WO2011081451A2 - Tri-phenyl compounds and organic electro-luminescent device using same - Google Patents

Abstract

The present invention relates to tri-phenyl compounds and an organic electro-luminescent device using the same. The compound of the present invention has an excellent hole injection and/or transferability and an excellent electron transferability and/or luminosity, especially blue and/or green luminosity. Applied to fluorescent or phosphorescent host materials, the organic electro-luminescent device can enhance properties such as luminescence efficiency, brightness, driving voltage and life time.

Description

Triphenylene compound and organic electroluminescent device comprising the same

The present invention includes a novel triphenylene compound having excellent electron transporting ability, hole injection and / or transporting ability, and / or luminous ability, and including the same in at least one organic layer, such as luminous efficiency, luminance, thermal stability, driving voltage, and lifetime. This is an improved organic electroluminescent device.

In general, organic light emitting phenomenon refers to a phenomenon in which light appears when electric energy is applied to an organic material. In other words, when the organic layer is positioned between the anode and the cathode, a voltage is applied between the two electrodes, and holes are injected into the organic layer and electrons are injected into the cathode. When the injected holes and electrons meet, excitons are formed, and when the excitons fall back to the ground, they shine.

The study of organic electroluminescent (EL) devices (hereinafter simply referred to as 'organic EL devices') led to blue electroluminescence using anthracene monocrystals in 1965, based on Bernanose's observation of organic thin film emission in the 1950s. According to (Tang), an organic EL device having a laminated structure divided into a functional layer of a hole layer and a light emitting layer has been proposed, and has been developed in the form of introducing each characteristic organic material layer in the device to make a high efficiency and long life organic EL device. This led to the development of specialized materials used for this.

Such organic EL devices include an indium tin oxide (ITO) substrate, an anode, a hole injection layer that selectively receives holes from an anode, a hole transport layer that selectively transfers holes, a light emitting layer where holes and electrons recombine to emit light, and optionally an electron It consists of an electron transporting layer for transferring the electrons, optionally an electron injection layer for receiving electrons from the cathode and the cathode.

The reason why the organic EL device is manufactured in multiple layers is that the movement speeds of the holes and the electrons are different. If the appropriate hole injection layer, the hole transport layer, the electron transport layer, and the electron injection layer are made, the holes and the electrons can be effectively transferred. The balance between the holes and the electrons in the device can be achieved to increase the luminous efficiency.

Electrons injected from the electron injection layer and holes transferred from the hole injection layer recombine in the emission layer to form excitons, and fall from the singlet excited state to the ground state and are called fluorescence, and fall from the triplet excited state to the ground state. Luminescence is called phosphorescence. Theoretically, when the exciton is generated when the carrier is recombined in the emission layer, the ratio of singlet and triplet excitons is generated at a ratio of 1: 3, and when phosphorescence is used, the internal quantum efficiency may be 100%.

In general, carbazole compounds such as CBP (4,4-dicarbazolybiphenyl) are used as the phosphorescent host material, and metal complex compounds containing heavy atoms such as Ir and Pt are widely used as the phosphorescent dopant material. It is used.

However, CBP, which is currently used phosphorescent host material, has a low glass transition temperature (Tg) of about 110 ° C., and crystallization in the device is easy, resulting in a very short lifespan of about 150 hours.

Accordingly, an object of the present invention is to provide a triphenylene-based compound having excellent electron transporting ability, hole injection and / or transporting ability, and / or light emitting ability (fluorescence or phosphorescence) and light emission efficiency, brightness, and thermal stability by including the same in at least one organic layer. To provide an organic EL device having improved characteristics such as driving voltage and lifetime.

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

Formula 1

Wherein X is a sulfur or oxygen atom;

R ₁ to R ₂₀ are each independently hydrogen, deuterium, halogen, substituted or unsubstituted C1-C40 alkyl, substituted or unsubstituted nuclear atom having 3 to 60 heterocycles, substituted or unsubstituted nuclear atom having 5 to 40 heteroaryl, substituted or unsubstituted C1-C40 alkoxy, substituted or unsubstituted C3-C40 cycloalkyl, substituted or unsubstituted heterocycloalkyl having 3 to 40 nuclear atoms, substituted or unsubstituted C5-C40 aryl, Substituted or unsubstituted C5-C60 aryloxy, (substituted or unsubstituted C5-C60 aryl) C1-C40 alkyl, substituted or unsubstituted C2-C40 alkenyl, substituted or unsubstituted C1-C40 alkylamine, ( Substituted or unsubstituted C5-C60 aryl) C1-C40 alkylamine, substituted or unsubstituted C1-C40 alkylsilyl, substituted or unsubstituted C5-C40 arylsilyl, substituted or unsubstituted C7-C40 ketoaryl, substituted Or unsubstituted C1-C40 haloalkyl or cyano, and R ₁ to R ₂₀ are adjacent to each other; May be combined with to form a fused aliphatic ring, a fused aromatic ring, a fused heteroaliphatic ring or a fused heteroaromatic ring having 5 to 40 nuclear atoms;

L is substituted or unsubstituted C5-C60 aryl, substituted or unsubstituted heteroatom having 3 to 60 heteroatoms, substituted or unsubstituted heteroatom having 5 to 40 heteroaryl, (substituted or unsubstituted C5- C60 aryl) C1-C40 alkyl, substituted or unsubstituted C5-C40 arylamine, substituted or unsubstituted C5-C60 aryloxy, substituted or unsubstituted C5-C40 arylsilyl, or substituted or unsubstituted C7-C40 Ketoaryl, when L has a substituent, adjacent substituents may be bonded to each other to form a fused aliphatic ring, a fused aromatic ring, a fused heteroaliphatic ring, or a fused heteroaromatic ring having 5 to 40 nuclear atoms.

In addition, the present invention, the anode; cathode; And at least one organic layer interposed between the anode and the cathode, wherein at least one of the organic layers includes the compound described above.

The compound of Chemical Formula 1 according to the present invention is used as a material for organic EL devices, and when used as a blue, green fluorescent or phosphorescent host material through a wide energy band gap, to 4,4-dicarbazolybiphenyl (CBP) conventionally used. Low power, high efficiency, high brightness, and improved durability and lifespan can be achieved. In addition, by including both the electronic substituent and the hole substituent in the molecule, it can be applied to the hole injection layer, hole transport layer, and / or electron transport layer material of the organic EL device including one or more organic layers between the anode and the cathode. have. Therefore, the organic EL device including the compound of the present invention can be greatly improved in terms of light emitting performance and lifetime, and thus can be effectively applied to a full color display panel and the like.

The present invention provides a compound represented by the formula (1), specifically, a triphenylene moiety that does not adequately exhibit its properties as a phosphorescent host due to inadequate triplet energy level, through a linker (L) containing an aryl group. By connecting the S-containing fused heterocyclic moieties with orbitals, the effect of stably forming triplet energy states through orbital mixing is induced, while the excited energy levels by functional groups By forming the desired energy bandgap of 3.0 eV <Δ <4.1 eV through the control of, it is possible to induce the triplet-triplet energy transition with a general phosphorescent dopant, and the phosphorescence of the device Triphenylene compounds having improved properties and improved electron and / or hole transport ability, luminous efficiency, driving voltage and lifetime characteristics ( triphenylene-based compounds).

In the compound of formula 1 of the present invention, X is a sulfur or oxygen atom. R ₁ to R ₂₀ are each independently hydrogen or an optional substituent, and such substituents are not particularly limited as long as they can form a desirable energy bandgap, and non-limiting examples thereof are deuterium, halogen, substituted or unsubstituted C1. -C40 alkyl (preferably C1-C8 alkyl), substituted or unsubstituted heterocyclic ring having 3 to 60 nuclear atoms (preferably heterocyclic ring having 3 to 24 nuclear atoms), substituted or unsubstituted nucleus Heteroaryl having 5 to 40 atoms (preferably heteroaryl having 5 to 24 nuclear atoms), substituted or unsubstituted C1-C40 alkoxy (preferably C1-C18 alkoxy), substituted or unsubstituted C3 -C40 cycloalkyl (preferably C3-C18 cycloalkyl), substituted or unsubstituted heterocycloalkyl having 3 to 40 nuclear atoms (preferably heterocycloalkyl having 3 to 18 nuclear atoms), substituted or Unsubstituted C5-C40 aryl (bar Directly C5-C24 aryl), substituted or unsubstituted C5-C60 aryloxy (preferably C5-C24 aryloxy), (substituted or unsubstituted C5-C60 aryl) C1-C40 alkyl (preferably Is (C5-C24 aryl) C1-C8 alkyl), substituted or unsubstituted C2-C40 alkenyl (preferably C2-C18 alkenyl), substituted or unsubstituted C1-C40 alkylamine (preferably , C1-C18 alkylamine), (substituted or unsubstituted C5-C60 aryl) C1-C40 alkylamine (preferably (C5-C24 aryl) C1-C18 alkylamine), substituted or unsubstituted C1-C40 Alkylsilyl (preferably C1-C18 alkylsilyl), substituted or unsubstituted C5-C40 arylsilyl (preferably C5-C18 arylsilyl), substituted or unsubstituted C7-C40 ketoaryl (preferably , C7-C20 ketoaryl), substituted or unsubstituted C1-C40 haloalkyl (preferably C1-C8 haloalkyl), cyano, and the like, and R ₁ to R ₂₀ may be bonded to a group adjacent to each other. 5 to 5 nuclear atoms 40 fused aliphatic rings, condensed aromatic rings, condensed heteroaliphatic rings or condensed heteroaromatic rings can be formed.

