KR101791122B1 - Benzo[c]carbazole compound that has substituent bearing pyridine ring, and organic electroluminescent element - Google Patents

Abstract

(상기 식 (1) 중, R은 아릴 또는 헤테로아릴이며, A 및 A'는, 각각 독립적으로, 수소, 상기 식 (A-1)∼(A-4)로 표시되는 기로부터 선택되는 하나이다. 단, A 및 A'가 모두 동시에 수소가 되는 것은 아니다.)An object of the present invention is to provide an organic electroluminescent device having excellent lifetime and drive voltage of a light emitting device. A benzo [c] carbazole compound represented by the following formula (1) is used as an electron transporting material to produce an organic electroluminescent device.

(Wherein R is aryl or heteroaryl, A and A 'are each independently selected from the group consisting of hydrogen and the groups represented by the formulas (A-1) to (A-4). Provided that A and A 'do not simultaneously become hydrogen.)

Description

[0001] The present invention relates to a benzo [c] carbazole compound having a substituent group containing pyridine and an organic electroluminescent device, and to an organic electroluminescent device using the benzo [c]

The present invention relates to a benzo [c] carbazole compound having a substituent containing pyridine, and an electron transport material, an organic electroluminescent device, a display device, and a lighting device using the same.

Conventionally, display devices using electroluminescent light emitting elements have been studied variously because they can be reduced in power and thinner, and organic electroluminescent devices made of organic materials have been actively studied since they are lightweight and easy to enlarge. Particularly, in the development of an organic material having a light emitting property including blue, which is one of the three primary colors of light, and the development of an organic material having a charge transporting ability (having a possibility of becoming a semiconductor or a superconductor) Compounds, and low-molecular compounds have been actively studied so far.

For example, there has been reported an organic electroluminescent device using a compound in which an aryl-heteroaryl group is substituted with an anthracene central skeleton such as a pyridyl group (Japanese Patent Application Laid-Open No. 2003-146951, Japanese Patent Application Laid- Japanese Patent Application Laid-Open No. 2005-170911, Patent Document 2, International Publication No. 2007/086552 pamphlet, Patent Document 3).

It is also reported that a compound in which the central skeleton is made of a combination of anthracene, binnaphthalene, or naphthalene and anthracene is used as a material for an organic electroluminescence device (for example, an electron transport layer or an electron injection layer material; an electron transporting material) (Japanese Patent Application Laid-open No. H8-12600, Patent Document 4, Japanese Patent Application Laid-open No. 2003-123983, Patent Document 5, Japanese Patent Application Laid-Open No. 11-297473, Patent Document 6) .

It has also been reported that a compound containing a carbazole ring and a pyridine ring or a pyrimidine ring is used as a charge transporting material (hole transporting and electron transporting) material (Japanese Patent Application Laid-Open No. 2006-199679; Patent Document 7, Japanese Patent Application Laid-Open No. 2005-268199, Patent Document 8).

Japanese Patent Application Laid-Open No. 2003-146951 Japanese Patent Application Laid-Open No. 2005-170911 International Publication No. 2007/086552 pamphlet Japanese Patent Application Laid-open No. H8-12600 Japanese Patent Application Laid-Open No. 2003-123983 Japanese Patent Application Laid-Open No. 11-297473 Japanese Patent Application Laid-Open No. 2006-199679 Japanese Patent Application Laid-Open No. 2005-268199

As described above, a compound in which an aryl group or a heteroaryl group is substituted for the central skeleton of anthracene, a compound using a combination of anthracene, binaphthalene, or naphthalene and anthracene as a central skeleton, a compound containing a carbazole ring and a pyridine ring or a pyrimidine ring These known materials do not satisfy satisfactorily satisfactory characteristics such as a long lifetime of the device and a lowering of the driving voltage of the light emitting element which are generally required for an electron transporting material. In such a situation, development of an electron transporting material having excellent lifetime and drive voltage of the light emitting element is required. In particular, a blue light emitting device can not obtain an electron transporting material having excellent characteristics as compared with a red or green light emitting device, and development of an electron transporting material preferable for improving the characteristics of the blue light emitting device is required.

DISCLOSURE OF THE INVENTION As a result of intensive investigations to solve the above-mentioned problems, the present inventors have found that, by using an organic electroluminescent device having an organic layer containing a compound represented by the following formula (1) as an electron transporting material, And an organic electroluminescent device excellent in balance with the driving voltage can be obtained, and the present invention has been accomplished.

[1] A benzo [c] carbazole compound represented by the following formula (1).

[Chemical Formula 1]

In the above formula (1)

R is a C6-C24 aryl or a C2-C24 heteroaryl; A and A 'are each independently selected from the group consisting of hydrogen, a group represented by the formula (A-1) (A-3), and the group represented by the above formula (A-4), provided that A and A 'are not all hydrogen at the same time,

The ring included in the structure of R, A and A 'may be substituted with alkyl having 1 to 6 carbon atoms, cyclohexyl or phenyl,

Furthermore, any hydrogen in the benzocarbazole skeleton constituting the compound represented by the formula (1), R, A and A 'substituted therein may be substituted with deuterium.

[2] R is a group selected from the group consisting of groups represented by the following formulas (R-1) to (R-20), A and A 'each independently represent hydrogen, (A-2-1) to (A-2-18), groups represented by the following formulas (A-3-1) to (A- 3-6), and the groups represented by the following formulas (A-4-1) to (A-4-6), but the case where A and A 'are both hydrogen at the same time , And the hydrogen atom in the benzocarbazole skeleton constituting the compound represented by the formula (1), the R, A and A 'substituted therein may be substituted with deuterium, Benzo [c] < / RTI > carbazole compound.

(2)

(3)

[3] R is a group selected from the group consisting of the groups represented by the formulas (R-1) to (R-14), A and A ' (A-3-1) to (A-3-1), groups represented by the above formulas (A-2-1) to The benzo [c] carbazole compound according to [1], wherein the benzo [c] carbazole compound is one selected from the group consisting of groups represented by formulas (A-4) to (A-6)

R is a group selected from the group consisting of the groups represented by the formulas (R-1) to (R-11), A and A ' (A-3-1) to (A-3-1), groups represented by the above formulas (A-2-1) to The benzo [c] carbazole compound according to [1], wherein the benzo [c] carbazole compound is one selected from the group consisting of the groups represented by formulas (A-4-1) to (A-4-1)

R is a group represented by the formula (R-1), formula (R-10) or formula (R-11), A and A ' (A-2) to (A-2-4), groups represented by the above formulas (A-2-7) to -9), a group represented by the formula (A-2-12), a group represented by the formula (A-2-15) The benzo [c] carbazole compound according to [1], wherein the benzo [c] carbazole compound is one selected from the group consisting of groups represented by formulas (A-4-1) to .

(A-1-1) to (A-1-1), wherein A and A 'are each independently a group represented by the formula (R-1) 3), a group represented by the formula (A-2-1), a group represented by the formula (A-2-2), a group represented by the formula (A-2-8) A group represented by the formula (A-2-12), a group represented by the formula (A-3-1) to (A-3-6) 3), wherein the benzo [c] carbazole compound is the compound represented by the formula (1).

[7] The benzo [c] carbazole compound according to [1], which is represented by the following formula (1-10).

[Chemical Formula 4]

[8] The benzo [c] carbazole compound according to [1], which is represented by the following formula (1-4).

[Chemical Formula 5]

[9] The benzo [c] carbazole compound according to [1], which is represented by the following formula (1-744).

[Chemical Formula 6]

[10] The benzo [c] carbazole compound according to [1], which is represented by the following formula (1-5).

(7)

[11] The benzo [c] carbazole compound according to [1], which is represented by the following formula (1-634).

[Chemical Formula 8]

[12] The benzo [c] carbazole compound according to [1], which is represented by the following formula (1-20).

[Chemical Formula 9]

[13] The benzo [c] carbazole compound according to [1], which is represented by the following formula (1-24).

[Chemical formula 10]

[14] The benzo [c] carbazole compound according to [1], which is represented by the following formula (1-743).

(11)

[15] The benzo [c] carbazole compound according to [1], which is represented by the following formula (1-8710).

[Chemical Formula 12]

[16] The benzo [c] carbazole compound according to [1], which is represented by the following formula (1-8711).

[Chemical Formula 13]

[17] The benzo [c] carbazole compound according to [1], which is represented by the following formula (1-8712).

[Chemical Formula 14]

[18] The benzo [c] carbazole compound according to [1], which is represented by the following formula (1-1).

[Chemical Formula 15]

[19] The benzo [c] carbazole compound according to [1], which is represented by the following formula (1-2).

[Chemical Formula 16]

[20] The benzo [c] carbazole compound according to [1], which is represented by the following formula (1-541).

[Chemical Formula 17]

[21] The benzo [c] carbazole compound according to [1], which is represented by the following formula (1-564).

[Chemical Formula 18]

[22] The benzo [c] carbazole compound according to [1], which is represented by the following formula (1-575).

[Chemical Formula 19]

[23] The benzo [c] carbazole compound according to [1], which is represented by the following formula (1-599).

[Chemical Formula 20]

[24] The benzo [c] carbazole compound according to [1], which is represented by the following formula (1-742).

[Chemical Formula 21]

[25] An electron transporting material comprising the compound according to any one of [1] to [24].

A pair of electrodes made of an anode and a cathode; a light emitting layer disposed between the pair of electrodes; and an electron transport layer and / or an electron transport layer disposed between the cathode and the light emitting layer, Or an electron injection layer.

[27] At least one of the electron transporting layer and the electron injecting layer may include 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 , And the organic electroluminescent device according to the above [26].

[28] At least one of the electron transporting layer and the electron injecting layer may be at least one selected from the group consisting of alkali metals, alkaline earth metals, rare earth metals, alkali metal oxides, alkali metal halides, alkaline earth metal oxides, alkaline earth metal halides, The organic electroluminescent device according to the above [27], further comprising at least one selected from the group consisting of an oxide of a metal, a halide of a rare earth metal, an organic complex of an alkali metal, an organic complex of an alkaline earth metal and an organic complex of a rare earth metal device.

[29] A display device comprising the organic electroluminescent device according to any one of [26] to [28].

[30] A lighting device comprising the organic electroluminescent device according to any one of [26] to [28].

According to a preferred embodiment of the present invention, it is possible to obtain an organic electroluminescent device which is particularly excellent in the lifetime of the light emitting device. Further, according to another preferred embodiment of the present invention, it is possible not only to realize an excellent device lifetime, but also to balance with a driving voltage. In addition, the preferable electron transporting material of the present invention can be preferably used for a blue light emitting device. According to this electron transporting material, a blue light emitting device having a lifetime comparable to that of a red or green light emitting device can be manufactured. Further, by using this organic electroluminescent device, a high-performance display device such as a full color display can be obtained.

1 is a schematic cross-sectional view showing an organic electroluminescent device according to the present embodiment.

1. The benzo [c] carbazole compound represented by the formula (1)

The benzo [c] carbazole compound having a substituent containing the pyridine of the present invention will be described in detail. The benzo [c] carbazole compound of the present invention is a compound represented by the following formula (1). The arbitrary hydrogen in the benzocarbazole skeleton constituting the compound represented by the formula (1), R, A and A 'substituted therein may be substituted with deuterium.

[Chemical Formula 22]

R in the formula (1) is aryl having 6 to 24 carbon atoms or heteroaryl having 2 to 24 carbon atoms.

A and A 'in the formula (1) are each independently selected from the group consisting of hydrogen, the group represented by the formula (A-1), the group represented by the formula (A- , The group represented by the formula (A-4) and the aryl having 6 to 18 carbon atoms, but either A or A 'is a group selected from the group consisting of the formulas (A-1) and Is one selected from the group consisting of groups represented by formulas (A-2), (A-3) and (A-4) That is, both A and A 'are not simultaneously the above-mentioned "aryl of 6 to 18 carbon atoms ".

(A-1), a group represented by the formula (A-2), a group represented by the formula (A- 3), and the group represented by the above formula (A-4), and both A and A 'are not hydrogen at the same time. That is, in this embodiment, both A and A 'are not simultaneously "aryl of 6 to 18 carbon atoms".

In the groups represented by the formulas (A-1) to (A-4), the bonding hands attached to the ring are connected to any carbon atoms constituting the ring, but two bonding hands are connected to the same carbon atom It does not. In the group represented by the formula (A-4), the bond between the pyridine ring and the naphthalene ring is attached to the two condensed rings of the naphthalene ring because the bond is connected to the benzo [c] carbazole of the naphthalene ring Quot; means that it is connected to any carbon atom other than carbon atoms.

The ring included in the structure of R, A, and A 'may be substituted with alkyl having 1 to 6 carbon atoms, cyclohexyl, or phenyl. Examples of the alkyl having 1 to 6 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert- butyl, n- pentyl, isopentyl, neopentyl, Hexyl, 1-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl and the like. Among them, methyl, isopropyl or tert-butyl is preferable as substituent for the ring included in the structure of R, A and A ', and tert-butyl is particularly preferable. The number of substituents is, for example, a maximum substitutable number, preferably 1 to 3, more preferably 1 to 2, and most preferably 1.

The "aryl having 6 to 24 carbon atoms" in R is preferably aryl having 6 to 16 carbon atoms, more preferably aryl having 6 to 12 carbon atoms.

Specific examples of "aryl" include phenyl which is monocyclic aryl, (2-, 3-, 4-) biphenylyl which is bicyclic aryl, (1-, 2-) naphthyl which is condensed bicyclic aryl, M-terphenyl-5'-yl, o-terphenyl-3'-yl, o-terphenyl-4'- Yl, o-terphenyl-2-yl, o-terphenyl-2-yl, P-terphenyl-3-yl, p-terphenyl-4-yl), condensed tricyclic aryl , Acenaphthylene (1-, 3-, 4-, 5-) yl, fluorene- (1-, 2-, 3-, 4-, (5'-phenyl-m-terphenyl-2-yl, 5'-phenyl-m-tert-butylphenyl) (1-, 2-yl) pyrene, which is a condensed tetracyclic aryl, such as phenyl, naphthyl, (1-, 2-, 3-) yl, naphthacene- (1-, 2-, 5-) yl, condensed pentacyclic aryl, , 5-, 6-) yl, and the like. Further, examples of the group in which the phenyl group is substituted at an optional position of the condensed-ring heteroaryl group are also exemplified. The number of substituents is, for example, a maximum substitutable number, preferably 1 to 3, more preferably 1 to 2, and most preferably 1. Among them, phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, and naphthyl substituted with phenyl are preferred.

The "heteroaryl having 2 to 24 carbon atoms" in R is preferably heteroaryl having 2 to 20 carbon atoms, more preferably heteroaryl having 2 to 15 carbon atoms, and most preferably 2 to 10 carbon atoms Lt; / RTI > The "heteroaryl" includes, for example, a heterocyclic group containing 1 to 5 hetero atoms selected from oxygen, sulfur and nitrogen in addition to carbon as a ring-constituting atom.

Examples of the substituent include furyl, thienyl, pyrrolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, oxadiazolyl, thiadiazolyl, triazolyl, tetrazolyl, pyrazolyl, pyridyl, Pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, indolyl, isoindolyl, 1H-indazolyl, benzoimidazolyl, benzoxazolyl, benzothiazolyl, 1H-benzotriazolyl, quinolinyl, iso Pyrimidinyl, pyrazinyl, pyrazinyl, pyrazinyl, pyrazinyl, pyrazinyl, phenothiazinyl, phenazinyl, indazolyl, quinazolinyl, quinolyl, quinazolyl, quinoxalinyl, phthalazinyl, naphthyridinyl, Benzyl, furazanyl, benzofuranyl, isobenzofuranyl, benzo [b] thienyl, phenoxathiinyl, thianthrenyl, and the like. Among them, pyridyl, quinolinyl and isoquinolinyl are preferable.

R is particularly preferably a group represented by the following formulas (R-1) to (R-20). Among them, groups represented by the following formulas (R-1) to (R-14) are preferable, groups represented by the following formulas (R-1) to (R-11) are more preferable, Most preferably a group represented by the formula (R-1), the formula (R-10) and the formula (R-11).

(23)

Examples of the group represented by the above formula (A-1) selected as A or A 'include 2-pyridinyl, 3-pyridinyl and 4-pyridinyl.

Examples of the group represented by the above formula (A-2) selected as A or A 'include 2,2'-bipyridine (3-, 4-, 5-, 6-) (2-, 4-, 5-, 6-, or 7-membered heterocycloalkyl) 5-, 6-) yl, 3,3'-bipyridine (2-, 4-, 5-, 6-) (2-, 3-, 5-, 6-) yl, 4,4'-bipyridyl, - bipyridine (2-, 3-, 5-, 6-) yl.

Examples of the group represented by the above formula (A-3) selected as A or A 'include (pyridin-2-yl) phenyl- (Pyridin-4-yl) phenyl-3-yl, (pyridin-2-yl) (Pyridin-3-yl) phenyl-4-yl, (pyridin-4-yl) phenyl-4-yl.

Examples of the group represented by the above formula (A-4) selected as A or A 'include 1- (2-pyridine) naphthalene- (2-, 3-, 4-, 5-, 6-, Naphthalene- (2-, 3-, 4-, 5-, 6-, 7- or 8- -, 4-, 5-, 6-, 7-, 8-), 2- (2-pyridin) naphthalene- 2- (3-pyridine) naphthalene- (1-, 3-, 4-, 5-, 6-, 7-, , 4-, 5-, 6-, 7-, 8-) yl.

The "aryl of 6 to 18 carbon atoms" selected as A or A 'is preferably aryl of 6 to 14 carbon atoms, more preferably aryl of 6 to 10 carbon atoms. For example, there is a group (the number of carbon atoms is limited to 18 or less) exemplified in the description of "aryl of 6 to 24 carbon atoms"

(A-1-1) to (A-1-3), groups represented by the following formulas (A-2-1) to A group represented by the following formulas (A-3-1) to (A-3-6), a group represented by the following formulas (A-4-1) to And groups represented by the following formulas (A-5-1) to (A-5-11).

≪ EMI ID =

A more preferable group as A or A 'is a group represented by the formula (A-1-1) to (A-1-3), a group represented by the formula (A-2-1) A group represented by the above formulas (A-3-1) to (A-3-6) and a group represented by the above formulas (A-4-1) to (A-4-6).

More preferred groups as A or A 'are groups represented by the above formulas (A-1-1) to (A-1-3), and groups represented by formulas (A-2-1) to (A- A group represented by the formulas (A-3-1) to (A-3-6) and a group represented by the formulas (A-4-1) to (A-4-3).

A more preferable group as A or A 'is a group represented by the formula (A-1-1) to (A-1-3), a group represented by the formula (A-2-1) A group represented by the formula (A-2-7) to (A-2-9), a group represented by the formula (A-2-12) A group represented by the formulas (A-3-1) to (A-3-6) and a group represented by the formulas (A-4-1) to (A-4-3).

(A-1-1) to (A-1-3), a group represented by the formula (A-2-1), a group represented by the formula 2-2), the group represented by the formula (A-2-8), the group represented by the formula (A-2-12), the groups represented by the formulas (A- 3-6) and the groups represented by the above formulas (A-4-1) to (A-4-3).

