WO2015111942A2 - Organic compound and organic electroluminescent element comprising same - Google Patents

Abstract

The present invention relates to an organic compound and an organic electroluminescent element comprising the same, and the organic compound of the present invention is used for an organic material layer, preferably, a light emission layer, of the organic electroluminescent element, and thus can improve the light emission efficiency, driving voltage, lifetime, and the like of the organic electroluminescent element.

Description

Organic compound and organic electroluminescent device comprising the same

The present invention relates to an organic compound and an organic electroluminescent device comprising the same.

In the organic electroluminescent device, when a voltage is applied between two electrodes, holes are injected into the organic material layer at the anode, and electrons are injected into the organic material layer at the cathode. When the injected holes and electrons meet, excitons are formed, and when the excitons fall to the ground, they shine. The material included in the organic material layer may be classified into a light emitting material, a hole injection material, a hole transport material, an electron transport material, an electron injection material, and the like according to its function.

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

The dopant material may be divided into a fluorescent dopant using an organic material and a phosphorescent dopant using a metal complex compound containing heavy atoms such as Ir and Pt. In this case, since phosphorescent dopants can theoretically improve luminous efficiency up to 4 times compared to fluorescent dopants, studies on phosphorescent dopants as well as phosphorescent hosts are being conducted.

At present, anthracene derivatives are known as fluorescent dopant / host materials used in the light emitting layer. In addition, as a phosphorescent dopant material used in the light emitting layer, metal complex compounds containing Ir such as Firpic, Ir (ppy) ₃ , and (acac) Ir (btp) ₂ are known, and as a phosphorescent host material, 4,4-dicarbazolybiphenyl (CBP) is known.

However, the existing materials are not satisfactory in terms of lifespan of the organic EL device due to low thermal stability due to low glass transition temperature, and still need improvement in terms of emission characteristics.

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

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

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

[Formula 1]

In Chemical Formula 1,

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

X ₂ and X ₃ are each independently N or C (R ₂ ),

Y ₁ to Y ₄ are each independently N or C (R ₁ ), and at least one of Y ₁ and Y ₂ , Y ₂ and Y _3, and Y ₃ and Y ₄ forms a condensed ring represented by Formula 2 below. and,

[Formula 2]

In Chemical Formula 2,

Dotted line is a portion that is bonded to the compound of Formula 1,

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

Y ₅ to Y ₈ are each independently N or C (R ₃ ),

At least one of X ₁ and X ₄ is N (Ar ₁ ),

Wherein R ₁ to R ₃ and Ar ₁ to Ar ₅ are each independently, hydrogen, deuterium, halogen group, nitro group, amino group, C ₁ ~ C ₄₀ alkyl group, C ₂ ~ C ₄₀ alkenyl group, C ₂ ~ C ₄₀ alkynyl group, C ₃ to C ₄₀ cycloalkyl group, nuclear atom 3 to 40 heterocycloalkyl group, C ₆ to C ₆₀ aryl group, nuclear atom 5 to 60 heteroaryl group, C ₁ to C ₄₀ Alkyloxy group, C ₆ ~ C ₆₀ aryloxy group, C ₁ ~ C ₄₀ alkylsilyl group, C ₆ ~ C ₆₀ arylsilyl group, C ₁ ~ C ₄₀ alkyl boron group, C ₆ ~ C ₆₀ the arylboronic group, C ₁ ~ C ₄₀ of the phosphine group, is selected from the group consisting of an aryl amine of the C ₁ ~ C ₄₀ phosphine oxide group, and a C ₆ ~ C ₆₀ of the, at this time, R ₁ to R ₃ and Ar ₁ At least one of Ar ₅ is a C ₆ ~ C ₆₀ Aryl group substituted with a cyano group or a heteroaryl group having 5 to 60 nuclear atoms substituted with a cyano group,

R ₁ to R ₃ form or not form a condensed ring with an adjacent group,

The alkyl group, alkenyl group, alkynyl group, cycloalkyl group, heterocycloalkyl group, aryl group, heteroaryl group, alkyloxy group, aryloxy group, alkylsilyl group, arylsilyl group of R ₁ to R ₃ and Ar ₁ to Ar ₅ , Alkyl boron group, aryl boron group, phosphine group, phosphine oxide group and arylamine group are each independently deuterium, halogen group, nitro group, amino group, C ₁ ~ C ₄₀ alkyl group, C ₂ ~ C ₄₀ alkenyl group , C ₂ ~ C ₄₀ Alkynyl group, C ₃ ~ C ₄₀ Cycloalkyl group, C ₃ ~ C ₄₀ heterocycloalkyl group, C ₆ ~ C ₆₀ Aryl group, Nuclear atoms 5 to 60 heteroaryl group, C ₁ -C ₄₀ alkyloxy group, C ₆ -C ₆₀ aryloxy group, C ₁ -C ₄₀ alkylsilyl group, C ₆ -C ₆₀ arylsilyl group, C ₁ -C ₄₀ alkylboron group, C ₆ ~ C ₆₀ aryl boron group, C ₁ ~ C ₄₀ of the phosphine group, C ₁ ~ C ₄₀ phosphine oxide group, and a C ₆ ~ substituted by one or more selected from the group consisting of an aryl amine of the C ₆₀ of the Or unsubstituted. Wherein when R ₁ to R ₃ and Ar ₁ to Ar ₅ are substituted with a plurality of substituents, the plurality of substituents are the same or different from each other.

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

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

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

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

Aryl in the present invention means a monovalent substituent derived from an aromatic hydrocarbon having 6 to 60 carbon atoms combined with a single ring or two or more rings. It may also include a form in which two or more rings are attached to each other (pendant) or condensed. Examples of such aryl include, but are not limited to, phenyl, naphthyl, phenanthryl, anthryl, and the like.

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

Aryloxy in the present invention is a monovalent substituent represented by RO-, wherein R means aryl having 6 to 60 carbon atoms. Examples of such aryloxy include, but are not limited to, phenyloxy, naphthyloxy, diphenyloxy, and the like.

Alkyloxy in the present invention is a monovalent substituent represented by R'O-, wherein R 'means an alkyl having 1 to 40 carbon atoms, and a linear, branched or cyclic structure It may include. Examples of such alkyloxy include, but are not limited to, methoxy, ethoxy, n-propoxy, 1-propoxy, t-butoxy, n-butoxy, pentoxy and the like.

Arylamine in the present invention means an amine substituted with aryl having 6 to 60 carbon atoms.

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

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

Alkylsilyl in the present invention is silyl substituted with alkyl having 1 to 40 carbon atoms, arylsilyl means silyl substituted with aryl having 6 to 60 carbon atoms.

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

Hereinafter, the present invention will be described.

1. New Organic Compounds

The organic compound of the present invention is a structure in which two indene moieties containing one or more heteroatoms such as N, O, and S are fused to each other to form a basic skeleton, and various substituents are bonded to each other. Is displayed.

In the phosphorescent layer of the organic EL device, the host should have a triplet energy gap higher than that of the dopant. That is, in order to effectively provide phosphorescence from the dopant, the energy of the lowest excited state of the host must be higher than the energy of the lowest emission state of the dopant. The compound represented by Formula 1 may exhibit a higher energy level than the dopant when used as a host because a specific substituent is introduced into the indene moiety having a wide singlet energy level and a high triplet energy level.

In addition, the compound represented by the formula (1) of the present invention includes at least one or more C ₆ ~ C ₆₀ aryl group substituted with a cyano group or at least one heteroaryl group having 5 to 60 nuclear atoms substituted with a cyano group Since it has a bipolar characteristic, when the host is used, the binding force between the holes and the electrons in the emission layer may be increased.

Meanwhile, the compound represented by Chemical Formula 1 of the present invention prevents the excitons generated in the light emitting layer from diffusing to the adjacent electron transport layer or the hole transport layer, thereby increasing the number of excitons that contribute to the light emission, so that the light emission efficiency when used in the light emitting auxiliary layer In addition, the life of the organic EL device can be improved.

In addition, the compound represented by the general formula (1) of the present invention exhibits a high glass transition temperature by introducing various substituents, especially aryl groups and / or heteroaryl groups, thereby significantly increasing the molecular weight of the compound. , CBP) can have better thermal stability. In addition, the compound represented by the formula (1) is effective in suppressing the crystallization of the organic material layer.

Therefore, when the compound represented by Chemical Formula 1 of the present invention is applied to the organic material layer of the organic EL device, the performance and lifespan characteristics of the organic EL device may be greatly improved. In addition, the lifespan of the organic EL device may maximize the performance of the full color OLED panel.

Such a compound represented by Formula 1 of the present invention may be embodied as a compound represented by the following formula (1a to 1f).

[Formula 1a]

[Formula 1b]

[Formula 1c]

[Formula 1d]

[Formula 1e]

[Formula 1f]

In Chemical Formulas 1a to 1f, X ₁ to X ₄ and Y ₁ to Y ₈ are the same as defined in Chemical Formula 1.

In Formulas 1a to 1f, Y ₁ to Y ₄ are N or C (R ₁ ), all of which are preferably C (R ₁ ), and Y ₅ to Y ₈ are N or C (R ₃ ), all of which are C that the (R ₃₎ are preferred. In this case, a plurality of R ₁ and R ₃ are the same or different from each other.

The compound represented by Chemical Formula 1 of the present invention may be further embodied by the compounds represented by the following Chemical Formulas B-1 to B-30, but is not limited thereto.

In Formulas B-1 to B-30, Ar ₁ and R ₁ to R ₃ are the same as defined in Formula 1. At this time, a plurality of R ₁ is the same or different from each other, a plurality of R ₂ is the same or different from each other, a plurality of R ₃ is the same or different from each other.

Meanwhile, in the compound represented by Chemical Formula 1, R ₁ to R ₃ and Ar ₁ to Ar ₅ are each independently hydrogen, deuterium, a halogen group, a nitro group, an amino group, an alkyl group of C ₁ to C ₄₀ , and C ₂ ~ C ₄₀ alkenyl group, C ₂ ~ C ₄₀ alkynyl group, C ₃ ~ C ₄₀ cycloalkyl group, a number of nuclear atoms of 3 to 40 heterocycloalkyl group, C ₆ ~ C ₆₀ aryl group, the number of nuclear atoms of 5 to the 60 heteroaryl group, C ₁ to C ₄₀ alkyloxy group, C ₆ to C ₆₀ aryloxy group, C ₁ to C ₄₀ alkylsilyl group, C ₆ to C ₆₀ arylsilyl group, C ₁ to C ₄₀ groups of an alkyl boron, an aryl boronic of _{C 6 ~ C 60, C 1} ~ C 40 phosphine group, C ₁ ~ C ₄₀ phosphine oxide group, and a C ₆ ~ are selected from the group consisting of an aryl amine of the C ₆₀ of the ,

R ₁ to R ₃ are each independently hydrogen, halogen, cyano group, C ₁ ~ C ₄₀ alkyl group, C ₆ ~ C ₆₀ aryl group, nuclear atoms 5 to 60 heteroaryl group and C ₆ ~ C It is preferably selected from the group consisting of ₆₀ arylamine groups,

Ar ₁ to Ar ₅ are each independently composed of a C ₆ ~ C ₆₀ aryl group, a heteroaryl group of 5 to 60 nuclear atoms, a C ₆ ~ C ₆₀ arylamine group and a C ₆ ~ C ₆₀ arylsilyl group It is preferably selected from the group.

In addition, at least one of R ₁ to R ₃ and Ar ₁ to Ar ₅ is a C ₆ ~ C ₆₀ aryl group substituted with a cyano group or a heteroaryl group having 5 to 60 nuclear atoms substituted with a cyano group, It is preferable that Ar ₁ is a C ₆ to C ₆₀ aryl group substituted with a cyano group or a heteroaryl group having 5 to 60 nuclear atoms substituted with a cyano group.

Specifically, R ₁ to R ₃ and Ar ₁ to Ar ₅ may each independently be selected from hydrogen or a substituent consisting of S1 to S204, or a substituent including one or more cyano groups in the selected substituent (bonded) have.

The compound represented by the formula (1) of the present invention can be synthesized in various ways with reference to the following synthesis examples.

2. Organic electroluminescent device

The present invention provides an organic electroluminescent device comprising a compound represented by the formula (1).

Specifically, the present invention includes an anode, a cathode and at least one organic material layer interposed between the anode and the cathode, at least one of the organic material layer comprises an organic electric field comprising at least one compound represented by the formula (1) Provided is a light emitting device.

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

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

The structure of the organic EL device of the present invention is not particularly limited, but a substrate, an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and a cathode may be sequentially stacked. An electron injection layer may be inserted on the electron transport layer. An insulating layer or an adhesive layer may be inserted between the electrode and the organic material layer interface.