The linker L is substituted or unsubstituted C5-C60 aryl, substituted or unsubstituted heteroatoms having 3 to 60 nuclear atoms, substituted or unsubstituted heteroaryl atoms having 5 to 40 heteroatoms, (substituted or unsubstituted C5-C60 aryl) C1-C40 alkyl, substituted or unsubstituted C5-C40 arylamine, substituted or unsubstituted C5-C60 aryloxy, substituted or unsubstituted C5-C40 arylsilyl, or substituted or unsubstituted C7 -C40 ketoaryl, where L has a substituent, adjacent substituents may be bonded to each other to form a fused aliphatic ring, a fused aromatic ring, a fused heteroaliphatic ring or a fused heteroaromatic ring having 5 to 40 nuclear atoms; have.

Wherein L, R ₁ to the R ₂₀ alkyl, heterocycle, heteroaryl, alkoxy, cycloalkyl, heterocycloalkyl, aryl, aryloxy, arylalkyl, alkenyl, alkyl amines, arylalkyl amines, alkyl silyl, aryl silyl, The substituents of ketoaryl and haloalkyl are each independently deuterium, halogen, C1-C40 alkyl, heterocycle having 3 to 60 nuclear atoms, heteroaryl having 5 to 40 nuclear atoms, C1-C40 alkoxy, C3-C40 cyclo Alkyl, heterocycloalkyl of 3 to 40 nuclear atoms, C5-C40 aryl, C5-C60 aryloxy, (C5-C60 aryl) C1-C40 alkyl, C2-C40 alkenyl, C1-C40 alkylamine, (C5- C60 aryl) C1-C40 alkylamine, C1-C40 alkylsilyl, C5-C40 arylsilyl, C7-C40 ketoaryl, C1-C40 haloalkyl and cyano. In addition, these substituents may each be further substituted with C1-C40 alkyl, C5-C40 aryl, heteroaryl having 5 to 40 nuclear atoms, and the like.

Compounds of formula (I) of the present invention may be represented by the following formula (I) or formula (Ib) as representative examples:

<Formula 1a>

<Formula 1b>

Where

X, L, R ₁ to R ₂₀ are as defined above.

The linker L may be selected from the group consisting of

Formula 2

The linker L may also be selected from the group consisting of

Formula 3

Where

R ₂₁ and R ₂₂ are as defined above,

At least one of the plurality of Z is a nitrogen atom and the rest are carbon atoms, and the hydrogen atom attached to Z is unsubstituted or deuterium, halogen, substituted or unsubstituted C1-C40 alkyl, substituted or unsubstituted nuclear atom, 3 to 3 Heteroaryl of 60, substituted or unsubstituted heteroaryl 5 to 40 heteroaryl, substituted or unsubstituted C1-C40 alkoxy, substituted or unsubstituted C3-C40 cycloalkyl, substituted or unsubstituted nuclear 3 To 40 heterocycloalkyl, substituted or unsubstituted C5-C40 aryl, substituted or unsubstituted C5-C60 aryloxy, (substituted or unsubstituted C5-C60 aryl) C1-C40 alkyl, substituted or unsubstituted C2 -C40 alkenyl, substituted or unsubstituted C1-C40 alkylamine, (substituted or unsubstituted C5-C60 aryl) C1-C40 alkylamine, substituted or unsubstituted C1-C40 alkylsilyl, substituted or unsubstituted C5 -C40 arylsilyl, substituted or unsubstituted C7-C40 ketoaryl, substituted or unsubstituted Substituted C1-C40 haloalkyl or cyano, and these substituents, R ₂₁ and R _22, may be bonded to groups adjacent to each other to form a fused aliphatic ring having 5 to 40 nuclear atoms, a condensed aromatic ring, a condensed heteroaliphatic It may form a ring or a condensed heteroaromatic ring.

The linker L is preferably a form in which the triphenylene and the S-containing condensed ring are linked by a meta bond.

The following formulas are representative examples of the compounds of formula 1 of the present invention, but the compounds of formula 1 of the present invention are not limited to those illustrated below.

As used herein, "unsubstituted alkyl" is a straight or branched chain saturated hydrocarbon of 1 to 40 carbon atoms, examples being methyl, ethyl, propyl, isobutyl. sec-butyl, pentyl, iso-amyl, hexyl and the like.

"Unsubstituted cycloalkyl" includes monocyclic or polycyclic non-aromatic hydrocarbon groups having 3 to 40 carbon atoms. Examples of such cycloalkyls include, but are not limited to, cyclopropyl, cyclopentyl, cyclohexyl, norbornyl, and the like.

"Unsubstituted alkoxy" means alkyl with 1 to 40 carbon atoms attached to oxygen and is interpreted to include a linear, branched or cyclic structure. Examples of alkoxy may include, but are not limited to, methoxy, ethoxy, n-propoxy, 1-propoxy, t-butoxy, n-butoxy, pentoxy and the like.

"Unsubstituted heterocycle" means an aromatic and / or non-aromatic ring having 3 to 60 nuclear atoms, wherein one or more carbons in the ring, preferably 1 to 3 carbons, are N, O or S And substituted with a heteroatom such as Non-limiting examples of heterocycles include 3-1H-benzimidazol-2-one, 2-tetrahydrofuranyl, 2-tetrahydrothiophenyl, 2-morpholinyl, 3-morpholinyl, 1-pyrroli Diyl, 1-piperazinyl, 2-piperazinyl, 4-thiazolidinyl, benzoxanyl, benzopyrrolidinyl, benzopiperidinyl, benzothianyl, etc. This includes. Furthermore, the heterocycles used herein are to be understood to include those condensed with one or more aromatic or non-aromatic rings. In the present invention, the heterocycle may be used in a superposition with heterocycloalkyl and heteroaryl.

"Unsubstituted aryl" means an aromatic moiety having 5 to 60 carbon atoms, singly or in combination of two or more rings, and is referred to herein as "aryloxy", "arylalkyl", "arylsilyl", and the like. Two or more rings may be attached in a simple or fused form with one another. Examples of aryl include, but are not limited to, phenyl, hydroxyphenyl, alkoxyphenyl, naphthyl, phenanthryl, anthryl, and the like.

"Unsubstituted heteroaryl" means a monoheterocyclic or polyheterocyclic aromatic moiety having 5 to 40 nuclear atoms, wherein at least one carbon in the ring, preferably 1 to 3 carbons, is N, O or S And substituted with a heteroatom such as It is understood that two or more rings may be attached in a simple or fused form to each other and further include a condensed form with an aryl group. Examples of heteroaryl include 6-membered monocyclic rings such as pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, triazinyl; Polycyclics such as phenoxathienyl, indolinzinyl, indolyl, purinyl, quinolyl, benzothiazole, carbazolyl It is understood to include a ring and to include 2-furanyl, N-imidazolyl, 2-isoxazolyl, 2-pyridinyl, 2-pyrimidinyl, and the like.

"Unsubstituted heterocycloalkyl" means a non-aromatic moiety of 3 to 40 nuclear atoms, in which one or more carbons in the ring, preferably 1 to 3 carbons, are replaced with a hetero atom such as N, O or S . Non-limiting examples thereof include morpholine, piperazine and the like.

"Unsubstituted alkenyl" means a radical comprising at least one carbon-carbon double bond at the center or terminus of an alkyl having from 2 to 40 carbon atoms. Examples of alkenyl include, but are not limited to, ethylene, propylene, butylene, hexylene, and the like.

"Unsubstituted aryloxy" includes phenyloxy, naphthyloxy, diphenyloxy and the like having 5 to 60 carbon atoms, and "unsubstituted arylalkyl" is also called aralkyl and benzyl, phenylethyl And the like.

"Alkylsilyl" is silyl substituted with alkyl having 1 to 40 carbon atoms, "arylsilyl" is silyl substituted with aryl having 5 to 40 carbon atoms, and "ketoaryl" means aryl having a carbonyl group attached thereto. "Haloalkyl" refers to alkyl substituted with halogen atoms such as fluorine, chlorine, bromine and the like.

Compounds of formula 1 of the present invention can be synthesized according to general synthetic methods ( Chem. Rev. , 60 : 313 (1960); J. Chem. SOC . 4482 (1955); Chem. Rev. 95: 2457 (1995) ) And so on). Detailed synthesis procedures for the compounds of the present invention will be described in detail in the synthesis examples described below.

The invention also includes an anode; 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 Formula 1 above. To provide.

The compound of Formula 1 may be included alone or in plurality.

The organic layer including the compound of Formula 1 of the present invention may be any one or more of a hole injection layer, a hole transport layer, an electron transport layer and a light emitting layer. In the present invention, the light emitting layer may include a phosphorescent dopant material or a fluorescent dopant material. Preferably, the compound of formula 1 of the present invention may be included in the organic EL device as a blue, green, and / or red phosphorescent host, a fluorescent host, a hole transport material, a hole injection material and / or an electron transport material. More preferably, the compound of formula 1 of the present invention may be included in the organic EL device as a phosphorescent host or a fluorescent host, particularly preferably as a phosphorescent host.

Since the compound of the present invention has a high glass transition temperature of 150 ℃ or more, when the compound is used as an organic layer of the organic EL device, since the crystallization is minimized in the organic EL device, the driving voltage of the device can be lowered, luminous efficiency, luminance , Thermal stability, and lifetime characteristics can be improved.

As a non-limiting example of the organic EL device structure according to the present invention, a substrate, an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and a cathode may be sequentially stacked, wherein the light emitting layer, hole injection layer, At least one of the hole transport layer and the electron transport layer may include a compound represented by Chemical Formula 1. An electron injection layer may be positioned on the electron transport layer.

