KR20130142816A - Novel compounds and organic electro luminescence device comprising the same - Google Patents

Abstract

The present invention relates to a compound denoted by chemical formula 1 and an organic electroluminescent device comprising the same. The organic electroluminescent device comprises the compound denoted by the chemical formula 1 in more than one organic layer, more desirably in a luminous layer for improving luminance efficiency, driving voltage, and lifetime. (In the chemical formula 1, X1-X4 and Y1-Y10 are defined by each specific explanation)

Description

TECHNICAL FIELD [0001] The present invention relates to a novel compound, and an organic electroluminescent device including the same. BACKGROUND OF THE INVENTION [0002]

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.

Electroluminescent (EL) devices, which led to blue electroluminescence using anthracene single crystals in 1965, were followed up with the observation of the organic thin film emission of Bernanose in the 1950s. In 1987, Layer and a functional layer of a light-emitting layer. Hereinafter, the organic electroluminescent device has been developed to introduce characteristic organic layers in the device to improve the efficiency and lifetime of the device.

In the organic electroluminescent device, when a voltage is applied between the two electrodes, holes are injected from the anode and electrons from the cathode are injected into the organic layer, and the injected holes and electrons meet to form an exciton. When the exciton formed drops to a ground state The light comes out. The material used as the organic material layer may be classified into a light emitting material, a hole injecting material, a hole transporting material, an electron transporting material, and an electron injecting material depending on functions.

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

The dopant material can be divided into a fluorescent dopant using an organic material and a phosphorescent dopant using a metal complex compound containing heavy atoms such as Ir and Pt. The development of a phosphorescent dopant has been studied not only for a phosphorescent dopant but also for a phosphorescent host since it can theoretically improve luminescence efficiency up to four times that of a fluorescent dopant.

To date, hole transport materials. NPB, BCP, and Alq ₃ are widely known as hole injecting materials and electron transporting materials, and anthracene derivatives are used as light emitting materials. In particular, metal complex compounds containing Ir such as Firpic, Ir (ppy) ₃ , (acac) Ir (btp) ₂ and the like, which have great advantages in terms of efficiency improvement of light emitting materials, are blue, green, It is used as a red phosphorescent dopant material, and CBP is used as a phosphorescent host material. In addition, Korean Patent Publication No. 2010-0108924 discloses an organic electroluminescent device using an azacarbazole derivative as a host material.

However, conventional luminescent materials have good luminescence characteristics, but have low glass transition temperature and poor thermal stability, which is not satisfactory in terms of lifetime of an organic electroluminescent device. Therefore, development of a luminescent material having excellent performance is required.

It is an object of the present invention to provide a novel compound which can be used as a host material of a light emitting layer and can improve the efficiency, lifetime and stability of a device when used in a light emitting layer of an organic electroluminescent device .

It is another object of the present invention to provide an organic electroluminescent device comprising the novel compound.

The present invention provides novel compounds of formula (1)

In Formula 1,

X ₁ to X ₄ are each independently CR ₁ or N, wherein the plural CR _{1 s} are the same or different from each other;

Y ₁ to Y ₁₀ are each independently CR ₂ or N, wherein the plurality of CR _{2 s} are the same or different from each other;

R ₁ and R ₂ are each independently hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C ₁ to C ₄₀ alkyl, substituted or unsubstituted C ₂ to C ₄₀ alkenyl, substituted or unsubstituted C for ₂ ~ C ₄₀ alkynyl group, a substituted or unsubstituted C ₃ ~ C ₄₀ cycloalkyl group, a substituted or unsubstituted nucleus atom to C40 heterocycloalkyl group, a substituted or unsubstituted C ₆ ~ C ₆₀ of the An aryl group, a substituted or unsubstituted heteroaryl group having 5 to 60 ring atoms, a substituted or unsubstituted C ₁ to C ₄₀ alkyloxy group, a substituted or unsubstituted C ₆ to C ₆₀ aryloxy group, a substituted Or an unsubstituted C ₁ to C ₄₀ alkylsilyl group, a substituted or unsubstituted C ₆ to C ₆₀ arylsilyl group and a substituted or unsubstituted C ₆ to C ₆₀ arylamine group, Each of R ₁ and R ₂ may form a fused ring with an adjacent group;

An alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a heterocycloalkyl group, an aryl group, a heteroaryl group, an alkyloxy group, an aryloxy group, an alkylsilyl group, an arylsilyl group and an arylamine group of R ₁ and R ₂ Each of which may be substituted with at least one substituent independently selected from the group consisting of deuterium, a halogen, a nitro group, a cyano group, a C ₁ to C ₄₀ alkyl group, a C ₂ to C ₄₀ alkenyl group, an amino group, a C ₃ to C ₄₀ cycloalkyl group, A C ₆ to C ₄₀ aryl group, a heteroaryl group having 5 to 40 nuclear atoms, a C ₁ to C ₄₀ alkyloxy group, a C ₆ to C ₆₀ aryloxy group, a C C ₁ to C ₄₀ alkylsilyl groups, C ₆ to C ₆₀ arylsilyl groups, C ₁ to C ₄₀ alkylboron groups, C ₆ to C ₆₀ arylboron groups, C ₆ to C ₆₀ arylphosphine groups, C ₆ ~ C ₆₀ aryl phosphine oxide group, and a C ₆ ~ is selected from the group consisting of an aryl amine of the C ₆₀ of, wherein a plurality of the substituents are the same or be different from each other There.

In addition, the present invention is an anode; cathode; And at least one organic material layer sandwiched between the anode and the cathode, wherein at least one of the one or more organic material layers includes a compound represented by the above formula (1) Device.

Herein, the organic compound layer including the compound represented by Formula 1 is selected from the group consisting of a hole injection layer, a hole transport layer, and a light emitting layer, and is preferably a light emitting layer. At this time, the compound represented by Formula 1 is a phosphorescent host material.

The compound represented by the general formula (1) according to the present invention is excellent in thermal stability and phosphorescent properties, and thus can be applied to an organic material layer, preferably a light emitting layer, of an organic electroluminescent device.

Therefore, when the compound represented by Formula 1 is included as the phosphorescent host material in the light emitting layer of the organic electroluminescent device, the efficiency (luminous efficiency and power efficiency), lifetime, brightness and driving voltage Can be improved, and the performance and lifetime of the full-color organic electroluminescence panel can be greatly improved.

Hereinafter, the present invention will be described in detail.

In the present invention, "unsubstituted alkyl" means a monovalent functional group obtained by removing a hydrogen atom from a linear or branched saturated hydrocarbon having 1 to 40 carbon atoms, and examples thereof include methyl, ethyl, propyl, isobutyl, sec-butyl, pentyl, iso-amyl, hexyl, and the like.

In the present invention, "unsubstituted alkenyl" means a monovalent functional group obtained by removing a hydrogen atom from a linear or branched unsaturated hydrocarbon having 2 to 40 carbon atoms and having at least one carbon-carbon double bond. do. Examples thereof include, but are not limited to, vinyl, allyl, isopropenyl, 2-butenyl, and the like.

In the present invention, "unsubstituted alkynyl" means a monovalent functional group obtained by removing a hydrogen atom from a straight-chain or branched-chain unsaturated hydrocarbon having 2 to 40 carbon atoms and having at least one carbon-carbon triple bond do. Examples thereof include, but are not limited to, ethynyl, 2-propynyl, and the like.

In the present invention, "unsubstituted cycloalkyl" means a monovalent functional group obtained by removing a hydrogen atom from a monocyclic or polycyclic non-aromatic hydrocarbon (saturated cyclic hydrocarbon) having 3 to 40 carbon atoms. Examples of such cycloalkyls include, but are not limited to, cyclopropyl, cyclopentyl, cyclohexyl, norbornyl, adamantine, and the like.

