WO2015099477A2 - Organic compound and organic light-emitting diode device using same - Google Patents

Abstract

The present invention relates to an organic compound and an organic light-emitting diode device comprising the same. The compound according to the present invention can be used for an organic layer of an organic light-emitting diode device preferably for a light-emitting layer, and can thereby improve light-emission efficiency, driving voltage and life expectancy of the organic light-emitting diode device.

Description

Organic Compounds and Organic Electroluminescent Devices Using the Same

The present invention relates to a novel organic 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 material layer at the anode, and electrons are injected into the organic material layer at the cathode. When the injected holes and electrons meet, excitons are formed, and when the excitons fall to the ground, they shine. The material included in the organic material layer may be classified into a light emitting material, a hole injection material, a hole transport material, an electron transport material, an electron injection material, and the like according to its function.

The light emitting material may be classified into blue, green, and red light emitting materials according to the light emitting color, and yellow and orange light emitting materials required to realize a better natural color. In addition, a host / dopant system may be used as a light emitting material to increase luminous efficiency through an increase in color purity and energy transfer.

The dopant material may 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. In this case, since phosphorescent dopants can theoretically improve luminous efficiency up to 4 times compared to fluorescent dopants, studies on phosphorescent dopants as well as phosphorescent hosts are being conducted.

At present, anthracene derivatives are known as fluorescent dopant / host materials used in the light emitting layer. In addition, as a phosphorescent dopant material used in the light emitting layer, metal complex compounds containing Ir, such as Firpic, Ir (ppy) ₃ , and (acac) Ir (btp) ₂ , are known. (CBP) is known.

However, existing materials have low glass transition temperature and poor thermal stability, and thus are not satisfactory in terms of lifespan in an organic EL device, and still need improvement in terms of light emission characteristics.

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

Moreover, an object of this invention is to provide the organic electroluminescent element containing the said organic compound.

In order to achieve the above object, the present invention provides a compound represented by the following formula (1) or (2).

[Formula 1]

[Formula 2]

In Chemical Formula 1 or 2,

At least _one of R ₁ and R ₂ , R ₂ and R ₃ , R ₃ and R ₄ , R ₅ and R ₆ , R ₆ and R ₇ , or R ₇ and R ₈ are bonded to each other to be represented by the following formula (3) Form a ring,

[Formula 3]

In Chemical Formula 3,

The dotted line is a part where condensation is made with Formula 1 or 2,

X ₁ is selected from the group consisting of C (Ar ₃ ) (Ar ₄ ), N (Ar ₅ ), O, S and Si (Ar ₆ ) (Ar ₇ ),

R ₁ to R ₁₂ are each independently hydrogen, other than those which form a condensed ring, a deuterium, a halogen, a cyano group, a nitro group, C ₁ ~ alkenyl group of the C ₄₀ alkyl group, C ₂ ~ C ₄₀ of, C ₂ ~ C ₄₀ Alkynyl group, C ₃ -C ₄₀ cycloalkyl group, C 3 -C 40 heterocycloalkyl group, C ₆ -C ₆₀ aryl group, nuclear atom 5-60 heteroaryl group, C ₁ -C ₄₀ Alkyloxy group, C ₆ ~ C ₆₀ aryloxy group, C ₃ ~ C ₄₀ alkylsilyl group, C ₆ ~ C ₆₀ arylsilyl group, C ₁ ~ C ₄₀ alkyl boron group, C ₆ ~ C ₆₀ aryl boron group, C ₆ ~ C ₆₀ aryl phosphine group, C ₆ ~ C ₆₀ aryl phosphine oxide group, and a C ₆ ~, or selected from the group consisting of an aryl amine of the C _60, the combined contiguous groups to form a condensed ring Can and

Ar ₁ to Ar ₇ are each independently C ₁ ~ C ₄₀ Alkyl group, C ₂ ~ C ₄₀ Alkenyl group, C ₂ ~ C ₄₀ Alkynyl group, C ₃ ~ C ₄₀ Cycloalkyl group, 3 to 40 nuclear atoms Heterocycloalkyl group, C ₆ ~ C ₆₀ aryl group, heteroaryl group having 5 to 60 nuclear atoms, C ₁ ~ C ₄₀ alkyloxy group, C ₆ ~ C ₆₀ aryloxy group, C ₃ ~ C ₄₀ Alkyl silyl group, C ₆ ~ C ₆₀ aryl silyl group, C ₁ ~ C ₄₀ alkyl boron group, C ₆ ~ C ₆₀ aryl boron group, C ₆ ~ C ₆₀ aryl phosphine group, C ₆ ~ C ₆₀ Aryl phosphine oxide group and C ₆ ~ C _{60 It} is selected from the group consisting of arylamine group,

The alkyl group, alkenyl group, alkynyl group of R ₁ to R ₁₂ and Ar ₁ to Ar ₇ . Cycloalkyl group, heterocycloalkyl group, aryl group, heteroaryl group, alkyloxy group, aryloxy group, alkylsilyl group, arylsilyl group, alkyl boron group, aryl boron group, aryl phosphine group, aryl phosphine oxide group and arylamine groups are each independently, C ₁ ~ C ₄₀ alkyl group, C ₂ ~ C ₄₀ alkenyl group, C ₂ ~ C ₄₀ alkynyl group, C ₃ ~ C ₄₀ cycloalkyl group, a number of nuclear atoms of 3 to 40 heterocycloalkyl group of the , C ₆ ~ C ₆₀ aryl group, nuclear atom 5 ~ 60 heteroaryl group, C ₁ ~ C ₄₀ alkyloxy group, C ₆ ~ C ₆₀ aryloxy group, C ₃ ~ C ₄₀ alkylsilyl group , C ₆ ~ C ₆₀ arylsilyl group, C ₁ ~ C ₄₀ alkyl boron group, C ₆ ~ C ₆₀ aryl boron group, C ₆ ~ C ₆₀ aryl phosphine group, C ₆ ~ C ₆₀ aryl phosphine Substituted or unsubstituted with one or more selected from the group consisting of an oxide group and a C ₆ -C ₆₀ arylamine group. In this case, when R ₁ to R ₁₂ and Ar ₁ to Ar ₇ are substituted with a plurality of substituents, the plurality of substituents are the same or different from each other.

In addition, the present invention is an organic electroluminescent device comprising an anode, a cathode and at least one organic layer interposed between the anode and the cathode, at least one of the at least one organic layer is represented by the formula (1) or (2) An organic electroluminescent device comprising a compound is provided.

In the present invention, alkyl refers to a monovalent substituent derived from a straight or branched chain 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, hexyl and the like.

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

Alkynyl in the present invention means a monovalent substituent derived from a straight or branched chain unsaturated hydrocarbon having 2 to 40 carbon atoms 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 60 carbon atoms combined with a single ring or two or more rings. In addition, a form in which two or more rings are attached to each other (pendant) or condensed may also be included. Examples of such aryl include, but are not limited to, phenyl, naphthyl, phenanthryl, anthryl, and the like.

Heteroaryl in the present invention means a monovalent substituent derived from monoheterocyclic or polyheterocyclic aromatic hydrocarbon having 5 to 60 nuclear atoms. At least one carbon in the ring, preferably 1 to 3 carbons, is substituted with a heteroatom such as N, O, S or Se. In addition, a form in which two or more rings are pendant or condensed with each other may be included, and may also include a form in which the two or more rings are condensed with an aryl group. Examples of such heteroaryl include 6-membered monocyclic rings such as pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, triazinyl, phenoxathienyl, indolinzinyl, indolyl ( polycyclic rings such as indolyl, purinyl, quinolyl, benzothiazole, carbazolyl and 2-furanyl, N-imidazolyl, 2-isoxazolyl , 2-pyridinyl, 2-pyrimidinyl, and the like, but are not limited thereto.

In the present invention, aryloxy is a monovalent substituent represented by RO-, wherein R means aryl having 6 to 60 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 represented by R'O-, wherein R 'means 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, pentoxy and the like.

In the present invention, arylamine means an amine substituted with aryl having 6 to 60 carbon atoms.

