JP5949354B2 - Carbazole compounds having substituents containing electron-accepting nitrogen-containing heteroaryl and organic electroluminescent devices - Google Patents

Description

  The present invention relates to a carbazole compound having a substituent containing an electron-accepting nitrogen-containing heteroaryl, and an electron transport material, an organic electroluminescent element, a display device, and a lighting device using the same.

  2. Description of the Related Art Conventionally, display devices using light emitting elements that emit electroluminescence have been studied variously because they can save power and can be thinned. Further, organic electroluminescent elements made of organic materials can be easily reduced in weight and size. Therefore, it has been actively studied. In particular, the development of organic materials with light emission characteristics such as blue, which is one of the three primary colors of light, and organic materials that have charge transporting ability (such as semiconductors and superconductors) such as holes and electrons The development of materials has been actively studied so far, regardless of whether it is a high molecular compound or a low molecular compound.

  For example, an organic electroluminescent device using a compound in which an aryl-heteroaryl such as a pyridyl group is substituted on the central skeleton of anthracene has been reported (Japanese Patent Laid-Open No. 2003-146951; Japanese Patent Laid-Open No. 2005-170911). Gazette; Patent Document 2, International Publication No. 2007/085652 Pamphlet; Patent Document 3).

  In addition, it is reported that compounds with a central skeleton of bianthracene, binaphthalene, or a combination of naphthalene and anthracene can be used as materials for organic electroluminescent devices (for example, materials for electron transport layers and electron injection layers; electron transport materials). (JP-A-8-12600; Patent Document 4, JP-A-2003-123983; Patent Document 5, JP-A-11-297473; Patent Document 6).

  Furthermore, it has been reported that a compound containing a carbazole ring and a pyridine ring or a pyrimidine ring is used as a charge transport (hole transport property and electron transport property) material (Japanese Patent Laid-Open No. 2006-199679; Patent Document 7, JP 2005-268199 A; Patent Literature 8, JP 2007-088433 A; Patent Literature 9, International Publication No. 2003/078541 Pamphlet; Patent Literature 10, International Publication No. 2003-080760 Pamphlet;

JP 2003-146951 A JP 2005-170911 A International Publication No. 2007/086552 Pamphlet JP-A-8-12600 JP 2003-123983 A JP 11-297473 A JP 2006-199679 A JP 2005-268199 A JP 2007-088433 A International Publication No. 2003/078541 Pamphlet International Publication No. 2003/080760 Pamphlet

  As described above, compounds in which the central skeleton of anthracene is substituted with an aryl group or heteroaryl, compounds using bianthracene, binaphthalene, or a combination of naphthalene and anthracene as the central skeleton, and carbazole rings, pyridine rings, and pyrimidine rings Although several compounds are known, these known materials do not satisfy the long life and high efficiency of the device, which are generally required for electron transport materials, in a sufficient and balanced manner. Under such circumstances, it is desired to develop an electron transport material that has an excellent lifetime and driving voltage of the light emitting element. In particular, for blue light-emitting elements, an electron transport material having superior characteristics compared to red and green light-emitting elements has not been obtained, and development of an electron transport material suitable for improving the characteristics of blue light-emitting elements is desired. ing.

  As a result of intensive studies to solve the above problems, the present inventors have made an organic electroluminescent device comprising an organic layer containing a compound represented by the following formula as an electron transport material, particularly in the lifetime of the device. The present inventors have found that an organic electroluminescence device excellent in balance with driving voltage can be obtained, and the present invention has been completed. That is, the present invention provides the following carbazole compounds.

上記式中、
ａは０または１であり、
Ｒは、炭素数１〜６のアルキルまたは炭素数３〜６のシクロアルキルで置換されていてもよい、炭素数６〜２４のアリールまたは炭素数２〜２４のヘテロアリールであり、
Ｈｙ_１は、炭素数１〜６のアルキルまたは炭素数３〜６のシクロアルキルで置換されていてもよい、炭素数２〜２４の電子受容性窒素含有へテロアリールであり、
Ａｒ_１は、炭素数１〜６のアルキルまたは炭素数３〜６のシクロアルキルで置換されていてもよい、炭素数６〜２４のアリーレンであり、Ａｒ_２は、炭素数１〜６のアルキルまたは炭素数３〜６のシクロアルキルで置換されていてもよい、炭素数６〜２４のアリールである。 [1] A carbazole compound represented by the following formula.

In the above formula,
a is 0 or 1,
R is aryl having 6 to 24 carbons or heteroaryl having 2 to 24 carbons, which may be substituted with alkyl having 1 to 6 carbons or cycloalkyl having 3 to 6 carbons;
Hy ₁ is an electron-accepting nitrogen-containing heteroaryl having 2 to 24 carbon atoms, which may be substituted with alkyl having 1 to 6 carbons or cycloalkyl having 3 to 6 carbons;
Ar ₁ is aryl having 6 to 24 carbon atoms which may be substituted with alkyl having 1 to 6 carbons or cycloalkyl having 3 to 6 carbons, and Ar ₂ is alkyl having 1 to 6 carbons or It is C6-C24 aryl which may be substituted by C3-C6 cycloalkyl.

上記式（１−２）中、Ｒ、Ｈｙ_１、Ａｒ_１およびＡｒ_２は、請求項１での定義と同じである。 [2] The carbazole compound according to the above [1], wherein a is 1, and is represented by the following formula (1-2).

In the above formula (1-2), R, Hy ₁ , Ar ₁ and Ar ₂ are the same as defined in claim 1.

上記式（１−４）中、Ｒ、Ｈｙ_１およびＡｒ_２は、請求項１での定義と同じである。 [3] The carbazole compound according to the above [1], wherein a is 0 and represented by the following formula (1-4).

In the above formula (1-4), R, Hy ₁ and Ar ₂ are the same as defined in claim 1.

[4] R is phenyl, biphenylyl, terphenylyl, quaterphenylyl, naphthyl, phenyl-substituted naphthyl, phenanthroli which may be substituted with alkyl having 1 to 6 carbons or cycloalkyl having 3 to 6 carbons. A group selected from the group consisting of nyl, pyridyl, bipyridyl, terpyridyl, quinolinyl, isoquinolinyl, pyrimidinyl, pyrazinyl, pyridazinyl and triazinyl;
Hy ₁ is pyridyl, bipyridyl, terpyridyl, pyrimidinyl, pyrazinyl, triazinyl, azaindolidinyl, benzimidazolyl, benzothiazolyl, benzo, which may be substituted with alkyl having 1 to 6 carbons or cycloalkyl having 3 to 6 carbons. A group selected from the group consisting of oxazolyl, indazolyl, purinyl, carbolinyl, naphthyridinyl, quinoxalinyl, quinolinyl, isoquinolinyl, pyridylquinolinyl, pyridylisoquinolinyl, acridinyl, phenanthrolinyl, phenazinyl and imidazopyridinyl And
Ar ₁ may be substituted with alkyl having 1 to 6 carbons or cycloalkyl having 3 to 6 carbons, benzene, naphthalene, anthracene, naphthacene, pentacene, biphenyl, acenaphthylene, fluorene, phenalene, phenanthrene, triphenylene, A divalent group having a structure selected from the group consisting of pyrene and perylene, and Ar ₂ is a monovalent group having a structure selected from the group consisting of these,
The carbazole compound according to any one of the above [1] to [3].

[5] R may be substituted with alkyl having 1 to 6 carbons or cycloalkyl having 3 to 6 carbons, phenyl, biphenylyl, terphenylyl, quaterphenylyl, naphthyl, phenyl-substituted naphthyl, phenanthroli A group selected from the group consisting of nyl, pyridyl, quinolinyl and isoquinolinyl;
Hy ₁ is pyridyl, bipyridyl, terpyridyl, pyrimidinyl, pyrazinyl, triazinyl, azaindolidinyl, benzimidazolyl, benzothiazolyl, benzo, which may be substituted with alkyl having 1 to 6 carbons or cycloalkyl having 3 to 6 carbons. A group selected from the group consisting of oxazolyl, quinolinyl, isoquinolinyl, pyridylquinolinyl, pyridylisoquinolinyl and imidazopyridinyl;
Ar ₁ is selected from the group consisting of benzene, naphthalene, anthracene, pyrene, triphenylene, fluorene, biphenyl, and perylene, which may be substituted with alkyl having 1 to 6 carbons or cycloalkyl having 3 to 6 carbons. A divalent group of the structure, Ar ₂ is a monovalent group of a structure selected from the group consisting of these,
The carbazole compound according to any one of the above [1] to [3].

Ｈｙ_１は、下記式（Ｈｙ−１−１）〜（Ｈｙ−１−３）で表される基、下記式（Ｈｙ−２−１）〜（Ｈｙ−２−１８）で表される基、下記式（Ｈｙ−３−１）〜（Ｈｙ−３−２７）で表される基からなる群から選択される基であり、

Ａｒ_１は、炭素数１〜６のアルキルまたは炭素数３〜６のシクロアルキルで置換されていてもよい、ベンゼン、ビフェニルおよびナフタレンからなる群から選択される構造の２価の基であり、Ａｒ_２は、これらからなる群から選択される構造の１価の基である、
上記［１］〜［３］のいずれかに記載するカルバゾール化合物。 [6] From the groups represented by the following formulas (R-1) to (R-20), which may be substituted with alkyl having 1 to 6 carbons or cycloalkyl having 3 to 6 carbons. A group selected from the group consisting of

Hy ₁ is a group represented by the following formulas (Hy-1-1) to (Hy-1-3), a group represented by the following formulas (Hy-2-1) to (Hy-2-18), A group selected from the group consisting of groups represented by the following formulas (Hy-3-1) to (Hy-3-27);

Ar ₁ is a divalent group having a structure selected from the group consisting of benzene, biphenyl and naphthalene, which may be substituted with alkyl having 1 to 6 carbons or cycloalkyl having 3 to 6 carbons; ₂ is a monovalent group having a structure selected from the group consisting of these,
The carbazole compound according to any one of the above [1] to [3].

[7] R is a group represented by the above formula (R-1) to formula (R-14), which may be substituted with alkyl having 1 to 6 carbons or cycloalkyl having 3 to 6 carbons. A group selected from the group consisting of
Hy ₁ is a group represented by the above formulas (Hy-1-1) to (Hy-1-3), or a group represented by the above formulas (Hy-2-1) to (Hy-2-18). A group selected from the group consisting of
Ar ₁ is 1,2-phenylene, 1,3-phenylene, 1,4-phenylene, 1,4-naphthalene-diyl, 1,5-naphthalene-diyl, 2,6-naphthalene-diyl and 2,7- A divalent group selected from the group consisting of naphthalene-diyl, Ar ₂ is a monovalent group selected from the group consisting of phenyl, biphenylyl, 1-naphthyl and 2-naphthyl;
The carbazole compound according to any one of the above [1] to [3].

[8] The carbazole compound according to the above [1], represented by the following formula (1-2-336), formula (1-4-98) or formula (1-4-100).

[9] The carbazole compound according to the above [1], represented by the following formula (1-2-290), formula (1-2-393) or formula (1-4-155).

上記式（１−５）中、ａ、Ｒ、Ｈｙ_１およびＡｒ_１は、上記［１］での定義と同じであり、
Ａｒ_３は水素または炭素数６〜１０のアリールであり、アントラセン環およびＡｒ_３は炭素数１〜６のアルキルまたは炭素数３〜６のシクロアルキルで置換されていてもよい。 [10] The carbazole compound described in the above [1] represented by the following formula (1-5).

In the above formula (1-5), a, R, Hy ₁ and Ar ₁ are the same as defined in [1] above,
Ar ₃ is hydrogen or aryl having 6 to 10 carbon atoms, and the anthracene ring and Ar ₃ may be substituted with alkyl having 1 to 6 carbon atoms or cycloalkyl having 3 to 6 carbon atoms.

[11] a is 0 or 1,
R is phenyl, biphenylyl, terphenylyl, quaterphenylyl, naphthyl, phenyl substituted naphthyl, phenanthrolinyl, pyridyl, which may be substituted with alkyl having 1 to 6 carbons or cycloalkyl having 3 to 6 carbons A group selected from the group consisting of bipyridyl, terpyridyl, quinolinyl, isoquinolinyl, pyrimidinyl, pyrazinyl, pyridazinyl and triazinyl,
Hy ₁ is pyridyl, bipyridyl, terpyridyl, pyrimidinyl, pyrazinyl, triazinyl, azaindolidinyl, benzimidazolyl, benzothiazolyl, benzo, which may be substituted with alkyl having 1 to 6 carbons or cycloalkyl having 3 to 6 carbons. A group selected from the group consisting of oxazolyl, indazolyl, purinyl, carbolinyl, naphthyridinyl, quinoxalinyl, quinolinyl, isoquinolinyl, pyridylquinolinyl, pyridylisoquinolinyl, acridinyl, phenanthrolinyl, phenazinyl and imidazopyridinyl And
Ar ₁ may be substituted with alkyl having 1 to 6 carbons or cycloalkyl having 3 to 6 carbons, benzene, naphthalene, anthracene, naphthacene, pentacene, biphenyl, acenaphthylene, fluorene, phenalene, phenanthrene, triphenylene, A divalent group having a structure selected from the group consisting of pyrene and perylene;
Ar ₃ is hydrogen, phenyl or naphthyl, the anthracene ring and Ar ₃ may be substituted with alkyl having 1 to 6 carbons or cycloalkyl having 3 to 6 carbons,
The carbazole compound described in the above [10].

[12] a is 0 or 1,
R is phenyl, biphenylyl, terphenylyl, quaterphenylyl, naphthyl, phenyl substituted naphthyl, phenanthrolinyl, pyridyl, which may be substituted with alkyl having 1 to 6 carbons or cycloalkyl having 3 to 6 carbons , A group selected from the group consisting of quinolinyl and isoquinolinyl,
Hy ₁ is pyridyl, bipyridyl, terpyridyl, pyrimidinyl, pyrazinyl, triazinyl, azaindolidinyl, benzimidazolyl, benzothiazolyl, benzo, which may be substituted with alkyl having 1 to 6 carbons or cycloalkyl having 3 to 6 carbons. A group selected from the group consisting of oxazolyl, quinolinyl, isoquinolinyl, pyridylquinolinyl, pyridylisoquinolinyl and imidazopyridinyl;
Ar ₁ is selected from the group consisting of benzene, naphthalene, anthracene, pyrene, triphenylene, fluorene, biphenyl, and perylene, which may be substituted with alkyl having 1 to 6 carbons or cycloalkyl having 3 to 6 carbons. A divalent group of structure,
Ar ₃ is hydrogen, phenyl or naphthyl, the anthracene ring and Ar ₃ may be substituted with alkyl having 1 to 6 carbons or cycloalkyl having 3 to 6 carbons,
The carbazole compound described in the above [10].

[13] a is 0 or 1,
R is a group consisting of groups represented by the above formulas (R-1) to (R-20), which may be substituted with alkyl having 1 to 6 carbons or cycloalkyl having 3 to 6 carbons. A group to be selected,
Hy ₁ is a group represented by the above formulas (Hy-1-1) to (Hy-1-3), a group represented by the above formulas (Hy-2-1) to (Hy-2-18), A group selected from the group consisting of groups represented by the above formulas (Hy-3-1) to (Hy-3-27);
Ar ₁ is a divalent group having a structure selected from the group consisting of benzene, biphenyl and naphthalene, which may be substituted with alkyl having 1 to 6 carbons or cycloalkyl having 3 to 6 carbons;
Ar ₃ is hydrogen, phenyl or naphthyl, the anthracene ring and Ar ₃ may be substituted with alkyl having 1 to 6 carbons or cycloalkyl having 3 to 6 carbons,
The carbazole compound described in the above [10].

[14] a is 0 or 1,
R is a group consisting of groups represented by the above formulas (R-1) to (R-14), which may be substituted with alkyl having 1 to 6 carbons or cycloalkyl having 3 to 6 carbons. A group to be selected,
Hy ₁ is a group represented by the above formulas (Hy-1-1) to (Hy-1-3), or a group represented by the above formulas (Hy-2-1) to (Hy-2-18). A group selected from the group consisting of
Ar ₁ is 1,2-phenylene, 1,3-phenylene, 1,4-phenylene, 1,4-naphthalene-diyl, 1,5-naphthalene-diyl, 2,6-naphthalene-diyl and 2,7- A divalent group selected from the group consisting of naphthalene-diyl,
Ar ₃ is phenyl, 1-naphthyl or 2-naphthyl,
The carbazole compound described in the above [10].

[15] The carbazole compound according to the above [1], represented by the following formula (1-5-2), formula (1-5-8) or formula (1-5-29).

[16] The carbazole compound described in the above [1], represented by the following formula (1-5-12).

[17] An electron transport material comprising the compound according to any one of [1] to [16].

[18] A pair of electrodes including an anode and a cathode, a light emitting layer disposed between the pair of electrodes, an electron transport material according to the above [17] disposed between the cathode and the light emitting layer. An organic electroluminescent device having an electron transport layer and / or an electron injection layer.

[19] At least one of the electron transport layer and the electron injection layer further includes at least one selected from the group consisting of a quinolinol-based metal complex, a pyridine derivative, a bipyridine derivative, a phenanthroline derivative, a borane derivative, and a benzimidazole derivative. The organic electroluminescent element as described in [18] above.

[20] At least one of the electron transport layer and the electron injection layer may further include an alkali metal, an alkaline earth metal, a rare earth metal, an alkali metal oxide, an alkali metal halide, an alkaline earth metal oxide, At least one selected from the group consisting of alkaline earth metal halides, rare earth metal oxides, rare earth metal halides, alkali metal organic complexes, alkaline earth metal organic complexes and rare earth metal organic complexes The organic electroluminescent element as described in [19] above.

[21] A display device comprising the organic electroluminescent element as described in any one of [18] to [20].

[22] A lighting device comprising the organic electroluminescent element according to any one of [18] to [20].

  According to the preferred embodiment of the present invention, an organic electroluminescent device excellent in the lifetime of the light emitting device can be obtained. In addition, according to another preferable aspect of the present invention, not only an excellent element lifetime can be realized, but also the balance with the driving voltage can be made excellent. According to a more preferred embodiment, an organic electroluminescent device having further improved driving voltage, external quantum efficiency and heat resistance can be obtained while maintaining the device life equal to or longer than these. Further, the preferred electron transport material of the present invention is particularly suitable for a blue light emitting element, and according to this electron transport material, a blue light emitting element having an element life comparable to a red or green light emitting element can be produced. Can do. Furthermore, by using this organic electroluminescent element, a high-performance display device such as a full-color display can be obtained.

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

1. Carbazole Compound Represented by Formula (1) The carbazole compound having a substituent containing an electron-accepting nitrogen-containing heteroaryl according to the present invention will be described in detail. The carbazole compound of the present invention is a compound represented by the following formula (1).

  In the above formula (1), a is 0 or 1, b is 0 or 1, and in the present application, an embodiment in which b = 0, that is, a compound represented by the following formula is preferred.

  The compound represented by the above formula includes an embodiment in which a = 0 or 1, that is, a compound represented by the following formula (1-4) or formula (1-2). Moreover, as a more concrete thing, there exists a compound represented by a following formula (1-5). In addition, the compound represented by the following formula (1-1) or formula (1-3) is an aspect of b = 1.

In Formula (1), R is aryl having 6 to 24 carbon atoms or heteroaryl having 2 to 24 carbon atoms. Hy ₁ and Hy ₂ are each independently an electron-accepting nitrogen-containing heteroaryl having 2 to 24 carbon atoms, and may be the same or different. Further, Ar ₁ and Ar ₂ are each independently arylene having 6 to 24 carbon atoms, but when b = 0, Ar ₂ is aryl having 6 to 24 carbon atoms.

R, Hy ₁ , Hy ₂ , Ar ₁ and Ar ₂ may each independently be substituted with alkyl having 1 to 6 carbons or cycloalkyl having 3 to 6 carbons. Examples of the alkyl having 1 to 6 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, isopentyl, neopentyl, t-pentyl, n-hexyl, Examples thereof include 1-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl and 2-ethylbutyl. Among these, methyl, isopropyl or t-butyl is preferable, and t-butyl is particularly preferable. Examples of the cycloalkyl having 3 to 6 carbon atoms include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclopentyl, cycloheptyl, methylcyclohexyl, cyclooctyl, and dimethylcyclohexyl. The number of substituents is, for example, the maximum possible number of substitution, preferably 1 to 3, more preferably 1 to 2, and still more preferably 1.

  The “aryl having 6 to 24 carbon atoms” in R is preferably an aryl having 6 to 16 carbon atoms, and more preferably an aryl having 6 to 12 carbon atoms.

  Specific examples of the “aryl” include monocyclic aryl phenyl, bicyclic aryl (2-, 3-, 4-) biphenylyl, and condensed bicyclic aryl (1-, 2-) naphthyl. Terphenylyl which is a tricyclic aryl (m-terphenyl-2′-yl, m-terphenyl-4′-yl, m-terphenyl-5′-yl, o-terphenyl-3′-yl, o -Terphenyl-4'-yl, p-terphenyl-2'-yl, m-terphenyl-2-yl, m-terphenyl-3-yl, m-terphenyl-4-yl, o-terphenyl 2-yl, o-terphenyl-3-yl, o-terphenyl-4-yl, p-terphenyl-2-yl, p-terphenyl-3-yl, p-terphenyl-4-yl) Acenaphth, which is a fused tricyclic aryl Ren- (1-, 3-, 4-, 5-) yl, fluorene- (1-, 2-, 3-, 4-, 9-) yl, phenalen- (1-, 2-) yl, (1 -, 2-, 3-, 4-, 9-) phenanthryl, quaterphenylyl (5'-phenyl-m-terphenyl-2-yl, 5'-phenyl-m-terphenyl) which is a tetracyclic aryl -3-yl, 5′-phenyl-m-terphenyl-4-yl, m-quaterphenylyl), condensed tetracyclic aryl triphenylene- (1-, 2-) yl, pyrene- (1- , 2-, 4-) yl, naphthacene- (1-, 2-, 5-) yl, fused pentacyclic aryl perylene- (1-, 2-, 3-) yl, pentacene- (1-, 2-, 5-, 6-) yl and the like. Moreover, the group etc. which the phenyl group substituted by the arbitrary positions of condensed ring system aryl are mention | raise | lifted. The number of substituents is, for example, the maximum possible number of substitution, preferably 1 to 3, more preferably 1 to 2, and still more preferably 1. Among these, phenyl, biphenylyl, terphenylyl, naphthyl, phenanthryl, phenylnaphthyl and those substituted with alkyl having 1 to 6 carbon atoms or cycloalkyl having 3 to 6 carbon atoms are preferable.

  The “heteroaryl having 2 to 24 carbon atoms” in R is preferably a heteroaryl having 2 to 20 carbon atoms, more preferably a heteroaryl having 2 to 15 carbon atoms, and particularly preferably 2 to 10 carbon atoms. Of heteroaryl. Examples of the “heteroaryl” include a heterocyclic group containing 1 to 5 heteroatoms selected from oxygen, sulfur and nitrogen in addition to carbon as a ring constituent atom.

  Examples of “heteroaryl” include furyl, thienyl, pyrrolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, oxadiazolyl, thiadiazolyl, triazolyl, tetrazolyl, pyrazolyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, indolyl, isoindolyl, 1H -Indazolyl, benzimidazolyl, benzoxazolyl, benzothiazolyl, 1H-benzotriazolyl, quinolinyl, isoquinolinyl, cinnolyl, quinazolyl, quinoxalinyl, phthalazinyl, naphthyridinyl, purinyl, pteridinyl, carbazolyl, acridinyl, phenoxazinyl, phenothiazinyl, phenothiazinyl, phenothiazinyl, phenothiazinyl Flazanyl, benzofuranyl, isobenzofura Le, benzo [b] thienyl, phenoxathiinyl, etc. thianthrenyl and the like. Among these, pyridyl, quinolinyl, isoquinolinyl and the like are preferable.

Particularly preferred as R is a group represented by the following formula (R-1) to formula (R-20). Among these, groups represented by the following formulas (R-1) to (R-14), and further groups represented by the following formulas (R-1) to (R-9) are particularly preferable. .

Hy ₁ and Hy ₂ are each independently an electron-accepting nitrogen-containing heteroaryl, and the electron-accepting nitrogen represents a nitrogen atom that forms a double bond with an adjacent atom.

  Examples of the electron-accepting nitrogen-containing heteroaryl include pyridyl, bipyridyl, terpyridyl, pyrimidinyl, pyrazinyl, triazinyl, azaindolidinyl, benzimidazolyl, benzothiazolyl, benzoxazolyl, indazolyl, purinyl, carbolinyl, naphthyridinyl, quinoxalinyl, quinolinyl, isoquinolinyl, Examples include pyridylquinolinyl, pyridylisoquinolinyl, acridinyl, phenanthrolinyl, phenazinyl and imidazopyridinyl. Among them, preferred are pyridyl, bipyridyl, terpyridyl, pyrimidinyl, pyrazinyl, triazinyl, azaindolizinyl, benzimidazolyl, benzothiazolyl, benzoxazolyl, quinolinyl, isoquinolinyl, pyridylquinolinyl, pyridylisoquinolinyl and imidazopyridinyl. Particularly preferred are pyridyl and bipyridyl.

Among the above, Hy ₁ or Hy ₂ are preferably groups represented by the following formulas (Hy-1-1) to (Hy-1-3), and the following formulas (Hy-2-1) to (Hy-2-). 18) and groups represented by the following formulas (Hy-3-1) to (Hy-3-27).

Hy ₁ or Hy ₂ is more preferably groups represented by the above formulas (Hy-1-1) to (Hy-1-3), and the above formulas (Hy-2-1) to (Hy-2-18). It is group represented by these.

Ar ₁ and Ar ₂ are each independently arylene having 6 to 24 carbon atoms, but when b = 0 (when there is no Hy ₂ group), Ar ₂ is aryl having 6 to 24 carbon atoms.

  As the arylene, a divalent group derived from an aromatic hydrocarbon group such as benzene, naphthalene, anthracene, naphthacene, pentacene, acenaphthylene, phenalene, phenanthrene, pyrene, triphenylene, fluorene, biphenyl, and perylene can be used. A divalent group derived from naphthalene is preferred.

  Divalent groups derived from benzene or naphthalene include 1,2-phenylene, 1,3-phenylene, 1,4-phenylene, 1,4-naphthalene-diyl, 1,5-naphthalene-diyl, 2,6- Naphthalene-diyl and 2,7-naphthalene-diyl are mentioned.

In the case of b = 0, the specific aryl of Ar ₂ includes the groups exemplified in the above description of R, and the groups represented by the above formulas (R-1) to (R-9) are preferable. The groups represented by the above formula (R-1), formula (R-6) and formula (R-7) are particularly preferred.

