WO2013147431A1 - Novel compound and organic electroluminescent element comprising same - Google Patents

Abstract

The present invention relates to a compound in which an azacarbazole-based compound and a condensed hetero ring moiety are bonded in such a way that a basic skeleton is formed, and various substituents are bonded thereto, and the present invention also relates to an organic electroluminescent element comprising the compound. The present invention, which is constituted in this way, can provide an electroluminescent element in which properties such as efficiency, life and stability are improved.

Description

New compound and organic electroluminescent device comprising same

The present invention relates to a novel compound and an organic electroluminescent device comprising the same, and more particularly to a compound used in the organic material layer of the organic electroluminescent device.

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. In this case, the material used as 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 a light emitting material representing blue, green, and red according to the light emission color, and a light emitting material representing yellow and orange required to implement natural colors. In addition, in order to increase luminous efficiency through increasing color purity and energy transfer, a host / dopant system may be used as the light emitting material.

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. At this time, since the phosphor can improve luminous efficiency up to four times as compared to the fluorescent material, research on phosphorescent host materials as well as phosphorescent dopant materials has been made.

As the phosphorescent dopant material, a metal complex compound including Ir such as Firpic, Ir (ppy) ₃ , and (acac) Ir (btp) ₂ is used, and CBP is used as the phosphorescent host material.

However, although the conventional light emitting materials have good light emission characteristics, they are not satisfactory in terms of lifespan of organic electroluminescent devices, and thus, development of light emitting materials having excellent performance is required.

In order to solve the above problems, an object of the present invention is to provide a novel compound and an organic electroluminescent device using the compound which can improve the efficiency, lifespan and stability of the organic electroluminescent device.

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

[Formula 1]

[Formula 2]

In Chemical Formula 2,

The dotted line means a moiety combined with Formula 1 to form a condensed ring, Z is selected from the group consisting of CAr ₂ Ar ₃ , NAr ₄ , O, S and SiAr ₅ Ar ₆ ,

Ar ₁ to Ar ₆ are each independently hydrogen, deuterium, halogen, cyano 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, the number of nuclear atoms of 3 to 40 heterocycloalkyl group, C ₆ ~ C ₆₀ aryl group, nuclear atoms aryl of from 5 to 60 heteroaryl group, a C ₁ ~ alkyloxy group of C _40, C ₆ ~ C ₆₀ is selected from the group consisting of an aryloxy group, a C ₁ to C ₄₀ alkylsilyl group, a C ₆ to C ₆₀ arylsilyl group, and a C ₆ to C ₆₀ arylamine group, and combine with an adjacent group to form a condensed ring. Can and

Y ₁ to Y ₈ are each independently CR ₂ or N,

R ₁ and R ₂ 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, 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 and aryloxy C _60, C ₁ ~ C ₄₀ alkyl silyl group, C ₆ to C ₆₀ aryl silyl group, and a C ₆ - is selected from the group consisting of an aryl amine of the C _60, the combined contiguous groups fused ring Can form,

Alkyl groups, alkenyl groups, alkynyl groups, cycloalkyl groups, heterocycloalkyl groups, aryl groups, heteroaryl groups, alkyloxy groups, aryloxy groups, alkylsilyl groups, arylsilyl groups of Ar ₁ to Ar ₆ , R ₁ and R ₂ ; And arylamine groups are each independently deuterium, halogen, nitro group, cyano group, amino group, C ₁ ~ C ₄₀ alkyl group, C ₂ ~ C ₄₀ alkenyl group, C ₂ ~ C ₄₀ alkynyl group, C ₃ ~ C ₄₀ Of cycloalkyl group, heterocycloalkyl group of 3 to 40 nuclear atoms, aryl group of C ₆ to C ₄₀ , heteroaryl group of 5 to 40 nuclear atoms, alkyloxy group of C ₁ to C ₄₀ , C ₆ to C ₆₀ It may be substituted with one or more selected from the group consisting of an aryloxy group, C ₁ ~ C ₄₀ Alkylsilyl group, C ₆ ~ C ₆₀ An arylsilyl group, and C ₆ ~ C ₆₀ An arylamine group. Herein, when two or more of Ar ₁ to Ar ₆ , R _1, and R ₂ are substituted with the substituents, the substituents may be the same as or different from each other. That is, the plurality of substituents may be the same or different from each other.

Alkyl of the present invention means a monovalent functional group obtained by removing a hydrogen atom from a straight or branched chain saturated hydrocarbon having 1 to 40 carbon atoms, and non-limiting examples thereof include methyl, ethyl, propyl, isobutyl, sec-butyl, pentyl , iso-amyl and hexyl.

Alkenyl of the present invention means a monovalent functional group obtained by removing a hydrogen atom from a straight or branched chain unsaturated hydrocarbon having 2 to 40 carbon atoms having at least one carbon-carbon double bond. Non-limiting examples thereof include vinyl, allyl, isopropenyl, 2-butenyl and the like.

Alkynyl of the present invention means a monovalent functional group obtained by removing a hydrogen atom from a straight or branched chain unsaturated hydrocarbon having 2 to 40 carbon atoms having at least one carbon-carbon triple bond. Non-limiting examples thereof include ethynyl, 2-propynyl and the like.

Cycloalkyl of the present invention means a monovalent functional group obtained by removing a hydrogen atom from a monocyclic or polycyclic non-aromatic hydrocarbon having 3 to 40 carbon atoms (saturated cyclic hydrocarbon). Non-limiting examples thereof include cyclopropyl, cyclopentyl, cyclohexyl, norbornyl, adamantine and the like.

Heterocycloalkyl of the present invention means monovalent functional groups obtained by removing hydrogen atoms from non-aromatic hydrocarbons (saturated cyclic hydrocarbons) having 3 to 40 nuclear atoms, and preferably at least one carbon in the ring, preferably 1 to 3 carbon atoms. Carbons are substituted with heteroatoms such as N, O or S. Non-limiting examples thereof include morpholine, piperazine and the like.

Aryl of the present invention means a monovalent functional group obtained by removing a hydrogen atom from an aromatic hydrocarbon having 6 to 60 carbon atoms in which a single ring or two or more rings are combined. In this case, the two or more rings may be attached in a simple or condensed form with each other. Non-limiting examples thereof include phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, anthryl and the like.

Heteroaryl of the present invention is a monovalent functional group obtained by removing a hydrogen atom from a monoheterocyclic or polyheterocyclic aromatic hydrocarbon having 5 to 60 nuclear atoms, and at least one carbon in the ring, preferably 1 to 3 carbons. Is substituted with a heteroatom such as nitrogen (N), oxygen (O), sulfur (S) or selenium (Se). In this case, the heteroaryl may be attached in a form in which two or more rings are simply attached or condensed with each other, and may also include a condensed form with an aryl group. Non-limiting examples of such heteroaryls include six-membered monocyclic rings such as pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, triazinyl; Polycyclics such as phenoxathienyl, indolinzinyl, indolyl, purinyl, quinolyl, benzothiazole, carbazolyl ring; And 2-furanyl, N-imidazolyl, 2-isoxazolyl, 2-pyridinyl, 2-pyrimidinyl, and the like.

The alkyloxy of the present invention means a monovalent functional group represented by RO-, wherein R is alkyl having 1 to 40 carbon atoms, and may include a linear, branched or cyclic structure. . Non-limiting examples of such alkyloxy include methoxy, ethoxy, n-propoxy, 1-propoxy, t-butoxy, n-butoxy, pentoxy and the like.

Aryloxy of the present invention means a monovalent functional group represented by R'0-, wherein R 'is an aryl having 6 to 60 carbon atoms. Non-limiting examples of such aryloxy include phenyloxy, naphthyloxy, diphenyloxy and the like.

Alkylsilyl of the present invention means silyl substituted with alkyl having 1 to 40 carbon atoms, arylsilyl means silyl substituted with aryl having 6 to 60 carbon atoms, and arylamine is amine substituted with aryl having 6 to 60 carbon atoms. Means.

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

On the other hand, the present invention comprises an anode, a cathode and at least one organic layer interposed between the anode and the cathode, wherein at least one of the at least one organic layer comprises a compound represented by the formula (1) It provides an organic electroluminescent device.

Hereinafter, the present invention will be described.

1. New Compound

The novel compound of the present invention forms a basic skeleton by condensation (fused) heterocyclic moiety to an azacarbazole-based compound, and is a compound in which various substituents are bonded to the compound represented by Formula 1 above.

Specifically, the compound represented by the formula (1) of the present invention is a compound containing one or more N (nitrogen) instead of C, carbon 1, 3 or 4 of the carbazole. That is, the compound represented by the formula (1) of the present invention is a compound represented by the following formula (3) or formula (4).