The most preferable group as A or A 'is a group represented by the formula (A-1-3), a group represented by the formula (A-2-1), a group represented by the formula (A-2-2) , A group represented by the formula (A-2-8), a group represented by the formula (A-2-12), a group represented by the formula (A-3-1) , A group represented by the formula (A-3-5), a group represented by the formula (A-3-6) and a group represented by the formula (A-4-3).

An example of a group preferred as A or A 'described above is optimal when R is phenyl or naphthyl in particular. In addition, A and A 'may be a group of the same structure or a group of a different structure.

Specific examples of the compound represented by the formula (1) include compounds represented by the following formulas (1-1) to (1-30), the following formulas (1-531) to (1-864) A compound represented by the following formulas (1-7831) to (1-7860), a compound represented by the following formulas (1-8361) to (1-8585) (1-8730), and compounds represented by the following formulas (1-9231) to (1-9455).

(25)

(26)

(27)

(28)

[Chemical Formula 29]

(30)

(31)

(32)

(33)

(34)

(35)

(36)

(37)

(38)

[Chemical Formula 39]

(40)

(41)

(42)

(43)

(44)

[Chemical Formula 45]

(46)

(47)

(48)

(49)

(50)

(51)

(52)

(53)

(54)

(55)

(56)

(57)

(58)

[Chemical Formula 59]

(60)

(61)

(62)

(63)

≪ EMI ID =

(65)

(66)

(67)

(68)

(69)

Among the compounds represented by the above formulas (1-1) to (1-864), the compounds represented by formulas (1-1) to (1-6), formulas (1-10) -15), Expressions (1-19) to (1-21), Expressions (1-24), Expressions (1-531) to Expressions (1-634), Expressions (1-645) 650), Expressions (1-664) to (1-669), Expressions (1-676) to Expressions (1-681), Expressions (1-688) to Expressions (1-693) ) To (1-705), (1-712) to (1-717), (1-724) to (1-729), (1-736) to (1-741) , Equation (1-744), equation (1-748) to equation (1-753), equation (1-760) to equation (1-765), equation (1-772) Compounds represented by formulas (1-784) to (1-789), and formulas (1-793) to (1-864) are preferable.

2. Preparation of benzo [c] carbazole compound of formula (1)

Next, the production method of the compound of the present invention will be described.

The compound of the present invention can be synthesized by a known synthesis method such as a Suzuki coupling reaction or a Negishi coupling reaction (for example, "Metal-Catalyzed Cross-Coupling Reactions- Second, Completely Revised and Enlarged Edition "). Further, both reactions can be combined and synthesized. A scheme for synthesizing the compound represented by the formula (1) by a Suzuki coupling reaction or a Negishi coupling reaction is illustrated below.

≪ Production method (1) of compound represented by formula (1) >

<Synthesis of a phenyl group having a reactive substituent or a pyridine having a naphthyl group>

First, a zinc chloride complex of pyridine is synthesized according to the following reaction scheme (1), and then a zinc chloride complex of pyridine and 1,4-dibromobenzene or 1,4-dibromonaphthalene are reacted according to the following reaction formula (2) 2- (4-bromophenyl) pyridine or 2- (4-bromonaphthalen-1-yl) pyridine can be synthesized.

(70)

Reaction formula (1)

Reaction formula (2)

In the reaction formula (1), "ZnCl ₂ .TM. TMEDA" is a tetramethylethylenediamine complex of zinc chloride. In "RLi" and "RMgX" in the above reaction formula (1), R represents a linear or branched alkyl group, preferably a straight chain or branched alkyl group having 1 to 4 carbon atoms, or a branched alkyl group having 3 to 4 carbon atoms, and X is halogen.

Although a method of synthesizing 2- (4-bromophenyl) pyridine and 2- (4-bromonaphthalen-1-yl) pyridine using 2-bromopyridine as a raw material has been illustrated, (4-bromophenyl) pyridine, 4- (4-bromophenyl) pyridine, and the like can be obtained by using pyridine or 4-bromopyridine and also by using iodide which is not a bromide. 3- (4-bromonaphthalen-1-yl) pyridine and 4- (4-bromonaphthalen-1-yl) pyridine can be obtained.

Further, here, using 1,4-dibromobenzene or 1,4-dibromonaphthalene as a raw material, 2- (4-bromophenyl) pyridine and 2- (4-bromonaphthalen- However, by using 1,3-dibromobenzene, 2,6-dibromonaphthalene or 2,7-dibromonaphthalene as a raw material, it is possible to obtain a dichlorosilane which is not a dibromoester, Bromo-4-iodobenzene) or a mixture thereof (for example, 1-bromo-4-iodobenzene, etc.) 2- (6-bromonaphthalen-2-yl) pyridine and 2- (7-bromonaphthalen-2-yl) pyridine.

Also, by coupling reaction of 1,4-dibromobenzene with pyridylboronic acid or pyridylboronic acid ester instead of 1,4-dibromobenzene with zinc chloride complex of pyridine, Can be obtained.

By appropriately selecting the raw materials, a phenyl group having various reactive substituent groups or a pyridine having a naphthyl group bonded thereto, which are raw materials for synthesis of the compound of the present invention represented by the formula (1), can be obtained.

<Synthesis of pyridyl-substituted phenyl / naphthylboronic acid and boronic acid ester>

Next, lithium 2- (4-bromophenyl) pyridine or 2- (4-bromonaphthalen-1-yl) pyridine is subjected to lithiation reaction using an organolithium reagent as shown in the following reaction formula (3) ), Or by using magnesium or an organic magnesium reagent as a Grignard reagent and reacting with trimethyl borate, triethyl borate or triisopropyl borate to obtain 4- (pyridin-2-yl) phenylboron Acid ester and 4- (pyridin-2-yl) naphthalene-1-ylboronic acid ester can be synthesized. Further, 4- (2-pyridyl) phenylboronic acid and 4- (pyridin-2-yl) naphthalene-1-ylboronic acid can be synthesized by hydrolyzing the boronic acid ester according to the following reaction formula (4) .

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Reaction formula (3)

Reaction formula (4)

In "RLi" and "RMgX" in the above reaction formula (3), R represents a linear or branched alkyl group, but is preferably a straight chain or branched alkyl group having 1 to 4 carbon atoms and a branched alkyl group having 3 to 4 carbon atoms, and X is halogen .

Alternatively, lithium 2- (4-bromophenyl) pyridine or 2- (4-bromonaphthalen-1-yl) pyridine may be substituted with lithium by using an organolithium reagent as shown in the following reaction formula (5) Or organic magnesium reagent as Grignard reagent and reacting with bis (pinacolato) diboron or 4,4,5,5-tetramethyl-1,3,2-dioxaborolane to form another 4- (Pyridin-2-yl) phenylboronic acid ester or 4- (pyridin-2-yl) naphthalene-1-ylboronic acid ester can be synthesized. (4-bromophenyl) pyridine or bis (pyranecarato) diboron or 4, 4 (trifluoromethyl) pyridine as shown in the following reaction formula (6) , 5,5-tetramethyl-1,3,2-dioxaborolane was subjected to a coupling reaction using a palladium catalyst and a base to obtain 4- (pyridin-2-yl) phenylboronic acid ester or 4- (Pyridin-2-yl) naphthalene-1-ylboronic acid ester can be synthesized.

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Reaction formula (5)

Reaction formula (6)

In "RLi" and "RMgX" in the above reaction formula (5), R represents a linear or branched alkyl group, preferably a straight chain or branched alkyl group having 1 to 4 carbon atoms, or a branched alkyl group having 3 to 4 carbon atoms, and X is halogen .

(4-bromophenyl) pyridine, 2- (3-bromophenyl) pyridine, 4- , 4- (4-bromophenyl) pyridine, 3- (3-bromophenyl) pyridine, 4- 2- (6-bromonaphthalen-2-yl) pyridine, 3- (4-bromomonaphthalene-1-yl) 2- (7-bromonaphthalen-2-yl) pyridine, 3- (7-bromo-naphthalen- The corresponding boronic acid / boronic acid ester can also be synthesized using position isomers such as naphthalene-2-yl) pyridine and 4- (7-bromonaphthalen-2-yl) pyridine.

In place of bromides such as 2- (4-bromophenyl) pyridine and 3- (4-bromonaphthalen-1-yl) pyridine in the above reaction scheme (3), (5) , Iodide or trifluoromethanesulfonate can be used in the same manner.

<Synthesis of bipyridine having reactive substituent>

First, a zinc chloride complex of pyridine is synthesized according to the following reaction scheme (7), and then zinc chloride complex of pyridine is reacted with 2,5-dibromopyridine according to the following reaction formula (8) to give 5-bromo- , 2'-bipyridine can be synthesized.

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Reaction (7)

Reaction formula (8)

In the reaction formula (7), "ZnCl ₂ .TM. EDEDA" is a tetramethylethylenediamine complex of zinc chloride. In "RLi" and "RMgX" in the above reaction formula (7), R represents a linear or branched alkyl group, preferably a straight chain or branched alkyl group having 1 to 4 carbon atoms, or a branched alkyl group having 3 to 4 carbon atoms, and X is halogen .

Here, a method of synthesizing 5-bromo-2,2'-bipyridine by using 2-bromopyridine as a raw material is exemplified. However, by using 3-bromopyridine or 4-bromopyridine as a raw material, By using iodide other than bromide, the corresponding target, i.e., 5-bromo-2,3'-bipyridine or 5-bromo-2,4'-bipyridine, can be obtained.

Further, although a method of synthesizing 5-bromo-2,2'-bipyridine by using 2,5-dibromobenzene as a raw material has been exemplified in this example, 2,4-dibromopyridine, 2,6 Dibromopyridine or 3,5-dibromopyridine, and further dichloro, diiodide, bis (trifluoromethane sulfonate) or a mixture thereof (for example, : 2-bromo-6-iodopyridine or the like), a corresponding target, i.e., 6-bromo-2,2'-bipyridine, 4-bromo-2,2'- .

Also, by coupling reaction of 2,5-dibromopyridine with pyridylboronic acid or pyridylboronic acid ester instead of 2,5-dibromopyridine with zinc chloride complex of pyridine, Can be obtained.

By appropriately selecting the raw materials, bipyridine having various reactive substituents, which are raw materials for synthesis of the compound of the present invention represented by the formula (1), can be obtained.

<Synthesis of bipyridine boronic acid / boronic acid ester>

Next, as shown in the following reaction formula (9), 5-bromo-2,2'-bipyridine is replaced with lithium using an organolithium reagent, or magnesium or an organic magnesium reagent is used as a Grignard reagent , Trimethyl borate, triethyl borate, triisopropyl borate or the like, a 2,2'-bipyridine boronic acid ester can be synthesized. Further, 2,2'-bipyridine boronic acid can be synthesized by hydrolyzing the 2,2'-bipyridine boronic acid ester according to the following reaction scheme (10).

&Lt; EMI ID =

Reaction formula (9)

Reaction formula (10)

In "RLi" and "RMgX" in the above reaction formula (9), R represents a linear or branched alkyl group, but is preferably a linear or branched alkyl group having 1 to 4 carbon atoms and a branched alkyl group having 3 to 4 carbon atoms, and X is halogen .

Alternatively, as shown in the following reaction formula (11), 5-bromo-2,2'-bipyridine may be replaced with lithium using an organolithium reagent, or magnesium or an organic magnesium reagent may be used as a Grignard reagent, Bis (pinacolato) diboron or 4,4,5,5-tetramethyl-1,3,2-dioxaborolane, other 2,2'-bipyridine boronic acid esters can be synthesized . Further, as shown in the following reaction formula (12), the reaction of 5-bromo-2,2'-bipyridine with bis (pinacolato) diboron or 4,4,5,5-tetramethyl- -Dioxaborolane is subjected to a coupling reaction using a palladium catalyst and a base to synthesize 2,2'-bipyridine boronic ester in the same manner.

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Reaction Scheme (11)

Reaction formula (12)

In the "RLi" and "RMgX" in the above reaction formula (11), R represents a linear or branched alkyl group, but is preferably a linear or branched alkyl group having 1 to 4 carbon atoms and a branched alkyl group having 3 to 4 carbon atoms, and X is halogen .

In the above Reaction Scheme (9), (11) or (12), a compound represented by the following general formula The corresponding boronic acid / boronic acid ester can also be synthesized using positional isomers such as 4'-bipyridine or 4-bromo-2,2'-bipyridine.

In the above reaction scheme (9), (11) or (12), it is also possible to use chloride, iodide or trifluoromethanesulfonate instead of bromide such as 5-bromo-2,2'-bipyridine , Can be synthesized in the same manner.

<Synthesis of aryl and boronic acid / boronic ester having reactive substituent>

When the "aryl of 6 to 18 carbon atoms" (for example, the group represented by formulas (A-5-1) to (A-5-11)) is selected as A or A ' Or the boronic acid / boronic acid ester can be commercially available or can be synthesized with reference to the above-described synthesis method.

&Lt; Synthesis 1 of central skeleton &

First, 1-methoxy-4- (4-methoxy-2-nitrophenyl) naphthalene is synthesized by a coupling reaction as shown in the following reaction formula (13). Although Suzuki coupling using boronic acid is exemplified in Reaction Scheme (13), Negishi coupling using zinc complex can also be used. Subsequently, a cyclization reaction (cyclization reaction) is carried out using triethyl phosphite or triphenylphosphine to obtain a benzo [c] carbazole derivative (BCz-A). This BCz-A is made into BCz-B by a coupling reaction using a palladium catalyst or a Ullmann reaction, followed by demethylation with boron tribromide or pyridine hydrochloride to give BCz-C. 7-phenyl-7H-benzo [c] carbazole-5,9-diylbis (trifluoromethanesulfonate), which is the central skeleton of the compound of the present invention, is then reacted with trifluoromethanesulfonic anhydride, Can be obtained.

[Formula 76]

Reaction formula (13)

The above-described reaction of the third step is a reaction of binding a portion corresponding to R in the compound represented by the formula (1), in which bromine or bromine of the corresponding aryl or heteroaryl in place of bromobenzene or iodobenzene Or an iodide, an intermediate having a substituent different from N can be synthesized.

&Lt; Synthesis 2 of central skeleton part &

The central skeleton portion may also be synthesized by performing the following procedure. First, 4,4 '- (2-nitro-1,4-phenylene) bis (1-methoxynaphthalene) is synthesized by a coupling reaction as shown in the following reaction scheme (13'). Suzuki coupling using boronic acid is exemplified in reaction formula (13 '), but Negishi coupling using zinc complex can also be used. Subsequently, a cyclization reaction is carried out using triethyl phosphite or triphenylphosphine to obtain a benzo [c] carbazole derivative (BCz-A '). (BCz-B '), followed by demethylation (BCz-C') and finally with trifluoromethanesulfonic anhydride in a manner as described above to give the center of the compound of the present invention Benzo [c] carbazol-9-yl) naphthalen-1-yl trifluoromethanesulfonate, which is a skeletal moiety, is prepared by reacting 4- (7-phenyl- Can be obtained.

[Formula 77]

Reaction scheme (13 ')

<Synthesis of diboronic acid ester in central skeleton part 1>

7-phenyl-7H-benzo [c] carbazole-5,9-diylbis (trifluoromethanesulfonate) and bis (pinacolato) obtained in the reaction scheme (13) Diboron or 4,4,5,5-tetramethyl-1,3,2-dioxaborolane is subjected to a coupling reaction using a palladium catalyst and a base to obtain 7-phenyl-7H-benzo [c] -5,9-diboronic acid ester can be synthesized.

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Reaction (14)

<Synthesis of diboronic acid ester in central skeleton part 2>

As shown in the following reaction scheme (14 '), 4- (7-phenyl-5 (((trifluoromethyl) sulfonyl) oxy) -7H-benzo [c] -Naphthalen-1-yl trifluoromethanesulfonate and bis (pinacolato) diboron or 4,4,5,5-tetramethyl-1,3,2-dioxaborolane with a palladium catalyst (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -9- (4- (4- , 4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) naphthalen-1-yl) -7H-benzo [c] carbazole.

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Reaction scheme (14 ')

<Synthesis of benzo [c] carbazole compound of the present invention by Suzuki coupling reaction>

Benzo [c] carbazole-5,9-diyl bis (trifluoromethanesulfonate) described above and a boronic acid or boron of 2-fold mol of pyridine as described in the following reaction scheme (15) The benzo [c] carbazole compound of the present invention can be synthesized by reacting a boronic acid or boronic acid ester of a phenyl / naphthyl substituted with an acid ester, a pyridyl substituted boronic acid or a boronic acid of a bipyridine or a boronic acid ester with a palladium catalyst in the presence of a base can do. Here, the 4-pyridylboronic acid / boronic acid ester, 4- (pyridin-2-yl) phenylboronic acid / boronic acid ester, 4- (pyridin- The synthesis method using 2,2'-bipyridin-5-ylboronic acid / boronic acid ester is exemplified, but the same positional isomers can also be synthesized. In addition, 4- (7-phenyl-5 (((trifluoromethyl) sulfonyl) oxy (trifluoromethyl) sulfonyl chloride was used instead of 7-phenyl-7H-benzo [ ) -7H-benzo [c] carbazol-9-yl) naphthalen-1-yl trifluoromethanesulfonate can also be used to synthesize the benzo [c] carbazole compound of the present invention.

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Reaction formula (15)

In the above reaction formula (15), R represents a linear or branched alkyl group, but is preferably a straight chain or branched alkyl group having 1 to 4 carbon atoms and a branched alkyl group having 3 to 4 carbon atoms.

Further, as shown in the following reaction formula (16), pyridine having a reactive substituent, phenyl group having a reactive substituent / naphthyl group bonded to 7-phenyl-7H-benzo [c] The benzo [c] carbazole compound of the present invention can be synthesized by reacting pyridine or bipyridine having a reactive substituent twice with a palladium catalyst in the presence of a base. Here, a synthetic method using a 4-reactor substituted pyridine, 2- (4-substituted-substituted phenyl) pyridine, 2- (4-substituted-substituted naphthalen- 1 -yl) pyridine or 5- However, it is also possible to synthesize the same by using the respective position isomers. In addition, 7-phenyl-7H-benzo [c] carbazole-5,9-diboronic acid ester was used instead of 7-phenyl-5- (4,4,5,5-tetramethyl- Naphthalen-1-yl) -7H-benzo [l, 5- c] carbazole can also be used to synthesize the benzo [c] carbazole compound of the present invention.

[Formula 81]

Reaction formula (16)

Further, as shown in the following reaction formula (17), the above-mentioned 7-phenyl-7H-benzo [c] carbazole-5,9-diyl bis (trifluoromethanesulfonate) Or a boronic acid ester, a boronic acid of a pyridyl-substituted phenyl / naphthylic acid or a boronic acid or a boronic acid of a bipyridine or a boronic acid ester is reacted with a palladium catalyst in the presence of a base to prepare an intermediate (step 1) A boronic acid or a boronic acid ester of a pyrimidine or a boronic acid or a boronic acid ester of a pyridyl-substituted phenyl / naphthyl or a boronic acid or a boronic acid ester of a bipyridine in the presence of a base and a palladium catalyst (Step 2) , The benzo [c] carbazole compound of the present invention can be synthesized. In addition, 4- (7-phenyl-5 (((trifluoromethyl) sulfonyl) oxy (trifluoromethyl) sulfonyl chloride was used instead of 7-phenyl-7H-benzo [ ) -7H-benzo [c] carbazol-9-yl) naphthalen-1-yl trifluoromethanesulfonate can also be used to synthesize the benzo [c] carbazole compound of the present invention.

