WO2018181370A1

WO2018181370A1 - Compound having azacarbazole structure, and organic electroluminescence device

Info

Publication number: WO2018181370A1
Application number: PCT/JP2018/012526
Authority: WO
Inventors: 安達　千波矢; 卓也上原
Original assignee: 保土谷化学工業株式会社; 国立大学法人九州大学
Priority date: 2017-03-28
Filing date: 2018-03-27
Publication date: 2018-10-04
Also published as: JP2020113557A

Abstract

[Problem] To provide: a host compound for a light-emitting layer, wherein the compound is a material for a highly efficient organic electroluminescence device, has a high excited triplet level, is capable of completely confining triplet excitons of phosphorescent and thermally activated delayed fluorescence (TADF) emitters, and has excellent thin film stability, i.e., has a high glass transition point (Tg); and a highly efficient and highly luminescent organic electroluminescence device using the compound. [Solution] The present invention provides an organic electroluminescence device which has a pair of electrodes and at least one organic layer sandwiched therebetween, the organic electroluminescence device being characterized in that the organic layer is a light-emitting layer, and a compound having an azacarbazole structure represented by general formula (1) is used as a material constituting the light-emitting layer.

Description

Compound having azacarbazole structure and organic electroluminescence device

The present invention relates to a compound suitable for an organic electroluminescence element which is a self-luminous element suitable for various display devices and the element, and more specifically, a compound having an azacarbazole structure, and an organic electroluminescence using the compound The present invention relates to an element (hereinafter abbreviated as an organic EL element).

Since the organic EL element is a self-luminous element, it has been actively researched because it is brighter and more visible than a liquid crystal element and can be clearly displayed.

In recent years, as an attempt to increase the luminous efficiency of an element, an element that generates phosphorescence using a phosphorescent material, that is, uses light emission from a triplet excited state has been developed. According to the theory of the excited state, when phosphorescent light emission is used, a remarkable improvement in light emission efficiency is expected in that light emission efficiency about four times that of conventional fluorescent light emission becomes possible.
In 1993, M.P. A. Baldo et al. Achieved an external quantum efficiency of 8% with a phosphorescent device using an iridium complex.
An element utilizing light emission by thermally activated delayed fluorescence (TADF) has also been developed. In 2011, Adachi et al. Of Kyushu University realized an external quantum efficiency of 5.3% with a device using a thermally activated delayed fluorescent material (see, for example, Non-Patent Document 1).

Since the phosphor emits concentration quenching, it is supported by doping a charge transporting compound generally called a host compound. The supported light emitter is called a guest compound. As this host compound, 4,4′-di (N-carbazolyl) biphenyl (hereinafter abbreviated as CBP) represented by the following formula has been generally used (see, for example, Non-Patent Document 2).

As research on phosphorescent and TADF light emitting devices progresses, the elucidation of the energy transfer process between the light emitter and the host compound advances, and in order to increase the light emission efficiency, the excitation triplet level of the host compound is the excitation triplet level of the light emitter. It has become clear that it must be higher.

When FIrpic, which is a blue phosphorescent light emitting material represented by the following formula, is doped into the CBP to form a host compound of the light emitting layer, the external quantum efficiency of the phosphorescent light emitting element remains at about 6%. This is thought to be because the triplet exciton level by FIrpic is insufficient because the excited triplet level of FIrpic is 2.67 eV, whereas the excited triplet level of CBP is as low as 2.57 eV. It was. This is demonstrated by the fact that the photoluminescence intensity of a thin film obtained by doping FIrpic into CBP shows temperature dependence (see Non-Patent Document 3).

As a host compound having a higher excited triplet level than CBP, the following 3,3′-di (9H-carbazol-9-yl) -1,1′-biphenyl (hereinafter abbreviated as mCBP) is known. However, the electron transport property is poor. For this reason, the element drive voltage has increased, and satisfactory element characteristics have not been obtained.

A material using an azacarbazole skeleton as a material with improved electron transport properties has also been reported (see, for example, Patent Document 1 and Patent Document 2). However, there is a need for materials that can further improve luminous efficiency and form a stable thin film.

WO2013-105569 Japanese Patent No. 5934337

It is an object of the present invention to have a high excitation triplet level as a material for a high-efficiency organic EL device, to completely confine triplet excitons of phosphorescence and TADF emitters, and to have high thin film stability. That is, it is to provide a host compound of a light emitting layer having a high glass transition point (Tg), and to provide a high-efficiency and high-brightness organic EL device using this compound.

The physical properties that the organic compound to be provided by the present invention should have include (1) high excitation triplet level, (2) bipolar transportability, and (3) stable thin film state. I can give you something. In addition, the physical characteristics that the organic EL element to be provided by the present invention should have include (1) high luminous efficiency, (2) high luminance, and (3) low practical driving voltage. Can give.

Therefore, in order to achieve the above object, the present inventors pay attention to the fact that the azacarbazole structure has a high excited triplet level and an electron transporting ability, and design a compound using the excited triplet level as an index. Thus, by chemically synthesizing and actually measuring the excited triplet level, a compound having a novel azacarbazole structure having characteristics suitable for phosphorescence and TADF light-emitting devices was found. Then, various organic EL devices were prototyped using the compound, and the characteristics of the devices were evaluated. As a result, the present invention was completed.

That is, according to the present invention, the following compound having an azacarbazole skeleton and an organic EL device are provided.

1) The present invention is a compound having an azacarbazole skeleton represented by the following general formula (1).

(1)

(In the formula, A, B, C, D, E, F, G, and H each represents at least one nitrogen atom and represents a carbon atom or a nitrogen atom, and X, Y, and Z are the same or different from each other. A substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, a substituted or unsubstituted condensed polycyclic aromatic group, an aromatic hydrocarbon group, an aromatic heterocyclic group or A disubstituted amino group substituted by a group selected from a condensed polycyclic aromatic group, wherein L is a single bond, a divalent group of a substituted or unsubstituted aromatic hydrocarbon, a substituted or unsubstituted aromatic heterocyclic ring; Represents a divalent group or a substituted or unsubstituted condensed polycyclic aromatic divalent group.If L is a single bond, the subscript n is 0. R ¹ to R ¹⁰ are the same or different from each other. Hydrogen atom, deuterium atom, fluorine atom, chlorine atom, cyano group , A trifluoromethyl group, a nitro group, a linear or branched alkyl group having 1 to 6 carbon atoms which may have a substituent, and a carbon atom having 5 to 10 carbon atoms which may have a substituent A cycloalkyl group, a linear or branched alkenyl group having 2 to 6 carbon atoms which may have a substituent, and a linear chain having 1 to 6 carbon atoms which may have a substituent Or a branched alkyloxy group, an optionally substituted cycloalkyloxy group having 5 to 10 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group , A substituted or unsubstituted condensed polycyclic aromatic group, a substituted or unsubstituted aryloxy group, or a disubstituted by a group selected from an aromatic hydrocarbon group, an aromatic heterocyclic group or a condensed polycyclic aromatic group A conversion amino group, a single bond, a substituted or unsubstituted methylene group, linked to each other through an oxygen atom or a sulfur atom may form a ring.)

2) Further, the present invention is a compound having an azacarbazole skeleton represented by the following general formula (1-1).

(1-1)

3) Further, the present invention is a compound having an azacarbazole skeleton represented by the following general formula (1-2).

(1-2)

(In the formula, at least one of A, B, C and D represents a nitrogen atom and represents a carbon atom or a nitrogen atom, and X, Y and Z may be the same or different from each other, and may be substituted or unsubstituted. Selected from aromatic hydrocarbon group, substituted or unsubstituted aromatic heterocyclic group, substituted or unsubstituted condensed polycyclic aromatic group, or aromatic hydrocarbon group, aromatic heterocyclic group or condensed polycyclic aromatic group And L represents a single bond, a divalent group of a substituted or unsubstituted aromatic hydrocarbon, a divalent group of a substituted or unsubstituted aromatic heterocyclic ring, or a substituted or unsubstituted group. Represents a substituted fused polycyclic aromatic divalent group, and if L is a single bond, the subscript n is 0. R ¹ to R ¹⁰ may be the same or different from each other, Hydrogen atom, fluorine atom, chlorine atom, cyano group, trifluorome A til group, a nitro group, an optionally substituted linear or branched alkyl group having 1 to 6 carbon atoms, and an optionally substituted cycloalkyl group having 5 to 10 carbon atoms A linear or branched alkenyl group having 2 to 6 carbon atoms which may have a substituent, or a linear or branched chain having 1 to 6 carbon atoms which may have a substituent An alkyloxy group, an optionally substituted cycloalkyloxy group having 5 to 10 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, substituted or An unsubstituted condensed polycyclic aromatic group, a substituted or unsubstituted aryloxy group, or a disubstituted amino group substituted by an aromatic hydrocarbon group, an aromatic heterocyclic group or a group selected from a condensed polycyclic aromatic group In Te single bond, a substituted or unsubstituted methylene group, linked to each other through an oxygen atom or a sulfur atom may form a ring.)

4) Further, the present invention is a compound having an azacarbazole skeleton represented by the following general formula (1-3).

(1-3)

(In the formula, at least one of A, B, C and D represents a nitrogen atom and represents a carbon atom or a nitrogen atom, and X and Y may be the same or different from each other, and are substituted or unsubstituted aromatic. A group selected from a hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, a substituted or unsubstituted condensed polycyclic aromatic group, or an aromatic hydrocarbon group, aromatic heterocyclic group or condensed polycyclic aromatic group L represents a disubstituted amino group substituted by a single bond, a substituted or unsubstituted aromatic hydrocarbon divalent group, a substituted or unsubstituted aromatic heterocyclic divalent group, or a substituted or unsubstituted aromatic group. Represents a condensed polycyclic aromatic divalent group, and if L is a single bond, the subscript n is 0. R ¹ to R ¹⁰ may be the same or different from each other, and may be a hydrogen atom or a deuterium atom. , Fluorine atom, chlorine atom, cyano group, trifluoromethyl Group, nitro group, optionally substituted linear or branched alkyl group having 1 to 6 carbon atoms, optionally substituted cycloalkyl group having 5 to 10 carbon atoms A linear or branched alkenyl group having 2 to 6 carbon atoms which may have a substituent, or a linear or branched group having 1 to 6 carbon atoms which may have a substituent. Alkyloxy group, optionally substituted cycloalkyloxy group having 5 to 10 carbon atoms, substituted or unsubstituted aromatic hydrocarbon group, substituted or unsubstituted aromatic heterocyclic group, substituted or unsubstituted A substituted condensed polycyclic aromatic group, a substituted or unsubstituted aryloxy group, or a disubstituted amino group substituted by a group selected from an aromatic hydrocarbon group, an aromatic heterocyclic group or a condensed polycyclic aromatic group There Single bond, a substituted or unsubstituted methylene group, linked to each other through an oxygen atom or a sulfur atom may form a ring.)