[Formula 3]

[Formula 4]

In Formulas 3 and 4, Ar ₁ , X ₁ , X ₃ , X ₄ , Y ₁ to Y ₈ and Z are the same as defined in Formula 1, at least one of X ₁ , X ₃ and X ₄ is N It is preferable that it is (nitrogen).

Such a compound represented by Formula 1 of the present invention is a combination of a variety of substituents (R ₁ , R ₂ and Ar ₁ to Ar ₆ ) to control the energy level of a conventional organic electroluminescent device material (for example, CBP ( 4,4-dicarbazolybiphenyl)) has a higher molecular weight and may exhibit a wider energy band gap (sky blue to red). In addition, the compound represented by the formula (1) of the present invention in which various substituents are introduced, the molecular weight is significantly increased, thereby improving the glass transition temperature, thereby having a higher thermal stability than the conventional materials.

Therefore, when the compound represented by Chemical Formula 1 of the present invention is used as a material of an organic electroluminescent device, not only phosphorescence properties of the device, but also electron and / or hole transporting ability, luminous efficiency, driving voltage, and lifetime characteristics may be improved. . In this case, the compound represented by Chemical Formula 1 of the present invention may be used as a material of the organic material layer of the organic EL device, preferably a hole injection layer, a hole transport layer or a light emitting layer, and more preferably a host material of the light emitting layer.

R ₁ , R _2, and Ar ₁ to Ar _{6, which} are substituents (functional groups) of the compound represented by Formula 1 of the present invention, may be any one of substituents represented by S1 to S138.

The compound represented by Chemical Formula 1 of the present invention may be selected from the group consisting of compounds represented by the following Chemical Formulas C-1 to C-30.

In the general formula C-1 to C-30, Y ₁ to Y _8, and defined for Ar ₁ to Ar ₆ are the same as defined in formula (I).

On the other hand, when the compound represented by the formula (1) of the present invention in consideration of a wide energy band gap and thermal stability, Z is preferably NAr ₄ . That is, the compound represented by Formula 1 of the present invention contains one or more N (nitrogen) instead of A, acarbazole-based compound (C (carbon) 1, 3 or 4 of the carbazole of Formula 1) To an indole group of formula 2 (bonded to carbons 1 and 2 or carbons 2 and 3 of carbazole of formula 1). The compound represented by Chemical Formula 1 of the present invention may be selected from the group consisting of compounds represented by the following Chemical Formulas D-1 to D-63.

In Chemical Formulas D-1 to D-63, the definitions for Ar ₁ and Ar ₄ are the same as those defined in Chemical Formula 1. Here, in consideration of the efficiency and life characteristics of the organic EL device, Ar ₁ and Ar ₄ are each independently C ₆ ~ C ₆₀ An aryl group, a nuclear atom of 5 to 60 heteroaryl group and C ₆ ~ It is preferably selected from the group consisting of C ₆₀ arylamine groups. Specific examples of the C ₆ ~ C ₆₀ aryl group, nuclear hetero atoms 5 to 60 heteroaryl group and C ₆ ~ C ₆₀ arylamine group is not particularly limited as long as known in the art.

Specific examples of the compound represented by Chemical Formula 1 of the present invention (C1-C1047) include the following compounds, but are not limited thereto.

Such a compound represented by Formula 1 of the present invention can be synthesized in various ways with reference to the synthesis process of the following examples.

2. Organic electroluminescent device

The present invention provides an organic electroluminescent device comprising an anode, a cathode and one or more organic material layers interposed between the anode and the cathode, wherein at least one of the one or more organic material layers is represented by Formula 1 described above. It is characterized by including the compound represented.

The organic material layer including the compound represented by Formula 1 of the present invention 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. Specifically, the organic material layer of the present invention is preferably a hole injection layer, a hole transport layer or a light emitting layer, more preferably a light emitting layer.

The light emitting layer of the organic electroluminescent device of the present invention may contain a host material (preferably a phosphorescent host material), and in this case, the host material may include a compound represented by Formula 1 above. When the light emitting layer includes the compound represented by Chemical Formula 1, the hole transporting ability is increased to increase the bonding force between the holes and the electrons in the light emitting layer, and thus, the organic electroluminescence having excellent efficiency (luminescence efficiency and power efficiency), lifetime, luminance and driving voltage An element can be provided.

The structure of the organic electroluminescent device of the present invention is not particularly limited, but may be formed of a structure in which a substrate, an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and a cathode are sequentially stacked. An electron injection layer may be further stacked 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 between the electrode and the organic material layer interface.

The material usable as the anode included in the organic electroluminescent device of the present invention is not particularly limited, but non-limiting examples include metals such as vanadium, chromium, copper, zinc, gold or alloys 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 or polyaniline; And carbon black and the like can be used.

The material usable as the negative electrode included in the organic electroluminescent device of the present invention is not particularly limited, but non-limiting examples include magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, or Metals such as lead or alloys thereof; And multilayer structure materials such as LiF / Al or LiO ₂ / Al, and the like.

The organic material layer included in the organic electroluminescent device of the present invention is known in the art except for including the compound represented by the formula (1) in any one of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer It may be made of a material.

The material usable as the substrate included in the organic electroluminescent device of the present invention is not particularly limited, but non-limiting examples may be used a silicon wafer, quartz, glass plate, metal plate, plastic film and sheet.

The organic electroluminescent device of the present invention can be manufactured by methods known in the art. The light emitting layer included in the organic material layer may be manufactured by vacuum deposition or solution coating. Examples of the solution coating method include, but are not limited to, spin coating, dip coating, doctor blading, inkjet printing, or thermal transfer.

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 IC-1

Step 1 Synthesis of 3-bromo-5- (2-nitrophenyl) pyridine

Add 18.96 g (80.0 mmol) of 3,5-dibromopyridine, 14.68 g (88.0 mmol) of 2-nitrophenylboronic acid, 9.60 g (240.0 mmol) of NaOH and 200 ml / 100 ml of THF / H ₂ O under nitrogen stream It was. 4.60 g (5 mol%) of Pd (PPh ₃ ) ₄ was added at 40 ° C. and stirred at 80 ° C. for 12 hours. After completion of the reaction, the mixture was extracted with methylene chloride, MgSO ₄ was added and filtered. After removal of the solvent of the filtered organic layer, 14.73 g (yield: 66%) of 3-bromo-5- (2-nitrophenyl) pyridine was obtained by using column chromatography.

¹ H-NMR: δ 7.67 (t, 1H), 7.93 (m, 3H), 8.43 (m, 2H), 9.44 (s, 1H)

<Step 2> Synthesis of 4-bromo-5H-pyrido [4,3-b] indole and 3-bromo-9H-pyrido [2,3-b] indole

Under nitrogen stream, 10.66 g (38.2 mmol) of 3-bromo-5- (2-nitrophenyl) pyridine, 25.04 g (95.44 mmol) of triphenylphosphine, and 100 ml of 1,2-dichlorobenzene were added and stirred for 12 hours. After the reaction was completed, 1,2-dichlorobenzene was removed and extracted with dichloromethane. The extracted organic layer was dried with MgSO _{4, and} then purified by column chromatography using 4-bromo-5H-pyrido [4,3-b] indole 3.02g (yield: 32%) and 3-bromo-9H-pyrido [ 2.30 g (yield: 35%) of 2,3-b] indole were obtained.

¹ H-NMR of 4-bromo-5H-pyrido [4,3-b] indole: δ 7.29 (t, 1H), 7.58 (m, 2H), 8.10 (d, 1H), 8.51 (s, 1H), 9.14 (s, 1 H), 10.42 (s, 1 H)

¹ H-NMR of 3-bromo-9H-pyrido [2,3-b] indole: δ 7.28 (t, 1H), 7.54 (m, 2H), 8.15 (m, 2H), 9.04 (s, 1H), 10.43 (s, 1 H)

<Step 3> Synthesis of 4- (2-nitrophenyl) -5H-pyrido [4,3-b] indole

Except for using 4-bromo-5H-pyrido [4,3-b] indole instead of 3,5-dibromopyridine, the same procedure as in <Step 1> of Preparation Example 1 was performed to obtain 4- (2-nitrophenyl)- 5H-pyrido [4,3-b] indole (5.84 g, yield 76%) was obtained.

¹ H-NMR: δ 7.28 (t, 1H), 7.59 (m, 3H), 8.01 (m, 3H), 8.11 (d, 1H), 8.94 (s, 1H), 9.24 (s, 1H), 10.42 ( s, 1 H)

Step 4 Synthesis of 4- (2-nitrophenyl) -5-phenyl-5H-pyrido [4,3-b] indole

4- (2-nitrophenyl) -5H-pyrido [4,3-b] indole (2.56g, 8.86mmol), 1-Iodobenzene (5.21g, 26.56mmol), Cu powder (0.11g, 1.77mmol) under nitrogen stream , K ₂ CO ₃ (2.44 g, 17.71 mmol), Na ₂ SO ₄ (2.52 g, 17.71 mmol), and nitrobenzene (100 ml) were mixed and stirred at 190 ° 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- (2-nitrophenyl) -5-phenyl-5H-pyrido [4,3-b] indole (2.46 g, yield 76%).

