JP2014198697A - Nitrogen-containing aromatic heterocyclic derivative, material for organic electroluminescent element and organic electroluminescent element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a nitrogen-containing aromatic heterocyclic derivative capable of achieving an organic EL element exhibiting high luminous efficiency at a low driving voltage.SOLUTION: There is provided a nitrogen-containing aromatic heterocyclic derivative represented by the following formula (1-1) or the like. (In the formula, any one of Cto Cis a nitrogen atom, and any one of Bto Bis a nitrogen atom, provided that Band C, Band C, Band C, and Band Care not simultaneously a nitrogen atom; among Cto Cand Bto B, 1 to 6 atoms which are not nitrogen atoms are carbon atoms bonded to *1; n is 1 to 6; and when n is 2 or more, each group may be same or different.)

Description

  The present invention relates to a nitrogen-containing aromatic heterocyclic derivative, an organic electroluminescent element material (organic EL element material) containing the nitrogen-containing aromatic heterocyclic derivative, and an organic material using the nitrogen-containing aromatic heterocyclic derivative. The present invention relates to an electroluminescence element (organic EL element).

  It has been reported that a compound having a naphthyridine structure has high electron transport performance. For example, Patent Document 1 discloses a compound having the same substituent at the 2-position and 7-position and / or 3-position and 6-position of 1,8-naphthyridine, or a compound containing two or three 1,8-naphthyridine structures. It is described that an organic EL element using the above exhibits high luminance light emission at a low applied voltage and is excellent in durability. In the examples, an organic EL device containing the naphthyridine compound in an electron transport layer or a light emission / electron transport layer is described.

  Patent Document 2 reports that one or two compounds having a 1,8-naphthyridine structure have high electron transport performance, and the exemplary compound has a dibenzofuranyl group having a 1,8-naphthyridine structure. The compound directly connected to is included. The example describes an organic EL device having an electron transport layer containing the naphthyridine compound.

  Patent Document 3 uses a compound having the same substituent at positions 2 and 6 and / or 3 and 7 of 1,5-naphthyridine and a compound having 2 or 3 1,5-naphthyridine structures. It is described that the organic EL element exhibits high luminance light emission at a low applied voltage and is excellent in durability. In the examples, an organic EL device containing the naphthyridine compound in an electron transport layer or a light emission / electron transport layer is described.

JP 2007-001878 A JP 2007-084458 A JP 2008-127446 A

  An organic EL element containing a naphthyridine compound has already been provided, but development of a naphthyridine compound capable of realizing an organic EL element exhibiting higher luminous efficiency at a low driving voltage is desired.

  As a result of intensive studies, the present inventors have found that an organic EL device using a nitrogen-containing aromatic heterocyclic derivative represented by the following formula (1-1), (1-2) or (1-3) has a low driving voltage. However, it has been found that it exhibits high luminous efficiency, and the present invention has been completed.

  Although the preferable aspect of this invention is given to the following, this invention is not limited to the following aspect.

（式中、Ｃ₁〜Ｃ₄のいずれか１つは窒素原子であり、Ｂ₁〜Ｂ₄のいずれか１つは窒素原子である。ただし、Ｂ₁とＣ₁、Ｂ₄とＣ₄、Ｂ₁とＣ₄、及びＢ₄とＣ₁が同時に窒素原子であることはない。Ｃ₁〜Ｃ₄及びＢ₁〜Ｂ₄のうち、窒素原子ではないものの１〜６個は^*１に結合する炭素原子である。
ｎは１〜６である。ｎが２以上のとき、それぞれの基は同一でも異なっていてもよい。
Ｃ₁〜Ｃ₄及びＢ₁〜Ｂ₄のうち、^*１に結合する炭素原子でも窒素原子でもないものは、それぞれ独立に、ＣＲ^Aを表す。Ｒ^Aは、水素原子、置換もしくは無置換の炭素数１〜１５の直鎖状もしくは分岐状のアルキル基、置換もしくは無置換の環形成炭素数３〜１５のシクロアルキル基、置換もしくは無置換のシリル基、置換もしくは無置換の環形成炭素数６〜３０のアリール基、置換もしくは無置換の環形成原子数５〜３０のヘテロアリール基、ハロゲン原子、又はシアノ基を表す。
Ｌは、単結合、置換もしくは無置換の環形成炭素数６〜３０のアリーレン基、又は置換もしくは無置換の環形成原子数５〜３０のヘテロアリーレン基を表わす。
Ａ₁〜Ａ₈は、それぞれ独立に、ＣＲ^Bまたは窒素原子を表し、Ｒ^Bは、水素原子、置換もしくは無置換の炭素数１〜１５の直鎖状もしくは分岐状のアルキル基、置換もしくは無置換の環形成炭素数３〜１５のシクロアルキル基、置換もしくは無置換のシリル基、置換もしくは無置換の環形成炭素数６〜３０のアリール基、置換もしくは無置換の環形成原子数５〜３０のヘテロアリール基、ハロゲン原子、又はシアノ基を表す。隣接する２つのＲ^Bが結合して、環の一部を形成する置換もしくは無置換の飽和もしくは不飽和の２価の基を形成してもよい。）

（式中、Ｃ₁〜Ｃ₄のいずれか１つは窒素原子であり、Ｂ₁〜Ｂ₄のいずれか１つは窒素原子である。ただし、Ｂ₁とＣ₁、Ｂ₄とＣ₄、Ｂ₁とＣ₄、及びＢ₄とＣ₁が同時に窒素原子であることはない。Ｃ₁〜Ｃ₄及びＢ₁〜Ｂ₄のうち、窒素原子ではないものの１〜６個は^*２に結合する炭素原子である。
ｎは前記と同様であり、ｎが２以上のとき、それぞれの基は同一でも異なっていてもよい。
Ｃ₁〜Ｃ₄及びＢ₁〜Ｂ₄のうち、^*２に結合する炭素原子でも窒素原子でもないものは、それぞれ独立に、ＣＲ^Aを表す。Ｒ^Aは前記と同様である。
Ｌは前記と同様である。
Ｒａは、置換もしくは無置換の環形成炭素数６〜３０のアリール基又は置換もしくは無置換の環形成原子数５〜３０のヘテロアリール基を表す。
Ａ₉〜Ａ₁₂のいずれか一つは、^*３に結合する炭素原子を表し、その他のＡ₉〜Ａ₁₂及びＡ₁₃〜Ａ₁₆は、それぞれ独立に、ＣＲ^Bまたは窒素原子を表し、Ｒ^Bは前記と同様である。）

（式中、Ｃ₁〜Ｃ₄のいずれか１つは窒素原子であり、Ｂ₁〜Ｂ₄のいずれか１つは窒素原子である。ただし、Ｂ₁とＣ₁、Ｂ₄とＣ₄、Ｂ₁とＣ₄、及びＢ₄とＣ₁が同時に窒素原子であることはない。Ｃ₁〜Ｃ₄及びＢ₁〜Ｂ₄のうち、窒素原子ではないものの１〜６個は^*４に結合する炭素原子である。
ｎは前記と同様であり、ｎが２以上のとき、それぞれの基は同一でも異なっていてもよい。
Ｃ₁〜Ｃ₄及びＢ₁〜Ｂ₄のうち、^*４に結合する炭素原子でも窒素原子でもないものは、それぞれ独立に、ＣＲ^Aを表す。Ｒ^Aは前記と同様である。
Ｌは前記と同様である。
Ｘは酸素原子、硫黄原子、ＳｉＲｂＲｃを表し、Ｒｂ及びＲｃは、それぞれ独立に、置換もしくは無置換の炭素数１〜１５の直鎖状もしくは分岐状のアルキル基、置換もしくは無置換の環形成炭素数３〜１５のシクロアルキル基、置換もしくは無置換の環形成炭素数６〜３０のアリール基、置換もしくは無置換の環形成原子数５〜３０のヘテロアリール基を表す。
Ａ₁₇〜Ａ₂₀のいずれか一つは、^*５に結合する炭素原子を表し、その他のＡ₁₇〜Ａ₂₀及びＡ₂₁〜Ａ₂₄は、それぞれ独立に、ＣＲ^Bまたは窒素原子を表し、Ｒ^Bは前記と同様である。） (1) A nitrogen-containing aromatic heterocyclic derivative represented by the following formula (1-1), (1-2) or (1-3).

(In the formula, any one of C _{1 to} C ₄ is a nitrogen atom, and any one of B _{1 to} B ₄ is a nitrogen atom, provided that B ₁ and C ₁ , B ₄ and C ₄ , B ₁ and C ₄ , and B ₄ and C ₁ are not nitrogen atoms at the same time ₁ to _{6 of} C _{1 to} C ₄ and B _{1 to} B ₄ that are not nitrogen atoms are bonded to ^* 1 Carbon atom.
n is 1-6. When n is 2 or more, each group may be the same or different.
Of C _{1 to} C ₄ and B _{1 to} B ₄ , those that are neither a carbon atom nor a nitrogen atom bonded to ^* 1 independently represent CR ^A. R ^A is a hydrogen atom, a substituted or unsubstituted linear or branched alkyl group having 1 to 15 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 15 ring carbon atoms, a substituted or unsubstituted group. It represents a silyl group, a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms, a substituted or unsubstituted heteroaryl group having 5 to 30 ring atoms, a halogen atom, or a cyano group.
L represents a single bond, a substituted or unsubstituted arylene group having 6 to 30 ring carbon atoms, or a substituted or unsubstituted heteroarylene group having 5 to 30 ring atoms.
A _{1 to} A ₈ each independently represent CR ^B or a nitrogen atom, and R ^B represents a hydrogen atom, a substituted or unsubstituted C 1-15 linear or branched alkyl group, substituted or unsubstituted. Substituted cycloalkyl group having 3 to 15 carbon atoms, substituted or unsubstituted silyl group, substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms, substituted or unsubstituted ring atoms having 5 to 30 ring atoms Represents a heteroaryl group, a halogen atom, or a cyano group. Two adjacent ^RBs may combine to form a substituted or unsubstituted saturated or unsaturated divalent group that forms part of the ring. )

(In the formula, any one of C _{1 to} C ₄ is a nitrogen atom, and any one of B _{1 to} B ₄ is a nitrogen atom, provided that B ₁ and C ₁ , B ₄ and C ₄ , B ₁ and C ₄ , and B ₄ and C ₁ are not nitrogen atoms at the same time, ₁ to _{6 of} C _{1 to} C ₄ and B _{1 to} B ₄ that are not nitrogen atoms are bonded to ^* 2. Carbon atom.
n is the same as described above, and when n is 2 or more, each group may be the same or different.
Among C _{1 to} C ₄ and B _{1 to} B ₄ , those that are neither a carbon atom nor a nitrogen atom bonded to ^* 2 independently represent CR ^A. R ^A is the same as described above.
L is the same as described above.
Ra represents a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms or a substituted or unsubstituted heteroaryl group having 5 to 30 ring atoms.
One of A ₉ to A ₁₂ represents a carbon atom bonded to ^* 3, other A ₉ to A ₁₂ and A ₁₃ to A ₁₆ each independently represent a CR ^B or a nitrogen atom, R ^B is the same as described above. )

(In the formula, any one of C _{1 to} C ₄ is a nitrogen atom, and any one of B _{1 to} B ₄ is a nitrogen atom, provided that B ₁ and C ₁ , B ₄ and C ₄ , B ₁ and C ₄ , and B ₄ and C ₁ are not nitrogen atoms at the same time ₁ to _{6 of} C _{1 to} C ₄ and B _{1 to} B ₄ that are not nitrogen atoms are bonded to ^* 4 Carbon atom.
n is the same as described above, and when n is 2 or more, each group may be the same or different.
Of C _{1 to} C ₄ and B _{1 to} B ₄ , those that are neither a carbon atom nor a nitrogen atom bonded to ^* 4 independently represent CR ^A. R ^A is the same as described above.
L is the same as described above.
X represents an oxygen atom, a sulfur atom, or SiRbRc, and Rb and Rc are each independently a substituted or unsubstituted linear or branched alkyl group having 1 to 15 carbon atoms, a substituted or unsubstituted ring-forming carbon. A cycloalkyl group having 3 to 15 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms, and a substituted or unsubstituted heteroaryl group having 5 to 30 ring atoms.
One of A ₁₇ to A ₂₀ represents a carbon atom bonded to ^* 5, other A ₁₇ to A ₂₀ and A ₂₁ to A ₂₄ each independently represent a CR ^B or a nitrogen atom, R ^B is the same as described above. )

（式（１−１ａ）、（１−１ｂ）、（１−１ｃ）、及び（１−１ｄ）において、Ｌ、ｎ及びＡ₁〜Ａ₈は、式（１−１）において定義したとおりである。
式（１−１ａ）のＲ₂〜Ｒ₆及びＲ₈の１〜６個は^*１に結合する単結合である。
式（１−１ｂ）のＲ₂〜Ｒ₅、Ｒ₇及びＲ₈の１〜６個は^*１に結合する単結合である。
式（１−１ｃ）のＲ₁、Ｒ₃〜Ｒ₆及びＲ₈の１〜６個は^*１に結合する単結合である。
式（１−１ｄ）のＲ₁、Ｒ₃〜Ｒ₅、Ｒ₇及びＲ₈の１〜６個は^*１に結合する単結合である。
式（１−１ａ）、（１−１ｂ）、（１−１ｃ）、及び（１−１ｄ）において、Ｒ₁〜Ｒ₈のうち、^*１に結合する単結合ではないものは、それぞれ独立に、水素原子、置換もしくは無置換の炭素数１〜１５の直鎖状もしくは分岐状のアルキル基、置換もしくは無置換の環形成炭素数３〜１５のシクロアルキル基、置換もしくは無置換のシリル基、置換もしくは無置換の環形成炭素数６〜３０のアリール基、置換もしくは無置換の環形成原子数５〜３０のヘテロアリール基、ハロゲン原子、又はシアノ基を表す。） (2) The nitrogen-containing composition according to (1), wherein the formula (1-1) is represented by the following formula (1-1a), (1-1b), (1-1c), or (1-1d) Aromatic heterocyclic derivatives

(In the formulas (1-1a), (1-1b), (1-1c), and (1-1d), L, n, and A _{1 to} A ₈ are as defined in the formula (1-1). is there.
1 to ₆ of R _{2 to} R ₆ and R _{8 in} the formula (1-1a) are single bonds bonded to ^* 1.
1-6 of R < ₂ ^> -R < ₅ ^> , R < ₇ ^> and R < ₈ ^{> of} Formula (1-1b) are single bonds couple | bonded with ^* 1.
1-6 of R < ₁ >, R < ₃ > -R < ₆ > and R < ₈ > of Formula (1-1c) are single bonds couple | bonded with ^* 1.
1-6 _{R 1, R 3 ~R 5,} R 7 and R ₈ of formula (1-1d) is a single bond to bond to ^* 1.
In formulas (1-1a), (1-1b), (1-1c), and (1-1d), among R _{1 to} R ₈ , those that are not a single bond bonded to ^* 1 are independently A hydrogen atom, a substituted or unsubstituted linear or branched alkyl group having 1 to 15 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 15 ring carbon atoms, a substituted or unsubstituted silyl group, A substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms, a substituted or unsubstituted heteroaryl group having 5 to 30 ring atoms, a halogen atom, or a cyano group. )

（式（１−２ａ）、（１−２ｂ）、（１−２ｃ）、及び（１−２ｄ）において、Ｌ、ｎ、Ｒａ及びＡ₉〜Ａ₁₆は、式（１−２）において定義したとおりである。
式（１−２ａ）のＲ₂〜Ｒ₆及びＲ₈の１〜６個は^*２に結合する単結合である。
式（１−２ｂ）のＲ₂〜Ｒ₅、Ｒ₇及びＲ₈の１〜６個は^*２に結合する単結合である。
式（１−２ｃ）のＲ₁、Ｒ₃〜Ｒ₆及びＲ₈の１〜６個は^*２に結合する単結合である。
式（１−２ｄ）のＲ₁、Ｒ₃〜Ｒ₅、Ｒ₇及びＲ₈の１〜６個は^*２に結合する単結合である。
式（１−２ａ）、（１−２ｂ）、（１−２ｃ）、及び（１−２ｄ）において、Ｒ₁〜Ｒ₈のうち、^*２に結合する単結合ではないものは、それぞれ独立に、水素原子、置換もしくは無置換の炭素数１〜１５の直鎖状もしくは分岐状のアルキル基、置換もしくは無置換の環形成炭素数３〜１５のシクロアルキル基、置換もしくは無置換のシリル基、置換もしくは無置換の環形成炭素数６〜３０のアリール基、置換もしくは無置換の環形成原子数５〜３０のヘテロアリール基、ハロゲン原子、又はシアノ基を表す。） (3) The nitrogen-containing composition according to (1), wherein the formula (1-2) is represented by the following formula (1-2a), (1-2b), (1-2c), or (1-2d) Aromatic heterocyclic derivatives

(In the formulas (1-2a), (1-2b), (1-2c), and (1-2d), L, n, Ra, and A _{9 to} A ₁₆ are defined in the formula (1-2). It is as follows.
1-6 of R < ₂ > -R < ₆ > and R < ₈ > of Formula (1-2a) are single bonds couple | bonded with ^* 2.
1-6 of R < ₂ > -R < ₅ >, R < ₇ > and R < ₈ > of Formula (1-2b) are single bonds couple | bonded with ^* 2.
1-6 of R < ₁ >, R < ₃ > -R < ₆ > and R < ₈ > of Formula (1-2c) are single bonds couple | bonded with ^* 2.
₁ to 6 of R ₁ , R _{3 to} R ₅ , R ₇ and R _{8 in} the formula (1-2d) are single bonds bonded to ^* 2.
In the formulas (1-2a), (1-2b), (1-2c), and (1-2d), among R _{1 to} R ₈ , those that are not a single bond bonded to ^* 2 are each independently A hydrogen atom, a substituted or unsubstituted linear or branched alkyl group having 1 to 15 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 15 ring carbon atoms, a substituted or unsubstituted silyl group, A substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms, a substituted or unsubstituted heteroaryl group having 5 to 30 ring atoms, a halogen atom, or a cyano group. )

（式（１−３ａ）、（１−３ｂ）、（１−３ｃ）、及び（１−３ｄ）において、Ｌ、ｎ、Ｘ及びＡ₁₇〜Ａ₂₄は、式（１−３）において定義したとおりである。
式（１−３ａ）のＲ₂〜Ｒ₆及びＲ₈の１〜６個は^*４に結合する単結合である。
式（１−３ｂ）のＲ₂〜Ｒ₅、Ｒ₇及びＲ₈の１〜６個は^*４に結合する単結合である。
式（１−３ｃ）のＲ₁、Ｒ₃〜Ｒ₆及びＲ₈の１〜６個は^*４に結合する単結合である。
式（１−３ｄ）のＲ₁、Ｒ₃〜Ｒ₅、Ｒ₇及びＲ₈の１〜６個は^*４に結合する単結合である。
式（１−３ａ）、（１−３ｂ）、（１−３ｃ）、及び（１−３ｄ）において、Ｒ₁〜Ｒ₈のうち、^*４に結合する単結合ではないものは、それぞれ独立に、水素原子、置換もしくは無置換の炭素数１〜１５の直鎖状もしくは分岐状のアルキル基、置換もしくは無置換の環形成炭素数３〜１５のシクロアルキル基、置換もしくは無置換のシリル基、置換もしくは無置換の環形成炭素数６〜３０のアリール基、置換もしくは無置換の環形成原子数５〜３０のヘテロアリール基、ハロゲン原子、又はシアノ基を表す。） (4) The nitrogen-containing composition according to (1), wherein the formula (1-3) is represented by the following formula (1-3a), (1-3b), (1-3c), or (1-3d) Aromatic heterocyclic derivatives.