5) Further, the present invention is a compound having an azacarbazole skeleton represented by the following general formula (1-4).

(1-4)

6) Further, the present invention is a compound having an azacarbazole skeleton represented by the following general formula (1-5).

(1-5)

(In the formula, at least one of A, B, C and D represents a nitrogen atom and represents a carbon atom or a nitrogen atom, and X and Y may be the same or different from each other, and are substituted or unsubstituted aromatic. A group selected from a hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, a substituted or unsubstituted condensed polycyclic aromatic group, or an aromatic hydrocarbon group, aromatic heterocyclic group or condensed polycyclic aromatic group L represents a disubstituted amino group substituted by a single bond, a substituted or unsubstituted aromatic hydrocarbon divalent group, a substituted or unsubstituted aromatic heterocyclic divalent group, or a substituted or unsubstituted aromatic group. Represents a condensed polycyclic aromatic divalent group, and if L is a single bond, the subscript n is 0. R ¹ to R ⁷ may be the same or different from each other, and may be a hydrogen atom or a deuterium atom. , Fluorine atom, chlorine atom, cyano group, trifluoromethyl , A nitro group, a linear or branched alkyl group having 1 to 6 carbon atoms which may have a substituent, a cycloalkyl group having 5 to 10 carbon atoms which may have a substituent, A linear or branched alkenyl group having 2 to 6 carbon atoms which may have a substituent, a linear or branched alkyl having 1 to 6 carbon atoms which may have a substituent Oxy group, optionally substituted cycloalkyloxy group having 5 to 10 carbon atoms, substituted or unsubstituted aromatic hydrocarbon group, substituted or unsubstituted aromatic heterocyclic group, substituted or unsubstituted A condensed polycyclic aromatic group, a substituted or unsubstituted aryloxy group, or a disubstituted amino group substituted by a group selected from an aromatic hydrocarbon group, an aromatic heterocyclic group or a condensed polycyclic aromatic group. The Single bond, a substituted or unsubstituted methylene group, linked to each other through an oxygen atom or a sulfur atom may form a ring.)

7) Further, the present invention is a compound having an azacarbazole skeleton represented by the following general formula (1-6).

(1-6)

8) In the organic EL device having a pair of electrodes and at least one organic layer sandwiched between the electrodes, the organic layer is a light emitting layer, and the aza represented by the general formula (1) An organic EL element using a compound having a carbazole structure as a constituent material of the light emitting layer.

General Formula (1), General Formula (1-1), X, Y, Z in General Formula (1-2) and General Formula (1-3), General Formula (1-4), General Formula (1- 5), “substituted or unsubstituted aromatic hydrocarbon group”, “substituted or unsubstituted aromatic heterocyclic group” represented by X and Y in general formula (1-6), or “substituted or unsubstituted The “aromatic hydrocarbon group”, “aromatic heterocyclic group”, or “fused polycyclic aromatic group” in the substituted condensed polycyclic aromatic group specifically includes a phenyl group, a biphenylyl group, a terphenylyl group. , Naphthyl group, anthracenyl group, phenanthrenyl group, fluorenyl group, indenyl group, pyrenyl group, perylenyl group, fluoranthenyl group, triphenylenyl group, pyridyl group, pyrimidinyl group, triazinyl group, furyl group, pyrrolyl group, thienyl group, quinolyl group , Soquinolyl, benzofuranyl, benzothienyl, indolyl, carbazolyl, benzoxazolyl, benzothiazolyl, quinoxalinyl, benzoimidazolyl, pyrazolyl, dibenzofuranyl, dibenzothienyl, naphthyridinyl, phenanthrolinyl Group, acridinyl group, carbolinyl group and the like.

General Formula (1), General Formula (1-1), X, Y, Z in General Formula (1-2) and General Formula (1-3), General Formula (1-4), General Formula (1- 5), “Substitution” in “Substituted aromatic hydrocarbon group”, “Substituted aromatic heterocyclic group” or “Substituted condensed polycyclic aromatic group” represented by X and Y in formula (1-6) As the “group”, specifically, deuterium atom, cyano group, nitro group; halogen atom such as fluorine atom, chlorine atom, bromine atom, iodine atom; methyl group, ethyl group, n-propyl group, isopropyl group, n -Butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, isohexyl, neohexyl, n-heptyl, isoheptyl, neohe Ptyl group, n-octyl group, isooctyl group, neooctyl group, etc. A linear or branched alkyl group having 1 to 8 carbon atoms; a linear or branched alkyloxy group having 1 to 8 carbon atoms such as a methyloxy group, an ethyloxy group, or a propyloxy group; a vinyl group, Alkenyl groups such as allyl groups; aryloxy groups such as phenyloxy groups and tolyloxy groups; arylalkyloxy groups such as benzyloxy groups and phenethyloxy groups; phenyl groups, biphenylyl groups, terphenylyl groups, naphthyl groups, anthracenyl groups, phenanthrenyl groups , Fluorenyl group, indenyl group, pyrenyl group, perylenyl group, fluoranthenyl group, triphenylenyl group and other aromatic hydrocarbon groups or condensed polycyclic aromatic groups; pyridyl group, pyrimidinyl group, triazinyl group, thienyl group, furyl group, Pyrrolyl group, quinolyl group, Aromatic heterocycles such as quinolyl, benzofuranyl, benzothienyl, indolyl, carbazolyl, benzoxazolyl, benzothiazolyl, quinoxalinyl, benzoimidazolyl, pyrazolyl, dibenzofuranyl, dibenzothienyl, carbolinyl A cyclic group; an aryl vinyl group such as a styryl group and a naphthyl vinyl group; and a group such as an acyl group such as an acetyl group and a benzoyl group. These substituents are further substituted by the above-exemplified substituents. May be. These substituents may be bonded to each other via a single bond, a substituted or unsubstituted methylene group, an oxygen atom or a sulfur atom to form a ring.

General Formula (1), General Formula (1-1), X, Y, Z in General Formula (1-2) and General Formula (1-3), General Formula (1-4), General Formula (1- 5) a disubstituted amino group substituted by a group selected from an aromatic hydrocarbon group, an aromatic heterocyclic group or a condensed polycyclic aromatic group represented by X and Y in the general formula (1-6) As the “substituted aromatic hydrocarbon group”, “substituted aromatic heterocyclic group” or “substituted condensed polycyclic aromatic group” in the formula (1), the above general formula (1), general formula (1-1), general formula ( 1-2) represented by X, Y, Z, and general formula (1-3), general formula (1-4), general formula (1-5), and X and Y in general formula (1-6) “Aromatics” in “substituted or unsubstituted aromatic hydrocarbon group”, “substituted or unsubstituted aromatic heterocyclic group”, or “substituted or unsubstituted condensed polycyclic aromatic group” Hydrocarbon group "may be mentioned the same ones as illustrated for the" aromatic heterocyclic group ", or" condensed polycyclic aromatic group ".
Further, these groups may have a substituent, and as the substituent, X, Y, Z in the general formula (1), general formula (1-1), general formula (1-2) and “Substituted aromatic hydrocarbon group” represented by X and Y in general formula (1-3), general formula (1-4), general formula (1-5), and general formula (1-6), “Substituted aromatic heterocyclic group” or “Substituted condensed polycyclic aromatic group” “Aromatic hydrocarbon group”, “Aromatic heterocyclic group” or “Condensed polycyclic aromatic group” may have “Substitution” The thing similar to what was shown regarding "group" can be mention | raise | lifted, and the aspect which can be taken can also mention the same thing.

General formula (1), general formula (1-1), general formula (1-2), general formula (1-3), general formula (1-4), general formula (1-5), general formula (1) -6) “Substituted or unsubstituted aromatic hydrocarbon group”, “substituted or unsubstituted aromatic heterocyclic group”, or “substituted or unsubstituted condensed polycyclic aromatic group” represented by L in −6) As the “aromatic hydrocarbon group”, “aromatic heterocyclic group” or “fused polycyclic aromatic group” in the above, specifically, a phenyl group, a biphenylyl group, a terphenylyl group, a naphthyl group, an anthracenyl group, a phenanthrenyl group , Fluorenyl, indenyl, pyrenyl, perylenyl, fluoranthenyl, triphenylenyl, pyridyl, pyrimidinyl, triazinyl, furyl, pyrrolyl, thienyl, quinolyl, isoquinolyl, benzo Ranyl group, benzothienyl group, indolyl group, carbazolyl group, benzoxazolyl group, benzothiazolyl group, quinoxalinyl group, benzoimidazolyl group, pyrazolyl group, dibenzofuranyl group, dibenzothienyl group, naphthyridinyl group, phenanthrolinyl group, acridinyl Group, carbolinyl group and the like.

General formula (1), general formula (1-1), general formula (1-2), general formula (1-3), general formula (1-4), general formula (1-5), general formula (1) As the “substituent” in the “substituted aromatic hydrocarbon group”, “substituted aromatic heterocyclic group”, or “substituted condensed polycyclic aromatic group” represented by L in −6), specifically, Deuterium atom, cyano group, nitro group; halogen atom such as fluorine atom, chlorine atom, bromine atom, iodine atom; methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert- Butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, isohexyl, neohexyl, n-heptyl, isoheptyl, neoheptyl, n-octyl, isooctyl Group, neooctyl group, etc. having 1 to 8 carbon atoms A linear or branched alkyl group; a linear or branched alkyloxy group having 1 to 8 carbon atoms such as a methyloxy group, an ethyloxy group or a propyloxy group; an alkenyl group such as a vinyl group or an allyl group; Aryloxy groups such as phenyloxy group and tolyloxy group; arylalkyloxy groups such as benzyloxy group and phenethyloxy group; phenyl group, biphenylyl group, terphenylyl group, naphthyl group, anthracenyl group, phenanthrenyl group, fluorenyl group, indenyl group, Aromatic hydrocarbon groups or condensed polycyclic aromatic groups such as pyrenyl group, perylenyl group, fluoranthenyl group, triphenylenyl group; pyridyl group, pyrimidinyl group, triazinyl group, thienyl group, furyl group, pyrrolyl group, quinolyl group, isoquinolyl group Group, benzof Aromatic heterocyclic groups such as nyl, benzothienyl, indolyl, carbazolyl, benzoxazolyl, benzothiazolyl, quinoxalinyl, benzoimidazolyl, pyrazolyl, dibenzofuranyl, dibenzothienyl, carbolinyl; Examples thereof include aryl vinyl groups such as a styryl group and a naphthyl vinyl group; groups such as acyl groups such as an acetyl group and a benzoyl group, and these substituents may be further substituted by the above-exemplified substituents. . These substituents may be bonded to each other via a single bond, a substituted or unsubstituted methylene group, an oxygen atom or a sulfur atom to form a ring.