In the compound represented by the formula (1-5), Ar ₂ in the compound represented by the formula (1-2) or the formula (1-4) is a “10-Ar ₃ -anthracen-9-yl” group. It can be said that it is a embodied compound (hereinafter, the “10-Ar ₃ -anthracen-9-yl” group may be simply referred to as Ar ₂ ). Therefore, this group may be substituted by alkyl having 1 to 6 carbons or cycloalkyl having 3 to 6 carbons, and Ar ₃ (hydrogen or aryl having 6 to 10 carbons) may be Ar as described above. This can be cited if it is consistent with the explanation in ₂ . More specifically, Ar ₃ includes hydrogen, phenyl, or naphthyl (1-naphthyl or 2-naphthyl).

In particular, in the case of the structure represented by the above formula (1-1), Hy ₁ and Hy ₂ may be the same or different, but are preferably the same, and Ar ₁ and Ar ₂ are also the same. Or may be different, but preferably the same.

In addition, all or part of the hydrogen atoms in carbazole and R, Ar ₁ , Ar ₂ , Hy ₁ or Hy ₂ substituted for carbazole, which constitute the compound represented by the above formula (1), are deuterium. There may be.

  Specific examples of the compound of the present invention include, for example, compounds represented by the following formulas (1-2-1) to (1-2-629) belonging to the compound represented by the formula (1-2). And compounds represented by the following formulas (1-4-1) to (1-4-561) belonging to the compounds represented by the above formula (1-4).

  Among the compounds represented by the above formula (1-2-1) to formula (1-2-629), among these, the above formula (1-2-1) to formula (1-242), formula ( 1-2-100) to formula (1-2117), formula (1-2156) to formula (1-2165), formula (1-2193) to formula (1-213) ), Formula (1-241) to Formula (1-2-261), Formula (1-2-289) to Formula (1-2-330), Formula (1-2-334) to Formula (1) -2-385), Formula (1-2389) to Formula (1-2-430), Formula (1-2434) to Formula (1-2466), Formula (1-2469) Formula (1-2510), Formula (1-2-513) to Formula (1-2-554), Formula (1-2557) to Formula (1-2-598), and Formula (1) -2-601) to formula (1-2-627) Compounds are more preferable.

  Among the compounds represented by the above formulas (1-4-1) to (1-4-561), among these, the above formulas (1-4-1) to (1-4-21), ( 1-449) to formula (1-4-69), formula (1-4-97) to formula (1-4-117), formula (1-4-145) to formula (1-4-161) ), Formula (1-4-163) to Formula (1-4-173), Formula (1-4-175) to Formula (1-4-195), Formula (1-4-223) to Formula (1) -243), Formula (1-4-271) to Formula (1-4-291), Formula (1-4-319) to Formula (1-4-339), Formula (1-4-367) To Formula (1-4-387), Formula (1-4-415) to Formula (1-4-435), Formula (1-4-463) to Formula (1-4-482), Formula (1- 4-484) to formula (1-4-503), formula (1-4-505) To Formula (1-4-524), Formula (1-4-526) to Formula (1-4-536), Formula (1-4-538) to Formula (1-4-553), and Formula (1) Compounds represented by -4-556) to formula (1-4-561) are preferable.

  Specific examples of the compound of the present invention are further represented by, for example, the following formulas (1-5-1) to (1-5-190) belonging to the compound represented by the formula (1-5). Compounds represented by the following formulas (1-5-201) to (1-5-390), compounds represented by the following formulas (1-5-401) to (1-5-590) , Compounds represented by the following formulas (1-5-601) to (1-5-669), compounds represented by the following formulas (1-5-701) to (1-5-769), A compound represented by formula (1-5-801) to formula (1-5-869), a compound represented by formula (1-5-901) to formula (1-5-969), 1-5-1001) to a compound represented by formula (1-5-1069), a compound represented by the following formula (1-5-1101) to formula (1-5-1169) , Compounds represented by the following formulas (1-5-1201) to (1-5-1269), compounds represented by the following formulas (1-51301) to (1-5-1369), And compounds represented by formula (1-51401) to formula (1-5-1469).

  Among the compounds represented by the above formulas (1-5-1) to (1-5-1469), among these, the above formulas (1-5-1) to (1-5-123), ( 1-5-201) to formula (1-5-323), formula (1-5-401) to formula (1-5-448), formula (1-5-452) to formula (1-5-523) ), Formula (1-5-601) to formula (1-5-648), formula (1-5-701) to formula (1-5-748), formula (1-5-801) to formula (1) -5-848), formula (1-5-901) to formula (1-5-948), formula (1-5-1001) to formula (1-5-1048), formula (1-5-1101) To Formula (1-5-1148), Formula (1-5-1201) to Formula (1-5-1248), Formula (1-51301) to Formula (1-5-1348), Formula (1- 5-1401) to formula (1-5 Compounds represented by 448) are preferred.

2. Method for Producing Compound Represented by Formula (1) Next, the method for producing the carbazole compound of the present invention will be described.
The carbazole compound of the present invention basically comprises a known compound and a known synthesis method such as Suzuki coupling reaction or Negishi coupling reaction (for example, “Metal-Catalyzed Cross-Coupling Reactions—Second, Completely Revised”). and Enlarged Edition ”). It can also be synthesized by combining both reactions. A scheme for synthesizing the carbazole compound represented by the formula (1) by Suzuki coupling reaction or Negishi coupling reaction is illustrated below.

<Method for Synthesizing Carbazole Compound Represented by Formula (1) (Part 1)>
<Synthesis of carbazole-2,7-diyl bis (trifluoromethanesulfonate) substituted with R at N-position: Cz-R-OTf>
As shown in the following reaction formula (1), a compound represented by “Cz-H-OMe” obtained by using a known synthesis method (Macromolecules, vol.35, pp.2122-2128 (2002)) Then, after introducing a substituent R by a coupling reaction using a palladium catalyst, an Ullmann reaction, or a nucleophilic substitution reaction using cesium carbonate to obtain a compound represented by “Cz-R-OMe”, tribromide Demethylation is performed with boron or pyridine hydrochloride to synthesize a compound represented by “Cz—R—OH”. Then, the compound represented by "Cz-R-OTf" is obtained by making it react with trifluoromethanesulfonic anhydride.

<Synthesis of 2,7-dibromocarbazole substituted with R at N-position: Cz-R-Br>
As shown in the following reaction formula (2), a known synthesis method (Chemistry of Materials, vol.16, pp.4736-4742 (2004), Journal of Organic Chemistry, vol.70, pp.5014-5019 (2005) The substituent R is introduced into the compound represented by “Cz—H—Br” obtained by using a coupling reaction or Ullmann reaction using a palladium catalyst or a nucleophilic substitution reaction using cesium carbonate. A compound represented by “Cz—R—Br” is obtained.

<Carbazole-2,7-diboronic acid ester substituted with R at N-position: Synthesis of Cz-R-BPin>
As shown in the following reaction formula (3), the compound represented by “Cz—R—OTf” or “Cz—R—Br” obtained as described above, and bis (pinacolato) diboron or 4,4 , 5,5-tetramethyl-1,3,2-dioxaborolane can be synthesized using a palladium catalyst and a base to synthesize a compound represented by "Cz-R-BPin". .

<Synthesis of Carbazole Compound According to the Present Invention>
Finally, as shown in the following reaction formulas (4) to (6), the compound represented by “Cz-R-OTf” or “Cz-R-BPin” obtained as described above and the reactivity The carbazole represented by the formula (1) is obtained by reacting “Hy _1- (Ar ₁ ) _a ” and “(Hy ₂ ) _b —Ar ₂ ” having a substituent of the above by Suzuki coupling or Negishi coupling. A compound can be obtained. Here, “Hy _1- (Ar ₁ ) _a ” and “(Hy ₂ ) _b —Ar ₂ ” mean groups bonded to the 2nd and 7th positions of the carbazole skeleton of the compound represented by the formula (1). , A and b are 0 or 1.

Here, Hy ₁ and Hy ₂ are each independently an optionally substituted electron-accepting nitrogen-containing heteroaryl having 2 to 24 carbon atoms, which may be the same or different, and Ar ₁ and Ar ₂ are each independently an arylene having 6 to 24 carbon atoms which may be substituted. However, when b = 0, Ar ₂ is an optionally substituted aryl having 6 to 24 carbon atoms.

Here, when “Hy _1- (Ar ₁ ) _a ” and “(Hy ₂ ) _b —Ar ₂ ” represent the same group, an electron obtained by bonding a reactive substituent to these groups The carbazole compound according to the present invention can be synthesized by using 2-fold moles of the accepting nitrogen-containing heteroaryl derivative. In addition, when “Hy _1- (Ar ₁ ) _a ” and “(Hy ₂ ) _b —Ar ₂ ” represent different groups, the respective electron acceptors in which reactive substituents are bonded to these groups. The carbazole derivative according to the present invention can be synthesized by reacting the functional nitrogen-containing heteroaryl derivative at the same time or in steps of 1 mole.

<Reagent used in reaction>
Specific examples of the palladium catalyst used in the Suzuki coupling reaction include tetrakis (triphenylphosphine) palladium (0): Pd (PPh ₃ ) ₄ , bis (triphenylphosphine) palladium (II) dichloride: PdCl ₂ (PPh ₃ ) ₂ , palladium (II) acetate: Pd (OAc) ₂ , tris (dibenzylideneacetone) dipalladium (0): Pd ₂ (dba) ₃ , tris (dibenzylideneacetone) dipalladium (0) chloroform complex: Pd ₂ (Dba) ₃ · CHCl ₃ , bis (dibenzylideneacetone) palladium (0): Pd (dba) ₂ , PdCl ₂ {P (t-Bu) _2- (p-NMe ₂ -Ph)} ₂ , palladium bis ( Dibenzylidene).

  In order to accelerate the reaction, a phosphine compound may be added to these palladium compounds in some cases. Specific examples of the phosphine compound include tri (t-butyl) phosphine, tricyclohexylphosphine, 1- (N, N-dimethylaminomethyl) -2- (di-t-butylphosphino) ferrocene, 1- (N, N-dibutylaminomethyl) -2- (di-t-butylphosphino) ferrocene, 1- (methoxymethyl) -2- (di-t-butylphosphino) ferrocene, 1,1′-bis (di-t-butylphos Fino) ferrocene, 2,2′-bis (di-t-butylphosphino) -1,1′-binaphthyl, 2-methoxy-2 ′-(di-t-butylphosphino) -1,1′-binaphthyl, or An example is 2-dicyclohexylphosphino-2 ′, 6′-dimethoxybiphenyl.

  Specific examples of bases used in the Suzuki coupling reaction include sodium carbonate, potassium carbonate, cesium carbonate, sodium bicarbonate, sodium hydroxide, potassium hydroxide, barium hydroxide, sodium ethoxide, sodium t-butoxide, sodium acetate. , Tripotassium phosphate, or potassium fluoride.

  Specific examples of the solvent used in the Suzuki coupling reaction include benzene, toluene, xylene, 1,2,4-trimethylbenzene, N, N-dimethylformamide, tetrahydrofuran, diethyl ether, t-butyl methyl ether, 1 1,4-dioxane, methanol, ethanol, cyclopentyl methyl ether or isopropyl alcohol. These solvents can be appropriately selected and may be used alone or as a mixed solvent.

Specific examples of the palladium catalyst used in the Negishi coupling reaction include tetrakis (triphenylphosphine) palladium (0): Pd (PPh ₃ ) ₄ , bis (triphenylphosphine) palladium (II) dichloride: PdCl ₂ (PPh ₃ ) ₂ , palladium (II) acetate: Pd (OAc) ₂ , tris (dibenzylideneacetone) dipalladium (0): Pd ₂ (dba) ₃ , tris (dibenzylideneacetone) dipalladium (0) chloroform complex: Pd ₂ (Dba) ₃ · CHCl ₃ , bis (dibenzylideneacetone) palladium (0): Pd (dba) ₂ , bis (tri-t-butylphosphino) palladium (0), or (1,1′-bis (diphenylphosphine) Fino) ferrocene) dichloropalladium (II): Pd (dpp ) Cl ₂ and dichloromethane complex.

  Specific examples of the solvent used in the Negishi coupling reaction include benzene, toluene, xylene, 1,2,4-trimethylbenzene, N, N-dimethylformamide, tetrahydrofuran, diethyl ether, t-butyl methyl ether, cyclopentyl. Examples include methyl ether or 1,4-dioxane. These solvents can be appropriately selected and may be used alone or as a mixed solvent.

<Synthesis of groups bonded to positions 2 and 7 of the carbazole skeleton of the compound represented by formula (1)>
“Hy _1- (Ar ₁ ) _a ” and “(Hy ₂ ) _b —Ar ₂ ” having a reactive substituent bonded thereto can be obtained by combining known reactions. The case where Hy ₁ and Hy ₂ are pyridyl groups and Ar ₁ and Ar ₂ are phenylene or naphthalenylene is shown.

<Synthesis of pyridyl-substituted bromophenyl / bromonaphthyl>
First, a pyridine zinc chloride complex is synthesized as shown in the following reaction formula (7), and then as shown in the following reaction formula (8), a pyridine zinc chloride complex and 1,4-dibromobenzene or 1,4-dibromo are synthesized. 2- (4-Bromophenyl) pyridine or 2- (4-bromonaphthalen-1-yl) pyridine can be synthesized by reacting with naphthalene.

In the reaction formula (7), “ZnCl ₂ · TMEDA” is a tetramethylethylenediamine complex of zinc chloride. R represents a linear or branched alkyl group, preferably a linear or branched alkyl group having 1 to 4 carbon atoms.

  Here, a synthesis method of 2- (4-bromophenyl) pyridine and 2- (4-bromonaphthalen-1-yl) pyridine using 2-bromopyridine as a raw material is exemplified, but 3-bromopyridine or 4 as a raw material. -By using bromopyridine and by using iodopyridine, the corresponding objects, ie 3- (4-bromophenyl) pyridine (or 3- (4-bromonaphthalen-1-yl) pyridine) and 4 respectively. -(4-Bromophenyl) pyridine (or 4- (4-bromonaphthalen-1-yl) pyridine) can be obtained. Further, here, a synthesis method of 2- (4-bromophenyl) pyridine and 2- (4-bromonaphthalen-1-yl) pyridine using 1,4-dibromobenzene or 1,4-dibromonaphthalene as a raw material is illustrated. However, by using 1,3-dibromobenzene, 2,6-dibromonaphthalene or 2,7-dibromonaphthalene as a raw material, dichloro, diiodo, bis (trifluoromethanesulfonate) or not dibromo The corresponding target product, that is, 2- (3-bromophenyl) pyridine, 2- (6-bromonaphthalen-2-yl) can also be obtained by using a mixture thereof (for example: 1-bromo-4-iodobenzene and the like). ) Pyridine and 2- (7-bromonaphthalen-2-yl) pyridine etc. Kill.

  Further, instead of reacting 1,4-dibromobenzene or the like with a pyridine zinc chloride complex, a similar target product can be obtained by reacting pyridylboronic acid or pyridylboronic acid ester (coupling reaction).

<Synthesis of pyridyl-substituted phenyl / naphthylboronic acid and boronate ester>
Next, as shown in the following reaction formula (9), 2- (4-bromophenyl) pyridine or 2- (4-bromonaphthalen-1-yl) pyridine is lithiated using an organolithium reagent, By using magnesium or an organic magnesium reagent as a Grignard reagent and reacting with trimethyl borate, triethyl borate or triisopropyl borate, 4- (pyridin-2-yl) phenylboronic acid ester and 4- (pyridine- 2-yl) naphthalen-1-ylboronic acid ester can be synthesized. Furthermore, as shown in the following reaction formula (10), 4- (2-pyridyl) phenylboronic acid and 4- (pyridin-2-yl) naphthalen-1-ylboronic acid are obtained by hydrolyzing the boronic acid ester. Can be synthesized.

  In the above reaction formula (9), R represents a linear or branched alkyl group, preferably a linear or branched alkyl group having 1 to 4 carbon atoms.

  Further, as shown in the following reaction formula (11), 2- (4-bromophenyl) pyridine or 2- (4-bromonaphthalen-1-yl) pyridine is lithiated using an organolithium reagent, or magnesium. Or an organomagnesium reagent to form a Grignard reagent and react with bis (pinacolato) diboron or 4,4,5,5-tetramethyl-1,3,2-dioxaborolane to produce other 4- (pyridine-2- Yl) phenylboronic acid esters and 4- (pyridin-2-yl) naphthalen-1-ylboronic acid esters can be synthesized. Further, as shown in the following reaction formula (12), 2- (4-bromophenyl) pyridine or 2- (4-bromonaphthalen-1-yl) pyridine and bis (pinacolato) diboron or 4,4,5, The same 4- (pyridin-2-yl) phenylboronic acid ester and 4- (pyridine) can also be obtained by subjecting 5-tetramethyl-1,3,2-dioxaborolane to a coupling reaction using a palladium catalyst and a base. -2-yl) naphthalen-1-ylboronic acid ester can be synthesized.

  In the above reaction formula (11), R represents a linear or branched alkyl group, preferably a linear or branched alkyl group having 1 to 4 carbon atoms.

  In the above reaction formula (9), (11) or (12), 3- (4-bromophenyl) pyridine, 4- (4-bromophenyl) pyridine, 2- (3-bromophenyl) pyridine, 3- (3-bromophenyl) pyridine, 4- (3-bromophenyl) pyridine, 3- (4-bromonaphthalen-1-yl) pyridine, 4- (4-bromonaphthalen-1-yl) pyridine, 2- (4 -Bromonaphthalen-1-yl) pyridine, 4- (4-bromonaphthalen-1-yl) pyridine, 2- (6-bromonaphthalen-2-yl) pyridine, 3- (6-bromonaphthalen-2-yl) Pyridine, 4- (6-bromonaphthalen-2-yl) pyridine, 2- (7-bromonaphthalen-2-yl) pyridine, 3- (7-bromonaphthalen-2-yl) pyridine Be used 4- (7-bromo-2-yl) regioisomer such pyridine can be synthesized corresponding boronic acid / boronate ester.

  In the reaction formula (9), (11) or (12), instead of bromide such as 2- (4-bromophenyl) pyridine and 3- (4-bromonaphthalen-1-yl) pyridine, A compound can be synthesized in the same manner using a compound, iodide or trifluoromethanesulfonate.

<Method for Synthesizing Carbazole Compound Represented by Formula (1) (Part 2)>
The carbazole compound of the present invention has a “Hy _1- (Ar ₁ ) _a —” group and a “(Hy ₂ ) _b —Ar ₂ —” group at the 2nd and 7th positions of the carbazole skeleton as described above. In addition to the method of bonding by, for example, “Ar ₁ (or Ar ₂ )” and “Hy ₁ (or Hy ₂ )” may be bonded in order to the carbazole skeleton as follows.

<Carbazole-2,7-diyl bis (trifluoromethanesulfonate) substituted with R at N-position: Synthesis of Cz-R-ArOTf>
As shown in the following reaction formula (13), an alkoxyaryl (for example, R = methoxy group or ethoxy group, Ar = phenyl or R, bonded to the compound represented by “Cz—H—Br” by a Suzuki coupling reaction) Naphthyl) is reacted with boronic acid to obtain a compound represented by “Cz—H—ArOR”, followed by a coupling reaction using a palladium catalyst, an Ullmann reaction, or a nucleophilic substitution reaction using cesium carbonate. Cz-R-ArOR "is synthesized. Next, demethylation is performed using boron tribromide, pyridine hydrochloride, or the like to synthesize a compound represented by “Cz—R—ArOH”. Then, the compound represented by "Cz-R-ArOTf" is obtained by making it react with trifluoromethanesulfonic anhydride. In the reaction formula (13), R which is an alkyl part of alkoxy and R which is a substituent bonded to the 9-position of carbazole are represented by the same symbol, but they may be the same or different.

<Synthesis of Carbazole Compound According to the Present Invention>
As shown in the following reaction formula (14) or reaction formula (15), the compound represented by “Cz—R—ArOTf” obtained as described above and “Hy ₁ ” having a reactive substituent. And by reacting “Hy ₂ ” with Suzuki coupling or Negishi coupling, the carbazole compound represented by the formula (1) can be obtained. Further, as shown in the following reaction formula (16), after the triflate is converted into a boronic acid ester using a Pd catalyst, this is converted into a halide or triflate of “Hy ₁ ” and “Hy ₂ ” with a Suzuki coupling reaction. The carbazole compound represented by the formula (1) can also be obtained by coupling them.

The synthesis method according to the above reaction formulas (13) to (16) is optimal for the synthesis of a carbazole compound in which Hy ₁ and Hy ₂ may be the same or different, but Ar ₁ and Ar ₂ are the same. is there.

<Synthesis Method of Carbazole Compound Represented by Formula (1-2), Formula (1-4), or Formula (1-5)>
In addition to the synthesis method described above, the carbazole compound represented by the formula (1-2), formula (1-4), or formula (1-5) may be prepared in advance by the “Ar ₂ —” group ( Alternatively, a “Hy ₁ (Ar ₁ ) _a —” group may be bonded after synthesizing a carbazole skeleton to which a “10-Ar ₃ -anthracen-9-yl” group) is bonded.

First, as shown in the following reaction formula (17), (4-methoxy-2-nitrophenyl) benzene having an “Ar ₂ —” group bonded to the 4-position is synthesized by a coupling reaction. Here, although Suzuki coupling using boronic acid is exemplified in the reaction formula (17), Negishi coupling using zinc complex can also be used. Next, a cyclization reaction is performed using triethyl phosphite or triphenylphosphine to obtain a carbazole derivative (Cz-A). The compound represented by “Cz-A” is converted to Cz-B by a coupling reaction using a palladium catalyst or an Ullmann reaction, and then demethylated with boron tribromide or pyridine hydrochloride to obtain Cz— C. Then, by reacting with trifluoromethanesulfonic anhydride, “Cz—R—Ar ₂ —OTf”, which is a carbazole skeleton to which the “Ar ₂ —” group is bonded, is obtained.

Next, the compound represented by “Cz—R—Ar ₂ -OTf” obtained as described above or a monoboronic acid ester compound derived from the compound (see the above reaction formula (3)) and reactivity By reacting “Hy _1- (Ar ₁ ) _a ” having the following substituents with Suzuki coupling or Negishi coupling (see the above reaction formulas (4) to (6)), the formula (1-2) ), A carbazole compound represented by formula (1-4) or formula (1-5) can be obtained.

Further, as shown in the following reaction formula (18), 1-methoxy-4- (4-chloro-2-nitrophenyl) benzene is synthesized by a coupling reaction. Here, although Suzuki coupling using boronic acid is exemplified in the reaction formula (18), Negishi coupling using zinc complex can also be used. Next, a cyclization reaction is performed using triethyl phosphite or triphenylphosphine to obtain a carbazole derivative (Cz-A ′), and then the compound represented by “Cz-A ′” is cupped using a palladium catalyst. Cz-B ′ is set by ring reaction or Ullmann reaction. Further, this compound represented by “Cz-B ′” is reacted with a boronic acid of an “Ar ₂ —” group by Suzuki coupling reaction to obtain Cz-B. Thereafter, in the same manner as in the above reaction formula (17), demethylation is performed with boron tribromide, pyridine hydrochloride or the like to obtain Cz-C, which is reacted with trifluoromethanesulfonic anhydride to obtain “Ar ₂ — "Cz-R-Ar ₂ -OTf" which is a carbazole skeleton to which a group is bonded is obtained.

Next, the compound represented by “Cz—R—Ar ₂ -OTf” obtained as described above or a monoboronic acid ester compound derived from the compound (see the above reaction formula (3)) and reactivity By reacting “Hy _1- (Ar ₁ ) _a ” having the following substituents with Suzuki coupling or Negishi coupling (see the above reaction formulas (4) to (6)), the formula (1-2) ), A carbazole compound represented by formula (1-4) or formula (1-5) can be obtained.

  In addition, the compounds of the present invention include those in which at least a part of the hydrogen atoms are substituted with deuterium. Such a compound can be obtained by using a raw material in which a desired position is deuterated. It can be synthesized in the same way.

3. Organic Electroluminescent Device The carbazole compound according to the present invention can be used as a material for an organic electroluminescent device, for example. Below, the organic electroluminescent element which concerns on this embodiment is demonstrated in detail based on drawing. FIG. 1 is a schematic cross-sectional view showing an organic electroluminescent element according to this embodiment.

<Structure of organic electroluminescence device>
An organic electroluminescent device 100 shown in FIG. 1 includes a substrate 101, an anode 102 provided on the substrate 101, a hole injection layer 103 provided on the anode 102, and a hole injection layer 103. A hole transport layer 104 provided on the light emitting layer 105, a light emitting layer 105 provided on the hole transport layer 104, an electron transport layer 106 provided on the light emitting layer 105, and an electron transport layer 106. And the cathode 108 provided on the electron injection layer 107.

  The organic electroluminescent element 100 is manufactured in the reverse order, for example, the substrate 101, the cathode 108 provided on the substrate 101, the electron injection layer 107 provided on the cathode 108, and the electron injection layer. An electron transport layer 106 provided on 107, a light-emitting layer 105 provided on the electron transport layer 106, a hole transport layer 104 provided on the light-emitting layer 105, and a hole transport layer 104 A structure including the hole injection layer 103 provided above and the anode 102 provided on the hole injection layer 103 may be employed.

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

  As an aspect of the layer constituting the organic electroluminescence device, in addition to the above-described configuration aspect of “substrate / anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode”, "Substrate / anode / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode", "substrate / anode / hole injection layer / light emitting layer / electron transport layer / electron injection layer / cathode", "substrate / Anode / hole injection layer / hole transport layer / light emitting layer / electron injection layer / cathode ”,“ substrate / anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / cathode ”,“ substrate ” / Anode / light emitting layer / electron transport layer / electron injection layer / cathode ”,“ substrate / anode / hole transport layer / light emitting layer / electron injection layer / cathode ”,“ substrate / anode / hole transport layer / light emitting layer / “Electron transport layer / cathode”, “substrate / anode / hole injection layer / light emitting layer / electron injection layer / cathode”, “substrate / anode / hole injection layer / light emitting layer / electron transport” Layer / cathode "," substrate / anode / light emitting layer / electron transporting layer / cathode "may be configured aspect of the" substrate / anode / light emitting layer / electron injection layer / cathode ".

<Substrate in organic electroluminescence device>
The substrate 101 serves as a support for the organic electroluminescent device 100, and usually quartz, glass, metal, plastic, or the like is used. The substrate 101 is formed into a plate shape, a film shape, or a sheet shape according to the purpose. For example, a glass plate, a metal plate, a metal foil, a plastic film, a plastic sheet, or the like is used. Of these, glass plates and transparent synthetic resin plates such as polyester, polymethacrylate, polycarbonate, polysulfone and the like are preferable. In the case of a glass substrate, soda lime glass, non-alkali glass, or the like is used, and the thickness only needs to be sufficient to maintain the mechanical strength. The upper limit value of the thickness is, for example, 2 mm or less, preferably 1 mm or less. The glass material is preferably alkali-free glass because it is better to have less ions eluted from the glass. However, soda lime glass with a barrier coat such as SiO ₂ is also commercially available, so it can be used. it can. Further, the substrate 101 may be provided with a gas barrier film such as a dense silicon oxide film on at least one surface in order to improve the gas barrier property, and a synthetic resin plate, film or sheet having a low gas barrier property is used as the substrate 101. When used, it is preferable to provide a gas barrier film.