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

Heterocycloalkyl in the present invention means a monovalent substituent derived from a non-aromatic hydrocarbon having 3 to 40 nuclear atoms, wherein at least one carbon in the ring, preferably 1 to 3 carbons is N, O, S or Se Is substituted with a hetero atom such as 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 60 carbon atoms.

Condensed ring in the present invention means a condensed aliphatic ring, a condensed aromatic ring, a condensed heteroaliphatic ring, a condensed heteroaromatic ring or a combination thereof.

Hereinafter, the present invention will be described.

1. New Organic Compounds

The compound of the present invention is a fused carbon ring (preferably a condensed heterocyclic moiety) is linked to the indoloindole moiety as a basic skeleton, and a variety of substituents are bonded, represented by the formula (1) or (2) .

Such compounds represented by the formula (1) or (2) of the present invention may be adjusted to HOMO and LUMO energy levels according to the type of substituents introduced into the basic skeleton can exhibit a wide bandgap and excellent carrier transport properties. Therefore, the compound represented by Formula 1 or 2 of the present invention can be usefully applied as an organic material layer material of the organic EL device.

For example, an electron withdrawing electron (EWG) having high electron absorption such as a nitrogen-containing heterocycle (eg, pyridine group, pyrimidine group, triazine group, etc.) may be bonded to the basic skeleton of the compound represented by Formula 1 or 2 above. In this case, since the entire molecule has a bipolar (bipolar) property to increase the binding force between the hole and the electron, it is advantageous as a host in the light emitting layer of the organic EL device. In addition, the compound represented by the formula (1) or (2) in which the electron withdrawing group is introduced is also useful for the electron injection layer or the electron transport layer of the organic EL device because of excellent carrier transport properties.

On the other hand, when the electron donor (EDG) having a large electron donor such as an arylamine group, carbazole group, terphenyl group, triphenylene group, etc. is bonded to the basic skeleton of the compound represented by Formula 1 or 2, the injection and transport of holes Since this is performed smoothly, it is also useful as a hole injection / transport layer or light emitting auxiliary layer material of an organic electroluminescent element.

In addition, the compound represented by the formula (1) or (2) has a high glass transition temperature due to the introduction of various substituents, especially aryl groups and / or heteroaryl groups in the basic skeleton to significantly increase the molecular weight of the conventional organic material layer material (for example , CBP) has better thermal stability. In addition, the compound represented by the formula (1) or (2) is effective in suppressing crystallization of the organic material layer.

Therefore, the organic electroluminescent device including the compound represented by Chemical Formula 1 or 2 of the present invention in the organic material layer can be greatly improved in performance and lifespan characteristics, and the full-color organic light emitting panel to which the organic electroluminescent device is applied also maximizes performance. Can be.

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 (4) to (9).

[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

In Formulas 4 to 9, Ar ₁ , Ar ₂ , X ₁ and R ₁ to R ₁₂ are the same as defined above.

In addition, the compound represented by the formula (2) of the present invention is preferably selected from the group consisting of compounds represented by the following formula (10 to 15).

[Formula 10]

[Formula 11]

[Formula 12]

[Formula 13]

[Formula 14]

[Formula 15]

In Chemical Formulas 10 to 15,

Ar ₁ , Ar ₂ , X ₁ and R ₁ to R ₁₂ are the same as defined above.

In the compounds represented by Formulas 4 to 15, one of R ₅ and R ₆ , R ₆ and R _7, or R ₇ and R ₈ may be bonded to each other to form or may not form a condensed ring as shown in Formula 3 above. .

The compound represented by the formula (1) or (2) of the present invention, X ₁ in the group consisting of C (Ar ₃ ) (Ar ₄ ), N (Ar ₅ ), O, S and Si (Ar ₆ ) (Ar ₇ ) In consideration of the characteristics of the organic EL device, X ₁ is preferably N (Ar ₅ ).

In addition, considering the wide bandgap and thermal stability of the compound, Ar ₁ , Ar ₂ and Ar ₅ in the compound represented by Formula 1 or 2 of the present invention are each independently an aryl group of C ₆ ~ C ₆₀ , or a nuclear atom It is preferable that it is a heteroaryl group of 5 to 60 numbers.

In addition, in the compound represented by Formula 1 or 2 of the present invention, except that forming a condensed ring, R ₁ to R ₁₂ are each independently hydrogen, halogen, cyano group, nitro group, C ₁ ~ C ₄₀ alkyl group, C ₆ ~ to be C ₆₀ aryl group, nuclear atoms selected from 5 to 60 heteroaryl group, and the group consisting of C ₆ - C ₆₀ aryl amines are preferred.

Specifically, in the compound represented by Formula 1 or 2 of the present invention, R ₁ to R ₁₂ except for forming Ar ₁ to Ar ₇ and a condensed ring are each independently hydrogen, or a structure represented by the following S1 to S204 ( Substituents), but is not limited thereto.

Such compounds represented by the formula (1) or (2) of the present invention may be further embodied by the formulas illustrated below. However, the compound represented by Formula 1 or 2 of the present invention is not limited to the compounds illustrated below.

2. Organic electroluminescent device

The present invention includes an anode, a cathode and at least one organic material layer interposed between the anode and the cathode, wherein at least one of the organic material layers includes at least one compound represented by Formula 1 or 2 Provided is an element.

The organic material layer including the compound represented by Formula 1 or 2 may be any one or more 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 or 2 may be included in the organic electroluminescent device as a light emitting layer material. In this case, the organic EL device may improve luminous efficiency, brightness, power efficiency, thermal stability, and device life.

In particular, the compound represented by Formula 1 or 2 of the present invention is preferably a phosphorescent host, a fluorescent host or a dopant of the light emitting layer, and more preferably a phosphorescent host of the light emitting layer.

The structure of the organic EL device of the present invention is not particularly limited, but a substrate, an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and a cathode may be sequentially stacked. In this case, at least one of the hole injection layer, the hole transport layer, and the light emitting layer may include at least one compound represented by Formula 1 or 2. An electron injection layer may be positioned on the electron transport layer.

In addition, the organic electroluminescent device of the present invention may have a structure in which an insulating layer or an adhesive layer is inserted at an interface between an electrode and an organic material layer.

In the organic electroluminescent device of the present invention, the organic material layer including the compound represented by Chemical Formula 1 or 2 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 forms an organic material layer and an electrode using materials and methods known in the art, except that at least one layer of the organic material layer is formed to include the compound represented by Chemical Formula 1 or 2 above. Can be prepared.

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

The anode material may be a metal such as vanadium, chromium, copper, zinc, gold or an alloy thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO); Combinations of metals and oxides such as ZnO: Al or SnO ₂ : 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 is not limited thereto.

The negative electrode material may be a metal such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, or lead or an alloy thereof; Multilayer structure materials such as LiF / Al or LiO ₂ / Al, and the like, but are not limited thereto.

The material used for the hole injection layer, the hole transport layer, the electron injection layer and the electron transport 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 the following Examples. However, the following examples are merely to illustrate the present invention and the present invention is not limited by the following examples.

Preparation Example 1 Synthesis of A3

<Step 1> Synthesis of 2- (3-bromo-2-nitrophenyl) -1-phenyl-1H-indole

2-bromo-1-phenyl-1H-indole, 10.9 g, (40.0 mmol), 3-bromo-2-nitrophenylboronic acid, 9.8 g (40.0 mmol), 2.3 g (5 mol%) of Pd (PPh) under nitrogen stream ₃ ) ₄ and 16.6 g (120.0 mmol) of potassium carbonate were added to 80 ml / 40 ml / 40 ml of Toluene / H ₂ O / Ethanol and stirred at 110 ° C. for 3 hours. After completion of the reaction, the organic layer was separated using methylene chloride and water was removed using MgSO ₄ . After removing the solvent of the organic layer was purified by column chromatography to give 2- (3-bromo-2-nitrophenyl) -1-phenyl-1H-indole (13.7g, 34.8mmol, 87% yield).