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Reaction (17)

In the reaction of the reaction formula (17), the purification operation may be carried out after completion of the first stage reaction, if necessary. Also, by using the boronic acid or the boronic acid ester of the pyridine different from the first step, the boronic acid of the pyridyl-substituted phenyl / naphthyl or the boronic acid or the boronic acid of the bipyridine or the boronic acid ester of the bipyridine, And a benzo [c] carbazole compound having a different substituent at the 9-position can be synthesized.

Also, by using an arylboronic acid such as phenylboronic acid or naphthylboronic acid in the 1-step or 2-step reaction, a benzo [c] carbazole compound in which the 5-position or 9-position of the benzocarbazolyl group is substituted with an aryl group Can be synthesized. This compound is a compound represented by the formula (A-5-1) to (A-5-11) in the compound represented by the formula (1) Represents a selected compound.

Similarly, pyridine having a reactive substituent group or pyridine having a reactive substituent group attached to a phenyl group / naphthyl group attached to the 7-phenyl-7H-benzo [c] carbazole-5,9-diboronic acid ester shown in the above reaction scheme (16) In the presence of a base, an aryl halide such as phenyl bromide or bromine naphthalene bonded to a phenyl / naphthyl group having a reactive substituent is reacted in two steps to obtain the benzo [c] carbazole Compounds can be synthesized.

Specific examples of the palladium catalyst used in the Suzuki coupling reaction include Pd (PPh ₃ ) ₄ , PdCl ₂ (PPh ₃ ) ₂ , Pd (OAc) ₂ , tris (dibenzylideneacetone) dipalladium Benzylideneacetone) dipalladium (0) chloroform complex, or bis (dibenzylideneacetone) palladium (0).

In order to promote the reaction, a phosphine compound may be added to these palladium compounds, as the case may be. Specific examples of the phosphine compound include tri (tert-butyl) phosphine, tricyclohexylphosphine, 1- (N, N-dimethylaminomethyl) -2- (ditert- butylphosphino) N, N-dibutylaminomethyl) -2- (ditert-butylphosphino) ferrocene, 1- (methoxymethyl) -2- (ditert- butylphosphino) ferrocene, 1,1'- (ditert-butylphosphino) -1,1'-binaphthyl, 2-methoxy-2 '- (ditert-butylphosphino) , 1'-binaphthyl, or 2-dicyclohexylphosphino-2 ', 6'-dimethoxybiphenyl.

Specific examples of the base used in the reaction include sodium carbonate, potassium carbonate, cesium carbonate, sodium hydrogencarbonate, sodium hydroxide, potassium hydroxide, barium hydroxide, sodium ethoxide, sodium tert-butoxide, sodium acetate, And potassium fluoride.

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

&Lt; Production method (2) of the compound represented by the formula (1) >

Although the synthesis method of the benzo [c] carbazole compound of the present invention by Suzuki coupling has been described, Negishi coupling may also be used.

First, as shown in the following reaction scheme (18), 4- (2-pyridyl) -1-bromobenzene, 4- Bromo-2,2'-bipyridine is replaced with lithium by using an organic lithium reagent, or magnesium or an organic magnesium reagent is used as a Grignard reagent and zinc chloride or zinc tetramethylethylenediamine complex (ZnCl ₂ · TMEDA) to synthesize respective zinc complexes.

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Reaction formula (18)

"ZnCl ₂ .TM. TMEDA" in the reaction formula (18) is a tetramethylethylenediamine complex of zinc chloride. In "RLi" and "RMgX" in the above reaction formula (18), R represents a straight chain or branched alkyl group, but is preferably a straight chain or branched alkyl group having from 1 to 4 carbon atoms and a branched alkyl group having from 3 to 4 carbon atoms.

Instead of bromide, iodide can be used to synthesize the same. Further, in this specification, the term "4-bromopyridine, 4- (2-pyridyl) -1-bromobenzene, 4- Pyridine is used as a raw material. However, the same positional isomers can also be synthesized.

<Synthesis of benzo [c] carbazole compound of the present invention by Negishi coupling reaction>

Finally, as shown in the following reaction scheme (19), 7-phenyl-7H-benzo [c] carbazole-5,9-diyl bis (trifluoromethanesulfonate) Bipyridyl-5-yn zinc complex in the presence of a palladium catalyst in the presence of a palladium catalyst, , The benzo [c] carbazole compound of the present invention can be synthesized. Also, as shown in the following reaction formula (20), the zinc complex of the above-mentioned zinc complex or the aryl group such as phenyl or naphthyl may be reacted in two steps as in the reaction formula (17) Benzo [c] carbazole compound can be synthesized. In addition, 4- (7-phenyl-5 (((trifluoromethyl) sulfonyl) oxy (trifluoromethyl) sulfonyl chloride was used instead of 7-phenyl-7H-benzo [ ) -7H-benzo [c] carbazol-9-yl) naphthalen-1-yl trifluoromethanesulfonate can also be used to synthesize the benzo [c] carbazole compound of the present invention.

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Reaction formula (19)

Reaction formula (20)

Specific examples of the palladium catalyst used in the Negishi coupling reaction include Pd (PPh ₃ ) ₄ , PdCl ₂ (PPh ₃ ) ₂ , Pd (OAc) ₂ , tris (dibenzylideneacetone) dipalladium Benzylidene acetone) dipalladium (0) chloroform complex, bis (dibenzylideneacetone) palladium (0), bis (tri tert-butylphosphino) palladium (0), or (1,1'- Pyrrolo) pyrrolo) pyrrolo) palladium (II).

Specific examples of the solvent used in the reaction include benzene, toluene, xylene, 1,2,4-trimethylbenzene, N, N-dimethylformamide, tetrahydrofuran, diethylether, tert- butylmethylether, cyclopentyl Methyl ether or 1,4-dioxane. These solvents may be appropriately selected and used alone or as a mixed solvent.

Benzo [c] carbazole compounds wherein the 5-position or 9-position is hydrogen,

In the benzo [c] carbazole compound of the present invention in which the 5-position or the 9-position is hydrogen, an intermediate is synthesized using a compound having no methoxy on one side of the starting material of the above reaction formula (13) To a coupling reaction of &lt; RTI ID = 0.0 &gt;

That is, the reaction was carried out in the same manner as in Reaction Scheme (13), except that 1-naphthaleneboronic acid was used instead of 4-methoxy-1-naphthaleneboronic acid to react with 4-chloro-3- c] carbazole in position 5 is hydrogen and position 9 is in triflate. By providing this monotriplate in a subsequent coupling reaction, a benzo [c] carbazole compound in which the 5-position is hydrogen can be obtained.

Further, the reaction was carried out according to the reaction scheme (13) by reacting 4-methoxy-1-naphthaleneboronic acid with 2-chloronitrobenzene instead of 4-chloro-3- ] Compounds can be synthesized in which the 9-position of carbazole is hydrogen and the 5-position is triflate. By providing this monotriplate in a subsequent coupling reaction, a benzo [c] carbazole compound in which the 9-position is hydrogen can be obtained.

3. Organic electroluminescent device

The benzo [c] carbazole compound having a substituent containing pyridine according to the present invention can be used, for example, as a material for an organic electroluminescent device. Hereinafter, the organic electroluminescent device according to the present embodiment will be described in detail with reference to the drawings. 1 is a schematic cross-sectional view showing an organic electroluminescent device according to the present embodiment.

&Lt; Structure of Organic Electroluminescent Device >

1 includes a substrate 101, an anode 102 provided on the substrate 101, a hole injection layer 103 provided on the anode 102, a hole injection layer 103 formed on the anode 102, A light emitting layer 105 provided on the hole transporting layer 104, an electron transporting layer 106 provided on the light emitting layer 105 and an electron transporting layer 106 formed on the electron transporting layer 106. The electron transporting layer 104 is formed on the electron transporting layer 103, An injecting layer 107, and a cathode 108 provided on the electron injecting layer 107.

The organic electroluminescent device 100 has a substrate 101 and a cathode 108 provided on the substrate 101. The organic electroluminescent device 100 includes a substrate 101, An electron transport layer 106 provided on the electron injection layer 107, a light emission layer 105 provided on the electron transport layer 106, a hole transport layer 104 provided on the light emission layer 105, A hole injection layer 103 provided on the transport layer 104 and an anode 102 provided on the hole injection layer 103 may be used.

It is not necessary that all of the layers described above are provided and that the minimum constitutional unit is constituted by the anode 102, the light emitting layer 105 and the electron transporting layer 106 and / or the electron injecting layer 107 and the cathode 108, The hole injection layer 103 and the hole transport layer 104 are arbitrarily installed layers. Each of the layers described above may be composed of a single layer or a plurality of layers.

Examples of the layer constituting the organic electroluminescence device include a substrate, an anode, a hole transporting layer, a light emitting layer, a light emitting layer, a light emitting layer, an electron transporting layer, Electron transport layer / electron injection layer / cathode "," substrate / anode / hole injection layer / hole transport layer / light emitting layer / electron injection layer "," substrate / anode / hole injection layer / light emitting layer / electron transport layer / electron injection layer / cathode " 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 " Anode / hole transporting layer / light emitting layer / electron transporting layer / cathode "," substrate / anode / hole injection layer / light emitting layer / electron injection layer / cathode "," substrate / anode / hole injection layer " / Light emitting layer / electron transporting layer / cathode "," substrate / anode / light emitting layer / electron transporting layer / cathode "," substrate / anode / light emitting layer / electron injection layer / cathode " The amount is even.

&Lt; Substrate in Organic Electroluminescent Device >

The substrate 101 serves as a support for the organic electroluminescent device 100, and typically 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, depending on the purpose. For example, a glass plate, a metal plate, a metal foil, a plastic film, a plastic sheet, or the like is used. Among them, a glass plate and a plate made of a transparent synthetic resin such as polyester, polymethacrylate, polycarbonate, polysulfone and the like are preferable. As the glass substrate, soda lime glass, alkali-free glass, or the like is used, and the thickness thereof is sufficient to maintain the mechanical strength. For example, it may be 0.2 mm or more. The upper limit of the thickness is, for example, 2 mm or less, preferably 1 mm or less. With respect to the material of the glass, since it is preferable that the elution ions from the glass are small, alkali-free glass is preferable, but soda-lime glass on which barrier coating such as SiO ₂ is performed is also commercially available. A gas barrier film such as a dense silicon oxide film may be formed on at least one surface of the substrate 101 in order to enhance the gas barrier property. In particular, a plate, film or sheet made of synthetic resin having low gas barrier property may be provided on the substrate 101 ), It is preferable to form a gas barrier film.

&Lt; Positive electrode in organic electroluminescent device >

The anode 102 serves to inject holes into the light emitting layer 105. [ When the hole injecting layer 103 and / or the hole transporting layer 104 are provided between the anode 102 and the light emitting layer 105, holes are injected into the light emitting layer 105 through the hole injecting layer 103 and / or the hole transporting layer 104.

As a material for forming the anode 102, an inorganic compound and an organic compound are exemplified. Examples of the inorganic compound include metals (aluminum, gold, silver, nickel, palladium, chromium and the like), metal oxides (indium oxide, tin oxide, indium-tin oxide (ITO), indium- , Metal halide (copper iodide, etc.), copper sulfide, carbon black, ITO glass and nesa glass. Examples of the organic compound include polythiophene such as poly (3-methylthiophene), conductive polymer such as polypyrrole, polyaniline, and the like. In addition, it can be appropriately selected from materials used as the anode of the organic electroluminescent device.

The resistance of the transparent electrode is not particularly limited as long as it can supply a sufficient current for light emission of the light emitting element, but it is preferable that the resistance is low in view of power consumption of the light emitting element. For example, an ITO substrate of 300 OMEGA / &amp; squ &amp; or less functions as an element electrode, but currently it is possible to supply a substrate of about 10 OMEGA / &amp; squ &amp; It is particularly preferable to use a low resistance product of 50 to 5? / ?. Thickness of ITO can be arbitrarily selected in accordance with the resistance value, but it is often used between 100 and 300 nm.

&Lt; Hole injection layer and hole transport layer in organic electroluminescent device >

The hole injection layer 103 serves to efficiently inject holes that migrate from the anode 102 into the light emitting layer 105 or into the hole transport layer 104. The hole transport layer 104 serves to efficiently transport the holes injected from the anode 102 or the holes injected from the anode 102 through the hole injection layer 103 to the light emitting layer 105. The hole injecting layer 103 and the hole transporting layer 104 are each formed of a mixture of one or more kinds of hole injecting and transporting materials or a mixture of a hole injecting and transporting material and a polymer binder. Further, an inorganic salt such as iron (III) chloride may be added to the hole injecting and transporting material to form a layer.

As the hole injecting and transporting material, it is necessary to efficiently inject and transport holes from the anode between the electrodes to which an electric field is applied. Therefore, it is preferable that the hole injecting efficiency is high and the injected holes are efficiently transported. For this purpose, it is preferable that impurities which are small in ionization potential, large in hole mobility, and excellent in stability are not easily generated during production and use.

As the material for forming the hole injection layer 103 and the hole transporting layer 104, a hole injection layer of a p-type semiconductor, a hole injection layer of an organic electroluminescence device, and a hole injection layer of a compound conventionally used as a hole transporting material in a photoconductive material, Any of the well-known ones used in the hole transport layer can be selected and used. Specific examples thereof include biscarbazole derivatives such as carbazole derivatives (N-phenylcarbazole, polyvinylcarbazole and the like), bis (N-allylcarbazole) and bis (N-alkylcarbazole), triarylamine Derivative [a polymer having an aromatic tertiary amino group in the main chain or side chain, 1,1-bis (4-di-p-tolylaminophenyl) cyclohexane, N, N'- -Methylphenyl) -4,4'-diaminophenyl, N, N'-diphenyl-N, N'-dinaphthyl-4,4'-diaminophenyl, N, N'- Di (3-methylphenyl) -4,4'-diphenyl-1,1'-diamine, N, N'-dinaphthyl-N, N'-diphenyl-4,4'- Triphenylamine derivatives such as 1'-diamine, 4,4 ', 4 "-tris (3-methylphenyl (phenyl) amino) triphenylamine, starburst amine derivatives and the like], stilbene derivatives, phthalocyanine derivatives (Metal-free, copper phthalocyanine, etc.), pyrazoline derivatives, hydrazone compounds, benzofuran derivatives and thiophene derivatives, oxadiazole derivatives , Porphyrin derivatives, and polysilanes. In the polymer system, a polycarbonate or a styrene derivative having the above monomer in the side chain, polyvinylcarbazole and polysilane, and the like are preferable, but a thin film necessary for the production of a light emitting device is formed , And a compound capable of injecting holes from the anode and capable of transporting holes is not particularly limited.

It is also known that the conductivity of an organic semiconductor is strongly influenced by 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. For doping the electron donor, a strong electron acceptor such as tetracyanoquinodimethane (TCNQ) or 2,3,5,6-tetrafluorotetracyano-1,4-benzoquinodimethane (F4TCNQ) (See, for example, M. Pfeiffer, A. Beyer, T. Fritz, K. Leo, Appl. Phys. Lett., 73 (22), 3202-3204 , M. Pheiffer, T. Fritz, K. Leo, Appl. Phys. Lett., 73 (6), 729-731 (1998)]. These produce so-called holes by the electron transfer process in the electron donor type base material (hole transport material). The conductivity of the base material varies greatly due to the number and mobility of holes. As the matrix material having the hole transporting property, for example, a benzidine derivative (TPD), a starburst amine derivative (TDATA etc.), or a specific metal phthalocyanine (particularly zinc phthalocyanine ZnPc and the like) 2005-167175).

&Lt; Light Emitting Layer in Organic Electroluminescent Device >

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 any compound (luminescent compound) that is excited by the recombination of holes and electrons to emit light (luminescent compound), which can form a stable thin film shape, and can emit strong luminescence (fluorescence and / ) &Lt; / RTI &gt; efficiency.

The light emitting layer may be composed of a single layer or a plurality of layers, each of which is formed by a light emitting material (host material, dopant material). Each of the host material and the dopant material may be one type or a combination of a plurality of types. The dopant material may be included in the entire host material or partially included. As a doping method, it can be formed by a co-evaporation method (co-evaporation method) with a host material, but may be vapor-deposited after mixing with a host material in advance.

The amount of the host material to be used differs depending on the kind of the host material and may be determined according to the characteristics of the host material. The amount of the host material to be used is preferably 50 to 99.999 wt%, more preferably 80 to 99.95 wt%, and most preferably 90 to 99.9 wt% of the entire light emitting material.

The amount of the dopant material to be used differs depending on the kind of the dopant material and may be determined according to the characteristics of the dopant material. The amount of the dopant to be used is preferably 0.001 to 50 wt%, more preferably 0.05 to 20 wt%, and most preferably 0.1 to 10 wt% of the entire light emitting material. Within the above-mentioned range, for example, concentration light extinction phenomenon can be prevented.

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

Examples of the host material include, but are not limited to, condensed ring derivatives such as anthracene and pyrene which have hitherto been known as phosphors, metal chelated oxinoid compounds including tris (8-quinolinolato) aluminum, bisstyryl anthracene derivatives A thiadiazole derivative, a thiadiazole derivative, a thiadiazole derivative, a thiadiazole derivative, a thiadiazole derivative, a thiadiazole derivative, a thiadiazole derivative, a pyridazine derivative, A polyphenylene vinylene derivative, a polyparaphenylene derivative, and a polythiophene derivative are preferably used in the polymer system.

In addition, as the host material, it is possible to appropriately select and use from among the compounds described in the Japanese Chemical Industry, June 2004, page 13, and the example references therein.

Further, the dopant material is not particularly limited, and existing compounds can be used and can be selected from various materials according to a desired luminescent color. Specific examples thereof include condensed ring derivatives such as phenanthrene, anthracene, pyrene, tetracene, pentacene, perylene, naphthopyrene, dibenzopyrene, rubrene and chrysene, benzoxazole derivatives, A thiazole derivative, a thiazole derivative, a thiazole derivative, a pyrazoline derivative, a stilbene derivative, a thiophene derivative, a thiazole derivative, a thiazole derivative, an imidazole derivative, a thiadiazole derivative, , Bisstyryl derivatives such as tetraphenylbutadiene derivatives, cyclopentadiene derivatives, bisstyryl anthracene derivatives and distyryl benzene derivatives (Japanese Patent Application Laid-open No. 1-245087), bistyryl arylene derivatives 2-247278), diazinedazine derivatives, furan derivatives, benzofuran derivatives, phenylisobenzofuran, dimethymethylisobenzofuran, di (2-methylphenyl) iso Isobenzofuran derivatives such as benzofuran, di (2-trifluoromethylphenyl) isobenzofuran and phenylisobenzofurane, dibenzofuran derivatives, 7-dialkylaminocoumarin derivatives, 7-piperidinocoumarin derivatives, 7- Coumarin derivatives such as hydroxy coumarin derivatives, 7-methoxy coumarin derivatives, 7-acetoxy coumarin derivatives, 3-benzthiazolyl coumarin derivatives, 3-benzimidazolyl coumarin derivatives and 3-benzoxazolyl coumarin derivatives, A pyridinium derivative, a carbothyryl derivative, an acridine derivative, a thiophene derivative, a thiophene derivative, a thiophene derivative, a thiophene derivative, a thiophene derivative, Oxazine derivatives, oxazine derivatives, oxazine derivatives, oxazine derivatives, oxazine derivatives, pyridine derivatives, pyrimidine derivatives, pyrimidine derivatives, There is provided a process for producing a compound represented by the general formula (1), which comprises reacting a compound represented by the general formula (1) or a pharmaceutically acceptable salt thereof with a compound selected from the group consisting of a phenol derivative, a pyrrole derivative, a pyromethene derivative, a perinone derivative, a pyrrolopyrrole derivative, a squarylium derivative, .