<Anode in organic electroluminescence device>
The anode 102 serves to inject holes into the light emitting layer 105. When the hole injection layer 103 and / or the hole transport layer 104 are provided between the anode 102 and the light emitting layer 105, holes are injected into the light emitting layer 105 through these layers. .

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

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

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

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

  As a material for forming the hole injection layer 103 and the hole transport layer 104, in a photoconductive material, a compound conventionally used as a charge transport material for holes, a p-type semiconductor, and a hole injection of an organic electroluminescent element are used. Any known material used for the layer and the hole transport layer can be selected and used. Specific examples thereof include carbazole derivatives (N-phenylcarbazole, polyvinylcarbazole, etc.), biscarbazole derivatives such as bis (N-arylcarbazole) or bis (N-alkylcarbazole), triarylamine derivatives (aromatic tertiary class). Polymer having amino group in main chain or side chain, 1,1-bis (4-di-p-tolylaminophenyl) cyclohexane, N, N′-diphenyl-N, N′-di (3-methylphenyl)- 4,4′-diaminobiphenyl, N, N′-diphenyl-N, N′-dinaphthyl-4,4′-diaminobiphenyl, N, N′-diphenyl-N, N′-di (3-methylphenyl)- 4,4′-diphenyl-1,1′-diamine, N, N′-dinaphthyl-N, N′-diphenyl-4,4′-diphenyl- , 1′-diamine, 4,4 ′, 4 ″ -tris (3-methylphenyl (phenyl) amino) triphenylamine and other triphenylamine derivatives, starburstamine derivatives, etc., stilbene derivatives, phthalocyanine derivatives (metal-free) , Copper phthalocyanine, etc.), pyrazoline derivatives, hydrazone compounds, benzofuran derivatives, thiophene derivatives, oxadiazole derivatives, heterocyclic compounds such as porphyrin derivatives, polysilanes, etc. In the polymer system, polycarbonate having the above monomers in the side chain And styrene derivatives, polyvinyl carbazole, and polysilane are preferable, but the compound is not particularly limited as long as it is a compound that can form a thin film necessary for manufacturing a light-emitting element, inject holes from the anode, and further transport holes. Absent.

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

<Light emitting layer in organic electroluminescent element>
The light emitting layer 105 emits light by recombining holes injected from the anode 102 and electrons injected from the cathode 108 between electrodes to which an electric field is applied. The material for forming the light-emitting layer 105 may be a compound that emits light by being excited by recombination of holes and electrons (a light-emitting compound), can form a stable thin film shape, and is in a solid state It is preferable that the compound exhibits a high emission (fluorescence and / or phosphorescence) efficiency.

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

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

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

  The light emitting material of the light emitting element according to the present embodiment may be either fluorescent or phosphorescent.

  The host material is not particularly limited, but has previously been known as a light emitter, such as fused ring derivatives such as anthracene and pyrene, metal chelated oxinoid compounds such as tris (8-quinolinolato) aluminum, bis Bisstyryl derivatives such as styryl anthracene derivatives and distyrylbenzene derivatives, tetraphenylbutadiene derivatives, coumarin derivatives, oxadiazole derivatives, pyrrolopyridine derivatives, perinone derivatives, cyclopentadiene derivatives, thiadiazolopyridine derivatives, pyrrolopyrrole derivatives, fluorene derivatives, For benzofluorene derivatives and polymer systems, polyphenylene vinylene derivatives, polyparaphenylene derivatives, and polythiophene derivatives are preferably used.

  In addition, as a host material, it can select from the compound etc. which were described in the chemical industry June, 2004 issue page 13, and the reference cited up, etc. suitably.

  Moreover, it does not specifically limit as dopant material, A known compound can be used and it can select from various materials according to a desired luminescent color. Specifically, for example, condensed ring derivatives such as phenanthrene, anthracene, pyrene, tetracene, pentacene, perylene, naphthopylene, dibenzopyrene, rubrene, and chrysene, benzoxazole derivatives, benzothiazole derivatives, benzimidazole derivatives, benzotriazole derivatives, Bisstyryl such as oxazole derivatives, oxadiazole derivatives, thiazole derivatives, imidazole derivatives, thiadiazole derivatives, triazole derivatives, pyrazoline derivatives, stilbene derivatives, thiophene derivatives, tetraphenylbutadiene derivatives, cyclopentadiene derivatives, bisstyrylanthracene derivatives and distyrylbenzene derivatives Derivatives (Japanese Patent Laid-Open No. 1-245087), bisstyrylarylene derivatives (Japanese Patent Laid-Open No. 2-2472) No. 8 publication), diazaindacene derivatives, furan derivatives, benzofuran derivatives, phenylisobenzofuran, dimesitylisobenzofuran, di (2-methylphenyl) isobenzofuran, di (2-trifluoromethylphenyl) isobenzofuran, phenylisobenzofuran, etc. Isobenzofuran derivatives, dibenzofuran derivatives, 7-dialkylaminocoumarin derivatives, 7-piperidinocoumarin derivatives, 7-hydroxycoumarin derivatives, 7-methoxycoumarin derivatives, 7-acetoxycoumarin derivatives, 3-benzothiazolylcoumarin derivatives, Coumarin derivatives such as 3-benzimidazolylcoumarin derivatives, 3-benzoxazolylcoumarin derivatives, dicyanomethylenepyran derivatives, dicyanomethylenethiopyran derivatives, polymethine derivatives, Anine derivatives, oxobenzoanthracene derivatives, xanthene derivatives, rhodamine derivatives, fluorescein derivatives, pyrylium derivatives, carbostyril derivatives, acridine derivatives, oxazine derivatives, phenylene oxide derivatives, quinacridone derivatives, quinazoline derivatives, pyrrolopyridine derivatives, furopyridine derivatives, 1, Examples include 2,5-thiadiazolopyrene derivatives, pyromethene derivatives, perinone derivatives, pyrrolopyrrole derivatives, squarylium derivatives, violanthrone derivatives, phenazine derivatives, acridone derivatives, deazaflavin derivatives, fluorene derivatives, and benzofluorene derivatives.

  Illustrated for each color light, blue to blue-green dopant materials include naphthalene, anthracene, phenanthrene, pyrene, triphenylene, perylene, fluorene, indene, chrysene and other aromatic hydrocarbon compounds and derivatives thereof, furan, pyrrole, thiophene, Aromatic complex such as silole, 9-silafluorene, 9,9'-spirobisilafluorene, benzothiophene, benzofuran, indole, dibenzothiophene, dibenzofuran, imidazopyridine, phenanthroline, pyrazine, naphthyridine, quinoxaline, pyrrolopyridine, thioxanthene Ring compounds and their derivatives, distyrylbenzene derivatives, tetraphenylbutadiene derivatives, stilbene derivatives, aldazine derivatives, coumarin derivatives, imidazoles, thiazoles, thiadiazos Azole derivatives such as benzene, carbazole, oxazole, oxadiazole, triazole and metal complexes thereof, and N, N′-diphenyl-N, N′-di (3-methylphenyl) -4,4′-diphenyl-1, Examples thereof include aromatic amine derivatives represented by 1′-diamine.

  Examples of green to yellow dopant materials include coumarin derivatives, phthalimide derivatives, naphthalimide derivatives, perinone derivatives, pyrrolopyrrole derivatives, cyclopentadiene derivatives, acridone derivatives, quinacridone derivatives, and naphthacene derivatives such as rubrene. A compound in which a substituent capable of increasing the wavelength such as aryl, heteroaryl, arylvinyl, amino, and cyano is introduced into the compound exemplified as the blue to blue-green dopant material is also a suitable example.

  Further, examples of the orange to red dopant material include naphthalimide derivatives such as bis (diisopropylphenyl) perylenetetracarboxylic imide, perinone derivatives, rare earth complexes such as Eu complexes having acetylacetone, benzoylacetone and phenanthroline as ligands, 4 -(Dicyanomethylene) -2-methyl-6- (p-dimethylaminostyryl) -4H-pyran and its analogs, metal phthalocyanine derivatives such as magnesium phthalocyanine and aluminum chlorophthalocyanine, rhodamine compounds, deazaflavin derivatives, coumarin derivatives, quinacridone Derivatives, phenoxazine derivatives, oxazine derivatives, quinazoline derivatives, pyrrolopyridine derivatives, squarylium derivatives, violanthrone derivatives, phenazine derivatives, phenoxazones Substituents such as aryls, heteroaryls, arylvinyls, aminos, cyanos and the like that can be used for the compounds exemplified as conductors and thiadiazolopyrene derivatives, and examples of blue-blue-green and green-yellow dopant materials. A compound into which a group is introduced is also a suitable example. Furthermore, a phosphorescent metal complex having iridium represented by tris (2-phenylpyridine) iridium (III) or platinum as a central metal is also a suitable example.

  In addition, as a dopant, it can select and use suitably from the compound etc. which were described in the chemical industry June, 2004 issue page 13, and the reference literature etc. which were raised to it.

  Among the dopant materials described above, perylene derivatives, borane derivatives, amine-containing styryl derivatives, aromatic amine derivatives, coumarin derivatives, pyran derivatives, iridium complexes, or platinum complexes are particularly preferable.

Examples of perylene derivatives include 3,10-bis (2,6-dimethylphenyl) perylene, 3,10-bis (2,4,6-trimethylphenyl) perylene, 3,10-diphenylperylene, 3,4- Diphenylperylene, 2,5,8,11-tetra-t-butylperylene, 3,4,9,10-tetraphenylperylene, 3- (1'-pyrenyl) -8,11-di (t-butyl) perylene 3- (9′-anthryl) -8,11-di (t-butyl) perylene, 3,3′-bis (8,11-di (t-butyl) perylenyl), and the like.
Also, JP-A-11-97178, JP-A-2000-133457, JP-A-2000-26324, JP-A-2001-267079, JP-A-2001-267078, JP-A-2001-267076, Perylene derivatives described in JP-A No. 2000-34234, JP-A No. 2001-267075, JP-A No. 2001-217077 and the like may be used.

Examples of the borane derivative include 1,8-diphenyl-10- (dimesitylboryl) anthracene, 9-phenyl-10- (dimesitylboryl) anthracene, 4- (9′-anthryl) dimesitylborylnaphthalene, 4- (10 ′). -Phenyl-9'-anthryl) dimesitylborylnaphthalene, 9- (dimesitylboryl) anthracene, 9- (4'-biphenylyl) -10- (dimesitylboryl) anthracene, 9- (4 '-(N-carbazolyl) phenyl) -10- (Dimesitylboryl) anthracene and the like.
Moreover, you may use the borane derivative described in the international publication 2000/40586 pamphlet.

Examples of the amine-containing styryl derivative include N, N, N ′, N′-tetra (4-biphenylyl) -4,4′-diaminostilbene, N, N, N ′, N′-tetra (1-naphthyl). -4,4'-diaminostilbene, N, N, N ', N'-tetra (2-naphthyl) -4,4'-diaminostilbene, N, N'-di (2-naphthyl) -N, N'-Diphenyl-4,4'-diaminostilbene, N, N'-di (9-phenanthryl) -N, N'-diphenyl-4,4'-diaminostilbene, 4,4'-bis [4 "-bis ( Diphenylamino) styryl] -biphenyl, 1,4-bis [4′-bis (diphenylamino) styryl] -benzene, 2,7-bis [4′-bis (diphenylamino) styryl] -9,9-dimethylfluorene 4,4′-bis (9-ethyl-3-carbazobi Nylene) -biphenyl, 4,4′-bis (9-phenyl-3-carbazovinylene) -biphenyl, and the like.
In addition, amine-containing styryl derivatives described in JP2003-347056A and JP2001-307884A may be used.

Examples of the aromatic amine derivative include N, N, N, N-tetraphenylanthracene-9,10-diamine, 9,10-bis (4-diphenylamino-phenyl) anthracene, and 9,10-bis (4- Di (1-naphthylamino) phenyl) anthracene, 9,10-bis (4-di (2-naphthylamino) phenyl) anthracene, 10-di-p-tolylamino-9- (4-di-p-tolylamino-1) -Naphthyl) anthracene, 10-diphenylamino-9- (4-diphenylamino-1-naphthyl) anthracene, 10-diphenylamino-9- (6-diphenylamino-2-naphthyl) anthracene, [4- (4-diphenyl) Amino-phenyl) naphthalen-1-yl] -diphenylamine, [6- (4-diphenylamino-phenyl) na Talen-2-yl] -diphenylamine, 4,4′-bis [4-diphenylaminonaphthalen-1-yl] biphenyl, 4,4′-bis [6-diphenylaminonaphthalen-2-yl] biphenyl, 4,4 "-Bis [4-diphenylaminonaphthalen-1-yl] -p-terphenyl, 4,4" -bis [6-diphenylaminonaphthalen-2-yl] -p-terphenyl, and the like.
Moreover, you may use the aromatic amine derivative described in Unexamined-Japanese-Patent No. 2006-156888.

Examples of the coumarin derivative include coumarin-6 and coumarin-334.
Moreover, you may use the coumarin derivative described in Unexamined-Japanese-Patent No. 2004-43646, Unexamined-Japanese-Patent No. 2001-76876, and Unexamined-Japanese-Patent No. 6-298758.

また、特開2005-126399号公報、特開2005-097283号公報、特開2002-234892号公報、特開2001-220577号公報、特開2001-081090号公報、および特開2001-052869号公報などに記載されたピラン誘導体を用いてもよい。 Examples of the pyran derivative include the following DCM and DCJTB.

Also, JP 2005-126399, JP 2005-097283, JP 2002-234892, JP 2001-220577, JP 2001-081090, and JP 2001-052869. Alternatively, pyran derivatives described in the above may be used.

また、特開2006-089398号公報、特開2006-080419号公報、特開2005-298483号公報、特開2005-097263号公報、および特開2004-111379号公報などに記載されたイリジウム錯体を用いてもよい。 Examples of the iridium complex include Ir (ppy) _{3 described} below.

Further, the iridium complexes described in JP-A-2006-089398, JP-A-2006-080419, JP-A-2005-298483, JP-A-2005-097263, JP-A-2004-111379, etc. It may be used.

また、特開2006-190718号公報、特開2006-128634号公報、特開2006-093542号公報、特開2004-335122号公報、および特開2004-331508号公報などに記載された白金錯体を用いてもよい。 Examples of the platinum complex include the following PtOEP.

Further, the platinum complexes described in JP-A-2006-190718, JP-A-2006-128634, JP-A-2006-093542, JP-A-2004-335122, JP-A-2004-331508, etc. It may be used.

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

  The electron injection / transport layer is a layer that is responsible for injecting electrons from the cathode and further transporting the electrons. It is desirable that the electron injection efficiency is high and the injected electrons are transported efficiently. For this purpose, it is preferable to use a substance that has a high electron affinity, a high electron mobility, excellent stability, and is unlikely to generate trapping impurities during production and use. However, considering the transport balance between holes and electrons, if the role of effectively preventing the holes from the anode from flowing to the cathode side without recombination is mainly played, the electron transport capability is much higher. Even if it is not high, the effect of improving the luminous efficiency is equivalent to that of a material having a high electron transport capability. Therefore, the electron injection / transport layer in this embodiment may include a function of a layer that can efficiently block the movement of holes.

  As a material (electron transport material) for forming the electron transport layer 106 or the electron injection layer 107, a compound represented by the above formula (1) can be used. Among these, in the present application, in particular, an embodiment in which a = 1 and b = 0 and an embodiment in which a = 0 and b = 0, that is, the above formula (1-2), formula (1-4) or formula (1-5) ) Is preferably used.

  The content of the compound represented by the above formula (1) in the electron transport layer 106 or the electron injection layer 107 differs depending on the type of the compound, and may be determined according to the characteristics of the compound. The standard of the content of the compound represented by the formula (1) is preferably 1 to 100% by weight, more preferably 10 to 100% by weight, based on the whole electron transport layer material (or electron injection layer material). More preferably, it is 50 to 100% by weight, and particularly preferably 80 to 100% by weight. When the compound represented by the formula (1) is not used alone (100% by weight), other materials described in detail below may be mixed.

  Other materials for forming the electron transport layer or electron injection layer include compounds conventionally used as electron transport compounds in photoconductive materials, and known materials used for electron injection layers and electron transport layers of organic electroluminescent devices. Any of these compounds can be selected and used.

  As a material used for the electron transport layer or the electron injection layer, a compound composed of an aromatic ring or a heteroaromatic ring composed of one or more atoms selected from carbon, hydrogen, oxygen, sulfur, silicon, and phosphorus, pyrrole It is preferable to contain at least one selected from a derivative, a condensed ring derivative thereof, and a metal complex having an electron-accepting nitrogen. Specifically, condensed ring aromatic ring derivatives such as naphthalene and anthracene, styryl aromatic ring derivatives represented by 4,4′-bis (diphenylethenyl) biphenyl, perinone derivatives, coumarin derivatives, naphthalimide derivatives, anthraquinones And quinone derivatives such as diphenoquinone, phosphorus oxide derivatives, carbazole derivatives other than the compound represented by the above formula (1), and indole derivatives. Examples of metal complexes having electron-accepting nitrogen include hydroxyazole complexes such as hydroxyphenyloxazole complexes, azomethine complexes, tropolone metal complexes, flavonol metal complexes, and benzoquinoline metal complexes. These materials can be used alone or in combination with different materials. Among them, anthracene derivatives such as 9,10-bis (2-naphthyl) anthracene, styryl aromatic ring derivatives such as 4,4′-bis (diphenylethenyl) biphenyl, 4,4′-bis (N-carbazolyl) biphenyl A carbazole derivative such as 1,3,5-tris (N-carbazolyl) benzene is preferably used from the viewpoint of durability.

  Specific examples of other electron transfer compounds include pyridine derivatives other than the compound represented by the above formula (1), naphthalene derivatives other than the compound represented by the formula (1), anthracene derivatives, phenanthroline derivatives, perinone derivatives, Coumarin derivatives, naphthalimide derivatives, anthraquinone derivatives, diphenoquinone derivatives, diphenylquinone derivatives, perylene derivatives, oxadiazole derivatives (1,3-bis [(4-t-butylphenyl) 1,3,4-oxadiazolyl] phenylene, etc.) Thiophene derivatives, triazole derivatives (N-naphthyl-2,5-diphenyl-1,3,4-triazole, etc.), thiadiazole derivatives, metal complexes of oxine derivatives, quinolinol metal complexes, quinoxaline derivatives, polymers of quinoxaline derivatives, benzazo Compounds, gallium complexes, pyrazole derivatives, perfluorinated phenylene derivatives, triazine derivatives, pyrazine derivatives, benzoquinoline derivatives (2,2'-bis (benzo [h] quinolin-2-yl) -9,9'-spiro Bifluorene, etc.), imidazopyridine derivatives, borane derivatives, benzimidazole derivatives (such as tris (N-phenylbenzoimidazol-2-yl) benzene), benzoxazole derivatives, benzothiazole derivatives, quinoline derivatives, oligopyridine derivatives such as terpyridine, Bipyridine derivatives, terpyridine derivatives (such as 1,3-bis (4 ′-(2,2 ′: 6′2 ″ -terpyridinyl)) benzene), naphthyridine derivatives (bis (1-naphthyl) -4- (1,8- Naphthyridin-2-yl) phenylphosphite Oxide, etc.), aldazine derivatives, carbazole derivatives other than the compounds represented by the above formula (1), indole derivatives, phosphorus oxide derivatives, such as bis-styryl derivatives.

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

  Although the above-mentioned materials are used alone, they may be mixed with different materials.

  Among the materials described above, quinolinol metal complexes, bipyridine derivatives, phenanthroline derivatives, borane derivatives or benzimidazole derivatives are preferable.

式中、Ｒ^１〜Ｒ^６は水素または置換基であり、ＭはＡｌ、Ｇａ、Ｂｅ、またはＺｎであり、ｎは２または３の整数である。 The quinolinol-based metal complex is a compound represented by the following general formula (E-1).

In the formula, R ^{1 to} R ⁶ are hydrogen or a substituent, M is Al, Ga, Be, or Zn, and n is an integer of 2 or 3.

  Specific examples of the quinolinol-based metal complex include tris (8-quinolinolato) aluminum, tris (4-methyl-8-quinolinolato) aluminum, tris (5-methyl-8-quinolinolato) aluminum, tris (3,4-dimethyl- 8-quinolinolato) aluminum, tris (4,5-dimethyl-8-quinolinolato) aluminum, tris (4,6-dimethyl-8-quinolinolato) aluminum, bis (2-methyl-8-quinolinolato) (phenolate) aluminum, bis (2-methyl-8-quinolinolato) (2-methylphenolato) aluminum, bis (2-methyl-8-quinolinolato) (3-methylphenolato) aluminum, bis (2-methyl-8-quinolinolato) (4- Methyl phenolate) alumini Bis (2-methyl-8-quinolinolato) (2-phenylphenolate) aluminum, bis (2-methyl-8-quinolinolato) (3-phenylphenolato) aluminum, bis (2-methyl-8-quinolinolato) (4-Phenylphenolate) aluminum, bis (2-methyl-8-quinolinolato) (2,3-dimethylphenolate) aluminum, bis (2-methyl-8-quinolinolato) (2,6-dimethylphenolate) aluminum Bis (2-methyl-8-quinolinolato) (3,4-dimethylphenolate) aluminum, bis (2-methyl-8-quinolinolato) (3,5-dimethylphenolate) aluminum, bis (2-methyl-8) -Quinolinolate) (3,5-di-t-butylphenolate) alumini Bis (2-methyl-8-quinolinolato) (2,6-diphenylphenolate) aluminum, bis (2-methyl-8-quinolinolato) (2,4,6-triphenylphenolato) aluminum, bis (2 -Methyl-8-quinolinolato) (2,4,6-trimethylphenolate) aluminum, bis (2-methyl-8-quinolinolato) (2,4,5,6-tetramethylphenolato) aluminum, bis (2- Methyl-8-quinolinolato) (1-naphtholato) aluminum, bis (2-methyl-8-quinolinolato) (2-naphtholato) aluminum, bis (2,4-dimethyl-8-quinolinolato) (2-phenylphenolato) aluminum Bis (2,4-dimethyl-8-quinolinolate) (3-phenylphenola) G) Aluminum, bis (2,4-dimethyl-8-quinolinolato) (4-phenylphenolate) aluminum, bis (2,4-dimethyl-8-quinolinolato) (3,5-dimethylphenolate) aluminum, bis ( 2,4-dimethyl-8-quinolinolato) (3,5-di-t-butylphenolate) aluminum, bis (2-methyl-8-quinolinolato) aluminum-μ-oxo-bis (2-methyl-8-quinolinolato) ) Aluminum, bis (2,4-dimethyl-8-quinolinolato) aluminum-μ-oxo-bis (2,4-dimethyl-8-quinolinolato) aluminum, bis (2-methyl-4-ethyl-8-quinolinolato) aluminum -Μ-oxo-bis (2-methyl-4-ethyl-8-quinolinolato) aluminum Bis (2-methyl-4-methoxy-8-quinolinolato) aluminum-μ-oxo-bis (2-methyl-4-methoxy-8-quinolinolato) aluminum, bis (2-methyl-5-cyano-8- Quinolinolato) aluminum-μ-oxo-bis (2-methyl-5-cyano-8-quinolinolato) aluminum, bis (2-methyl-5-trifluoromethyl-8-quinolinolato) aluminum-μ-oxo-bis (2- Methyl-5-trifluoromethyl-8-quinolinolato) aluminum, bis (10-hydroxybenzo [h] quinoline) beryllium and the like.

式中、Ｇは単なる結合手またはｎ価の連結基を表し、ｎは２〜８の整数である。また、ピリジン−ピリジンまたはピリジン−Ｇの結合に用いられない炭素は置換されていてもよい。 A bipyridine derivative is a compound represented by the following general formula (E-2).

In the formula, G represents a simple bond or an n-valent linking group, and n is an integer of 2 to 8. Further, carbon not used for bonding of pyridine-pyridine or pyridine-G may be substituted.

Examples of G in the general formula (E-2) include the following structural formulas. In addition, R in the following structural formula is each independently hydrogen, methyl, ethyl, isopropyl, cyclohexyl, phenyl, 1-naphthyl, 2-naphthyl, biphenylyl, or terphenylyl.

  Specific examples of the pyridine derivative include 2,5-bis (2,2′-bipyridin-6-yl) -1,1-dimethyl-3,4-diphenylsilole, 2,5-bis (2,2′- Bipyridin-6-yl) -1,1-dimethyl-3,4-dimesitylsilole, 2,5-bis (2,2′-bipyridin-5-yl) -1,1-dimethyl-3,4 Diphenylsilole, 2,5-bis (2,2′-bipyridin-5-yl) -1,1-dimethyl-3,4-dimesitylsilole, 9,10-di (2,2′-bipyridine-6) -Yl) anthracene, 9,10-di (2,2'-bipyridin-5-yl) anthracene, 9,10-di (2,3'-bipyridin-6-yl) anthracene, 9,10-di (2 , 3′-bipyridin-5-yl) anthracene, 9,10-di (2, '-Bipyridin-6-yl) -2-phenylanthracene, 9,10-di (2,3'-bipyridin-5-yl) -2-phenylanthracene, 9,10-di (2,2'-bipyridine) 6-yl) -2-phenylanthracene, 9,10-di (2,2′-bipyridin-5-yl) -2-phenylanthracene, 9,10-di (2,4′-bipyridin-6-yl) 2-phenylanthracene, 9,10-di (2,4′-bipyridin-5-yl) -2-phenylanthracene, 9,10-di (3,4′-bipyridin-6-yl) -2-phenyl Anthracene, 9,10-di (3,4'-bipyridin-5-yl) -2-phenylanthracene, 3,4-diphenyl-2,5-di (2,2′-bipyridin-6-yl) thiophene, 3,4-dipheni -2,5-di (2,3'-bipyridin-5-yl) thiophene, 6'6 "-di (2-pyridyl) 2,2 ': 4', 4": 2 ", 2" '-qua Examples include terpyridine.

式中、Ｒ^１〜Ｒ^８は水素または置換基であり、隣接する基は互いに結合して縮合環を形成してもよく、Ｇは単なる結合手またはｎ価の連結基を表し、ｎは２〜８の整数である。また、一般式（Ｅ−３−２）のＧとしては、例えば、ビピリジン誘導体の欄で説明したものと同じものがあげられる。 A phenanthroline derivative is a compound represented by the following general formula (E-3-1) or (E-3-2).

In the formula, R ^{1 to} R ⁸ are hydrogen or a substituent, adjacent groups may be bonded to each other to form a condensed ring, G represents a simple bond or an n-valent linking group, and n represents 2 It is an integer of ~ 8. Moreover, as G of general formula (E-3-2), the same thing as what was demonstrated in the column of the bipyridine derivative is mention | raise | lifted, for example.