General formula (1), general formula (1-1), general formula (1-2), general formula (1-3), general formula (1-4), general formula (1-5), general formula (1) -6) “a divalent group of a substituted or unsubstituted aromatic hydrocarbon”, “a divalent group of a substituted or unsubstituted aromatic heterocyclic ring” or “a substituted or unsubstituted condensed polyvalent group” represented by L in "Aromatic carbonization" of "substituted or unsubstituted aromatic hydrocarbon", "substituted or unsubstituted aromatic heterocycle" or "substituted or unsubstituted condensed polycyclic aromatic" in "ring aromatic divalent group" Specific examples of “hydrogen”, “aromatic heterocycle” or “fused polycyclic aromatic” include benzene, biphenyl, terphenyl, tetrakisphenyl, styrene, naphthalene, anthracene, acenaphthalene, fluorene, phenanthrene, indane, and pyrene. , Triphenylene, pyridi , Pyrimidine, triazine, pyrrole, furan, thiophene, quinoline, isoquinoline, benzofuran, benzothiophene, indoline, carbazole, carboline, benzoxazole, benzothiazole, quinoxaline, benzimidazole, pyrazole, dibenzofuran, dibenzothiophene, naphthyridine, phenanthroline, acridinine, etc. Can give.
And general formula (1), general formula (1-1), general formula (1-2), general formula (1-3), general formula (1-4), general formula (1-5), general formula “A divalent group of a substituted or unsubstituted aromatic hydrocarbon”, “a divalent group of a substituted or unsubstituted aromatic heterocyclic ring” represented by L in (1-6) or “substituted or unsubstituted The “condensed polycyclic aromatic divalent group” represents a divalent group formed by removing two hydrogen atoms from the above “aromatic hydrocarbon”, “aromatic heterocycle” or “fused polycyclic aromatic”.
In addition, these divalent groups may have a substituent, and examples of the substituent include general formula (1), general formula (1-1), general formula (1-2), and general formula (1-3 ), A general formula (1-4), a general formula (1-5), a “substituted aromatic hydrocarbon group”, a “substituted aromatic heterocyclic group” represented by L in the general formula (1-6) or The same thing as what was shown regarding the "substituent" in a "substituted condensed polycyclic aromatic group" can be mention | raise | lifted, and the aspect which can be taken can also mention the same thing.

R ¹ to R ^{10 in} formula (1), formula (1-1), formula (1-2), formula (1-3), formula (1-4), and formula (1- 5) “a linear or branched alkyl group having 1 to 6 carbon atoms which may have a substituent” represented by R ¹ to R ⁷ in formula (1-6); In the “cycloalkyl group having 5 to 10 carbon atoms which may have a substituent” or “the linear or branched alkenyl group having 2 to 6 carbon atoms which may have a substituent” "C1-C6 linear or branched alkyl group", "C5-C10 cycloalkyl group" or "C2-C6 linear or branched alkenyl group" Specific examples include methyl group, ethyl group, n-propyl group, isopropyl group, and n-butyl group. Til, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, cyclopentyl, cyclohexyl, 1-adamantyl, 2-adamantyl, vinyl, allyl, iso Examples thereof include a propenyl group and a 2-butenyl group, and these groups may be bonded to each other via a single bond, a substituted or unsubstituted methylene group, an oxygen atom or a sulfur atom to form a ring.

R ¹ to R ^{10 in} formula (1), formula (1-1), formula (1-2), formula (1-3), formula (1-4), and formula (1- 5) “a linear or branched alkyl group having 1 to 6 carbon atoms having a substituent” represented by R ¹ to R ⁷ in formula (1-6), “carbon having a substituent” Specific examples of the “substituent” in the “cycloalkyl group having 5 to 10 atoms” or “the linear or branched alkenyl group having 2 to 6 carbon atoms having a substituent” include a deuterium atom, Cyano group, nitro group; halogen atom such as fluorine atom, chlorine atom, bromine atom and iodine atom; linear or branched alkyloxy having 1 to 6 carbon atoms such as methyloxy group, ethyloxy group and propyloxy group Groups; alkenyl groups such as vinyl groups and allyl groups; Aryloxy groups such as phenyloxy group and tolyloxy group; arylalkyloxy groups such as benzyloxy group and phenethyloxy group; phenyl group, biphenylyl group, terphenylyl group, naphthyl group, anthracenyl group, phenanthrenyl group, fluorenyl group, indenyl group, Aromatic hydrocarbon groups or condensed polycyclic aromatic groups such as pyrenyl group, perylenyl group, fluoranthenyl group, triphenylenyl group; pyridyl group, pyrimidinyl group, triazinyl group, thienyl group, furyl group, pyrrolyl group, quinolyl group, isoquinolyl group Group, benzofuranyl group, benzothienyl group, indolyl group, carbazolyl group, benzoxazolyl group, benzothiazolyl group, quinoxalinyl group, benzoimidazolyl group, pyrazolyl group, dibenzofuranyl group, dibenzothienyl group , There may be mentioned groups such as aromatic heterocyclic groups such as carbolinyl group, these substituents may further the exemplified substituents may be substituted. These substituents may be bonded to each other via a single bond, a substituted or unsubstituted methylene group, an oxygen atom or a sulfur atom to form a ring.

R ¹ to R ^{10 in} formula (1), formula (1-1), formula (1-2), formula (1-3), formula (1-4), and formula (1- 5) “a linear or branched alkyloxy group having 1 to 6 carbon atoms which may have a substituent” represented by R ¹ to R ⁷ in formula (1-6); “Linear or branched alkyloxy group having 1 to 6 carbon atoms” in “optionally substituted cycloalkyloxy group having 5 to 10 carbon atoms” or “C5 to 10 carbon atoms” Specific examples of the cycloalkyloxy group include a methyloxy group, an ethyloxy group, an n-propyloxy group, an isopropyloxy group, an n-butyloxy group, a tert-butyloxy group, an n-pentyloxy group, and an n-hexyloxy group. Group, cyclopentyloxy Ci group, cyclohexyloxy group, cycloheptyloxy group, cyclooctyloxy group, 1-adamantyloxy group, 2-adamantyloxy group, etc., and these groups are single bonds, substituted or unsubstituted methylene groups And may be bonded to each other via an oxygen atom or a sulfur atom to form a ring.

R ¹ to R ^{10 in} formula (1), formula (1-1), formula (1-2), formula (1-3), formula (1-4), and formula (1- 5) “a linear or branched alkyloxy group having 1 to 6 carbon atoms having a substituent” represented by R ¹ to R ⁷ in formula (1-6) or “having a substituent The “substituent” in the cycloalkyloxy group having 5 to 10 carbon atoms is a straight chain having 1 to 6 carbon atoms having a substituent represented by R ¹ to R ¹⁰ in the general formula (1). “Chain or branched alkyl group”, “Substituent substituted cycloalkyl group having 5 to 10 carbon atoms”, or “Substituent linear or branched alkenyl group having 2 to 6 carbon atoms” The same as those shown for the “substituent” in The possible modes are the same.

R ¹ to R ^{10 in} formula (1), formula (1-1), formula (1-2), formula (1-3), formula (1-4), and formula (1- 5), “substituted or unsubstituted aromatic hydrocarbon group”, “substituted or unsubstituted aromatic heterocyclic group” represented by R ¹ to R ⁷ in formula (1-6), or “substituted” Alternatively, the “aromatic hydrocarbon group”, “aromatic heterocyclic group”, or “fused polycyclic aromatic group” in the “unsubstituted fused polycyclic aromatic group” includes the above general formula (1), general formula ( 1-1) X, Y, Z in formula (1-2) and formula (1-3), formula (1-4), formula (1-5), formula (1-6) "Substituted or unsubstituted aromatic hydrocarbon group", "substituted or unsubstituted aromatic heterocyclic group", or "substituted or unsubstituted condensed polycyclic aromatic group" represented by X or Y And the same as those shown for the “aromatic hydrocarbon group”, “aromatic heterocyclic group”, or “fused polycyclic aromatic group”.
Further, these groups may have a substituent, and as the substituent, X, Y, Z in the general formula (1), general formula (1-1), general formula (1-2) and “Substituted aromatic hydrocarbon group” represented by X and Y in general formula (1-3), general formula (1-4), general formula (1-5), and general formula (1-6), “Substituted aromatic heterocyclic group” or “Substituted condensed polycyclic aromatic group” “Aromatic hydrocarbon group”, “Aromatic heterocyclic group” or “Condensed polycyclic aromatic group” may have “Substitution” The thing similar to what was shown regarding "group" can be mention | raise | lifted, and the aspect which can be taken can also mention the same thing.

R ¹ to R ^{10 in} formula (1), formula (1-1), formula (1-2), formula (1-3), formula (1-4), and formula (1- 5) The “aryloxy group” in the “substituted or unsubstituted aryloxy group” represented by R ¹ to R ⁷ in the general formula (1-6) is specifically a phenyloxy group, biphenylyl Oxy, terphenylyloxy, naphthyloxy, anthracenyloxy, phenanthrenyloxy, fluorenyloxy, indenyloxy, triphenylenyloxy, pyrenyloxy, perylenyloxy, etc. These groups may be bonded to each other via a single bond, a substituted or unsubstituted methylene group, an oxygen atom or a sulfur atom to form a ring.
Further, these groups may have a substituent, and as the substituent, X, Y, Z in the general formula (1), general formula (1-1), general formula (1-2) and “Substituted aromatic hydrocarbon group” represented by X and Y in general formula (1-3), general formula (1-4), general formula (1-5), and general formula (1-6), “Substituted aromatic heterocyclic group” or “Substituted condensed polycyclic aromatic group” “Aromatic hydrocarbon group”, “Aromatic heterocyclic group” or “Condensed polycyclic aromatic group” may have “Substitution” The thing similar to what was shown regarding "group" can be mention | raise | lifted, and the aspect which can be taken can also mention the same thing.