Examples of the blue-green-blue dopant material include blue light-emitting materials such as aromatic hydrocarbon compounds and derivatives thereof such as naphthalene, anthracene, phenanthrene, pyrene, triphenylene, perylene, fluorene, indene, And examples thereof include thiophene, silole, 9-silafluorene, 9,9'-spirobisilafluorene, benzothiophene, benzofuran, indole, dibenzothiophene, dibenzofurane, imidazopyridine, phenanthroline, pyrazine, Aromatic heterocyclic compounds or derivatives thereof such as naphthylidine, quinoxaline, pyrrolopyridine and thioxanthene, distyrylbenzene derivatives, tetraphenylbutadiene derivatives, stilbene derivatives, aldazine derivatives, coumarin derivatives, imidazoles, thiazoles , Azole derivatives such as thiadiazole, carbazole, oxazole, oxadiazole and triazole and metal complexes thereof, and N, N'-diphenyl-N, N'-di (3-methylphenyl) '- diphenyl-1,1'-diamine, and the like.

Examples of the rust-yellow dopant material include coumarin derivatives, phthalimide derivatives, naphthalimide derivatives, perinone derivatives, pyrrolopyrrole derivatives, cyclopentadiene derivatives, acridone derivatives, quinacridone derivatives, Naphthacene derivatives such as naphthacene derivatives such as naphthacene derivatives and the like, and compounds obtained by introducing a substituent capable of long wavelength, such as aryl, heteroaryl, arylvinyl, amino or cyano, into a compound exemplified as the blue- Can also be mentioned as preferred examples.

Examples of the orange to red dopant materials include naphthalimide derivatives such as bis (diisopropylphenyl) perylenetetracarboxylic acid imide, perynone derivatives, Eu complexes using acetylacetone, benzoyl acetone and phenanthroline as ligands (Dicyanomethylene) -2-methyl-6- (p-dimethylaminostyryl) -4H-pyran and its analogues, metal phthalocyanine derivatives such as magnesium phthalocyanine and aluminum chlorophthalocyanine, rhodamine compounds , A deazaplain derivative, a coumarin derivative, a quinacridone derivative, a phenoxazine derivative, an oxazine derivative, a quinazoline derivative, a pyrrolopyridine derivative, a squarylium derivative, a bioranthrone derivative, a phenazine derivative, , And thiadiazolo pyrene derivatives, and examples of the blue-blue green and green-yellow dopant materials include aryl, he Preferred examples include compounds in which a substituent capable of long wavelength conversion is introduced, such as teroaryl, arylvinyl, amino, cyano, and the like. Preferable examples are phosphorescent metal complexes composed of iridium represented by tris (2-phenylpyridine) iridium (III) or platinum as a central metal.

In addition, as the dopant, it is possible to appropriately select and use from among the compounds described in the Japanese Chemical Industry, June 2004, page 13, and the example references therein.

Of the above-mentioned dopant materials, 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 the perylene derivative include 3,10-bis (2,6-dimethylphenyl) perylene, 3,10-bis (2,4,6-trimethylphenyl) perylene, 3,10- Tetra-tert-butylperylene, 3,4,9,10-tetraphenylpiperylene, 3- (1'-pyrenyl) - (Tert-butyl) perylene, 3- (9'-anthryl) -8,11-di -Butyl) perylenyl) and the like.

Japanese Patent Application Laid-open No. 11-97178, Japanese Patent Application Publication No. 2000-133457, Japanese Patent Application Publication No. 2000-26324, Japanese Patent Application Laid-Open No. 2001-267079, Japanese Patent Application Japanese Patent Application Laid-Open No. 2001-267078, Japanese Patent Application Laid-Open No. 2001-267076, Japanese Patent Application Laid-Open No. 2000-34234, Japanese Patent Application Laid-Open No. 2001-267075, and Japanese Patent Application Laid-open No. 2001-217077 Perylene derivatives described in, for example, JP-A-10-196059 may also be used.

Examples of the borane derivative include 1,8-diphenyl-10- (dimethyisilbyl) anthracene, 9-phenyl-10- (dimethyisilbyl) anthracene, 4- (9'- (Dimethylacetylboryl) anthracene, 9- (4'-biphenylyl) -10- (dimethylaniline) Triboryl) anthracene, and 9- (4 '- (N-carbazolyl) phenyl) -10- (dimethyisilbyl) anthracene.

Borane derivatives described in WO 2000/40586 pamphlet and the like may also be used.

Examples of the amine-containing styryl derivative include N, N, N ', N'-tetra (4-biphenylyl) -4,4'- diaminostilbene, N, N, N ', N'-tetra (2-naphthyl) -4,4'-diaminostilbene, N, -Di (2-naphthyl) -N, N'-diphenyl-4,4'-diaminostilbene, N, N'- Bis [4'-bis (diphenylamino) styryl] - 4'-diaminostilbene, 4,4'-bis [ Benzene, 2,7-bis [4'-bis (diphenylamino) styryl] -9,9-dimethylfluorene, 4,4'- , 4,4'-bis (9-phenyl-3-carbazovinylene) -biphenyl, etc. Further, Japanese Patent Application Laid-Open No. 2003-347056 and Japanese Patent Application Laid-Open No. 2001-307884 An amine-containing styryl derivative may be used.

Examples of the aromatic amine derivative include N, N, N, N-tetraphenyl anthracene-9,10-diamine, 9,10-bis (4-diphenylamino- phenyl) anthracene, 9,10- Di (2-naphthylamino) phenyl) anthracene, 10-di-p-tolylamino-9- Diphenylamino-9- (6-diphenylamino-2-naphthyl) anthracene, 10-diphenylamino- Naphthalen-1-yl] -diphenylamine (prepared by reacting [4- (4-diphenylamino-phenyl) , 4,4'-bis [4-diphenylaminaphthalen-1-yl] biphenyl, 4,4'- Bis [4-diphenylaminonaphthalen-1-yl] -p-terphenyl, 4,4 "-bis [6-di Phenylaminonaphthalen-2-yl] -p-terphenyl.

An aromatic amine derivative described in Japanese Patent Application Laid-Open No. 2006-156888 may also be used.

Examples of coumarin derivatives include coumarin-6 and coumarin-334.

Also, coumarin derivatives described in Japanese Patent Application Publication Nos. 2004-43646, 2001-76876, and 6-298758 may be used.

Examples of the pyran derivative include the following DCM and DCJTB.

(85)

Japanese Patent Application Laid-Open No. 2005-126399, Japanese Patent Application Laid-Open No. 2005-097283, Japanese Patent Application Laid-Open No. 2002-234892, Japanese Patent Application Laid-Open No. 2001-220577, Japanese Patent Application Laid Open 2001-081090, and Japanese Patent Application Laid-Open No. 2001-052869 may be used.

As the iridium complex, the following Ir (ppy) ₃ can be exemplified.

&Lt; EMI ID =

Japanese Patent Application Laid-Open No. 2006-089398, Japanese Patent Application Laid-Open No. 2006-080419, Japanese Patent Application Laid-Open No. 2005-298483, Japanese Patent Application Laid-Open No. 2005-097263, and Japanese Patent Application An iridium complex described in Publication No. 2004-111379 may be used.

As the platinum complex, PtOEP and the like shown below can be exemplified.

[Chemical Formula 87]

Further, Japanese Patent Application Laid-Open Nos. 2006-190718, 2006-128634, 2006-093542, 2004-335122, and Japanese Patent Application A platinum complex disclosed in Publication No. 2004-331508 may be used.

&Lt; Electron injection layer and electron transport layer in organic electroluminescent device >

The electron injection layer 107 serves to efficiently inject electrons moving from the cathode 108 into the light emitting layer 105 or the electron transporting layer 106. The electron transporting layer 106 serves to efficiently transport electrons injected from the cathode 108 or electrons injected from the cathode 108 through the electron injection layer 107 into the light emitting layer 105. The electron transporting layer 106 and the electron injecting layer 107 are each formed by laminating or mixing one or more kinds of electron transporting / injecting materials or by a mixture of an electron transporting / injecting material and a polymer binder.

The electron injection / transport layer is a layer which is responsible for injecting electrons from the cathode and transporting electrons, and has high electron injection efficiency, so that it is preferable to efficiently transport injected electrons. For this purpose, it is preferable that the electron affinity is high, the electron mobility is high, the stability is excellent, and the impurities which become trap are not easily generated at the time of production and use. However, when the balance of holes and electrons is taken into consideration, it is important to improve the luminous efficiency even when the electron transporting ability is not so high, in the case of mainly performing the function of efficiently preventing the holes from being recombined in the anode and flowing to the cathode side. The effect is equivalent to that of materials with high electron transport capability. Therefore, the electron injecting and transporting layer in the present embodiment may also include the function of a layer capable of effectively blocking the movement of holes.

As the material (electron transporting material) for forming the electron transporting layer 106 or the electron injecting layer 107, the compound represented by the above formula (1) can be used.

The content of the compound represented by the formula (1) in the electron transporting layer 106 or the electron injecting layer 107 differs depending on the kind 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, and still more preferably 10 to 100% by weight of the total of the material for the electron transporting layer By weight is 50 to 100% by weight, 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.

As the material for forming the other electron transporting layer or the electron injecting layer, a known compound which is conventionally used as an electron transporting compound in a photoconductive material, a known compound used in an electron injecting layer and an electron transporting layer of an organic electroluminescent device Can be used.

Examples of the material used for the electron transporting layer or the electron injecting layer include compounds containing an aromatic ring or a heterocyclic ring composed of at least one atom selected from carbon, hydrogen, oxygen, sulfur, silicon, and phosphorus, pyrrole derivatives and condensed ring derivatives thereof , And a metal complex having electron-accepting nitrogen. Specific examples include condensed ring aromatic ring derivatives such as naphthalene and anthracene, styryl aromatic ring derivatives represented by 4,4'-bis (diphenylethenyl) biphenyl, perinone derivatives, coumarin derivatives, naphthalimide derivatives , Quinone derivatives such as anthraquinone and diphenoquinone, phosphorus oxide derivatives, carbazole derivatives, and indole derivatives. Examples of the metal complex having electron-accepting nitrogen include a hydroxyazole complex such as a hydroxyphenyloxazole complex, an azomethine complex, a tropolone metal complex, a flavonol metal complex, and a benzoquinoline metal complex have. These materials may be used alone or in combination with different materials. Among them, styryl type aromatic ring derivatives such as anthracene derivatives such as 9,10-bis (2-naphthyl) anthracene and 4,4'-bis (diphenylethenyl) biphenyl, 4,4'-bis -Carbazolyl) biphenyl, and 1,3,5-tris (N-carbazolyl) benzene are more preferably used from the viewpoint of durability.

Specific examples of other electron transfer compounds include pyridine derivatives other than the compound represented by the formula (1), naphthalene derivatives of the compound represented by the formula (1), anthracene derivatives, phenanthroline derivatives, (1, 3-bis [4-tert-butylphenyl] 1,3,4-thiadiazole derivatives, naphthalimide derivatives, anthraquinone derivatives, diphenoquinone derivatives, diphenylquinone derivatives, perylene derivatives, oxadiazole derivatives Oxadiazolyl] phenylene), thiophene derivatives, triazole derivatives (such as N-naphthyl-2,5-diphenyl-1,3,4-triazole), thiadiazole derivatives, metal complexes of oxine derivatives , A quinolinol-based metal complex, a quinoxaline derivative, a polymer of a quinoxaline derivative, a benzazole compound, a gallium complex, a pyrazole derivative, a perfluorinated phenylene derivative, a triazine derivative, a pyrazine derivative, a benzoquinoline derivative (2, 2'-bis (benzo [h] quinolin-2-yl) -9,9'- Benzimidazole derivatives such as tris (N-phenylbenzimidazol-2-yl) benzene), benzoxazole derivatives, benzothiazole derivatives, quinoline derivatives, terpyridine, and the like), imidazopyridine derivatives, (4'- (2,2 ': 6'2 "-terpyridinyl) benzene, etc.), naphthyridine derivatives (bis (1- Naphthyl) -4- (1,8-naphthyridin-2-yl) phenylphosphine oxide), an aldazine derivative, a carbazole derivative other than the compound represented by the formula (1), an indole derivative, Derivatives, bisstyryl derivatives, and the like.

A metal complex having electron-accepting nitrogen may also be used. For example, a metal complex such as a quinolinol-based metal complex or a hydroxyphenyloxazole complex, an azomethine complex, a tropolone metal complex, a flavonol metal complex , And benzoquinoline metal complexes.

The above-described materials may be used alone, or may be mixed with other materials.

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

The quinolinol-based metal complex is a compound represented by the following formula (E-1).

[Formula 88]

In the formulas, R ¹ to R ⁶ are hydrogen or a substituent, M is Li, Al, Ga, Be, or Zn, and n is an integer of 1 to 3.

Specific examples of quinolinol-based metal complexes include lithium 8-quinolinolato, tris (8-quinolinolato) aluminum, tris (4-methyl-8- quinolinolato) aluminum, tris Quinolinolato) aluminum, tris (3,4-dimethyl-8-quinolinolato) aluminum, tris (4,5- 8-quinolinolato) aluminum, bis (2-methyl-8-quinolinolato) (phenolato) aluminum, bis (2-methyl-8-quinolinolato) aluminum, bis (2-methyl-8-quinolinolato) (2-methyl-8-quinolinolato) (3-phenylphenolato) aluminum, bis (2-methyl-8-quinolinolato) Aluminum (4-phenylphenolato) aluminum, bis (2-methyl-8-quinolinolato) Aluminum (2-methyl-8-quinolinolato) (3,4-dimethylphenolato) aluminum, bis (2- (3,5-dimethylphenolato) aluminum, bis (2-methyl-8-quinolinolato) 2-methyl-8-quinolinolato) (2,6-diphenylphenolato) aluminum, bis (2-methyl-8- quinolinolato) (2,4,6-trimethylphenolato) aluminum, bis (2-methyl-8-quinolinolato) (2,4,5,6-tetramethyl (2-methyl-8-quinolinolato) aluminum, bis (2-methyl-8-quinolinolato) (2-phenylphenolato) aluminum, bis (2,4-dimethyl-8-quinolinolato) (3-phenylphenolato) aluminum, bis -Dimethyl-8-quinolinolato) (4-phenylphenol A Aluminum, bis (2,4-dimethyl-8-quinolinolato) (3,5-dimethylphenolato) aluminum, bis bis (2-methyl-8-quinolinolato) aluminum, bis (2,4-dimethyl (2-methyl-4-ethyl-8-quinolinolato) aluminum-quinolinolato) aluminum- (2-methyl-4-methoxy-8-quinolinolato) aluminum-mu-oxo-bis (2-methyl- -Methyl-4-methoxy-8-quinolinolato) aluminum, bis (2-methyl-5-cyano- Quinolinolato) aluminum, bis (2-methyl-5-trifluoromethyl-8-quinolinolato) aluminum- Quinolinolato) aluminum, bis (10-lower And the like can be de-hydroxy-benzo [h] quinoline) beryllium.

The bipyridine derivative is a compound represented by the following formula (E-2).

(89)

In the formulas, G represents a mating bond or an n-linking group, and n is an integer of 2 to 8. The carbon which is not used for the coupling of pyridine-pyridine or pyridine-G may be substituted.

 Examples of G in the general formula (E-2) include those represented by the following structural formulas. R in the following structural formulas are each independently hydrogen, methyl, ethyl, isopropyl, cyclohexyl, phenyl, 1-naphthyl, 2-naphthyl, biphenyl or terphenyl.

(90)

Specific examples of pyridine derivatives include 2,5-bis (2,2'-bipyridyl-6-yl) -1,1-dimethyl-3,4-diphenylsilole, 2,5- -Bipyridyl-6-yl) -1,1-dimethyl-3,4-dimemethylsilyl chloride, 2,5-bis (2,2'- (2,2'-bipyridyl-5-yl) -1,1-dimethyl-3,4-dimemethylsilylol 9,10-di , 2,2'-bipyridyl-5-yl) anthracene, 9,10-di (2,3'-bipyridyl- Di (2,3'-bipyridyl-5-yl) anthracene, 9,10-di Anthracene, 9,10-di (2,3'-bipyridyl-5-yl) -2-phenylanthracene, 9,10-di (2,2'-bipyridyl- (2,2'-bipyridyl-5-yl) -2-phenylanthracene, 9,10-di Anthracene, 9,10-di (2,4'-bipyridyl-5-yl) Anthracene, 9,10-di (3,4'-bipyridyl-5-yl) -2-phenylanthracene, 3,4-diphenyl- 6-yl) thiophene, 3,4-diphenyl-2,5-di (2,3'-bipyridyl- ) 2,2 ': 4', 4 ": 2 &quot;, 2" '- quarter pyridine and the like.

The phenanthroline derivative is a compound represented by the following formula (E-3-1) or (E-3-2).

[Formula 91]

In the formulas, 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 bonded or n-valent connecting group, and n is an integer of 2 to 8. Examples of G in the general formula (E-3-2) include the same ones as described for the above-mentioned non-pyridine derivatives.

Specific examples of the phenanthroline derivatives include 4,7-diphenyl-1,10-phenanthroline, 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline, 9,10- (1,10-phenanthroline-5-yl) pyridine, 1,3,5-tri (1,10-phenanthroline- 5-yl) benzene, 9,9'-difluorobis (1,10-phenanthroline-5-yl), bathocuproine or 1,3- -Henanthrene-9-yl) benzene, and the like.

Particularly, a 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 luminescence over a long period of time, a material having excellent thermal stability and thin film forming property is preferable, and among the phenanthroline derivatives, the substituent itself has a three-dimensional steric structure, or a three-dimensional repulsion with the phenanthroline skeleton Dimensional structure by a steric repulsion with a substituent, or a structure in which a plurality of phenanthroline skeletons are connected to each other. Further, when a plurality of phenanthroline skeletons are connected, a compound having a conjugated bond, a substituted or unsubstituted aromatic hydrocarbon, and a substituted or unsubstituted aromatic heterocycle in the connecting unit is more preferable.

The borane derivative is a compound represented by the following formula (E-4), and details are disclosed in Japanese Patent Application Laid-Open No. 2007-27587.