¹ H-NMR: δ 7.28 (m, 2H), 7.59 (m, 6H), 8.00 (m, 4H), 8.55 (d, 1H), 8.94 (s, 1H), 9.23 (s, 1H),

Step 5 Synthesis of IC-1

<Step 2 of Preparation Example 1 except that 4- (2-nitrophenyl) -5-phenyl-5H-pyrido [4,3-b] indole was used instead of 3-bromo-5- (2-nitrophenyl) pyridine > The same procedure as in the following to obtain the target compound IC-1 (1.84 g, yield 82%).

¹ H-NMR: δ 7.29 (m, 3H), 7.58 (m, 7H), 7.99 (m, 2H), 8.52 (d, 1H), 9.51 (s, 1H), 10.43 (s, 1H)

Preparation Example 2 Synthesis of IC-2

Step 1 Synthesis of 5'-bromo-3-nitro-2,3'-bipyridine

Except for using 3-nitropyridin-2-ylboronic acid instead of 2-nitrophenylboronic acid, 5'-bromo-3-nitro-2,3'-bipyridine was prepared in the same manner as in <Step 1> of Preparation Example 1. Got it.

¹ H-NMR: δ 7.61 (t, 1H), 8.61 (m, 2H), 8.90 (m, 2H), 9.93 (s, 1H)

<Step 2> Synthesis of A-1

Except for using 5'-bromo-3-nitro-2,3'-bipyridine instead of 3-bromo-5- (2-nitrophenyl) pyridine was carried out in the same manner as in <Step 2> of Preparation Example 1 -1 was obtained.

¹ H-NMR: δ 7.22 (t, 1H), 7.97 (d, 1H), 8.41 (m, 2H), 9.23 (s, 1H), 10.46 (s, 1H)

<Step 3> Synthesis of A-2

Except for using A-1 instead of 3,5-dibromopyridine A-2 was obtained by the same procedure as in <Step 1> of Preparation Example 1.

¹ H-NMR: δ 7.24 (t, 1H), 7.63 (t, 1H), 7.99 (m, 4H), 8.43 (d, 1H), 8.96 (s, 1H), 9.25 (s, 1H), 10.48 ( s, 1 H)

<Step 4> Synthesis of A-3

Except for using A-2 instead of 4- (2-nitrophenyl) -5H-pyrido [4,3-b] indole A-3 was obtained in the same manner as in <Step 4> of Preparation Example 1.

¹ H-NMR: δ 7.22 (t, 1H), 7.51 (m, 6H), 8.01 (m, 4H), 8.43 (d, 1H), 8.99 (s, 1H), 9.24 (s, 1H)

Step 5 Synthesis of IC-2

Except for using A-3 instead of 3-bromo-5- (2-nitrophenyl) pyridine was subjected to the same process as in <Step 2> of Preparation Example 1 to obtain the target compound IC-2.

¹ H-NMR: δ 7.24 (m, 2H), 7.50 (m, 7H), 7.98 (m, 2H), 8.43 (d, 1H), 9.53 (s, 1H), 10.48 (s, 1H)

Preparation Example 3 Synthesis of IC-3

<Step 1> Synthesis of 5-bromo-3- (2-nitrophenyl) pyridazine

Except for using 3,5-dibromopyridazine instead of 3,5-dibromopyridine was subjected to the same process as in <Step 1> of Preparation Example 1 to obtain 5-bromo-3- (2-nitrophenyl) pyridazine.

¹ H-NMR: δ 7.67 (t, 1H), 8.01 (m, 4H), 9.01 (s, 1H)

<Step 2> Synthesis of 4-bromo-5H-pyridazino [4,3-b] indole

Except for using 5-bromo-3- (2-nitrophenyl) pyridazine instead of 3-bromo-5- (2-nitrophenyl) pyridine, the same procedure as in <Step 2> of Preparation Example 1 was performed. 5H-pyridazino [4,3-b] indole was obtained.

¹ H-NMR: δ 7.29 (t, 1H), 7.65 (m, 2H), 8.15 (d, 1H), 9.42 (s, 1H), 10.46 (s, 1H)

<Step 3> Synthesis of 4- (2-nitrophenyl) -5H-pyridazino [4,3-b] indole

Except for using 4-bromo-5H-pyridazino [4,3-b] indole instead of 3,5-dibromopyridine, the same procedure as in <Step 1> of Preparation Example 1 was carried out to provide 4- (2-nitrophenyl)- 5H-pyridazino [4,3-b] indole was obtained.

¹ H-NMR: δ 7.29 (t, 1H), 7.53 (m, 3H), 7.98 (m, 4H), 9.42 (s, 1H), 10.45 (s, 1H)

Step 4 Synthesis of 4- (2-nitrophenyl) -5-phenyl-5H-pyridazino [4,3-b] indole

Preparation Example 1 except for using 4- (2-nitrophenyl) -5H-pyridazino [4,3-b] indole instead of 4- (2-nitrophenyl) -5H-pyrido [4,3-b] indole The same procedure as in <Step 4> was performed to obtain 4- (2-nitrophenyl) -5-phenyl-5H-pyridazino [4,3-b] indole.

¹ H-NMR: δ 7.28 (m, 2H), 7.57 (m, 6H), 8.00 (d, 1H), 8.69 (m, 2H), 8.98 (d, 1H), 9.85 (s, 1H)

Step 5 Synthesis of IC-3

<Step 2 of Preparation Example 1 except that 4- (2-nitrophenyl) -5-phenyl-5H-pyridazino [4,3-b] indole was used instead of 3-bromo-5- (2-nitrophenyl) pyridine > The same procedure as in the following to obtain the target compound IC-3.

¹ H-NMR: δ 7.26 (m, 3H), 7.51 (m, 5H), 7.99 (m, 2H), 8.44 (d, 1H), 8.74 (d, 1H), 10.46 (s, 1H)

Preparation Example 4 Synthesis of IC-4

<Step 1> Synthesis of 4- (3-nitropyridin-2-yl) -5H-pyrido [4,3-b] indole

Except for using 4-bromo-5H-pyridazino [4,3-b] indole instead of 3,5-dibromopyridine, the same procedure as in <Step 1> of Preparation Example 2 was carried out to provide 4- (3-nitropyridin-2 -yl) -5H-pyrido [4,3-b] indole was obtained.

¹ H-NMR: δ 7.28 (t, 1H), 7.53 (m, 3H), 8.12 (d, 1H), 8.62 (d, 1H), 9.00 (m, 2H), 9.75 (s, 1H), 10.48 ( s, 1 H)

<Step 2> Synthesis of 4- (3-nitropyridin-2-yl) -5-phenyl-5H-pyrido [4,3-b] indole

Except for using 4- (3-nitropyridin-2-yl) -5H-pyrido [4,3-b] indole instead of 4- (2-nitrophenyl) -5H-pyrido [4,3-b] indole The same procedure as in <Step 4> of Preparation Example 1 was obtained to obtain 4- (3-nitropyridin-2-yl) -5-phenyl-5H-pyrido [4,3-b] indole.

¹ H-NMR: δ 7.29 (m, 2H), 7.59 (m, 6H), 7.96 (d, 1H), 8.56 (m, 2H), 9.04 (m, 2H), 9.75 (s, 1H)

Step 3 Synthesis of IC-4

Preparation Example 1 except that 4- (3-nitropyridin-2-yl) -5-phenyl-5H-pyrido [4,3-b] indole was used instead of 3-bromo-5- (2-nitrophenyl) pyridine IC-4 was obtained by the same procedure as in <Step 2>.

¹ H-NMR: δ 7.28 (m, 3H), 7.56 (m, 5H), 7.94 (m, 2H), 8.49 (m, 2H), 9.51 (s, 1H), 10.46 (s, 1H)

Preparation Example 5 Synthesis of IC-5

<Step 1> Synthesis of 3- (2-nitrophenyl) -9H-pyrido [2,3-b] indole

The same process as in <Step 1> of Preparation Example 1, except that 3-bromo-9H-pyrido [2,3-b] indole synthesized in <Step 2> of Preparation Example 1 was used instead of 3,5-dibromopyridine. Was carried out to obtain 3- (2-nitrophenyl) -9H-pyrido [2,3-b] indole.

