KR20150061149A - Organic light-emitting compound and organic electroluminescent device comprising the same - Google Patents

Abstract

The present invention relates to a novel organic compound and an organic electroluminescent device including the same. In the present invention, provided is an organic electroluminescent device, which has improved properties like light efficiency, driving voltage and longevity by introducing a light-emitting layer including an organic compound as a host material.

Description

TECHNICAL FIELD [0001] The present invention relates to an organic electroluminescent compound, and an organic electroluminescent device including the electroluminescent compound.

The present invention relates to a novel organic luminescent compound and an organic electroluminescent device comprising the compound.

In the organic electroluminescent device, when a voltage is applied between two electrodes, holes are injected into the organic layer in the anode, and electrons are injected into the organic layer in the cathode. When the injected holes and electrons meet, an exciton is formed. When the exciton falls to the ground state, light is emitted. The material contained in the organic material layer may be classified into a light emitting material, a hole injecting material, a hole transporting material, an electron transporting material, an electron injecting material, or the like depending on its function.

The luminescent material may be classified into blue, green, and red luminescent materials according to luminescent colors, and yellow and orange luminescent materials necessary to realize better natural colors. A host / dopant system can be used as a luminescent material to increase the luminous efficiency through increase of color purity and energy transfer.

The dopant material can be divided into a fluorescent dopant using an organic material and a phosphorescent dopant using a metal complex compound containing heavy atoms such as Ir and Pt. Since the phosphorescent dopant can theoretically improve the luminous efficiency up to 4 times as compared with the fluorescent dopant, studies on the phosphorescent dopant as well as the phosphorescent host have been conducted.

Currently, anthracene derivatives are known as fluorescent dopant / host materials used in the light emitting layer. As phosphorescent dopant materials used for the light emitting layer, metal complex compounds including Ir such as Firpic, Ir (ppy) ₃ , (acac) Ir (btp) ₂ and the like are known. As phosphorescent host materials, 4,4-dicarbazolybiphenyl (CBP) is known.

However, since the conventional materials have low glass transition temperature and poor thermal stability, they are not satisfactory in terms of lifetime in organic electroluminescent devices, and still need improvement in terms of luminescent properties.

Korea public patent 2011-0066763

In order to solve the above problems, it is an object of the present invention to provide a novel organic compound having a high glass transition temperature, excellent thermal stability, and improved luminescence properties.

Another object of the present invention is to provide an organic electroluminescent device comprising the organic compound.

In order to achieve the above object, the present invention provides a compound represented by the following general formula (1).

[Chemical Formula 1]

In Formula 1,

R ₁ and R ₂ or R ₂ and R ₃ form a fused ring represented by the following formula (2)

(2)

In Formula 2,

The dotted line is a moiety bonded to the formula (1)

X ₁ to X ₁₂ are each independently N or C (R ₄ )

Y ₁ is selected from the group consisting of C (Ar ₂ ) (Ar ₃ ), N (Ar ₄ ), O, S and Si (Ar ₅ ) (Ar ₆ )

Wherein R ₁ to R ₄ are each independently hydrogen, deuterium, a halogen, a cyano group, a nitro group, C ₁ ~ alkynyl group of C ₄₀ alkyl group, C ₂ ~ C ₄₀ alkenyl group, C ₂ ~ C ₄₀ of, C ₃ ~ C ₄₀ cycloalkyl group, the number of nuclear atoms of 3 to 40 of the heterocycloalkyl of the alkyl group, C ₆ ~ C ₆₀ aryl group, the number of nuclear atoms of 5 to 60 heteroaryl group, C ₁ ~ alkyloxy group of C _40, C ₆ ~ C ₆₀ aryloxy group, C ₃ ~ C ₄₀ alkylsilyl group, C ₆ ~ C ₆₀ aryl silyl group, a alkyl boronic of C ₁ ~ C _40, an aryl boronic a C ₆ ~ C _60, C ₆ ~ C ₆₀ aryl phosphine group, C ₆ ~ C ₆₀ aryl phosphine oxide group, and a C ₆ ~ selected from the group consisting of C ₆₀ aryl amine, or by combining adjacent groups may form a fused ring,

Each of Ar ₁ to Ar ₆ is independently a C ₁ to C ₄₀ alkyl group, a C ₂ to C ₄₀ alkenyl group, a C ₂ to C ₄₀ alkynyl group, a C ₃ to C ₄₀ cycloalkyl group, A C ₆ to C ₆₀ aryl group, a heteroaryl group having 5 to 60 nuclear atoms, a C ₁ to C ₄₀ alkyloxy group, a C ₆ to C ₆₀ aryloxy group, a C ₃ to C ₆ heteroaryl group, ₄₀ alkylsilyl group, C ₆ ~ C ₆₀ aryl silyl group, C ₁ ~ C ₄₀ group of an alkyl boron, C ₆ ~ C group ₆₀ arylboronic of, C ₆ ~ aryl phosphine of C ₆₀ pingi, C ₆ ~ C ₆₀ aryl phosphine oxide group, and a C ₆ ~ C ₆₀ of is selected from the group consisting of an aryl amine,

The alkyl group, alkenyl group, alkynyl group, cycloalkyl group, heterocycloalkyl group, aryl group, heteroaryl group, alkyloxy group, aryloxy group, alkylsilyl group and arylsilyl group of R ₁ to R ₄ and Ar ₁ to Ar ₆ , An alkylboron group, an arylboron group, an arylphosphine group, an arylphosphine oxide group and an arylamine group are each independently a C ₁ to C ₄₀ alkyl group, a C ₂ to C ₄₀ alkenyl group, a C ₂ to C ₄₀ alkoxy group, group, C ₃ ~ C ₄₀ cycloalkyl group, the number of nuclear atoms of 3 to 40 hetero cycloalkyl, heteroaryl of C ₆ ~ C ₆₀ aryl group, the number of nuclear atoms of 5 to 60 aryl group, C ₁ ~ C ₄₀ alkyloxy A C ₆ to C ₆₀ aryloxy group, a C ₃ to C ₄₀ alkylsilyl group, a C ₆ to C ₆₀ arylsilyl group, a C ₁ to C ₄₀ alkylboron group, a C ₆ to C ₆₀ arylboron group, may be substituted with at least one member selected from the group consisting of an arylamine C ₆ ~ C ₆₀ aryl phosphine group, C ₆ ~ C ₆₀ aryl phosphine oxide group, and a C ₆ ~ C ₆₀ of. When substituted with a plurality of substituents, they may be the same or different.