R ¹ to R ^{10 in} formula (1), formula (1-1), formula (1-2), formula (1-3), formula (1-4), and formula (1- 5) A disubstituted substituent substituted with a group selected from an aromatic hydrocarbon group, an aromatic heterocyclic group or a condensed polycyclic aromatic group represented by R ¹ to R ⁷ in formula (1-6) The “aromatic hydrocarbon group”, “aromatic heterocyclic group” or “condensed polycyclic aromatic group” in the “amino group” includes X, Y in the general formula (1) and general formula (1-1). , Z, and general formula (1-2), general formula (1-3), general formula (1-4), general formula (1-5), represented by X and Y in general formula (1-6) “Aromatic carbonization” in “substituted or unsubstituted aromatic hydrocarbon group”, “substituted or unsubstituted aromatic heterocyclic group”, or “substituted or unsubstituted condensed polycyclic aromatic group” Examples thereof include those similar to those shown for “hydrogen group”, “aromatic heterocyclic group”, or “fused polycyclic aromatic group”.
These groups may have a substituent. Examples of the substituent include X, Y and Z in the general formula (1) and general formula (1-1), and the general formula (1-2), “Substituted aromatic hydrocarbon group” represented by X and Y in general formula (1-3), general formula (1-4), general formula (1-5), and general formula (1-6), “Substituted aromatic heterocyclic group” or “Substituted condensed polycyclic aromatic group” “Aromatic hydrocarbon group”, “Aromatic heterocyclic group” or “Condensed polycyclic aromatic group” may have “Substitution” The thing similar to what was shown regarding "group" can be mention | raise | lifted, and the aspect which can be taken can also mention the same thing.

X, Y and Z in the general formula (1) are preferably a diphenylamino group and a dimethylacridinyl group, more preferably a carbazolyl group and a diphenylacridinyl group, and particularly preferably a 3,9'-bicarbazolyl group.

As L in the general formula (1), a phenyl group is preferable, and a single bond is more preferable.

R ¹ to R ¹⁰ in the general formula (1) are preferably a hydrogen atom or a deuterium atom, and more preferably a hydrogen atom from the viewpoint of synthesis.

The compound having an azacarbazole structure represented by the general formula (1) preferably used in the present invention has a higher excited triplet level than conventional materials, has an ability to confine excellent triplet excitons, and is a thin film The state is stable.

The compound having an azacarbazole structure represented by the general formula (1) preferably used in the present invention can be used as a constituent material of a light emitting layer of an organic EL device. By using the compound represented by the general formula (1), which is superior in bipolar transportability as compared with conventional materials, the light emission efficiency is improved and the practical driving voltage is lowered.

The compound having an azacarbazole structure represented by the general formula (1) preferably used in the present invention is useful as a host compound of a light emitting layer of an organic EL device, and an organic EL device is produced using the compound. Thus, the highly efficient organic EL device of the present invention can be obtained.

1 is a ¹ H-NMR chart of the compound of Example 1 of the present invention (Compound 1). FIG. 2 is a ¹ H-NMR chart of the compound of Example 2 of the present invention (Compound 2). FIG. 3 is a ¹ H-NMR chart of the compound of Example 3 of the present invention (Compound 4). FIG. 3 is a ¹ H-NMR chart of the compound of Example 4 of the present invention (Compound 5). FIG. 3 is a diagram showing organic EL element configurations of Examples 11 to 13 and Comparative Example 1.

The compound having an azacarbazole structure of the present invention can be synthesized, for example, as follows.
First, γ-carboline (5H-pyrido [4,3-b] indole) is synthesized from 1- (pyridin-4-yl) -1H-benzo [d] [1,2,3] triazole by Greve-Ullmann reaction. be able to. By reacting this γ-carboline with 1,4-dibromobenzene, 5- (4-bromophenyl) -5H-pyrido [4,3-b] indole can be synthesized. A compound having an azacarbazole structure of the present invention can be synthesized by subjecting the carboline derivative having a bromo group to a condensation reaction such as a Backwald-Hartwig reaction or an Ullmann reaction.

Further, 5-phenyl-5H-pyrido [4,3-b] indole is synthesized by reacting γ-carboline with iodobenzene, and then brominated with N-bromosuccinimide or the like to give 8- Bromo-5-phenyl-5H-pyrido [4,3-b] indole can be synthesized. A compound having a carboline structure of the present invention can be synthesized by subjecting the carboline derivative having a bromo group to a condensation reaction such as a Backwald-Hartwig reaction or an Ullmann reaction.

It should be noted that bromo-substituted products with different substitution positions can be obtained by changing dibromobenzene with different substitution positions, reagents for bromination, and conditions.

Specific examples of preferable compounds among the compounds having a carboline structure represented by the general formula (1) are shown below, but the present invention is not limited to these compounds.

(Compound 1)

(Compound 2)

(Compound 3)

(Compound 4)

(Compound 5)

(Compound 6)

(Compound 7)

(Compound 8)

(Compound 9)

(Compound 10)

(Compound 11)

(Compound 12)

(Compound 13)

(Compound 14)

(Compound 15)

(Compound 16)

(Compound 17)

(Compound 18)

(Compound 19)

(Compound 20)

(Compound 21)

(Compound 22)

(Compound 23)

(Compound 24)

(Compound 25)

(Compound 26)

(Compound 27)

(Compound 28)

(Compound 29)

(Compound 30)

(Compound 31)

(Compound 32)

(Compound 33)

(Compound 34)

(Compound 35)

(Compound 36)

(Compound 37)

(Compound 38)

(Compound 39)

(Compound 40)

(Compound 41)

(Compound 42)

(Compound 43)

(Compound 44)

(Compound 45)

(Compound 46)

(Compound 47)

(Compound 48)

(Compound 49)

(Compound 50)

(Compound 51)

(Compound 52)

(Compound 53)

(Compound 54)

(Compound 55)

(Compound 56)

(Compound 57)

(Compound 58)

(Compound 59)

(Compound 60)

(Compound 61)

(Compound 62)

(Compound 63)

(Compound 64)

(Compound 65)

(Compound 66)

(Compound 67)

(Compound 68)

(Compound 69)

(Compound 70)

(Compound 71)

(Compound 72)

(Compound 73)

(Compound 74)

(Compound 75)

(Compound 76)

(Compound 77)

(Compound 78)

(Compound 79)

(Compound 80)

(Compound 81)

(Compound 82)

(Compound 83)

(Compound 84)

(Compound 85)

(Compound 86)

(Compound 87)

(Compound 88)

(Compound 89)

(Compound 90)

(Compound 91)

(Compound 92)

(Compound 93)

(Compound 94)

(Compound 95)

(Compound 96)

(Compound 97)

(Compound 98)

(Compound 99)

(Compound 100)

(Compound 101)

(Compound 102)

(Compound 103)

(Compound 104)

(Compound 105)

(Compound 106)

(Compound 107)

(Compound 108)

(Compound 109)

(Compound 110)

(Compound 111)

These compounds were purified by column chromatography, adsorption purification using silica gel, activated carbon, activated clay, etc., recrystallization or crystallization using a solvent, sublimation purification, and the like. The compound was identified by NMR analysis. As a physical property value, a glass transition point (Tg) and a work function were measured. The glass transition point (Tg) is an index of the stability of the thin film state, and the work function is an index of the energy level as the light emitting host material.

The glass transition point (Tg) was measured with a high sensitivity differential scanning calorimeter (DSC6200, manufactured by Seiko Instruments Inc.) using powder.

The work function was measured using an atmospheric photoelectron spectrometer (AC-3 type, manufactured by Riken Keiki Co., Ltd.) by forming a 100 nm thin film on the ITO substrate.

The excited triplet level of the compound of the present invention can be calculated from the measured phosphorescence spectrum. The phosphorescence spectrum can be measured using a commercially available spectrophotometer. As a general method for measuring phosphorescence spectrum, a method in which it is dissolved in a solvent and irradiated with excitation light at a low temperature (for example, see Non-Patent Document 4) or vapor deposited on a silicon substrate to form a thin film at a low temperature. There is a method of irradiating excitation light and measuring a phosphorescence spectrum. The excited triplet level can be calculated by reading the wavelength of the first peak on the short wavelength side of the phosphorescence spectrum or the wavelength of the rising position on the short wavelength side and converting it to the light energy value according to the following equation. The excited triplet level is an indicator of the confinement of triplet excitons in the phosphorescent emitter.

Where E is the value of light energy, h is Planck's constant (6.63 × 10 ⁻³⁴ Js), c is the speed of light (3.00 × 10 ⁸ m / s), and λ is the short wavelength of the phosphorescence spectrum. This represents the wavelength (nm) of the rising edge. And 1 eV becomes 1.60 × 10 ⁻¹⁹ J.

As the structure of the organic EL device of the present invention, on the substrate, an anode, a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer, a cathode, And those having an electron injection layer between the electron transport layer and the cathode. In these multi-layer structures, it is possible to omit some organic layers, for example, on the substrate sequentially, anode, hole transport layer, light emitting layer, electron transport layer, electron injection layer, cathode, An anode, a hole transport layer, a light emitting layer, an electron transport layer, and a cathode can also be used.

The light emitting layer, the hole transport layer, and the electron transport layer may have a structure in which two or more layers are laminated.

As the anode of the organic EL element of the present invention, an electrode material having a large work function such as ITO or gold is used.

As a hole injection layer of the organic EL device of the present invention, in addition to a porphyrin compound typified by copper phthalocyanine, a naphthalene diamine derivative, a starburst type triphenylamine derivative, three or more triphenylamine structures in the molecule, Triphenylamine trimers and tetramers such as arylamine compounds having a structure linked by a divalent group containing no bond or hetero atom, acceptor heterocyclic compounds such as hexacyanoazatriphenylene, and coating-type polymers Materials can be used. These materials can be formed into a thin film by a known method such as a spin coating method or an ink jet method in addition to a vapor deposition method.

