g (0.1 mol) of compound d
Into a three-necked flask, and set the outside temperature to 30 with a mantle heater.
Stir vigorously at 0 ° C. As the reaction proceeds, the contents of the flask dissolve. After stirring for about 2 hours, the mixture was cooled to room temperature, extracted with chloroform and a saturated aqueous solution of sodium hydrogen carbonate, the organic phase was collected, dried over sodium sulfate, filtered, and the solvent was distilled off under reduced pressure. (Hexane-ethyl acetate, 9/1 to 7
/ 3, vol / vol) to obtain 14.3 g of compound e as a brown solid (78% yield from isatin).
Obtained. Method for synthesizing compound f 5.5 g (30 mmol) of compound e, 4.8 of phthalimide
g (33 mmol), zinc chloride 9.4 g (69 mmol),
After stirring 50 mL of dimethylaniline at 150 ° C for 2 hours, the mixture was stirred at 180 ° C for 4 hours. The reaction solution was cooled to room temperature, 200 mL of a 3N hydrochloric acid aqueous solution was added, and the mixture was stirred at 90 ° C. for 1 hour. After cooling to room temperature, the precipitated solid was separated by filtration.
The obtained solid was washed with water, and recrystallized from chloroform and ethanol to give compound f as yellow crystals.
5 g (yield 69%) was obtained. Method for synthesizing compound 2 Compound f 1.0 g (3.2 mmol), DBU 0.48 m
1.0 mL (7.0 mmol) of BF ₃ diethyl ether complex was added dropwise to 100 mL of L (3.2 mmol) toluene at room temperature, and the mixture was heated under reflux for 4 hours. After the reaction solution was cooled to room temperature, the precipitated crystals were separated by filtration. The recrystallization operation was performed twice with acetonitrile, and 500 mg of Compound 2 was obtained.
(43% yield). 277 ° C (decomposition temperature)

Example 3 Synthesis of Compound 3

Method for synthesizing compound g

[0083]

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6.76 g (40 mmol) of compound b, 8.05 g (44 mmol) of saccharin, 12.5 g of zinc chloride
(91 mmol), 70 mL of dimethylaniline at 150 ° C
, And then stirred at 180 ° C. for 5 hours. The reaction solution was cooled to room temperature, 300 mL of a 3N aqueous hydrochloric acid solution was added, and 9
After stirring at 0 ° C. for 1 hour, the mixture was cooled to room temperature, and the precipitated solid was separated by filtration to obtain 3.5 g of compound g as red crystals (yield: 26%). Method for synthesizing compound 3 Compound g 1.0 g (3.0 mmol), DBU 0.45 m
0.76 mL (6.0 mmol) of BF ₃ diethyl ether complex was added dropwise to 100 mL of L (3.0 mmol) toluene at room temperature, and the mixture was refluxed for 5 hours. After the reaction solution was cooled to room temperature, the precipitated crystals were separated by filtration. The recrystallization operation was performed twice with acetonitrile, and 200 mg of compound 3 was obtained.
(18% yield). 317 ° C (decomposition temperature)

Example 4 Evaluation of Production of Light-Emitting Element IT was placed on a glass substrate of 25 mm × 25 mm × 0.7 mm.
O was formed to a thickness of 150 nm to obtain a transparent support substrate. After etching and washing this transparent support substrate, 40 mg of poly (N-vinylcarbazole) and PBD (2-
(4-biphenylyl) -5- (4-tert-butylphenyl) -1,3,4-oxadiazole) 12 m
g, 0.5 mg of the compound shown in Table 1 was dissolved in 1,2-dichloroethane (3 ml) and spin-coated on a washed ITO substrate. The thickness of the generated organic thin film was about 120 nm. A mask (a mask having a light-emitting area of 4 mm × 5 mm) patterned on the organic thin film was provided, and magnesium: silver = 10: 1 was co-deposited in a vapor deposition apparatus at 50 nm, and then silver was vapor-deposited at 50 nm. Using a Toyo Technica source measure unit 2400 type, a DC constant voltage is applied to the light emitting element to emit light, and the luminance is measured by a luminance meter B of Topcon Corporation.
M-8 and emission wavelength were measured using a spectrum analyzer PMA-11 manufactured by Hamamatsu Photonics. Table 1 shows the results.