  Specific examples of the phenanthroline derivative include 4,7-diphenyl-1,10-phenanthroline, 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline, 9,10-di (1,10-phenanthroline- 2-yl) anthracene, 2,6-di (1,10-phenanthroline-5-yl) pyridine, 1,3,5-tri (1,10-phenanthroline-5-yl) benzene, 9,9′-difluor -Bis (1,10-phenanthroline-5-yl), bathocuproin, 1,3-bis (2-phenyl-1,10-phenanthroline-9-yl) benzene and the like.

  In particular, the case where a phenanthroline derivative is used for an electron transport layer and an electron injection layer will be described. In order to obtain stable light emission over a long period of time, a material excellent in thermal stability and thin film formation is desired, and among phenanthroline derivatives, the substituent itself has a three-dimensional structure, or a phenanthroline skeleton or Those having a three-dimensional structure by steric repulsion with an adjacent substituent or those having a plurality of phenanthroline skeletons linked to each other are preferred. Furthermore, when linking a plurality of phenanthroline skeletons, a compound containing a conjugated bond, a substituted or unsubstituted aromatic hydrocarbon, or a substituted or unsubstituted aromatic heterocycle in the linking unit is more preferable.

式中、Ｒ^１１およびＲ^１２は、それぞれ独立して、水素、アルキル、置換されていてもよいアリール、置換シリル、置換されていてもよい窒素含有複素環、またはシアノの少なくとも一つであり、Ｒ^１３〜Ｒ^１６は、それぞれ独立して、置換されていてもよいアルキル、または置換されていてもよいアリールであり、Ｘは、置換されていてもよいアリーレンであり、Ｙは、置換されていてもよい炭素数１６以下のアリール、置換ボリル、または置換されていてもよいカルバゾールであり、そして、ｎはそれぞれ独立して０〜３の整数である。 The borane derivative is a compound represented by the following general formula (E-4), and is disclosed in detail in JP-A-2007-27587.

Wherein R ¹¹ and R ¹² are each independently at least one of hydrogen, alkyl, optionally substituted aryl, substituted silyl, optionally substituted nitrogen-containing heterocycle, or cyano, R ^{13 to} R ¹⁶ are each independently an optionally substituted alkyl or an optionally substituted aryl, X is an optionally substituted arylene, and Y is a substituted And optionally substituted aryl having 16 or less carbon atoms, substituted boryl, or optionally substituted carbazole, and n is each independently an integer of 0 to 3.

式中、Ｒ^１１およびＲ^１２は、それぞれ独立して、水素、アルキル、置換されていてもよいアリール、置換シリル、置換されていてもよい窒素含有複素環、またはシアノの少なくとも一つであり、Ｒ^１３〜Ｒ^１６は、それぞれ独立して、置換されていてもよいアルキル、または置換されていてもよいアリールであり、Ｒ^２１およびＲ^２２は、それぞれ独立して、水素、アルキル、置換されていてもよいアリール、置換シリル、置換されていてもよい窒素含有複素環、またはシアノの少なくとも一つであり、Ｘ^１は、置換されていてもよい炭素数２０以下のアリーレンであり、ｎはそれぞれ独立して０〜３の整数であり、そして、ｍはそれぞれ独立して０〜４の整数である。 Among the compounds represented by the general formula (E-4), the compounds represented by the following general formula (E-4-1), and further the following general formulas (E-4-1-1) to (E-4) The compound represented by -1-4) is preferable. Specific examples include 9- [4- (4-Dimesitylborylnaphthalen-1-yl) phenyl] carbazole, 9- [4- (4-Dimesitylborylnaphthalen-1-yl) naphthalen-1-yl. Carbazole and the like.

Wherein R ¹¹ and R ¹² are each independently at least one of hydrogen, alkyl, optionally substituted aryl, substituted silyl, optionally substituted nitrogen-containing heterocycle, or cyano, R ^{13 to} R ¹⁶ are each independently an optionally substituted alkyl, or an optionally substituted aryl, and R ²¹ and R ²² are each independently hydrogen, alkyl, substituted. At least one of optionally substituted aryl, substituted silyl, optionally substituted nitrogen-containing heterocyclic ring, or cyano, X ¹ is an optionally substituted arylene having 20 or less carbon atoms, and n is each Each independently represents an integer of 0 to 3, and each m independently represents an integer of 0 to 4;

各式中、Ｒ^３１〜Ｒ^３４は、それぞれ独立して、メチル、イソプロピルまたはフェニルのいずれかであり、そして、Ｒ^３５およびＲ^３６は、それぞれ独立して、水素、メチル、イソプロピルまたはフェニルのいずれかである。

In each formula, R ^{31 to} R ³⁴ are each independently methyl, isopropyl or phenyl, and R ³⁵ and R ³⁶ are each independently hydrogen, methyl, isopropyl or phenyl. It is.

式中、Ｒ^１１およびＲ^１２は、それぞれ独立して、水素、アルキル、置換されていてもよいアリール、置換シリル、置換されていてもよい窒素含有複素環、またはシアノの少なくとも一つであり、Ｒ^１３〜Ｒ^１６は、それぞれ独立して、置換されていてもよいアルキル、または置換されていてもよいアリールであり、Ｘ^１は、置換されていてもよい炭素数２０以下のアリーレンであり、そして、ｎはそれぞれ独立して０〜３の整数である。 Among the compounds represented by the general formula (E-4), a compound represented by the following general formula (E-4-2), and a compound represented by the following general formula (E-4-2-1) Is preferred.

Wherein R ¹¹ and R ¹² are each independently at least one of hydrogen, alkyl, optionally substituted aryl, substituted silyl, optionally substituted nitrogen-containing heterocycle, or cyano, R ^{13 to} R ¹⁶ are each independently an optionally substituted alkyl or an optionally substituted aryl, X ¹ is an optionally substituted arylene having 20 or less carbon atoms, And n is an integer of 0-3 each independently.

式中、Ｒ^３１〜Ｒ^３４は、それぞれ独立して、メチル、イソプロピルまたはフェニルのいずれかであり、そして、Ｒ^３５およびＲ^３６は、それぞれ独立して、水素、メチル、イソプロピルまたはフェニルのいずれかである。

In the formula, R ^{31 to} R ³⁴ are each independently any of methyl, isopropyl or phenyl, and R ³⁵ and R ³⁶ are each independently any of hydrogen, methyl, isopropyl or phenyl It is.

式中、Ｒ^１１およびＲ^１２は、それぞれ独立して、水素、アルキル、置換されていてもよいアリール、置換シリル、置換されていてもよい窒素含有複素環、またはシアノの少なくとも一つであり、Ｒ^１３〜Ｒ^１６は、それぞれ独立して、置換されていてもよいアルキル、または置換されていてもよいアリールであり、Ｘ^１は、置換されていてもよい炭素数１０以下のアリーレンであり、Ｙ^１は、置換されていてもよい炭素数１４以下のアリールであり、そして、ｎはそれぞれ独立して０〜３の整数である。 Among the compounds represented by the general formula (E-4), a compound represented by the following general formula (E-4-3-3), and further, the following general formula (E-4-3-1) or (E-4) The compound represented by -3-2) is preferable.

Wherein R ¹¹ and R ¹² are each independently at least one of hydrogen, alkyl, optionally substituted aryl, substituted silyl, optionally substituted nitrogen-containing heterocycle, or cyano, R ^{13 to} R ¹⁶ are each independently an optionally substituted alkyl or an optionally substituted aryl, X ¹ is an optionally substituted arylene having 10 or less carbon atoms, Y ¹ is an optionally substituted aryl having 14 or less carbon atoms, and n is each independently an integer of 0 to 3.

各式中、Ｒ^３１〜Ｒ^３４は、それぞれ独立して、メチル、イソプロピルまたはフェニルのいずれかであり、そして、Ｒ^３５およびＲ^３６は、それぞれ独立して、水素、メチル、イソプロピルまたはフェニルのいずれかである。

In each formula, R ^{31 to} R ³⁴ are each independently methyl, isopropyl or phenyl, and R ³⁵ and R ³⁶ are each independently hydrogen, methyl, isopropyl or phenyl. It is.

式中、Ａｒ^１〜Ａｒ^３はそれぞれ独立に水素または置換されてもよい炭素数６〜３０のアリールである。特に、Ａｒ^１が置換されてもよいアントリルであるベンゾイミダゾール誘導体が好ましい。 The benzimidazole derivative is a compound represented by the following general formula (E-5).

In the formula, Ar ^{1 to} Ar ³ are each independently hydrogen or aryl having 6 to 30 carbon atoms which may be substituted. In particular, a benzimidazole derivative which is anthryl optionally substituted with Ar ¹ is preferable.

  Specific examples of the aryl having 6 to 30 carbon atoms include phenyl, 1-naphthyl, 2-naphthyl, acenaphthylene-1-yl, acenaphthylene-3-yl, acenaphthylene-4-yl, acenaphthylene-5-yl, and fluorene-1- Yl, fluoren-2-yl, fluoren-3-yl, fluoren-4-yl, fluoren-9-yl, phenalen-1-yl, phenalen-2-yl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl, 9-phenanthryl, 1-anthryl, 2-anthryl, 9-anthryl, fluoranthen-1-yl, fluoranthen-2-yl, fluoranthen-3-yl, fluoranthen-7-yl, fluoranthen-8-yl, Triphenylene-1-yl, triphenylene-2-yl, pyreth -1-yl, pyren-2-yl, pyren-4-yl, chrysen-1-yl, chrysen-2-yl, chrysen-3-yl, chrysen-4-yl, chrysen-5-yl, chrysene-6 -Yl, naphthacene-1-yl, naphthacene-2-yl, naphthacene-5-yl, perylene-1-yl, perylene-2-yl, perylene-3-yl, pentacene-1-yl, pentasen-2-yl , Pentacene-5-yl and pentacene-6-yl.

  Specific examples of the benzimidazole derivative include 1-phenyl-2- (4- (10-phenylanthracen-9-yl) phenyl) -1H-benzo [d] imidazole, 2- (4- (10- (naphthalene-2) -Yl) anthracen-9-yl) phenyl) -1-phenyl-1H-benzo [d] imidazole, 2- (3- (10- (naphthalen-2-yl) anthracen-9-yl) phenyl) -1- Phenyl-1H-benzo [d] imidazole, 5- (10- (naphthalen-2-yl) anthracen-9-yl) -1,2-diphenyl-1H-benzo [d] imidazole, 1- (4- (10 -(Naphthalen-2-yl) anthracen-9-yl) phenyl) -2-phenyl-1H-benzo [d] imidazole, 2- (4- (9,10-di (naphthalene) 2-yl) anthracen-2-yl) phenyl) -1-phenyl-1H-benzo [d] imidazole, 1- (4- (9,10-di (naphthalen-2-yl) anthracen-2-yl) phenyl ) -2-phenyl-1H-benzo [d] imidazole, 5- (9,10-di (naphthalen-2-yl) anthracen-2-yl) -1,2-diphenyl-1H-benzo [d] imidazole is there.

The electron transport layer or the electron injection layer may further contain a substance capable of reducing the material forming the electron transport layer or the electron injection layer. As this reducing substance, various substances can be used as long as they have a certain reducing ability. For example, alkali metal, alkaline earth metal, rare earth metal, alkali metal oxide, alkali metal halide, alkali Group consisting of earth metal oxides, alkaline earth metal halides, rare earth metal oxides, rare earth metal halides, alkali metal organic complexes, alkaline earth metal organic complexes, and rare earth metal organic complexes At least one selected from can be preferably used.
Preferred reducing substances include alkali metals such as Na (work function 2.36 eV), K (2.28 eV), Rb (2.16 eV) or Cs (1.95 eV), and Ca (2. 9eV), Sr (2.0 to 2.5 eV) or Ba (2.52 eV), and alkaline earth metals such as those having a work function of 2.9 eV or less are particularly preferable. Among these, a more preferable reducing substance is an alkali metal of K, Rb or Cs, more preferably Rb or Cs, and most preferably Cs. These alkali metals have particularly high reducing ability, and by adding a relatively small amount to the material forming the electron transport layer or the electron injection layer, the luminance of the organic EL element can be improved and the lifetime can be extended. Further, as a reducing substance having a work function of 2.9 eV or less, a combination of two or more alkali metals is also preferable. Particularly, a combination containing Cs, such as Cs and Na, Cs and K, Cs and Rb, A combination of Cs, Na and K is preferred. By containing Cs, the reducing ability can be efficiently exhibited, and by adding to the material for forming the electron transport layer or the electron injection layer, the luminance of the organic EL element can be improved and the lifetime can be extended.

<Cathode in organic electroluminescence device>
The cathode 108 serves to inject electrons into the light emitting layer 105 through the electron injection layer 107 and the electron transport layer 106.

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

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

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

<Method for producing organic electroluminescent element>
Each layer constituting the organic electroluminescent element is formed by a method such as vapor deposition, resistance heating vapor deposition, electron beam vapor deposition, sputtering, molecular lamination method, printing method, spin coating method, casting method, or coating method. The film can be formed by forming a thin film. The thickness of each layer formed in this way is not particularly limited and can be appropriately set according to the properties of the material, but is usually in the range of 2 nm to 5000 nm. The film thickness can usually be measured with a crystal oscillation type film thickness measuring device or the like. When a thin film is formed using a vapor deposition method, the vapor deposition conditions vary depending on the type of material, the target crystal structure and association structure of the film, and the like. Deposition conditions generally include boat heating temperature +50 to + 400 ° C., vacuum degree 10 ⁻⁶ to 10 ⁻³ Pa, deposition rate 0.01 to 50 nm / sec, substrate temperature −150 to + 300 ° C., film thickness 2 nm to 5 μm. It is preferable to set appropriately within the range.

  Next, as an example of a method for producing an organic electroluminescent device, an organic electric field composed of an anode / hole injection layer / hole transport layer / a light emitting layer composed of a host material and a dopant material / electron transport layer / electron injection layer / cathode. A method for manufacturing a light-emitting element will be described. A thin film of an anode material is formed on a suitable substrate by vapor deposition or the like to produce an anode, and then a thin film of a hole injection layer and a hole transport layer is formed on the anode. A host material and a dopant material are co-evaporated to form a thin film to form a light emitting layer. An electron transport layer and an electron injection layer are formed on the light emitting layer, and a thin film made of a cathode material is formed by vapor deposition. By forming it as a cathode, a desired organic electroluminescent element can be obtained. In the preparation of the above-described organic electroluminescence device, the order of preparation may be reversed, and the cathode, electron injection layer, electron transport layer, light emitting layer, hole transport layer, hole injection layer, and anode may be fabricated in this order. Is possible.

  When a DC voltage is applied to the organic electroluminescent device thus obtained, the anode may be applied with a positive polarity and the cathode with a negative polarity. Luminescence can be observed from the electrode side (anode or cathode, and both). The organic electroluminescence device emits light when a pulse current or an alternating current is applied. The alternating current waveform to be applied may be arbitrary.

<Application examples of organic electroluminescent devices>
The present invention can also be applied to a display device provided with an organic electroluminescent element or a lighting device provided with an organic electroluminescent element.
A display device or an illuminating device including an organic electroluminescent element can be manufactured by a known method such as connecting the organic electroluminescent element according to the present embodiment and a known driving device, such as direct current driving, pulse driving, or alternating current. It can be driven by appropriately using a known driving method such as driving.

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

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

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

  Examples of the illuminating device include an illuminating device such as indoor lighting, a backlight of a liquid crystal display device, and the like (for example, JP 2003-257621 A, JP 2003-277741 A, JP 2004-119211 A). Etc.) The backlight is mainly used for the purpose of improving the visibility of a display device that does not emit light, and is used for a liquid crystal display device, a clock, an audio device, an automobile panel, a display board, a sign, and the like. In particular, as a backlight for liquid crystal display devices, especially personal computers for which thinning is an issue, considering that conventional methods are made of fluorescent lamps and light guide plates, it is difficult to reduce the thickness. The backlight using the light emitting element according to the embodiment is thin and lightweight.

<Synthesis Example of Compound Represented by Formula (1-4-98)>

Synthesis of 2- (4′-methoxy-2′-nitro- [1,1′-biphenyl] -4-yl) naphthalene 4- (Naphthalen-2-yl) phenylboronic acid (25 g), 1-chloro-4 A flask containing methoxy-2-nitrobenzene (18.9 g), tripotassium phosphate (42.8 g), Pd (PPh ₃ ) ₄ (0.5 g), tetrahydrofuran (225 ml) and water (22.5 ml) The mixture was stirred at reflux temperature for 17 hours under a nitrogen atmosphere. The reaction solution was cooled to room temperature, water was added, and the precipitate was collected by suction filtration. The obtained solid was washed with methanol, dissolved in heated chlorobenzene, and filtered with suction using a Kiriyama funnel covered with silica gel. The filtrate was evaporated under reduced pressure and the resulting solid was washed with ethyl acetate to give 2- (4′-methoxy-2′-nitro- [1,1′-biphenyl] -4-yl) naphthalene (31.3 g). Got.

Synthesis of 2-methoxy-7- (naphthalen-2-yl) -9H-carbazole 2- (4′-methoxy-2′-nitro- [1,1′-biphenyl] -4 obtained as described above A flask containing -yl) naphthalene (30.0 g), triphenylphosphine (110.7 g) and N, N-dimethylacetamide (170 ml) was stirred at reflux temperature for 7 hours under a nitrogen atmosphere. Thereafter, the solvent was distilled off under reduced pressure, and the obtained solid was washed with toluene and then tetrahydrofuran in this order to obtain 2-methoxy-7- (naphthalen-2-yl) -9H-carbazole (19.1 g). .

Synthesis of 2-methoxy-7- (naphthalen-2-yl) -9-phenyl-9H-carbazole 2-methoxy-7- (naphthalen-2-yl) -9H-carbazole (19 .1 g), bromobenzene (13.9 g), palladium acetate (0.27 g), tri-t-butylphosphine (0.72 g), tripotassium phosphate (37.6 g), and xylene (180 ml). Was stirred at reflux temperature for 14 hours under a nitrogen atmosphere. After cooling the reaction solution to room temperature, toluene and water were added for liquid separation, and the solvent of the organic layer was distilled off under reduced pressure. Subsequently, it is purified by silica gel column chromatography (toluene / heptane = 1/1 (volume ratio)), the solvent is distilled off under reduced pressure, and the resulting solid is washed with heptane to give 2-methoxy-7- (naphthalene-2 -Yl) -9-phenyl-9H-carbazole (23.0 g) was obtained.

Synthesis of 7- (naphthalen-2-yl) -9-phenyl-9H-carbazol-2-ol 2-methoxy-7- (naphthalen-2-yl) -9-phenyl-9H obtained as described above A flask containing carbazole (23.0 g), pyridine hydrochloride (33.3 g) and 1-methyl-2-pyrrolidone (20 ml) was stirred at reflux temperature for 4 hours under a nitrogen atmosphere. After cooling the reaction solution to about 80 ° C., water was added and washed while hot. Next, the reaction solution was dissolved in a toluene / ethanol mixed solvent and dehydrated with sodium sulfate, and then the solvent was distilled off under reduced pressure. The precipitated solid was further washed with heptane to obtain 7- (naphthalen-2-yl) -9-phenyl-9H-carbazol-2-ol (22.2 g).

Synthesis of 7- (naphthalen-2-yl) -9-phenyl-9H-carbazol-2-yl trifluoromethanesulfonate 7- (Naphthalen-2-yl) -9-phenyl-9H obtained as described above -A flask containing carbazol-2-ol (22.2 g) and pyridine (145 ml) was cooled in an ice bath, and trifluoromethanesulfonic anhydride (24.4 g) was added dropwise thereto. After completion of the dropwise addition, the mixture was stirred at room temperature for 2 hours, and the solid precipitated by adding water was collected by suction filtration. The obtained solid was washed with water, dissolved in toluene, and subjected to suction filtration with a Kiriyama funnel covered with silica gel. The obtained filtrate was distilled off under reduced pressure to obtain 7- (naphthalen-2-yl) -9-phenyl-9H-carbazol-2-yl trifluoromethanesulfonate (28.9 g).

Compound represented by formula (1-4-98): Synthesis of 2- (naphthalen-2-yl) -9-phenyl-7- (pyridin-3-yl) -9H-carbazole 7- (Naphthalen-2-yl) -9-phenyl-9H-carbazol-2-yl trifluoromethanesulfonate (2.33 g), 3-pyridineboronic acid (0.61 g), Pd (dba) ₂ (0 0.08 g), tricyclohexylphosphine (0.06 g), tripotassium phosphate (1.91 g) and N, N-dimethylacetamide (18 ml) were stirred at 120 ° C. for 3 hours. The reaction solution was cooled to room temperature, water was added, and the precipitated solid was collected by suction filtration. The obtained solid was washed with water and then dissolved in heated toluene, and the insoluble matter was removed by hot filtration. Further purification was performed by silica gel column chromatography (toluene / ethyl acetate mixed solvent). At this time, referring to the method described in “Chemical Doujin Shuppan Co., Ltd., page 94”, the ratio of ethyl acetate in the developing solution was gradually increased. The target product was eluted by increasing the amount to 1. The solvent was distilled off under reduced pressure, and 2- (naphthalen-2-yl) -9-phenyl-7- (pyridin-3-yl) -9H-carbazole, which is a compound represented by the formula (1-4-98) ( 1.3 g) was obtained.

The structure of the compound obtained by NMR measurement was confirmed.
¹ H-NMR (500 MHz, CDCl ₃ ): δ = 8.93 (m, 1H), 8.60 (dd, 1H), 8.27 (d, 2H), 8.11 (m, 1H), 7 .90-7.97 (m, 3H), 7.88 (d, 1H), 7.82 (dd, 1H), 7.65-7.75 (m, 6H), 7.47-7.61 (M, 5H), 7.37 (m, 1H).

<Synthesis Example of Compound Represented by Formula (1-4-100)>

Synthesis of 2- (naphthalen-2-yl) -9-phenyl-7- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -9H-carbazole 7- (Naphthalen-2-yl) -9-phenyl-9H-carbazol-2-yl trifluoromethanesulfonate (19.7 g), bis (pinacolato) diboron (11.6 g), Pd (dppf) Cl ₂ (0 .6 g), potassium acetate (11.2 g) and cyclopentyl methyl ether (190 ml) were stirred at reflux temperature under a nitrogen atmosphere for 4 hours. The reaction solution was cooled to room temperature, and ethyl acetate and water were added to separate the layers. The solid obtained by evaporating the solvent under reduced pressure was purified by silica gel column chromatography (toluene), and 2- (naphthalen-2-yl) -9-phenyl-7- (4,4,5,5-tetramethyl). -1,3,2-dioxaborolan-2-yl) -9H-carbazole (18.4 g) was obtained.

Compound represented by formula (1-4-100); synthesis of 2-([2,2′-bipyridin] -5-yl) -7- (naphthalen-2-yl) -9-phenyl-9H-carbazole 2- (Naphthalen-2-yl) -9-phenyl-7- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -9H obtained as described above -Carbazole (4.0 g), 5-bromo-2,2'-bipyridine (1.9 g), tripotassium phosphate (3.4 g), Pd (dba) ₂ (0.09 g), tricyclohexylphosphine (0 0.07 g), toluene (29 ml), ethanol (3 ml) and water (3 ml) were stirred at reflux temperature for 14 hours. The reaction solution was cooled to room temperature, methanol was added and the precipitated solid was collected by suction filtration. The obtained solid was washed with water and then with methanol and then dissolved in heated toluene, and the insoluble matter was removed by hot filtration. Furthermore, after purification by active alumina column chromatography (toluene), recrystallization from a toluene / ethyl acetate mixed solvent, 2-([2,2′-bipyridine] which is a compound represented by the formula (1-4-100) -5-yl) -7- (naphthalen-2-yl) -9-phenyl-9H-carbazole (4.0 g) was obtained.

The structure of the compound obtained by NMR measurement was confirmed.
¹ H-NMR (500 MHz, CDCl ₃ ): δ = 9.01 (m, 1H), 8.72 (m, 1H), 8.49 (dd, 1H), 8.47 (d, 1H), 8 .29 (m, 2H), 8.10 (m, 2H), 7.81-7.95 (m, 5H), 7.66-7.74 (m, 6H), 7.63 (dd, 1H) ), 7.47-7.59 (m, 4H), 7.33 (m, 1H).

<Synthesis Example of Compound Represented by Formula (1-2-336)>

Synthesis of 2- (naphthalen-2-yl) -9-phenyl-7- (4- (pyridin-4-yl) phenyl) -9H-carbazole 2- (Naphthalen-2-yl) -9- synthesized above Phenyl-7- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -9H-carbazole (2.0 g), 4- (4-bromophenyl) pyridine (0. 9 g), tripotassium phosphate (1.7 g), Pd (dba) ₂ (0.07 g), tricyclohexylphosphine (0.05 g), toluene (15 ml), ethanol (1.5 ml) and water (1.5 ml) ) Was stirred at reflux temperature for 6 hours. The reaction solution was cooled to room temperature, methanol was added and the precipitated solid was collected by suction filtration. The obtained solid was washed with water and then with methanol, dissolved in toluene, and filtered with suction using a Kiriyama funnel covered with activated alumina. After the solvent was distilled off under reduced pressure, the residue was purified by amino group-modified silica gel (NH DM1020: manufactured by Fuji Silysia) column chromatography (toluene). The solid obtained by distilling off the solvent under reduced pressure was further washed with ethyl acetate, and 2- (naphthalen-2-yl) -9-phenyl-7-, which is a compound represented by the formula (1-2-336). (4- (Pyridin-4-yl) phenyl) -9H-carbazole (1.5 g) was obtained.

The structure of the compound obtained by NMR measurement was confirmed.
¹ H-NMR (CDCl ₃ ): δ = 8.69 (dd, 2H), 8.27 (m, 2H), 8.11 (m, 1H), 7.92 (m, 2H), 7.88 (D, 1H), 7.78-7.84 (d, 3H), 7.61-7.76 (m, 10H), 7.47-7.57 (m, 5H).

<Synthesis Example of Compound Represented by Formula (1-2-290)>

Synthesis of 4-chloro-4′-methoxy-2-nitro-1,1′-biphenyl 4-methoxyphenylboronic acid (19.8 g), 1-bromo-4-chloro-2-nitrobenzene (30.8 g), A flask containing potassium carbonate (27.6 g), Pd (PPh ₃ ) ₄ (4.5 g), toluene (520 ml) and water (104 ml) was stirred at reflux temperature for 4 hours under a nitrogen atmosphere. The reaction solution was cooled to room temperature and then separated, then the solvent of the organic layer was distilled off under reduced pressure, and the resulting solid was purified with a silica gel short column (toluene). The solvent was distilled off under reduced pressure, and the resulting solid was washed with heptane to obtain 4-chloro-4′-methoxy-2-nitro-1,1′-biphenyl (30.6 g).

Synthesis of 2-chloro-7-methoxy-9H-carbazole 4-chloro-4′-methoxy-2-nitro-1,1′-biphenyl (30.6 g), triphenylphosphine ( A flask containing 76.1 g) and orthodichlorobenzene (232 ml) was stirred at reflux temperature for 8 hours under a nitrogen atmosphere. Thereafter, the solvent was distilled off under reduced pressure, and the resulting solid was purified by silica gel column chromatography (chlorobenzene). After the solvent was distilled off under reduced pressure, the residue was washed with heptane to give 2-chloro-7-methoxy-9H-carbazole (19.5 g).