According to another aspect of the present invention, cathode; And at least one organic material layer interposed between the anode and the cathode, wherein at least one of the one or more organic material layers comprises a compound represented by Formula 1 do.

In the present invention, alkyl means a monovalent substituent derived from a linear or branched saturated hydrocarbon having 1 to 40 carbon atoms. Examples thereof include, but are not limited to, methyl, ethyl, propyl, isobutyl, sec-butyl, pentyl, iso-amyl and hexyl.

In the present invention, alkenyl means a monovalent substituent derived from a straight-chain or branched-chain unsaturated hydrocarbon having 2 to 40 carbon atoms and having at least one carbon-carbon double bond. Examples thereof include, but are not limited to, vinyl, allyl, isopropenyl, 2-butenyl, and the like.

In the present invention, alkynyl means a monovalent substituent derived from a straight-chain or branched-chain unsaturated hydrocarbon having 2 to 40 carbon atoms and having at least one carbon-carbon triple bond. Examples thereof include, but are not limited to, ethynyl, 2-propynyl, and the like.

In the present invention, aryl means a monovalent substituent derived from an aromatic hydrocarbon having 6 to 40 carbon atoms in which a single ring or two or more rings are combined. Also, a form in which two or more rings are pendant or condensed with each other may be included. Examples of such aryl include, but are not limited to, phenyl, naphthyl, phenanthryl, anthryl, and the like.

In the present invention, heteroaryl means a monovalent substituent derived from a monoheterocyclic or polyheterocyclic aromatic hydrocarbon having 5 to 40 nuclear atoms. Wherein at least one of the carbons, preferably one to three carbons, is replaced by a heteroatom such as N, O, S or Se. It is also possible to include a form in which two or more rings are pendant or condensed with each other, and further, a condensed form with an aryl group may be included. Examples of such heteroaryls include 6-membered monocyclic rings such as pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, triazinyl, phenoxathienyl, indolizinyl, indolyl indolyl), purinyl, quinolyl, benzothiazole, carbazolyl, and heterocyclic rings such as 2-furanyl, N-imidazolyl, 2- , 2-pyridinyl, 2-pyrimidinyl, and the like, but are not limited thereto.

In the present invention, aryloxy is a monovalent substituent represented by RO-, and R represents aryl having 6 to 40 carbon atoms. Examples of such aryloxy include, but are not limited to, phenyloxy, naphthyloxy, diphenyloxy, and the like.

In the present invention, alkyloxy is a monovalent substituent group represented by R'O-, wherein R 'represents alkyl having 1 to 40 carbon atoms, and includes a linear, branched or cyclic structure can do. Examples of alkyloxy include, but are not limited to, methoxy, ethoxy, n-propoxy, 1-propoxy, t-butoxy, n-butoxy and pentoxy.

In the present invention, arylamine refers to an amine substituted with aryl having 6 to 40 carbon atoms.

In the present invention, cycloalkyl means a monovalent substituent derived from a monocyclic or polycyclic non-aromatic hydrocarbon having 3 to 40 carbon atoms. Examples of such cycloalkyls include, but are not limited to, cyclopropyl, cyclopentyl, cyclohexyl, norbornyl, adamantine, and the like.

In the present invention, heterocycloalkyl means a monovalent substituent derived from a non-aromatic hydrocarbon having 3 to 40 nuclear atoms, wherein at least one carbon atom, preferably 1 to 3 carbons, of the ring is N, O, S or Se Lt; / RTI > Examples of such heterocycloalkyl include, but are not limited to, morpholine, piperazine, and the like.

In the present invention, alkylsilyl is silyl substituted with alkyl having 1 to 40 carbon atoms, and arylsilyl means silyl substituted with aryl having 6 to 40 carbon atoms.

In the present invention, the condensed rings refer to condensed aliphatic rings, condensed aromatic rings, condensed heteroaliphatic rings, condensed heteroaromatic rings, or a combination thereof.

The compound represented by the general formula (1) of the present invention has excellent thermal stability and luminescent properties and can be used as a material of an organic material layer of an organic electroluminescent device. In particular, when the compound represented by Formula 1 of the present invention is used as a phosphorescent host material, it is possible to produce an organic electroluminescent device having excellent light emitting performance, low driving voltage, high efficiency, and long life time, A full color display panel having improved performance and lifetime can be manufactured.

Hereinafter, the present invention will be described in detail.

1. New organic compounds

The compound represented by formula (1) of the present invention is characterized in that a fused bicyclic ring or a condensed heterocyclic ring is bonded to the 5H-quinoxalino [3,2,1-jk] carbazole moiety.

The compound represented by Formula 1 of the present invention may have a wide band gap (sky blue to red) by controlling various energy levels by introducing various substituents.

Specifically, when various aromatic rings are introduced into a 5H-quinoxalino [3,2,1-jk] carbazole moiety having excellent hole transporting ability, an electron withdrawing group (EWG) Since the electron donor has a large electron donating group (EDG), the whole molecule exhibits bipolar characteristics, and the bonding force between holes and electrons increases. Therefore, the compound represented by the formula (1) But it is also applicable to a hole transporting layer, a hole injecting layer and an electron transporting layer.

Further, the compound represented by the formula (1) of the present invention has a high glass transition temperature and excellent thermal stability because the molecular weight of the compound is significantly increased due to various aromatic ring substituents.

Therefore, when the compound represented by the formula (1) of the present invention is used as a material for the hole injection layer, the hole transporting layer or the light emitting layer of an organic electroluminescent device, the efficiency and the efficiency of the organic electroluminescent device The life can be improved. Further, the lifetime of the organic electroluminescent device can be maximized by maximizing the performance of the full-color organic electroluminescent panel.

The compound represented by the formula (1) of the present invention is preferably selected from the group consisting of the compounds represented by the following formulas (3) to (6).

(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

In Formulas 3 to 6, X ₁ to X ₁₂ , Ar ₁ , Y _1, and R ₁ to R ₃ are the same as defined above.