In the present invention, "unsubstituted heterocycloalkyl" means a monovalent functional group obtained by removing a hydrogen atom from a non-aromatic hydrocarbon (saturated cyclic hydrocarbon) having 3 to 40 nuclear atoms, wherein at least one of the rings Carbon, preferably 1 to 3 carbons, is substituted with a heteroatom such as N, O or S. Non-limiting examples thereof include morpholine, piperazine, and the like.

In the present invention, the term "unsubstituted aryl" 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, or may be attached in a pendant or fused form. Non-limiting examples thereof include phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, anthryl, and the like.

In the present invention, "unsubstituted heteroaryl" means a monovalent functional group obtained by removing a hydrogen atom from a monoheterocyclic or polyheterocyclic aromatic hydrocarbon having 5 to 60 nuclear atoms, in which at least one carbon in the ring is N (Nitrogen), O (oxygen), S (sulfur) or Se (selenium), wherein the heteroaryl is attached in such a way that two or more rings are pendant or fused to each other And may also include condensed forms with aryl groups. Non-limiting examples of such heteroaryls include 6-membered monocyclic rings such as pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, triazinyl, Such as phenoxathienyl, indolizinyl, indolyl, purinyl, quinolyl, benzothiazole, carbazolyl, and the like. Click ring, and 2- Furanyl, N-imidazolyl, 2-isoxazolyl, 2-pyridinyl, 2-pyrimidinyl and the like.

In the present invention, "unsubstituted alkyloxy" means a monovalent functional group represented by RO-, wherein R is an alkyl having 1 to 40 carbon atoms, which may be linear, branched or cyclic cyclic structure. Examples of such 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, "unsubstituted aryloxy" means a monovalent functional group represented by R'O-, wherein R 'is aryl having 6 to 60 carbon atoms. Non-limiting examples of aryloxy include phenyloxy, naphthyloxy, diphenyloxy and the like.

In the present invention, "unsubstituted alkylsilyl" means silyl substituted with alkyl having 1 to 40 carbon atoms, "unsubstituted arylsilyl" means silyl substituted with aryl having 6 to 60 carbon atoms, and " Unsubstituted arylamine "means an amine substituted with aryl having 6 to 60 carbon atoms.

Further, in the present invention, the term "fused ring" means a condensed aliphatic ring, a condensed aromatic ring, a condensed heteroaliphatic ring, a condensed heteroaromatic ring, or a combination thereof.

<Novel compound>

The novel compound according to the present invention has a structure in which a heterocyclic moiety is fused to a quinoxalino carbazole moiety to form a basic skeleton and various substituents are bonded to the basic skeleton. (1). The compound represented by the formula (1) is excellent in phosphorescence characteristics, has excellent electron and / or hole transporting ability, can improve the luminous efficiency, power efficiency, driving voltage and lifetime characteristics of the device, The material of one of the hole injection layer, the hole transport layer and the light emitting layer, more preferably the material of the light emitting layer (particularly, the hole injection layer, the hole transport layer, the light emitting layer, the electron transport layer and the electron injection layer) , Phosphorescent host material). Accordingly, when the organic electroluminescent device includes the compound of Formula 1, the organic electroluminescent device can improve the luminous efficiency, power efficiency, lifetime, brightness, and driving voltage.

The compound represented by Formula 1 has bipolar characteristics by introducing various substituents into a basic skeleton formed by condensation of a quinoxalino carbazole moiety and a heterocyclic moiety, The balance between hole and electron mobility can be controlled to improve the recombination efficiency of holes and electrons, and therefore, it is expected to exhibit excellent phosphorescence characteristics.

In addition, the compound represented by Formula 1 has a wide energy band gap (sky blue to red) by controlling energy levels by various substituents introduced into the basic skeleton. Accordingly, when the compound of Formula 1 is used in an organic electroluminescent device, the phosphorescence characteristics of the device can be improved, and the hole injecting ability and / or transporting ability, luminous efficiency, driving voltage, lifetime characteristics and the like can be improved.

In addition, the compound represented by Formula 1 has a significantly increased molecular weight due to various substituents introduced into the basic skeleton, thereby improving the glass transition temperature. As a result, the conventional organic electroluminescence device material (for example, CBP [4,4-dicarbazolybiphenyl]). Therefore, the organic electroluminescent device comprising the compound represented by the formula (1) of the present invention can greatly improve durability and lifetime characteristics.

In addition, when the compound of Chemical Formula 1 according to the present invention is employed as a hole injecting layer material, a hole transporting layer material, or a light emitting layer material, preferably a light emitting layer material of an organic electroluminescent device, It is possible to exert an excellent effect in terms of efficiency and life span. Therefore, the compound according to the present invention can greatly contribute to improvement of the performance and lifetime of the organic electroluminescent device, and further, the lifetime of the organic electroluminescent device can maximize the performance of the full-color organic electroluminescent panel.

In the compound represented by Formula 1 according to the present invention, it is preferable that at least one of X ₁ to X ₄ is nitrogen (N).

It is preferable that at least one of Y ₁ to Y ₁₀ is nitrogen (N).

R ₁ and R ₂ may be the same or different and are each independently selected from the group consisting of hydrogen, substituted or unsubstituted C ₆ -C ₆₀ (preferably C ₆ -C ₂₅ ) aryl, substituted or unsubstituted the number of nuclear atoms of 5 to 40 heteroaryl group, and a (preferably C ₆ ~ C ₂₀₎ substituted or unsubstituted C ₆ ~ C ₆₀ ring group consisting of an aryl amine of the (preferably a number of nuclear atoms of 5 to 32) . &Lt; / RTI &gt;

At this time, one or more substituents which may be introduced into each of the aryl group, heteroaryl group and arylamine group of R ₁ and R ₂ are independently selected from the group consisting of deuterium, a halogen, a nitro group, a cyano group, a C ₁ to C ₄₀ alkyl group preferably C ₁ ~ alkyl group of _{C 10), C 2 ~ C} 40 alkenyl group (preferably C ₂ ~ alkenyl group of C _10), amino group, C ₃ ~ C ₄₀ cycloalkyl group (preferably a C ₃ ~ C ₁₈ cycloalkyl group), nuclear atoms, 3 to 40 heterocycloalkyl group (preferably a heterocycloalkyl group of nuclear atoms of 3 to 18), C ₆ ~ C ₄₀ aryl group (preferably a C ₆ ~ C ₁₈ aryl group), a heteroaryl group of nuclear atoms of 5 to 40 heteroaryl group (preferably, from 5 to 18 nuclear atoms), alkyloxy group of C ₁ ~ C ₄₀ (preferably C ₁ ~ C ₁₀ of the alkyloxy group), a C ₆ ~ C ₆₀ of the aryloxy group (preferably a C ₆ ~ C ₁₈ aryloxy group), C ₁ ~ C ₄₀ alkyl silyl group (preferably a C ₁ ~ C ₁₀ of Kill silyl group), C arylsilyl group of ₆ ~ C ₆₀ (preferably C arylsilyl group of _{6 ~ C 18), C 1} ~ C 40 alkyl boron group (preferably an alkyl boron of C ₁ ~ C ₁₀ group), C ₆ ~ arylboronic group of C ₆₀ aryl boron group (preferably C ₆ ~ C ₁₈ in), an aryl phosphine group), a C ₆ ~ C ₆₀ aryl phosphine group (preferably a C ₆ ~ C ₁₈ of , An arylphosphine oxide group of C ₆ to C ₆₀ (preferably an arylphosphine oxide group of C ₆ to C ₁₈ ) and an arylamine group of C ₆ to C ₆₀ (preferably a C ₆ to C ₂₀ arylamine Group), wherein the plurality of substituents may be the same or different from each other.

More preferably, R ₁ and R ₂ are each independently selected from the group consisting of hydrogen, or substituents S1 to S166, but is not limited thereto.