GC-Mass (Theoretical value: 393.23 g / mol, Measured value: 393 g / mol)

1H-NMR: δ 6.78 (s, 1H), 6.82 ~ 6.85 (m, 1H), 7.28 (m, 1H), 7.41 ~ 7.48 (m, 5H), 7.76 ~ 7.79 (m, 2H), 7.91 ~ 7.94 ( m, 3H)

Step 2 Synthesis of 1-bromo-5-phenyl-5,10-dihydroindolo [3,2-b] indole

Under nitrogen stream, add 13.7 g (34.8 mmol) of 2- (3-bromo-2-nitrophenyl) -1-phenyl-1H-indole, 22.8 g (87.0 mmol) of triphenylphosphine, and 140 ml of 1,2-dichlorobenzene for 12 hours. Stirred. After completion of the reaction, 1,2-dichlorobenzene was removed, the organic layer was separated using methylene chloride, and water was removed using MgSO ₄ . After removing the solvent of the organic layer was purified by column chromatography to give 1-bromo-5-phenyl-5,10-dihydroindolo [3,2-b] indole (9.2g, 25.4mmol, 73% yield).

GC-Mass (Theoretical value: 361.23 g / mol, Measured value: 361 g / mol)

1 H-NMR: δ 7.16 to 7.56 (s, 9H), 7.91 (d, 1H), 8.02 (d, 1H), 8.71 (m, 1H), 9.98 (s, 1H)

Step 3 Synthesis of 1-bromo-5,10-diphenyl-5,10-dihydroindolo [3,2-b] indole

9.2 g (25.4 mmol) 1-bromo-5-phenyl-5,10-dihydroindolo [3,2-b] indole under nitrogen stream, 15.6 g (76.2 mmol) iodobenzene, 1.1 g (17.8 mmol) Cu powder, K ₂ 7.0 g (50.8 mmol) of CO ₃ and 70 ml of nitrobenzene were mixed and stirred at 200 ° C. for 12 hours. After completion of the reaction, nitrobenzene was removed, the organic layer was separated with methylene chloride, and water was removed using MgSO ₄ . After removing the solvent of the organic layer was purified by column chromatography to give 1-bromo-5,10-diphenyl-5,10-dihydroindolo [3,2-b] indole (8.7g, 20.0mmol, 79% yield).

GC-Mass (Theoretical value: 437.33 g / mol, Measured value: 437 g / mol)

1 H-NMR: δ 7.11 (t, 1H), 7.21 to 28 (m, 3H), 7.41 to 7.57 (m, 10H), 7.91 (d, 1H), 8.65 (d, 1H), 8.71 (d, 1H)

Step 4 Synthesis of 1- (2-nitrophenyl) -5,10-diphenyl-5,10-dihydroindolo [3,2-b] indole

8.7 g of 1-bromo-5,10-diphenyl-5,10-dihydroindolo [3,2-b] indole under nitrogen stream, (20.0 mmol), 3.3 g (20.0 mmol) of 2-nitrophenylboronic acid, 1.1 g (5 mol) %) Of Pd (PPh ₃ ) ₄ and 8.3 g (60.0 mmol) of potassium carbonate were added to 80 ml / 40 ml / 40 ml of Toluene / H ₂ O / Ethanol and stirred at 110 ° C. for 3 hours. After completion of the reaction, the organic layer was separated using methylene chloride and water was removed using MgSO ₄ . After removing the solvent of the organic layer and purified by column chromatography 1- (2-nitrophenyl) -5,10-diphenyl-5,10-dihydroindolo [3,2-b] indole (7.7g, 16.0mmol, 80% yield) Got.

GC-Mass (Theoretical value: 479.53 g / mol, Measured value: 479 g / mol)

1 H-NMR: δ 7.24 to 7.72 (m, 3H), 7.42 to 56 (m, 11H), 7.61 to 7.94 (m, 4H), 8.25 (d, 1H), 8.69 to 8.72 (m, 2H)

Step 5 Synthesis of A3

7.7 g (16.0 mmol) of 1- (2-nitrophenyl) -5,10-diphenyl-5,10-dihydroindolo [3,2-b] indole under nitrogen stream, 10.5 g (40.0 mmol) of triphenylphosphine, 1,2-dichlorobenzene 80 ml was added and stirred for 12 hours. After completion of the reaction, 1,2-dichlorobenzene was removed, the organic layer was separated using methylene chloride, and water was removed using MgSO ₄ . After removing the solvent of the organic layer was purified by column chromatography to give A3 (5.5g, 12.3mmol, 77% yield).

GC-Mass (Theoretical value: 447.53 g / mol, Measured value: 447 g / mol)

1 H-NMR: δ 7.24 to 7.31 (m, 3H), 7.41 to 7.61 (m, 13H), 7.91 (d, 1H), 8.09 (d, 1H), 8.41 (d, 1H), 8.71 (d, 1H) , 9.94 (s, 1H)

Preparation Example 2 Synthesis of B3 and B4

<Step 1> Synthesis of 2- (4-bromo-2-nitrophenyl) -1-phenyl-1H-indole

10.9 g (40.0 mmol) of 2-bromo-1-phenyl-1H-indole, 9.8 g (40.0 mmol) of 4-bromo-2-nitrophenylboronic acid, 2.3 g (5 mol%) of Pd (PPh ₃ ) ₄ under nitrogen stream , potassium carbonate, 16.6 g (120.0 mmol) and 80 ml / 40 ml / 40 ml of Toluene / H ₂ O / Ethanol were added and stirred at 110 ° C. for 2 hours. After completion of the reaction, the organic layer was separated using methylene chloride and water was removed using MgSO ₄ . After removing the solvent of the organic layer was purified by column chromatography to give 2- (4-bromo-2-nitrophenyl) -1-phenyl-1H-indole (13.4g, 34.0mmol, 85% yield).

GC-Mass (Theoretical value: 393.23 g / mol, Measured value: 393 g / mol)

1H-NMR: δ 6.87 (s, 1H), 6.85 (m, 1H), 7.29 (m, 1H), 7.41 ~ 7.54 (m, 5H), 7.91 ~ 7.93 (m, 3H), 8.01 (d, 1H) , 8.61 (d, 1H)

<Step 2> Synthesis of 2-bromo-5-phenyl-5,10-dihydroindolo [3,2-b] indole

Under nitrogen stream, add 13.4 g (34.0 mmol) of 2- (4-bromo-2-nitrophenyl) -1-phenyl-1H-indole, 22.3 g (85.0 mmol) of triphenylphosphine, and 140 ml of 1,2-dichlorobenzene for 12 hours. Stirred. After completion of the reaction, 1,2-dichlorobenzene was removed, the organic layer was separated using methylene chloride, and water was removed using MgSO ₄ . After removing the solvent of the organic layer was purified by column chromatography to give 2-bromo-5-phenyl-5,10-dihydroindolo [3,2-b] indole (9.0g, 24.8mmol, 73% yield).

GC-Mass (Theoretical value: 361.23 g / mol, Measured value: 361 g / mol)

1 H-NMR: δ 7.21-7.31 (m, 3H), 7.41-54 (m, 6H), 7.91-7.94 (m, 2H), 8.71 (d, 1H), 9.96 (s, 1H)

Step 3 Synthesis of 2-bromo-5,10-diphenyl-5,10-dihydroindolo [3,2-b] indole

9.0 g (24.8 mmol) of 1-bromo-5-phenyl-5,10-dihydroindolo [3,2-b] indole under nitrogen stream, 15.2 g (74.5 mmol) of iodobenzene, 1.1 g (17.4 mmol) of Cu powder, K ₂ 6.9 g (49.6 mmol) of CO ₃ and 70 ml of nitrobenzene were mixed and stirred at 200 ° C. for 12 hours. After completion of the reaction, nitrobenzene was removed, the organic layer was separated with methylene chloride, and water was removed using MgSO ₄ . After removing the solvent of the organic layer was purified by column chromatography to give 2-bromo-5,10-diphenyl-5,10-dihydroindolo [3,2-b] indole (8.7g, 20.0mmol, 81% yield).