X ₁ to X ₁₂ are each independently selected from N or C (R ₄ ). When considering the characteristics of the organic electroluminescent device, it is preferable that all of them are C (R ₄ ). Wherein the plurality of R < ₄ > s are the same or different from each other.

Y ₁ is selected from the group consisting of C (Ar ₂ ) (Ar ₃ ), N (Ar ₄ ), O, S and Si (Ar ₅ ) (Ar ₆ ) N (Ar ₄ ).

Specifically, the compound represented by the formula (1) of the present invention is preferably selected from the group consisting of compounds represented by the following formulas (7) to (10).

(7)

[Chemical Formula 8]

[Chemical Formula 9]

[Chemical formula 10]

In Formulas 7 to 10, R ₁ to R ₄ , Ar ₁ and Ar ₄ are the same as defined above.

Considering the wide band gap and thermal stability of the compound represented by the formula (1) of the present invention, each of Ar ₁ to Ar ₆ is independently a C ₆ to C ₆₀ aryl group or a heteroaryl group having 5 to 60 nuclear atoms .

In addition, R ₁ to R ₄ in the compounds represented by formula (1) of the present invention are each independently hydrogen, halogen, cyano, C ₁ to C ₄₀ alkyl, C ₆ to C ₆₀ aryl , A heteroaryl group having 5 to 60 nuclear atoms and an arylamine group having ₆ to ₆₀ carbon atoms.

Specifically, in the compound of the formula (1) of the present invention, each of R ₁ to R ₄ except for forming Ar ₁ to Ar ₆ and a condensed ring is independently selected from the group consisting of hydrogen or a structure (substituent) represented by the following S1 to S204 Can be selected.

The compounds represented by formula (1) of the present invention may be represented by the following compounds represented by the following formulas (C-1) to (C-179), but the compounds represented by formula (1) of the present invention are not limited thereto.

2. Organic electroluminescent device

The present invention relates to an organic electroluminescent device comprising a cathode, a cathode, and at least one organic layer interposed between the anode and the cathode, wherein at least one of the organic layers includes at least one compound represented by Formula 1 to provide.

The organic material layer containing the compound represented by Formula 1 may be at least one of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer. Preferably, the compound represented by Formula 1 may be included in an organic electroluminescent device as a light emitting layer material. In this case, the light emitting efficiency, brightness, power efficiency, thermal stability, and device lifetime of the organic electroluminescent device can be improved.

In particular, the compound represented by the general formula (1) of the present invention is preferably a phosphorescent host, a fluorescent host or a dopant material of the light emitting layer, more preferably a phosphorescent host of the light emitting layer.

The structure of the organic electroluminescent device of the present invention is not particularly limited, but may be a substrate, an anode, a hole injecting layer, a hole transporting layer, a light emitting layer, an electron transporting layer, and a cathode sequentially laminated. At this time, at least one of the hole injecting layer, the hole transporting layer and the light emitting layer may contain at least one compound represented by the above formula (1). An electron injection layer may be disposed on the electron transport layer.

Also, the organic electroluminescent device of the present invention may have a structure in which an insulating layer or an adhesive layer is interposed between the electrode and the organic layer interface.

In the organic electroluminescent device of the present invention, the organic material layer containing the compound represented by Formula 1 may be formed by a vacuum deposition method or a solution coating method. Examples of the solution coating method include, but are not limited to, spin coating, dip coating, doctor blading, inkjet printing, or thermal transfer.

The organic electroluminescent device of the present invention is manufactured by forming an organic layer and an electrode using materials and methods known in the art, except that one or more layers of the organic layers are formed so as to include the compound represented by Formula 1 .

For example, a silicon wafer, quartz or glass plate, a metal plate, a plastic film or a sheet can be used as the substrate.

Examples of the positive electrode material include metals such as vanadium, chromium, copper, zinc, and gold, or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); ZnO: Al or SnO _2: a combination of a metal and an oxide such as Sb; Conductive polymers such as polythiophene, poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (PEDT), polypyrrole and polyaniline; Or carbon black, but are not limited thereto.

Examples of the negative electrode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin or lead or alloys thereof; Layer structure materials such as LiF / Al or LiO ₂ / Al, but are not limited thereto.

The material used for the hole injecting layer, the hole transporting layer, the electron injecting layer and the electron transporting layer is not particularly limited as long as it is a conventional material known in the art.

Hereinafter, the present invention will be described in detail with reference to examples. However, the following examples are illustrative of the present invention and are not intended to limit the scope of the present invention.

[Preparation Example 1] Synthesis of IC-1

<Step 1> Synthesis of 1-bromo-2-chloro-9- (2-nitrophenyl) -9H-carbazole

(13.3 g, 46.17 mmol), 1-iodo-2-nitrobenzene (17.3 g, 69.26 mmol), Cu powder (0.29 g, 4.62 mmol), K ₂ CO ₃ (6.38 g, 46.17 mmol), Na ₂ SO ₄ (6.56 g, 46.17 mmol) and nitrobenzene (200 ml) were mixed and stirred at 200? For 12 hours.

After completion of the reaction, the nitrobenzene was removed. The organic layer was separated with methylene chloride, and water was removed using MgSO ₄ . The solvent was removed from the organic layer from which water had been removed and then purified by column chromatography to obtain 1-bromo-2-chloro-9- (2-nitrophenyl) -9H-carbazole (12.4 g, yield 67%).

^{1 H-NMR: δ 6.90 (} d, 1H), 7.31 (m, 2H), 7.71 (t, 1H), 7.95 (m, 4H), 8.26 (d, 1H), 8.55 (d, 1H)

<Step 2> Synthesis of 2- (1-bromo-2-chloro-9H-carbazol-9-yl) aniline

(12.0 g, 30.0 mmol) was dissolved in 50 ml of THF under a hydrogen atmosphere, and then 10% Pd / C (1 g) was added thereto. The mixture was stirred at room temperature Stir for 12 hours.

After completion of the reaction, the reaction mixture was filtered through a Celite filter and then purified by column chromatography to obtain 2- (1-bromo-2-chloro-9H-carbazol-9-yl) aniline (9.25 g, yield 83%).

