JP2023101374A - Azabenzofluoranthene compound, material for organic electroluminescent devices, electron transport material for organic electroluminescent devices and organic electroluminescent device - Google Patents

Abstract

To provide an organic electroluminescent device having improved service life properties and a novel azabenzofluoranthene compound suitable for making the same.SOLUTION: An azabenzofluoranthene compound has a specific structure represented by the formula (1). Provided also are a material for organic electroluminescent devices and an organic electroluminescent device, each of which contains the azabenzofluoranthene compound.SELECTED DRAWING: Figure 1

Description

The present invention relates to an azabenzofluoranthene compound, an organic electroluminescence device material containing the azabenzofluoranthene compound, an electron transport material for an organic electroluminescence device, and an organic electroluminescence device.

Organic electroluminescence devices have begun to be put into practical use, mainly for small mobile applications. However, performance improvement is essential for further expansion of applications, and materials with high current efficiency, low driving voltage, high luminous efficiency characteristics, and long life characteristics are required. Patent Literature 1 and Patent Literature 2 disclose azabenzofluoranthene compounds, which are materials for organic electroluminescent (organic electroluminescence) devices.

Japanese Patent Application Laid-Open No. 2008-56658 Korean Patent Publication No. 1020180074176

However, it cannot be said that the azabenzofluoranthene compounds described in Patent Documents 1 and 2 sufficiently satisfy the longevity characteristics.

Accordingly, one aspect of the present invention is directed to providing a novel azabenzofluoranthene compound that contributes to the production of an organic electroluminescent device that can be driven for a long time. there is

Furthermore, still another aspect of the present invention is directed to providing an organic electroluminescent device with improved lifetime characteristics.

The present invention relates to the following [1] to [8].

[1] An azabenzofluoranthene compound represented by formula (1).

In formula (1),
Each Ar is independently an optionally substituted monocyclic ring, an optionally condensed ring, or a structure in which these are linked (i) an aromatic having 6 to 60 carbon atoms group hydrocarbon group,
(ii) a heteroaromatic group having 3 to 60 carbon atoms;
(iii) an arylamino group having 6 to 60 carbon atoms or (iv) a group composed of a combination of any two or more selected from (i) to (iii) above.
n represents an integer of 1-5.
A is a group represented by formula (A).

In formula (A),
Each X is independently C—H or a nitrogen atom.
^* 1 and ^* 2 each independently represent a hydrogen atom or a condensed ring position, and when ^* 1 or ^* 2 represents a condensed ring position, either ^* 1 or ^* 2 has a benzene ring or a pyridine ring. Represents a condensed structure.
One nitrogen atom is included in the skeleton represented by formula (A).
At least one hydrogen atom of the skeleton represented by formula (A) is substituted with Ar.
Any hydrogen atom of the skeleton represented by formula (A) may be substituted.

[2] The azabenzofluoranthene compound according to [1], wherein the skeleton represented by formula (A) is any one of the following formulas (A-1) to (A-6).

[3] The azabenzofluoranthene compound according to [2], wherein the skeleton represented by formula (A) is any one of formulas (A-1) to (A-3).

[4] Each Ar is independently an optionally substituted single ring, an optionally connected condensed ring, or a structure in which these are connected (i) 6 carbon atoms ~60 aromatic hydrocarbon groups,
(ii) a heteroaromatic group having 3 to 60 carbon atoms, composed of atoms selected from the group consisting of hydrogen atoms, carbon atoms, nitrogen atoms, oxygen atoms, and sulfur atoms, or
(iii) The azabenzofluoranthene compound according to any one of [1] to [3], which is a group composed of any combination of two or more selected from (i) and (ii).

[5] The substituents of Ar and A are deuterium atom, fluorine atom, chlorine atom, bromine atom, iodine atom, formyl group, cyano group, nitro group, alkyl group having 1 to 20 carbon atoms, and the number of carbon atoms. 1-20 alkenyl groups, 1-20 carbon cycloalkyl groups, 1-20 carbon bicycloalkyl groups, 1-20 carbon tricycloalkyl groups, 1-10 carbon alkoxy groups, 6 carbon atoms -40 aryl group, heteroaryl group with 3 to 40 carbon atoms, P(=O)(Ar') ₂ , C(=O)Ar', B(Ar') ₂ , B(OAr') ₂ , OSO ₂ Ar', S(=O)Ar' and Si(Ar') are one or more groups selected from the group consisting of ₃ ;
Each Ar' independently represents one or more groups selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 60 carbon atoms and a heteroaryl group having 3 to 60 carbon atoms. ;
The azabenzofluoranthene compound according to any one of [1] to [4].

[6] The azabenzofluoranthene compound according to any one of [1] to [5], wherein the formula (1) is any one of the following formulas E01 to E03, E18, E80 and E85.

[7] A material for an organic electroluminescence device containing the azabenzofluoranthene compound according to any one of [1] to [6].

[8] An electron-transporting material for an organic electroluminescence device, containing the azabenzofluoranthene compound according to any one of [1] to [6].

[9] An organic electroluminescence device containing the azabenzofluoranthene compound according to any one of [1] to [6].

According to one embodiment of the present invention, it is possible to provide a novel azabenzofluoranthene compound that contributes to the manufacture of an organic electroluminescence device that can be driven for a long time.

Also, according to another aspect of the present invention, it is possible to provide an organic electroluminescence device with improved lifetime characteristics.

1 is a schematic cross-sectional view showing an example of a lamination structure of an organic electroluminescence device according to one aspect of the present invention; FIG. FIG. 3 is a schematic cross-sectional view showing another example of the layered structure of the organic electroluminescence device according to one aspect of the present invention (structure of device example-1).

Each aspect of the present invention will be described in detail below.

[Azabenzofluoranthene compound]
An azabenzofluoranthene compound according to one embodiment of the present invention is represented by formula (1).

[About Ar]
In formula (1), each Ar is independently
(i) an aromatic hydrocarbon group having 6 to 60 carbon atoms,
(ii) a heteroaromatic group having 3 to 60 carbon atoms;
(iii) an arylamino group having 6 to 60 carbon atoms, or (iv) a group composed of a combination of any two or more selected from the above (i) to (iii). Ar may be a monocyclic ring that may be linked, a condensed ring that may be linked, or a structure in which these are linked, and may be substituted with a substituent described below.

Among them, Ar is preferably the above (i), (ii), or a group composed of any combination of two or more selected from these, from the viewpoint of the life characteristics of the organic electroluminescence device.

Specific examples of aromatic hydrocarbon groups having 6 to 60 carbon atoms include phenyl, naphthyl, phenanthryl, anthnyl, pyrenyl, perylenyl, fluorenyl, dimethylfluorenyl, diphenylfluorenyl, triphenylenyl group, fluoranthenyl group, benzofluoranthenyl group, chrysenyl group, dibenzochrysenyl group, dinaphthochrysenyl group and the like.

Specific examples of heteroaromatic groups having 3 to 60 carbon atoms include pyridyl, pyrimidyl, pyrazyl, triazinyl, quinolyl, isoquinolyl, nadityridinyl, acridinyl, phenanthrolinyl, and phenanthridinyl. pyrrolyl group, indolyl group, indolizinyl group, carbazolyl group, carbazolyl group, benzocarbazolyl group, benzocarbolinyl group, furanyl group, benzofuranyl group, dibenzofuranyl group, xanthenyl group, spiroxanthenyl group, benzoxane a thenyl group, a thienyl group, a benzothienyl group, a dibenzothienyl group, an oxazolyl group, a benzoxazolyl group, a thiazolyl group, a benzothiazolyl group, an azabenzofluoranthenyl group, and the like.

Specific examples of the arylamino group having 6 to 60 carbon atoms include phenylamino group, diphenylamino group, biphenylylamino group, dibiphenylylamino group, naphthylamino group, dinaphthylamino group and the like.

Specific examples of groups composed of a combination of any two or more selected from an aromatic hydrocarbon group having 6 to 60 carbon atoms, a heteroaromatic group having 3 to 60 carbon atoms, and an arylamino group having 6 to 60 carbon atoms Examples include the structures exemplified below.

Ar is a group composed of a phenyl group, a naphthyl group, an azabenzofluoranthenyl group, a triazinyl group, a fluoranthenyl group, a benzofluoranthenyl group, and a triazinylphenyl group. It is preferable from the viewpoint of characteristics.

By definition, Ar may contain a group represented by formula (A) described below. In this case, the compound of formula (1) may contain two or more azabenzofluoranthenyl groups represented by formula (A). In this case, among a plurality of azabenzofluoranthenyl groups represented by formula (A), any one that satisfies the requirements of formula (A) can be a group represented by formula (A) described later. can. Others that satisfy the requirements of Ar become Ar.

[About n]
In formula (1), n is an integer of 1-5. n can be appropriately determined from the viewpoint of the function or handleability depending on the application such as an electron transport material for an organic electroluminescence device, which will be described later. For example, from this point of view, n is preferably 3 or less, more preferably 2 or less.

[About A]
In formula (1), A is a group represented by formula (A) below.

In formula (A), each X is independently CH or a nitrogen atom. However, the nitrogen atom is only one of X at most. CH is at least one of X; When ^* 1 or ^* 2 below represents the position of the structure in which the pyridine ring is condensed, both of X are C—H.

In formula (A), ^* 1 and ^* 2 each independently represent a hydrogen atom or a condensed ring position. When ^* 1 or ^* 2 represents a condensed ring position, either ^* 1 or ^* 2 represents a structure in which a benzene ring or a pyridine ring is condensed. Hereinafter, the structure represented by formula (A) is also referred to as "the skeleton represented by formula (A)". The “skeleton represented by formula (A)” is a structure in which a benzene ring or a pyridine ring is fused to either ^* 1 or ^* 2 when ^* 1 or ^* 2 represents a fused ring position. include.

