JP2019129309A - Organic electroluminescent element - Google Patents

Abstract

To provide an organic EL element having excellent light emission efficiency and exhibiting well-balanced performance.SOLUTION: By manufacturing an organic EL element using a material for a light emitting layer including a pyrene-based compound represented by the following formula (2) as a host material and a polycyclic aromatic compound in which a plurality of aromatic rings is linked with a boron atom and a nitrogen atom or an oxygen atom as a dopant material, the organic EL element having, for example, excellent light emission efficiency is provided. In the above formula (2), at least one hydrogen atom in a pyrene moiety may be substituted by an aryl having 6 to 10 carbon atoms or the like; Ar represents an aryl having 14 to 40 carbon atoms or a heteroaryl having 12 to 40 carbon atoms, and these groups may be substituted by an aryl having 6 to 10 carbon atoms or the like; s and p each independently represent an integer of 1 or 2, and s and p do not simultaneously represent 2; and one or more hydrogen atoms in a compound represented by the formula (2) may be each independently substituted by a halogen atom, cyano, or a deuterium atom.

Description

  The present invention relates to an organic electroluminescent element having a light emitting layer containing a polycyclic aromatic compound as a dopant material and a specific pyrene compound as a host material, a display device and a lighting device using the same.

  Conventionally, various researches have been made on display devices using light emitting elements that emit light in an electric field because power saving and thickness reduction are possible, and further, organic electroluminescent elements (hereinafter, organic EL elements) made of organic materials are lightweight It has been actively studied because it is easy to In particular, regarding the development of organic materials with emission characteristics such as blue, which is one of the three primary colors of light, and the combination of multiple materials that provide optimal emission characteristics, both high molecular compounds and low molecular compounds have been actively used so far. It has been studied.

  The organic EL element has a structure composed of a pair of electrodes composed of an anode and a cathode, and a single layer or a plurality of layers disposed between the pair of electrodes and containing an organic compound. Examples of the layer containing an organic compound include a light-emitting layer and a charge transport / injection layer that transports or injects charges such as holes and electrons. Various organic materials suitable for these layers have been developed.

  As a material for the light emitting layer, for example, a benzofluorene compound has been developed (International Publication No. 2004/061047). Further, as a hole transport material, for example, a triphenylamine compound has been developed (Japanese Patent Laid-Open No. 2001-172232). As an electron transport material, for example, an anthracene compound has been developed (Japanese Patent Laid-Open No. 2005-170911).

  In recent years, a compound in which a plurality of aromatic rings are condensed with boron or the like as a central atom has been reported (International Publication No. 2015/102118). In this document, a compound in which a plurality of aromatic rings are condensed is selected as a dopant material for the light emitting layer, and an anthracene compound (BH1 on page 442) is selected in particular, since a large number of materials are described as a host material. The organic EL element evaluation in the case of having been carried out is carried out, but the other combinations are not specifically verified, and if the combinations constituting the light emitting layer are different, the light emission characteristics will be different. The properties that can be obtained from are not yet known.

International Publication No. 2004/061047 JP 2001-172232 JP JP 2005-170911 A International Publication No.2015 / 102118

  As described above, various materials used for organic EL elements have been developed. However, in order to further improve the light emission characteristics and increase the choice of materials for the light emitting layer, it is desired to develop a material combination different from the conventional one. ing. In particular, it is not known about organic EL characteristics (especially optimum light emission characteristics) obtained from other than the specific host and dopant combinations reported in the examples of Patent Document 4.

  As a result of intensive studies to solve the above problems, the present inventors have found that a light emitting layer containing a polycyclic aromatic compound in which a plurality of aromatic rings are linked by a boron atom and a nitrogen atom or an oxygen atom and a specific pyrene compound The present invention was completed by finding that an excellent organic EL device can be obtained by arranging an organic EL device between a pair of electrodes.

  According to a preferred embodiment of the present invention, it is possible to provide a compound represented by the formula (1) and a compound represented by the formula (2) which can be combined with the compound to obtain an optimum light emission characteristic, and combine them. By producing an organic EL element using the light emitting layer material, an organic EL element having excellent chromaticity, driving voltage, and quantum efficiency can be provided.

Item 1.
An organic electroluminescent device comprising a pair of electrodes comprising an anode and a cathode, and a light emitting layer disposed between the pair of electrodes,
The light emitting layer includes at least one of a compound represented by the following general formula (1) and a multimer having a plurality of structures represented by the following general formula (1), and a pyrene system represented by the following general formula (2): An organic electroluminescent device comprising at least one compound.
In the above formula (1),
Ring A, ring B and ring C are each independently an aryl ring or a heteroaryl ring, and at least one hydrogen in these rings may be substituted.
X ¹ and X ² are each independently> O or> N-R, and R in> N-R is optionally substituted aryl, optionally substituted heteroaryl, or optionally substituted And R in> N—R may be bonded to the A ring, B ring and / or C ring via a linking group or a single bond, and ,
At least one hydrogen in the compound or structure represented by formula (1) may be each independently substituted with halogen, cyano or deuterium.
In the above formula (2),
s pyrene moieties and p Ar moieties are bonded at any position of * of the pyrene moiety and any position of the Ar moiety;
At least one hydrogen of the pyrene moiety is each independently an aryl having 6 to 10 carbon atoms, a heteroaryl having 2 to 11 carbon atoms, an alkyl having 1 to 30 carbon atoms, a cycloalkyl having 3 to 24 carbon atoms, or a carbon number. Optionally substituted with 2 to 30 alkenyl, 1 to 30 carbon alkoxy or 6 to 30 aryloxy, wherein at least one hydrogen independently represents aryl having 6 to 10 carbon atoms. , C2-C11 heteroaryl, C1-C30 alkyl, C3-C24 cycloalkyl, C2-C30 alkenyl, C1-C30 alkoxy or C6-C30 aryl May be substituted with oxy,
Ar is each independently an aryl having 14 to 40 carbon atoms or a heteroaryl having 12 to 40 carbon atoms, and at least one hydrogen in each of them is independently an aryl having 6 to 10 carbon atoms, Substituted with 2-11 heteroaryl, C1-C30 alkyl, C3-C24 cycloalkyl, C2-C30 alkenyl, C1-C30 alkoxy or C6-C30 aryloxy May have been
s and p are each independently an integer of 1 or 2, and s and p are not simultaneously 2; when s is 2, the two pyrene moieties are structurally identical including the substituent And p may be 2 or two Ar moieties may be structurally identical or different, including substituents, and
At least one hydrogen in the compound represented by Formula (2) may be independently substituted with halogen, cyano or deuterium.

Item 2.
Item 2. The organic electroluminescent device according to Item 1, wherein each of Ar's independently is a group represented by the following general formula (Ar-1) or (Ar-2).
In each of the above formulas,
Z is> CR ₂ ,>N—R,> O or>S;
R in CR ₂ is each independently alkyl of 1 to 6 carbons, cycloalkyl of 3 to 14 carbons, aryl of 6 to 12 carbons or heteroaryl of 2 to 12 carbons, And at least one hydrogen in the heteroaryl may be substituted with alkyl having 1 to 4 carbons or cycloalkyl having 5 to 10 carbons, and R may be bonded to each other to form a ring;
> R in N—R is alkyl having 1 to 4 carbons, cycloalkyl having 5 to 10 carbons, aryl having 6 to 12 carbons or heteroaryl having 2 to 12 carbons, and in the aryl and heteroaryl At least one hydrogen may be substituted by alkyl having 1 to 4 carbons or cycloalkyl having 5 to 10 carbons,
R ¹ to R ⁸ and R ¹⁰ to R ¹⁹ each independently represent hydrogen, aryl having 6 to 10 carbon atoms, heteroaryl having 2 to 11 carbon atoms, alkyl having 1 to 30 carbon atoms, or 3 to 24 carbon atoms Cycloalkyl, alkenyl having 2 to 30 carbon atoms, alkoxy having 1 to 30 carbon atoms or aryloxy having 6 to 30 carbon atoms, wherein at least one hydrogen is alkyl having 1 to 6 carbon atoms or 3 to 3 carbon atoms. 14 may be substituted with cycloalkyl, adjacent groups of R ¹ to R ⁸ or adjacent groups of R ¹⁰ to R ¹⁹ may be bonded to each other to form a condensed ring, The rings formed are each independently an aryl having 6 to 10 carbons, a heteroaryl having 2 to 11 carbons, an alkyl having 1 to 30 carbons, and a cycloalkyl having 3 to 24 carbons. It may be substituted by C2-C30 alkenyl, C1-C30 alkoxy or C6-C30 aryloxy, and at least one hydrogen in these may be C1-C6 alkyl or C3-C3. Optionally substituted with -14 cycloalkyl, and
At least one hydrogen in the group represented by Formula (Ar-1) or Formula (Ar-2) may be each independently substituted with halogen, cyano or deuterium.
In the formula (2), the pyrene moiety is bonded at any position in the group represented by the formula (Ar-1) or the formula (Ar-2).

Item 3.
Item 3. The organic electroluminescence device according to item 1 or 2, wherein the compound represented by the general formula (1) is a compound represented by the following general formula (1 ').
(In the above formula (1 ′),
R ¹ to R ¹¹ are each independently hydrogen, aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, alkyl, cycloalkyl, alkoxy or aryloxy, in which at least one hydrogen And each of R ¹ to R ¹¹ may be independently substituted with aryl, heteroaryl, alkyl or cycloalkyl, and adjacent ones of R ¹ to R ¹¹ may be combined to form a ring, b ring or c ring May form an aryl ring or a heteroaryl ring, and at least one hydrogen in the formed ring is independently aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, alkyl , Cycloalkyl, alkoxy And at least one hydrogen in each of them may be independently substituted with aryl, heteroaryl, alkyl or cycloalkyl.
X ¹ and X ² are each independently> O or> N-R, wherein R in> N-R is aryl having 6 to 12 carbons, heteroaryl having 2 to 15 carbons, or 1 to 6 carbons Or at least one hydrogen in the aryl or heteroaryl may be substituted with alkyl having 1 to 4 carbons or cycloalkyl having 5 to 10 carbons, and R of the> N—R may be bonded to the a ring, b ring and / or c ring by —O—, —S—, —C (—R) ₂ — or a single bond, R in C (-R) _2- is alkyl having 1 to 6 carbons or cycloalkyl having 3 to 14 carbons, and
At least one hydrogen in the compound represented by the formula (1 ′) may be each independently substituted with halogen, cyano or deuterium.

Item 4.
The Ars are each independently any one of the following Formula (Ar-1-1) to Formula (Ar-1-12) and Formula (Ar-2-1) to Formula (Ar-2-4) Item 4. The organic electroluminescent device according to any one of Items 1 to 3, which is a group represented by:
In each of the above formulas,
Z is> CR ₂ ,>N—R,> O or>S;
> Rs in CR ₂ are each independently alkyl having 1 to 6 carbons, cycloalkyl having 3 to 14 carbons or aryl having 6 to 12 carbons, and Rs are bonded to each other to form a ring. You can,
R in> N—R is alkyl having 1 to 4 carbons, cycloalkyl having 5 to 10 carbons, or aryl having 6 to 12 carbons,
At least one hydrogen in the groups represented by the above formulas is each independently aryl having 6 to 10 carbon atoms, heteroaryl having 2 to 11 carbon atoms, alkyl having 1 to 30 carbon atoms, or 3 to 24 carbon atoms. And may be substituted with a cycloalkyl of
At least one hydrogen in the groups represented by the formulas may be independently substituted with halogen, cyano or deuterium;
In Formula (2), the pyrene moiety is represented by any of Formula (Ar-1-1) to Formula (Ar-1-12) and Formula (Ar-2-1) to Formula (Ar-2-4). Bond at any position in the group.

Item 5.
5. The organic electroluminescent device according to any one of Items 1 to 4, wherein the pyrene compound represented by the general formula (2) is a compound represented by any one of the following structural formulas.

Item 6.
The electron transport layer and / or the electron injection layer disposed between the cathode and the light emitting layer, at least one of the electron transport layer and the electron injection layer is a borane derivative, a pyridine derivative, a fluoranthene derivative, BO Containing at least one selected from the group consisting of a series derivative, anthracene derivative, benzofluorene derivative, phosphine oxide derivative, pyrimidine derivative, carbazole derivative, triazine derivative, benzimidazole derivative, phenanthroline derivative, and quinolinol metal complex The organic electroluminescent element as described in any one of 1-5.

Item 7.
The electron transport layer and / or the electron injection layer may further be selected from alkali metals, alkaline earth metals, rare earth metals, oxides of alkali metals, halides of alkali metals, oxides of alkaline earth metals, and alkaline earth metals. Item 6 contains at least one selected from the group consisting of halides, oxides of rare earth metals, halides of rare earth metals, organic complexes of alkali metals, organic complexes of alkaline earth metals, and organic complexes of rare earth metals The organic electroluminescent element of description.

Item 8.
Item 8. A display device comprising the organic electroluminescent element according to any one of items 1 to 7.

Item 9.
Item 8. A lighting device comprising the organic electroluminescent element according to any one of items 1 to 7.

Item 10.
The pyrene type-compound represented by following General formula (2).
In the above formula,
The s pyrene moieties and the p Ar moieties are combined at any position of * in the pyrene moiety and at any position of the Ar moiety,
At least one hydrogen of the pyrene moiety is each independently an aryl having 6 to 10 carbons, a heteroaryl having 2 to 11 carbons, an alkyl having 1 to 30 carbons, a cycloalkyl having 3 to 24 carbons, It may be substituted by 1 to 30 alkenyl, alkoxy having 1 to 30 carbon or aryloxy having 1 to 30 carbon, and at least one hydrogen in these may be alkyl having 1 to 6 carbon or 3 to 14 carbon And may be substituted by cycloalkyl of
Ar is a group represented by the following general formula (Ar-1) or general formula (Ar-3),
In each of the above formulas,
Z is> CR ₂ ,
R in CR ₂ is each independently alkyl of 1 to 6 carbons, cycloalkyl of 3 to 14 carbons, aryl of 6 to 12 carbons or heteroaryl of 2 to 12 carbons, And at least one hydrogen in heteroaryl and heteroaryl may be substituted with alkyl having 1 to 4 carbon atoms or cycloalkyl having 5 to 10 carbon atoms, and R may combine with each other to form a ring,
R ¹ to R ⁸ and R ²⁰ to R ³⁵ each independently represent hydrogen, aryl having 6 to 10 carbon atoms, heteroaryl having 2 to 11 carbon atoms, alkyl having 1 to 30 carbon atoms, or 3 to 24 carbon atoms Cycloalkyl, alkenyl having 1 to 30 carbons, alkoxy having 1 to 30 carbons or aryloxy having 1 to 30 carbons, and at least one hydrogen in these is alkyl having 1 to 6 carbons or 3 to 3 carbons. 14 may be substituted with cycloalkyl, adjacent groups of R ¹ to R ⁸ are bonded to each other to form a condensed ring, and adjacent groups of R ²⁰ to R ³⁵ are bonded to each other. And the formed ring may be independently an aryl having 6 to 10 carbon atoms, a heteroaryl having 2 to 11 carbon atoms, or an alkyl having 1 to 30 carbon atoms. The cycloalkyl having 3 to 24 carbon atoms, the alkenyl having 1 to 30 carbon atoms, the alkoxy having 1 to 30 carbon atoms or the aryloxy having 1 to 30 carbon atoms may be substituted, and at least one hydrogen in these may be substituted with carbon atoms. Optionally substituted with 1-6 alkyl or C3-C14 cycloalkyl, and
s and p are each independently an integer of 1 or 2, s and p can not be 2 at the same time, and when s is 2, two pyrene moieties are structurally identical including substituents And p may be 2 or two Ar moieties may be structurally identical or different, including substituents.
At least one hydrogen in the compound represented by Formula (2) may be independently substituted with halogen, cyano or deuterium.

Item 11.
Item 11. The pyrene-based compound according to Item 10, represented by any one of the following structural formulas.

  According to a preferred embodiment of the present invention, there are provided a polycyclic aromatic compound represented by the formula (1) and a pyrene compound represented by the formula (2) capable of obtaining optimum light emission characteristics in combination therewith. By manufacturing an organic EL element using a material for a light emitting layer formed by combining these, an organic EL element having particularly well-balanced performance with excellent light emission efficiency can be provided.

  In addition, the compound of the general formula (1) and the multimer thereof can be expected to lower the melting point and sublimation temperature by introducing a cycloalkyl group. This means that in sublimation purification, which is almost indispensable as a purification method for materials for organic devices such as organic EL elements that require high purity, purification can be performed at a relatively low temperature, so that thermal decomposition of the material is avoided. Means This is also true for the vacuum deposition process, which is an effective means for producing organic devices such as organic EL elements, and the process can be performed at a relatively low temperature, so thermal decomposition of the material can be avoided. As a result, high performance organic devices can be obtained. Moreover, since many of the above-mentioned multimers have a high sublimation temperature due to high molecular weight, high flatness, etc., a decrease in sublimation temperature by introducing a cycloalkyl group becomes more effective. In addition, since the solubility in an organic solvent is improved by introducing a cycloalkyl group, it can also be applied to device fabrication using a coating process. Further, concentration quenching can be suppressed by introducing a large size substituent such as cycloalkyl. However, the present invention is not particularly limited to these principles.

It is a schematic sectional drawing which shows the organic EL element which concerns on this embodiment.

1. The organic electroluminescent device of the present invention is an organic electroluminescent device having a pair of electrodes consisting of an anode and a cathode, and a light emitting layer disposed between the pair of electrodes. At least one of a polycyclic aromatic compound represented by the formula (1) and a multimer having a plurality of structures represented by the following general formula (1), and a pyrene-based compound represented by the following general formula (2): It is an organic electroluminescent element containing at least one.
In addition, the definition of the code | symbol in Formula (1) and (2) is the same as the definition mentioned above, hereafter, the definition of a code | symbol also in other formulas is the code | symbol in the corresponding formula mentioned above unless there is particular notice. The definition is the same as

2. Polycyclic aromatic compound and multimer thereof The polycyclic aromatic compound and multimer used in the present invention are a compound represented by the following general formula (1) or a structure represented by the following general formula (1). Or a compound represented by the following general formula (1 ′) or a polymer having a plurality of structures represented by the following general formula (1 ′). These compounds basically function as dopants.

The A ring, B ring and C ring in the general formula (1) are each independently an aryl ring or a heteroaryl ring, and at least one hydrogen in these rings may be substituted with a substituent. This substituent is substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted diarylamino, substituted or unsubstituted diheteroarylamino, substituted or unsubstituted arylheteroarylamino (aryl and An amino group having a heteroaryl), substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkoxy or substituted or unsubstituted aryloxy is preferable. When these groups have a substituent, examples of the substituent include aryl, heteroaryl, alkyl and cycloalkyl. The aryl ring or heteroaryl ring is a 5-membered ring or 6-membered ring sharing a bond with the central condensed bicyclic structure composed of the central element B (boron), X ¹ and X ² (1). It is preferable to have.

Here, the “condensed bicyclic structure” means that two saturated hydrocarbon rings composed of the central element B (boron), X ¹ and X ² shown in the center of the general formula (1) are condensed. Means structure. The “6-membered ring sharing a bond with the condensed bicyclic structure” means, for example, a ring (benzene ring (6-membered ring)) condensed to the condensed bicyclic structure as shown in the general formula (1 ′). Means. In addition, “the aryl ring or heteroaryl ring (which is A ring) has this 6-membered ring” means that the A ring is formed only by this 6-membered ring or includes this 6-membered ring. It means that another ring etc. is further condensed to this 6-membered ring to form an A ring. In other words, the term “aryl ring or heteroaryl ring having a 6-membered ring (which is an A ring)” as used herein means that a 6-membered ring constituting all or part of the A ring is fused to the condensed bicyclic structure. Means that The same description applies to “B ring (b ring)”, “C ring (c ring)”, and “5-membered ring”.

A ring (or B ring, C ring) in the general formula (1) is a ring in the general formula (1 ′) and its substituents R ^{1 to} R ³ (or b ring and its substituents R ^{8 to} R ¹¹ , c ring and its substituents R ^{4 to} R ⁷ ). That is, the general formula (1 ′) corresponds to a structure in which “A to C rings having a six-membered ring” are selected as the A to C rings of the general formula (1). In that sense, each ring of the general formula (1 ′) is represented by a to c in lower case.

In the general formula (1 ′), adjacent groups of the substituents R ^{1 to} R ¹¹ of the a ring, b ring, and c ring are bonded to each other to form an aryl ring or a heteroaryl ring together with the a ring, b ring, or c ring. And at least one hydrogen in the ring formed is substituted with aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, alkyl, cycloalkyl, alkoxy or aryloxy And at least one hydrogen in these may be substituted with aryl, heteroaryl, alkyl or cycloalkyl. Therefore, the polycyclic aromatic compound represented by the general formula (1 ′) is represented by the following formula (1′-1) and formula (1 ′) depending on the mutual bonding form of the substituents in the a ring, b ring and c ring. As shown in -2), the ring structure constituting the compound changes. A ′ ring, B ′ ring and C ′ ring in each formula correspond to A ring, B ring and C ring in general formula (1), respectively.

If the A ′ ring, B ′ ring and C ′ ring in the above formulas (1′-1) and (1′-2) are described in the general formula (1 ′), the substituents R ^{1 to} R ¹¹ Each of the adjacent groups is bonded to each other to represent an aryl ring or heteroaryl ring formed together with the a ring, the b ring and the c ring, respectively (other ring structures can be formed by condensing the a ring, the b ring or the c ring A condensed ring). Although not shown in the formula, there are also compounds in which all of the a ring, b ring and c ring are changed to the A ′ ring, the B ′ ring and the C ′ ring. As can be seen from the above formulas (1′-1) and (1′-2), for example, b-ring R ⁸ and c-ring R ⁷ , b-ring R ¹¹ and a-ring R ¹ , c Ring R ⁴ and ring a R ^{3 and the} like do not correspond to “adjacent groups”, and these are not bonded. That is, “adjacent group” means an adjacent group on the same ring.

  The compounds represented by the above formulas (1′-1) and (1′-2) are, for example, a benzene ring, an indole ring, and a pyrrole ring with respect to a benzene ring which is a ring (or b ring or c ring), A compound having an A ′ ring (or a B ′ ring or a C ′ ring) formed by condensation of a benzofuran ring or a benzothiophene ring, which is formed by forming a fused ring A ′ (or a fused ring B ′ or a fused ring) C ′) is a naphthalene ring, a carbazole ring, an indole ring, a dibenzofuran ring or a dibenzothiophene ring, respectively.