¹ H-NMR: δ 7.28 (t, 1H), 7.56 (m, 3H), 8.02 (m, 4H), 8.12 (d, 1H), 9.25 (s, 1H), 10.47 (s, 1H)

<Step 2> Synthesis of 3- (2-nitrophenyl) -9-phenyl-9H-pyrido [2,3-b] indole

Preparation Example 1 except for using 3- (2-nitrophenyl) -9H-pyrido [2,3-b] indole instead of 4- (2-nitrophenyl) -5H-pyrido [4,3-b] indole 3- (2-nitrophenyl) -9-phenyl-9H-pyrido [2,3-b] indole was obtained in the same manner as in <Step 4>.

¹ H-NMR: δ 7.29 (m, 2H), 7.59 (m, 6H), 7.96 (m, 5H), 8.46 (d, 1H), 9.24 (s, 1H)

Step 3 Synthesis of IC-5

<Step 2 of Preparation Example 1 except that 3- (2-nitrophenyl) -9-phenyl-9H-pyrido [2,3-b] indole was used instead of 3-bromo-5- (2-nitrophenyl) pyridine > The same process as in the above to obtain the target compound IC-5.

¹ H-NMR: δ 7.28 (m, 3H), 7.57 (m, 7H), 7.94 (m, 2H), 8.49 (d, 1H), 9.51 (s, 1H), 10.45 (s, 1H)

Preparation Example 6 Synthesis of IC-6

Step 1 Synthesis of 2- (3,5-dichloropyridin-2-yl) aniline

14.60 g (80.0 mmol) of 2,3,5-trichloropyridine, 19.28 g (88.0 mmol) of 2- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) under nitrogen stream Aniline, 9.60 g (240.0 mmol) of NaOH and 200 ml / 100 ml of THF / H ₂ O were added and stirred. 4.60 g (5 mol%) of Pd (PPh ₃ ) ₄ was added at 40 ° C. and stirred at 80 ° C. for 12 hours. After completion of the reaction, the mixture was extracted with methylene chloride, MgSO ₄ was added and filtered. After removal of the solvent of the filtered organic layer, 14.53 g (yield: 76%) of 2- (3,5-dichloropyridin-2-yl) aniline was obtained using column chromatography.

¹ H-NMR: δ 5.67 (s, 2H), 6.83 (m, 2H), 7.22 (t, 1H), 7.88 (s, 1H), 8.49 (s, 1H), 9.43 (d, 1H)

<Step 2> Synthesis of 3-chloro-5H-pyrido [3,2-b] indole

2- (3,5-dichloropyridin-2-yl) aniline (14.53 g, 60.77 mmol), Cu powder (0.39 g, 6.08 mmol), K ₂ CO ₃ (12.58 g, 91.16 mmol), Na ₂ SO under nitrogen stream ₄ (12.76 g, 91.16 mmol) and nitrobenzene (300 ml) were mixed and stirred at 190 ° C. for 12 h. 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-chloro-5H-pyrido [3,2-b] indole (8.25 g, yield 67%).

¹ H-NMR: δ 7.28 (t, 1H), 7.59 (m, 2H), 8.01 (m, 2H), 8.75 (s, 1H), 10.93 (s, 1H)

<Step 3> Synthesis of 3-chloro-5-phenyl-5H-pyrido [3,2-b] indole

3-chloro-5H-pyrido [3,2-b] indole (8.25 g, 40.72 mmol), 1-Iodobenzene (24.92 g, 122.16 mmol), Cu powder (0.13 g, 2.04 mmol), K ₂ CO under nitrogen stream ₃ (8.43 g, 61.08 mmol), Na ₂ SO ₄ (8.55 g, 61.08 mmol) and nitrobenzene (100 ml) were mixed and stirred at 190 ° C. for 12 h. 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-chloro-5-phenyl-5H-pyrido [3,2-b] indole (8.97 g, yield 79%).

¹ H-NMR: δ 7.28 (m, 2H), 7.55 (m, 5H), 7.98 (m, 2H), 8.75 (m, 2H)

Step 4 Synthesis of 3- (2-nitrophenyl) -5-phenyl-5H-pyrido [3,2-b] indole

3-chloro-5-phenyl-5H-pyrido [3,2] instead of 2,3,5-trichloropyridine and 2- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) aniline -b] 3- (2-nitrophenyl) -5-phenyl-5H-pyrido [3,2- by following the same procedure as in <Step 1> of Preparation Example 6, except that indole and 2-nitrophenylboronic acid were used. b] indole (9.52 g, yield 81%) was obtained.

¹ H-NMR: δ 7.28 (m, 2H), 7.56 (m, 6H), 8.01 (m, 5H), 8.74 (d, 1H), 9.24 (s, 1H)

Step 5 Synthesis of IC-6

9.52 g (26.06 mmol) of 3- (2-nitrophenyl) -5-phenyl-5H-pyrido [3,2-b] indole, 20.50 g (78.17 mmol) of triphenylphosphine and 150 ml of 1,2-dichlorobenzene under nitrogen stream After stirring for 12 hours. After the reaction was completed, 1,2-dichlorobenzene was removed and extracted with dichloromethane. The extracted organic layer was removed with water by MgSO ₄ , and obtained the target compound IC-6 (3.91 g, yield 45%) by using column chromatography.

¹ H-NMR: δ 7.27 (m, 3H), 7.59 (m, 8H), 8.09 (m, 2H), 8.74 (d, 1H), 10.92 (s, 1H)

Preparation Example 7 Synthesis of IC-7

Synthesis of 3- (3-nitropyridin-2-yl) -5-phenyl-5H-pyrido [3,2-b] indole

Except for using 3-nitropyridin-2-ylboronic acid instead of 2-nitrophenylboronic acid, the same procedure as in <Step 4> of Preparation Example 6 was performed to obtain 3- (3-nitropyridin-2-yl) -5-phenyl- 5H-pyrido [3,2-b] indole (8.54 g, yield 79%) was obtained.

¹ H-NMR: δ 7.28 (m, 2H), 7.57 (m, 6H), 8.00 (d, 1H), 8.56 (m, 2H), 8.84 (m, 2H), 9.74 (s, 1H)

Step 2 Synthesis of IC-7

3- (3-nitropyridin-2-yl) -5-phenyl-5H-pyrido [3,2-b] instead of 3- (2-nitrophenyl) -5-phenyl-5H-pyrido [3,2-b] indole Except for using indole was carried out the same process as in <Step 5> of Preparation Example 6 to obtain the target compound IC-7 (4.12 g, yield 48%).

¹ H-NMR: δ 7.26 (m, 3H), 7.59 (m, 6H), 8.00 (m, 2H), 8.46 (d, 1H), 8.74 (d, 1H), 10.94 (s, 1H)

Preparation Example 8 Synthesis of IC-8

Step 1 Synthesis of 5- (biphenyl-3-yl) -3-chloro-5H-pyrido [3,2-b] indole

A 5- (biphenyl-3-yl) -3-chloro-5H-pyrido [3,2- was carried out in the same manner as in <Step 3> of Preparation Example 6, except that 3-iodobiphenyl was used instead of 1-Iodobenzene. b] indole (5.58 g, 72% yield) was obtained.

¹ H-NMR: δ 7.24 (m, 2H), 7.57 (m, 8H), 8.01 (m, 3H), 8.78 (m, 2H)

<Step 2> Synthesis of 5- (biphenyl-3-yl) -3- (2-nitrophenyl) -5H-pyrido [3,2-b] indole

Except for using 5- (biphenyl-3-yl) -3-chloro-5H-pyrido [3,2-b] indole instead of 3-chloro-5-phenyl-5H-pyrido [3,2-b] indole Then, the same process as in <Step 4> of Preparation Example 6 was carried out to 5- (biphenyl-3-yl) -3- (2-nitrophenyl) -5H-pyrido [3,2-b] indole (5.01 g, yield 81%).

¹ H-NMR: δ 7.28 (m, 2H), 7.55 (m, 9H), 8.05 (m, 6H), 8.72 (d, 1H), 9.26 (s, 1H)

Step 3 Synthesis of IC-8

5- (biphenyl-3-yl) -3- (2-nitrophenyl) -5H-pyrido [3,2- instead of 3- (2-nitrophenyl) -5-phenyl-5H-pyrido [3,2-b] indole Except for using b] indole, the same procedure as in <Step 5> of Preparation Example 6 was performed to obtain IC-8 (2.33 g, yield 42%) as a target compound.

¹ H-NMR: δ 7.29 (m, 3H), 7.53 (m, 11H), 7.98 (m, 3H), 8.72 (d, 1H), 10.95 (s, 1H)

Preparation Example 9 Synthesis of IC-9

Synthesis of 3-chloro-5- (4,6-diphenyl-1,3,5-triazin-2-yl) -5H-pyrido [3,2-b] indole

Except for using 2-chloro-4,6-diphenyl-1,3,5-triazine instead of 1-Iodobenzene, the same procedure as in <Step 3> of Preparation Example 6 was performed to obtain 3-chloro-5- (4 , 6-diphenyl-1,3,5-triazin-2-yl) -5H-pyrido [3,2-b] indole (5.16 g, 69% yield) was obtained.