GC-Mass (Theoretical value: 437.33 g / mol, Measured value: 437 g / mol)

1 H-NMR: δ 7.16-7.31 (m, 3H), 7.41-7.54 (m, 10H), 7.91 (d, 1H), 8.28 (d, 1H), 8.72-8.74 (m, 2H)

Step 4 Synthesis of 2- (2-nitrophenyl) -5,10-diphenyl-5,10-dihydroindolo [3,2-b] indole

2-bromo-5,10-diphenyl-5,10-dihydroindolo [3,2-b] indole (8.7 g instead of 1-bromo-5,10-diphenyl-5,10-dihydroindolo [3,2-b] indole 20.0 mmol), except that 2- (2-nitrophenyl) -5,10-diphenyl-5,10-dihydroindolo [3,2-b was carried out in the same manner as in <Step 4> of Preparation Example 1 ] indole (7.2 g, 15.0 mmol, yield 75%) was obtained.

GC-Mass (Theoretical value: 479.53 g / mol, Measured value: 479 g / mol)

1 H-NMR: δ 7.41 to 7.54 (m, 16H), 7.75 (d, 1H), 7.91 (d, 1H), 8.07 (d, 1H), 8.44 (d, 1H), 8.71 (d, 1H)

Step 5 Synthesis of B3 and B4

2- (2-nitrophenyl) -5,10-diphenyl-5,10-dihydroindolo [3, instead of 1- (2-nitrophenyl) -5,10-diphenyl-5,10-dihydroindolo [3,2-b] indole Except for using 2-b] indole (7.2 g, 15.0 mmol), B3 (2.2 g, 5.0 mmol, yield 33%) and B4 (2.0 g) were subjected to the same process as in <Step 5> of Preparation Example 1. , 4.4 mmol, yield 29%).

GC-Mass of B3 (Theoretical value: 447.53 g / mol, Measured value: 447 g / mol)

1 H-NMR: δ 7.23 to 7.31 (m, 3H) 7.41 to 7.59 (m, 12H) 7.81 to 7.87 (m, 2H) 8.08 (d, 1H), 8.39 (d, 1H), 8.65 (d, 1H), 9.94 (s, 1 H)

GC-Mass of B4 (Theoretical value: 447.53 g / mol, Measured value: 447 g / mol)

1 H-NMR: δ 7.41 to 7.58 (m, 17H), 7.91 (d, 1H), 8.08 (d, 1H), 8.71 (d, 1H), 9.95 (s, 1H)

Preparation Example 3 Synthesis of C3 and C4

<Step 1> Synthesis of 2- (5-bromo-2-nitrophenyl) -1-phenyl-1H-indole

10.9 g of 2-bromo-1-phenyl-1H-indole under nitrogen stream, (40.0 mmol), 9.8 g (40.0 mmol) of 5-bromo-2-nitrophenylboronic acid, 2.3 g (5 mol%) of Pd (PPh ₃ ) ₄ and 16.6 g (120.0 mmol) of potassium carbonate were added to 80 ml / 40 ml / 40 ml of Toluene / H ₂ O / Ethanol and stirred at 110 ° C. for 2 hours. After completion of the reaction, the organic layer was separated using methylene chloride and water was removed using MgSO ₄ . After removing the solvent of the organic layer was purified by column chromatography to give 2- (5-bromo-2-nitrophenyl) -1-phenyl-1H-indole (13.5g, 34.0mmol, yield 86%).

GC-Mass (Theoretical value: 393.23 g / mol, Measured value: 393 g / mol)

1H-NMR: δ 6.80 (s, 1H), 6.86 (t, 1H), 7.32 (m, 1H), 7.44-7.57 (m, 5H), 7.71 (s, 1H), 7.93-7.96 (m, 3H) , 8.19 (d, 1 H)

<Step 2> Synthesis of 3-bromo-5-phenyl-5,10-dihydroindolo [3,2-b] indole

Under nitrogen stream, add 13.5 g (34.4 mmol) of 2- (5-bromo-2-nitrophenyl) -1-phenyl-1H-indole, 22.6 g (86.0 mmol) of triphenylphosphine, and 140 ml of 1,2-dichlorobenzene for 12 hours. Stirred. After completion of the reaction, 1,2-dichlorobenzene was removed, the organic layer was separated using methylene chloride, and water was removed using MgSO ₄ . After removing the solvent of the organic layer was purified by column chromatography to give 3-bromo-5-phenyl-5,10-dihydroindolo [3,2-b] indole (9.2g, 25.5mmol, 74% yield).

GC-Mass (Theoretical value: 361.23 g / mol, Measured value: 361 g / mol)

1 H-NMR: δ 7.21 to 7.57 (m, 9H), 7.91 (d, 1H), 8.02 (d, 1H), 8.71 (d, 1H), 7.93 (s, 1H)

<Step 3> Synthesis of 3-bromo-5,10-diphenyl-5,10-dihydroindolo [3,2-b] indole

9.2 g (25.5 mmol) of 3-bromo-5-phenyl-5,10-dihydroindolo [3,2-b] indole under nitrogen stream, 15.6 g (76.4 mmol) of iodobenzene, 1.1 g (17.8 mmol) of Cu powder, K ₂ 7.0 g (50.9 mmol) of CO ₃ and 70 ml of nitrobenzene were mixed and stirred at 200 ° C. for 12 hours. After completion of the reaction, nitrobenzene was removed, the organic layer was separated with methylene chloride, and water was removed using MgSO ₄ . After removing the solvent of the organic layer was purified by column chromatography to give 3-bromo-5,10-diphenyl-5,10-dihydroindolo [3,2-b] indole (8.7g, 20.0mmol, 79% yield).

GC-Mass (Theoretical value: 437.33 g / mol, Measured value: 437 g / mol)

1 H-NMR: δ 7.21 to 7.28 (m, 3H) 7.41 to 7.55 (m, 10H), 7.69 (d, 1H), 7.78 (d, 1H), 7.91 (d, 1H). 8.72 (d, 1 H)

Step 4 Synthesis of 3- (2-nitrophenyl) -5,10-diphenyl-5,10-dihydroindolo [3,2-b] indole

3-bromo-5,10-diphenyl-5,10-dihydroindolo [3,2-b] indole (8.7g instead of 1-bromo-5,10-diphenyl-5,10-diphydroindolo [3,2-b] indole , 20.0 mmol) was prepared by the same procedure as in <Step 4> of Preparation Example 1 to 3- (2-nitrophenyl) -5,10-diphenyl-5,10-dihydroindolo [3,2-b] Indole (7.1 g, 14.8 mmol, yield 74%) was obtained.

GC-Mass (Theoretical value: 479.53 g / mol, Measured value: 479 g / mol)

1 H-NMR: δ 7.24 to 7.31 (m, 2H), 7.42 to 7.75 (m, 11H), 7.71 (s, 1H), 7.90 to 8.01 (m, 5H), 8.16 (d, 1H), 8.72 (d, 1H)

Step 5 Synthesis of C3 and C4

3- (2-nitrophenyl) -5,10-diphenyl-5,10-dihydroindolo [3, instead of 1- (2-nitrophenyl) -5,10-diphenyl-5,10-dihydroindolo [3,2-b] indole Except for using 2-b] indole (7.1 g, 14.8 mmol), C3 (2.5 g, 5.5 mmol, yield 37%) and C4 (2.1 g, 4.6 mmol, yield 31%).

