JP2021147377A - Nitrogen-containing heterocyclic compound and use thereof - Google Patents

Abstract

To provide a nitrogen-containing heterocyclic compound that has high luminous efficiency and has a narrow half-width of a luminescence peak.SOLUTION: A nitrogen-containing heterocyclic compound is illustrated by the following formula (embodiment 1). There are also provided a fluorescent material and an organic EL element containing the nitrogen-containing heterocyclic compound.SELECTED DRAWING: None

Description

Nitrogen-containing heterocyclic compounds and techniques related to their use are disclosed.

Searches for light emitting materials for organic light emitting devices such as organic light emitting diodes (OLEDs) are being conducted. As the light emitting material, it is required that various characteristics such as light emitting color (light emitting maximum wavelength, full width at half maximum, CIE), light emitting efficiency and the like are preferable.

（式中、Ａｒ_１〜Ａｒ_６は、それぞれ独立してハロゲン、シアノ、Ｃ_１−６アルキル基、Ｃ_１−６フルオロアルキル基、Ｃ_６−３０芳香環、Ｃ_３−３０ヘテロ芳香環で置換されている又は置換されていないＣ_６−６０芳香環又はヘテロ芳香環である）
で表される化合物をOLEDに使用することが記載されている。 Patent Document 1 describes the following formulas I and II:

(In the formula, Ar _{1 to} Ar ₆ are independently substituted with halogen, cyano, C _1-6 alkyl group, C _1-6 fluoroalkyl group, C _6-30 aromatic ring, and C _3-30 hetero aromatic ring, respectively. _{C 6-60} aromatic or heteroaromatic ring with or without substitution)
It is described that the compound represented by is used for OLED.

Chinese Patent Application Publication No. 1094563326

The present inventors have found that the compounds described in Patent Document 1 do not have sufficient luminous efficiency. Further, the present inventors have studied various structures of the compound in order to improve the luminous efficiency of the compound described in Patent Document 1. As a result, when Ar ₁ is replaced with a phenoxazine ring or the like, the luminous efficiency is rather improved. It was found that the amount was further reduced and the half-value width of the emission peak was widened.

A main object of the present invention is to provide a nitrogen-containing heterocyclic compound having high luminous efficiency and a narrow full width at half maximum of emission peak, and a technique relating to its use.

（式中、
Ｘは、単結合、−Ｃ(Ｒ^１９)_２−、−Ｏ−、−Ｓ−、又は−Ｎ(Ｒ^２０)−であり、
Ｒ^１１〜Ｒ^２０は、それぞれ、水素原子、電子吸引性基、又は電子供与性基であり（但し、Ｒ^１１〜Ｒ^２０のうち、少なくとも１個は電子吸引性基である）、
波線は、Ａとの結合部位を示す）
で表される基であり、Ａは、下記式（３）：

（式中、
Ａｒ_１〜Ａｒ_３は、それぞれ、置換基を有していてもよい芳香環であり、
Ａｒ_２の置換基及びＡｒ_３の置換基は、互いに結合して置換基を有していてもよい環を形成していてもよく、
Ｒ^２１及びＲ^２２は、それぞれ、水素原子、オキソ基、チオキソ基、又は置換基を有していてもよい芳香環基である（但し、Ｒ^２１及びＲ^２２の一方がオキソ基又はチオキソ基である場合、他方は存在しない）、又はＲ^２１及びＲ^２２は、互いに結合して置換基を有していてもよい環を形成しており、
Ｒ^２３及びＲ^２４は、それぞれ、水素原子、オキソ基、チオキソ基、又は置換基を有していてもよい芳香環基である（但し、Ｒ^２３及びＲ^２４の一方がオキソ基又はチオキソ基である場合、他方は存在しない）、又はＲ^２３及びＲ^２４は、互いに結合して置換基を有していてもよい環を形成しており、
波線は、Ｄとの結合部位を示す）
で表される基である］。
本発明は、この知見に基づいてさらに検討を重ねて完成したものである。 As a result of diligent studies to solve the above problems, the present inventors have been able to increase the luminous efficiency and increase the luminous efficiency by adopting the structure represented by the following formula (1) as the structure of the compound. We found that the half-value width of the emission peak can be narrowed:
DA (1)
[During the ceremony,
D is the following equation (2):

(During the ceremony,
X is a single bond, -C (R ¹⁹ ) _2- , -O-, -S-, or -N (R ²⁰ )-.
R ^{11 to} R ²⁰ are hydrogen atoms, electron-withdrawing groups, or electron-donating groups, respectively (provided that ^{at least one of R 11 to} R ²⁰ is an electron-withdrawing group).
The wavy line indicates the binding site with A)
A is a group represented by the following formula (3):

(During the ceremony,
Ar _{1 to} Ar ₃ are aromatic rings that may have a substituent, respectively.
The substituent of Ar _{2 and} the substituent of Ar ₃ may be bonded to each other to form a ring which may have a substituent.
R ²¹ and R ²² are aromatic ring groups which may have a hydrogen atom, an oxo group, a thioxo group, or a substituent, respectively (provided that one of R ²¹ and R ²² is an oxo group or a thioxo group. In some cases, the other does not exist), or R ²¹ and R ²² are attached to each other to form a ring that may have substituents.
R ²³ and R ²⁴ are aromatic ring groups which may have a hydrogen atom, an oxo group, a thioxo group, or a substituent, respectively (provided that one of R ²³ and R ²⁴ is an oxo group or a thioxo group. In some cases, the other does not exist), or R ²³ and R ²⁴ are attached to each other to form a ring that may have substituents.
The wavy line indicates the binding site with D)
It is a group represented by].
The present invention has been further studied and completed based on this finding.

（式中、
Ｘは、単結合、−Ｃ(Ｒ^１９)_２−、−Ｏ−、−Ｓ−、又は−Ｎ(Ｒ^２０)−であり、
Ｒ^１１〜Ｒ^２０は、それぞれ、水素原子、電子吸引性基、又は電子供与性基であり（但し、Ｒ^１１〜Ｒ^２０のうち、少なくとも１個は電子吸引性基である）、
波線は、Ａとの結合部位を示す）
で表される基であり、Ａは、下記式（３）：

（式中、
Ａｒ_１〜Ａｒ_３は、それぞれ、置換基を有していてもよい芳香環であり、
Ａｒ_２の置換基及びＡｒ_３の置換基は、互いに結合して置換基を有していてもよい環を形成していてもよく、
Ｒ^２１及びＲ^２２は、それぞれ、水素原子、オキソ基、チオキソ基、又は置換基を有していてもよい芳香環基である（但し、Ｒ^２１及びＲ^２２の一方がオキソ基又はチオキソ基である場合、他方は存在しない）、又はＲ^２１及びＲ^２２は、互いに結合して置換基を有していてもよい環を形成しており、
Ｒ^２３及びＲ^２４は、それぞれ、水素原子、オキソ基、チオキソ基、又は置換基を有していてもよい芳香環基である（但し、Ｒ^２３及びＲ^２４の一方がオキソ基又はチオキソ基である場合、他方は存在しない）、又はＲ^２３及びＲ^２４は、互いに結合して置換基を有していてもよい環を形成しており、
波線は、Ｄとの結合部位を示す）
で表される基である］。
項２．
式（２）において、Ｘが単結合である、項１に記載の化合物。
項３．
式（２）において、Ｒ^１２及びＲ^１７が電子吸引性基である、項１又は２に記載の化合物。
項４．
式（２）において、Ｒ^１２及びＲ^１７が、それぞれ、パーフルオロアルキル基又はシアノ基である、項１又は２に記載の化合物。
項５．
式（２）において、Ｒ^１３及びＲ^１６が電子供与性基である、項１〜４のいずれかに記載の化合物。
項６．
式（２）において、Ｒ^１３及びＲ^１６が、それぞれ、アルキル基、アルコキシ基、トリアルキルシリル基、置換基を有していてもよいシクロアルキル基、又は置換基を有していてもよい芳香環基である、項１〜４のいずれかに記載の化合物。
項７．
式（２）において、Ｒ^１１、Ｒ^１４、Ｒ^１５、及びＲ^１８が水素原子である、項１〜６のいずれかに記載の化合物。
項８．
式（３）において、Ａｒ_１〜Ａｒ_３が、それぞれ、ベンゼン環、ナフタレン環、フルオレン環、アントラセン環、フェナントレン環、フルオランテン環、テトラセン環、テトラフェン環、クリセン環、トリフェニレン環、ピレン環、ピリジン環、キノリン環、イソキノリン環、シノリン環、キノキサリン環、フタラジン環、フェナジン環、フェナントリジン環、フェナントロリン環、又はアセナフト［１，２−ｂ］ピラジン環であり、これらの環は置換基を有していてもよい、項１〜７のいずれかに記載の化合物。
項９．
式（３）において、Ｒ^２１及びＲ^２２の一方がオキソ基であり、他方が存在しない、項１〜８のいずれかに記載の化合物。
項１０．
式（３）において、Ｒ^２３及びＲ^２４の一方がオキソ基であり、他方が存在しない、項１〜９のいずれかに記載の化合物。
項１１．
式（３）において、Ｒ^２１〜Ｒ^２４が、置換基を有していてもよい芳香環基である、項１〜８のいずれかに記載の化合物。
項１２．
式（３）において、Ｒ^２１及びＲ^２２が互いに結合して、１，３−ジオキソラン環、１，３−ジチオラン環、フルオレン環、９，１０−ジヒドロアントラセン環、又はアントラセン−９（１０Ｈ）−オン環を形成している、項１〜８のいずれかに記載の化合物。
項１３．
式（３）において、Ｒ^２３及びＲ^２４が互いに結合して、１，３−ジオキソラン環、１，３−ジチオラン環、フルオレン環、９，１０−ジヒドロアントラセン環、又はアントラセン−９（１０Ｈ）−オン環を形成している、項１〜８及び１２のいずれかに記載の化合物。
項１４．
式（３）が、下記式（３Ａ）：

（式中、
Ｒ^２５及びＲ^２６は、それぞれ、オキソ基、チオキソ基、又は置換基を有していてもよい芳香環基である（但し、Ｒ^２５及びＲ^２６の一方がオキソ基又はチオキソ基である場合、他方は存在しない）、又はＲ^２５及びＲ^２６は、互いに結合して置換基を有していてもよい環を形成しており、
Ａｒ_１〜Ａｒ_３及びＲ^２１〜Ｒ^２４は前記と同じである）。
で表される基である、項１〜１３のいずれかに記載の化合物。
項１５．
式（３Ａ）において、Ｒ^２５及びＲ^２６の一方がオキソ基であり、他方が存在しない、項１４に記載の化合物。
項１６．
式（３Ａ）において、Ｒ^２５及びＲ^２６が互いに結合して、１，３−ジオキソラン環、１，３−ジチオラン環、フルオレン環、９，１０−ジヒドロアントラセン環、又はアントラセン−９（１０Ｈ）−オン環を形成している、項１４に記載の化合物。
項１７．
Ｄが、下記の群：

（式中、Ｍｅはメチル基、ｉ−Ｐｒはイソプロピル基、ｔ−Ｂｕはターシャリーブチル基、Ｐｈはフェニル基、波線はＡとの結合部位を示す）
から選択される基であり、Ａが、下記の群：

（式中、波線はＤとの結合部位を示す）
から選択される基である、項１に記載の化合物。
項１８．
項１〜１７のいずれかに記載の化合物を含む蛍光材料。
項１９．
項１〜１７のいずれかに記載の化合物を含む有機発光素子。
項２０．
有機ＥＬ素子である、項１９に記載の有機発光素子。 The present invention includes the following aspects.
Item 1.
Compound represented by the following formula (1):
DA (1)
[During the ceremony,
D is the following equation (2):

(During the ceremony,
X is a single bond, -C (R ¹⁹ ) _2- , -O-, -S-, or -N (R ²⁰ )-.
R ^{11 to} R ²⁰ are hydrogen atoms, electron-withdrawing groups, or electron-donating groups, respectively (provided that ^{at least one of R 11 to} R ²⁰ is an electron-withdrawing group).
The wavy line indicates the binding site with A)
A is a group represented by the following formula (3):