X ¹ and X ² in the general formula (1) are each independently> O or> N—R, and R in> N—R is optionally substituted aryl or optionally substituted. A heteroaryl, an optionally substituted alkyl or an optionally substituted cycloalkyl, wherein R in the> N—R may be bonded to the B ring and / or the C ring by a linking group or a single bond; The linking group is preferably -O-, -S- or -C (-R) _2- . In addition, R of the said "-C (-R) _2- " is hydrogen, an alkyl, or a cycloalkyl. This description is the same for X ¹ and X ² in the general formula (1 ′).

Here, the definition that “R of N—R is bonded to the A ring, B ring and / or C ring by a linking group or a single bond” in the general formula (1) is defined by the general formula (1 ′). Corresponds to the definition that “R in N—R is bonded to the a ring, b ring and / or c ring by —O—, —S—, —C (—R) ₂ — or a single bond”. To do.

This definition can be expressed as a compound represented by the following formula (1′-3-1) and having a ring structure in which X ¹ and X ² are incorporated into the fused ring B ′ and the fused ring C ′. That is, for example, a B ′ ring formed by condensation of another ring so as to incorporate X ¹ (or X ² ) into the benzene ring which is the b ring (or c ring) in the general formula (1 ′) ( Or a compound having a C ′ ring). The fused ring B '(or fused ring C') formed and formed is, for example, a phenoxazine ring, a phenothiazine ring or an acridine ring.

Further, the above definition is a ring structure represented by the following formula (1′-3-2) or the formula (1′-3-3), in which X ¹ and / or X ² is incorporated into the fused ring A ′ It can also be expressed by a compound having. That is, for example, a compound having an A ′ ring formed by condensation of other rings such that X ¹ (and / or X ² ) is incorporated into a benzene ring which is a ring in the general formula (1 ′) is there. The fused ring A 'formed and formed is, for example, a phenoxazine ring, a phenothiazine ring or an acridine ring.

Examples of the “aryl ring” that is the A ring, the B ring, and the C ring in the general formula (1) include an aryl ring having 6 to 30 carbon atoms, preferably an aryl ring having 6 to 16 carbon atoms, The aryl ring of 6 to 12 is more preferable, and the aryl ring of 6 to 10 carbon atoms is particularly preferable. In addition, this "aryl ring" is an aryl ring defined by the general formula (1 ') and formed by "groups adjacent to each other of R ^{1 to} R ¹¹ being combined with the a ring, b ring or c ring In addition, since the a ring (or b ring, c ring) is already composed of a benzene ring having 6 carbon atoms, the total carbon number 9 of the condensed ring in which a 5-membered ring is condensed is the lower limit. It becomes carbon number.

  Specific examples of the “aryl ring” include a benzene ring which is a monocyclic ring, a biphenyl ring which is a bicyclic ring, a naphthalene ring which is a fused bicyclic ring, and a terphenyl ring which is a tricyclic ring (m-terphenyl, o -Terphenyl, p-terphenyl), condensed tricyclic system, acenaphthylene ring, fluorene ring, phenalene ring, phenanthrene ring, condensed tetracyclic system triphenylene ring, pyrene ring, naphthacene ring, condensed pentacyclic system Perylene ring, pentacene ring and the like can be mentioned.

Examples of the “heteroaryl ring” which is ring A, ring B and ring C in the general formula (1) include a heteroaryl ring having 2 to 30 carbon atoms, preferably a heteroaryl ring having 2 to 25 carbon atoms The heteroaryl ring having 2 to 20 carbon atoms is more preferable, the heteroaryl ring having 2 to 15 carbon atoms is further preferable, and the heteroaryl ring having 2 to 10 carbon atoms is particularly preferable. Moreover, as the “heteroaryl ring”, for example, a heterocyclic ring containing 1 to 5 hetero atoms selected from oxygen, sulfur and nitrogen in addition to carbon as a ring constituting atom can be mentioned. In addition, this “heteroaryl ring” is a heterocycle formed together with a ring, b ring or c ring by bonding adjacent groups of “R ^{1 to} R ¹¹ ” defined in the general formula (1 ′). Since the a ring (or b ring or c ring) is already composed of a benzene ring having 6 carbon atoms, the total number of carbon atoms of the condensed ring condensed with a 5-membered ring is It becomes the lower limit carbon number.

  Specific examples of the “heteroaryl ring” include pyrrole ring, oxazole ring, isoxazole ring, thiazole ring, isothiazole ring, imidazole ring, oxadiazole ring, thiadiazole ring, triazole ring, tetrazole ring, pyrazole ring, Pyridine ring, pyrimidine ring, pyridazine ring, pyrazine ring, triazine ring, indole ring, isoindole ring, 1H-indazole ring, benzimidazole ring, benzoxazole ring, benzothiazole ring, 1H-benzotriazole ring, quinoline ring, isoquinoline ring Cinnoline ring, quinazoline ring, quinoxaline ring, phthalazine ring, naphthyridine ring, purine ring, pteridine ring, carbazole ring, acridine ring, phenoxathiin ring, phenoxazine ring, phenothiazine ring, phenazine ring, i Dorijin ring, a furan ring, benzofuran ring, isobenzofuran ring, a dibenzofuran ring, a thiophene ring, benzothiophene ring, dibenzothiophene ring, furazan ring, and thianthrene ring.

  At least one hydrogen in the above “aryl ring” or “heteroaryl ring” is the first substituent, which is substituted or unsubstituted “aryl”, substituted or unsubstituted “heteroaryl”, substituted or unsubstituted "Diarylamino", substituted or unsubstituted "diheteroarylamino", substituted or unsubstituted "arylheteroarylamino", substituted or unsubstituted "alkyl", substituted or unsubstituted "cycloalkyl", substituted or unsubstituted An aryl of “aryl”, “heteroaryl” or “diarylamino” as the first substituent, which may be substituted with unsubstituted “alkoxy” or substituted or unsubstituted “aryloxy” , “Diheteroarylamino” heteroaryl, “aryl heteroarylamino” aryl and heteroaryl Le, also monovalent group as the aryl of the "aryloxy" described above "aryl" or "heteroaryl ring" and the like.

  Further, the “alkyl” as the first substituent may be either linear or branched, and examples thereof include linear alkyl having 1 to 24 carbon atoms and branched alkyl having 3 to 24 carbon atoms. C1-C18 alkyl (C3-C18 branched alkyl) is preferable, C1-C12 alkyl (C3-C12 branched alkyl) is more preferable, C1-C6 alkyl (C3-C6 branched alkyl) is more preferable, and C1-C4 alkyl (C3-C4 branched alkyl) is particularly preferable.

  Specific examples of the alkyl include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, isopentyl, neopentyl, t-pentyl, n-hexyl and 1-methyl Pentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, n-heptyl, 1-methylhexyl, n-octyl, t-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propyl Pentyl, n-nonyl, 2,2-dimethylheptyl, 2,6-dimethyl-4-heptyl, 3,5,5-trimethylhexyl, n-decyl, n-undecyl, 1-methyldecyl, n-dodecyl, n- Tridecyl, 1-hexylheptyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl Le, n- octadecyl, such as n- eicosyl, and the like.

  The “cycloalkyl” as the first substituent is cycloalkyl having 3 to 24 carbon atoms, cycloalkyl having 3 to 20 carbon atoms, cycloalkyl having 3 to 16 carbon atoms, or cycloalkyl having 3 to 14 carbon atoms. Cycloalkyl having 5 to 10 carbon atoms, cycloalkyl having 5 to 8 carbon atoms, cycloalkyl having 5 to 6 carbon atoms, and cycloalkyl having 5 carbon atoms.

  Specific cycloalkyls include cyclopropyl, methylcyclopropyl, cyclobutyl, methylcyclobutyl, cyclopentyl, methylcyclopentyl, cyclohexyl, methylcyclohexyl, cycloheptyl, methylcycloheptyl, cyclooctyl, methylcyclooctyl, cyclononyl, methylcyclononyl , Cyclodecyl, methylcyclodecyl, bicyclo [1.0.1] butyl, bicyclo [1.1.1] pentyl, bicyclo [2.0.1] pentyl, bicyclo [1.2.1] hexyl, bicyclo [3 And 0.1] hexyl, bicyclo [2.1.2] heptyl, bicyclo [2.2.2] octyl, adamantyl, diamantyl, decahydronaphthalenyl, decahydroazulenyl and the like.

  Examples of the “alkoxy” as the first substituent include straight chain alkoxy having 1 to 24 carbon atoms or branched alkoxy having 3 to 24 carbon atoms. C1-C18 alkoxy (C3-C18 branched alkoxy) is preferable, C1-C12 alkoxy (C3-C12 branched alkoxy) is more preferable, C1-C6 Of alkoxy (C3-C6 branched alkoxy) is more preferable, and C1-C4 alkoxy (C3-C4 branched alkoxy) is particularly preferable.

  Specific examples of the alkoxy include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, t-butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy and the like.

  The first substituent, substituted or unsubstituted "aryl", substituted or unsubstituted "heteroaryl", substituted or unsubstituted "diarylamino", substituted or unsubstituted "diheteroarylamino", substituted Or unsubstituted “arylheteroarylamino”, substituted or unsubstituted “alkyl”, substituted or unsubstituted “cycloalkyl”, substituted or unsubstituted “alkoxy”, or substituted or unsubstituted “aryloxy” Are described as substituted or unsubstituted, in which at least one hydrogen may be substituted with a second substituent. The second substituent includes, for example, aryl, heteroaryl, alkyl or cycloalkyl, and specific examples thereof include the monovalent groups of the above-mentioned "aryl ring" or "heteroaryl ring", Reference can be made to the description of "alkyl" or "cycloalkyl" as a substituent of 1. In addition, in the aryl and heteroaryl as the second substituent, at least one hydrogen in them is aryl such as phenyl (specific examples are the groups described above), alkyl such as methyl (specific examples are the groups described above), cyclohexyl, and the like. A group substituted with cycloalkyl (specific examples are the groups described above) is also included in the aryl and heteroaryl as the second substituent. For example, when the second substituent is a carbazolyl group, the carbazolyl group in which at least one hydrogen at position 9 is substituted with an aryl such as phenyl or an alkyl such as methyl or a cycloalkyl such as cyclohexyl is also a second Is included in the heteroaryl as a substituent.

Examples of the aryl, heteroaryl, aryl of diarylamino, heteroaryl of diheteroarylamino, aryl and heteroaryl of arylheteroarylamino, or aryl of aryloxy in R ^{1 to} R ¹¹ in General Formula (1 ′) Examples thereof include monovalent groups of the “aryl ring” or the “heteroaryl ring” described in the formula (1). In addition, as the alkyl, cycloalkyl, or alkoxy in R ^{1 to} R ¹¹ , see the description of “alkyl”, “cycloalkyl”, and “alkoxy” as the first substituent in the description of the general formula (1). can do. Furthermore, aryl, heteroaryl, alkyl or cycloalkyl as a substituent to these groups are also the same. Further, when adjacent groups of R ^{1 to} R ¹¹ are bonded to form an aryl ring or a heteroaryl ring together with the a ring, b ring or c ring, the heteroaryl which is a substituent for these rings The same applies to diarylamino, diheteroarylamino, arylheteroarylamino, alkyl, cycloalkyl, alkoxy or aryloxy and further substituents such as aryl, heteroaryl, alkyl or cycloalkyl.

R in> N—R in X ¹ and X ² in the general formula (1) is aryl, heteroaryl, alkyl or cycloalkyl which may be substituted with the above-mentioned second substituent, aryl, heteroaryl, At least one hydrogen in alkyl or cycloalkyl may be substituted, for example, by alkyl or cycloalkyl. Examples of the aryl, heteroaryl, alkyl and cycloalkyl include the groups described above. Particularly, aryl having 6 to 10 carbon atoms (for example, phenyl, naphthyl and the like), heteroaryl having 2 to 15 carbon atoms (for example, carbazolyl and the like), alkyl having 1 to 4 carbon atoms (for example, methyl, ethyl and the like), and 3 to 16 carbon atoms. Of cycloalkyl such as bicyclooctyl and adamantyl are preferred. This description is the same for X ¹ and X ² in the general formula (1 ′).

R in “—C (—R) ₂ —” which is a linking group in the general formula (1) is hydrogen, alkyl or cycloalkyl, and examples of the alkyl or cycloalkyl include the groups described above. In particular, alkyl having 1 to 4 carbon atoms (for example, methyl, ethyl, etc.) is preferable. The description is the same for "-C (-R) _2- " which is a linking group in the general formula (1 ').

  The present invention also relates to a multimer of polycyclic aromatic compounds having a plurality of unit structures represented by the general formula (1), preferably a polycyclic aroma having a plurality of unit structures represented by the general formula (1 ′). It is a multimer of group compounds. The multimer is preferably a 2- to 6-mer, more preferably a 2- to 3-mer, and particularly preferably a dimer. The multimer may be in a form having a plurality of the unit structures in one compound, and for example, the unit structure is a single bond, or a linking group such as an alkylene group having 1 to 3 carbon atoms, a phenylene group, or a naphthylene group. In addition to a plurality of bonded forms, a form in which any of the rings (A ring, B ring or C ring, a ring, b ring or c ring) contained in the unit structure is bonded in a shared manner to a plurality of unit structures Or any ring (A ring, B ring or C ring, a ring, b ring or c ring) contained in the unit structure may be bonded together in a fused manner. Good.

  Examples of such multimers include the following formula (1′-4), formula (1′-4-1), formula (1′-4-2), formula (1′-5-1) to formula (1). The multimer compound represented by (1'-5-4) or Formula (1'-6) is mentioned. The multimeric compound represented by the following formula (1′-4), when it is described by the general formula (1 ′), shares a benzene ring which is an a ring, and a plurality of general formulas (1 ′) It is a multimeric compound having the unit structure shown in one compound. In addition, the multimeric compounds represented by the following formula (1′-4-1) can be represented by two general formulas (2 It is a multimeric compound having a unit structure represented by 1 ′) in one compound. In addition, the multimeric compounds represented by the following formula (1′-4-2) can be represented by three general formulas (3 It is a multimeric compound having a unit structure represented by 1 ′) in one compound. In addition, the multimeric compounds represented by the following formulas (1′-5-1) to (1′-5-4) are b-rings (or c-rings) as described in general formula (1 ′). A multimeric compound having a unit structure represented by a plurality of general formulas (1 ′) in one compound so as to share a certain benzene ring. Further, the multimer compound represented by the following formula (1′-6) can be, for example, a benzene ring which is a b ring (or an a ring, a c ring) of a certain unit structure, if it is described by the general formula (1 ′) A multimeric compound having a unit structure represented by a plurality of general formulas (1 ′) in one compound so that a benzene ring which is a b ring (or a ring or c ring) of a certain unit structure is condensed. It is.

  The multimeric compound includes a multimerized form represented by formula (1′-4), formula (1′-4-1) or formula (1′-4-2), and formula (1′-5-1). A multimer in combination with any of the formula (1′-5-4) or the multimerized form represented by the formula (1′-6) may be used, and the formula (1′-5-1) A multimer in which the multimerized form represented by any one of the formulas (1′-5-4) and the multimerized form represented by the formula (1′-6) may be combined. Multimerization forms represented by (1′-4), formula (1′-4-1) or formula (1′-4-2) and formulas (1′-5-1) to (1′-5) -4) may be a multimer in which the multimerized form represented by any of the above and the multimerized form represented by the formula (1′-6) are combined.

The hydrogen in the chemical structure of the polycyclic aromatic compound represented by the general formula (1) or (1 ′) and the multimer thereof is all or partly substituted with halogen, cyano or deuterium. Also good. For example, in Formula (1), A ring, B ring, C ring (A to C ring is an aryl ring or heteroaryl ring), a substituent to A to C ring, and X ¹ and X ² are> N The hydrogen in R (= aryl, heteroaryl, alkyl, cycloalkyl) when -R may be substituted with halogen, cyano or deuterium, among which all or part of the hydrogens in aryl and heteroaryl are halogen And an embodiment substituted with cyano or deuterium. Halogen is fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine, more preferably fluorine or chlorine.

  Specific examples of the polycyclic aromatic compound of the present invention include compounds represented by the following structural formulas. In the following structural formulae, "Me" is a methyl group, "tBu" is a tertiary butyl group, "iPr" is an isopropyl group, "Ph" is a phenyl group, and "D" is deuterium.

3. The method for producing the polycyclic aromatic compound represented by the formula (1) and the multimer thereof The polycyclic aromatic compound represented by the general formula (1) or (1 ′) and the multimer thereof It can manufacture according to the method described in many well-known references including the 102118 gazette. For reference, the specific production method of the polycyclic aromatic compound is described in the synthesis examples described later.

Basically, an intermediate is first prepared by bonding A ring (a ring), B ring (b ring) and C ring (c ring) with a linking group (a group including X ¹ and X ² ). (First reaction), and then final formation by combining A ring (a ring), B ring (b ring) and C ring (c ring) with a linking group (group containing central element B (boron)) Product can be produced (second reaction). In the first reaction, for example, in the case of an etherification reaction, general reactions such as a nucleophilic substitution reaction and Ullmann reaction can be used, and in the case of an amination reaction, a general reaction such as a Buchwald-Heartwig reaction can be used. In the second reaction, a tandem hetero Friedel-Crafts reaction (continuous aromatic electrophilic substitution reaction, the same applies hereinafter) can be used. In addition, the desired position can be obtained by using a halogenated, cyanated or deuterated raw material or adding a halogenation, cyanation or deuteration step anywhere in these reaction steps. Halogenated, cyanated or deuterated compounds can be prepared.

In the second reaction, as shown in the following schemes (1) and (2), a central element B (boron) for bonding the A ring (a ring), the B ring (b ring) and the C ring (c ring) is introduced. In the following, the case where X ¹ and X ² are> O is shown as an example. First, a hydrogen atom and n- butyllithium between ^{X 1} and ^{X 2,} ortho-metalated with sec- butyllithium or t- butyl lithium, and the like. Next, boron trichloride, boron tribromide, etc. are added, and after lithium-boron metal exchange is performed, a tandem Bora Friedel-Crafts reaction is performed by adding a Bronsted base such as N, N-diisopropylethylamine. You can get things. In the second reaction, a Lewis acid such as aluminum trichloride may be added to accelerate the reaction. In addition, the definition of the code | symbol in each structural formula in following scheme (1) and (2) is the same as the definition mentioned above.

  In addition, although said scheme (1) and (2) mainly show the manufacturing method of the polycyclic aromatic compound represented by General formula (1) or (1 '), about the multimer, plural are mentioned. Can be produced by using an intermediate having A ring (a ring), B ring (b ring) and C ring (c ring). The details will be described in the following schemes (3) to (5). In this case, the target product can be obtained by setting the amount of the reagent such as butyl lithium to be doubled or tripled.

In addition, even when X ¹ and X ² are> N—R or when either is> N—R, it can be produced in the same manner as described above by using an amine compound as an intermediate. .

  Specific examples of the solvent used in each of the above schemes are t-butylbenzene and xylene.

  Further, as an orthometalation reagent, alkyllithiums such as methyllithium, n-butyllithium, sec-butyllithium, t-butyllithium, lithium diisopropylamide, lithium tetramethylpiperidide, lithium hexamethyldisilazide, potassium Organic alkali compounds such as hexamethyldisilazide may be mentioned.

Also, as Brönsted base, N, N-diisopropylethylamine, triethylamine, 2,2,6,6-tetramethylpiperidine, 1,2,2,6,6-pentamethylpiperidine, N, N-dimethylaniline, N, N-dimethyl toluidine, 2,6-lutidine, sodium tetraphenylborate, potassium tetraphenylborate, triphenylborane, tetraphenylsilane, Ar ₄ BNa, Ar ₄ BK, Ar ₃ B, Ar ₄ Si , Ar is aryl such as phenyl) and the like.

Examples of Lewis acids include AlCl ₃ , AlBr ₃ , AlF ₃ , BF ₃ .OEt ₂ , BCl ₃ , BBr ₃ , GaCl ₃ , GaBr ₃ , InCl ₃ , InBr ₃ , In (OTf) ₃ , SnCl ₄ , SnBr ₄ , AgOTf, ScCl ₃ , Sc (OTf) ₃ , ZnCl ₂ , ZnBr ₂ , Zn (OTf) ₂ , MgCl ₂ , MgBr ₂ , Mg (OTf) ₂ , LiOTf, NaOTf, KOTf, Me ₃ SiOTf, Cu (OTf) ₂ ) CuCl ₂ , YCl ₃ , Y (OTf) ₃ , TiCl ₄ , TiBr ₄ , TiBr ₄ , ZrCl ₄ , ZrBr ₄ , FeCl ₃ , FeBr ₃ , CoCl ₃ , CoBr _{3 and the} like.

4. The pyrene compound represented by the general formula (2) The pyrene compound represented by the general formula (2) basically functions as a host.

In the above formula (2),
s pyrene moieties and p Ar moieties are bonded at any position of * of the pyrene moiety and any position of the Ar moiety;
At least one hydrogen of the pyrene moiety is each independently an aryl having 6 to 10 carbon atoms, a heteroaryl having 2 to 11 carbon atoms, an alkyl having 1 to 30 carbon atoms, a cycloalkyl having 3 to 24 carbon atoms, or a carbon number. Optionally substituted with 2 to 30 alkenyl, 1 to 30 carbon alkoxy or 6 to 30 aryloxy, wherein at least one hydrogen independently represents aryl having 6 to 10 carbon atoms. , C2-C11 heteroaryl, C1-C30 alkyl, C3-C24 cycloalkyl, C2-C30 alkenyl, C1-C30 alkoxy or C6-C30 aryl May be substituted with oxy,
Ar is each independently an aryl having 14 to 40 carbon atoms or a heteroaryl having 12 to 40 carbon atoms, and at least one hydrogen in each of them is independently an aryl having 6 to 10 carbon atoms, Substituted with 2-11 heteroaryl, C1-C30 alkyl, C3-C24 cycloalkyl, C2-C30 alkenyl, C1-C30 alkoxy or C6-C30 aryloxy May have been
s and p are each independently an integer of 1 or 2, and s and p are not simultaneously 2; when s is 2, the two pyrene moieties are structurally identical including the substituent And p may be 2 or two Ar moieties may be structurally identical or different, including substituents, and
At least one hydrogen in the compound represented by the formula (2) may be independently substituted with halogen, cyano or deuterium.

Ar is aryl having 14 to 40 carbons or heteroaryl having 12 to 40 carbons, to which various substituents may be bonded. Specific examples of Ar include the following general formula (Ar-1) or general formula And a group represented by the formula (Ar-2). R ¹ to R ⁸ and R ¹⁰ to R ¹⁹ are substituents.