¹ H-NMR: δ 7.27 (m, 2H), 7.58 (m, 6H), 8.01 (m, 2H), 8.29 (m, 4H), 8.74 (m, 2H)

<Step 2> Synthesis of 5- (4,6-diphenyl-1,3,5-triazin-2-yl) -3- (2-nitrophenyl) -5H-pyrido [3,2-b] indole

3-chloro-5- (4,6-diphenyl-1,3,5-triazin-2-yl) -5H-pyrido [instead of 3-chloro-5-phenyl-5H-pyrido [3,2-b] indole Except for using 3,2-b] indole, the same procedure as in <Step 4> of Preparation Example 6 was carried out to give 5- (4,6-diphenyl-1,3,5-triazin-2-yl)- 3- (2-nitrophenyl) -5H-pyrido [3,2-b] indole (5.32 g, yield 84%) was obtained.

¹ H-NMR: δ 7.29 (m, 2H), 7.55 (m, 7H), 8.01 (m, 5H), 8.30 (m, 4H), 8.74 (d, 1H), 9.24 (s, 1H)

Step 3 Synthesis of IC-9

5- (4,6-diphenyl-1,3,5-triazin-2-yl) -3- (2 instead of 3- (2-nitrophenyl) -5-phenyl-5H-pyrido [3,2-b] indole Except for using -nitrophenyl) -5H-pyrido [3,2-b] indole, the same procedure as in <Step 5> of Preparation Example 6 was carried out to obtain the target compound IC-9 (2.20 g, yield 44%) Got.

¹ H-NMR: δ 7.28 (m, 3H), 7.53 (m, 9H), 7.98 (m, 2H), 8.27 (m, 4H), 8.47 (d, 1H), 10.95 (s, 1H)

Preparation Example 10 Synthesis of IC-10

Step 1 Synthesis of 2,5-bis (2-nitrophenyl) pyrazine

Except for using 2,5-dichloropyrazine instead of 3-chloro-5-phenyl-5H-pyrido [3,2-b] indole, the same procedure as in <Step 4> of Preparation Example 6 was performed. Bis (2-nitrophenyl) pyrazine (12.21 g, yield 71%) was obtained.

¹ H-NMR: δ 7.67 (t, 2H), 8.01 (m, 6H), 8.80 (s, 2H)

<Step 2> Synthesis of IC-10

<Step 5> of Preparation Example 6, except that 2,5-bis (2-nitrophenyl) pyrazine was used instead of 3- (2-nitrophenyl) -5-phenyl-5H-pyrido [3,2-b] indole. By the same process as in the title compound IC-10 (3.42 g, yield 35%) was obtained.

¹ H-NMR: δ 7.35 (t, 2H), 7.55 (m, 4H), 8.05 (m, 2H), 10.42 (s, 2H)

Preparation Example 11 Synthesis of IC-11

Step 1 Synthesis of 2,5-bis (2-nitrophenyl) pyridine

Except for using 2,5-dichloropyridine instead of 3-chloro-5-phenyl-5H-pyrido [3,2-b] indole, the same procedure as in <Step 4> of Preparation Example 6 was performed. Bis (2-nitrophenyl) pyridine (11.52 g, yield 76%) was obtained.

¹ H-NMR: δ 7.67 (m, 3H), 8.00 (m, 7H), 8.75 (s, 1H)

Step 2 Synthesis of IC-11

<Step 5> of Preparation Example 6, except that 2,5-bis (2-nitrophenyl) pyridine was used instead of 3- (2-nitrophenyl) -5-phenyl-5H-pyrido [3,2-b] indole IC-11 (4.06 g, 44%) as a target compound was obtained.

¹ H-NMR: δ 7.29 (t, 2H), 7.55 (m, 4H), 7.75 (s, 1H), 8.11 (t, 1H), 10.44 (s, 2H)

Synthesis Example 1 Synthesis of Mat-1

IC-1 (4.33g, 13.00mmol), 3,3 '-(5-bromo-1,3-phenylene) dipyridine (8.09g, 26.00mmol), Cu powder (compound prepared in Preparation Example 1) under nitrogen stream 0.09 g, 1.30 mmol), K ₂ CO ₃ (3.58 g, 26.00 mmol), Na ₂ SO ₄ (3.70 g, 26.00 mmol) and nitrobenzene (100 ml) were mixed and stirred at 190 ° 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 the title compound Mat-1 (5.13 g, yield 70%).

Exact Mass: 563 g / mol

Elemental Analysis: C, 83.10; H, 4. 47; N, 12.43

Synthesis Example 2 Synthesis of Mat-2

Except for using 1-bromo-3,5-diphenylbenzene instead of 3,3 '-(5-bromo-1,3-phenylene) dipyridine, the same procedure as in Synthesis Example 1 was carried out to obtain the target compound Mat-2 ( 4.39 g, yield 59%).

Exact Mass: 561 g / mol

Elemental Analysis: C, 87.67; H, 4. 85; N, 7.48

Synthesis Example 3 Synthesis of Mat-3

Except for using 2-bromo-4,6-diphenylpyridine instead of 3,3 '-(5-bromo-1,3-phenylene) dipyridine, the same procedure as in Synthesis Example 1 was carried out to obtain the target compound Mat-3 ( 4.55 g, 61% yield).

Exact Mass: 562 g / mol

Elemental Analysis: C, 85.38; H, 4. 66; N, 9.96

Synthesis Example 4 Synthesis of Mat-4

IC-1 (4.33 g, 13.00 mmol), 2-chloro-4,6-diphenylpyrimidine (6.94 g, 26.00 mmol), NaH (3.74 g, 15.60 mmol), and DMF (compounds prepared in Preparation Example 1) under nitrogen stream 80 ml) was mixed and stirred at room temperature for 3 hours. After the reaction was completed, water was added, the solid compound was filtered and purified by column chromatography to obtain Mat-4 (6.09 g, yield 83%) as a target compound.

Exact Mass: 563 g / mol

Elemental Analysis: C, 83.10; H, 4. 47; N, 12.43

Synthesis Example 5 Synthesis of Mat-5

Except for using 2-chloro-4,6-diphenyl-1,3,5-triazine instead of 2-chloro-4,6-diphenylpyrimidine, the same procedure as in Synthesis Example 4 was carried out to obtain the target compound Mat-5 ( 6.15 g, yield 84%).

Exact Mass: 564 g / mol

Elemental Analysis: C, 80.83; H, 4. 28; N, 14.88

Synthesis Example 6 Synthesis of Mat-6

The same procedure as in Synthesis Example 4 was performed except that 2,4-di (biphenyl-3-yl) -6-chloro-1,3,5-triazine was used instead of 2-chloro-4,6-diphenylpyrimidine. Mat-6 (5.73 g, yield 75%) was obtained as a target compound.

Exact Mass: 716 g / mol

Elemental Analysis: C, 83.78; H, 4.50; N, 11.72

Synthesis Example 7 Synthesis of Mat-7

Except for using IC-2 instead of IC-1 to perform the same procedure as in Synthesis Example 1 to obtain the title compound Mat-7 (4.77 g, yield 65%).

Exact Mass: 564 g / mol

Elemental Analysis: C, 80.83; H, 4. 28; N, 14.88

Synthesis Example 8 Synthesis of Mat-8

Except for using IC-2 instead of IC-1 to perform the same procedure as in Synthesis Example 2 to obtain the target compound Mat-8 (5.20 g, 71% yield).

Exact Mass: 562 g / mol

Elemental Analysis: C, 85.38; H, 4. 66; N, 9.96

Synthesis Example 9 Synthesis of Mat-9

Except for using IC-2 instead of IC-1 to obtain the target compound Mat-9 (6.44 g, 88% yield) was carried out in the same manner as in Synthesis Example 3.

Exact Mass: 563 g / mol

Elemental Analysis: C, 83.10; H, 4. 47; N, 12.43

Synthesis Example 10 Synthesis of Mat-10

Except for using IC-2 instead of IC-1 to obtain the target compound Mat-10 (6.17 g, yield 84%) was carried out in the same manner as in Synthesis Example 4.

Exact Mass: 564 g / mol

Elemental Analysis: C, 80.83; H, 4. 28; N, 14.88

Synthesis Example 11 Synthesis of Mat-11

Except for using IC-2 instead of IC-1 to perform the same procedure as in Synthesis Example 5 to obtain the target compound Mat-11 (5.86 g, yield 80%).

Exact Mass: 565 g / mol

Elemental Analysis: C, 78.57; H, 4.10; N, 17.33

Synthesis Example 12 Synthesis of Mat-12

Except for using IC-2 instead of IC-1 to perform the same procedure as in Synthesis Example 6 to obtain the target compound Mat-12 (5.09 g, yield 68%).