&Lt; EMI ID =

Wherein R ¹¹ and R ¹² are each independently at least one of hydrogen, alkyl, optionally substituted aryl, substituted silyl, optionally substituted nitrogen-containing heterocyclic ring or cyano, and R ¹³ to R ¹⁶ are , Each independently represents optionally substituted alkyl or optionally substituted aryl, X is optionally substituted arylene, and Y is optionally substituted aryl, substituted aryl, or substituted or unsubstituted And n is each independently an integer of 0 to 3.

Among the compounds represented by the above-mentioned 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 -4) is preferable. Specific examples include 9- [4- (4-dimetylthiophenylboronaphthalen-1-yl) phenyl] carbazole, Carbazole and the like.

&Lt; EMI ID =

Wherein R ¹¹ and R ¹² are each independently at least one of hydrogen, alkyl, optionally substituted aryl, substituted silyl, optionally substituted nitrogen-containing heterocyclic ring or cyano, and R ¹³ to R ¹⁶ are , And R ²¹ and R ²² are each independently selected from the group consisting of hydrogen, alkyl, optionally substituted aryl, substituted silyl, optionally substituted nitrogen-containing heterocyclic group, summons, or cyano, and at least one of the furnace, X ¹ is an arylene group having a carbon number of 20 or less that may be substituted, n are each independently an integer from 0 to 3, and, m are each independently an integer of 0 to 4 to be.

(94)

In the formulas, R ³¹ to R ³⁴ are each independently any one of methyl, isopropyl, and phenyl, and R ³⁵ and R ³⁶ are each independently any one of hydrogen, methyl, isopropyl, and phenyl .

Among the compounds represented by the above general formula (E-4), the compounds represented by the following general formula (E-4-2) and further the compounds represented by the following general formula (E-4-2-1) .

&Lt; EMI ID =

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

&Lt; EMI ID =

Wherein 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.

Among the compounds represented by the above general formula (E-4), the compounds represented by the following general formula (E-4-3), furthermore, the compounds represented by the following general formulas (E-4-3-1) -2) is preferable.

[Formula 97]

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

(98)

In the formulas, R ³¹ to R ³⁴ are each independently any one of methyl, isopropyl, and phenyl, and R ³⁵ and R ³⁶ are each independently any one of hydrogen, methyl, isopropyl, and phenyl .

The benzimidazole derivative is a compound represented by the following formula (E-5).

[Formula 99]

Wherein Ar ^{1 to} Ar ³ are each independently hydrogen or aryl having 6 to 30 carbon atoms which may be substituted. Particularly preferred is anthryl benzoimidazole derivatives in which Ar ¹ may be substituted.

Specific examples of the aryl having 6 to 30 carbon atoms include phenyl, 1-naphthyl, 2-naphthyl, acenaphthylene-1-yl, acenaphthylene- Yl, phenalen-1-yl, phenalen-2-yl, fluoren-3-yl, fluoren- 2-yl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl, Yl, triphenylene-1-yl, triphenylene-2-yl, fluorenen-2-yl, fluorenen-2-yl, fluoranthene- Yl, chrysene-4-yl, chrysene-1-yl, chrysene-2-yl, Yl, naphthacen-2-yl, naphthacen-5-yl, perylen-1-yl, perylen- Pentacene-1-yl, pentacene-2-yl, pentacene-5-yl, pentacene-6-yl.

Specific examples of benzimidazole derivatives include 1-phenyl-2- (4- (10-phenylanthracen-9-yl) phenyl) -1H- benzo [d] imidazole, 2- (4- (10- Phenyl) -1H-benzo [d] imidazole and 2- (3- (10- (naphthalen-2-yl) anthracene- Benzo [d] imidazole, 1-phenyl-1H- benzo [d] imidazole, 5- (10- (naphthalen- Benzo [d] imidazole, 2- (4- (9,10-di (naphthalene-2-yl) Benzo [d] imidazole, 1- (4- (9,10-di (naphthalen-2-yl) anthracene- 2- yl) Benzo [d] imidazole, 5- (9,10-di (naphthalen-2-yl) anthracene- ] Imidazole.

The electron transporting layer or the electron injecting layer may further include a material capable of reducing the material forming the electron transporting layer or the electron injecting layer. The reducing material may be any of a variety of materials as long as it has a certain reducing property. For example, an alkali metal, an alkaline earth metal, a rare earth metal, an oxide of an alkali metal, a halide of an alkali metal, an oxide of an alkaline earth metal, At least one selected from the group consisting of a halide of a rare earth metal, an oxide of a rare earth metal, a halide of a rare earth metal, an organic complex of an alkali metal, an organic complex of an alkaline earth metal, and an organic complex of a rare earth metal is preferably used .

Preferred examples of the reducing material include alkaline metals such as Na (work function 2.36 eV), K (work function 2.28 eV), Rb (work function 2.16 eV) or Cs (work function 1.95 eV) An alkaline earth metal such as Sr (work function 2.0 to 2.5 eV) or Ba (work function 2.52 eV), and particularly preferably has a work function of 2.9 eV or less. Among these, preferred reducing materials are alkali metals of K, Rb or Cs, more preferably Rb or Cs, and most preferably Cs. These alkali metals can improve the luminescence brightness and the longevity of the organic EL element by adding a relatively small amount to the material that forms the electron transporting layer or the electron injecting layer, particularly the reducing ability. It is also preferable to use a combination of two or more kinds of alkali metals among them, particularly a combination containing Cs, for example, Cs and Na, Cs and K, Cs and Rb, or combinations thereof. The combination of Cs, Na and K is preferred. By including Cs, the reducing ability can be efficiently exhibited. By adding the Cs to a material for forming the electron transporting layer or the electron injecting layer, it is possible to improve the luminescence brightness and the longevity of the organic EL device.

&Lt; Negative electrode in organic electroluminescent 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 electrons can be efficiently injected into the organic layer, but the same material as the material for forming the anode 102 can be used. Among them, metals such as tin, magnesium, indium, calcium, aluminum, silver, copper, nickel, chromium, gold, platinum, iron, zinc, lithium, sodium, potassium, cesium and magnesium or their alloys Aluminum-magnesium alloy, magnesium-indium alloy, and aluminum-lithium alloy such as lithium fluoride / aluminum). In order to increase the electron injection efficiency and improve the device characteristics, alloys containing lithium, sodium, potassium, cesium, calcium, magnesium, or their low work function metals are effective. However, these low work function metals are generally unstable in the atmosphere. In order to solve this problem, for example, a method is known in which an organic layer is doped with a small amount of lithium, cesium or magnesium to use an electrode with high stability. As other dopants, inorganic salts such as lithium fluoride, cesium fluoride, lithium oxide, and cesium oxide may also be used. However, the present invention is not limited thereto.

In order to protect the electrodes, metals such as platinum, gold, silver, copper, iron, tin, aluminum and indium or alloys using these metals and inorganic materials such as silica, titanium dioxide and silicon nitride, polyvinyl alcohol , Vinyl chloride, a hydrocarbon-based polymer compound, and the like. The manufacturing method of these electrodes is not particularly limited as long as they can conduct (resistance), such as resistance heating, electron beam beam, sputtering, ion plating, and coating.

&Lt; Binder agent usable in each layer >

The above materials used for the hole injection layer, the hole transporting layer, the light emitting layer, the electron transporting layer, and the electron injecting layer can form each layer independently. However, as the polymer binder, polyvinyl chloride, polycarbonate, polystyrene, poly Polybutadiene, hydrocarbon resins, ketone resins, phenoxy resins, polysulfones, polyamides, ethylcellulose, acetic acid, and the like. A solvent soluble resin such as a vinyl resin, an ABS resin and a polyurethane resin or a curable resin such as a phenol resin, a xylene resin, a petroleum resin, a urea resin, a melamine resin, an unsaturated polyester resin, an alkyd resin, .

&Lt; Method of manufacturing organic electroluminescent device &

Each layer constituting the organic electroluminescence device can be formed by a method such as vapor deposition, resistance heating deposition, electron beam deposition, sputtering, molecular lamination, printing, spin coating, casting, To form a thin film. The film thickness of each layer thus formed is not particularly limited and may 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 be generally measured by a crystal oscillation type film thickness measuring apparatus or the like. In the case of thinning using a vapor deposition method, the deposition conditions differ depending on the kind of the material, the intended crystal structure of the film, and the association structure. The deposition conditions are generally in the range of boat heating temperature 50 to 400 占 폚, vacuum degree 10 ^-6 to 10 ^-3 Pa, deposition rate 0.01 to 50 nm / sec, substrate temperature 150 to 300 占 폚, It is desirable to set it appropriately.

Next, as an example of a method of manufacturing an organic electroluminescent device, a method of manufacturing an organic electroluminescent device comprising an anode / a hole injecting layer / a hole transporting layer / a light emitting layer / electron transporting layer / electron injecting layer / cathode made of a host material and a dopant material . A thin film of a cathode material is formed on a suitable substrate by a vapor deposition method or the like to produce a cathode, and then a thin film of a hole injection layer and a hole transporting layer is formed on the anode. A thin film made of a host material and a dopant material is formed thereon 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 material for a negative electrode is formed by evaporation or the like to form a cathode. An organic electroluminescent device can be obtained. In the production of the organic electroluminescent device described above, the cathode, the electron injecting layer, the electron transporting layer, the light emitting layer, the hole transporting layer, the hole injecting layer, and the anode may be fabricated in this order in reverse order.

When a direct current voltage is applied to the thus obtained organic electroluminescent device, the positive electrode may be applied with a positive polarity and the negative electrode may be applied with a negative polarity. When a voltage of approximately 2 to 40 V is applied, a transparent or semitransparent electrode Or cathode, and both) can be observed. Further, this organic electroluminescent element emits light even when a pulse current or an alternating current is applied. The waveform of the applied alternating current may be any waveform.

&Lt; Example of application of organic electroluminescent device &

The present invention can also be applied to a display device having an organic electroluminescent device or a lighting device having an organic electroluminescent device. The display device or the lighting device provided with the organic electroluminescent device can be manufactured by a known method such as connecting the organic electroluminescent device according to the present embodiment and a known driving device, A known driving method such as driving can be appropriately used.

As the display device, there are, for example, 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, Japanese Patent Application Laid-Open No. Hei 10-335066, Japanese Patent Application Laid-open No. 2003-321546, Japanese Patent Application Laid-open No. 2004-281086, etc.). As a display method of the display, for example, there is a matrix and / or a segmentation method. The matrix display and the segment display may coexist in the same panel.

The matrix means a pixel for display arranged two-dimensionally such as a lattice type or a mosaic type, and displays a character or an image as a set of pixels. The shape and size of the pixel are determined depending on the application. For example, in the case of a large-sized display such as a display panel, a square pixel having one side of 300 mu m or less is used for image and character display of a PC, a monitor, and a television, . In the case of monochrome display, pixels of the same color can be arranged. In the case of color display, red, green and blue pixels are arranged and displayed. In this case, there are delta type and stripe type as typical types. As a driving method of the matrix, either a line sequential driving method or an active matrix may be used. The line-sequential drive has a simple structure. However, in consideration of the operating characteristics, the active matrix may be superior. Therefore, the line-sequential drive needs to be separately used according to the application.

In the segmentation type (type), a pattern is formed so as to display predetermined information, and the determined area is made to emit light. The time and temperature display in a digital clock or a thermometer, an operation state display of an audio apparatus, And a panel display of an automobile.

As the illumination device, there are, for example, an illumination device such as an indoor illumination, a backlight of a liquid crystal display device (for example, Japanese Patent Application Publication No. 2003-257621, Japanese Patent Application Publication No. 2003-277741, Japanese Patent Application Laid-Open No. 2004-119211, etc.). The backlight is used mainly for the purpose of improving the visibility of a display device which does not emit light and is used for a liquid crystal display device, a clock, an audio device, an automobile panel, a display panel, and a marking. Particularly, as a backlight of a liquid crystal display device, in particular, a PC for which thinning is a problem, a backlight using the light emitting device according to the present embodiment is thin, considering that the conventional method is made of a fluorescent lamp or a light guide plate, Lightweight features.

[Example]

&Lt; Synthesis Example of Compound Represented by Formula (1-10) >

First, to a solution prepared by adding 2- (4-bromophenyl) pyridine (15 g) and bis (pinacolato) diboron (19.5 g) to cyclopentyl methyl ether (CPME) (64 ml) , Palladium acetate (Pd (OAc) ₂ ) (0.4 g), triphenylphosphine (PPh ₃ ) (1.5 g) and potassium acetate (AcOK) (18.9 g) were added with stirring at room temperature. Thereafter, the reaction solution was stirred at reflux temperature for 2 hours, cooled to room temperature, and added with aqueous solution of ethylenediaminetetraacetic acid (EDTA) (35 ml) and toluene (500 ml). The organic material from which the salt was removed by washing with water was purified by activated carbon column chromatography (toluene). Thus, 2- (4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl) pyridine (11.2 g) was obtained.

Next, a mixture of 2- (4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl) pyridine (6.9 g) (IPA) solution (3: 1 by volume ratio) containing 2-phenyl-7H-benzo [c] carbazole-5,9-diyl bis (trifluoromethanesulfonate) under the 37 ml), a nitrogen atmosphere, was added with stirring palladium acetate (0.1 g), triphenylphosphine (0.3 g) and tripotassium phosphate _{(K 3 PO 4) (9.4} g) at room temperature. Thereafter, the reaction solution was stirred at reflux temperature for 5 hours, cooled to room temperature, and added with aqueous solution of ethylenediaminetetraacetic acid (EDTA) (50 ml) and toluene (500 ml). The organic material from which the salt was removed by washing with water was purified by an activated carbon column chromatography (toluene / ethyl acetate = 10/1 (volume ratio)) to obtain a compound represented by the formula (1-10) (4- (pyridin-2-yl) phenyl) -7H-benzo [c] carbazole (1.2 g).

(100)

The structure of the obtained compound was confirmed by NMR measurement.

^{1 H-NMR (500 MHz,} CDCl 3): δ = 8.97 (d, 1H), 8.74 (m, 3H), 8.11 (m, 5H), 7.76 (m, 9H), 7.54 (m, 6H), 7.47 (m, 2 H), 7.45 (m, 1 H), 7.35-7.23 (m, 2 H).

&Lt; Synthesis Example of Compound Represented by Formula (1-4) >

First, 5-phenyl-7H-benzo [c] carbazole-5,9-diylbis (trifluoromethanesulfonate) (5.9 g) and bis (pinacolato) diboron were added to cyclopentyl methyl ether Dichloropalladium (II) (0.41 g) and potassium acetate (5.9 g) (1,1'-bis (diphenylphosphino) ferrocene) were stirred at room temperature in a nitrogen atmosphere, Respectively. Thereafter, after stirring at reflux temperature for 4 hours, the reaction solution was cooled to room temperature, water and ethyl acetate were added, and washing operation was carried out. Subsequently, methanol was added, and the mixture was washed by heating and refluxing with stirring. Thus, 7-phenyl-7H-benzo [c] carbazole-5,9-diboronic acid ester (5.3 g) was obtained.

Then, 7-phenyl-7H-benzo [c] carbazole-5,9-diboronic acid ester (prepared as described above) (50 ml) was added to pseudo cumene (1,2,4-trimethylbenzene) (Dibenzylideneacetone) palladium (0) (Pd (dba) ₂ ) (0.6) in a nitrogen atmosphere was added to a solution of 5-bromo-2,2'-bipyridine g), tricyclohexylphosphine (PCy ₃ ) (0.6 g) and tripotassium phosphate (K ₃ PO ₄ ) (9.4 g) were added with stirring at room temperature. Thereafter, after stirring at 150 ° C for 5 hours, the reaction solution was cooled to room temperature, and an aqueous solution of ethylenediaminetetraacetic acid (EDTA) and ethyl acetate were added, and washing with water was carried out. The organic material from which the salt was removed by washing with water was treated with a silica gel short column (ethyl acetate), and then purified by activated alumina column chromatography (toluene / ethyl acetate = 9/1 (volume ratio)). Further, reprecipitation was performed by adding heptane to the toluene solution to obtain a 5,9-di ([2,2'-bipyridine] -5-yl) -7-phenyl- 7H-benzo [c] carbazole (2.5 g).

(101)

The structure of the obtained compound was confirmed by NMR measurement.

^{1 H-NMR (500 MHz,} CDCl 3): δ = 9.02 (m, 1H), 8.98 (d, 1H), 8.86 (m, 1H), 8.80 (d, 1H), 8.75 (m, 2H), 8.55 (d, IH), 8.45-8.53 (m, 3H), 8.13 (dd, IH), 8.00-8.08 (m, 2H), 7.75-7.89 , 2H), 7.51 (t, 1H), 7.30-7.37 (m, 2H).

<Synthesis Example of Compound Represented by Formula (1-744)> [

To a solution of 7-phenyl-7H-benzo [c] carbazole-5,9-diboronic acid ester (4.9 g) and 4- (3-bromo Mo phenyl) pyridine (4.6 g, under a nitrogen atmosphere, triphenylphosphine palladium catalyst (Pd (PPh ₃ at a part solution for)) ₄₎ (0.5 g) and tripotassium phosphate _{(K 3 PO 4) (12} g ) Was added with stirring at room temperature. Thereafter, after stirring at 160 DEG C for 12 hours, the reaction solution was cooled to room temperature, and an aqueous solution of ethylenediaminetetraacetic acid (EDTA) and ethyl acetate were added, followed by washing with water. The organic substance from which the salt was removed by washing with water was purified by activated alumina column chromatography (toluene / ethyl acetate = 4/6 (volume ratio)). Recrystallization from toluene was conducted to obtain the compound represented by formula (1-744) Phenyl-5,9-bis (3- (pyridin-4-yl) phenyl) 7H-benzo [c] carbazole (3.5 g).

&Lt; EMI ID =

The structure of the obtained compound was confirmed by NMR measurement.

¹ H-NMR (500 MHz, CDCl ₃ ):? = 8.89 (d, IH), 8.77 (d, IH), 8.69 (m, 4H), 8.01 (m, 2H), 7.69-7.77 (m, 4H), 7.50-7.67 (m, 14H), 7.47 (t, 1H).

&Lt; Synthesis Example of Compound Represented by Formula (1-5)

Phenyl-7H-benzo [c] carbazole-5,9-diboronic acid ester (5.0 g) and 5-bromo-2 , 3'-bipyridine (5.0 g) in one portion and the solution was added while under a nitrogen _{atmosphere, Pd (PPh 3) 4 (} 0.5 g) and stirred at room temperature tricalcium phosphate potassium (12 g). Thereafter, the mixture was stirred at 150 DEG C for 20 hours, the reaction solution was cooled to room temperature, and an aqueous solution of ethylenediaminetetraacetic acid (EDTA) was added thereto, and a solid in the liquid was collected by suction filtration. Then, it was purified by activated alumina column chromatography (eluent: toluene / ethyl acetate mixed solvent). At this time, with reference to the method described in "Introduction to Organic Chemistry Experiment (1) -Material Handling Method and Separation and Refinement Method", Kagaku Dojin Publishing Co., Ltd., page 94, the ratio of ethyl acetate in the developing solution was gradually increased to elute the target substance . Recrystallization from chlorobenzene gave 5,9-di ([2,3'-bipyridine] -5-yl) -7-phenyl-7H-benzo [c ] Carbazole (1.9 g).