In formula (A), the skeleton represented by formula (A) contains one nitrogen atom. That is, when one of X is a nitrogen atom, the ring structure fused with ^* 1 or ^* 2 does not contain a nitrogen atom. Also, when any of X is CH, it contains one nitrogen atom in the ring structure fused with ^* 1 or ^* 2. In other words, when both X are CH, one of the ring structures fused with ^* 1 or ^* 2 is a ring structure containing one nitrogen atom, such as a pyridine ring.

The group represented by formula (A) contains the structure of fluoranthene. Groups of formula (A) may contain ring structures that are fused at ^* 1 or ^* 2. In this specification, a structure containing the ring structure is also referred to as a benzofluoranthene structure. The group represented by formula (A) contains one nitrogen atom in the entire skeleton structure including the ring structure. In this specification, a group having a structure in which one of the carbon atoms in the skeleton structure is replaced with a nitrogen atom is also referred to as an azabenzofluoranthenyl group.

In formula (A), at least one hydrogen atom of the skeleton represented by formula (A) is replaced with Ar. n hydrogen atoms in the skeleton represented by formula (A) are replaced with Ar. The substitution position of Ar in the skeleton represented by formula (A) is not limited.

The skeleton represented by formula (A) (azabenzofluoranthene skeleton) is preferably any one of formulas (A-1) to (A-6) from the viewpoint of ease of synthesis.

Among them, the skeleton represented by formula (A) is more preferably any one of formulas (A-1) to (A-3) from the viewpoint of life characteristics when incorporated into an organic electroluminescent device.

[About substituents]
In formula (A), any hydrogen atom in the skeleton represented by formula (A) may be substituted with a substituent.

Examples of substituents that Ar in formula (1) and the skeleton represented by formula (A) may have include a deuterium atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a formyl group, and a cyano group. , a nitro group, an alkyl group having 1 to 20 carbon atoms which may be branched or cyclic or cyclic in a cage, an alkenyl group having 2 to 20 carbon atoms which may be branched or cyclic, carbon which may be branched or cyclic alkynyl groups of 1 to 20 carbon atoms, alkoxy groups of 1 to 20 carbon atoms, monocyclic or optionally linked aromatic hydrocarbon groups of 6 to 20 carbon atoms, monocyclic or optionally linked 3 to 20 carbon atoms heteroaromatic groups of, P(=O)(Ar') ₂ , C(=O)Ar', B(Ar') ₂ , B(OAr') ₂ , OSO ₂ Ar' and Si(Ar') ₄ is included.

Ar′ each independently represents one or more groups consisting of an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 60 carbon atoms and a heteroaryl group having 3 to 60 carbon atoms. .

The substituents may be one or more in each of Ar and A, and in a plurality of cases they may be the same or different. Also, the substitution position of the substituent is not limited.

Substituents for Ar are not limited, but from the viewpoint of ease of synthesis, phenyl group, naphthyl group, azabenzofluoranthenyl group, triazinyl group, fluoranthenyl group, benzofluoranthenyl group, triazinylphenyl or adamantyl group. In addition, from the viewpoint of ease of synthesis, the substitution position of the substituent in Ar is the 10th or 12th position in the case of formula (A-1), and the 11th position in the case of formula (A-2). preferable.

Substituents in A are not limited, but from the viewpoint of ease of synthesis, phenyl group, naphthyl group, azabenzofluoranthenyl group, triazinyl group, fluoranthenyl group, benzofluoranthenyl group, triazinylphenyl or adamantyl group.

Specific examples of the azabenzofluoranthene compound represented by Formula (1) are shown below. In addition, the azabenzofluoranthene compound in the present invention is not limited to these.

Azabenzofluoranthene compounds can be used, for example, in organic electronic device applications such as organic electroluminescent devices and photoelectric devices.

<Method for Synthesizing Azabenzofluoranthene Compound>
The azabenzofluoranthene compound represented by formula (1) undergoes a coupling reaction represented by the following formula (R1) or (R2) in the presence of a metal catalyst (e.g., palladium compound, nickel compound, copper compound) and a base. It is possible to synthesize by

In formula R1 and formula R2,
Ar, A are synonymous with formula (1);
M represents a metal-containing group;
Y represents a leaving group.
n is an integer of 1-5.

Specific examples of the metal-containing group M include boronic acids represented by B(OR) ₂ , chain or cyclic boronate esters, ZnCl, ZnBr, MgCl, MgBr and MgI. Leaving groups include halogen atoms and trifluoromethanesulfonate (TfO) groups.

Known palladium catalysts and bases applicable to the coupling reaction can be used, such as tetrakis(triphenylphosphine)palladium as the palladium catalyst and potassium phosphate as the base. The coupling reaction can be carried out in a solvent, and the solvent can be a mixed solvent of one or more suitable solvents from the viewpoint of reaction yield, such as a mixed solvent of THF and water.

The product of the coupling reaction can be isolated by appropriately combining general purification treatments such as recrystallization, column chromatography, sublimation purification, and preparative HPLC as necessary. Also, the structure of the obtained product can be confirmed by known analytical methods such as nuclear magnetic resonance (NMR), infrared spectroscopy and mass spectrometry.

<Materials for Organic Electroluminescent Devices>
A material for an organic electroluminescence device according to one aspect of the present invention contains an azabenzofluoranthene compound represented by formula (1). The azabenzofluoranthene compounds described above are expected to exhibit various electrical functionalities when used as materials for functional layers of organic electronic devices. This is because the azabenzofluoranthene compound is expected to exhibit electrical functions due to a plurality of π-conjugated aromatic ring structures, and that the azabenzofluoranthene compound is used as a functional layer material. This is because, in some cases, expression of moderate intermolecular interaction is expected. The moderate expression of the intermolecular interaction is achieved by the fact that the aromatic ring structures are bonded to each other with single bonds, so that the azabenzofluoranthene compound used as the functional material has a relatively bulky molecular structure. can be attributed to The material for an organic electroluminescence device according to one aspect of the present invention may be composed only of the above-described azabenzofluoranthene compound or the azabenzofluoranthene compound as long as the desired characteristics and performance are exhibited. In addition to the compound, it may further contain other components such as dopants. Also, the azabenzofluoranthene compound may be used as a dopant for other functional material compounds.

<Electron transport material for organic electroluminescence device>
An electron-transporting material for an organic electroluminescent device according to one aspect of the present invention contains an azabenzofluoranthene compound represented by formula (1). The azabenzofluoranthene compound described above can be suitably used, for example, as an electron-transporting material for an organic electroluminescence device. The electron-transporting material for an organic electroluminescent device according to one aspect of the present invention may be composed only of the above-described azabenzofluoranthene compound, or may be composed of only the above-described azabenzofluoranthene compound, as long as the desired characteristics and performance are exhibited. In addition to the oranthene compound, it may further contain other components such as dopants.

<Organic electroluminescent device>
Hereinafter, an organic electroluminescence device (hereinafter sometimes simply referred to as an “organic electroluminescence device”) according to one aspect of the present invention will be described.

An organic electroluminescent device according to one aspect of the present invention contains an azabenzofluoranthene compound represented by formula (1). In the organic electroluminescent device, the azabenzofluoranthene compound is contained in the organic electroluminescent device in a state in which the above-described organic electroluminescent device material or organic electroluminescent device electron transport material is applied.

An organic electroluminescent device according to one aspect of the present invention comprises an anode, a cathode, and one or more organic thin film layers including at least a light emitting layer, and at least one of the organic thin film layers contains the above azabenzofluorane. Contains ten compounds. The configuration of the organic electroluminescent element is not limited, but includes, for example, the following configurations (i) to (vi).
(i): anode/light emitting layer/cathode (ii): anode/hole transport layer/light emitting layer/cathode (iii): anode/light emitting layer/electron transport layer/cathode (iv): anode/hole transport layer/ Emissive layer/electron transport layer/cathode (v): anode/hole injection layer/hole transport layer/emissive layer/electron transport layer/electron injection layer/cathode (vi): anode/hole injection layer/hole transport Layer/electron-blocking layer/light-emitting layer/hole-blocking layer/electron-transporting layer/electron-injecting layer/cathode

Although the azabenzofluoranthene compound may be contained in any of the above layers, the group consisting of the light-emitting layer and the layer between the light-emitting layer and the cathode in terms of excellent light-emitting properties of the organic electroluminescent device. It is preferably contained in one or more selected layers. Therefore, in the case of the structures shown in (i) to (vi) above, the azabenzofluoranthene compound may be contained in one or more layers selected from the group consisting of the light-emitting layer, the electron-transporting layer, and the electron-injecting layer. preferable.

Hereinafter, the organic electroluminescence device according to one aspect of the present invention will be described in more detail with reference to FIG. 1, taking the above configuration (v) as an example.

Note that the organic electroluminescent device shown in FIG. 1 has a so-called bottom emission type device configuration, but the organic electroluminescent device according to one aspect of the present invention is not limited to the bottom emission type device configuration. That is, the organic electroluminescent device according to one aspect of the present invention may have other known device configurations such as top emission type.

FIG. 1 is a schematic cross-sectional view showing an example of a lamination structure of an organic electroluminescence device according to one aspect of the present invention. FIG. 2 is a schematic cross-sectional view showing another example of the lamination structure of the organic electroluminescence device according to one aspect of the present invention.

The organic electroluminescent device 100 comprises a substrate 1, an anode 2, a hole injection layer 3, a hole transport layer 4, a light emitting layer 5, an electron transport layer 6, an electron injection layer 7 and a cathode 8 in this order. However, some of these layers may be omitted, or conversely, other layers may be added. For example, a hole-blocking layer may be provided between the light-emitting layer 5 and the electron-transporting layer 6, the hole-injecting layer 3 may be omitted, and the hole-transporting layer 4 may be provided directly on the anode 2. good too.