Exact Mass: 717 g / mol

Elemental Analysis: C, 81.99; H, 4. 35; N, 13.66

Synthesis Example 13 Synthesis of Mat-13

Except for using IC-3 instead of IC-1 to obtain the target compound Mat-13 (4.91 g, yield 68%) was carried out in the same manner as in Synthesis Example 1.

Exact Mass: 564 g / mol

Elemental Analysis: C, 80.83; H, 4. 28; N, 14.88

Synthesis Example 14 Synthesis of Mat-14

Except for using IC-3 instead of IC-1 to carry out the same procedure as in Synthesis Example 2 to obtain the target compound Mat-14 (5.27 g, 72% yield).

Exact Mass: 562 g / mol

Elemental Analysis: C, 85.38; H, 4. 66; N, 9.96

Synthesis Example 15 Synthesis of Mat-15

Except for using IC-3 instead of IC-1 to obtain the target compound Mat-15 (6.37 g, 87% yield) was carried out in the same manner as in Synthesis Example 3.

Exact Mass: 563 g / mol

Elemental Analysis: C, 83.10; H, 4. 47; N, 12.43

Synthesis Example 16 Synthesis of Mat-16

Except for using IC-3 instead of IC-1 to carry out the same procedure as in Synthesis Example 4 to obtain the target compound Mat-16 (6.17 g, 84% yield).

Exact Mass: 564 g / mol

Elemental Analysis: C, 80.83; H, 4. 28; N, 14.88

Synthesis Example 17 Synthesis of Mat-17

Except for using IC-3 instead of IC-1 to perform the same procedure as in Synthesis Example 5 to obtain the target compound Mat-17 (5.94 g, 81% yield).

Exact Mass: 565 g / mol

Elemental Analysis: C, 78.57; H, 4.10; N, 17.33

Synthesis Example 18 Synthesis of Mat-18

Except for using IC-3 instead of IC-1 to obtain the target compound Mat-18 (5.22 g, yield 70%) in the same manner as in Synthesis Example 6.

Exact Mass: 717 g / mol

Elemental Analysis: C, 81.99; H, 4. 35; N, 13.66

Synthesis Example 19 Synthesis of Mat-19

Except for using IC-4 instead of IC-1 to carry out the same procedure as in Synthesis Example 1 to obtain the target compound Mat-19 (5.12 g, 71% yield).

Exact Mass: 564 g / mol

Elemental Analysis: C, 80.83; H, 4. 28; N, 14.88

Synthesis Example 20 Synthesis of Mat-20

Except for using IC-4 instead of IC-1 to perform the same procedure as in Synthesis Example 2 to obtain the target compound Mat-20 (5.34 g, 73% yield).

Exact Mass: 562 g / mol

Elemental Analysis: C, 85.38; H, 4. 66; N, 9.96

Synthesis Example 21 Synthesis of Mat-21

Except for using IC-4 instead of IC-1 to perform the same procedure as in Synthesis Example 3 to obtain the target compound Mat-21 (6.24 g, yield 85%).

Exact Mass: 563 g / mol

Elemental Analysis: C, 83.10; H, 4. 47; N, 12.43

Synthesis Example 22 Synthesis of Mat-22

Except for using IC-4 instead of IC-1 to carry out the same procedure as in Synthesis Example 4 to obtain the target compound Mat-22 (6.18 g, 84% yield).

Exact Mass: 564 g / mol

Elemental Analysis: C, 80.83; H, 4. 28; N, 14.88

Synthesis Example 23 Synthesis of Mat-23

Except for using IC-4 instead of IC-1 to carry out the same process as in Synthesis Example 5 to obtain the target compound Mat-23 (6.44 g, 88% yield).

Exact Mass: 565 g / mol

Elemental Analysis: C, 78.57; H, 4.10; N, 17.33

Synthesis Example 24 Synthesis of Mat-24

Except for using IC-4 instead of IC-1 to perform the same procedure as in Synthesis Example 6 to obtain the target compound Mat-24 (5.40 g, 72% yield).

Exact Mass: 717 g / mol

Elemental Analysis: C, 81.99; H, 4. 35; N, 13.66

Synthesis Example 25 Synthesis of Mat-25

Except for using IC-5 instead of IC-1 to obtain the target compound Mat-25 (4.98 g, yield 69%) was carried out in the same manner as in Synthesis Example 1.

Exact Mass: 563 g / mol

Elemental Analysis: C, 83.10; H, 4. 47; N, 12.43

Synthesis Example 26 Synthesis of Mat-26

Except for using IC-5 instead of IC-1 to perform the same procedure as in Synthesis Example 2 to obtain the target compound Mat-26 (5.35 g, 73% yield).

Exact Mass: 561 g / mol

Elemental Analysis: C, 87.67; H, 4. 85; N, 7.48

Synthesis Example 27 Synthesis of Mat-27

Except for using IC-5 instead of IC-1 to obtain the target compound Mat-27 (6.05 g, yield 82%) was carried out in the same manner as in Synthesis Example 3.

Exact Mass: 562 g / mol

Elemental Analysis: C, 85.38; H, 4. 66; N, 9.96

Synthesis Example 28 Synthesis of Mat-28

Except for using IC-5 instead of IC-1 to perform the same procedure as in Synthesis Example 4 to obtain the target compound Mat-28 (6.05 g, 82% yield).

Exact Mass: 563 g / mol

Elemental Analysis: C, 83.10; H, 4. 47; N, 12.43

Synthesis Example 29 Synthesis of Mat-29

Except for using IC-5 instead of IC-1 to perform the same procedure as in Synthesis Example 5 to obtain the target compound Mat-29 (6.26 g, yield 85%).

Exact Mass: 564 g / mol

Elemental Analysis: C, 80.83; H, 4. 28; N, 14.88

Synthesis Example 30 Synthesis of Mat-30

Except for using IC-5 instead of IC-1 to carry out the same procedure as in Synthesis Example 6 to obtain the target compound Mat-30 (5.61 g, yield 75%).

Exact Mass: 716 g / mol

Elemental Analysis: C, 83.78; H, 4.50; N, 11.72

Synthesis Example 31 Synthesis of Mat-31

Except for using IC-6 instead of IC-1 to obtain the target compound Mat-31 (7.64 g, yield 68%) was carried out in the same manner as in Synthesis Example 2.

Exact Mass: 561 g / mol

Elemental Analysis: C, 87.67; H, 4. 85; N, 7.48

Synthesis Example 32 Synthesis of Mat-32

Except for using IC-6 instead of IC-1 to carry out the same procedure as in Synthesis Example 1 to obtain the target compound Mat-32 (7.22 g, 64% yield).

Exact Mass: 563 g / mol

Elemental Analysis: C, 83.10; H, 4. 47; N, 12.43

Synthesis Example 33 Synthesis of Mat-33

Except for using IC-6 instead of IC-1 to obtain the target compound Mat-33 (7.43 g, yield 66%) was carried out in the same manner as in Synthesis Example 3.

Exact Mass: 562 g / mol

Elemental Analysis: C, 85.38; H, 4. 66; N, 9.96

Synthesis Example 34 Synthesis of Mat-34

Except for using IC-6 instead of IC-1 to carry out the same procedure as in Synthesis Example 4 to obtain the target compound Mat-34 (9.93 g, 88% yield).

Exact Mass: 563 g / mol

Elemental Analysis: C, 83.10; H, 4. 47; N, 12.43

Synthesis Example 35 Synthesis of Mat-35

Except for using IC-6 instead of IC-1 to carry out the same procedure as in Synthesis Example 5 to obtain the target compound Mat-35 (10.06 g, 89% yield).

Exact Mass: 564 g / mol

Elemental Analysis: C, 80.83; H, 4. 28; N, 14.88

Synthesis Example 36 Synthesis of Mat-36

Except for using IC-6 instead of IC-1 to perform the same procedure as in Synthesis Example 6 to obtain the target compound Mat-36 (12.19 g, yield 85%).

Exact Mass: 716 g / mol

Elemental Analysis: C, 83.78; H, 4.50; N, 11.72

Synthesis Example 37 Synthesis of Mat-37

Except for using IC-7 instead of IC-1 to perform the same procedure as in Synthesis Example 2 to obtain the target compound Mat-37 (7.76 g, 69% yield).

Exact Mass: 562 g / mol

Elemental Analysis: C, 85.38; H, 4. 66; N, 9.96

Synthesis Example 38 Synthesis of Mat-38

Except for using IC-7 instead of IC-1 to perform the same procedure as in Synthesis Example 1 to obtain the target compound Mat-38 (8.02 g, 71% yield).