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

The organic electroluminescent device of the present invention may be manufactured by forming an organic material layer and an electrode using materials and methods known in the art, except that at least one layer of the organic material layer is formed to include the compound represented by Chemical Formula 1. have.

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

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

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

In addition, the material used as the hole injection layer, the hole transport layer, the electron injection layer and the electron transport layer is not particularly limited as long as it is a conventional material known in the art.

Hereinafter, the present invention will be described in detail with reference to the following Examples. However, the following examples are merely to illustrate the present invention and the present invention is not limited by the following examples.

Preparation Example 1 Synthesis of PC-1

<Step 1> Synthesis of 5- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -1H-indole

5-bromo-1H-indole (25 g, 0.128 mol), 4,4,4 ', 4', 5,5, 5 ', 5'-octamethyl-2,2'-bi (1,3) under nitrogen stream , 2-dioxaborolane) (48.58 g, 0.191 mol), Pd (dppf) Cl ₂ (5.2 g, 5 mol), KOAc (37.55 g, 0.383 mol) and 1,4-dioxane (500 ml) were mixed and 130 ° C Stir at 12 h. After the reaction was completed, the mixture was extracted with ethyl acetate and then dried with MgSO ₄ , purified by column chromatography (Hexane: EA = 10: 1 (v / v)), and purified by 5- (4,4,5,5-tetramethyl). -1,3,2-dioxaborolan-2-yl) -1H-indole (22.32 g, yield 72%) was obtained.

¹ H-NMR: δ 1.24 (s, 12H), 6.45 (d, 1H), 7.27 (d, 1H), 7.42 (d, 1H), 7.52 (d, 1H), 7.95 (s, 1H), 8.21 ( s, 1 H)

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

1-bromo-2-nitrobenzene (15.23 g, 75.41 mmol) under nitrogen stream, 5- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) obtained in <Step 1> above -1H-indole (22 g, 90.49 mmol), NaOH (9.05 g, 226.24 mmol) and THF / H ₂ O (400 ml / 200 ml) were mixed and then Pd (PPh ₃ ) ₄ (4.36 g) at 40 ° C. , 5 mol%) was added and stirred at 80 ° C. for 12 hours. After completion of the reaction, the mixture was extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent in the organic layer obtained was purified by column chromatography (Hexane: EA = 3: 1 (v / v)) to give 5- (2-nitrophenyl) -1H-indole (11.32 g, 63% yield).

¹ H-NMR: δ 6.47 (d, 1H), 7.25 (d, 1H), 7.44 (d, 1H), 7.53 (d, 1H), 7.65 (t, 1H), 7.86 (t, 1H), 7.95 ( s, 1H), 8.00 (d, 1H), 8.09 (t, 1H), 8.20 (s, 1H)

<Step 3> Synthesis of 5- (2-nitrophenyl) -1-phenyl-1H-indole

5- (2-nitrophenyl) -1H-indole (11 g, 46.17 mmol), iodobenzene (14.13 g, 69.26 mmol), Cu powder (0.29 g, 4.62 mmol), K ₂ obtained in the above <Step 2> under a nitrogen stream CO ₃ (6.38 g, 46.17 mmol), Na ₂ SO ₄ (6.56 g, 46.17 mmol) and nitrobenzene (200 ml) were mixed and stirred at 190 ° C. for 12 h. After completion of the reaction, nitrobenzene was removed, the organic layer was separated with methylene chloride, and water was removed using MgSO ₄ . The solvent was removed from the organic layer, which was freed of water, and then purified by column chromatography (Hexane: MC = 3: 1 (v / v)) to give 5- (2-nitrophenyl) -1-phenyl-1H-indole (10.30 g, yield). 71%).

¹ H-NMR: δ 6.48 (d, 1H), 7.26 (d, 1H), 7.45 (m, 3H), 7.55 (m, 4H), 7.63 (t, 1H), 7.84 (t, 1H), 7.93 ( s, 1H), 8.01 (d, 1H), 8.11 (t, 1H)

<Step 4> Synthesis of PC-1

5- (2-nitrophenyl) -1-phenyl-1H-indole (5 g, 15.91 mmol), triphenylphosphine (10.43 g, 39.77 mmol) and 1,2-dichlorobenzene (50 ml) obtained in <Step 3> under a nitrogen stream. ) Was mixed and stirred for 12 hours. After the reaction was completed, 1,2-dichlorobenzene was removed and extracted with dichloromethane. Water was removed with MgSO _4, and the resulting organic layer was purified by column chromatography (Hexane: MC = 3: 1 (v / v)) to obtain PC-1 (2.38 g, yield 53%).

¹ H-NMR: δ 6.99 (d, 1H), 7.12 (t, 1H), 7.27 (t, 1H), 7.32 (d, 1H), 7.41 (t, 1H), 7.50 (d, 1H), 7.60 ( m, 5H), 7.85 (d, 1H), 8.02 (d, 1H), 10.59 (s, 1H)

Preparation Example 2 Synthesis of PC-2

PC-2 was obtained by the same procedure as in <Step 4> of Preparation Example 1 using 5- (2-nitrophenyl) -1-phenyl-1H-indole, triphenylphosphine and 1,2-dichlorobenzene.

¹ H-NMR: δ 6.98 (d, 1H), 7.13 (t, 1H), 7.26 (t, 1H), 7.33 (d, 1H), 7.42 (t, 1H), 7.51 (s, 1H), 7.61 ( m, 5H), 7.84 (d, 1H), 8.03 (s, 1H), 10.58 (s, 1H)

Preparation Example 3 Synthesis of PC-3

Step 1 Synthesis of 6- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -1H-indole

Except for using 6-bromo-1H-indole instead of 5-bromo-1H-indole by following the same procedure as in <Step 1> of Preparation Example 1 6- (4,4,5,5-tetramethyl- 1,3,2-dioxaborolan-2-yl) -1H-indole was obtained.

¹ H-NMR: δ 1.25 (s, 12H), 6.52 (d, 1H), 7.16 (d, 1H), 7.21 (d, 1H), 7.49 (d, 1H), 7.53 (s, 1H), 8.15 ( s, 1 H)

Step 2 Synthesis of 6- (2-nitrophenyl) -1H-indole

6- (4,4,5,5-tetramethyl- obtained in <Step 1> instead of 5- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -1H-indole Except for using 1,3,2-dioxaborolan-2-yl) -1H-indole, 6- (2-nitrophenyl) -1H-indole was prepared in the same manner as in <Step 2> of Preparation Example 1. Got it.

¹ H-NMR: δ 6.57 (d, 1H), 7.07 (d, 1H), 7.24 (d, 1H), 7.35 (s, 1H), 7.43 (t, 1H), 7.50 (d, 1H), 7.58 ( t, 1H), 7.66 (d, 1H), 7.78 (d, 1H), 8.19 (s, 1H)

<Step 3> Synthesis of 6- (2-nitrophenyl) -1-phenyl-1H-indole

The same procedure as in <Step 3> of Preparation Example 1 was performed except that 6- (2-nitrophenyl) -1H-indole obtained in <Step 2> was used instead of 5- (2-nitrophenyl) -1H-indole. 6- (2-nitrophenyl) -1-phenyl-1H-indole was obtained.

¹ H-NMR: δ 6.81 (d, 1H), 7.12 (t, 1H), 7.22 (t, 1H), 7.35 (s, 1H), 7.43 (d, 1H), 7.51 (m, 3H), 7.56 ( m, 2H), 7.62 (m, 2H), 7.85 (d, 1H), 8.02 (d, 1H)

<Step 4> Synthesis of PC-3

Preparation Example 1, except that 6- (2-nitrophenyl) -1-phenyl-1H-indole obtained in <Step 3> instead of 5- (2-nitrophenyl) -1-phenyl-1H-indole PC-3 was obtained by performing the same procedure as in <Step 4>.

¹ H-NMR: δ 6.80 (d, 1H), 7.11 (t, 1H), 7.23 (t, 1H), 7.42 (d, 1H), 7.50 (m, 3H), 7.57 (m, 2H), 7.63 ( m, 2H), 7.86 (d, 1H), 8.03 (d, 1H), 9.81 (s, 1H)

Preparation Example 4 Synthesis of PC-4

The same procedure as in <Step 4> of Preparation Example 1, except that 6- (2-nitrophenyl) -1-phenyl-1H-indole is used instead of 5- (2-nitrophenyl) -1-phenyl-1H-indole Was performed to obtain PC-4.

¹ H-NMR: δ 6.81 (d, 1H), 7.12 (t, 1H), 7.22 (t, 1H), 7.43 (s, 1H), 7.51 (m, 3H), 7.58 (m, 2H), 7.64 ( m, 2H), 7.85 (d, 1H), 8.02 (s, 1H), 9.82 (s, 1H)

Preparation Example 5 Synthesis of PC-5

<Step 1> Synthesis of 4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -1H-indole

Except for using 4-bromo-1H-indole instead of 5-bromo-1H-indole by performing the same process as in <Step 1> of Preparation Example 1 4- (4,4,5,5-tetramethyl- 1,3,2-dioxaborolan-2-yl) -1H-indole was obtained.

¹ H NMR: δ 1.26 (s, 12H), 6.43 (d, 1H), 7.26 (t, 1H), 7.48 (d, 1H), 7.74 (d, 1H), 7.85 (d, 1H), 8.23 (s , 1H)

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

4- (4,4,5,5-tetramethyl- obtained in <Step 1> instead of 5- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -1H-indole Except for using 1,3,2-dioxaborolan-2-yl) -1H-indole, 4- (2-nitrophenyl) -1H-indole was prepared in the same manner as in <Step 2> of Preparation Example 1 above. Got it.

¹ H NMR: δ 6.45 (d, 1H), 7.27 (t, 1H), 7.50 (d, 1H), 7.66 (t, 1H), 7.75 (d, 1H), 7.89 (m, 2H), 7.99 (d , 1H), 8.04 (d, 1H), 8.24 (s, 1H)

<Step 3> Synthesis of 4- (2-nitrophenyl) -1-phenyl-1H-indole

Except for using 4- (2-nitrophenyl) -1H-indole obtained in <Step 2> instead of 5- (2-nitrophenyl) -1H-indole, the same procedure as in <Step 3> of Preparation Example 1 was performed. 4- (2-nitrophenyl) -1-phenyl-1H-indole was obtained.

¹ H NMR: δ 6.47 (d, 1H), 7.28 (t, 1H), 7.47 (m, 2H), 7.52 (m, 2H), 7.60 (m, 2H), 7.67 (t, 1H), 7.75 (d , 1H), 7.89 (m, 2H), 8.00 (d, 1H), 8.06 (d, 1H)

Step 4 Synthesis of PC-5

Except for using 4- (2-nitrophenyl) -1-phenyl-1H-indole obtained in <Step 3> instead of 5- (2-nitrophenyl) -1-phenyl-1H-indole < PC-5 was obtained by following the same procedure as in Step 4>.

¹ H NMR: δ 6.49 (d, 1H), 7.29 (t, 1H), 7.46 (m, 2H), 7.54 (m, 2H), 7.61 (d, 1H), 7.69 (t, 1H), 7.74 (d , 1H), 7.88 (m, 2H), 8.01 (d, 1H), 8.04 (d, 1H), 8.23 (s, 1H)

Preparation Example 6 Synthesis of PC-6

<Step 1> Synthesis of 7- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -1H-indole

Except for using 7-bromo-1H-indole instead of 5-bromo-1H-indole by following the same procedure as in <Step 1> of Preparation Example 1 7- (4,4,5,5-tetramethyl-1 , 3,2-dioxaborolan-2-yl) -1H-indole was obtained.

¹ H NMR: δ 1.25 (s, 12H), 6.43 (d, 1H), 7.25 (d, 1H), 7.45 (t, 1H), 7.56 (d, 1H), 7.71 (d, 1H), 8.22 (s , 1H)

Step 2 Synthesis of 7- (2-nitrophenyl) -1H-indole

5- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -1H-indole instead of 7- (4,4,5,5-tetramethyl- obtained in <Step 1> Except for using 1,3,2-dioxaborolan-2-yl) -1H-indole to obtain 7- (2-nitrophenyl) -1H-indole in the same manner as in <Step 2> of Preparation Example 1 .

¹ H NMR: δ 6.42 (d, 1H), 7.24 (d, 1H), 7.43 (t, 1H), 7.55 (d, 1H), 7.70 (m, 2H), 7.88 (t, 1H), 8.01 (d , 1H), 8.11 (d, 1H), 8.23 (s, 1H)

<Step 3> Synthesis of 7- (2-nitrophenyl) -1-phenyl-1H-indole

The same procedure as in <Step 3> of Preparation Example 1 was performed except that 7- (2-nitrophenyl) -1H-indole obtained in <Step 2> was used instead of 5- (2-nitrophenyl) -1H-indole. To obtain 7- (2-nitrophenyl) -1-phenyl-1H-indole.