Further, a single layer having the functions of a plurality of layers, such as an electron injection/transport layer having both the function of an electron injection layer and the function of an electron transport layer in a single layer. It may be a configuration provided instead of. Furthermore, for example, the single-layer hole transport layer 4 and the single-layer electron transport layer 6 may each consist of a plurality of layers.

<Layer containing azabenzofluoranthene compound>
In the structural example shown in FIG. 1, the organic electroluminescence device 100 contains the above azabenzofluoranthene compound in one or more layers selected from the group consisting of the light-emitting layer 5, the electron transport layer 6 and the electron injection layer . In particular, the electron transport layer 6 preferably contains an azabenzofluoranthene compound. In addition, the azabenzofluoranthene compound may be contained in a plurality of layers included in the organic electroluminescence device.

An organic electroluminescence device 100 in which the electron transport layer 6 contains an azabenzofluoranthene compound will be described below.

[Substrate 1]
The substrate 1 is not particularly limited, and substrates that can be used in ordinary organic electroluminescence devices can be used. For example, a glass plate, a quartz plate, a plastic plate and the like can be used.

[Anode 2]
An anode 2 is provided on the substrate 1 (on the hole injection layer 3 side).

As the material for the anode, compounds that can be used in ordinary organic electroluminescence devices can be used. Examples include metals, alloys, electrically conductive compounds, and mixtures thereof with a large work function (eg, 4 eV or more). Specific examples of materials for the anode include metals such as Au; conductive transparent materials such as CuI, indium tin oxide (ITO), SnO ₂ and ZnO.

[Hole injection layer 3, hole transport layer 4]
A hole injection layer 3 and a hole transport layer 4 are provided in this order from the anode 2 side between the anode 2 and a light emitting layer 5 to be described later.

Materials for the hole injection layer and the hole transport layer have at least one of hole injection, hole transport, and electron barrier properties. Materials for the hole injection layer and the hole transport layer may be either organic or inorganic, and compounds that can be used in ordinary organic electroluminescence devices can be used.

The hole injection layer and the hole transport layer may have a single structure composed of one or more materials, or may have a laminated structure composed of multiple layers having the same composition or different compositions.

The hole transport layer 4 may have a laminated structure of two or more layers. For example, the hole-transporting layer 4 is a laminated type in which a first hole-transporting layer 1051 and a second hole-transporting layer 1052 are provided in this order from the anode 2 side, like the organic electroluminescent element 200 shown in FIG. It may be the hole transport layer 105 . The second hole transport layer 1052 can be used as an electron blocking layer in the configuration (vi) above.

[Light emitting layer 5]
A light-emitting layer 5 is provided between the hole-transporting layer 4 and an electron-transporting layer 6, which will be described later.

As a material for the light-emitting layer, light-emitting materials that can be used in ordinary organic electroluminescent devices can be used. Examples thereof include phosphorescent materials, fluorescent materials, and heat-activated delayed fluorescent materials.

The emissive layer may consist of a single small molecule material or a single polymeric material, but more commonly consists of a host material doped with a guest compound. Emission comes primarily from dopants and can have any color.

Also, the luminescent material is not limited to being contained only in the luminescent layer. For example, the light-emitting material may be contained in a layer (hole-transporting layer 4 or electron-transporting layer 6) adjacent to the light-emitting layer. With such a configuration, the luminous efficiency of the organic electroluminescence device can be further enhanced.

The light-emitting layer may have a single-layer structure composed of one or more materials, or may have a laminated structure composed of a plurality of layers having the same composition or different compositions.

[Electron transport layer 6]
An electron transport layer 6 is provided between the light emitting layer 5 and an electron injection layer 7 which will be described later.

The electron transport layer preferably contains an azabenzofluoranthene compound. In addition to the pyrimidine compound, the electron transport layer may further contain one or more selected from conventionally known electron transport materials.

When the azabenzofluoranthene compound is not contained in the electron-transporting layer but is contained in another layer, one or more selected from conventionally known electron-transporting materials may be used as the electron-transporting material constituting the electron-transporting layer. can be done.

Conventionally known electron-transporting materials include alkali metal complexes, alkaline earth metal complexes, earth metal complexes, and the like. Alkali metal complexes, alkaline earth metal complexes, and earth metal complexes include, for example, 8-hydroxyquinolinatolithium (Liq), bis(8-hydroxyquinolinato)zinc, and bis(8-hydroxyquinolinato)copper. , bis(8-hydroxyquinolinato)manganese, tris(8-hydroxyquinolinato)aluminum, tris(2-methyl-8-hydroxyquinolinato)aluminum, tris(8-hydroxyquinolinato)gallium, bis (10-hydroxybenzo[h]quinolinate) beryllium, bis(10-hydroxybenzo[h]quinolinate)zinc, bis(2-methyl-8-quinolinato)chlorogallium, bis(2-methyl-8-quinolinate)(o -cresolato)gallium, bis(2-methyl-8-quinolinato)-1-naphtholatoaluminum, bis(2-methyl-8-quinolinato)-2-naphtholatogallium, and the like.

The electron-transporting layer may have a single-layer structure composed of one or more materials, or may have a laminated structure composed of multiple layers having the same composition or different compositions.

In the organic electroluminescent device according to this aspect, an electron injection layer may be provided for the purpose of improving electron injection properties and improving device characteristics (e.g., luminous efficiency, low voltage drive, or high durability).

The electron transport layer 6 may have a laminated structure of two or more layers. For example, the electron-transporting layer 6 is a laminated electron-transporting layer provided in the order of the first electron-transporting layer 1071 and the second electron-transporting layer 1072 from the light-emitting layer 5 side, like the organic electroluminescent element 200 shown in FIG. It may be layer 107 . The first electron transport layer 1071 can be used as a hole blocking layer in the configuration (vi) above.

The azabenzofluoranthene compound according to one aspect of the present invention can be used in both or either one of the first electron-transporting layer and the second electron-transporting layer.

[Electron injection layer 7]
An electron injection layer 7 is provided between the electron transport layer 6 and a cathode 8 which will be described later.

As the material for the electron injection layer, compounds that can be used in ordinary organic electroluminescence devices can be used. Examples thereof include organic compounds such as fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, fluorenylidenemethane, anthraquinodimethane, and anthrone.

Materials for the electron injection layer include various oxides and fluorides such as SiO ₂ , AlO, SiN, SiON, AlON, GeO, LiO, LiON, TiO, TiON, TaO, TaON, TaN, LiF, C, and Yb. , nitrides, and oxynitrides. Azabenzofluoranthene compounds according to one aspect of the present invention can also be used.

[Cathode 8]
A cathode 8 is provided on the electron injection layer 7 .

As the material for the cathode, compounds that can be used in ordinary organic electroluminescence devices can be used. Examples include metals with a small work function (hereinafter also referred to as electron-injecting metals), alloys, electrically conductive compounds, and mixtures thereof. Here, a metal with a small work function is, for example, a metal of 4 eV or less.

A mixture of an electron-injecting metal and a second metal that has a higher work function and is more stable, such as magnesium/silver mixture, magnesium/aluminum mixture, magnesium/indium mixture, aluminum/aluminum oxide (Al ₂ O ₃ ) mixtures, lithium/aluminum mixtures, etc. are preferred.

[Method of Forming Each Layer]
Each layer except for the electrodes (anode, cathode) described above is formed by thinning by a known method such as vacuum deposition, spin coating, casting, and LB (Langmuir-Blodgett method). can do. The material for each layer may be used alone, or if necessary, it may be used together with a material such as a binder resin and a solvent.

The thickness of each layer thus formed is not limited and can be appropriately selected depending on the situation, and is usually in the range of 5 nm to 5 μm.

The anode and cathode can be formed by thinning the electrode material by methods such as vapor deposition and sputtering. A pattern may be formed through a mask of a desired shape during vapor deposition or sputtering, or a pattern of a desired shape may be formed by photolithography after forming a thin film by vapor deposition or sputtering.

The film thickness of the anode and cathode is preferably 1 μm or less, more preferably 10 nm or more and 200 nm or less.

The layer containing the azabenzofluoranthene compound may be formed in combination with the conventionally known electron-transporting material. Therefore, for example, an azabenzofluoranthene compound and a conventionally known electron-transporting material may be co-deposited, or a layer of a conventionally known electron-transporting material may be laminated on a layer of the azabenzofluoranthene compound. good.

The organic electroluminescence element may be used as a kind of lamp for illumination or as a light source for exposure, a type of projection device for projecting an image onto a screen or the like, or a type of display for directly viewing still or moving images. You may use it as a device (display).

When the organic electroluminescence element is used as a display device for reproducing moving images, the drive system may be a simple matrix (passive matrix) system or an active matrix system. Further, by using two or more kinds of organic electroluminescent elements having different emission colors, it is possible to produce a full-color display device.

With such a configuration, it is possible to provide an organic electroluminescence device that further exhibits long-life characteristics. This is expected to contribute to the development of image display technology with even longer life. Therefore, according to the embodiment of the present invention, from the viewpoint of disseminating information transmission technology and reducing the burden on the environment caused by waste, it is possible to improve motivation to work, develop industry, and sustain development related to environmental conservation. It is expected to contribute to the achievement of the goals (SDGs).

The present invention is not limited to the above-described embodiments, and various modifications are possible within the scope of the claims. Embodiments obtained by appropriately combining technical means disclosed in different embodiments are also included in the technical scope of the present invention.

EXAMPLES The present invention will be described in more detail below based on examples, but the present invention should not be construed as being limited by these examples.

In the following examples, ¹ H-NMR spectra were measured using Bruker AVANCE III 400 or AVANCE III HD 400 NMR (manufactured by BRUKER).

Further, the luminous properties of the organic electroluminescence elements in the following examples were evaluated by applying a direct current to the fabricated elements at room temperature and using a luminance meter (product name: BM-9, manufactured by Topcon Technohouse).