^{1 H-NMR: δ 6.28 (} s, 2H), δ 6.90 (d, 1H), 7.28 (m, 2H), 7.71 (t, 1H), 7.95 (m, 4H), 8.26 (d, 1H), 8.55 (d, 1 H)

<Step 3> Synthesis of 6-chloro-5H-quinoxalino [3,2,1-jk] carbazole

Pd ₂ (dba) ₃ (0.91 g, 1.00 mmol), (t-Bu) 2- (1-bromo-2-chloro-9H-carbazol-9- yl) aniline (7.43 g, 20.00 mmol) ₃ P (0.80 g, 4.0 mmol) and sodium tert-butoxide (5.76 g, 60.0 mmol) were added to 100 ml toluene and the mixture was stirred at 110? For 12 hours.

After completion of the reaction, the reaction mixture was extracted with methylene chloride, and the mixture was filtered with MgSO ₄ . After removing the solvent of the filtered organic layer, 6-chloro-5H-quinoxalino [3,2,1-jk] carbazole (4.42 g, yield 76%) was obtained by column chromatography.

^{1 H-NMR: δ 4.01 (} s, 1H), δ 6.63 (d, 1H), 6.77 (d, 1H), 7.24 (m, 2H), 7.38 (m, 4H), 7.94 (d, 1H), 8.52 (d, 1 H)

<Step 4> Synthesis of 6- (2-nitrophenyl) -5H-quinoxalino [3,2,1-jk] carbazole

(3.76 g, 15.0 mmol), 2-nitrophenylboronic acid (3.76 g, 22.5 mmol), NaOH (1.80 g, 45.0 mmol) and THF _{/ H 2 O (80 ml /} 40 ml) were mixed, and then insert the _{Pd (PPh 3) 4 (0.87} g, 5 mol%) at 40? and the mixture was stirred at 80? for 12 hours.

After completion of the reaction, the reaction mixture was extracted with methylene chloride, and the mixture was added with MgSO ₄ and filtered. The solvent was removed from the obtained organic layer and then purified by column chromatography to obtain 6- (2-nitrophenyl) -5H-quinoxalino [3,2,1-jk] carbazole (3.85 g, yield 68%).

^{1 H-NMR: δ 4.01 (} s, 1H), δ 6.63 (d, 1H), δ 6.95 (t, 1H), 7.24 (m, 2H), 7.35 (m, 2H), 7.60 (m, 3H), 7.92 (m, 2 H), 8.03 (m, 2 H), 8.54 (d, 1 H)

Step 5 Synthesis of 6- (2-nitrophenyl) -5-phenyl-5H-quinoxalino [3,2,1-jk] carbazole

Iodobenzene (3.12 g, 15.3 mmol) and Cu powder (0.07 g, 1.02 mmol) were added to a solution of 6- (2-nitrophenyl) -5H- quinoxalino [3,2,1- , K ₂ CO ₃ (1.41 g, 10.2 mmol), Na ₂ SO ₄ (1.45 g, 10.2 mmol) and nitrobenzene (80 ml) were mixed and stirred at 200 ° C for 12 hours.

After completion of the reaction, the nitrobenzene was removed. The organic layer was separated with methylene chloride, and water was removed using MgSO ₄ . The solvent was removed from the organic layer from which water had been removed and then purified by column chromatography to obtain 3.28 g (yield 71%) of 6- (2-nitrophenyl) -5-phenyl-5H- quinoxalino [3,2,1- .

^{1 H-NMR: δ 6.63 (} d, 2H), δ 6.95 (m, 2H), 7.24 (m, 3H), 7.35 (m, 2H), 7.60 (m, 3H), 7.92 (m, 3H), 8.03 (m, 3 H), 8.54 (d, 1 H)

<Step 6> Synthesis of IC-1

5-phenyl-5H-quinoxalino [3,2,1-jk] carbazole (3.17 g, 7.00 mmol), triphenylphosphine (5.51 g, 21.00 mmol) and 1,2- dichlorobenzene (50 ml) were mixed and stirred for 12 hours.

After completion of the reaction, 1,2-dichlorobenzene was removed and extracted with dichloromethane. Water was removed from the resulting organic layer with MgSO ₄ and purified by column chromatography to obtain IC-1 (2.24 g, yield 76%).

^{1 H-NMR: δ 6.63 (} d, 2H), δ 6.95 (m, 2H), 7.24 (m, 3H), 7.35 (m, 2H), 7.60 (m, 2H), 7.92 (m, 3H), 8.03 (m, 3 H), 8.54 (d, 1 H),? 10.1 (s, 1 H)

[Preparation Example 2] Synthesis of IC-2 and IC-3

<Step 1> Synthesis of 1-bromo-3-chloro-9- (2-nitrophenyl) -9H-carbazole

Except that 1-bromo-3-chloro-9H-carbazole (13.0 g, 46.17 mmol) was used instead of 1-bromo-2-chloro-9H-carbazole in the step 1 of Preparation Example 1, bromo-3-chloro-9- (2-nitrophenyl) -9H-carbazole (12.4 g, yield 67%).

^{1 H-NMR: δ 7.29 (} m, 3H), 7.50 (s, 1H), 7.71 (t, 1H), 7.93 (m, 3H), 8.26 (d, 1H), 8.55 (d, 1H)

<Step 2> Synthesis of 2- (1-bromo-3-chloro-9H-carbazol-9-yl) aniline

Bromo-3-chloro-9- (2-nitrophenyl) -9H-carbazole (12.0 g, 9.2 mmol) was used in the Step 2 of Preparation Example 1 instead of 1-bromo-2-chloro-9- 3-chloro-9H-carbazol-9-yl) aniline (9.25 g, yield 83%).

^{1 H-NMR: δ 6.28 (} s, 2H), δ 6.63 (d, 1H), δ 6.94 (t, 1H), 7.28 (m, 5H), 7.50 (s, 1H), 7.95 (d, 1H), 8.55 (d, 1 H)

<Step 3> Synthesis of 7-chloro-5H-quinoxalino [3,2,1-jk] carbazole

(1-bromo-3-chloro-9H-carbazol-9-yl) aniline (prepared in Step 3 of Preparation Example 1 instead of 2- (1-bromo-2-chloro-9H- g, 20.00 mmol) was used to synthesize 7-chloro-5H-quinoxalino [3,2,1-jk] carbazole (4.42 g, yield 76%).