¹ H NMR: δ 6.43 (d, 1H), 7.26 (d, 1H), 7.44 (m, 3H), 7.56 (m, 4H), 7.71 (m, 2H), 7.89 (t, 1H), 8.02 (d , 1H), 8.10 (d, 1H)

<Step 4> Synthesis of PC-6

Except for using 7- (2-nitrophenyl) -1-phenyl-1H-indole obtained in <Step 3> instead of 5- (2-nitrophenyl) -1-phenyl-1H-indole < PC-6 was obtained by following the same procedure as in Step 4>.

¹ H NMR: δ 6.45 (d, 1H), 7.24 (d, 1H), 7.45 (m, 3H), 7.57 (m, 3H), 7.63 (d, 1H), 7.70 (d, 1H), 7.88 (t , 1H), 8.00 (d, 1H), 8.09 (d, 1H), 8.22 (s, 1H)

Preparation Example 7 Synthesis of PC-7

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

Except for using 2,4-dibromo-1-nitrobenzene instead of 1-bromo-2-nitrobenzene, the process was carried out in the same manner as in <Step 2> of Preparation Example 1 to 5- (5-bromo-2-nitrophenyl)- 1H-indole was obtained.

¹ H NMR: δ 6.45 (d, 1H), 7.26 (d, 1H), 7.45 (d, 1H), 7.55 (d, 1H), 7.64 (d, 1H), 7.85 (d, 1H), 7.96 (s , 1H), 8.13 (s, 1H), 8.21 (s, 1H)

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

Except for using 5- (5-bromo-2-nitrophenyl) -1H-indole obtained in <Step 1> instead of 5- (2-nitrophenyl) -1H-indole and <Step 3> of Preparation Example 1 The same procedure was followed to obtain 5- (5-bromo-2-nitrophenyl) -1-phenyl-1H-indole.

¹ H NMR: δ 6.44 (d, 1H), 7.25 (d, 1H), 7.46 (m, 3H), 7.56 (m, 4H), 7.65 (d, 1H), 7.86 (d, 1H), 7.95 (s , 1H), 8.11 (s, 1H)

<Step 3> Synthesis of PC-7

Preparation except using 5- (5-bromo-2-nitrophenyl) -1-phenyl-1H-indole obtained in <Step 2> instead of 5- (2-nitrophenyl) -1-phenyl-1H-indole PC-7 was obtained by performing the same procedure as in <Step 4> of Example 1.

¹ H-NMR: δ 6.45 (d, 1H), 7.26 (d, 1H), 7.38 (m, 2H), 7.45 (d, 1H), 7.51 (d, 1H), 7.57 (m, 3H), 7.64 ( d, 1H), 7.85 (d, 1H), 8.10 (s, 1H), 8.23 (s, 1H)

Preparation Example 8 Synthesis of PC-8

<Step 1> Synthesis of 6- (5-bromo-2-nitrophenyl) -1H-indole

2,4-dibromo-1-nitrobenzene and 6- instead of 1-bromo-2-nitrobenzene and 5- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -1H-indole Except for using (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -1H-indole, the same procedure as in <Step 2> of Preparation Example 1 was performed. (5-bromo-2-nitrophenyl) -1H-indole was obtained.

¹ H NMR: δ 6.51 (d, 1H), 7.31 (d, 1H), 7.50 (d, 1H), 7.60 (d, 1H), 7.69 (d, 1H), 7.90 (d, 1H), 8.01 (s , 1H), 8.14 (s, 1H), 8.25 (s, 1H)

<Step 2> Synthesis of 6- (5-bromo-2-nitrophenyl) -1-phenyl-1H-indole

Except for using 6- (5-bromo-2-nitrophenyl) -1H-indole obtained in <Step 1> instead of 5- (2-nitrophenyl) -1H-indole and <Step 3> of Preparation Example 1 The same procedure was followed to obtain 6- (5-bromo-2-nitrophenyl) -1-phenyl-1H-indole.

¹ H NMR: δ 6.49 (d, 1H), 7.30 (d, 1H), 7.51 (m, 3H), 7.61 (m, 4H), 7.70 (d, 1H), 7.91 (d, 1H), 8.00 (s , 1H), 8.16 (s, 1H)

<Step 3> Synthesis of PC-8

Preparation except for using 6- (5-bromo-2-nitrophenyl) -1-phenyl-1H-indole obtained in <Step 2> instead of 5- (2-nitrophenyl) -1-phenyl-1H-indole PC-8 was obtained by performing the same procedure as in <Step 4> of Example 1.

¹ H-NMR: δ 6.47 (d, 1H), 7.28 (d, 1H), 7.40 (m, 2H), 7.47 (d, 1H), 7.53 (d, 1H), 7.59 (m, 3H), 7.66 ( d, 1H), 7.87 (d, 1H), 8.12 (s, 1H), 8.25 (s, 1H)

Preparation Example 9 Synthesis of PC-9

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

5-bromo-1H-indole (25 g, 0.13 mol), Iodobenzene (31.22 g, 0.15 mol), Pd (OAc) ₂ (1.43 g, 5 mol%), Triphenylphosphine (1.67 g, 5 mol%) under nitrogen stream , KOAc (37.55 g, 0.38 mol) and H ₂ O (300 ml) were mixed and stirred at 110 ° C. for 24 h. After the reaction was completed, the mixture was extracted with ethyl acetate and then dried with MgSO ₄ , purified by column chromatography (Hexane: EA = 10: 1 (v / v)) to obtain 5-bromo-2-phenyl-1H-indole ( 16.66 g, yield 48%).

¹ H-NMR: δ 6.89 (dd, 1H), 7.20 (dd, 1H), 7.34 (m, 1H), 7.36 (d, 1H), 7.47 (t, 2H), 7.71 (d, 1H), 7.86 ( dd, 2H), 11.74 (s, 1H)

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

2-nitrophenylboronic acid (11.04 g, 66.14 mmol) under nitrogen stream, 5-bromo-2-phenyl-1H-indole (15 g, 55.12 mmol), NaOH (6.61 g, 165.36 mmol) obtained in <Step 1> above And THF / H ₂ O (200 ml / 100 ml) were mixed, Pd (PPh ₃ ) ₄ (3.18 g, 5 mol) was added at 40 ° C., and the mixture was stirred at 80 ° C. for 12 hours. After completion of the reaction, the mixture was extracted with methylene chloride, MgSO ₄ was added and filtered. The solvent was removed from the obtained organic layer, and then purified by column chromatography (Hexane: EA = 5: 1 (v / v)) to give 5- (2-nitrophenyl) -2-phenyl-1H-indole (10.74 g, yield 62%). Got.

¹ H-NMR: δ 6.88 (dd, 1H), 7.21 (d, 1H), 7.32 (m, 1H), 7.34 (d, 1H), 7.46 (m, 3H), 7.64 (m, 2H), 7.77 ( d, 2H), 8.02 (d, 2H), 11.73 (s, 1H)

<Step 3> Synthesis of 5- (2-nitrophenyl) -1,2-diphenyl-1H-indole

Except for using 5- (2-nitrophenyl) -2-phenyl-1H-indole obtained in <Step 2> instead of 5- (2-nitrophenyl) -1H-indole and <Step 3> of Preparation Example 1 The same procedure was followed to obtain 5- (2-nitrophenyl) -1,2-diphenyl-1H-indole.

GC-Mass (Theoretical value: 390.14 g / mol, Measured value: 390 g / mol)

Step 4 Synthesis of PC-9

Preparation Example except for using 5- (2-nitrophenyl) -1,2-diphenyl-1H-indole obtained in <Step 3> instead of 5- (2-nitrophenyl) -1-phenyl-1H-indole PC-9 was obtained by performing the same procedure as in <Step 4> of 1.

GC-Mass (Theoretical value: 358.15 g / mol, Measured value: 358 g / mol)

Preparation Example 10 Synthesis of PC-10

<Step 1> Synthesis of 6-chloro-2-phenyl-1H-indole

Except for using 6-chloro-1H-indole and bromobenzene instead of 5-bromo-1H-indole and Iodobenzene to the same process as in <Step 1> of Preparation Example 9 6-chloro-2-phenyl-1H got -indole

¹ H-NMR: δ 6.92 (d, 1H), 7.02 (dd, 1H), 7.33 (t, 1H), 7.41 (s, 1H), 7.47 (t, 2H), 7.54 (d, 1H), 7.85 ( d, 2H), 11.68 (s, 1H)

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

Except for using 6-chloro-2-phenyl-1H-indole obtained in <step 1> instead of 5-bromo-2-phenyl-1H-indole the same procedure as in <step 2> of Preparation Example 9 6- (2-nitrophenyl) -2-phenyl-1H-indole was obtained.

¹ H-NMR: δ 6.91 (d, 1H), 7.03 (d, 1H), 7.31 (t, 1H), 7.42 (s, 1H), 7.48 (m, 3H), 7.53 (d, 1H), 7.76 ( m, 3H), 8.01 (d, 2H), 11.66 (s, 1H)

Step 3 Synthesis of 6- (2-nitrophenyl) -1,2-diphenyl-1H-indole

Except for using 6- (2-nitrophenyl) -2-phenyl-1H-indole obtained in <Step 2> instead of 5- (2-nitrophenyl) -1H-indole and <Step 3> of Preparation Example 1 The same procedure was followed to obtain 6- (2-nitrophenyl) -1,2-diphenyl-1H-indole.

GC-Mass (Theoretical value: 390.14 g / mol, Measured value: 390 g / mol)

Step 4 Synthesis of 6- (2-nitrophenyl) -1,2-diphenyl-1H-indole

Preparation Example except for using 6- (2-nitrophenyl) -1,2-diphenyl-1H-indole obtained in <Step 2> instead of 5- (2-nitrophenyl) -1-phenyl-1H-indole PC-10 was obtained in the same manner as in <Step 4> of 1.

GC-Mass (Theoretical value: 358.15 g / mol, Measured value: 358 g / mol)

Preparation Example 11 Synthesis of PC-11

<Step 1> Synthesis of 6-chloro-3-phenyl-1H-indole

6-chloro-1H-indole (25 g, 0.17 mol), bromobenzene (31.19 g, 0.20 mol), Pd (OAc) ₂ (1.86 g, 5 mol), Triphenylphosphine (2.17 g, 5 mol%), under nitrogen stream K ₂ CO ₃ (68.64 g, 0.50 mol) and 1,4-dioxane (300 ml) were mixed and stirred at 130 ° C. for 18 hours. After completion of the reaction, the mixture was extracted with ethyl acetate, followed by removing water with MgSO ₄ , and purified by column chromatography (Hexane: EA = 10: 1 (v / v)) to obtain 6-chloro-3-phenyl-1H-indole ( 24.5 g, yield 65%) was obtained.

¹ H-NMR: δ 7.10 (dd, 1H), 7.25 (m, 1H), 7.43 (t, 2H), 7.49 (d, 1H), 7.67 (dd, 2H), 7.73 (d, 1H), 7.85 ( d, 1 H), 11.49 (s, 1 H)

<Step 2> Synthesis of 6- (2-nitrophenyl) -3-phenyl-1H-indole

Except for using 6-chloro-3-phenyl-1H-indole obtained in <step 1> instead of 5-bromo-2-phenyl-1H-indole the same procedure as in <step 2> of Preparation Example 9 6- (2-nitrophenyl) -3-phenyl-1H-indole was obtained.

¹ H-NMR: δ 7.11 (d, 1H), 7.26 (m, 1H), 7.44 (t, 2H), 7.48 (m, 2H), 7.55 (m, 3H), 7.61 (d, 1H), 7.73 ( d, 1H), 8.00 (d, 2H), 11.48 (s, 1H)

<Step 3> Synthesis of 6- (2-nitrophenyl) -1,3-diphenyl-1H-indole

Except for using 6- (2-nitrophenyl) -3-phenyl-1H-indole obtained in <Step 2> instead of 5- (2-nitrophenyl) -1H-indole and <Step 3> of Preparation Example 1 The same procedure was followed to obtain 6- (2-nitrophenyl) -1,3-diphenyl-1H-indole.

GC-Mass (Theoretical value: 390.14 g / mol, Measured value: 390 g / mol)

Step 4 Synthesis of 6- (2-nitrophenyl) -1,3-diphenyl-1H-indole

Preparation Example except for using 6- (2-nitrophenyl) -1,3-diphenyl-1H-indole obtained in <Step 3> instead of 5- (2-nitrophenyl) -1-phenyl-1H-indole PC-11 was obtained by performing the same procedure as in <Step 4> of 1.