Moreover, in the group represented by the formula (Ar-2), as an example in which adjacent R ¹⁸ and R ¹⁹ are bonded to each other to form a condensed ring, a group represented by the following general formula (Ar-3) can be given. It is done. R ²⁰ to R ³⁵ are substituents.

More specific examples of the group represented by Formula (Ar-1) or Formula (Ar-2) include groups represented by any of the following general formulas. Among these, Formula (Ar-1-1), Formula (Ar-1-2), Formula (Ar-1-3), Formula (Ar-1-4), Formula (Ar-2-2) or Formula The group represented by (Ar-2-4) is preferable, and the formula (Ar-1-2), the formula (Ar-1-3), the formula (Ar-1-4) or the formula (Ar-2-4) Is more preferable. In the following structural formulas, substituents are not clearly shown, but at least one hydrogen in each structure may be substituted. In addition, the group represented by a following formula (Ar-2-4) is corresponded to the group represented by the said Formula (Ar-3).

Ar as C14 to C40 or heteroaryl as C12 to C40 as Ar, the first substituent to the pyrene moiety (aryl having 6 to 10 carbons, heteroaryl having 2 to 11 carbons, carbon number 1) -30 alkyl, cycloalkyl having 3 to 24 carbon atoms, alkenyl having 2 to 30 carbon atoms, alkoxy having 1 to 30 carbon atoms or aryloxy having 6 to 30 carbon atoms, preferably aryl having 6 to 10 carbon atoms) and Second substituent to the first substituent (aryl having 6 to 10 carbon atoms, heteroaryl having 2 to 11 carbon atoms, alkyl having 1 to 30 carbon atoms, cycloalkyl having 3 to 24 carbon atoms, 2 carbon atoms To 30 alkenyl, alkoxy having 1 to 30 carbons or aryloxy having 6 to 30 carbons, preferably aryl having 6 to 10 carbons, and a substituent to Ar (formula (Ar- ^{R 1 to R 8)} of the formula (Ar-2) of the ^{R 10} from ^{R 19,} wherein ^{(R 35} and, from Ar-3) of ^{R 20,} wherein (Ar-1-1) ~ Formula (Ar-2 -4) are substituents not specified in the above, aryl having 6 to 10 carbon atoms, heteroaryl having 2 to 11 carbon atoms, alkyl having 1 to 30 carbon atoms, cycloalkyl having 3 to 24 carbon atoms, carbon number 2 The following describes the alkenyl of 1 to 30, the alkoxy of 1 to 30 carbon, and the aryloxy of 6 to 30 carbon, preferably an alkyl of 1 to 30 carbon, in the following.

  The aryl having 14 to 40 carbon atoms or heteroaryl having 12 to 40 carbon atoms as Ar is preferably an aryl having 14 to 35 carbon atoms or a heteroaryl having 12 to 35 carbon atoms, more preferably 14 to 30 carbon atoms. Or aryl having 12 to 30 carbon atoms, more preferably aryl having 14 to 25 carbon atoms or heteroaryl having 12 to 25 carbon atoms, particularly preferably aryl having 14 to 20 carbon atoms or carbon number 12 -20 heteroaryl, most preferably aryl having 14-18 carbon atoms or heteroaryl having 12-18 carbon atoms.

  Specific aryls include monocyclic phenyl, bicyclic biphenylyl, condensed bicyclic naphthyl, tricyclic terphenylyl (m-terphenylyl, o-terphenylyl, p-terphenylyl), condensed Examples include tricyclic anthracenyl, acenaphthylenyl, fluorenyl, phenalenyl, phenanthrenyl, fused tetracyclic triphenylenyl, naphthacenyl, fused pentacyclic perylenyl and pentacenyl.

  Specific examples of heteroaryl include pyrrolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, oxadiazolyl, thiadiazolyl, triazolyl, triazolyl, pyrazolyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, indolyl, isoindolyl, 1H-indazolyl, Benzimidazolyl, benzoxazolyl, benzothiazolyl, 1H-benzotriazolyl, quinolyl, isoquinolyl, cinnolyl, quinazolyl, quinoxalinyl, phthalazinyl, naphthyridinyl, purinyl, pteridinyl, carbazolyl, acridinyl, phenoxazinyl, phenoxazinyl, phenothiazinyl, phenazinyl, Indolizinyl, furyl, benzofuranyl, isobenzofurani , Dibenzofuranyl, thienyl, benzo [b] thienyl, dibenzothienyl, furazanyl, oxadiazolyl, thianthrenyl, naphthaldehyde benzofuranyl and naphthoxycarbonyl benzothienyl, and the like.

  In addition, with regard to the first substituent to the pyrene moiety and the second substituent to the first substituent, and the substituent to Ar, examples of the aryl having 6 to 10 carbon atoms include phenyl or naphthyl. Specific examples of the heteroaryl having 2 to 11 carbon atoms can be cited from the heteroaryl groups described above.

  The aryloxy having 6 to 30 carbon atoms is a group in which hydrogen of a hydroxyl group is substituted with aryl having 6 to 30 carbon atoms, preferably the aryl is an aryl having 6 to 25 carbon atoms, more preferably carbon The aryl group is an aryl group having a number of 6 to 20, more preferably an aryl having a carbon number of 6 to 15, particularly preferably an aryl having a carbon number of 6 to 10, and specific examples of the aryl are cited from among the aforementioned aryl groups. can do.

  The alkyl having 1 to 30 carbons may be either straight chain or branched, and for example, linear alkyl having 1 to 24 carbons or branched alkyl having 3 to 24 carbons is preferable, and alkyl having 1 to 18 carbons. (C3-C18 branched chain alkyl) is more preferable, C1-C12 alkyl (C3-C12 branched alkyl) is still more preferable, C1-C6 alkyl (C3-C6) Branched-chain alkyl) is particularly preferred, particularly preferably alkyl having 1 to 4 carbon atoms (branched alkyl having 3 to 4 carbon atoms), methyl, ethyl, isopropyl or t-butyl being more preferable among them, and methyl Or t-butyl is most preferred.

  Specific examples of the alkyl include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, isopentyl, neopentyl, t-pentyl, n-hexyl and 1-methyl Pentyl, 4-methyl-2-pentyl, 3, 3-dimethylbutyl, 2-ethylbutyl, n-heptyl, 1-methylhexyl, n-octyl, t-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propyl Pentyl, n-nonyl, 2,2-dimethylheptyl, 2,6-dimethyl-4-heptyl, 3,5,5-trimethylhexyl, n-decyl, n-undecyl, 1-methyldecyl, n-dodecyl, n- Tridecyl, 1-hexylheptyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl Le, n- octadecyl and n- eicosyl and the like.

  The cycloalkyl having 3 to 24 carbon atoms is, for example, a cycloalkyl having 3 to 20 carbon atoms, a cycloalkyl having 3 to 16 carbon atoms, a cycloalkyl having 3 to 14 carbon atoms, a cycloalkyl having 5 to 10 carbon atoms, or a carbon number. 5-8 cycloalkyl, C5-C6 cycloalkyl, C5-C cycloalkyl, etc. are mentioned.

  Specific cycloalkyls include cyclopropyl, methylcyclopropyl, cyclobutyl, methylcyclobutyl, cyclopentyl, methylcyclopentyl, cyclohexyl, methylcyclohexyl, cycloheptyl, methylcycloheptyl, cyclooctyl, methylcyclooctyl, cyclononyl, methylcyclononyl , Cyclodecyl, methylcyclodecyl, bicyclo [1.0.1] butyl, bicyclo [1.1.1] pentyl, bicyclo [2.0.1] pentyl, bicyclo [1.2.1] hexyl, bicyclo [3 And 0.1] hexyl, bicyclo [2.1.2] heptyl, bicyclo [2.2.2] octyl, adamantyl, diamantyl, decahydronaphthalenyl, decahydroazulenyl and the like.

  The alkenyl having 2 to 30 carbons is, for example, preferably alkenyl having 2 to 20 carbons, more preferably alkenyl having 2 to 10 carbons, and still more preferably alkenyl having 2 to 6 carbons, in particular Preferably it is C2-C4 alkenyl.

  Specific examples of the alkenyl include vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-hexenyl, 2 And -hexenyl, 3-hexenyl, 4-hexenyl and 5-hexenyl and the like.

  The alkoxy having 1 to 30 carbons is, for example, preferably alkoxy having 1 to 24 carbons (branched alkoxy having 3 to 24 carbons), more preferably alkoxy having 1 to 18 carbons (3 to 3 carbons). 18 branched chain alkoxy), more preferably alkoxy having 1 to 12 carbon atoms (branched alkoxy having 3 to 12 carbon atoms), particularly preferably alkoxy having 1 to 6 carbon atoms (3 to 3 carbon atoms). 6 branched chain alkoxy), and most preferably alkoxy having 1 to 4 carbon atoms (branched alkoxy having 3 to 4 carbon atoms).

  Specific examples of the alkoxy include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, s-butoxy, t-butoxy, pentyloxy, hexyloxy, heptyloxy and octyloxy.

In Formula (Ar-1) and Formula (Ar-2), adjacent groups among R ¹ to R ⁸ and adjacent groups among R ¹⁰ to R ¹⁹ are bonded to each other to form a condensed ring. May be. The adjacent group is a combination other than R ⁴ and R ⁵ or R ¹³ and R ¹⁴ , and examples thereof include R ¹ and R ^{2 and the} like. Thus, the structure in which the condensed ring is formed is the above-mentioned formula (Ar-1-2) to formula (Ar-1-12) or the above-mentioned formula (Ar-2-2) to formula (Ar-2-4) ( Formula (Ar-3)). On the other hand, Formula (Ar-1-1) and Formula (Ar-2-1) have a structure that does not contain a fused ring. Examples of the condensed ring formed include a benzene ring, a naphthalene ring, a phenanthrene ring, a thiophene ring, a pyrrole ring, or a furan ring, and is preferably an aryl ring such as a benzene ring, a naphthalene ring, or a phenanthrene ring, More preferred is a benzene ring.

  A fused ring formed by bonding adjacent groups to each other is an aryl having 6 to 10 carbon atoms, a heteroaryl having 2 to 11 carbon atoms, an alkyl having 1 to 30 carbon atoms, a cycloalkyl having 3 to 24 carbon atoms, carbon It may be substituted with alkenyl having 2 to 30 carbon atoms, alkoxy having 1 to 30 carbon atoms or aryloxy having 6 to 30 carbon atoms, and these may be substituted with alkyl having 1 to 6 carbon atoms or cycloalkyl having 3 to 14 carbon atoms. And the detailed description of these groups can refer to the above description.

Z is> CR ₂ ,>N—R,> O or> S, and among these, preferably> CR ₂ or> O, more preferably> CR ₂ and> CR ₂ R (alkyl having 1 to 6 carbons, cycloalkyl having 3 to 14 carbons, alkyl having 1 to 4 carbons, or aryl having 6 to 12 carbons optionally substituted with cycloalkyl having 5 to 10 carbons, Or an alkyl having 1 to 4 carbon atoms or a heteroaryl having 2 to 12 carbon atoms which may be substituted with a cycloalkyl having 5 to 10 carbon atoms, and R (alkyl having 1 to 4 carbon atoms) in> N—R Cycloalkyl having 5 to 10 carbon atoms, alkyl having 1 to 4 carbon atoms, or aryl having 6 to 12 carbon atoms which may be substituted with cycloalkyl having 5 to 10 carbon atoms, or alkyl having 1 to 4 carbon atoms Also Also for C2-C12 heteroaryl optionally substituted with C5-C10 cycloalkyl), details of these groups should be referred to the description of alkyl, cycloalkyl, aryl and heteroaryl above. Can do.

For> CR ₂ which is Z, the R may be bonded to each other to form a ring, and in this case, a spiro structure is formed.

  The above formula (2) means that s pyrene moieties and p Ar moieties are bonded at the * position (position 1 and / or position 2) of the pyrene moiety, and s and p are respectively Independently, it is an integer of 1 or 2, and s and p can not be 2 simultaneously. Since the pyrene moiety is a symmetrical structure, in the case of s = 1, p = 1 or s = 2, p = 1, the 1st and 2nd places of the pyrene moiety can be indicated by two asterisks *, s = 1, In the case of p = 2, it is indicated by 6 * that two Ar moieties can be bonded to 6 positions of the pyrene moiety, respectively. When s is 2, the two pyrene moieties may be structurally identical or different, including substituents, and when p is 2, the two Ar moieties include substituents. It may be structurally the same or different. That is, as described above, various substituents may be bonded to the pyrene structure as described above, and when the substituents are bonded, the pyrene moiety includes the bonded substituent. Similarly, the Ar moiety also constitutes an Ar moiety including a bound substituent. And, when a plurality of pyrene moieties and Ar moieties are included in the pyrene compound represented by the formula (2), the pyrene moieties including the substituent and the Ar moieties including the substituent are structurally the same, respectively. May be different and are preferably the same.

In the pyrene moiety, Ar is attached at position * (1- and / or 2-position) in the pyrene moiety, but conversely, the pyrene moiety is attached at any position in the Ar moiety. Also good. For example, in Formula (Ar-1) or Formula (Ar-2), which is an example of Ar, a pyrene moiety may be bonded at any position of R ¹ to R ⁸ and R ¹⁰ to R ¹⁹ , and When adjacent groups are bonded to each other to form a fused ring, they may be bonded to the fused ring. Further, when a substituent such as aryl is selected as R ¹ to R ⁸ and R ¹⁰ to R ¹⁹ , any position in the aryl, or R as R of> CR ₂ and> N—R as Z The substituent of may be bonded at any position on the aryl when selected. Among these bonding positions, any position of R ¹ to R ⁸ or R ¹⁰ to R ¹⁹ in Formula (Ar-1) or Formula (Ar-2) is preferable. These explanations are the same for the lower formulas of the formula (Ar-1) and the formula (Ar-2).

  Further, all or part of the hydrogen in the pyrene compound represented by the formula (2) may be substituted with halogen, cyano or deuterium. For example, in Formula (2), hydrogen in the pyrene moiety or Ar moiety can be replaced with halogen, cyano, or deuterium. Halogen is fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine, more preferably fluorine.

  Specific examples of the pyrene compound of the present invention include compounds represented by the following structural formulas. In the following structural formulae, “Me” is methyl, “Et” is ethyl, “tBu” is tertiary butyl, “iPr” is isopropyl, and “D” is deuterium.

  Among the above compounds, the formula (2-1), the formula (2-2) to the formula (2-20), the formula (2-41) to the formula (2-43), the formula (2-46), the formula ( 2-47) to Formula (2-173), Formula (2-174), Formula (2-175) to Formula (2-215), Formula (2-351) to Formula (2-354), Formula (2) -356), formula (2-357), formula (2-358), formula (2-359), formula (2-360) to formula (2-430), formula (2-1001), formula (2- 1002) to Formula (2-1012), Formula (2-1080), Formula (2-1081) to Formula (2-1091) are preferable.

  Moreover, Formula (2-1), Formula (2-46), Formula (2-174), Formula (2-350), Formula (2-356), Formula (2-359), Formula (2-1001) And compounds represented by any one of formulas (2-1080) are more preferable.

5. Method for producing pyrene compound represented by formula (2) The pyrene compound represented by formula (2) has a structure in which various substituents are bonded to the pyrene skeleton or the skeleton of the compound represented by Ar. And can be manufactured using known methods. An intermediate is produced by a commonly used halogenation reaction, boron oxidation reaction or boronic acid esterification reaction, and the produced intermediate is used for the Suzuki coupling reaction, other metalation reactions, and crossing via metal species. By performing a coupling reaction (Negishi coupling reaction, Kumada-Tamao coupling reaction, Kosugi-Umeda-Stille coupling reaction, etc.), a pyrene compound represented by the formula (2) can be appropriately produced. it can. Also, after preparing an intermediate having a substituent such as an alkoxy group such as a methoxy group and converting it to an -OH form by demethylation reaction using a pyridine hydrochloride etc, a reagent such as trifluoromethanesulfonic acid is used The pyrene compound represented by the formula (2) can also be produced by converting it into a sulfonic acid ester and performing a cross coupling reaction such as a Suzuki coupling reaction. In addition, as intermediates having these halogen, boronic acid, boronic acid ester or sulfonic acid ester, commercially available materials can also be used. For reference, in the synthesis examples described later, a specific method for producing the pyrene compound is described.

6). Organic electroluminescent element Below, the organic EL element which concerns on this embodiment is demonstrated in detail based on drawing. FIG. 1 is a schematic cross-sectional view showing an organic EL element according to this embodiment.

<Structure of Organic Electroluminescent Device>
The organic EL element 100 shown in FIG. 1 includes a substrate 101, an anode 102 provided on the substrate 101, a hole injection layer 103 provided on the anode 102, and a hole injection layer 103. Provided on the hole transport layer 104 provided, the light emitting layer 105 provided on the hole transport layer 104, the electron transport layer 106 provided on the light emitting layer 105, and the electron transport layer 106 The electron injection layer 107 and the cathode 108 provided on the electron injection layer 107 are provided.

  Note that the organic EL element 100 is, for example, the substrate 101, the cathode 108 provided on the substrate 101, the electron injection layer 107 provided on the cathode 108, and the electron injection layer 107 in reverse manufacturing order. An electron transport layer 106 provided on the light emitting layer 105, a light emitting layer 105 provided on the electron transport layer 106, a hole transport layer 104 provided on the light emitting layer 105, and a hole transport layer 104. The hole injection layer 103 provided on the hole injection layer 103 and the anode 102 provided on the hole injection layer 103 may be used.

  Not all of the above layers are necessary, and the minimum structural unit is composed of the anode 102, the light emitting layer 105, and the cathode 108, and the hole injection layer 103, the hole transport layer 104, the electron transport layer 106, and the electron injection. The layer 107 is an arbitrarily provided layer. Each of the layers may be a single layer or a plurality of layers.

  As an aspect of the layer which comprises an organic EL element, in addition to the above-mentioned structural aspect of "substrate / anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode", “Substrate / anode / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode”, “substrate / anode / hole injection layer / light emitting layer / electron transport layer / electron injection layer / cathode”, “substrate / Anode / hole injection layer / hole transport layer / light emitting layer / electron injection layer / cathode "," substrate / anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / cathode "," substrate / Anode / light emitting layer / electron transport layer / electron injection layer / cathode ”,“ substrate / anode / hole transport layer / light emitting layer / electron injection layer / cathode ”,“ substrate / anode / hole transport layer / light emitting layer / electron ” "Transport layer / cathode", "substrate / anode / hole injection layer / emission layer / electron injection layer / cathode", "substrate / anode / hole injection layer / emission layer / electron transport layer" Cathode "," substrate / anode / light emitting layer / electron transporting layer / cathode "may be configured aspect of the" substrate / anode / light emitting layer / electron injection layer / cathode ".

<Substrate in Organic Electroluminescent Device>
The substrate 101 is a support for the organic EL element 100, and quartz, glass, metal, plastic, etc. are usually used. The substrate 101 is formed into a plate shape, a film shape, or a sheet shape according to the purpose. For example, a glass plate, a metal plate, a metal foil, a plastic film, a plastic sheet, or the like is used. Of these, glass plates and transparent synthetic resin plates such as polyester, polymethacrylate, polycarbonate, polysulfone and the like are preferable. In the case of a glass substrate, soda lime glass, alkali-free glass, or the like may be used, and the thickness may be sufficient to maintain mechanical strength. The upper limit value of the thickness is, for example, 2 mm or less, preferably 1 mm or less. With regard to the material of glass, alkali-free glass is preferable because less elution ions from glass is preferable, but soda lime glass with a barrier coat such as SiO ₂ may also be commercially available. it can. The substrate 101 may be provided with a gas barrier film such as a dense silicon oxide film on at least one side in order to enhance the gas barrier properties, and a plate, a film or a sheet made of a synthetic resin having particularly low gas barrier properties as the substrate 101 When used, it is preferable to provide a gas barrier film.

<Anode in Organic Electroluminescent Device>
The anode 102 plays a role of injecting holes into the light emitting layer 105. In the case where the hole injection layer 103 and / or the hole transport layer 104 is provided between the anode 102 and the light emitting layer 105, holes are injected into the light emitting layer 105 via these. .

  Materials forming the anode 102 include inorganic compounds and organic compounds. Examples of inorganic compounds include metals (aluminum, gold, silver, nickel, palladium, chromium, etc.), metal oxides (oxides of indium, oxides of tin, indium-tin oxide (ITO), indium-zinc oxide Products (IZO), metal halides (copper iodide, etc.), copper sulfide, carbon black, ITO glass, Nesa glass, and the like. Examples of the organic compound include polythiophene such as poly (3-methylthiophene), conductive polymer such as polypyrrole and polyaniline, and the like. In addition, it can select suitably and use it out of the substance used as an anode of organic EL element.

  The resistance of the transparent electrode is not limited as long as it can supply a sufficient current for light emission of the light emitting element, but is preferably low resistance from the viewpoint of power consumption of the light emitting element. For example, an ITO substrate of 300 Ω / sq or less functions as a device electrode, but at present it is also possible to supply a substrate of about 10 Ω / sq, for example 100 to 5 Ω / sq, preferably 50 to 5 Ω. It is particularly desirable to use a low resistance product of / □. The thickness of ITO can be arbitrarily selected according to the resistance value, but is usually used in a range of 50 to 300 nm.

<Hole Injection Layer in Organic Electroluminescent Device, Hole Transport Layer>
The hole injection layer 103 plays a role of efficiently injecting holes moving from the anode 102 into the light emitting layer 105 or into the hole transport layer 104. The hole transport layer 104 plays a role of efficiently transporting holes injected from the anode 102 or holes injected from the anode 102 via the hole injection layer 103 to the light emitting layer 105. The hole injection layer 103 and the hole transport layer 104 are each formed by laminating and mixing one or two or more hole injecting / transporting materials, or a mixture of a hole injecting / transporting material and a polymer binder. Be done. In addition, an inorganic salt such as iron (III) chloride may be added to the hole injecting / transporting material to form a layer.

  As the hole injecting / transporting substance, it is necessary to efficiently inject / transport holes from the positive electrode between the electrodes given an electric field, the hole injection efficiency is high, and the injected holes are efficiently transported. It is desirable to do. For this purpose, it is preferable to use a substance that has a low ionization potential, a high hole mobility, excellent stability, and is less likely to generate trapping impurities during production and use.