Representative examples of the compound represented by the formula (1) according to the present invention include, but are not limited to, the following compounds.

The compound represented by formula (I) according to the invention can be synthesized according to the general synthetic method (Chem Rev, 60:.. .. 313 (1960); J. Chem SOC 4482 (1955); Chem Rev. 95.: 2457 (1995)). Detailed synthesis of the compound of the present invention will be described in detail in Synthesis Examples to be described later.

&Lt; Organic electroluminescent device &

The present invention provides an organic electroluminescent device including the compound represented by the above-mentioned formula (1).

Specifically, the organic electroluminescent device according to the present invention includes an anode, a cathode, and at least one organic layer sandwiched between the anode and the cathode, wherein at least one of the one or more organic layers includes And a compound represented by the above formula (1).

Here, the organic compound layer containing the compound represented by Formula 1 may be at least one of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer. Preferably, the organic compound layer including the compound of Formula 1 may be a hole injection layer, a hole transporting layer, or a light emitting layer, more preferably a light emitting layer.

The light emitting layer of the organic electroluminescent device according to the present invention may contain a host material (preferably, a phosphorescent host material), wherein any of the compounds represented by the above formula (1) may be used as a host material. When the light emitting layer contains one of the compounds represented by the above formula (1), the hole transporting ability is increased to increase the bonding force between the hole and the electron in the light emitting layer. Therefore, efficiency (luminous efficiency and power efficiency), lifetime, And the like can be provided.

The structure of the organic electroluminescent device according to the present invention is not particularly limited, and may include 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. Here, the electron injection layer may be further stacked on the electron transporting layer. In addition, the organic electroluminescent device according to the present invention may have a structure in which an anode, one or more organic layers and an anode are sequentially stacked, and an insulating layer or an adhesive layer is interposed between the electrodes and the organic layer.

On the other hand, the material that can be used as the anode included in the organic electroluminescent device according to 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), and indium zinc oxide (IZO); ZnO: Al or SnO _2: a combination of a metal and an oxide such as Sb; Conductive polymers such as polythiophene, poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (PEDT), polypyrrole or polyaniline; And carbon black.

Examples of materials usable as an anode included in the organic electroluminescent device according to the present invention include, but are not limited to, magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, Tin, or lead, or alloys thereof; And a multilayer structure material such as LiF / Al or LiO ₂ / Al.

The organic compound layer included in the organic electroluminescent device according to the present invention may be any one of the hole injecting layer, the hole transporting layer, the light emitting layer, the electron transporting layer and the electron injecting layer, preferably the hole injecting layer, The light emitting layer can be formed using materials and methods known in the art, except for the use of any of the light emitting layers, more preferably the light emitting layer.

Materials that can be used as the substrate included in the organic electroluminescent device according to the present invention are not particularly limited, but examples thereof include silicon wafers, quartz, glass plates, metal plates, plastic films and sheets.

Such an organic electroluminescent device of the present invention may be manufactured by a method known in the art, wherein the light emitting layer included in the organic material layer may be manufactured by a vacuum deposition method or a solution coating method. Here, 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 examples. However, the following examples are for illustrative purposes only and are not intended to limit the scope of the present invention.

[Preparation Example 1] Synthesis of Compound Com-1

<Step 1> Synthesis of 4'-bromo-2-nitrobiphenyl

9.48 g (40.0 mmol) of 1,4-dibromobenzene, 7.34 g (44.0 mmol) of 2-nitrophenylboronic acid, 4.80 g (120.0 mmol) of NaOH and 200 ml / 100 ml of THF / H ₂ O were added under a stream of nitrogen Followed by stirring to obtain a reaction mixture. Then, 2.30 g (5 mol%) of Pd (PPh ₃ ) ₄ was added to the reaction mixture at 40 ° C, followed by stirring at 80 ° C for 12 hours. After completion of the reaction, extraction with methylene chloride, adding MgSO ₄ , and filtering were performed to obtain an organic layer. Thereafter, the solvent was removed from the filtered organic layer, and 6.36 g (yield: 57%) of 4'-bromo-2-nitrobiphenyl was obtained by column chromatography.

¹ H-NMR:? 7.53 (d, 1 H), 7.67 (m, 3H), 7.90

&Lt; Step 2 > 2- bromo -9H- of carbazole  synthesis

5.33 g (19.10 mmol) of 4'-bromo-2-nitrobiphenyl obtained in Step 1 of Preparation Example 1 was placed in a nitrogen stream together with 12.52 g (47.72 mmol) of triphenylphosphine and 50 ml of 1,2-dichlorobenzene, Lt; / RTI > After completion of the reaction, 1,2-dichlorobenzene was removed and extraction was performed with dichloromethane to obtain an organic layer. Then, water was removed from the extracted organic layer using MgSO _4, and 3.82 g (yield: 81%) of 2-bromo-9H-carbazole was obtained by column chromatography.

¹ H-NMR:? 7.31 (m, 2H), 7.56 (m, 3H), 8.01 (d,

<Step 3> Synthesis of 2- (4-nitropyridin-3-yl) -9H-carbazole

Except that 2-bromo-9H-carbazole was used instead of 1,4-dibromobenzene used in <Step 1> of Preparation Example 1 and 3-nitropyridin-4-ylboronic acid was used instead of 2-nitrophenylboronic acid. (4-nitropyridin-3-yl) -9H-carbazole (3.84 g, yield: 85%) was obtained in the same manner as in <Step 1> of Example 1.

^{1 H-NMR: δ 7.30 (} t, 1H), 7.56 (m, 3H), 7.80 (d, 1H), 7.92 (d, 1H), 8.13 (m, 3H), 9.50 (s, 1H), 10.41 ( s, 1 H)

&Lt; Step 4 > Com Synthesis of -1

Step 2 of Preparation Example 1 was repeated except that 2- (4-nitropyridin-3-yl) -9H-carbazole was used instead of 4'-bromo-2-nitrobiphenyl used in Step 2 of Preparation Example 1 >, Compound Com-1 (3.07 g, yield: 90%) was obtained.

^{1 H-NMR: δ 7.32 (} t, 2H), 7.51 (m, 4H), 8.12 (d, 2H), 8.43 (d, 1H), 9.51 (s, 1H), 10.43 (s, 2H)

[Preparation Example 2] Synthesis of Compound Com-2

<Step 1> Synthesis of 1,4-bis (4-nitropyridin-3-yl) benzene

9.48 g (40.0 mmol) of 1,4-dibromobenzene, 14.78 g (88.0 mmol) of 2-nitrophenylboronic acid, 4.8 g (120.0 mmol) of NaOH and 200 ml / 100 ml of THF / H ₂ O were added under a nitrogen stream Followed by stirring to obtain a reaction mixture. Then, 2.30 g (5 mol%) of Pd (PPh ₃ ) ₄ was added to the reaction mixture at 40 ° C, followed by stirring at 80 ° C for 12 hours. After completion of the reaction, extraction with methylene chloride, adding MgSO ₄ , and filtering were performed to obtain an organic layer. Thereafter, the solvent was removed from the filtered organic layer, and 6.69 g (yield: 52%) of 1,4-bis (4-nitropyridin-3-yl) benzene was obtained by column chromatography.

^{1 H-NMR: δ 7.26 (} s, 4H), 7.93 (d, 2H), 8.15 (d, 2H), 9.52 (s, 2H)

&Lt; Step 2 > Com - 2 of  synthesis

6.15 g (19.10 mmol) of 1,4-bis (4-nitropyridin-3-yl) benzene obtained in Step 1 of Preparation Example 2 was dissolved in 50 ml of a 1,2- And stirred for 12 hours. After completion of the reaction, 1,2-dichlorobenzene was removed and extraction was performed with dichloromethane to obtain an organic layer. Thereafter, water was removed from the extracted organic layer using MgSO ₄ , and 3.94 g (yield: 80%) of Compound Com-2 was obtained by column chromatography.