In addition, as described above, the organic EL device according to the present invention may not only have a structure in which an anode, at least one organic layer, and a cathode are sequentially stacked, but an insulating layer or an adhesive layer may be inserted at the interface between the electrode and the organic layer.

In the organic EL device of the present invention, the organic layer including the compound of Formula 1 may be formed by vacuum deposition or solution coating. Examples of the solution application include spin coating, dip coating, doctor blading, inkjet printing or thermal transfer method, but is not limited thereto.

The organic EL device of the present invention forms an organic layer and an electrode using materials and methods known in the art, except that at least one of the organic layers is formed to include the compound represented by the formula (1) of the present invention. can do.

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

The anode material may be a metal such as vanadium, chromium, copper, zinc, gold or an alloy thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO); Combinations of oxides with metals such as ZnO: Al or SnO ₂ : Sb; Conductive polymers such as polythiophene, poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (PEDT), polypyrrole and polyaniline; Or carbon black, but is not limited thereto.

Cathode materials include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin or lead or alloys thereof; Multilayer structure materials such as LiF / Al or LiO ₂ / Al, and the like, but are not limited thereto.

The hole injection layer, the hole transport layer, the electron transport layer and the electron injection layer are not particularly limited, and conventional materials known in the art may be used.

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 4,4,5,5-Tetramethyl-2- (triphenylene-2-yl) -1,3,2-dioxaborolane

<Step 1> Synthesis of 2-Bromotriphenylene

Scheme 1

Triphenylene (50 g, 219.0 mmol) was dissolved in 750 ml of Chloroform and 51 ml (438.0 mmol) of Trimethyl phosphate, and the solution was heated and stirred at 60 ° C. in a nitrogen atmosphere.

Bromine (35 g, 219.0 mmol) was slowly added dropwise to the reaction mixture for 9 hours, heated to 60 ° C. in a nitrogen atmosphere for 3 hours, stirred, and cooled to room temperature. Then, a saturated aqueous sodium thiosulphate solution (350 ml) was added to the reaction mixture. After termination, only organic solution was collected using a separating funnel, and then washed three times with 50 ml of Brine.

The extract was dried with excess Magnesium sulphate, filtered and washed, and the filtrate was concentrated under reduced pressure. The concentrate was dissolved in excess dichloromethane, filtered using Silica gel, concentrated under reduced pressure, recrystallized from Acetone / Hexane (500 ml / 2000 ml), filtered and dried to give the title compound as a white solid (56 g, yield: 83%). Obtained.

GC-Mass (Theoretical value: 306.00 g / mol, Measured value: 306 g / mol)

<Step 2> Synthesis of 4,4,5,5-Tetramethyl-2- (triphenylene-2-yl) -1,3,2-dioxaborolane

Scheme 2

Compound (50 g, 164 mmol) obtained in <Step 1>, 4,4,4 ', 4', 5,5,5 ', 5'-octamethyl-2,2'-bi (1,3,2 -dioxaborolane) (83 g, 327 mmol), Pd (dffp) 2Cl2 (4.08 g, 4.92 mmol), and potassium acetate (48 g, 490 mmol) were added to the flask and dissolved in 810 ml of 1,4-dioxane under nitrogen atmosphere. It was then stirred at reflux for 12 hours.

After the reaction was completed, 400 ml of iced water was added and extracted three times with 50 ml of dichloromethane. The extract was dried over an excess of Magnesium sulphate, filtered, and the filtrate was concentrated under reduced pressure. The crude product was purified by silica gel column chromatography (n-Hexane: Dichloromethane = 4: 1 (v: v)) to afford the title compound (40.5 g, yield 68%) as a white solid.

GC-Mass (Theoretical value: 354.18 g / mol, Measured value: 354 g / mol)

¹ H-NMR (THF-d ₈ , 500 MHz) δ (ppm) 1.4 (S, 12H), 7.65 (m, 4H), 8.0 (m, 2H), 8.73 (m, 3H), 8.78 (m, 2H) , 9.14 (S, 1 H)

Synthesis Example 1 Synthesis of Compound Inv A-2

Scheme 3

Step 1 Synthesis of Compound 1

Thianthren-1-ylboronic acid (10.2 g, 39.3 mmol), 1-bromo-3-Iodobenzene (16.7 g, 58.9 mmol) and Pd (PPh ₃ ) ₄ (0.45 g, 0.393 mmol) were added to the flask and toluene under nitrogen atmosphere. After dissolving in a mixed solvent of 196 mL and 98 mL of Ethanol, 98 mL of an aqueous solution of Potassium Carbonate (8.1 g, 58.9 mmol) was added thereto, followed by stirring under reflux for 12 hours.

After the reaction was terminated and extracted three times with 50 ml of dichloromethane, the extract was dried with excess Magnesium sulphate, filtered and the filtrate was concentrated under reduced pressure. The crude product was purified by silica gel column chromatography (n-Hexane: Dichloromethane = 4: 1 (v: v)) to give the title compound (9.5 g, yield 65%) as a white solid.

GC-Mass (Theoretical value: 369.95 g / mol, Measured value: 369 g / mol)

Step 2 Synthesis of Compound Inv A-2

Compound (7.12 g, 20.09 mmol) finally synthesized in Preparation Example 1, Compound 1 (7.4 g, 20.09 mmol) synthesized in <Step 1>, and Pd (PPh ₃ ) ₄ (0.23 g, 0.201 mmol) were prepared. The flask was dissolved in 133 ml of Toluene under a nitrogen atmosphere, and 67 ml of an aqueous solution of Potassium Carbonate (5.55 g, 40.2 mmol) was added thereto, followed by stirring under reflux for 12 hours.

After the reaction was terminated and extracted three times with 50 ml of dichloromethane, the extract was dried with excess Magnesium sulphate, filtered and the filtrate was concentrated under reduced pressure. The crude product was purified by silica gel column chromatography (n-Hexane: Dichloromethane = 7: 3 (v: v)) to afford the title compound Inv A-2 (6.2 g, yield 60%) as a white solid.

GC-Mass (Theoretical value: 518.69 g / mol, Measured value: 518 g / mol)

¹ H-NMR (THF-d ₈ , 500 MHz) δ (ppm) 6.80 (m, 2H), 6.86 (m, 1H), 6.96 (m, 1H), 7.00 (m, 3H), 7.33 (m, 1H) , 7.44 (m, 2H), 7.70 (S, 1H), 7.82 (m, 1H), 7.88 (m, 2H), 8.04 (m, 1H), 8.12 (m, 2H), 8.18 (m, 1H), 8.93 (m, 2 H), 9.15 (S, 1 H)

Synthesis Example 2 Synthesis of Compound Inv A-4

Scheme 4

Step 1 Synthesis of Compound 2

Thianthren-1-ylboronic acid (10.2 g, 39.3 mmol), 15 g (58.9 mmol) of 1,3-Dibromo-5-fluorobenzene and Pd (PPh ₃ ) ₄ (0.45 g, 0.393 mmol) were placed in a flask and placed under a nitrogen atmosphere. After dissolving in a mixed solvent of 196 ml of toluene and 98 ml of ethanol, 98 ml of an aqueous solution of sodium carbonate (6.3 g, 58.9 mmol) was added thereto, followed by stirring under reflux for 12 hours.

After the reaction was terminated and extracted three times with 50 ml of dichloromethane, the extract was dried with excess Magnesium sulphate, filtered and the filtrate was concentrated under reduced pressure. The crude product was purified by silica gel column chromatography (n-Hexane: Dichloromethane = 4: 1 (v: v)) to give compound 2 (9.1 g, yield 60%) as a white solid.

GC-Mass (Theoretical value: 387.94 g / mol, Measured value: 387 g / mol)

Step 2 Synthesis of Compound Inv A-4

The compound (7.5 g, 21.17 mmol) finally synthesized in Preparation Example 1, flask 2 (7.4 g, 19.25 mmol) and Pd (PPh ₃ ) ₄ (0.22 g, 0.193 mmol) synthesized in <Step 1> were flasked. After dissolving in 128 ml of Toluene under nitrogen atmosphere, 64 ml of an aqueous solution of sodium carbonate (4.1 g, 38.5 mmol) was added thereto, and the mixture was stirred under reflux for 12 hours.

After completion of the reaction, the mixture was extracted three times with 50 ml of dichloromethane, and the extract was dried over Magnesium sulphate, filtered, and the filtrate was concentrated under reduced pressure. The crude product was purified by silica gel column chromatography (n-Hexane: Dichloromethane = 7: 3 (v: v)) to afford the title compound Inv A-4 (7.4 g, 72% yield) as a white solid.

GC-Mass (Theoretical value: 536.68 g / mol, Measured value: 536 g / mol)

¹ H-NMR (THF-d ₈ , 500MHz) δ (ppm) 6.80 ~ 6.86 (m, 3H), 6.96 ~ 7.02 (m, 4H), 7.15 (m, 2H), 7.47 (S, 1H), 7.82 ~ 7.88 (m, 4H), 8.04 (m, 1H), 8.12-8.18 (m, 3H), 8.93 (m, 2H), 9.15 (S, 1H)

Synthesis Example 3 Synthesis of Compound Inv A-12

Scheme 5

<Step 1> Synthesis of Compound 3

Thianthren-1-ylboronic acid (30 g, 22.58 mmol), 1,3,5-Tribromobenzene (84.7 g, 22.58 mmol) and Pd (PPh ₃ ) ₄ (0.26 g, 0.226 mmol) were added to the flask and toluene under nitrogen atmosphere. After dissolving in 151 mL, 75 mL of an aqueous solution of sodium carbonate (4.8 g, 45.2 mmol) was added thereto, followed by stirring under reflux for 12 hours.