As a material for forming the hole injection layer 103 and the hole transport layer 104, a compound conventionally used as a charge transport material for holes in a photoconductive material, a p-type semiconductor, and a hole injection layer of an organic EL element are used. Any compound can be selected and used from known compounds used for the hole transport layer. Specific examples thereof include carbazole derivatives (N-phenylcarbazole, polyvinylcarbazole, etc.), biscarbazole derivatives such as bis (N-arylcarbazole) or bis (N-alkylcarbazole), triarylamine derivatives (aromatic tertiary class). Polymer having amino in the main chain or side chain, 1,1-bis (4-di-p-tolylaminophenyl) cyclohexane, N, N'-diphenyl-N, N'-di (3-methylphenyl) -4 , 4′-diaminobiphenyl, N, N′-diphenyl-N, N′-dinaphthyl-4,4′-diaminobiphenyl, N, N′-diphenyl-N, N′-di (3-methylphenyl) -4 , 4'-diphenyl-1,1'-diamine, N, N'-dinaphthyl -N, N'-diphenyl-4,4'-diphenyl-1,1'-diamine, N , N ^{4 '-} diphenyl ^{-N 4,} N ^4' - bis (9-phenyl -9H- carbazol-3-yl) - [1,1'-biphenyl] ^{-4,4'-diamine, N 4,} N 4 , N ^{4 ′} , N ^{4 ′} -tetra [1,1′-biphenyl] -4-yl)-[1,1′-biphenyl] -4,4′-diamine, 4,4 ′, 4 ′ ′-tris ( Triphenylamine derivatives such as 3-methylphenyl (phenyl) amino) triphenylamine, starburst amine derivatives, stilbene derivatives, phthalocyanine derivatives (metal free, copper phthalocyanine etc.), pyrazoline derivatives, hydrazone compounds, benzofuran derivatives, etc. Thiophene derivatives, oxadiazole derivatives, quinoxaline derivatives (eg, 1,4,5,8,9,12-hexaazatriphenylene-2,3,6,7,1 (11-hexacarbonitrile etc.), heterocyclic compounds such as porphyrin derivatives, polysilane etc. In the polymer system, polycarbonates or styrene derivatives having the above-mentioned monomer in the side chain, polyvinylcarbazole, polysilane etc. are preferred, but There is no particular limitation as long as it is a compound that can form a thin film necessary for the fabrication, inject holes from the anode, and further transport holes.

  It is also known that the conductivity of the organic semiconductor is strongly affected by its doping. Such an organic semiconductor matrix material is composed of a compound having a good electron donating property or a compound having a good electron accepting property. Strong electron acceptors such as tetracyanoquinone dimethane (TCNQ) or 2,3,5,6-tetrafluorotetracyano-1,4-benzoquinone dimethane (F4TCNQ) are known for doping of electron donor materials. (For example, the document “M. Pfeiffer, A. Beyer, T. Fritz, K. Leo, Appl. Phys. Lett., 73 (22), 3202-3204 (1998)”) and the document “J. Blochwitz, M Pheiffer, T. Fritz, K. Leo, Appl. Phys. Lett., 73 (6), 729-731 (1998)). These generate so-called holes by the electron transfer process in the electron donating base substance (hole transporting substance). Depending on the number of holes and the mobility, the conductivity of the base material changes considerably. Known matrix substances having hole transporting properties include, for example, benzidine derivatives (TPD and the like), starburst amine derivatives (TDATA and the like), and specific metal phthalocyanines (particularly zinc phthalocyanine (ZnPc) and the like) ( JP-A-2005-167175).

<Light emitting layer in organic electroluminescent device>
The light emitting layer 105 is a layer that emits light by recombining holes injected from the anode 102 and electrons injected from the cathode 108 between electrodes to which an electric field is applied. The material for forming the light-emitting layer 105 may be a compound that emits light by being excited by recombination of holes and electrons (a light-emitting compound), can form a stable thin film shape, and is in a solid state Preferably, they are compounds that exhibit strong luminescence (fluorescence) efficiency. In the present invention, as a material for the light emitting layer, for example, a pyrene-based compound represented by the above general formula (2) as a host material and a polycyclic aromatic compound represented by, for example, the above general formula (1) as a dopant material. Compounds and their multimers can be used.

  The light emitting layer may be either a single layer or a plurality of layers, and each is formed of a light emitting layer material (host material, dopant material). Each of the host material and the dopant material may be of one type or a combination of two or more. The dopant material may be included in the host material as a whole, or may be included partially. As a doping method, it can be formed by a co-evaporation method with a host material, but it may be pre-mixed with the host material and then simultaneously deposited.

  The amount of host material used varies depending on the type of host material, and may be determined in accordance with the characteristics of the host material. The amount of the host material used is preferably 50 to 99.999% by weight, more preferably 80 to 99.95% by weight, and still more preferably 90 to 99.9% by weight of the entire light emitting layer material. It is.

  The amount of dopant material used depends on the type of dopant material, and may be determined according to the characteristics of the dopant material. The standard of the amount of dopant used is preferably 0.001 to 50% by weight, more preferably 0.05 to 20% by weight, and further preferably 0.1 to 10% by weight of the entire material for the light emitting layer. is there. The above range is preferable in that, for example, the concentration quenching phenomenon can be prevented.

  Host materials that can be used in combination with the pyrene-based compound represented by the formula (2) include fused ring derivatives such as anthracene, bisstyryl anthracene derivatives and distyrylbenzene derivatives that have been known as light emitters. Derivatives, tetraphenylbutadiene derivatives, cyclopentadiene derivatives, fluorene derivatives, benzofluorene derivatives, and the like.

  The dopant material that can be used in combination with the polycyclic aromatic compound represented by the formula (1) and its multimer is not particularly limited, and known compounds can be used, and various compounds can be used according to the desired emission color. You can choose from various materials. Specifically, for example, condensed ring derivatives such as phenanthrene, anthracene, tetracene, pentacene, perylene, rubrene and chrysene, benzoxazole derivatives, benzothiazole derivatives, benzimidazole derivatives, benzotriazole derivatives, oxazole derivatives, oxadiazole derivatives, Bistyryl derivatives such as thiazole derivatives, imidazole derivatives, thiadiazole derivatives, triazole derivatives, pyrazoline derivatives, stilbene derivatives, thiophene derivatives, tetraphenylbutadiene derivatives, cyclopentadiene derivatives, bisstyrylanthracene derivatives and distyrylbenzene derivatives (Japanese Patent Laid-Open No. 1-245087) Gazette), bisstyrylarylene derivatives (JP-A-2-247278), diazaindacene derivatives, Derivatives, benzofuran derivatives, phenylisobenzofuran, dimesitylisobenzofuran, di (2-methylphenyl) isobenzofuran, di (2-trifluoromethylphenyl) isobenzofuran, phenylbenzobenzofuran derivatives, dibenzofuran derivatives, 7-dialkylaminocoumarin derivatives, 7-piperidinocoumarin derivatives, 7-hydroxycoumarin derivatives, 7-methoxycoumarin derivatives, 7-acetoxycoumarin derivatives, 3-benzothiazolylcoumarin derivatives, 3-benzoimidazolylcoumarin derivatives, 3- Coumarin derivatives such as benzoxazolyl coumarin derivatives, dicyanomethylenepyran derivatives, dicyanomethylenethiopyran derivatives, polymethine derivatives, cyanine derivatives, oxobenzoanthracene Conductor, xanthene derivative, rhodamine derivative, fluorescein derivative, pyrylium derivative, carbostyril derivative, acridine derivative, oxazine derivative, phenylene oxide derivative, quinacridone derivative, quinazoline derivative, pyrrolopyridine derivative, furopyridine derivative, pyromethene derivative, perinone derivative, pyrrolopyrrole derivative , Squarylium derivatives, violanthrone derivatives, phenazine derivatives, acridone derivatives, deazaflavin derivatives, fluorene derivatives, and benzofluorene derivatives.

<Electron Injection Layer in Organic Electroluminescent Device, Electron Transport Layer>
The electron injection layer 107 plays a role of efficiently injecting electrons moving from the cathode 108 into the light emitting layer 105 or into the electron transport layer 106. The electron transport layer 106 plays a role of efficiently transporting electrons injected from the cathode 108 or electrons injected from the cathode 108 through the electron injection layer 107 to the light emitting layer 105. The electron transport layer 106 and the electron injection layer 107 are each formed by laminating and mixing one or more electron transport / injection materials, or a mixture of an electron transport / injection material and a polymer binder.

  The electron injecting / transporting layer is a layer that injects electrons from the cathode and is responsible for transporting the electrons. It is desirable that the electron injection efficiency is high and the injected electrons are efficiently transported. For this purpose, it is preferable to use a substance that has a high electron affinity, a high electron mobility, excellent stability, and is unlikely to generate trapping impurities during production and use. However, considering the transport balance of holes and electrons, the electron transport capacity is so large when it mainly plays a role of being able to efficiently block the flow of holes from the anode to the cathode side without recombination. Even if it is not high, the effect of improving the light emission efficiency is equal to that of a material having a high electron transport capacity. Therefore, the electron injection / transport layer in this embodiment may include a function of a layer that can efficiently block the movement of holes.

  As a material (electron transport material) which forms the electron transport layer 106 or the electron injection layer 107, a compound conventionally conventionally used as an electron transport compound in a photoconductive material, used for an electron injection layer and an electron transport layer of an organic EL element It can be selected arbitrarily from the known compounds.

  As a material used for the electron transport layer or the electron injection layer, a compound composed of an aromatic ring or a heteroaromatic ring composed of one or more atoms selected from carbon, hydrogen, oxygen, sulfur, silicon and phosphorus, It is preferable to contain at least one selected from pyrrole derivatives, condensed ring derivatives thereof, and metal complexes having electron-accepting nitrogen. Specifically, condensed ring aromatic ring derivatives such as naphthalene and anthracene, styryl aromatic ring derivatives represented by 4,4′-bis (diphenylethenyl) biphenyl, perinone derivatives, coumarin derivatives, naphthalimide derivatives Quinone derivatives such as anthraquinone and diphenoquinone, phosphorus oxide derivatives, carbazole derivatives and indole derivatives. Examples of metal complexes having electron-accepting nitrogen include hydroxyazole complexes such as hydroxyphenyloxazole complexes, azomethine complexes, tropolone metal complexes, flavonol metal complexes, and benzoquinoline metal complexes. These materials may be used alone or in combination with different materials.

  Specific examples of other electron transfer compounds include pyridine derivatives, naphthalene derivatives, anthracene derivatives, phenanthroline derivatives, perinone derivatives, coumarin derivatives, naphthalimide derivatives, anthraquinone derivatives, diphenoquinone derivatives, diphenylquinone derivatives, perylene derivatives, oxadiazoles. Derivatives (1,3-bis [(4-t-butylphenyl) 1,3,4-oxadiazolyl] phenylene etc.), thiophene derivatives, triazole derivatives (N-naphthyl-2,5-diphenyl-1,3,4-) Triazole, etc.), thiadiazole derivatives, metal complexes of oxine derivatives, quinolinol metal complexes, quinoxaline derivatives, polymers of quinoxaline derivatives, benzazole compounds, gallium complexes, pyrazole derivatives, perfluorinated phen Lene derivatives, triazine derivatives, pyrazine derivatives, benzoquinoline derivatives (2,2′-bis (benzo [h] quinolin-2-yl) -9,9′-spirobifluorene, etc.), imidazopyridine derivatives, borane derivatives, benzo Imidazole derivatives (such as tris (N-phenylbenzimidazol-2-yl) benzene), benzoxazole derivatives, benzothiazole derivatives, quinoline derivatives, oligopyridine derivatives such as terpyridine, bipyridine derivatives, terpyridine derivatives (1,3-bis (4 '-(2,2': 6'2 "-terpyridinyl)) benzene), naphthyridine derivatives (bis (1-naphthyl) -4- (1,8-naphthyridin-2-yl) phenylphosphine oxide), aldazine Derivatives, carbazole derivatives, india Le derivatives, phosphorus oxide derivatives, such as bis-styryl derivatives.

  In addition, metal complexes having electron-accepting nitrogen can also be used, such as hydroxyazole complexes such as quinolinol-based metal complexes and hydroxyphenyloxazole complexes, azomethine complexes, tropolone metal complexes, flavonol metal complexes, and benzoquinoline metal complexes. can give.

  The above-described materials may be used alone or in combination with different materials.

  Among the materials described above, borane derivatives, pyridine derivatives, fluoranthene derivatives, BO derivatives, anthracene derivatives, benzofluorene derivatives, phosphine oxide derivatives, pyrimidine derivatives, carbazole derivatives, triazine derivatives, benzimidazole derivatives, phenanthroline derivatives, and quinolinol metals Complexes are preferred.

Borane derivative
The borane derivative is, for example, a compound represented by the following general formula (ETM-1), and is disclosed in detail in Japanese Patent Application Laid-Open No. 2007-27587.
In the above formula (ETM-1), R ¹¹ and R ¹² are each independently hydrogen, alkyl, cycloalkyl, aryl which may be substituted, silyl which is substituted, or nitrogen which may be substituted It is at least one of a heterocyclic ring or cyano, and R ^{13 to} R ¹⁶ are each independently an optionally substituted alkyl, an optionally substituted cycloalkyl or an optionally substituted aryl. , X is an optionally substituted arylene, Y is an optionally substituted aryl having 16 or less carbon atoms, a substituted boryl, or an optionally substituted carbazolyl, and n Are each independently an integer of 0 to 3. Also, the substituent “optionally substituted” or “substituted” includes aryl, heteroaryl, alkyl or cycloalkyl and the like.

Among the compounds represented by the above general formula (ETM-1), compounds represented by the following general formula (ETM-1-1) and compounds represented by the following general formula (ETM-1-2) are preferable.
In formula (ETM-1-1), R ¹¹ and R ¹² are each independently hydrogen, alkyl, cycloalkyl, aryl which may be substituted, silyl which is substituted, nitrogen which may be substituted A heterocyclic group containing at least one of cyano and R ^{13 to} R ¹⁶ each independently represents an optionally substituted alkyl, an optionally substituted cycloalkyl, or an optionally substituted aryl. Each of R ²¹ and R ²² is independently hydrogen, alkyl, cycloalkyl, optionally substituted aryl, substituted silyl, optionally substituted nitrogen-containing heterocycle, or cyano; is one, X ¹ is arylene of more than 20 carbon atoms which may be substituted, n is each independently represents an integer of 0 to 3, To, m is an integer of independently 0-4. Also, the substituent “optionally substituted” or “substituted” includes aryl, heteroaryl, alkyl or cycloalkyl and the like.
In the formula (ETM-1-2), R ¹¹ and R ¹² are each independently hydrogen, alkyl, cycloalkyl, aryl which may be substituted, silyl which is substituted, nitrogen which may be substituted A heterocyclic group containing at least one of cyano and R ^{13 to} R ¹⁶ each independently represents an optionally substituted alkyl, an optionally substituted cycloalkyl, or an optionally substituted aryl. And X ¹ is an optionally substituted arylene having 20 or less carbon atoms, and n is each independently an integer of 0 to 3. Also, the substituent “optionally substituted” or “substituted” includes aryl, heteroaryl, alkyl or cycloalkyl and the like.

Specific examples of X ¹ include divalent groups represented by the following formulas (X-1) to (X-9).
(In each formula, R ^a is each independently an alkyl group, a cycloalkyl group or a phenyl group which may be substituted.)

Specific examples of this borane derivative include the following compounds.

  The borane derivative can be produced using known starting materials and known synthetic methods.

<Pyridine derivative>
The pyridine derivative is, for example, a compound represented by the following formula (ETM-2), and preferably a compound represented by the formula (ETM-2-1) or the formula (ETM-2-2).

  φ is an n-valent aryl ring (preferably an n-valent benzene ring, naphthalene ring, anthracene ring, fluorene ring, benzofluorene ring, phenalene ring, phenanthrene ring or triphenylene ring), and n is an integer of 1 to 4. is there.

In the above formula (ETM-2-1), R ^{11 to} R ¹⁸ each independently represent hydrogen, alkyl (preferably alkyl having 1 to 24 carbon atoms), or cycloalkyl (preferably cyclo alkyl having 3 to 12 carbon atoms). Alkyl) or aryl (preferably aryl having 6 to 30 carbon atoms).

In the above formula (ETM-2-2), R ¹¹ and R ¹² each independently represent hydrogen, alkyl (preferably alkyl having 1 to 24 carbon atoms), or cycloalkyl (preferably cycloalkenyl having 3 to 12 carbon atoms) R ¹¹ and R ¹² may be combined to form a ring, which is alkyl) or aryl (preferably aryl having 6 to 30 carbon atoms).

  In each formula, the "pyridine-based substituent" is any one of the following formulas (Py-1) to (Py-15), and the pyridine-based substituent is each independently an alkyl having 1 to 4 carbon atoms or carbon It may be substituted by the number 5-10 cycloalkyl. Further, the pyridine-based substituent may be bonded to φ, anthracene ring or fluorene ring in each formula through a phenylene group or a naphthylene group.

The pyridine-based substituent is any one of the above formulas (Py-1) to (Py-15), and among these, any of the following formulas (Py-21) to (Py-44). Is preferred.

  At least one hydrogen in each pyridine derivative may be substituted with deuterium, and among the two “pyridine-based substituents” in the above formulas (ETM-2-1) and (ETM-2-2) One of them may be replaced by aryl.

The “alkyl” in R ^{11 to} R ¹⁸ may be linear or branched, and examples thereof include linear alkyl having 1 to 24 carbon atoms or branched alkyl having 3 to 24 carbon atoms. Preferred “alkyl” is alkyl having 1 to 18 carbons (branched alkyl having 3 to 18 carbons). More preferable “alkyl” is alkyl having 1 to 12 carbons (branched alkyl having 3 to 12 carbons). More preferable “alkyl” is alkyl having 1 to 6 carbon atoms (branched alkyl having 3 to 6 carbon atoms). Particularly preferred “alkyl” is alkyl having 1 to 4 carbon atoms (branched alkyl having 3 to 4 carbon atoms).

  Specific examples of “alkyl” include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, isopentyl, neopentyl, t-pentyl, n-hexyl, 1 -Methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, n-heptyl, 1-methylhexyl, n-octyl, t-octyl, 1-methylheptyl, 2-ethylhexyl, 2 -Propylpentyl, n-nonyl, 2,2-dimethylheptyl, 2,6-dimethyl-4-heptyl, 3,5,5-trimethylhexyl, n-decyl, n-undecyl, 1-methyldecyl, n-dodecyl, n-tridecyl, 1-hexylheptyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-hept Decyl, n- octadecyl, such as n- eicosyl, and the like.

  The description of the said alkyl can be quoted as a C1-C4 alkyl substituted by a pyridine-type substituent.

Examples of “cycloalkyl” in R ^{11 to} R ¹⁸ include cycloalkyl having 3 to 12 carbon atoms. Preferred "cycloalkyl" is cycloalkyl having 3 to 10 carbons. More preferable "cycloalkyl" is cycloalkyl having 3 to 8 carbon atoms. More preferable "cycloalkyl" is cycloalkyl having 3 to 6 carbon atoms.
Specific examples of “cycloalkyl” include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclopentyl, cycloheptyl, methylcyclohexyl, cyclooctyl, and dimethylcyclohexyl.

  As the cycloalkyl having 5 to 10 carbon atoms to be substituted with the pyridine-based substituent, the description of the above cycloalkyl can be cited.

As “aryl” in R ^{11 to} R ¹⁸ , preferable aryl is aryl having 6 to 30 carbon atoms, more preferable aryl is aryl having 6 to 18 carbon atoms, and more preferably aryl having 6 to 14 carbon atoms And particularly preferably aryl having 6 to 12 carbon atoms.

  Specific examples of “aryl having 6 to 30 carbon atoms” include phenyl as monocyclic aryl, (1-, 2-) naphthyl as condensed bicyclic aryl, and acenaphthylene- (as condensed tricyclic aryl. 1-, 3-, 4-, 5-) yl, fluorene- (1-, 2-, 3-, 4-, 9-) yl, phenalen- (1-, 2-) yl, (1-, 2 -, 3-, 4-, 9-) phenanthryl, fused tetracyclic aryl triphenylene- (1-, 2-) yl, pyrene- (1-, 2-, 4-) yl, naphthacene- (1- , 2-, 5-) yl, condensed pentacyclic aryl perylene- (1-, 2-, 3-) yl, pentacene- (1-, 2-, 5-, 6-) yl and the like. .

  Preferred examples of the “aryl having 6 to 30 carbon atoms” include phenyl, naphthyl, phenanthryl, chrysenyl, triphenylenyl and the like, more preferred are phenyl, 1-naphthyl, 2-naphthyl and phenanthryl, and particularly preferred are phenyl, 1 -Naphthyl or 2-naphthyl is mentioned.

R ¹¹ and R ¹² in the above formula (ETM-2-2) may be bonded to form a ring. As a result, the 5-membered ring of the fluorene skeleton includes cyclobutane, cyclopentane, cyclopentene, cyclopentadiene, Cyclohexane, fluorene, indene and the like may be spiro-bonded.

Specific examples of the pyridine derivative include the following compounds.

  This pyridine derivative can be produced using known starting materials and known synthesis methods.

<Fluoranthene derivative>
The fluoranthene derivative is, for example, a compound represented by the following general formula (ETM-3), and is disclosed in detail in International Publication No. 2010/134352.

In the above formula (ETM-3), X ^{12 to} X ²¹ are hydrogen, halogen, linear, branched or cyclic alkyl, linear, branched or cyclic alkoxy, substituted or unsubstituted aryl, or substituted or unsubstituted Represents heteroaryl. Here, as the substituent when substituted, aryl, heteroaryl, alkyl, cycloalkyl and the like can be mentioned.

Specific examples of the fluoranthene derivative include the following compounds.

<BO derivatives>
The BO derivative is, for example, a polycyclic aromatic compound represented by the following formula (ETM-4) or a multimer of polycyclic aromatic compounds having a plurality of structures represented by the following formula (ETM-4).

R ^{1 to} R ¹¹ are each independently hydrogen, aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, alkyl, cycloalkyl, alkoxy or aryloxy, and at least one hydrogen thereof May be substituted with aryl, heteroaryl, alkyl or cycloalkyl.

Further, adjacent groups among R ^{1 to} R ¹¹ may be combined to form an aryl ring or heteroaryl ring together with the a ring, b ring or c ring, and at least one hydrogen in the formed ring May be substituted with aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, alkyl, cycloalkyl, alkoxy or aryloxy, wherein at least one hydrogen is aryl, heteroaryl, alkyl or It may be substituted with cycloalkyl.

  In addition, at least one hydrogen in the compound or structure represented by the formula (ETM-4) may be substituted with halogen or deuterium.