^{1 H-NMR: δ 4.01 (} s, 1H), δ 6.63 (d, 1H), 6.93 (m, 2H), 7.28 (m, 4H), 7.94 (d, 1H), 8.52 (d, 1H)

<Step 4> Synthesis of 7- (2-nitrophenyl) -5H-quinoxalino [3,2,1-jk] carbazole

5-quinoxalino [3,2,1-jk] carbazole (4.36 g, 15.0 mmol) was used in place of 6-chloro-5H-quinoxalino [3,2,1- (2-nitrophenyl) -5H-quinoxalino [3,2,1-jk] carbazole (3.85 g, yield 68%) was obtained.

^{1 H-NMR: δ 4.01 (} s, 1H), δ 6.50 (s, 1H), δ 6.63 (d, 1H), δ 6.95 (t, 1H), 7.29 (m, 5H), 7.67 (t, 1H) , 7.97 (m, 3 H), 8.54 (d, 1 H)

Step 5 Synthesis of 7- (2-nitrophenyl) -5-phenyl-5H-quinoxalino [3,2,1-jk] carbazole

(2-nitrophenyl) -5H-quinoxalino [3,2,1-jk] carbazole in place of 6- (2-nitrophenyl) -5H-quinoxalino [3,2,1- (2-nitrophenyl) -5-phenyl-5H-quinoxalino [3,2,1-jk] carbazole (3.28 g, yield 71%) was synthesized in the same manner, ).

^{1 H-NMR: δ 6.50 (} s, 1H), δ 6.63 (d, 3H), δ 6.81 (t, 1H), δ 6.94 (t, 1H), 7.28 (m, 7H), 7.67 (t, 1H) , 7.96 (m, 4 H), 8.54 (d, 1 H)

&Lt; Step 6 > Synthesis of IC-2 and IC-3

5-phenyl-5H-quinoxalino [3,2,1-jk] carbazole in place of 6- (2-nitrophenyl) -5- , 2.1-jk] carbazole (3.17 g, 7.00 mmol), and then purified by column chromatography to obtain IC-2 (0.94 g, yield 32% 1.03 g, yield 35%).

¹ of IC-2 H-NMR: δ 6.63 (d, 3H), δ 6.81 (t, 1H), δ 6.93 (m, 2H), 7.29 (m, 7H), 7.50 (t, 1H), 7.63 (d 1H), 7.94 (d, IH), 8.12 (d, IH), 8.54

¹ H-NMR of the IC-3: δ 6.28 (s , 1H), δ 6.63 (d, 3H), δ 6.81 (t, 1H), δ 6.93 (t, 1H), 7.29 (m, 7H), 7.50 ( 1H), 7.63 (d, IH), 7.94 (d, IH), 8.12

[Synthesis Example 1] Synthesis of C-1

(3.91 g, 9.3 mmol), bromobenzene (1.75 g, 11.16 mmol), Cu powder (0.29 g, 4.65 mmol) and K ₂ CO ₃ (1.28 g, 9.3 mmol) were added to a solution of the compound prepared in Preparation Example 1 mixing _{mmol), Na 2 SO 4 (} 2.64 g, 18.61 mmol) , and nitrobenzene (80 ml) and stirred at 190? for 12 hours.

After the reaction was completed, the nitrobenzene was removed, the organic layer was separated with methylene chloride, and water was removed using MgSO ₄ . The solvent of the organic layer was removed, and the residue was purified by column chromatography to obtain the target compound C-1 (2.82 g, yield 61%).

GC-Mass (calculated: 497.19 g / mol, measured: 497 g / mol)

[Synthesis Example 2] Synthesis of C-4

C-4 (2.57 g, yield 55%) was obtained in the same manner as in Synthesis Example 1, except that 1-bromo-D5-benzene (1.87 g, 11.16 mmol) was used instead of bromobenzene.

GC-Mass (calculated: 502.22 g / mol, measured: 502 g / mol)

[Synthesis Example 3] Synthesis of C-5

C-5 (2.77 g, yield 57%) was obtained in the same manner as in Synthesis Example 1, except that 3-bromobenzonitrile (2.02 g, 11.16 mmol) was used instead of bromobenzene.

GC-Mass (calculated: 522.60 g / mol, measured: 522 g / mol)

[Synthesis Example 4] Synthesis of C-7

C-7 (3.33 g, yield 54%) was obtained in the same manner as in Synthesis Example 1, except that 3-bromo-N, N-diphenylaniline (3.61 g, 11.16 mmol) was used instead of bromobenzene.

GC-Mass (theory: 664.79 g / mol, measured: 664 g / mol)

[Synthesis Example 5] Synthesis of C-12

(3.45 g, yield 56%) was obtained in the same manner as in Synthesis Example 1, except that 4- (3-bromophenyl) dibenzo [b, d] furan (3.60 g, 11.16 mmol) .

GC-Mass (calculated: 663.76 g / mol, measured: 663 g / mol)

[Synthesis Example 6] Synthesis of C-13

(4.21 g, 10.00 mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine (3.20 g, 12.00 mmol) and Pd ₂ (dba) ₃ (0.46 g, 0.5 an mmol), (t-Bu) 3 P (0.40 g, 2.0 mmol), sodium tert-butoxide (2.88 g, 30.0 mmol) into a 50 ml toluene was stirred at 110? for 12 hours.

After completion of the reaction, the reaction mixture was extracted with methylene chloride, and the mixture was filtered with MgSO ₄ . After removing the solvent of the filtered organic layer, C-13 (4.11 g, yield 63%) was obtained by column chromatography.

GC-Mass (calculated: 652.74 g / mol, measured: 652 g / mol)

[Synthesis Example 7] Synthesis of C-17

C-17 (3.49 g, yield 58%) was obtained in the same manner as in Synthesis Example 1, except that 2-bromotriphenylene (3.42 g, 11.16 mmol) was used instead of bromobenzene.

GC-Mass (calculated: 647.76 g / mol, measured: 647 g / mol)

[Synthesis Example 8] Synthesis of C-20

C-20 (3.52 g, yield 61%) was obtained in the same manner as in Synthesis Example 1, except that diphenylphosphinic bromide (3.13 g, 11.16 mmol) was used instead of bromobenzene.