After completion of the reaction, the mixture was extracted three times with 50 ml of dichloromethane, and the extract was dried over Magnesium sulphate, filtered, and the filtrate was concentrated under reduced pressure. The crude product was purified by silica gel column chromatography (n-Hexane: Dichloromethane = 4: 1 (v: v)) to give compound 3 (10.2 g, yield 83%) as a white solid.

GC-Mass (Theoretical value: 447.86 g / mol, Measured value: 447 g / mol)

Step 2 Synthesis of Compound 4

Compound 3 (20.0 g, 44.9 mmol), 3-Pyridineboronic acid (5.52 g, 44.9 mmol) and Pd (PPh ₃ ) ₄ (0.52 g, 0.449 mmol) synthesized in <Step 1> were placed in a flask under nitrogen atmosphere. After dissolving in a mixed solvent of 225 ml of toluene and 112 ml of ethanol, 112 ml of an aqueous solution of sodium carbonate (6.3 g, 58.9 mmol) was added thereto, and the mixture was stirred under reflux for 12 hours.

After the reaction was terminated and extracted three times with 50 ml of dichloromethane, the extract was dried with excess Magnesium sulphate, filtered and the filtrate was concentrated under reduced pressure. The crude product was purified by silica gel column chromatography (n-Hexane: Dichloromethane = 4: 1 (v: v)) to give compound 4 (13 g, yield 65%) as a white solid.

GC-Mass (Theoretical value: 446.98 g / mol, Measured value: 447 g / mol)

Step 3 Synthesis of Compound Inv A-12

The compound (8.0 g, 22.58 mmol) finally synthesized in Preparation Example 1, Compound 4 (10.1 g, 22.58 mmol) and Pd (PPh ₃ ) ₄ (0.26 g, 0.226 mmol) synthesized in <Step 2> were flasked. After dissolving in 151 mL of Toluene under nitrogen atmosphere, 75 mL of an aqueous solution of sodium carbonate (4.8 g, 45.2 mmol) was added thereto, and the mixture was stirred under reflux for 12 hours.

After the reaction was terminated and extracted three times with 50 ml of dichloromethane, the extract was dried with excess Magnesium sulphate, filtered and the filtrate was concentrated under reduced pressure. The crude product was purified by silica gel column chromatography (n-Hexane: Dichloromethane = 4: 1 (v: v)) to afford the title compound Inv A-12 (9.14 g, 68% yield) as a white solid.

GC-Mass (Theoretical value: 595.14 g / mol, Measured value: 595 g / mol)

¹ H-NMR (THF-d ₈ , 500 MHz) δ (ppm) 6.80 to 6.96 (m, 4H), 6.96 to 7.02 (m, 4H), 7.44 (m, 1H), 7.66 (S, 3H), 7.82 to 7.88 (m, 4H), 7.97 (m, 1H), 8.04 (m, 1H), 8.12-8.18 (m, 3H), 8.70 (m, 1H), 8.81 (S, 1H), 8.93 (m, 2H) , 9.15 (m, 1 H)

Synthesis Example 4 Synthesis of Compound Inv A-28

Scheme 6

Step 1 Synthesis of Compound 5

Thianthren-1-ylboronic acid (10.2 g, 39.3 mmol), 2,6-Dibromopyridine (14 g, 58.9 mmol) and Pd (PPh ₃ ) ₄ (0.45 g, 0.393 mmol) were added to the flask and 196 mL of Toluene under nitrogen atmosphere. After dissolving in 98 mL of ethanol and solvent, 98 mL of an aqueous solution of sodium carbonate (6.3 g, 58.9 mmol) was added thereto, followed by stirring under reflux for 12 hours.

After completion of the reaction, the mixture was extracted three times with 50 ml of dichloromethane, and the extract was dried over Magnesium sulphate, filtered, and the filtrate was concentrated under reduced pressure. The crude product was purified by silica gel column chromatography (n-Hexane: Dichloromethane = 4: 1 (v: v)) to give compound 5 (9.3 g, yield 64%) as a white solid.

GC-Mass (Theoretical value: 369.95 g / mol, Measured value: 369 g / mol)

Step 2 Synthesis of Compound Inv A-28

The compound (8.5 g, 24.0 mmol) finally synthesized in Preparation Example 1, Compound 5 (8.9 g, 24.0 mmol) and Pd (PPh ₃ ) ₄ (0.28 g, 0.24 mmol) synthesized in <Step 1> were flasked. After dissolving in 160 ml of Toluene under nitrogen atmosphere, 80 ml of an aqueous solution of sodium carbonate (5.09 g, 48.0 mmol) was added thereto, and the mixture was stirred under reflux for 12 hours.

After completion of the reaction, the mixture was extracted three times with 50 ml of dichloromethane, and the extract was dried over Magnesium sulphate, filtered, and the filtrate was concentrated under reduced pressure. The crude product was purified by silica gel column chromatography (n-Hexane: Dichloromethane = 7: 3 (v: v)) to afford the title compound Inv A-28 (8.7 g, yield 70%) as a white solid.

GC-Mass (Theoretical value: 519.11 g / mol, Measured value: 519 g / mol)

¹ H-NMR (THF-d ₈ , 500 MHz) δ (ppm) 6.80 (m, 2H), 6.89 (m, 1H), 7.00 to 7.02 (m, 3H), 7.14 to 7.19 (m, 3H), 7.53 ( m, 1H), 7.82-7.88 (m, 4H), 8.12 (m, 2H), 8.21 (m, 1H), 8.55 (m, 1H), 8.93 (m, 2H), 9.66 (S, 1H).

Synthesis Example 5 Synthesis of Compound Inv A-29

Scheme 7

Step 1 Synthesis of Compound 6

Thianthren-1-ylboronic acid (11.3 g, 43.3 mmol), 2-Bromo-5-iodopyridine (14 g, 64.9 mmol) and Pd (PPh ₃ ) ₄ (0.50 g, 0.433 mmol) were placed in a flask and toluene under nitrogen atmosphere. After dissolving in a mixed solvent of 217 mL and 108 mL of ethanol, 108 mL of an aqueous solution of sodium carbonate (6.9 g, 64.9 mmol) was added thereto, and the mixture was stirred under reflux for 12 hours.

After completion of the reaction, the mixture was extracted three times with 50 ml of dichloromethane, and the extract was dried over Magnesium sulphate, filtered, and the filtrate was concentrated under reduced pressure. The crude product was purified by silica gel column chromatography (n-Hexane: Dichloromethane = 7: 3 (v: v)) to give compound 6 (10.4 g, yield 65%) as a white solid.

GC-Mass (Theoretical value: 370.94 g / mol, Measured value: 370 g / mol)

Step 2 Synthesis of Compound Inv A-29

The final compound (8.5 g, 24.0 mmol) synthesized in Preparation Example 1, the compound 6 (8.9 g, 24.0 mmol) and Pd (PPh ₃ ) ₄ (0.28 g, 0.24 mmol) synthesized in the <step 1> flask It was dissolved in 160 ml of Toluene under a nitrogen atmosphere, and 80 ml of an aqueous solution of sodium carbonate (5.09 g, 48.0 mmol) was added thereto, followed by stirring under reflux for 12 hours.

After the reaction was terminated and extracted three times with 50 ml of dichloromethane, the extract was dried with excess Magnesium sulphate, filtered and the filtrate was concentrated under reduced pressure. The crude product was purified by silica gel column chromatography (n-Hexane: Dichloromethane = 4: 1 (v: v)) to afford the title compound Inv A-29 (8.5 g, yield 68%) as a white solid.

GC-Mass (Theoretical value: 519.11 g / mol, Measured value: 519 g / mol)

¹ H-NMR (THF-d ₈ , 500 MHz) δ (ppm) 6.80 to 6.96 (m, 4H), 6.96 to 7.02 (m, 4H), 7.60 (m, 1H), 7.69 (m, 1H), 7.82 to 7.88 (m, 4H), 8.12 (m, 2H), 8.21 (m, 1H), 8.55 (m, 1H), 8.78 (m, 1H), 8.93 (m, 2H), 9.66 (S, 1H).

Synthesis Example 6 Synthesis of Compound Inv A-30

Scheme 8

Step 1 Synthesis of Compound 7

Thianthren-1-ylboronic acid (10.6 g, 40.6 mmol), 5-Bromo-2-chloropyrimidine (7.9 g, 40.6 mmol) and Pd (PPh ₃ ) ₄ (0.47 g, 0.406 mmol) were placed in a flask and toluene under nitrogen atmosphere. After dissolving in 203 mL, 102 mL of an aqueous solution of sodium carbonate (6.9 g, 64.9 mmol) was added thereto, followed by stirring under reflux for 12 hours.

After the reaction was terminated and extracted three times with 50 ml of dichloromethane, the extract was dried with excess Magnesium sulphate, filtered and the filtrate was concentrated under reduced pressure. The crude product was purified by silica gel column chromatography (n-Hexane: Dichloromethane = 7: 3 (v: v)) to give compound 7 (9.32 g, yield 70%) as a white solid.

GC-Mass (Theoretical value: 327.99 g / mol, Measured value: 328 g / mol)

Step 2 Synthesis of Compound Inv A-30

The compound (8.5 g, 24.0 mmol) finally synthesized in Preparation Example 1, Compound 7 (7.87 g, 24.0 mmol) and Pd (PPh ₃ ) ₄ (0.28 g, 0.24 mmol) synthesized in <Step 1> were flasked. It was dissolved in 160 ml of Toluene under nitrogen atmosphere, and 80 ml of an aqueous solution of sodium carbonate (5.09 g, 48.0 mmol) was added thereto, followed by stirring under reflux for two days.