GC-Mass of C3 (Theoretical value: 447.53 g / mol, Measured value: 447 g / mol)

1 H-NMR: δ 7.24 to 7.55 (m, 17H), 7.92 (d, 1H), 8.11 (s, 1H), 8.72 (d, 1H), 9.96 (s, 1H)

GC-Mass of C4 (Theoretical value: 447.53 g / mol, Measured value: 447 g / mol)

1 H-NMR: δ 7.24 to 7.31 (m, 3H), 7.44 to 7.56 (m, 12H), 7.93 to 7.95 (m, 3H), 8.09 (d, 1H), 8.72 (d, 1H), 9.96 (s, 1H)

Preparation Example 4 Synthesis of D3

<Step 1> Synthesis of 2- (2-bromo-6-nitrophenyl) -1-phenyl-1H-indole

10.9 g (40.0 mmol) of 2-bromo-1-phenyl-1H-indole, 9.8 g (40.0 mmol) of 2-bromo-6-nitrophenylboronic acid, 2.3 g (5 mol%) of Pd (PPh ₃ ) ₄ under nitrogen stream 16.6 g (120.0 mmol) of potassium carbonate was added to 80 ml / 40 ml / 40 ml of Toluene / H ₂ O / Ethanol and stirred at 110 ° C. for 2 hours. After completion of the reaction, the organic layer was separated using methylene chloride and water was removed using MgSO ₄ . After removing the solvent of the organic layer was purified by column chromatography to give 2- (2-bromo-6-nitrophenyl) -1-phenyl-1H-indole (13.5g, 34.0mmol, yield 86%).

GC-Mass (Theoretical value: 393.23 g / mol, Measured value: 393 g / mol)

1H-NMR: δ 6.78 (s, 1H), 8.85 (m, 1H), 7.31 (m, 1H), 7.47 ~ 7.53 (m, 6H), 7.93 ~ 7.94 (m, 3H), 8.02 (d, 1H)

<Step 2> Synthesis of 4-bromo-5-phenyl-5,10-dihydroindolo [3,2-b] indole

Under nitrogen stream, add 13.5 g (34.4 mmol) of 2- (2-bromo-6-nitrophenyl) -1-phenyl-1H-indole, 22.6 g (86.0 mmol) of triphenylphosphine, and 140 ml of 1,2-dichlorobenzene for 12 hours. Stirred. After completion of the reaction, 1,2-dichlorobenzene was removed, the organic layer was separated using methylene chloride, and water was removed using MgSO ₄ . After removing the solvent of the organic layer was purified by column chromatography to give 4-bromo-5-phenyl-5,10-dihydroindolo [3,2-b] indole (9.3g, 25.8mmol, 75% yield).

GC-Mass (Theoretical value: 361.23 g / mol, Measured value: 361 g / mol)

1 H-NMR: δ 7.24 to 7.72 (m, 4H), 7.41 to 7.56 (m, 6H), 7.91 (d, 1H), 8.71 (d, 1H), 9.97 (s, 1H)

<Step 3> Synthesis of 4-bromo-5,10-diphenyl-5,10-dihydroindolo [3,2-b] indole

9.3 g (25.8 mmol) of 4-bromo-5-phenyl-5,10-dihydroindolo [3,2-b] indole under nitrogen stream, 15.8 g (77.4 mmol) of iodobenzene, 1.2 g (18.1 mmol) of Cu powder, K ₂ 7.1 g (51.6 mmol) of CO ₃ and 80 ml of nitrobenzene were mixed and stirred at 200 ° C. for 12 hours. After completion of the reaction, nitrobenzene was removed, the organic layer was separated with methylene chloride, and water was removed using MgSO ₄ . After removing the solvent of the organic layer was purified by column chromatography to give 4-bromo-5,10-diphenyl-5,10-dihydroindolo [3,2-b] indole (8.7g, 20.0mmol, 78% yield).

GC-Mass (Theoretical value: 437.33 g / mol, Measured value: 437 g / mol)

1 H-NMR: δ 7.14-7.28 (d, 4H), 7.42-7.55 (m, 10H), 7.84-7.97 (m, 2H), 8.74 (d, 1H)

Step 4 Synthesis of 4- (2-nitrophenyl) -5,10-diphenyl-5,10-dihydroindolo [3,2-b] indole

4-bromo-5,10-diphenyl-5,10-dihydroindolo [3,2-b] indole (8.7g instead of 1-bromo-5,10-diphenyl-5,10-dihydroindolo [3,2-b] indole , 20.0mmol) was subjected to the same process as in <Step 4> of Preparation Example 1 to 4- (2-nitrophenyl) -5,10-diphenyl-5,10-dihydroindolo [3,2-b] Indole (7.0 g, 14.6 mmol, yield 73%) was obtained.

GC-Mass (Theoretical value: 479.53 g / mol, Measured value: 479 g / mol)

1 H-NMR: δ 7.22-7.54 (m, 14H), 7.86-8.03 (m, 6H), 8.75 (d, 1H)

Step 5 Synthesis of D3

4- (2-nitrophenyl) -5,10-diphenyl-5,10-dihydroindolo [3, instead of 1- (2-nitrophenyl) -5,10-diphenyl-5,10-dihydroindolo [3,2-b] indole Except for using 2-b] indole (7.0g, 14.6mmol) was carried out the same procedure as in <Step 5> of Preparation Example 1 to obtain D3 (4.8g, 10.7mmol, 73% yield).

GC-Mass (Theoretical value: 447.53 g / mol, Measured value: 447 g / mol)

1 H-NMR: δ 7.24 to 7.31 (m, 2H), 7.42 to 7.56 (m, 13H), 7.93 to 7.95 (m, 2H), 8.08 (d, 1H), 8.71 (d, 2H), 9.97 (s, 1H)

Synthesis Example 1 Synthesis of R1

5.5 g (12.3 mmol) of A3, 5'-chloro-1,1 ', 3', 1 "-Terphenyl 3.6 g (13.6 mmol), 0.6 g (5 mol%) of Pd ₂ (dba) ₃ under nitrogen stream 0.1 g (0.6 mmol) of tri-tert-butylphosphine and 3.6 g (37.0 mmol) of sodium tert-butoxide were added to 90 ml of Toluenel and stirred at 110 ° C. for 4 hours. After the reaction was terminated, the organic layer was separated with methylene chloride, and then water was removed using MgSO ₄ . Purified by column chromatography to obtain the title compound R1 (5.1g, 7.5mmol, 61% yield).

GC-Mass (Theoretical value: 675.82 g / mol, Measured value: 675 g / mol)

Synthesis Example 2 Synthesis of R2

Except for using 2-chloro-4,6-diphenylpyridine 3.6g (13.6mmol) instead of 5'-chloro-1,1 ', 3', 1 ”-Terphenyl Compound R2 (5.3 g, 7.8 mmol, yield 63%) was obtained.

GC-Mass (Theoretical value: 676.81 g / mol, Measured value: 676 g / mol)

Synthesis Example 3 Synthesis of R3

Synthesis Example 1 except that 3.6 g (13.6 mmol) of 2'-chloro-6'-phenyl-2,4'-bipyridine was used instead of 5'-chloro-1,1 ', 3', 1 ”-Terphenyl. By the same process as in the title compound R3 (5.6g, 8.3mmol, 67% yield) was obtained.

GC-Mass (Theoretical value: 677.79 g / mol, Measured value: 677.79 g / mol)

Synthesis Example 4 Synthesis of R20

Except for using 4.7 g (13.6 mmol) of 2- (3-chlorophenyl) -4,6-diphenyl-1,3,5-triazine instead of 5'-chloro-1,1 ', 3', 1 ”-Terphenyl And the same procedure as in Synthesis Example 1 was carried out to obtain the target compound R20 (6.0g, 7.9mmol, 64% yield).

GC-Mass (Theoretical value: 754.88 g / mol, Measured value: 754.88 g / mol)

Synthesis Example 5 Synthesis of R25

Except for using 2-chloro-4-phenylquinazoline 3.3g (13.6mmol) instead of 5'-chloro-1,1 ', 3', 1 ”-Terphenyl was carried out the same procedure as in Synthesis Example 1 R25 (5.1 g, 7.9 mmol, yield 64%) was obtained.

GC-Mass (Theoretical value: 651.76 g / mol, Measured value: 651 g / mol)

Synthesis Example 6 Synthesis of R26

2.2 g (5.0 mmol) of B3, 5'-chloro-1,1 ', 3', 1 "-Terphenyl 1.4 g (5.4 mmol), 0.2 g (5 mol%) of Pd ₂ (dba) ₃ , under nitrogen stream 0.1 g (0.6 mmol) of -tert-butylphosphine and 1.4 g (14.9 mmol) of sodium tert-butoxide were added to 50 ml of Toluenel and stirred at 110 ° C. for 4 hours. After the reaction was terminated, the organic layer was separated with methylene chloride, and then water was removed using MgSO ₄ . Purified by column chromatography to obtain the title compound R26 (2.0g, 3.0mmol, 61% yield).