  About description of the form of substituent and ring formation in Formula (ETM-4), the description of the polycyclic aromatic compound represented by the said General formula (1) can be cited.

Specific examples of this BO derivative include the following compounds.

  This BO-based derivative can be produced using known starting materials and known synthesis methods.

<Anthracene derivative>
One of the anthracene derivatives is a compound represented by the following formula (ETM-5-1), for example.

Ar is each independently divalent benzene or naphthalene, and R ^{1 to} R ⁴ are each independently hydrogen, alkyl having 1 to 6 carbons, cycloalkyl having 3 to 6 carbons or carbon number 6-20 aryl.

  Ar may be each independently selected from divalent benzene or naphthalene, and two Ar may be different or the same, but the same from the viewpoint of easiness of synthesis of anthracene derivative Is preferred. Ar is bonded to pyridine to form "a moiety consisting of Ar and pyridine", and this moiety is, for example, anthracene as a group represented by any of the following formulas (Py-1) to (Py-12) Combined with

  Among these groups, a group represented by any one of the above formulas (Py-1) to (Py-9) is preferable, and any one of the above formulas (Py-1) to (Py-6) is represented. More preferred. The two “sites consisting of Ar and pyridine” bonded to anthracene may have the same or different structures, but preferably have the same structure from the viewpoint of the ease of synthesis of the anthracene derivative. However, from the viewpoint of device characteristics, it is preferable that the structures of the two “sites composed of Ar and pyridine” are the same or different.

The alkyl having 1 to 6 carbon atoms in R ^{1 to} R ⁴ may be linear or branched. That is, it is C1-C6 linear alkyl or C3-C6 branched alkyl. More preferably, it is a C1-C4 alkyl (C3-C4 branched alkyl). Specific examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, isopentyl, neopentyl, t-pentyl, n-hexyl, 1-methylpentyl, 4-methyl-2-pentyl, 3, 3-dimethylbutyl, 2-ethylbutyl and the like, and methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl or t-butyl are preferable. More preferred are methyl, ethyl, or t-butyl.

Specific examples of the cycloalkyl having 3 to 6 carbon atoms in R ^{1 to} R ⁴ include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclopentyl, cycloheptyl, methylcyclohexyl, cyclooctyl, and dimethylcyclohexyl.

The aryl having 6 to 20 carbon atoms for R ¹ to R ^4, preferably an aryl of 6 to 16 carbon atoms, more preferably an aryl having 6 to 12 carbon atoms, particularly preferably an aryl having 6 to 10 carbon atoms.

  Specific examples of “C6-C20 aryl” include monocyclic aryl phenyl, (o-, m-, p-) tolyl, (2,3-, 2,4-, 2,5- , 2,6-, 3,4-, 3,5-) xylyl, mesityl (2,4,6-trimethylphenyl), (o-, m-, p-) cumenyl, bicyclic aryl (2 -, 3-, 4-) biphenylyl, (1-, 2-) naphthyl which is a condensed bicyclic aryl, terphenylyl (m-terphenyl-2'-yl, m-terphenyl-4) which is a tricyclic aryl '-Yl, m-terphenyl-5'-yl, o-terphenyl-3'-yl, o-terphenyl-4'-yl, p-terphenyl-2'-yl, m-terphenyl-2 -Yl, m-terphenyl-3-yl, m-terphenyl-4-yl, o-terphenyl 2-yl, o-terphenyl-3-yl, o-terphenyl-4-yl, p-terphenyl-2-yl, p-terphenyl-3-yl, p-terphenyl-4-yl) Anthracene- (1-, 2-, 9-) yl, acenaphthylene- (1-, 3-, 4-, 5-) yl, fluorene- (1-, 2-, 3), which are fused tricyclic aryls -, 4-, 9-) yl, phenalene- (1-, 2-) yl, (1-, 2-, 3-, 4-, 9-) phenanthryl, triphenylene- (1) which is a fused tetracyclic aryl group -, 2-) yl, pyrene- (1-, 2-, 4-) yl, tetracene- (1-, 2-, 5-) yl, perylene- (1-, 2-) which is a fused pentacyclic aryl , 3-) Ill and the like.

  Preferred "C6-C20 aryl" is phenyl, biphenylyl, terphenylyl or naphthyl, more preferably phenyl, biphenylyl, 1-naphthyl, 2-naphthyl or m-terphenyl-5'-yl, More preferably, it is phenyl, biphenylyl, 1-naphthyl or 2-naphthyl, most preferably phenyl.

One of the anthracene derivatives is, for example, a compound represented by the following formula (ETM-5-2).

Ar ^{1 's} each independently represent a single bond, divalent benzene, naphthalene, anthracene, fluorene or phenalene.

Ar ² is each independently an aryl having 6 to 20 carbon atoms, and the same description as “aryl having 6 to 20 carbon atoms” in the above formula (ETM-5-1) can be cited. C6-C16 aryl is preferable, C6-C12 aryl is more preferable, and C6-C10 aryl is especially preferable. Specific examples include phenyl, biphenylyl, naphthyl, terphenylyl, anthracenyl, acenaphthylenyl, fluorenyl, phenalenyl, phenanthryl, triphenylenyl, pyrenyl, tetracenyl, perylenyl and the like.

R ^{1 to} R ⁴ are each independently hydrogen, alkyl having 1 to 6 carbons, cycloalkyl having 3 to 6 carbons or aryl having 6 to 20 carbons, and the above formula (ETM-5-1) The explanation in can be cited.

Specific examples of these anthracene derivatives include the following compounds.

  These anthracene derivatives can be produced using known raw materials and known synthesis methods.

<Benzofluorene derivative>
The benzofluorene derivative is, for example, a compound represented by the following formula (ETM-6).

Ar ¹ is each independently an aryl having 6 to 20 carbon atoms, and the same description as “aryl having 6 to 20 carbon atoms” in the above formula (ETM-5-1) can be cited. C6-C16 aryl is preferable, C6-C12 aryl is more preferable, and C6-C10 aryl is especially preferable. Specific examples include phenyl, biphenylyl, naphthyl, terphenylyl, anthracenyl, acenaphthylenyl, fluorenyl, phenalenyl, phenanthryl, triphenylenyl, pyrenyl, tetracenyl, perylenyl and the like.

Ar ² is independently hydrogen, alkyl (preferably alkyl having 1 to 24 carbon atoms), cycloalkyl (preferably cycloalkyl having 3 to 12 carbon atoms) or aryl (preferably aryl having 6 to 30 carbon atoms). And two Ar ^{2 's} may combine to form a ring.

The “alkyl” in Ar ² may be linear or branched, and examples thereof include linear alkyl having 1 to 24 carbon atoms or branched alkyl having 3 to 24 carbon atoms. Preferred “alkyl” is alkyl having 1 to 18 carbons (branched alkyl having 3 to 18 carbons). More preferable “alkyl” is alkyl having 1 to 12 carbons (branched alkyl having 3 to 12 carbons). More preferable “alkyl” is alkyl having 1 to 6 carbon atoms (branched alkyl having 3 to 6 carbon atoms). Particularly preferred “alkyl” is alkyl having 1 to 4 carbon atoms (branched alkyl having 3 to 4 carbon atoms). Specific “alkyl” includes methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, n-hexyl, 1 -Methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, n-heptyl, 1-methylhexyl and the like.

Examples of “cycloalkyl” in Ar ² include cycloalkyl having 3 to 12 carbon atoms. Preferred "cycloalkyl" is cycloalkyl having 3 to 10 carbons. More preferable "cycloalkyl" is cycloalkyl having 3 to 8 carbon atoms. More preferable "cycloalkyl" is cycloalkyl having 3 to 6 carbon atoms. Specific examples of “cycloalkyl” include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclopentyl, cycloheptyl, methylcyclohexyl, cyclooctyl, and dimethylcyclohexyl.

As “aryl” in Ar ² , preferred aryl is aryl having 6 to 30 carbon atoms, more preferred aryl is aryl having 6 to 18 carbon atoms, still more preferred is aryl having 6 to 14 carbon atoms, Preferably it is C6-C12 aryl.

  Specific examples of "aryl having 6 to 30 carbon atoms" include phenyl, naphthyl, acenaphthyrenyl, fluorenyl, phenalenyl, phenanthryl, triphenylenyl, pyrenyl, naphthacenyl, perylenyl, pentacenyl and the like.

Two Ar ² may be bonded to form a ring. As a result, cyclobutane, cyclopentane, cyclopentene, cyclopentadiene, cyclohexane, fluorene, or indene is spiro-bonded to the 5-membered ring of the fluorene skeleton. May be

Specific examples of the benzofluorene derivative include the following compounds.

  This benzofluorene derivative can be produced using a known raw material and a known synthesis method.

<Phosphine oxide derivative>
The phosphine oxide derivative is, for example, a compound represented by the following formula (ETM-7-1). The details are also described in WO 2013/079217.
R ⁵ is a substituted or unsubstituted alkyl having 1 to 20 carbons, cycloalkyl having 3 to 20 carbons, aryl having 6 to 20 carbons or heteroaryl having 5 to 20 carbons,
R ⁶ is CN, substituted or unsubstituted alkyl having 1 to 20 carbons, cycloalkyl having 3 to 20 carbons, heteroalkyl having 1 to 20 carbons, aryl having 6 to 20 carbons, having 5 to 5 carbons 20 heteroaryl, alkoxy having 1 to 20 carbons or aryloxy having 6 to 20 carbons,
R ⁷ and R ⁸ are each independently substituted or unsubstituted aryl having 6 to 20 carbon atoms or heteroaryl having 5 to 20 carbon atoms,
R ⁹ is oxygen or sulfur;
j is 0 or 1, k is 0 or 1, r is an integer of 0 to 4, and q is an integer of 1 to 3.
Here, as the substituent when substituted, aryl, heteroaryl, alkyl, cycloalkyl and the like can be mentioned.

The phosphine oxide derivative may be a compound represented by the following formula (ETM-7-2), for example.

R ^{1 to} R ³ may be the same or different, and hydrogen, alkyl group, cycloalkyl group, aralkyl group, alkenyl group, cycloalkenyl group, cycloalkenyl group, alkynyl group, alkoxy group, alkylthio group, cycloalkylthio group, aryl ether group Arylthioether group, aryl group, heterocyclic group, halogen, cyano group, aldehyde group, carbonyl group, carboxyl group, amino group, nitro group, silyl group, and condensed ring formed between adjacent substituents It is chosen from

Ar ¹ may be the same or different, and is an arylene group or a heteroarylene group. Ar ² may be the same or different, and is an aryl group or a heteroaryl group. However, at least one of Ar ¹ and Ar ² has a substituent or forms a condensed ring with an adjacent substituent. n is an integer of 0 to 3. When n is 0, there is no unsaturated structure, and when n is 3, R ¹ does not exist.

  Among these substituents, the alkyl group is, for example, a saturated aliphatic hydrocarbon group such as a methyl group, an ethyl group, a propyl group or a butyl group, which may be unsubstituted or substituted. The substituent in the case of being substituted is not particularly limited, and examples thereof include an alkyl group, an aryl group, and a heterocyclic group, and this point is common to the following description. Further, the number of carbon atoms of the alkyl group is not particularly limited, but is usually in the range of 1 to 20 from the viewpoint of availability and cost.

  The cycloalkyl group is a saturated alicyclic hydrocarbon group such as cyclopropyl, cyclohexyl, norbornyl, adamantyl and the like, which may be unsubstituted or substituted. The carbon number of the alkyl group moiety is not particularly limited, but is usually in the range of 3 to 20.

  The aralkyl group is, for example, an aromatic hydrocarbon group via an aliphatic hydrocarbon such as benzyl group or phenylethyl group, and both the aliphatic hydrocarbon and the aromatic hydrocarbon may be substituted even without substitution. It doesn't matter. The carbon number of the aliphatic moiety is not particularly limited, but is usually in the range of 1 to 20.

  Moreover, an alkenyl group shows the unsaturated aliphatic hydrocarbon group containing double bonds, such as a vinyl group, an allyl group, and a butadienyl group, for example, This may be unsubstituted or substituted. Although carbon number of an alkenyl group is not specifically limited, Usually, it is the range of 2-20.

  Moreover, a cycloalkenyl group shows the unsaturated alicyclic hydrocarbon group containing double bonds, such as a cyclopentenyl group, a cyclopentadienyl group, a cyclohexene group etc., and this may be unsubstituted or substituted, It doesn't matter.

  The alkynyl group represents an unsaturated aliphatic hydrocarbon group containing a triple bond such as an acetylenyl group, which may be unsubstituted or substituted. Although carbon number of an alkynyl group is not specifically limited, Usually, it is the range of 2-20.

  The alkoxy group refers to, for example, an aliphatic hydrocarbon group via an ether bond such as a methoxy group, and the aliphatic hydrocarbon group may be unsubstituted or substituted. The carbon number of the alkoxy group is not particularly limited, but is usually in the range of 1 to 20.

  The alkylthio group is a group in which an oxygen atom of an ether bond of an alkoxy group is substituted with a sulfur atom.

  The cycloalkylthio group is a group in which an oxygen atom of an ether bond of a cycloalkoxy group is substituted with a sulfur atom.

  The aryl ether group is, for example, an aromatic hydrocarbon group via an ether bond such as a phenoxy group, and the aromatic hydrocarbon group may be unsubstituted or substituted. The carbon number of the aryl ether group is not particularly limited, but is usually in the range of 6 to 40.

  The aryl thioether group is a group in which an oxygen atom of an ether bond of an aryl ether group is substituted with a sulfur atom.

  Moreover, an aryl group shows aromatic hydrocarbon groups, such as a phenyl group, a naphthyl group, a biphenyl group, a phenanthryl group, a terphenyl group, a pyrenyl group, for example. The aryl group may be unsubstituted or substituted. The carbon number of the aryl group is not particularly limited, but is usually in the range of 6 to 40.

  The heterocyclic group is a cyclic structural group having an atom other than carbon, such as furanyl group, thiophenyl group, oxazolyl group, pyridyl group, quinolinyl group, carbazolyl group, etc., and this group is unsubstituted or substituted. It doesn't matter. The carbon number of the heterocyclic group is not particularly limited, but is usually in the range of 2 to 30.

  Halogen is fluorine, chlorine, bromine or iodine.

  The aldehyde group, carbonyl group, and amino group may include a group substituted with an aliphatic hydrocarbon, an alicyclic hydrocarbon, an aromatic hydrocarbon, a heterocyclic ring, or the like.

  Further, the aliphatic hydrocarbon, alicyclic hydrocarbon, aromatic hydrocarbon, and heterocyclic ring may be unsubstituted or substituted.

  The silyl group indicates, for example, a silicon compound group such as a trimethylsilyl group, which may be unsubstituted or substituted. The carbon number of the silyl group is not particularly limited, but is usually in the range of 3 to 20. Moreover, the number of silicon is 1-6 normally.

The condensed ring formed between adjacent substituents includes, for example, Ar ¹ and R ² , Ar ¹ and R ³ , Ar ² and R ² , Ar ² and R ³ , R ² and R ³ , Ar ¹ and It is a conjugated or non-conjugated fused ring formed between Ar ^{2 and the} like. Here, when n is 1, it may be formed conjugated or non-conjugated fused ring with two of R ¹ each other. These fused rings may contain nitrogen, oxygen and sulfur atoms in the ring structure, and may be fused to another ring.

Specific examples of this phosphine oxide derivative include the following compounds.

  The phosphine oxide derivative can be produced using known raw materials and known synthetic methods.

<Pyrimidine derivative>
The pyrimidine derivative is, for example, a compound represented by the following formula (ETM-8), and preferably a compound represented by the following formula (ETM-8-1). Details are also described in International Publication No. 2011/021689.

  Ar is each independently an optionally substituted aryl or an optionally substituted heteroaryl. n is an integer of 1 to 4, preferably an integer of 1 to 3, and more preferably 2 or 3.

  Examples of “aryl” of “optionally substituted aryl” include aryl having 6 to 30 carbon atoms, preferably aryl having 6 to 24 carbon atoms, more preferably aryl having 6 to 20 carbon atoms, More preferred is aryl having 6 to 12 carbon atoms.

  Specific "aryl" is phenyl which is monocyclic aryl, (2-, 3-, 4-) biphenylyl which is bicyclic aryl, (1-, 2-) naphthyl which is fused bicyclic aryl. Or terphenylyl (m-terphenyl-2′-yl, m-terphenyl-4′-yl, m-terphenyl-5′-yl, o-terphenyl-3′-yl, o, which is a tricyclic aryl group, o -Terphenyl-4'-yl, p-terphenyl-2'-yl, m-terphenyl-2-yl, m-terphenyl-3-yl, m-terphenyl-4-yl, o-terphenyl 2-yl, o-terphenyl-3-yl, o-terphenyl-4-yl, p-terphenyl-2-yl, p-terphenyl-3-yl, p-terphenyl-4-yl) Acenaphth, which is a fused tricyclic aryl Ren- (1-, 3-, 4-, 5-) yl, fluorene- (1-, 2-, 3-, 4-, 9-) yl, phenalen- (1-, 2-) yl, (1 -, 2-, 3-, 4-, 9-) phenanthryl, tetracyclic aryl quaterphenylyl (5'-phenyl-m-terphenyl-2-yl, 5'-phenyl-m-terphenyl -3-yl, 5'-phenyl-m-terphenyl-4-yl, m-quaterphenylyl), fused tetracyclic aryl triphenylene- (1-, 2-) yl, pyrene- (1-) , 2-, 4-) yl, naphthacene- (1-, 2-, 5-) yl, fused pentacyclic aryl perylene- (1-, 2-, 3-) yl, pentacene- (1-, 2-, 5-, 6-yl, etc.

  Examples of “heteroaryl” of “optionally substituted heteroaryl” include, for example, heteroaryl having 2 to 30 carbon atoms, and heteroaryl having 2 to 25 carbon atoms is preferable, and hetero having 2 to 20 carbon atoms Aryl is more preferred, heteroaryl having 2 to 15 carbons is more preferred, and heteroaryl having 2 to 10 carbons is particularly preferred. Examples of the heteroaryl include heterocycles containing 1 to 5 heteroatoms selected from oxygen, sulfur and nitrogen in addition to carbon as ring constituent atoms.

  Specific examples of heteroaryl include furyl, thienyl, pyrrolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, pyrazolyl, oxadiazolyl, furazanyl, thiadiazolyl, triazolyl, tetrazolyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, benzofuranyl, Isobenzofuranyl, benzo [b] thienyl, indolyl, isoindolyl, 1H-indazolyl, benzoimidazolyl, benzoxazolyl, benzothiazolyl, 1H-benzotriazolyl, quinolyl, isoquinolyl, cinnolyl, quinazolyl, quinoxalinyl, phthalazinyl, naphthyridinyl, purinyl Pteridinyl, carbazolyl, acridinyl, phenoxazinyl, phenothiazinyl, Najiniru, phenoxathiinyl, thianthrenyl, etc. indolizinyl the like.

  The aryl and heteroaryl may be substituted, and may be substituted with, for example, the aryl or heteroaryl.

Specific examples of this pyrimidine derivative include the following compounds.

  The pyrimidine derivative can be produced using known starting materials and known synthetic methods.

<Carbazole Derivative>
The carbazole derivative is, for example, a compound represented by the following formula (ETM-9), or a multimer in which a plurality of compounds are linked via a single bond or the like. Details are described in US Publication No. 2014/0197386.

  Ar is each independently an optionally substituted aryl or an optionally substituted heteroaryl. n is each independently an integer of 0 to 4, preferably an integer of 0 to 3, more preferably 0 or 1.

  Examples of “aryl” of “optionally substituted aryl” include aryl having 6 to 30 carbon atoms, preferably aryl having 6 to 24 carbon atoms, more preferably aryl having 6 to 20 carbon atoms, More preferred is aryl having 6 to 12 carbon atoms.

  Specific "aryl" is phenyl which is monocyclic aryl, (2-, 3-, 4-) biphenylyl which is bicyclic aryl, (1-, 2-) naphthyl which is fused bicyclic aryl. Or terphenylyl (m-terphenyl-2′-yl, m-terphenyl-4′-yl, m-terphenyl-5′-yl, o-terphenyl-3′-yl, o, which is a tricyclic aryl group, o -Terphenyl-4'-yl, p-terphenyl-2'-yl, m-terphenyl-2-yl, m-terphenyl-3-yl, m-terphenyl-4-yl, o-terphenyl 2-yl, o-terphenyl-3-yl, o-terphenyl-4-yl, p-terphenyl-2-yl, p-terphenyl-3-yl, p-terphenyl-4-yl) Acenaphth, which is a fused tricyclic aryl Ren- (1-, 3-, 4-, 5-) yl, fluorene- (1-, 2-, 3-, 4-, 9-) yl, phenalen- (1-, 2-) yl, (1 -, 2-, 3-, 4-, 9-) phenanthryl, tetracyclic aryl quaterphenylyl (5'-phenyl-m-terphenyl-2-yl, 5'-phenyl-m-terphenyl -3-yl, 5'-phenyl-m-terphenyl-4-yl, m-quaterphenylyl), fused tetracyclic aryl triphenylene- (1-, 2-) yl, pyrene- (1-) , 2-, 4-) yl, naphthacene- (1-, 2-, 5-) yl, fused pentacyclic aryl perylene- (1-, 2-, 3-) yl, pentacene- (1-, 2-, 5-, 6-yl, etc.

  Examples of “heteroaryl” of “optionally substituted heteroaryl” include, for example, heteroaryl having 2 to 30 carbon atoms, and heteroaryl having 2 to 25 carbon atoms is preferable, and hetero having 2 to 20 carbon atoms Aryl is more preferred, heteroaryl having 2 to 15 carbons is more preferred, and heteroaryl having 2 to 10 carbons is particularly preferred. Examples of the heteroaryl include heterocycles containing 1 to 5 heteroatoms selected from oxygen, sulfur and nitrogen in addition to carbon as ring constituent atoms.

  Specific examples of heteroaryl include furyl, thienyl, pyrrolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, pyrazolyl, oxadiazolyl, furazanyl, thiadiazolyl, triazolyl, tetrazolyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, benzofuranyl, Isobenzofuranyl, benzo [b] thienyl, indolyl, isoindolyl, 1H-indazolyl, benzoimidazolyl, benzoxazolyl, benzothiazolyl, 1H-benzotriazolyl, quinolyl, isoquinolyl, cinnolyl, quinazolyl, quinoxalinyl, phthalazinyl, naphthyridinyl, purinyl Pteridinyl, carbazolyl, acridinyl, phenoxazinyl, phenothiazinyl, Najiniru, phenoxathiinyl, thianthrenyl, etc. indolizinyl the like.