After the reaction was terminated and extracted three times with 50 ml of dichloromethane, the extract was dried with excess Magnesium sulphate, filtered and the filtrate was concentrated under reduced pressure. The crude product was purified by silica gel column chromatography (n-Hexane: Dichloromethane = 7: 3 (v: v)) to afford the title compound Inv A-30 (8.5 g, 68% yield) as a white solid.

GC-Mass (Theoretical value: 520.11 g / mol, Measured value: 520 g / mol)

¹ H-NMR (THF-d ₈ , 500 MHz) δ (ppm) 6.80 to 6.66 (m, 3H), 6.96 to 7.02 (m, 4H), 7.82 to 7.88 (m, 4H), 8.04 (m, 1H), 8.12-8.18 (m, 3H), 8.84 (m, 2H), 8.93 (m, 2H), 9.15 (S, 1H)

Synthesis Example 7 Synthesis of Compound Inv B-2

Scheme 9

Step 1 Synthesis of Compound 8

Phenoxathiin-4-ylboronic acid (8.8g, 39.3mmol), 1-bromo-3-Iodobenzene (16.7 g, 58.9 mmol) and Pd (PPh ₃ ) ₄ (0.45 g, 0.393 mmol) were added to the flask and toluene under nitrogen atmosphere. After dissolving in a mixed solvent of 196 mL and 98 mL of Ethanol, 98 mL of an aqueous solution of Potassium carbonate (8.1 g, 58.9 mmol) was added thereto, followed by stirring under reflux for 12 hours.

After the reaction was terminated and extracted three times with 50 ml of dichloromethane, the extract was dried with excess Magnesium sulphate, filtered and the filtrate was concentrated under reduced pressure. The crude product was purified by silica gel column chromatography (n-Hexane: Dichloromethane = 4: 1 (v: v)) to give compound 8 (9.3 g, yield 67%) as a white solid.

GC-Mass (Theoretical value: 353.97 g / mol, Measured value: 353 g / mol)

<Step 2> Synthesis of Compound Inv B-2

The compound (7.12 g, 20.09 mmol) finally synthesized in Preparation Example 1, flask 8 (7.1 g, 20.09 mmol) and Pd (PPh ₃ ) ₄ (0.23 g, 0.201 mmol) synthesized in <Step 1> were flasked. It was dissolved in 133 mL of Toluene under nitrogen atmosphere, and 67 mL of an aqueous solution of Potassium carbonate (5.55 g, 40.2 mmol) was added thereto, followed by stirring under reflux for 12 hours.

After the reaction was terminated and extracted three times with 50 ml of dichloromethane, the extract was dried with excess Magnesium sulphate, filtered and the filtrate was concentrated under reduced pressure. The crude product was purified by silica gel column chromatography (n-Hexane: Dichloromethane = 7: 3 (v: v)) to afford the title compound Inv B-2 (6.6 g, yield 65%) as a white solid.

GC-Mass (Theoretical value: 502.14 g / mol, Measured value: 502 g / mol)

¹ H-NMR (THF-d ₈ , 500 MHz) δ (ppm) 6.72 (m, 1H), 6.84 (m, 1H), 6.96 (m, 1H), 7.12 to 7.18 (m, 4H), 7.38 to 7.44 ( m, 3H), 7.70 (S, 1H), 7.82-7.88 (m, 4H), 8.04 (m, 1H), 8.12-8.18 (m, 3H), 8.93 (m, 2H), 9.15 (S, 1H) .

Synthesis Example 8 Synthesis of Compound Inv B-4

Scheme 10

Step 1 Synthesis of Compound 9

Phenoxathiin-4-ylboronic acid (8.8 g, 39.3 mmol), 1,3-Dibromo-5-fluorobenzene (15 g, 58.9 mmol) and Pd (PPh ₃ ) ₄ (0.45 g, 0.393 mmol) were added to the flask and nitrogen atmosphere. After dissolving in a mixed solvent of 196 ml of Toluene and 98 ml of ethanol, 98 ml of an aqueous solution of sodium carbonate (6.3 g, 58.9 mmol) was added thereto, followed by stirring under reflux for 12 hours.

After the reaction was terminated and extracted three times with 50 ml of dichloromethane, the extract was dried with excess Magnesium sulphate, filtered and the filtrate was concentrated under reduced pressure. The crude product was purified by silica gel column chromatography (n-Hexane: Dichloromethane = 4: 1 (v: v)) to give compound 9 (9.4 g, 64% yield) as a white solid.

GC-Mass (Theoretical value: 371.96 g / mol, Measured value: 371 g / mol)

Step 2 Synthesis of Compound Inv B-4

The compound (7.5 g, 21.17 mmol) finally synthesized in Preparation Example 1, flask 9 (7.2 g, 19.25 mmol) and Pd (PPh ₃ ) ₄ (0.22 g, 0.193 mmol) synthesized in <Step 1> were flasked. After dissolving in 128 ml of Toluene under nitrogen atmosphere, 64 ml of an aqueous solution of sodium carbonate (4.1 g, 38.5 mmol) was added thereto, and the mixture was stirred under reflux for 12 hours.

After the reaction was terminated and extracted three times with 50 ml of dichloromethane, the extract was dried with excess Magnesium sulphate, filtered and the filtrate was concentrated under reduced pressure. The crude product was purified by silica gel column chromatography (n-Hexane: Dichloromethane = 7: 3 (v: v)) to afford the title compound Inv B-4 (7.7 g, 77% yield) as a white solid.

GC-Mass (Theoretical value: 520.13 g / mol, Measured value: 520 g / mol)

¹ H-NMR (THF-d ₈ , 500 MHz) δ (ppm) 6.72 (m, 1H), 6.84 (m, 1H), 6.96 (m, 1H), 7.15 (m, 2H), 7.47 (S, 1H) , 7.82-7.88 (m, 4H), 8.04 (m, 1H), 8.12-8.18 (m, 3H), 8.93 (m, 2H), 9.15 (S, 1H).

Synthesis Example 9 Synthesis of Compound Inv B-12

Scheme 11

Step 1 Synthesis of Compound 10

Phenoxathiin-4-ylboronic acid (5.1 g, 22.58 mmol), 1,3,5-Tribromobenzene (7.1 g, 22.58 mmol) and Pd (PPh ₃ ) ₄ (0.26 g, 0.226 mmol) were added to the flask and toluene under nitrogen atmosphere. After dissolving in 151 mL, 75 mL of an aqueous solution of sodium carbonate (4.8 g, 45.2 mmol) was added thereto, followed by stirring under reflux for 12 hours.

After the reaction was terminated and extracted three times with 50 ml of dichloromethane, the extract was dried with excess Magnesium sulphate, filtered and the filtrate was concentrated under reduced pressure. The crude product was purified by silica gel column chromatography (n-Hexane: Dichloromethane = 4: 1 (v: v)) to give compound 10 (7.8 g, yield 80%) as a white solid.

GC-Mass (Theoretical value: 431.88 g / mol, Measured value: 432 g / mol)

Step 2 Synthesis of Compound 11

Compound 10 (19.4 g, 44.9 mmol), 3-Pyridineboronic acid (5.52 g, 44.9 mmol) and Pd (PPh ₃ ) ₄ (0.52 g, 0.449 mmol) synthesized in <Step 1> were placed in a flask under nitrogen atmosphere. After dissolving in a mixed solvent of 225 ml of toluene and 112 ml of ethanol, 112 ml of an aqueous solution of sodium carbonate (6.3 g, 58.9 mmol) was added thereto, and the mixture was stirred under reflux for 12 hours.

After the reaction was terminated and extracted three times with 50 ml of dichloromethane, the extract was dried with excess Magnesium sulphate, filtered and the filtrate was concentrated under reduced pressure. The crude product was purified by silica gel column chromatography (n-Hexane: Dichloromethane = 4: 1 (v: v)) to give compound 11 (12.8 g, 66% yield) as a white solid.

GC-Mass (Theoretical value: 431 g / mol, Measured value: 431 g / mol)

Step 3 Synthesis of Compound B-12

The compound (8.0 g, 22.58 mmol) finally synthesized in Preparation Example 1, the compound 11 (9.7 g, 22.58 mmol) and Pd (PPh ₃ ) ₄ (0.26 g, 0.226 mmol) synthesized in <Step 2> were flasked. After dissolving in 151 ml of Toluene under nitrogen atmosphere, 75 ml of an aqueous solution of sodium carbonate (4.8 g, 45.2 mmol) was added thereto, and the mixture was stirred under reflux for 12 hours.

After the reaction was terminated and extracted three times with 50 ml of dichloromethane, the extract was dried with excess Magnesium sulphate, filtered and the filtrate was concentrated under reduced pressure. The crude product was purified by silica gel column chromatography (n-Hexane: Dichloromethane = 7: 3 (v: v)) to afford the title compound Inv B-12 (8.4 g, 64% yield) as a white solid.

GC-Mass (Theoretical value: 579.17 g / mol, Measured value: 579 g / mol)

¹ H-NMR (THF-d ₈ , 500 MHz) δ (ppm) 6.72 (m, 1H), 6.84 (m, 1H), 6.96 (m, 1H), 7.12 to 7.18 (m, 4H), 7.44 (m, 1H), 7.66 (S, 3H), 7.82-7.88 (m, 4H), 7.97 (m, 1H), 8.04 (m, 1H), 8.12-8.18 (m, 3H), 8.70 (m, 1H), 8.81 (S, 1 H), 8.93 (m, 2 H), 9.15 (m, 1 H).