GC-Mass (Theoretical value: 675.82 g / mol, Measured value: 675 g / mol)

Synthesis Example 7 Synthesis of R27

Except for using 2-chloro-4,6-diphenylpyridine 1.5g (5.4mmol) instead of 5'-chloro-1,1 ', 3', 1 ”-Terphenyl The compound R27 (2.0 g, 3.0 mmol, yield 61%) was obtained.

GC-Mass (Theoretical value: 676.81 g / mol, Measured value: 676 g / mol)

Synthesis Example 8 Synthesis of R28

Synthesis Example 6 except that 2'-chloro-6'-phenyl-2,4'-bipyridine 1.5g (5.4 mmol) was used instead of 5'-chloro-1,1 ', 3', 1 ”-Terphenyl. 2.1 g (3.1 mmol, Yield 63%) of the title compound was obtained by performing the same procedure as described above.

GC-Mass (Theoretical value: 677.79 g / mol, Measured value: 677.79 g / mol)

Synthesis Example 9 Synthesis of R45

Except for using 1.9g (5.4mmol) of 2- (3-chlorophenyl) -4,6-diphenyl-1,3,5-triazine instead of 5'-chloro-1,1 ', 3', 1 ”-Terphenyl Then, the same procedure as in Synthesis Example 6 was performed to obtain R45 (2.4 g, 3.1 mmol, 63% yield) as a target compound.

GC-Mass (Theoretical value: 754.88 g / mol, Measured value: 754.88 g / mol)

Synthesis Example 10 Synthesis of R50

Except for using 2-chloro-4-phenylquinazoline 1.3g (5.4mmol) instead of 5'-chloro-1,1 ', 3', 1 ”-Terphenyl was carried out in the same manner as in Synthesis Example 6 R50 (2.1 g, 7.9 mmol, yield 65%) was obtained.

GC-Mass (Theoretical value: 651.76 g / mol, Measured value: 651 g / mol)

Synthesis Example 11 Synthesis of R51

Under nitrogen stream, B4 2.0 g (4.4 mmol), 5'-chloro-1,1 ', 3', 1 "-Terphenyl 1.3 g (4.8 mmol), 0.2 g (5 mol%) Pd ₂ (dba) ₃ , 0.1 g (0.6 mmol) of tri-tert-butylphosphine and 1.3 g (13.1 mmol) of sodium tert-butoxide were added to 30 ml of Toluenel and stirred at 110 ° C. for 4 hours. After the reaction was terminated, the organic layer was separated with methylene chloride, and then water was removed using MgSO ₄ . Purified by column chromatography to obtain the title compound R51 (1.8g, 3.0mmol, 61% yield).

GC-Mass (Theoretical value: 675.82 g / mol, Measured value: 675 g / mol)

Synthesis Example 12 Synthesis of R52

The same procedure as in Synthesis Example 11 was carried out except that 2-chloro-4,6-diphenylpyridine 1.3g (4.8mmol) was used instead of 5'-chloro-1,1 ', 3', 1 ”-Terphenyl. Compound R52 (2.0 g, 3.0 mmol, yield 68%) was obtained.

GC-Mass (Theoretical value: 676.81 g / mol, Measured value: 676 g / mol)

Synthesis Example 13 Synthesis of R53

Synthesis Example 11 except that 2'-chloro-6'-phenyl-2,4'-bipyridine 1.3g (4.8 mmol) was used instead of 5'-chloro-1,1 ', 3', 1 ”-Terphenyl. By the same process as in the title compound R53 (2.0g, 3.1mmol, yield 68%) was obtained.

GC-Mass (Theoretical value: 677.79 g / mol, Measured value: 677.79 g / mol)

Synthesis Example 14 Synthesis of R70

Except for using 1.7g (4.8mmol) of 2- (3-chlorophenyl) -4,6-diphenyl-1,3,5-triazine instead of 5'-chloro-1,1 ', 3', 1 ”-Terphenyl Then, the same process as in Synthesis Example 11 was carried out to obtain R70 (2.1 g, 2.8 mmol, 65% yield) as a target compound.

GC-Mass (Theoretical value: 754.88 g / mol, Measured value: 754.88 g / mol)

Synthesis Example 15 Synthesis of R75

Except for using 2-chloro-4-phenylquinazoline 1.2g (4.8mmol) instead of 5'-chloro-1,1 ', 3', 1 ”-Terphenyl was carried out in the same manner as in Synthesis Example 11 R75 (1.8 g, 2.8 mmol, yield 65%) was obtained.

GC-Mass (Theoretical value: 651.76 g / mol, Measured value: 651 g / mol)

Synthesis Example 16 Synthesis of R76

2.5 g (5.5 mmol) of C3, 5'-chloro-1,1 ', 3', 1 "-Terphenyl 1.6 g (6.0 mmol), 0.3 g (5 mol%) of Pd ₂ (dba) ₃ under nitrogen stream; 0.1 g (0.6 mmol) of tri-tert-butylphosphine and 1.6 g (16.4 mmol) of sodium tert-butoxide were added to 40 ml of Toluenel and stirred at 110 ° C. for 4 hours. After the reaction was terminated, the organic layer was separated with methylene chloride, and then water was removed using MgSO ₄ . Purified by column chromatography to obtain the title compound R76 (2.4g, 3.5mmol, 64% yield).

GC-Mass (Theoretical value: 675.82 g / mol, Measured value: 675 g / mol)

Synthesis Example 17 Synthesis of R77

The same procedure as in Synthesis Example 16 was conducted except that 2-chloro-4,6-diphenylpyridine 1.6g (6.0 mmol) was used instead of 5'-chloro-1,1 ', 3', 1 ”-Terphenyl. Compound R77 (2.3 g, 3.3 mmol, yield 61%) was obtained.

GC-Mass (Theoretical value: 676.81 g / mol, Measured value: 676 g / mol)

Synthesis Example 18 Synthesis of R78

Synthesis Example 16 except that 2'-chloro-6'-phenyl-2,4'-bipyridine 1.6g (6.0 mmol) was used instead of 5'-chloro-1,1 ', 3', 1 ”-Terphenyl To obtain the target compound R78 (2.3g, 3.4mmol, 62% yield).

GC-Mass (Theoretical value: 677.79 g / mol, Measured value: 677.79 g / mol)

Synthesis Example 19 Synthesis of R95

Except for using 2.1 g (6.0 mmol) of 2- (3-chlorophenyl) -4,6-diphenyl-1,3,5-triazine instead of 5'-chloro-1,1 ', 3', 1 ”-Terphenyl The same procedure as in Synthesis Example 16 was carried out to obtain R95 (2.8 g, 3.7 mmol, yield 67%) as a target compound.

GC-Mass (Theoretical value: 754.88 g / mol, Measured value: 754.88 g / mol)

Synthesis Example 20 Synthesis of R100

Except for using 1.5 g (6.0 mmol) of 2-chloro-4-phenylquinazoline instead of 5'-chloro-1,1 ', 3', 1 ”-Terphenyl, the same procedure as in Synthesis Example 16 was carried out. R100 (2.4 g, 3.7 mmol, yield 67%) was obtained.

GC-Mass (Theoretical value: 651.76 g / mol, Measured value: 651 g / mol)

Synthesis Example 21 Synthesis of R101

2.1 g (4.6 mmol) of C4, 5'-chloro-1,1 ', 3', 1 "-Terphenyl 1.3 g (5.0 mmol), 0.2 g (5 mol%) of Pd ₂ (dba) ₃ under nitrogen stream; 0.1 g (0.6 mmol) of tri-tert-butylphosphine and 1.3 g (13.8 mmol) of sodium tert-butoxide were added to 30 ml of Toluenel and stirred at 110 ° C. for 4 hours. After the reaction was terminated, the organic layer was separated with methylene chloride, and then water was removed using MgSO ₄ . Purified by column chromatography to obtain the title compound R101 (2.0g, 2.9mmol, 64% yield).