(During the ceremony,
Ar _{1 to} Ar ₃ are aromatic rings that may have a substituent, respectively.
The substituent of Ar _{2 and} the substituent of Ar ₃ may be bonded to each other to form a ring which may have a substituent.
R ²¹ and R ²² are aromatic ring groups which may have a hydrogen atom, an oxo group, a thioxo group, or a substituent, respectively (provided that one of R ²¹ and R ²² is an oxo group or a thioxo group. In some cases, the other does not exist), or R ²¹ and R ²² are attached to each other to form a ring that may have substituents.
R ²³ and R ²⁴ are aromatic ring groups which may have a hydrogen atom, an oxo group, a thioxo group, or a substituent, respectively (provided that one of R ²³ and R ²⁴ is an oxo group or a thioxo group. In some cases, the other does not exist), or R ²³ and R ²⁴ are attached to each other to form a ring that may have substituents.
The wavy line indicates the binding site with D)
It is a group represented by].
Item 2.
Item 2. The compound according to Item 1, wherein X is a single bond in the formula (2).
Item 3.
Item 2. The compound according to Item 1 or 2, wherein in the formula (2), R ¹² and R ^{17 are electron-withdrawing groups.}
Item 4.
Item 2. The compound according to Item 1 or 2, wherein in the formula (2), R ¹² and R ^{17 are perfluoroalkyl groups or cyano groups, respectively.}
Item 5.
Item 4. The compound according to any one of Items 1 to 4, wherein in the formula (2), R ¹³ and R ^{16 are electron-donating groups.}
Item 6.
In formula (2), R ¹³ and R ¹⁶ have an alkyl group, an alkoxy group, a trialkylsilyl group, a cycloalkyl group which may have a substituent, or an aromatic group which may have a substituent, respectively. Item 4. The compound according to any one of Items 1 to 4, which is a ring group.
Item 7.
Item 6. The compound according to any one of Items 1 to 6, wherein in the formula (2), R ¹¹ , R ¹⁴ , R ¹⁵ and R ^{18 are hydrogen atoms.}
Item 8.
In the formula (3), Ar _{1 to} Ar ₃ are benzene ring, naphthalene ring, fluorene ring, anthracene ring, phenanthrene ring, fluorantene ring, tetracene ring, tetraphen ring, chrysen ring, triphenylene ring, pyrene ring and pyridine, respectively. A ring, a quinoline ring, an isoquinoline ring, a synolin ring, a quinoxaline ring, a phthalazine ring, a phenazine ring, a phenanthrene ring, a phenanthrene ring, or an acenaft [1,2-b] pyrazine ring, and these rings have a substituent. Item 2. The compound according to any one of Items 1 to 7, which may be used.
Item 9.
Item 4. The compound according to any one of Items 1 to 8, wherein in the formula (3), one of R ²¹ and R ^{22 is an oxo group and the other is absent.}
Item 10.
Item 4. The compound according to any one of Items 1 to 9, wherein in the formula (3), one of R ²³ and R ^{24 is an oxo group and the other is absent.}
Item 11.
Item 2. The compound according to any one of Items 1 to 8, wherein in the formula (3), R ^{21 to} R ^{24 are aromatic ring groups which may have a substituent.}
Item 12.
In formula (3), R ²¹ and R ²² are bonded to each other to form a 1,3-dioxolane ring, a 1,3-dithiolane ring, a fluorene ring, a 9,10-dihydroanthracene ring, or anthracene-9 (10H)-. Item 2. The compound according to any one of Items 1 to 8, which forms an on-ring.
Item 13.
In formula (3), R ²³ and R ²⁴ are bonded to each other to form a 1,3-dioxolane ring, a 1,3-dithiolane ring, a fluorene ring, a 9,10-dihydroanthracene ring, or anthracene-9 (10H)-. Item 2. The compound according to any one of Items 1 to 8 and 12, which forms an on-ring.
Item 14.
Equation (3) is the following equation (3A):

(During the ceremony,
R ²⁵ and R ²⁶ are aromatic ring groups which may have an oxo group, a thioxo group, or a substituent, respectively (provided that one of R ²⁵ and R ²⁶ is an oxo group or a thioxo group). The other does not exist), or R ²⁵ and R ²⁶ are attached to each other to form a ring that may have substituents.
Ar _{1 to} Ar ₃ and R ^{21 to} R ²⁴ are the same as described above).
Item 2. The compound according to any one of Items 1 to 13, which is a group represented by.
Item 15.
Item 4. The compound according to Item 14, wherein in formula (3A), one of R ²⁵ and R ²⁶ is an oxo group and the other is absent.
Item 16.
In formula (3A), R ²⁵ and R ²⁶ combine with each other to form a 1,3-dioxolane ring, a 1,3-dithiolane ring, a fluorene ring, a 9,10-dihydroanthracene ring, or anthracene-9 (10H)-. Item 2. The compound according to Item 14, which forms an on-ring.
Item 17.
D is the following group:

(In the formula, Me is a methyl group, i-Pr is an isopropyl group, t-Bu is a tertiary butyl group, Ph is a phenyl group, and a wavy line indicates the binding site with A).
A group selected from the following groups:

(In the formula, the wavy line indicates the binding site with D)
Item 2. The compound according to Item 1, which is a group selected from.
Item 18.
A fluorescent material containing the compound according to any one of Items 1 to 17.
Item 19.
An organic light emitting device containing the compound according to any one of Items 1 to 17.
Item 20.
Item 2. The organic light emitting device according to Item 19, which is an organic EL element.

INDUSTRIAL APPLICABILITY According to the present invention, a nitrogen-containing heterocyclic compound having high luminous efficiency and a narrow half-value width of emission peak, and a technique relating to its use are provided.

FIG. 1 is ^{a diagram showing a 1} H NMR spectrum of Intermediate 1. FIG. 2 is ^{a diagram showing a 1} H NMR spectrum of Intermediate 2. FIG. 3 is ^{a diagram showing a 1} H NMR spectrum of Comparative Example 1. FIG. 4 is ^{a diagram showing a 1} H NMR spectrum of Comparative Example 2. FIG. 5 is ^{a diagram showing a 1} H NMR spectrum of Example 1. FIG. 6 is ^{a diagram showing a 19} F NMR spectrum of Example 1. FIG. 7 is ^{a diagram showing a 1} H NMR spectrum of Example 2. FIG. 8 is ^{a diagram showing a 19} F NMR spectrum of Example 2.

<Definition>
In the present specification, unless otherwise specified, "halogen atom" is used in the sense of including a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.

In the present specification, unless otherwise specified, the "alkyl group" means a linear or branched saturated hydrocarbon group, and specifically, for example, a methyl group, an ethyl group, or a propyl group (n). -Propyl group, isopropyl group), butyl group (n-butyl group, isobutyl group, sec-butyl group, tert-butyl group), pentyl group, hexyl group and other C _1-20 alkyl groups.

In the present specification, unless otherwise specified, the "perfluoroalkyl group" means a group in which all hydrogen atoms of the alkyl group are substituted with fluorine atoms, and specifically, for example, a trifluoromethyl group. , Pentafluoroethyl group, heptafluoropropyl group (heptafluoron-propyl group or heptafluoroi-propyl group) and other perfluoroC _1-12 alkyl groups.

In the present specification, unless otherwise specified, the "alkoxy group" means a group in which an oxygen atom is bonded to the terminal of the alkyl group, and specifically, for example, a methoxy group, an ethoxy group, or a propoxy group (n). − Propoxy group, isopropoxy group), butoxy group (n-butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group) and other C _1-12 alkoxy groups can be mentioned.

In the present specification, unless otherwise specified, the "alkylsulfanyl group" means a group in which a sulfur atom is bonded to the terminal of the alkyl group, and specifically, for example, a methylsulfanyl group, an ethylsulfanyl group, or propyl. _{Examples thereof include C 1-12} alkyl sulfanyl groups such as a sulfanyl group (n-propyl sulfanyl group, isopropyl sulfanyl group) and a butyl sulfanyl group.

In the present specification, unless otherwise specified, the "alkylcarbonyl group" means a group in which a carbonyl group (-C (= O)-) is bonded to the end of the alkyl group, and specifically, for example, for example. _{Examples thereof include (C 1-12} alkyl) carbonyl groups such as methylcarbonyl group, ethylcarbonyl group, propylcarbonyl group (n-propylcarbonyl group, isopropylcarbonyl group) and butylcarbonyl group.

In the present specification, unless otherwise specified, the "alkylsulfonyl group" means a group in which a sulfonyl group (-S (= O) _2- ) is bonded to the end of the alkyl group, and specifically, for example. , Methylsulfonyl group, ethylsulfonyl group, propylsulfonyl group (n-propylsulfonyl group, isopropylsulfonyl group), butylsulfonyl group and other C _1-12 alkylsulfonyl groups.

In the present specification, unless otherwise specified, the "cycloalkyl group" includes a cycloC _5-20 alkyl group such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and a cyclooctyl group.

In the present specification, unless otherwise specified, the "trialkylsilyl group" means a group in which the three alkyl groups are bonded to a silicon atom, and specifically, for example, a trimethylsilyl group and a triethylsilyl group. _{Examples thereof include a tri-C 1-4} alkylsilyl group such as a triisopropylsilyl group and a tert-butyldimethylsilyl group.

Unless otherwise specified, the term "aromatic ring" is used herein to include an arene ring and a heteroarene ring.

The number of carbon atoms in the arene ring is not particularly limited, but is, for example, 6 to 40, preferably 6 to 30, more preferably 6 to 28, and even more preferably 6 to 26. The arene ring is preferably a benzene ring or a fused ring having a structure in which a plurality of benzene rings are condensed. Examples of the arene ring include a benzene ring, a naphthalene ring, a fluorene ring, an anthracene ring, a phenanthrene ring, a fluoranthene ring, a tetracene ring, a tetraphen ring, a chrysen ring, a triphenylene ring, a pyrene ring, a benzopyrene ring, a perylene ring, and a coronene ring. Examples include a coronene ring, a phenalene ring, and a triangulene ring.

The number of ring-constituting atoms in the heteroarene ring is not particularly limited, but is, for example, 5 to 40 members. The heteroarene ring may be a monocyclic type or a polycyclic type (for example, a two- to four-ring type). The heteroarene ring is preferably a heteroarene ring containing at least one heteroatom selected from an oxygen atom, a sulfur atom, and a nitrogen atom as a ring-constituting atom. Examples of the heteroarene ring include an oxygen-containing heteroarene ring (eg, furan ring, benzofuran ring, dibenzo [b, d] furan ring) and a sulfur-containing heteroarene ring (eg, thiophene ring, benzothiophene ring, dibenzo [b]. , D] Thiophene ring), nitrogen-containing heteroarene ring (eg, pyrrole ring, pyrazole ring, imidazole ring, 1,2,3-triazole ring, 1,2,4-triazole ring, pyridine ring, pyridazine ring, pyrimidine ring) , Pyrazine ring, 1,3,5-triazole ring, indole ring, indazole ring, benzimidazole ring, quinoline ring, isoquinoline ring, sinoline ring, quinoxaline ring, phthalazine ring, naphthylidine ring, purine ring, acrydin ring, phenazine ring, Phenantridin ring, phenanthroline ring, acenaft [1,2-b] pyrazine ring), oxygen and nitrogen-containing heteroarene ring (eg, oxazole ring, isooxazole ring, benzoxazole ring, phenoxazine ring), sulfur and nitrogen-containing Heteroarene rings (eg, thiazole ring, isothiazole ring, benzothiazole ring, phenothiazine ring) can be mentioned.

In the present specification, unless otherwise specified, "aromatic ring group" means a group obtained by removing one hydrogen atom from the aromatic ring. The aromatic ring group includes a group obtained by removing one hydrogen atom from the arene ring (aryl group) and a group obtained by removing one hydrogen atom from the heteroarene ring (heteroaryl group).

_{Examples of the aryl group include C 6-18} aryl groups such as a phenyl group, a naphthyl group, a fluorenyl group, an anthrasenyl group, a triphenylenyl group and a pyrenyl group.

Examples of the heteroaryl group include a 5-membered or 6-membered monocyclic heteroaryl group and a 2- to 4-cyclic heteroaryl group. Examples of the 5- or 6-membered monocyclic heteroaryl group include an oxygen-containing heteroaryl group such as a frill group; a sulfur-containing heteroaryl group such as a thienyl group; a pyrrolyl group, a pyrazolyl group, an imidazolyl group, a triazil group and a pyridyl group. , Pyridazyl group, pyrimidyl group, pyrazil group, triazinyl group and other nitrogen-containing heteroaryl groups. Examples of the bi-tetracyclic heteroaryl group include an oxygen-containing heteroaryl group such as a benzofuryl group and a dibenzofuryl group; a sulfur-containing heteroaryl group such as a benzothienyl group and a dibenzothienyl group; an indolyl group, a quinolyl group and an isoquinolyl group. , Carbazolyl group, acridyl group and other nitrogen-containing heteroaryl groups.