GC-Mass (calculated: 621.66 g / mol, measured: 621 g / mol)

[Synthesis Example 9] Synthesis of C-21

(C-21) was obtained in the same manner as in Synthesis Example 6, except that 2-chloro-4-phenylquinazoline (2.88 g, 12.00 mmol) was used instead of 2-chloro-4,6-diphenyl- (3.31 g, yield 58%).

GC-Mass (calculated: 625.72 g / mol, measured: 625 g / mol)

[Synthesis Example 10] Synthesis of C-22

2-phenylpyrimidine (2.28 g, 12.00 mmol) was used in place of 2-chloro-4,6-diphenyl-1,3,5-triazine in the same manner as in Synthesis Example 6, (3.53 g, yield 66%).

GC-Mass (calculated: 575.21 g / mol, measured: 575 g / mol)

[Synthesis Example 11] Synthesis of C-23

C-23 (3.52 g, 11.16 mmol) was obtained in the same manner as in Synthesis Example 1, except for using 2- (3-bromophenyl) -4,6-diphenyl-1,3,5-triazine g, yield: 52%).

GC-Mass (728.27 g / mol, measured: 728 g / mol)

[Synthesis Example 12] Synthesis of C-25

Except that 3-bromo-9- (4,6-diphenyl-1,3,5-triazin-2-yl) -9H-carbazole (5.31 g, 11.16 mmol) was used in place of bromobenzene. C-25 (3.80 g, yield 50%) as a target compound was obtained.

GC-Mass (calculated: 817.30 g / mol, measured: 817 g / mol)

[Synthesis Example 13] Synthesis of C-30

(3.91 g, 9.3 mmol), bromobenzene (1.75 g, 11.16 mmol), Cu powder (0.29 g, 4.65 mmol) and K ₂ CO ₃ (1.28 g, 9.3 mmol) were added to a solution of the compound prepared in Preparation Example 2 mixing _{mmol), Na 2 SO 4 (} 2.64 g, 18.61 mmol) , and nitrobenzene (80 ml) and stirred at 190? for 12 hours.

After the reaction was completed, the nitrobenzene was removed, the organic layer was separated with methylene chloride, and water was removed using MgSO ₄ . The solvent of the organic layer was removed, and the residue was purified by column chromatography to obtain the target compound C-30 (2.633 g, yield 57%).

GC-Mass (calculated: 497.19 g / mol, measured: 497 g / mol)

[Synthesis Example 14] Synthesis of C-38

2-chloro-4-phenylpyrimidine (2.28 g, 12.00 mmol), Pd ₂ (dba) ₃ (0.46 g, 0.5 mmol), (t-Bu) ₃ P (0.40 g, 2.0 mmol) and sodium tert-butoxide (2.88 g, 30.0 mmol) were added to 50 ml toluene and stirred at 110? For 12 hours.

After completion of the reaction, the reaction mixture was extracted with methylene chloride, and the mixture was filtered with MgSO ₄ . After removing the solvent of the filtered organic layer, C-38 (3.73 g, yield 65%) was obtained by column chromatography.

GC-Mass (calculated: 575.21 g / mol, measured: 575 g / mol)

[Synthesis Example 15] Synthesis of C-40

C-40 (3.62 g, yield 60%) was obtained in the same manner as in Synthesis Example 13, except that 1-bromo-3,5-diphenylbenzene (3.44 g, 11.16 mmol) was used instead of bromobenzene.

GC-Mass (calculated: 649.25 g / mol, measured: 649 g / mol)

[Synthesis Example 16] Synthesis of C-46

(4.00 g, yield 57%) was obtained in the same manner as in Synthesis Example 13, except for using 4- (4-bromophenyl) -6-phenyldibenzo [b, d] thiophene (4.62 g, 11.16 mmol) instead of bromobenzene. %).

GC-Mass (calculated: 755.24 g / mol, measured: 755 g / mol)

[Synthesis Example 17] Synthesis of C-51

C-51 (4.42 g, yield 68%) was obtained in the same manner as in Synthesis Example 14, except that 2-chloro-4,6-diphenylpyrimidine (3.19 g, 12 mmol) &Lt; / RTI &gt;

GC-Mass (calculated: 651.24 g / mol, measured: 651 g / mol)

[Synthesis Example 18] Synthesis of C-55

C-55 (3.72 g, 11.16 mmol) was obtained in the same manner as in Synthesis Example 13, except for using 2- (3-bromophenyl) -4,6-diphenyl-1,3,5- g, yield: 57%).

GC-Mass (728.27 g / mol, measured: 728 g / mol)

[Synthesis Example 19] Synthesis of C-56

The objective compound C-56 (3.72 g, 11.16 mmol) was obtained in the same manner as in Synthesis Example 13, except for using 2- (4-bromophenyl) -4,6-diphenyl-1,3,5- g, yield: 57%).

GC-Mass (728.27 g / mol, measured: 728 g / mol)

[Synthesis Example 20] Synthesis of C-57

(3.33 g, 11.16 mmol) was obtained in the same manner as in Synthesis Example 13, except that 2- (3-bromophenyl) -4-phenyl-1,3,5- Yield: 55%).

GC-Mass (theory: 652.24 g / mol, measured: 652 g / mol)

[Synthesis Example 21] Synthesis of C-59

(3.44 g, yield 50%) was obtained in the same manner as in Synthesis Example 13, except that 4'-bromo-N, N-diphenylbiphenyl-4-amine (4.45 g, 11.16 mmol) was used instead of bromobenzene. .

GC-Mass (calculated: 740.29 g / mol, measured: 740 g / mol)

[Synthesis Example 22] Synthesis of C-100

(3.91 g, 9.3 mmol), 1-bromo-3-fluorobenzene (1.93 g, 11.16 mmol), Cu powder (0.29 g, 4.65 mmol), K ₂ CO a _{3 (1.28 g, 9.3 mmol)} , Na 2 SO 4 (2.64 g, 18.61 mmol) , and nitrobenzene (80 ml) were mixed and stirred at 190? for 12 hours.

After the reaction was completed, the nitrobenzene was removed, the organic layer was separated with methylene chloride, and water was removed using MgSO ₄ . The solvent of the organic layer was removed, and the residue was purified by column chromatography to obtain the target compound C-100 (2.92 g, yield 61%).