GC-Mass (Theoretical value: 675.82 g / mol, Measured value: 675 g / mol)

Synthesis Example 22 Synthesis of R102

Except for using 2-chloro-4,6-diphenylpyridine 1.3g (5.0mmol) instead of 5'-chloro-1,1 ', 3', 1 ”-Terphenyl Compound R102 (2.0 g, 2.9 mmol, Yield 64%) was obtained.

GC-Mass (Theoretical value: 676.81 g / mol, Measured value: 676 g / mol)

Synthesis Example 23 Synthesis of R103

Synthesis Example 21 except that 2'-chloro-6'-phenyl-2,4'-bipyridine 1.4g (5.0 mmol) was used instead of 5'-chloro-1,1 ', 3', 1 "-Terphenyl. By the same process as in the title compound R103 (2.0 g, 2.9mmol, 66% yield) was obtained.

GC-Mass (Theoretical value: 677.79 g / mol, Measured value: 677.79 g / mol)

Synthesis Example 24 Synthesis of R120

Except for using 1.7g (5.0mmol) of 2- (3-chlorophenyl) -4,6-diphenyl-1,3,5-triazine instead of 5'-chloro-1,1 ', 3', 1 ”-Terphenyl Then, the same procedure as in Synthesis Example 21 was carried out to obtain R120 (2.2 g, 2.9 mmol, 66% yield) as a target compound.

GC-Mass (Theoretical value: 754.88 g / mol, Measured value: 754.88 g / mol)

Synthesis Example 25 Synthesis of R125

Except for using 2-chloro-4-phenylquinazoline 1.2g (5.0mmol) instead of 5'-chloro-1,1 ', 3', 1 ”-Terphenyl was carried out in the same manner as in Synthesis Example 21 R125 (2.0 g, 3.1 mmol, yield 67%) was obtained.

GC-Mass (Theoretical value: 651.76 g / mol, Measured value: 651 g / mol)

Synthesis Example 26 Synthesis of R126

D3 4,8g (10.7mmol), 5'-chloro-1,1 ', 3', 1 ”-Terphenyl 3.1g (11.7mmol), 0.5g (5 mol%) Pd ₂ (dba) ₃ under nitrogen stream , tri-tert-butylphosphine 0.1g (0.6mmol) and sodium tert-butoxide 3.1g (32.0mmol) were added to 100ml of Toluenel and stirred at 110 ° C for 4 hours. After the reaction was terminated, the organic layer was separated with methylene chloride, and then water was removed using MgSO ₄ . Purified by column chromatography to obtain the title compound R126 (4.6g, 6.8mmol, 64% yield).

GC-Mass (Theoretical value: 675.82 g / mol, Measured value: 675 g / mol)

Synthesis Example 27 Synthesis of R127

Except for using 2-chloro-4,6-diphenylpyridine 3.1g (11.7mmol) instead of 5'-chloro-1,1 ', 3', 1 ”-Terphenyl Compound R127 (4.5 g, 6.6 mmol, yield 62%) was obtained.

GC-Mass (Theoretical value: 676.81 g / mol, Measured value: 676 g / mol)

Synthesis Example 28 Synthesis of R128

Synthesis Example 26 except that 2'-chloro-6'-phenyl-2,4'-bipyridine 3.1 g (11.7 mmol) was used instead of 5'-chloro-1,1 ', 3', 1 ”-Terphenyl. To carry out the same process as in the title compound R128 (4.5 g, 6.6mmol, yield 62%).

GC-Mass (Theoretical value: 677.79 g / mol, Measured value: 677.79 g / mol)

Synthesis Example 29 Synthesis of R145

Except for using 4.0 g (11.7 mmol) of 2- (3-chlorophenyl) -4,6-diphenyl-1,3,5-triazine instead of 5'-chloro-1,1 ', 3', 1 ”-Terphenyl Then, the same procedure as in Synthesis Example 26 was performed to obtain R145 (5.0 g, 6.6 mmol, yield 62%) as a target compound.

GC-Mass (Theoretical value: 754.88 g / mol, Measured value: 754.88 g / mol)

Synthesis Example 30 Synthesis of R150

Except for using 2-chloro-4-phenylquinazoline 2.8g (11.7mmol) instead of 5'-chloro-1,1 ', 3', 1 ”-Terphenyl was carried out in the same manner as in Synthesis Example 26 R150 (4.5 g, 6.9 mmol, yield 65%) was obtained.

GC-Mass (Theoretical value: 651.76 g / mol, Measured value: 651 g / mol)

Examples 1 to 18 Fabrication of Green Organic Electroluminescent Devices

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

First, a glass substrate coated with ITO (Indium tin oxide) having a thickness of 1500 된 was ultrasonically washed with distilled water. After washing the distilled water, ultrasonic cleaning with a solvent such as isopropyl alcohol, acetone, methanol, etc., dried and transferred to a UV OZONE cleaner (Power sonic 405, Hwasin Tech), and then the substrate is cleaned for 5 minutes by UV and vacuum evaporator The substrate was transferred to.

M-MTDATA (60 nm) / TCTA (80 nm) / 90% on the ITO transparent electrode thus prepared + 10% Ir (ppy) ₃ (30nm) / BCP (10 nm) / Alq ₃ The device was fabricated by laminating in the order of (30 nm) / LiF (1 nm) / Al (200 nm).

Comparative Example 1 Fabrication of Green Organic Electroluminescent Device

A device was manufactured in the same manner as in Example 1, except that CBP was used instead of the R1 compound as a light emitting host material when the emission layer was formed.

The structures of m-MTDATA, TCTA, Ir (ppy) ₃ , BCP and CBP used in Examples 1 to 18 and Comparative Example 1 are as follows.

[Evaluation Example 1]

For each of the green organic electroluminescent devices prepared in Examples 1 to 18 and Comparative Example 1, the driving voltage, current efficiency, and emission peak at a current density of 10 mA / cm 2 were measured, and the results are shown in Table 1 below. .

Table 1 Sample Host Driving voltage (V) Light emitting peak (nm) Current efficiency (cd / A) Example 1 R1 6.2 515 41.2 Example 2 R3 6.1 515 41.1 Example 3 R20 6.2 515 41.2 Example 4 R26 6.3 514 41.7 Example 5 R28 5.9 515 40.5 Example 6 R45 5.5 515 41.2 Example 7 R51 6.2 515 40.9 Example 8 R53 6.4 515 41.1 Example 9 R70 6.4 514 42.1 Example 10 R76 6.2 514 41.5 Example 11 R78 6.9 514 41.5 Example 12 R95 6.2 515 41.2 Example 13 R101 6.1 515 41.1 Example 14 R103 6.2 515 41.2 Example 15 R120 6.3 514 41.7 Example 16 R126 5.9 515 40.5 Example 17 R128 5.5 515 41.2 Example 18 R145 6.2 515 40.9 Comparative Example 1 CBP 7.1 517 37.0

As shown in Table 1 above, the case where the compound of the present invention was used for the light emitting layer of the green organic electroluminescent device (Examples 1 to 18) was compared with the case where the conventional CBP was used for the light emitting layer of the green organic electroluminescent device (Comparative Example 1) It was confirmed that the efficiency and the driving voltage are excellent.

Examples 19 to 30 Fabrication of Red Organic Electroluminescent Devices

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

First, a glass substrate coated with ITO (Indium tin oxide) having a thickness of 1500 된 was ultrasonically washed with distilled water. After washing the distilled water, ultrasonic cleaning with a solvent such as isopropyl alcohol, acetone, methanol, etc., dried and transferred to a UV OZONE cleaner (Power sonic 405, Hwasin Tech), and then the substrate is cleaned for 5 minutes by UV and vacuum evaporator The substrate was transferred to.