GC-Mass (Theoretical value: 358.15 g / mol, Measured value: 358 g / mol)

Preparation Example 12 Synthesis of PC-12

<Step 1> Synthesis of 5-bromo-2,3-diphenyl-1H-indole

Except for using 5-bromo-2-phenyl-1H-indole instead of 6-chloro-1H-indole by performing the same process as in <Step 1> of Preparation Example 11 5-bromo-2,3-diphenyl -1 H-indole was obtained.

¹ H-NMR: δ 7.23 (d, 1H), 7.31 (t, 2H), 7.43 (m, 6H), 7.67 (d, 1H), 7.71 (d, 1H), 7.84 (d, 2H), 11.34 ( s, 1 H)

<Step 2> Synthesis of 5- (2-nitrophenyl) -2,3-diphenyl-1H-indole

Except for using 5-bromo-2,3-diphenyl-1H-indole obtained in <step 1> instead of 5-bromo-2-phenyl-1H-indole is the same as <step 2> of Preparation Example 9 The procedure was followed to obtain 5- (2-nitrophenyl) -2,3-diphenyl-1H-indole.

GC-Mass (Theoretical value: 390.14 g / mol, Measured value: 390 g / mol)

<Step 3> Synthesis of 5- (2-nitrophenyl) -1,2,3-triphenyl-1H-indole

<Step 3 of Preparation Example 1, except that 5- (2-nitrophenyl) -2,3-diphenyl-1H-indole obtained in <Step 2> was used instead of 5- (2-nitrophenyl) -1H-indole. > The same process as in to obtain 5- (2-nitrophenyl) -1,2,3-triphenyl-1H-indole.

GC-Mass (Theoretical value: 466.17 g / mol, Measured value: 466 g / mol)

Step 4 Synthesis of PC-12

Except for using 5- (2-nitrophenyl) -1,2,3-triphenyl-1H-indole obtained in <Step 3> instead of 5- (2-nitrophenyl) -1-phenyl-1H-indole PC-12 was obtained by performing the same procedure as <Step 4> of Preparation Example 1.

GC-Mass (Theoretical value: 434.18 g / mol, Measured value: 434 g / mol)

Preparation Example 13 Synthesis of PC-13

<Step 1> Synthesis of 6-chloro-2,3-diphenyl-1H-indole

Except for using 6-chloro-2-phenyl-1H-indole instead of 6-chloro-1H-indole to perform the same process as in <Step 1> of Preparation Example 11 6-chloro-2,3-diphenyl -1 H-indole was obtained.

¹ H-NMR: δ 7.18 (d, 1H), 7.29 (t, 2H), 7.50 (m, 6H), 7.62 (d, 1H), 7.75 (d, 1H), 7.89 (d, 2H), 11.35 ( s, 1 H)

<Step 2> Synthesis of 6- (2-nitrophenyl) -2,3-diphenyl-1H-indole

Except for using 6-chloro-2,3-diphenyl-1H-indole obtained in <step 1> instead of 5-bromo-2-phenyl-1H-indole is the same as <step 2> of Preparation Example 9 The procedure was followed to obtain 6- (2-nitrophenyl) -2,3-diphenyl-1H-indole.

GC-Mass (Theoretical value: 390.14 g / mol, Measured value: 390 g / mol)

<Step 3> Synthesis of 6- (2-nitrophenyl) -1,2,3-triphenyl-1H-indole

<Step 3 of Preparation Example 1, except that 6- (2-nitrophenyl) -2,3-diphenyl-1H-indole obtained in <Step 2> was used instead of 5- (2-nitrophenyl) -1H-indole. 6- (2-nitrophenyl) -1,2,3-triphenyl-1H-indole was obtained by following the same procedure as>.

GC-Mass (Theoretical value: 466.17 g / mol, Measured value: 466 g / mol)

<Step 4> Synthesis of PC-13

Except for using 6- (2-nitrophenyl) -1,2,3-triphenyl-1H-indole obtained in <Step 3> instead of 5- (2-nitrophenyl) -1-phenyl-1H-indole PC-13 was obtained by performing the same procedure as <Step 4> of Preparation Example 1.

GC-Mass (Theoretical value: 434.18 g / mol, Measured value: 434 g / mol)

Preparation 14 Synthesis of IC-1

<Step 1> Synthesis of 5- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -1H-indazole

5-bromo-1H-indazole (25.22 g, 0.128 mol), 4,4,4 ', 4', 5,5, 5 ', 5'-octamethyl-2,2'-bi (1,3) under nitrogen stream , 2-dioxaborolane) (48.58 g, 0.191 mol), Pd (dppf) Cl ₂ (5.2 g, 5 mol), KOAc (37.55 g, 0.383 mol) and 1,4-dioxane (500 ml) were mixed and 130 ° C Stir at 12 h. After the reaction was completed, the mixture was extracted with ethyl acetate and then dried with MgSO ₄ , purified by column chromatography (Hexane: EA = 10: 1 (v / v)), and purified by 5- (4,4,5,5-tetramethyl). -1,3,2-dioxaborolan-2-yl) -1H-indazole (22.49 g, yield 72%) was obtained.

¹ H-NMR: δ 1.24 (s, 12H), 7.60 (d, 1H), 8.15 (m, 2H), 8.34 (d, 1H), 12.34 (s, 1H)

<Step 2> Synthesis of 5- (2-nitrophenyl) -1H-indazole

1-bromo-2-nitrobenzene (15.23 g, 75.41 mmol) under nitrogen stream, 5- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) obtained in <Step 1> above -1H-indazole (22.09 g, 90.49 mmol), NaOH (9.05 g, 226.24 mmol) and THF / H ₂ O (400 ml / 200 ml) were mixed and then Pd (PPh ₃ ) ₄ (4.36 g) at 40 ° C. , 5 mol%) was added and stirred at 80 ° C. for 12 hours. After completion of the reaction, the mixture was extracted with methylene chloride, MgSO ₄ was added and filtered. The solvent was removed from the organic layer and purified by column chromatography (Hexane: EA = 3: 1 (v / v)) to obtain 5- (2-nitrophenyl) -1H-indazole (13.64 g, 63% yield).

¹ H-NMR: δ 7.64 (m, 2H), 7.90 (m, 1H), 8.05 (m, 3H), 8.21 (s, 1H), 8.38 (d, 1H), 12.24 (s, 1H)

<Step 3> Synthesis of 5- (2-nitrophenyl) -1-phenyl-1H-indazole

5- (2-nitrophenyl) -1H-indazole (11.04 g, 46.17 mmol), iodobenzene (14.13 g, 69.26 mmol), Cu powder (0.29 g, 4.62 mmol), K ₂ obtained in the above <Step 2> under a nitrogen stream CO ₃ (6.38 g, 46.17 mmol), Na ₂ SO ₄ (6.56 g, 46.17 mmol) and nitrobenzene (200 ml) were mixed and stirred at 190 ° C. for 12 h. After completion of the reaction, nitrobenzene was removed, the organic layer was separated with methylene chloride, and water was removed using MgSO ₄ . The solvent was removed from the organic layer, which was then freed from water, and purified by column chromatography (Hexane: MC = 3: 1 (v / v)) to give 5- (2-nitrophenyl) -1-phenyl-1H-indazole (10.34 g, yield 71%).

¹ H-NMR: δ 7.48 (t, 1H), 7.62 (m, 6H), 7.90 (m, 1H), 8.05 (m, 3H), 8.37 (m, 2H)

Step 4 Synthesis of IC-1

5- (2-nitrophenyl) -1-phenyl-1H-indazole (5.01 g, 15.91 mmol), triphenylphosphine (10.43 g, 39.77 mmol) and 1,2-dichlorobenzene (50 ml) obtained in <Step 3> under a nitrogen stream. ) Was mixed and stirred for 12 hours. After the reaction was completed, 1,2-dichlorobenzene was removed and extracted with dichloromethane. The obtained organic layer was removed with MgSO _4, and purified by column chromatography (Hexane: MC = 3: 1 (v / v)) to obtain IC-1 (2.39 g, yield 53%).

¹ H-NMR: δ 7.29 (t, 1H), 7.45 (m, 3H), 7.60 (m, 5H), 8.12 (d, 1H), 8.33 (d, 2H), 10.09 (s, 1H)

Preparation Example 15 Synthesis of IC-2

<Step 1> Synthesis of 6- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -1H-indazole

Except for using 6-bromo-1H-indazole instead of 5-bromo-1H-indazole, 6- (4,4,5,5-tetramethyl- was carried out in the same manner as in <Step 1> of Preparation Example 14 above. 1,3,2-dioxaborolan-2-yl) -1H-indazole was obtained.

¹ H-NMR: δ 1.25 (s, 12H), 7.48 (d, 1H), 7.89 (m, 2H), 8.21 (s, 1H), 12.15 (s, 1H)

Step 2 Synthesis of 6- (2-nitrophenyl) -1H-indazole

5- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -1H-indazole instead of 6- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan A 6- (2-nitrophenyl) -1H-indazole was obtained in the same manner as in <Step 2> of Preparation Example 14, except that 2-yl) -1H-indazole was used.

¹ H-NMR: δ 7.49 (d, 1H), 7.67 (t, 1H), 7.85 (s, 1H), 7.94 (m, 2H), 8.03 (m, 2H), 8.20 (s, 1H), 12.2 ( s, 1 H)

<Step 3> Synthesis of 6- (2-nitrophenyl) -1-phenyl-1H-indazole

Except for using 6- (2-nitrophenyl) -1H-indazole instead of 5- (2-nitrophenyl) -1H-indazole, 6- (2- nitrophenyl) -1-phenyl-1H-indole was obtained.

¹ H-NMR: δ 7.47 (m, 2H), 7.62 (m, 5H), 7.83 (s, 1H), 7.95 (m, 2H), 8.02 (m, 2H), 8.39 (s, 1H)

Step 4 Synthesis of IC-2

The same process as in <Step 4> of Preparation Example 14, except that 6- (2-nitrophenyl) -1-phenyl-1H-indazole is used instead of 5- (2-nitrophenyl) -1-phenyl-1H-indazole Was carried out to obtain IC-2.

¹ H-NMR: δ 7.27 (m, 2H), 7.45 (t, 1H), 7.54 (m, 6H), 7.95 (d, 1H), 8.12 (d, 1H), 8.37 (s, 1H), 10.53 ( s, 1 H)

Preparation Example 16 Synthesis of IC-3

The same process as in <Step 4> of Preparation Example 14, except that 6- (2-nitrophenyl) -1-phenyl-1H-indazole is used instead of 5- (2-nitrophenyl) -1-phenyl-1H-indazole Was carried out to obtain IC-3.

¹ H-NMR: δ 7.29 (t, 1H), 7.45 (t, 1H), 7.50 (m, 1H), 7.58 (m, 6H), 7.88 (s, 1H), 8.11 (d, 1H), 8.33 ( s, 1H), 10.64 (s, 1H)

Preparation 17 Synthesis of IC-4

<Step 1> Synthesis of 4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -1H-indazole

Except for using 4-bromo-1H-indazole instead of 5-bromo-1H-indazole, 4- (4,4,5,5-tetramethyl- was carried out in the same manner as in <Step 1> of Preparation Example 14 above. 1,3,2-dioxaborolan-2-yl) -1H-indazole was obtained.

¹ H NMR: δ 1.26 (s, 12H), 7.43 (d, 1H), 7.66 (t, 1H), 8.28 (m, 2H), 12.23 (s, 1H)

<Step 2> Synthesis of 4- (2-nitrophenyl) -1H-indazole

4- (4,4,5,5-tetramethyl- obtained in <Step 1> instead of 5- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -1H-indazole Except for using 1,3,2-dioxaborolan-2-yl) -1H-indazole, 4- (2-nitrophenyl) -1H-indazole was prepared in the same manner as in <Step 2> of Preparation Example 14 above. Got it.

¹ H NMR: δ 7.49 (d, 1H), 7.68 (m, 2H), 7.90 (t, 1H), 8.01 (m, 2H), 8.24 (m, 2H), 12.39 (s, 1H)

<Step 3> Synthesis of 4- (2-nitrophenyl) -1-phenyl-1H-indazole

Except for using 4- (2-nitrophenyl) -1H-indazole obtained in <Step 2> instead of 5- (2-nitrophenyl) -1H-indazole, the same procedure as in <Step 3> of Preparation Example 14 was performed. 4- (2-nitrophenyl) -1-phenyl-1H-indazole was obtained.

¹ H NMR: δ 7.47 (m, 2H), 7.64 (m, 6H), 7.90 (t, 1H), 8.00 (m, 2H), 8.31 (m, 2H)

Step 4 Synthesis of IC-4

Except for using 4- (2-nitrophenyl) -1-phenyl-1H-indazole obtained in <Step 3> instead of 5- (2-nitrophenyl) -1-phenyl-1H-indazole IC-4 was obtained by the same procedure as in step 4>.