(In the formulas (1-3a), (1-3b), (1-3c), and (1-3d), L, n, X, and A _{17 to} A ₂₄ are defined in the formula (1-3). It is as follows.
1 to ₆ of R _{2 to} R ₆ and R _{8 in} the formula (1-3a) are single bonds bonded to ^* 4.
1 to 6 of R _{2 to} R ₅ , R ₇ and R _{8 in} the formula (1-3b) are a single bond bonded to ^* 4.
1-6 R _1, R ₃ ~R ₆ and R ₈ of formula (1-3c) is a single bond to bond to ^* 4.
1-6 _{R 1, R 3 ~R 5,} R 7 and R ₈ of formula (1-3d) is a single bond to bond to ^* 4.
In formulas (1-3a), (1-3b), (1-3c), and (1-3d), among R _{1 to} R ₈ , those that are not a single bond bonded to ^* 4 are independently selected. A hydrogen atom, a substituted or unsubstituted linear or branched alkyl group having 1 to 15 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 15 ring carbon atoms, a substituted or unsubstituted silyl group, A substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms, a substituted or unsubstituted heteroaryl group having 5 to 30 ring atoms, a halogen atom, or a cyano group. )

（式中、Ｂ₁〜Ｂ₄、Ｃ₁〜Ｃ₄、ｎ及びＬは、式（１−１）で定義したとおりである。
Ｒ₅₇〜Ｒ₆₄は、それぞれ独立に、水素原子、置換もしくは無置換の炭素数１〜１５の直鎖状もしくは分岐状のアルキル基、置換もしくは無置換の環形成炭素数３〜１５のシクロアルキル基、置換もしくは無置換のシリル基、置換もしくは無置換の環形成炭素数６〜３０のアリール基、置換もしくは無置換の環形成原子数５〜３０のヘテロアリール基、ハロゲン原子、又はシアノ基を表す。
Ｒ₅₇〜Ｒ₆₄の隣接する２つの基が結合して、環の一部を形成する置換もしくは無置換の飽和もしくは不飽和の２価の基を形成してもよい。） (5) The nitrogen-containing aromatic heterocyclic derivative according to (1), wherein the formula (1-1) is represented by the following formula (1-1e).

(In the formula, B _{1 to} B ₄ , C _{1 to} C ₄ , n and L are as defined in Formula (1-1).
R _{57 to} R ₆₄ each independently represent a hydrogen atom, a substituted or unsubstituted linear or branched alkyl group having 1 to 15 carbon atoms, or a substituted or unsubstituted cycloalkyl having 3 to 15 ring carbon atoms. A substituted or unsubstituted silyl group, a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms, a substituted or unsubstituted heteroaryl group having 5 to 30 ring atoms, a halogen atom, or a cyano group. Represent.
Two adjacent groups of R _{57 to} R ₆₄ may combine to form a substituted or unsubstituted saturated or unsaturated divalent group forming a part of the ring. )

（式中、Ｂ₁〜Ｂ₄、Ｃ₁〜Ｃ₄、Ｒａ、ｎ及びＬは、式（１−２）で定義したとおりである。
Ｒ₅₇〜Ｒ₆₀のいずれか一つは^*３に結合する単結合である。その他のＲ₅₇〜Ｒ₆₀及びＲ₆₁〜Ｒ₆₄は、それぞれ独立に、水素原子、置換もしくは無置換の炭素数１〜１５の直鎖状もしくは分岐状のアルキル基、置換もしくは無置換の環形成炭素数３〜１５のシクロアルキル基、置換もしくは無置換のシリル基、置換もしくは無置換の環形成炭素数６〜３０のアリール基、置換もしくは無置換の環形成原子数５〜３０のヘテロアリール基、ハロゲン原子、又はシアノ基を表す。
その他のＲ₅₇〜Ｒ₆₀及びＲ₆₁〜Ｒ₆₄の隣接する２つの基が結合して、環の一部を形成する置換もしくは無置換の飽和もしくは不飽和の２価の基を形成してもよい。） (6) The nitrogen-containing aromatic heterocyclic derivative according to (1), wherein the formula (1-2) is represented by the following formula (1-2e).

(In the formula, B _{1 to} B ₄ , C _{1 to} C ₄ , Ra, n, and L are as defined in Formula (1-2).
Any one of R _{57 to} R ₆₀ is a single bond bonded to ^* 3. The other R _{57 to} R ₆₀ and R _{61 to} R ₆₄ are each independently a hydrogen atom, a substituted or unsubstituted C 1-15 linear or branched alkyl group, a substituted or unsubstituted ring formation. A cycloalkyl group having 3 to 15 carbon atoms, a substituted or unsubstituted silyl group, a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms, and a substituted or unsubstituted heteroaryl group having 5 to 30 ring atoms. Represents a halogen atom or a cyano group.
The other two adjacent groups of R _{57 to} R ₆₀ and R _{61 to} R ₆₄ may combine to form a substituted or unsubstituted saturated or unsaturated divalent group that forms part of the ring. Good. )

（式中、Ｂ₁〜Ｂ₄、Ｃ₁〜Ｃ₄、Ｘ、ｎ及びＬは、式（１−３）で定義したとおりである。
Ｒ₅₇〜Ｒ₆₀のいずれか一つは^*５に結合する単結合である。その他のＲ₅₇〜Ｒ₆₀及びＲ₆₁〜Ｒ₆₄は、それぞれ独立に、水素原子、置換もしくは無置換の炭素数１〜１５の直鎖状もしくは分岐状のアルキル基、置換もしくは無置換の環形成炭素数３〜１５のシクロアルキル基、置換もしくは無置換のシリル基、置換もしくは無置換の環形成炭素数６〜３０のアリール基、置換もしくは無置換の環形成原子数５〜３０のヘテロアリール基、ハロゲン原子、又はシアノ基を表す。
その他のＲ₅₇〜Ｒ₆₀及びＲ₆₁〜Ｒ₆₄の隣接する２つの基が結合して、環の一部を形成する置換もしくは無置換の飽和もしくは不飽和の２価の基を形成してもよい。） (7) The nitrogen-containing aromatic heterocyclic derivative according to (1), wherein the formula (1-3) is represented by the following formula (1-3e).

(In the formula, B _{1 to} B ₄ , C _{1 to} C ₄ , X, n and L are as defined in Formula (1-3).
Any one of R _{57 to} R ₆₀ is a single bond bonded to ^* 5. The other R _{57 to} R ₆₀ and R _{61 to} R ₆₄ are each independently a hydrogen atom, a substituted or unsubstituted C 1-15 linear or branched alkyl group, a substituted or unsubstituted ring formation. A cycloalkyl group having 3 to 15 carbon atoms, a substituted or unsubstituted silyl group, a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms, and a substituted or unsubstituted heteroaryl group having 5 to 30 ring atoms. Represents a halogen atom or a cyano group.
The other two adjacent groups of R _{57 to} R ₆₀ and R _{61 to} R ₆₄ may combine to form a substituted or unsubstituted saturated or unsaturated divalent group that forms part of the ring. Good. )

（式中、Ｂ₁〜Ｂ₄、Ｃ₁〜Ｃ₄、ｎ及びＬは式（１−１）で定義したとおりである。
Ｒ₆₁〜Ｒ₆₄のいずれか一つは^*６に結合する単結合である。その他のＲ₆₁〜Ｒ₆₄及びＲ₅₇〜Ｒ₆₀は、それぞれ独立に、水素原子、置換もしくは無置換の炭素数１〜１５の直鎖状もしくは分岐状のアルキル基、置換もしくは無置換の環形成炭素数３〜１５のシクロアルキル基、置換もしくは無置換のシリル基、置換もしくは無置換の環形成炭素数６〜３０のアリール基、置換もしくは無置換の環形成原子数５〜３０のヘテロアリール基、ハロゲン原子、又はシアノ基を表す。
その他のＲ₆₁〜Ｒ₆₄及びＲ₅₇〜Ｒ₆₀の隣接する２つの基が結合して、環の一部を形成する置換もしくは無置換の飽和もしくは不飽和の２価の基を形成してもよい。
Ｒ₆₅〜Ｒ₆₈のいずれか一つは^*７に結合する単結合である。その他のＲ₆₅〜Ｒ₆₈及びＲ₆₉〜Ｒ₇₂は、それぞれ独立に、水素原子、置換もしくは無置換の炭素数１〜１５の直鎖状もしくは分岐状のアルキル基、置換もしくは無置換の環形成炭素数３〜１５のシクロアルキル基、置換もしくは無置換のシリル基、置換もしくは無置換の環形成炭素数６〜３０のアリール基、置換もしくは無置換の環形成原子数５〜３０のヘテロアリール基、ハロゲン原子、又はシアノ基を表す。
その他のＲ₆₅〜Ｒ₆₈及びＲ₆₉〜Ｒ₇₂の隣接する２つの基が結合して、環の一部を形成する置換もしくは無置換の飽和もしくは不飽和の２価の基を形成してもよい。
Ｒｆは、置換もしくは無置換の環形成炭素数６〜３０のアリール基又は置換もしくは無置換の環形成原子数５〜３０のヘテロアリール基を表す。） (8) The nitrogen-containing aromatic heterocyclic derivative according to (1) or (5), wherein the formula (1-1) or (1-1e) is represented by the following formula (1-1f).

(In the formula, B _{1 to} B ₄ , C _{1 to} C ₄ , n and L are as defined in Formula (1-1).
Any one of R _{61 to} R ₆₄ is a single bond bonded to ^* 6. The other R _{61 to} R ₆₄ and R _{57 to} R ₆₀ are each independently a hydrogen atom, a substituted or unsubstituted C 1-15 linear or branched alkyl group, a substituted or unsubstituted ring formation. A cycloalkyl group having 3 to 15 carbon atoms, a substituted or unsubstituted silyl group, a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms, and a substituted or unsubstituted heteroaryl group having 5 to 30 ring atoms. Represents a halogen atom or a cyano group.
The other two adjacent groups of R _{61 to} R ₆₄ and R _{57 to} R ₆₀ may combine to form a substituted or unsubstituted saturated or unsaturated divalent group that forms part of the ring. Good.
Any one of R _{65 to} R ₆₈ is a single bond bonded to ^* 7. The other R _{65 to} R ₆₈ and R _{69 to} R ₇₂ are each independently a hydrogen atom, a substituted or unsubstituted C 1-15 linear or branched alkyl group, a substituted or unsubstituted ring formation. A cycloalkyl group having 3 to 15 carbon atoms, a substituted or unsubstituted silyl group, a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms, and a substituted or unsubstituted heteroaryl group having 5 to 30 ring atoms. Represents a halogen atom or a cyano group.
The other two adjacent groups of R _{65 to} R ₆₈ and R _{69 to} R ₇₂ may combine to form a substituted or unsubstituted saturated or unsaturated divalent group that forms part of the ring. Good.
Rf represents a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms or a substituted or unsubstituted heteroaryl group having 5 to 30 ring atoms. )

（式中、Ｂ₁〜Ｂ₄、Ｃ₁〜Ｃ₄、Ｒａ、ｎ及びＬは式（１−２）で定義したとおりである。
Ｒ₅₇〜Ｒ₆₀のいずれか一つは^*３に結合する単結合である。Ｒ₆₁〜Ｒ₆₄のいずれか一つは^*６に結合する単結合である。その他のＲ₅₇〜Ｒ₆₀及びその他のＲ₆₁〜Ｒ₆₄は、それぞれ独立に、水素原子、置換もしくは無置換の炭素数１〜１５の直鎖状もしくは分岐状のアルキル基、置換もしくは無置換の環形成炭素数３〜１５のシクロアルキル基、置換もしくは無置換のシリル基、置換もしくは無置換の環形成炭素数６〜３０のアリール基、置換もしくは無置換の環形成原子数５〜３０のヘテロアリール基、ハロゲン原子、又はシアノ基を表す。
その他のＲ₅₇〜Ｒ₆₀及びその他のＲ₆₁〜Ｒ₆₄の隣接する２つの基が結合して、環の一部を形成する置換もしくは無置換の飽和もしくは不飽和の２価の基を形成してもよい。
Ｒ₆₅〜Ｒ₆₈のいずれか一つは^*７に結合する単結合である。その他のＲ₆₅〜Ｒ₆₈及びＲ₆₉〜Ｒ₇₂は、それぞれ独立に、水素原子、置換もしくは無置換の炭素数１〜１５の直鎖状もしくは分岐状のアルキル基、置換もしくは無置換の環形成炭素数３〜１５のシクロアルキル基、置換もしくは無置換のシリル基、置換もしくは無置換の環形成炭素数６〜３０のアリール基、置換もしくは無置換の環形成原子数５〜３０のヘテロアリール基、ハロゲン原子、又はシアノ基を表す。
その他のＲ₆₅〜Ｒ₆₈及びＲ₆₉〜Ｒ₇₂の隣接する２つの基が結合して、環の一部を形成する置換もしくは無置換の飽和もしくは不飽和の２価の基を形成してもよい。
Ｒｆは、置換もしくは無置換の環形成炭素数６〜３０のアリール基又は置換もしくは無置換の環形成原子数５〜３０のヘテロアリール基を表す。） (9) The nitrogen-containing aromatic heterocyclic derivative according to (1) or (6), wherein the formula (1-2) or (1-2e) is represented by the following formula (1-2f).

(In the formula, B _{1 to} B ₄ , C _{1 to} C ₄ , Ra, n and L are as defined in Formula (1-2).
Any one of R _{57 to} R ₆₀ is a single bond bonded to ^* 3. Any one of R _{61 to} R ₆₄ is a single bond bonded to ^* 6. Other R _{57 to} R ₆₀ and other R _{61 to} R ₆₄ are each independently a hydrogen atom, a substituted or unsubstituted linear or branched alkyl group having 1 to 15 carbon atoms, a substituted or unsubstituted group. A cycloalkyl group having 3 to 15 ring carbon atoms, a substituted or unsubstituted silyl group, a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms, a substituted or unsubstituted hetero ring having 5 to 30 ring atoms An aryl group, a halogen atom, or a cyano group is represented.
The other two adjacent groups of R _{57 to} R ₆₀ and the other R _{61 to} R ₆₄ are combined to form a substituted or unsubstituted saturated or unsaturated divalent group that forms part of the ring. May be.
Any one of R _{65 to} R ₆₈ is a single bond bonded to ^* 7. The other R _{65 to} R ₆₈ and R _{69 to} R ₇₂ are each independently a hydrogen atom, a substituted or unsubstituted C 1-15 linear or branched alkyl group, a substituted or unsubstituted ring formation. A cycloalkyl group having 3 to 15 carbon atoms, a substituted or unsubstituted silyl group, a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms, and a substituted or unsubstituted heteroaryl group having 5 to 30 ring atoms. Represents a halogen atom or a cyano group.
The other two adjacent groups of R _{65 to} R ₆₈ and R _{69 to} R ₇₂ may combine to form a substituted or unsubstituted saturated or unsaturated divalent group that forms part of the ring. Good.
Rf represents a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms or a substituted or unsubstituted heteroaryl group having 5 to 30 ring atoms. )

（式中、Ｂ₁〜Ｂ₄、Ｃ₁〜Ｃ₄、Ｘ、ｎ及びＬは式（１−３）で定義したとおりである。
Ｒ₅₇〜Ｒ₆₀のいずれか一つは^*５に結合する単結合である。Ｒ₆₁〜Ｒ₆₄のいずれか一つは^*６に結合する単結合である。その他のＲ₅₇〜Ｒ₆₀及びその他のＲ₆₁〜Ｒ₆₄は、それぞれ独立に、水素原子、置換もしくは無置換の炭素数１〜１５の直鎖状もしくは分岐状のアルキル基、置換もしくは無置換の環形成炭素数３〜１５のシクロアルキル基、置換もしくは無置換のシリル基、置換もしくは無置換の環形成炭素数６〜３０のアリール基、置換もしくは無置換の環形成原子数５〜３０のヘテロアリール基、ハロゲン原子、又はシアノ基を表す。
その他のＲ₅₇〜Ｒ₆₀及びその他のＲ₆₁〜Ｒ₆₄の隣接する２つの基が結合して、環の一部を形成する置換もしくは無置換の飽和もしくは不飽和の２価の基を形成してもよい。
Ｒ₆₅〜Ｒ₆₈のいずれか一つは^*７に結合する単結合である。その他のＲ₆₅〜Ｒ₆₈及びＲ₆₉〜Ｒ₇₂は、それぞれ独立に、水素原子、置換もしくは無置換の炭素数１〜１５の直鎖状もしくは分岐状のアルキル基、置換もしくは無置換の環形成炭素数３〜１５のシクロアルキル基、置換もしくは無置換のシリル基、置換もしくは無置換の環形成炭素数６〜３０のアリール基、置換もしくは無置換の環形成原子数５〜３０のヘテロアリール基、ハロゲン原子、又はシアノ基を表す。
その他のＲ₆₅〜Ｒ₆₈及びＲ₆₉〜Ｒ₇₂の隣接する２つの基が結合して、環の一部を形成する置換もしくは無置換の飽和もしくは不飽和の２価の基を形成してもよい。
Ｒｆは、置換もしくは無置換の環形成炭素数６〜３０のアリール基又は置換もしくは無置換の環形成原子数５〜３０のヘテロアリール基を表す。） (10) The nitrogen-containing aromatic heterocyclic derivative according to (1) or (7), wherein the formula (1-3) or (1-3e) is represented by the following formula (1-3f).

(In the formula, B _{1 to} B ₄ , C _{1 to} C ₄ , X, n, and L are as defined in Formula (1-3).
Any one of R _{57 to} R ₆₀ is a single bond bonded to ^* 5. Any one of R _{61 to} R ₆₄ is a single bond bonded to ^* 6. Other R _{57 to} R ₆₀ and other R _{61 to} R ₆₄ are each independently a hydrogen atom, a substituted or unsubstituted linear or branched alkyl group having 1 to 15 carbon atoms, a substituted or unsubstituted group. A cycloalkyl group having 3 to 15 ring carbon atoms, a substituted or unsubstituted silyl group, a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms, a substituted or unsubstituted hetero ring having 5 to 30 ring atoms An aryl group, a halogen atom, or a cyano group is represented.
The other two adjacent groups of R _{57 to} R ₆₀ and the other R _{61 to} R ₆₄ are combined to form a substituted or unsubstituted saturated or unsaturated divalent group that forms part of the ring. May be.
Any one of R _{65 to} R ₆₈ is a single bond bonded to ^* 7. The other R _{65 to} R ₆₈ and R _{69 to} R ₇₂ are each independently a hydrogen atom, a substituted or unsubstituted C 1-15 linear or branched alkyl group, a substituted or unsubstituted ring formation. A cycloalkyl group having 3 to 15 carbon atoms, a substituted or unsubstituted silyl group, a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms, and a substituted or unsubstituted heteroaryl group having 5 to 30 ring atoms. Represents a halogen atom or a cyano group.
The other two adjacent groups of R _{65 to} R ₆₈ and R _{69 to} R ₇₂ may combine to form a substituted or unsubstituted saturated or unsaturated divalent group that forms part of the ring. Good.
Rf represents a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms or a substituted or unsubstituted heteroaryl group having 5 to 30 ring atoms. )

（式中、Ｂ₁〜Ｂ₄、Ｃ₁〜Ｃ₄、ｎ及びＬは式（１−１）で定義したとおりであり、Ｒ₅₇〜Ｒ₆₀、Ｒ₆₁、Ｒ₆₃及びＲ₆₄は式（１−１ｅ）で定義したとおりであり、Ｒｆ及びＲ₆₅〜Ｒ₇₂は式（１−１ｆ）で定義したとおりである。） (11) Said (1) said Formula (1-1), (1-1e) or (1-1f) is represented by following formula (1-1g), (1-1h) or (1-1i) The nitrogen-containing aromatic heterocyclic derivative as described in (5) or (8).

(In the formula, B _{1 to} B ₄ , C _{1 to} C ₄ , n and L are as defined in the formula (1-1), and R _{57 to} R ₆₀ , R ₆₁ , R ₆₃ and R ₆₄ are represented by the formula ( 1-1e) and Rf and R _{65 to} R ₇₂ are as defined in formula (1-1f).

（式中、Ｂ₁〜Ｂ₄、Ｃ₁〜Ｃ₄、ｎ及びＬは式（１−２）で定義したとおりであり、Ｒ₅₇〜Ｒ₆₀、Ｒ₆₁、Ｒ₆₃、Ｒ₆₄及びＲａは式（１−２ｅ）で定義したとおりであり、Ｒｆ及びＲ₆₅〜Ｒ₇₂は式（１−２ｆ）で定義したとおりである。） (12) The above formula (1-2), (1-2e) or (1-2f) is represented by the following formula (1-2g) or (1-2h) (1), (6) or ( The nitrogen-containing aromatic heterocyclic derivative as described in 9).

(In the formula, B _{1 to} B ₄ , C _{1 to} C ₄ , n and L are as defined in the formula (1-2), and R _{57 to} R ₆₀ , R ₆₁ , R ₆₃ , R ₆₄ and Ra are (As defined in formula (1-2e), Rf and R _{65 to} R ₇₂ are as defined in formula (1-2f).)

（式中、Ｂ₁〜Ｂ₄、Ｃ₁〜Ｃ₄、ｎ及びＬは式（１−３）で定義したとおりであり、Ｒ₅₇〜Ｒ₆₀、Ｒ₆₁、Ｒ₆₃及びＲ₆₄は式（１−３ｅ）で定義したとおりであり、Ｒｆ及びＲ₆₅〜Ｒ₇₂は式（１−３ｆ）で定義したとおりである。） (13) The formula (1-3), (1-3e) or (1-3f) is represented by the following formula (1-3g) or (1-3h). The nitrogen-containing aromatic heterocyclic derivative as described in 10).