Synthesis Example 10 Synthesis of Compound Inv B-28

Scheme 12

Step 1 Synthesis of Compound 12

Phenoxathiin-4-ylboronic acid (9.6 g, 39.3 mmol), 2,6-Dibromopyridine (14 g, 58.9 mmol), and Pd (PPh ₃ ) ₄ (0.45 g, 0.393 mmol) were placed in a flask and Toluene 196 under nitrogen atmosphere. After dissolving in a mixed solvent of ㎖ and Ethanol 98 ㎖ 98 ml of an aqueous solution of sodium carbonate (6.3 g, 58.9 mmol) was added and stirred under reflux for 12 hours.

After the reaction was terminated and extracted three times with 50 ml of dichloromethane, the extract was dried with excess Magnesium sulphate, filtered and the filtrate was concentrated under reduced pressure. The crude product was purified by silica gel column chromatography (n-Hexane: Dichloromethane = 4: 1 (v: v)) to give compound 12 (9.3 g, yield 67%) as a white solid.

GC-Mass (Theoretical value: 353.97 g / mol, Measured value: 354 g / mol)

Step 2 Synthesis of Compound Inv B-28

The compound (8.5 g, 24.0 mmol) finally synthesized in Preparation Example 1, Compound 12 (8.5 g, 24.0 mmol) and Pd (PPh ₃ ) ₄ (0.28 g, 0.24 mmol) synthesized in <Step 1> were flasked. It was dissolved in 160 ml of Toluene under a nitrogen atmosphere, and 80 ml of an aqueous solution of sodium carbonate (5.09 g, 48.0 mmol) was added thereto, followed by stirring under reflux for 12 hours.

After the reaction was terminated and extracted three times with 50 ml of dichloromethane, the extract was dried with excess Magnesium sulphate, filtered and the filtrate was concentrated under reduced pressure. The crude product was purified by silica gel column chromatography (n-Hexane: Dichloromethane = 7: 3 (v: v)) to afford the title compound Inv B-28 (8.7 g, 72% yield) as a white solid.

GC-Mass (Theoretical value: 503.13 g / mol, Measured value: 503 g / mol)

¹ H-NMR (THF-d ₈ , 500 MHz) δ (ppm) 6.72 (m, 1H), 6.87 (m, 1H), 6.96 (m, 1H), 7.14 to 7.19 (m, 6H), 7.82 to 7.88 ( m, 4H), 8.12 (m, 2H), 8.21 (m, 1H), 8.55 (m, 1H), 8.64 (m, 1H), 8.93 (m, 2H), 9.66 (S, 1H).

Synthesis Example 11 Synthesis of Compound Inv B-29

Scheme 13

Step 1 Synthesis of Compound 13

Phenoxathiin-4-ylboronic acid (10.8 g, 43.3 mmol), 2-Bromo-5-iodopyridine (14 g, 64.9 mmol) and Pd (PPh ₃ ) ₄ (0.50 g, 0.433 mmol) were added to the flask and toluene under nitrogen atmosphere. After dissolving in a mixed solvent of 217 mL and 108 mL of ethanol, 108 mL of an aqueous solution of sodium carbonate (6.9 g, 64.9 mmol) was added thereto, and the mixture was stirred under reflux for 12 hours.

After the reaction was terminated and extracted three times with 50 ml of dichloromethane, the extract was dried with excess Magnesium sulphate, filtered and the filtrate was concentrated under reduced pressure. The crude product was purified by silica gel column chromatography (n-Hexane: Dichloromethane = 7: 3 (v: v)) to give compound 13 (10.8 g, yield 70%) as a white solid.

GC-Mass (Theoretical value: 354.97 g / mol, Measured value: 355 g / mol)

Step 2 Synthesis of Compound Inv B-29

Final compound (8.5 g, 24.0 mmol) synthesized in Preparation Example 1, Compound 13 (8.5 g, 24.0 mmol), and Pd (PPh ₃ ) ₄ (0.28 g, 0.24 mmol) synthesized in <Step 1> were prepared The mixture was dissolved in 160 ml of Toluene under a nitrogen atmosphere, and 80 ml of an aqueous solution of sodium carbonate (5.09 g, 48.0 mmol) was added thereto, followed by stirring under reflux for 12 hours.

After the reaction was terminated and extracted three times with 50 ml of dichloromethane, the extract was dried with excess Magnesium sulphate, filtered and the filtrate was concentrated under reduced pressure. The crude product was purified by silica gel column chromatography (n-Hexane: Dichloromethane = 4: 1 (v: v)) to afford the title compound Inv B-29 (8.7 g, 72% yield) as a white solid.

GC-Mass (Theoretical value: 503.13 g / mol, Measured value: 503 g / mol)

¹ H-NMR (THF-d ₈ , 500 MHz) δ (ppm) 6.72 (m, 1H), 6.84 (m, 1H), 6.96 (m, 1H), 7.12 to 7.18 (m, 4H), 7.60 (m, 1H), 7.69 (m, 1H), 7.82-7.88 (m, 4H), 8.12 (m, 2H), 8.21 (m, 1H), 8.55 (m, 1H), 8.78 (m, 1H), 8.93 (m , 2H), 9.66 (S, 1H).

Synthesis Example 12 Synthesis of Compound Inv B-30

Scheme 14

Step 1 Synthesis of Compound 14

Phenoxathiin-4-ylboronic acid (9.9 g, 40.6 mmol), 5-Bromo-2-chloropyrimidine (7.9 g, 40.6 mmol) and Pd (PPh ₃ ) ₄ (0.47 g, 0.406 mmol) were placed in a flask and toluene under nitrogen atmosphere. After dissolving in 203 mL, 102 mL of an aqueous solution of sodium carbonate (6.9 g, 64.9 mmol) was added thereto, followed by stirring under reflux for 12 hours.

After the reaction was terminated and extracted three times with 50 ml of dichloromethane, the extract was dried with excess Magnesium sulphate, filtered and the filtrate was concentrated under reduced pressure. The crude product was purified by silica gel column chromatography (n-Hexane: Dichloromethane = 7: 3 (v: v)) to give compound 14 (9.5 g, yield 75%) as a white solid.

GC-Mass (Theoretical value: 312.02 g / mol, Measured value: 312 g / mol)

<Step 2> Synthesis of Compound Inv B-30

The compound (8.5 g, 24.0 mmol) finally synthesized in Preparation Example 1, the compound 14 (7.5 g, 24.0 mmol) and Pd (PPh ₃ ) ₄ (0.28 g, 0.24 mmol) synthesized in <Step 1> were flasked. It was dissolved in 160 ml of Toluene under a nitrogen atmosphere, and 80 ml of an aqueous solution of sodium carbonate (5.09 g, 48.0 mmol) was added thereto, followed by stirring under reflux for two days.

After the reaction was terminated and extracted three times with 50 ml of dichloromethane, the extract was dried with excess Magnesium sulphate, filtered and the filtrate was concentrated under reduced pressure. The crude product was purified by silica gel column chromatography (n-Hexane: Dichloromethane = 7: 3 (v: v)) to afford the title compound Inv B-30 (8.7 g, 72% yield) as a white solid.

GC-Mass (Theoretical value: 504.13 g / mol, Measured value: 504 g / mol)

¹ H-NMR (THF-d ₈ , 500 MHz) δ (ppm) 6.72 (m, 1H), 6.84 (m, 1H), 6.96 (m, 1H), 7.12 to 7.18 (m, 4H), 7.82 to 7

Preparation Example 2 Synthesis of triphenylene-2,7-diyl bis (trifluoromethanesulfonate)

< Step 1> Synthesis of Compound 15 (3,3'-dimethoxy-o-terphenyl)

Scheme 15

1,2-dibromobenzene (50 g, 214 mmol), 3-methoxyphenylboronic acid (65.1 g, 428 mmol) and Pd (PPh ₃ ) ₄ (4.95 g, 4.28 mmol) were added to the flask and dissolved in 1.4 L of Toluene under nitrogen atmosphere. Then, 1.2 L of an aqueous solution of sodium carbonate (118.2 g, 856 mmol) was added thereto, and the mixture was stirred under reflux for 12 hours.

After completion of the reaction, the mixture was extracted three times with 200 ml of dichloromethane, and the extract was dried over Magnesium sulphate, filtered, and the filtrate was concentrated under reduced pressure. The crude product was purified by silica gel column chromatography (n-Hexane: Dichloromethane = 4: 1 (v: v)) to give compound 15 (43.5 g, yield 70%) as a white solid.

GC-Mass (Theoretical value: 290.13 g / mol, Measured value: 290 g / mol)

Step 2 Synthesis of Compound 16 (2,7-dimethoxytriphenylene)

Scheme 16

Compound 15 (40 g, 137 mmol) obtained in <Step 1> was placed in a flask, dissolved in 1 L of dichloromethane under a nitrogen atmosphere, and then Iron (III) chloride (44.4 g, 274 mmol) was added thereto at room temperature for 12 hours. Was stirred. Thereafter, 2 equivalents of iron (III) choloride were further added, followed by stirring for an hour, and 1 liter of methyl alcohol and water were added at a ratio of 1: 1.

After the reaction was completed, the organic layer was separated, dried over Magnesium sulphate, filtered and the filtrate was concentrated under reduced pressure. The crude product was separated by silica gel column chromatography (n-Hexane: Dichloromethane = 2: 3 (v: v)) to give 31.6 g of product which was recrystallized in 600 ml of acetonitrile to give a pale yellow solid compound 16 (28 g, Yield 70%) was obtained.