Exact Mass: 564 g / mol

Elemental Analysis: C, 80.83; H, 4. 28; N, 14.88

Synthesis Example 39 Synthesis of Mat-39

Except for using IC-7 instead of IC-1 to carry out the same procedure as in Synthesis Example 3 to obtain the target compound Mat-39 (8.80 g, yield 78%).

Exact Mass: 563 g / mol

Elemental Analysis: C, 83.10; H, 4. 47; N, 12.43

Synthesis Example 40 Synthesis of Mat-40

Except for using IC-7 instead of IC-1 to carry out the same procedure as in Synthesis Example 4 to obtain the title compound Mat-40 (9.72 g, yield 86%).

Exact Mass: 564 g / mol

Elemental Analysis: C, 80.83; H, 4. 28; N, 14.88

Synthesis Example 41 Synthesis of Mat-41

Except for using IC-7 instead of IC-1 to carry out the same procedure as in Synthesis Example 5 to obtain the target compound Mat-41 (9.40 g, 83% yield).

Exact Mass: 565 g / mol

Elemental Analysis: C, 78.57; H, 4.10; N, 17.33

Synthesis Example 42 Synthesis of Mat-42

Except for using IC-7 instead of IC-1 to perform the same procedure as in Synthesis Example 6 to obtain the target compound Mat-42 (10.77 g, yield 75%).

Exact Mass: 717 g / mol

Elemental Analysis: C, 81.99; H, 4. 35; N, 13.66

Synthesis Example 43 Synthesis of Mat-43

Except for using IC-8 instead of IC-1 to perform the same procedure as in Synthesis Example 2 to obtain the target compound Mat-43 (8.68 g, yield 68%).

Exact Mass: 637 g / mol

Elemental Analysis: C, 88.51; H, 4.90; N, 6.59

Synthesis Example 44 Synthesis of Mat-44

Except for using IC-8 instead of IC-1 to carry out the same procedure as in Synthesis Example 1 to obtain the target compound Mat-44 (9.22 g, 72% yield).

Exact Mass: 639 g / mol

Elemental Analysis: C, 84.48; H, 4.57; N, 10.95

Synthesis Example 45 Synthesis of Mat-45

Except for using IC-8 instead of IC-1 to obtain the target compound Mat-45 (11.12 g, 87% yield) was carried out in the same manner as in Synthesis Example 3.

Exact Mass: 638 g / mol

Elemental Analysis: C, 86.49; H, 4.73; N, 8.77

Synthesis Example 46 Synthesis of Mat-46

Except for using IC-8 instead of IC-1 to carry out the same procedure as in Synthesis Example 4 to obtain the target compound Mat-46 (10.50 g, 82% yield).

Exact Mass: 639 g / mol

Elemental Analysis: C, 84.48; H, 4.57; N, 10.95

Synthesis Example 47 Synthesis of Mat-47

Except for using IC-8 instead of IC-1 to carry out the same procedure as in Synthesis Example 5 to obtain the target compound Mat-47 (11.15 g, 87% yield).

Exact Mass: 640 g / mol

Elemental Analysis: C, 82.48; H, 4.40; N, 13.12

Synthesis Example 48 Synthesis of Mat-48

Except for using IC-8 instead of IC-1 to carry out the same procedure as in Synthesis Example 6 to obtain the target compound Mat-48 (11.74 g, 74% yield).

Exact Mass: 792 g / mol

Elemental Analysis: C, 84.83; H, 4.58; N, 10.60

Synthesis Example 49 Synthesis of Mat-49

IC-9 (9.78 g, 20.00 mmol), 1-bromobenzene (4.07 g, 30.00 mmol), Cu powder (0.13 g, 2.00 mmol), K ₂ CO ₃ (4.14 g), which is a compound prepared in Preparation Example 9, under nitrogen stream. , 30.00 mmol), Na ₂ SO ₄ (4.26 g, 30.00 mmol) and nitrobenzene (70 ml) were mixed and stirred at 190 ° 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 the title compound Mat-49 (8.70 g, 77% yield).

Exact Mass: 564 g / mol

Elemental Analysis: C, 80.83; H, 4. 28; N, 14.88

Synthesis Example 50 Synthesis of Mat-50

Except for using 3-bromopyridine instead of 1-bromobenzene was carried out in the same manner as in Synthesis Example 49 to obtain the target compound Mat-50 (8.26 g, 73% yield).

Exact Mass: 565 g / mol

Elemental Analysis: C, 78.57; H, 4.10; N, 17.33

Synthesis Example 51 Synthesis of Mat-51

Except for using 3-bromobiphenyl instead of 1-bromobenzene to give the target compound Mat-51 (9.62 g, yield 75%) was carried out in the same manner as in Synthesis Example 49.

Exact Mass: 640 g / mol

Elemental Analysis: C, 82.48; H, 4.40; N, 13.12

Synthesis Example 52 Synthesis of Mat-52

Except for using 1-bromo-3,5-diphenylbenzene instead of 1-bromobenzene was carried out in the same manner as in Synthesis Example 49 to obtain the target compound Mat-52 (11.33 g, yield 79%).

Exact Mass: 716 g / mol

Elemental Analysis: C, 83.78; H, 4.50; N, 11.72

Synthesis Example 53 Synthesis of Mat-53

Except for using 2-bromo-4,6-diphenylpyridine instead of 1-bromobenzene was carried out in the same manner as in Synthesis Example 49 to obtain the target compound Mat-53 (9.48 g, 66% yield).

Exact Mass: 717 g / mol

Elemental Analysis: C, 81.99; H, 4. 35; N, 13.66

Synthesis Example 54 Synthesis of Mat-54

Except for using 2-bromo-4,6-diphenylpyrimidine instead of 1-bromobenzene was carried out the same procedure as in Synthesis Example 49 to obtain the target compound Mat-54 (9.92 g, 69% yield).

Exact Mass: 718 g / mol

Elemental Analysis: C, 80.20; H, 4. 21; N, 15.59

Synthesis Example 55 Synthesis of Mat-55

Except for using IC-10 instead of IC-9 was carried out in the same manner as in Synthesis Example 49 to obtain an intermediate compound IC-10-1 (4.89 g, 73% yield). Except for using IC-10-1 instead of IC-1 to perform the same procedure as in Synthesis Example 5 to obtain the target compound Mat-55 (7.35 g, yield 89%).

Exact Mass: 565 g / mol

Elemental Analysis: C, 78.57; H, 4.10; N, 17.33

Synthesis Example 56 Synthesis of Mat-56

Except for using IC-10-1 of Synthesis Example 55 instead of IC-1 to obtain the target compound Mat-56 (7.18 g, 87% yield) by the same procedure as in Synthesis Example 4.

Exact Mass: 564 g / mol

Elemental Analysis: C, 80.83; H, 4. 28; N, 14.88

Synthesis Example 57 Synthesis of Mat-57

Except for using IC-10-1 of Synthesis Example 55 instead of IC-1 to obtain the target compound Mat-57 (8.61 g, 81% yield) by the same procedure as in Synthesis Example 6.

Exact Mass: 717 g / mol

Elemental Analysis: C, 81.99; H, 4. 35; N, 13.66

Synthesis Example 58 Synthesis of Mat-58

Except for using IC-11 instead of IC-1 to perform the same procedure as in Synthesis Example 3 to obtain the target compound Mat-58 (4.15 g, yield 58%).

Exact Mass: 715 g / mol

Elemental Analysis: C, 85.57; H, 4.65; N, 9.78

Synthesis Example 59 Synthesis of Mat-59

Except for using IC-11 instead of IC-1 to perform the same procedure as in Synthesis Example 4 to obtain the target compound Mat-59 (6.39 g, 89% yield).

Exact Mass: 717 g / mol

Elemental Analysis: C, 81.99; H, 4. 35; N, 13.66

Synthesis Example 60 Synthesis of Mat-60

Except for using IC-11 instead of IC-1 to perform the same procedure as in Synthesis Example 5 to obtain the target compound Mat-60 (5.39 g, yield 75%).

Exact Mass: 719 g / mol

Elemental Analysis: C, 78.43; H, 4.06; N, 17.51

Examples 1 to 60 Fabrication of Green Organic EL Device

After the high purity sublimation purification of the Mat-1 to Mat-60 compound by a commonly known method, a green organic EL device was manufactured according to the following procedure.

First, an ITO (Indium tin oxide) was ultrasonically cleaned with distilled water to a glass substrate coated with a thin film of 1500Å thickness. 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), the substrate is cleaned by UV for 5 minutes and vacuum evaporator The substrate was transferred to.

M-MTDATA (60nm) / TCTA (80nm) / Mat-1 to Mat-60 compound + 10% Ir (ppy) ₃ (300nm) / BCP (10nm) / Alq ₃ (30nm) on the thus prepared ITO transparent electrode An organic EL device was fabricated by laminating in order of / LiF (1 nm) / Al (200 nm).