[Examples of azabenzofluoranthene compounds]
Synthesis Example-1 (synthesis of compound E01)

12-[4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]acenaphtho[1,2-b]quinoline (4.3 g, 9 .4 mmol), 1,2-dibromobenzene (0.54 mL, 4.5 mmol), tris(dibenzylideneacetone)dipalladium(0) (0.13 g, 0.14 mmol) and 2-dicyclohexylphosphino-2′, 4′,6′-triisopropylbiphenyl (0.27 g, 0.56 mmol) was suspended in THF (80 mL). A 2M potassium carbonate aqueous solution (28 mL, 56 mmol) was added to this suspension, and the mixture was stirred at 80° C. for 18 hours. After filtering the reaction solution while it is hot, the obtained solid is washed with water, methanol and hexane. Bis(acenaphtho[1,2-b]quinolin-12-yl)-1,1′:2′,1″-terphenyl was obtained (2.8 g, 85%). The NMR data of compound E01 are shown below.
¹ H-NMR (400 MHz, CDCl ₃ ) δ (ppm): 8.45 (brd, J = 7.4 Hz, 2H), 8.26 (brd, J = 8.7 Hz, 2H), 7.81-7 .72 (m, 8H), 7.67-7.61 (m, 12H), 7.55 (brd, J = 8.1 Hz, 4H), 7.00 (dd, J = 8.1, 7. 4Hz, 2H), 6.92 (brd, J = 7.4Hz, 2H).

Synthesis Example-2 (synthesis of compound E02)

Under an argon atmosphere, 10-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)acenaphtho[1,2-b]quinoline (3.0 g, 7.9 mmol), 1 , 2-dibromobenzene (0.47 mL, 3.9 mmol) and dichlorobis(triphenylphosphine)palladium (0.18 g, 0.26 mmol) were suspended in THF (80 mL). A 2M potassium carbonate aqueous solution (26 mL, 52 mmol) was added to this suspension, and the mixture was stirred at 80° C. for 18 hours. After filtering the reaction solution, water was added to deposit a precipitate. After filtering the precipitate, the solid obtained by washing with water, methanol and hexane was dissolved in chloroform, activated carbon was added, and the mixture was stirred for 30 minutes. The mixture was stirred for 1 minute, and the insoluble matter was removed by celite filtration. After distilling off the low-boiling components from the filtrate under reduced pressure, the obtained solid was dissolved in toluene heated to 120° C., allowed to stand at room temperature, and the precipitated solid was collected by filtration to give 1,2-bis( Acenaphtho[1,2-b]quinolin-10-yl)benzene was obtained (1.0 g, 48%). NMR data for compound E02 are shown below.
¹ H-NMR (400 MHz, CDCl ₃ ) δ (ppm): 8.37 (d, J = 7.0 Hz, 2H), 8.33 (s, 2H), 8.02 (d, J = 8.7 Hz , 2H), 7.98 (d, J = 8.2 Hz, 2H), 7.96 (d, J = 7.0 Hz, 2H), 7.91 (d, J = 8.2 Hz, 2H), 7 .80 (d, J = 2.0 Hz, 2H), 7.76 (dd, J = 8.0, 7.0 Hz, 2H), 7.70-7.67 (m, J = Hz, 2H), 7.66 (dd, J=8.2, 7.0Hz, 2H), 7.59-7.56 (m, 2H), 7.55 (dd, J=8.7, 2.0Hz, 2H) .

Synthesis Example-3 (synthesis of compound E03)

Under an argon atmosphere, 11-(4,4,5,5-tetramethyl-1,3,2-dioxoborolan-2-yl)acephenantrileno[5,4-b]pyridine (9.08 g, 23. 9 mmol), 1,2-dibromobenzene (1.78 g, 7.6 mmol) and tetrakis(triphenylphosphine)palladium (0.97 g, 0.84 mmol) were suspended in THF (80 mL). A 2M potassium carbonate aqueous solution (50 mL, 100 mmol) was added to this suspension, and the mixture was stirred at 80° C. for 13 hours. After adding chloroform and water to this solution, the organic layer was extracted, and the organic layer was washed with saturated brine. After sodium sulfate and activated carbon were added to the organic layer and the mixture was stirred, the mixture was filtered through celite to remove low-boiling fractions under reduced pressure. The obtained solid was purified by column chromatography (hexane:ethyl acetate=100:0 to 50:50), and low-boiling fractions were distilled off. The resulting solid was suspended in toluene (150 mL), heated to 110° C. to dissolve, allowed to cool to room temperature, half the solvent was removed under reduced pressure, and the precipitate was collected by filtration. 1,2-Diacephenanthyleno[5,4-b]pyridine was obtained (932 mg, 21% yield). The NMR data of compound E03 are shown below.
¹ H-NMR (400 MHz, CDCl ₃ ) δ (ppm): 8.58 (d, J = 8.1 Hz, 2H), 8.49 (d, J = 2.0 Hz, 2H), 8.44 (s , 2H), 8.42 (d, J = 8.2 Hz, 2H), 8.06 (d, J = 2.0 Hz, 2H), 8.02 (d, J = 7.9 Hz, 2H), 7 .83 (d, J=7.1 Hz, 2H), 7.69-7.57 (m, 10H).

Synthesis Example-4 (synthesis of compound E77)
10-(4-((3r,5r,7r)-adamantan-1-yl)phenyl)acenaphtho[1,2-b]quinoline

Under an argon atmosphere, 10-chloroacenaphtho[1,2-b]quinoline (0.10 g, 0.35 mmol), 2-(4-((3r,5r,7r)-adamantan-1-yl)phenyl)-5, 5-dimethyl-1,3,2-dioxaborinane (120 g, 0.37 mmol), palladium acetate (2.2 mg, 0.010 mmol) and 2-dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl ( 10 mg, 0.021 mmol) was suspended in THF (20 mL). A 2M potassium carbonate aqueous solution (0.57 mL, 1.2 mmol) was added to this suspension, and the mixture was stirred at 80° C. for 18 hours. After filtering the reaction solution, water and hexane are added to precipitate a precipitate, and the filtered precipitate is washed with water, methanol and hexane. 10-(4-((3r,5r,7r)-adamantane-1 -yl)phenyl)acenaphtho[1,2-b]quinoline was obtained (0.14 g, 84%). NMR data for compound E77 are shown below.
¹ H-NMR (400 Hz, CDCl ₃ ) δ (ppm): 8.58 (s, 1H), 8.45 (d, J = 7.0 Hz, 1H), 8.28 (d, J = 8.6 Hz , 1 H), 8.13 (d, J = 2.1 Hz, 1 H), 8.08 (d, J = 7.0 Hz, 1 H), 8.03 (d, J = 8.1 Hz, 1 H), 8 .00 (dd, J = 8.6, 2.1 Hz, 1 H), 7.97 (d, J = 8.1 Hz, 1 H), 7.82 (dd, J = 8.1, 7.0 Hz, 1 H ), 7.74 (dd, J = 8.1, 7.0 Hz, 1H), 7.74 (d, J = 8.4 Hz, 2H), 7.53 (d, J = 8.4 Hz, 2H) , 2.15 (brs, 3H), 2.01 (d, J=2.6Hz, 6H), 1.82 (m, 6H).

Synthesis Example-5 (synthesis of compound E78)
4-(10-(4-(acenaphtho[1,2-b]quinolin-12-yl)phenyl)anthracen-9-yl)benzonitrile

Under an argon atmosphere, 12-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)acenaphtho[1,2-b]quinoline (0.10 g, 0 .22 mmol), 4-(10-bromoanthracen-9-yl)benzonitrile (87 mg, 0.24 mmol), palladium acetate (1.5 mg, 0.0066 mmol) and 2-dicyclohexylphosphino-2′,4′, 6'-Triisopropylbiphenyl (6.3 mg, 0.013 mmol) was suspended in THF (2 mL). A 2M potassium carbonate aqueous solution (0.36 mL, 0.73 mmol) was added to this suspension, and the mixture was stirred at 80° C. for 18 hours. After filtering the reaction solution, water and hexane are added to deposit a precipitate, and the filtered precipitate is washed with water, methanol and hexane to give 4-(10-(4-(acenaphtho[1,2-b]). ]quinolin-12-yl)phenyl)anthracen-9-yl)benzonitrile (0.12 g, 88%). NMR data for compound E78 are shown below.
¹ H-NMR (400 Hz, CDCl ₃ ) δ (ppm): 8.55 (d, J = 7.0 Hz, 1H), 8.37 (brd, J = 8.4 Hz, 1H), 8.06 (d , J = 8.0Hz, 1H), 8.03-7.92 (m, 6H), 7.89-7.78 (m, 6H), 7.69 (brd, J = 8.0Hz, 2H) , 7.66-7.50 (m, 6H), 7.50-7.43 (m, 2H), 7.25 (d, J=7.0Hz, 1H).