GC-Mass (Theoretical value: 288.12 g / mol, Measured value: 288 g / mol),

Step 3 Synthesis of Compound 17 (2,7-dihydroxytriphenylene)

Scheme 17

Compound 16 (25 g, 86 mmol) and pyridine hydrochloride (100 g, 86 mmol) obtained in the above <Step 2> were placed in a flask and stirred at reflux for 90 minutes at 220 ° C. under a nitrogen atmosphere. After the reaction was completed, the crude product was washed with excess water to give compound 17 (20 g, yield 88%).

GC-Mass (Theoretical value: 260.08 g / mol, Measured value: 260 g / mol),

Step 4 Synthesis of Compound 18 (triphenylene-2,7-diyl bis (trifluoromethanesulfonate))

Scheme 18

Compound 17 (20 g, 77 mmol) obtained in <Step 3> was placed in a flask, dissolved in 385 ml of pyridine under a nitrogen atmosphere, and stirred at 0 ° C. Trifluoromethanesylfonyl anhydride (43.5 g, 154 mmol) was slowly added dropwise thereto, followed by stirring at room temperature for 12 hours.

After the reaction was completed, the reaction product was concentrated under reduced pressure, the solid obtained was placed in a flask, and 500 ml of methyl alcohol was added thereto. The mixture was stirred and filtered for 1 hour to obtain 35 g of a mixture of white solids. The crude product was recrystallized from hexane / dichloromethane to give compound 18 (28 g, yield: 68%) as a white solid.

GC-Mass (Theoretical value: 523.98 g / mol, Measured value: 524 g / mol),

¹ H-NMR (THF-d ₈ , 500 MHz) δ (ppm) 7.83 to 7.85 (m, 4H), 8.07 (m, 2H), 8.52 (m, 2H), 9.0 (m, 2H)

Preparation Example 3 Synthesis of 4,4,5,5-tetramethyl-2- (3- (thianthren-1-yl) phenyl) -1,3,2-dioxaborolane

Scheme 19

Compound 1 (60.7 g, 164 mmol) obtained in <Step 1> of Synthesis Example 1, 4,4,4 ', 4', 5,5,5 ', 5'-octamethyl-2,2'-bi ( 1,3,2-dioxaborolane) (83 g, 327 mmol), Pd (dffp) ₂ Cl ₂ (4.08 g, 4.92 mmol) and potassium acetate (48 g, 490 mmol) were added to the flask and 1,4 under nitrogen atmosphere. It was dissolved in 810 ml of -dioxane and stirred under reflux for 12 hours.

After the reaction was completed, 400 ml of iced water was added and extracted three times with 50 ml of dichloromethane. The extract was dried over an excess of Magnesium sulphate, filtered, and the filtrate was concentrated under reduced pressure. The crude product was purified by silica gel column chromatography (n-Hexane: Dichloromethane = 4: 1 (v: v)) to give the title compound (54.8 g, yield 80%) as a white solid.

GC-Mass (Theoretical value: 418.12 g / mol, Measured value: 418 g / mol).

¹ H-NMR (THF-d ₈ , 500 MHz) δ (ppm) 1.26 (S, 12H), 6.80 to 6.86 (m, 3H), 6.96 to 7.02 (m, 4H) 7.2 (m, 1H), 7.3 (m , 1H), 7.5 (m, 2H).

Preparation Example 4 Synthesis of 4,4,5,5-tetramethyl-2- (3- (phenoxathiin-4-yl) phenyl) -1,3,2-dioxaborolane

Scheme 20

Compound 8 (58 g, 164 mmol) obtained in <Step 1> of Synthesis Example 7, 4,4,4 ', 4', 5,5,5 ', 5'-octamethyl-2,2'-bi ( 1,3,2-dioxaborolane) (83 g, 327 mmol), Pd (dffp) ₂ Cl ₂ (4.08 g, 4.92 mmol) and potassium acetate (48 g, 490 mmol) were added to the flask and 1,4 under nitrogen atmosphere. It was dissolved in 810 ml of -dioxane and stirred under reflux for 12 hours.

After the reaction was completed, 400 ml of iced water was added and extracted three times with 50 ml of dichloromethane. The extract was dried over an excess of Magnesium sulphate, filtered, and the filtrate was concentrated under reduced pressure. The crude product was purified by silica gel column chromatography (n-Hexane: Dichloromethane = 4: 1 (v: v)) to give the title compound (49.4 g, yield 68%) as a white solid.

GC-Mass (Theoretical value: 402.12 g / mol, Measured value: 402 g / mol)

¹ H-NMR (THF-d ₈ , 500 MHz) δ (ppm) 1.26 (S, 12H), 6.72 (m, 1H), 6.84 (m, 1H), 6.96 (m, 1H), 7.12 to 7.20 (m, 5H), 7.3 (m, 1 H), 7.5 (m, 2H).

Synthesis Example 13 Synthesis of Compound Inv G-2

Scheme 21

Step 1 Synthesis of Compound 19

Compound 18 (11 g, 21 mmol), phenylboronic acid (2.6 g, 21 mmol), and Pd (PPh ₃ ) ₄ (0.24 g, 0.21 mmol), which were finally synthesized in Preparation Example 2, were placed in a flask, and then toluene 140 was added under a nitrogen atmosphere. 70 ml of an aqueous solution of sodium carbonate (4.4 g, 31.5 mmol) was added thereto, and the mixture was stirred under reflux for 12 hours.

After the reaction was terminated and extracted three times with 50 ml of dichloromethane, the extract was dried with excess Magnesium sulphate, filtered and the filtrate was concentrated under reduced pressure. The crude product was purified by silica gel column chromatography (n-Hexane: Dichloromethane = 7: 3 (v: v)) to give compound 19 (7.7 g, 81% yield) as a solid.

GC-Mass (Theoretical value: 452.07 g / mol, Measured value: 452 g / mol)

Step 2 Synthesis of Compound Inv G-2

The compound (10.2 g, 24.3 mmol), which was finally synthesized in Preparation Example 3, the compound 19 (10.9 g, 24.3 mmol) and Pd (PPh ₃ ) ₄ (0.28 g, 0.24 mmol), synthesized in <Step 1>, were flasked. It was dissolved in 160 ml of Toluene under a nitrogen atmosphere, and 80 ml of an aqueous solution of sodium carbonate (5.09 g, 48.0 mmol) was added thereto, followed by stirring under reflux for two days.

After the reaction was terminated and extracted three times with 50 ml of dichloromethane, the extract was dried with excess Magnesium sulphate, filtered and the filtrate was concentrated under reduced pressure. The crude product was purified by silica gel column chromatography (n-Hexane: Dichloromethane = 4: 1 (v: v)) to afford the title compound Inv G-2 (7.5 g, yield 60%) as a white solid.

GC-Mass (Theoretical value: 594.15 g / mol, Measured value: 594 g / mol)

¹ H-NMR (THF-d ₈ , 500 MHz) δ (ppm) 6.80 to 6.86 (m, 3H), 6.96 to 7.02 (m, 4H), 7.38 to 7.48 (m, 6H) 7.70 to 7.75 (m, 3H) , 7.82 to 7.88 (m, 2H), 8.10 to 8.12 (m, 3H), 8.34 (m, 2H), 8.93 to 8.99 (m, 3H).

Synthesis Example 14 Synthesis of Compound Inv G-10

Scheme 22

Step 1 Synthesis of Compound 19

Compound 18 (21.3 g, 40.6 mmol), phenylboronic acid (5 g, 40.6 mmol), and Pd (PPh ₃ ) ₄ (0.47 g, 0.406 mmol), which were finally synthesized in Preparation Example 2, were placed in a flask under a nitrogen atmosphere. After dissolving in 203 mL of toluene, 102 mL of an aqueous solution of sodium carbonate (6.9 g, 64.9 mmol) was added thereto, and the mixture was stirred under reflux for 12 hours.

After the reaction was terminated and extracted three times with 50 ml of dichloromethane, the extract was dried with excess Magnesium sulphate, filtered and the filtrate was concentrated under reduced pressure. The crude product was purified by silica gel column chromatography (n-Hexane: Dichloromethane = 7: 3 (v: v)) to give compound 19 (14.9 g, yield 82%) as a solid.

GC-Mass (Theoretical value: 452.07 g / mol, Measured value: 452 g / mol)

Step 2 Synthesis of Compound Inv G-10

Compound (9.6 g, 24.0 mmol), finally synthesized in Preparation Example 4, Compound 19 (10.8 g, 24.0 mmol) and Pd (PPh ₃ ) ₄ (0.28 g, 0.24 mmol), synthesized in <Step 1> To the flask was dissolved in 160 ml of Toluene under a nitrogen atmosphere, and 80 ml of an aqueous solution of Sodium Carbonate (5.09 g, 48.0 mmol) was added thereto, followed by stirring under reflux for two days.

After the reaction was terminated and extracted three times with 50 ml of dichloromethane, the extract was dried with excess Magnesium sulphate, filtered and the filtrate was concentrated under reduced pressure. The crude product was purified by silica gel column chromatography (n-Hexane: Dichloromethane = 4: 1 (v: v)) to afford the title compound Inv G-10 (8.7 g, 72% yield) as a white solid.

GC-Mass (Theoretical value: 578.17 g / mol, Measured value: 578 g / mol)

¹ H-NMR (THF-d ₈ , 500 MHz) δ (ppm) 6.72 (m, 1H), 6.84 (m, 1H), 6.96 (m, 1H), 7.12 to 7.18 (m, 4H), 7.38 to 7, 48 (m, 5H), 7.70-7.88 (m, 5H), 8.10-8.12 (m, 3H), 8.34 (m, 2H), 8.93-8.99 (m, 3H).