¹ H NMR: δ 7.30 (t, 1H), 7.52 (m, 7H), 8.08 (m, 2H), 8.35 (m, 2H), 10.21 (s, 1H)

Preparation Example 18 Synthesis of IC-5

<Step 1> Synthesis of 7- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -1H-indazole

Except for using 7-bromo-1H-indazole instead of 5-bromo-1H-indazole, the procedure of 7- (4,4,5,5-tetramethyl-1 was carried out in the same manner as in <Step 1> of Preparation Example 14 , 3,2-dioxaborolan-2-yl) -1H-indazole was obtained.

¹ H NMR: δ 1.25 (s, 12H), 7.44 (t, 1H), 7.62 (d, 1H), 7.95 (d, 1H), 8.36 (s, 1H), 12.51 (s, 1H)

Step 2 Synthesis of 7- (2-nitrophenyl) -1H-indazole

Instead of 5- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -1H-indazole, 7- (4,4,5,5-tetramethyl- obtained in <Step 1> above Except that 1,3,2-dioxaborolan-2-yl) -1H-indazole was used, 7- (2-nitrophenyl) -1H-indazole was obtained in the same manner as in <Step 2> of Preparation Example 14. .

¹ H NMR: δ 7.62 (m, 3H), 7.95 (m, 4H), 8.22 (s, 1H), 12.47 (s, 1H)

<Step 3> Synthesis of 7- (2-nitrophenyl) -1-phenyl-1H-indazole

The same procedure as in <Step 3> of Preparation Example 14 was performed except that 7- (2-nitrophenyl) -1H-indazole obtained in <Step 2> was used instead of 5- (2-nitrophenyl) -1H-indazole. 7- (2-nitrophenyl) -1-phenyl-1H-indazole was obtained.

¹ H NMR: δ 7.58 (m, 8H), 7.89 (m, 2H), 8.02 (m, 2H), 8.39 (s, 1H)

Step 4 Synthesis of IC-5

Except for using 7- (2-nitrophenyl) -1-phenyl-1H-indazole obtained in <Step 3> instead of 5- (2-nitrophenyl) -1-phenyl-1H-indazole IC-5 was obtained by the same procedure as in step 4>.

¹ H NMR: δ 7.28 (t, 1H), 7.55 (m, 7H), 7.92 (d, 2H), 8.14 (d, 1H), 8.33 (s, 1H), 10.70 (s, 1H)

Preparation Example 19 Synthesis of BOC-1 & BOC-2

Step 1 Synthesis of N- (2,4-dibromophenyl) benzamide

2,4-dibromoaniline (250.9 g, 1.0 mol) was added to the reactor, and methylene chloride (1,000 ml) was added thereto, followed by stirring. Benzoyl chloride (116 mL, 1.0 mol) and pyridine (161.8 mL, 2.0 mol) were added dropwise to the reactor, followed by stirring at room temperature for 2 hours. After completion of the reaction, the mixture was extracted with methylene chloride, followed by water removal with MgSO ₄ , and purified by column chromatography (Hexane: EA = 4: 1 (v / v)) to obtain N- (2,4-dibromophenyl) benzamide (252.1 g, yield 71%).

¹ H-NMR: δ 7.52 (d, 1H), 7.59 (d, 1H), 7.63 (dd, 2H), 7.70 (t, 1H), 7.98 (s, 1H), 8.03 (d, 2H), 9.15 ( b, 1H)

<Step 2> Synthesis of 6-bromo-2-phenylbenzo [d] oxazole

N- (2,4-dibromophenyl) benzamide (251.1 g, 710 mmol), K ₂ CO ₃ (196.3 g, 1420 mmol) and DMSO (7100 ml) were mixed under nitrogen stream and stirred at 140 ° C. for 1.5 hours. After completion of the reaction, the mixture was extracted with ethyl acetate, followed by removing water with MgSO ₄ , and purified by column chromatography (Hexane: EA = 9: 1 (v / v)) to obtain 6-bromo-2-phenylbenzo [d] oxazole ( 147.9 g, yield 76%).

¹ H-NMR: δ 7.41 (t, 1H) 7.43 (s, 1H), 7.51 (m, 3H), 7.60 (d, 1H), 8.05 (d, 2H)

<Step 3> Synthesis of 2-phenyl-6- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) benzo [d] oxazole

6-bromo-2-phenylbenzo [d] oxazole (147.9 g, 540.0 mmol), 4,4,4 ', 4', 5,5, 5 ', 5'-octamethyl-2,2'-bi under nitrogen stream (1,3,2-dioxaborolane) (150.8 g, 594.0 mmol), Pd (dppf) Cl ₂ (62.4 g, 54.0 mmol), KOAc (152.5 g, 1.62 mol) and 1,4-Dioxane (2800 ml) Mix and stir at 130 ° C. for 12 h. After the reaction was completed, the mixture was extracted with ethyl acetate, followed by removing moisture with MgSO ₄ , and purified by column chromatography (Hexane: EA = 7: 1 (v / v)) to 2-phenyl-6- (4,4,5 , 5-tetramethyl-1,3,2-dioxaborolan-2-yl) benzo [d] oxazole (133.5 g, yield 77%) was obtained.

¹ H-NMR: δ 1.24 (s, 12H) 7.41 (d, 1H), 7.44 (s, 1H), 7.51 (dd, 2H), 7.62 (d, 1H), 7.75 (s, 1H), 8.05 (d , 2H)

Step 4 Synthesis of 6- (2-nitrophenyl) -2-phenylbenzo [d] oxazole

2-phenyl-6- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) benzo [d] oxazole (133.5 g, 415.8 mmol), 1-bromo-2 under nitrogen stream -nitrobenzene (92.4 g, 457.4 mmol), Pd (PPh ₃ ) ₄ (24.0 g, 20.8 mmol), K ₂ CO ₃ (143.7 g, 1.04 mol), 1,4-dioxane / H ₂ O (400 ml / 100 ml) were mixed and stirred at 120 ° C. for 4 hours. After the reaction was terminated and extracted with methylene chloride, MgSO ₄ was added and filtered. The solvent was removed from the organic layer and purified by column chromatography (Hexane: EA = 7: 1 (v / v)) to give 6- (2-nitrophenyl) -2-phenylbenzo [d] oxazole (110.5 g, 84% yield). Got.

¹ H-NMR: δ 7.41-7.51 (m, 4H), 7.67-7.68 (m, 2H), 7.79 (d, 1H), 7.90 (dd, 1H), 8.00-8.05 (m, 4H)

Step 5 Synthesis of BOC-1 and BOC-2

Under nitrogen stream, 6- (2-nitrophenyl) -2-phenylbenzo [d] oxazole (110.5 g, 349 mmol), triphenylphosphine (274.6 g, 1047 mmol) and 1,2-dichlorobenzene 1500 ml were added thereto, followed by stirring for 12 hours. . After the reaction was completed, 1,2-dichlorobenzene was removed, extracted with dichloromethane, MgSO ₄ was added and filtered. The solvent was removed from the organic layer, and the residue was purified by column chromatography (Hexane: MC = 4: 1 (v / v)) to obtain BOC-1 (55.6g, 56%) and BOC-2 (32.7g, yield). 33%) was obtained.

¹ H-NMR of BOC-1: δ 7.23-7.29 (m, 2H), 7.41-7.51 (m, 4H), 7.63 (d, 1H), 8.05-8.12 (m, 4H), 10.1 (b, 1H)

¹ H-NMR of BOC-2: δ 7.29 (dd, 1H), 7.40-7.55 (m, 7H), 8.05-8.12 (m, 3H), 10.1 (b, 1H)

Preparation Example 20 Synthesis of BOC-3

Step 1 Synthesis of 6- (5-bromo-2-nitrophenyl) -2-phenylbenzo [d] oxazole

2-phenyl-6- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) benzo [d] oxazole (133.5 g, 415.8 mmol), 4-bromo-2 under nitrogen stream -iodo-1-nitrobenzene (150.0 g, 457.4 mmol), Pd (PPh ₃ ) ₄ (24.0 g, 20.8 mmol), K ₂ CO ₃ (143.7 g, 1.04 mol), 1,4-dioxane / H ₂ O ( 400 ml / 100 ml) were mixed and stirred at 120 ° C. for 4 hours. After the reaction was terminated and extracted with methylene chloride, MgSO ₄ was added and filtered. The solvent was removed from the organic layer and purified by column chromatography (Hexane: EA = 8: 1 (v / v)) to give 6- (5-bromo-2-nitrophenyl) -2-phenylbenzo [d] oxazole (138 g, Yield 84%).

¹ H-NMR: δ 7.41 (t, 1H) 7.48 (s, 1H), 7.51 (dd, 2H), 7.68 (d, 1H), 7.72 (s, 1H), 7.79 (d, 1H), 7.98 (d , 1H), 8.05 (d, 2H), 8.21 (d, 1H)

<Step 2> Synthesis of 7-bromo-2-phenyl-10H-oxazole [5,4-a] carbazole with 8-bromo-2-phenyl-5H-oxazole [4,5-b] carbazole

12 hours after adding 1500 ml of 6- (5-bromo-2-nitrophenyl) -2-phenylbenzo [d] oxazole (138g, 349 mmol), triphenylphosphine (274.6 g, 1047 mmol) and 1,2-dichlorobenzene under nitrogen stream Was stirred. After the reaction was completed, 1,2-dichlorobenzene was removed, extracted with dichloromethane, MgSO ₄ was added and filtered. The solvent was removed from the organic layer and purified by column chromatography (Hexane: MC = 4: 1 (v / v)) to obtain 7-bromo-2-phenyl-10H-oxazole [5,4-a] carbazole (70.1 g, Yield 53%) and 8-bromo-2-phenyl-5H-oxazole [4,5-b] carbazole (41.0g, 31% yield).

¹ H-NMR of 7-bromo-2-phenyl-10H-oxazole [5,4-a] carbazole: δ 7.23 (d, 1H), 7.41 (t, 1H) 7.42 (d, 1H), 7.51 (dd, 2H), 7.52 (d, 1H), 8.05 (m, 3H), 8.12 (d, 1H), 10.1 (b, 1H)

¹ H-NMR of 8-bromo-2-phenyl-5H-oxazole [4,5-b] carbazole: δ 7.40 (s, 1H), 7.41 (t, 1H) 7.42 (d, 1H), 7.51 (dd, 2H), 7.52 (d, 1H), 7.55 (s, 1H), 8.05 (m, 3H), 10.1 (b, 1H)

<Step 3> Synthesis of 2-phenyl-7- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -10H-oxazolo [5,4-a] carbazole

7-bromo-2-phenyl-10H-oxazolo [5,4-a] carbazole (70.1 g, 193.0 mmol), 4,4,4 ', 4', 5,5, 5 ', 5'- under nitrogen stream octamethyl-2,2'-bi (1,3,2-dioxaborolane) (53.9 g, 212.3 mmol), Pd (dppf) Cl ₂ (22.3 g, 19.3 mmol), KOAc (54.5 g, 579 mmol) and 1, 4-Dioxane (1000 ml) was mixed and stirred at 130 ° C. for 12 h. After the reaction was completed, the mixture was extracted with ethyl acetate, followed by removing moisture with MgSO ₄ , and purified by column chromatography (Hexane: EA = 7: 1 (v / v)) to 2-phenyl-7- (4,4,5 , 5-tetramethyl-1,3,2-dioxaborolan-2-yl) -10H-oxazolo [5,4-a] carbazole (64.1 g, yield 81%) was obtained.

¹ H-NMR: δ 1.24 (s, 12H) 7.41 (d, 1H), 7.44 (s, 1H), 7.51 (dd, 2H), 7.62 (d, 1H), 7.75 (s, 1H), 8.05 (d , 2H), 10.1 (b, 1H)

Step 4 Synthesis of BOC-3

2-phenyl-7- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -10H-oxazolo [5,4-a] carbazole (64.1 g, 156.2 mmol) under nitrogen stream ), iodobenzene (19 mL, 171.8 mmol), Pd (PPh ₃ ) ₄ (9.02 g, 7.81 mmol), K ₂ CO ₃ (53.8 g, 390.5 m mol), 1,4-dioxane / H ₂ O (160 ml / 40 ml) were mixed and stirred at 120 ° C. for 4 hours. After the reaction was terminated and extracted with methylene chloride, MgSO ₄ was added and filtered. The solvent was removed from the obtained organic layer, and then purified by column chromatography (Hexane: EA = 8: 1 (v / v)) to obtain BOC-3 (48.4 g, yield 86%).