Synthesis Example-6 (synthesis of compound E79)
N-([1,1′-biphenyl]-4-yl)-N-(4-(acenaphtho[1,2-b]quinolin-10-yl)phenyl)-[1,1′-biphenyl]-4 - amines

Under an argon atmosphere, 10-chloroacenaphtho[1,2-b]quinoline (0.10 g, 0.35 mmol), N,N-di(4-biphenylyl)-4-(4,4,5,5-tetramethyl- 1,3,2-dioxaborolan-2-yl)aniline (191 mg, 0.37 mmol), palladium acetate (2.2 mg, 0.010 mmol) and 2-dicyclohexylphosphino-2′,4′,6′-triisopropyl Biphenyl (10 mg, 0.021 mmol) was suspended in THF (2 mL). A 2M potassium carbonate aqueous solution (0.57 mL, 1.2 mmol) was added to this suspension, and the mixture was stirred at 80° C. for 16 hours. After filtering the reaction solution, water and hexane are added to deposit a precipitate, and the filtered precipitate is washed with water, methanol and hexane to obtain N-([1,1'-biphenyl]-4-yl). -N-(4-(acenaphtho[1,2-b]quinolin-10-yl)phenyl)-[1,1′-biphenyl]-4-amine was obtained (0.22 g, 97%). NMR data for compound E79 are shown below.
¹ H-NMR (400 Hz, CDCl ₃ ) δ (ppm): 8.57 (s, 1H), 8.45 (brd, J = 7.0 Hz, 1H), 8.29 (d, J = 8.6 Hz , 1 H), 8.12 (d, J = 2.1 Hz, 1 H), 8.08 (d, J = 7.0 Hz, 1 H), 8.03 (d, J = 8.2 Hz, 1 H), 8 .00 (dd, J = 8.6, 2.1 Hz, 1 H), 7.97 (d, J = 8.2 Hz, 1 H), 7.82 (dd, J = 8.2, 7.0 Hz, 1 H ), 7.74 (dd, J = 8.2, 7.0 Hz, 1 H), 7.71 (brd, J = 8.6 Hz, 2 H), 7.62 (brd, J = 7.4 Hz, 4 H) , 7.56 (brd, J=8.6 Hz, 4H), 7.45 (brd, J=7.4, 7.4 Hz, 4H), 7.33 (brt, J=7.4 Hz, 2H), 7.32 (brd, J=8.6 Hz, 2H), 7.28 (brd, J=8.6 Hz, 4H).

Synthesis Example-7 (synthesis of compound E80)
12-(4′-phenyl-[1,1′:2′,1″-terphenyl]-4-yl)acenaphtho[1,2-b]quinoline

12-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)acenaphtho[1,2-b]quinoline (2.5 g, 5 .4 mmol), (1,1′:3′,1″-terphenyl-6′-yl)trifluoromethanesulfonate (2.2 g, 5.9 mmol), palladium acetate (0.036 g, 0.66 mmol) and 2-dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl (0.15 g, 0.32 mmol) were suspended in THF (270 mL). A 2M potassium carbonate aqueous solution (9.7 mL, 19 mmol) was added to this suspension, and the mixture was stirred at 80° C. for 18 hours. After filtering the reaction solution, water and hexane were added to deposit a precipitate, and the filtered precipitate was washed with water, methanol and hexane. The resulting solid was dissolved in chloroform, activated carbon was added, the mixture was stirred for 30 minutes, and insoluble matter was removed by celite filtration. After distilling off the low-boiling components from the filtrate under reduced pressure, the resulting solid was dissolved in toluene heated to 120° C., and the precipitated solid was collected by filtration at room temperature to give 12-(4′- Phenyl-[1,1′:2′,1″-terphenyl]-4-yl)acenaphtho[1,2-b]quinoline was obtained (1.4 g, 46%). NMR data for compound E80 is shown below.
¹ H-NMR (400 Hz, CDCl ₃ ) δ (ppm): 8.48 (brd, J = 7.1 Hz, 1H), 8.28 (brd, J = 8.3 Hz, 1H), 8.02 (d , J=8.1 Hz, 1 H), 7.89 (d, J=8.3 Hz, 1 H), 7.82 (dd, J=8.1, 7.1 Hz, 1 H), 7.79-7. 67 (m, 7H), 7.54-7.46 (m, 6H), 7.45-7.32 (m, 8H), 6.96 (d, J=7.0Hz, 1H).

Synthesis Example-8 (synthesis of compound E85)

11-Chloroacephenantrileno[5,4-b]pyridine (1.37 g, 4.8 mmol), 4-(4,4,5,5-tetramethyl-1,3,2-dioxoborolane under argon atmosphere -2-yl)-4′-phenyl-1,1′:2′,1″-terphenyl (2.3 g, 5.3 mmol), palladium acetate (61 mg, 0.3 mmol) and 2-dicyclohexylphosphino -2',4',6'-Triisopropylbiphenyl (242 mg, 0.5 mmol) was suspended in THF (45 mL). A 2M potassium carbonate aqueous solution (10 mL, 20 mmol) was added to this suspension, and the mixture was stirred at 80° C. for 17 hours. After adding chloroform and water to this solution, the organic layer was extracted. After sodium sulfate and activated charcoal were added to the organic layer and the mixture was stirred, it was filtered through celite. After removing low-boiling fractions under reduced pressure, water, methanol and hexane were added and collected by filtration. 11-(4′-Phenyl-1,1′:2′,1″-terphenyl-4-yl)acephenantrileno[5,4-b] was obtained by repeatedly recrystallizing the filtrate from xylene. ] gave pyridine (1.1 g, 41%). NMR data for compound E85 are shown below.
¹ H-NMR (400 MHz, CDCl ₃ ) δ (ppm): 8.86 (d, J = 2.1 Hz, 1H), 8.72 (d, J = 8.2 Hz, 1H), 8.64 (s , 1 H), 8.59 (d, J = 8.1 Hz, 1 H), 8.37 (d, J = 2.1 Hz, 1 H), 8.17 (brd, J = 8.4 Hz, 1 H), 8 .07 (d, J = 7.0 Hz, 1 H), 7.85 (dd, J = 8.2, 8.1 Hz, 1 H), 7.77 (ddd, J = 8.2, 7.0, 1 .4Hz, 1H), 7.72-7.68 (m, 5H), 7.64 (brd, J = 8.4Hz, 2H), 7.60 (brd, J = 8.5Hz, 1H), 7 .50-7.47 (m, 2H), 7.40-7.37 (m, 1H). 7.37 (brd, J=8.4Hz, 2H), 7.31-7.27 (m, 5H).

Synthesis Example-9 (synthesis of compound E18)

11-Chloroacephenantrileno[5,4-b]pyridine (2.20 g, 7.6 mmol), 2-(4-((3r,5r,7r)-adamantan-1-yl)phenyl under argon atmosphere )-5,5-dimethyl-1,3,2-dioxaborinane (2.7 g, 8.4 mmol), palladium acetate (86 mg, 0.4 mmol) and 2-dicyclohexylphosphino-2′,4′,6′- Triisopropylbiphenyl (369 mg, 0.8 mmol) was suspended in THF (65 mL). A 5M aqueous solution of sodium hydroxide (6 mL, 30 mmol) was added to this suspension, and the mixture was stirred at 80° C. for 17 hours. After allowing to cool to room temperature, water, methanol and hexane were added and the precipitate was collected by filtration. The filtered product was suspended in toluene (300 mL), heated to 110° C., added with activated charcoal, stirred, and then filtered through celite. By distilling off the low-boiling fraction to half, filtering off the precipitated solid, and repeating recrystallization with toluene (100 mL), 11-(4-((3r,5r,7r)-adamantane-1) was obtained. -yl)phenyl)acephenantrileno[5,4-b]pyridine was obtained (2.2 g, 63%). NMR data for compound E18 are shown below.
¹ H-NMR (400 MHz, CDCl ₃ ) δ (ppm): 8.86 (d, J = 2.1 Hz, 1H), 8.72 (d, J = 8.0 Hz, 1H), 8.62 (s , 1 H), 8.58 (d, J = 8.2 Hz, 1 H), 8.36 (d, J = 2.0 Hz, 1 H), 8.16 (d, J = 7.3 Hz, 1 H), 8 .08 (d, J = 7.1 Hz, 1 H), 7.84 (dd, J = 8.1, 7.2 Hz, 1 H), 7.77 (ddd, J = 8.3, 7.0, 1 .3Hz, 1H), 7.70 (brd, J = 8.5Hz, 2H), 7.71-7, 67 (m, 1H), 7.54 (brd, J = 8.5Hz, 2H), 2 .15 (brs, 3H), 2.00 (d, J=2.7Hz, 6H), 1.85-1.78 (m, 6H).

Synthesis Example-10 (synthesis of compound E86)

10-chloroacenaphtho[1,2-b]quinoline (113 mg, 0.4 mmol), diphenylamine (86 mg, 0.5 mmol), palladium acetate (4.8 mg, 21 μmol), 2-dicyclohexylphosphino-2 under argon atmosphere. ',4',6'-Triisopropylbiphenyl (18 mg, 38 μmol) and sodium tert-butoxide (136 mg, 1.4 mmol) were dissolved in toluene (0.8 mL) and stirred at 110° C. for 16 hours. After adding chloroform and water to this solution, the organic layer was extracted, sodium sulfate and activated charcoal were added to the organic layer, the mixture was stirred, filtered through celite, and low-boiling fractions were removed under reduced pressure. The resulting solid was purified by column chromatography (hexane:ethyl acetate=100:0-90:10) to give 10-(diphenylamino)acenaphtho[1,2-b]quinoline (124 mg, yield: rate 70%). NMR data for compound E86 are shown below.
¹ H-NMR (400 MHz, CDCl ₃ ) δ (ppm): 8.38 (d, J = 6.6 Hz, 1 H), 8.28 (s, 1 H), 8.07 (d, J = 9.0 Hz , 1 H), 7.99 (d, J = 7.9 Hz, 1 H), 7.96 (d, J = 6.9 Hz, 1 H), 7.94 (d, J = 8.0 Hz, 1 H), 7 .79 (dd, J = 8.2, 7.0 Hz, 1 H), 7.69 (dd, J = 8.3, 6.9 Hz, 1 H), 7.51 (dd, J = 9.0, 2 .6Hz, 1H), 7.46 (d, J=2.6Hz, 1H), 7.32 (dd, J=7.4, 7.3Hz, 4H), 7.20 (brd, J=7. 4Hz, 4H), 7.10 (brt, J = 7.3Hz, 2H).