^{1 H-NMR: δ 7.31 (} m, 2H), 7.56 (m, 3H), 8.01 (d, 1H), 8.12 (d, 1H), 10.41 (s, 2H)

[Preparation Example 3] Synthesis of Compound Com-3

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

2-Nitrophenylboronic acid, 4.8 g (120.0 mmol) of NaOH and 200 ml / 100 ml of THF / H ₂ O were added to a solution of 9.48 g (40.0 mmol) of 2,5-dibromopyridine, 14.69 g Followed by stirring to obtain a reaction mixture. Then, 2.30 g (5 mol%) of Pd (PPh ₃ ) ₄ was added to the reaction mixture at 40 ° C, followed by stirring at 80 ° C for 12 hours. After completion of the reaction, extraction with methylene chloride, adding MgSO ₄ , and filtering were performed to obtain an organic layer. The solvent was removed from the filtered organic layer and 6.42 g (yield: 50%) of 2,5-bis (2-nitrophenyl) pyridine was obtained by column chromatography.

¹ H-NMR:? 7.69 (m, 3H), 7.98 (m, 6H), 8.56 (d,

<Step 2> Synthesis of Compound Com-3

6.13 g (19.10 mmol) of 2,5-bis (2-nitrophenyl) pyridine obtained in Step 1 of Preparation Example 3 were placed in a nitrogen stream together with 12.52 g (47.72 mmol) of triphenylphosphine and 50 ml of 1,2-dichlorobenzene Stir for 12 hours. After completion of the reaction, 1,2-dichlorobenzene was removed and extraction was performed with dichloromethane to obtain an organic layer. Thereafter, water was removed from the extracted organic layer using MgSO _4, and 3.97 g (yield: 81%) of Compound Com-3 was obtained by column chromatography.

^{1 H-NMR: δ 7.31 (} t, 2H), 7.67 (m, 4H), 8.12 (d, 2H), 9.51 (s, 1H), 10.41 (s, 2H)

[Preparation Example 4] Synthesis of Compound Com-4

<Step 1> Synthesis of 3,6-bis (2-nitrophenyl) pyridazine

3-dibromopyridazine, 14.69 g (88.0 mmol) of 2-nitrophenylboronic acid, 4.8 g (120.0 mmol) of NaOH and 200 ml / 100 ml of THF / H ₂ O were added under nitrogen stream, Followed by stirring to obtain a reaction mixture. Then, 2.30 g (5 mol%) of Pd (PPh ₃ ) ₄ was added to the reaction mixture at 40 ° C, followed by stirring at 80 ° C for 12 hours. After completion of the reaction, extraction with methylene chloride, adding MgSO ₄ , and filtering were performed to obtain an organic layer. Thereafter, the solvent was removed from the filtered organic layer, and 6.83 g (yield: 53%) of 3,6-bis (2-nitrophenyl) pyridazine was obtained by column chromatography.

^{1 H-NMR: δ 7.71 (} m, 4H), 7.98 (m, 6H)

<Step 2> Synthesis of Compound Com-4

6.15 g (19.10 mmol) of 3,6-bis (2-nitrophenyl) pyridazine obtained in Step 1 of Preparation Example 4 was placed in a nitrogen stream together with 12.52 g (47.72 mmol) of triphenylphosphine and 50 ml of 1,2-dichlorobenzene Stir for 12 hours. After completion of the reaction, 1,2-dichlorobenzene was removed and extraction was performed with dichloromethane to obtain an organic layer. Thereafter, water was removed from the extracted organic layer using MgSO ₄ , and 3.84 g (yield: 78%) of Compound Com-4 was obtained by column chromatography.

^{1 H-NMR: δ 7.30 (} t, 2H), 7.50 (t, 2H), 7.63 (d, 2H), 8.12 (d, 2H), 10.41 (s, 2H)

[Synthesis Example 1] Synthesis of Compound Mat-1

Dihydroindolo [2,3-a] carbazole (2.0 g, 7.80 mmol), 1,2-dibromobenzene (2.02 g, 8.58 mmol) and Pd ₂ (dba) ₃ (0.21 g, 0.23 mmol) , P (t-bu) ₃ (0.15 g, 0.78 mmol), NaO (t-bu) (1.87 g, 19.5 mmol) and toluene (20 ml) were mixed and stirred at 110 ° C for 12 hours.

After the reaction was completed, the organic layer was separated with ethyl acetate, and water was removed from the organic layer using MgSO ₄ . Thereafter, the solvent was removed from the organic layer and then purified by column chromatography to obtain Mat-1 (1.28 g, yield: 50%).

GC-Mass (theory: 330.38 g / mol, measurement: 330 g / mol)

[ Synthetic example  2] Compound Mat - 2 of  synthesis

2-one (1.28 g, yield) was obtained in the same manner as in Synthesis Example 1, except that 2,3-dibromopyridine (2.02 g, 8.58 mmol) was used instead of 1,2-dibromobenzene used in Synthesis Example 1 : 50%).

GC-Mass (theory: 331.37 g / mol, measured: 331 g / mol)

[ Synthetic example  3] Compound Mat Synthesis of -4

Compound Mat-4 (1.29 g, yield) was obtained in the same manner as in Synthesis Example 1, except that 4,5-dibromopyrimidine (2.03 g, 8.58 mmol) was used instead of 1,2-dibromobenzene used in Synthesis Example 1 : 50%).

GC-Mass (calculated: 332.36 g / mol, measured: 332 g / mol)

[ Synthetic example  4] compound Mat Synthesis of -5

Compound Mat-5 (1.29 g, yield) was obtained in the same manner as in Synthesis Example 1, except that 2,3-dibromopyrazine (2.03 g, 8.58 mmol) was used instead of 1,2-dibromobenzene used in Synthesis Example 1 50%).

GC-Mass (calculated: 332.36 g / mol, measured: 332 g / mol)

[ Synthetic example  5] Compound Mat Synthesis of -14

2,3-dibromopyridine (2.02 g, 8.58 mmol), Pd ₂ (dba) ₃ (0.21 g, 0.23 mmol), P (t -bu) ₃ (0.15 g, 0.78 mmol), NaO (t-bu) (1.87 g, 19.5 mmol) and toluene (20 ml) were mixed and stirred at 110 ° C for 12 hours.

After the reaction was completed, the organic layer was separated with ethyl acetate, and water was removed from the organic layer using MgSO ₄ . Thereafter, the solvent was removed from the organic layer and then purified by column chromatography to obtain a compound Mat-14 (1.28 g, yield: 50%).

GC-Mass (calculated: 332.36 g / mol, measured: 332 g / mol)

[ Synthetic example  6] compound Mat Synthesis of -32

Compound Mat-32 (1.29 g, yield) was obtained in the same manner as in Synthesis Example 5, except that 4,5-dibromopyrimidine (2.03 g, 8.58 mmol) was used in place of 2,3-dibromopyridine used in Synthesis Example 5 : 50%).

GC-Mass (calculated: 333.35 g / mol, measured: 333 g / mol)

[ Synthetic example  7] compound Mat Synthesis of -40

Compound Mat-40 (1.29 g, yield) was obtained in the same manner as in Synthesis Example 5, except that 2,3-dibromopyrazine (2.03 g, 8.58 mmol) was used instead of 2,3-dibromopyridine used in Synthesis Example 5 : 50%).