M-MTDATA (60 nm) / TCTA (80 nm) / 90% on each of the prepared ITO transparent electrodes + 10% (piq) ₂ Ir (acac) (30 nm) / BCP (10 nm) The device was manufactured by laminating in order of / Alq ₃ (30 nm) / LiF (1 nm) / Al (200 nm).

Comparative Example 2

A device was manufactured in the same manner as in Example 19, except that CBP was used instead of the R 2 compound as the light emitting host material.

The structures of m-MTDATA, TCTA, BCP and CBP used in Examples 19 to 30 and Comparative Example 2 are as described above, and the structure of (piq) ₂ Ir (acac) is as follows.

[Evaluation Example 2]

For each of the red organic electroluminescent devices prepared in Examples 19 to 30 and Comparative Example 2, the driving voltage, the light emission peak, and the current efficiency at a current density of 10 mA / cm 2 were measured, and the results are shown in Table 2 below. .

TABLE 2 Sample Host Driving voltage (V) Light emitting peak (nm) Current efficiency (cd / A) Example 19 R2 4.4 621 12.4 Example 20 R25 4.3 621 11.2 Example 21 R27 4.1 620 12.1 Example 22 R50 4.1 621 11.9 Example 23 R52 4.4 621 12.4 Example 24 R75 4.2 621 12.4 Example 25 R77 4.1 621 11.2 Example 26 R100 4.0 620 12.1 Example 27 R102 4.2 621 11.9 Example 28 R125 4.3 621 12.4 Example 29 R127 4.8 622 11.4 Example 30 R150 4.4 620 12.3 Comparative Example 2 CBP 5.5 622 9,1

As shown in Table 2, the case where the compound of the present invention was used for the light emitting layer of the red organic electroluminescent device (Examples 19 to 30) was compared to the case where the conventional CBP was used for the light emitting layer of the red organic electroluminescent device (Comparative Example 2). It was confirmed that the efficiency and the driving voltage are excellent.

The compound represented by Formula 1 or 2 of the present invention can be used as a material of the organic material layer of the organic electroluminescent device because of its excellent thermal stability and luminescent properties. In particular, when the compound represented by Formula 1 of the present invention is used as a phosphorescent host material, an organic electroluminescent device having excellent light emission performance, low driving voltage, high efficiency, and long life compared to a conventional host material can be manufactured. Full color display panels with improved performance and lifetime can also be manufactured.

Claims (9)

Compound represented by the following formula (1) or (2): [Formula 1]

[Formula 2]

In Chemical Formula 1 or 2, At least _one of R ₁ and R ₂ , R ₂ and R ₃ , R ₃ and R ₄ , R ₅ and R ₆ , R ₆ and R ₇ or R ₇ and R ₈ forms a condensed ring represented by the following Chemical Formula 3 , [Formula 3]

In Chemical Formula 3, The dotted line is a part where condensation is made with Formula 1 or 2, X ₁ is selected from the group consisting of C (Ar ₃ ) (Ar ₄ ), N (Ar ₅ ), O, S and Si (Ar ₆ ) (Ar ₇ ), R ₁ to R ₁₂ are each independently hydrogen, deuterium, halogen, cyano group, nitro group, C ₁ ~ C ₄₀ alkyl group, C ₂ ~ C ₄₀ alkenyl group, C ₂ ~ C ₄₀ alkynyl group, C ₃ ~ C ₄₀ cycloalkyl group, C 3 -C 40 heterocycloalkyl group, C ₆ -C ₆₀ aryl group, C _5-60 heteroaryl group, C ₁ -C ₄₀ alkyloxy group, C _6- C ₆₀ aryloxy group, C ₃ ~ C ₄₀ alkylsilyl group, C ₆ ~ C ₆₀ arylsilyl group, C ₁ ~ C ₄₀ alkyl boron group, C ₆ ~ C ₆₀ aryl boron group, C ₆ ~ C ₆₀ aryl phosphine group, C ₆ ~ C ₆₀ aryl phosphine oxide group and C ₆ ~ C ₆₀ arylamine group selected from the group consisting of or combine with adjacent groups to form a condensed ring, Ar ₁ to Ar ₇ are each independently C ₁ ~ C ₄₀ Alkyl group, C ₂ ~ C ₄₀ Alkenyl group, C ₂ ~ C ₄₀ Alkynyl group, C ₃ ~ C ₄₀ Cycloalkyl group, 3 to 40 nuclear atoms Heterocycloalkyl group, C ₆ ~ C ₆₀ aryl group, heteroaryl group having 5 to 60 nuclear atoms, C ₁ ~ C ₄₀ alkyloxy group, C ₆ ~ C ₆₀ aryloxy group, C ₃ ~ C ₄₀ Alkyl silyl group, C ₆ ~ C ₆₀ aryl silyl group, C ₁ ~ C ₄₀ alkyl boron group, C ₆ ~ C ₆₀ aryl boron group, C ₆ ~ C ₆₀ aryl phosphine group, C ₆ ~ C ₆₀ Aryl phosphine oxide group and C ₆ ~ C _{60 It} is selected from the group consisting of arylamine group, The alkyl group, alkenyl group, alkynyl group of R ₁ to R ₁₂ and Ar ₁ to Ar ₇ . Cycloalkyl group, heterocycloalkyl group, aryl group, heteroaryl group, alkyloxy group, aryloxy group, alkylsilyl group, arylsilyl group, alkyl boron group, aryl boron group, aryl phosphine group, aryl phosphine oxide group and arylamine groups are each independently, C ₁ ~ C ₄₀ alkyl group, C ₂ ~ C ₄₀ alkenyl group, C ₂ ~ C ₄₀ alkynyl group, C ₃ ~ C ₄₀ cycloalkyl group, a number of nuclear atoms of 3 to 40 heterocycloalkyl group of the , C ₆ ~ C ₆₀ aryl group, nuclear atom 5 ~ 60 heteroaryl group, C ₁ ~ C ₄₀ alkyloxy group, C ₆ ~ C ₆₀ aryloxy group, C ₃ ~ C ₄₀ alkylsilyl group , C ₆ ~ C ₆₀ arylsilyl group, C ₁ ~ C ₄₀ alkyl boron group, C ₆ ~ C ₆₀ aryl boron group, C ₆ ~ C ₆₀ aryl phosphine group, C ₆ ~ C ₆₀ aryl phosphine Substituted or unsubstituted with one or more selected from the group consisting of an oxide group and a C ₆ -C ₆₀ arylamine group. The method of claim 1, Compound represented by Formula 1 is selected from the group consisting of compounds represented by the following formula 4 to 9. [Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

In Chemical Formulas 4 to 9, Ar ₁ , Ar ₂ , X ₁ and R ₁ to R ₁₂ are the same as defined in claim 1. The method of claim 1, Compound represented by Formula 2 is selected from the group consisting of compounds represented by the following formula 10 to 15. [Formula 10]

[Formula 11]

[Formula 12]

[Formula 13]

[Formula 14]

[Formula 15]

In Chemical Formulas 10 to 15, Ar ₁ , Ar ₂ , X ₁ and R ₁ to R ₁₂ are the same as defined in claim 1. The method of claim 1, X ₁ is N (Ar ₅ ). The method of claim 4, wherein Ar ₅ is a C ₆ ~ C ₆₀ An aryl group or a nuclear atom of 5 to 60 heteroaryl group. The method of claim 1, Ar ₁ and Ar ₂ are each independently a C ₆ ~ C ₆₀ aryl group or a nuclear atom of 5 to 60 heteroaryl group. An organic electroluminescent device comprising an anode, a cathode, and at least one organic layer interposed between the anode and the cathode. At least one of the one or more organic material layers is an organic electroluminescent device comprising the compound according to any one of claims 1 to 6. The method of claim 7, wherein The organic light emitting device comprising the compound is selected from the group consisting of a hole injection layer, a hole transport layer, an electron transport layer and a light emitting layer. The method of claim 8, The organic material layer containing the compound is a light emitting layer, The organic electroluminescent device of which the compound is a phosphorescent host of the light emitting layer.