Synthesis Example-11 (synthesis of compound E87)

8,10-dibromoacenaphtho[1,2-b]quinoline (102 mg, 0.25 mmol), 4-biphenylboronic acid (110 mg, 0.56 mol) and tetrakis(triphenylphosphine)palladium (30) under an argon atmosphere. .5 mg, 26 μmol) was suspended in THF (2.5 mL). A 2M potassium carbonate aqueous solution (0.8 mL, 1.6 mmol) was added to this suspension, and the mixture was stirred at 80° C. for 9 hours. After allowing to cool to room temperature, water and methanol were added, and the precipitate was collected by filtration. The filtered product was suspended in toluene (20 mL), heated to 110° C., added with activated charcoal, stirred, and then filtered through celite. Low-boiling components were distilled off, the precipitate was collected by filtration, and recrystallization from toluene (5 mL) was repeated to obtain 8,10-di([1,1′-biphenyl]-4-yl)acenaphtho[1]. ,2-b]quinoline was obtained (25 mg, 18% yield). NMR data for compound E87 are shown below.
¹ H-NMR (400 MHz, CDCl ₃ ) δ (ppm): 8.65 (s, 1H), 8.32 (d, J = 6.5 Hz, 1H), 8.19 (d, J = 2.0 Hz , 1 H), 8.15 (d, J = 2.1 Hz, 1 H), 8.10 (d, J = 7.1 Hz, 1 H), 8.08 (brd, J = 8.5 Hz, 2 H), 8 .00 (d, J = 7.9 Hz, 1 H), 7.97 (d, J = 8.1 Hz, 1 H), 7.92 (brd, J = 8.5 Hz, 2 H), 7.83 (brd, J = 8.5Hz, 2H), 7.80-7.73 (m, 6H), 7.70 (brd, J = 8.4Hz, 2H), 7.54-7.48 (m, 4H), 7.43-7.37 (m, 2H).

Synthesis Example-12 (synthesis of compound E88)

12-(4-chlorophenyl)acenaphtho[1,2-b]quinoline (2.1 g, 5.9 mmol), 2-(4-((3r,5r,7r)-adamantan-1-yl) under argon atmosphere phenyl)-5,5-dimethyl-1,3,2-dioxaborinane (2.0 g, 6.2 mmol), palladium acetate (0.040 g, 0.18 mmol) and 2-dicyclohexylphosphino-2′,4′, 6′-Triisopropylbiphenyl (0.17 g, 0.35 mmol) was suspended in THF (60 mL). A 2M potassium carbonate aqueous solution (9.7 mL, 19 mmol) was added to this suspension, and the mixture was stirred at 80° C. for 18 hours. After filtering the reaction solution, water and hexane were added to deposit a precipitate, and the filtered precipitate was washed with water, methanol and hexane. The obtained solid is dissolved in toluene heated to 120° C., and the precipitated solid is collected by filtration after standing at room temperature to obtain 12-(4′-((3r, 5r, 7r)-adamantane-1- yl)-[1,1′-biphenyl]-4-yl)acenaphtho[1,2-b]quinoline was obtained (1.4 g, 46%). NMR data for compound E88 are shown below.
¹ H-NMR (400 Hz, CDCl ₃ ) δ (ppm): 8.49 (d, J = 7.0 Hz, 1H), 8.30 (brd, J = 8.4 Hz, 1H), 8.00 (d , J = 8.2Hz, 1H), 7.91 (brd, 8.2Hz, 2H), 7.85 (d, J = 8.2Hz, 1H), 7.83-7.70 (m, 3H) , 7.76 (brd, J=8.2 Hz, 2H), 7.62 (brd, J=8.2 Hz, 2H), 7.55 (brd, J=8.2 Hz, 2H), 7.49 ( ddd, J = 8.4, 7.0, 1.3 Hz, 1H), 7.41 (dd, J = 8.2, 7.0 Hz, 1H), 7.00 (d, J = 7.0 Hz, 1H), 2.16 (brs, 3H), 2.01 (brs, 6H), 1.88-1.88 (m, 6H).

Synthesis Example-13 (synthesis of compound E89)

A DMF suspension of 3-bromofluoreno[9,1-gh]quinoline (2.0 g, 6.0 mmol) and copper (2.2 g, 35 mmol) was stirred at 110° C. for 16 hours. Aqueous ammonia was added to the obtained suspension, and the solid obtained by filtering was washed with water, methanol and hexane. After extracting the solid with hot toluene and filtering, the low-boiling components were distilled off under reduced pressure, further dissolved in hot toluene, and allowed to stand at room temperature to give 3,3′-bifluoreno[9,1-gh]. Quinoline was obtained (0.51 g, 33%). NMR data for compound E89 are shown below.
¹ H-NMR (400 Hz, CDCl ₃ ) δ (ppm): 8.17 (s, 2H), 8.16 (d, J = 7.2 Hz, 2H), 8.09 (dd, J = 8.0 , 1.8 Hz, 2H), 8.07 (brd, 7.3 Hz, 2H), 8.03 (brd, J = 7.3 Hz, 2H), 7.85 (dd, J = 4.3, 1. 8Hz, 2H), 7.75 (d, J = 7.2Hz, 2H), 7.51 (ddd, J = 7.3, 7.3, 1.3Hz, 2H), 7.46 (ddd, J = 7.3, 7.3, 1.3 Hz, 2H), 7.03 (dd, J = 8.0, 4.3 Hz, 2H).

Synthesis Reference Example -1
10-chloroacenaphtho[1,2-b]quinoline

1-Acenaphthenone (3.7 g, 22 mmol) was dissolved in DMF (18 mL) in a pressure vessel, and 2-amino-5-chlorobenzaldehyde (3.5 g, 22 mmol) and chlorotrimethylsilane (12 mL, 96 mmol) were added. Stir at 100° C. for 24 hours. The reaction solution was filtered at room temperature, and the obtained solid was washed with DMF, methanol and hexane to obtain 10-chloroacenaphtho[1,2-b]quinoline (4.5 g, 71%). NMR data of the obtained compound are shown below.
¹ H-NMR (400 Hz, CDCl ₃ ) δ (ppm): 9.60 (d, J = 7.0 Hz, 1H), 9.01 (d, J = 8.9 Hz, 1H), 8.94 (s , 1 H), 8.30 (d, J = 7.0 Hz, 1 H), 8.29 (d, J = 8.1 Hz, 1 H), 8.15 (d, J = 8.2 Hz, 1 H), 8 .06 (d, J = 2.1 Hz, 1 H), 7.97 (dd, J = 8.1, 7.0 Hz, 1 H), 7.87 (dd, J = 8.1, 7.0 Hz, 1 H ), 7.83 (dd, J=8.9, 2.1 Hz, 1 H).

Synthesis reference example-2
10-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)acenaphtho[1,2-b]quinoline

Under an argon atmosphere, 10-chloroacenaphtho[1,2-b]quinoline (3.0 g, 10 mmol), bispinacolato diboron (3.2 g, 13 mmol), palladium acetate (0.070 g, 0.31 mmol), 2- Dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl (0.30 g, 0.62 mmol) and potassium acetate (3.7 g, 37 mmol) were suspended in THF (100 mL) at 80° C. Stirred for 16 hours. After extraction with chloroform, sodium sulfate and activated carbon were added to the extract and stirred for 30 minutes. After removing insoluble matter by celite filtration, the solid obtained by distilling off the low-boiling components from the obtained filtrate under reduced pressure was washed with methanol to obtain 10-(4,4,5,5-tetramethyl -1,3,2-dioxaborolan-2-yl)acenaphtho[1,2-b]quinoline was obtained (3.1 g, 79%). NMR data of the obtained compound are shown below.
¹ H-NMR (400 Hz, CDCl ₃ ) δ (ppm): 8.55 (s, 1H), 8.46 (brd, J=7.0 Hz, 1H), 8.45 (brs, 1H), 8. 22 (d, J=8.4Hz, 1H), 8.10 (dd, J=8.4, 1.3Hz, 1H), 8.07 (brd, J=7.0Hz, 1H), 8.04 (brd, J = 8.3 Hz, 1H), 7.97 (brd, J = 8.1 Hz, 1H), 7.81 (dd, J = 8.1, 7.0 Hz, 1H), 7.74 ( dd, J=8.3, 7.0 Hz, 1H), 1.42(s, 12H).

Synthetic Reference Example-3
12-(4-chlorophenyl)acenaphtho[1,2-b]quinoline

1-Acenaphthenone (3.7 g, 22 mmol) was dissolved in DMF (22 mL) in a pressure vessel, and (2-aminophenyl)(4-chlorophenyl)methanone (5.0 g, 22 mmol) and chlorotrimethylsilane (12 mL, 95 mmol) were dissolved. ) was added and stirred at 100° C. for 24 hours. The reaction solution was filtered at room temperature, and the obtained solid was washed with DMF, methanol and hexane to obtain 12-(4-chlorophenyl)acenaphtho (6.9 g, 86%). NMR data of the obtained compound are shown below.
¹ H-NMR (400 Hz, CDCl ₃ ) δ (ppm): 9.82 (d, J = 7.4 Hz, 1H), 9.26 (d, J = 8.6 Hz, 1H), 8.29 (J = 8.2Hz, 1H), 8.07 (d, J = 8.2Hz, 1H), 8.04-7.97 (m, 2H), 7.81-7.70 (m, 4H), 7 .62-7.52 (m, 3H), 7.11 (d, J=7.4Hz, 1H).