GC-Mass (calculated: 333.35 g / mol, measured: 333 g / mol)

[ Synthetic example  8] compound Mat - 38 of  synthesis

(2.0 g, 7.74 mmol), 4,5-dibromopyrimidine (2.01 g, 8.51 mmol), Pd ₂ (dba) ₃ (0.21 g, 0.23 mmol) and P -bu) ₃ (0.15 g, 0.77 mmol), NaO (t-bu) (1.87 g, 19.5 mmol) and toluene (20 ml) were mixed and stirred at 110 ° C for 12 hours

After the reaction was completed, the organic layer was separated with ethyl acetate, and water was removed from the organic layer using MgSO ₄ . Thereafter, the solvent was removed from the organic layer and then purified by column chromatography to obtain a compound Mat-38 (1.28 g, yield: 50%).

GC-Mass (calculated: 332.36 g / mol, measured: 332 g / mol)

[ Synthetic example  9] Compound Mat - Of 39  synthesis

Compound Mat-39 (1.29 g, yield) was obtained in the same manner as in Synthesis Example 8, except that 2,3-dibromopyridine (2.00 g, 8.51 mmol) was used in place of 4,5-dibromopyrimidine used in Synthesis Example 8 : 50%).

GC-Mass (theory: 332.35 g / mol, measured: 333 g / mol)

[ Synthetic example  10] compound Mat Synthesis of -41

Compound (Mat-41) (1.29 g, yield) was obtained in the same manner as in Synthesis Example 8, except that 2,3-dibromopyrazine (2.01 g, 8.51 mmol) was used instead of 4,5-dibromopyrimidine used in Synthesis Example 8 : 50%).

GC-Mass (theory: 334.33 g / mol, measured: 334 g / mol)

[ Synthetic example  11] compound Mat - Thirty-five  synthesis

The compound Com-3 (2.0 g, 7.77 mmol), 4,5-dibromopyrimidine (2.02 g, 8.58 mmol), Pd ₂ (dba) ₃ (0.21 g, 0.23 mmol) and P -bu) ₃ (0.15 g, 0.78 mmol), NaO (t-bu) (1.87 g, 19.5 mmol) and toluene (20 ml) were mixed and stirred at 110 ° C for 12 hours.

After the reaction was completed, the organic layer was separated with ethyl acetate, and water was removed from the organic layer using MgSO ₄ . Thereafter, the solvent was removed from the organic layer and then purified by column chromatography to obtain a compound Mat-35 (1.28 g, yield: 50%).

GC-Mass (theory: 333.10 g / mol, measured: 333 g / mol)

[ Synthetic example  12] compounds Mat Synthesis of -21

Compound (Mat-21) (1.29 g, yield) was obtained in the same manner as in Synthesis Example 11, except that 3,4-dibromopyridine (2.01 g, 8.58 mmol) was used in place of 4,5-dibromopyrimidine used in Synthesis Example 11. [ : 50%).

GC-Mass (calculated: 332.36 g / mol, measured: 332 g / mol)

[ Synthetic example  13] compound Mat Synthesis of -43

Compound (Mat-43) (1.29 g, yield) was obtained in the same manner as in Synthesis Example 11, except that 2,3-dibromopyrazine (2.03 g, 8.58 mmol) was used in place of 4,5-dibromopyrimidine used in Synthesis Example 11 : 50%).

GC-Mass (calculated: 333.35 g / mol, measured: 333 g / mol)

[ Synthetic example  14] Compound Mat - 37  synthesis

(2.0 g, 8.53 mmol), Pd ₂ (dba) ₃ (0.21 g, 0.23 mmol) and P (t) were added to a solution of the compound Com-4 (2.0 g, 7.74 mmol), 4,5-dibromopyrimidine -bu) ₃ (0.15 g, 0.77 mmol), NaO (t-bu) (1.87 g, 19.5 mmol) and toluene (20 ml) were mixed and stirred at 110 ° C for 12 hours.

After the reaction was completed, the organic layer was separated with ethyl acetate, and water was removed from the organic layer using MgSO ₄ . Thereafter, the solvent was removed from the organic layer and then purified by column chromatography to obtain a compound Mat-37 (1.28 g, yield: 50%).

GC-Mass (calculated: 332.36 g / mol, measured: 332 g / mol)

[Synthesis Example 15] Synthesis of Compound Mat-51

Compound Mat-51 (1.29 g, yield) was obtained in the same manner as in Synthesis Example 13, except that 4,5-dibromopyridazine (2.01 g, 8.51 mmol) was used in place of 4,5-dibromopyrimidine used in Synthesis Example 14. [ : 50%).

GC-Mass (theory: 332.35 g / mol, measured: 333 g / mol)

[ Synthetic example  16] compound Mat - 44 of  synthesis

Compound (Mat-44) (1.29 g, yield) was obtained in the same manner as in Synthesis Example 13, except that 2,3-dibromopyrazine (2.01 g, 8.51 mmol) was used in place of 4,5-dibromopyrimidine used in Synthesis Example 14. [ : 50%).

GC-Mass (theory: 334.33 g / mol, measured: 334 g / mol)

[Synthesis Example 17] Synthesis of Compound Mat-166

&Lt; Step 1 > IC Synthesis of -1

Dihydroindolo [2,3-a] carbazole (5.0 g, 19.5 mmol), 2,3,5-tribromopyridine (7.39 g, 23.4 mmol), Pd ₂ (dba) ₃ (1.07 g, 1.17 mixing mmol), P (t-bu ) 3 (0.39 g, 1.95 mmol), NaO (t-bu) (9.37g, 97.5 mmol), and toluene (200 ml) and stirred at 110 ℃ for 12 hours.

After completion of the reaction, the reaction mixture was extracted with ethyl acetate, added with MgSO ₄ , and filtered to obtain an organic layer. Thereafter, the solvent was removed from the filtered organic layer, and then, the compound IC-1 (3.28 g, yield: 41%) was obtained by column chromatography.

GC-Mass (theory: 410.27 g / mol, measurement: 410 g / mol)

&Lt; Step 2 > Mat Synthesis of -166

Compound IC-1 (3.0 g, 7.31 mmol) obtained in Step 1 of Preparation Example 17 was reacted with 2,4-diphenyl-6- (4,4,5,5-tetramethyl-1,3,2 -dioxaborolan-2-yl) -1,3,5- triazine (3.15 g, 8.77 mmol), NaOH (0.87 g, 21.93 mmol), Pd (PPh 3) 4 (0.25 g, 0.21 mmol) and 1,4- dioxane / H ₂ O (30 ml / 8 ml), followed by stirring at 100 ° C for 12 hours.

After completion of the reaction, the reaction mixture was extracted with ethyl acetate, added with MgSO ₄ and filtered to obtain an organic layer. Thereafter, the solvent was removed from the filtered organic layer, and then, Mat-166 (2.67 g, yield: 65%) was obtained by column chromatography.

GC-Mass (Theoretical value: 562.62 g / mol, Measured value: 562 g / mol)

[ Synthetic example  18] compound Mat - 73  synthesis

2,4-diphenyl-6- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -1,3,5-triazine used in <Step 2> Step 2 of Synthesis Example 17 was repeated except that 4,4,5,5-tetramethyl-2-phenyl-1,3,2-dioxaborolane (1.80 g, 8.77 mmol) To obtain Compound Mat-73 (2.65 g, yield: 65%).

GC-Mass (theory: 407.47 g / mol, measurement: 407 g / mol)

[ Synthetic example  19] Compound Mat - 154 of  synthesis

2,4-diphenyl-6- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -1,3,5-triazine used in <Step 2> Except that 4,6-diphenyl-2- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl (3.13 g, 8.77 mmol) Compound Mat-73 (1.93 g, yield: 65%) was obtained in the same manner as in <Step 2> of Example 17.

GC-Mass (calculated: 560.65 g / mol, measured: 560 g / mol)

[ Synthetic example  20] compound Mat Synthesis of -170

2,4-diphenyl-6- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -1,3,5-triazine used in <Step 2> Except that 4,6-diphenyl-2- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) pyrimidine (1.80 g, 8.77 mmol) Compound Mat-170 (2.66 g, yield: 65%) was obtained in the same manner as in <Step 2> of Example 17.