(In the formula, B _{1 to} B ₄ , C _{1 to} C ₄ , n and L are as defined in Formula (1-3), and R _{57 to} R ₆₀ , R ₆₁ , R ₆₃ and R ₆₄ are the formulas ( 1-3e) and Rf and R _{65 to} R ₇₂ are as defined in formula (1-3f).)

(14) A material for an organic electroluminescence device comprising the nitrogen-containing aromatic heterocyclic derivative according to any one of (1) to (13).

(15) An organic electroluminescence device having an anode, a cathode, and at least one organic thin film layer between the anode and the cathode, wherein at least one of the organic thin film layers is any one of (1) to (13) An organic electroluminescence device comprising the nitrogen-containing aromatic heterocyclic derivative according to claim 1.

(16) The organic thin film layer includes a light emitting layer and a cathode side organic thin film layer disposed between the light emitting layer and the cathode, and the cathode side organic thin film layer is the nitrogen-containing aromatic heterocyclic derivative. The organic electroluminescence device according to (15), containing

(17) The organic thin film layer has a light emitting layer and an electron transport layer disposed between the light emitting layer and the cathode, and the electron transport layer contains the nitrogen-containing aromatic heterocyclic derivative. (15) The organic electroluminescent element as described in.

(18) The organic electroluminescence device according to (15), wherein the organic thin film layer has a light emitting layer, and the light emitting layer contains the nitrogen-containing aromatic heterocyclic derivative.

(19) The organic electroluminescent element according to any one of (16) to (18), wherein the light emitting layer further contains a phosphorescent material.

(20) The organic electroluminescence device according to (19), wherein the phosphorescent material is an orthometalated complex of iridium, osmium, or platinum.

(21) An electronic device comprising the organic electroluminescence element according to any one of (15) to (20).

  An organic EL device using a nitrogen-containing aromatic heterocyclic derivative represented by the following formula (1-1), (1-2) or (1-3) exhibits high luminous efficiency even at a low driving voltage.

It is the schematic which shows the structure of an example of the organic EL element of this invention.

  In the present invention, “ab” in the expression “X group having a substituted or unsubstituted carbon number (ring carbon number, ring atom number) ab” represents carbon in which the X group is unsubstituted. This represents the number or the number of atoms, and does not include the carbon and atom of the optional substituent that the X group has. The substituted X group represents a -X-substituent.

  The definition of “hydrogen atom” includes isotopes having different numbers of neutrons, that is, light hydrogen (protium), deuterium (deuterium), and tritium (tritium).

In the following, an optional substituent when referred to as “substituted or unsubstituted” is an alkyl group having 1 to 50 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms; 3 to 50 ring carbon atoms, preferably A cycloalkyl group having 3 to 6, more preferably 5 or 6; an aryl group having 6 to 50 ring carbon atoms, preferably 6 to 24, more preferably 6 to 12 ring atoms; 6 to 50 ring carbon atoms, preferably 6 To 24, more preferably an aryl group having 6 to 12 aryl groups, and an alkyl moiety having 1 to 50 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms; an amino group; 1 to 50 carbon atoms A mono- or dialkylamino group having an alkyl group of 1 to 10, more preferably 1 to 5; an aryl group having 6 to 50 ring carbon atoms, preferably 6 to 24, more preferably 6 to 12 carbon atoms. You Mono- or diarylamino group; an alkoxy group having an alkyl group having 1 to 50 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms; 6 to 50 ring carbon atoms, preferably 6 to 24 carbon atoms, more preferably An aryloxy group having an aryl group of 6 to 12; an alkyl group having 1 to 50 carbon atoms, preferably 1 to 10, more preferably 1 to 5 carbon atoms and a ring carbon number of 6 to 50, preferably 6 to 24, more preferably Is a mono-, di- or tri-substituted silyl group having a group selected from 6 to 12 aryl groups; 5 to 50 ring-forming atoms, preferably 5 to 24, more preferably 5 to 12 hetero atoms (nitrogen A heterocyclic group containing 1 to 5, preferably 1 to 3, more preferably 1 to 2 carbon atoms; 1 to 50 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 5 atoms. 5 A haloalkyl group having 1 to 8, preferably 1 to 5, more preferably 1 to 3 halogen atoms (fluorine atom, chlorine atom, bromine atom, iodine atom); halogen atom (fluorine atom, chlorine atom) A group and an atom selected from the group consisting of a cyano group and a nitro group.
Among the above substituents, a halogen atom, a cyano group, a trialkylsilyl group having an alkyl group having 1 to 5 carbon atoms, an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 5 or 6 carbon atoms, and ring-forming carbon A group and an atom selected from the group consisting of aryl groups of several 6 to 12 are preferred.

The nitrogen-containing aromatic heterocyclic derivative is represented by the following formula (1-1), (1-2) or (1-3).

In Formula (1-1), any one of C _{1 to} C ₄ is a nitrogen atom, and any one of B _{1 to} B ₄ is a nitrogen atom. However, B ₁ and C ₁ , B ₄ and C ₄ , B ₁ and C ₄ , and B ₄ and C ₁ are not nitrogen atoms at the same time. That is, the case where the following structure (A) is a 1,8-naphthyridine structure and a 1,5-naphthyridine structure are excluded.

Among C _{1 to} C ₄ and B _{1 to} B ₄ , 1 to 6, preferably 1 to 2, but not nitrogen atoms are carbon atoms bonded to ^* 1.
n is 1-6, Preferably it is 1-2. When n is 2 or more, each group may be the same or different.

Of C _{1 to} C ₄ and B _{1 to} B ₄ , those that are neither a carbon atom nor a nitrogen atom bonded to ^* 1 independently represent CR ^A.
R ^A is a hydrogen atom, a substituted or unsubstituted linear or branched alkyl group having 1 to 15 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 15 ring carbon atoms, a substituted or unsubstituted group. Represents a silyl group, a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms, a substituted or unsubstituted heteroaryl group having 5 to 30 ring atoms, a halogen atom, or a cyano group, preferably a hydrogen atom A substituted or unsubstituted linear or branched alkyl group having 1 to 15 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 15 ring carbon atoms, a substituted or unsubstituted ring carbon number 6 to Represents a 30 aryl group, a substituted or unsubstituted heteroaryl group having 5 to 30 ring atoms or a cyano group, more preferably a hydrogen atom, a substituted or unsubstituted carbon atom of 1; 15 a linear or branched alkyl group, a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms, a substituted or unsubstituted heteroaryl group having 5 to 30 ring atoms, or a cyano group More preferably, it is a hydrogen atom, a substituted or unsubstituted linear or branched alkyl group having 1 to 15 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms, or a substituted or unsubstituted group. Represents a heteroaryl group having 5 to 30 ring atoms, particularly preferably a hydrogen atom or a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms.

  L represents a single bond, a substituted or unsubstituted arylene group having 6 to 30 ring carbon atoms, or a substituted or unsubstituted heteroarylene group having 5 to 30 ring atoms, preferably a single bond or substituted or unsubstituted. Represents an arylene group having 6 to 30 ring carbon atoms, more preferably a substituted or unsubstituted arylene group having 6 to 30 ring carbon atoms.

A _{1 to} A ₈ are each independently CR ^B or a nitrogen atom. 1-4 nitrogen atoms of A ₁ to A _8, is preferably other is CR ^B, 1 to 2 amino nitrogen atom, more preferably other is CR ^B, the A ₁ to A ₈ More preferably, all are CR ^B.
R ^B represents a hydrogen atom, a substituted or unsubstituted linear or branched alkyl group having 1 to 15 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 15 ring carbon atoms, a substituted or unsubstituted group; Represents a silyl group, a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms, a substituted or unsubstituted heteroaryl group having 5 to 30 ring atoms, a halogen atom, or a cyano group, preferably a hydrogen atom A substituted or unsubstituted linear or branched alkyl group having 1 to 15 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 15 ring carbon atoms, a substituted or unsubstituted ring carbon number 6 to Represents a 30 aryl group, a substituted or unsubstituted heteroaryl group having 5 to 30 ring atoms or a cyano group, more preferably a hydrogen atom, a substituted or unsubstituted carbon atom of 1; 15 a linear or branched alkyl group, a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms, a substituted or unsubstituted heteroaryl group having 5 to 30 ring atoms, or a cyano group More preferably, it is a hydrogen atom, a substituted or unsubstituted linear or branched alkyl group having 1 to 15 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms, or a substituted or unsubstituted group. Represents a heteroaryl group having 5 to 30 ring atoms, particularly preferably a hydrogen atom or a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms.
Two adjacent ^RBs may combine to form a substituted or unsubstituted saturated or unsaturated divalent group that forms part of the ring.
By bonding two adjacent R ^B, The ring they form together with the two carbon atoms attached, for example, a pyrrole ring, a furan ring, a thiophene ring, a pyrazole ring, an imidazole ring, a triazole ring, an oxazole ring , Thiazole ring, pyrroline ring, tetrahydropyridine ring, cyclopentene ring, cyclohexene ring, benzene ring, pyridine ring, pyrazine ring, pyridazine ring, indene ring, 1,1-dimethylindene ring, indole ring, N-phenylindole ring, benzofuran Ring, benzothiophene ring and the like.

In Formula (1-2), any one of C _{1 to} C ₄ is a nitrogen atom, and any one of B _{1 to} B ₄ is a nitrogen atom. However, B ₁ and C ₁ , B ₄ and C ₄ , B ₁ and C ₄ , and B ₄ and C ₁ are not nitrogen atoms at the same time.
Among C ₁ -C ₄ and B ₁ .about.B _4, 1 to 6 amino although not a nitrogen atom, preferably 1-2 carbon atoms attached to ^* 2.
n is the same as described above, and when n is 2 or more, each group may be the same or different.
Among C _{1 to} C ₄ and B _{1 to} B ₄ , those that are neither a carbon atom nor a nitrogen atom bonded to ^* 2 independently represent CR ^A. R ^A is the same as described above.
L is the same as described above.
Ra represents a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms or a substituted or unsubstituted heteroaryl group having 5 to 30 ring atoms, preferably a substituted or unsubstituted ring carbon number 6 Represents an aryl group of ˜30.
Any one of A _{9 to} A ₁₂ , preferably A ₁₀ or A ₁₁ , more preferably A ₁₁ represents a carbon atom bonded to ^* 3, and other A _{9 to} A ₁₂ and A _{13 to} A ₁₆ are Each independently is CR ^B or a nitrogen atom. Of the other A _{9 to} A ₁₂ and A _{13 to} A ₁₆ , 1 to 4 are preferably nitrogen atoms, and the others are preferably CR ^B , more preferably 1 to 2 are nitrogen atoms and others are CR ^B. More preferably, all of other A _{9 to} A ₁₂ and A _{13 to} A ₁₆ are CR ^B. R ^B is the same as described above, and two adjacent R ^B may be bonded to each other to form the ring together with two carbon atoms to which they are bonded.

In Formula (1-3), any one of C _{1 to} C ₄ is a nitrogen atom, and any one of B _{1 to} B ₄ is a nitrogen atom. However, B ₁ and C ₁ , B ₄ and C ₄ , B ₁ and C ₄ , and B ₄ and C ₁ are not nitrogen atoms at the same time.
Among C _{1 to} C ₄ and B _{1 to} B ₄ , 1 to 6, preferably 1 to 2, but not nitrogen atoms are carbon atoms bonded to ^* 4.
n is the same as described above, and when n is 2 or more, each group may be the same or different.
Of C _{1 to} C ₄ and B _{1 to} B ₄ , those that are neither a carbon atom nor a nitrogen atom bonded to ^* 4 independently represent CR ^A. R ^A is the same as described above.
L is the same as described above.
X represents an oxygen atom, a sulfur atom, or SiRbRc, preferably an oxygen atom or a sulfur atom, and more preferably an oxygen atom. Rb and Rc are each independently a substituted or unsubstituted linear or branched alkyl group having 1 to 15 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 15 ring carbon atoms, a substituted or unsubstituted group. A substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms or a substituted or unsubstituted heteroaryl group having 5 to 30 ring atoms, preferably a substituted or unsubstituted straight chain or branched chain having 1 to 15 carbon atoms Alkyl group, substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms, or substituted or unsubstituted heteroaryl group having 5 to 30 ring atoms, more preferably substituted or unsubstituted carbon atoms 1 to 15 linear or branched alkyl group, or substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms.
Any one of A _{17 to} A ₂₀ , preferably A ₁₈ or A ₁₉ , more preferably A ₁₉ represents a carbon atom bonded to ^* 5, and other A _{17 to} A ₂₀ and A _{21 to} A ₂₄ are Each independently is CR ^B or a nitrogen atom. Among other A ₁₇ to A ₂₀ and A ₂₁ to A _24, 1 to 4 atoms are nitrogen atoms, it is preferred others are CR ^B, 1 to 2 amino nitrogen atom, that others are CR ^B More preferably, all of the other A _{17 to} A ₂₀ and A _{21 to} A ₂₄ are CR ^B. R ^B is the same as described above, and two adjacent R ^B may be bonded to each other to form the ring together with two carbon atoms to which they are bonded.

In the formulas (1-1), (1-2), and (1-3), the following structure (A) has the following 1,6-naphthyridine structure, 1,7-naphthyridine structure, 2,6-naphthyridine structure, or A 2,7-naphthyridine structure is preferred (substituent is omitted).

Directly substituted or unsubstituted carbon having 1 to 15 (preferably 1 to 10, more preferably 1 to 5) represented by R ^A , R ^B , Rb and Rc in formulas (1-1) to (1-3) In the chain or branched alkyl group, examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an s-butyl group, a t-butyl group, Pentyl group (including isomer group), hexyl group (including isomer group), heptyl group (including isomer group), octyl group (including isomer group), nonyl group (including isomer group), Examples include decyl group (including isomer group), undecyl group (including isomer group), and dodecyl group (including isomer group), and include methyl group, ethyl group, n-propyl group, isopropyl group, n -Butyl group, isobutyl group, s-butyl group, t A butyl group and a pentyl group (including an isomer group) are preferable, and a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an s-butyl group, and a t-butyl group are more preferable. A methyl group, an ethyl group, an isopropyl group and a t-butyl group are particularly preferable.

The substituted or unsubstituted ring-forming carbon number 3-15 (preferably 3-6, more preferably 5 or 6) represented by R ^A , R ^B , Rb and Rc in formulas (1-1) to (1-3) In this cycloalkyl group, examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, an adamantyl group, and the like, and a cyclopentyl group and a cyclohexyl group are preferable.

The substituted or unsubstituted ring carbon atoms represented by R ^A , R ^B , Ra, Rb and Rc in the formulas (1-1) to (1-3) are 6 to 30 (preferably 6 to 24, more preferably 6 to 6). In the aryl group of 18), the aryl group includes phenyl, naphthylphenyl, biphenylyl, terphenylyl, naphthyl, acenaphthylenyl, anthryl, benzoanthryl, aceanthryl, phenanthryl, benzo [c ] Phenanthryl group, phenalenyl group, fluorenyl group, picenyl group, pentaphenyl group, pyrenyl group, chrysenyl group, benzo [g] chrysenyl group, s-indacenyl group, as-indacenyl group, fluoranthenyl group, benzo [k] full Oranthenyl group, triphenylenyl group, benzo [b] triphenylenyl group, perylenyl group, etc. Among them, a phenyl group, biphenylyl group, terphenylyl group, a naphthyl group are preferred, a phenyl group, biphenylyl group, more preferably terphenylyl group, a phenyl group is particularly preferred.

The substituted silyl group represented by R ^A and R ^{B in the} formulas (1-1) to (1-3) is the alkyl group having 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and the ring. A mono-, di- or trisubstituted silyl group having a group selected from aryl groups having 6 to 30 carbon atoms, preferably 6 to 24 carbon atoms, more preferably 6 to 18 carbon atoms; trimethylsilyl group, triethylsilyl group, tributylsilyl group Group, dimethylethylsilyl group, t-butyldimethylsilyl group, vinyldimethylsilyl group, propyldimethylsilyl group, dimethylisopropylsilyl group, dimethylpropylsilyl group, dimethylbutylsilyl group, dimethyltertiarybutylsilyl group, diethylisopropylsilyl group , Phenyldimethylsilyl group, diphenylmethylsilyl group, diphenyl tertiary butyl group And a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group, a vinyldimethylsilyl group, and a propyldimethylsilyl group.

The number of substituted or unsubstituted ring atoms represented by R ^A , R ^B , Ra, Rb and Rc in formulas (1-1) to (1-3) is 5 to 30 (preferably 6 to 24, more preferably 6 to In the heteroaryl group of 18), the heteroaryl group contains at least 1, preferably 1-5 heteroatoms, for example, nitrogen, sulfur and oxygen atoms. Examples of the heteroaryl group include a pyrrolyl group, a furyl group, a thienyl group, a pyridyl group, a pyridazinyl group, a pyrimidinyl group, a pyrazinyl group, a triazinyl group, an imidazolyl group, an oxazolyl group, a thiazolyl group, an isoxazolyl group, an isothiazolyl group. Oxadiazolyl group, thiadiazolyl group, triazolyl group, tetrazolyl group, indolyl group, isoindolyl group, benzofuranyl group, isobenzofuranyl group, benzothiophenyl group, isobenzothiophenyl group, indolizinyl group, quinolidinyl group, quinolyl group, isoquinolyl group , Cinnolyl group, phthalazinyl group, quinazolinyl group, quinoxalinyl group, benzimidazolyl group, benzoxazolyl group, benzthiazolyl group, indazolyl group, benzisoxazolyl group, benzine Examples include isothiazolyl group, dibenzofuranyl group, dibenzothiophenyl group, carbazolyl group, phenanthridinyl group, acridinyl group, phenanthrolinyl group, phenazinyl group, phenothiazinyl group, phenoxazinyl group, and xanthenyl group. Group, thienyl group, pyridyl group, pyridazinyl group, pyrimidinyl group, pyrazinyl group, triazinyl group, benzofuranyl group, benzothiophenyl group, dibenzofuranyl group, dibenzothiophenyl group are preferable, benzofuranyl group, benzothiophenyl group, dibenzofuran Nyl group and dibenzothiophenyl group are more preferable.

The halogen atoms represented by R ^A and R ^{B in} formulas (1-1) to (1-3) are a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is particularly preferable.

  In the substituted or unsubstituted arylene group having 6 to 30 ring carbon atoms (preferably 6 to 24, more preferably 6 to 18) represented by L in the formulas (1-1) to (1-3), the arylene group Are phenyl group, naphthylphenyl group, biphenylyl group, terphenylyl group, naphthyl group, acenaphthylenyl group, anthryl group, benzoanthryl group, aceanthryl group, phenanthryl group, benzo [c] phenanthryl group, phenalenyl group, fluorenyl group, picenyl Group, pentaphenyl group, pyrenyl group, chrysenyl group, benzo [g] chrysenyl group, s-indacenyl group, as-indacenyl group, fluoranthenyl group, benzo [k] fluoranthenyl group, triphenylenyl group, benzo [b] One aryl group selected from a triphenylenyl group and a perylenyl group; A divalent group obtained by removing an elementary atom, preferably a phenylene group, a biphenyldiyl group, a terphenyldiyl group or a naphthalenediyl group, more preferably a phenylene group, a biphenyldiyl group or a terphenyldiyl group, and a phenylene group. Particularly preferred.

  In the substituted or unsubstituted heteroarylene group having 5 to 30 ring atoms represented by L in the formulas (1-1) to (1-3), the heteroarylene group is at least one, preferably 1 to 5 A divalent group obtained by removing one hydrogen atom from an aromatic heterocyclic compound containing a heteroatom such as a nitrogen atom, a sulfur atom and an oxygen atom. Examples of the aromatic heterocyclic compound include pyrrole, furan, thiophene, pyridine, pyridazine, pyrimidine, pyrazine, triazine, imidazole, oxazole, thiazole, pyrazole, isoxazole, isothiazole, oxadiazole, thiadiazole, triazole, tetrazole, and indole. , Isoindole, benzofuran, isobenzofuran, benzothiophene, isobenzothiophene, indolizine, quinolidine, quinoline, isoquinoline, cinnoline, phthalazinin, quinazoline, quinoxaline, benzimidazole, benzoxazole, benzthiazole, indazole, benzisoxazole, benz Isothiazole, dibenzofuran, dibenzothiophene, carbazole, phenanthridine, acridine, phen Ntororin, phenazine, phenothiazine, phenoxazine, xanthene, and the like. The heteroarylene group is preferably a divalent residue of furan, thiophene, pyridine, pyridazine, pyrimidine, pyrazine, triazine, benzofuran, benzothiophene, dibenzofuran, dibenzothiophene, and 2 of benzofuran, benzothiophene, dibenzofuran, dibenzothiophene. A valent residue is more preferred.