Synthesis Reference Example-4
12-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)acenaphtho[1,2-b]quinoline

12-(4-chlorophenyl)acenaphtho (4.5 g, 12 mmol), bispinacolato diboron (3.8 g, 15 mmol), palladium acetate (0.084 g, 0.37 mmol), 2-dicyclohexylphosphino under argon atmosphere. -2′,4′,6′-triisopropylbiphenyl (0.35 g, 0.74 mmol) and potassium acetate (4.4 g, 45 mmol) were suspended in THF (125 mL) and stirred at 80° C. for 16 hours. bottom. After extraction with chloroform, sodium sulfate and activated carbon were added to the extract and stirred for 30 minutes. After removing insoluble matter by celite filtration, the solid obtained by distilling off the low-boiling components from the obtained filtrate under reduced pressure was washed with methanol to give 12-(4-(4,4,5,5 -tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)acenaphtho[1,2-b]quinoline (4.5 g, 80%). NMR data of the obtained compound are shown below.
¹ H-NMR (400 Hz, CDCl ₃ ) δ (ppm): 8.48 (d, J = 7.2 Hz, 1H), 8.28 (brd, J = 8.3 Hz, 1H), 8.11 (d , J=8.1 Hz, 2H), 8.00 (brd, J=8.1 Hz, 1H), 7.85 (brd, J=8.1 Hz, 1H), 7.81 (dd, J=8. 1, 7.2Hz, 1H), 7.63 (ddd, J = 8.3, 7.0, 1.5Hz, 1H), 7.63 (dd, J = 8.3, 1.3Hz, 1H) , 7.57 (brd, J=8.1 Hz, 2H), 7.44 (ddd, J=8.3, 7.0, 1.3 Hz, 1H), 7.41 (dd, J=8.1 , 7.0 Hz, 1 H), 6.93 (brd, J=7.0 Hz, 1 H), 1.45 (s, 12 H).

Synthesis Reference Example-5
3-bromo-5-chloro-2-(phenanthren-9-yl)pyridine

Under an argon atmosphere, 9-phenanthreneboronic acid (11 g, 48 mmol), 2,3-dibromo-5-chloropyridine (13 g, 48 mmol) and tetrakis(triphenylphosphine)palladium (1.7 g, 1.4 mmol) were added to toluene. (160 mL). A 2M potassium carbonate aqueous solution (50 mL, 100 mmol) was added to this suspension, and the mixture was stirred at 85° C. for 17 hours. After cooling to room temperature, chloroform and water were added to the solution, the organic layer was extracted, and the organic layer was washed with saturated brine. After sodium sulfate was added to the organic layer and the mixture was stirred, it was filtered through celite to remove low-boiling fractions under reduced pressure. The resulting solid was purified by column chromatography (hexane:chloroform = 100:0 to 55:45), and the low-boiling components were distilled off to give 3-bromo-5-chloro-2-(phenanthrene-9- yl)pyridine was obtained (15 g, 87% yield). NMR data of the obtained compound are shown below.
¹ H-NMR (400 MHz, CDCl ₃ ) δ (ppm): 8.79 (d, J = 8.3 Hz, 1H), 8.75 (d, J = 8.4 Hz, 1H), 8.71 (d , J=2.2 Hz, 1 H), 8.12 (d, J=2.2 Hz, 1 H), 7.93 (dd, J=7.9, 1.4 Hz, 1 H), 7.76 (s, 1H), 7.72 (ddd, J = 8.4, 7.0, 1.4Hz, 1H), 7.69 (ddd, J = 8.3, 7.0, 1.4Hz, 1H), 7 .64 (ddd, J=8.0, 7.1, 1.2 Hz, 1H), 7.54 (ddd, J=8.2, 7.0, 1.2 Hz, 1H), 7.43 (ddd , J=8.2, 0.9 Hz, 1 H).

Synthesis Reference Example-6
11-chloroacephenantrileno[5,4-b]pyridine

Under an argon atmosphere, 3-bromo-5-chloro-2-(phenanthren-9-yl)pyridine (9.08 g, 23.9 mmol), 1,2-dibromobenzene (10.3 g, 27.9 mmol), tris (Dibenzylideneacetone)dipalladium (2.57 g, 2.8 mmol), tricyclohexylphosphine (3.35 g, 12.0 mmol) were suspended in xylene (140 mL). Diazabicycloundecene (18.9 g, 117 mmol) was added to this suspension and stirred at 150° C. for 24 hours. After allowing to cool to room temperature, the solvent was removed under reduced pressure, water and methanol were added, and the precipitate was collected by filtration. The filtered product was suspended in xylene (200 mL), heated to 130° C., added with activated charcoal, stirred, and then filtered through celite. After removing the solvent under reduced pressure until half of the solvent was removed, the mixture was allowed to cool to room temperature, and the precipitate was collected by filtration to obtain 11-chloroacephenanetrileno[5,4-b]pyridine (3.9 g, yield 49%). NMR data of the obtained compound are shown below.
¹ H-NMR (400 MHz, CDCl ₃ ) δ (ppm): 8.71 (d, J = 8.3 Hz, 1H), 8.60 (d, J = 8.3 Hz, 1H), 8.60 (s , 1 H), 8.57 (d, J = 2.2 Hz, 1 H), 8.15 (brd, J = 8.1 Hz, 1 H), 8.15 (d, J = 2.2 Hz, 1 H), 8 .02 (d, J = 7.1 Hz, 1 H), 7.84 (dd, J = 8.2, 7.2 Hz, 1 H), 7.78 (ddd, J = 8.1, 6.9, 1 .4 Hz, 1 H), 7.70 (ddd, J=7.9, 6.8, 1.3 Hz, 1 H).

Synthesis reference example-7
11-(4,4,5,5-tetramethyl-1,3,2-dioxoborolan-2-yl)acephenantrileno[5,4-b]pyridine

Under an argon atmosphere, 11-chloroacephenantrileno[5,4-b]pyridine (10.1 g, 35.2 mmol), bis(pinacolato)diboron (9.36 g, 36.9 mmol), palladium acetate ( 0.41 g, 1.8 mmol), 2-dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl (1.68 g, 3.5 mmol) and potassium acetate (12.7 g, 129 mmol) in THF (170 mL). ) and stirred at 80° C. for 14.5 hours. After allowing to cool to room temperature, chloroform and water were added to the reaction mixture, the organic layer was extracted, and the organic layer was washed with saturated brine. After adding sodium sulfate and activated carbon to the organic layer and stirring, 11-(4,4,5,5-tetramethyl-1,3,2-dioxoborolane) was obtained by filtering through celite and removing low-boiling fractions under reduced pressure. -2-yl)acephenantrileno[5,4-b]pyridine was obtained (17.9 g, crude yield quant.). This was used in the next reaction without purification. NMR data of the obtained compound are shown below.
¹ H-NMR (400 MHz, CDCl ₃ ) δ (ppm): 9.00 (d, J = 1.5 Hz, 1H), 8.72 (d, J = 8.1 Hz, 1H), 8.70 (s , 1H), 8.58 (d, J = 1.5Hz, 1H), 8.56 (d, J = 8.2Hz, 1H), 8.17 (dd, J = 8.3, 1.2Hz, 1H), 8.05 (d, J = 6.8Hz, 1H), 7.83 (dd, J = 8.2, 7.2Hz, 1H), 7.77 (ddd, J = 8.0, 7 .0, 1.4 Hz, 1 H), 7.69 (ddd, J = 7.9, 6.8, 1.2 Hz, 1 H), 1.43 (s, 12 H).

Synthesis Reference Example-8
8,10-dibromoacenaphtho[1,2-b]quinoline

1-Acenaphthenone (3.0 g, 18 mmol) was dissolved in DMF (18 mL) in a pressure vessel, and 2-amino-3,5-dibromobenzaldehyde (5.0 g, 18 mmol) and chlorotrimethylsilane (9.9 mL, 78 mmol) were dissolved. ) was added and stirred at 100° C. for 24 hours. The reaction solution was filtered at room temperature, and the resulting solid was washed with DMF, methanol and hexane, and purified by column chromatography (CHCl ₃ :Hex=1:1) to give 8,10-dibromoacena. Phtho[1,2-b]quinoline was obtained (0.29 g, 4%). NMR data of the obtained compound are shown below.
¹ H-NMR (400 Hz, CDCl ₃ ) δ (ppm): 8.53 (d, J = 7.1 Hz, 1H), 8.40 (d, J = 1.2 Hz, 1H), 8.15 (d , J = 2.2 Hz, 1 H), 8.09 (d, J = 7.1 Hz, 1 H), 8.06 (d, J = 8.1 Hz, 1 H), 8.05 (brs, 1 H), 8 .01 (d, J = 8.1 Hz, 1 H), 7.83 (dd, J = 8.1, 7.1 Hz, 1 H), 7.76 (dd, J = 8.1, 7.1 Hz, 1 H ).

Synthesis Reference Example-9
Fluoreno[9,1-gh]quinoline

To 3-aminofluoranthene (10 g, 47 mmol) was added glycerin (8.5 mL, 92 mmol), iron sulfate heptahydrate (0.70 g, 0.46 mmol), nitrobenzene (3.0 mL, 29 mmol), boric acid (2. 8 g, 45 mmol) and sulfuric acid (6.6 mL, 120 mmol) were added and stirred at 120° C. for 72 hours. After quenching with aqueous ammonia, the solution extracted with chloroform was filtered through a silica pad. The solid obtained by distilling off the low-boiling components from the filtrate under reduced pressure was washed with methanol and hexane to obtain fluoreno[9,1-gh]quinoline (5.6 g, 47%). NMR data of the obtained compound are shown below.
¹ H-NMR (400 Hz, CDCl ₃ ) δ (ppm): 9.02 (dd, J = 4.5, 1.7 Hz, 1H), 8.89 (d, J = 8.2 Hz, 1H), 8 .34 (dd, J = 8.1, 1.7 Hz, 1 H), 8.17 (s, 1 H), 8.08 (d. J = 7.2 Hz, 1 H), 8.01 (brd, J = 7.0Hz, 1H), 7.94 (brd, J = 7.0Hz, 1H), 7.84 (dd, J = 8.2, 7.2Hz, 1H), 7.51 (dd, J = 8 .1, 4.5Hz, 1H), 7.49-7.38 (m, 2H).