Synthesis of 2-chloro-7-methoxy-9-phenyl-9H-carbazole 2-chloro-7-methoxy-9H-carbazole (19.5 g), bromobenzene (19.8 g) obtained as described above, A flask containing palladium acetate (0.8 g), tri-t-butylphosphine (2.0 g), tripotassium phosphate (71.5 g), and xylene (250 ml) was stirred at reflux temperature for 6 hours under a nitrogen atmosphere. did. After cooling the reaction solution to room temperature, toluene and water were added for liquid separation, and the solvent of the organic layer was distilled off under reduced pressure. Subsequently, it is purified by silica gel column chromatography (toluene / heptane = 2/1 (volume ratio)), the solvent is distilled off under reduced pressure, and the resulting solid is washed with methanol to give 2-chloro-7-methoxy-9-. Phenyl-9H-carbazole (24.1 g) was obtained.

Synthesis of 2-methoxy-7- (naphthalen-1-yl) -9-phenyl-9H-carbazole 2-chloro-7-methoxy-9-phenyl-9H-carbazole (9.2 g) obtained as described above. ), 1-naphthaleneboronic acid (5.7 g), Pd (dba) ₂ (0.9 g), tricyclohexylphosphine (0.6 g), tripotassium phosphate (12.7 g), toluene (105 ml), ethanol ( The flask containing 15 ml) and water (15 ml) was stirred at reflux temperature for 8 hours under a nitrogen atmosphere. After cooling the reaction solution to room temperature, toluene and water were added for liquid separation, and the solvent of the organic layer was distilled off under reduced pressure. Subsequently, the residue was purified with a silica gel short column (toluene) to obtain 2-methoxy-7- (naphthalen-1-yl) -9-phenyl-9H-carbazole (12.8 g).

Synthesis of 7- (naphthalen-1-yl) -9-phenyl-9H-carbazol-2-ol 2-methoxy-7- (naphthalen-1-yl) -9-phenyl-9H obtained as described above A flask containing carbazole (12.8 g), pyridine hydrochloride (17.3 g) and 1-methyl-2-pyrrolidone (10 ml) was stirred at reflux temperature for 4 hours under nitrogen atmosphere. After cooling the reaction solution to room temperature, water and ethyl acetate were added for liquid separation, and the solvent of the organic layer was distilled off under reduced pressure. Subsequently, the obtained oily substance was purified by silica gel column chromatography (toluene) to obtain 7- (naphthalen-1-yl) -9-phenyl-9H-carbazol-2-ol (11.7 g).

Synthesis of 7- (Naphthalen-1-yl) -9-phenyl-9H-carbazol-2-yl trifluoromethanesulfonate 7- (Naphthalen-1-yl) -9-phenyl-9H obtained as described above -A flask containing carbazol-2-ol (11.7 g) and pyridine (75 ml) was cooled in an ice bath, and trifluoromethanesulfonic anhydride (16.9 g) was added dropwise thereto. After completion of the dropping, the mixture was stirred overnight at room temperature, and the solid precipitated by adding water was collected by suction filtration. The obtained solid was washed with water and then purified by silica gel column chromatography (heptane / toluene), and 7- (naphthalen-1-yl) -9-phenyl-9H-carbazol-2-yl trifluoromethanesulfonate (12. 8 g) was obtained. At this time, the target product was eluted by gradually increasing the ratio of toluene in the developing solution.

Synthesis of 2- (naphthalen-1-yl) -9-phenyl-7- (4- (pyridin-3-yl) phenyl) -9H-carbazole 7- (Naphthalen-1-yl obtained as described above ) -9-phenyl-9H-carbazol-2-yl trifluoromethanesulfonate (2.33 g), 3- (4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolane-2- Yl) phenyl) pyridine (1.4 g), Pd (PPh ₃ ) ₄ (0.17 g), tripotassium phosphate (2.1 g) and N, N-dimethylacetamide (20 ml) at 120 ° C. Stir for 4 hours. The reaction solution was cooled to room temperature, water was added, and the precipitated solid was collected by suction filtration. The obtained solid was washed with water and then dissolved in heated toluene, and the insoluble matter was removed by hot filtration. Further, 2- (naphthalen-1-yl) -9-phenyl-7- (4), which is a compound represented by the formula (1-2-290), is purified by silica gel column chromatography (toluene / ethyl acetate mixed solvent). -(Pyridin-3-yl) phenyl) -9H-carbazole (0.7 g) was obtained. At this time, the target product was eluted by gradually increasing the ratio of ethyl acetate in the developing solution.

The structure of the compound obtained by NMR measurement was confirmed.
¹ H-NMR (500 MHz, CDCl ₃ ): δ = 8.91 (m, 1H), 8.61 (dd, 1H), 8.27 (d, 2H), 7.96 (d, 1H), 7 .92 (t, 2H), 7.86 (d, 1H), 7.79 (d, 2H), 7.56-7.69 (m, 8H), 7.37-7.55 (m, 8H) ).

<Synthesis Example of Compound Represented by Formula (1-4-54)>

Synthesis of 2- (naphthalen-1-yl) -9-phenyl-7- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -9H-carbazole 7- (Naphthalen-1-yl) -9-phenyl-9H-carbazol-2-yl trifluoromethanesulfonate (7.0 g), bis (pinacolato) diboron (4.11 g), Pd (dppf) Cl ₂ (0 .3 g), potassium acetate (4.0 g) and cyclopentyl methyl ether (68 ml) were stirred at reflux temperature for 4 hours under a nitrogen atmosphere. The reaction solution was cooled to room temperature, and water and ethyl acetate were added for liquid separation. The solvent was distilled off under reduced pressure, and the resulting solid was purified by silica gel column chromatography (toluene) to give 2- (naphthalen-1-yl) -9-phenyl-7- (4,4,5,5-tetramethyl). -1,3,2-dioxaborolan-2-yl) -9H-carbazole (6.1 g) was obtained.

Synthesis of 2-([2,4′-bipyridin] -5-yl) -7- (naphthalen-1-yl) -9-phenyl-9H-carbazole 2- (Naphthalene-1 obtained as described above -Yl) -9-phenyl-7- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -9H-carbazole (1.9 g), 5-bromo-2, A flask containing 4′-bipyridine (0.9 g), tripotassium phosphate (1.7 g), Pd (PPh ₃ ) ₄ (0.2 g) and N, N-dimethylacetamide (16 ml) was stirred at reflux temperature for 16 minutes. Stir for hours. The reaction solution was cooled to room temperature, water was added, and the precipitated solid was collected by suction filtration. The obtained solid was washed with water and then with methanol and then dissolved in heated toluene, and the insoluble matter was removed by hot filtration. Further, 2-([2,4′-bipyridin] -5-yl) -7-, which is a compound represented by the formula (1-4-54), is purified by silica gel chromatography (toluene / ethyl acetate mixed solvent). (Naphthalen-1-yl) -9-phenyl-9H-carbazole (0.9 g) was obtained.

The structure of the compound obtained by NMR measurement was confirmed.
¹ H-NMR (500 MHz, CDCl ₃ ): δ = 9.06 (m, 1H), 8.74 (dd, 2H), 8.32 (d, 1H), 8.27 (d, 1H), 8 .08 (dd, 1H), 7.85-7.97 (m, 6H), 7.57-7.67 (m, 6H), 7.41-7.55 (m, 7H).

<Synthesis Example of Compound Represented by Formula (1-2-393)>

Synthesis of 2-([1,1′-biphenyl] -3-yl) -7-methoxy-9-phenyl-9H-carbazole 2-chloro-7-methoxy-9-phenyl- obtained as described above 9H-carbazole (6.5 g), [1,1′-biphenyl] -3-ylboronic acid (5.0 g), Pd (dba) ₂ (0.6 g), tricyclohexylphosphine (0.4 g), phosphoric acid A flask containing tripotassium (8.9 g), toluene (84 ml) and water (8 ml) was stirred at reflux temperature for 9 hours under a nitrogen atmosphere. After cooling the reaction solution to room temperature, water and toluene were added for liquid separation, and the solvent of the organic layer was distilled off under reduced pressure. Subsequently, the residue was purified by silica gel column chromatography (heptane / toluene mixed solvent) to give 2-([1,1′-biphenyl] -3-yl) -7-methoxy-9-phenyl-9H-carbazole (9.3 g). Obtained.

Synthesis of 7-([1,1′-biphenyl] -3-yl) -9-phenyl-9H-carbazol-2-ol 2-([1,1′-biphenyl]-obtained as described above A flask containing 3-yl) -7-methoxy-9-phenyl-9H-carbazole (9.3 g) and pyridine hydrochloride (36.7 g) was stirred at reflux temperature for 6 hours under a nitrogen atmosphere. After cooling the reaction solution to room temperature, water and ethyl acetate were added for liquid separation, and the solvent of the organic layer was distilled off under reduced pressure. The oily substance thus obtained was purified by silica gel column chromatography (toluene), and 7-([1,1′-biphenyl] -3-yl) -9-phenyl-9H-carbazol-2-ol (9. 5 g) was obtained.

Synthesis of 7-([1,1′-biphenyl] -3-yl) -9-phenyl-9H-carbazol-2-yl trifluoromethanesulfonate 7-([1,1 ′ -Biphenyl] -3-yl) -9-phenyl-9H-carbazol-2-ol (9.5 g) and pyridine (53 ml) were cooled in an ice bath to which trifluoromethanesulfonic anhydride ( 11.9 g) was added dropwise. After completion of the dropping, the mixture was stirred overnight at room temperature, and the solid precipitated by adding water was collected by suction filtration. The obtained solid was washed with water and then purified by silica gel column chromatography (toluene), and 7-([1,1′-biphenyl] -3-yl) -9-phenyl-9H-carbazol-2-yl trifluoromethane. Sulfonate (11.2 g) was obtained.

Synthesis of 2-([1,1′-biphenyl] -3-yl) -9-phenyl-7- (3- (pyridin-3-yl) phenyl) -9H-carbazole 7 -([1,1'-biphenyl] -3-yl) -9-phenyl-9H-carbazol-2-yl trifluoromethanesulfonate (2.4 g), 3- (3- (4,4,5,5 -Tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl) pyridine (1.3 g), Pd (PPh ₃ ) ₄ (0.15 g), tripotassium phosphate (1.9 g) and N, N A flask containing dimethylacetamide (18 ml) was stirred at 120 ° C. for 4 hours. The reaction solution was cooled to room temperature, water was added, and the precipitated solid was collected by suction filtration. The obtained solid was washed with water and then dissolved in heated toluene, and the insoluble matter was removed by hot filtration. Further purification was performed by silica gel column chromatography (toluene / ethyl acetate mixed solvent). At this time, the target product was eluted by gradually increasing the ratio of ethyl acetate in the developing solution. The solvent was distilled off under reduced pressure, the resulting solid was washed with heptane, and 2-([1,1′-biphenyl] -3-yl) -9, which is a compound represented by the formula (1-2-393) -Phenyl-7- (3- (pyridin-3-yl) phenyl) -9H-carbazole (2.1 g) was obtained. At this time, the target product was eluted by gradually increasing the ratio of ethyl acetate in the developing solution.

The structure of the compound obtained by NMR measurement was confirmed.
¹ H-NMR (500 MHz, CDCl ₃ ): δ = 8.91 (m, 1H), 8.62 (dd, 1H), 8.24 (m, 2H), 7.93 (m, 1H), 7 .83 (m, 2H), 7.44-7.71 (m, 19H), 7.38 (m, 2H).

<Synthesis Example of Compound Represented by Formula (1-4-155)>

2-([1,1′-biphenyl] -3-yl) -9-phenyl-7- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -9H— Synthesis of carbazole 7-([1,1′-biphenyl] -3-yl) -9-phenyl-9H-carbazol-2-yl trifluoromethanesulfonate (6.0 g), bis (pinacolato) diboron synthesized above A flask containing (3.4 g), Pd (dppf) Cl ₂ (0.3 g), potassium acetate (3.2 g) and cyclopentyl methyl ether (55 ml) was stirred at reflux temperature for 4 hours under a nitrogen atmosphere. The reaction solution was cooled to room temperature, and water and ethyl acetate were added for liquid separation. After distilling off the solvent under reduced pressure, the residue was purified by activated carbon column chromatography (toluene) and 2-([1,1′-biphenyl] -3-yl) -9-phenyl-7- (4, 4, 5, 5 -Tetramethyl-1,3,2-dioxaborolan-2-yl) -9H-carbazole (6.1 g) was obtained.

Synthesis of 2-([1,1′-biphenyl] -3-yl) -7-([2,3′-bipyridin] -6-yl) -9-phenyl-9H-carbazole obtained as described above. 2-([1,1′-biphenyl] -3-yl) -9-phenyl-7- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -9H - carbazole (2.1 g), 6- bromo-2,3'-bipyridine (1.0 g), tripotassium phosphate _{(1.7g), Pd (PPh 3} ) 4 (0.2g) and N, N- A flask containing dimethylacetamide (16 ml) was stirred at reflux temperature for 5 hours. The reaction solution was cooled to room temperature, water was added, and the precipitated solid was collected by suction filtration. The obtained solid was washed with water and then with methanol and then dissolved in heated toluene, and the insoluble matter was removed by hot filtration. Further, 2-([1,1′-biphenyl] -3-yl) -7-, which is a compound represented by the formula (1-4-155), is purified by silica gel chromatography (toluene / ethyl acetate mixed solvent). ([2,3′-bipyridin] -6-yl) -9-phenyl-9H-carbazole (1.6 g) was obtained.

The structure of the compound obtained by NMR measurement was confirmed.
¹ H-NMR (500 MHz, CDCl ₃ ): δ = 9.32 (m, 1H), 8.67 (dd, 1H), 8.44 (m, 1H), 8.26 (t, 2H), 8 .17 (m, 1H), 8.11 (dd, 1H), 7.79-7.87 (m, 3H), 7.35-7.71 (m, 17H).

<Synthesis Example of Compound Represented by Formula (1-1-856)>

Synthesis of 2,7-dimethoxy-9- (naphthalen-1-yl) -9H-carbazole 2,7-dimethoxy-9H-carbazole (10 g) synthesized according to a method described in known literature, 1-fluoronaphthalene ( 9.7 g), a flask containing cesium carbonate (17.2 g) and dimethyl sulfoxide (150 ml) was stirred at 150 ° C. for 11 hours under a nitrogen atmosphere. Thereafter, the reaction solution was cooled to room temperature, the precipitate was separated by suction filtration, water and toluene were added, and a water washing operation was performed. Subsequently, the residue was purified by silica gel chromatography (toluene / ethyl acetate = 5/1 (volume ratio)) to obtain 2,7-dimethoxy-9- (naphthalen-1-yl) -9H-carbazole (12.4 g).

Synthesis of 9- (naphthalen-1-yl) -9H-carbazole-2,7-diol 2,7-Dimethoxy-9- (naphthalen-1-yl) -9H-carbazole (12 0.0 g) was dissolved in dichloromethane (100 ml) under a nitrogen atmosphere and cooled with brine. Boron tribromide in 1M dichloromethane (75 ml) was added dropwise thereto, and after completion of the dropwise addition, the mixture was stirred at room temperature for 16 hours. The reaction was stopped by adding water, and the solution neutralized with aqueous sodium hydrogen carbonate was separated using a separatory funnel. After the dichloromethane layer was concentrated, it was purified by silica gel column chromatography (toluene / ethyl acetate = 10/1 (volume ratio)), and 9- (naphthalen-1-yl) -9H-carbazole-2,7-diol (11. 1 g) was obtained.

Synthesis of 9- (naphthalen-1-yl) -9H-carbazole-2,7-diyl bis (trifluoromethanesulfonate) 9- (naphthalen-1-yl) -9H-carbazole- obtained as described above 2,7-diol (11.0 g) was dissolved in pyridine (100 ml) under a nitrogen atmosphere and cooled with ice water. Trifluoromethanesulfonic anhydride (25 g) was added dropwise thereto, and the mixture was stirred at room temperature for 15 hours after completion of the addition. Water was added to stop the reaction, and the reaction solution was transferred to a separatory funnel and extracted with ethyl acetate. The solid obtained by concentrating with an evaporator was washed with methanol, water and methanol in this order, and then recrystallized from a mixed solvent of THF / ethanol to give 9- (naphthalen-1-yl) -9H-carbazole-2,7. -Diyl bis (trifluoromethanesulfonate) (12.7g) was obtained.

Synthesis of 9- (naphthalen-1-yl) -2,7-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -9H-carbazole Cyclopentyl methyl ether (100 ml 9- (naphthalen-1-yl) -9H-carbazole-2,7-diyl bis (trifluoromethanesulfonate) (9.5 g) and bis (pinacolato) diboron (9. 0 g) was added with stirring bis (dibenzylideneacetone) palladium (0) (1.4 g), tricyclohexylphosphine (1.6 g) and potassium acetate (4.7 g) at room temperature under a nitrogen atmosphere. added. Then, after stirring at reflux temperature for 4 hours, the reaction solution was cooled to room temperature, toluene was added, and the precipitate was separated by suction filtration. The filtrate was concentrated with an evaporator and purified by silica gel column chromatography (toluene). Subsequently, recrystallization from a dichloromethane / ethanol mixed solvent gave 9- (naphthalen-1-yl) -2,7-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)- 9H-carbazole (3.6 g) was obtained.

Synthesis of compound represented by formula (1-1-856); 9- (naphthalen-1-yl) -2,7-bis (3- (pyridin-4-yl) phenyl) -9H-carbazole 9- (Naphthalen-1-yl) -2,7-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -9H-carbazole (3 .5 g), 4- (3-bromophenyl) pyridine (3.3 g), sodium carbonate (2.7 g) and Pd (PPh ₃ ) ₄ (0.5 g) under an argon atmosphere under toluene ( 30 ml), ethanol (10 ml) and water (10 ml) were added and stirred at reflux temperature for 13 hours. The reaction solution was cooled to room temperature, water was added, and washing operation was performed. The organic substance from which the salt was removed by the water washing operation was purified by activated alumina column chromatography (toluene / ethyl acetate = 1/4 (volume ratio)), and finally the compound represented by the formula (1-1-856) 9- (Naphthalen-1-yl) -2,7-bis (3- (pyridin-4-yl) phenyl) -9H-carbazole (1.1 g) was obtained.

The structure of the compound obtained by NMR measurement was confirmed.
¹ H-NMR (500 MHz, CDCl ₃ ): δ = 8.65 (dd, 4H), 8.3 (d, 2H), 8.08 (dd, 1H), 8.04 (d, 1H), 7 .77 (m, 2H), 7.68-7.75 (m, 2H), 7.52-7.62 (m, 7H), 7.45-7.49 (m, 6H), 7.35 -7.41 (m, 2H), 7.21 (m, 2H).

<Synthesis Example of Compound Represented by Formula (1-1-854)>

Synthesis of 9- (Naphthalen-1-yl) -2,7-bis (3- (pyridin-2-yl) phenyl) -9H-carbazole 9- (Naphthalen-1-yl) -2,7-bis (4 , 4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -9H-carbazole (3.0 g), 2- (3-bromophenyl) pyridine (3.2 g), potassium carbonate ( 3.0 g) and PdCl ₂ {P (t-Bu) _2- (p-NMe ₂ -Ph)} ₂ (Johnson Massey, Pd-132) (0.05 g) in a flask with argon Below, toluene (25 ml) and water (2.5 ml) were added, and the mixture was stirred at reflux temperature for 6 hours. After cooling the reaction solution to room temperature, toluene and water were added for liquid separation, and toluene was distilled off under reduced pressure. The obtained concentrate was purified by amino group-modified silica gel (NH DM1020: manufactured by Fuji Silysia) column chromatography (heptane / ethyl acetate = 3/1 (volume ratio)). Subsequently, it is purified by activated alumina column chromatography (toluene / ethyl acetate = 50/1 (volume ratio)), and finally 9- (naphthalene-1), which is a compound represented by the formula (1-1-854) -Il) -2,7-bis (3- (pyridin-2-yl) phenyl) -9H-carbazole (0.9 g) was obtained.

The structure of the compound obtained by NMR measurement was confirmed.
¹ H-NMR (CDCl ₃ ): δ = 8.67 (m, 2H), 8.29 (d, 2H), 8.16 (m, 2H), 8.05 (d, 1H), 8.01 (D, 1H), 7.88 (d, 2H), 7.66-7.74 (m, 6H), 7.65 (d, 2H), 7.56 (d, 2H), 7.53 ( t, 1H), 7.45 (t, 2H), 7.40 (d, 1H), 7.15 (t, 1H), 7.25 (m, 2H), 7.20 (m, 2H).

<Synthesis Example of Compound Represented by Formula (1-1-855)>

Synthesis of 9- (Naphthalen-1-yl) -2,7-bis (3- (pyridin-3-yl) phenyl) -9H-carbazole 9- (Naphthalen-1-yl) -2,7-bis (4 , 4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -9H-carbazole (3.0 g), 3- (3-bromophenyl) pyridine (3.2 g), potassium carbonate ( 3.0 g) and PdCl ₂ {P (t-Bu) _2- (p-NMe ₂ -Ph)} ₂ (Johnson Massey, Pd-132) (0.04 g) in an argon atmosphere. Then, toluene (25 ml) and water (2.5 ml) were added, and the mixture was stirred at reflux temperature for 4 and a half hours. After cooling the reaction solution to room temperature, toluene and water were added for liquid separation, and toluene was distilled off under reduced pressure. The obtained concentrate was purified by activated alumina column chromatography (toluene / ethyl acetate = 5/1 (volume ratio)). Subsequently, it is purified by column chromatography (heptane / ethyl acetate = 3/1 (volume ratio)) with amino group-modified silica gel (NH DM1020: manufactured by Fuji Silysia), and finally represented by the formula (1-1-855). The compound 9- (naphthalen-1-yl) -2,7-bis (3- (pyridin-3-yl) phenyl) -9H-carbazole (0.7 g) was obtained.

The structure of the compound obtained by NMR measurement was confirmed.
¹ H-NMR (CDCl ₃ ): δ = 8.83 (m, 2H), 8.58 (m, 2H), 8.30 (d, 2H), 8.07 (d, 1H), 8.02 (D, 1H), 7.85 (d, 2H), 7.67-7.78 (m, 4H), 7.61 (d, 2H), 7.56 (m, 3H), 7.49 ( m, 4H), 7.30-7.40 (m, 4H), 7.21 (s, 2H).

<Synthesis Example of Compound Represented by Formula (1-1-851)>

Synthesis of 9- (Naphthalen-1-yl) -2,7-bis (4- (pyridin-2-yl) phenyl) -9H-carbazole 9- (Naphthalen-1-yl) -2,7-bis (4 , 4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -9H-carbazole (3.0 g), 2- (4-bromophenyl) pyridine (2.8 g), sodium carbonate ( 2.4 g) and Pd (PPh ₃ ) ₄ (0.2 g) were charged with toluene (17 ml), ethanol (6 ml) and water (6 ml) under an argon atmosphere and stirred at reflux temperature for 12 hours and a half. did. After cooling the reaction solution to room temperature, water was added and a solid was obtained by suction filtration. Subsequently, the obtained solid was purified by activated alumina column chromatography (developing solution: chlorobenzene / ethyl acetate mixed solvent). At this time, referring to the method described in “Chemical Doujin Shuppan Co., Ltd., page 94”, the ratio of ethyl acetate in the developing solution was gradually increased. The target product was eluted by increasing the amount to 1. Subsequently, it is recrystallized from orthodichlorobenzene, and finally 9- (naphthalen-1-yl) -2,7-bis (4- (pyridine-), which is a compound represented by the formula (1-1-851). 2-yl) phenyl) -9H-carbazole (1.0 g) was obtained.

  Attempts were made to confirm the structure of the compound obtained by NMR measurement, but due to the low solubility, the resolution was poor and could not be confirmed well. However, liquid chromatography mass spectrometry (LCMS) confirmed the molecular weight of the target compound represented by the formula (1-1-851).

<Synthesis Example of Compound Represented by Formula (1-1-852)>

Synthesis of 9- (Naphthalen-1-yl) -2,7-bis (4- (pyridin-3-yl) phenyl) -9H-carbazole 9- (Naphthalen-1-yl) -2,7-bis (4 , 4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -9H-carbazole (3.0 g), 3- (4-bromophenyl) pyridine (3.2 g), potassium carbonate ( 3.0 g) and PdCl ₂ {P (t-Bu) _2- (p-NMe ₂ -Ph)} ₂ (Johnson Massey, Pd-132) (0.04 g) in an argon atmosphere. Then, toluene (25 ml) and water (2.5 ml) were added, and the mixture was stirred at reflux temperature for 5 and a half hours. After cooling the reaction solution to room temperature, water was added and a solid was obtained by suction filtration. The obtained solid was washed with water and then with methanol. Further, recrystallization from N, N-dimethylformamide and finally 9- (naphthalen-1-yl) -2,7-bis (4-), which is a compound represented by the formula (1-1-852) (Pyridin-3-yl) phenyl) -9H-carbazole (0.7 g) was obtained.

The structure of the compound obtained by NMR measurement was confirmed.
¹ H-NMR (CDCl ₃ ): δ = 8.85 (m, 2H), 8.57 (dd, 2H), 8.30 (d, 2H), 8.10 (m, 1H), 8.05 (D, 1H), 7.86 (m, 2H), 7.72 (m, 2H), 7.66 (m, 4H), 7.62 (dd, 2H), 7.55-7.60 ( m, 5H), 7.32-7.41 (m, 4H), 7.23 (m, 2H).

<Synthesis Example of Compound Represented by Formula (1-1-853)>

Synthesis of 9- (Naphthalen-1-yl) -2,7-bis (4- (pyridin-4-yl) phenyl) -9H-carbazole 9- (Naphthalen-1-yl) -2,7-bis (4 , 4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -9H-carbazole (3.0 g), 3- (4-bromophenyl) pyridine (3.2 g), potassium carbonate ( 3.0 g) and PdCl ₂ {P (t-Bu) _2- (p-NMe ₂ -Ph)} ₂ (Johnson Massey, Pd-132) (0.04 g) in an argon atmosphere. Then, toluene (25 ml) and water (2.5 ml) were added, and the mixture was stirred at reflux temperature for 6 and a half hours. After cooling the reaction solution to room temperature, water was added and a solid was obtained by suction filtration. The obtained solid was washed with water, then with methanol and further with ethyl acetate, and further purified by activated alumina column chromatography (developing solution: chlorobenzene / ethyl acetate mixed solvent). At this time, the target product was eluted by gradually increasing the ratio of ethyl acetate in the developing solution. After distilling off the solvent under reduced pressure, recrystallization from chlorobenzene and then N, N-dimethylformamide, finally 9- (naphthalen-1-yl, which is a compound represented by the formula (1-1-853) ) -2,7-bis (4- (pyridin-4-yl) phenyl) -9H-carbazole (0.5 g) was obtained.