The nitrogen-containing aromatic heterocyclic derivative represented by the formula (1-1) is preferably represented by the following formula (1-1a), (1-1b), (1-1c), or (1-1d). The

In the formulas (1-1a), (1-1b), (1-1c), and (1-1d), L, n, and A _{1 to} A ₈ are as defined in the formula (1-1). .
1 to ₆ of R _{2 to} R ₆ and R ₈ in formula (1-1a), preferably 1 to 2, more preferably 1 or 2 of R ₂ , R ₄ and R ₆ , more preferably R _2. , R ₄ and R ₆ are each a single bond bonded to ^* 1.
1 to 6 of R _{2 to} R ₅ , R ₇ and R ₈ in formula (1-1b), preferably 1 to 2, more preferably 1 or 2 of R ₂ , R ₄ and R ₇ , and more preferably Is a single bond in which one of R ₂ , R ₄ and R ₇ is bonded to ^* 1.
_{1 to 6} of R ₁ , R _{3 to} R ₆ and R ₈ in formula (1-1c), preferably 1 to 2, more preferably 1 or 2 of R ₁ , R ₃ , R ₆ and R ₈ More preferably, one of R ₁ , R ₃ , R ₆ and R ₈ is a single bond bonded to ^* 1.
₁ to 6 of R ₁ , R _{3 to} R ₅ , R ₇ and R ₈ in formula (1-1d), preferably 1 to 2, more preferably ₁ of R ₁ , R ₃ , R ₅ and R ₇ . Or two, more preferably one of R ₁ , R ₃ , R ₅ and R ₇ is a single bond bonded to ^* 1.

In formulas (1-1a), (1-1b), (1-1c), and (1-1d), among R _{1 to} R ₈ , those that are not a single bond that binds to ^* 1 are the CR ^A cyclo is the same as R ^a, each independently, a hydrogen atom, a substituted or unsubstituted straight or branched alkyl group having 1 to 15 carbon atoms, a substituted or unsubstituted ring carbon atoms of 3 to 15 An alkyl group, a substituted or unsubstituted silyl group, a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms, a substituted or unsubstituted heteroaryl group having 5 to 30 ring atoms, a halogen atom, or a cyano group; Represents.

The nitrogen-containing aromatic heterocyclic derivative represented by the formula (1-2) is preferably represented by the following formula (1-2a), (1-2b), (1-2c), or (1-2d). The

In the formulas (1-2a), (1-2b), (1-2c), and (1-2d), L, n, Ra, and A _{9 to} A ₁₆ are as defined in the formula (1-2). It is.
1 to ₆ of R _{2 to} R ₆ and R ₈ in formula (1-2a), preferably 1 to 2, more preferably 1 or 2 of R ₂ , R ₄ and R ₆ , and more preferably R _2. , R ₄ and R ₆ are each a single bond bonded to ^* 2.
1 to 6 of R _{2 to} R ₅ , R ₇ and R ₈ in formula (1-2b), preferably 1 to 2, more preferably 1 or 2 of R ₂ , R ₄ and R ₇ , and more preferably Is a single bond in which one of R ₂ , R ₄ and R ₇ is bonded to ^* 2.
1-6 R _1, R ₃ to R ₆ and R ₈ of formula (1-2c), preferably 1 to 2, more preferably 1 or 2 R _1, R _3, R ₆ and R ₈ More preferably, one of R ₁ , R ₃ , R ₆ and R ₈ is a single bond bonded to ^* 2.
₁ to 6 of R ₁ , R _{3 to} R ₅ , R ₇ and R ₈ in formula (1-2d), preferably 1 to 2, more preferably ₁ of R ₁ , R ₃ , R ₅ and R ₇ . Or two, more preferably one of R ₁ , R ₃ , R ₅ and R ₇ is a single bond bonded to ^* 2.

In formulas (1-2a), (1-2b), (1-2c), and (1-2d), among R _{1 to} R ₈ , those that are not a single bond that binds to ^* 2 are the CR ^A cyclo is the same as R ^a, each independently, a hydrogen atom, a substituted or unsubstituted straight or branched alkyl group having 1 to 15 carbon atoms, a substituted or unsubstituted ring carbon atoms of 3 to 15 An alkyl group, a substituted or unsubstituted silyl group, a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms, a substituted or unsubstituted heteroaryl group having 5 to 30 ring atoms, a halogen atom, or a cyano group; Represents.

The nitrogen-containing aromatic heterocyclic derivative represented by the formula (1-3) is preferably represented by the following formula (1-3a), (1-3b), (1-3c), or (1-3d). Is done.

In the formulas (1-3a), (1-3b), (1-3c), and (1-3d), L, n, X, and A _{17 to} A ₂₄ are as defined in the formula (1-3). It is.
1 to ₆ of R _{2 to} R ₆ and R ₈ in formula (1-3a), preferably 1 to 2, more preferably 1 or 2 of R ₂ , R ₄ and R ₆ , more preferably R _2. , One of R ₄ and R ₆ is a single bond bonded to ^* 4.
1 to 6 of R _{2 to} R ₅ , R ₇ and R ₈ in formula (1-3b), preferably 1 to 2, more preferably 1 or 2 of R ₂ , R ₄ and R ₇ , more preferably Is a single bond in which one of R ₂ , R ₄ and R ₇ is bonded to ^* 4.
1-6 R _1, R ₃ to R ₆ and R ₈ of formula (1-3c), preferably 1 to 2, more preferably 1 or 2 R _1, R _3, R ₆ and R ₈ More preferably, one of R ₁ , R ₃ , R ₆ and R ₈ is a single bond bonded to ^* 4.
₁ to 6 of R ₁ , R _{3 to} R ₅ , R ₇ and R ₈ in formula (1-3d), preferably 1 to 2, more preferably ₁ of R ₁ , R ₃ , R ₅ and R ₇ . Or two, more preferably one of R ₁ , R ₃ , R ₅ and R ₇ is a single bond bonded to ^* 4.

In formulas (1-3a), (1-3b), (1-3c), and (1-3d), among R _{1 to} R ₈ , those that are not a single bond bonded to ^* 4 are the CR ^A cyclo is the same as R ^a, each independently, a hydrogen atom, a substituted or unsubstituted straight or branched alkyl group having 1 to 15 carbon atoms, a substituted or unsubstituted ring carbon atoms of 3 to 15 An alkyl group, a substituted or unsubstituted silyl group, a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms, a substituted or unsubstituted heteroaryl group having 5 to 30 ring atoms, a halogen atom, or a cyano group; Represents.

The nitrogen-containing aromatic heterocyclic derivative represented by the formula (1-1) is preferably represented by the following formula (1-1e).

In Formula (1-1e), B _{1 to} B ₄ , C _{1 to} C ₄ , n, and L are as defined in Formula (1-1).
R _{57 to} R ₆₄ are the same as R ^{B of} CR ^B , and each independently represents a hydrogen atom, a substituted or unsubstituted linear or branched alkyl group having 1 to 15 carbon atoms, a substituted or unsubstituted group. A cycloalkyl group having 3 to 15 ring carbon atoms, a substituted or unsubstituted silyl group, a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms, a substituted or unsubstituted ring atom having 5 to 30 ring atoms. A heteroaryl group, a halogen atom or a cyano group is represented.
Two adjacent groups of R _{57 to} R ₆₄ may combine to form the divalent group described for R ^B.

The nitrogen-containing aromatic heterocyclic derivative represented by the formula (1-2) is preferably represented by the following formula (1-2e).

In Formula (1-2e), B _{1 to} B ₄ , C _{1 to} C ₄ , Ra, n, and L are as defined in Formula (1-2).
Any one of R _{57 to} R ₆₀ , preferably R ₅₈ or R ₅₉ , more preferably R ₅₉ is a single bond bonded to ^* 3. The other R _{57 to} R ₆₀ and R _{61 to} R ₆₄ are the same as R ^{B of} CR ^B and are each independently a hydrogen atom, a substituted or unsubstituted C 1-15 linear or branched group. Alkyl group, substituted or unsubstituted cycloalkyl group having 3 to 15 ring carbon atoms, substituted or unsubstituted silyl group, substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms, substituted or unsubstituted A heteroaryl group having 5 to 30 ring atoms, a halogen atom, or a cyano group is represented.
Two other adjacent groups of R _{57 to} R ₆₀ and R _{61 to} R ₆₄ may combine to form the divalent group described for R ^B.

The nitrogen-containing aromatic heterocyclic derivative represented by the formula (1-3) is preferably represented by the following formula (1-3e).

In formula (1-3e), B _{1 to} B ₄ , C _{1 to} C ₄ , X, n, and L are as defined in formula (1-3).
Any one of R _{57 to} R ₆₀ , preferably R ₅₈ or R ₅₉ , more preferably R ₅₉ is a single bond bonded to ^* 5. The other R _{57 to} R ₆₀ and R _{61 to} R ₆₄ are the same as R ^{B of} CR ^B and are each independently a hydrogen atom, a substituted or unsubstituted C 1-15 linear or branched group. Alkyl group, substituted or unsubstituted cycloalkyl group having 3 to 15 ring carbon atoms, substituted or unsubstituted silyl group, substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms, substituted or unsubstituted A heteroaryl group having 5 to 30 ring atoms, a halogen atom, or a cyano group is represented.
Two other adjacent groups of R _{57 to} R ₆₀ and R _{61 to} R ₆₄ may combine to form the divalent group described for R ^B.

The nitrogen-containing aromatic heterocyclic derivative represented by the formula (1-1) or (1-1e) is preferably represented by the following formula (1-1f).

In Formula (1-1f), B _{1 to} B ₄ , C _{1 to} C ₄ , n, and L are as defined in Formula (1-1).
Any one of R _{61 to} R ₆₄ , preferably R ₆₂ or R ₆₃ , more preferably R ₆₃ is a single bond bonded to ^* 6. Other R ₆₁ to R ₆₄ and R ₅₇ to R ₆₀ are the the same as R ^B of CR ^B, each independently, a hydrogen atom, a substituted or unsubstituted 1 to 15 carbon atoms linear or branched Alkyl group, substituted or unsubstituted cycloalkyl group having 3 to 15 ring carbon atoms, substituted or unsubstituted silyl group, substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms, substituted or unsubstituted A heteroaryl group having 5 to 30 ring atoms, a halogen atom, or a cyano group is represented.
The other two adjacent groups of R _{61 to} R ₆₄ and R _{57 to} R ₆₀ may combine to form the divalent group described for R ^B.
Any one of R _{65 to} R ₆₈ , preferably R ₆₆ or R ₆₇ , more preferably R ₆₇ is a single bond bonded to ^* 7. Other R _{65 to} R ₆₈ and R _{69 to} R ₇₂ are defined in the same manner as R ^{B of} CR ^B and are each independently a hydrogen atom, a substituted or unsubstituted C 1-15 linear or branched group. Alkyl group, substituted or unsubstituted cycloalkyl group having 3 to 15 ring carbon atoms, substituted or unsubstituted silyl group, substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms, substituted or unsubstituted Represents a heteroaryl group having 5 to 30 ring atoms, a halogen atom, or a cyano group.
Two other adjacent groups of R _{65 to} R ₆₈ and R _{69 to} R ₇₂ may combine to form the divalent group described for R ^B.
Rf is defined similarly to Ra, and represents a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms or a substituted or unsubstituted heteroaryl group having 5 to 30 ring atoms.

The nitrogen-containing aromatic heterocyclic derivative represented by the formula (1-2) or (1-2e) is preferably represented by the following formula (1-2f).

In formula (1-2f), B _{1 to} B ₄ , C _{1 to} C ₄ , Ra, n, and L are as defined in formula (1-2).
Any one of R _{57 to} R ₆₀ , preferably R ₅₈ or R ₅₉ , more preferably R ₅₉ is a single bond bonded to ^* 3. Any one of R _{61 to} R ₆₄ , preferably R ₆₂ or R ₆₃ , more preferably R ₆₃ is a single bond bonded to ^* 6. The other R _{57 to} R ₆₀ and the other R _{61 to} R ₆₄ are the same as R ^{B of} CR ^B and are each independently a hydrogen atom, a substituted or unsubstituted straight chain having 1 to 15 carbon atoms or Branched alkyl group, substituted or unsubstituted cycloalkyl group having 3 to 15 ring carbon atoms, substituted or unsubstituted silyl group, substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms, substituted or unsubstituted It represents a substituted heteroaryl group having 5 to 30 ring atoms, a halogen atom, or a cyano group.
Two other adjacent groups of R _{57 to} R ₆₀ and other R _{61 to} R ₆₄ may combine to form the divalent group described for R ^B.
Any one of R _{65 to} R ₆₈ , preferably R ₆₆ or R ₆₇ , more preferably R ₆₇ is a single bond bonded to ^* 7. Other R _{65 to} R ₆₈ and R _{69 to} R ₇₂ are defined in the same manner as R ^{B of} CR ^B and are each independently a hydrogen atom, a substituted or unsubstituted C 1-15 linear or branched group. Alkyl group, substituted or unsubstituted cycloalkyl group having 3 to 15 ring carbon atoms, substituted or unsubstituted silyl group, substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms, substituted or unsubstituted Represents a heteroaryl group having 5 to 30 ring atoms, a halogen atom, or a cyano group.
Two other adjacent groups of R _{65 to} R ₆₈ and R _{69 to} R ₇₂ may combine to form the divalent group described for R ^B.
Rf is defined similarly to Ra, and represents a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms or a substituted or unsubstituted heteroaryl group having 5 to 30 ring atoms.

The nitrogen-containing aromatic heterocyclic derivative represented by the formula (1-3) or (1-3e) is preferably represented by the following formula (1-3f).

In formula (1-3f), B _{1 to} B ₄ , C _{1 to} C ₄ , X, n, and L are as defined in formula (1-3).
Any one of R _{57 to} R ₆₀ , preferably R ₅₈ or R ₅₉ , more preferably R ₅₉ is a single bond bonded to ^* 5. Any one of R _{61 to} R ₆₄ , preferably R ₆₂ or R ₆₃ , more preferably R ₆₃ is a single bond bonded to ^* 6. The other R _{57 to} R ₆₀ and the other R _{61 to} R ₆₄ are the same as R ^{B of} CR ^B and are each independently a hydrogen atom, a substituted or unsubstituted straight chain having 1 to 15 carbon atoms or Branched alkyl group, substituted or unsubstituted cycloalkyl group having 3 to 15 ring carbon atoms, substituted or unsubstituted silyl group, substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms, substituted or unsubstituted It represents a substituted heteroaryl group having 5 to 30 ring atoms, a halogen atom, or a cyano group.
Two other adjacent groups of R _{57 to} R ₆₀ and other R _{61 to} R ₆₄ may combine to form the divalent group described for R ^B.
Any one of R _{65 to} R ₆₈ , preferably R ₆₆ or R ₆₇ , more preferably R ₆₇ is a single bond bonded to ^* 7. Other R _{65 to} R ₆₈ and R _{69 to} R ₇₂ are defined in the same manner as R ^{B of} CR ^B and are each independently a hydrogen atom, a substituted or unsubstituted C 1-15 linear or branched group. Alkyl group, substituted or unsubstituted cycloalkyl group having 3 to 15 ring carbon atoms, substituted or unsubstituted silyl group, substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms, substituted or unsubstituted Represents a heteroaryl group having 5 to 30 ring atoms, a halogen atom, or a cyano group.
Two other adjacent groups of R _{65 to} R ₆₈ and R _{69 to} R ₇₂ may combine to form the divalent group described for R ^B.
Rf is defined similarly to Ra, and represents a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms or a substituted or unsubstituted heteroaryl group having 5 to 30 ring atoms.

The nitrogen-containing aromatic heterocyclic derivative represented by the formula (1-1), (1-1e) or (1-1f) is preferably the following formula (1-1g), (1-1h) or (1 -1i).

In formulas (1-1g), (1-1h), and (1-1i), B _{1 to} B ₄ , C _{1 to} C ₄ , n, and L are as defined in formula (1-1), and R _{57 to} R ₆₀ , R ₆₁ , R ₆₃ and R ₆₄ are as defined in formula (1-1e), and Rf and R _{65 to} R ₇₂ are as defined in formula (1-1f).

The nitrogen-containing aromatic heterocyclic derivative represented by the formula (1-2), (1-2e) or (1-2f) is preferably represented by the following formula (1-2g) or (1-2h). The

In the formulas (1-2g) and (1-2h), B _{1 to} B ₄ , C _{1 to} C ₄ , n and L are as defined in the formula (1-2), and R _{57 to} R ₆₀ , R ₆₁ , R ₆₃ , R ₆₄ and Ra are as defined in formula (1-2e), and Rf and R _{65 to} R ₇₂ are as defined in formula (1-2f).

The nitrogen-containing aromatic heterocyclic derivative represented by the formula (1-3), (1-3e) or (1-3f) is preferably represented by the following formula (1-3g) or (1-3h). The

In the formulas (1-3g) and (1-3h), B _{1 to} B ₄ , C _{1 to} C ₄ , n and L are as defined in the formula (1-3), and R _{57 to} R ₆₀ , R ₆₁ , R ₆₃ and R ₆₄ are as defined in formula (1-3e), and Rf and R _{65 to} R ₇₂ are as defined in formula (1-3f).

The nitrogen-containing aromatic heterocyclic derivative represented by the formula (1-1), (1-2) or (1-3) can be synthesized by the method described in the following synthesis example and a method according to the method. I can do it.
Since the nitrogen-containing aromatic heterocyclic derivative contains a naphthyridine structure, it has a high electron-injecting property and electron-transporting property, and since it also contains a hole-transporting unit such as a carbazole structure, it is bipolar, so a phosphorescent host and an electron-transporting layer Suitable as a material. An organic EL device having a light-emitting layer containing the nitrogen-containing aromatic heterocyclic derivative as a phosphorescent host or an electron transporting layer containing the nitrogen-containing aromatic heterocyclic derivative can be driven at a low voltage, and can be driven at a low voltage. Below shows high luminous efficiency.

  Although the specific example of this nitrogen-containing aromatic heterocyclic derivative is shown below, it is not limited to the following compound.

Organic EL Element Next, the organic EL element of the present invention will be described.
The organic EL device of the present invention has one or more organic thin film layers between the cathode and the anode. At least one of the organic thin film layers is a light emitting layer. At least one of the organic thin film layers contains a nitrogen-containing aromatic heterocyclic derivative represented by the formula (1-1) or (1-2).
Examples of the organic thin film layer containing the nitrogen-containing aromatic heterocyclic derivative include an anode-side organic thin film layer (hole transport layer, hole injection layer, etc.) provided between the anode and the light emitting layer, a light emitting layer, Examples include, but are not limited to, a cathode-side organic thin film layer (electron transport layer, electron injection layer, etc.), a space layer, a blocking layer, and the like provided between the cathode and the light emitting layer. The nitrogen-containing aromatic heterocyclic derivative may be contained in any of the above layers, for example, a host material or a dopant material in the light emitting layer of the fluorescent light emitting unit, a host material in the light emitting layer of the phosphorescent light emitting unit, It can be used for a hole transport layer, a hole blocking layer, and an electron transport layer. The organic thin film layer containing the nitrogen-containing aromatic heterocyclic derivative is particularly preferably a light emitting layer, a hole blocking layer or an electron transporting layer.

  The organic EL element of the present invention may be a fluorescent or phosphorescent monochromatic light emitting element, a fluorescent / phosphorescent hybrid white light emitting element, or a simple type having a single light emitting unit. A tandem type having a plurality of light emitting units may be used, and among them, a phosphorescent type is preferable. Here, the “light emitting unit” refers to a minimum unit that includes one or more organic layers, one of which is a light emitting layer, and can emit light by recombination of injected holes and electrons.