  The aryl and heteroaryl may be substituted, and may be substituted with, for example, the aryl or heteroaryl.

  The carbazole derivative may be a multimer in which a plurality of compounds represented by the above formula (ETM-9) are bonded by a single bond or the like. In this case, in addition to a single bond, an aryl ring (preferably a polyvalent benzene ring, naphthalene ring, anthracene ring, fluorene ring, benzofluorene ring, phenalene ring, phenanthrene ring or triphenylene ring) may be used.

Specific examples of the carbazole derivative include the following compounds.

  This carbazole derivative can be produced using known raw materials and known synthetic methods.

<Triazine derivative>
The triazine derivative is, for example, a compound represented by the following formula (ETM-10), preferably a compound represented by the following formula (ETM-10-1). Details are described in US Publication No. 2011/0156013.

  Ar is each independently an optionally substituted aryl or an optionally substituted heteroaryl. n is an integer of 1 to 3, preferably 2 or 3.

  Examples of “aryl” of “optionally substituted aryl” include aryl having 6 to 30 carbon atoms, preferably aryl having 6 to 24 carbon atoms, more preferably aryl having 6 to 20 carbon atoms, More preferred is aryl having 6 to 12 carbon atoms.

  Specific "aryl" is phenyl which is monocyclic aryl, (2-, 3-, 4-) biphenylyl which is bicyclic aryl, (1-, 2-) naphthyl which is fused bicyclic aryl. Or terphenylyl (m-terphenyl-2′-yl, m-terphenyl-4′-yl, m-terphenyl-5′-yl, o-terphenyl-3′-yl, o, which is a tricyclic aryl group, o -Terphenyl-4'-yl, p-terphenyl-2'-yl, m-terphenyl-2-yl, m-terphenyl-3-yl, m-terphenyl-4-yl, o-terphenyl 2-yl, o-terphenyl-3-yl, o-terphenyl-4-yl, p-terphenyl-2-yl, p-terphenyl-3-yl, p-terphenyl-4-yl) Acenaphth, which is a fused tricyclic aryl Ren- (1-, 3-, 4-, 5-) yl, fluorene- (1-, 2-, 3-, 4-, 9-) yl, phenalen- (1-, 2-) yl, (1 -, 2-, 3-, 4-, 9-) phenanthryl, tetracyclic aryl quaterphenylyl (5'-phenyl-m-terphenyl-2-yl, 5'-phenyl-m-terphenyl -3-yl, 5'-phenyl-m-terphenyl-4-yl, m-quaterphenylyl), fused tetracyclic aryl triphenylene- (1-, 2-) yl, pyrene- (1-) , 2-, 4-) yl, naphthacene- (1-, 2-, 5-) yl, fused pentacyclic aryl perylene- (1-, 2-, 3-) yl, pentacene- (1-, 2-, 5-, 6-yl, etc.

  Examples of “heteroaryl” of “optionally substituted heteroaryl” include, for example, heteroaryl having 2 to 30 carbon atoms, and heteroaryl having 2 to 25 carbon atoms is preferable, and hetero having 2 to 20 carbon atoms Aryl is more preferred, heteroaryl having 2 to 15 carbons is more preferred, and heteroaryl having 2 to 10 carbons is particularly preferred. Examples of the heteroaryl include heterocycles containing 1 to 5 heteroatoms selected from oxygen, sulfur and nitrogen in addition to carbon as ring constituent atoms.

  Specific examples of heteroaryl include furyl, thienyl, pyrrolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, pyrazolyl, oxadiazolyl, furazanyl, thiadiazolyl, triazolyl, tetrazolyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, benzofuranyl, Isobenzofuranyl, benzo [b] thienyl, indolyl, isoindolyl, 1H-indazolyl, benzoimidazolyl, benzoxazolyl, benzothiazolyl, 1H-benzotriazolyl, quinolyl, isoquinolyl, cinnolyl, quinazolyl, quinoxalinyl, phthalazinyl, naphthyridinyl, purinyl Pteridinyl, carbazolyl, acridinyl, phenoxazinyl, phenothiazinyl, Najiniru, phenoxathiinyl, thianthrenyl, etc. indolizinyl the like.

  The aryl and heteroaryl may be substituted, and may be substituted with, for example, the aryl or heteroaryl.

Specific examples of the triazine derivative include the following compounds.

  This triazine derivative can be produced using a known raw material and a known synthesis method.

<Benzimidazole derivative>
The benzimidazole derivative is, for example, a compound represented by the following formula (ETM-11).

φ is an n-valent aryl ring (preferably an n-valent benzene ring, naphthalene ring, anthracene ring, fluorene ring, benzofluorene ring, phenalene ring, phenanthrene ring or triphenylene ring), and n is an integer of 1 to 4. Yes, the “benzimidazole-based substituent” means that the pyridyl group in the “pyridine-based substituent” in the above formula (ETM-2), formula (ETM-2-1) and formula (ETM-2-2) is benzo The substituent is an imidazole group, and at least one hydrogen in the benzimidazole derivative may be substituted by deuterium.

R ¹¹ in the benzimidazole group is hydrogen, alkyl having 1 to 24 carbon atoms, cycloalkyl having 3 to 12 carbon atoms or aryl having 6 to 30 carbon atoms, and the above-mentioned formula (ETM-2-1) and formula ( The description of R ¹¹ in ETM-2-2) can be cited.

Further, φ is preferably an anthracene ring or a fluorene ring, and the structure in this case can refer to the description in the above formula (ETM-2-1) or the formula (ETM-2-2). R ^{11 to} R ¹⁸ in the formula can be referred to the description of the above formula (ETM-2-1) or the formula (ETM-2-2). Moreover, although the said Formula (ETM-2-1) or Formula (ETM-2-2) is demonstrated in the form which two pyridine type substituents couple | bonded, when replacing these with a benzimidazole type substituent, both are carried out. The pyridine-based substituent of may be replaced with a benzimidazole-based substituent (ie, n = 2), and any one pyridine-based substituent may be replaced with a benzoimidazole-based substituent and the other pyridine-based substituent may be R ¹¹ May be replaced by ~ R ¹⁸ (ie n = 1). Furthermore, for example, at least one of R ^{11 to} R ¹⁸ in the above formula (ETM-2-1) may be replaced with a benzimidazole based substituent, and “pyridine based substituent” may be replaced with R ^{11 to} R ¹⁸ .

As a specific example of this benzimidazole derivative, for example, 1-phenyl-2- (4- (10-phenylanthracene-9-yl) phenyl) -1H-benzo [d] imidazole, 2- (4- (10- Naphthalen-2-yl) anthracen-9-yl) phenyl) -1-phenyl-1H-benzo [d] imidazole, 2- (3- (10- (naphthalen-2-yl) anthracen-9-yl) phenyl) -1-phenyl-1H-benzo [d] imidazole, 5- (10- (naphthalen-2-yl) anthracen-9-yl) -1,2-diphenyl-1H-benzo [d] imidazole, 1- (4 -(10- (Naphthalen-2-yl) anthracen-9-yl) phenyl) -2-phenyl-1H-benzo [d] imidazole, 2- (4- (9,10) Di (naphthalen-2-yl) anthracen-2-yl) phenyl) -1-phenyl-1H-benzo [d] imidazole, 1- (4- (9,10-di (naphthalen-2-yl) anthracene-2) -Yl) phenyl) -2-phenyl-1H-benzo [d] imidazole, 5- (9,10-di (naphthalen-2-yl) anthracen-2-yl) -1,2-diphenyl-1H-benzo [ d] and imidazole.

  This benzimidazole derivative can be produced using a known raw material and a known synthesis method.

<Phenanthroline derivative>
The phenanthroline derivative is, for example, a compound represented by the following formula (ETM-12) or formula (ETM-12-1). Details are described in International Publication No. 2006/021982.

  φ is an n-valent aryl ring (preferably an n-valent benzene ring, naphthalene ring, anthracene ring, fluorene ring, benzofluorene ring, phenalene ring, phenanthrene ring or triphenylene ring), and n is an integer of 1 to 4. is there.

R ^{11 to} R ^{18 in} each formula are each independently hydrogen, alkyl (preferably alkyl having 1 to 24 carbon atoms), cycloalkyl (preferably cycloalkyl having 3 to 12 carbon atoms) or aryl (preferably carbon) Of 6 to 30 aryl). In the above formula (ETM-12-1), any one of R ^{11 to} R ¹⁸ is bonded to φ which is an aryl ring.

  At least one hydrogen in each phenanthroline derivative may be substituted with deuterium.

Alkyl in R ¹¹ to R ^18, cycloalkyl and aryl may be cited to the description of ^R 11 ^{to R 18} in the formula (ETM-2). Further, in addition to the above-mentioned example, for example, the following structural formula is given. In the following structural formulae, each R is independently hydrogen, methyl, ethyl, isopropyl, cyclohexyl, phenyl, 1-naphthyl, 2-naphthyl, biphenylyl or terphenylyl.

Specific examples of this phenanthroline derivative include, for example, 4,7-diphenyl-1,10-phenanthroline, 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline, 9,10-di (1,10- Phenanthroline-2-yl) anthracene, 2,6-di (1,10-phenanthroline-5-yl) pyridine, 1,3,5-tri (1,10-phenanthroline-5-yl) benzene, 9,9 ′ -Difluoro-bis (1,10-phenanthroline-5-yl), bathocuproin, 1,3-bis (2-phenyl-1,10-phenanthroline-9-yl) benzene, compounds represented by the following structural formula, and the like can give.

  This phenanthroline derivative can be produced using a known raw material and a known synthesis method.

<Quinolinol metal complex>
The quinolinol metal complex is, for example, a compound represented by the following general formula (ETM-13).
In the formula, R ^{1 to} R ⁶ are each independently hydrogen, fluorine, alkyl, cycloalkyl, aralkyl, alkenyl, cyano, alkoxy or aryl, and M is Li, Al, Ga, Be or Zn, n is an integer of 1 to 3.

  Specific examples of quinolinol metal complexes include 8-quinolinol lithium, tris (8-quinolinolato) aluminum, tris (4-methyl-8-quinolinolato) aluminum, tris (5-methyl-8-quinolinolato) aluminum, tris (3) , 4-Dimethyl-8-quinolinolato) aluminum, tris (4,5-dimethyl-8-quinolinolato) aluminum, tris (4,6-dimethyl-8-quinolinolato) aluminum, bis (2-methyl-8-quinolinolato) (aluminum) Phenolate) aluminum, bis (2-methyl-8-quinolinolato) (2-methylphenolato) aluminum, bis (2-methyl-8-quinolinolato) (3-methylphenolato) aluminum, bis (2-methyl-8- Quinolinolato) (4-me Ruphenolate) aluminum, bis (2-methyl-8-quinolinolato) (2-phenylphenolate) aluminum, bis (2-methyl-8-quinolinolato) (3-phenylphenolate) aluminum, bis (2-methyl-8- Quinolinolato) (4-phenylphenolato) aluminum, bis (2-methyl-8-quinolinolato) (2,3-dimethylphenolato) aluminum, bis (2-methyl-8-quinolinolato) (2,6-dimethylphenolate ) Aluminum, bis (2-methyl-8-quinolinolato) (3,4-dimethylphenolate) aluminum, bis (2-methyl-8-quinolinolato) (3,5-dimethylphenolate) aluminum, bis (2-methyl) -8-quinolinolate) (3,5-di-tert-butyl) (Ruphenolate) aluminum, bis (2-methyl-8-quinolinolato) (2,6-diphenylphenolate) aluminum, bis (2-methyl-8-quinolinolato) (2,4,6-triphenylphenolate) aluminum, bis (2-Methyl-8-quinolinolato) (2,4,6-trimethylphenolate) aluminum, bis (2-methyl-8-quinolinolato) (2,4,5,6-tetramethylphenolate) aluminum, bis ( 2-Methyl-8-quinolinolato) (1-naphtholato) aluminum, bis (2-methyl-8-quinolinolato) (2-naphtholate) aluminum, bis (2,4-dimethyl-8-quinolinolato) (2-phenylphenolate ) Aluminum, bis (2,4-dimethyl-8-quinolinolate) ) (3-phenylphenolate) aluminum, bis (2,4-dimethyl-8-quinolinolato) (4-phenylphenolate) aluminum, bis (2,4-dimethyl-8-quinolinolato) (3,5-dimethylphenol) Lat) aluminum, bis (2,4-dimethyl-8-quinolinolato) (3,5-di-t-butylphenolate) aluminum, bis (2-methyl-8-quinolinolato) aluminum-μ-oxo-bis (2 -Methyl-8-quinolinolato) aluminum, bis (2,4-dimethyl-8-quinolinolato) aluminum-μ-oxo-bis (2,4-dimethyl-8-quinolinolato) aluminum, bis (2-methyl-4-ethyl) -8-quinolinolato) aluminum-μ-oxo-bis (2-methyl-4-ethyl-8) Quinolinolato) aluminum, bis (2-methyl-4-methoxy-8-quinolinolato) aluminum-μ-oxo-bis (2-methyl-4-methoxy-8-quinolinolato) aluminum, bis (2-methyl-5-cyano- 8-quinolinolato) aluminium-μ-oxo-bis (2-methyl-5-cyano-8-quinolinolato) aluminum, bis (2-methyl-5-trifluoromethyl-8-quinolinolato) aluminum-μ-oxo-bis (a) 2-methyl-5-trifluoromethyl-8-quinolinolato) aluminum, bis (10-hydroxybenzo [h] quinoline) beryllium and the like.

  This quinolinol-based metal complex can be produced using a known raw material and a known synthesis method.

<Thiazole derivatives and benzothiazole derivatives>
The thiazole derivative is, for example, a compound represented by the following formula (ETM-14-1).
The benzothiazole derivative is, for example, a compound represented by the following formula (ETM-14-2).

Φ in each formula is an n-valent aryl ring (preferably an n-valent benzene ring, naphthalene ring, anthracene ring, fluorene ring, benzofluorene ring, phenalene ring, phenanthrene ring or triphenylene ring), and n is 1 to 4 The “thiazole-based substituent” and “benzothiazole-based substituent” are “pyridine-based” in the above formula (ETM-2), formula (ETM-2-1) and formula (ETM-2-2). The pyridyl group in the “substituent group” is a substituent in which the following thiazole group or benzothiazole group is replaced, and at least one hydrogen in the thiazole derivative and the benzothiazole derivative may be substituted by deuterium.

Further, φ is preferably an anthracene ring or a fluorene ring, and the structure in this case can refer to the description in the above formula (ETM-2-1) or the formula (ETM-2-2). In the formula, R ^{11 to} R ¹⁸ can be referred to the description of the above formula (ETM-2-1) or formula (ETM-2-2). Moreover, although the said Formula (ETM-2-1) or Formula (ETM-2-2) is demonstrated by the form which two pyridine-type substituents couple | bonded, these are thiazole-type substituents (or benzothiazole-type substitution) Group), both pyridine-based substituents may be replaced by a thiazole-based substituent (or a benzothiazole-based substituent) (ie, n = 2), or one of the pyridine-based substituents may be a thiazole-based substituent. It may be replaced with a group (or benzothiazole substituent) and the other pyridine substituent may be replaced with R ^{11 to} R ¹⁸ (that is, n = 1). Furthermore, for example, at least one of R ^{11 to} R ¹⁸ in the above formula (ETM-2-1) is replaced with a thiazole substituent (or a benzothiazole substituent) to convert “pyridine based substituent” into R ^{11 to} R ¹⁸ You may replace by.

  These thiazole derivatives or benzothiazole derivatives can be produced using known raw materials and known synthesis methods.

  The electron transport layer or the electron injection layer may further contain a substance capable of reducing the material forming the electron transport layer or the electron injection layer. As this reducing substance, various substances can be used as long as they have a certain reducing ability. For example, alkali metals, alkaline earth metals, rare earth metals, alkali metal oxides, alkali metal halides, alkalis. From the group consisting of earth metal oxides, alkaline earth metal halides, rare earth metal oxides, rare earth metal halides, alkali metal organic complexes, alkaline earth metal organic complexes and rare earth metal organic complexes At least one selected can be suitably used.

  Preferred reducing substances include alkali metals such as Na (work function 2.36 eV), K (2.28 eV), Rb (2.16 eV) or Cs (1.95 eV), and Ca (2. 9eV), Sr (2.0 to 2.5 eV) or Ba (2.52 eV), and alkaline earth metals such as those having a work function of 2.9 eV or less are particularly preferable. Among these, a more preferable reducing substance is an alkali metal of K, Rb or Cs, more preferably Rb or Cs, and most preferably Cs. These alkali metals have particularly high reducing ability, and by adding a relatively small amount to the material forming the electron transport layer or the electron injection layer, the luminance of the organic EL element can be improved and the lifetime can be extended. Further, as a reducing substance having a work function of 2.9 eV or less, a combination of two or more alkali metals is also preferable. Particularly, a combination containing Cs, such as Cs and Na, Cs and K, Cs and Rb, or A combination of Cs, Na and K is preferred. By containing Cs, the reducing ability can be efficiently exhibited, and by adding to the material for forming the electron transport layer or the electron injection layer, the luminance of the organic EL element can be improved and the lifetime can be extended.

<Cathode in organic electroluminescence device>
The cathode 108 plays a role of injecting electrons into the light emitting layer 105 via the electron injection layer 107 and the electron transport layer 106.

  The material for forming the cathode 108 is not particularly limited as long as it can efficiently inject electrons into the organic layer, but the same material as the material for forming the anode 102 can be used. Among them, metals such as tin, indium, calcium, aluminum, silver, copper, nickel, chromium, gold, platinum, iron, zinc, lithium, sodium, potassium, cesium and magnesium or alloys thereof (magnesium-silver alloy, magnesium -Indium alloys, aluminum-lithium alloys such as lithium fluoride / aluminum) are preferred. Lithium, sodium, potassium, cesium, calcium, magnesium, or alloys containing these low work function metals are effective for increasing the electron injection efficiency and improving device characteristics. However, these low work function metals are often often unstable in the atmosphere. In order to improve this point, for example, a method is known in which an organic layer is doped with a small amount of lithium, cesium or magnesium and a highly stable electrode is used. As other dopants, inorganic salts such as lithium fluoride, cesium fluoride, lithium oxide, and cesium oxide can also be used. However, it is not limited to these.

  Furthermore, for electrode protection, metals such as platinum, gold, silver, copper, iron, tin, aluminum and indium, or alloys using these metals, and inorganic materials such as silica, titania and silicon nitride, polyvinyl alcohol, vinyl chloride Lamination of hydrocarbon polymer compounds and the like is a preferred example. The method for producing these electrodes is not particularly limited as long as conduction can be achieved, such as resistance heating, electron beam evaporation, sputtering, ion plating, and coating.

<Binder that may be used in each layer>
The materials used for the hole injection layer, the hole transport layer, the light emitting layer, the electron transport layer, and the electron injection layer described above can form each layer independently, but polyvinyl chloride, polycarbonate, or the like as a polymer binder Polystyrene, poly (N-vinylcarbazole), polymethyl methacrylate, polybutyl methacrylate, polyester, polysulfone, polyphenylene oxide, polybutadiene, hydrocarbon resin, ketone resin, phenoxy resin, polyamide, ethyl cellulose, vinyl acetate resin, ABS resin, polyurethane resin Etc., and can be used by dispersing it in a solvent-soluble resin such as phenol resin, xylene resin, petroleum resin, urea resin, melamine resin, unsaturated polyester resin, alkyd resin, epoxy resin, silicone resin, etc. is there.

<Method for producing organic electroluminescent element>
Each layer constituting the organic EL element is a thin film formed by a method such as vapor deposition, resistance heating vapor deposition, electron beam vapor deposition, sputtering, molecular lamination method, printing method, spin coat method or cast method, coating method, etc. Thus, it can be formed. There is no limitation in particular about the film thickness of each layer formed in this way, Although it can set suitably according to the property of material, it is usually in the range of 2 nm-5000 nm. The film thickness can usually be measured with a crystal oscillation type film thickness measuring device or the like. When a thin film is formed using a vapor deposition method, the vapor deposition conditions vary depending on the type of material, the target crystal structure and association structure of the film, and the like. Deposition conditions generally include boat heating temperature +50 to + 400 ° C., vacuum degree 10 ⁻⁶ to 10 ⁻³ Pa, deposition rate 0.01 to 50 nm / sec, substrate temperature −150 to + 300 ° C., film thickness 2 nm to 5 μm. It is preferable to set appropriately within the range.

  Next, as an example of a method for producing an organic EL element, an organic EL element composed of an anode / hole injection layer / hole transport layer / a light emitting layer composed of a host material and a dopant material / electron transport layer / electron injection layer / cathode The production method of is described. A thin film of an anode material is formed on a suitable substrate by vapor deposition or the like to produce an anode, and then a thin film of a hole injection layer and a hole transport layer is formed on the anode. A host material and a dopant material are co-evaporated to form a thin film to form a light emitting layer. An electron transport layer and an electron injection layer are formed on the light emitting layer, and a thin film made of a cathode material is formed by vapor deposition. By forming it as a cathode, a target organic EL element can be obtained. In the production of the above-mentioned organic EL device, the production order can be reversed, and the cathode, the electron injection layer, the electron transport layer, the light emitting layer, the hole transport layer, the hole injection layer, and the anode can be produced in this order. It is.

  When a DC voltage is applied to the organic EL device thus obtained, the anode may be applied with a positive polarity and the cathode with a negative polarity. When a voltage of about 2 to 40 V is applied, a transparent or translucent electrode is applied. Luminescence can be observed from the side (anode or cathode, and both). The organic EL element also emits light when a pulse current or an alternating current is applied. The alternating current waveform to be applied may be arbitrary.

<Application examples of organic electroluminescent devices>
The present invention can also be applied to a display device provided with an organic EL element or a lighting device provided with an organic EL element.
The display device or the illumination device provided with the organic EL element can be manufactured by a known method such as connecting the organic EL element according to the present embodiment and a known drive device, and DC drive, pulse drive, AC drive, etc. It can drive using a well-known drive method suitably.

  Examples of the display device include a panel display such as a color flat panel display, and a flexible display such as a flexible color organic electroluminescence (EL) display (for example, JP-A-10-335066 and JP-A-2003-321546). Gazette, JP-A-2004-281086, etc.). Examples of the display method of the display include a matrix and / or segment method. Note that the matrix display and the segment display may coexist in the same panel.