The structure of the compound obtained by NMR measurement was confirmed.
¹ H-NMR (CDCl ₃ ): δ = 8.64 (m, 4H), 8.31 (d, 2H), 8.12 (t, 1H), 8.06 (d, 1H), 7.73 (M, 2H), 7.60-7.70 (m, 10H), 7.57 (m, 1H), 7.49 (m, 4H), 7.39 (m, 2H), 7.23 ( m, 2H).

<Synthesis Example of Compound Represented by Formula (1-1-1198)>

Synthesis of 9-([1,1′-biphenyl] -3-yl) -2,7-dibromo-9H-carbazole 2,7-bromo-9H-carbazole (26.9 g), 3-fluoro-1,1 A flask containing '-biphenyl (21.4 g), cesium carbonate (40.5 g) and dimethyl sulfoxide (400 ml) was stirred at 170 ° C. for 22 and a half hours under a nitrogen atmosphere. Thereafter, the reaction solution was cooled to room temperature, and water and ethyl acetate were added to separate the layers. Ethyl acetate was distilled off under reduced pressure, and the resulting solid was dissolved in heated chloroform and filtered while hot. The obtained filtrate was adsorbed on silica gel, dried, and charged in silica gel chromatography (developing solution: heptane / toluene mixed solvent) prepared separately. The target product was eluted by gradually increasing the ratio of toluene in the developing solution. Further, recrystallization from heptane gave 9-([1,1′-biphenyl] -3-yl) -2,7-dibromo-9H-carbazole (4.2 g).

Synthesis of 9-([1,1′-biphenyl] -3-yl) -2,7-bis (4- (pyridin-2-yl) phenyl) -9H-carbazole First, using a palladium catalyst, By coupling (4-bromophenyl) pyridine and bis (pinacolato) diboron, 2- (4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) Phenyl) pyridine was synthesized. Next, 9-([1,1′-biphenyl] -3-yl) -2,7-dibromo-9H-carbazole (1.5 g), 2- (4- (4,4,5,5-tetra Methyl-1,3,2-dioxaborolan-2-yl) phenyl) pyridine (1.8 g), potassium carbonate (1.7 g) and PdCl ₂ {P (t-Bu) _2- (p-NMe ₂ -Ph) } Toluene (15 ml) and water (3 ml) were placed in a flask containing ₂ (Johnson Massey, Pd-132) (0.06 g) under an argon atmosphere, and stirred at reflux temperature for 8 hours. The reaction solution was cooled to room temperature, and water and chloroform were added for liquid separation. Chloroform was distilled off under reduced pressure, and the resulting solid was purified by amino group-modified silica gel (NH DM1020: manufactured by Fuji Silysia) column chromatography (heptane / toluene = 1/2 (volume ratio)). After distilling off the solvent under reduced pressure, the residue was washed with ethyl acetate, and finally 9-([1,1′-biphenyl] -3-yl) which is a compound represented by the formula (1-1-1198). -2,7-bis (4- (pyridin-2-yl) phenyl) -9H-carbazole (0.3 g) was obtained.

The structure of the compound obtained by NMR measurement was confirmed.
¹ H-NMR (CDCl ₃ ): δ = 8.70 (m, 2H), 8.23 (d, 2H), 8.07 (d, 4H), 7.87 (m, 1H), 7.60 -7.80 (m, 17H), 7.46 (t, 2H), 7.37 (t, 1H), 7.22 (m, 2H).

<Synthesis Example of Compound Represented by Formula (1-1-1202)>

Synthesis of 9-([1,1′-biphenyl] -3-yl) -2,7-bis (3- (pyridin-3-yl) phenyl) -9H-carbazole First, using a palladium catalyst, By coupling reaction of (3-bromophenyl) pyridine and bis (pinacolato) diboron, 3- (3- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) Phenyl) pyridine was synthesized. Next, 9-([1,1′-biphenyl] -3-yl) -2,7-dibromo-9H-carbazole (1.5 g), 3- (3- (4,4,5,5-tetra Methyl-1,3,2-dioxaborolan-2-yl) phenyl) pyridine (1.8 g), potassium carbonate (1.7 g) and PdCl ₂ {P (t-Bu) _2- (p-NMe ₂ -Ph) } Toluene (15 ml) and water (3 ml) were placed in a flask containing ₂ (Johnson Massey, Pd-132) (0.06 g) under an argon atmosphere, and stirred at reflux temperature for 11 hours. The reaction solution was cooled to room temperature, and water and toluene were added for liquid separation. Toluene was distilled off under reduced pressure, and the resulting solid was purified by amino group-modified silica gel (NH DM1020: manufactured by Fuji Silysia) column chromatography (developing solution: heptane / ethyl acetate = 1/1 (volume ratio)), and finally And 9-([1,1′-biphenyl] -3-yl) -2,7-bis (3- (pyridin-3-yl), which is a compound represented by the formula (1-1-1202). Phenyl) -9H-carbazole (0.7 g) was obtained.

The structure of the compound obtained by NMR measurement was confirmed.
¹ H-NMR (CDCl ₃ ): δ = 8.90 (m, 2H), 8.61 (dd, 2H), 8.25 (d, 2H), 7.90 (m, 2H), 7.87 (M, 1H), 7.83 (s, 2H), 7.60-7.75 (m, 11H), 7.54 (m, 4H), 7.43 (t, 2H), 7.36 ( m, 3H).

<Synthesis Example of Compound Represented by Formula (1-1-98)>

Synthesis of 2,7-bis (4-ethoxynaphthalen-1-yl) -9H-carbazole 2,7-dibromo-9H-carbazole (20 g), (4-ethoxynaphthalen-1-yl) boronic acid (33.2 g) ), Pd (PPh ₃ ) ₄ (2.1 g), and tripotassium phosphate (52.3 g) were charged with toluene (150 ml) and water (15 ml) under an argon atmosphere at reflux temperature for 2 hours. Stir. The reaction solution was cooled to room temperature, an ethylenediaminetetraacetic acid (EDTA) aqueous solution was added, and the precipitate was collected by suction filtration. The obtained solid was washed with methanol, recrystallized from chlorobenzene, and further washed with toluene to obtain 2,7-bis (4-ethoxynaphthalen-1-yl) -9H-carbazole (22.6 g). .

Synthesis of 2,7-bis (4-ethoxynaphthalen-1-yl) -9-phenyl-9H-carbazole 2,7-bis (4-ethoxynaphthalen-1-yl) -9H obtained as described above -Of carbazole (22.5 g), bromobenzene (10.4 g), palladium acetate (0.2 g), tri-t-butylphosphine (0.5 g), tripotassium phosphate (28.2 g) and xylene (200 ml). The flask was stirred at reflux temperature for 12 and a half hours under an argon atmosphere. The reaction solution was cooled to room temperature, an ethylenediaminetetraacetic acid (EDTA) aqueous solution was added, and the precipitate was collected by suction filtration. The obtained solid was washed with methanol, dissolved in heated chlorobenzene, and filtered while hot using a Kiriyama funnel covered with activated alumina. Crystals precipitated by gradually distilling off the obtained filtrate under reduced pressure were collected by suction filtration, and 2,7-bis (4-ethoxynaphthalen-1-yl) -9-phenyl-9H-carbazole (21 0.8 g) was obtained.

Synthesis of 4,4 ′-(9-phenyl-9H-carbazol-2,7-diyl) bis (naphthalen-1-ol) 2,7-bis (4-ethoxynaphthalene-1) obtained as described above -Il) -9-phenyl-9H-carbazole (21.8 g), pyridine hydrochloride (86.0 g) and a flask containing N-methylpyrrolidone (25 ml) were stirred in an oil bath heated to 220 ° C. for 11 hours. did. The reaction solution was cooled to room temperature and washed repeatedly with water and methanol warmed to about 75 ° C., whereby 4,4 ′-(9-phenyl-9H-carbazole-2,7-diyl) bis (naphthalene-1- All) (19.3 g) was obtained.

Synthesis of (9-phenyl-9H-carbazole-2,7-diyl) bis (naphthalene-4,1-diyl) bis (trifluoromethanesulfonate) 4,4 ′-(9- Phenyl-9H-carbazol-2,7-diyl) bis (naphthalen-1-ol) (19.3 g) was dissolved in pyridine (100 ml) under a nitrogen atmosphere and cooled with ice water. Trifluoromethanesulfonic anhydride (31.0 g) was added dropwise thereto, and the mixture was stirred at room temperature for 22 hours after completion of the dropwise addition. Water was added and the precipitate was obtained by suction filtration. The resulting precipitate was washed with water and then with methanol. Further, the product was purified by activated alumina column chromatography (developing solution: toluene), and (9-phenyl-9H-carbazole-2,7-diyl) bis (naphthalene-4,1-diyl) bis (trifluoromethanesulfonate) (18 0.5 g) was obtained.

Synthesis of 9-phenyl-2,7-bis (4- (pyridin-3-yl) naphthalen-1-yl) -9H-carbazole (9-phenyl-9H-carbazole-2, obtained as described above) 7-diyl) bis (naphthalene-4,1-diyl) bis (trifluoromethanesulfonate) (3.0 g), 3-pyridineboronic acid (1.2 g), Pd (PPh ₃ ) ₄ (0.2 g) and N, N-dimethylformamide (18 ml) was added to a flask containing tripotassium phosphate (3.2 g) under an argon atmosphere, and the mixture was stirred at 110 ° C. for 7 and a half hours. The reaction solution was cooled to room temperature, an ethylenediaminetetraacetic acid (EDTA) aqueous solution was added, and the precipitate was collected by suction filtration. The obtained precipitate was washed with methanol, dissolved in heated chlorobenzene, and filtered while hot. The obtained filtrate was distilled off under reduced pressure and purified by amino group-modified silica gel (NH DM1020: manufactured by Fuji Silysia) column chromatography (developing solution: toluene / ethyl acetate = 10/1 (volume ratio)), and finally, 9-phenyl-2,7-bis (4- (pyridin-3-yl) naphthalen-1-yl) -9H-carbazole (0.9 g) which is a compound represented by the formula (1-1-98) Got.

The structure of the compound obtained by NMR measurement was confirmed.
¹ H-NMR (CDCl ₃ ): δ = 8.81 (m, 2H), 8.71 (dd, 2H), 8.34 (d, 2H), 8.07 (m, 2H), 7.87 (M, 4H), 7.64 (m, 2H), 7.59 (m, 4H), 7.44-7.55 (m, 12H), 7.38 (t, 1H).

<Synthesis Example of Compound Represented by Formula (1-1-99)>

Synthesis of 9-phenyl-2,7-bis (4- (pyridin-4-yl) naphthalen-1-yl) -9H-carbazole (9-phenyl-9H-carbazole-2,7-diyl) bis (naphthalene- 4,1-diyl) bis (trifluoromethanesulfonate) (2.0 g), 4-pyridineboronic acid (1.2 g), Pd (dba) ₂ (0.1 g), tricyclohexylphosphine (0.1 g) and N, N-dimethylacetamide (12 ml) was added to a flask containing tripotassium phosphate (3.2 g) under an argon atmosphere, and the mixture was stirred at reflux temperature for 10 hours and a half. The reaction solution was cooled to room temperature, an ethylenediaminetetraacetic acid (EDTA) aqueous solution was added, and the precipitate was collected by suction filtration. The obtained precipitate was washed with methanol, and then purified by activated alumina column chromatography (developing solution: toluene / ethyl acetate = 10/1 (volume ratio)), and finally, by the formula (1-1-99) 9-Phenyl-2,7-bis (4- (pyridin-4-yl) naphthalen-1-yl) -9H-carbazole (0.4 g), which is the represented compound, was obtained.

The structure of the compound obtained by NMR measurement was confirmed.
¹ H-NMR (CDCl ₃ ): δ = 8.76 (m, 4H), 8.34 (d, 2H), 8.06 (m, 2H), 7.91 (m, 2H), 7.64 (D, 2H), 7.59 (m, 4H), 7.45-7.55 (m, 14H), 7.38 (t, 1H).

<Synthesis Example of Compound Represented by Formula (1-1-1455)>

Synthesis of 2,7-bis (3-methoxyphenyl) -9H-carbazole 2,7-dibromo-9H-carbazole (30 g), 3-methoxyphenylboronic acid (35.1 g), PdCl ₂ {P (t-Bu ) _2- (p-NMe ₂ -Ph)} ₂ (Johnson Massey, Pd-132) (0.32 g) and potassium carbonate (51.0 g) in a flask under an argon atmosphere with toluene (185 ml) ) And water (18 ml) were added and stirred at reflux temperature for 1.5 hours. The reaction solution was cooled to room temperature, and ethyl acetate and water were added for liquid separation. The solid obtained by distilling off the solvent under reduced pressure was purified by silica gel column chromatography (developing solution: toluene / ethyl acetate = 10/1 (volume ratio)), and 2,7-bis (3-methoxyphenyl) -9H. -Carbazole (35.0 g) was obtained.

Synthesis of 9-([1,1 ′: 3 ′, 1 ″ -terphenyl] -5′-yl) -2,7-bis (3-methoxyphenyl) -9H-carbazole 2,7-bis (3-methoxyphenyl) -9H-carbazole (10.0 g), 5′-bromo-1,1 ′: 3 ′, 1 ″ -terphenyl (12.2 g), palladium acetate (0. 12 g), tri-t-butylphosphine (0.32 g), tripotassium phosphate (16.8 g) and xylene (88 ml) were stirred at reflux temperature for 20 hours under an argon atmosphere. The reaction solution was cooled to room temperature, and an aqueous solution of ethylenediaminetetraacetic acid (EDTA) was added for liquid separation. The solvent was distilled off under reduced pressure, the residue was purified by silica gel column chromatography (developing solution: toluene), and methanol was added to the oil obtained by distilling off the solvent under reduced pressure to perform reprecipitation. 9-([1 , 1 ′: 3 ′, 1 ″ -terphenyl] -5′-yl) -2,7-bis (3-methoxyphenyl) -9H-carbazole (11.5 g).

Synthesis of 3,3 ′-(9-([1,1 ′: 3 ′, 1 ″ -terphenyl] -5′-yl) -9H-carbazol-2,7-diyl) diphenol The resulting 9-([1,1 ′: 3 ′, 1 ″ -terphenyl] -5′-yl) -2,7-bis (3-methoxyphenyl) -9H-carbazole (11.5 g) and pyridine A flask containing hydrochloride (121.0 g) was stirred in an oil bath heated to 210 ° C. for 10 hours. The reaction mixture was cooled to room temperature and washed repeatedly with water and methanol to give 3,3 ′-(9-([1,1 ′: 3 ′, 1 ″ -terphenyl] -5′-yl) -9H. -Carbazole-2,7-diyl) diphenol (10.6 g) was obtained.

(9-([1,1 ′: 3 ′, 1 ″ -terphenyl] -5′-yl) -9H-carbazol-2,7-diyl) bis (3,1-phenylene) bis (trifluoromethanesulfonate ) 3,3 ′-(9-([1,1 ′: 3 ′, 1 ″ -terphenyl] -5′-yl) -9H-carbazole-2,7- Diyl) diphenol (10.6 g) was dissolved in pyridine (53 ml) under a nitrogen atmosphere and cooled with ice water. Trifluoromethanesulfonic anhydride (15.6 g) was added dropwise thereto, and the mixture was stirred at room temperature for 16 hours after completion of the dropwise addition. Water was added, and the precipitate was collected by suction filtration. The obtained precipitate was washed with water and then with methanol. Further purification was performed by silica gel column chromatography (developing solution: toluene / heptane = 1/1 (volume ratio)). The solvent was distilled off under reduced pressure, and methanol was added to the resulting oily substance to perform reprecipitation, and (9-([1,1 ′: 3 ′, 1 ″ -terphenyl] -5′-yl) -9H— Carbazole-2,7-diyl) bis (3,1-phenylene) bis (trifluoromethanesulfonate) (12.7 g) was obtained.

Synthesis of 9-([1,1 ′: 3 ′, 1 ″ -terphenyl] -5′-yl) -2,7-bis (3- (pyridin-3-yl) phenyl) -9H-carbazole (9-([1,1 ′: 3 ′, 1 ″ -terphenyl] -5′-yl) -9H-carbazol-2,7-diyl) bis (3,1-phenylene) thus obtained Bis (trifluoromethanesulfonate) (4.0 g), 3-pyridineboronic acid (1.4 g), Pd (dba) ₂ (0.15 g), tricyclohexylphosphine (0.12 g) and tripotassium phosphate (4 0.0 g) was added with N, N-dimethylacetamide (20 ml) under an argon atmosphere and stirred at 120 ° C. for 5 hours. The reaction solution was cooled to room temperature, an ethylenediaminetetraacetic acid (EDTA) aqueous solution was added, and the precipitate was collected by suction filtration. Subsequently, it was dissolved in toluene, and water was added to separate the layers. The solvent was distilled off under reduced pressure and purified by amino group-modified silica gel (NH DM1020: manufactured by Fuji Silysia) column chromatography (developing solution: toluene / ethyl acetate = 20/1 (volume ratio)), and then recrystallized from toluene. 9-([1,1 ′: 3 ′, 1 ″ -terphenyl] -5′-yl) -2,7-bis (3- (pyridin-3-yl) phenyl) -9H-carbazole (1.2 g )

The structure of the compound obtained by NMR measurement was confirmed.
¹ H-NMR (CDCl ₃ ): δ = 8.90 (m, 2H), 8.60 (dd, 2H), 8.27 (d, 2H), 7.96 (m, 1H), 7.91 (M, 2H), 7.85 (m, 5H), 7.68-7.73 (m, 6H), 7.63 (dd, 2H), 7.54 (m, 5H), 7.46 ( t, 4H), 7.33-7.41 (m, 4H).

<Synthesis Example of Compound Represented by Formula (1-5-2)>

<Synthesis of 2-methoxy-9-phenyl-7- (10-phenylanthracen-9-yl) -9H-carbazole>
Under a nitrogen atmosphere, 2-chloro-7-methoxy-9-phenyl-9H-carbazole (8 g), (10-phenylanthracen-9-yl) boronic acid (9.3 g), Pd (dba) ₂ (0.75 g ), Tricyclohexylphosphine (0.55 g), tripotassium phosphate (11.04 g), 105 ml of a mixed solvent of toluene and ethanol (toluene / ethanol = 6/1 (volume ratio)) and 10 ml of water were added to the flask and reflux temperature was added. For 5 hours. After completion of the heating, the reaction solution was cooled and filtered to obtain the solid product 1 as a crude product 1. The organic layer in the filtrate was separated and dried over anhydrous sodium sulfate, the desiccant was removed, and the solid obtained by distilling off the solvent under reduced pressure was used as crude product 2. Thereafter, the crude products 1 and 2 were combined and subjected to short column purification (solvent: toluene) with silica gel. Further, reprecipitation was performed with methanol to obtain an intermediate compound 2-methoxy-9-phenyl-7- (10-phenylanthracen-9-yl) -9H-carbazole (10.99 g).

<Synthesis of 9-phenyl-7- (10-phenylanthracen-9-yl) -9H-carbazol-2-ol>
Under nitrogen atmosphere, the intermediate compounds 2-methoxy-9-phenyl-7- (10-phenylanthracen-9-yl) -9H-carbazole (10.99 g), pyridine hydrochloride (24.3 g) and 1-methyl- 2-Pyrrolidone (11 ml) was placed in a flask and heated at reflux temperature for 5 hours. After completion of heating, the reaction solution was cooled, water was added, and the mixture was washed while hot. Thereafter, the crude product was dissolved in toluene and dried over anhydrous sodium sulfate, the desiccant was removed, the solvent was distilled off under reduced pressure, and the intermediate compound 9-phenyl-7- (10-phenylanthracen-9-yl) was removed. ) -9H-carbazol-2-ol (11.4 g) was obtained.

<Synthesis of 9-phenyl-7- (10-phenylanthracen-9-yl) -9H-carbazol-2-yl trifluoromethanesulfonate>
Under a nitrogen atmosphere, the intermediate compounds 9-phenyl-7- (10-phenylanthracen-9-yl) -9H-carbazol-2-ol (11.4 g) and pyridine (85 ml) were placed in a flask and cooled to 0 ° C. After that, trifluoromethanesulfonic anhydride (11.8 g) was slowly added dropwise. Thereafter, the reaction solution was stirred at 0 ° C. for 1 hour and at room temperature for 2 hours. Next, water was added to the reaction solution, the precipitate (crude product) was filtered, and the resulting crude product was subjected to short column purification (solvent: toluene) with silica gel to obtain an intermediate compound 9-phenyl-7- (10 -Phenylanthracen-9-yl) -9H-carbazol-2-yl trifluoromethanesulfonate (12.1 g) was obtained.

<Synthesis of 9-phenyl-2- (10-phenylanthracen-9-yl) -7-pyridin-3-yl) -9H-carbazole>
Under a nitrogen atmosphere, the intermediate compound 9-phenyl-7- (10-phenylanthracen-9-yl) -9H-carbazol-2-yl trifluoromethanesulfonate (2.5 g), 3-pyridineboronic acid (0.53 g) ), Pd (dba) ₂ (0.067 g), tricyclohexylphosphine (0.049 g), tripotassium phosphate (1.65 g) and N, N-dimethylacetamide (16 ml) in a flask and stirred. Heat at 4 ° C. for 4 hours. After completion of the reaction, water was added to the reaction solution, the precipitate (crude product) was filtered, and the resulting crude product was subjected to short column purification with silica gel (solvent: toluene / ethyl acetate = 1/2 (volume ratio)), Further, after silica gel column purification (solvent: toluene / ethyl acetate = 10/1 (volume ratio)), purification by sublimation was performed to obtain the target compound (1-5-2): 9-phenyl-2- ( 10-Phenylanthracen-9-yl) -7- (pyridin-3-yl) -9H-carbazole (1.12 g) was obtained.

The structure of the compound (1-5-2) was confirmed by MS spectrum and NMR measurement.
¹ H-NMR (CDCl ₃ ): δ = 8.96 (s, 1H), 8.61 (d, 1H), 8.37 (q, 2H), 7.98 (d, 1H), 7.76 ~ 7.31 (m, 23H).

Other physical properties were as follows.
Glass transition temperature (Tg): 153.7 ° C
[Measurement equipment: Diamond DSC (manufactured by PERKIN-ELMER); Measurement conditions: Cooling rate 200 ° C / Min.

<Synthesis Example of Compound Represented by Formula (1-5-8)>

<Synthesis of 9-phenyl-2- (10-phenylanthracen-9-yl) -7- (3- (pyridin-3-yl) phenyl) -9H-carbazole>
Under nitrogen atmosphere, the intermediate compound 9-phenyl-7- (10-phenylanthracen-9-yl) -9H-carbazol-2-yl trifluoromethanesulfonate (2.0 g), 3- (3- (4,4 , 5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl) pyridine (0.92 g), tetrakis (triphenylphosphine) palladium (0) (Pd (PPh ₃ ) ₄ ) (0. 11 g), tripotassium phosphate (1.32 g) and N, N-dimethylacetamide (15 ml) were stirred in a flask and heated at 120 ° C. for 5 hours. After completion of the reaction, water was added to the reaction solution, the precipitate (crude product) was filtered, and the resulting crude product was subjected to short column purification with silica gel (solvent: toluene / ethyl acetate = 1/2 (volume ratio)), Furthermore, after silica gel column purification (solvent: toluene / ethyl acetate = 10/1 (volume ratio)), purification by sublimation was performed, and the target compound (1-5-8): 9-phenyl-2- ( 10-phenylanthracen-9-yl) -7- (3- (pyridin-3-yl) phenyl) -9H-carbazole (1.2 g) was obtained.

The structure of the compound (1-5-8) was confirmed by MS spectrum and NMR measurement.
¹ H-NMR (CDCl ₃ ): δ = 8.94 (s, 1H), 8.64 (d, 1H), 8.37 (q, 2H), 7.96 (d, 1H), 7.88 (S, 1H), 7.77-7.31 (m, 26H).

Other physical properties were as follows.
Glass transition temperature (Tg): 147.7 ° C
[Measurement equipment: Diamond DSC (manufactured by PERKIN-ELMER); Measurement conditions: Cooling rate 200 ° C / Min.

<Synthesis Example of Compound Represented by Formula (1-5-29)>

<Synthesis of 9-phenyl-2- (10-phenylanthracen-9-yl) -7- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -9H-carbazole >
Under nitrogen atmosphere, intermediate compounds 9-phenyl-7- (10-phenylanthracen-9-yl) -9H-carbazol-2-yl trifluoromethanesulfonate (4.0 g), bis (pinacolato) diboron (1.89 g) ), (1,1′-bis (diphenylphosphino) ferrocene) dichloropalladium (II) in dichloromethane complex (1: 1) (Pd (dppf) Cl ₂ .CH ₂ Cl ₂ ) (0.15 g), potassium acetate (1.83 g) and cyclopentyl methyl ether (31 ml) were placed in a flask and stirred and refluxed for 4 hours. After completion of the heating, the reaction solution was cooled and 150 ml of water was added. Then, the reaction mixture was extracted with ethyl acetate, dried over anhydrous sodium sulfate, the desiccant was removed, the solvent was distilled off under reduced pressure, and the resulting crude product was purified with activated carbon for a short column (solvent: toluene). went. Further, reprecipitation was performed with heptane, and the intermediate compound 9-phenyl-2- (10-phenylanthracen-9-yl) -7- (4,4,5,5-tetramethyl-1,3,2- Dioxaborolan-2-yl) -9H-carbazole (3.0 g) was obtained.

<Synthesis of 2-([2,3′-bipyridin] -5-yl) -9-phenyl-7- (10-phenylanthracen-9-yl) -9H-carbazole>
Intermediate compound 9-phenyl-2- (10-phenylanthracen-9-yl) -7- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl under nitrogen atmosphere ) -9H-carbazole (1.5 g), 5-bromo-2,3′-bipyridine (0.62 g), tetrakis (triphenylphosphine) palladium (0) (Pd (PPh ₃ ) ₄ ) (0.11 g) , Tripotassium phosphate (1.02 g) and N, N-dimethylacetamide (10 ml) were stirred in a flask and heated at 120 ° C. for 5 hours. After completion of the reaction, water is added to the reaction solution, the precipitate (crude product) is filtered, the obtained crude product is dissolved in toluene by heating, dried over anhydrous sodium sulfate, the desiccant is removed, and the solvent is distilled under reduced pressure. Column purification (solvent: toluene / ethyl acetate = 5/1 (volume ratio)) was performed on the crude product silica gel obtained after the above, and further purification by sublimation was performed to obtain the target compound (1-5-29): 0.67 g of 2-([2,3′-bipyridin] -5-yl) -9-phenyl-7- (10-phenylanthracen-9-yl) -9H-carbazole was obtained.

The structure of the compound (1-5-29) was confirmed by MS spectrum and NMR measurement.
¹ H-NMR (CDCl ₃ ): δ = 9.28 (s, 1H), 9.08 (s, 1H), 8.68 (d, 1H), 8.39 (t, 3H), 8.11 (D, 1H), 7.86 (d, 1H), 7.77-7.32 (m, 23H).