Accordingly, typical element configurations of simple organic EL elements include the following element configurations.
(1) Anode / light emitting unit / cathode The above light emitting unit may be a laminated type having a plurality of phosphorescent light emitting layers and fluorescent light emitting layers. In that case, the light emitting unit is generated by a phosphorescent light emitting layer between the light emitting layers. In order to prevent the excitons from diffusing into the fluorescent light emitting layer, a space layer may be provided. A typical layer structure of the light emitting unit is shown below.
(A) Hole transport layer / light emitting layer (/ electron transport layer)
(B) Hole transport layer / first phosphorescent light emitting layer / second phosphorescent light emitting layer (/ electron transport layer)
(C) Hole transport layer / phosphorescent layer / space layer / fluorescent layer (/ electron transport layer)
(D) Hole transport layer / first phosphorescent light emitting layer / second phosphorescent light emitting layer / space layer / fluorescent light emitting layer (/ electron transport layer)
(E) Hole transport layer / first phosphorescent light emitting layer / space layer / second phosphorescent light emitting layer / space layer / fluorescent light emitting layer (/ electron transport layer)
(F) Hole transport layer / phosphorescent layer / space layer / first fluorescent layer / second fluorescent layer (/ electron transport layer)
(G) Hole transport layer / electron blocking layer / light emitting layer (/ electron transport layer)
(H) Hole transport layer / light emitting layer / hole blocking layer (/ electron transport layer)
(I) Hole transport layer / fluorescent light emitting layer / triplet blocking layer (/ electron transport layer)

Each phosphorescent or fluorescent light-emitting layer may have a different emission color. Specifically, in the laminated light emitting layer (d), hole transport layer / first phosphorescent light emitting layer (red light emitting) / second phosphorescent light emitting layer (green light emitting) / space layer / fluorescent light emitting layer (blue light emitting) / Examples include a layer configuration such as an electron transport layer.
An electron blocking layer may be appropriately provided between each light emitting layer and the hole transport layer or the space layer. Further, a hole blocking layer may be appropriately provided between each light emitting layer and the electron transport layer. By providing the electron blocking layer or the hole blocking layer, electrons or holes can be confined in the light emitting layer, the charge recombination probability in the light emitting layer can be increased, and the light emission efficiency can be improved.

The following element structure can be mentioned as a typical element structure of a tandem type organic EL element.
(2) Anode / first light emitting unit / intermediate layer / second light emitting unit / cathode Here, as the first light emitting unit and the second light emitting unit, for example, the same light emitting unit as that described above is selected independently. can do.
The intermediate layer is generally called an intermediate electrode, an intermediate conductive layer, a charge generation layer, an electron extraction layer, a connection layer, or an intermediate insulating layer, and has electrons in the first light emitting unit and holes in the second light emitting unit. A known material structure to be supplied can be used.

  In FIG. 1, schematic structure of an example of the organic EL element of this invention is shown. The organic EL element 1 includes a substrate 2, an anode 3, a cathode 4, and a light emitting unit 10 disposed between the anode 3 and the cathode 4. The light emitting unit 10 includes a light emitting layer 5 including at least one phosphorescent light emitting layer including a phosphorescent host material and a phosphorescent dopant (phosphorescent material). A hole injection layer / hole transport layer 6 or the like may be formed between the light emitting layer 5 and the anode 3, and an electron injection layer / electron transport layer 7 or the like may be formed between the light emitting layer 5 and the cathode 4. Further, an electron blocking layer (not shown) may be provided on the light emitting layer 5 on the anode 3 side, and a hole blocking layer (not shown) may be provided on the light emitting layer 5 on the cathode 4 side. Thereby, electrons and holes can be confined in the light emitting layer 5, and the exciton generation probability in the light emitting layer 5 can be increased.

  In this specification, a host combined with a fluorescent dopant (fluorescent material) is referred to as a fluorescent host, and a host combined with a phosphorescent dopant is referred to as a phosphorescent host. The fluorescent host and the phosphorescent host are not distinguished only by the molecular structure. That is, the phosphorescent host means a material constituting a phosphorescent light emitting layer containing a phosphorescent dopant, and does not mean that it cannot be used as a material constituting a fluorescent light emitting layer. The same applies to the fluorescent host.

Substrate The organic EL device of the present invention is produced on a light-transmitting substrate. The light-transmitting substrate is a substrate that supports the organic EL element, and is preferably a smooth substrate having a light transmittance in the visible region of 400 nm to 700 nm of 50% or more. Specifically, a glass plate, a polymer plate, etc. are mentioned. Examples of the glass plate include those using soda lime glass, barium / strontium-containing glass, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass, quartz and the like as raw materials. Examples of the polymer plate include those using polycarbonate, acrylic, polyethylene terephthalate, polyether sulfide, polysulfone and the like as raw materials.

Anode The anode of the organic EL element plays a role of injecting holes into the hole transport layer or the light emitting layer, and it is effective to use one having a work function of 4.5 eV or more. Specific examples of the anode material include indium tin oxide alloy (ITO), tin oxide (NESA), indium zinc oxide, gold, silver, platinum, copper, and the like. The anode can be produced by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering. When light emitted from the light emitting layer is extracted from the anode, it is preferable that the transmittance of light in the visible region of the anode is greater than 10%. The sheet resistance of 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 nm to 1 μm, preferably 10 to 200 nm.

Cathode The cathode plays a role of injecting electrons into the electron injection layer, the electron transport layer, or the light emitting layer, and is preferably formed of a material having a small work function. The cathode material is not particularly limited, and specifically, indium, aluminum, magnesium, magnesium-indium alloy, magnesium-aluminum alloy, aluminum-lithium alloy, aluminum-scandium-lithium alloy, magnesium-silver alloy and the like can be used. Similarly to the anode, the cathode can be produced by forming a thin film by a method such as vapor deposition or sputtering. Moreover, you may take out light emission from the cathode side as needed.

Light-emitting layer An organic layer having a light-emitting function, and when a doping system is employed, includes a host material and a dopant material. At this time, the host material mainly has a function of encouraging recombination of electrons and holes and confining excitons in the light emitting layer, and the dopant material efficiently emits excitons obtained by recombination. It has a function.
In the case of a phosphorescent element, the host material mainly has a function of confining excitons generated by the dopant in the light emitting layer.

Here, the light emitting layer employs, for example, a double host (also referred to as host / cohost) that adjusts the carrier balance in the light emitting layer by combining an electron transporting host and a hole transporting host. Also good.
Moreover, you may employ | adopt the double dopant from which each dopant light-emits by putting in 2 or more types of dopant materials with a high quantum yield. Specifically, a mode in which yellow emission is realized by co-evaporating a host, a red dopant, and a green dopant to make the light emitting layer common is used.

The above light-emitting layer is a laminate in which a plurality of light-emitting layers are stacked, so that electrons and holes are accumulated at the light-emitting layer interface, and the recombination region is concentrated at the light-emitting layer interface to improve quantum efficiency. Can do.
The ease of injecting holes into the light emitting layer may be different from the ease of injecting electrons, and the hole transport ability and electron transport ability expressed by the mobility of holes and electrons in the light emitting layer may be different. May be different.

A light emitting layer can be formed by well-known methods, such as a vapor deposition method, a spin coat method, LB method, for example. The light emitting layer can also be formed by thinning a solution obtained by dissolving a binder such as a resin and a material compound in a solvent by a spin coating method or the like.
The light emitting layer is preferably a molecular deposited film. The molecular deposited film is a thin film formed by deposition from a material compound in a gas phase state or a film formed by solidifying from a material compound in a solution state or a liquid phase state. The thin film (molecular accumulation film) formed by the LB method can be classified by the difference in the aggregation structure and the higher-order structure, and the functional difference resulting therefrom.

  The phosphorescent dopant (phosphorescent material) that forms the light emitting layer is a compound that can emit light from the triplet excited state, and is not particularly limited as long as it emits light from the triplet excited state, but Ir, Pt, Os, Au, Cu, An organometallic complex containing at least one metal selected from Re and Ru and a ligand is preferable. The ligand preferably has an ortho metal bond. A metal complex containing a metal atom selected from Ir, Os and Pt is preferred in that the phosphorescent quantum yield is high and the external quantum efficiency of the light emitting device can be further improved, and an iridium complex, an osmium complex, or a platinum complex. Are more preferable, iridium complexes and platinum complexes are more preferable, and orthometalated iridium complexes are particularly preferable.

  There is no restriction | limiting in particular in content in the light emitting layer of a phosphorescent dopant, Although it can select suitably according to the objective, For example, 0.1-70 mass% is preferable and 1-30 mass% is more preferable. If the phosphorescent dopant content is 0.1% by mass or more, sufficient light emission can be obtained, and if it is 70% by mass or less, concentration quenching can be avoided.

Specific examples of preferred organometallic complexes as phosphorescent dopants are shown below.

The phosphorescent host is a compound having a function of efficiently emitting the phosphorescent dopant by efficiently confining the triplet energy of the phosphorescent dopant in the light emitting layer. Although the nitrogen-containing aromatic heterocyclic derivative of the present invention is useful as a phosphorescent host, compounds other than the nitrogen-containing aromatic heterocyclic derivative of the present invention can be appropriately selected as the phosphorescent host according to the above-mentioned purpose.
The nitrogen-containing aromatic heterocyclic derivative of the present invention and other compounds may be used in combination as a phosphorescent host material in the same light-emitting layer, and when there are a plurality of light-emitting layers, The nitrogen-containing aromatic heterocyclic derivative of the present invention may be used as the phosphorescent host material, and a compound other than the nitrogen-containing aromatic heterocyclic derivative of the present invention may be used as the phosphorescent host material of another light emitting layer. Further, the nitrogen-containing aromatic heterocyclic derivative of the present invention can be used in an organic layer other than the light emitting layer. In that case, as the phosphorescent host of the light emitting layer, other than the nitrogen-containing aromatic heterocyclic derivative of the present invention. These compounds may be used.

  Specific examples of compounds other than the nitrogen-containing aromatic heterocyclic derivative of the present invention and suitable as a phosphorescent host include carbazole derivatives, triazole derivatives, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazolines. Derivatives, pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aromatic tertiary amine compounds, styrylamine compounds, aromatic dimethylidene compounds , Porphyrin compounds, anthraquinodimethane derivatives, anthrone derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, carbodiimide derivatives, fluorenylide Typical examples are metal complexes of methane derivatives, distyrylpyrazine derivatives, heterocyclic tetracarboxylic anhydrides such as naphthaleneperylene, phthalocyanine derivatives, 8-quinolinol derivatives, metal phthalocyanines, benzoxazole and benzothiazole. Various metal complexes such as polysilane compounds, poly (N-vinylcarbazole) derivatives, aniline copolymers, thiophene oligomers, conductive polymer oligomers such as polythiophene, polythiophene derivatives, polyphenylene derivatives, polyphenylene vinylene derivatives, polyfluorene derivatives, etc. Examples thereof include polymer compounds. A phosphorescent host may be used independently and may use 2 or more types together. Specific examples include the following compounds.

  The organic EL device of the present invention may have a light emitting layer containing a fluorescent light emitting material, that is, a fluorescent light emitting layer. As the fluorescent light emitting layer, known fluorescent light emitting materials can be used. The fluorescent material is preferably at least one selected from anthracene derivatives, fluoranthene derivatives, styrylamine derivatives and arylamine derivatives, and more preferably anthracene derivatives and arylamine derivatives. In particular, an anthracene derivative is preferable as the host material, and an arylamine derivative is preferable as the dopant. Specifically, suitable materials described in International Publication No. 2010/134350 and International Publication No. 2010/134352 are selected. The nitrogen-containing aromatic heterocyclic derivative of the present invention may be used as a fluorescent light-emitting material for the fluorescent light-emitting layer or as a host material for the fluorescent light-emitting layer.

The ring-forming carbon number of the anthracene derivative as the fluorescent light-emitting material is preferably 26 to 100, more preferably 26 to 80, and still more preferably 26 to 60. More specifically, the anthracene derivative is preferably an anthracene derivative represented by the following formula (10).

(In the above formula (10), Ar ³¹ and Ar ³² are each independently a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms or a heterocyclic group having 5 to 50 ring atoms.
R ^{81 to} R ⁸⁸ each independently represents a hydrogen atom, a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms, a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms, substituted or unsubstituted A substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 50 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 50 carbon atoms, a substituted or unsubstituted ring carbon number of 6 to 6 50 aryloxy groups, substituted or unsubstituted arylthio groups having 6 to 50 ring carbon atoms, substituted or unsubstituted alkoxycarbonyl groups having 2 to 50 carbon atoms, substituted or unsubstituted silyl groups, carboxyl groups, halogen atoms , A cyano group, a nitro group or a hydroxyl group. )
The aryl group having 6 to 50 ring carbon atoms is preferably an aryl group having 6 to 40 ring carbon atoms, and more preferably an aryl group having 6 to 30 ring carbon atoms.
The heterocyclic group having 5 to 50 ring atoms is preferably a heterocyclic group having 5 to 40 ring atoms, and more preferably a heterocyclic group having 5 to 30 ring atoms.
As said C1-C50 alkyl group, a C1-C30 alkyl group is preferable, a C1-C10 alkyl group is more preferable, and a C1-C5 alkyl group is further more preferable.
As said C1-C50 alkoxy group, a C1-C30 alkoxy group is preferable, A C1-C10 alkoxy group is more preferable, A C1-C5 alkoxy group is more preferable.
The aralkyl group having 7 to 50 carbon atoms is preferably an aralkyl group having 7 to 30 carbon atoms, and more preferably an aralkyl group having 7 to 20 carbon atoms.
The aryloxy group having 6 to 50 ring carbon atoms is preferably an aryloxy group having 6 to 40 ring carbon atoms, and more preferably an aryloxy group having 6 to 30 ring carbon atoms.
The arylthio group having 6 to 50 ring carbon atoms is preferably an arylthio group having 6 to 40 ring carbon atoms, and more preferably an arylthio group having 6 to 30 ring carbon atoms.
The alkoxycarbonyl group having 2 to 50 carbon atoms is preferably an alkoxycarbonyl group having 2 to 30 carbon atoms, more preferably an alkoxycarbonyl group having 2 to 10 carbon atoms, and further preferably an alkoxycarbonyl group having 2 to 5 carbon atoms. .
Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.
In particular, Ar ³¹ and Ar ³² are preferably a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms.
Moreover, as an anthracene derivative represented by Formula (10), the anthracene derivative represented by following formula (10-1) is preferable.

(In the above formula (10-1), Ar ³³ is a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms or a heterocyclic group having 5 to 50 ring atoms. R ^{81 to} R ⁸⁸ are R ⁸⁹ is the same as defined for R ^{81 to} R ^88. a is an integer of 1 to 7.)
R ^{81 to} R ⁸⁸ are preferably the same as described above. Also it preferred for R ⁸⁹ is also the same as R ⁸¹ to R ^88. a is preferably an integer of 1 to 3, and more preferably 1 or 2.
The aryl group having 6 to 50 ring carbon atoms represented by Ar ³³ is preferably an aryl group having 6 to 40 ring carbon atoms, more preferably an aryl group having 6 to 30 ring carbon atoms, and 6 to 6 ring forming carbon atoms. 20 aryl groups are more preferable, and aryl groups having 6 to 12 ring carbon atoms are particularly preferable.

The arylamine derivative as the fluorescent light-emitting material is preferably an aryldiamine derivative, more preferably an aryldiamine derivative containing a pyrene skeleton, and further preferably an aryldiamine derivative containing a pyrene skeleton and a dibenzofuran skeleton.
More specifically, the aryldiamine derivative is preferably an aryldiamine derivative represented by the following formula (11).

(In the formula (11), Ar ^{34 to} Ar ³⁷ are each independently a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms or a substituted or unsubstituted heteroaryl group having 5 to 50 ring atoms. Represents.
L ²¹ represents a substituted or unsubstituted arylene group having 6 to 50 ring carbon atoms or a substituted or unsubstituted heteroarylene group having 5 to 50 ring atoms. )
The aryl group having 6 to 50 ring carbon atoms is preferably an aryl group having 6 to 30 ring carbon atoms, more preferably an aryl group having 6 to 20 ring carbon atoms, and an aryl group having 6 to 12 ring carbon atoms. A group is more preferable, and a phenyl group and a naphthyl group are particularly preferable.
The heteroaryl group having 5 to 50 ring atoms is preferably a heteroaryl group having 5 to 40 ring atoms, more preferably a heteroaryl group having 5 to 30 ring atoms, and 5 to 5 ring forming atoms. More preferred are 20 heteroaryl groups. Examples of the heteroaryl group include a carbazolyl group, a dibenzofuranyl group, a dibenzothiophenyl group, and the like, and a dibenzofuranyl group is preferable. Preferable substituents for the heteroaryl group include aryl groups having 6 to 30 ring carbon atoms (preferably 6 to 20, more preferably 6 to 12), and more preferably a phenyl group and a naphthyl group.
The arylene group having 6 to 50 ring carbon atoms is preferably an arylene group having 6 to 40 ring carbon atoms, more preferably an arylene group having 6 to 30 ring carbon atoms, and an arylene group having 6 to 20 ring carbon atoms. The group is more preferable, and the pyrenyl group is particularly preferable.

The light emitting layer may be a double host (also referred to as a host / cohost). Specifically, the carrier balance in the light emitting layer may be adjusted by combining an electron transporting host and a hole transporting host in the light emitting layer.
Moreover, it is good also as a double dopant. In the light emitting layer, each dopant emits light by adding two or more dopant materials having a high quantum yield. For example, a yellow light emitting layer may be realized by co-evaporating a host, a red dopant, and a green dopant.

Moreover, a light emitting layer may contain a hole transport material, an electron transport material, and a polymer binder as needed.
Furthermore, the thickness of the light emitting layer is preferably 5 to 50 nm, more preferably 7 to 50 nm, and most preferably 10 to 50 nm. If the thickness is less than 5 nm, it is difficult to form a light emitting layer, and it may be difficult to adjust the chromaticity. If the thickness exceeds 50 nm, the driving voltage may increase.

Electron-donating dopant The organic EL device of the present invention preferably has an electron-donating dopant in the interface region between the cathode and the light emitting unit. According to such a configuration, it is possible to improve the light emission luminance and extend the life of the organic EL element. Here, the electron donating dopant means a material containing a metal having a work function of 3.8 eV or less, and specific examples thereof include alkali metals, alkali metal complexes, alkali metal compounds, alkaline earth metals, alkaline earths. Examples thereof include at least one selected from metal complexes, alkaline earth metal compounds, rare earth metals, rare earth metal complexes, rare earth metal compounds, and the like.

  Examples of the alkali metal include Na (work function: 2.36 eV), K (work function: 2.28 eV), Rb (work function: 2.16 eV), Cs (work function: 1.95 eV), and the like. A function of 2.9 eV or less is particularly preferable. Of these, K, Rb, and Cs are preferred, Rb and Cs are more preferred, and Cs is most preferred. Examples of the alkaline earth metal include Ca (work function: 2.9 eV), Sr (work function: 2.0 eV to 2.5 eV), Ba (work function: 2.52 eV), and the like. The thing below 9 eV is especially preferable. Examples of rare earth metals include Sc, Y, Ce, Tb, Yb, and the like, and those having a work function of 2.9 eV or less are particularly preferable.

Examples of the alkali metal compound include alkali oxides such as Li ₂ O, Cs ₂ O, and K ₂ O, and alkali halides such as LiF, NaF, CsF, and KF, and LiF, Li ₂ O, and NaF are preferable. Examples of the alkaline earth metal compound include BaO, SrO, CaO, and Ba _x Sr _1-x O (0 <x <1), Ba _x Ca _1-x O (0 <x <1) mixed with these. BaO, SrO, and CaO are preferable. The rare earth metal _{compound, YbF 3, ScF 3, ScO} 3, Y 2 O 3, Ce 2 O 3, GdF 3, TbF 3 and the _{like, YbF 3, ScF 3, TbF} 3 are preferable.

  The alkali metal complex, alkaline earth metal complex, and rare earth metal complex are not particularly limited as long as each metal ion contains at least one of an alkali metal ion, an alkaline earth metal ion, and a rare earth metal ion. The ligands include quinolinol, benzoquinolinol, acridinol, phenanthridinol, hydroxyphenyl oxazole, hydroxyphenyl thiazole, hydroxydiaryl thiadiazole, hydroxydiaryl thiadiazole, hydroxyphenylpyridine, hydroxyphenylbenzimidazole, hydroxybenzotriazole, Hydroxyfulborane, bipyridyl, phenanthroline, phthalocyanine, porphyrin, cyclopentadiene, β-diketones, azomethines, and derivatives thereof are preferred, but not limited thereto.

  As an addition form of the electron donating dopant, it is preferable to form a layered or island shape in the interface region. As a forming method, while depositing an electron donating dopant by resistance heating vapor deposition, an organic compound (light emitting material or electron injecting material) that forms an interface region is simultaneously deposited, and the electron donating dopant is dispersed in the organic compound. Is preferred. The dispersion concentration is organic compound: electron-donating dopant = 100: 1 to 1: 100, preferably 5: 1 to 1: 5 in molar ratio.