  In the matrix, pixels for display are two-dimensionally arranged in a lattice shape, a mosaic shape, or the like, and a character or an image is displayed by a set of pixels. The shape and size of the pixel are determined by the application. For example, square pixels with a side of 300 μm or less are usually used for displaying images and characters on personal computers, monitors, and televisions. Also, in the case of a large display such as a display panel, pixels with a side of mm order are used. become. In monochrome display, pixels of the same color may be arranged, but in color display, red, green and blue pixels are displayed side by side. In this case, there are typically a delta type and a stripe type. As a method of driving this matrix, either a line sequential driving method or an active matrix may be used. The line-sequential driving has an advantage that the structure is simple. However, the active matrix may be superior in consideration of the operation characteristics, so that it is necessary to properly use it depending on the application.

  In the segment system (type), a pattern is formed so as to display predetermined information, and a predetermined region is caused to emit light. For example, the time and temperature display in a digital clock or a thermometer, the operation state display of an audio device or an electromagnetic cooker, the panel display of an automobile, and the like can be mentioned.

  Examples of the illuminating device include an illuminating device such as indoor lighting, a backlight of a liquid crystal display device, and the like (for example, JP 2003-257621 A, JP 2003-277741 A, JP 2004-119211 A). Etc.). The backlight is used mainly for the purpose of improving the visibility of a display device that does not emit light, and is used for a liquid crystal display device, a clock, an audio device, an automobile panel, a display panel, a sign, and the like. In particular, as a backlight for a liquid crystal display device, especially a personal computer application where thinning is an issue, considering that it is difficult to thin the conventional method because it is made of a fluorescent lamp or a light guide plate, this embodiment The backlight using the light emitting element according to the present invention is thin and lightweight.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited to these. First, synthesis examples of the polycyclic aromatic compound and the pyrene compound will be described below.

Synthesis Example (1): Synthesis of Compound (1-290)

Under a nitrogen atmosphere, a flask containing methyl 4-methoxy salicylate (50.0 g) and pyridine (dehydrated) (350 ml) was cooled with an ice bath. Then trifluoromethanesulfonic anhydride (154.9 g) was added dropwise to this solution. After the addition was completed, the ice bath was removed, and the mixture was stirred at room temperature for 2 hours, and water was added to stop the reaction. After adding toluene and separating an organic layer, methyl 4-methoxy-2-(((trifluoromethyl) sulfonyl) oxy) benzoate was obtained by refine | purifying with a silica gel short pass column (eluent: toluene). (86.0 g).

In a nitrogen atmosphere, methyl 4-methoxy-2-(((trifluoromethyl) sulfonyl) oxy) benzoate (23.0 g), (4- (diphenylamino) phenyl) boronic acid (25.4 g), phosphoric acid tribasic To a suspension of potassium (31.1 g), toluene (184 ml), ethanol (27.6 ml) and water (27.6 ml), add Pd (PPh ₃ ) ₄ (2.5 g) and reflux for 3 hours It stirred. The reaction solution was cooled to room temperature, water and toluene were added to separate the organic layer, and the solvent of the organic layer was distilled off under reduced pressure. The obtained solid was purified by silica gel column (eluent: heptane / toluene mixed solvent) to obtain methyl 4 '-(diphenylamino) -5-methoxy- [1,1'-biphenyl] -2-carboxylate (29.7 g). At this time, referring to the method described in “Chemistry Publishing Co., Ltd., page 94”, the ratio of toluene in the eluent was gradually increased. Increased to elute the desired product.

Under a nitrogen atmosphere, a solution of methyl 4 ′-(diphenylamino) -5-methoxy- [1,1′-biphenyl] -2-carboxylate (11.4 g) in THF (111.4 ml) was cooled in a water bath. To the solution, methylmagnesium bromide THF solution (1.0 M, 295 ml) was added dropwise. After completion of the dropwise addition, the water bath was removed and the temperature was raised to reflux temperature and stirred for 4 hours. After cooling in an ice bath, the reaction was quenched by the addition of aqueous ammonium chloride solution, ethyl acetate was added, the organic layer was separated, and the solvent was evaporated under reduced pressure. The obtained solid is purified with a silica gel column (eluent: toluene) to give 2- (4 '-(diphenylamino) -5-methoxy- [1,1'-biphenyl] -2-yl) propan-2-ol (8.3 g) was obtained.

Under a nitrogen atmosphere, 2- (4 ′-(diphenylamino) -5-methoxy- [1,1′-biphenyl] -2-yl) propan-2-ol (27.0 g), TAYCACURE-15 (13.5 g) ) And toluene (162 ml) were stirred at reflux temperature for 2 hours. The reaction solution is cooled to room temperature, and after passing through a silica gel short path column (eluent: toluene) to remove TAYCACURE-15, the solvent is distilled off under reduced pressure to obtain 6-methoxy-9,9'-. Dimethyl-N, N-diphenyl-9H-fluoren-2-amine was obtained (25.8 g).

6-methoxy-9,9'-dimethyl-N, N-diphenyl-9H-fluoren-2-amine (25.0 g), pyridine hydrochloride (36.9 g) and N-methyl-2-pyrrolidone under nitrogen atmosphere The flask containing (NMP) (22.5 ml) was stirred at reflux temperature for 6 hours. The reaction solution was cooled to room temperature, water and ethyl acetate were added, and the organic layer was separated. After distilling off the solvent under reduced pressure, 7- (diphenylamino) -9,9′-dimethyl-9H-fluoren-3-ol was obtained by purification with a silica gel column (eluent: toluene) (22.0 g). ).

Under a nitrogen atmosphere, 7- (diphenylamino) -9,9'-dimethyl-9H-fluoren-3-ol (14.1 g), 2-bromo-1,3-difluorobenzene (3.6 g), potassium carbonate ( The flask containing 12.9 g) and NMP (30 ml) was heated and stirred at reflux temperature for 5 hours. After stopping the reaction, the reaction solution was cooled to room temperature, water was added, and the deposited precipitate was collected by suction filtration. The resulting precipitate is washed with water and then with methanol and then purified with a silica gel column (eluent: heptane / toluene mixed solvent) to give 6,6 '-((2-bromo-1,3-phenylene) Bis (oxy)) bis (9,9-dimethyl-N, N-diphenyl-9H-fluoren-2-amine) was obtained (12.6 g). At this time, the target product was eluted by gradually increasing the ratio of toluene in the eluent.

Under a nitrogen atmosphere, 6,6 '-((2-bromo-1,3-phenylene) bis (oxy)) bis (9,9-dimethyl-N, N-diphenyl-9H-fluoren-2-amine) (11) 0.0 g) and xylene (60.5 ml) were cooled to −40 ° C., and 2.6 M n-butyllithium hexane solution (5.1 ml) was added dropwise. After completion of dropping, the mixture was stirred at this temperature for 0.5 hour, then heated to 60 ° C. and stirred for 3 hours. Then, after pressure-reducing a reaction liquid and distilling off the low boiling-point component, it cooled to -40 degreeC and added the boron tribromide (4.3g). The mixture was warmed to room temperature and stirred for 0.5 hour, then cooled to 0 ° C., N-ethyl-N-isopropylpropan-2-amine (3.8 g) was added, and the mixture was heated and stirred at 125 ° C. for 8 hours. The reaction solution was cooled to room temperature, and an aqueous sodium acetate solution was added to stop the reaction, and then toluene was added to separate the organic layer. The organic layer was purified with a silica gel short pass column, then with a silica gel column (eluent: heptane / toluene = 4 (volume ratio)), and further with an activated carbon column (eluent: toluene) to obtain a compound (1-290) ( 1.2 g).

The structure of the compound (1-290) obtained by NMR measurement was confirmed.
¹ H-NMR (400 MHz, CDCl ₃ ): δ = 8.64 (s, 2H), 7.75 (m, 3H), 7.69 (d, 2H), 7.30 (t, 8H), 7 .25 (s, 2H), 7.20 (m, 10H), 7.08 (m, 6H), 1.58 (s, 12H).

Synthesis Example (2): Synthesis of Compound (1-139)

The compound (1-139) was synthesized using the same method as the synthesis example described above.

The structure of the compound (1-139) obtained by NMR measurement was confirmed.
¹ H-NMR (500 MHz, CDCl ₃ ): δ = 1.47 (s, 36H), 2.17 (s, 3H), 5.97 (s, 2H), 6.68 (d, 2H), 7 28 (d, 4H), 7.49 (dd, 2H), 7.67 (d, 4H), 8.97 (d, 2H).

Synthesis Example (3): Synthesis of Compound (1-151)

The compound (1-151) was synthesized using the same method as the synthesis example described above.

The structure of the compound (1-151) obtained by NMR measurement was confirmed.
¹ H-NMR (500 MHz, CDCl ₃ ): δ = 1.46 (s, 18 H), 1.47 (s, 18 H), 6.14 (d, 2 H), 6.75 (d, 2 H), 7 24 (t, 1 H), 7. 29 (d, 4 H), 7.52 (dd, 2 H), 7.67 (d, 4 H), 8.99 (d, 2 H).

Synthesis Example (4): Synthesis of Compound (2-1) “11,11-Diphenyl-6- (pyren-1-yl) -11H-benzo [a] fluorene”

In a nitrogen atmosphere, 1-bromo-2-methoxynaphthalene (9.5 g), bis (pinacolato) diboron (12.2 g), potassium acetate (11.8 g), and palladium catalyst (1,1′-bis ( Diphenylphosphino) ferrocene) palladium (II) dichloride.dichloromethane complex (0.98 g) and cyclopentyl methyl ether (CPME, 143 mL) were placed in a flask and stirred at reflux temperature for 4 hours under a nitrogen atmosphere. The reaction solution was cooled to room temperature, water was added, and ethyl acetate was further added for liquid separation and extraction. The organic layer was separated, dried, concentrated, and purified on an activated carbon short pass column (eluent: toluene) to obtain Intermediate A (11.3 g).

Under a nitrogen atmosphere, intermediate A (11.3 g), methyl 2-bromobenzoate (8.6 g), potassium phosphate (16.9 g), tetrakis (triphenylphosphine) palladium (1.4 g) as a palladium catalyst, Toluene (85 mL), ethanol (17 mL) and water (9 mL) were charged into a flask and stirred at reflux temperature for 7 hours under a nitrogen atmosphere. The reaction solution was cooled to room temperature, water was added, and toluene was further added for liquid separation and extraction. The organic layer was separated, dried and concentrated, and the crude product was purified by silica gel column (eluent: toluene) to obtain Intermediate B (9.1 g).

Under a nitrogen atmosphere, Intermediate B (9.1 g) and tetrahydrofuran (THF, 21 mL) were placed in a flask and cooled in an ice bath, and then a 1M phenylmagnesium bromide / THF solution (94 mL) was added dropwise under a nitrogen atmosphere. And stirred at reflux temperature for 3 hours. After cooling, a saturated aqueous ammonium chloride solution was added to stop the reaction, and then ethyl acetate was added to perform solvent extraction. The organic layer was separated, dried and concentrated, and the crude product was purified by silica gel column (eluent: toluene) to obtain Intermediate C (12.3 g).

Under a nitrogen atmosphere, Intermediate C (12.3 g) and acetic acid (117 mL) were placed in the flask, a drop of concentrated sulfuric acid was added thereto, and the mixture was stirred at 90 ° C. for 3 hours under a nitrogen atmosphere. After cooling, water was added and the precipitate was filtered, washed with water and dried, yielding intermediate D (10.6 g).

In a nitrogen atmosphere, Intermediate D (10.6 g), pyridine hydrochloride (15.4 g) and N-methylpyrrolidone (NMP, 10 mL) were charged into a flask and stirred at 185 ° C. for 4 hours under a nitrogen atmosphere. After cooling, water was added and the precipitate was filtered, and the precipitate was washed with water and dried to give Intermediate E (10.1 g).

Under a nitrogen atmosphere, Intermediate E (10 g) and pyridine (100 mL) were put in a flask and cooled with an ice bath, and then under nitrogen atmosphere, trifluoromethanesulfonic anhydride (18.3 g) was added dropwise. After stirring for 3 hours, water was added to stop the reaction. The precipitate was filtered and purified by silica gel short path column (eluent: toluene) to obtain Intermediate F (13.4 g).

Intermediate F (3 g), 1-pyreneboronic acid (2.1 g), potassium phosphate (2.5 g) under a nitrogen atmosphere, tetrakis (triphenylphosphine) palladium (0.2 g) as a palladium catalyst, 1,2, 4-Trimethylbenzene (24 mL), t-butyl alcohol (3 mL) and water (1.5 mL) were placed in a flask and stirred at reflux temperature for 4 hours under a nitrogen atmosphere. The reaction solution was cooled to room temperature, water was added, and toluene was further added for liquid separation extraction. The organic layer is separated, dried and concentrated, and the crude product is purified by silica gel column (eluent: toluene / heptane = 3/1 (volume ratio)) and then purified by sublimation to obtain compound (2-1). Obtained (1.2 g).

The structure of the compound (2-1) obtained by NMR measurement was confirmed.
¹ H-NMR (CDCl ₃ ): 6.0 (d, 1 H), 6.6 (dt, 1 H), 7.0 (dt, 1 H), 7.2 to 7.5 (m, 13 H), 7 9 to 8.0 (m, 5 H), 8.0 (t, 1 H), 8.2 to 8.3 (m, 5 H), 8.4 (d, 1 H).

Synthesis Example (5): Synthesis of Compound (2-46) “6- (6- (Naphthalen-2-yl) pyren-1-yl) -11,11-diphenyl-11H-benzo [a] fluorene”

Under nitrogen atmosphere, 1,6-dibromopyrene (3.5 g), 2-naphthylboronic acid (1.7 g), potassium carbonate (2.7 g), tetrakis (triphenylphosphine) palladium (0.3 g) as a palladium catalyst. , Toluene (35 mL), and water (9 mL) were placed in a flask and stirred at reflux temperature for 3 hours under a nitrogen atmosphere. The reaction solution was cooled to room temperature, water was added, and toluene was further added for liquid separation and extraction. The organic layer was separated, dried and concentrated, and the crude product was purified by silica gel column (eluent: toluene / heptane = 6/1 (volume ratio)) to obtain an intermediate G (2.1 g).

Intermediate F (7 g), bis (pinacolato) diboron (4.1 g), potassium acetate (4.0 g) under a nitrogen atmosphere, (1,1′-bis (diphenylphosphino) ferrocene) palladium (II) as a palladium catalyst ) Dichloride-dichloromethane complex (0.3 g) and cyclopentyl methyl ether (CPME, 67 mL) were placed in a flask and stirred at reflux temperature for 4 hours under nitrogen atmosphere. The reaction solution was cooled to room temperature, water was added, and ethyl acetate was further added for liquid separation and extraction. The organic layer was separated, dried, concentrated, and purified on an activated carbon short pass column (eluent: toluene) to obtain Intermediate H (4.6 g).

Intermediate G (0.8 g), Intermediate H (0.9 g), potassium phosphate (0.9 g) under nitrogen atmosphere, tetrakis (triphenylphosphine) palladium (0.1 g) as a palladium catalyst, 1, 2 2,4-trimethylbenzene (12 mL), t-butyl alcohol (2 mL) and water (1 mL) were charged into a flask and stirred at reflux temperature for 14 hours under a nitrogen atmosphere. The reaction solution was cooled to room temperature, water was added, toluene was further added, and liquid separation extraction was performed. The organic layer is separated, dried and concentrated, and the crude product is purified with a silica gel column (eluent: toluene / heptane = 1/3 (volume ratio)) and then purified by sublimation to give compound (2-46). Obtained (1.0 g).

The structure of the compound (2-46) obtained by NMR measurement was confirmed.
¹ H-NMR (CDCl ₃ ): 6.0 (d, 1 H), 6.6 (dt, 1 H), 7.0 (dt, 1 H), 7.2 to 7.6 (m, 15 H), 7 8 to 8.2 (m, 14 H), 8.2 to 8.3 (m, 2 H).

Synthesis Example (6): Synthesis of Compound (2-1001) “3,9-di (pyren-1-yl) spiro [benzo [a] fluorene-11,9′-fluorene]”

Under a nitrogen atmosphere, a flask containing pyrene-1-boronic acid (5 g), ethylene glycol (3.8 g) and toluene (30 mL) was stirred at reflux temperature for 3 hours. After the reaction, the reaction mixture was cooled, water was added and the mixture was stirred to separate the organic layer, and then the organic layer was concentrated under reduced pressure to obtain a crude product. The crude product was passed through a silica gel short pass column (eluent: toluene), and then the eluate was concentrated to obtain 2- (pyren-1-yl) -1,3,2-dioxaborolane (4.2 g). .

Intermediate I (3.8 g), 2- (pyren-1-yl) -1,3,2-dioxaborolane (3.3 g), palladium synthesized by the method described in Japanese Patent Publication No. 2009-184993 under a nitrogen atmosphere Chlorophenylallyl [1,3-bis (2,6-diisopropylphenyl) imidazol-2-ylidene] palladium (II) (19 mg), potassium carbonate (3.2 g), tetrabutylammonium bromide (TBAB, 0. 6 g), cyclopentyl methyl ether (CPME, 20 mL) and water (2 mL) were charged into a flask, and heated and stirred at reflux temperature for 9 hours. After the reaction, the reaction solution was cooled and added with water and stirred, and then the precipitate was filtered. The precipitate is dried, dissolved in chlorobenzene by heating, filtered through a silica gel short pass column (eluent: toluene), and the solid obtained by concentrating the eluate is filtered, dried, and purified by sublimation. This gave compound (2-1001) (2.2 g).

The structure of the compound (2-1001) obtained by NMR measurement was confirmed.
¹ H-NMR (CDCl ₃ ): 6.9 to 7.0 (m, 4 H), 7.2 (t, 2 H), 7.4 (dd, 1 H), 7.4 (dt, 2 H), 7 7 (dd, 1 H), 7.8 to 7.9 (m, 2 H), 7.9 to 8.1 (m, 9 H), 8.1 to 8.2 (m, 13 H).

Synthesis Example (7): Synthesis of Compound (2-350) “2- (Pyrene-1-yl) triphenylene”

In a flask under a nitrogen atmosphere, 4,4,5,5-tetramethyl-2- (triphenylene-2-yl) -1,3,2-dioxaborolane (3.0 g), 1-bromopyrene (2.2 g), palladium As a catalyst, chlorophenylallyl [1,3-bis (2,6-diisopropylphenyl) imidazol-2-ylidene] palladium (II) (25 mg), potassium carbonate (2.2 g), tetrabutylammonium bromide (TBAB, 0. 2). 8 g), cyclopentyl methyl ether (CPME, 20 mL) and water (2 mL) were charged into a flask, and heated and stirred at reflux temperature for 2 hours. After the reaction, the reaction solution was cooled and added with water and stirred, and then the precipitate was filtered. The precipitate is dried, dissolved in chlorobenzene by heating, filtered through a silica gel short pass column (eluent: toluene), the solid obtained by concentrating the eluate is filtered, dried, and purified by sublimation. Compound (2-350) was obtained (3.3 g).

The structure of the compound (2-350) obtained by NMR measurement was confirmed.
¹ H-NMR (CDCl ₃ ): 7.6 to 7.7 (m, 4 H), 7.9 (dd, 1 H), 8.0 (m, 2 H), 8.1 to 8.2 (m, 5 (m, 2 H) 4H), 8.2 (m, 1H), 8.3 (m, 2H), 8.7 to 8.8 (m, 4H), 8.8 (d, 1H), 8.9 (d, 1H) ).

Synthesis Example (8): Synthesis of Compound (2-1080) “3,9-bis (7- (t-butyl) pyrene-2-yl) spiro [benzo [a] fluorene-11,9′-fluorene]”

Intermediate J (1.7 g), 2-bromo-7- (t-butyl) pyrene (2 g) synthesized by the method described in WO 2015/141608 under a nitrogen atmosphere, chlorophenyl allyl [as a palladium catalyst] 1,3-Bis (2,6-diisopropylphenyl) imidazol-2-ylidene] palladium (II) (9 mg), potassium carbonate (1.6 g), tetrabutylammonium bromide (TBAB, 0.3 g), cyclopentyl methyl Ether (CPME, 20 mL) and water (2 mL) were charged into the flask and stirred with heating at reflux for 4 hours. After the reaction, the reaction solution was cooled and added with water and stirred, and then the precipitate was filtered. The precipitate is dried, dissolved in chlorobenzene by heating, filtered through a silica gel short pass column (eluent: toluene), and the solid obtained by concentrating the eluate is filtered, dried, and purified by sublimation. Gave compound (2-1080) (1.6 g).

The structure of the compound (2-1080) obtained by NMR measurement was confirmed.
¹ H-NMR (CDCl ₃ ): 1.6 (s, 9H), 1.6 (s, 9H), 6.9 (d, 2H), 6.9 (d, 1H), 7.1 (dt , 2H), 7.2 (d, 1 H), 7.5 (dt, 2 H), 7.6 (dd, 1 H), 7.9 (dd, 1 H), 8.0 to 8.2 (m, 19H), 8.3 (s, 3H).

Synthesis Example (9): Synthesis of Compound (2-174) “2- (pyren-1-yl) naphtho [2,3-b] benzofuran”

2-bromobenzo [b] naphtho [2,3-d] furan (1.1 g) synthesized by the method described in 1-pyreneboronic acid (1.0 g), WO 2014/141725 under a nitrogen atmosphere Put tetrakis (triphenylphosphine) palladium (0.09 g), potassium phosphate (1.7 g), xylene (15 mL), t-butyl alcohol (5 mL) and water (3 mL) as a palladium catalyst in a flask and reflux temperature And stirred for 2 hours. After the reaction, the reaction solution was cooled, water and ethyl acetate were added to the reaction solution, and the mixture was stirred. The precipitate was dried, dissolved in chlorobenzene by heating, filtered through a silica gel short pass column (eluent: toluene), and the solid obtained by concentrating the eluate was further purified by chlorobenzene / reprecipitation. The obtained solid was dried and purified by sublimation to obtain a compound (2-174) (1.0 g).

The structure of the compound (2-174) obtained by NMR measurement was confirmed.
¹ H-NMR (CDCl ₃ ): 7.5 (m, 1 H), 7.5-7.6 (m, 1 H), 7.7-7.8 (m, 2 H), 8.0-8. 3 (m, 13H), 8.5 (s, 1H).