In the present specification, unless otherwise specified, an "electron donating group (donor group)" represents a group in which Hammett's σp is negative. Hansch, C.et.al., Chem.Rev., 91,165-195 (1991) can be referred to for a description of Hammett's σp and the numerical values of each group. Examples of the electron donating group include an alkyl group such as a methyl group, an isopropyl group and a tertiary butyl group, a cycloalkyl group such as a cyclohexyl group, a phenyl group, a naphthyl group, an anthracenyl group, a triphenylenyl group, a pyrenyl group and a fluorenyl group. Alkyl group such as aryl group, methoxy group, alkylsulfanyl group such as methionyl group, alkylsilyl group such as trimethylsilyl group, pyridyl group, imidazolyl group, pyrazolyl group, oxazolyl group, thiazolyl group, indolyl group, pyrrolyl group, quinolyl group. , Heteroaryl groups such as benzofuryl group and benzothienyl group.

In the present specification, unless otherwise specified, the "electron-withdrawing group (accepting group)" means a group other than an electron-donating group, for example, an alkylcarbonyl group (acyl group), an alkylsulfonyl group, or a per. Examples thereof include a fluoroalkyl group, a cyano group and a nitro group.

（式中、
Ｘは、単結合、−Ｃ(Ｒ^１９)_２−、−Ｏ−、−Ｓ−、又は−Ｎ(Ｒ^２０)−であり、
Ｒ^１１〜Ｒ^２０は、それぞれ、水素原子、電子吸引性基、又は電子供与性基であり（但し、Ｒ^１１〜Ｒ^２０のうち、少なくとも１個は電子吸引性基である）、
波線は、Ａとの結合部位を示す）
で表される基であり、Ａは、下記式（３）：

（式中、
Ａｒ_１〜Ａｒ_３は、それぞれ、置換基を有していてもよい芳香環であり、
Ａｒ_２の置換基及びＡｒ_３の置換基は、互いに結合して置換基を有していてもよい環を形成していてもよく、
Ｒ^２１及びＲ^２２は、それぞれ、水素原子、オキソ基（＝Ｏ）、チオキソ基（＝Ｓ）、又は置換基を有していてもよい芳香環基である（但し、Ｒ^２１及びＲ^２２の一方がオキソ基又はチオキソ基である場合、他方は存在しない）、又はＲ^２１及びＲ^２２は、互いに結合して置換基を有していてもよい環を形成しており、
Ｒ^２３及びＲ^２４は、それぞれ、水素原子、オキソ基、チオキソ基、又は置換基を有していてもよい芳香環基である（但し、Ｒ^２３及びＲ^２４の一方がオキソ基又はチオキソ基である場合、他方は存在しない）、又はＲ^２３及びＲ^２４は、互いに結合して置換基を有していてもよい環を形成しており、
波線は、Ｄとの結合部位を示す）
で表される基である］。 <Compound>
In one embodiment, the compound of the present invention is preferably a compound represented by the following formula (1):
DA (1)
[During the ceremony,
D is the following equation (2):

(During the ceremony,
X is a single bond, -C (R ¹⁹ ) _2- , -O-, -S-, or -N (R ²⁰ )-.
R ^{11 to} R ²⁰ are hydrogen atoms, electron-withdrawing groups, or electron-donating groups, respectively (provided that ^{at least one of R 11 to} R ²⁰ is an electron-withdrawing group).
The wavy line indicates the binding site with A)
A is a group represented by the following formula (3):

(During the ceremony,
Ar _{1 to} Ar ₃ are aromatic rings that may have a substituent, respectively.
The substituent of Ar _{2 and} the substituent of Ar ₃ may be bonded to each other to form a ring which may have a substituent.
R ²¹ and R ²² are aromatic ring groups which may have a hydrogen atom, an oxo group (= O), a thioxo group (= S), or a substituent, respectively (provided that R ²¹ and R ²² have an aromatic ring group. If one is an oxo group or a thioxo group, the other does not exist), or R ²¹ and R ²² are bonded to each other to form a ring which may have a substituent.
R ²³ and R ²⁴ are aromatic ring groups which may have a hydrogen atom, an oxo group, a thioxo group, or a substituent, respectively (provided that one of R ²³ and R ²⁴ is an oxo group or a thioxo group. In some cases, the other does not exist), or R ²³ and R ²⁴ are attached to each other to form a ring that may have substituents.
The wavy line indicates the binding site with D)
It is a group represented by].

Equation (2)
X is preferably a single bond.

When R ^{11 to} R ²⁰ are electron-withdrawing groups, the electron-withdrawing group is preferably a perfluoroalkyl group or a cyano group, more preferably a perfluoroC _1-4 alkyl group or a cyano group. It is more preferably a perfluoroC _1-3 alkyl group or a cyano group, even more preferably a perfluoroC _1-2 alkyl group or a cyano group, and particularly preferably a trifluoromethyl group or a cyano group.

When R ^{11 to} R ²⁰ are electron-donating groups, the electron-donating group is preferably an alkyl group, an alkoxy group, a trialkylsilyl group, a cycloalkyl group which may have a substituent, or a substituent. It is an aromatic ring group which may have a C _1-6 alkyl group, a C _1-6 alkoxy group, a tri C _1-6 alkylsilyl group, and a C _{5 which may have a substituent. It has a -12} cycloalkyl group, a C _6-18 aryl group which may have a substituent, a 5- or 6-membered monocyclic heteroaryl group which may have a substituent, or a substituent. It may be a bi- to tetracyclic heteroaryl group, more preferably a C _1-4 alkyl group, a C _1-4 alkoxy group, a tri C _1-4 alkyl silyl group, a C _5-7 cycloalkyl group, C _{6 A -14} aryl group, a 5- or 6-membered monocyclic nitrogen-containing heteroaryl group which may have a substituent, or a 2- to tetracyclic nitrogen-containing heteroaryl group which may have a substituent. .. The substituent which may be substituted with the cycloalkyl group or the aromatic ring group is preferably an aromatic ring group, more preferably an aryl group, still more preferably a C _6-12 aryl group, and particularly preferably. Is a C _6-10 aryl group. The number of the substituents is, for example, 1, 2, 3, or 4.

R ¹¹ , R ¹⁴ , R ¹⁵ and R ¹⁸ are preferably hydrogen atoms.
R ¹² , R ¹³ , R ¹⁶ and R ¹⁷ are preferably electron-withdrawing or electron-donating groups. R ¹² and R ¹⁷ may be electron-donating groups, but are preferably electron-withdrawing groups. R ¹³ and R ¹⁶ may be electron-withdrawing groups, but are preferably electron-donating groups.

It is also preferable that R ¹¹ , R ¹⁴ , R ¹⁵ and R ¹⁸ are hydrogen atoms, R ¹² and R ¹⁷ are electron donating groups, and R ¹³ and R ¹⁶ are electron attracting groups, but R ^More preferably, 11, R ¹⁴ , R ¹⁵ and R ¹⁸ are hydrogen atoms, R ¹² and R ¹⁷ are electron-withdrawing groups, and R ¹³ and R ¹⁶ are electron-donating groups.

Two R ¹⁹ may being the same or different.
R ¹⁹ and R ²⁰ are each preferably an alkyl group or an aromatic ring group which may have a substituent, more preferably an aromatic ring group which may have a substituent, and further preferably. May have a C _6-18 aryl group, which may have a substituent, a 5- or 6-membered monocyclic heteroaryl group, which may have a substituent, or two to two, which may have a substituent. It is a tetracyclic heteroaryl group, particularly preferably having a C _6-14 aryl group, a 5- or 6-membered monocyclic nitrogen-containing heteroaryl group which may have a substituent, or a substituent. It is also a good bi-tetracyclic nitrogen-containing heteroaryl group. The substituent which may be substituted with the aromatic ring group is preferably an aromatic ring group, more preferably an aryl group, further preferably a C _6-12 aryl group, and particularly preferably C _6-10. It is an aryl group. The number of the substituents is, for example, 1, 2, 3, or 4.

（式中、Ｍｅはメチル基、ｉ−Ｐｒはイソプロピル基、ｔ−Ｂｕはターシャリーブチル基、Ｐｈはフェニル基、波線はＡとの結合部位を示す）。 The group represented by the formula (2) is preferably a group selected from the following group:

(In the formula, Me is a methyl group, i-Pr is an isopropyl group, t-Bu is a tertiary butyl group, Ph is a phenyl group, and a wavy line indicates a binding site with A).

Equation (3)
Ar _{1 to} Ar _{3 are C 6-20} arene rings which may have a substituent, or monocyclic or two to four ring heteroarene rings which may have a substituent, respectively. Is preferable, and it is more preferably a C _6-18 arene ring, or a monocyclic or 2- to 4-cyclic nitrogen-containing heteroarene ring which may have a substituent, and a benzene ring, a naphthalene ring, a fluorene ring, and the like. Anthracene ring, phenanthrene ring, fluorantene ring, tetracene ring, tetraphene ring, chrysen ring, triphenylene ring, pyrene ring, pyridine ring, quinoline ring, isoquinoline ring, sinoline ring, quinoxaline ring, phthalazine ring, phenazine ring, phenanthridine ring. , A phenanthroline ring, or an ashenaft [1,2-b] pyrazine ring (these rings may have substituents). The substituent which may be substituted with the allene ring or the heteroarene ring is preferably a halogen atom, an alkyl group, a cyano group, an aryl group, or a heteroaryl group, and more preferably a fluorine atom, C _1-4 alkyl. A group, a cyano group, a C _6-10 aryl group, or a 5- or 6-membered monocyclic heteroaryl group. The number of the substituents is, for example, 1, 2, 3, or 4.

（式中、
Ｒ^２５及びＲ^２６は、それぞれ、オキソ基、チオキソ基、又は置換基を有していてもよい芳香環基である（但し、Ｒ^２５及びＲ^２６の一方がオキソ基又はチオキソ基である場合、他方は存在しない）、又はＲ^２５及びＲ^２６は、互いに結合して置換基を有していてもよい環を形成しており、
Ａｒ_１〜Ａｒ_３及びＲ^２１〜Ｒ^２４は前記と同じである）。 In one embodiment, the Ar ₂ substituent and the Ar ₃ substituent can be bonded to each other to form a ring which may have a substituent. In this embodiment, the formula (3) can be represented by, for example, the following formula (3A):

(During the ceremony,
R ²⁵ and R ²⁶ are aromatic ring groups which may have an oxo group, a thioxo group, or a substituent, respectively (provided that one of R ²⁵ and R ²⁶ is an oxo group or a thioxo group). The other does not exist), or R ²⁵ and R ²⁶ are attached to each other to form a ring that may have substituents.
Ar _{1 to} Ar ₃ and R ^{21 to} R ²⁴ are the same as described above).

In one preferred embodiment, one of R ²⁵ and R ²⁶ is an oxo group and the other is absent.

In another preferred embodiment, R ²⁵ and R ²⁶ are aromatic ring groups, each of which may have a substituent. In this embodiment, R ²⁵ and R ²⁶ are C 6-18 aryl groups, which may have substituents, or monocyclic or two to tetracyclic _heteros, which may have substituents, respectively. It is preferably an aryl group, which is a C _6-14 aryl group which may have a substituent, or a monocyclic or bi-tetracyclic nitrogen-containing heteroaryl group which may have a substituent. Is more preferable. Further, in the embodiment, it is also preferable that ^{R 25} and R ²⁶ are C _6-14 ^{aryl groups which may have a substituent, and R 25} may have a substituent C _6-14. It is also preferable that the aryl group, R ^26, is a monocyclic or di-tetracyclic nitrogen-containing heteroaryl group which may have a substituent. The substituent which may be substituted with the aryl group or the heteroaryl group is preferably a halogen atom, an alkyl group, a cyano group, or an aryl group. The number of the substituents is, for example, 1, 2, 3, or 4.

In yet another preferred embodiment, R ²⁵ and R ²⁶ are attached to each other to form a ring that may have substituents. The ring is preferably a 1,3-dioxolane ring, a 1,3-dithiolane ring, a fluorene ring, a 9,10-dihydroanthracene ring, or an anthracene-9 (10H) -on ring. The substituent which may be substituted on the ring is preferably a halogen atom, an alkyl group, a cyano group, or an aryl group. Preferably, the number of the substituents is, for example, 1, 2, 3, or 4.