Other physical properties were as follows.
Glass transition temperature (Tg): 167.3 ° C
[Measurement equipment: Diamond DSC (manufactured by PERKIN-ELMER); Measurement conditions: Cooling rate 200 ° C / Min.

<Synthesis Example of Compound Represented by Formula (1-5-12)>

<Synthesis of 9-phenyl-2- (10-phenylanthracen-9-yl) -7- (4- (pyridin-4-yl) phenyl) -9H-carbazole>
Under nitrogen atmosphere, intermediate compound 9-phenyl-2- (10-phenylanthracen-9-yl) -7- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -9H-carbazole (1.5 g), 4- (4-bromophenyl) pyridine (0.68 g), tetrakis (triphenylphosphine) palladium (0) (Pd (PPh ₃ ) ₄ ) (0.06 g), phosphorus Tripotassium acid (1.02 g) and N, N-dimethylacetamide (14 ml) were stirred in a flask and heated at 120 ° C. for 5 hours. After heating, water was added to the reaction solution cooled to room temperature, and the precipitate (crude product) was filtered. The obtained crude product was dissolved in toluene by heating, and silica gel short column purification (solvent: toluene) was performed. The solvent was distilled off under reduced pressure, and the resulting concentrate was dissolved again in toluene. Ethyl acetate was added to this toluene solution, and the resulting precipitate was collected by filtration. After performing the reprecipitation step with toluene and ethyl acetate five times, the product was further purified by sublimation, and the target compound (1-5-12): 9-phenyl-2- (10-phenylanthracen-9-yl)- 1.1 g of 7- (4- (pyridin-4-yl) phenyl) -9H-carbazole was obtained.

The structure of the compound (1-5-12) was confirmed by MS spectrum and NMR measurement.
¹ H-NMR (CDCl ₃ ): δ = 8.69 (dd, 2H), 8.39 (d, 1H), 8.35 (d, 1H), 7.84 (d, 2H), 7.76 -7.30 (m, 26H).

Other physical properties were as follows.
Glass transition temperature (Tg): 174.8 ° C
[Measurement equipment: Diamond DSC (manufactured by PERKIN-ELMER); Measurement conditions: Cooling rate 200 ° C / Min.

  By appropriately changing the raw material compound, another carbazole compound of the present invention can be synthesized by a method according to the synthesis example described above. In addition, the compounds of the present invention include those in which at least a part of the hydrogen atoms are substituted with deuterium. Such a compound can be obtained by using a raw material in which a desired position is deuterated. It can be synthesized in the same way.

  Examples will be shown below for illustrating the present invention in more detail, but the present invention is not limited to these examples.

<Examples 1 to 6 and Comparative Examples 1 and 2>
Time for producing the electroluminescent elements according to Examples 1 to 6 and Comparative Examples 1 and ² and holding the driving start voltage (V) in the constant current driving test and 80% (1600 cd / m ² ) or more of the initial luminance. (H) was measured. Hereinafter, examples and comparative examples will be described in detail.

Table 1 below shows the material configuration of each layer in the devices according to Examples 1 to 6 and Comparative Examples 1 and 2.

In Table 1, “HI” is N ⁴ , N ^{4 ′} -diphenyl-N ⁴ , N ^{4 ′} -bis (9-phenyl-9H-carbazol-3-yl)-[1,1′-biphenyl] -4, 4′-diamine, “NPD” is N, N′-diphenyl-N, N′-dinaphthyl-4,4′-diaminobiphenyl, compound (A) is 9- (4- (naphthalen-1-yl) phenyl) 10-phenyl anthracene, compound (B) ^{N 5, N 5, N 9} , N 9 -7,7- hexaphenyl -7H- benzo [c] fluorene-5,9-diamine, compound (C) 2 , 7-di ([2,4′-bipyridin] -6-yl) -9-phenyl-9H-carbazole, compound (D) is 9,10-di ([2,2′-bipyridin] -5-yl. ) Anthracene, and “Liq” is 8-quinolinol lithium The The chemical structure is shown below.

<Example 1>
<Device Using Compound (1-2-336) for Electron Transport Layer>
A glass substrate of 26 mm × 28 mm × 0.7 mm (manufactured by Optoscience Co., Ltd.) obtained by polishing ITO deposited to a thickness of 180 nm by sputtering to 150 nm was used as a transparent support substrate. This transparent support substrate is fixed to a substrate holder of a commercially available vapor deposition apparatus (manufactured by Showa Vacuum Co., Ltd.), and a molybdenum vapor deposition boat containing HI, a molybdenum vapor deposition boat containing NPD, and compound (A) are placed therein. Molybdenum vapor deposition boat, molybdenum vapor deposition boat containing compound (B), molybdenum vapor deposition boat containing compound (1-2-336), molybdenum vapor deposition boat containing Liq, magnesium A molybdenum boat and a tungsten evaporation boat containing silver were installed.

The following layers were sequentially formed on the ITO film of the transparent support substrate. The vacuum chamber was depressurized to 5 × 10 ⁻⁴ Pa, first, a vapor deposition boat containing HI was heated to deposit to a film thickness of 40 nm to form a hole injection layer, and then NPD entered. The vapor deposition boat was heated and vapor-deposited so that it might become a film thickness of 30 nm, and the positive hole transport layer was formed. Next, the vapor deposition boat containing the compound (A) and the vapor deposition boat containing the compound (B) were heated at the same time to form a light emitting layer by vapor deposition to a film thickness of 35 nm. The deposition rate was adjusted so that the weight ratio of compound (A) to compound (B) was approximately 95 to 5. Next, the evaporation boat containing the compound (1-2-336) was heated and evaporated to a thickness of 20 nm to form an electron transport layer. The deposition rate of each layer was 0.01 to 1 nm / second.

  Thereafter, the evaporation boat containing Liq was heated to deposit at a deposition rate of 0.01 to 0.1 nm / second so as to have a film thickness of 1 nm. Next, a boat containing magnesium and a boat containing silver were heated at the same time and evaporated to a film thickness of 100 nm to form a cathode. At this time, the deposition rate was adjusted so that the atomic ratio of magnesium and silver was 10: 1, and a cathode was formed so that the deposition rate was 0.1 to 10 nm / second, thereby obtaining an organic electroluminescent device.

When a direct current voltage was applied using the ITO electrode as the anode and the magnesium / silver electrode as the cathode, blue light emission with a wavelength of about 460 nm was obtained. Further, when a constant current driving test was performed with a current density for obtaining an initial luminance of 2000 cd / m ² , the driving test start voltage was 6.90 V, and the luminance was 80% (1600 cd / m ² ) or more of the initial luminance. The holding time was 225 hours.

<Example 2>
<Element Using Compound (1-4-98) for Electron Transport Layer>
An organic EL device was obtained by the method according to Example 1 except that the compound (1-2-336) was changed to the compound (1-4-98). A constant current driving test was carried out using an ITO electrode as an anode and a magnesium / silver electrode as a cathode at a current density for obtaining an initial luminance of 2000 cd / m ² . The driving test starting voltage was 6.35 V, and the time for maintaining the luminance of 80% or more of the initial luminance was 100 hours.

<Example 3>
<Element Using Compound (1-4-100) for Electron Transport Layer>
An organic EL device was obtained by the method according to Example 1 except that the compound (1-2-336) was changed to the compound (1-4-100). A constant current driving test was carried out using an ITO electrode as an anode and a magnesium / silver electrode as a cathode at a current density for obtaining an initial luminance of 2000 cd / m ² . The driving test start voltage was 7.16 V, and the time for maintaining the luminance of 80% or more of the initial luminance was 200 hours.

<Example 4>
<Device Using Compound (1-2-290) for Electron Transport Layer>
An organic EL device was obtained by the method according to Example 1 except that the compound (1-2-336) was changed to the compound (1-2-290). A constant current driving test was carried out using an ITO electrode as an anode and a magnesium / silver electrode as a cathode at a current density for obtaining an initial luminance of 2000 cd / m ² . The drive test start voltage was 7.91 V, and the time for maintaining the luminance of 80% or more of the initial luminance was 233 hours.

<Example 5>
<Device Using Compound (1-2-393) for Electron Transport Layer>
An organic EL device was obtained by the method according to Example 1 except that the compound (1-2-336) was changed to the compound (1-2-393). A constant current driving test was carried out using an ITO electrode as an anode and a magnesium / silver electrode as a cathode at a current density for obtaining an initial luminance of 2000 cd / m ² . The driving test start voltage was 7.41 V, and the time for maintaining the luminance of 80% or more of the initial luminance was 312 hours.

<Example 6>
<Element Using Compound (1-4-155) for Electron Transport Layer>
An organic EL device was obtained by the method according to Example 1 except that the compound (1-2-336) was changed to the compound (1-4-155). A constant current driving test was carried out using an ITO electrode as an anode and a magnesium / silver electrode as a cathode at a current density for obtaining an initial luminance of 2000 cd / m ² . The driving test start voltage was 5.34 V, and the time for maintaining the luminance of 80% or more of the initial luminance was 298 hours.

<Comparative Example 1>
An organic EL device was obtained by the method according to Example 1 except that the compound (1-2-336) was changed to the compound (C). A constant current driving test was carried out using an ITO electrode as an anode and a magnesium / silver electrode as a cathode at a current density for obtaining an initial luminance of 2000 cd / m ² . The driving test starting voltage was 4.87 V, and the time for maintaining the luminance of 80% or more of the initial luminance was 26 hours.

<Comparative example 2>
An organic EL device was obtained by the method according to Example 1 except that the compound (1-2-336) was changed to the compound (D). A constant current driving test was carried out using an ITO electrode as an anode and a magnesium / silver electrode as a cathode at a current density for obtaining an initial luminance of 2000 cd / m ² . The driving test start voltage was 4.89 V, and the time for maintaining the luminance of 80% or more of the initial luminance was 20 hours.

The above results are summarized in Table 2.

<Reference Example 1 and Comparative Example 3>
The electroluminescence device according to Reference Example 1 and Comparative Example 3 is manufactured, and the driving start voltage (V) in the constant current driving test, the time (h) for maintaining the luminance of 90% (1800 cd / m ² ) or more of the initial luminance. And the external quantum efficiency at 1000 cd / m ² was measured. Hereinafter, reference examples and comparative examples thereof will be described in detail.

  Note that the quantum efficiency of a light-emitting element includes an internal quantum efficiency and an external quantum efficiency. The ratio of external energy injected as electrons (or holes) into the light-emitting layer of the light-emitting element is converted into photons purely. What is shown is the internal quantum efficiency. On the other hand, the external quantum efficiency is calculated based on the amount of photons emitted to the outside of the light emitting element, and some of the photons generated in the light emitting layer are absorbed inside the light emitting element. The external quantum efficiency is lower than the internal quantum efficiency because it is continuously reflected and is not emitted outside the light emitting element.

The external quantum efficiency is measured as follows. A voltage / current generator R6144 manufactured by Advantest Corporation was used to apply a voltage at which the luminance of the element was 1000 cd / m ² to cause the element to emit light. Using a spectral radiance meter SR-3AR manufactured by TOPCON, the spectral radiance in the visible light region was measured from the direction perpendicular to the light emitting surface. Assuming that the light emitting surface is a completely diffusing surface, the value obtained by dividing the measured spectral radiance value of each wavelength component by the wavelength energy and multiplying by π is the number of photons at each wavelength. Next, the number of photons in the entire wavelength region observed was integrated to obtain the total number of photons emitted from the device. The value obtained by dividing the applied current value by the elementary charge is the number of carriers injected into the device, and the number obtained by dividing the total number of photons emitted from the device by the number of carriers injected into the device is the external quantum efficiency.

Table 3 below shows the material structure of each layer in the electroluminescent device according to the produced Reference Example 1 and Comparative Example 3.

In Table 3, “CuPc” is copper phthalocyanine, “NPD” is N, N′-diphenyl-N, N′-dinaphthyl-4,4′-diaminobiphenyl, and compound (E) is 9-phenyl-10- [6 - (1,1 ';3,1') terphenyl-5-yl] naphthalene-2-yl anthracene, compound (B) ^{N 5, N 5, N 9} , N 9 -7,7- hexaphenyl -7H-benzo [c] fluorene-5,9-diamine, compound (F) is 9,10-bis (4- (pyridin-4-yl) phenyl) anthracene, and "Liq" is 8-quinolinol lithium . The chemical structure is shown below.

<Reference Example 1>
<Element Using Compound (1-1-856) for Electron Transport Layer>
A glass substrate of 26 mm × 28 mm × 0.7 mm (manufactured by Optoscience Co., Ltd.) obtained by polishing ITO deposited to a thickness of 180 nm by sputtering to 150 nm was used as a transparent support substrate. This transparent support substrate is fixed to a substrate holder of a commercially available vapor deposition apparatus (manufactured by Vacuum Kiko Co., Ltd.), a molybdenum vapor deposition boat containing CuPc, a molybdenum vapor deposition boat containing NPD, and a compound (E) Molybdenum vapor deposition boat, molybdenum vapor deposition boat containing compound (B), molybdenum vapor deposition boat containing compound represented by formula (1-1-856), molybdenum vapor deposition containing Liq A boat, a molybdenum boat containing magnesium, and a tungsten evaporation boat containing silver were installed.

The following layers were sequentially formed on the ITO film of the transparent support substrate. The vacuum chamber was depressurized to 5 × 10 ⁻⁴ Pa, first, the vapor deposition boat containing CuPc was heated and vapor deposited to a film thickness of 50 nm to form a hole injection layer, and then NPD entered. The vapor deposition boat was heated and vapor-deposited so that it might become a film thickness of 30 nm, and the positive hole transport layer was formed. Next, the vapor deposition boat containing the compound (E) and the vapor deposition boat containing the compound (B) were heated at the same time to form a light emitting layer by vapor deposition to a film thickness of 35 nm. The deposition rate was adjusted so that the weight ratio of compound (E) to compound (B) was approximately 95 to 5. Next, the evaporation boat containing the compound represented by the formula (1-1-856) was heated and evaporated to a thickness of 15 nm to form an electron transport layer. The deposition rate of each layer was 0.01 to 1 nm / second.

  Thereafter, the evaporation boat containing Liq was heated to deposit at a deposition rate of 0.01 to 0.1 nm / second so as to have a film thickness of 1 nm. Next, a boat containing magnesium and a boat containing silver were heated at the same time and evaporated to a film thickness of 100 nm to form a cathode. At this time, the deposition rate was adjusted so that the atomic ratio of magnesium and silver was 10: 1, and a cathode was formed so that the deposition rate was 0.1 to 10 nm / second, thereby obtaining an organic electroluminescent device.

When a direct current voltage was applied using the ITO electrode as the anode and the magnesium / silver electrode as the cathode, blue light emission with a wavelength of about 460 nm was obtained. In addition, a constant current driving test was performed at a current density for obtaining an initial luminance of 2000 cd / m ² . The drive test start voltage was 5.07 V, and the time for maintaining the luminance of 90% (1800 cd / m ² ) or more of the initial luminance was 212 hours. In addition, the external quantum efficiency of this device at 1000 cd / m ² was 7.25%.

<Comparative Example 3>
<Device Using Compound (F) for Electron Transport Layer>
An organic EL device was obtained in the same manner as in Reference Example 1 except that the compound represented by the formula (1-1-856) was changed to the compound represented by the compound (F). When a direct current voltage was applied using the ITO electrode as the anode and the magnesium / silver electrode as the cathode, blue light emission with a wavelength of about 455 nm was obtained. In addition, a constant current driving test was performed at a current density for obtaining an initial luminance of 2000 cd / m ² . The driving test start voltage was 4.64 V, and the time for maintaining the luminance of 90% (1800 cd / m ² ) or more of the initial luminance was 42 hours. In addition, the external quantum efficiency of this device at 1000 cd / m ² was 6.58%.

The above results are summarized in Table 4.

<Reference Examples 2-9 and Comparative Examples 4-6>
Electroluminescent devices according to Examples 2 to 9 and Comparative Examples 4 to 6 were prepared, and each had a driving start voltage (V) in a constant current driving test and a luminance of 80% (1600 cd / m ² ) or more of the initial luminance. Measurements of retention time (h) and external quantum efficiency at 1000 cd / m ² were performed. Hereinafter, reference examples and comparative examples thereof will be described in detail. The method for measuring the external quantum efficiency is as described above.

Table 5 below shows the material configuration of each layer in the devices according to Reference Examples 2-9 and Comparative Examples 4-6.

In Table 5, “HI” is N ⁴ , N ^{4 ′} -diphenyl-N ⁴ , N ^{4 ′} -bis (9-phenyl-9H-carbazol-3-yl)-[1,1′-biphenyl] -4, 4′-diamine, compound (G) is 9-phenyl-10- (4-phenylnaphthalen-1-yl) anthracene, and compound (C) is 2,7-di ([2,4′-bipyridine] -6- Yl) -9-phenyl-9H-carbazole, compound (H) is 9,10-bis (4- (pyridin-4-yl) naphthalen-1-yl) anthracene, compound (I) is 9,10-bis ( 4- (Pyridin-2-yl) phenyl) anthracene.

<Reference Example 2>
<Element Using Compound (1-1-854) for Electron Transport Layer>
A glass substrate of 26 mm × 28 mm × 0.7 mm (manufactured by Optoscience Co., Ltd.) obtained by polishing ITO deposited to a thickness of 180 nm by sputtering to 150 nm was used as a transparent support substrate. This transparent support substrate is fixed to a substrate holder of a commercially available vapor deposition apparatus (manufactured by Showa Vacuum Co., Ltd.), and a molybdenum vapor deposition boat containing HI, a molybdenum vapor deposition boat containing NPD, and compound (G) are placed therein. Molybdenum vapor deposition boat, molybdenum vapor deposition boat containing compound (B), molybdenum vapor deposition boat containing compound (1-1-854), molybdenum vapor deposition boat containing Liq, magnesium A molybdenum boat and a tungsten evaporation boat containing silver were installed.

The following layers were sequentially formed on the ITO film of the transparent support substrate. The vacuum chamber was depressurized to 5 × 10 ⁻⁴ Pa, first, a vapor deposition boat containing HI was heated to deposit to a film thickness of 40 nm to form a hole injection layer, and then NPD entered. The vapor deposition boat was heated and vapor-deposited to a film thickness of 25 nm to form a hole transport layer. Next, the vapor deposition boat containing the compound (G) and the vapor deposition boat containing the compound (B) were heated at the same time to form a light emitting layer by vapor deposition to a film thickness of 25 nm. The deposition rate was adjusted so that the weight ratio of the compound (G) to the compound (B) was approximately 95 to 5. Next, the evaporation boat containing the compound (1-1-854) was heated and evaporated to a thickness of 20 nm to form an electron transport layer. The deposition rate of each layer was 0.01 to 1 nm / second.

  Thereafter, the evaporation boat containing Liq was heated to deposit at a deposition rate of 0.01 to 0.1 nm / second so as to have a film thickness of 1 nm. Next, a boat containing magnesium and a boat containing silver were heated at the same time and evaporated to a film thickness of 100 nm to form a cathode. At this time, the deposition rate was adjusted so that the atomic ratio of magnesium and silver was 10: 1, and the cathode was formed so that the deposition rate was 0.1 to 10 nm / second, to obtain an organic electroluminescent device.

When a direct current voltage was applied using the ITO electrode as the anode and the magnesium / silver electrode as the cathode, blue light emission with a wavelength of about 460 nm was obtained. Further, when a constant current driving test was performed with a current density for obtaining an initial luminance of 2000 cd / m ² , the driving test start voltage was 6.23 V, and the luminance was 80% (1600 cd / m ² ) or more of the initial luminance. The holding time was 170 hours. In addition, the external quantum efficiency of this device at 1000 cd / m ² was 4.39%.

<Reference Example 3>
<Device Using Compound (1-1-855) for Electron Transport Layer>
An organic EL device was obtained by a method according to Reference Example 2 except that the compound (1-1-854) was replaced with the compound (1-1-855). A constant current driving test was carried out using an ITO electrode as an anode and a magnesium / silver electrode as a cathode at a current density for obtaining an initial luminance of 2000 cd / m ² . The drive test start voltage was 5.16 V, and the time for maintaining the luminance of 80% or more of the initial luminance was 321 hours. In addition, the external quantum efficiency of this device at 1000 cd / m ² was 6.79%.

<Reference Example 4>
<Element Using Compound (1-1-856) for Electron Transport Layer>
An organic EL device was obtained by a method according to Reference Example 2 except that the compound (1-1-854) was replaced with the compound (1-1-856). A constant current driving test was carried out using an ITO electrode as an anode and a magnesium / silver electrode as a cathode at a current density for obtaining an initial luminance of 2000 cd / m ² . The driving test starting voltage was 4.84 V, and the time for maintaining the luminance of 80% or more of the initial luminance was 198 hours. In addition, the external quantum efficiency of this device at 1000 cd / m ² was 5.29%.

<Reference Example 5>
<Element Using Compound (1-1-851) for Electron Transport Layer>
An organic EL device was obtained by a method according to Reference Example 2 except that the compound (1-1-854) was replaced with the compound (1-1-851). A constant current driving test was carried out using an ITO electrode as an anode and a magnesium / silver electrode as a cathode at a current density for obtaining an initial luminance of 2000 cd / m ² . The driving test start voltage was 4.83 V, and the time for maintaining the luminance of 80% or more of the initial luminance was 334 hours. Moreover, the external quantum efficiency in 1000 cd / m < ² > of this element was 5.01%.

<Reference Example 6>
<Element Using Compound (1-1-852) for Electron Transport Layer>
An organic EL device was obtained by a method according to Reference Example 2 except that the compound (1-1-854) was replaced with the compound (1-1-852). A constant current driving test was carried out using an ITO electrode as an anode and a magnesium / silver electrode as a cathode at a current density for obtaining an initial luminance of 2000 cd / m ² . The driving test start voltage was 5.08 V, and the time for maintaining the luminance of 80% or more of the initial luminance was 289 hours. In addition, the external quantum efficiency of this device at 1000 cd / m ² was 6.59%.

<Reference Example 7>
<Element Using Compound (1-1-853) for Electron Transport Layer>
An organic EL device was obtained by a method according to Reference Example 2 except that the compound (1-1-854) was replaced with the compound (1-1-853). A constant current driving test was carried out using an ITO electrode as an anode and a magnesium / silver electrode as a cathode at a current density for obtaining an initial luminance of 2000 cd / m ² . The drive test starting voltage was 4.03 V, and the time for maintaining the luminance of 80% or more of the initial luminance was 229 hours. In addition, the external quantum efficiency of this device at 1000 cd / m ² was 6.89%.

<Reference Example 8>
<Element Using Compound (1-1-98) for Electron Transport Layer>
An organic EL device was obtained by a method according to Reference Example 2 except that the compound (1-1-854) was changed to the compound (1-1-98). A constant current driving test was carried out using an ITO electrode as an anode and a magnesium / silver electrode as a cathode at a current density for obtaining an initial luminance of 2000 cd / m ² . The drive test start voltage was 5.51 V, and the time for maintaining the luminance of 80% or more of the initial luminance was 235 hours. In addition, the external quantum efficiency of this device at 1000 cd / m ² was 5.95%.

<Reference Example 9>
<Element Using Compound (1-1-99) for Electron Transport Layer>
An organic EL device was obtained by a method according to Reference Example 2 except that the compound (1-1-854) was changed to the compound (1-1-99). A constant current driving test was carried out using an ITO electrode as an anode and a magnesium / silver electrode as a cathode at a current density for obtaining an initial luminance of 2000 cd / m ² . The driving test start voltage was 6.35 V, and the time for maintaining the luminance of 80% or more of the initial luminance was 186 hours. In addition, the external quantum efficiency of this device at 1000 cd / m ² was 4.91%.

<Comparative example 4>
An organic EL device was obtained by a method according to Reference Example 2 except that the compound (1-1-854) was changed to the compound (C). A constant current driving test was carried out using an ITO electrode as an anode and a magnesium / silver electrode as a cathode at a current density for obtaining an initial luminance of 2000 cd / m ² . The drive test start voltage was 3.57 V, and the time for maintaining the luminance of 80% or more of the initial luminance was 114 hours. Moreover, the external quantum efficiency in 1000 cd / m < ² > of this element was 5.20%.

<Comparative Example 5>
An organic EL device was obtained by a method according to Reference Example 2 except that the compound (1-1-854) was changed to the compound (H). A constant current driving test was carried out using an ITO electrode as an anode and a magnesium / silver electrode as a cathode at a current density for obtaining an initial luminance of 2000 cd / m ² . The driving test start voltage was 3.61 V, and the time for maintaining the luminance of 80% or more of the initial luminance was 120 hours. Moreover, the external quantum efficiency in 1000 cd / m < ² > of this element was 5.12%.

<Comparative Example 6>
An organic EL device was obtained by a method according to Reference Example 2 except that the compound (1-1-854) was changed to the compound (I). A constant current driving test was carried out using an ITO electrode as an anode and a magnesium / silver electrode as a cathode at a current density for obtaining an initial luminance of 2000 cd / m ² . The driving test start voltage was 4.05 V, and the time for maintaining the luminance of 80% or more of the initial luminance was 135 hours. In addition, the external quantum efficiency of this device at 1000 cd / m ² was 6.20%.

The above results are summarized in Table 6.

Next, examples of the organic EL device using the compound represented by the formula (1-5) are shown.
The organic EL elements according to Examples 7 to 14 were prepared, and the driving voltage (V), the EL emission wavelength (nm), and the external quantum efficiency (%), which are characteristics at 1000 cd / m ² emission, were measured, respectively. In addition, when the device was driven at a constant current at a current density at which a luminance of 2000 cd / m ² was obtained, the time for maintaining the luminance of 80% (1600 cd / m ² ) or more of the initial luminance was measured. Examples 10 and 14 are also comparative examples for showing a remarkable effect of the compound represented by the formula (1-5).

Table 7 below shows the material configuration of each layer in the produced organic EL elements according to Examples 7 to 14.

In Table 7, “HI” is N ⁴ , N ^{4 ′} -diphenyl-N ⁴ , N ^{4 ′} -bis (9-phenyl-9H-carbazol-3-yl)-[1,1′-biphenyl] -4, 4′-diamine, “HT” is N ⁴ , N ⁴ , N ^{4 ′} , N ^{4 ′} -tetra [1,1′-biphenyl] -4-yl- [1,1′-biphenyl] -4,4 ′ - diamine, "BH" are 9-phenyl-10- (4-phenyl-1-yl) anthracene, "BD" is 7,7, - dimethyl ^-N 5, ^{N 9} - diphenyl ^-N 5, ^{N 9} - Bis (4- (trimethylsilanyl) phenyl) -7H-benzo [c] fluorene-5,9-diamine. “Liq” is 8-quinolinol lithium. The chemical structure is shown below.