As a hole transport layer of the organic EL device of the present invention, in addition to a compound containing an m-carbazolylphenyl group, N, N′-diphenyl-N, N′-di (m-tolyl) -benzidine (hereinafter referred to as “a”) N, N′-diphenyl-N, N′-di (α-naphthyl) -benzidine (hereinafter abbreviated as NPD), N, N, N ′, N′-tetrabiphenylylbenzidine, etc. Benzidine derivatives, 1,1-bis [(di-4-tolylamino) phenyl] cyclohexane (hereinafter abbreviated as TAPC), various triphenylamine trimers and tetramers, and carbazole derivatives can be used. . These may be formed alone, but may be used as a single layer formed by mixing with other materials, layers formed alone, mixed layers formed, or A stacked structure of layers formed by mixing with a layer formed alone may be used. In addition, as a hole injection / transport layer, a coating type such as poly (3,4-ethylenedioxythiophene) (hereinafter abbreviated as PEDOT) / poly (styrene sulfonate) (hereinafter abbreviated as PSS) is used. These polymer materials can be used. These materials can be formed into a thin film by a known method such as a spin coating method or an ink jet method in addition to a vapor deposition method.

In addition, in a hole injection layer or a hole transport layer, a material in which trisbromophenylamine hexachloroantimony is further P-doped to a material usually used for the layer, or a polymer having a TPD structure in its partial structure A compound or the like can be used.

As an electron blocking layer of the organic EL device of the present invention, 4,4 ′, 4 ″ -tri (N-carbazolyl) triphenylamine (hereinafter abbreviated as TCTA), 9,9-bis [4- (carbazole- 9-yl) phenyl] fluorene, 1,3-bis (carbazol-9-yl) benzene (hereinafter abbreviated as mCP), 2,2-bis (4-carbazol-9-ylphenyl) adamantane (hereinafter Ad) Carbazole derivatives such as 9- [4- (carbazol-9-yl) phenyl] -9- [4- (triphenylsilyl) phenyl] -9H-fluorene And a compound having an electron blocking action such as a compound having a triarylamine structure can be used. These may be formed alone, but may be used as a single layer formed by mixing with other materials, layers formed alone, mixed layers formed, or A stacked structure of layers formed by mixing with a layer formed alone may be used. These materials can be formed into a thin film by a known method such as a spin coating method or an ink jet method in addition to a vapor deposition method.

As the light emitting layer of the organic EL device of the present invention, various metal complexes such as metal complexes of quinolinol derivatives including tris (8-hydroxyquinoline) aluminum (hereinafter abbreviated as Alq ₃ ), anthracene derivatives, bisstyrylbenzene derivatives , Pyrene derivatives, oxazole derivatives, polyparaphenylene vinylene derivatives, and the like can be used. The light-emitting layer may be composed of a host material and a dopant material. In this case, a compound having a triphenylsilylpyridyl group and a carbazole ring structure represented by the general formula (1) of the present invention as the host material, mCP , Thiazole derivatives, benzimidazole derivatives, polydialkylfluorene derivatives, and the like can be used. As the dopant material, quinacridone, coumarin, rubrene, anthracene, perylene and derivatives thereof, benzopyran derivatives, rhodamine derivatives, aminostyryl derivatives, and the like can be used. These may be formed alone, but may be used as a single layer formed by mixing with other materials, layers formed alone, mixed layers formed, or A stacked structure of layers formed by mixing with a layer formed alone may be used.

Further, a phosphorescent light emitting material can be used as the light emitting material. As the phosphorescent emitter, a phosphorescent emitter of a metal complex such as iridium or platinum can be used. Green phosphorescent emitters such as Ir (ppy) ₃ , blue phosphorescent emitters such as FIrpic and FIr6, and red phosphorescent emitters such as Btp ₂ Ir (acac) and Ir (piq) ₃ are used. As a host material, a compound having a triphenylsilylpyridyl group and a carbazole ring structure represented by the general formula (1) of the present invention, a hole injection / transport host material such as CBP, TCTA, mCP, etc. A carbazole derivative or the like can be used. As an electron transporting host material, p-bis (triphenylsilyl) benzene (hereinafter abbreviated as UGH2) or 2,2 ′, 2 ″-(1,3,5-phenylene) -tris (1-phenyl) -1H-benzimidazole) (hereinafter abbreviated as TPBI) and the like can be used. These may be formed alone, but may be used as a single layer formed by mixing with other materials, layers formed alone, mixed layers formed, or A stacked structure of layers formed by mixing with a layer formed alone may be used.

In order to avoid concentration quenching, it is preferable to dope the phosphorescent light-emitting material into the host material by co-evaporation in the range of 1 to 30 weight percent with respect to the entire light-emitting layer.

These materials can be formed into a thin film by a known method such as a spin coating method or an ink jet method in addition to a vapor deposition method.

In addition, an element having a structure in which a light-emitting layer manufactured using a compound having a different work function as a host material is stacked adjacent to a light-emitting layer manufactured using the compound of the present invention can be manufactured (for example, non-patented). Reference 5).

As the hole blocking layer of the organic EL device of the present invention, a phenanthroline derivative such as bathocuproine (hereinafter abbreviated as BCP), aluminum (III) bis (2-methyl-8-quinolinato) -4-phenylphenolate (hereinafter referred to as “BCP”). In addition to metal complexes of quinolinol derivatives such as BAlq), various rare earth complexes, oxazole derivatives, triazole derivatives, triazine derivatives, and the like can be used. These materials may also serve as the material for the electron transport layer. These may be formed alone, but may be used as a single layer formed by mixing with other materials, layers formed alone, mixed layers formed, or A stacked structure of layers formed by mixing with a layer formed alone may be used. These materials can be formed into a thin film by a known method such as a spin coating method or an ink jet method in addition to a vapor deposition method.

As an electron transport layer of the organic EL device of the present invention, various metal complexes, triazole derivatives, triazine derivatives, oxadiazole derivatives, thiadiazole derivatives, carbodiimide derivatives, quinoxaline, as well as metal complexes of quinolinol derivatives including Alq ₃ and BAlq. Derivatives, phenanthroline derivatives, silole derivatives, benzimidazole derivatives such as TPBI, and the like can be used. These may be formed alone, but may be used as a single layer formed by mixing with other materials, layers formed alone, mixed layers formed, or A stacked structure of layers formed by mixing with a layer formed alone may be used. These materials can be formed into a thin film by a known method such as a spin coating method or an ink jet method in addition to a vapor deposition method.

As the electron injection layer of the organic EL device of the present invention, an alkali metal salt such as lithium fluoride and cesium fluoride, an alkaline earth metal salt such as magnesium fluoride, and a metal oxide such as aluminum oxide can be used. In the preferred selection of the electron transport layer and the cathode, this can be omitted.

Furthermore, in the electron injecting layer or the electron transporting layer, a material usually used for the layer and further doped with a metal such as cesium can be used.

As the cathode of the organic EL device of the present invention, an electrode material having a low work function such as aluminum or an alloy having a lower work function such as a magnesium silver alloy, a magnesium indium alloy, or an aluminum magnesium alloy is used as the electrode material.

Hereinafter, embodiments of the present invention will be specifically described with reference to examples. However, the present invention is not limited to the following examples.

<Synthesis of 9,9-diphenyl-10- (5-phenyl-5H-pyrido [4,3-b] indol-8-yl) -9,10-dihydroacridine (Compound 1)>
In a reaction vessel purged with nitrogen, 5H-pyrido [4,3-b] indole (100 g), iodobenzene (79.5 mL), copper powder (18.9 g), potassium carbonate (164 g), dimethyl sulfoxide (4.2 mL) ) Was suspended in toluene (200 mL). While removing toluene, the mixture was heated to 170 ° C. and stirred for 3 hours. After cooling to 120 ° C., toluene (1 L) was added, and the mixture was stirred at 90 ° C. for 30 minutes. The mixture was allowed to cool to 80 ° C. and then filtered. NH silica gel was added to the filtrate and stirred for 30 minutes, followed by filtration. The solvent was distilled off to obtain a light brown oil of 5-phenyl-5H-pyrido [4,3-b] indole (yield 77%).
In a nitrogen-substituted reaction vessel, 5-phenyl-5H-pyrido [4,3-b] indole (111 g) was dissolved in chloroform (770 mL). Bromine (218 g) was added dropwise to the reaction solution, and the mixture was stirred at 60 ° C. for 1 hour. Saturated aqueous sodium thiosulfate solution (600 mL) was added while allowing the reaction vessel to bathe in water. Thereafter, the mixture was neutralized with an aqueous potassium carbonate solution and extracted with chloroform. NH silica gel was added to the organic layer and stirred for 30 minutes, followed by filtration, and the solvent of the filtrate was distilled off. Toluene (1 L) was added to the obtained concentrate and dissolved, and then silica gel was added to adsorb the target product. After filtration, an eluent (1 L, chloroform / methanol = 9/1) was added to silica gel, and the mixture was stirred and filtered. The solvent was distilled off to obtain white solid of 8-bromo-5-phenyl-5H-pyrido [4,3-b] indole (yield 81%).
In a reaction vessel purged with nitrogen, 9,9-diphenyl-9,10-dihydroacridine (1.24 g), 8-bromo-5-phenyl-5H-pyrido [4,3-b] indole (1.00 g), Tri-tert-butylphosphonium tetrafluoroborate (0.13 g) and sodium-tert-butoxide (0.34 g) were suspended in toluene (100 mL). The reaction system was purged with argon three times, tris (dibenzylideneacetone) dipalladium (0) chloroform adduct (0.10 g) was added, and the mixture was heated to reflux for 22 hours. After cooling to room temperature, saturated saline was added to stop the reaction. After performing Celite filtration, extraction was performed with ethyl acetate, and the solvent was distilled off. The resulting concentrate was purified by column chromatography, and 9,9-diphenyl-10- (5-phenyl-5H-pyrido [4,3-b] indol-8-yl) -9,10-dihydroacridine ( A white powder having a yield of 37% was obtained.

The structure of the obtained white solid was identified using NMR. ^The results of ¹ H-NMR measurement are shown in FIG.
^The following 29 hydrogen signals were detected by ¹ H-NMR (CDCl ₃ ).
δ (ppm) = 6.48 (2H), 6.87-6.90 (2H), 6.93 (2H), 7.01-7.06 (6H), 7.17 (1H), 7. 25-7.32 (7H), 7.54-7.57 (2H), 7.60 (2H), 7.65-7.768 (2H), 7.87 (1H), 8.55 (1H), 9.26 (1H).