GC-Mass (calculated: 515.18 g / mol, measured: 515 g / mol)

[Synthesis Example 23] Synthesis of C-102

The target compound C-102 (2.91 g, yield 55%) was obtained in the same manner as in Synthesis Example 22, except that (3-bromophenyl) trimethylsilane (2.54 g, 11.16 mmol) was used in place of 1-bromo-3-fluorobenzene.

GC-Mass (calculated: 569.23 g / mol, measured: 569 g / mol)

[Synthesis Example 24] Synthesis of C-103

C-103 (2.25 g, yield 54%) was obtained in the same manner as in Synthesis Example 22, except that bromoethane (1.19 g, 11.16 mmol) was used instead of 1-bromo-3-fluorobenzene.

GC-Mass (calculated: 449.19 g / mol, measured: 449 g / mol)

[Synthesis Example 25] Synthesis of C-108

108 (3.50 g, yield 54%) was obtained in the same manner as in Synthesis Example 22, except that 2-bromo-1,3-diphenylbenzene (3.44 g, 11.16 mmol) was used in place of 1-bromo- &Lt; / RTI &gt;

GC-Mass (calculated: 649.25 g / mol, measured: 649 g / mol)

[Synthesis Example 26] Synthesis of C-114

C-114 (3.63 g, yield 59%) was obtained in the same manner as in Synthesis Example 22, except that (4-bromophenyl) diphenylborane (3.57 g, 11.16 mmol) was used in place of 1-bromo-3-fluorobenzene.

GC-Mass (calculated: 661.27 g / mol, measured: 661 g / mol)

[Synthesis Example 27] Synthesis of C-118

Pd ₂ (dba) ₃ (0.46 g, 0.5 mmol), (t-Bu) ₃ P (2-chloro-4-phenylquinazoline) (2.88 g, 12.00 mmol), IC- (0.40 g, 2.0 mmol) and sodium tert-butoxide (2.88 g, 30.0 mmol) were added to 50 ml toluene and stirred at 110? For 12 hours.

After completion of the reaction, the reaction mixture was extracted with methylene chloride, and the mixture was filtered with MgSO ₄ . After removing the solvent of the filtered organic layer, the target compound C-118 (4.18 g, yield 67%) was obtained by column chromatography.

GC-Mass (calculated: 625.23 g / mol, measured: 625 g / mol)

[Synthesis Example 28] Synthesis of C-123

Except that 2-bromophenyl-4,6-diphenyl-1,3,5-triazine (4.32 g, 11.16 mmol) was used in place of 1-bromo-3-fluorobenzene. C-123 (3.72 g, yield 55%).

GC-Mass (728.27 g / mol, measured: 728 g / mol)

[Synthesis Example 29] Synthesis of C-124

The objective Compound (1) was prepared in the same manner as in Synthesis Example 22, except that 2- (4-bromophenyl) -4,6-diphenyl-1,3,5-triazine (4.32 g, 11.16 mmol) was used in place of 1-bromo- C-124 (3.99 g, yield 59%).

GC-Mass (728.27 g / mol, measured: 728 g / mol)

[Synthesis Example 30] Synthesis of C-125

The title compound was prepared by the same procedure for Synthesis Example 22 except for using 2- (3-bromophenyl) -4-phenyl-1,3,5-triazine (3.47 g, 11.16 mmol) instead of 1-bromo-3- -125 (3.39 g, yield 56%).

GC-Mass (theory: 652.24 g / mol, measured: 652 g / mol)

[Synthesis Example 31] Synthesis of C-126

Except that 3-bromo-9- (4,6-diphenyl-1,3,5-triazin-2-yl) -9H-carbazole (5.31 g, 11.16 mmol) was used in place of 1-bromo-3- C-126 (3.87 g, yield 51%) was obtained in the same manner as in Example 22.

GC-Mass (calculated: 817.30 g / mol, measured: 817 g / mol)

[Examples 1 to 31] Preparation of green organic electroluminescent device

The compound synthesized in Synthesis Example was subjected to high purity sublimation purification by a conventionally known method, and then a green organic electroluminescent device was manufactured according to the following procedure.

First, a glass substrate coated with ITO (Indium Tin Oxide) with a thickness of 1500 Å was ultrasonically washed with distilled water. After the distilled water was washed, the substrate was ultrasonically washed with a solvent such as isopropyl alcohol, acetone, or methanol, dried and transferred to a UV OZONE cleaner (Power Sonic 405, Hoshin Tech), the substrate was cleaned using UV for 5 minutes, The substrate was transferred.

(60 nm) / TCTA (80 nm) / 90% compound of each of Synthetic Examples 1 to 31 + 10% Ir (ppy) ₃ (30 nm) / BCP (10 nm) on an ITO transparent substrate / Alq ₃ (30 nm) / LiF (1 nm) / Al (200 nm) in this order.

[Comparative Example 1] Production of green organic electroluminescent device

A green organic electroluminescent device was prepared in the same manner as in Example 1, except that CBP was used instead of the compound of Synthesis Example 1 as a luminescent host material in forming the light emitting layer.

The structures of m-MTDATA, TCTA, Ir (ppy) ₃ , CBP and BCP used in Examples 1 to 31 and Comparative Example 1 are as follows.

[Evaluation example]

The driving voltage, current efficiency and emission peak at the current density of 10 mA / cm 2 were measured for each of the green organic electroluminescent devices prepared in Examples 1 to 31 and Comparative Example 1, and the results are shown in Table 1 below .

Sample Host The driving voltage (V) Emission peak (nm) Current efficiency (cd / A) Example 1 C-1 6.87 517 39.1 Example 2 C-4 6.49 516 41.0 Example 3 C-5 6.81 518 40.9 Example 4 C-7 6.81 518 39.7 Example 5 C-12 6.78 517 40.0 Example 6 C-13 6.87 517 41.5 Example 7 C-17 6.49 518 41.8 Example 8 C-20 6.80 517 40.8 Example 9 C-21 6.78 517 41.2 Example 10 C-22 6.81 518 41.6 Example 11 C-23 6.87 516 40.2 Example 12 C-25 6.83 518 40.1 Example 13 C-30 6.72 516 40.7 Example 14 C-38 6.66 518 39.1 Example 15 C-40 6.66 517 39.3 Example 16 C-46 6.87 518 41.0 Example 17 C-51 6.66 516 40.7 Example 18 C-55 6.71 518 39.1 Example 19 C-56 6.72 518 39.9 Example 20 C-57 6.87 517 39.3 Example 21 C-59 6.93 517 41.1 Example 22 C-100 6.71 518 42.2 Example 23 C-102 6.72 516 40.7 Example 24 C-103 6.66 518 39.1 Example 25 C-108 6.66 517 39.3 Example 26 C-114 6.87 518 41.0 Example 27 C-118 6.66 516 40.7 Example 28 C-123 6.71 518 39.1 Example 29 C-124 6.72 518 39.9 Example 30 C-125 6.87 517 39.3 Example 31 C-126 6.93 517 41.1 Comparative Example 1 CBP 6.93 516 38.2