¹ H-NMR: δ 7.23 (d, 1H) 7.41-7.52 (m, 8H), 7.69 (d, 1H), 7.77 (s, 1H), 7.87 (d, 1H), 8.05-8.12 (m, 3H) , 10.1 (b, 1H)

Preparation 21 Synthesis of BOC-4

<Step 1> Synthesis of 2-phenyl-8- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -5H-oxazolo [4,5-b] carbazole

8-bromo-2-phenyl-5H-oxazolo [4,5-b] carbazole (41.0 g, 112.9 mmol), 4,4,4 ', 4', 5,5, 5 ', 5'- under nitrogen stream octamethyl-2,2'-bi (1,3,2-dioxaborolane) (31.5 g, 124.2 mmol), Pd (dppf) Cl ₂ (13.1 g, 11.3 mmol), KOAc (31.9 g, 338.7 mmol) and 1, 4-Dioxane (700 ml) was mixed and stirred at 130 ° C. for 12 h. After completion of the reaction, the mixture was extracted with ethyl acetate, followed by removal of water with MgSO ₄ , and purification with column chromatography (Hexane: EA = 7: 1 (v / v)) to 2-phenyl-8- (4,4,5 , 5-tetramethyl-1,3,2-dioxaborolan-2-yl) -5H-oxazolo [4,5-b] carbazole (39.4 g, yield 85%) was obtained.

¹ H-NMR: δ 1.24 (s, 12H) 7.41 (d, 1H), 7.40 (s, 1H), 7.51 (m, 3H), 7.55 (s, 1H), 7.63 (d, 1H), 7.98 (s , 1H), 8.05 (d, 2H), 10.1 (b, 1H)

Step 2 Synthesis of BOC-4

2-phenyl-8- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -5H-oxazolo [4,5-b] carbazole (39.4 g, 96.0 mmol) under nitrogen stream ), iodobenzene (11.8 mL, 105.6 mmol), Pd (PPh ₃ ) ₄ (5.55 g, 4.80 mmol), K ₂ CO ₃ (39.8 g, 288 mmol), 1,4-dioxane / H ₂ O (100 ml / 25 ml) were mixed and stirred at 120 ° C. for 4 hours. After the reaction was terminated and extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent in the organic layer obtained was purified by column chromatography (Hexane: EA = 8: 1 (v / v)) to give BOC-4 (29.8 g, 89% yield).

¹ H-NMR: δ 7.40-7.55 (m, 10H), 7.69 (d, 1H), 7.77 (s, 1H), 7.87 (d, 1H), 8.05 (d, 2H), 10.1 (b, 1H)

Preparation 22 Synthesis of BOC-5

2-phenyl-7- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -10H-oxazolo [5,4-a] carbazole (64.1 g, 156.2 mmol) under nitrogen stream ), 4-bromo-N, N-diphenylaniline (55.7 g, 171.8 mmol), Pd (PPh ₃ ) ₄ (9.02 g, 7.81 mmol), K ₂ CO ₃ (53.8 g, 390.5 mmol), 1,4-dioxane / H ₂ O (160 ml / 40 ml) was mixed and stirred at 120 ° C. for 4 hours. After the reaction was terminated and extracted with methylene chloride, MgSO ₄ was added and filtered. The solvent was removed from the obtained organic layer, and then purified by column chromatography (Hexane: EA = 8: 1 (v / v)) to obtain BOC-5 (77.9 g, yield 88%).

¹ H-NMR: δ 6.63-6.69 (m, 6H), 6.81 (t, 2H), 7.20-7.23 (m, 5H), 7.40-7.54 (m, 5H), 7.69-7.87 (m, 3H), 8.05 -8.12 (m, 3H), 10.1 (b, 1H)

Preparation 23 Synthesis of BOC-6

2-phenyl-8- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -5H-oxazolo [4,5-b] carbazole (39.4 g, 96.0 mmol) under nitrogen stream ), 4-bromo-N, N-diphenylaniline (34.2 g, 105.6 mmol), Pd (PPh ₃ ) ₄ (5.55 g, 4.80 mmol), K ₂ CO ₃ (39.8 g, 288 mmol), 1,4-dioxane / H ₂ O (100 ml / 25 ml) was mixed and stirred at 120 ° C. for 4 hours. After the reaction was terminated and extracted with methylene chloride, MgSO ₄ was added and filtered. The solvent was removed from the obtained organic layer and purified by column chromatography (Hexane: EA = 8: 1 (v / v)) to obtain BOC-6 (48.4 g, yield 89%).

¹ H-NMR: δ 6.63-6.69 (m, 6H), 6.81 (t, 2H), 7.20 (dd, 4H), 7.40-7.54 (m, 7H), 7.69-7.87 (m, 3H), 8.05 (d , 2H), 10.1 (b, 1H)

Preparation 24 Synthesis of BOC-7

2-phenyl-7- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -10H-oxazolo [5,4-a] carbazole (64.1 g, 156.2 mmol) under nitrogen stream ), 2-bromo-9,9-dimethyl-10-phenyl-9,10-dihydroacridine (62.6 g, 171.8 mmol), Pd (PPh ₃ ) ₄ (9.02 g, 7.81 mmol), K ₂ CO ₃ (53.8 g , 390.5 mmol), 1,4-dioxane / H ₂ O (160 ml / 40 ml) were mixed and stirred at 120 ° C. for 4 hours. After the reaction was terminated and extracted with methylene chloride, MgSO ₄ was added and filtered. The solvent was removed from the organic layer and purified by column chromatography (Hexane: EA = 10: 1 (v / v)) to obtain BOC-7 (75.4 g, yield 85%).

¹ H-NMR: δ 1.72 (s, 6H) 6.55-6.63 (m, 4H), 6.73 (dd, 1H), 6.81 (t, 1H), 7.02-7.05 (m, 2H), 7.20-7.23 (m, 3H), 7.36-7.41 (m, 2H), 7.51-7.69 (m, 4H), 7.77 (s, 1H), 7.87 (d, 1H), 8.05-8.12 (m, 3H), 10.1 (b, 1H)

Preparation 25 Synthesis of BOC-8

2-phenyl-8- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -5H-oxazolo [4,5-b] carbazole (39.4 g, 96.0 mmol) under nitrogen stream ), 2-bromo-9,9-dimethyl-10-phenyl-9,10-dihydroacridine (38.5 g, 105.6 mmol), Pd (PPh ₃ ) ₄ (5.55 g, 4.80 mmol), K ₂ CO ₃ (39.8 g , 288 mmol), 1,4-dioxane / H ₂ O (100 ml / 25 ml) were mixed and stirred at 120 ° C. for 4 hours. After the reaction was terminated and extracted with methylene chloride, MgSO ₄ was added and filtered. The solvent was removed from the organic layer and purified by column chromatography (Hexane: EA = 10: 1 (v / v)) to obtain BOC-8 (45.2 g, yield 83%).

¹ H-NMR: δ 1.72 (s, 6H) 6.55-6.63 (m, 4H), 6.73-6.81 (m, 2H), 7.02-7.05 (m, 2H), 7.20 (dd, 2H), 7.36-7.41 ( m, 3H), 7.51-7.55 (m, 3H), 7.61 (s, 1H), 7.69 (d, 1H), 7.77 (s, 1H), 7.87 (d, 1H), 8.05 (d, 2H), 10.1 (b, 1H)

Preparation 26 Synthesis of BTC-1 & BTC-2

Step 1 Synthesis of N- (2,4-dibromophenyl) benzothioamide

N- (2,4-dibromophenyl) benzamide (266.2 g, 0.75 mol) was added to the reactor, and toluene (3,000 ml) was added thereto, followed by stirring. Lawesson's reagent (229.2 g, 0.53 mol) was added dropwise to the reactor and stirred at 110 ° C. for 4 hours. After completion of the reaction, the mixture was extracted with methylene chloride and then water was removed with MgSO ₄ , purified by column chromatography (Hexane: EA = 7: 1 (v / v)) and purified by N- (2,4-dibromophenyl) benzothioamide ( 263.5 g, yield 95%).

¹ H-NMR: δ 6.41 (d, 1H), 7.29 (d, 1H), 7.44-7.45 (m, 3H), 7.75 (s, 1H), 7.98 (d, 2H), 8.59 (b, 1H)

<Step 2> Synthesis of 6-bromo-2-phenylbenzo [d] thiazole

N- (2,4-dibromophenyl) benzothioamide (263.5 g, 710 mmol), K ₂ CO ₃ (196.3 g, 1420 mmol) and DMSO (7100 ml) were mixed under nitrogen stream and stirred at 140 ° C. for 1.5 hours. After completion of the reaction, the mixture was extracted with ethyl acetate, followed by removing water with MgSO ₄ , and purified by column chromatography (Hexane: EA = 10: 1 (v / v)) to obtain 6-bromo-2-phenylbenzo [d] thiazole ( 156.6 g, yield 76%) was obtained.

¹ H-NMR: δ 7.41 (t, 1H) 7.51 (dd, 2H), 7.64 (d, 1H), 7.72 (d, 1H), 8.03 (d, 2H), 8.83 (s, 1H)

<Step 3> Synthesis of 2-phenyl-6- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) benzo [d] thiazole

6-bromo-2-phenylbenzo [d] thiazole (156.6 g, 540.0 mmol), 4,4,4 ', 4', 5,5, 5 ', 5'-octamethyl-2,2'-bi under nitrogen stream (1,3,2-dioxaborolane) (150.8 g, 594.0 mmol), Pd (dppf) Cl ₂ (62.4 g, 54.0 mmol), KOAc (152.5 g, 1.62 mol) and 1,4-Dioxane (2800 ml) Mix and stir at 130 ° C. for 12 h. After the reaction was completed, the mixture was extracted with ethyl acetate, followed by removing moisture with MgSO ₄ , and purified by column chromatography (Hexane: EA = 8: 1 (v / v)) to 2-phenyl-6- (4,4,5 , 5-tetramethyl-1,3,2-dioxaborolan-2-yl) benzo [d] thiazole (140.2 g, yield 77%) was obtained.

¹ H-NMR: δ 1.24 (s, 12H) 7.38 (d, 1H), 7.41 (t, 1H), 7.51 (dd, 2H), 7.75 (d, 1H), 7.95 (s, 1H), 8.03 (d , 2H)

Step 4 Synthesis of 6- (2-nitrophenyl) -2-phenylbenzo [d] thiazole

2-phenyl-6- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) benzo [d] thiazole (140.2 g, 415.7 mmol), 1-bromo-2 under nitrogen stream -nitrobenzene (92.4 g, 457.4 mmol), Pd (PPh ₃ ) ₄ (24.0 g, 20.8 mmol), K ₂ CO ₃ (143.7 g, 1.04 mol), 1,4-dioxane / H ₂ O (400 ml / 100 ml) were mixed and stirred at 120 ° C. for 4 hours. After the reaction was terminated and extracted with methylene chloride, MgSO ₄ was added and filtered. The solvent was removed from the obtained organic layer and purified by column chromatography (Hexane: EA = 6: 1 (v / v)) to give 6- (2-nitrophenyl) -2-phenylbenzo [d] thiazole (116.1 g, 84% yield). Got.

¹ H-NMR: δ 7.41-7.51 (m, 3H), 7.67 (dd, 1H), 7.77-7.90 (m, 3H), 8.00-8.05 (m, 4H), 8.34 (s, 1H)

Step 5 Synthesis of BTC-1 and BTC-2

6- (2-nitrophenyl) -2-phenylbenzo [d] thiazole (116.1 g, 349 mmol), triphenylphosphine (274.6 g, 1047 mmol) and 1,2-dichlorobenzene under nitrogen were added thereto and stirred for 12 hours. . After the reaction was completed, 1,2-dichlorobenzene was removed, extracted with dichloromethane, MgSO ₄ was added and filtered. The solvent was removed from the obtained organic layer, and then purified by column chromatography (Hexane: MC = 6: 1 (v / v)) to obtain BTC-1 (55.6 g, yield 53%) and BTC-2 (38.8g, yield 37%). Obtained.

¹ H-NMR of BTC-1: δ 7.29 (dd, 1H), 7.41-7.63 (m, 6H), 7.75 (d, 1H), 8.03-8.12 (m, 3H), 10.1 (b, 1H)

¹ H-NMR of BTC-2: δ 7.29 (dd, 1H), 7.41-7.51 (m, 4H), 7.63 (d, 1H), 8.03-8.12 (m, 4H), 8.23 (s, 1H), 10.1 (b, 1H)

Preparation 27 Synthesis of BTC-3

<Step 1> Synthesis of 6- (5-bromo-2-nitrophenyl) -2-phenylbenzo [d] thiazole

2-phenyl-6- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) benzo [d] thiazole (140.2 g, 415.7 mmol), 4-bromo-2 under nitrogen stream -iodo-1-nitrobenzene (150.0 g, 457.4 mmol), Pd (PPh ₃ ) ₄ (24.0 g, 20.8 mmol), K ₂ CO ₃ (143.7 g, 1.04 mol), 1,4-dioxane / H ₂ O ( 400 ml / 100 ml) were mixed and stirred at 120 ° C. for 4 hours. After the reaction was terminated and extracted with methylene chloride, MgSO ₄ was added and filtered. The solvent was removed from the organic layer and purified by column chromatography (Hexane: EA = 7: 1 (v / v)) to give 6- (5-bromo-2-nitrophenyl) -2-phenylbenzo [d] thiazole (143.5 g, Yield 84%).