&Lt; EMI ID =

The structure of the obtained compound was confirmed by NMR measurement.

^{1 H-NMR (500 MHz,} CDCl 3): δ = 9.26 (m, 2H), 9.07 (m, 1H), 8.99 (d, 1H), 8.91 (m, 1H), 8.80 (d, 1H), 8.69 (m, 2H), 8.40 (m, 2H), 8.10 (dd, IH), 8.03 (d, IH), 7.99 m, 2H), 7.66 (m, 4H), 7.50-7.60 (m, 3H), 7.45 (m, 2H).

&Lt; Synthesis Example of Compound Represented by Formula (1-20) >

Phenyl-7H-benzo [c] carbazole-5,9-diboronic acid ester (5.1 g) and 6-bromo-2 , the addition of a 3'-bipyridine (4.6 g) solution was added while under a nitrogen _{atmosphere, Pd (PPh 3) 4 (} 0.5 g) and stirred at room temperature tricalcium phosphate potassium (12 g). Thereafter, the mixture was stirred at 120 DEG C for 5 hours, and then the reaction solution was cooled to room temperature, methanol was added, and a solid in the liquid was collected by suction filtration. This solid was washed with aqueous solution of ethylenediaminetetraacetic acid (EDTA), followed by water and methanol. Recrystallization from chlorobenzene gave 5,9-di ([2,3'-bipyridine] -6-yl) -7-phenyl-7H-benzo [c ] Carbazole (4.5 g).

&Lt; EMI ID =

The structure of the obtained compound was confirmed by NMR measurement.

^{1 H-NMR (500 MHz,} CDCl 3): δ = 9.34 (m, 1H), 9.29 (m, 1H), 9.00 (d, 1H), 8.80 (d, 1H), 8.66 (m, 2H), 8.40 1H), 7.65-7.72 (m, 5H), 7.61 (m, 2H) , 1H), 7.49-7.58 (m, 2H), 7.37-7.45 (m, 2H).

&Lt; Synthesis Example of Compound Represented by Formula (1-24) >

Phenyl-7H-benzo [c] carbazole-5,9-diboronic acid ester (5.0 g) and 5-bromo-3 4,4'-bipyridine (5.0 g) in one portion and the solution was added while under a nitrogen _{atmosphere, Pd (PPh 3) 4 (} 1.2 g) and stirred at room temperature tricalcium phosphate potassium (11.7 g). Thereafter, after stirring at reflux temperature for 16 hours, the reaction solution was cooled to room temperature, and an aqueous solution of ethylenediaminetetraacetic acid (EDTA) and toluene were added to separate the solution. The solvent was distilled off under reduced pressure and then purified by silica gel column chromatography (eluent: toluene / ethyl acetate mixed solvent) to obtain 5,9-di ([3,4 ' -Bipyridin-5-yl) -7-phenyl-7H-benzo [c] carbazole (1.0 g). At this time, the ratio of ethyl acetate in the developing solution was gradually increased to elute the target product.

&Lt; EMI ID =

The structure of the obtained compound was confirmed by NMR measurement.

^{1 H-NMR (500 MHz,} CDCl 3): δ = 8.99 (m, 3H), 8.86 (m, 2H), 8.82 (d, 1H), 8.75 (m, 4H), 8.16 (m, 1H), 8.09 (m, 1H), 7.95 (d, 1H), 7.85 (t, 1H), 7.75 (dd, 1H), 7.63-7.72 (m, 5H), 7.51-7.60 (m, 7H).

&Lt; Synthesis Example of Compound Represented by Formula (1-634) >

Step 1: (4-Methoxy-1-yl) boronic acid (43.1 g), 1,4- dibromo-2-nitrobenzene (25.0 g), tri potassium phosphate (182 g), Pd (PPh 3 ) ₄ (2.5 g), pseudocumene (1,2,4-trimethylbenzene) (1000 ml), tert-butyl alcohol (200 ml) and water (40 ml) Lt; / RTI &gt; for 2 hours. The reaction solution was cooled to room temperature, water and toluene were added thereto to separate the liquid, and then the solvent was distilled off under reduced pressure to obtain 4,4 '- (2-nitro-1,4-phenylene) bis (1-methoxynaphthalene ) (32.5 g). This preparation was used in the next step without purification.

Step 2: A flask containing 4,4 '- (2-nitro-1,4-phenylene) bis (1-methoxynaphthalene) (27.7 g) and triethyl phosphite (64 ml) Lt; / RTI &gt; The reaction solution was cooled to room temperature, methanol was added, and the precipitated solid was collected by suction filtration. The solid was further washed with methanol to obtain 5-methoxy-9- (4-methoxynaphthalen-1-yl) -7H-benzo [c] carbazole (25.0 g).

Step 3: 25.0 g of 5-methoxy-9- (4-methoxynaphthalen- 1 -yl) -7H-benzo [c] carbazole, bromobenzene (11.7 g), bis (dibenzylideneacetone) Palladium (0) (1.8 g), [1,1'-biphenyl] -2-yldi-tert-butylphosphine (2.2 g), potassium carbonate (25.7 g) and shudokumen Trimethylbenzene) (250 ml) was stirred at 155 占 폚 for 4 hours. The reaction solution was cooled to room temperature, water and toluene were added thereto to separate the layers, and then the solvent was distilled off under reduced pressure. The resulting solid was further washed with methanol to obtain 5-methoxy-9- (4-methoxynaphthalen-1-yl) -7-phenyl-7H-benzo [c] carbazole (23.0 g).

Step 4: A flask containing 5-methoxy-9- (4-methoxynaphthalen-l-yl) -7-phenyl-7H-benzo [c] carbazole (23.0 g) and pyridine hydrochloride Followed by stirring at 200 DEG C for 1 hour. The reaction solution was cooled to room temperature, added with water and stirred, and then an insoluble solid was collected by suction filtration. The solid was further washed with water to obtain 9- (4-hydroxynaphthalen-1-yl) -7-phenyl-7H-benzo [c] carbazol-5-ol (22.0 g).

Step 5: A flask containing 9- (4-hydroxynaphthalen-1-yl) -7-phenyl-7H-benzo [c ]carbazol-5-ol (22.0 g) and pyridine (250 ml) Ice bath), and trifluoromethanesulfonic anhydride (50.2 g) was added dropwise. After completion of dropwise addition, the mixture was stirred at room temperature for 1 hour to complete the reaction. Thereafter, toluene and water were added to separate the layers, and the organic layer was washed with 1 N hydrochloric acid and then with sodium hydrogencarbonate. The solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography (heptane / toluene = 9/1 (volume ratio)) and the solvent was distilled off under reduced pressure. The obtained solid was washed with heptane to obtain 4- 7 - (((trifluoromethyl) sulfonyl) oxy) -7H-benzo [c] carbazol-9-yl) naphthalen-1-yl trifluoromethanesulfonate (23.1 g).

&Lt; EMI ID =

Benzo [c] carbazol-9-yl) naphthalene-l- (2-fluorophenyl) yl methanesulfonate (11.5 g) in trifluoroacetic acid, and 4-pyridineboronic acid (4.9 g), tri potassium phosphate (13.7 g), Pd (PPh 3) 4 (2.8 g), the shoe Tokuyama men (1,2,4 -Trimethylbenzene) (100 ml), tert-butyl alcohol (10 ml) and water (10 ml) was stirred at reflux temperature for 4 hours. The reaction solution was cooled to room temperature, and toluene and water were added thereto to separate the layers. The solvent was distilled off under reduced pressure, and the resulting solid was washed with methanol, then dissolved in chlorobenzene by heating, and subjected to hot filtration. The solvent was distilled off under reduced pressure, and then methanol was added to effect reprecipitation. The resulting solid was recrystallized from nitrobenzene to give 7-phenyl-5- (pyridin-4-yl) -9- (4- (pyridin-4-yl) naphthalene- -Yl) -7H-benzo [c] carbazole (2.9 g).

&Lt; EMI ID =

The structure of the obtained compound was confirmed by NMR measurement.

^{1 H-NMR (500 MHz,} CDCl 3): δ = 9.03 (d, 1H), 8.80 (d, 1H), 8.76 (m, 4H), 8.10 (m, 1H), 8.00 (d, 1H), 7.92 (m, 1H), 7.82 (t, 1H), 7.60-7.68 (m, 7H), 7.47-7.54 (m, 10H).

&Lt; Synthesis Example of Compound Represented by Formula (1-743)

Dichloropalladium (II) was added to a solution of 6.0 g of 3- (3-bromophenyl) pyridine, 7.8 g of bis (pinacolato) diboron and 1,1'-bis (diphenylphosphino) (0.6 g), potassium acetate (AcOK) (7.6 g) and cyclopentyl methyl ether (CPME) (52 ml) was stirred at reflux temperature for 3 hours. The reaction solution was cooled to room temperature, and an aqueous solution of ethylenediaminetetraacetic acid (EDTA) and toluene were added thereto, followed by washing with water. The solvent was distilled off under reduced pressure, and the resulting solid was purified by activated carbon column chromatography (toluene) to obtain 3- (3- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan- Yl) phenyl) pyridine (6.0 g).

Then, 4.1 g of 3- (3- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl) pyridine -phenyl -7H- benzo [c] carbazole-diyl -5,9- bis (methanesulfonate trifluoroacetate) (3.8 g), tripotassium phosphate (2.7 g), Pd (PPh 3) 4 (0.2 g), A flask containing shudokumen (1,2,4-trimethylbenzene) (13 ml), isopropyl alcohol (2.6 ml) and water (0.5 ml) was stirred at reflux temperature for 6 hours under a nitrogen atmosphere. The reaction solution was cooled to room temperature, and an aqueous solution of ethylenediaminetetraacetic acid (EDTA) and toluene were added to separate the layers. The solvent was distilled off under reduced pressure, and the resulting solid was purified by alumina column chromatography (eluent: toluene / ethyl acetate mixed solvent). At this time, the ratio of ethyl acetate in the developing solution was gradually increased to elute the target product. Thereafter, recrystallization was performed from chlorobenzene to obtain 7-phenyl-5,9-bis (3- (pyridin-3-yl) phenyl) -7H-benzo [c] (0.7 g).

(108)

The structure of the obtained compound was confirmed by NMR measurement.

^{1 H-NMR (500 MHz,} CDCl 3): δ = 8.98 (d, 1H), 8.92 (d, 2H), 8.76 (d, 1H), 8.62 (m, 2H), 8.05 (d, 1H), 7.93 (m, 2H), 7.87 (m, 1H), 7.45-7.81 (m, 17H), 7.38 (t, 2H).

&Lt; Synthesis Example of Compound Represented by Formula (1-8710) >

Step 1: Under nitrogen atmosphere, 38.6 g of 5,9-dimethoxy-7H-benzo [c] carbazole, 38.8 g of 1-fluoronaphthalene, 90.6 g of cesium carbonate, and dimethylsulfoxide (DMSO) ml) was heated and stirred at 145 占 폚 for 4 hours. After the reaction solution was cooled to room temperature, the salt was removed by suction filtration, and DMSO was distilled off under reduced pressure. The obtained solid was washed with methanol and then purified by silica gel column chromatography (eluent: heptane / toluene = 1/1 (volume ratio)) to obtain 5,9-dimethoxy-7- (naphthalen- -Benzo [c] &lt; / RTI &gt; carbazole (32.5 g).

Step 2: Under nitrogen atmosphere, 5,9-dimethoxy-7- (naphthalen-1-yl) -7H-benzo [c] carbazole (42.5 g), pyridine hydrochloride (NMP) (43 ml) was heated and stirred at 200 占 폚 for 1.5 hours. The reaction solution was cooled to room temperature, and water and ethyl acetate were added to separate the layers. The solvent was distilled off under reduced pressure and then purified by silica gel short column to obtain 7- (naphthalen-1-yl) -7H-benzo [c] carbazole-5,9-diol (45 g).

Step 3:

The flask containing 7- (naphthalen-1-yl) -7H-benzo [c] carbazole-5,9-diol (45 g) and pyridine (130 ml) was cooled in an ice bath under a nitrogen atmosphere, (71.1 g) was added dropwise thereto. After completion of the dropwise addition, the mixture was stirred at room temperature for 16 hours to terminate the reaction. Water was added, and the solid in the liquid was collected by suction filtration. The resulting solid was washed with methanol and then purified by silica gel column chromatography (eluent: toluene) to obtain 7- (naphthalen-1-yl) -7H-benzo [c] Trifluoromethanesulfonate) (63.2 g) was obtained.

(109)

(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl) pyridine (8.4 g) obtained in the above manner and 7 (Trifluoromethanesulfonate) (6.4 g), tripotassium phosphate (8.5 g), Pd (PPh ₃ ), and triphenylphosphine ₄ (1.1 g), the shoe Tokuyama men (1,2,4-trimethylbenzene) (75 ml), tert- butyl alcohol (5 ml) and water (1 ml) flask containing the mixture was stirred at reflux 10 hours . The reaction solution was cooled to room temperature, and an aqueous solution of ethylenediaminetetraacetic acid (EDTA) and toluene were added to separate the layers. The solvent was distilled off under reduced pressure, and the obtained solid was dissolved in chlorobenzene by heating, and filtration was carried out while heating. The solvent was distilled off under reduced pressure, and the obtained solid was recrystallized from chlorobenzene to obtain 7- (naphthalen-1-yl) -5,9-bis (4- (pyridin- Yl) phenyl) -7H-benzo [c] carbazole (1.8 g).

(110)

The structure of the obtained compound was confirmed by NMR measurement.

^{1 H-NMR (500 MHz,} CDCl 3): δ = 9.02 (d, 1H), 8.80 (d, 1H), 8.70 (m, 2H), 8.09 (m, 2H), 8.03 (m, 5H), 7.69 2H), 7.23 (m, 2H), 7.18 (s, 1H), 7.8-7.83 (m, ).

&Lt; Synthesis Example of Compound Represented by Formula (1-8711) >

First, 6.4 g of 7- (naphthalen-1-yl) -7H-benzo [c] carbazole-5,9-diyl bis (trifluoromethanesulfonate), bis (pinacolato) diboron flask containing 0.32 g of dichloropalladium (II), 5.9 g of potassium acetate and 50 ml of cyclopentyl methyl ether (CPME) in the same manner as in Example 1, Were stirred in a nitrogen atmosphere at a reflux temperature for 4 hours. The reaction solution was cooled to room temperature, water and ethyl acetate were added to the reaction mixture, washed with water, and then methanol was added, followed by heating and refluxing and agitation. Thus, 7- (naphthalen-1-yl) -7H-benzo [c] carbazole-5,9-diboronic acid ester (5.7 g) was obtained.

Next, a mixture of 7- (naphthalen-1-yl) -7H-benzo [c] carbazole-5,9-diboronic acid ester (5.2 g) and 3- (4- bromophenyl) pyridine , Triphenyl phosphate (9.2 g), Pd (PPh ₃ ) ₄ (0.50 g), 1,2,4-trimethylbenzene The flask containing water (1.4 ml) was stirred in a nitrogen atmosphere at a reflux temperature for 4 hours. The reaction solution was cooled to room temperature, an aqueous solution of ethylenediaminetetraacetic acid (EDTA) was added, and a solid was obtained by suction filtration. Subsequently, after washing with methanol, chlorobenzene was added and heated, and unnecessary matter was filtered by suction filtration. Thereafter, the solvent was distilled off under reduced pressure, and the residue was recrystallized from chlorobenzene to obtain 7- (naphthalene-1-yl) -5,9-bis (4- (pyridin- Yl) phenyl) -7H-benzo [c] carbazole (4.4 g).

(111)

The structure of the obtained compound was confirmed by NMR measurement.

^{1 H-NMR (500 MHz,} CDCl 3): δ = 9.03 (d, 1H), 8.87 (m, 2H), 8.81 (d, 1H), 8.09 (t, 2H), 8.03 (d, 1H), 7.67 -7.93 (m, 9H) 7.46-7.65 (m, 9H), 7.27-7.39 (m, 5H), 7.17 (s, 1H).

&Lt; Synthesis Example of Compound Represented by Formula (1-8712) >

Benzo [c] carbazole-5,9-diboronic acid ester (4.8 g), 4- (4-bromophenyl) pyridine (4.5 g), tripotassium phosphate (Pd) (PPh ₃ ) ₄ (0.46 g), 1,2,4-trimethylbenzene (predominant) (30 ml), tert-butyl alcohol (6 ml) The flask was stirred under a nitrogen atmosphere at a reflux temperature for 2 hours. The reaction solution was cooled to room temperature, an aqueous solution of ethylenediaminetetraacetic acid (EDTA) was added, and a solid was obtained by suction filtration. Subsequently, after washing with methanol, chlorobenzene was added and heated, and unnecessary matter was filtered by suction filtration. Thereafter, the solvent was distilled off under reduced pressure, and the residue was recrystallized from chlorobenzene to obtain 7- (naphthalene-1-yl) -5,9-bis (4- (pyridin- Yl) phenyl) -7H-benzo [c] carbazole (3.5 g) was obtained.

(112)

The structure of the obtained compound was confirmed by NMR measurement.

^{1 H-NMR (500 MHz,} CDCl 3): δ = 9.03 (d, 1H), 8.81 (d, 1H), 8.66 (m, 4H), 8.11 (d, 1H), 8.05 (t, 2H), 7.83 (t, 1H), 7.65-7.80 (m, 9H) 7.49-7.59 (m, 8H), 7.36 (m, 2H), 7.29 (m,

&Lt; Synthesis Example of Compound Represented by Formula (1-1) >

A solution of 7-phenyl-7H-benzo [c] carbazole-5,9-diyl bis (trifluoromethanesulfonate) (7.3 g), 2-pyridyl bromide 0.5 M- PPh ₃ ) ₄ (0.96 g) was stirred in a nitrogen atmosphere at a reflux temperature for 2 hours. The reaction solution was cooled to room temperature, and an aqueous solution of ethylenediaminetetraacetic acid (EDTA) and ethyl acetate were added to separate the layers. Further, the organic layer was washed with saturated brine, and the solvent was distilled off under reduced pressure. Subsequently, purification was carried out by silica gel chromatography (developing solution: ethyl acetate / toluene = 1/20 (volume ratio)) and recrystallization was conducted from toluene to obtain a compound represented by the formula (1-1) 9-bis (pyridin-2-yl) -7H-benzo [c] carbazole (1.2 g) was obtained.

(113)

The structure of the obtained compound was confirmed by NMR measurement.