In one preferred embodiment, one of R ²¹ and R ²² is an oxo group and the other is absent.

In another preferred embodiment, R ²¹ and R ²² are aromatic ring groups, each of which may have a substituent. In this embodiment, R ²¹ and R ²² are C 6-18 aryl groups, which may have substituents, or monocyclic or two to tetracyclic _heteros, which may have substituents, respectively. It is preferably an aryl group, which is a C _6-14 aryl group which may have a substituent, or a monocyclic or bi-tetracyclic nitrogen-containing heteroaryl group which may have a substituent. Is more preferable. Further, in the embodiment, it is also preferable that ^{R 21} and R ²² are C _6-14 ^{aryl groups which may have a substituent, and R 21} may have a substituent C _6-14. It is also preferable that the aryl group, R ²² is a monocyclic or di-tetracyclic nitrogen-containing heteroaryl group which may have a substituent. The substituent which may be substituted with the aryl group or the heteroaryl group is preferably a halogen atom, an alkyl group, a cyano group, or an aryl group. The number of the substituents is, for example, 1, 2, 3, or 4.

In yet another preferred embodiment, R ²¹ and R ²² are attached to each other to form a ring that may have substituents. The ring is preferably a 1,3-dioxolane ring, a 1,3-dithiolane ring, a fluorene ring, a 9,10-dihydroanthracene ring, or an anthracene-9 (10H) -on ring. The substituent which may be substituted on the ring is preferably a halogen atom, an alkyl group, a cyano group, or an aryl group. Preferably, the number of the substituents is, for example, 1, 2, 3, or 4.

In one preferred embodiment, one of R ²³ and R ²⁴ is an oxo group and the other is absent.

In another preferred embodiment, R ²³ and R ²⁴ are aromatic ring groups, each of which may have a substituent. In this embodiment, R ²³ and R ²⁴ are C 6-18 aryl groups, which may have substituents, or monocyclic or two to tetracyclic _heteros, which may have substituents, respectively. It is preferably an aryl group, which is a C _6-14 aryl group which may have a substituent, or a monocyclic or bi-tetracyclic nitrogen-containing heteroaryl group which may have a substituent. Is more preferable. Further, in the embodiment, it is also preferable that ^{R 23} and R ²⁴ are C _6-14 ^{aryl groups which may have a substituent, and R 23} may have a substituent C _6-14. It is also preferable that the aryl group, R ^24, is a monocyclic or di-tetracyclic nitrogen-containing heteroaryl group which may have a substituent. The substituent which may be substituted with the aryl group or the heteroaryl group is preferably a halogen atom, an alkyl group, or a cyano group.

In yet another preferred embodiment, R ²³ and R ²⁴ are attached to each other to form a ring that may have substituents. The ring is preferably a 1,3-dioxolane ring, a 1,3-dithiolane ring, a fluorene ring, a 9,10-dihydroanthracene ring, or an anthracene-9 (10H) -on ring. The substituent which may be substituted on the ring is preferably a halogen atom, an alkyl group, a cyano group, or an aryl group. Preferably, the number of the substituents is, for example, 1, 2, 3, or 4.

The combination of R ²¹ and R ²² may be different from the combination of ^{R 23} and R ^{24, but is preferably the same.} Further, the combination of ^{R 21} and R ²² may be different from the combination of ^{R 25} and R ^{26, but is preferably the same.}

（式中、波線はＤとの結合部位を示す）。 The group represented by the formula (3) is preferably a group selected from the following group:

(In the equation, the wavy line indicates the binding site with D).

The half width of the emission peak of the compound of the present invention may be preferably 50 nm or less, more preferably 45 nm or less, further preferably 40 nm or less, or 10 nm or more. ^{The full width at half maximum can be determined by measuring the emission spectrum when a solution (concentration: 1 × 10-5} M) in which the compound of the present invention is dissolved is irradiated with excitation light at 340 nm at room temperature. In the emission spectrum, the spectrum width of half the peak top intensity is defined as the half width (FWHM, Full Width Half Maximum).

The luminous efficiency (PLQY) of the compound of the present invention is preferably 50% or more, more preferably 55% or more, still more preferably 60% or more. Luminous efficiency (PLQY) is a value when a solution (concentration: 1 × ^10-5 M) in which the compound of the present invention is dissolved is irradiated with excitation light at 340 nm at room temperature, and is an absolute PL quantum yield measuring device (for example). , Hamamatsu Photonics Quantaurus-QY C11347-01) can be used for measurement.

The HOMO level of the compound of the present invention may preferably be -5.0 eV or less or -5.5 eV or less, and is -7.0 eV or more, -6.5 eV or more, or -6.4 eV or more. You may. Due to such a HOMO level, compatibility with peripheral materials such as host materials is excellent. The HOMO level can be measured using an atmospheric photoelectron spectrometer (for example, AC-3 manufactured by RIKEN Keiki Co., Ltd.).

（式中、Ｘ及びＲ^１１〜Ｒ^１８は前記と同じである）
で表される化合物を、下記式（５）：

（式中、Ｚは、ハロゲン原子であり、Ａｒ_１〜Ａｒ_３及びＲ^２１〜Ｒ^２４は前記と同じである）
で表される化合物と反応させる工程を含む方法により製造することができる。 Method for producing a compound represented by the formula (1) The compound represented by the formula (1) is not particularly limited, but for example, the following formula (4):

(In the formula, X and R ^{11 to} R ¹⁸ are the same as above)
The compound represented by the following formula (5):

(In the formula, Z is a halogen atom, and Ar _{1 to} Ar ₃ and R ^{21 to} R ²⁴ are the same as described above.)
It can be produced by a method including a step of reacting with a compound represented by.

Equation (5)
Z is preferably a fluorine atom, a chlorine atom, or a bromine atom.

（式中、
Ｒ^３及びＲ^４は、それぞれ、アルコキシ基であり、
Ｚ^３及びＺ^４は、それぞれ、ハロゲン原子であり、
Ｚ及びＡｒ_１〜Ａｒ_３は前記と同じである）
により製造することができる。 The compound represented by the formula (5) can be produced by a combination of known reactions.
For example, in the formula (5), one of R ²¹ and R ²² is an oxo group and the other is absent, and one of R ²³ and R ²⁴ is an oxo group and the other is absent (that is, the following formula). The compound represented by (12)) is, for example, the following reaction scheme:

(During the ceremony,
R ³ and R ⁴ are alkoxy groups, respectively, and are
Z ³ and Z ⁴ are halogen atoms, respectively, and
Z and Ar _{1 to} Ar ₃ are the same as above)
Can be manufactured by

[Step (I)]
The step (I) is a step of reacting the compounds represented by the formulas (6) to (8) to obtain the compound represented by the formula (9).

In the formulas (7) and (8), R ³ and R ⁴ are preferably _{C 1-6} alkoxy groups, respectively, and _{more preferably C 1-4} alkoxy groups.

Z ³ and Z ⁴ may be the same as Z, but are preferably different from Z. As a combination of Z, Z ³ , and Z ^4,
A combination in which Z is a fluorine atom and Z ³ and Z ⁴ are chlorine, bromine, or iodine atoms;
A combination in which Z is a chlorine atom and Z ³ and Z ⁴ are bromine or iodine atoms; or a combination in which Z is a bromine atom and Z ³ and Z ⁴ are iodine atoms is preferred.

The total amount of the compounds represented by the formulas (7) and (8) used is 1 mol or more, 1.5 mol or more, or 2 mol or more with respect to 1 mol of the compound represented by the formula (6). It is preferably 5 mol or less, 4.5 mol or less, or 4 mol or less.

The reaction of step (I) is preferably carried out in the presence of a solvent. The solvent is not particularly limited as long as the reaction component can be dissolved, and is, for example, ether (eg, diethyl ether, dipropyl ether, dibutyl ether), aromatic hydrocarbon (eg, toluene, xylene), amide (eg, eg). : Dimethylformamide) and the like. As the solvent, one type can be used alone or two or more types can be mixed and used.

The reaction of step (I) is preferably carried out in the presence of a base. As the base, for example, n- _{butyllithium, NaH, K 2 CO 3,} Cs 2 CO 3, t- butoxy sodium, t-butoxy potassium, etc. These combinations of two or more thereof. When using n-butyllithium, refer to International Publication No. 2008/1178226, Chemistry of Materials, 2010, 22 (7), 2403-2410, etc. When using NaH, Korean Patent Application Publication No. 2018- You can refer to No. 063708 and so on.

The reaction of step (I) is preferably carried out in the presence of a catalyst. Examples of the catalyst include transition metal catalysts such as copper catalysts and palladium catalysts. When a palladium catalyst is used, International Publication No. 2011/08902, International Publication No. 2015/137472, and the like can be referred to.

[Process (II)]
Step (II) is a step of hydrolyzing the compound represented by the formula (9) to obtain the compound represented by the formula (10). Hydrolysis can be carried out by a conventional method (for example, hydrolysis with sodium hydroxide).

[Process (III)]
Step (III) is represented by formula (12) by reacting the compound represented by the formula (10) with a halogenating agent (step (IIIa)) and subsequently reacting with Lewis acid (step (IIIb)). This is the process of obtaining a compound.

The halogenating agent is not particularly limited, and examples thereof include thionyl chloride, phosphoryl chloride, sulfuryl chloride, phosphorus trichloride, phosphorus pentachloride, and combinations of two or more thereof.

The halogenating agent is preferably used so as to be, for example, 1.0 mol or more or 2.0 mol or more, and 100 mol or less or 50 mol or less, with respect to 1 mol of the compound represented by the formula (9). It is preferable to use it so as to be.

The reaction temperature and reaction time of step (IIIa) are not particularly limited as long as the reaction proceeds. The reaction temperature of the step (IIIa) may be, for example, 25 ° C. or higher, 30 ° C. or higher, 35 ° C. or higher, or 40 ° C. or higher, or 100 ° C. or lower. The reaction time of step (IIIa) may be, for example, 0.5 hours or more, 1 hour or more, or 24 hours or less.

The Lewis acid is not particularly limited, and examples thereof include aluminum chloride, aluminum bromide, tin (IV) chloride, antimony fluoride (V), boron fluoride, zinc chloride, and a combination of two or more thereof.

Lewis acid is preferably used in an amount of, for example, 2.0 mol or more or 4.0 mol or more, and 40 mol or less or 20 mol or less, with respect to 1 mol of the compound represented by the formula (9). It is preferable to use it so as to become.

The reaction temperature and reaction time of step (IIIb) are not particularly limited as long as the reaction proceeds. The reaction temperature of step (IIIb) may be, for example, −40 ° C. or higher, −35 ° C. or higher, or −30 ° C. or higher, 30 ° C. or lower, 25 ° C. or lower, 20 ° C. or lower, 15 ° C. or lower, 10 ° C. or lower. It may be 5 ° C. or lower, or 1 ° C. or lower. The reaction time of step (IIIb) may be, for example, 1 hour or more, 3 hours or more, or 6 hours or more, and may be 48 hours or less, 42 hours or less, 36 hours or less, or 30 hours or less.

The reaction of step (III) is preferably carried out in the presence of a solvent. The solvent is not particularly limited as long as the reaction component can be dissolved, but an aprotic solvent is preferable. Examples of the solvent include halogenated hydrocarbons (eg, dichloromethane, dichloroethane), aromatic hydrocarbons substituted with electron-attracting groups (eg, nitrobenzene), and the like. As the solvent, one type can be used alone or two or more types can be mixed and used.

In formula (5), one of R ²¹ and R ²² is a thioxo group and the other is absent, and one of R ²³ and R ²⁴ is a thioxo group and the other is absent. It can be produced by the same method as the compound represented.

In the formula (5), the compounds in which R ^{21 to} R ²⁴ are aromatic ring groups which may have a substituent are, for example, Synthetic Metals 2015, 205, 70-77, Tetrahedron Letters 2015, 56 (10), It can be manufactured by the method described in 1233-1238 and the like.