¹ H-NMR: δ 7.41 (t, 1H), 7.51 (dd, 2H), 7.72 (s, 1H), 7.77 (d, 1H), 7.81 (d, 1H), 7.98 (d, 1H), 8.03 ( d, 2H), 8.21 (d, 1H), 8.34 (s, 1H)

Step 2 Synthesis of 7-bromo-2-phenyl-10H-thiazolo [5,4-a] carbazole with 8-bromo-2-phenyl-5H-thiazolo [4,5-b] carbazole

1,500 ml of 6- (5-bromo-2-nitrophenyl) -2-phenylbenzo [d] thiazole (143.5 g, 349 mmol), triphenylphosphine (274.6 g, 1047 mmol) and 1,2-dichlorobenzene under nitrogen stream Stir for hours. After the reaction was completed, 1,2-dichlorobenzene was removed, extracted with dichloromethane, MgSO ₄ was added and filtered. The solvent was removed from the obtained organic layer, and then purified by column chromatography (Hexane: MC = 5: 1 (v / v)) to obtain 7-bromo-2-phenyl-10H-thiazolo [5,4-a] carbazole (73.2 g, Yield 55%) and 8-bromo-2-phenyl-5H-thiazolo [4,5-b] carbazole (42.8g, yield 32%).

¹ H-NMR of 7-bromo-2-phenyl-10H-thiazolo [5,4-a] carbazole: δ 7.41-7.42 (m, 2H), 7.51-7.55 (m, 4H), 7.75 (d, 1H) , 8.03-8.05 (m, 3H), 10.1 (b, 1H)

¹ H-NMR of 8-bromo-2-phenyl-5H-thiazolo [4,5-b] carbazole: δ 7.41-7.42 (m, 2H), 7.51-7.55 (m, 3H), 8.03 (d, 2H) , 8.05 (s, 1H), 8.12 (s, 1H), 8.23 (s, 1H), 10.1 (b, 1H)

<Step 3> Synthesis of 2-phenyl-7- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -10H-thiazolo [5,4-a] carbazole

7-bromo-2-phenyl-10H-thiazolo [5,4-a] carbazole (73.2 g, 193.0 mmol), 4,4,4 ', 4', 5,5, 5 ', 5'- under nitrogen stream octamethyl-2,2'-bi (1,3,2-dioxaborolane) (53.9 g, 212.3 mmol), Pd (dppf) Cl ₂ (22.3 g, 19.3 mmol), KOAc (54.5 g, 579 mmol) and 1, 4-Dioxane (1000 ml) was mixed and stirred at 130 ° C. for 12 h. After the reaction was completed, the mixture was extracted with ethyl acetate, followed by removing moisture with MgSO ₄ , and purified by column chromatography (Hexane: EA = 8: 1 (v / v)) to 2-phenyl-7- (4,4,5 , 5-tetramethyl-1,3,2-dioxaborolan-2-yl) -10H-thiazolo [5,4-a] carbazole (66.6 g, yield 81%) was obtained.

¹ H-NMR: δ 1.24 (s, 12H) 7.41 (t, 1H), 7.51-7.55 (m, 4H), 7.63 (d, 1H), 7.75 (d, 1H), 7.98 (s, 1H), 8.03 (d, 2H), 10.1 (b, 1H)

Step 4 Synthesis of BTC-3

2-phenyl-7- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -10H-thiazolo [5,4-a] carbazole (66.6 g, 156.2 mmol) under a nitrogen stream ), iodobenzene (19.1 mL, 171.8 mmol), Pd (PPh ₃ ) ₄ (9.02 g, 7.81 mmol), K ₂ CO ₃ (53.8 g, 390.5 m mol), 1,4-dioxane / H ₂ O (160 ml / 40 ml) were mixed and stirred at 120 ° C. for 4 hours. After the reaction was terminated and extracted with methylene chloride, MgSO ₄ was added and filtered. The solvent was removed from the organic layer and purified by column chromatography (Hexane: EA = 8: 1 (v / v)) to obtain BTC-3 (50.0 g, yield 85%).

¹ H-NMR: δ 7.41-7.55 (m, 9H), 7.69-7.77 (m, 3H), 7.87 (d, 1H), 8.03 (d, 2H), 10.1 (b, 1H)

Preparation 28 Synthesis of BTC-4

<Step 1> Synthesis of 2-phenyl-8- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -5H-thiazolo [4,5-b] carbazole

8-bromo-2-phenyl-5H-thiazolo [4,5-b] carbazole (42.8 g, 112.8 mmol), 4,4,4 ', 4', 5,5, 5 ', 5'- under nitrogen stream octamethyl-2,2'-bi (1,3,2-dioxaborolane) (31.5 g, 124.2 mmol), Pd (dppf) Cl ₂ (13.1 g, 11.3 mmol), KOAc (31.9 g, 338.7 mmol) and 1, 4-Dioxane (700 ml) was mixed and stirred at 130 ° C. for 12 h. After the reaction was completed, the mixture was extracted with ethyl acetate, followed by removing moisture with MgSO ₄ , and purified by column chromatography (Hexane: EA = 8: 1 (v / v)) to 2-phenyl-8- (4,4,5 , 5-tetramethyl-1,3,2-dioxaborolan-2-yl) -5H-thiazolo [4,5-b] carbazole (40.9 g, yield 85%) was obtained.

¹ H-NMR: δ 1.24 (s, 12H) 7.41 (t, 1H), 7.50-7.51 (m, 3H), 7.63 (d, 1H), 7.98 (s, 1H), 8.03 (d, 2H), 8.12 (s, 1H), 8.23 (s, 1H), 10.1 (b, 1H)

<Step 2> Synthesis of BTC-4

2-phenyl-8- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -5H-thiazolo [4,5-b] carbazole (40.9 g, 96.0 mmol under nitrogen stream ), iodobenzene (11.8 mL, 105.6 mmol), Pd (PPh ₃ ) ₄ (5.55 g, 4.80 mmol), K ₂ CO ₃ (39.8 g, 288 mmol), 1,4-dioxane / H ₂ O (100 ml / 25 ml) were mixed and stirred at 120 ° C. for 4 hours. After the reaction was terminated and extracted with methylene chloride, MgSO ₄ was added and filtered. The solvent was removed from the organic layer and purified by column chromatography (Hexane: EA = 10: 1 (v / v)) to obtain BTC-4 (30.4 g, yield 84%).

¹ H-NMR: δ 7.41-7.52 (m, 8H), 7.69 (d, 1H) 7.77 (s, 1H), 7.87 (d, 1H), 8.03 (d, 2H), 8.12 (s, 1H), 8.23 (s, 1H), 10.1 (b, 1H)

Preparation Example 29 Synthesis of BTC-5

2-phenyl-7- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -10H-thiazolo [5,4-a] carbazole (66.6 g, 156.2 mmol) under a nitrogen stream ), 4-bromo-N, N-diphenylaniline (55.7 g, 171.8 mmol), Pd (PPh ₃ ) ₄ (9.02 g, 7.81 mmol), K ₂ CO ₃ (53.8 g, 390.5 mmol), 1,4-dioxane / H ₂ O (160 ml / 40 ml) was mixed and stirred at 120 ° C. for 4 hours. After the reaction was terminated and extracted with methylene chloride, MgSO ₄ was added and filtered. The solvent was removed from the organic layer and purified by column chromatography (Hexane: EA = 10: 1 (v / v)) to obtain BTC-5 (72.2 g, yield 85%).

¹ H-NMR: δ 6.63-6.69 (m, 6H), 6.81 (t, 2H), 7.20 (dd, 4H), 7.41 (t, 1H), 7.51-7.55 (m, 5H), 7.69 (d, 1H ), 7.75 (d, 1H), 7.77 (s, 1H), 7.87 (d, 1H), 8.03 (d, 2H), 10.1 (b, 1H)

Preparation Example 30 Synthesis of BTC-6

2-phenyl-8- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -5H-thiazolo [4,5-b] carbazole (40.9 g, 96.0 mmol under nitrogen stream ), 4-bromo-N, N-diphenylaniline (34.2 g, 105.6 mmol), Pd (PPh ₃ ) ₄ (5.55 g, 4.80 mmol), K ₂ CO ₃ (39.8 g, 288 mmol), 1,4-dioxane / H ₂ O (100 ml / 25 ml) was mixed and stirred at 120 ° C. for 4 hours. After the reaction was terminated and extracted with methylene chloride, MgSO ₄ was added and filtered. The solvent was removed from the organic layer and purified by column chromatography (Hexane: EA = 8: 1 (v / v)) to obtain BTC-6 (42.8 g, yield 81%).

¹ H-NMR: δ 6.63-6.69 (m, 6H), 6.81 (t, 2H), 7.20 (dd, 4H), 7.41 (t, 1H), 7.51-7.54 (m, 4H), 7.69 (d, 1H ), 7.77 (s, 1H), 7.87 (d, 1H), 8.03 (d, 2H), 8.12 (s, 1H), 8.23 (s, 1H), 10.1 (b, 1H)

Preparation Example 31 Synthesis of BTC-7

2-phenyl-7- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -10H-thiazolo [5,4-a] carbazole (66.6 g, 156.2 mmol) under a nitrogen stream ), 2-bromo-9,9-dimethyl-10-phenyl-9,10-dihydroacridine (62.6 g, 171.8 mmol), Pd (PPh ₃ ) ₄ (9.02 g, 7.81 mmol), K ₂ CO ₃ (53.8 g , 390.5 mmol), 1,4-dioxane / H ₂ O (160 ml / 40 ml) were mixed and stirred at 120 ° C. for 4 hours. After the reaction was terminated and extracted with methylene chloride, MgSO ₄ was added and filtered. The solvent was removed from the organic layer and purified by column chromatography (Hexane: EA = 12: 1 (v / v)) to obtain BTC-7 (79.3 g, yield 87%).

¹ H-NMR: δ 1.72 (s, 6H) 6.55-6.63 (m, 4H), 6.73 (dd, 1H), 6.81 (t, 1H), 7.02-7.05 (m, 2H), 7.20 (dd, 2H) , 7.36 (d, 1H), 7.41 (t, 1H), 7.51-7.61 (m, 4H), 7.69-7.75 (m, 3H), 7.87 (d, 1H), 8.03 (d, 2H), 10.1 (b , 1H)

Preparation 32 Synthesis of BTC-8

2-phenyl-8- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -5H-thiazolo [4,5-b] carbazole (40.9 g, 96.0 mmol under nitrogen stream ), 2-bromo-9,9-dimethyl-10-phenyl-9,10-dihydroacridine (38.5 g, 105.6 mmol), Pd (PPh ₃ ) ₄ (5.55 g, 4.80 mmol), K ₂ CO ₃ (39.8 g , 288 mmol), 1,4-dioxane / H ₂ O (100 ml / 25 ml) were mixed and stirred at 120 ° C. for 4 hours. After the reaction was terminated and extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent in the obtained organic layer was purified by column chromatography (Hexane: EA = 10: 1 (v / v)) to give BTC-8 (45.4 g, 81% yield).

¹ H-NMR: δ 1.72 (s, 6H) 6.55-6.63 (m, 4H), 6.73-6.81 (m, 2H), 7.02-7.05 (m, 2H), 7.20 (dd, 2H), 7.36-7.61 ( m, 5H), 7.69 (d, 1H), 7.77 (s, 1H), 7.87 (d, 1H), 8.03 (d, 2H), 8.12 (s, 1H), 8.23 (s, 1H), 10.1 (b , 1H)

Synthesis Example 1 Synthesis of Inv-1

PC-1 (3 g, 10.63 mmol), 3'-Bromo-biphenyl-4-carbonitrile (2.89 g, 11.20 mmol), Pd (OAc) ₂ (0.12 g, 5 mol%), NaO (t-) under nitrogen stream bu) (2.04 g, 21.25 mmol), P (t-bu) ₃ (0.21 g, 1.06 mmol) and Toluene (100 ml) were mixed and stirred at 110 ° C. for 12 h. After completion of the reaction, the mixture was extracted with ethyl acetate and then water was removed with MgSO ₄ , and purified by column chromatography (Hexane: EA = 2: 1 (v / v)) to obtain Inv-1 (4.02 g, yield 82). %) Was obtained.