GC-Mass (calculated: 561.63 g / mol, measured: 561 g / mol)

[Synthesis Example 21] Synthesis of Compound Mat-188

<Step 1> Synthesis of Compound IC-2

The procedure of Step 1 of Synthesis Example 17 was repeated except that Compound A-1 was used instead of 11,12-dihydroindolo [2,3-a] carbazole used in Step 1 of Synthesis Example 17 Compound IC-2 (3.37 g, yield: 42%) was obtained.

GC-Mass (theory: 411.25 g / mol, measurement: 411 g / mol)

&Lt; Step 2 > Mat Synthesis of -188

Compound IC-2 (3.0 g, 7.31 mmol) obtained in Step 1 of Synthesis Example 21 was reacted with 2,4-diphenyl-6- (4,4,5,5-tetramethyl- dioxaborolan-2-yl) -1,3,5- triazine (3.15 g, 8.77 mmol), NaOH (0.87 g, 21.93 mmol), Pd (PPh 3) 4 (0.25 g, 0.21 mmol) and 1,4-dioxane / H ₂ O (30 ml / 8 ml) and stirred at 100 ° C for 12 hours.

After completion of the reaction, the reaction mixture was extracted with ethyl acetate, added with MgSO ₄ , and filtered to obtain an organic layer. Thereafter, the solvent was removed from the filtered organic layer, and then, Mat-188 (2.67 g, yield: 65%) was obtained by column chromatography.

GC-Mass (calculated: 563.61 g / mol, measured: 563 g / mol)

[Synthesis Example 22] Synthesis of Compound Mat-81

<Step 1> Synthesis of Compound IC-3

Except that 4,6-dibromo-2,3-diiodopyridine (11.42 g, 23.4 mmol) was used instead of the 2,3,5-tribromopyridine used in Step 1 of Synthesis Example 17, Step 1] to obtain the compound IC-3 (3.98 g, yield: 42%).

GC-Mass (calculated: 489.16 g / mol, measured: 489 g / mol)

&Lt; Step 2 > Mat Synthesis of -81

The compound IC-3 (3.57 g, 7.31 mmol) obtained in Step 1 of Synthesis Example 22 was reacted with 4,4,5,5-tetramethyl-2-phenyl-1,3,2-dioxaborolane , 17.54 mmol), NaOH (0.87 g, 21.93 mmol), Pd (PPh 3) 4 (0.25 g, 0.21 mmol) and _{1,4-dioxane / H 2 O (} 30 ml / 8 ml) and then a mixture of 100 ℃ Lt; / RTI &gt; for 12 hours.

After completion of the reaction, the reaction mixture was extracted with ethyl acetate, added with MgSO ₄ and filtered to obtain an organic layer. Thereafter, the solvent was removed from the filtered organic layer, and then the compound Mat-81 (2.29 g, yield: 65%) was obtained by column chromatography.

GC-Mass (calculated: 483.17 g / mol, measured: 483 g / mol)

[ Synthetic example  23] compound Mat Synthesis of -83

Instead of 4,4,5,5-tetramethyl-2-phenyl-1,3,2-dioxaborolane used in Step 2 of Synthesis Example 22, 3- (4,4,5,5-tetramethyl- Compound Mat-166 (2.66 g, yield 65%) was obtained in the same manner as in <Step 2> of the above Synthesis Example 22, except that 2-dioxaborolan-2-yl pyridine (3.59 g, 17.54 mmol) ).

GC-Mass (calculated: 561.63 g / mol, measured: 561 g / mol)

[Synthesis Example 24] Synthesis of Mat-109

&Lt; Step 1 > IC Synthesis of -4

Except that 2,6-dibromo-3,4-diiodopyridine (11.42 g, 23.4 mmol) was used instead of 4,6-dibromo-2,3-diiodopyridine used in Step 1 of Synthesis Example 22, The compound IC-4 (4.29 g, yield: 42%) was obtained in the same manner as in <Step 1> of Example 22.

GC-Mass (calculated: 489.16 g / mol, measured: 489 g / mol)

&Lt; Step 2 > Mat Synthesis of -109

The compound IC-4 (3.57 g, 7.31 mmol) obtained in Step 1 of Synthesis Example 24 was reacted with 4,4,5,5-tetramethyl-2-phenyl-1,3,2-dioxaborolane (3.58 g, mixed with 17.54 mmol), NaOH (0.87 g , 21.93 mmol), Pd (PPh 3) 4 (0.25 g, 0.21 mmol) and _{1,4-dioxane / H 2 O (} 30 ml / 8 ml) , and then, 100 ℃ Lt; / RTI &gt; for 12 hours.

After completion of the reaction, the reaction mixture was extracted with ethyl acetate, added with MgSO ₄ , and filtered to obtain an organic layer. Thereafter, the solvent was removed from the filtered organic layer, and then, Mat-109 (2.40 g, yield: 68%) was obtained by column chromatography.

GC-Mass (calculated: 483.17 g / mol, measured: 483 g / mol)

[ Synthetic example  25] Mat - 110's  synthesis

Instead of 4,4,5,5-tetramethyl-2-phenyl-1,3,2-dioxaborolane used in Step 2 of Synthesis Example 24, 2- (4,4,5,5-tetramethyl- Mat-166 (2.66 g, yield 65%) was obtained in the same manner as in [Step 2] of Preparation Example 24, except that 2-dioxaborolan-2-yl) pyridine (3.59 g, 17.54 mmol) &Lt; / RTI >

GC-Mass (calculated: 561.63 g / mol, measured: 561 g / mol)

[Synthesis Example 26] Synthesis of Mat-125

&Lt; Step 1 > IC Synthesis of -5

Step 1 of Synthesis Example 17 was repeated except that 2,4-dibromo-5,6-diiodopyrimidine (11.44 g, 23.4 mmol) was used instead of 2,3,5-tribromopyridine used in Synthesis Example 17 To give compound IC-5 (3.82 g, yield: 40%).

GC-Mass (calculated: 490.15 g / mol, measured: 490 g / mol)

&Lt; Step 2 > Mat Synthesis of -125

The compound IC-5 (3.58 g, 7.31 mmol) obtained in Step 1 of Synthesis Example 26 was reacted with 4,4,5,5-tetramethyl-2-phenyl-1,3,2-dioxaborolane (3.58 g, mixed with 17.54 mmol), NaOH (0.87 g , 21.93 mmol), Pd (PPh 3) 4 (0.25 g, 0.21 mmol) and _{1,4-dioxane / H 2 O (} 30 ml / 8 ml) , and then, 100 ℃ Lt; / RTI &gt; for 12 hours.

After completion of the reaction, the reaction mixture was extracted with ethyl acetate, added with MgSO ₄ , and filtered to obtain an organic layer. Thereafter, the solvent was removed from the filtered organic layer, and then, Mat-125 (2.34 g, yield: 66%) was obtained by column chromatography.

GC-Mass (calculated: 484.55 g / mol, measured: 484 g / mol)

[ Synthetic example  27] compound Mat - 127  synthesis

3- (4,4,5,5-tetramethyl-1,3,2-dioxaborolane) was used instead of the 4,4,5,5-tetramethyl-2-phenyl-1,3,2-dioxaborolane used in <Step 2> 127 (2.66 g, yield: 65%) was obtained in the same manner as in <Step 2> of the above Synthesis Example 26, except that 2-dioxaborolan-2-yl pyridine (3.58 g, 17.54 mmol) ).

GC-Mass (calculated: 486.53 g / mol, measured: 486 g / mol)

[Synthesis Example 28] Synthesis of Compound Mat-189

<Step 1> Synthesis of Compound IC-6

Compound Mat-1 (2.0 g, 7.80 mmol) obtained in Synthetic Example 1 was mixed with NBS (1.52 g, 8.58 mmol) and chloroform (40 ml) under a nitrogen stream and stirred at room temperature for 8 hours.