In the case where the electron donating dopant is formed in a layered form, after forming the light emitting material or the electron injecting material, which is an organic layer at the interface, in a layered form, the reducing dopant is vapor-deposited by a resistance heating vapor deposition method. .1 nm to 15 nm. When the electron donating dopant is formed in an island shape, after forming the light emitting material and the electron injecting material, which are organic layers at the interface, in an island shape, the electron donating dopant is deposited by resistance heating vapor deposition alone, preferably The island is formed with a thickness of 0.05 nm to 1 nm.
In the organic EL device of the present invention, the ratio of the main component to the electron donating dopant is preferably in the molar ratio of main component: electron donating dopant = 5: 1 to 1: 5, and 2: 1 to 1: 2. More preferably.

Electron Transport Layer The electron transport layer is an organic layer formed between the light emitting layer and the cathode, and has a function of transporting electrons from the cathode to the light emitting layer. When the electron transport layer is composed of a plurality of layers, an organic layer close to the cathode may be referred to as an electron injection layer. The electron injection layer has a function of efficiently injecting electrons from the cathode into the organic layer unit. The nitrogen-containing aromatic heterocyclic derivative of the present invention can also be used as an electron transport material contained in the electron transport layer. When the electron transport layer is composed of one layer or a plurality of layers, the electron transport layer adjacent to the light emitting layer may be referred to as a hole blocking layer. The nitrogen-containing aromatic heterocyclic derivative of the present invention can also be used as a hole blocking material contained in the hole blocking layer.

As the electron transporting material used for the electron transporting layer, an aromatic heterocyclic compound containing one or more heteroatoms in the molecule is preferably used, and a nitrogen-containing ring derivative is particularly preferable. The nitrogen-containing ring derivative is preferably an aromatic ring having a nitrogen-containing 6-membered ring or 5-membered ring skeleton, or a condensed aromatic ring compound having a nitrogen-containing 6-membered ring or 5-membered ring skeleton.
As this nitrogen-containing ring derivative, for example, a nitrogen-containing ring metal chelate complex represented by the following formula (A) is preferable.

R ^{2 to} R ⁷ in formula (A) are each independently a hydrogen atom, a deuterium atom, a halogen atom, a hydroxyl group, an amino group, a hydrocarbon group having 1 to 40 carbon atoms, or an alkoxy group having 1 to 40 carbon atoms. , An aryloxy group having 6 to 50 carbon atoms, an alkoxycarbonyl group, or an aromatic heterocyclic group having 5 to 50 ring carbon atoms, which may be substituted.

Examples of the halogen atom include fluorine, chlorine, bromine, iodine and the like.
Examples of the amino group which may be substituted include an alkylamino group, an arylamino group and an aralkylamino group.
The alkylamino group and the aralkylamino group are represented as —NQ ¹ Q ² . Q ¹ and Q ² each independently represents an alkyl group having 1 to 20 carbon atoms or an aralkyl group having 1 to 20 carbon atoms. One of Q ¹ and Q ² may be a hydrogen atom or a deuterium atom.
The arylamino group is represented as —NAr ¹ Ar ^2, and Ar ¹ and Ar ² each independently represent a non-condensed aromatic hydrocarbon group or a condensed aromatic hydrocarbon group having 6 to 50 carbon atoms. One of Ar ¹ and Ar ² may be a hydrogen atom or a deuterium atom.

The hydrocarbon group having 1 to 40 carbon atoms includes an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, and an aralkyl group.
The alkoxycarbonyl group is represented as —COOY ′, and Y ′ represents an alkyl group having 1 to 20 carbon atoms.
M is aluminum (Al), gallium (Ga) or indium (In), and is preferably In.
L is a group represented by the following formula (A ′) or (A ″).

In formula (A ′), R ^{8 to} R ¹² are each independently a hydrogen atom, a deuterium atom, or a substituted or unsubstituted hydrocarbon group having 1 to 40 carbon atoms, and groups adjacent to each other are cyclic structures May be formed. In the formula (A ″), R ^{13 to} R ²⁷ are each independently a hydrogen atom, a deuterium atom, or a substituted or unsubstituted hydrocarbon group having 1 to 40 carbon atoms, and groups adjacent to each other are An annular structure may be formed.

The hydrocarbon group having 1 to 40 carbon atoms represented by R ^{8 to} R ¹² and R ^{13 to} R ^{27 in the} formula (A ′) and the formula (A ″) is represented by R ^{2 to} R ⁷ in the formula (A). The divalent groups in the case where the adjacent groups of R ^{8 to} R ¹² and R ^{13 to} R ²⁷ form a cyclic structure include tetramethylene, pentamethylene, hexa Examples include methylene group, diphenylmethane-2,2′-diyl group, diphenylethane-3,3′-diyl group, diphenylpropane-4,4′-diyl group and the like.

As the electron transport compound used for the electron transport layer, 8-hydroxyquinoline or a metal complex of its derivative, an oxadiazole derivative, and a nitrogen-containing heterocyclic derivative are preferable. As a specific example of the metal complex of 8-hydroxyquinoline or a derivative thereof, a metal chelate oxinoid compound containing a chelate of oxine (generally 8-quinolinol or 8-hydroxyquinoline), for example, tris (8-quinolinol) aluminum is used. Can do. And as an oxadiazole derivative, the following can be mentioned.

In the above formula, Ar ¹⁷ , Ar ¹⁸ , Ar ¹⁹ , Ar ²¹ , Ar ²² and Ar ²⁵ each represent a substituted or unsubstituted aromatic hydrocarbon group or condensed aromatic hydrocarbon group having 6 to 50 carbon atoms, Ar ¹⁷ and Ar ¹⁸ , Ar ¹⁹ and Ar ²¹ , Ar ²² and Ar ²⁵ may be the same or different. Examples of the aromatic hydrocarbon group or the condensed aromatic hydrocarbon group include a phenyl group, a naphthyl group, a biphenyl group, an anthranyl group, a perylenyl group, and a pyrenyl group. Examples of these substituents include an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and a cyano group.

Ar ²⁰ , Ar ^23, and Ar ²⁴ each represent a substituted or unsubstituted divalent aromatic hydrocarbon group or condensed aromatic hydrocarbon group having 6 to 50 carbon atoms, and Ar ²³ and Ar ²⁴ are identical to each other. But it can be different. Examples of the divalent aromatic hydrocarbon group or condensed aromatic hydrocarbon group include a phenylene group, a naphthylene group, a biphenylene group, an anthranylene group, a peryleneylene group, and a pyrenylene group. Examples of these substituents include an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and a cyano group.

As these electron transfer compounds, those having good thin film forming properties are preferably used. Specific examples of these electron transfer compounds include the following.

The nitrogen-containing heterocyclic derivative as the electron transfer compound is a nitrogen-containing heterocyclic derivative composed of an organic compound having the following formula, and includes a nitrogen-containing compound that is not a metal complex. Examples thereof include a 5-membered ring or 6-membered ring containing a skeleton represented by the following formula (B) and a structure represented by the following formula (C).

In the formula (C), X represents a carbon atom or a nitrogen atom. Z ₁ and Z ₂ each independently represents an atomic group capable of forming a nitrogen-containing heterocycle.

The nitrogen-containing heterocyclic derivative is more preferably an organic compound having a nitrogen-containing aromatic polycyclic group consisting of a 5-membered ring or a 6-membered ring. Further, in the case of such a nitrogen-containing aromatic polycyclic group having a plurality of nitrogen atoms, the nitrogen-containing compound having a skeleton obtained by combining the above formulas (B) and (C) or the above formula (B) and the following formula (D) Aromatic polycyclic organic compounds are preferred.

The nitrogen-containing group of the nitrogen-containing aromatic polycyclic organic compound is selected from, for example, nitrogen-containing heterocyclic groups represented by the following formulae.

  In each of the above formulas, R is an aromatic hydrocarbon group or condensed aromatic hydrocarbon group having 6 to 40 carbon atoms, an aromatic heterocyclic group or condensed aromatic heterocyclic group having 3 to 40 carbon atoms, or 1 to 1 carbon atoms. 20 is an alkyl group or an alkoxy group having 1 to 20 carbon atoms, n is an integer of 0 to 5, and when n is an integer of 2 or more, a plurality of R may be the same or different from each other.

Furthermore, preferred specific compounds include nitrogen-containing heterocyclic derivatives represented by the following formula (D1).
^{HAr-L 1 -Ar 1 -Ar 2} (D1)
In the formula (D1), HAr is a substituted or unsubstituted nitrogen-containing heterocyclic group having 3 to 40 carbon atoms, and L ¹ is a single bond, a substituted or unsubstituted aromatic hydrocarbon having 6 to 40 carbon atoms. A group, a condensed aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group having 3 to 40 carbon atoms or a condensed aromatic heterocyclic group, and Ar ¹ is a substituted or unsubstituted 2 to 6 carbon atom having 2 to 6 carbon atoms. And Ar ² is a substituted or unsubstituted aromatic hydrocarbon group having 6 to 40 carbon atoms, a condensed aromatic hydrocarbon group, or a substituted or unsubstituted aromatic group having 3 to 40 carbon atoms. It is a heterocyclic group or a condensed aromatic heterocyclic group.

HAr is selected from the following group, for example.

L ¹ is selected from the following group, for example.

Ar ¹ is selected from, for example, arylanthranyl groups of the following formulas (D2) and (D3).

In formula (D2) and formula (D3), R ^{1 to} R ¹⁴ are each independently a hydrogen atom, a deuterium atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkoxy having 1 to 20 carbon atoms. Group, an aryloxy group having 6 to 40 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group or condensed aromatic hydrocarbon group having 6 to 40 carbon atoms, or a substituted or unsubstituted aromatic group having 3 to 40 carbon atoms A heterocyclic group or a condensed aromatic heterocyclic group, Ar ³ is a substituted or unsubstituted aromatic hydrocarbon group having 6 to 40 carbon atoms, a condensed aromatic hydrocarbon group, or a substituted or unsubstituted carbon number of 3 to 3; 40 aromatic heterocyclic groups or condensed aromatic heterocyclic groups. Further, R ^{1 to} R ⁸ may be nitrogen-containing heterocyclic derivatives each of which is a hydrogen atom or a deuterium atom.

Ar ² is selected from the following group, for example.

In addition to these, the following compounds are also preferably used as the nitrogen-containing aromatic polycyclic organic compound as the electron transfer compound.

In formula (D4), R _{1 to} R ₄ each independently represent a hydrogen atom, a deuterium atom, a substituted or unsubstituted aliphatic group having 1 to 20 carbon atoms, a substituted or unsubstituted carbon number of 3 to 20 An aliphatic cyclic group, a substituted or unsubstituted aromatic ring group having 6 to 50 carbon atoms, a substituted or unsubstituted heterocyclic group having 3 to 50 carbon atoms, and X ₁ and X ₂ are each independently Represents an oxygen atom, a sulfur atom, or a dicyanomethylene group.

In addition, the following compounds are also preferably used as the electron transfer compound.

In the formula (D5), R ¹ , R ² , R ³ and R ⁴ are the same or different groups, and are an aromatic hydrocarbon group or a condensed aromatic hydrocarbon group represented by the following formula (D6) It is.

In the formula (D6), R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are the same or different from each other, and are a hydrogen atom, a deuterium atom, a saturated or unsaturated alkoxy group having 1 to 20 carbon atoms. Group, a saturated or unsaturated alkyl group having 1 to 20 carbon atoms, an amino group, or an alkylamino group having 1 to 20 carbon atoms. At least one of R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ is a group other than a hydrogen atom or a deuterium atom.

  Further, the electron transport compound may be a polymer compound containing the nitrogen-containing heterocyclic group or the nitrogen-containing heterocyclic derivative.

The electron transport layer of the organic EL device of the present invention particularly preferably contains at least one nitrogen-containing heterocyclic derivative represented by the following formulas (E) to (G).

(In Formula (E) to Formula (G), Z ¹ , Z ² and Z ³ are each independently a nitrogen atom or a carbon atom.
R ¹ and R ² are each independently a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms, a substituted or unsubstituted heteroaryl group having 5 to 50 ring atoms, substituted or unsubstituted carbon They are a C1-C20 alkyl group, a substituted or unsubstituted C1-C20 haloalkyl group, or a substituted or unsubstituted C1-C20 alkoxy group.
n is an integer of 0 to 5, and when n is an integer of 2 or more, the plurality of R ¹ may be the same or different from each other. Further, two adjacent R ^{1 's} may be bonded to each other to form a substituted or unsubstituted hydrocarbon ring.
Ar ¹ is a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms or a substituted or unsubstituted heteroaryl group having 5 to 50 ring atoms.
Ar ² is a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted haloalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, substituted Alternatively, it is an unsubstituted aryl group having 6 to 50 ring carbon atoms or a substituted or unsubstituted heteroaryl group having 5 to 50 ring atoms.
However, either Ar ¹ or Ar ² is a substituted or unsubstituted condensed aromatic hydrocarbon ring group having 10 to 50 ring carbon atoms or a substituted or unsubstituted condensed aromatic group having 9 to 50 ring atoms. It is a heterocyclic group.
Ar ³ is a substituted or unsubstituted arylene group having 6 to 50 ring carbon atoms or a substituted or unsubstituted heteroarylene group having 5 to 50 ring atoms.
L ¹ , L ^2, and L ³ are each independently a single bond, a substituted or unsubstituted arylene group having 6 to 50 ring carbon atoms, or a substituted or unsubstituted divalent ring having 9 to 50 ring atoms. A condensed aromatic heterocyclic group. )

Examples of the aryl group having 6 to 50 ring carbon atoms include phenyl, naphthyl, anthryl, phenanthryl, naphthacenyl, chrysenyl, pyrenyl, biphenyl, terphenyl, tolyl, fluoranthenyl, fluorenyl Group and the like.
Examples of heteroaryl groups having 5 to 50 ring atoms include pyrrolyl, furyl, thienyl, silolyl, pyridyl, quinolyl, isoquinolyl, benzofuryl, imidazolyl, pyrimidyl, carbazolyl, selenophenyl Group, oxadiazolyl group, triazolyl group, pyrazinyl group, pyridazinyl group, triazinyl group, quinoxalinyl group, acridinyl group, imidazo [1,2-a] pyridinyl group, imidazo [1,2-a] pyrimidinyl group and the like.
Examples of the alkyl group having 1 to 20 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group.
Examples of the haloalkyl group having 1 to 20 carbon atoms include groups obtained by substituting one or more hydrogen atoms of the alkyl group with at least one halogen atom selected from fluorine, chlorine, iodine and bromine.
Examples of the alkoxy group having 1 to 20 carbon atoms include groups having the alkyl group as an alkyl moiety.
Examples of the arylene group having 6 to 50 ring carbon atoms include a group obtained by removing one hydrogen atom from the aryl group.
Examples of the divalent condensed aromatic heterocyclic group having 9 to 50 ring atoms include groups obtained by removing one hydrogen atom from the condensed aromatic heterocyclic group described as the heteroaryl group.

Although the film thickness of an electron carrying layer is not specifically limited, Preferably it is 1 nm-100 nm.
Moreover, it is preferable to use an insulator or a semiconductor as an inorganic compound in addition to the nitrogen-containing ring derivative as a component of the electron injection layer that can be provided adjacent to the electron transport layer. If the electron injection layer is made of an insulator or a semiconductor, current leakage can be effectively prevented and the electron injection property can be improved.

As such an insulator, it is preferable to use at least one metal compound selected from the group consisting of alkali metal chalcogenides, alkaline earth metal chalcogenides, alkali metal halides and alkaline earth metal halides. If the electron injection layer is composed of these alkali metal chalcogenides or the like, it is preferable in that the electron injection property can be further improved. Specifically, preferable alkali metal chalcogenides include, for example, Li ₂ O, K ₂ O, Na ₂ S, Na ₂ Se, and Na ₂ O, and preferable alkaline earth metal chalcogenides include, for example, CaO, BaO. , SrO, BeO, BaS and CaSe. Further, preferable alkali metal halides include, for example, LiF, NaF, KF, LiCl, KCl, and NaCl. Examples of preferable alkaline earth metal halides include fluorides such as CaF ₂ , BaF ₂ , SrF ₂ , MgF ₂ and BeF ₂ , and halides other than fluorides.

  Further, as a semiconductor, an oxide, nitride, or oxynitride containing at least one element of Ba, Ca, Sr, Yb, Al, Ga, In, Li, Na, Cd, Mg, Si, Ta, Sb, and Zn. One kind alone or a combination of two or more kinds of products may be mentioned. In addition, the inorganic compound constituting the electron injection layer is preferably a microcrystalline or amorphous insulating thin film. If the electron injection layer is composed of these insulating thin films, a more uniform thin film is formed, and pixel defects such as dark spots can be reduced. Examples of such inorganic compounds include alkali metal chalcogenides, alkaline earth metal chalcogenides, alkali metal halides, and alkaline earth metal halides.

  When such an insulator or semiconductor is used, the preferred thickness of the layer is about 0.1 nm to 15 nm. Further, the electron injection layer in the present invention is preferable even if it contains the above-mentioned electron donating dopant.

Hole transport layer An organic layer formed between the light emitting layer and the anode, and has a function of transporting holes from the anode to the light emitting layer. When the hole transport layer is composed of a plurality of layers, an organic layer close to the anode may be defined as a hole injection layer. The hole injection layer has a function of efficiently injecting holes from the anode into the organic layer unit. The nitrogen-containing aromatic heterocyclic derivative of the present invention can also be used as a hole transport material contained in the hole transport layer.
As another material for forming the hole transport layer, an aromatic amine compound, for example, an aromatic amine derivative represented by the following formula (H) is preferably used.

In the formula (H), Ar ^{1 to} Ar ⁴ represent a substituted or unsubstituted aromatic hydrocarbon group having 6 to 50 ring carbon atoms or a condensed aromatic hydrocarbon group, a substituted or unsubstituted ring forming atom number of 5 to 5 50 aromatic heterocyclic groups or condensed aromatic heterocyclic groups, or a group in which these aromatic hydrocarbon groups or condensed aromatic hydrocarbon groups and aromatic heterocyclic groups or condensed aromatic heterocyclic groups are bonded.
In the formula (H), L represents a substituted or unsubstituted aromatic hydrocarbon group or condensed aromatic hydrocarbon group having 6 to 50 ring carbon atoms, or a substituted or unsubstituted ring atom number of 5 to 50. Represents an aromatic heterocyclic group or a condensed aromatic heterocyclic group.

Specific examples of the compound of formula (H) are shown below.

An aromatic amine represented by the following formula (J) is also preferably used for forming the hole transport layer.

In the formula (J), the definition of Ar ^{1 to} Ar ^{3 is the same as} the definition of Ar ^{1 to} Ar ^{4 in} the formula (H). Specific examples of the compound of formula (J) are shown below, but are not limited thereto.

The hole transport layer of the organic EL device of the present invention may have a two-layer structure of a first hole transport layer (anode side) and a second hole transport layer (cathode side).
Although the film thickness of a positive hole transport layer is not specifically limited, It is preferable that it is 10-200 nm.

In the organic EL device of the present invention, a layer containing an acceptor material may be bonded to the anode side of the hole transport layer or the first hole transport layer. This is expected to reduce drive voltage and manufacturing costs.
As the acceptor material, a compound represented by the following formula (K) is preferable.

(In the formula (K), R _{21 to} R ₂₆ may be the same as or different from each other, and each independently represents a cyano group, —CONH ₂ , a carboxyl group, or —COOR ₂₇ (R ₂₇ is a group having 1 to 20 carbon atoms). Represents an alkyl group or a cycloalkyl group having 3 to 20 carbon atoms, provided that one or more pairs of R ₂₁ and R ₂₂ , R ₂₃ and R ₂₄ , and R ₂₅ and R ₂₆ are combined. A group represented by -CO-O-CO- may be formed.)
Examples of R ₂₇ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, a cyclopentyl group, and a cyclohexyl group.
The thickness of the layer containing the acceptor material is not particularly limited, but is preferably 5 to 20 nm.

n / p doping In the above-described hole transport layer and electron transport layer, as described in Japanese Patent No. 3695714, by doping (n) of donor material and doping (p) of acceptor material, The carrier injection ability can be adjusted.
A typical example of n doping is a method of doping a metal such as Li or Cs into an electron transport material, and a typical example of p doping is F ₄ TCNQ (2, 3, 5, 6) as a hole transport material. -Tetrafluoro-7,7,8,8-tetracyanoquinodimethane) and the like.

Space layer The space layer is, for example, in the case of laminating a fluorescent light emitting layer and a phosphorescent light emitting layer, for the purpose of adjusting the carrier balance so as not to diffuse excitons generated in the phosphorescent light emitting layer into the fluorescent light emitting layer. This is a layer provided between the fluorescent light emitting layer and the phosphorescent light emitting layer. In addition, the space layer can be provided between the plurality of phosphorescent light emitting layers.
Since the space layer is provided between the light emitting layers, a material having both electron transport properties and hole transport properties is preferable. In order to prevent diffusion of triplet energy in the adjacent phosphorescent light emitting layer, the triplet energy is preferably 2.6 eV or more. Examples of the material used for the space layer include the same materials as those used for the above-described hole transport layer. As a material for the space layer, the nitrogen-containing aromatic heterocyclic derivative of the present invention can also be used.