<Synthesis of 10- (4- (5H-pyrido [4,3-b] indol-5-yl) phenyl-9,9-diphenyl-9,10-dihydroacridine (Compound 2)>
1,4-Dibromobenzene (28.07 g), copper powder (0.96 g), potassium carbonate (8.24 g), and dimethyl sulfoxide (0.7 mL) were suspended in ODB (40 mL) in a reaction vessel purged with nitrogen. I let you. After stirring at 170 ° C. for 1 hour, 5H-pyrido [4,3-b] indole (5.00 g) was added and stirred at that temperature for 8 hours. After cooling to 50 ° C., chloroform (100 mL) was added and stirred for 30 minutes. After performing Celite filtration, the solvent was distilled off. The obtained concentrate was purified by column chromatography to obtain a pale yellow powder of 5- (4-bromophenyl) -5H-pyrido [4,3-b] indole (yield 67%).
In a nitrogen-substituted reaction vessel, 9,9-diphenyl-9,10-dihydroacridine (3.00 g), 5- (4-bromophenyl) -5H-pyrido [4,3-b] indole (3.50 g) N-phenyl-2- (di-tert-butylphosphino) indole (0.36 g) and sodium-tert-butoxide (0.91 g) were suspended in toluene (100 mL). The reaction system was purged with argon three times, tris (dibenzylideneacetone) dipalladium (0) chloroform adduct (0.28 g) was added, and the mixture was heated to reflux for 9 hours. After cooling to room temperature, saturated saline was added to stop the reaction. After performing Celite filtration, extraction was performed with ethyl acetate, and the solvent was distilled off. The resulting concentrate was purified by column chromatography, and 10- (4- (5H-pyrido [4,3-b] indol-5-yl) phenyl-9,9-diphenyl-9,10-dihydroacridine ( A light yellow powder having a yield of 36% was obtained.

The structure of the obtained pale yellow solid was identified using NMR. ^The results of ¹ H-NMR measurement are shown in FIG.
^The following 29 hydrogen signals were detected by ¹ H-NMR (CDCl ₃ ).
δ (ppm) = 6.58 (2H), 6.95 (4H), 7.02 (4H), 7.13-7.17 (2H), 7.27-7.30 (6H), 7. 33 (2H), 7.40-7.43 (2H), 7.51-7.54 (2H), 7.72 (2H), 8.24 (1H), 8.57 (1H), 9. 41 (1H).

<Synthesis of 9- (5-phenyl-5H-pyrido [4,3-b] indol-8-yl) -9H-3,9'-bicarbazole (Compound 4)>
In a reaction vessel purged with nitrogen, 9H-3,9′-bicarbazole (1.14 g), 8-bromo-5-phenyl-5H-pyrido [4,3-b] indole (1.00 g), potassium phosphate (1.33 g) was suspended in 1,4-dioxane (30 mL), and trans-1,2-diaminocyclohexane (0.11 g) and then copper iodide (0.18 g) were added, and the mixture was heated to reflux for 21 hours. . After cooling to room temperature, saturated saline was added to stop the reaction. After performing Celite filtration, extraction was performed with toluene, and the solvent was distilled off. The resulting concentrate was purified by column chromatography to obtain 9- (5-phenyl-5H-pyrido [4,3-b] indol-8-yl) -9H-3,9′-bicarbazole (yield 63 %) Of white powder.

The structure of the resulting white powder was identified using NMR. ^The results of ¹ H-NMR measurement are shown in FIG.
^The following 26 hydrogen signals were detected by ¹ H-NMR (DMSO-d ₆ ).
δ (ppm) = 7.29-7.36 (3H), 7.38 (2H), 7.44-7.48 (4H), 7.52 (1H), 7.61-7.67 (3H ), 7.73-7.83 (5H), 7.85 (1H), 8.29 (2H), 8.39 (1H), 8.56 (1H), 8.58 (1H), 8. 83 (1H), 9.61 (1H).

<Synthesis of 9- (4- (5H-pyrido [4,3-b] indol-5-yl) phenyl) -9H-3,9'-bicarbazole (Compound 5)>
In a reaction vessel purged with nitrogen, 9H-3,9′-bicarbazole (1.00 g), 5- (4-bromophenyl) -5H-pyrido [4,3-b] indole (1.13 g), phosphoric acid Suspend potassium (1.34 g) in 1,4-dioxane (30 mL), add trans-1,2-diaminocyclohexane (0.11 g), then copper iodide (0.20 g), and heat to reflux for 32 hours. did. After cooling to room temperature, saturated saline was added to stop the reaction. After performing Celite filtration, extraction was performed with toluene, and the solvent was distilled off. The obtained concentrate was purified by column chromatography, and 9- (4- (5H-pyrido [4,3-b] indol-5-yl) phenyl) -9H-3,9′-bicarbazole (yield) 79%) white powder.

The structure of the resulting white powder was identified using NMR. ^The results of ¹ H-NMR measurement are shown in FIG.
^The following 26 hydrogen signals were detected by ¹ H-NMR (DMSO-d ₆ ).
δ (ppm) = 7.31 (2H), 7.36-7.41 (3H), 7.44-7.47 (3H), 7.69 (3H), 7.67-7.70 (3H) ), 7.86 (1H), 8.02 (2H), 8.07 (2H), 8.30 (2H), 8.40 (1H), 8.43 (1H), 8.57 (1H) 8.60 (1H), 9.54 (1H).

About the compound of this invention, the glass transition point was calculated | required with the highly sensitive differential scanning calorimeter (The Seiko Instruments make, DSC200).
Glass transition point Compound N / A of Example 1 of the present invention
Inventive Example 2 Compound 141 ° C.
Inventive Example 3 Compound 152 ° C.
Inventive Example 4 Compound 150 ° C.

Using the compound of the present invention, a deposited film with a thickness of 100 nm was formed on an ITO substrate, and the work function was measured with an atmospheric photoelectron spectrometer (AC-3 type, manufactured by Riken Keiki Co., Ltd.).
Work Function Compound of the Invention Example 1 5.92 eV
Inventive Example 2 compound 5.85 eV
Compound of Example 3 of the present invention 5.80 eV
Compound of Example 4 of the present invention 5.98 eV
mCBP 6.20eV

Thus, the compound of the present invention has an energy level suitable as a material for the light emitting layer, which is comparable to that of mCBP generally used as a light emitting host.

For the compound of Example 1 of the present invention (Compound 1), a 10 ⁻⁵ mol / L toluene solution was prepared. When this toluene solution was irradiated with ultraviolet light at 300 K while passing nitrogen, fluorescence having a peak wavelength of 392 nm was observed.

In Example 7, instead of the compound of Example 1 of the present invention (Compound 1), a 10 ⁻⁵ mol / L toluene solution of the compound of Example 2 of the present invention (Compound 2) was prepared, and the characteristics were evaluated in the same manner. Went. As a result, fluorescence having a peak wavelength of 373 nm was observed.

In Example 7, instead of the compound of Example 1 of the present invention (Compound 1), a 10 ⁻⁵ mol / L toluene solution of the compound of Example 3 of the present invention (Compound 4) was prepared, and the characteristics were evaluated in the same manner. Went. As a result, fluorescence having a peak wavelength of 371 nm was observed.

In Example 7, instead of the compound of Example 1 of the present invention (Compound 1), a 10 ⁻⁵ mol / L toluene solution of the compound of Example 4 of the present invention (Compound 5) was prepared, and the characteristics were evaluated in the same manner. Went. As a result, fluorescence having a peak wavelength of 369 nm was observed.

As shown in FIG. 5, the organic EL element has a hole injection layer 3, a first hole transport layer 4, and a second hole transport on a glass substrate 1 on which an ITO electrode is previously formed as a transparent anode 2. The layer 5, the light emitting layer 6, the hole blocking layer 7, the electron transport layer 8, the electron injection layer 9, and the cathode (aluminum electrode) 10 were deposited in this order.
Specifically, the glass substrate 1 on which ITO having a thickness of 100 nm was formed was washed with an organic solvent, and then the surface was washed by UV ozone treatment. Then, this glass substrate with an ITO electrode was mounted in a vacuum vapor deposition machine and the pressure was reduced to 0.001 Pa or less.
Subsequently, NPD was formed as a hole injection layer 3 so as to cover the transparent anode 2 so as to have a film thickness of 30 nm at a deposition rate of 2.0 Å / sec. On this hole injection layer 3, TCTA was formed as a first hole transport layer 4 so as to have a film thickness of 20 nm at a deposition rate of 2.0 Å / sec. On this first hole transport layer 4, the second hole transport layer 5 was formed such that the compound of Example 2 of the present invention (Compound 2) had a film thickness of 15 nm at a deposition rate of 2.0 Å / sec. . On this second hole transport layer 5, as the light emitting layer 6, the compound of Example 2 of the present invention (Compound 2) and the light emitting material 2- [4- [3- (N-phenyl-9H-carbazole) shown below are used. -3-yl) -9H-carbazol-9-yl] phenyl] -4,6-diphenyl-1,3,5-triazine (compound 112), the deposition rate ratio of which is compound of compound of Example 2 of the present invention (compound 2) ): Luminescent material (compound 112) = binary deposition was performed at a deposition rate of 85:15 to form a film thickness of 20 nm. On this light emitting layer 6, DPEPO and TPBi were formed as a hole blocking layer 7 by binary vapor deposition at a vapor deposition rate of DPEPO: TPBi = 1: 1 so as to have a film thickness of 10 nm. On the hole blocking layer 7, TPBi was formed as an electron transport layer 8 so as to have a film thickness of 30 nm at a deposition rate of 2.0 Å / sec. On the electron transport layer 8, lithium fluoride was formed as the electron injection layer 9 so as to have a film thickness of 0.7 nm at a deposition rate of 0.1 Å / sec. Finally, aluminum was deposited to a thickness of 100 nm to form the cathode 10. About the produced organic EL element, the characteristic measurement was performed at normal temperature in air | atmosphere.