After completion of the reaction, the reaction mixture was extracted with ethyl acetate, added with MgSO ₄ , and filtered to obtain an organic layer. Thereafter, the solvent was removed from the filtered organic layer, and then column chromatography was used to obtain compound IC-6 (2.84 g, yield 89%).

GC-Mass (theory: 409.28 g / mol, measurement: 409 g / mol)

&Lt; Step 2 > Mat Synthesis of -189

(2.98 g, 7.31 mmol) obtained in Step 1 of Synthesis Example 28 was reacted with 4,4,5,5-tetramethyl-2-phenyl-1,3,2-dioxaborolane (1.79 g, 8.77 mmol), NaOH (0.87 g , 21.93 mmol), Pd (PPh 3) 4 (0.25 g, 0.21 mmol) and _{1,4-dioxane / H 2 O (} 30 ml / 8 ml) and mixed, and then, 100 ℃ Lt; / RTI &gt; for 12 hours.

After completion of the reaction, the reaction mixture was extracted with ethyl acetate, added with MgSO ₄ , and filtered to obtain an organic layer. Thereafter, the solvent was removed from the filtered organic layer, and then the compound Mat-189 (2.08 g, yield: 70%) was obtained by column chromatography.

GC-Mass (theory: 406.48 g / mol, measurement: 406 g / mol)

[ Synthetic example  29] compound Mat - 197's  synthesis

Diphenyl-6- (4,4,5,5-tetramethyl-2-phenyl-1,3,2-dioxaborolane used in Step 2 of Synthesis Example 28 instead of 4,4,5,5- Step 2 of Synthesis Example 28 was carried out except that tetramethyl-1,3,2-dioxaborolan-2-yl) -1,3,5-triazine (3.15 g, 8.77 mmol) To obtain Compound Mat-197 (2.66 g, yield: 65%).

GC-Mass (calculated: 561.63 g / mol, measured: 561 g / mol)

[ Synthetic example  30] Compound Mat - 200  synthesis

4,4,5,5-tetramethyl-2-phenyl-1,3,2-dioxaborolane used in Step 2 of Synthesis Example 28 was used instead of 9- (4,6-diphenyl-1,3,5- 2-yl) -3- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -9H-carbazole (4.59 g, 8.77 mmol) The compound Mat-200 (3.18 g, yield: 60%) was obtained in the same manner as in <Step 2> of Synthesis Example 28.

GC-Mass (Theoretical value: 726.82 g / mol, Measured value: 726 g / mol)

[ Synthetic example  31] Compound Mat - 202's  synthesis

Compound IC-6 (2.98 g, 7.31 mmol) obtained in Step 1 of Synthesis Example 28 was reacted with 4,4,5,5-tetramethyl-N, N-diphenyl-1,3,2-dioxaborolan- -amine (2.59 g, 8.77 mmol) , NaOH (0.87 g, 21.93 mmol), Pd (PPh 3) 4 (0.25 g, 0.21 mmol) and _{1,4-dioxane / H 2 O (} 30 ml / 8 ml) and After mixing, the mixture was stirred at 100 DEG C for 12 hours.

After completion of the reaction, the reaction mixture was extracted with ethyl acetate, added with MgSO ₄ , and filtered to obtain an organic layer. Thereafter, the solvent was removed from the filtered organic layer, and then the compound Mat-202 (2.54 g, yield: 70%) was obtained by column chromatography.

GC-Mass (calculated: 497.59 g / mol, measured: 497 g / mol)

[Synthesis Example 32] Synthesis of Compound Mat-222

<Step 1> Synthesis of Compound IC-7

The compound Mat-1 (2.0 g, 7.80 mmol) obtained in Synthetic Example 1 was mixed with NBS (3.04 g, 17.16 mmol) and chloroform (40 ml) under a nitrogen stream, followed by stirring at room temperature for 8 hours.

After completion of the reaction, the reaction mixture was extracted with ethyl acetate, added with MgSO ₄ , and filtered to obtain an organic layer. Thereafter, the solvent was removed from the filtered organic layer, and then, the compound IC-7 (3.50 g, yield: 92%) was obtained by column chromatography.

GC-Mass (calculated: 488.17 g / mol, measured: 488 g / mol)

&Lt; Step 2 > Mat - 222  synthesis

Compound (IC-7) (3.56 g, 7.31 mmol) obtained in Step 1 of Synthesis Example 32 was reacted with 2- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan- pyridine (3.58 g, 17.54 mmol) , NaOH (0.87 g, 21.93 mmol), Pd (PPh 3) 4 (0.25 g, 0.21 mmol), 1,4-dioxane (30 ml) and H ₂ O (8 ml) and After mixing, the mixture was stirred at 100 DEG C for 12 hours.

After completion of the reaction, the reaction mixture was extracted with ethyl acetate, added with MgSO ₄ , and filtered to obtain an organic layer. Thereafter, the solvent was removed from the filtered organic layer, and then the compound Mat-222 (2.30 g, yield: 65%) was obtained by column chromatography.

GC-Mass (calculated: 484.55 g / mol, measured: 484 g / mol)

[Synthesis Example 33] Synthesis of Compound Mat-209

&Lt; Step 1 > IC Synthesis of -8

Compound Mat-5 (2.0 g, 7.80 mmol) obtained in Synthetic Example 4 was mixed with NBS (3.04 g, 17.16 mmol) and chloroform (40 ml) under a nitrogen stream and stirred at room temperature for 8 hours.

After completion of the reaction, the reaction mixture was extracted with ethyl acetate, added with MgSO ₄ , and filtered to obtain an organic layer. Thereafter, the solvent was removed from the filtered organic layer, and then, the compound IC-8 (2.88 g, yield: 90%) was obtained by column chromatography.

GC-Mass (theory: 411.25 g / mol, measurement: 411 g / mol)

&Lt; Step 2 > Mat Synthesis of -209

Compound IC-8 (3.00 g, 7.31 mmol) obtained in Step 1 of Synthesis Example 33 was reacted with 2,4-diphenyl-6- (4,4,5,5-tetramethyl- dioxaborolan-2-yl) -1,3,5- triazine (3.14 g, 8.77 mmol), NaOH (0.87 g, 21.93 mmol), Pd (PPh 3) 4 (0.25 g, 0.21 mmol) and 1,4-dioxane / H ₂ O (30 ml / 8 ml), followed by stirring at 100 ° C for 12 hours.

After completion of the reaction, the reaction mixture was extracted with ethyl acetate, added with MgSO ₄ , and filtered to obtain an organic layer. Thereafter, the solvent was removed from the filtered organic layer, and then, Mat-209 (2.55 g, yield: 62%) was obtained by column chromatography.

GC-Mass (calculated: 563.61 g / mol, measured: 563 g / mol)

[Example 1] Production of green organic EL device

The compound Mat-1 synthesized in Synthesis Example 1 was subjected to high purity sublimation purification by a conventionally known method, and then a green organic EL device was prepared according to the following procedure.

A glass substrate coated with ITO (Indium tin oxide) having a thickness of 1500 mm 3 was ultrasonically cleaned with distilled water. After the distilled water was washed, it was ultrasonically washed with a solvent such as isopropyl alcohol, acetone, or methanol, dried, transferred to a UV OZONE cleaner (Power sonic 405, Hoshin Tech), and then the substrate was cleaned using UV for 5 minutes The substrate was transferred to a vacuum evaporator.

(60 nm) / TCTA (80 nm) / Compound Mat-1 + 10% Ir (ppy) ₃ (300 nm) / BCP (10 nm) / Alq ₃ (80 nm) synthesized in Synthesis Example 1 was formed on the ITO transparent electrode prepared as described above. (30 nm) / LiF (1 nm) / Al (200 nm) in this order to form an organic EL device.