（式中、Ｚ及びＡｒ_１〜Ａｒ_３は前記と同じである）
で表される化合物は、例えば、式（１２）で表される化合物をアセタール化することにより製造することができる。アセタール化の方法は、Org. Synth. 1973, 5, 303、J. Am. Chem. Soc. 1977, 99, 2818、Tetrahedron 1981, 37, 3899などを参照できる。 In formula (5), a compound in which R ²¹ and R ²² are bonded to each other to form a 1,3-dioxolane ring, and R ²³ and R ²⁴ are bonded to each other to form a 1,3-dioxolane ring, that is, , The following formula (13):

(In the formula, Z and Ar _{1 to} Ar ₃ are the same as above)
The compound represented by (12) can be produced, for example, by acetalizing the compound represented by the formula (12). For the method of acetalization, refer to Org. Synth. 1973, 5, 303, J. Am. Chem. Soc. 1977, 99, 2818, Tetrahedron 1981, 37, 3899 and the like.

In formula (5), the compound in which R ²¹ and R ²² are bonded to each other to form a 1,3-dithiolane ring and R ²³ and R ²⁴ are bonded to each other to form a 1,3-dithiolane ring is a compound. It can be produced by the same method as the compound represented by the formula (13).

In the formula (5), the compound in which R ²¹ and R ²² are bonded to each other to form a fluorene ring and R ²³ and R ²⁴ are bonded to each other to form a fluorene ring is described in, for example, Chinese Patent Application Publication No. It can be manufactured by the method described in 108191865 or the like.

In formula (5), R ²¹ and R ²² combine with each other to form a 9,10-dihydroanthracene ring or anthracene-9 (10H) -on ring, and R ²³ and R ²⁴ combine with each other to form 9,10. The compound forming the −dihydroanthracene ring or the anthracene-9 (10H) -on ring can be produced, for example, by the method described in Chinese Patent Application Publication No. 108383847.

Reaction conditions of the compound represented by the formula (4) and the compound represented by the formula (5) The compound represented by the formula (5) is 0. It is preferably used so as to be 5 mol or more, 0.6 mol or more, 0.7 mol or more, or 0.8 mol or more, and 2.5 mol or less, 2 mol or less, 1.5 mol or less, or 1 It is preferable to use it so that it is 2 mol or less.

In one embodiment, the reaction is preferably carried out in the presence of a solvent. The solvent is not particularly limited as long as the reaction component can be dissolved, and is, for example, ether (eg, diethyl ether, dipropyl ether, dibutyl ether), amine (eg, chain amine such as triethylamine, N-methylpyrrolidone). Cyclic amines such as), amides (eg, dimethylformamide), sulfoxides (eg, dimethylsulfoxide) and the like. As the solvent, one type can be used alone or two or more types can be mixed and used.

In one embodiment, the reaction is preferably carried out in the presence of a base. As the base, for example, n- _{butyllithium, NaH, K 2 CO 3,} Cs 2 CO 3, t- butoxy sodium, t-butoxy potassium, etc. These combinations of two or more thereof. When using n-butyllithium, refer to International Publication No. 2008/1178226, Chemistry of Materials, 2010, 22 (7), 2403-2410, etc. When using NaH, Korean Patent Application Publication No. 2018- You can refer to No. 063708 and so on.

In one embodiment, the reaction can be carried out in the presence of a catalyst. Examples of the catalyst include transition metal catalysts such as copper catalysts and palladium catalysts. When a palladium catalyst is used, International Publication No. 2011/08902, International Publication No. 2015/137472, and the like can be referred to.

The reaction conditions of the compound represented by the formula (4) and the compound represented by the formula (5) are, for example, RSC advances 2015, 5 (77), 63130-63134, Angew. Chem. Int. Ed. 2011, 50. , 6722-6737, J. Phys. Chem. C. 2012, 116 (15), 8699-8706, Inorganica Chimica Acta 357 (2004) 4335-4340, Adv.Mater. 15 (2014) 034202, J.Org.Chem The conditions described in .62 (2) (2003) 452, Chem.Eur.J., 2008,14,2443, J. Am. Chem. Soc. 2006, 128, 8742-8743, etc. can be adopted.

<Fluorescent material>
In one embodiment, the fluorescent material of the present invention preferably contains the compound of the present invention. The fluorescent material can be suitably used, for example, as a light emitting material for an organic light emitting device described later.

<Organic light emitting element>
In one embodiment, the organic light emitting device of the present invention preferably contains the compound of the present invention.

Examples of the organic light emitting element include an organic photoluminescence element (organic PL element) and an organic electroluminescence element (organic EL element). The organic light emitting element is preferably an organic EL element.

The organic EL element preferably has an anode, a cathode, and an organic layer formed between the anode and the cathode.

The organic layer preferably includes at least a light emitting layer, and may be composed of only a light emitting layer, or may include one or more other organic layers in addition to the light emitting layer. Other organic layers include, for example, injection layers (eg, hole injection layer, electron injection layer), blocking layers (eg, electron blocking layer, hole blocking layer, exciton blocking layer), transport layers (eg, positive). Hole transport layer, electron transport layer) and the like. The hole transport layer may be a hole injection transport layer having a hole injection function, and the electron transport layer may be an electron injection transport layer having an electron injection function.

The organic EL element may be a bottom emission type that extracts the light generated in the light emitting layer from the substrate side, or may be a top emission type that extracts the light generated in the light emitting layer from the opposite side of the substrate. In any type, the electrode formed on the substrate side may be an anode or a cathode. The electrode on the side that extracts light is preferably transparent, and the electrode on the opposite side may or may not be transparent.

The organic EL element is preferably supported by a substrate. The substrate is not particularly limited as long as it is conventionally used for organic EL elements, and for example, a substrate made of glass, transparent plastic, quartz, silicon, or the like can be used.

As the anode in the organic EL element, a metal having a large work function (for example, 4 eV or more), an alloy, an electrically conductive compound, and a mixture thereof as an electrode material are preferably used. Specific examples of such electrode materials include metals such as Au and transparent conductive materials such as _{CuI, indium tin oxide (ITO), SnO 2, and ZnO.} Further, a material such as IDIXO (In ₂ O _3- ZnO) capable of producing an amorphous transparent conductive film may be used. The anode may form a thin film by a method such as vapor deposition or sputtering of the electrode material to form a pattern having a desired shape by a photolithography method. May be formed. Alternatively, when a coatable material such as an organic conductive compound is used, a wet film forming method such as a printing method or a coating method can also be used. When extracting light from the anode, it is desirable to increase the transmittance to more than 10%, and the sheet resistance as the anode is preferably several hundred Ω / □ or less. The film thickness of the anode depends on the material, but is usually selected in the range of 10 to 1000 nm, preferably 10 to 200 nm.

As the cathode, a metal having a small work function (for example, 4 eV or less) (electron-injectable metal), an alloy, an electrically conductive compound, or a mixture thereof as an electrode material is preferably used. Specific examples of such electrode materials include sodium, sodium-potassium alloy, magnesium, lithium, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al ₂ O). ₃ ) A mixture, a lithium / aluminum mixture, aluminum and the like are suitable. The cathode can be produced by forming a thin film of an electrode material by a method such as thin film deposition or sputtering. Further, the sheet resistance as a cathode is preferably several hundred Ω / □ or less. The film thickness of the cathode is usually selected in the range of 10 nm to 5 μm, preferably 50 to 200 nm. It is preferable that either the anode or the cathode of the organic EL element is transparent or translucent because the emission brightness is improved. Further, by using the transparent conductive material mentioned in the description of the anode for the cathode, a transparent or translucent cathode can be produced, and an element in which both the anode and the cathode have transparency can be produced.

The light emitting layer is a layer that emits light (eg, fluorescent light emission, delayed fluorescent light emission, or both) after excitons are generated by recombination of holes and electrons injected from each of the anode and cathode. Is preferable. The light emitting layer may be a layer containing a light emitting material alone, but is preferably a layer containing a light emitting material and a host material. As the light emitting material, the compound of the present invention (one type or two or more types) can be used. The host material is not particularly limited, but it is preferable to use an organic compound in which at least one of the excitation singlet energy and the excitation triplet energy has a value higher than that of the compound of the present invention. Further, the host material is preferably an organic compound having a hole transporting ability and an electron transporting ability, preventing a long wavelength of light emission, and having a high glass transition temperature.

Further, when a compound exhibiting TADF property is included in the light emitting layer as a third component (assist dopant compound) in the light emitting layer containing the host material and the light emitting material, it is effective in developing high luminous efficiency (H. Nakanоtani, et al. , Nature Compound, 2014, 5, 4016-4022). By generating 25% singlet excitons and 75% triplet excitons on the assist dopant compound by electric field excitation, the triplet excitons generate singlet excitons with inverse intersystem crossing (RISC). can do. The energy of the singlet excitons is transferred to the light emitting material, and the light emitting material can emit light. Therefore, theoretically 100% of the exciton energy can be used to make the light emitting material emit light, and high luminous efficiency is exhibited.

The content of the compound of the present invention in the light emitting layer is preferably 0.1% by mass or more, more preferably 1% by mass or more, and preferably 50% by mass or less, preferably 20% by mass. It is more preferably 10% by mass or less, and further preferably 10% by mass or less.

The injection layer is preferably a layer provided between the electrode and the organic layer in order to reduce the driving voltage or improve the emission brightness. The injection layer includes a hole injection layer and an electron injection layer. The injection layer may be provided between the anode and the light emitting layer or the hole transport layer, and between the cathode and the light emitting layer or the electron transport layer.

The blocking layer is preferably a layer capable of blocking the diffusion of charges (electrons or holes) and / or excitons existing in the light emitting layer to the outside of the light emitting layer. The electron blocking layer can be arranged between the light emitting layer and the hole transporting layer, and can prevent electrons from passing through the light emitting layer toward the hole transporting layer. Similarly, the hole blocking layer can be placed between the light emitting layer and the electron transporting layer to prevent holes from passing through the light emitting layer towards the electron transporting layer. The electron blocking layer and the hole blocking layer can also function as exciton blocking layers, respectively. The electron blocking layer or exciton blocking layer referred to in the present specification is used in the sense that one layer includes a layer having the functions of an electron blocking layer and an exciton blocking layer.

The hole blocking layer has a function of an electron transporting layer in a broad sense. The hole blocking layer has a role of blocking the holes from reaching the electron transporting layer while transporting electrons, which can improve the recombination probability of electrons and holes in the light emitting layer. As the material of the hole blocking layer, a material of the electron transport layer described later can be used as needed.

The electron blocking layer has a function of transporting holes in a broad sense. The electron blocking layer has a role of blocking electrons from reaching the hole transporting layer while transporting holes, which can improve the probability of recombination of electrons and holes in the light emitting layer. ..

The exciton blocking layer is preferably a layer for blocking excitons generated by recombination of holes and electrons in the light emitting layer from diffusing into the charge transport layer. By inserting the exciton blocking layer, excitons can be efficiently confined in the light emitting layer, and the luminous efficiency of the device can be improved. The exciton blocking layer can be inserted into either the anode side or the cathode side adjacent to the light emitting layer, and both can be inserted at the same time. That is, when the exciton blocking layer is provided on the anode side, the layer can be inserted between the hole transport layer and the light emitting layer adjacent to the light emitting layer, and when inserted on the cathode side, the light emitting layer and the light emitting layer can be inserted. The layer can be inserted adjacent to the light emitting layer between the cathode and the light emitting layer. Further, a hole injection layer, an electron blocking layer and the like can be provided between the anode and the exciton blocking layer adjacent to the anode side of the light emitting layer. An electron injection layer, an electron transport layer, a hole blocking layer, and the like can be provided between the cathode and the exciton blocking layer adjacent to the cathode side of the light emitting layer. When the blocking layer is arranged, it is preferable that at least one of the excited singlet energy and the excited triplet energy of the material used as the blocking layer is higher than the excited singlet energy and the excited triplet energy of the light emitting material.

The hole transport layer is preferably made of a hole transport material having a function of transporting holes, and the hole transport layer may be provided as a single layer or a plurality of layers. As the hole transporting material, a material having either injection or transport of holes or an electron barrier property is preferable, and it may be either an organic substance or an inorganic substance. Examples of the hole transporting material that can be used include triazole derivative, oxadiazole derivative, imidazole derivative, carbazole derivative, indolocarbazole derivative, polyarylalkane derivative, pyrazoline derivative and pyrazolone derivative, phenylenediamine derivative, arylamine derivative, and amino. Examples thereof include substituted chalcone derivatives, oxazole derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilben derivatives, silazane derivatives, aniline-based copolymers, and conductive polymer oligomers, particularly thiophene oligomers. As the hole transport material, it is preferable to use a porphyrin compound, an aromatic tertiary amine compound, and a styrylamine compound, and it is more preferable to use an aromatic tertiary amine compound. Inorganic semiconductors such as molybdenum oxide can also be used as the hole transport material.