(Compound 112)

As shown in FIG. 5, the organic EL element has a hole injection layer 3, a first hole transport layer 4, and a second hole transport on a glass substrate 1 on which an ITO electrode is previously formed as a transparent anode 2. The layer 5, the light emitting layer 6, the hole blocking layer 7, the electron transport layer 8, the electron injection layer 9, and the cathode (aluminum electrode) 10 were deposited in this order.
Specifically, the glass substrate 1 on which ITO having a thickness of 100 nm was formed was washed with an organic solvent, and then the surface was washed by UV ozone treatment. Then, this glass substrate with an ITO electrode was mounted in a vacuum vapor deposition machine and the pressure was reduced to 0.001 Pa or less.
Subsequently, NPD was formed as a hole injection layer 3 so as to cover the transparent anode 2 so as to have a film thickness of 30 nm at a deposition rate of 2.0 Å / sec. On this hole injection layer 3, TCTA was formed as a first hole transport layer 4 so as to have a film thickness of 20 nm at a deposition rate of 2.0 Å / sec. On this first hole transport layer 4, the compound (compound 4) of Example 3 of the present invention was formed as a second hole transport layer 5 so as to have a film thickness of 15 nm at a deposition rate of 2.0 Å / sec. . On this second hole transport layer 5, as the light emitting layer 6, the compound of Example 3 of the present invention (Compound 4) and the light emitting material (Compound 112) are deposited. 4): The light-emitting material (compound 112) was subjected to binary vapor deposition at a vapor deposition rate of 85:15 to form a film thickness of 20 nm. On this light emitting layer 6, DPEPO and TPBi were formed as a hole blocking layer 7 by binary vapor deposition at a vapor deposition rate of DPEPO: TPBi = 1: 1 so as to have a film thickness of 10 nm. On the hole blocking layer 7, TPBi was formed as an electron transport layer 8 so as to have a film thickness of 30 nm at a deposition rate of 2.0 Å / sec. On the electron transport layer 8, lithium fluoride was formed as the electron injection layer 9 so as to have a film thickness of 0.7 nm at a deposition rate of 0.1 Å / sec. Finally, aluminum was deposited to a thickness of 100 nm to form the cathode 10. About the produced organic EL element, the characteristic measurement was performed at normal temperature in air | atmosphere.

As shown in FIG. 5, the organic EL element has a hole injection layer 3, a first hole transport layer 4, and a second hole transport on a glass substrate 1 on which an ITO electrode is previously formed as a transparent anode 2. The layer 5, the light emitting layer 6, the hole blocking layer 7, the electron transport layer 8, the electron injection layer 9, and the cathode (aluminum electrode) 10 were deposited in this order.
Specifically, the glass substrate 1 on which ITO having a thickness of 100 nm was formed was washed with an organic solvent, and then the surface was washed by UV ozone treatment. Then, this glass substrate with an ITO electrode was mounted in a vacuum vapor deposition machine and the pressure was reduced to 0.001 Pa or less.
Subsequently, NPD was formed as a hole injection layer 3 so as to cover the transparent anode 2 so as to have a film thickness of 30 nm at a deposition rate of 2.0 Å / sec. On this hole injection layer 3, TCTA was formed as a first hole transport layer 4 so as to have a film thickness of 20 nm at a deposition rate of 2.0 Å / sec. On this first hole transport layer 4, the compound (Compound 5) of Example 4 of the present invention was formed as a second hole transport layer 5 so as to have a film thickness of 15 nm at a deposition rate of 2.0 Å / sec. . On this second hole transport layer 5, as the light emitting layer 6, the compound (compound 5) of Example 4 of the present invention and the light emitting material (Compound 112) are deposited. 5): The light emitting material (compound 112) was subjected to binary vapor deposition at a vapor deposition rate of 85:15 to form a film thickness of 20 nm. On this light emitting layer 6, DPEPO and TPBi were formed as a hole blocking layer 7 by binary vapor deposition at a vapor deposition rate of DPEPO: TPBi = 1: 1 so as to have a film thickness of 10 nm. On the hole blocking layer 7, TPBi was formed as an electron transport layer 8 so as to have a film thickness of 30 nm at a deposition rate of 2.0 Å / sec. On the electron transport layer 8, lithium fluoride was formed as the electron injection layer 9 so as to have a film thickness of 0.7 nm at a deposition rate of 0.1 Å / sec. Finally, aluminum was deposited to a thickness of 100 nm to form the cathode 10. About the produced organic EL element, the characteristic measurement was performed at normal temperature in air | atmosphere.

Luminescence when DC voltage is applied to the organic EL device produced using the compound of Example 2 (Compound 2), the compound of Example 3 (Compound 4), and the compound of Example 4 (Compound 5) of the present invention. Table 1 summarizes the measurement results of the characteristics.

[Comparative Example 1]
For comparison, the materials of the second hole transport layer 5 and the light-emitting layer 6 in Examples 11 to 13 were changed from the compound of Example 3 (Compound 4) to mCBP, and the same conditions as in Examples 11 to 13 were used. Thus, an organic EL element was produced. About the produced organic EL element, the characteristic measurement was performed at normal temperature in air | atmosphere. Table 1 summarizes the measurement results of the light emission characteristics when a DC voltage was applied to the produced organic EL element.

As shown in Table 1, the voltage when a current density of 10 mA / cm ² was passed was 7.8 V in Example 11 and 7.8 V in Example 11 compared to 7.8 V in Comparative Example 1 using mCBP. In 6.8V and Example 13, the value which was substantially equal to 7.0V or fell was shown. For the luminance, substantially equal with respect to 1116cd / ^{m 2} of Comparative Example 1 using mCBP, Example 11, 1107cd / ^{m 2,} Example 12, 1550cd / ^{m 2,} and 1237cd / ^{m 2} in Example 13, Or it showed a greatly improved value. Further, with respect to 11.3cd / A of Comparative Example 1 using mCBP also emission efficiency, Example 11, 11.8cd / ^{m 2,} Example 12, 14.7cd / ^{m 2,} in Examples 13 13 The value was almost equal to or greatly improved to 0.6 cd / m ² . Furthermore, the power efficiency is 4.56 lm / W in Comparative Example 1 using mCBP, but is 4.64 lm / W in Example 11, 6.79 lm / W in Example 12, and 6.12 lm / W in Example 13. The value was almost the same as W or greatly improved.

As described above, it was found that the organic EL device using the compound of the present invention can achieve a significant decrease in driving voltage and a significant improvement in light emission efficiency as compared with a device using mCBP.

The compound having azacarbazole of the present invention has good thin film stability and is excellent as a material for the light emitting layer, particularly as a host material for the light emitting layer. Moreover, the brightness | luminance and luminous efficiency of the conventional organic EL element can be improved markedly by producing an organic EL element using this compound.

1 Glass substrate 2 Transparent anode 3 Hole injection layer 4 First hole transport layer 5 Second hole transport layer 6 Light emitting layer 7 Hole blocking layer 8 Electron transport layer 9 Electron injection layer 10 Cathode

Claims

A compound having an azacarbazole skeleton represented by the following general formula (1).

(1)
(In the formula, A, B, C, D, E, F, G, and H each represents at least one nitrogen atom and represents a carbon atom or a nitrogen atom, and X, Y, and Z are the same or different from each other. A substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, a substituted or unsubstituted condensed polycyclic aromatic group, an aromatic hydrocarbon group, an aromatic heterocyclic group or A disubstituted amino group substituted by a group selected from a condensed polycyclic aromatic group, wherein L is a single bond, a divalent group of a substituted or unsubstituted aromatic hydrocarbon, a substituted or unsubstituted aromatic heterocyclic ring; Represents a divalent group or a substituted or unsubstituted condensed polycyclic aromatic divalent group.If L is a single bond, the subscript n is 0. R 1 to R 10 are the same or different from each other. Hydrogen atom, deuterium atom, fluorine atom, chlorine atom, cyano group , A trifluoromethyl group, a nitro group, a linear or branched alkyl group having 1 to 6 carbon atoms which may have a substituent, and a carbon atom having 5 to 10 carbon atoms which may have a substituent A cycloalkyl group, a linear or branched alkenyl group having 2 to 6 carbon atoms which may have a substituent, and a linear chain having 1 to 6 carbon atoms which may have a substituent Or a branched alkyloxy group, an optionally substituted cycloalkyloxy group having 5 to 10 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group , A substituted or unsubstituted condensed polycyclic aromatic group, a substituted or unsubstituted aryloxy group, or a disubstituted by a group selected from an aromatic hydrocarbon group, an aromatic heterocyclic group or a condensed polycyclic aromatic group A conversion amino group, a single bond, a substituted or unsubstituted methylene group, linked to each other through an oxygen atom or a sulfur atom may form a ring.)
A compound having an azacarbazole skeleton represented by the following general formula (1-1).

(1-1)
(In the formula, A, B, C, D, E, F, G, and H each represents at least one nitrogen atom and represents a carbon atom or a nitrogen atom, and X, Y, and Z are the same or different from each other. A substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, a substituted or unsubstituted condensed polycyclic aromatic group, an aromatic hydrocarbon group, an aromatic heterocyclic group or A disubstituted amino group substituted by a group selected from a condensed polycyclic aromatic group, wherein L is a single bond, a divalent group of a substituted or unsubstituted aromatic hydrocarbon, a substituted or unsubstituted aromatic heterocyclic ring; Represents a divalent group or a substituted or unsubstituted condensed polycyclic aromatic divalent group.If L is a single bond, the subscript n is 0. R 1 to R 10 are the same or different from each other. Hydrogen atom, deuterium atom, fluorine atom, chlorine atom, cyano group , A trifluoromethyl group, a nitro group, a linear or branched alkyl group having 1 to 6 carbon atoms which may have a substituent, and a carbon atom having 5 to 10 carbon atoms which may have a substituent A cycloalkyl group, a linear or branched alkenyl group having 2 to 6 carbon atoms which may have a substituent, and a linear chain having 1 to 6 carbon atoms which may have a substituent Or a branched alkyloxy group, an optionally substituted cycloalkyloxy group having 5 to 10 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group , A substituted or unsubstituted condensed polycyclic aromatic group, a substituted or unsubstituted aryloxy group, or a disubstituted by a group selected from an aromatic hydrocarbon group, an aromatic heterocyclic group or a condensed polycyclic aromatic group A conversion amino group, a single bond, a substituted or unsubstituted methylene group, linked to each other through an oxygen atom or a sulfur atom may form a ring.)
A compound having an azacarbazole skeleton represented by the following general formula (1-2).