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

[Examples 2 to 33] Preparation of green organic EL device

A green organic EL device was fabricated in the same manner as in Example 1 except that the compounds synthesized in Synthesis Examples 2 to 33 were used in place of the compound Mat-1 used as a host material in the formation of the light emitting layer in Example 1 .

[Comparative Example 1] Production of green organic EL device

A green organic EL device was prepared in the same manner as in Example 1, except that CBP was used instead of the compound Mat-1 used as a host material in the formation of the light emitting layer. The structure of CBP used is as follows.

[Evaluation example]

The driving voltage, current efficiency and emission peak at the current density of 10 mA / cm 2 were measured for the green organic EL devices prepared in each of Examples 1 to 33 and Comparative Example 1, and the results are shown in Table 1 below.

Host substance The driving voltage (V) Emission peak (nm) Current efficiency (cd / A) Example 1 Mat-1 6.47 521 40.3 Example 2 Mat-2 6.41 521 41.0 Example 3 Mat-4 6.53 523 41.5 Example 4 Mat-5 6.50 522 41.5 Example 5 Mat-14 6.54 520 41.8 Example 6 Mat-32 6.50 520 42.0 Example 7 Mat-40 6.61 520 40.5 Example 8 Mat-38 6.60 521 40.8 Example 9 Mat-39 6.60 519 40.0 Example 10 Mat-41 6.55 520 41.0 Example 11 Mat-35 6.49 519 40.5 Example 12 Mat-21 6.45 519 40.1 Example 13 Mat-43 6.60 520 40.7 Example 14 Mat-37 6.55 521 40.2 Example 15 Mat-51 6.58 522 40.9 Example 16 Mat-44 6.57 521 41.0 Example 17 Mat-166 6.50 522 42.9 Example 18 Mat-73 6.55 520 42.0 Example 19 Mat-154 6.60 520 42.5 Example 20 Mat-170 6.45 522 42.2 Example 21 Mat-188 6.40 522 41.7 Example 22 Mat-81 6.55 521 41.9 Example 23 Mat-83 6.50 523 42.0 Example 24 Mat-109 6.51 521 42.1 Example 25 Mat-110 6.60 520 41.2 Example 26 Mat-125 6.62 520 42.7 Example 27 Mat-127 6.65 520 42.4 Example 28 Mat-189 6.58 523 41.0 Example 29 Mat-197 6.55 522 42.0 Example 30 Mat-200 6.60 522 42.3 Example 31 Mat-202 6.49 521 41.0 Example 32 Mat-222 6.57 521 40.9 Example 33 Mat-209 6.50 522 41.3 Comparative Example 1 CBP 6.93 516 38.2

As a result of the experiment, as can be seen from the above Table 1, the green (green) compounds prepared in Examples 1 to 32, respectively, which use the compounds according to the present invention (the compounds synthesized in Synthesis Examples 1 to 33 respectively) It was confirmed that the organic EL device exhibited better performance than the green organic EL device of Comparative Example 1 using the host material (CBP) in terms of current efficiency and driving voltage.

Claims (6)

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

(In Formula 1,
X ₁ to X ₄ are each independently CR ₁ or N, wherein the plural CR _{1 s} are the same or different from each other;
Y ₁ to Y ₁₀ are each independently CR ₂ or N, wherein the plurality of CR _{2 s} are the same or different from each other;
R ₁ and R ₂ are each independently hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C ₁ to C ₄₀ alkyl, substituted or unsubstituted C ₂ to C ₄₀ alkenyl, substituted or unsubstituted C for ₂ ~ C ₄₀ alkynyl group, a substituted or unsubstituted C ₃ ~ C ₄₀ cycloalkyl group, a substituted or unsubstituted nucleus atom to C40 heterocycloalkyl group, a substituted or unsubstituted C ₆ ~ C ₆₀ of the An aryl group, a substituted or unsubstituted heteroaryl group having 5 to 60 ring atoms, a substituted or unsubstituted C ₁ to C ₄₀ alkyloxy group, a substituted or unsubstituted C ₆ to C ₆₀ aryloxy group, a substituted Or an unsubstituted C ₁ to C ₄₀ alkylsilyl group, a substituted or unsubstituted C ₆ to C ₆₀ arylsilyl group and a substituted or unsubstituted C ₆ to C ₆₀ arylamine group, Each of R ₁ and R ₂ may form a fused ring with an adjacent group;
An alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a heterocycloalkyl group, an aryl group, a heteroaryl group, an alkyloxy group, an aryloxy group, an alkylsilyl group, an arylsilyl group and an arylamine group of R ₁ and R ₂ Each of which may be substituted with at least one substituent independently selected from the group consisting of deuterium, a halogen, a nitro group, a cyano group, a C ₁ to C ₄₀ alkyl group, a C ₂ to C ₄₀ alkenyl group, an amino group, a C ₃ to C ₄₀ cycloalkyl group, A C ₆ to C ₄₀ aryl group, a heteroaryl group having 5 to 40 nuclear atoms, a C ₁ to C ₄₀ alkyloxy group, a C ₆ to C ₆₀ aryloxy group, a C C ₁ to C ₄₀ alkylsilyl groups, C ₆ to C ₆₀ arylsilyl groups, C ₁ to C ₄₀ alkylboron groups, C ₆ to C ₆₀ arylboron groups, C ₆ to C ₆₀ arylphosphine groups, C ₆ ~ C ₆₀ aryl phosphine oxide group, and a C ₆ ~ is selected from the group consisting of an aryl amine of the C ₆₀ of, wherein a plurality of the substituents are the same or be different from each other Yes). The compound according to claim 1, wherein at least one of X ₁ to X ₄ is N. According to claim 1, wherein R ₁ and R ₂ are each independently hydrogen, substituted or unsubstituted C ₆ ~ C ₆₀ aryl group, substituted or unsubstituted heteroaryl group having 5 to 40 nuclear atoms, and substituted Or an unsubstituted C ₆ ~ C ₆₀ arylamine group,
In this case, one or more substituents that may be introduced to each of the aryl group, heteroaryl group, and arylamine group of R ₁ and R ₂ are each independently deuterium, halogen, nitro group, cyano group, C ₁ ~ C ₄₀ alkyl group, C ₂ ~ C ₄₀ alkenyl group, amino group, C ₃ to C ₄₀ cycloalkyl group, nuclear atom 3 to 40 heterocycloalkyl group, C ₆ to C ₄₀ aryl group, nuclear atom 5 to 40 heteroaryl group, C ₁ ~ C ₄₀ alkyloxy group of, C ₆ ~ aryloxy C _60, C ₁ ~ C ₄₀ alkyl silyl group, C ₆ ~ aryl silyl group of C _60, C ₁ ~ C ₄₀ group of an alkyl boron, C ₆ a ~ C group ₆₀ arylboronic of, C ₆ ~ C ₆₀ aryl phosphine group, C ₆ ~ C aryl phosphine oxide ₆₀ group and a C ₆ ~ is selected from the group consisting of an aryl amine of the C _60, wherein a plurality of substituents Compounds characterized by being identical or different from each other. anode; cathode; And at least one organic material layer interposed between the anode and the cathode, the organic electroluminescent device comprising:
At least one of the one or more organic material layer is an organic electroluminescent device, characterized in that it comprises a compound represented by the formula (1) according to any one of claims 1 to 3. 5. The organic electroluminescent device according to claim 4, wherein the organic compound layer including the compound represented by Formula 1 is selected from the group consisting of a hole injection layer, a hole transport layer, and a light emitting layer. 5. The organic electroluminescent device according to claim 4, wherein the organic compound layer including the compound represented by Formula 1 is a light emitting layer,
Wherein the compound represented by Formula 1 is a phosphorescent host material.