Synthesis Example (10): Synthesis of Compound (2-356) “2- (Pyren-1-yl) dibenzo [g, p] chrysene”

Under a nitrogen atmosphere, 3-bromodibenzo [g, p] chrysene (14 g) and tetrahydrofuran (THF, 200 mL) synthesized by the method described in Japanese Patent Publication No. 2011-006397 were placed in a flask to obtain a homogeneous solution, and then dried. The mixture was cooled to −78 ° C. in an ice-acetone bath, and a 1.6 M n-butyllithium / hexane solution (28 mL) was added dropwise. After stirring for 0.5 hours at the same temperature, 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (12.8 g) was added. After stirring for 3 hours at the same temperature, the temperature was raised and diluted hydrochloric acid was added to stop the reaction. Toluene was added and extracted, and then the organic layer was concentrated. The resulting crude product was purified by a silica gel column (eluent: toluene / heptane = 7/3 (volume ratio)) to obtain intermediate K ( 11.5 g).

Intermediate K (1.0 g), 1-bromopyrene (0.59 g), bis (di-t-butyl (4-dimethylaminophenyl) phosphine) dichloropalladium (16 mg) as a palladium catalyst, and potassium phosphate (under nitrogen atmosphere) 0.9 g), xylene (10 mL), t-butyl alcohol (3 mL) and water (2 mL) were charged into a flask and stirred at reflux temperature for 2 hours. After the reaction, the reaction solution was cooled, water and ethyl acetate were added and the mixture was stirred, and then the deposited precipitate was filtered. The obtained crude product was purified by a silica gel short path column (eluent: toluene) and then purified by reprecipitation with toluene / heptane. The obtained solid was dried and purified by sublimation to obtain a compound (2-356) (0.7 g).

The structure of the compound (2-356) obtained by NMR measurement was confirmed.
¹ H-NMR (CDCl ₃ ): 7.7 (m, 6H), 7.9 (dd, 1H) 8.0 to 8.1 (m, 2H), 8.1 to 8.3 (m, 5H) ), 8.3 (d, 1 H), 8.4 (d, 1 H), 8.7 to 8.8 (m, 5 H), 8.9 (m, 1 H), 8.9 (d, 1 H) 9.0 (d, 1H).

Synthesis Example (11): Synthesis of Compound (2-359) “1,6-bis (naphtho [2,3-b] benzofuran-2-yl) -3a ¹ , 5a ¹ -dihydropyrene”

Under a nitrogen atmosphere, 2-bromobenzo [b] naphtho [2,3-d] furan (10.8 g) and tetrahydrofuran (THF, 200 mL) synthesized by the method described in International Publication No. 2014/141725 were placed in a flask. And cooled to -78 ° C in a dry ice-acetone bath. Thereto was added dropwise a 1.6 M n-butyllithium / heptane solution (25 mL). After stirring for 1 hour at the same temperature, 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (10 g) was added. After stirring at the same temperature for 2 hours, the temperature was raised and dilute hydrochloric acid was added to stop the reaction. Toluene was added and extracted, and then the organic layer was concentrated. The resulting crude product was purified with a silica gel column (eluent: toluene / heptane = 7/3 (volume ratio)) to obtain intermediate L ( 9.2 g).

Under a nitrogen atmosphere, 1,6-dibromopyrene (1.0 g), intermediate L (2.0 g), bis (di-t-butyl (4-dimethylaminophenyl) phosphine) dichloropalladium (20 mg), phosphorus as a palladium catalyst Potassium acid (2.4 g), xylene (15 mL), t-butyl alcohol (3 mL) and water (2 mL) were charged to the flask and stirred at reflux temperature for 2 hours. After the reaction, the reaction solution was cooled, water and ethyl acetate were added and stirred, and then the deposited precipitate was filtered. The resulting crude product was purified by silica gel short path column (eluent: toluene), and then washed with hot chlorobenzene and purified. The obtained solid was dried and purified by sublimation to obtain a compound (2-359) (1.6 g).

The compound (2-359) obtained by LC-MS measurement was confirmed.
MS (ACPI) m / z = 635 (M + H)

  By appropriately changing the raw material compounds, other compounds used in the present invention can be synthesized by a method according to the synthesis examples described above.

  Hereinafter, in order to describe the present invention in more detail, examples of the organic EL device using the compound of the present invention are shown, but the present invention is not limited thereto.

The organic EL elements according to Examples 1 to 12 and Comparative Example 1 were manufactured, and the voltage (V), the emission wavelength (nm) and the external quantum efficiency (%), which are characteristics at 1000 cd / m ² emission, were measured.

  The quantum efficiency of a light emitting device includes an internal quantum efficiency and an external quantum efficiency. The internal quantum efficiency is that the external energy injected as electrons (or holes) into the light emitting layer of the light emitting device is converted into pure photons. Rate is shown. On the other hand, the external quantum efficiency is calculated based on the amount of photons emitted to the outside of the light emitting device, and some of the photons generated in the light emitting layer continue to be absorbed or reflected inside the light emitting device. In other words, the external quantum efficiency is lower than the internal quantum efficiency because it is not emitted to the outside of the light emitting element.

The external quantum efficiency is measured as follows. Using a voltage / current generator R6144 manufactured by ADVANTEST CORPORATION, a voltage at which the luminance of the device reached 1000 cd / m ² was applied to cause the device to emit light. The spectral radiance in the visible light region was measured from the direction perpendicular to the light emitting surface using a TOPCON company spectral radiance meter SR-3AR. Assuming that the light emitting surface is a complete diffusion surface, the number of photons at each wavelength is a value obtained by dividing the measured value of the spectral radiance of each wavelength component by the wavelength energy and multiplying by π. Subsequently, the photon number was integrated in all the observed wavelength regions, and it was set as the total photon number emitted from the element. The external quantum efficiency is the value obtained by dividing the total number of photons emitted from the device by the number of carriers injected into the device, where the number of carriers injected into the device is the value obtained by dividing the applied current value by the elementary charge.

  Table 1 below shows the material configuration of each layer in the organic EL elements according to Examples 1 to 12 and Comparative Example 1 and EL characteristic data.

In Table 1, “HI” is N ⁴ , N ^{4 ′} -diphenyl-N ⁴ , N ^{4 ′} -bis (9-phenyl-9H-carbazol-3-yl)-[1,1′-biphenyl] -4, 4′-diamine, “HAT-CN” is 1,4,5,8,9,12-hexaazatriphenylene hexacarbonitrile, “HT-1” is N-([1,1′-biphenyl] ] -4-yl-9,9-dimethyl-N- [4- (9-phenyl-9H-carbazol-3-yl) phenyl) -9H-fluoren-2-amine [1,1'-biphenyl] -4 -Amine, "HT-2" is N, N-bis (4- (dibenzo [b, d] furan-4-yl) phenyl)-[1,1 ': 4', 1 "-terphenyl] -4-amine, “HT-3” is N-([1,1′-biphenyl] -2-yl -N- (9,9-dimethyl-9H-fluoren-2-yl) -9,9'-spirobi [fluorene] -4-amine, "ET-1" is 4,6,8,10-tetra Phenyl [1,4] benzoxabolinino [2,3,4-kl] phenoxaborin, “ET-2” is 3,3 ′-((2-phenylanthracene-9,10-diyl) bis (4,1-phenylene)) bis (4-methylpyridine), “ET-3” is 9- (7- (dimesitylboryl) -9,9-dimethyl-9H-fluoren-2-yl) -3, 6-dimethyl-9H-carbazole, "ET-4" is 4- (3- (4- (10-phenylanthracene-9-yl) naphthalen-1-yl) phenyl) pyridine, and Comparative Example Compound A is 9-([1,2′-Binaphthalene] -7-i ) Is a 10-phenyl anthracene. The chemical structure is shown below together with “Liq”.

Example 1
<Device of host is compound (2-1) and dopant is compound (1-139)>
A glass substrate of 26 mm × 28 mm × 0.7 mm (manufactured by Optoscience Co., Ltd.) obtained by polishing ITO deposited to a thickness of 180 nm by sputtering to 150 nm was used as a transparent support substrate. The transparent support substrate is fixed to a substrate holder of a commercially available vapor deposition apparatus (manufactured by Showa Vacuum Co., Ltd.), and HI, HAT-CN, HT-1, HT-2, compound (2-1), compound (1-139) ), A molybdenum evaporation boat containing ET-1 and ET-2, and an aluminum nitride evaporation boat containing Liq, magnesium and silver, respectively.

The following layers were sequentially formed on the ITO film of the transparent support substrate. The vacuum chamber is depressurized to 5 × 10 ⁻⁴ Pa, and first, HI is heated to deposit to a film thickness of 40 nm, and then HAT-CN is heated to deposit to a film thickness of 5 nm, Next, HT-1 is heated and deposited to a film thickness of 15 nm, and then HT-2 is heated and deposited to a film thickness of 10 nm to form a four-hole injection / transport layer Formed. Next, the compound (2-1) and the compound (1-139) were simultaneously heated to deposit a film thickness of 25 nm to form a light emitting layer. The deposition rate was adjusted so that the weight ratio of the compound (2-1) and the compound (1-139) was approximately 98 to 2. Next, ET-1 was heated and evaporated to a film thickness of 5 nm to form an electron transport layer 1. Next, ET-2 and Liq were simultaneously heated and evaporated to a film thickness of 25 nm to form an electron transport layer 2. The deposition rate was adjusted so that the weight ratio of ET-2 to Liq was approximately 50:50. The deposition rate of each layer was 0.01 to 1 nm / second. Thereafter, Liq is heated to deposit 1 nm thick at a deposition rate of 0.01 to 0.1 nm / sec, and then magnesium and silver are simultaneously heated to deposit 100 nm thick. A cathode was formed to obtain an organic EL device. At this time, the deposition rate was adjusted between 0.1 nm and 10 nm / sec so that the atomic ratio of magnesium to silver was 10: 1.

A direct current voltage was applied to the ITO electrode as an anode and a magnesium / silver electrode as a cathode, and the characteristics at a light emission of 1000 cd / m ² were measured. Blue light emission having a wavelength of 462 nm was obtained. The driving voltage was 4.1 V, and the external quantum efficiency was 6.7%.

<Examples 2 to 12 and Comparative Example 1>
The materials described in Table 1 were selected as the materials of the respective layers, and an organic EL device was obtained by the method according to Example 1. In Example 11, ET-1 and LIq were co-evaporated to a thickness of 30 nm to form one electron transport layer. The organic EL characteristics were also evaluated in the same manner as in Example 1 (Table 1). In addition, blue light emission was obtained in all the elements.

  As described above, some of the compounds according to the present invention were evaluated as materials for the light emitting layer of the organic EL device and showed their usefulness, but other compounds that were not evaluated also have the same basic skeleton, It is a compound having a similar structure as a whole, and it can be understood by those skilled in the art that it is an excellent light emitting layer material.

  According to a preferred embodiment of the present invention, there are provided a polycyclic aromatic compound represented by the formula (1) and a pyrene compound represented by the formula (2) capable of obtaining optimum light emission characteristics in combination therewith. By manufacturing an organic EL element using a material for a light emitting layer formed by combining these, an organic EL element having particularly well-balanced performance with excellent light emission efficiency can be provided.

DESCRIPTION OF SYMBOLS 100 Organic electroluminescent element 101 Substrate 102 Anode 103 Hole injection layer 104 Hole transport layer 105 Light emitting layer 106 Electron transport layer 107 Electron injection layer 108 Cathode

Claims (11)

An organic electroluminescent device comprising a pair of electrodes comprising an anode and a cathode, and a light emitting layer disposed between the pair of electrodes,
The light emitting layer includes at least one of a compound represented by the following general formula (1) and a multimer having a plurality of structures represented by the following general formula (1), and a pyrene system represented by the following general formula (2): An organic electroluminescent device comprising at least one compound.
In the above formula (1),
Ring A, ring B and ring C are each independently an aryl ring or a heteroaryl ring, and at least one hydrogen in these rings may be substituted.
X ¹ and X ² are each independently> O or> N-R, and R in> N-R is optionally substituted aryl, optionally substituted heteroaryl, or optionally substituted And R in> N—R may be bonded to the A ring, B ring and / or C ring via a linking group or a single bond, and ,
At least one hydrogen in the compound or structure represented by formula (1) may be each independently substituted with halogen, cyano or deuterium.
In the above formula (2),
The s pyrene moieties and the p Ar moieties are combined at any position of * in the pyrene moiety and at any position of the Ar moiety,
At least one hydrogen of the pyrene moiety is each independently an aryl having 6 to 10 carbon atoms, a heteroaryl having 2 to 11 carbon atoms, an alkyl having 1 to 30 carbon atoms, a cycloalkyl having 3 to 24 carbon atoms, or a carbon number. Optionally substituted with 2 to 30 alkenyl, 1 to 30 carbon alkoxy or 6 to 30 aryloxy, wherein at least one hydrogen independently represents aryl having 6 to 10 carbon atoms. , C2-C11 heteroaryl, C1-C30 alkyl, C3-C24 cycloalkyl, C2-C30 alkenyl, C1-C30 alkoxy or C6-C30 aryl May be substituted with oxy,
Ar is each independently an aryl having 14 to 40 carbon atoms or a heteroaryl having 12 to 40 carbon atoms, and at least one hydrogen in each of them is independently an aryl having 6 to 10 carbon atoms, Substituted with 2-11 heteroaryl, C1-C30 alkyl, C3-C24 cycloalkyl, C2-C30 alkenyl, C1-C30 alkoxy or C6-C30 aryloxy May have been
s and p are each independently an integer of 1 or 2, and s and p are not simultaneously 2; when s is 2, the two pyrene moieties are structurally identical including the substituent And p may be 2 or two Ar moieties may be structurally identical or different, including substituents, and
At least one hydrogen in the compound represented by Formula (2) may be independently substituted with halogen, cyano or deuterium. The organic electroluminescent device according to claim 1, wherein Ar is a group represented by general formula (Ar-1) or general formula (Ar-2) independently.
In each of the above formulas,
Z is> CR ₂ ,>N—R,> O or>S;
R in CR ₂ is each independently alkyl of 1 to 6 carbons, cycloalkyl of 3 to 14 carbons, aryl of 6 to 12 carbons or heteroaryl of 2 to 12 carbons, And at least one hydrogen in heteroaryl and heteroaryl may be substituted with alkyl having 1 to 4 carbon atoms or cycloalkyl having 5 to 10 carbon atoms, and R may combine with each other to form a ring,
> R in N—R is alkyl having 1 to 4 carbons, cycloalkyl having 5 to 10 carbons, aryl having 6 to 12 carbons or heteroaryl having 2 to 12 carbons, and in the aryl and heteroaryl At least one hydrogen may be substituted by alkyl having 1 to 4 carbons or cycloalkyl having 5 to 10 carbons,
R ¹ to R ⁸ and R ¹⁰ to R ¹⁹ each independently represent hydrogen, aryl having 6 to 10 carbon atoms, heteroaryl having 2 to 11 carbon atoms, alkyl having 1 to 30 carbon atoms, or 3 to 24 carbon atoms Cycloalkyl, alkenyl having 2 to 30 carbon atoms, alkoxy having 1 to 30 carbon atoms or aryloxy having 6 to 30 carbon atoms, wherein at least one hydrogen is alkyl having 1 to 6 carbon atoms or 3 to 3 carbon atoms. 14 may be substituted with cycloalkyl, adjacent groups of R ¹ to R ⁸ or adjacent groups of R ¹⁰ to R ¹⁹ may be bonded to each other to form a condensed ring, The rings formed are each independently an aryl having 6 to 10 carbons, a heteroaryl having 2 to 11 carbons, an alkyl having 1 to 30 carbons, and a cycloalkyl having 3 to 24 carbons. It may be substituted by C2-C30 alkenyl, C1-C30 alkoxy or C6-C30 aryloxy, and at least one hydrogen in these may be C1-C6 alkyl or C3-C3. Optionally substituted with -14 cycloalkyl, and
At least one hydrogen in the group represented by Formula (Ar-1) or Formula (Ar-2) may be each independently substituted with halogen, cyano or deuterium.
In the formula (2), the pyrene moiety is bonded at any position in the group represented by the formula (Ar-1) or the formula (Ar-2). The organic electroluminescent element as described in Claim 1 or 2 whose compound represented by the said General formula (1) is a compound represented by following General formula (1 ').
(In the above formula (1 ′),
R ¹ to R ¹¹ are each independently hydrogen, aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, alkyl, cycloalkyl, alkoxy or aryloxy, in which at least one hydrogen And each of R ¹ to R ¹¹ may be independently substituted with aryl, heteroaryl, alkyl or cycloalkyl, and adjacent ones of R ¹ to R ¹¹ may be combined to form a ring, b ring or c ring May form an aryl ring or a heteroaryl ring, and at least one hydrogen in the formed ring is independently aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, alkyl , Cycloalkyl, alkoxy And at least one hydrogen in each of them may be independently substituted with aryl, heteroaryl, alkyl or cycloalkyl.
X ¹ and X ² are each independently> O or> N-R, wherein R in> N-R is aryl having 6 to 12 carbons, heteroaryl having 2 to 15 carbons, or 1 to 6 carbons Or at least one hydrogen in the aryl or heteroaryl may be substituted with alkyl having 1 to 4 carbons or cycloalkyl having 5 to 10 carbons, and R of the> N—R may be bonded to the a ring, b ring and / or c ring by —O—, —S—, —C (—R) ₂ — or a single bond, R in C (-R) _2- is alkyl having 1 to 6 carbons or cycloalkyl having 3 to 14 carbons, and
At least one hydrogen in the compound represented by the formula (1 ′) may be each independently substituted with halogen, cyano or deuterium. The Ars are each independently any one of the following Formula (Ar-1-1) to Formula (Ar-1-12) and Formula (Ar-2-1) to Formula (Ar-2-4) The organic electroluminescent element in any one of Claims 1-3 which is group represented by these.
In each of the above formulas,
Z is> CR ₂ ,>N—R,> O or>S;
> Rs in CR ₂ are each independently alkyl having 1 to 6 carbons, cycloalkyl having 3 to 14 carbons or aryl having 6 to 12 carbons, and Rs are bonded to each other to form a ring. You can,
R in> N—R is alkyl having 1 to 4 carbons, cycloalkyl having 5 to 10 carbons, or aryl having 6 to 12 carbons,
At least one hydrogen in the groups represented by the above formulas is each independently aryl having 6 to 10 carbon atoms, heteroaryl having 2 to 11 carbon atoms, alkyl having 1 to 30 carbon atoms, or 3 to 24 carbon atoms. And may be substituted with a cycloalkyl of
At least one hydrogen in the groups represented by the formulas may be independently substituted with halogen, cyano or deuterium;
In Formula (2), the pyrene moiety is represented by any of Formula (Ar-1-1) to Formula (Ar-1-12) and Formula (Ar-2-1) to Formula (Ar-2-4). Bond at any position in the group. The organic electroluminescent element according to any one of claims 1 to 4, wherein the pyrene compound represented by the general formula (2) is a compound represented by any one of the following structural formulas.
  An electron transport layer and / or an electron injection layer disposed between the cathode and the light emitting layer, wherein at least one of the electron transport layer and the electron injection layer is a borane derivative, a pyridine derivative, a fluoranthene derivative, BO The at least one selected from the group consisting of anthracene derivatives, anthracene derivatives, benzofluorene derivatives, phosphine oxide derivatives, pyrimidine derivatives, carbazole derivatives, triazine derivatives, benzimidazole derivatives, phenanthroline derivatives, and quinolinol metal complexes, Item 6. The organic electroluminescent device according to any one of Items 1 to 5.   The electron transport layer and / or the electron injection layer further includes an alkali metal, an alkaline earth metal, a rare earth metal, an alkali metal oxide, an alkali metal halide, an alkaline earth metal oxide, or an alkaline earth metal. The material contains at least one selected from the group consisting of halides, rare earth metal oxides, rare earth metal halides, alkali metal organic complexes, alkaline earth metal organic complexes and rare earth metal organic complexes. The organic electroluminescent element as described in 6.   The display apparatus provided with the organic electroluminescent element in any one of Claims 1-7.   The illuminating device provided with the organic electroluminescent element in any one of Claims 1-7. The pyrene type-compound represented by following General formula (2).
In the above formula,
The s pyrene moieties and the p Ar moieties are combined at any position of * in the pyrene moiety and at any position of the Ar moiety,
At least one hydrogen of the pyrene moiety is each independently an aryl having 6 to 10 carbons, a heteroaryl having 2 to 11 carbons, an alkyl having 1 to 30 carbons, a cycloalkyl having 3 to 24 carbons, It may be substituted by 1 to 30 alkenyl, alkoxy having 1 to 30 carbon or aryloxy having 1 to 30 carbon, and at least one hydrogen in these may be alkyl having 1 to 6 carbon or 3 to 14 carbon And may be substituted by cycloalkyl of
Ar is a group represented by the following general formula (Ar-1) or general formula (Ar-3),
In each of the above formulas,
Z is> CR ₂ ,
R in CR ₂ is each independently alkyl of 1 to 6 carbons, cycloalkyl of 3 to 14 carbons, aryl of 6 to 12 carbons or heteroaryl of 2 to 12 carbons, And at least one hydrogen in heteroaryl and heteroaryl may be substituted with alkyl having 1 to 4 carbon atoms or cycloalkyl having 5 to 10 carbon atoms, and R may combine with each other to form a ring,
R ¹ to R ⁸ and R ²⁰ to R ³⁵ each independently represent hydrogen, aryl having 6 to 10 carbon atoms, heteroaryl having 2 to 11 carbon atoms, alkyl having 1 to 30 carbon atoms, or 3 to 24 carbon atoms Cycloalkyl, alkenyl having 1 to 30 carbons, alkoxy having 1 to 30 carbons or aryloxy having 1 to 30 carbons, and at least one hydrogen in these is alkyl having 1 to 6 carbons or 3 to 3 carbons. 14 may be substituted with cycloalkyl, adjacent groups of R ¹ to R ⁸ are bonded to each other to form a condensed ring, and adjacent groups of R ²⁰ to R ³⁵ are bonded to each other. And the formed ring may be independently an aryl having 6 to 10 carbon atoms, a heteroaryl having 2 to 11 carbon atoms, or an alkyl having 1 to 30 carbon atoms. The cycloalkyl having 3 to 24 carbon atoms, the alkenyl having 1 to 30 carbon atoms, the alkoxy having 1 to 30 carbon atoms or the aryloxy having 1 to 30 carbon atoms may be substituted, and at least one hydrogen in these may be substituted with carbon atoms. Optionally substituted with 1-6 alkyl or C3-C14 cycloalkyl, and
s and p are each independently an integer of 1 or 2, s and p can not be 2 at the same time, and when s is 2, two pyrene moieties are structurally identical including substituents And p may be 2 or two Ar moieties may be structurally identical or different, including substituents.
At least one hydrogen in the compound represented by Formula (2) may be independently substituted with halogen, cyano or deuterium. The pyrene compound represented by any one of the following structural formulas.