Blocking Layer The organic EL device of the present invention preferably has a blocking layer such as an electron blocking layer, a hole blocking layer, or a triplet blocking layer in a portion adjacent to the light emitting layer. Here, the electron blocking layer is a layer that prevents electrons from leaking from the light emitting layer to the hole transport layer, and the hole blocking layer is a layer that prevents holes from leaking from the light emitting layer to the electron transport layer. is there. As the material for the hole blocking layer, the nitrogen-containing aromatic heterocyclic derivative of the present invention can also be used.
The triplet blocking layer prevents the triplet excitons generated in the light emitting layer from diffusing into the surrounding layers, and confins the triplet excitons in the light emitting layer, thereby transporting electrons other than the light emitting dopant of the triplet excitons. It has a function of suppressing energy deactivation on the molecules of the layer.
In the case where a triplet blocking layer is provided, in the phosphorescent device, when the triplet energy of the phosphorescent dopant in the light emitting layer is E ^T _d and the triplet energy of the compound used as the triplet blocking layer is E ^T _TB , E ^T _d < If the energy level relationship of E ^T _TB is satisfied, the triplet exciton of the phosphorescent dopant is confined (cannot move to other molecules) due to the energy relationship, and the energy deactivation path other than light emission on the dopant is interrupted. It is assumed that light can be emitted with high efficiency. However, even if the relationship of E ^T _d <E ^T _TB is satisfied, if this energy difference ΔE ^T = E ^T _TB −E ^T _d is small, under the environment of room temperature, which is the actual element driving environment, , endothermically triplet excitons overcame this energy difference Delta] E ^T by thermal energy near is considered to be possible to move to another molecule. In particular, in the case of phosphorescence emission, the exciton lifetime is longer than that of fluorescence emission, so that the influence of the endothermic exciton transfer process is likely to appear. The energy difference ΔE ^T is preferably as large as possible relative to the thermal energy at room temperature, more preferably 0.1 eV or more, and particularly preferably 0.2 eV or more. On the other hand, in a fluorescent element, the nitrogen-containing aromatic heterocyclic derivative of the present invention can be used as a material for a triplet blocking layer having a TTF element configuration described in International Publication WO2010 / 134350A1.

In addition, the electron mobility of the material constituting the triplet blocking layer is desirably 10 ⁻⁶ cm ² / Vs or more in the range of electric field strength of 0.04 to 0.5 MV / cm. As a method for measuring the electron mobility of an organic material, several methods such as the Time of Flight method are known. Here, the electron mobility is determined by impedance spectroscopy.
The electron injection layer is desirably 10 ⁻⁶ cm ² / Vs or more in the range of electric field strength of 0.04 to 0.5 MV / cm. This is because electron injection from the cathode to the electron transport layer is promoted, and further, electron injection to the adjacent blocking layer and light emitting layer is also promoted, thereby enabling driving at a lower voltage.

  The organic EL element containing the nitrogen-containing aromatic heterocyclic derivative is suitably used for various electronic devices. For example, displays of personal computers, monitors, televisions, mobile phones, etc .; clocks, thermometer time and temperature indications; audio equipment, dashboard operating status indications; liquid crystal displays, clocks, audio equipment, dashboards, etc. backlights; It is used as a light source for optical storage media, electrophotographic copying machines, etc .; lighting devices used for home lighting, interior lighting, lighting up of products and exhibits, and the like.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.

アルゴン雰囲気下、４’−ブロモアセトフェノン１０ｇ（５０ｍｍｏｌ）、カルバゾール８．４ｇ（５０ｍｍｏｌ）、酢酸パラジウム１１０ｍｇ（０．５ｍｍｏｌ）、トリ−ｔ−ブチルホスホニウムテトラフルオロほう酸塩４４０ｍｇ（１．５ｍｍｏｌ）、炭酸カリウム２１ｇ（１５２ｍｍｏｌ）にキシレン３００ｍｌを混合し、約１２０℃で７時間加熱・還流した。水、ジクロロメタンを加え、不溶分を除去後、ジクロロメタン抽出、水洗を行った。硫酸ナトリウムで乾燥後、溶媒を除去し、酢酸エチル−ｎ−ヘキサンから再結晶を行うことで、中間体Ａ１を白色固体として得た。９．６ｇ（収率６７％） Synthesis of intermediate A1

Under an argon atmosphere, 4'-bromoacetophenone 10 g (50 mmol), carbazole 8.4 g (50 mmol), palladium acetate 110 mg (0.5 mmol), tri-t-butylphosphonium tetrafluoroborate 440 mg (1.5 mmol), potassium carbonate 21 g (152 mmol) was mixed with 300 ml of xylene and heated and refluxed at about 120 ° C. for 7 hours. Water and dichloromethane were added to remove insolubles, followed by extraction with dichloromethane and washing with water. After drying with sodium sulfate, the solvent was removed, and recrystallization from ethyl acetate-n-hexane gave Intermediate A1 as a white solid. 9.6 g (67% yield)

Synthesis of Intermediates B1 to B4 Intermediates B1 to B4 were synthesized by the method described in WO2005 / 9967 (JANSSEN PHARMACEUTICA, NV) and Tetrahedron Letters, 2007, vol. 48, p. 4707-4710.

アルゴン雰囲気下、１０．０ｇの中間体Ｂ１、４’−ブロモアセトフェノン１１．０ｇに水酸化カリウムエタノール溶液（水酸化カリウム８．５ｇをエタノール１００ｍＬに溶解）を加え、約９０℃で２２時間加熱撹拌した。反応終了後、塩化アンモニウム水溶液を加え、ジクロロメタン抽出、水洗を行った。硫酸ナトリウムで乾燥後、溶媒を減圧溜去した。シリカゲルカラムクロマトグラフィにて、未反応の原料を除去し、さらに酢酸エチルで、結晶化・洗浄を行うことで、中間体Ｃ１を白色固体として得た。１６．６ｇ（収率９１％） Synthesis of intermediate C1

Under argon atmosphere, potassium hydroxide ethanol solution (8.5 g of potassium hydroxide dissolved in 100 mL of ethanol) was added to 10.0 g of intermediate B1, 4′-bromoacetophenone 11.0 g, and the mixture was heated and stirred at about 90 ° C. for 22 hours. did. After completion of the reaction, an aqueous ammonium chloride solution was added, followed by extraction with dichloromethane and washing with water. After drying with sodium sulfate, the solvent was distilled off under reduced pressure. The unreacted raw material was removed by silica gel column chromatography, and further, crystallization and washing were performed with ethyl acetate to obtain Intermediate C1 as a white solid. 16.6 g (91% yield)

中間体Ｃ１の合成において、４’−ブロモアセトフェノンの代わりに３’−ブロモアセトフェノンを用いた以外は同様の操作を行うことにより、中間体Ｃ２を白色固体として得た。６．４ｇ（収率７１％）。 Synthesis of intermediate C2

Intermediate C2 was obtained as a white solid by performing the same operation as in the synthesis of intermediate C1, except that 3′-bromoacetophenone was used instead of 4′-bromoacetophenone. 6.4 g (71% yield).

中間体Ｃ１の合成において、中間体Ｂ１の代わりに中間体Ｂ３を、４’−ブロモアセトフェノンの代わりにアセトフェノンを用いた以外は同様の操作を行うことにより、中間体Ｃ３を白色固体として得た。９．８ｇ（収率７５％）。 Synthesis of intermediate C3

In the synthesis of Intermediate C1, Intermediate C3 was obtained as a white solid by performing the same operation except that Intermediate B3 was used instead of Intermediate B1 and acetophenone was used instead of 4′-bromoacetophenone. 9.8 g (75% yield).

中間体Ｃ１の合成において、中間体Ｂ１の代わりに中間体Ｂ４を、４’−ブロモアセトフェノンの代わりにアセトフェノンを用いた以外は同様の操作を行うことにより、中間体Ｃ４を白色固体として得た。１０．５ｇ（収率８２％）。 Synthesis of intermediate C4

In the synthesis of Intermediate C1, Intermediate C4 was obtained as a white solid by performing the same operation except that Intermediate B4 was used instead of Intermediate B1 and acetophenone was used instead of 4′-bromoacetophenone. 10.5 g (82% yield).

中間体Ｃ１の合成において、中間体Ｂ１の代わりに中間体Ｂ３を用いた以外は同様の操作を行うことにより、中間体Ｃ５を白色固体として得た。７．４ｇ（収率９４％）。 Synthesis of intermediate C5

In the synthesis of intermediate C1, intermediate C5 was obtained as a white solid by performing the same operation except that intermediate B3 was used instead of intermediate B1. 7.4 g (94% yield).

中間体Ｃ１の合成において、中間体Ｂ１の代わりに中間体Ｂ４を、４’−ブロモアセトフェノンの代わりに３’−ブロモアセトフェノンを用いた以外は同様の操作を行うことにより、中間体Ｃ６を白色固体として得た。６．４ｇ（収率８３％）。 Synthesis of intermediate C6

In the synthesis of Intermediate C1, Intermediate C6 was converted into a white solid by performing the same operation except that Intermediate B4 was used instead of Intermediate B1 and 3′-bromoacetophenone was used instead of 4′-bromoacetophenone. Got as. 6.4 g (83% yield).

アルゴン雰囲気下、１．５ｇ（７．６ｍｍｏｌ）の中間体Ｂ１、２．２ｇ（７．７ｍｍｏｌ）の中間体Ａ１に水酸化カリウムエタノール溶液（水酸化カリウム１．３ｇをエタノール２０ｍＬに溶解）を加え、約９０℃で１５時間加熱撹拌した。反応終了後、塩化アンモニウム水溶液を加え、ジクロロメタン抽出、水洗を行った。硫酸ナトリウムで乾燥後、溶媒を減圧溜去し、シリカゲルカラムクロマトグラフィにて、未反応の原料を除去し、さらに酢酸エチルで、結晶化・洗浄を行うことで、白色固体を得た。ＦＤ−ＭＳ（フィールドディソープションマススペクトル）の測定により、得られた化合物を化合物１と同定した。１．７ｇ（収率５１％）。 Synthesis Example 1: Compound 1

Under an argon atmosphere, 1.5 g (7.6 mmol) of intermediate B1 and 2.2 g (7.7 mmol) of intermediate A1 were added potassium hydroxide ethanol solution (1.3 g of potassium hydroxide dissolved in 20 mL of ethanol). And stirred at about 90 ° C. for 15 hours. After completion of the reaction, an aqueous ammonium chloride solution was added, followed by extraction with dichloromethane and washing with water. After drying over sodium sulfate, the solvent was distilled off under reduced pressure, unreacted raw materials were removed by silica gel column chromatography, and crystallization and washing were further performed with ethyl acetate to obtain a white solid. The obtained compound was identified as Compound 1 by measurement of FD-MS (Field Desorption Mass Spectrum). 1.7 g (51% yield).

アルゴン雰囲気下、３．０ｇ（８．３ｍｍｏｌ）の中間体Ｃ１、カルバゾール１．５ｇ（９．０ｍｍｏｌ）、酢酸パラジウム２０ｍｇ（０．０９ｍｍｏｌ）、トリ−ｔ−ブチルホスホニウムテトラフルオロほう酸塩７５ｍｇ（０．２６ｍｍｏｌ）、炭酸カリウム３．５ｇ（２５ｍｍｏｌ）にキシレン４０ｍｌを混合し、約１４０℃で３１時間加熱・還流した。反応終了後、塩化アンモニウム水溶液を加え、ジクロロメタン抽出、水洗を行った。硫酸ナトリウムで乾燥後、溶媒を減圧溜去した。シリカゲルカラムクロマトグラフィにて、未反応の原料を除去し、さらに酢酸エチルで、結晶化・洗浄を行うことで、白色固体を得た。ＮＭＲの比較により、得られた化合物は合成例１で合成した化合物１と同一であることを確認した。２．９ｇ（収率７９％）。 Synthesis Example 2: Compound 1

Under an argon atmosphere, 3.0 g (8.3 mmol) of intermediate C1, 1.5 g (9.0 mmol) of carbazole, 20 mg (0.09 mmol) of palladium acetate, 75 mg of tri-t-butylphosphonium tetrafluoroborate (0. 26 mmol) and 3.5 g (25 mmol) of potassium carbonate were mixed with 40 ml of xylene and heated and refluxed at about 140 ° C. for 31 hours. After completion of the reaction, an aqueous ammonium chloride solution was added, followed by extraction with dichloromethane and washing with water. After drying with sodium sulfate, the solvent was distilled off under reduced pressure. Unreacted raw materials were removed by silica gel column chromatography, and crystallization and washing were further performed with ethyl acetate to obtain a white solid. NMR comparison confirmed that the obtained compound was the same as Compound 1 synthesized in Synthesis Example 1. 2.9 g (79% yield).

合成例２において、中間体Ｃ１の代わりに中間体Ｃ２を用いた以外は同様の操作を行うことにより、淡黄色固体を得た。ＦＤ−ＭＳの測定により、得られた化合物を化合物２と同定した。１．８ｇ（収率５０％）。 Synthesis Example 3: Compound 2

In Synthesis Example 2, a light yellow solid was obtained by performing the same operation except that Intermediate C2 was used instead of Intermediate C1. The compound obtained was identified as Compound 2 by FD-MS measurement. 1.8 g (yield 50%).

合成例２において、中間体Ｃ１の代わりに中間体Ｃ３を用いた以外は同様の操作を行うことにより、白色固体を得た。ＦＤ−ＭＳの測定により、得られた化合物を化合物３と同定した。３．３ｇ（収率８８％）。 Synthesis Example 4: Compound 3

A white solid was obtained in the same manner as in Synthesis Example 2 except that Intermediate C3 was used instead of Intermediate C1. The compound obtained was identified as Compound 3 by FD-MS measurement. 3.3 g (88% yield).

合成例２において、中間体Ｃ１の代わりに中間体Ｃ４を用いた以外は同様の操作を行うことにより、淡黄色固体を得た。ＦＤ−ＭＳの測定により、得られた化合物を化合物４と同定した。２．４ｇ（収率６６％）。 Synthesis Example 5: Compound 4

In Synthesis Example 2, a light yellow solid was obtained by performing the same operation except that Intermediate C4 was used instead of Intermediate C1. The compound obtained was identified as Compound 4 by FD-MS measurement. 2.4 g (66% yield).

アルゴン雰囲気下、３．０ｇ（６．８ｍｍｏｌ）の中間体Ｃ５、カルバゾール２．５ｇ（１５ｍｍｏｌ）、酢酸パラジウム３３ｍｇ（０．１５ｍｍｏｌ）、トリ−ｔ−ブチルホスホニウムテトラフルオロほう酸塩１２０ｍｇ（０．４１ｍｍｏｌ）、炭酸カリウム５．７ｇ（４１ｍｍｏｌ）にキシレン６０ｍｌを混合し、約１４０℃で３９時間加熱・還流した。反応終了後、塩化アンモニウム水溶液を加え、ジクロロメタン抽出、水洗を行った。硫酸ナトリウムで乾燥後、溶媒を減圧溜去した。シリカゲルカラムクロマトグラフィにて、未反応の原料を除去し、さらに酢酸エチルで、結晶化・洗浄を行うことで淡黄色固体を得た。ＦＤ−ＭＳの測定により、得られた化合物を化合物５と同定した。２．１ｇ（収率５１％）。 Synthesis Example 6: Compound 5

Under an argon atmosphere, 3.0 g (6.8 mmol) of intermediate C5, carbazole 2.5 g (15 mmol), palladium acetate 33 mg (0.15 mmol), tri-t-butylphosphonium tetrafluoroborate 120 mg (0.41 mmol) Then, 5.7 g (41 mmol) of potassium carbonate was mixed with 60 ml of xylene and heated and refluxed at about 140 ° C. for 39 hours. After completion of the reaction, an aqueous ammonium chloride solution was added, followed by extraction with dichloromethane and washing with water. After drying with sodium sulfate, the solvent was distilled off under reduced pressure. Unreacted raw materials were removed by silica gel column chromatography, and crystallization and washing were further performed with ethyl acetate to obtain a pale yellow solid. The obtained compound was identified as Compound 5 by FD-MS measurement. 2.1 g (51% yield).

合成例６において、中間体Ｃ５の代わりに中間体Ｃ６を用いた以外は同様の操作を行うことにより、淡黄色固体を得た。ＦＤ−ＭＳの測定により、得られた化合物を化合物６と同定した。４．０ｇ（収率９０％）。 Synthesis Example 7: Compound 6

A pale yellow solid was obtained in the same manner as in Synthesis Example 6 except that Intermediate C6 was used instead of Intermediate C5. The obtained compound was identified as Compound 6 by FD-MS measurement. 4.0 g (90% yield).

合成例２において、カルバゾールの代わりに３−（９Ｈ−２−カルバゾリル）−９−フェニルカルバゾールを用いた以外は同様の操作を行うことにより、淡黄色固体を得た。ＦＤ−ＭＳの測定により、得られた化合物を化合物７と同定した。３．０ｇ（収率９０％）。 Synthesis Example 8: Compound 7

A pale yellow solid was obtained in the same manner as in Synthesis Example 2 except that 3- (9H-2-carbazolyl) -9-phenylcarbazole was used instead of carbazole. The compound obtained was identified as Compound 7 by FD-MS measurement. 3.0 g (90% yield).

化合物１の合成例 （２） において、中間体Ｃ１の代わりに中間体Ｃ２を、カルバゾールの代わりに３−（９Ｈ−２−カルバゾリル）−９−フェニルカルバゾールを用いた以外は同様の操作を行うことにより、淡黄色固体を得た。ＦＤ−ＭＳの測定により、得られた化合物を化合物８と同定した。１．２ｇ（収率３５％）。 Synthesis Example 9: Compound 8

The same operation as in Synthesis Example (2) of Compound 1 except that Intermediate C2 was used instead of Intermediate C1 and 3- (9H-2-carbazolyl) -9-phenylcarbazole was used instead of carbazole Gave a pale yellow solid. The compound obtained was identified as Compound 8 by the FD-MS measurement. 1.2 g (35% yield).

Example 1
(1) Manufacture of organic EL element A glass substrate (manufactured by Geomatic Co., Ltd.) with an ITO transparent electrode (thickness 77 nm) of 25 mm × 75 mm × 1.1 mm was subjected to ultrasonic cleaning in isopropyl alcohol for 5 minutes, then UV Ozone cleaning was performed for 30 minutes.
The glass substrate with an ITO transparent electrode after washing was mounted on a substrate holder of a vacuum deposition apparatus, and the following compound (HI) was first deposited so as to cover the transparent electrode to form a 5 nm-thick hole injection layer.
Next, the following compound HT-1 was vapor-deposited on the hole injection layer to form a first hole transport layer having a film thickness of 65 nm.
Next, the following compound HT-2 was deposited on the first hole transport layer to form a second hole transport layer having a thickness of 10 nm.
Further, Compound 1 (host) and Ir (bzq) ₃ (phosphorescent material) were co-evaporated on the second hole transport layer to form a light emitting layer having a thickness of 25 nm. Ir (bzq) ₃ concentration was 10% by weight of the total amount of the host compound 1 and Ir (bzq) _3.
On the light emitting layer, the following compound ET was vapor-deposited to form an electron transport layer having a thickness of 35 nm.
Next, LiF was deposited on the electron transport layer at a film formation rate of 0.1 angstrom / min to form an electron injecting electrode (cathode) having a thickness of 1 nm.
Finally, metal Al was vapor-deposited on the electron injecting electrode to form a metal cathode having a thickness of 80 nm, and an organic EL element was produced.

(2) Measurement of luminous efficiency (current efficiency) The organic EL device produced as described above is made to emit light by direct current drive, and current is passed between the anode and the cathode so that the current density becomes 1.00 mA / cm ^2. Voltage (unit: V) was measured, the spectral radiance spectrum at that time was measured with a spectral radiance meter CS-1000 (manufactured by Konica Minolta Co., Ltd.), and the luminous efficiency (unit: : Cd / A was calculated and the results are shown in Table 1.

Comparative Example 1
An organic EL device was produced in the same manner as in Example 1 except that the following compound A was used instead of the compound 1.

Comparative Example 2
An organic EL device was produced in the same manner as in Example 1 except that the following compound B described in JP-A-2007-001878 was used instead of compound 1.