Synthesis Reference Example-10
3-bromofluoreno[9,1-gh]quinoline

Under an argon atmosphere, a toluene solution of fluoreno[9,1-gh]quinoline (5.0 g, 20 mmol), palladium acetate (0.26 g, 1.1 mmol) and N-bromosuccinimide (3.9 g, 22 mmol) was heated at 80°C. and stirred for 16 hours. The precipitate formed by adding hexane to the resulting solution was collected by filtration and washed with methanol and hexane to obtain 3-bromofluoreno[9,1-gh]quinoline (5.7 g, 85% ). NMR data of the obtained compound are shown below.
¹ H-NMR (400 Hz, CDCl ₃ ) δ (ppm): 9.14 (dd, J = 4.4, 1.8 Hz, 1H), 8.34 (dd, J = 8.0, 1.8 Hz, 1H), 8.21 (s, 1H), 8.13 (d, J = 7.6Hz, 1H), 7.99 (m, 1H), 7.92 (m, 1H), 7.86 (d , J=7.6 Hz, 1 H), 7.61 (dd, J=8.0, 4.4 Hz, 1 H), 7.49-7.41 (m, 2 H).

[Examples of organic electroluminescence devices]
Structural formulas and abbreviations of compounds used for production and performance evaluation of organic electroluminescence devices are shown below.

Device example-1 (see Fig. 2)
(Preparation of substrate 101 and anode 102)
As a substrate having an anode on its surface, a glass substrate with an ITO transparent electrode, in which an indium-tin oxide (ITO) film (thickness: 110 nm) with a width of 2 mm was patterned in stripes, was prepared. Then, after washing the substrate with isopropyl alcohol, the surface was treated by ozone ultraviolet washing.

(Preparation for vacuum deposition)
Each layer was vacuum-deposited on the surface-treated substrate after cleaning by a vacuum deposition method to laminate each layer.

First, the glass substrate was introduced into a vacuum deposition tank, and the pressure was reduced to 1.0×10 ⁻⁴ Pa. Then, each layer was produced in the following order according to the film forming conditions of each layer.

(Preparation of hole injection layer 103)
A hole injection layer 103 was produced by depositing a 10 nm film of HTL purified by sublimation and NDP-9 at a ratio of 99:1 (mass ratio). The deposition rate was 0.15 nm/sec.

(Preparation of first hole transport layer 1051)
A first hole transport layer 1051 was produced by forming a film of HTL purified by sublimation to a thickness of 85 nm at a rate of 0.15 nm/sec.

(Preparation of second hole transport layer 1052)
Sublimation-purified EBL-1 was deposited at a rate of 0.15 nm/second to a thickness of 5 nm to form a second hole transport layer 1052 .

(Production of light-emitting layer 106)
Sublimation-purified BH-1 and BD-1 were deposited at a ratio of 95:5 (mass ratio) to form a film having a thickness of 20 nm to prepare a light-emitting layer 106 . The deposition rate was 0.18 nm/sec.

(Preparation of first electron transport layer 1071)
Sublimation-purified HBL-1 was deposited at a rate of 0.05 nm/second to a thickness of 6 nm to prepare a first electron transport layer 1071 .

(Preparation of second electron transport layer 1072)
Compound E01 and Liq were deposited at a ratio of 50:50 (mass ratio) to a thickness of 25 nm to prepare a second electron transport layer 1072 . The deposition rate was 0.15 nm/sec.

(Preparation of cathode 109)
Finally, a metal mask was placed perpendicular to the ITO stripes on the substrate, and a cathode 108 was formed. The cathode was formed by depositing ytterbium, silver/magnesium (mass ratio 9/1), and silver in this order to thicknesses of 2 nm, 12 nm, and 90 nm, respectively, to form a three-layer structure. The deposition rate of ytterbium was 0.02 nm/second, the deposition rate of silver/magnesium was 0.5 nm/second, and the deposition rate of silver was 0.2 nm/second.

As described above, an organic electroluminescence device 200 having a light emitting area of 4 mm ² as shown in FIG. 2 was produced. The film thickness of each of the formed layers and the cathode was measured with a stylus film thickness meter (DEKTAK, manufactured by Bruker).

Furthermore, this device was sealed in a nitrogen atmosphere glove box with an oxygen and water concentration of 1 ppm or less. Sealing was performed by using a bisphenol F type epoxy resin (manufactured by Nagase ChemteX Corporation) between the glass sealing cap and the film formation substrate (element).

Device example-2
An organic electroluminescence device was produced in the same manner as in Device Example-1, except that Compound E02 was used instead of Compound E01.

Device Example-3
An organic electroluminescence device was produced in the same manner as in Device Example-1, except that Compound E03 was used instead of Compound E01.

Device Example-4
An organic electroluminescence device was produced in the same manner as in Device Example-1, except that Compound E18 was used instead of Compound E01.

Device Example-5
An organic electroluminescence device was produced in the same manner as in Device Example-1, except that Compound E80 was used instead of Compound E01.

Device Example-6
An organic electroluminescence device was produced in the same manner as in Device Example-1, except that Compound E85 was used instead of Compound E01.

Device comparison example-1
An organic electroluminescence device was produced in the same manner as in Device Example-1, except that ETL-1 was used in place of Compound E01.

[evaluation]
A direct current was applied to the organic electroluminescence devices produced in Device Examples-1 to Device Examples-6 and Device Comparative Example-1, and the current value was maintained at a front luminance of 1000 cd/m ² continuously. driven. The time required for the luminance at that time to decrease from 1000 cd/m ² to 950 cd/m ² was measured as a life characteristic. Note that the life characteristics are relative values with the result of the device of Device Comparative Example-1 as a reference value (100). Table 1 shows the measurement results obtained.

From Table 1, it is clear that compounds E01, E02, E03, E18, E80 and E85 all enhance the lifetime characteristics of organic electroluminescent devices compared to triazine compounds known as electron transport materials.

INDUSTRIAL APPLICABILITY The present invention can be used for organic electroluminescence devices exhibiting long-life characteristics. In addition, the present invention can be suitably used as an electron-transporting material for improving the lifetime characteristics of organic transistors other than organic electroluminescent devices.

100, 200 organic electroluminescent device 1, 101 substrate 2, 102 anode 3, 103 hole injection layer 4, 105 hole transport layer 5, 106 light emitting layer 6, 107 electron transport layer 7 electron injection layer 8, 108 cathode 1051 th One hole transport layer 1052 Second hole transport layer 1071 First electron transport layer 1072 Second electron transport layer

Claims (9)

Azabenzofluoranthene compound represented by formula (1):
(In formula (1),
Each Ar is independently an optionally substituted monocyclic ring, an optionally condensed ring, or a structure in which these are linked (i) an aromatic having 6 to 60 carbon atoms group hydrocarbon group,
(ii) a heteroaromatic group having 3 to 60 carbon atoms;
(iii) an arylamino group having 6 to 60 carbon atoms or (iv) a group composed of a combination of any two or more selected from the above (i) to (iii);
n represents an integer from 1 to 5;
A is a group represented by formula (A);
In formula (A),
each X is independently C—H or a nitrogen atom;
^* 1 and ^* 2 each independently represent a hydrogen atom or a condensed ring position, and when ^* 1 or ^* 2 represents a condensed ring position, either ^* 1 or ^* 2 has a benzene ring or a pyridine ring. represents a fused structure;
containing one nitrogen atom in the skeleton represented by formula (A);
at least one hydrogen atom of the skeleton represented by formula (A) is substituted with said Ar;
Any hydrogen atom of the skeleton represented by formula (A) may be substituted. ) The azabenzofluoranthene compound according to claim 1, wherein the skeleton represented by the formula (A) is any one of the following formulas (A-1) to (A-6).
The azabenzofluoranthene compound according to claim 2, wherein the skeleton represented by formula (A) is any one of formulas (A-1) to (A-3). Each of the Ars is independently a monocyclic ring that may be linked, a condensed ring that may be linked, or a structure in which these are linked, optionally substituted (i) having 6 to 60 carbon atoms an aromatic hydrocarbon group,
(ii) a heteroaromatic group having 3 to 60 carbon atoms, composed of atoms selected from the group consisting of hydrogen atoms, carbon atoms, nitrogen atoms, oxygen atoms, and sulfur atoms, or
4. The azabenzofluoranthene compound according to any one of claims 1 to 3, wherein (iii) a group composed of any combination of two or more selected from (i) and (ii). The substituents of Ar and A are deuterium atom, fluorine atom, chlorine atom, bromine atom, iodine atom, formyl group, cyano group, nitro group, alkyl group having 1 to 20 carbon atoms, and 1 to 20 carbon atoms. alkenyl group, cycloalkyl group having 1 to 20 carbon atoms, bicycloalkyl group having 1 to 20 carbon atoms, tricycloalkyl group having 1 to 20 carbon atoms, alkoxy group having 1 to 10 carbon atoms, alkoxy group having 1 to 10 carbon atoms, 6 to 40 carbon atoms aryl group, heteroaryl group having 3 to 40 carbon atoms, P(=O)(Ar') ₂ , C(=O)Ar', B(Ar') ₂ , B(OAr') ₂ , OSO ₂ Ar' , S(=O)Ar' and Si(Ar') are one or more groups selected from the group consisting of ₃ ;
Each Ar' is independently one or more groups selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 60 carbon atoms and a heteroaryl group having 3 to 60 carbon atoms. ;
The azabenzofluoranthene compound according to any one of claims 1 to 3. The azabenzofluoranthene compound according to claim 1, wherein the formula (1) is any one of the following formulas E01 to E03, E18, E80 and E85.
A material for an organic electroluminescence device containing the azabenzofluoranthene compound according to claim 1 . An electron-transporting material for an organic electroluminescence device, comprising the azabenzofluoranthene compound according to claim 1 . An organic electroluminescence device containing the azabenzofluoranthene compound according to claim 1 .

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