(1-2)
(In the formula, at least one of A, B, C and D represents a nitrogen atom and represents a carbon atom or a nitrogen atom, and X, Y and Z may be the same or different from each other, and may be substituted or unsubstituted. Selected from aromatic hydrocarbon group, substituted or unsubstituted aromatic heterocyclic group, substituted or unsubstituted condensed polycyclic aromatic group, or aromatic hydrocarbon group, aromatic heterocyclic group or condensed polycyclic aromatic group And L represents a single bond, a divalent group of a substituted or unsubstituted aromatic hydrocarbon, a divalent group of a substituted or unsubstituted aromatic heterocyclic ring, or a substituted or unsubstituted group. Represents a substituted fused polycyclic aromatic divalent group, and if L is a single bond, the subscript n is 0. R 1 to R 10 may be the same or different from each other, Hydrogen atom, fluorine atom, chlorine atom, cyano group, trifluorome A til group, a nitro group, an optionally substituted linear or branched alkyl group having 1 to 6 carbon atoms, and an optionally substituted cycloalkyl group having 5 to 10 carbon atoms A linear or branched alkenyl group having 2 to 6 carbon atoms which may have a substituent, or a linear or branched chain having 1 to 6 carbon atoms which may have a substituent An alkyloxy group, an optionally substituted cycloalkyloxy group having 5 to 10 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, substituted or An unsubstituted condensed polycyclic aromatic group, a substituted or unsubstituted aryloxy group, or a disubstituted amino group substituted by an aromatic hydrocarbon group, an aromatic heterocyclic group or a group selected from a condensed polycyclic aromatic group In Te single bond, a substituted or unsubstituted methylene group, linked to each other through an oxygen atom or a sulfur atom may form a ring.)
A compound having an azacarbazole skeleton represented by the following general formula (1-3).

(1-3)
(In the formula, at least one of A, B, C and D represents a nitrogen atom and represents a carbon atom or a nitrogen atom, and X and Y may be the same or different from each other, and are substituted or unsubstituted aromatic. A group selected from a hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, a substituted or unsubstituted condensed polycyclic aromatic group, or an aromatic hydrocarbon group, aromatic heterocyclic group or condensed polycyclic aromatic group L represents a disubstituted amino group substituted by a single bond, a substituted or unsubstituted aromatic hydrocarbon divalent group, a substituted or unsubstituted aromatic heterocyclic divalent group, or a substituted or unsubstituted aromatic group. Represents a condensed polycyclic aromatic divalent group, and if L is a single bond, the subscript n is 0. R 1 to R 10 may be the same or different from each other, and may be a hydrogen atom or a deuterium atom. , Fluorine atom, chlorine atom, cyano group, trifluoromethyl Group, nitro group, optionally substituted linear or branched alkyl group having 1 to 6 carbon atoms, optionally substituted cycloalkyl group having 5 to 10 carbon atoms A linear or branched alkenyl group having 2 to 6 carbon atoms which may have a substituent, or a linear or branched group having 1 to 6 carbon atoms which may have a substituent. Alkyloxy group, optionally substituted cycloalkyloxy group having 5 to 10 carbon atoms, substituted or unsubstituted aromatic hydrocarbon group, substituted or unsubstituted aromatic heterocyclic group, substituted or unsubstituted A substituted condensed polycyclic aromatic group, a substituted or unsubstituted aryloxy group, or a disubstituted amino group substituted by a group selected from an aromatic hydrocarbon group, an aromatic heterocyclic group or a condensed polycyclic aromatic group There Single bond, a substituted or unsubstituted methylene group, linked to each other through an oxygen atom or a sulfur atom may form a ring.)
A compound having an azacarbazole skeleton represented by the following general formula (1-4).

(1-4)
(In the formula, at least one of A, B, C and D represents a nitrogen atom and represents a carbon atom or a nitrogen atom, and X and Y may be the same or different from each other, and are substituted or unsubstituted aromatic. A group selected from a hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, a substituted or unsubstituted condensed polycyclic aromatic group, or an aromatic hydrocarbon group, aromatic heterocyclic group or condensed polycyclic aromatic group L represents a disubstituted amino group substituted by a single bond, a substituted or unsubstituted aromatic hydrocarbon divalent group, a substituted or unsubstituted aromatic heterocyclic divalent group, or a substituted or unsubstituted aromatic group. Represents a condensed polycyclic aromatic divalent group, and if L is a single bond, the subscript n is 0. R 1 to R 10 may be the same or different from each other, and may be a hydrogen atom or a deuterium atom. , Fluorine atom, chlorine atom, cyano group, trifluoromethyl Group, nitro group, optionally substituted linear or branched alkyl group having 1 to 6 carbon atoms, optionally substituted cycloalkyl group having 5 to 10 carbon atoms A linear or branched alkenyl group having 2 to 6 carbon atoms which may have a substituent, or a linear or branched group having 1 to 6 carbon atoms which may have a substituent. Alkyloxy group, optionally substituted cycloalkyloxy group having 5 to 10 carbon atoms, substituted or unsubstituted aromatic hydrocarbon group, substituted or unsubstituted aromatic heterocyclic group, substituted or unsubstituted A substituted condensed polycyclic aromatic group, a substituted or unsubstituted aryloxy group, or a disubstituted amino group substituted by a group selected from an aromatic hydrocarbon group, an aromatic heterocyclic group or a condensed polycyclic aromatic group There Single bond, a substituted or unsubstituted methylene group, linked to each other through an oxygen atom or a sulfur atom may form a ring.)
A compound having an azacarbazole skeleton represented by the following general formula (1-5).

(1-5)
(In the formula, at least one of A, B, C and D represents a nitrogen atom and represents a carbon atom or a nitrogen atom, and X and Y may be the same or different from each other, and are substituted or unsubstituted aromatic. A group selected from a hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, a substituted or unsubstituted condensed polycyclic aromatic group, or an aromatic hydrocarbon group, aromatic heterocyclic group or condensed polycyclic aromatic group L represents a disubstituted amino group substituted by a single bond, a substituted or unsubstituted aromatic hydrocarbon divalent group, a substituted or unsubstituted aromatic heterocyclic divalent group, or a substituted or unsubstituted aromatic group. Represents a condensed polycyclic aromatic divalent group, and if L is a single bond, the subscript n is 0. R 1 to R 7 may be the same or different from each other, and may be a hydrogen atom or a deuterium atom. , Fluorine atom, chlorine atom, cyano group, trifluoromethyl , A nitro group, a linear or branched alkyl group having 1 to 6 carbon atoms which may have a substituent, a cycloalkyl group having 5 to 10 carbon atoms which may have a substituent, A linear or branched alkenyl group having 2 to 6 carbon atoms which may have a substituent, a linear or branched alkyl having 1 to 6 carbon atoms which may have a substituent Oxy group, optionally substituted cycloalkyloxy group having 5 to 10 carbon atoms, substituted or unsubstituted aromatic hydrocarbon group, substituted or unsubstituted aromatic heterocyclic group, substituted or unsubstituted A condensed polycyclic aromatic group, a substituted or unsubstituted aryloxy group, or a disubstituted amino group substituted by a group selected from an aromatic hydrocarbon group, an aromatic heterocyclic group or a condensed polycyclic aromatic group. The Single bond, a substituted or unsubstituted methylene group, linked to each other through an oxygen atom or a sulfur atom may form a ring.)
A compound having an azacarbazole skeleton represented by the following general formula (1-6).

(1-6)
(In the formula, at least one of A, B, C and D represents a nitrogen atom and represents a carbon atom or a nitrogen atom, and X and Y may be the same or different from each other, and are substituted or unsubstituted aromatic. A group selected from a hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, a substituted or unsubstituted condensed polycyclic aromatic group, or an aromatic hydrocarbon group, aromatic heterocyclic group or condensed polycyclic aromatic group L represents a disubstituted amino group substituted by a single bond, a substituted or unsubstituted aromatic hydrocarbon divalent group, a substituted or unsubstituted aromatic heterocyclic divalent group, or a substituted or unsubstituted aromatic group. Represents a condensed polycyclic aromatic divalent group, and if L is a single bond, the subscript n is 0. R 1 to R 7 may be the same or different from each other, and may be a hydrogen atom or a deuterium atom. , Fluorine atom, chlorine atom, cyano group, trifluoromethyl , A nitro group, a linear or branched alkyl group having 1 to 6 carbon atoms which may have a substituent, a cycloalkyl group having 5 to 10 carbon atoms which may have a substituent, A linear or branched alkenyl group having 2 to 6 carbon atoms which may have a substituent, a linear or branched alkyl having 1 to 6 carbon atoms which may have a substituent Oxy group, optionally substituted cycloalkyloxy group having 5 to 10 carbon atoms, substituted or unsubstituted aromatic hydrocarbon group, substituted or unsubstituted aromatic heterocyclic group, substituted or unsubstituted A condensed polycyclic aromatic group, a substituted or unsubstituted aryloxy group, or a disubstituted amino group substituted by a group selected from an aromatic hydrocarbon group, an aromatic heterocyclic group or a condensed polycyclic aromatic group. The Single bond, a substituted or unsubstituted methylene group, linked to each other through an oxygen atom or a sulfur atom may form a ring.)
In an organic electroluminescence device having a pair of electrodes and at least one organic layer sandwiched therebetween, the organic layer is a light emitting layer, and a compound having an azacarbazole structure represented by the following general formula (1): An organic electroluminescence device characterized by being used as a constituent material of the light emitting layer.

(1)
(In the formula, A, B, C, D, E, F, G, and H each represents at least one nitrogen atom and represents a carbon atom or a nitrogen atom, and X, Y, and Z are the same or different from each other. A substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, a substituted or unsubstituted condensed polycyclic aromatic group, an aromatic hydrocarbon group, an aromatic heterocyclic group or A disubstituted amino group substituted by a group selected from a condensed polycyclic aromatic group, wherein L is a single bond, a divalent group of a substituted or unsubstituted aromatic hydrocarbon, a substituted or unsubstituted aromatic heterocyclic ring; Represents a divalent group or a substituted or unsubstituted condensed polycyclic aromatic divalent group.If L is a single bond, the subscript n is 0. R 1 to R 10 are the same or different from each other. Hydrogen atom, deuterium atom, fluorine atom, chlorine atom, cyano group , A trifluoromethyl group, a nitro group, a linear or branched alkyl group having 1 to 6 carbon atoms which may have a substituent, and a carbon atom having 5 to 10 carbon atoms which may have a substituent A cycloalkyl group, a linear or branched alkenyl group having 2 to 6 carbon atoms which may have a substituent, and a linear chain having 1 to 6 carbon atoms which may have a substituent Or a branched alkyloxy group, an optionally substituted cycloalkyloxy group having 5 to 10 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group , A substituted or unsubstituted condensed polycyclic aromatic group, a substituted or unsubstituted aryloxy group, or a disubstituted by a group selected from an aromatic hydrocarbon group, an aromatic heterocyclic group or a condensed polycyclic aromatic group A conversion amino group, a single bond, a substituted or unsubstituted methylene group, linked to each other through an oxygen atom or a sulfur atom may form a ring.)