The electron transport layer is preferably made of a material having a function of transporting electrons, and the electron transport layer may be provided with a single layer or a plurality of layers. The electron transporting material (which may also serve as a hole blocking material) preferably has a function of transferring electrons injected from the cathode to the light emitting layer. Examples of the electron transporting layer that can be used include nitro-substituted fluorene derivatives, diphenylquinone derivatives, thiopyrandioxide derivatives, carbodiimides, freolenidenemethane derivatives, anthracinodimethane and anthrone derivatives, and oxadiazole derivatives. Further, among the above oxadiazole derivatives, a thiadiazole derivative in which the oxygen atom of the oxadiazole ring is replaced with a sulfur atom, and a quinoxaline derivative having a quinoxaline ring known as an electron attractant can also be used as an electron transport material. .. Further, a polymer material in which these materials are introduced into a polymer chain or these materials are used as a polymer main chain can also be used. Further, an inorganic semiconductor such as zinc oxide can also be used as an electron transport material.

When producing an organic EL device, the compound of the present invention may be used not only for the light emitting layer but also for a layer other than the light emitting layer. At that time, the compound of the present invention used for the light emitting layer and the compound of the present invention used for the layer other than the light emitting layer may be the same or different. For example, the compound of the present invention may be used for the above-mentioned injection layer, blocking layer (eg, hole blocking layer, electron blocking layer, exciton blocking layer), hole transport layer, electron transport layer and the like.

The film forming method for these layers is not particularly limited, and may be formed by either a dry process or a wet process.

Hereinafter, preferable materials that can be used for the organic electroluminescence device will be specifically exemplified. However, the materials that can be used in the present invention are not limitedly interpreted by the following exemplary compounds. Further, even a compound exemplified as a material having a specific function can be diverted as a material having another function. In addition, R, R', and R _{1 to} R ₁₀ in the structural formulas of the following exemplified compounds each independently represent a hydrogen atom or a substituent. X represents a carbon atom or a complex atom forming a ring skeleton, n represents an integer of 3 to 5, Y represents a substituent, and m represents an integer of 0 or more.

Preferred compounds that can also be used as the host material for the light emitting layer are listed. In order to match the HOMO / LUMO level of the luminescent material to be used, the HOMO / LUMO level of the host material can be adjusted by appropriately introducing a substituent into the basic skeleton of the following exemplified compound. For example, by introducing a cyano group or a perfluoroalkyl group into the basic skeleton of the following exemplified compound, a compound having a deepened HOMO / LUMO level can be obtained, which can be used as a host material or a peripheral compound. As the host material, it is also a bipolar character (flow good both holes and electrons) may be a unipolar resistance, but high excited triplet energy level E _T1 than the light emitting material Is preferable. More preferred host material has a bipolar property, those high excited triplet energy level E _T1 than the light emitting material.

Next, examples of preferable compounds that can be used as the hole injection material will be given.

Next, examples of preferable compounds that can be used as an electron injection material will be given.

Next, examples of preferable compounds that can be used as a hole blocking material are given.

Next, examples of preferable compounds that can be used as an electron blocking material are given.

Next, examples of preferable compounds that can be used as a hole transport material will be given.

Next, examples of preferable compounds that can be used as an electron transport material will be given.

Examples of preferable compounds as materials that can be further added are given. For example, it can be added as a stabilizing material.

The organic EL element of the present invention can be applied to any of a single element, an element having a structure arranged in an array, and a structure in which an anode and a cathode are arranged in an XY matrix. The organic light emitting device such as the organic EL device of the present invention can be further applied to various applications. For example, it is possible to manufacture an organic electroluminescence display device using the organic EL element of the present invention. For details, see "Organic EL Display" by Shizushi Tokito, Chihaya Adachi, and Hideyuki Murata (Ohmsha). Can be referred to. In particular, the organic EL device of the present invention can also be applied to organic electroluminescence lighting and backlight, which are in great demand. Further, the organic light emitting device of the present invention can be applied to an organic light emitting diode.

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited thereto.

(Synthesis of Intermediate 1)

4-Fluoroaniline (6.3 g), methyl 2-iodobenzoate (44.6 g), potassium carbonate (23.5 g), copper powder (1.1 g), copper iodide in a 200 mL eggplant flask under a nitrogen atmosphere. (810 mg) was added and dissolved in dinormal butyl ether (75 mL). After stirring at 140 ° C. for 54 hours, the reaction solution was hot filtered. The filtrate was washed with ethyl acetate (50 mL) and the filtrate was concentrated under vacuum. Isopropanol (20 mL) was added to the obtained black oily substance, and the mixture was allowed to stand at 5 ° C. The precipitate was collected by filtration and then subjected to a short column (ethyl acetate) to obtain Intermediate 1 (9.9 g, yield 46%). The ¹ H NMR spectrum of Intermediate 1 is shown in FIG.

(Synthesis of Intermediate 2)

Intermediate 1 (8.9 g) was placed in a 300 mL eggplant flask under a nitrogen atmosphere, and ethanol (90 mL) and a 2.5 M aqueous sodium hydroxide solution (90 mL) were added. The reaction mixture was heated under reflux for 2 hours, allowed to cool, and chloroform (180 mL) and saturated aqueous sodium chloride solution (90 mL) were added to separate the solutions. After washing the aqueous layer with chloroform (15 mL × 2), an aqueous hydrochloric acid solution was added to adjust the pH to 1. The precipitated solid was extracted with chloroform (50 mL) and the organic layer was concentrated under vacuum. The obtained green powder was suspended in isopropanol (30 mL), water (10 mL) was added, and the insoluble material was collected by filtration. By drying the filtrate, Intermediate 2 (7.5 g, yield 91%) was obtained. The ¹ H NMR spectrum of Intermediate 2 is shown in FIG.

(Synthesis of Comparative Example 1)

Intermediate 2 (2.4 g) was placed in a 100 mL eggplant flask under a nitrogen atmosphere, and oxalyl chloride (22 mL) was added. After heating under reflux for 1 hour, the mixture was allowed to cool, and an excess amount of oxalyl chloride was distilled off under vacuum. Methylene chloride (20 mL) was added to the residue, and the mixture was stirred and then the solvent was distilled off again. Methylene chloride (100 mL) was added to the residue to dissolve it, and then the reaction solution was cooled to −30 ° C. Aluminum chloride (9.1 g) was added and the mixture was stirred at room temperature for 28 hours. The reaction solution was poured into a 1 M aqueous sodium hydroxide solution (300 mL) and extracted with methylene chloride (200 mL). The organic layer was washed with 1 M aqueous sodium hydroxide solution (50 mL x 2), dried over sodium sulfate, and concentrated under vacuum. The obtained yellow powder was suspended in acetone (40 mL), and the insoluble material was collected by filtration to obtain Comparative Example 1 (1.66 g, yield 77%). ^{The 1} H NMR spectrum of Comparative Example 1 is shown in FIG.

(Synthesis of Comparative Example 2)

Sodium hydride (60 wt% oil dispersion, 241 mg) was placed in a 300 mL eggplant flask under a nitrogen atmosphere, and the mixture was suspended and washed with hexane. After removing hexane, it was suspended in DMF (200 mL). After stirring under ice-cooling, phenoxazine (1.11 g) was added and the mixture was stirred at room temperature for 1 hour. Comparative Example 1 (2 g) was added, and the mixture was stirred at 130 ° C. for 21 hours. The obtained crude product was subjected to silica gel column chromatography (hexane: ethyl acetate = 4: 1) to obtain Comparative Example 2 (928 mg, 32%). ^{The 1} H NMR spectrum of Comparative Example 2 is shown in FIG.

(Synthesis of Example 1)

In a nitrogen atmosphere, 2,7-bis (trifluoromethyl) carbazole (182 mg), Comparative Example 1 (96 mg), and cesium carbonate (294 mg) were placed in a 100 mL eggplant flask and dissolved in NMP (4 mL). After stirring at 140 ° C. for 7 hours, the mixture was allowed to cool. A saturated aqueous sodium chloride solution (10 mL) was added to the reaction solution, and the precipitate was collected by filtration. Example 1 (233 mg, yield 94%) was obtained by washing the filtrate with water and isopropanol. ^{The 1} H NMR spectrum and the ¹⁹ F NMR spectrum of Example 1 are shown in FIGS. 5 and 6, respectively.

(Synthesis of Example 2)

In a nitrogen atmosphere, 2,7-bis (trifluoromethyl) -3,6-diphenylcarbazole (150 mg), Comparative Example 1 (96 mg), and cesium carbonate (294 mg) were placed in a 100 mL eggplant flask and added to NMP (4 mL). It was dissolved. After stirring at 140 ° C. for 7 hours, the mixture was allowed to cool. A saturated aqueous sodium chloride solution (10 mL) was added to the reaction solution, and the precipitate was collected by filtration. Example 2 (161 mg, yield 71%) was obtained by washing the filtrate with water and isopropanol. ^{The 1} H NMR spectrum and the ¹⁹ F NMR spectrum of Example 2 are shown in FIGS. 7 and 8, respectively.

(Maximum emission wavelength (λmax), full width at half maximum, CIE)
Λmax, half-price width, and CIE of Comparative Examples and Examples ^{show the emission spectrum when a toluene solution of luminescent material (luminescent material concentration: 1 × 10-5} M) is irradiated with excitation light at 340 nm at room temperature. The measurement was performed using Fluoromax 4 manufactured by HORIBA, Ltd., and the measurement was performed as follows based on the emission spectrum.
λmax was measured by the wavelength of the peak top.
The full width at half maximum was measured by the spectral width of half the value of the peak top intensity.
CIE was measured by chromaticity coordinates based on CIE 1931.

(Luminous efficiency (PLQY))
The PLQY of Comparative Examples and Examples is a value when a toluene solution of a light emitting material (light emitting material concentration: 1 × ^10-5 M) is irradiated with excitation light of 340 nm at room temperature, and is a value when an absolute PL quantum yield measuring device (absolute PL quantum yield measuring device). It was measured using Quantaurus-QY C11347-01) manufactured by Hamamatsu Photonics.

(HOMO level)
The HOMO levels of Comparative Examples and Examples were measured using an atmospheric photoelectron spectrometer (AC-3 manufactured by RIKEN Keiki Co., Ltd.). As the measurement sample, a light emitting material vacuum-deposited on an ITO substrate so as to have a film thickness of 50 nm was used. The measurement was carried out with an ultraviolet light intensity of 10 nW and a measurement range of -4.00 eV to -7.00 eV (in increments of 0.05 eV), and the energy threshold value of photoelectron emission during ultraviolet irradiation was set as the HOMO level.

(Luminous efficiency (device))
The luminous efficiency (device) of Comparative Examples and Examples was determined by the luminous efficiency of the organic EL element. The luminous efficiency of the organic EL element was measured by obtaining the maximum value of the external quantum efficiency (EQE) at a ^{brightness of 10 cd / m 2} or more using an external quantum efficiency measuring device (C9920-12) manufactured by Hamamatsu Photonics. The organic EL device was manufactured by a vacuum vapor deposition method as follows. HAT-CN vapor deposition film 60 nm, TrisPCz vapor deposition film 20 nm, mCBP vapor deposition film 5 nm, co-deposited film of light emitting material and mCBP (light emitting material concentration 1 wt%) 30 nm on a patterned ITO substrate at a vacuum degree of 10 ^{-4 Pa order.} , T2T thin-film film 10 nm, BPyTP2 thin-film film 20 nm, Liq thin-film film 2 nm, and aluminum thin-film film 100 nm were laminated in this order and sealed to prepare an organic EL element having ^{a light emitting area of 4 mm 2.} The structures of HAT-CN, TrisPCz, mCBP, T2T, BpyTP2, and Liq are as follows.

The results are shown in Table 1.