[0086]

[Table 1]

As can be seen from the results shown in Table 1, it was found that the compound of the present invention functions as a dope dye and has sharp emission with a narrow half width as compared with the comparative compound.

Embodiment 5 After etching and cleaning the ITO substrate in the same manner as in Embodiment 4,
PD (N, N'-bis (3-methylphenyl) -N,
N′-diphenylbenzidine) of about 40 nm, the compounds listed in Table 2 and Zn (OXD) ₂ were each deposited at a deposition rate of 0.0
Vapor deposition was performed at a substrate temperature of room temperature in a vacuum of 10 ⁻³ to 10 ⁻⁴ Pa so that the film thickness was about 60 nm at 04 nm / sec and 0.4 nm / sec. Co-deposited. Next, a cathode was deposited in the same manner as in Example 1 to produce a light-emitting element.

[0089]

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[0090]

[Table 2]

As is clear from the results shown in Table 2, in the device using the compound of the present invention, a sharp emission having a narrow half width was obtained by doping the compound of the present invention even in the vapor deposition method, and the luminous efficiency was improved. Was found to improve.

[0092]

According to the present invention, a light emitting device having a narrow half width, high color purity, and capable of emitting light with high luminance and high efficiency can be obtained. In addition, good light-emitting characteristics can be obtained even by a coating method with low luminance, and an element can be manufactured which is advantageous in terms of manufacturing cost.

Claims (6)

[Claims] 1. A light emitting device material, which is a compound represented by the following general formula (I) or a tautomer thereof. Embedded image (Wherein, R ₁ represents a hydrogen atom or a substituent. X ₁ and X ₂ each represent a halogen atom, a carboxylate group,
Represents an aliphatic hydrocarbon group, an aryl group or a heterocyclic group. X ₁ and X ₂ may be linked. Q ₁ represents an atom group necessary for forming a nitrogen-containing heterocyclic ring. Q ₂ represents an atom group necessary for forming a nitrogen-containing heterocyclic ring. However,
Q ₁ and Q ₂ are not pyrrole rings at the same time. ) 2. A light emitting device material comprising a compound represented by the following general formula (II) or a tautomer thereof. Embedded image (Wherein, R ₁ , R ₂ , R ₃ , R ₄ and R ₅ each represent a hydrogen atom or a substituent, and if possible, may combine with each other to form a ring. X ₁ and X ₂ Represents a halogen atom, a carboxylate group, an aliphatic hydrocarbon group,
Represents an aryl group or a heterocyclic group. X ₁ and X ₂ may be linked. Q ₂ represents an atom group necessary for forming a nitrogen-containing heterocyclic ring. ) 3. A compound represented by the following general formula (III) or a tautomer thereof. Embedded image (Wherein, R ₁ , R ₂ , and R ₃ each represent a hydrogen atom or a substituent, and if possible, may be linked to each other to form a ring. X ₁ and X ₂ each represent a halogen atom, carboxy acrylate group, an aliphatic hydrocarbon group, .X ₁ and X ₂ which represents an aryl group or a heterocyclic group may be linked .Y carbonyl group ,, sulfo group, .Q ₃ to a sulfonyl group or a phosphonyl group, Q ₄ represents an atom group necessary for forming a ring.) 4. A light emitting device material comprising a compound represented by the general formula (III) or a tautomer thereof. 5. A light-emitting element in which a light-emitting layer or a plurality of organic compound thin layers including a light-emitting layer is formed between a pair of electrodes, wherein at least one of the light-emitting elements has the general formula (I), (II), Alternatively, a light-emitting element comprising a layer containing at least one compound represented by (III) or a tautomer thereof. 6. A light-emitting element having a light-emitting layer or a plurality of organic compound thin layers including the light-emitting layer formed between a pair of electrodes, wherein at least one of the light-emitting elements has the general formula (I), (II) or (II) according to claim 1 to 4. Or a layer in which at least one compound represented by (III) or a tautomer thereof is dispersed in a polymer.