The structures of m-MTDATA, TCTA, Ir (ppy) ₃ and BCP used are as follows.

Comparative Example 1

A green organic EL device was manufactured in the same manner as in Example 1, except that the following CBP was used instead of the compound Mat-1 as a light emitting host material when forming the emission layer.

Comparative Example 2

A green organic EL device was manufactured in the same manner as in Example 1, except that Com-1, instead of Compound Mat-1, was used as a light emitting host material when forming the emission layer.

[Evaluation example]

For each of the green organic EL devices fabricated in Examples 1-60 and Comparative Examples 1 and 2, the driving voltage, current efficiency, and emission peak at current density of 10 mA / cm 2 were measured, and the results are shown in Table 1 below. .

Table 1

	Host	Drive voltage (V)	Emission Peak (nm)	Current efficiency (cd / A)
Example 1	Mat-1	6.67	518	40.3
Example 2	Mat-2	6.61	518	40.9
Example 3	Mat-3	6.63	519	41.0
Example 4	Mat-4	6.59	517	41.2
Example 5	Mat-5	6.54	516	41.8
Example 6	Mat-6	6.50	515	42.0
Example 7	Mat-7	6.68	518	40.5
Example 8	Mat-8	6.62	517	40.8
Example 9	Mat-9	6.63	518	41.0
Example 10	Mat-10	6.58	516	41.2
Example 11	Mat-11	6.52	517	41.7
Example 12	Mat-12	6.51	518	42.2
Example 13	Mat-13	6.67	516	40.1
Example 14	Mat-14	6.63	516	40.2
Example 15	Mat-15	6.63	517	41.7
Example 16	Mat-16	6.57	517	41.3
Example 17	Mat-17	6.52	518	41.2
Example 18	Mat-18	6.51	518	42.7
Example 19	Mat-19	6.69	518	40.2
Example 20	Mat-20	6.61	518	40.2
Example 21	Mat-21	6.63	516	41.7
Example 22	Mat-22	6.55	517	41.2
Example 23	Mat-23	6.50	516	41.2
Example 24	Mat-24	6.51	518	42.7
Example 25	Mat-25	6.66	518	40.2
Example 26	Mat-26	6.62	519	40.3
Example 27	Mat-27	6.63	516	41.4
Example 28	Mat-28	6.58	519	41.3
Example 29	Mat-29	6.55	516	41.4
Example 30	Mat-30	6.52	517	42.6
Example 31	Mat-31	6.63	518	42.3
Example 32	Mat-32	6.64	516	42.7
Example 33	Mat-33	6.65	517	43.0
Example 34	Mat-34	6.51	518	41.2
Example 35	Mat-35	6.67	516	41.7
Example 36	Mat-36	6.56	516	42.0
Example 37	Mat-37	6.54	516	42.3
Example 38	Mat-38	6.56	516	42.4
Example 39	Mat-39	6.56	515	40.2
Example 40	Mat-40	6.64	515	42.7
Example 41	Mat-41	6.65	517	40.2
Example 42	Mat-42	6.51	518	40.3
Example 43	Mat-43	6.67	516	40.3
Example 44	Mat-44	6.63	517	40.1
Example 45	Mat-45	6.62	518	39.9
Example 46	Mat-46	6.62	517	40.2
Example 47	Mat-47	6.62	518	40.3
Example 48	Mat-48	6.61	518	41.4
Example 49	Mat-49	6.69	518	41.3
Example 50	Mat-50	6.61	518	42.7
Example 51	Mat-51	6.63	516	43.0
Example 52	Mat-52	6.55	515	41.2
Example 53	Mat-53	6.50	515	41.2
Example 54	Mat-54	6.53	517	42.7
Example 55	Mat-55	6.51	518	40.2
Example 56	Mat-56	6.62	516	40.3
Example 57	Mat-57	6.63	515	41.4
Example 58	Mat-58	6.66	515	40.7
Example 59	Mat-59	6.70	517	40.6
Example 60	Mat-60	6.53	518	40.5
Comparative Example 1	CBP	6.93	516	38.2
Comparative Example 2	Com-1	6.70	520	38.5

Compound represented by Formula 1 of the present invention can be applied to the organic material layer of the organic electroluminescent device because of its excellent thermal stability and phosphorescence properties. In particular, when the compound represented by Formula 1 of the present invention is used as a phosphorescent host material of the light emitting layer among the organic material layers, an organic electroluminescent device having excellent light emission performance, low driving voltage, high efficiency and long life can be manufactured, and furthermore, performance, lifetime This greatly improved full color display panel can also be manufactured.

Claims (8)

1. Compound represented by the following formula (1):

   [Formula 1]

   

   In Chemical Formula 1,

   X ₁ to X ₄ are each independently CR ₁ or N, wherein at least one of X ₁ to X ₄ is N,

   X ₁ and X ₂ , or one of X ₂ and X ₃ combine with a compound represented by Formula 2 to form a condensed ring,

   [Formula 2]

   

   In Chemical Formula 2,

   Dashed line means a part which is combined with Formula 1 to form a condensed ring,

   Z is selected from the group consisting of CAr ₂ Ar ₃ , NAr ₄ , O, S and SiAr ₅ Ar ₆ ,

   Ar ₁ to Ar ₆ are each independently hydrogen, deuterium, halogen, cyano 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, the number of nuclear atoms of 3 to 40 heterocycloalkyl group, C ₆ ~ C ₆₀ aryl group, nuclear atoms aryl of from 5 to 60 heteroaryl group, a C ₁ ~ alkyloxy group of C _40, C ₆ ~ C ₆₀ is selected from the group consisting of an aryloxy group, a C ₁ to C ₄₀ alkylsilyl group, a C ₆ to C ₆₀ arylsilyl group, and a C ₆ to C ₆₀ arylamine group, and combine with an adjacent group to form a condensed ring. Can and

   Y ₁ to Y ₈ are each independently CR ₂ or N,

   R ₁ and R ₂ 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, 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 and aryloxy C _60, C ₁ ~ C ₄₀ alkyl silyl group, C ₆ to C ₆₀ aryl silyl group, and a C ₆ - is selected from the group consisting of an aryl amine of the C _60, the combined contiguous groups fused ring Can form,

   Alkyl groups, alkenyl groups, alkynyl groups, cycloalkyl groups, heterocycloalkyl groups, aryl groups, heteroaryl groups, alkyloxy groups, aryloxy groups, alkylsilyl groups, arylsilyl groups of Ar ₁ to Ar ₆ , R ₁ and R ₂ ; And arylamine groups are each independently deuterium, halogen, nitro group, cyano group, amino group, C ₁ ~ C ₄₀ alkyl group, C ₂ ~ C ₄₀ alkenyl group, C ₂ ~ C ₄₀ alkynyl group, C ₃ ~ C ₄₀ Of cycloalkyl group, heterocycloalkyl group of 3 to 40 nuclear atoms, aryl group of C ₆ to C ₄₀ , heteroaryl group of 5 to 40 nuclear atoms, alkyloxy group of C ₁ to C ₄₀ , C ₆ to C ₆₀ It may be substituted with one or more selected from the group consisting of an aryloxy group, C ₁ ~ C ₄₀ Alkylsilyl group, C ₆ ~ C ₆₀ An arylsilyl group, and C ₆ ~ C ₆₀ An arylamine group.
2. The method of claim 1,

   Z in Formula 2 is NAr ₄ characterized in that the compound.
3. The method of claim 1,

   Compound represented by Formula 1 is selected from the group consisting of compounds represented by the following formula C-1 to C-30:

   

   

   In Chemical Formulas C-1 to C-30, Y ₁ to Y ₈ and Ar ₁ to Ar ₆ are the same as defined in claim 1.
4. The method of claim 1,

   Compound represented by Formula 1 is selected from the group consisting of compounds represented by the following formula D-1 to D-63:

   

   

   

   

   In Formulas D-1 to D-63, Ar ₁ and Ar ₄ are the same as defined in claim 1.
5. The method of claim 4, wherein

   Ar ₁ and Ar ₄ are each independently selected from the group consisting of a C ₆ ~ C ₆₀ aryl group, a heteroaryl group of 5 to 60 nuclear atoms and an arylamine group of C ₆ ~ C ₆₀ .
6. 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 layer is an organic electroluminescent device, characterized in that the organic material layer comprising a compound according to any one of claims 1 to 5.
7. The method of claim 6,

   The organic material layer containing the compound is an organic electroluminescent device, characterized in that the hole injection layer, hole transport layer or light emitting layer.
8. The method of claim 6,

   The organic material layer containing the compound is a light emitting layer, the compound is an organic electroluminescent device, characterized in that the phosphorescent host of the light emitting layer.