（式中、
Ｘは、単結合、−Ｃ(Ｒ^１９)_２−、−Ｏ−、−Ｓ−、又は−Ｎ(Ｒ^２０)−であり、Ｒ^１１〜Ｒ^２０は、それぞれ、水素原子、電子求引性基、又は電子供与性基であり（但し、Ｒ^１１〜Ｒ^２０のうち、少なくとも１個は電子求引性基である）、
波線は、Ａとの結合部位を示す）
で表される基であり、Ａは、下記式（３）：

（式中、
Ａｒ_１〜Ａｒ_３は、それぞれ、置換基を有していてもよい芳香環であり、
Ａｒ_２の置換基及びＡｒ_３の置換基は、互いに結合して置換基を有していてもよい環を形成していてもよく、
Ｒ^２１及びＲ^２２は、それぞれ、水素原子、オキソ基、チオキソ基、又は置換基を有していてもよい芳香環基である（但し、Ｒ^２１及びＲ^２２の一方がオキソ基又はチオキソ基である場合、他方は存在しない）、又はＲ^２１及びＲ^２２は、互いに結合して置換基を有していてもよい環を形成しており、
Ｒ^２３及びＲ^２４は、それぞれ、水素原子、オキソ基、チオキソ基、又は置換基を有していてもよい芳香環基である（但し、Ｒ^２３及びＲ^２４の一方がオキソ基又はチオキソ基である場合、他方は存在しない）、又はＲ^２３及びＲ^２４は、互いに結合して置換基を有していてもよい環を形成しており、
波線は、Ｄとの結合部位を示す）
で表される基である］。
本発明は、この知見に基づいてさらに検討を重ねて完成したものである。 As a result of diligent studies to solve the above problems, the present inventors have been able to increase the luminous efficiency and increase the luminous efficiency by adopting the structure represented by the following formula (1) as the structure of the compound. We found that the half-value width of the emission peak can be narrowed:
DA (1)
[During the ceremony,
D is the following equation (2):

(During the ceremony,
X is a single _{^{bond, -C (R 19) 2 -}} , - O -, - S-, or -N ^{(R 20)} - a ^and, R 11 ^{to R 20} are each a hydrogen atom, an electron withdrawing group, or an electron donating group (provided ^that, among R 11 ^{to R 20,} at least one is an electron-withdrawing group),
The wavy line indicates the binding site with A)
A is a group represented by the following formula (3):

(During the ceremony,
Ar _{1 to} Ar ₃ are aromatic rings that may have a substituent, respectively.
The substituent of Ar _{2 and} the substituent of Ar ₃ may be bonded to each other to form a ring which may have a substituent.
R ²¹ and R ²² are aromatic ring groups which may have a hydrogen atom, an oxo group, a thioxo group, or a substituent, respectively (provided that one of R ²¹ and R ²² is an oxo group or a thioxo group. In some cases, the other does not exist), or R ²¹ and R ²² are attached to each other to form a ring that may have substituents.
R ²³ and R ²⁴ are aromatic ring groups which may have a hydrogen atom, an oxo group, a thioxo group, or a substituent, respectively (provided that one of R ²³ and R ²⁴ is an oxo group or a thioxo group. In some cases, the other does not exist), or R ²³ and R ²⁴ are attached to each other to form a ring that may have substituents.
The wavy line indicates the binding site with D)
It is a group represented by].
The present invention has been further studied and completed based on this finding.

（式中、
Ｘは、単結合、−Ｃ(Ｒ^１９)_２−、−Ｏ−、−Ｓ−、又は−Ｎ(Ｒ^２０)−であり、Ｒ^１１〜Ｒ^２０は、それぞれ、水素原子、電子求引性基、又は電子供与性基であり（但し、Ｒ^１１〜Ｒ^２０のうち、少なくとも１個は電子求引性基である）、
波線は、Ａとの結合部位を示す）
で表される基であり、Ａは、下記式（３）：

（式中、
Ａｒ_１〜Ａｒ_３は、それぞれ、置換基を有していてもよい芳香環であり、
Ａｒ_２の置換基及びＡｒ_３の置換基は、互いに結合して置換基を有していてもよい環を形成していてもよく、
Ｒ^２１及びＲ^２２は、それぞれ、水素原子、オキソ基、チオキソ基、又は置換基を有していてもよい芳香環基である（但し、Ｒ^２１及びＲ^２２の一方がオキソ基又はチオキソ基である場合、他方は存在しない）、又はＲ^２１及びＲ^２２は、互いに結合して置換基を有していてもよい環を形成しており、
Ｒ^２３及びＲ^２４は、それぞれ、水素原子、オキソ基、チオキソ基、又は置換基を有していてもよい芳香環基である（但し、Ｒ^２３及びＲ^２４の一方がオキソ基又はチオキソ基である場合、他方は存在しない）、又はＲ^２３及びＲ^２４は、互いに結合して置換基を有していてもよい環を形成しており、
波線は、Ｄとの結合部位を示す）
で表される基である］。
項２．
式（２）において、Ｘが単結合である、項１に記載の化合物。
項３．
式（２）において、Ｒ^１２及びＲ^１７が電子求引性基である、項１又は２に記載の化合物。
項４．
式（２）において、Ｒ^１２及びＲ^１７が、それぞれ、パーフルオロアルキル基又はシアノ基である、項１又は２に記載の化合物。
項５．
式（２）において、Ｒ^１３及びＲ^１６が電子供与性基である、項１〜４のいずれかに記載の化合物。
項６．
式（２）において、Ｒ^１３及びＲ^１６が、それぞれ、アルキル基、アルコキシ基、トリアルキルシリル基、置換基を有していてもよいシクロアルキル基、又は置換基を有していてもよい芳香環基である、項１〜４のいずれかに記載の化合物。
項７．
式（２）において、Ｒ^１１、Ｒ^１４、Ｒ^１５、及びＲ^１８が水素原子である、項１〜６のいずれかに記載の化合物。
項８．
式（３）において、Ａｒ_１〜Ａｒ_３が、それぞれ、ベンゼン環、ナフタレン環、フルオレン環、アントラセン環、フェナントレン環、フルオランテン環、テトラセン環、テトラフェン環、クリセン環、トリフェニレン環、ピレン環、ピリジン環、キノリン環、イソキノリン環、シノリン環、キノキサリン環、フタラジン環、フェナジン環、フェナントリジン環、フェナントロリン環、又はアセナフト［１，２−ｂ］ピラジン環であり、これらの環は置換基を有していてもよい、項１〜７のいずれかに記載の化合物。
項９．
式（３）において、Ｒ^２１及びＲ^２２の一方がオキソ基であり、他方が存在しない、項１〜８のいずれかに記載の化合物。
項１０．
式（３）において、Ｒ^２３及びＲ^２４の一方がオキソ基であり、他方が存在しない、項１〜９のいずれかに記載の化合物。
項１１．
式（３）において、Ｒ^２１〜Ｒ^２４が、置換基を有していてもよい芳香環基である、項１〜８のいずれかに記載の化合物。
項１２．
式（３）において、Ｒ^２１及びＲ^２２が互いに結合して、１，３−ジオキソラン環、１，３−ジチオラン環、フルオレン環、９，１０−ジヒドロアントラセン環、又はアントラセン−９（１０Ｈ）−オン環を形成している、項１〜８のいずれかに記載の化合物。
項１３．
式（３）において、Ｒ^２３及びＲ^２４が互いに結合して、１，３−ジオキソラン環、１，３−ジチオラン環、フルオレン環、９，１０−ジヒドロアントラセン環、又はアントラセン−９（１０Ｈ）−オン環を形成している、項１〜８及び１２のいずれかに記載の化合物。
項１４．
式（３）が、下記式（３Ａ）：

（式中、
Ｒ^２５及びＲ^２６は、それぞれ、オキソ基、チオキソ基、又は置換基を有していてもよい芳香環基である（但し、Ｒ^２５及びＲ^２６の一方がオキソ基又はチオキソ基である場合、他方は存在しない）、又はＲ^２５及びＲ^２６は、互いに結合して置換基を有していてもよい環を形成しており、
Ａｒ_１〜Ａｒ_３及びＲ^２１〜Ｒ^２４は前記と同じである）。
で表される基である、項１〜１３のいずれかに記載の化合物。
項１５．
式（３Ａ）において、Ｒ^２５及びＲ^２６の一方がオキソ基であり、他方が存在しない、項１４に記載の化合物。
項１６．
式（３Ａ）において、Ｒ^２５及びＲ^２６が互いに結合して、１，３−ジオキソラン環、１，３−ジチオラン環、フルオレン環、９，１０−ジヒドロアントラセン環、又はアントラセン−９（１０Ｈ）−オン環を形成している、項１４に記載の化合物。
項１７．
Ｄが、下記の群：

（式中、Ｍｅはメチル基、ｉ−Ｐｒはイソプロピル基、ｔ−Ｂｕはターシャリーブチル基、Ｐｈはフェニル基、波線はＡとの結合部位を示す）
から選択される基であり、Ａが、下記の群：

（式中、波線はＤとの結合部位を示す）
から選択される基である、項１に記載の化合物。
項１８．
項１〜１７のいずれかに記載の化合物を含む蛍光材料。
項１９．
項１〜１７のいずれかに記載の化合物を含む有機発光素子。
項２０． 有機ＥＬ素子である、項１９に記載の有機発光素子。 The present invention includes the following aspects.
Item 1.
Compound represented by the following formula (1):
DA (1)
[During the ceremony,
D is the following equation (2):

(During the ceremony,
X is a single _{^{bond, -C (R 19) 2 -}} , - O -, - S-, or -N ^{(R 20)} - a ^and, R 11 ^{to R 20} are each a hydrogen atom, an electron withdrawing group, or an electron donating group (provided ^that, among R 11 ^{to R 20,} at least one is an electron-withdrawing group),
The wavy line indicates the binding site with A)
A is a group represented by the following formula (3):

(During the ceremony,
Ar _{1 to} Ar ₃ are aromatic rings that may have a substituent, respectively.
The substituent of Ar _{2 and} the substituent of Ar ₃ may be bonded to each other to form a ring which may have a substituent.
R ²¹ and R ²² are aromatic ring groups which may have a hydrogen atom, an oxo group, a thioxo group, or a substituent, respectively (provided that one of R ²¹ and R ²² is an oxo group or a thioxo group. In some cases, the other does not exist), or R ²¹ and R ²² are attached to each other to form a ring that may have substituents.
R ²³ and R ²⁴ are aromatic ring groups which may have a hydrogen atom, an oxo group, a thioxo group, or a substituent, respectively (provided that one of R ²³ and R ²⁴ is an oxo group or a thioxo group. In some cases, the other does not exist), or R ²³ and R ²⁴ are attached to each other to form a ring that may have substituents.
The wavy line indicates the binding site with D)
It is a group represented by].
Item 2.
Item 2. The compound according to Item 1, wherein X is a single bond in the formula (2).
Item 3.
Item 2. The compound according to Item 1 or 2 ^{, wherein R 12} and R ¹⁷ are electron - attracting groups in the formula (2).
Item 4.
Item 2. The compound according to Item 1 or 2, wherein in the formula (2), R ¹² and R ^{17 are perfluoroalkyl groups or cyano groups, respectively.}
Item 5.
Item 4. The compound according to any one of Items 1 to 4, wherein in the formula (2), R ¹³ and R ^{16 are electron-donating groups.}
Item 6.
In formula (2), R ¹³ and R ¹⁶ have an alkyl group, an alkoxy group, a trialkylsilyl group, a cycloalkyl group which may have a substituent, or an aromatic group which may have a substituent, respectively. Item 4. The compound according to any one of Items 1 to 4, which is a ring group.
Item 7.
Item 6. The compound according to any one of Items 1 to 6, wherein in the formula (2), R ¹¹ , R ¹⁴ , R ¹⁵ and R ^{18 are hydrogen atoms.}
Item 8.
In the formula (3), Ar _{1 to} Ar ₃ are benzene ring, naphthalene ring, fluorene ring, anthracene ring, phenanthrene ring, fluorantene ring, tetracene ring, tetraphen ring, chrysen ring, triphenylene ring, pyrene ring and pyridine, respectively. A ring, a quinoline ring, an isoquinoline ring, a synolin ring, a quinoxaline ring, a phthalazine ring, a phenazine ring, a phenanthrene ring, a phenanthrene ring, or an acenaft [1,2-b] pyrazine ring, and these rings have a substituent. Item 2. The compound according to any one of Items 1 to 7, which may be used.
Item 9.
Item 4. The compound according to any one of Items 1 to 8, wherein in the formula (3), one of R ²¹ and R ^{22 is an oxo group and the other is absent.}
Item 10.
Item 4. The compound according to any one of Items 1 to 9, wherein in the formula (3), one of R ²³ and R ^{24 is an oxo group and the other is absent.}
Item 11.
Item 2. The compound according to any one of Items 1 to 8, wherein in the formula (3), R ^{21 to} R ^{24 are aromatic ring groups which may have a substituent.}
Item 12.
In formula (3), R ²¹ and R ²² are bonded to each other to form a 1,3-dioxolane ring, a 1,3-dithiolane ring, a fluorene ring, a 9,10-dihydroanthracene ring, or anthracene-9 (10H)-. Item 2. The compound according to any one of Items 1 to 8, which forms an on-ring.
Item 13.
In formula (3), R ²³ and R ²⁴ are bonded to each other to form a 1,3-dioxolane ring, a 1,3-dithiolane ring, a fluorene ring, a 9,10-dihydroanthracene ring, or anthracene-9 (10H)-. Item 2. The compound according to any one of Items 1 to 8 and 12, which forms an on-ring.
Item 14.
Equation (3) is the following equation (3A):