表１の結果より、本発明の含窒素芳香族複素環誘導体を用いた実施例１の有機ＥＬ素子は、比較例１及び比較例２と比較して、低駆動電圧で、且つ、良好な発光効率を示すことがわかる。

From the results in Table 1, the organic EL device of Example 1 using the nitrogen-containing aromatic heterocyclic derivative of the present invention has a low driving voltage and good light emission as compared with Comparative Example 1 and Comparative Example 2. It turns out that efficiency is shown.

DESCRIPTION OF SYMBOLS 1 Organic electroluminescent element 2 Substrate 3 Anode 4 Cathode 5 Light emitting layer 6 Hole injection layer / hole transport layer 7 Electron injection layer / electron transport layer 10 Light emitting unit

Claims (21)

A nitrogen-containing aromatic heterocyclic derivative represented by the following formula (1-1), (1-2) or (1-3).

(In the formula, any one of C _{1 to} C ₄ is a nitrogen atom, and any one of B _{1 to} B ₄ is a nitrogen atom, provided that B ₁ and C ₁ , B ₄ and C ₄ , B ₁ and C ₄ , and B ₄ and C ₁ are not nitrogen atoms at the same time ₁ to _{6 of} C _{1 to} C ₄ and B _{1 to} B ₄ that are not nitrogen atoms are bonded to ^* 1 Carbon atom.
n is 1-6. When n is 2 or more, each group may be the same or different.
Of C _{1 to} C ₄ and B _{1 to} B ₄ , those that are neither a carbon atom nor a nitrogen atom bonded to ^* 1 independently represent CR ^A. R ^A is a hydrogen atom, a substituted or unsubstituted linear or branched alkyl group having 1 to 15 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 15 ring carbon atoms, a substituted or unsubstituted group. It represents a silyl group, a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms, a substituted or unsubstituted heteroaryl group having 5 to 30 ring atoms, a halogen atom, or a cyano group.
L represents a single bond, a substituted or unsubstituted arylene group having 6 to 30 ring carbon atoms, or a substituted or unsubstituted heteroarylene group having 5 to 30 ring atoms.
A _{1 to} A ₈ each independently represent CR ^B or a nitrogen atom, and R ^B represents a hydrogen atom, a substituted or unsubstituted C 1-15 linear or branched alkyl group, substituted or unsubstituted. Substituted cycloalkyl group having 3 to 15 carbon atoms, substituted or unsubstituted silyl group, substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms, substituted or unsubstituted ring atoms having 5 to 30 ring atoms Represents a heteroaryl group, a halogen atom, or a cyano group. Two adjacent ^RBs may combine to form a substituted or unsubstituted saturated or unsaturated divalent group that forms part of the ring. )

(In the formula, any one of C _{1 to} C ₄ is a nitrogen atom, and any one of B _{1 to} B ₄ is a nitrogen atom, provided that B ₁ and C ₁ , B ₄ and C ₄ , B ₁ and C ₄ , and B ₄ and C ₁ are not nitrogen atoms at the same time, ₁ to _{6 of} C _{1 to} C ₄ and B _{1 to} B ₄ that are not nitrogen atoms are bonded to ^* 2. Carbon atom.
n is the same as described above, and when n is 2, each group may be the same or different.
Among C _{1 to} C ₄ and B _{1 to} B ₄ , those that are neither a carbon atom nor a nitrogen atom bonded to ^* 2 independently represent CR ^A. R ^A is the same as described above.
L is the same as described above.
Ra represents a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms or a substituted or unsubstituted heteroaryl group having 5 to 30 ring atoms.
One of A ₉ to A ₁₂ represents a carbon atom bonded to ^* 3, other A ₉ to A ₁₂ and A ₁₃ to A ₁₆ each independently represent a CR ^B or a nitrogen atom, R ^B is the same as described above. )

(In the formula, any one of C _{1 to} C ₄ is a nitrogen atom, and any one of B _{1 to} B ₄ is a nitrogen atom, provided that B ₁ and C ₁ , B ₄ and C ₄ , B ₁ and C ₄ , and B ₄ and C ₁ are not nitrogen atoms at the same time ₁ to _{6 of} C _{1 to} C ₄ and B _{1 to} B ₄ that are not nitrogen atoms are bonded to ^* 4 Carbon atom.
n is the same as described above, and when n is 2, each group may be the same or different.
Of C _{1 to} C ₄ and B _{1 to} B ₄ , those that are neither a carbon atom nor a nitrogen atom bonded to ^* 4 independently represent CR ^A. R ^A is the same as described above.
L is the same as described above.
X represents an oxygen atom, a sulfur atom, or SiRbRc, and Rb and Rc are each independently a substituted or unsubstituted linear or branched alkyl group having 1 to 15 carbon atoms, a substituted or unsubstituted ring-forming carbon. A cycloalkyl group having 3 to 15 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms, and a substituted or unsubstituted heteroaryl group having 5 to 30 ring atoms.
One of A ₁₇ to A ₂₀ represents a carbon atom bonded to ^* 5, other A ₁₇ to A ₂₀ and A ₂₁ to A ₂₄ each independently represent a CR ^B or a nitrogen atom, R ^B is the same as described above. ) The nitrogen-containing aromatic heterocycle according to claim 1, wherein the formula (1-1) is represented by the following formula (1-1a), (1-1b), (1-1c), or (1-1d). Derivative

(In the formulas (1-1a), (1-1b), (1-1c), and (1-1d), L, n, and A _{1 to} A ₈ are as defined in the formula (1-1). is there.
1 to ₆ of R _{2 to} R ₆ and R _{8 in} the formula (1-1a) are single bonds bonded to ^* 1.
1-6 of R < ₂ ^> -R < ₅ ^> , R < ₇ ^> and R < ₈ ^{> of} Formula (1-1b) are single bonds couple | bonded with ^* 1.
1-6 of R < ₁ >, R < ₃ > -R < ₆ > and R < ₈ > of Formula (1-1c) are single bonds couple | bonded with ^* 1.
1-6 _{R 1, R 3 ~R 5,} R 7 and R ₈ of formula (1-1d) is a single bond to bond to ^* 1.
In formulas (1-1a), (1-1b), (1-1c), and (1-1d), among R _{1 to} R ₈ , those that are not a single bond bonded to ^* 1 are independently A hydrogen atom, a substituted or unsubstituted linear or branched alkyl group having 1 to 15 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 15 ring carbon atoms, a substituted or unsubstituted silyl group, A substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms, a substituted or unsubstituted heteroaryl group having 5 to 30 ring atoms, a halogen atom, or a cyano group. ) The nitrogen-containing aromatic heterocycle according to claim 1, wherein the formula (1-2) is represented by the following formula (1-2a), (1-2b), (1-2c), or (1-2d). Derivative

(In the formulas (1-2a), (1-2b), (1-2c), and (1-2d), L, n, Ra, and A _{9 to} A ₁₆ are defined in the formula (1-2). It is as follows.
1-6 of R < ₂ > -R < ₆ > and R < ₈ > of Formula (1-2a) are single bonds couple | bonded with ^* 2.
1-6 of R < ₂ > -R < ₅ >, R < ₇ > and R < ₈ > of Formula (1-2b) are single bonds couple | bonded with ^* 2.
1-6 of R < ₁ >, R < ₃ > -R < ₆ > and R < ₈ > of Formula (1-2c) are single bonds couple | bonded with ^* 2.
₁ to 6 of R ₁ , R _{3 to} R ₅ , R ₇ and R _{8 in} the formula (1-2d) are single bonds bonded to ^* 2.
In the formulas (1-2a), (1-2b), (1-2c), and (1-2d), among R _{1 to} R ₈ , those that are not a single bond bonded to ^* 2 are each independently A hydrogen atom, a substituted or unsubstituted linear or branched alkyl group having 1 to 15 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 15 ring carbon atoms, a substituted or unsubstituted silyl group, A substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms, a substituted or unsubstituted heteroaryl group having 5 to 30 ring atoms, a halogen atom, or a cyano group. ) The nitrogen-containing aromatic heterocycle according to claim 1, wherein the formula (1-3) is represented by the following formula (1-3a), (1-3b), (1-3c), or (1-3d). Derivative.

(In the formulas (1-3a), (1-3b), (1-3c), and (1-3d), L, n, X, and A _{17 to} A ₂₄ are defined in the formula (1-3). It is as follows.
1 to ₆ of R _{2 to} R ₆ and R _{8 in} the formula (1-3a) are single bonds bonded to ^* 4.
1 to 6 of R _{2 to} R ₅ , R ₇ and R _{8 in} the formula (1-3b) are a single bond bonded to ^* 4.
1-6 R _1, R ₃ ~R ₆ and R ₈ of formula (1-3c) is a single bond to bond to ^* 4.
1-6 _{R 1, R 3 ~R 5,} R 7 and R ₈ of formula (1-3d) is a single bond to bond to ^* 4.
In formulas (1-3a), (1-3b), (1-3c), and (1-3d), among R _{1 to} R ₈ , those that are not a single bond bonded to ^* 4 are independently selected. A hydrogen atom, a substituted or unsubstituted linear or branched alkyl group having 1 to 15 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 15 ring carbon atoms, a substituted or unsubstituted silyl group, A substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms, a substituted or unsubstituted heteroaryl group having 5 to 30 ring atoms, a halogen atom, or a cyano group. ) The nitrogen-containing aromatic heterocyclic derivative according to claim 1, wherein the formula (1-1) is represented by the following formula (1-1e).

(In the formula, B _{1 to} B ₄ , C _{1 to} C ₄ , n and L are as defined in Formula (1-1).
R _{57 to} R ₆₄ each independently represent a hydrogen atom, a substituted or unsubstituted linear or branched alkyl group having 1 to 15 carbon atoms, or a substituted or unsubstituted cycloalkyl having 3 to 15 ring carbon atoms. A substituted or unsubstituted silyl group, a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms, a substituted or unsubstituted heteroaryl group having 5 to 30 ring atoms, a halogen atom, or a cyano group. Represent.
Two adjacent groups of R _{57 to} R ₆₄ may combine to form a substituted or unsubstituted saturated or unsaturated divalent group forming a part of the ring. ) The nitrogen-containing aromatic heterocyclic derivative according to claim 1, wherein the formula (1-2) is represented by the following formula (1-2e).

(In the formula, B _{1 to} B ₄ , C _{1 to} C ₄ , Ra, n, and L are as defined in Formula (1-2).
Any one of R _{57 to} R ₆₀ is a single bond bonded to ^* 3. The other R _{57 to} R ₆₀ and R _{61 to} R ₆₄ are each independently a hydrogen atom, a substituted or unsubstituted C 1-15 linear or branched alkyl group, a substituted or unsubstituted ring formation. A cycloalkyl group having 3 to 15 carbon atoms, a substituted or unsubstituted silyl group, a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms, and a substituted or unsubstituted heteroaryl group having 5 to 30 ring atoms. Represents a halogen atom or a cyano group.
The other two adjacent groups of R _{57 to} R ₆₀ and R _{61 to} R ₆₄ may combine to form a substituted or unsubstituted saturated or unsaturated divalent group that forms part of the ring. Good. ) The nitrogen-containing aromatic heterocyclic derivative according to claim 1, wherein the formula (1-3) is represented by the following formula (1-3e).

(In the formula, B _{1 to} B ₄ , C _{1 to} C ₄ , X, n and L are as defined in Formula (1-3).
Any one of R _{57 to} R ₆₀ is a single bond bonded to ^* 5. The other R _{57 to} R ₆₀ and R _{61 to} R ₆₄ are each independently a hydrogen atom, a substituted or unsubstituted C 1-15 linear or branched alkyl group, a substituted or unsubstituted ring formation. A cycloalkyl group having 3 to 15 carbon atoms, a substituted or unsubstituted silyl group, a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms, and a substituted or unsubstituted heteroaryl group having 5 to 30 ring atoms. Represents a halogen atom or a cyano group.
The other two adjacent groups of R _{57 to} R ₆₀ and R _{61 to} R ₆₄ may combine to form a substituted or unsubstituted saturated or unsaturated divalent group that forms part of the ring. Good. ) The nitrogen-containing aromatic heterocyclic derivative according to claim 1 or 5, wherein the formula (1-1) or (1-1e) is represented by the following formula (1-1f).

(In the formula, B _{1 to} B ₄ , C _{1 to} C ₄ , n and L are as defined in Formula (1-1).
Any one of R _{61 to} R ₆₄ is a single bond bonded to ^* 6. The other R _{61 to} R ₆₄ and R _{57 to} R ₆₀ are each independently a hydrogen atom, a substituted or unsubstituted C 1-15 linear or branched alkyl group, a substituted or unsubstituted ring formation. A cycloalkyl group having 3 to 15 carbon atoms, a substituted or unsubstituted silyl group, a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms, and a substituted or unsubstituted heteroaryl group having 5 to 30 ring atoms. Represents a halogen atom or a cyano group.
The other two adjacent groups of R _{61 to} R ₆₄ and R _{57 to} R ₆₀ may combine to form a substituted or unsubstituted saturated or unsaturated divalent group that forms part of the ring. Good.
Any one of R _{65 to} R ₆₈ is a single bond bonded to ^* 7. The other R _{65 to} R ₆₈ and R _{69 to} R ₇₂ are each independently a hydrogen atom, a substituted or unsubstituted C 1-15 linear or branched alkyl group, a substituted or unsubstituted ring formation. A cycloalkyl group having 3 to 15 carbon atoms, a substituted or unsubstituted silyl group, a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms, and a substituted or unsubstituted heteroaryl group having 5 to 30 ring atoms. Represents a halogen atom or a cyano group.
The other two adjacent groups of R _{65 to} R ₆₈ and R _{69 to} R ₇₂ may combine to form a substituted or unsubstituted saturated or unsaturated divalent group that forms part of the ring. Good.
Rf represents a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms or a substituted or unsubstituted heteroaryl group having 5 to 30 ring atoms. ) The nitrogen-containing aromatic heterocyclic derivative according to claim 1 or 6, wherein the formula (1-2) or (1-2e) is represented by the following formula (1-2f).

(In the formula, B _{1 to} B ₄ , C _{1 to} C ₄ , Ra, n and L are as defined in Formula (1-2).
Any one of R _{57 to} R ₆₀ is a single bond bonded to ^* 3. Any one of R _{61 to} R ₆₄ is a single bond bonded to ^* 6. Other R _{57 to} R ₆₀ and other R _{61 to} R ₆₄ are each independently a hydrogen atom, a substituted or unsubstituted linear or branched alkyl group having 1 to 15 carbon atoms, a substituted or unsubstituted group. A cycloalkyl group having 3 to 15 ring carbon atoms, a substituted or unsubstituted silyl group, a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms, a substituted or unsubstituted hetero ring having 5 to 30 ring atoms An aryl group, a halogen atom, or a cyano group is represented.
The other two adjacent groups of R _{57 to} R ₆₀ and the other R _{61 to} R ₆₄ are combined to form a substituted or unsubstituted saturated or unsaturated divalent group that forms part of the ring. May be.
Any one of R _{65 to} R ₆₈ is a single bond bonded to ^* 7. The other R _{65 to} R ₆₈ and R _{69 to} R ₇₂ are each independently a hydrogen atom, a substituted or unsubstituted C 1-15 linear or branched alkyl group, a substituted or unsubstituted ring formation. A cycloalkyl group having 3 to 15 carbon atoms, a substituted or unsubstituted silyl group, a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms, and a substituted or unsubstituted heteroaryl group having 5 to 30 ring atoms. Represents a halogen atom or a cyano group.
The other two adjacent groups of R _{65 to} R ₆₈ and R _{69 to} R ₇₂ may combine to form a substituted or unsubstituted saturated or unsaturated divalent group that forms part of the ring. Good.
Rf represents a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms or a substituted or unsubstituted heteroaryl group having 5 to 30 ring atoms. ) The nitrogen-containing aromatic heterocyclic derivative according to claim 1 or 7, wherein the formula (1-3) or (1-3e) is represented by the following formula (1-3f).

(In the formula, B _{1 to} B ₄ , C _{1 to} C ₄ , X, n, and L are as defined in Formula (1-3).
Any one of R _{57 to} R ₆₀ is a single bond bonded to ^* 5. Any one of R _{61 to} R ₆₄ is a single bond bonded to ^* 6. Other R _{57 to} R ₆₀ and other R _{61 to} R ₆₄ are each independently a hydrogen atom, a substituted or unsubstituted linear or branched alkyl group having 1 to 15 carbon atoms, a substituted or unsubstituted group. A cycloalkyl group having 3 to 15 ring carbon atoms, a substituted or unsubstituted silyl group, a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms, a substituted or unsubstituted hetero ring having 5 to 30 ring atoms An aryl group, a halogen atom, or a cyano group is represented.
The other two adjacent groups of R _{57 to} R ₆₀ and the other R _{61 to} R ₆₄ are combined to form a substituted or unsubstituted saturated or unsaturated divalent group that forms part of the ring. May be.
Any one of R _{65 to} R ₆₈ is a single bond bonded to ^* 7. The other R _{65 to} R ₆₈ and R _{69 to} R ₇₂ are each independently a hydrogen atom, a substituted or unsubstituted C 1-15 linear or branched alkyl group, a substituted or unsubstituted ring formation. A cycloalkyl group having 3 to 15 carbon atoms, a substituted or unsubstituted silyl group, a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms, and a substituted or unsubstituted heteroaryl group having 5 to 30 ring atoms. Represents a halogen atom or a cyano group.
The other two adjacent groups of R _{65 to} R ₆₈ and R _{69 to} R ₇₂ may combine to form a substituted or unsubstituted saturated or unsaturated divalent group that forms part of the ring. Good.
Rf represents a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms or a substituted or unsubstituted heteroaryl group having 5 to 30 ring atoms. ) The formula (1-1), (1-1e) or (1-1f) is represented by the following formula (1-1g), (1-1h) or (1-1i). The nitrogen-containing aromatic heterocyclic derivative described in 1.

(In the formula, B _{1 to} B ₄ , C _{1 to} C ₄ , n and L are as defined in the formula (1-1), and R _{57 to} R ₆₀ , R ₆₁ , R ₆₃ and R ₆₄ are represented by the formula ( 1-1e) and Rf and R _{65 to} R ₇₂ are as defined in formula (1-1f). The nitrogen-containing aroma according to claim 1, 6 or 9, wherein the formula (1-2), (1-2e) or (1-2f) is represented by the following formula (1-2g) or (1-2h). Group heterocyclic derivatives.

(In the formula, B _{1 to} B ₄ , C _{1 to} C ₄ , n and L are as defined in the formula (1-2), and R _{57 to} R ₆₀ , R ₆₁ , R ₆₃ , R ₆₄ and Ra are (As defined in formula (1-2e), Rf and R _{65 to} R ₇₂ are as defined in formula (1-2f).) The nitrogen-containing aroma according to claim 1, 7 or 10, wherein the formula (1-3), (1-3e) or (1-3f) is represented by the following formula (1-3g) or (1-3h). Group heterocyclic derivatives.

(In the formula, B _{1 to} B ₄ , C _{1 to} C ₄ , n and L are as defined in Formula (1-3), and R _{57 to} R ₆₀ , R ₆₁ , R ₆₃ and R ₆₄ are the formulas ( 1-3e) and Rf and R _{65 to} R ₇₂ are as defined in formula (1-3f).)   The material for organic electroluminescent elements containing the nitrogen-containing aromatic heterocyclic derivative in any one of Claims 1-13.   It is an organic electroluminescent element which has an anode, a cathode, and an at least 1 layer of organic thin film layer between an anode and a cathode, Comprising: At least 1 layer of an organic thin film layer is any one of Claims 1-13. An organic electroluminescence device comprising a nitrogen-containing aromatic heterocyclic derivative.   The organic thin film layer has a light emitting layer and a cathode side organic thin film layer disposed between the light emitting layer and the cathode, and the cathode side organic thin film layer contains the nitrogen-containing aromatic heterocyclic derivative. The organic electroluminescent element according to claim 15.   The organic thin film layer has a light emitting layer and an electron transport layer disposed between the light emitting layer and the cathode, and the electron transport layer contains the nitrogen-containing aromatic heterocyclic derivative. The organic electroluminescent element of description.   The organic electroluminescence device according to claim 15, wherein the organic thin film layer has a light emitting layer, and the light emitting layer contains the nitrogen-containing aromatic heterocyclic derivative.   The organic electroluminescent element according to claim 16, wherein the light emitting layer further contains a phosphorescent material.   The organic electroluminescent device according to claim 19, wherein the phosphorescent material is an orthometalated complex of iridium, osmium, or platinum.   The electronic device which comprises the organic electroluminescent element of any one of Claims 15-20.

Images