<Example 7>
<Device Using Compound (1-5-2) for Electron Transport Layer>
A glass substrate of 26 mm × 28 mm × 0.7 mm (manufactured by Optoscience Co., Ltd.) obtained by polishing ITO deposited to a thickness of 180 nm by sputtering to 150 nm was used as a transparent support substrate. This transparent support substrate is fixed to a substrate holder of a commercially available vapor deposition apparatus (made by Showa Vacuum Co., Ltd.), a molybdenum vapor deposition boat containing HI, a molybdenum vapor deposition boat containing HT, and a molybdenum vapor vessel containing BH. Vapor deposition boat, molybdenum vapor deposition boat with BD, molybdenum vapor deposition boat with compound (1-5-2) of the present invention, molybdenum vapor deposition boat with Liq, magnesium molybdenum A vapor deposition boat and a molybdenum vapor deposition boat containing silver were mounted.

The following layers were sequentially formed on the ITO film of the transparent support substrate. The vacuum chamber was depressurized to 5 × 10 ⁻⁴ Pa, and first, a vapor deposition boat containing HI was heated to deposit to a film thickness of 45 nm to form a hole injection layer, and then HT entered. The vapor deposition boat was heated and vapor-deposited to a film thickness of 25 nm to form a hole transport layer. Next, a vapor deposition boat containing BH and a vapor deposition boat containing BD were heated at the same time so as to have a film thickness of 20 nm to form a light emitting layer. The deposition rate was adjusted so that the weight ratio of BH to BD was approximately 95: 5. Next, the vapor deposition boat containing the compound (1-5-2) and the vapor deposition boat containing Liq were heated at the same time to be vapor-deposited to a film thickness of 30 nm to form an electron transport layer. The deposition rate was adjusted so that the weight ratio of the compound (1-5-2) and Liq was approximately 1: 1. The deposition rate of each layer was 0.01 to 1 nm / second.

  Thereafter, the evaporation boat containing Liq was heated to deposit at a deposition rate of 0.01 to 0.1 nm / second so as to have a film thickness of 1 nm. Next, a boat containing magnesium and a boat containing silver were heated at the same time and evaporated to a film thickness of 100 nm to form a cathode. At this time, the vapor deposition rate was adjusted so that the atomic ratio of magnesium and silver was 10: 1, and the organic EL device was obtained so that the vapor deposition rate was 0.01 to 2 nm / second.

Using the ITO electrode as the anode and the Liq / magnesium + silver electrode as the cathode, the characteristics at 1000 cd / m ² emission were measured. The driving voltage was 3.87 V and the external quantum efficiency was 6.38% (blue emission with a wavelength of about 455 nm). Met. In addition, as a result of conducting a constant current driving test with a current density for obtaining an initial luminance of 2000 cd / m ² , the time for maintaining the luminance of 80% (1600 cd / m ² ) or more of the initial value was 351 hours.

<Example 8>
<Element Using Compound (1-5-8) for Electron Transport Layer>
An organic EL device was obtained by the method according to Example 7 except that the compound (1-5-2) was changed to the compound (1-5-8). When the characteristics at 1000 cd / m ² emission were measured, the driving voltage was 3.61 V and the external quantum efficiency was 7.59% (blue emission with a wavelength of about 455 nm). Further, the time for maintaining the luminance of 80% or more of the initial luminance was 314 hours.

<Example 9>
<Element Using Compound (1-5-29) for Electron Transport Layer>
An organic EL device was obtained by the method according to Example 7 except that the compound (1-5-2) was changed to the compound (1-5-29). When the characteristics at 1000 cd / m ² emission were measured, the driving voltage was 3.48 V and the external quantum efficiency was 6.88% (blue emission with a wavelength of about 455 nm). The time for maintaining the luminance of 80% or more of the initial luminance was 285 hours.

<Example 10>
<Element Using Compound (1-4-98) for Electron Transport Layer>
An organic EL device was obtained by the method according to Example 7 except that the compound (1-5-2) was changed to the compound (1-4-98). When the characteristics at 1000 cd / m ² emission were measured, the drive voltage was 3.94 V and the external quantum efficiency was 5.79% (blue emission with a wavelength of about 455 nm). Further, the time for maintaining the luminance of 80% or more of the initial luminance was 320 hours.
In addition, Example 10 is also a comparative example for showing a remarkable effect of the compound represented by the formula (1-5).

<Example 11>
<Device Using Compound (1-5-2) for Electron Transport Layer>
A glass substrate of 26 mm × 28 mm × 0.7 mm (manufactured by Optoscience Co., Ltd.) obtained by polishing ITO deposited to a thickness of 180 nm by sputtering to 150 nm was used as a transparent support substrate. This transparent support substrate is fixed to a substrate holder of a commercially available vapor deposition apparatus (made by Showa Vacuum Co., Ltd.), a molybdenum vapor deposition boat containing HI, a molybdenum vapor deposition boat containing HT, and a molybdenum vapor vessel containing BH. Vapor deposition boat, molybdenum vapor deposition boat with BD, molybdenum vapor deposition boat with compound (1-5-2) of the present invention, molybdenum vapor deposition boat with Liq, and tungsten with aluminum Evaporation boat was installed.

The following layers were sequentially formed on the ITO film of the transparent support substrate. The vacuum chamber was depressurized to 5 × 10 ⁻⁴ Pa, and first, a vapor deposition boat containing HI was heated to deposit to a film thickness of 45 nm to form a hole injection layer, and then HT entered. The vapor deposition boat was heated and vapor-deposited to a film thickness of 25 nm to form a hole transport layer. Next, a vapor deposition boat containing BH and a vapor deposition boat containing BD were heated at the same time so as to have a film thickness of 20 nm to form a light emitting layer. The deposition rate was adjusted so that the weight ratio of BH to BD was approximately 95: 5. Next, the vapor deposition boat containing the compound (1-5-2) and the vapor deposition boat containing Liq were heated at the same time to be vapor-deposited to a film thickness of 30 nm to form an electron transport layer. The deposition rate was adjusted so that the weight ratio of the compound (1-5-2) and Liq was approximately 1: 1. The deposition rate of each layer was 0.01 to 1 nm / second.

  Thereafter, the evaporation boat containing Liq was heated to deposit at a deposition rate of 0.01 to 0.1 nm / second so as to have a film thickness of 1 nm. Next, the evaporation boat containing aluminum was heated to form a cathode by depositing aluminum at a deposition rate of 0.01 to 2 nm / second so as to have a film thickness of 100 nm, thereby obtaining an organic EL element.

Using the ITO electrode as the anode and the Liq / aluminum electrode as the cathode, the characteristics at 1000 cd / m ² emission were measured. The driving voltage was 4.25 V and the external quantum efficiency was 6.90% (blue emission with a wavelength of about 454 nm). It was. In addition, as a result of conducting a constant current driving test with a current density for obtaining an initial luminance of 2000 cd / m ² , the time for maintaining the luminance of 80% (1600 cd / m ² ) or more of the initial value was 241 hours.

<Example 12>
<Element Using Compound (1-5-8) for Electron Transport Layer>
An organic EL device was obtained by the method according to Example 11 except that the compound (1-5-2) was changed to the compound (1-5-8). When the characteristics at 1000 cd / m ² emission were measured, the drive voltage was 3.89 V and the external quantum efficiency was 7.92% (blue emission with a wavelength of about 455 nm). Further, the time for maintaining the luminance of 80% or more of the initial luminance was 232 hours.

<Example 13>
<Element Using Compound (1-5-29) for Electron Transport Layer>
An organic EL device was obtained by the method according to Example 11 except that the compound (1-5-2) was changed to the compound (1-5-29). When the characteristics at 1000 cd / m ² emission were measured, the driving voltage was 3.63 V and the external quantum efficiency was 7.70% (blue emission with a wavelength of about 456 nm). The time for maintaining the luminance of 80% or more of the initial luminance was 285 hours.

<Example 14>
<Device Using Compound (1-2-336) for Electron Transport Layer>
An organic EL device was obtained by the method according to Example 11 except that the compound (1-5-2) was changed to the compound (1-2-336). When the characteristics at 1000 cd / m ² emission were measured, the drive voltage was 4.44 V and the external quantum efficiency was 5.46% (blue emission with a wavelength of about 455 nm). Further, the time for maintaining the luminance of 80% or more of the initial luminance was 237 hours.
In addition, Example 14 is also a comparative example for showing the remarkable effect of the compound represented by Formula (1-5).

The above results are summarized in Table 8.

Furthermore, the organic EL elements according to Examples 15 and 16 were prepared, and the driving voltage (V), the EL emission wavelength (nm), and the external quantum efficiency (%), which are characteristics at the time of 1000 cd / m ² emission, were measured. Next, the time for maintaining the luminance of 80% (1600 cd / m ² ) or more of the initial luminance when the device was driven at a constant current at a current density at which a luminance of 2000 cd / m ² was obtained was measured.

Table 7 below shows the material structure of each layer in the manufactured organic EL elements according to Examples 15 and 16.

<Example 15>
<Element Using Compound (1-5-12) for Electron Transport Layer>
A glass substrate of 26 mm × 28 mm × 0.7 mm (manufactured by Optoscience Co., Ltd.) obtained by polishing ITO deposited to a thickness of 180 nm by sputtering to 150 nm was used as a transparent support substrate. This transparent support substrate is fixed to a substrate holder of a commercially available vapor deposition apparatus (made by Showa Vacuum Co., Ltd.), a molybdenum vapor deposition boat containing HI, a molybdenum vapor deposition boat containing HT, and a molybdenum vapor vessel containing BH. Vapor deposition boat, molybdenum vapor deposition boat with BD, molybdenum vapor deposition boat with compound (1-5-12) of the present invention, molybdenum vapor deposition boat with Liq, magnesium molybdenum A vapor deposition boat and a molybdenum vapor deposition boat containing silver were mounted.

The following layers were sequentially formed on the ITO film of the transparent support substrate. The vacuum chamber was depressurized to 5 × 10 ⁻⁴ Pa, and first, a vapor deposition boat containing HI was heated to deposit to a film thickness of 45 nm to form a hole injection layer, and then HT entered. The vapor deposition boat was heated and vapor-deposited to a film thickness of 25 nm to form a hole transport layer. Next, a vapor deposition boat containing BH and a vapor deposition boat containing BD were heated at the same time so as to have a film thickness of 20 nm to form a light emitting layer. The deposition rate was adjusted so that the weight ratio of BH to BD was approximately 95: 5. Next, the vapor deposition boat containing the compound (1-5-12) and the vapor deposition boat containing Liq were heated at the same time to be vapor-deposited so as to have a film thickness of 30 nm, thereby forming an electron transport layer. The deposition rate was adjusted so that the weight ratio of the compound (1-5-12) and Liq was approximately 1: 1. The deposition rate of each layer was 0.01 to 1 nm / second.

  Thereafter, the evaporation boat containing Liq was heated to deposit at a deposition rate of 0.01 to 0.1 nm / second so as to have a film thickness of 1 nm. Next, a boat containing magnesium and a boat containing silver were heated at the same time and evaporated to a film thickness of 100 nm to form a cathode. At this time, the vapor deposition rate was adjusted so that the atomic ratio of magnesium and silver was 10: 1, and the organic EL device was obtained so that the vapor deposition rate was 0.01 to 2 nm / second.

Using the ITO electrode as the anode and the Liq / magnesium + silver electrode as the cathode, the characteristics at 1000 cd / m ² emission were measured. The driving voltage was 3.61 V and the external quantum efficiency was 6.37% (blue emission with a wavelength of about 458 nm). Met. Further, as a result of conducting a constant current driving test with a current density for obtaining an initial luminance of 2000 cd / m ² , the time for maintaining the luminance of 80% (1600 cd / m ² ) or more of the initial value was 245 hours.

<Example 16>
<Element Using Compound (1-5-12) for Electron Transport Layer>
A glass substrate of 26 mm × 28 mm × 0.7 mm (manufactured by Optoscience Co., Ltd.) obtained by polishing ITO deposited to a thickness of 180 nm by sputtering to 150 nm was used as a transparent support substrate. This transparent support substrate is fixed to a substrate holder of a commercially available vapor deposition apparatus (made by Showa Vacuum Co., Ltd.), a molybdenum vapor deposition boat containing HI, a molybdenum vapor deposition boat containing HT, and a molybdenum vapor vessel containing BH. Vapor deposition boat, molybdenum vapor deposition boat with BD, molybdenum vapor deposition boat with compound (1-5-12) of the present invention, molybdenum vapor deposition boat with Liq, and tungsten with aluminum Evaporation boat was installed.

The following layers were sequentially formed on the ITO film of the transparent support substrate. The vacuum chamber was depressurized to 5 × 10 ⁻⁴ Pa, and first, a vapor deposition boat containing HI was heated to deposit to a film thickness of 45 nm to form a hole injection layer, and then HT entered. The vapor deposition boat was heated and vapor-deposited to a film thickness of 25 nm to form a hole transport layer. Next, a vapor deposition boat containing BH and a vapor deposition boat containing BD were heated at the same time so as to have a film thickness of 20 nm to form a light emitting layer. The deposition rate was adjusted so that the weight ratio of BH to BD was approximately 95: 5. Next, the vapor deposition boat containing the compound (1-5-12) and the vapor deposition boat containing Liq were heated at the same time to be vapor-deposited so as to have a film thickness of 30 nm, thereby forming an electron transport layer. The deposition rate was adjusted so that the weight ratio of the compound (1-5-12) and Liq was approximately 1: 1. The deposition rate of each layer was 0.01 to 1 nm / second.

  Thereafter, the evaporation boat containing Liq was heated to deposit at a deposition rate of 0.01 to 0.1 nm / second so as to have a film thickness of 1 nm. Next, the evaporation boat containing aluminum was heated to form a cathode by depositing aluminum at a deposition rate of 0.01 to 2 nm / second so as to have a film thickness of 100 nm, thereby obtaining an organic EL element.

Using the ITO electrode as the anode and the Liq / aluminum electrode as the cathode, the characteristics at 1000 cd / m ² emission were measured. The drive voltage was 4.20 V and the external quantum efficiency was 6.51% (blue emission with a wavelength of about 457 nm). It was. Further, as a result of conducting a constant current driving test with a current density for obtaining an initial luminance of 2000 cd / m ² , the time for maintaining the luminance of 80% (1600 cd / m ² ) or more of the initial value was 280 hours.

The above results are summarized in Table 10.

Finally, the glass transition temperatures of the compounds used in the examples are summarized in Table 11 together with the comparative compounds. It can be seen from the table that the compound represented by the formula (1-5) has a glass transition temperature higher than that of the comparative compound and is excellent in heat resistance.

According to a preferred aspect of the present invention, it is possible to provide an organic electroluminescent element that improves the lifetime of the light emitting element and has an excellent balance with the driving voltage, a display device including the organic electroluminescent element, and a lighting device including the organic electroluminescent element. it can.
In addition, when the compound represented by the formula (1-5) is used, an organic electric field in which driving voltage, external quantum efficiency and heat resistance are further improved (element lifetime is equal to or greater than that of other invention compounds). A light-emitting element can be provided.

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

Claims (22)

A carbazole compound represented by the following formula.

In the above formula,
a is 0 or 1,
R is aryl having 6 to 24 carbons or heteroaryl having 2 to 24 carbons, which may be substituted with alkyl having 1 to 6 carbons or cycloalkyl having 3 to 6 carbons;
Hy ₁ is carbon number 2 containing a nitrogen atom which forms a double bond with an adjacent atom, which may be substituted with alkyl having 1 to 6 carbons or cycloalkyl having 3 to 6 carbons ~ 24 heteroaryl ,
Ar ₁ is aryl having 6 to 24 carbon atoms which may be substituted with alkyl having 1 to 6 carbons or cycloalkyl having 3 to 6 carbons, and Ar ₂ is alkyl having 1 to 6 carbons or It is C6-C24 aryl which may be substituted by C3-C6 cycloalkyl. The carbazole compound according to claim 1, wherein a is 1, and is represented by the following formula (1-2).

In the above formula (1-2), R, Hy ₁ , Ar ₁ and Ar ₂ are the same as defined in claim 1. The carbazole compound according to claim 1, wherein a is 0 and represented by the following formula (1-4).

In the above formula (1-4), R, Hy ₁ and Ar ₂ are the same as defined in claim 1. R is phenyl, biphenylyl, terphenylyl, quaterphenylyl, naphthyl, phenyl substituted naphthyl, phenanthrolinyl, pyridyl, which may be substituted with alkyl having 1 to 6 carbons or cycloalkyl having 3 to 6 carbons A group selected from the group consisting of bipyridyl, terpyridyl, quinolinyl, isoquinolinyl, pyrimidinyl, pyrazinyl, pyridazinyl and triazinyl,
Hy ₁ is pyridyl, bipyridyl, terpyridyl, pyrimidinyl, pyrazinyl, triazinyl, azaindolidinyl, benzimidazolyl, benzothiazolyl, benzo, which may be substituted with alkyl having 1 to 6 carbons or cycloalkyl having 3 to 6 carbons. A group selected from the group consisting of oxazolyl, indazolyl, purinyl, carbolinyl, naphthyridinyl, quinoxalinyl, quinolinyl, isoquinolinyl, pyridylquinolinyl, pyridylisoquinolinyl, acridinyl, phenanthrolinyl, phenazinyl and imidazopyridinyl And
Ar ₁ may be substituted with alkyl having 1 to 6 carbons or cycloalkyl having 3 to 6 carbons, benzene, naphthalene, anthracene, naphthacene, pentacene, biphenyl, acenaphthylene, fluorene, phenalene, phenanthrene, triphenylene, A divalent group having a structure selected from the group consisting of pyrene and perylene, and Ar ₂ is a monovalent group having a structure selected from the group consisting of these,
The carbazole compound according to any one of claims 1 to 3. R is phenyl, biphenylyl, terphenylyl, quaterphenylyl, naphthyl, phenyl substituted naphthyl, phenanthrolinyl, pyridyl, which may be substituted with alkyl having 1 to 6 carbons or cycloalkyl having 3 to 6 carbons , A group selected from the group consisting of quinolinyl and isoquinolinyl,
Hy ₁ is pyridyl, bipyridyl, terpyridyl, pyrimidinyl, pyrazinyl, triazinyl, azaindolidinyl, benzimidazolyl, benzothiazolyl, benzo, which may be substituted with alkyl having 1 to 6 carbons or cycloalkyl having 3 to 6 carbons. A group selected from the group consisting of oxazolyl, quinolinyl, isoquinolinyl, pyridylquinolinyl, pyridylisoquinolinyl and imidazopyridinyl;
Ar ₁ is selected from the group consisting of benzene, naphthalene, anthracene, pyrene, triphenylene, fluorene, biphenyl, and perylene, which may be substituted with alkyl having 1 to 6 carbons or cycloalkyl having 3 to 6 carbons. A divalent group of the structure, Ar ₂ is a monovalent group of a structure selected from the group consisting of these,
The carbazole compound according to any one of claims 1 to 3. R is a group consisting of groups represented by the following formulas (R-1) to (R-20), which may be substituted with alkyl having 1 to 6 carbons or cycloalkyl having 3 to 6 carbons. A group to be selected,

Hy ₁ represents the following formula (Hy-1-1) to formula (Hy-1-3), the following formula (Hy-2-1) to the formula (Hy-2-18), and the following formula (Hy-3-1). ) To formula (Hy-3-8), the following formula (Hy-3-10), the following formula (Hy-3-12) to the formula (Hy-3-27) .

Ar ₁ is a divalent group having a structure selected from the group consisting of benzene, biphenyl and naphthalene, which may be substituted with alkyl having 1 to 6 carbons or cycloalkyl having 3 to 6 carbons; ₂ is a monovalent group having a structure selected from the group consisting of these,
The carbazole compound according to any one of claims 1 to 3. R is a group consisting of groups represented by the above formulas (R-1) to (R-14), which may be substituted with alkyl having 1 to 6 carbons or cycloalkyl having 3 to 6 carbons. A group to be selected,
Hy ₁ is a group represented by the above formulas (Hy-1-1) to (Hy-1-3), or a group represented by the above formulas (Hy-2-1) to (Hy-2-18). A group selected from the group consisting of
Ar ₁ is 1,2-phenylene, 1,3-phenylene, 1,4-phenylene, 1,4-naphthalene-diyl, 1,5-naphthalene-diyl, 2,6-naphthalene-diyl and 2,7- A divalent group selected from the group consisting of naphthalene-diyl, Ar ₂ is a monovalent group selected from the group consisting of phenyl, biphenylyl, 1-naphthyl and 2-naphthyl;
The carbazole compound according to any one of claims 1 to 3. The carbazole compound according to claim 1, which is represented by the following formula (1-2-336), formula (1-4-98) or formula (1-4-100).

The carbazole compound according to claim 1, which is represented by the following formula (1-2-290), formula (1-2-393), or formula (1-4-155).

The carbazole compound according to claim 1 represented by the following formula (1-5).

In the above formula (1-5), a, R, Hy ₁ and Ar ₁ are the same as defined in claim 1,
Ar ₃ is hydrogen or aryl having 6 to 10 carbon atoms, and the anthracene ring and Ar ₃ may be substituted with alkyl having 1 to 6 carbon atoms or cycloalkyl having 3 to 6 carbon atoms. a is 0 or 1,
R is phenyl, biphenylyl, terphenylyl, quaterphenylyl, naphthyl, phenyl substituted naphthyl, phenanthrolinyl, pyridyl, which may be substituted with alkyl having 1 to 6 carbons or cycloalkyl having 3 to 6 carbons A group selected from the group consisting of bipyridyl, terpyridyl, quinolinyl, isoquinolinyl, pyrimidinyl, pyrazinyl, pyridazinyl and triazinyl,
Hy ₁ is pyridyl, bipyridyl, terpyridyl, pyrimidinyl, pyrazinyl, triazinyl, azaindolidinyl, benzimidazolyl, benzothiazolyl, benzo, which may be substituted with alkyl having 1 to 6 carbons or cycloalkyl having 3 to 6 carbons. A group selected from the group consisting of oxazolyl, indazolyl, purinyl, carbolinyl, naphthyridinyl, quinoxalinyl, quinolinyl, isoquinolinyl, pyridylquinolinyl, pyridylisoquinolinyl, acridinyl, phenanthrolinyl, phenazinyl and imidazopyridinyl And
Ar ₁ may be substituted with alkyl having 1 to 6 carbons or cycloalkyl having 3 to 6 carbons, benzene, naphthalene, anthracene, naphthacene, pentacene, biphenyl, acenaphthylene, fluorene, phenalene, phenanthrene, triphenylene, A divalent group having a structure selected from the group consisting of pyrene and perylene;
Ar ₃ is hydrogen, phenyl or naphthyl, the anthracene ring and Ar ₃ may be substituted with alkyl having 1 to 6 carbons or cycloalkyl having 3 to 6 carbons,
The carbazole compound according to claim 10. a is 0 or 1,
R is phenyl, biphenylyl, terphenylyl, quaterphenylyl, naphthyl, phenyl substituted naphthyl, phenanthrolinyl, pyridyl, which may be substituted with alkyl having 1 to 6 carbons or cycloalkyl having 3 to 6 carbons , A group selected from the group consisting of quinolinyl and isoquinolinyl,
Hy ₁ is pyridyl, bipyridyl, terpyridyl, pyrimidinyl, pyrazinyl, triazinyl, azaindolidinyl, benzimidazolyl, benzothiazolyl, benzo, which may be substituted with alkyl having 1 to 6 carbons or cycloalkyl having 3 to 6 carbons. A group selected from the group consisting of oxazolyl, quinolinyl, isoquinolinyl, pyridylquinolinyl, pyridylisoquinolinyl and imidazopyridinyl;
Ar ₁ is selected from the group consisting of benzene, naphthalene, anthracene, pyrene, triphenylene, fluorene, biphenyl, and perylene, which may be substituted with alkyl having 1 to 6 carbons or cycloalkyl having 3 to 6 carbons. A divalent group of structure,
Ar ₃ is hydrogen, phenyl or naphthyl, the anthracene ring and Ar ₃ may be substituted with alkyl having 1 to 6 carbons or cycloalkyl having 3 to 6 carbons,
The carbazole compound according to claim 10. a is 0 or 1,
R is a group consisting of groups represented by the above formulas (R-1) to (R-20), which may be substituted with alkyl having 1 to 6 carbons or cycloalkyl having 3 to 6 carbons. A group to be selected,
Hy ₁ is a group represented by the above formulas (Hy-1-1) to (Hy-1-3), a group represented by the above formulas (Hy-2-1) to (Hy-2-18), A group selected from the group consisting of groups represented by the above formulas (Hy-3-1) to (Hy-3-27);
Ar ₁ is a divalent group having a structure selected from the group consisting of benzene, biphenyl and naphthalene, which may be substituted with alkyl having 1 to 6 carbons or cycloalkyl having 3 to 6 carbons;
Ar ₃ is hydrogen, phenyl or naphthyl, the anthracene ring and Ar ₃ may be substituted with alkyl having 1 to 6 carbons or cycloalkyl having 3 to 6 carbons,
The carbazole compound according to claim 10. a is 0 or 1,
R is a group consisting of groups represented by the above formulas (R-1) to (R-14), which may be substituted with alkyl having 1 to 6 carbons or cycloalkyl having 3 to 6 carbons. A group to be selected,
Hy ₁ is a group represented by the above formulas (Hy-1-1) to (Hy-1-3), or a group represented by the above formulas (Hy-2-1) to (Hy-2-18). A group selected from the group consisting of
Ar ₁ is 1,2-phenylene, 1,3-phenylene, 1,4-phenylene, 1,4-naphthalene-diyl, 1,5-naphthalene-diyl, 2,6-naphthalene-diyl and 2,7- A divalent group selected from the group consisting of naphthalene-diyl,
Ar ₃ is phenyl, 1-naphthyl or 2-naphthyl,
The carbazole compound according to claim 10. The carbazole compound according to claim 1, which is represented by the following formula (1-5-2), formula (1-5-8) or formula (1-5-29).

The carbazole compound according to claim 1, which is represented by the following formula (1-5-12).

  The electron transport material containing the compound in any one of Claims 1-16.   An electron transport containing an electron transport material according to claim 17, wherein the electron transport material is disposed between a pair of electrodes composed of an anode and a cathode, a light emitting layer disposed between the pair of electrodes, and the cathode and the light emitting layer. An organic electroluminescent device having a layer and / or an electron injection layer.   At least one of the electron transport layer and the electron injection layer further contains at least one selected from the group consisting of quinolinol-based metal complexes, pyridine derivatives, bipyridine derivatives, phenanthroline derivatives, borane derivatives, and benzimidazole derivatives. The organic electroluminescent element according to claim 18.   At least one of the electron transport layer and the electron injection layer may further include an alkali metal, alkaline earth metal, rare earth metal, alkali metal oxide, alkali metal halide, alkaline earth metal oxide, alkaline earth Containing at least one selected from the group consisting of metal halides, rare earth metal oxides, rare earth metal halides, alkali metal organic complexes, alkaline earth metal organic complexes and rare earth metal organic complexes, The organic electroluminescent element according to claim 19.   A display device comprising the organic electroluminescent element according to claim 18.   The illuminating device provided with the organic electroluminescent element in any one of Claims 18-20.

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