(During the ceremony,
R ²⁵ and R ²⁶ are aromatic ring groups which may have an oxo group, a thioxo group, or a substituent, respectively (provided that one of R ²⁵ and R ²⁶ is an oxo group or a thioxo group). The other does not exist), or R ²⁵ and R ²⁶ are attached to each other to form a ring that may have substituents.
Ar _{1 to} Ar ₃ and R ^{21 to} R ²⁴ are the same as described above).
Item 2. The compound according to any one of Items 1 to 13, which is a group represented by.
Item 15.
Item 4. The compound according to Item 14, wherein in formula (3A), one of R ²⁵ and R ²⁶ is an oxo group and the other is absent.
Item 16.
In formula (3A), R ²⁵ and R ²⁶ combine with each other to form a 1,3-dioxolane ring, a 1,3-dithiolane ring, a fluorene ring, a 9,10-dihydroanthracene ring, or anthracene-9 (10H)-. Item 2. The compound according to Item 14, which forms an on-ring.
Item 17.
D is the following group:

(In the formula, Me is a methyl group, i-Pr is an isopropyl group, t-Bu is a tertiary butyl group, Ph is a phenyl group, and a wavy line indicates the binding site with A).
A group selected from the following groups:

(In the formula, the wavy line indicates the binding site with D)
Item 2. The compound according to Item 1, which is a group selected from.
Item 18.
A fluorescent material containing the compound according to any one of Items 1 to 17.
Item 19.
An organic light emitting device containing the compound according to any one of Items 1 to 17.
Item 20. Item 2. The organic light emitting device according to Item 19, which is an organic EL element.

In the present specification, unless otherwise specified, the "electron - attracting group (acceptor group)" means a group other than an electron-donating group, for example, an alkylcarbonyl group (acyl group), an alkylsulfonyl group, and the like. Examples thereof include a perfluoroalkyl group, a cyano group and a nitro group.

（式中、
Ｘは、単結合、−Ｃ(Ｒ^１９)_２−、−Ｏ−、−Ｓ−、又は−Ｎ(Ｒ^２０)−であり、Ｒ^１１〜Ｒ^２０は、それぞれ、水素原子、電子求引性基、又は電子供与性基であり（但し、Ｒ^１１〜Ｒ^２０のうち、少なくとも１個は電子求引性基である）、
波線は、Ａとの結合部位を示す）
で表される基であり、Ａは、下記式（３）：

（式中、
Ａｒ_１〜Ａｒ_３は、それぞれ、置換基を有していてもよい芳香環であり、
Ａｒ_２の置換基及びＡｒ_３の置換基は、互いに結合して置換基を有していてもよい環を形成していてもよく、
Ｒ^２１及びＲ^２２は、それぞれ、水素原子、オキソ基（＝Ｏ）、チオキソ基（＝Ｓ）、又は置換基を有していてもよい芳香環基である（但し、Ｒ^２１及びＲ^２２の一方がオキソ基又はチオキソ基である場合、他方は存在しない）、又はＲ^２１及びＲ^２２は、互いに結合して置換基を有していてもよい環を形成しており、
Ｒ^２３及びＲ^２４は、それぞれ、水素原子、オキソ基、チオキソ基、又は置換基を有していてもよい芳香環基である（但し、Ｒ^２３及びＲ^２４の一方がオキソ基又はチオキソ基である場合、他方は存在しない）、又はＲ^２３及びＲ^２４は、互いに結合して置換基を有していてもよい環を形成しており、
波線は、Ｄとの結合部位を示す）
で表される基である］。 <Compound>
In one embodiment, the compound of the present invention is preferably a compound represented by the following formula (1):
DA (1)
[During the ceremony,
D is the following equation (2):

(During the ceremony,
X is a single _{^{bond, -C (R 19) 2 -}} , - O -, - S-, or -N ^{(R 20)} - a ^and, R 11 ^{to R 20} are each a hydrogen atom, an electron withdrawing group, or an electron donating group (provided ^that, among R 11 ^{to R 20,} at least one is an electron-withdrawing group),
The wavy line indicates the binding site with A)
A is a group represented by the following formula (3):

(During the ceremony,
Ar _{1 to} Ar ₃ are aromatic rings that may have a substituent, respectively.
The substituent of Ar _{2 and} the substituent of Ar ₃ may be bonded to each other to form a ring which may have a substituent.
R ²¹ and R ²² are aromatic ring groups which may have a hydrogen atom, an oxo group (= O), a thioxo group (= S), or a substituent, respectively (provided that R ²¹ and R ²² have an aromatic ring group. If one is an oxo group or a thioxo group, the other does not exist), or R ²¹ and R ²² are bonded to each other to form a ring which may have a substituent.
R ²³ and R ²⁴ are aromatic ring groups which may have a hydrogen atom, an oxo group, a thioxo group, or a substituent, respectively (provided that one of R ²³ and R ²⁴ is an oxo group or a thioxo group. In some cases, the other does not exist), or R ²³ and R ²⁴ are attached to each other to form a ring that may have substituents.
The wavy line indicates the binding site with D)
It is a group represented by].

When R ^{11 to} R ²⁰ are electron - attracting groups, the electron - attracting group is preferably a perfluoroalkyl group or a cyano group, more preferably a perfluoroC _1-4 alkyl group or a cyano group. Yes, more preferably a perfluoroC _1-3 alkyl group or a cyano group, even more preferably a perfluoroC _1-2 alkyl group or a cyano group, and particularly preferably a trifluoromethyl group or a cyano group.

R ¹¹ , R ¹⁴ , R ¹⁵ and R ¹⁸ are preferably hydrogen atoms.
R ¹² , R ¹³ , R ¹⁶ and R ¹⁷ are preferably electron - triggering or electron-donating groups. R ¹² and R ¹⁷ may be an electron donating group, but is preferably an electron withdrawing group. R ¹³ and R ¹⁶ may be electron - withdrawing groups, but are preferably electron-donating groups.

^{R 11, R 14, R 15} , and ^{R 18} are hydrogen ^{atoms, R 12} and ^{R 17} is an electron donating group, and it is also preferable ^{R 13} and ^{R 16} is an electron-attracting group, ^{R 11, R 14, R 15} , and ^{R 18} are hydrogen ^{atoms, R 12} and ^{R 17} each represent an electron attractive group, and more preferably ^{R 13} and ^{R 16} is an electron-donating group.

Claims (20)

Compound represented by the following formula (1):
DA (1)
[During the ceremony,
D is the following equation (2):

(During the ceremony,
X is a single bond, -C (R ¹⁹ ) _2- , -O-, -S-, or -N (R ²⁰ )-.
R ^{11 to} R ²⁰ are hydrogen atoms, electron-withdrawing groups, or electron-donating groups, respectively (provided that ^{at least one of R 11 to} R ²⁰ is an electron-withdrawing group).
The wavy line indicates the binding site with A)
A is a group represented by the following formula (3):

(During the ceremony,
Ar _{1 to} Ar ₃ are aromatic rings that may have a substituent, respectively.
The substituent of Ar _{2 and} the substituent of Ar ₃ may be bonded to each other to form a ring which may have a substituent.
R ²¹ and R ²² are aromatic ring groups which may have a hydrogen atom, an oxo group, a thioxo group, or a substituent, respectively (provided that one of R ²¹ and R ²² is an oxo group or a thioxo group. In some cases, the other does not exist), or R ²¹ and R ²² are attached to each other to form a ring that may have substituents.
R ²³ and R ²⁴ are aromatic ring groups which may have a hydrogen atom, an oxo group, a thioxo group, or a substituent, respectively (provided that one of R ²³ and R ²⁴ is an oxo group or a thioxo group. In some cases, the other does not exist), or R ²³ and R ²⁴ are attached to each other to form a ring that may have substituents.
The wavy line indicates the binding site with D)
It is a group represented by]. The compound according to claim 1, wherein X is a single bond in the formula (2). The compound according to claim 1 or 2 ^{, wherein R 12} and R ¹⁷ are electron-withdrawing groups in the formula (2). The compound according to claim 1 or 2, wherein in the formula (2), R ¹² and R ^{17 are perfluoroalkyl groups or cyano groups, respectively.} The compound according to any one of claims 1 to 4 ^{, wherein R 13} and R ¹⁶ are electron-donating groups in the formula (2). In formula (2), R ¹³ and R ¹⁶ have an alkyl group, an alkoxy group, a trialkylsilyl group, a cycloalkyl group which may have a substituent, or an aromatic group which may have a substituent, respectively. The compound according to any one of claims 1 to 4, which is a ring group. The compound according to any one of claims 1 to 6, wherein in the formula (2), R ¹¹ , R ¹⁴ , R ¹⁵ and R ^{18 are hydrogen atoms.} In the formula (3), Ar _{1 to} Ar ₃ are benzene ring, naphthalene ring, fluorene ring, anthracene ring, phenanthrene ring, fluorantene ring, tetracene ring, tetraphen ring, chrysen ring, triphenylene ring, pyrene ring and pyridine, respectively. A ring, a quinoline ring, an isoquinoline ring, a synolin ring, a quinoxaline ring, a phthalazine ring, a phenazine ring, a phenanthrene ring, a phenanthrene ring, or an acenaft [1,2-b] pyrazine ring, and these rings have a substituent. The compound according to any one of claims 1 to 7, which may be used. The compound according to any one of claims 1 to 8, wherein in the formula (3), one of R ²¹ and R ^{22 is an oxo group and the other does not exist.} The compound according to any one of claims 1 to 9, wherein in the formula (3), one of R ²³ and R ^{24 is an oxo group and the other does not exist.} The compound according to any one of claims 1 to 8, wherein in the formula (3), R ^{21 to} R ^{24 are aromatic ring groups which may have a substituent.} In formula (3), R ²¹ and R ²² are bonded to each other to form a 1,3-dioxolane ring, a 1,3-dithiolane ring, a fluorene ring, a 9,10-dihydroanthracene ring, or anthracene-9 (10H)-. The compound according to any one of claims 1 to 8, which forms an on-ring. In formula (3), R ²³ and R ²⁴ are bonded to each other to form a 1,3-dioxolane ring, a 1,3-dithiolane ring, a fluorene ring, a 9,10-dihydroanthracene ring, or anthracene-9 (10H)-. The compound according to any one of claims 1 to 8 and 12, which forms an on-ring. Equation (3) is the following equation (3A):

(During the ceremony,
R ²⁵ and R ²⁶ are aromatic ring groups which may have an oxo group, a thioxo group, or a substituent, respectively (provided that one of R ²⁵ and R ²⁶ is an oxo group or a thioxo group). The other does not exist), or R ²⁵ and R ²⁶ are attached to each other to form a ring that may have substituents.
Ar _{1 to} Ar ₃ and R ^{21 to} R ²⁴ are the same as described above).
The compound according to any one of claims 1 to 13, which is a group represented by. The compound according to claim 14, wherein in formula (3A), one of R ²⁵ and R ²⁶ is an oxo group and the other is absent. In formula (3A), R ²⁵ and R ²⁶ combine with each other to form a 1,3-dioxolane ring, a 1,3-dithiolane ring, a fluorene ring, a 9,10-dihydroanthracene ring, or anthracene-9 (10H)-. The compound according to claim 14, which forms an on-ring. D is the following group:

(In the formula, Me is a methyl group, i-Pr is an isopropyl group, t-Bu is a tertiary butyl group, Ph is a phenyl group, and a wavy line indicates the binding site with A).
A group selected from the following groups:

(In the formula, the wavy line indicates the binding site with D)
The compound according to claim 1, which is a group selected from. A fluorescent material containing the compound according to any one of claims 1 to 17. An organic light emitting device containing the compound according to any one of claims 1 to 17. The organic light emitting element according to claim 19, which is an organic EL element.

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