<Examples 1 to 14> Fabrication of Organic EL Devices

A glass substrate coated with ITO (Indium tin oxide) having a thickness of 1500 Å was washed with distilled water ultrasonically. After washing with distilled water, ultrasonic cleaning with a solvent such as isopropyl alcohol, acetone, methanol, etc. is dried and transferred to a UV OZONE cleaner (Power sonic 405, Hwasin Tech). The substrate was transferred to the depositor.

M-MTDATA (60 nm) / TCTA (80 nm) / each compound synthesized in Synthesis Example 1-14 on the prepared ITO transparent electrode + 10% Ir (ppy) ₃ (300 nm) / BCP (10 nm) / Alq 3 (30 nm) ) / LiF (1 nm) / Al (200 nm) in order to manufacture an organic EL device.

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

Comparative Example 1 Fabrication of Organic EL Device

An organic EL device was manufactured in the same manner as in Example 1, except that CBP was used as a light emitting host material, instead of the compound prepared in Synthesis Example, to form an emission layer.

<Evaluation Example>

For each organic EL device manufactured in Example 1-14 and Comparative Example 1, the driving voltage, current efficiency, emission peak, and luminance at green light were measured, and the results are shown in Table 1 below.

Table 1

As can be seen from the results of Table 1 above, when the compound according to the present invention was used as the light emitting layer of the green organic EL device (Example), it was compared with the green organic EL device using the CBP (Comparative Example 1). It can be seen that it shows excellent performance in terms of efficiency and voltage.

Although the preferred embodiments of the present invention have been described above, the present invention is not limited thereto, and various modifications and changes can be made within the scope of the claims and the detailed description of the invention. It is natural to belong.

Claims (8)

Compound represented by the following formula (1): <Formula 1> Where X is sulfur or oxygen atom; R ₁ to R ₂₀ are each independently hydrogen, deuterium, halogen, substituted or unsubstituted C1-C40 alkyl, substituted or unsubstituted nuclear atom having 3 to 60 heterocycles, substituted or unsubstituted nuclear atom having 5 to 40 heteroaryl, substituted or unsubstituted C1-C40 alkoxy, substituted or unsubstituted C3-C40 cycloalkyl, substituted or unsubstituted heterocycloalkyl having 3 to 40 nuclear atoms, substituted or unsubstituted C5-C40 aryl, Substituted or unsubstituted C5-C60 aryloxy, (substituted or unsubstituted C5-C60 aryl) C1-C40 alkyl, substituted or unsubstituted C2-C40 alkenyl, substituted or unsubstituted C1-C40 alkylamine, ( Substituted or unsubstituted C5-C60 aryl) C1-C40 alkylamine, substituted or unsubstituted C1-C40 alkylsilyl, substituted or unsubstituted C5-C40 arylsilyl, substituted or unsubstituted C7-C40 ketoaryl, substituted Or unsubstituted C1-C40 haloalkyl or cyano, and R ₁ to R ₂₀ are adjacent to each other; May be combined with to form a fused aliphatic ring, a fused aromatic ring, a fused heteroaliphatic ring or a fused heteroaromatic ring having 5 to 40 nuclear atoms; L is substituted or unsubstituted C5-C60 aryl, substituted or unsubstituted heteroatom having 3 to 60 heteroatoms, substituted or unsubstituted heteroatom having 5 to 40 heteroaryl, (substituted or unsubstituted C5- C60 aryl) C1-C40 alkyl, substituted or unsubstituted C5-C40 arylamine, substituted or unsubstituted C5-C60 aryloxy, substituted or unsubstituted C5-C40 arylsilyl, or substituted or unsubstituted C7-C40 Ketoaryl, when L has a substituent, adjacent substituents may be bonded to each other to form a fused aliphatic ring, a fused aromatic ring, a fused heteroaliphatic ring, or a fused heteroaromatic ring having 5 to 40 nuclear atoms. The method of claim 1, Wherein L, R ₁ to the R ₂₀ alkyl, heterocycle, heteroaryl, alkoxy, cycloalkyl, heterocycloalkyl, aryl, aryloxy, arylalkyl, alkenyl, alkyl amines, arylalkyl amines, alkyl silyl, aryl silyl, The substituents of ketoaryl and haloalkyl are each independently deuterium, halogen, C1-C40 alkyl, heterocycle having 3 to 60 nuclear atoms, heteroaryl having 5 to 40 nuclear atoms, C1-C40 alkoxy, C3-C40 cyclo Alkyl, heterocycloalkyl of 3 to 40 nuclear atoms, C5-C40 aryl, C5-C60 aryloxy, (C5-C60 aryl) C1-C40 alkyl, C2-C40 alkenyl, C1-C40 alkylamine, (C5- C60 aryl) C1-C40 alkylamine, C1-C40 alkylsilyl, C5-C40 arylsilyl, C7-C40 ketoaryl, C1-C40 haloalkyl and cyano. The method of claim 1, The compound of formula 1 is a compound characterized in that the compound of formula 1a or 1b: <Formula 1a>

<Formula 1b>

Where X, L, R ₁ to R ₂₀ are as defined in claim 1. The method of claim 1, Wherein L is a compound characterized in that it is selected from the group consisting of: <Formula 2>

Where R ₂₁ to R ₂₄ are each independently hydrogen, deuterium, halogen, substituted or unsubstituted C1-C40 alkyl, substituted or unsubstituted heteroatom having 3 to 60 heterocycles, substituted or unsubstituted nucleus 5 to 5 40 heteroaryl, substituted or unsubstituted C1-C40 alkoxy, substituted or unsubstituted C3-C40 cycloalkyl, substituted or unsubstituted heterocycloalkyl having 3 to 40 nuclear atoms, substituted or unsubstituted C5-C40 aryl, Substituted or unsubstituted C5-C60 aryloxy, (substituted or unsubstituted C5-C60 aryl) C1-C40 alkyl, substituted or unsubstituted C2-C40 alkenyl, substituted or unsubstituted C1-C40 alkylamine, ( Substituted or unsubstituted C5-C60 aryl) C1-C40 alkylamine, substituted or unsubstituted C1-C40 alkylsilyl, substituted or unsubstituted C5-C40 arylsilyl, substituted or unsubstituted C7-C40 ketoaryl, substituted or unsubstituted C1-C40 alkyl, and halo or cyano ring, R ₂₁ to R ₂₄ are adjacent to each other And it may be bonded to form a condensed (fused) aliphatic ring, a condensed aromatic ring, a condensed heterocyclic aliphatic ring or fused heteroaromatic ring of 5 to 40 nuclear atoms. The method of claim 1, Wherein L is selected from the group consisting of <Formula 3>

Where R ₂₁ and R ₂₂ are each independently hydrogen, deuterium, halogen, substituted or unsubstituted C1-C40 alkyl, substituted or unsubstituted heteroatom having 3 to 60 heterocycles, substituted or unsubstituted nucleus 5 to 5 40 heteroaryl, substituted or unsubstituted C1-C40 alkoxy, substituted or unsubstituted C3-C40 cycloalkyl, substituted or unsubstituted heterocycloalkyl having 3 to 40 nuclear atoms, substituted or unsubstituted C5-C40 aryl, Substituted or unsubstituted C5-C60 aryloxy, (substituted or unsubstituted C5-C60 aryl) C1-C40 alkyl, substituted or unsubstituted C2-C40 alkenyl, substituted or unsubstituted C1-C40 alkylamine, ( Substituted or unsubstituted C5-C60 aryl) C1-C40 alkylamine, substituted or unsubstituted C1-C40 alkylsilyl, substituted or unsubstituted C5-C40 arylsilyl, substituted or unsubstituted C7-C40 ketoaryl, substituted Or unsubstituted C1-C40 haloalkyl or cyano; At least one of the plurality of Z is a nitrogen atom and the rest are carbon atoms, and the hydrogen atom attached to Z is unsubstituted or deuterium, halogen, substituted or unsubstituted C1-C40 alkyl, substituted or unsubstituted nuclear atom, 3 to 3 Heteroaryl of 60, substituted or unsubstituted heteroaryl 5 to 40 heteroaryl, substituted or unsubstituted C1-C40 alkoxy, substituted or unsubstituted C3-C40 cycloalkyl, substituted or unsubstituted nuclear 3 To 40 heterocycloalkyl, substituted or unsubstituted C5-C40 aryl, substituted or unsubstituted C5-C60 aryloxy, (substituted or unsubstituted C5-C60 aryl) C1-C40 alkyl, substituted or unsubstituted C2 -C40 alkenyl, substituted or unsubstituted C1-C40 alkylamine, (substituted or unsubstituted C5-C60 aryl) C1-C40 alkylamine, substituted or unsubstituted C1-C40 alkylsilyl, substituted or unsubstituted C5 -C40 arylsilyl, substituted or unsubstituted C7-C40 ketoaryl, substituted or unsubstituted Substituted C1-C40 haloalkyl or cyano, and these substituents, R ₂₁ and R _22, may be bonded to groups adjacent to each other to form a fused aliphatic ring having 5 to 40 nuclear atoms, a condensed aromatic ring, a condensed heteroaliphatic It may form a ring or a condensed heteroaromatic ring. anode; cathode; And at least one organic layer interposed between the anode and the cathode, the organic electroluminescent device comprising: At least one of the organic layers comprises an organic electroluminescent device, characterized in that the compound according to any one of claims 1 to 5. The method of claim 6, The organic layer is an organic electroluminescent device, characterized in that selected from the group consisting of a light emitting layer, an electron transport layer, a hole injection layer and a hole transport layer. The method of claim 6, The compound is an organic electroluminescent device, characterized in that the phosphorescent host material or a fluorescent host material.