As shown in Table 1, when the compound of the present invention was applied to the light emitting layer of the green organic electroluminescent device (Examples 1 to 31), the efficiency and the driving voltage of the conventional CBP (Comparative Example 1) Performance. &Lt; / RTI &gt;

Claims (7)

A compound represented by the following formula (1):
[Chemical Formula 1]

In Formula 1,
R ₁ and R ₂ or R ₂ and R ₃ form a fused ring represented by the following formula (2)
(2)

In Formula 2,
The dotted line is a moiety bonded to the formula (1)
X ₁ to X ₁₂ are each independently N or C (R ₄ )
Y ₁ is selected from the group consisting of C (Ar ₂ ) (Ar ₃ ), N (Ar ₄ ), O, S and Si (Ar ₅ ) (Ar ₆ )
Wherein R ₁ to R ₄ are each independently hydrogen, deuterium, a halogen, a cyano group, a nitro group, C ₁ ~ alkynyl group of C ₄₀ alkyl group, C ₂ ~ C ₄₀ alkenyl group, C ₂ ~ C ₄₀ of, C ₃ ~ C ₄₀ cycloalkyl group, the number of nuclear atoms of 3 to 40 of the heterocycloalkyl of the alkyl group, C ₆ ~ C ₆₀ aryl group, the number of nuclear atoms of 5 to 60 heteroaryl group, C ₁ ~ alkyloxy group of C _40, C ₆ ~ C ₆₀ aryloxy group, C ₃ ~ C ₄₀ alkylsilyl group, C ₆ ~ C ₆₀ aryl silyl group, a alkyl boronic of C ₁ ~ C _40, an aryl boronic a C ₆ ~ C _60, C ₆ ~ C ₆₀ aryl phosphine group, C ₆ ~ C ₆₀ aryl phosphine oxide group, and a C ₆ ~ selected from the group consisting of C ₆₀ aryl amine, or by combining adjacent groups may form a fused ring,
Each of Ar ₁ to Ar ₆ is independently a C ₁ to C ₄₀ alkyl group, a C ₂ to C ₄₀ alkenyl group, a C ₂ to C ₄₀ alkynyl group, a C ₃ to C ₄₀ cycloalkyl group, A C ₆ to C ₆₀ aryl group, a heteroaryl group having 5 to 60 nuclear atoms, a C ₁ to C ₄₀ alkyloxy group, a C ₆ to C ₆₀ aryloxy group, a C ₃ to C ₆ heteroaryl group, ₄₀ alkylsilyl group, C ₆ ~ C ₆₀ aryl silyl group, C ₁ ~ C ₄₀ group of an alkyl boron, C ₆ ~ C group ₆₀ arylboronic of, C ₆ ~ aryl phosphine of C ₆₀ pingi, C ₆ ~ C ₆₀ aryl phosphine oxide group, and a C ₆ ~ C ₆₀ of is selected from the group consisting of an aryl amine,
The alkyl group, alkenyl group, alkynyl group, cycloalkyl group, heterocycloalkyl group, aryl group, heteroaryl group, alkyloxy group, aryloxy group, alkylsilyl group and arylsilyl group of R ₁ to R ₄ and Ar ₁ to Ar ₆ , An alkylboron group, an arylboron group, an arylphosphine group, an arylphosphine oxide group and an arylamine group are each independently a C ₁ to C ₄₀ alkyl group, a C ₂ to C ₄₀ alkenyl group, a C ₂ to C ₄₀ alkoxy group, group, C ₃ ~ C ₄₀ cycloalkyl group, the number of nuclear atoms of 3 to 40 hetero cycloalkyl, heteroaryl of C ₆ ~ C ₆₀ aryl group, the number of nuclear atoms of 5 to 60 aryl group, C ₁ ~ C ₄₀ alkyloxy A C ₆ to C ₆₀ aryloxy group, a C ₃ to C ₄₀ alkylsilyl group, a C ₆ to C ₆₀ arylsilyl group, a C ₁ to C ₄₀ alkylboron group, a C ₆ to C ₆₀ arylboron group, may be substituted with at least one member selected from the group consisting of an arylamine C ₆ ~ C ₆₀ aryl phosphine group, C ₆ ~ C ₆₀ aryl phosphine oxide group, and a C ₆ ~ C ₆₀ of. The method according to claim 1,
Wherein the compound represented by the formula (1) is selected from the group consisting of compounds represented by the following formulas (3) to (6).
(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

In the above formulas 3 to 6,
X ₁ to X ₁₂ , Ar ₁ , Y ₁ and R ₁ to R ₃ are the same as defined in claim 1. The method according to claim 1,
Wherein the compound represented by the formula (1) is selected from the group consisting of compounds represented by the following formulas (7) to (10).
(7)

[Chemical Formula 8]

[Chemical Formula 9]

[Chemical formula 10]

In the above formulas (7) to (10)
R ₁ to R ₄ , Ar ₁ and Ar ₄ are the same as defined in claim 1. The method according to claim 1,
Each of Ar ₁ to Ar ₆ is independently a C ₆ to C ₆₀ aryl group or a heteroaryl group having 5 to 60 nuclear atoms. anode; cathode; And at least one organic material layer interposed between the anode and the cathode, the organic electroluminescent device comprising:
Wherein at least one of the one or more organic layers includes a compound according to any one of claims 1 to 4. 6. The method of claim 5,
Wherein the organic material layer is selected from the group consisting of a hole injection layer, a hole transporting layer, and a light emitting layer. 6. The method of claim 5,
The organic compound layer containing the compound is a light emitting layer,
Wherein the compound is a phosphorescent host of the light emitting layer.