^{1 H-NMR (500 MHz,} CDCl 3): δ = 8.97 (d, 1H), 8.79 (m, 1H), 8.76 (d, 1H), 8.70 (m, 1H), 8.15 (m, 2H), 8.08 (d, 1H), 7.73-7.84 (m, 4H), 7.58-7.68 (m, 6H), 7.46-7.55 (m, 2H), 7.33 (m,

&Lt; Synthesis Example of Compound Represented by Formula (1-2) >

Pyridine boronic acid (2.5 g), sodium carbonate (4.0 g), Pd (4-fluorophenyl) borane (PPh ₃ ) ₄ (0.5 g), toluene (40 ml), ethanol (12 ml) and water (12 ml) was stirred at a reflux temperature for 2 hours under a nitrogen atmosphere. The reaction solution was cooled to room temperature, and saturated brine and ethyl acetate were added to separate the layers. The solvent was distilled off under reduced pressure and the obtained solid was purified by silica gel chromatography (developing solution: toluene / ethyl acetate = 1/1 (volume ratio)) and then recrystallized from heptane and recrystallized from ethanol, Phenyl-5,9-bis (pyridin-3-yl) -7H-benzo [c] carbazole (2.1 g).

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The structure of the obtained compound was confirmed by NMR measurement.

^{1 H-NMR (500 MHz,} CDCl 3): δ = 9.06 (m, 2H), 8.77 (m, 2H), 8.69 (m, 1H), 8.59 (m, 1H), 7.97 (m, 1H), 7.93 (d, IH), 7.86 (m, IH), 7.81 (t, IH), 7.61-7. 71 (m, 6H), 7.56 (m, 1H).

<Synthesis Example of Compound Represented by Formula (1-541)> [

First, a solution of 7-phenyl-7H-benzo [c] carbazole-5,9-diylbis (trifluoromethanesulfonate) (14.7 g), a 0.5 M solution of 2- Methylpyridyl bromide in 50 ml of THF, of _{Pd (PPh 3) 4 (0.87} g) and the flask containing THF (50 ml), and the mixture was stirred for 3 hours at reflux temperature under a nitrogen atmosphere. The reaction solution was cooled to room temperature, and an aqueous solution of ethylenediaminetetraacetic acid (EDTA) and ethyl acetate were added to separate the layers. The organic layer was washed with saturated brine, and the solvent was distilled off under reduced pressure. The residue was purified by silica gel chromatography (eluent: ethyl acetate / toluene = 1/100 (volume ratio)) and recrystallized from ethanol to obtain 7-phenyl-9- (pyridin- c] carbazol-5-yl trifluoromethanesulfonate (5.1 g).

(2.8 g), (4- (pyridin-2-yl) -7H-benzo [c] (1.3 g), sodium carbonate (1.2 g), Pd (PPh ₃ ) ₄ (0.31 g), toluene (12 ml), ethanol (4 ml) and water (4 ml) Was stirred in a nitrogen atmosphere at a reflux temperature for 1.5 hours. The reaction solution was cooled to room temperature, and an aqueous solution of ethylenediaminetetraacetic acid (EDTA) and ethyl acetate were added to separate the layers. Further, the organic layer was washed with saturated brine, and the solvent was distilled off under reduced pressure. The resulting solid was purified by silica gel column chromatography (eluent: toluene / ethyl acetate mixed solvent). At this time, the ratio of ethyl acetate in the developing solution was gradually increased to elute the target product. Thereafter, the solvent was distilled off under reduced pressure, and the obtained solid was washed with ethyl acetate to obtain the compound 7-phenyl-9- (pyridin-2-yl) -5- (4- (pyridine Yl) phenyl) -7H-benzo [c] carbazole (0.4 g).

(115)

The structure of the obtained compound was confirmed by NMR measurement.

¹ H-NMR (500 MHz, CDCl ₃ ):? = 8.97 (d, IH), 8.80 (m, IH), 8.75 (d, 2H), 7.73-7.83 (m, 8H), 7.63-7.70 (m, 5H), 7.61 ), 7.23 (m, 1 H).

&Lt; Synthesis Example of Compound Represented by Formula (1-564)

Benzo [c] carbazol-9-yl) naphthalen-1-yl trifluoromethanesulfo (trifluoromethyl) sulfonyl) oxy) carbonate (6.0 g), 2-pyridyl was stirred for 3 hours at 0.5 mol / lTHF solution (50 ml) and Pd (PPh ₃₎ a reflux flask containing ₄ (0.25 g) temperature of zinc bromide. The reaction solution was cooled to room temperature, and an aqueous solution of ethylenediaminetetraacetic acid (EDTA) and ethyl acetate were added to separate the layers. The solvent was distilled off under reduced pressure, and the resulting solid was purified by activated alumina column chromatography (eluent: toluene / ethyl acetate mixed solvent) and then purified by silica gel column chromatography (eluent: toluene / ethyl acetate mixed solvent) (7-phenyl-5- (pyridin-2-yl) -9- (4-pyridin-2-yl) naphthalen- 1 -yl) -7H-benzo [c ] Carbazole (0.4 g). At this time, in both of the above two types of chromatography, the ratio of ethyl acetate in the developing solution was gradually increased to elute the target product.

&Lt; EMI ID =

The structure of the obtained compound was confirmed by NMR measurement.

^{1 H-NMR (500 MHz,} CDCl 3): δ = 9.01 (d, 1H), 8.80 (m, 3H), 8.16 (m, 2H), 8.09 (d, 1H), 7.77-7.86 (d, 3H) , 7.72 (s, 1H), 7.57-7.67 (m, 10H), 7.43-7.53 (m, 4H), 7.35 (m, 2H).

&Lt; Synthesis Example of Compound Represented by Formula (1-575)

First, 7-phenyl-7H-benzo [c] carbazole-5,9-diyl bis (trifluoromethanesulfonate (5.9 g), 3- pyridine boronic acid (1.4 g), sodium carbonate _{Pd (PPh 3) 4 (0.23} g), toluene (21 ml), ethanol (7 ml) and the flask containing the water (7 ml), under a nitrogen atmosphere and stirred for 2 hours at reflux temperature. at room temperature the reaction solution , And an aqueous solution of ethylenediaminetetraacetic acid (EDTA) and ethyl acetate were added to separate the layers. The solvent was distilled off under reduced pressure, and the resulting solid was purified by silica gel column chromatography (eluent: toluene / ethyl acetate mixed solvent) . The solvent was distilled off under reduced pressure, and the obtained solid was washed with methanol, and then recrystallized from ethanol to obtain 7-phenyl- 9- (Pyridin-3-yl) -7H-benzo [c] carbazole Luo to give the methane sulfonate (2.5 g).

Next, 7-phenyl-9- (pyridin-3-yl) -7H-benzo [c] carbazole trifluoromethanesulfonate (1.3 g), (4- ) Phenyl) boronic acid (1.3 g), sodium carbonate (1.2 g), Pd (PPh ₃ ) ₄ (0.31 g), toluene (12 ml), ethanol (4 ml) , And the mixture was stirred at a reflux temperature for 1.5 hours under a nitrogen atmosphere. The reaction solution was cooled to room temperature, and an aqueous solution of ethylenediaminetetraacetic acid (EDTA) and toluene were added to separate the layers. Further, the organic layer was washed with saturated brine, and the solvent was distilled off under reduced pressure. The resulting solid was washed with methanol followed by ethyl acetate and recrystallized from toluene to obtain the compound 7-phenyl-5- (4- (pyridin-2-yl) phenyl) -9- (Pyridin-3-yl) -7H-benzo [c] carbazole (1.1 g).

(117)

The structure of the obtained compound was confirmed by NMR measurement.

^{1 H-NMR (500 MHz,} CDCl 3): δ = 8.98 (d, 1H), 8.79 (m, 1H), 8.71-8.76 (m, 2H), 8.69 (m, 1H), 8.10 (d, 2H) , 7.93 (d, 1H), 7.87 (dt, 1H), 7.75-7.82 (m, 7H), 7.63-7.69 (m, 4H), 7.55 1H), &lt; / RTI &gt; 7.23 (m, 1H).

&Lt; Synthesis Example of Compound Represented by Formula (1-599)

Benzo [c] carbazol-9-yl) naphthalen-1-yl trifluoromethanesulfo (trifluoromethyl) sulfonyl) oxy) (3.6 g), triphenylphosphate (3.6 g), Pd (PPh ₃ ) ₄ (0.25 g), 1,2-dimethoxyethane (18 ml) and water ) Was stirred at reflux temperature for 12 hours. The reaction solution was cooled to room temperature, an aqueous solution of ethylenediaminetetraacetic acid (EDTA) was added, and a solid in the liquid was collected by suction filtration. Subsequently, the residue was purified by activated alumina column chromatography (eluent: toluene / ethyl acetate mixed solvent) to obtain 7-phenyl-5- (pyridin-3-yl) -9- (Pyridin-3-yl) naphthalen-1-yl) -7H-benzo [c] carbazole (1.0 g). At this time, the ratio of ethyl acetate in the developing solution was gradually increased to elute the target product.

(118)

The structure of the obtained compound was confirmed by NMR measurement.

^{1 H-NMR (500 MHz,} CDCl 3): δ = 9.03 (d, 1H), 8.80 (m, 3H), 8.70 (m, 2H), 8.10 (m, 1H), 7.96 (d, 1H), 7.89 (m, 3H), 7.82 (t, 1H), 7.58-7.67 (m, 7H), 7.43-7.54 (m, 8H).

&Lt; Synthesis Example of Compound Represented by Formula (1-742)

7-phenyl-7H-benzo [c] carbazole-5,9-diboronic acid ester (5.0 g) and 2- (3-bromo) the parent phenyl) pyridine solution was added (4.7 g), it was added while under a nitrogen atmosphere, Pd (PPh ₃₎ was stirred for ₄ (3.6 g) and tripotassium phosphate (11.7 g) at room temperature. Thereafter, after stirring for 16 hours at the reflux temperature, the reaction solution was cooled to room temperature, and an aqueous solution of ethylenediaminetetraacetic acid (EDTA) and toluene were added to separate the layers. The solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography (eluent: toluene / ethyl acetate mixed solvent). At this time, the ratio of ethyl acetate in the developing solution was gradually increased to elute the target product. The colored component was removed by an activated carbon column (eluent: toluene) to obtain a compound represented by the formula (1-742), 7-phenyl-5,9-bis (3- (pyridin- -7H-benzo [c] &lt; / RTI &gt; carbazole (0.5 g).

(119)

The structure of the obtained compound was confirmed by NMR measurement.

¹ H-NMR (500 MHz, CDCl ₃ )? = 8.96 (d, 1H), 8.69-8.77 (m, 3H), 8.29 (m, , 8.02 (m, 1 H), 7.97 (m, 1H), 7.71-7.81 (m, 7H), 7.54-7.66 (m, 7H), 7.50 , 2H).

&Lt; Synthesis Example of Compound Represented by Formula (1-335) >

(1.9 g), 7-phenyl-7H-benzo [c] carbazole-5,9-diylbis (trifluoromethanesulfonate) (5.9 g), potassium acetate (0.02 g ), Triphenylphosphine (0.03 g), tripotassium phosphate (K ₃ PO ₄ ) (8.5 g) and THF / isopropyl alcohol (IPA) solution (3: 1 by volume) And the mixture was stirred under a nitrogen atmosphere at a reflux temperature for 0.5 hours. The reaction solution was cooled to room temperature, water and ethyl acetate were added to separate the layers, and then the solvent was distilled off under reduced pressure. The resulting solid was washed with methanol to obtain 9- (naphthalen-2-yl) -7-phenyl-7H-benzo [c] carbazol-5-yl trifluoromethanesulfonate (5.4 g).

Step 2: Synthesis of 9- (naphthalen-2-yl) -7-phenyl-7H-benzo [c] carbazol-5-yl trifluoromethanesulfonate (5.4 g), bis (pinacolato) diboron g), (1,1'-bis (diphenylphosphino) ferrocene) dichloropalladium (II) (0.16 g), potassium acetate (2.9 g) and cyclopentyl methyl ether (30 ml) Lt; / RTI &gt; for 4 hours. The reaction solution was cooled to room temperature, water and ethyl acetate were added to separate the layers, and then the solvent was distilled off under reduced pressure. The resultant solid was washed with methanol to obtain 9- (naphthalen-2-yl) -7-phenyl-5- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan- ) -7H-benzo [c] carbazole (4.9 g).

The resulting 9- (naphthalene-2-yl) -7-phenyl-5- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan- benzo [c] carbazole (4.9 g), 2- (4- bromophenyl) pyridine (2.5 g), Pd (PPh 3) 4 (0.3 g), tripotassium phosphate _{(K 3 PO 4) (12.0} g ) And 1,2,4-trimethylbenzene (shodokumen) (50 ml) were stirred at a reflux temperature. 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, followed by methanol, and further with heating with heptane, and then purified by activated alumina column chromatography (eluent: toluene / ethyl acetate mixed solvent). At this time, with reference to the method described in "Introduction to Organic Chemistry Experiment (1) -Material Handling Method and Separation and Refinement Method", Kagaku Dojin Publishing Co., Ltd., page 94, the ratio of ethyl acetate in the developing solution was gradually increased to elute the target substance . After the solvent was distilled off under reduced pressure, the resulting solid was dissolved in chlorobenzene by heating, and heptane was added to effect re-precipitation to obtain the compound 9- (naphthalene-2-yl) -7-phenyl -5- (4- (pyridin-2-yl) phenyl) -7H-benzo [c] carbazole (3.3 g).

(120)

The structure of the obtained compound was confirmed by NMR measurement.

^{1 H-NMR (500 MHz,} CDCl 3): δ = 8.93 (d, 1H), 8.71 (d, 1H), 8.68 (m, 1H), 8.06 (d, 2H), 8.01 (d, 1H), 7.95 (s, 1H), 7.83-7.93 (m, 3H), 7.70-7.80 (m, 7H), 7.58-7.65 (t, 1 H), 7.2 (m, 1 H).

Other derivative compounds of the present invention can be synthesized by the method according to the above-mentioned synthesis example by suitably changing the compound of the starting material.

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

&Lt; Examples 1 to 3 and Comparative Examples 1 and 2 >

The electroluminescence devices according to Examples 1 to 3 and Comparative Examples 1 and 2 were manufactured and the driving start voltage V in the constant current driving test and the time h for maintaining the luminance of 80% Respectively. Examples and Comparative Examples are described below in detail.

Table 1 shows the material composition of each layer in the electroluminescent device according to Examples 1 to 3 and Comparative Examples 1 and 2 thus manufactured.

[Table 1]

In Table 1, "CuPc" represents copper phthalocyanine, "NPD" represents N, N'-diphenyl-N, N'-dinaphthyl-4,4'-diaminophenyl, (B) is a compound represented by the formula: N ⁵ , N ⁵ , N ⁹ , N ⁹ -7 (2-phenylanthracene-9,10-diyl) di-2, 2 ', 5'- -Bipyridine, the compound (D) is 2-phenyl-9,10-bis [4- (2-pyridyl) phenyl] anthracene and each has the following chemical structure.

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&Lt; Example 1 >

&Lt; Device using Compound (1-10) as an electron transporting layer >

A 26 mm x 28 mm x 0.7 mm glass substrate (manufactured by Optoscience Co., Ltd.) obtained by grinding ITO formed to a thickness of 180 nm to 150 nm by sputtering was used as a transparent support substrate. The transparent support substrate was fixed to a substrate holder of a commercially available vapor deposition apparatus (manufactured by Vacuum Kogyo Co., Ltd.), and molybdenum-containing boats containing CuPc, molybdenum-containing boats containing NPD, molybdenum containing compound (A) A molybdenum booster boat containing a compound (B), a molybdenum booster boat containing a compound represented by Formula (1-10), a molybdenum booster boat containing lithium fluoride, and a tungsten containing aluminum The boats were installed.

The following layers were successively formed on the ITO film of the transparent support substrate. The vacuum tank was evacuated to 5 x 10 &lt; ^-4 &gt; Pa. First, an evaporation boat containing CuPc was heated to form a hole injection layer having a film thickness of 100 nm to form a hole injection layer. Was heated to deposit a film having a thickness of 30 nm to form a hole transporting layer. Next, the evaporation boats containing the compound (A) and the evaporation boats containing the compound (B) were heated at the same time to deposit a film having a film thickness of 35 nm to form a light emitting layer. The deposition rate was controlled so that the weight ratio of compound (A) to compound (B) was approximately 95: 5. Next, an evaporation boat containing a compound represented by the formula (1-10) was heated to deposit a film having a thickness of 15 nm to form an electron transport layer. The deposition rate of each layer was 0.01 to 1 nm / sec.

Thereafter, the deposition boat containing lithium fluoride was heated to deposit at a deposition rate of 0.003-0.1 nm / sec so that the film thickness became 0.5 nm, and then the evaporation boat containing aluminum was heated to a film thickness of 100 nm By evaporation at a deposition rate of 0.01 to 10 nm / sec so as to obtain an organic electroluminescent device.

When a DC voltage was applied to the ITO electrode as a positive electrode and the lithium fluoride / aluminum electrode as a negative electrode, blue light emission with a wavelength of about 455 nm was obtained. Further, a constant current driving test was carried out by the current density for obtaining an initial luminance of 2000 cd / m &lt; ^{2 &} gt ;. The driving test starting voltage was 5.78 V, and the time for maintaining the luminance of 80% (1600 cd / m ² ) or more of the initial luminance was 166 hours.

&Lt; Example 2 >

&Lt; Device using Compound (1-4) as electron transport layer >

An organic EL device was obtained in the same manner as in Example 1 except that the compound represented by Formula (1-10) was changed to the compound represented by Formula (1-4). A constant current driving test was carried out by using a current density to obtain an initial luminance of 2000 cd / m &lt; ² &gt; with the ITO electrode as a positive electrode and the lithium fluoride / aluminum electrode as a negative electrode. The driving test starting voltage was 7.75 V, and the time for maintaining the luminance of 80% or more of the initial luminance was 393 hours.

&Lt; Example 3 >

&Lt; Device using Compound (1-744) as electron transport layer >

An organic EL device was obtained in the same manner as in Example 1 except that the compound represented by the formula (1-10) was changed to the compound represented by the formula (1-744). A constant current driving test was carried out by using a current density to obtain an initial luminance of 2000 cd / m &lt; ² &gt; with the ITO electrode as a positive electrode and the lithium fluoride / aluminum electrode as a negative electrode. The driving test starting voltage was 5.93 V, and the time for maintaining the luminance of 80% or more of the initial luminance was 213 hours.

&Lt; Comparative Example 1 &

An organic EL device was obtained in the same manner as in Example 1 except that the compound represented by the formula (1-10) was changed to the compound (C). A constant current driving test was carried out by using a current density to obtain an initial luminance of 2000 cd / m &lt; ² &gt; with the ITO electrode as a positive electrode and the lithium fluoride / aluminum electrode as a negative electrode. The driving test starting voltage was 4.78 V, and the time for maintaining the luminance of 80% or more of the initial luminance was 39 hours.

&Lt; Comparative Example 2 &

An organic EL device was obtained in the same manner as in Example 1 except that the compound represented by the formula (1-10) was changed to the compound (D). A constant current driving test was carried out by using a current density to obtain an initial luminance of 2000 cd / m &lt; ² &gt; with the ITO electrode as a positive electrode and the lithium fluoride / aluminum electrode as a negative electrode. The driving test starting voltage was 4.74 V, and the time for maintaining the luminance of 80% or more of the initial luminance was 24 hours.

Table 2 summarizes the above results.

[Table 2]

&Lt; Examples 4 to 13 and Comparative Examples 3 and 4 >

The electroluminescence devices according to Examples 4 to 13 and Comparative Examples 3 and 4 were manufactured and the driving start voltage V in the constant current driving test and the time h for maintaining the luminance of 80% Respectively. Examples and Comparative Examples are described below in detail.

Table 3 shows the material composition of each layer in the electroluminescent device according to Examples 4 to 13 and Comparative Examples 3 and 4 thus prepared.

[Table 3]

In Table 3, "HI" refers to N ⁴ , N ^{4 '} -diphenyl -N ⁴ , N ^4' -bis (9-phenyl-9H-carbazol- (4-phenyl-10- (4-phenylnaphthalen-1-yl) anthracene, compound (F) is 9,10- Pyridin] -5-yl) anthracene, and the compound (G) is 2,7-di ([2,4'-bipyridin] -6-yl) -9-phenyl-9H-carbazole. Together with "Liq"

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<Example 4>

&Lt; Device using Compound (1-10) as an electron transporting layer >

A glass substrate of 26 mm x 28 mm x 0.7 mm (manufactured by Optoscience Co., Ltd.), in which ITO formed to a thickness of 180 nm by polishing was polished to 150 nm by sputtering was used as a transparent support substrate. The transparent support substrate was fixed to a substrate holder of a commercially available vapor deposition apparatus (manufactured by Showa Vacuum Co., Ltd.), and molybdenum-containing boats containing HI, molybdenum-containing boats containing NPD, molybdenum containing compound (E) A molybdenum booster boat containing compound (B), a molybdenum booster boat containing compound represented by Formula (1-10), a molybdenum booster boat containing Liq, a molybdenum boat containing magnesium, A silver tungsten boat was installed.

The following layers were successively formed on the ITO film of the transparent support substrate. The vacuum tank was evacuated to 5 x 10 &lt; ^-4 &gt; Pa. First, an evacuation boat containing HI was heated to form a hole injection layer so as to have a film thickness of 40 nm. Subsequently, Was heated to deposit a film having a thickness of 30 nm to form a hole transporting layer. Next, the evaporation boats containing the compound (E) and the evaporation boats containing the compound (B) were simultaneously heated to form a light emitting layer having a film thickness of 35 nm. The deposition rate was controlled so that the weight ratio of compound (E) to compound (B) was approximately 95: 5. Next, an evaporation boat containing a compound represented by the formula (1-10) was heated to deposit a film having a thickness of 15 nm to form an electron transport layer. The deposition rate of each layer was 0.01 to 1 nm / sec.

Thereafter, the evaporation boats containing Liq were heated to deposit at a deposition rate of 0.01 to 0.1 nm / sec so that the film thickness became 1 nm. Subsequently, a boat containing magnesium and a boat containing silver were heated at the same time to deposit a film having a thickness of 100 nm to form a cathode. At this time, an organic electroluminescent device was obtained by controlling the deposition rate so that the ratio of atomic ratio of magnesium and silver was 10: 1, and the deposition rate was 0.1 nm to 10 nm.

When a DC voltage was applied to the ITO electrode as a positive electrode and the magnesium / silver electrode as a negative electrode, blue light emission with a wavelength of about 460 nm was obtained. Further, when the constant current driving test was performed by the current density for obtaining the initial luminance of 2000 cd / m ² , the driving test starting voltage was 5.09 V, and the luminance of 80% (1600 cd / m ² ) or more of the initial luminance was maintained The time was 245 hours.

&Lt; Example 5 >

&Lt; Device using Compound (1-5) as an electron transporting layer >

An organic EL device was obtained in the same manner as in Example 4 except that the compound (1-10) was changed to the compound (1-5). A constant current driving test was carried out by using a current density to obtain an initial luminance of 2000 cd / m &lt; ² &gt; with the ITO electrode as a positive electrode and the magnesium / silver electrode as a negative electrode. The driving test starting voltage was 4.13 V, and the time for maintaining the luminance of 80% or more of the initial luminance was 246 hours.

&Lt; Example 6 >

&Lt; Device using Compound (1-634) as electron transport layer >

An organic EL device was obtained in the same manner as in Example 4 except that the compound (1-10) was changed to the compound (1-634). A constant current driving test was carried out by using a current density to obtain an initial luminance of 2000 cd / m &lt; ² &gt; with the ITO electrode as a positive electrode and the magnesium / silver electrode as a negative electrode. The driving test starting voltage was 5.41 V, and the time for maintaining the luminance of 80% or more of the initial luminance was 400 hours.

&Lt; Example 7 >

&Lt; Device using Compound (1-744) as electron transport layer >

An organic EL device was obtained in the same manner as in Example 4 except that the compound (1-10) was changed to the compound (1-744). A constant current driving test was carried out by using a current density to obtain an initial luminance of 2000 cd / m &lt; ² &gt; with the ITO electrode as a positive electrode and the magnesium / silver electrode as a negative electrode. The driving test starting voltage was 4.96 V, and the time for maintaining the luminance of 80% or more of the initial luminance was 231 hours.

&Lt; Example 8 >

&Lt; Device using Compound (1-20) as electron transport layer >

An organic EL device was obtained in the same manner as in Example 4 except that the compound (1-10) was changed to the compound (1-20). A constant current driving test was carried out by using a current density to obtain an initial luminance of 2000 cd / m &lt; ² &gt; with the ITO electrode as a positive electrode and the magnesium / silver electrode as a negative electrode. The driving test starting voltage was 3.54 V, and the time for maintaining the luminance of 80% or more of the initial luminance was 132 hours.

&Lt; Example 9 >

&Lt; Device using Compound (1-24) as electron transport layer >

An organic EL device was obtained in the same manner as in Example 4 except that the compound (1-10) was changed to the compound (1-24). A constant current driving test was carried out by using a current density to obtain an initial luminance of 2000 cd / m &lt; ² &gt; with the ITO electrode as a positive electrode and the magnesium / silver electrode as a negative electrode. The driving test starting voltage was 5.26 V, and the time for maintaining the luminance of 80% or more of the initial luminance was 265 hours.

&Lt; Example 10 >

&Lt; Device using Compound (1-743) as electron transport layer >

An organic EL device was obtained in the same manner as in Example 4 except that the compound (1-10) was changed to the compound (1-743). A constant current driving test was carried out by using a current density to obtain an initial luminance of 2000 cd / m &lt; ² &gt; with the ITO electrode as a positive electrode and the magnesium / silver electrode as a negative electrode. The driving test starting voltage was 4.61 V, and the time for maintaining the luminance of 80% or more of the initial luminance was 315 hours.

&Lt; Example 11 >

&Lt; Device using Compound (1-8710) as electron transport layer >

An organic EL device was obtained in the same manner as in Example 4 except that the compound (1-10) was changed to the compound (1-8710). A constant current driving test was carried out by using a current density to obtain an initial luminance of 2000 cd / m &lt; ² &gt; with the ITO electrode as a positive electrode and the magnesium / silver electrode as a negative electrode. The driving test starting voltage was 4.83 V, and the time for maintaining the luminance of 80% or more of the initial luminance was 430 hours.

&Lt; Example 12 >

&Lt; Device using Compound (1-8711) as electron transport layer >

An organic EL device was obtained in the same manner as in Example 4 except that the compound (1-10) was changed to the compound (1-8711). A constant current driving test was carried out by using a current density to obtain an initial luminance of 2000 cd / m &lt; ² &gt; with the ITO electrode as a positive electrode and the magnesium / silver electrode as a negative electrode. The driving test starting voltage was 3.85 V, and the time for maintaining the luminance of 80% or more of the initial luminance was 229 hours.

&Lt; Example 13 >

&Lt; Device using Compound (1-8712) as electron transport layer >

An organic EL device was obtained in the same manner as in Example 4 except that the compound (1-10) was changed to the compound (1-8712). A constant current driving test was carried out by using a current density to obtain an initial luminance of 2000 cd / m &lt; ² &gt; with the ITO electrode as a positive electrode and the magnesium / silver electrode as a negative electrode. The driving test starting voltage was 4.00 V, and the time for maintaining the luminance of 80% or more of the initial luminance was 240 hours.

&Lt; Comparative Example 3 &

An organic EL device was obtained in the same manner as in Example 4 except that the compound (1-10) was changed to the compound (F). A constant current driving test was carried out by using a current density to obtain an initial luminance of 2000 cd / m &lt; ² &gt; with the ITO electrode as a positive electrode and the magnesium / silver electrode as a negative electrode. As a result, the driving test starting voltage was 3.86 V, and the time for maintaining the luminance of 80% or more of the initial luminance was 196 hours.

&Lt; Comparative Example 4 &

An organic EL device was obtained in the same manner as in Example 4 except that the compound (1-10) was changed to the compound (G). A constant current driving test was carried out by using a current density to obtain an initial luminance of 2000 cd / m &lt; ² &gt; with the ITO electrode as a positive electrode and the magnesium / silver electrode as a negative electrode. As a result, the driving test starting voltage was 3.87 V, and the time for maintaining the luminance of 80% or more of the initial luminance was 120 hours.

Table 4 summarizes the above results.

[Table 4]

&Lt; Reference Example 1 and Comparative Example 5 >

An electroluminescent device according to Reference Example 1 and Comparative Example 5 was manufactured and the driving start voltage (V) in the constant current driving test and the time (h) for maintaining the luminance of 80% or more of the initial luminance were measured. Hereinafter, Reference Examples and Comparative Examples will be described in detail.

Table 5 shows the material composition of each layer in the electroluminescent device according to Reference Example 1 and Comparative Example 5 manufactured.

[Table 5]

In Table 5, "CuPc" denotes copper phthalocyanine, "NPD" denotes N, N'-diphenyl-N, N'-dinaphthyl-4,4'-diaminophenyl, (B) is N5, N5, N9, N9-7,7-hexaphenyl-7H-tetrakis (2-phenylanthracene-9,10-diyl) di-2,2'-bipyridine, and the compound (C) . &Lt; / RTI &gt;

(123)

&Lt; Reference Example 1 &

&Lt; Device using Compound (1-335) as electron transport layer >

A 26 mm x 28 mm x 0.7 mm glass substrate (manufactured by Optoscience Co., Ltd.) obtained by grinding ITO formed to a thickness of 180 nm to 150 nm by sputtering was used as a transparent support substrate. The transparent support substrate was fixed to a substrate holder of a commercially available vapor deposition apparatus (manufactured by Vacuum Kagaku Co., Ltd.), and molybdenum-containing boats containing CuPc, molybdenum-containing boats containing NPD, molybdenum containing compound (A) A molybdenum booster boat containing compound (B), a molybdenum booster boat containing compound represented by formula (1-335), a molybdenum booster boat containing lithium fluoride, and a tungsten boat containing aluminum The boats were installed.

The following layers were successively formed on the ITO film of the transparent support substrate. The vacuum tank was evacuated to 5 x 10 &lt; ^-4 &gt; Pa. First, an evaporation boat containing CuPc was heated to form a hole injection layer having a film thickness of 100 nm to form a hole injection layer. Was heated to deposit a film having a thickness of 30 nm to form a hole transporting layer. Next, the evaporation boats containing the compound (A) and the evaporation boats containing the compound (B) were heated at the same time to deposit a film having a film thickness of 35 nm to form a light emitting layer. The deposition rate was controlled so that the weight ratio of compound (A) to compound (B) was approximately 95: 5. Next, an evaporation boat containing a compound represented by Formula (1-335) was heated to deposit a film having a thickness of 15 nm to form an electron transport layer. The deposition rate of each layer was 0.01 to 1 nm / sec.

Thereafter, the deposition boat containing lithium fluoride was heated to deposit at a deposition rate of 0.003-0.1 nm / sec so that the film thickness became 0.5 nm, and then the evaporation boat containing aluminum was heated to a film thickness of 100 nm By evaporation at a deposition rate of 0.01 to 10 nm / sec so as to obtain an organic electroluminescent device.

When a DC voltage was applied to the ITO electrode as a positive electrode and the lithium fluoride / aluminum electrode as a negative electrode, blue light emission with a wavelength of about 455 nm was obtained. Further, a constant current driving test was carried out by the current density for obtaining an initial luminance of 2000 cd / m &lt; ^{2 &} gt ;. The driving test starting voltage was 6.10 V, and the time to maintain the luminance of 80% (1600 cd / m ² ) or more of the initial luminance was 600 hours.

&Lt; Comparative Example 5 &

An organic EL device was obtained in the same manner as in Reference Example 1 except that the compound represented by Formula (1-335) was changed to Compound (C). A constant current driving test was carried out by using a current density to obtain an initial luminance of 2000 cd / m &lt; ² &gt; with the ITO electrode as a positive electrode and the lithium fluoride / aluminum electrode as a negative electrode. The driving test starting voltage was 4.78 V, and the time for maintaining the luminance of 80% or more of the initial value was 39 hours.

Table 6 summarizes the above results.

[Table 6]

[Industrial applicability]

According to a preferred embodiment of the present invention, it is possible to provide an organic electroluminescent device which improves the lifetime of the light emitting device, and which is excellent in balance with the driving voltage, a display device including the organic electroluminescent device, and a lighting device including the same.

100: organic electroluminescent device 101: substrate
102: Positive electrode 103: Hole injection layer
104: Hole transport layer 105: Light emitting layer
106: electron transport layer 107: electron injection layer
108: cathode

Claims (30)

A benzo [c] carbazole compound represented by the following formula (1):
(124)

In the above formula (1)
R is aryl having 6 to 24 carbon atoms or heteroaryl having 2 to 24 carbon atoms,
A and A 'each independently represent hydrogen, a group represented by the formula (A-1), a group represented by the formula (A-2), a group represented by the formula (A-3) Is one selected from the group consisting of the group represented by the formula (A-4), but not both A and A 'are simultaneously hydrogen,
The ring included in the structure of R, A and A 'may be substituted with alkyl having 1 to 6 carbon atoms, cyclohexyl or phenyl,
The benzocarbazole skeleton constituting the compound represented by the formula (1), any hydrogen in the R, A and A 'substituted therein may be substituted with deuterium. The method according to claim 1,
R is a group selected from the group consisting of groups represented by the following formulas (R-1) to (R-20)
A and A 'each independently represent hydrogen, a group represented by the following formulas (A-1-1) to (A-1-3), the following formulas (A- A group represented by the following formulas (A-3-1) to (A-3-6), and a group represented by the following formulas (A-4-1) to But A and A 'are not both hydrogen at the same time,
The benzo [c] carbazole compound, which may be substituted with deuterium, is a benzocarbazole skeleton constituting the compound represented by the formula (1), any hydrogen in R, A and A '
(125)

(126)

. 3. The method of claim 2,
R is a group selected from the group consisting of the groups represented by the formulas (R-1) to (R-14)
A and A 'each independently represent a group represented by the formula (A-1-1) to (A-1-3), a group represented by the formula (A-2-1) A group represented by the formula (A-3-1) to (A-3-6) and a group represented by the formula (A-4-1) A benzo [c] carbazole compound, which is a selected one. 3. The method of claim 2,
R is a group selected from the group consisting of the groups represented by the formulas (R-1) to (R-11)
A and A 'each independently represent a group represented by the formula (A-1-1) to (A-1-3), a group represented by the formula (A-2-1) A group represented by the formula (A-3-1) to (A-3-6) and a group represented by the formula (A-4-1) to (A-4-3) A benzo [c] carbazole compound, which is a selected one. 3. The method of claim 2,
R is a group represented by the formula (R-1), the formula (R-10) or the formula (R-11)
A and A 'each independently represent a group represented by the formula (A-1-1) to (A-1-3), a group represented by the formula (A-2-1) A group represented by the formula (A-2-7) to (A-2-9), a group represented by the formula (A-2-12) A group represented by the formula (A-3-1) to (A-3-6) and a group represented by the formula (A-4-1) to (A-4-3) A benzo [c] carbazole compound, which is a selected one. 3. The method of claim 2,
R is a group represented by the formula (R-1) or (R-11)
A and A 'each independently represent a group represented by the formula (A-1-1) to (A-1-3), a group represented by the formula (A-2-1) (A-2-2), the group represented by the formula (A-2-8), the group represented by the formula (A-2-12) And a group represented by the formula (A-4-1) to (A-4-3), wherein the benzo [c] carbazole compound is one selected from the group consisting of a benzo [c] The method according to claim 1,
A benzo [c] carbazole compound represented by the following formula (1-10):
(127)

. The method according to claim 1,
A benzo [c] carbazole compound represented by the following formula (1-4):
(128)

. The method according to claim 1,
A benzo [c] carbazole compound represented by the following formula (1-744):
&Lt; EMI ID =

. The method according to claim 1,
A benzo [c] carbazole compound represented by the following formula (1-5):
(130)

. The method according to claim 1,
A benzo [c] carbazole compound represented by the following formula (1-634):
[Formula 131]

. The method according to claim 1,
A benzo [c] carbazole compound represented by the following formula (1-20):
(132)

. The method according to claim 1,
The benzo [c] carbazole compound represented by the following formula (1-24):
(133)

. The method according to claim 1,
A benzo [c] carbazole compound represented by the following formula (1-743):
(134)

. The method according to claim 1,
A benzo [c] carbazole compound represented by the following formula (1-8710):
(135)

. The method according to claim 1,
A benzo [c] carbazole compound represented by the following formula (1-8711):
&Lt; EMI ID =

. The method according to claim 1,
A benzo [c] carbazole compound represented by the following formula (1-8712):
(137)

. The method according to claim 1,
The benzo [c] carbazole compound represented by the following formula (1-1):
&Lt; EMI ID =

. The method according to claim 1,
A benzo [c] carbazole compound represented by the following formula (1-2):
[Chemical Formula 139]

. The method according to claim 1,
A benzo [c] carbazole compound represented by the following formula (1-541):
&Lt; EMI ID =

. The method according to claim 1,
A benzo [c] carbazole compound represented by the following formula (1-564):
(141)

. The method according to claim 1,
A benzo [c] carbazole compound represented by the following formula (1-575):
(142)

. The method according to claim 1,
A benzo [c] carbazole compound represented by the following formula (1-599):
(143)

. The method according to claim 1,
A benzo [c] carbazole compound represented by the following formula (1-742):
(144)

. An electron transporting material containing the compound according to any one of claims 1 to 24. A pair of electrodes made of a positive electrode and a negative electrode;
A light emitting layer disposed between the pair of electrodes; And
An electron transporting layer disposed between the cathode and the light emitting layer and containing the electron transporting material according to claim 25 and /
Lt; / RTI &gt; 27. The method of claim 26,
Wherein at least one of the electron transporting layer and the electron injecting layer further contains 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 , An organic electroluminescent element. 28. The method of claim 27,
Wherein at least one of the electron transporting layer and the electron injecting layer is made of an alkali metal, an alkaline earth metal, a rare earth metal, an oxide of an alkali metal, an alkali metal halide, an alkaline earth metal oxide, a halide of an alkaline earth metal, Wherein the organic electroluminescent device further comprises at least one selected from the group consisting of an oxide, a halide of a rare earth metal, an organic complex of an alkali metal, an organic complex of an alkaline earth metal, and an organic complex of a rare earth metal. 26. A display device comprising the organic electroluminescent device according to claim 26. 29. An illumination device comprising the organic electroluminescent device according to claim 26.

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