GC-Mass (Theoretical value: 459.54 g / mol, Measured value: 459 g / mol)

Synthesis Example 2 Synthesis of Inv-2

Except for using 3'-Bromo-biphenyl-3,5-dicarbonitrile instead of 3'-Bromo-biphenyl-4-carbonitrile was carried out in the same manner as in Synthesis Example 1 Inv-2 (3.45 g, 67%).

GC-Mass (Theoretical value: 484.55 g / mol, Measured value: 484 g / mol)

Synthesis Example 3 Synthesis of Inv-3

Inv, a target compound, was prepared in the same manner as in Synthesis Example 1, except that PC-2 and 3'-Bromo-biphenyl-3-carbonitrile were used instead of PC-1 and 3'-Bromo-biphenyl-4-carbonitrile. -3 (4.15 g, 85%) was obtained.

GC-Mass (Theoretical value: 459.54 g / mol, Measured value: 459 g / mol)

Synthesis Example 4 Synthesis of Inv-4

Inv, a target compound, was prepared in the same manner as in Synthesis Example 1, except that 3'-Bromo-biphenyl-3-carbonitrile was used instead of 3'-Bromo-biphenyl-4-carbonitrile instead of PC-1. -4 (3.71 g, 76%) was obtained.

GC-Mass (Theoretical value: 459.54 g / mol, Measured value: 459 g / mol)

Synthesis Example 5 Synthesis of Inv-5

Except for using PC-4 instead of PC-1 was carried out the same procedure as in Synthesis Example 1 to obtain the target compound Inv-5 (4.20 g, 86%).

GC-Mass (Theoretical value: 459.54 g / mol, Measured value: 459 g / mol)

Synthesis Example 6 Synthesis of Inv-6

Inv-, the target compound, was prepared in the same manner as in Synthesis Example 1, except that PC-5 and 8-Bromo-dibenzothiophene-2-carbonitrile were used instead of PC-1 and 3'-Bromo-biphenyl-4-carbonitrile. 6 (3.28 g, 63%) was obtained.

GC-Mass (Theoretical value: 489.59 g / mol, Measured value: 489 g / mol)

Synthesis Example 7 Synthesis of Inv-7

Inv- as a target compound was performed in the same manner as in Synthesis Example 1, except that PC-6 and 8-Bromo-dibenzofuran-2-carbonitrile were used instead of PC-1 and 3'-Bromo-biphenyl-4-carbonitrile. 7 (3.07 g, 61%) was obtained.

GC-Mass (Theoretical value: 473.52 g / mol, Measured value: 473 g / mol)

Synthesis Example 8 Synthesis of Inv-8

Under nitrogen stream, mix PC-7 (5 g, 13.84 mmol), phenylboronic acid (2.03 g, 16.61 mmol), NaOH (1.66 g, 41.52 mmol) and THF / H ₂ O (100 ml / 500 ml), Pd (PPh ₃ ) ₄ (0.80 g, 5 mol%) was added at 40 ° C. and stirred at 80 ° C. for 12 hours. After completion of the reaction, the mixture was extracted with methylene chloride, MgSO ₄ was added and filtered. The solvent was removed from the obtained organic layer, and then purified by column chromatography (Hexane: EA = 3: 1 (v / v)) to obtain PC-7-1. Thereafter, PC-7-1 was used instead of PC-1 to obtain Inv-8 (4.67 g, 82%) as a target compound.

GC-Mass (Theoretical value: 535.64 g / mol, Measured value: 535 g / mol)

Synthesis Example 9 Synthesis of Inv-9

Inv-9 (5.59 g, 75%) was obtained by the same procedure as in Synthesis Example 8, except that 9-phenyl-9H-carbazol-3-ylboronic acid was used instead of phenylboronic acid.

GC-Mass (Theoretical value: 700.83 g / mol, Measured value: 700 g / mol)

Synthesis Example 10 Synthesis of Inv-10

Exc 10 (4.44 g, 78%) was obtained by the same procedure as in Synthesis Example 8, except that PC-8 was used instead of PC-1.

GC-Mass (Theoretical value: 535.64 g / mol, Measured value: 535 g / mol)

Synthesis Example 11 Synthesis of Inv-11

The same procedure as in Synthesis Example 8 was performed except that PC-8 and 9- (4,6-diphenylpyridin-2-yl) -9H-carbazol-3-ylboronic acid were used instead of PC-1 and phenylboronic acid. Inv-11 (6.90 g, 76%) was obtained as the target compound.

GC-Mass (Theoretical value: 854.01 g / mol, Measured value: 854 g / mol)

Synthesis Example 12 Synthesis of Inv-12

Inv-12 (3.32 g) was prepared by the same procedure as in Synthesis Example 1, except that PC-9 and 4-Bromo-benzonitrile were used instead of PC-1 and 3'-Bromo-biphenyl-4-carbonitrile. , 68%).

GC-Mass (Theoretical value: 459.54 g / mol, Measured value: 459 g / mol)

Synthesis Example 13 Synthesis of Inv-13

Except for using PC-10 and 3'-Bromo-biphenyl-3,5-dicarbonitrile instead of PC-1 and 3'-Bromo-biphenyl-4-carbonitrile was carried out the same procedure as in Synthesis Example 1 Phosphorus Inv-13 (3.75 g, 63%) was obtained.

GC-Mass (Theoretical value: 560.65 g / mol, Measured value: 560 g / mol)

Synthesis Example 14 Synthesis of Inv-14

Inv, a target compound, was prepared in the same manner as in Synthesis Example 1, except that PC-11 and 3'-Bromo-biphenyl-3-carbonitrile were used instead of PC-1 and 3'-Bromo-biphenyl-4-carbonitrile. -14 (3.75 g, 63%) was obtained.

GC-Mass (Theoretical value: 535.64 g / mol, Measured value: 535 g / mol)

Synthesis Example 15 Synthesis of Inv-15

Except for using PC-12 instead of PC-1 was carried out the same procedure as in Synthesis Example 1 to obtain the target compound Inv-15 (3.75 g, 78%).

GC-Mass (Theoretical value: 611.73 g / mol, Measured value: 611 g / mol)

Synthesis Example 16 Synthesis of Inv-16

Inv-16 (3.47 g) was prepared by the same procedure as in Synthesis Example 1, except that PC-13 and 3-Bromo-benzonitrile were used instead of PC-1 and 3'-Bromo-biphenyl-4-carbonitrile. , 61%).

GC-Mass (Theoretical value: 535.64 g / mol, Measured value: 535 g / mol)

Synthesis Example 17 Synthesis of Inv-17

Exc-17 (3.47 g, 61%) was obtained by the same procedure as in Synthesis Example 1, except that IC-1 was used instead of PC-1.

GC-Mass (Theoretical value: 460.53 g / mol, Measured value: 460 g / mol)

Synthesis Example 18 Synthesis of Inv-18

Except for using IC-1 and 5-bromo-1,1 ', 3', 1 ''-Terphenyl-4,4 ''-dicarbonitrile instead of PC-1 and 3'-Bromo-biphenyl-4-carbonitrile Was carried out in the same manner as in Synthesis Example 1 to obtain Inv-18 (3.94 g, 66%) as a target compound.

GC-Mass (Theoretical value: 561.63 g / mol, Measured value: 561 g / mol)

Synthesis Example 19 Synthesis of Inv-19

Inv, a target compound, was prepared in the same manner as in Synthesis Example 1, except that IC-2 and 4'-Bromo-biphenyl-3-carbonitrile were used instead of PC-1 and 3'-Bromo-biphenyl-4-carbonitrile. -19 (4.01 g, 82%) was obtained.

GC-Mass (Theoretical value: 460.53 g / mol, Measured value: 460 g / mol)

Synthesis Example 20 Synthesis of Inv-20

Exc-20 (3.72 g, 76%) was obtained by the same procedure as in Synthesis Example 1, except that IC-3 was used instead of PC-1.

GC-Mass (Theoretical value: 460.53 g / mol, Measured value: 460 g / mol)

Synthesis Example 21 Synthesis of Inv-21

The same procedure as in Synthesis Example 1 except for using IC-4 and 7-Bromo-9,9-dimethyl-9H-fluorene-2-carbonitrile instead of PC-1 and 3'-Bromo-biphenyl-4-carbonitrile Inv-21 (3.99, 75%) was obtained as the target compound.

GC-Mass (Theoretical value: 500.59 g / mol, Measured value: 500 g / mol)

Synthesis Example 22 Synthesis of Inv-22

Inv- as the target compound was carried out in the same manner as in Synthesis Example 1, except that IC-5 and 7-Bromo-triphenylene-2-carbonitrile were used instead of PC-1 and 3'-Bromo-biphenyl-4-carbonitrile. 22 (3.86, 68%) was obtained.

GC-Mass (Theoretical value: 534.61 g / mol, Measured value: 534 g / mol)

Synthesis Example 23 Synthesis of Inv-23

Exc-23 (3.29 g, 67%) was obtained by the same procedure as in Synthesis Example 1, except that BOC-1 was used instead of PC-1.

GC-Mass (Theoretical value: 461.51 g / mol, Measured value: 461 g / mol)

Synthesis Example 24 Synthesis of Inv-24

Inv, a target compound, was prepared in the same manner as in Synthesis Example 1, except that BOC-1 and 3'-Bromo-biphenyl-3-carbonitrile were used instead of PC-1 and 3'-Bromo-biphenyl-4-carbonitrile. -24 (3.53, 72%) was obtained.

GC-Mass (Theoretical value: 461.51 g / mol, Measured value: 461 g / mol)

Synthesis Example 25 Synthesis of Inv-25

Synthesis Example 1 except for using BOC-2 and 2'-bromo-9,9'-Spirobi [9H-fluorene] -2-carbonitrile instead of PC-1 and 3'-Bromo-biphenyl-4-carbonitrile Inv-25 (5.04, 76%) as a target compound was obtained.

GC-Mass (Theoretical value: 623.70 g / mol, Measured value: 623 g / mol)

Synthesis Example 26 Synthesis of Inv-26

Except for using BOC-2 and 3'-Bromo-biphenyl-3,5-dicarbonitrile instead of PC-1 and 3'-Bromo-biphenyl-4-carbonitrile, the same procedure as in Synthesis Example 1 was carried out. Phosphorus Inv-26 (3.26, 63%) was obtained.

GC-Mass (Theoretical value: 486.52 g / mol, Measured value: 486 g / mol)

Synthesis Example 27 Synthesis of Inv-27

Except for using BOC-3 and 4-Bromo-benzonitrile instead of PC-1 and 3'-Bromo-biphenyl-4-carbonitrile, the same procedure as in Synthesis Example 1 was carried out to obtain Inv-27 (3.39, 69%).

GC-Mass (Theoretical value: 461.51 g / mol, Measured value: 461 g / mol)

Synthesis Example 28 Synthesis of Inv-28

Inv, a target compound, was prepared in the same manner as in Synthesis Example 1, except that BOC-3 and 3'-Bromo-biphenyl-3-carbonitrile were used instead of PC-1 and 3'-Bromo-biphenyl-4-carbonitrile. -28 (4.29, 75%) was obtained.

GC-Mass (Theoretical value: 537.61 g / mol, Measured value: 537 g / mol)

Synthesis Example 29 Synthesis of Inv-29

Exc-29 (4.69, 82%) was obtained by the same procedure as in Synthesis Example 1, except that BOC-4 was used instead of PC-1.

GC-Mass (Theoretical value: 537.61 g / mol, Measured value: 537 g / mol)

Synthesis Example 30 Synthesis of Inv-30

Synthesis Example 1 except for using BOC-4 and 9- (3-Bromo-phenyl) -9H-carbazole-3,6-dicarbonitrile instead of PC-1 and 3'-Bromo-biphenyl-4-carbonitrile The same procedure was followed to obtain the target compound Inv-30 (3.67, 53%).

GC-Mass (Theoretical value: 651.71 g / mol, Measured value: 651 g / mol)

Synthesis Example 31 Synthesis of Inv-31

Except for using BOC-5 and 4-Bromo-benzonitrile instead of PC-1 and 3'-Bromo-biphenyl-4-carbonitrile, the same procedure as in Synthesis Example 1 was carried out to obtain Inv-31 (4.14, 62%).

GC-Mass (Theoretical value: 628.72 g / mol, Measured value: 628 g / mol)

Synthesis Example 32 Synthesis of Inv-32

Exc-32 (4.35, 58%) was obtained by the same procedure as in Synthesis Example 1, except that BOC-5 was used instead of PC-1.

GC-Mass (Theoretical value: 704.82 g / mol, Measured value: 704 g / mol)

Synthesis Example 33 Synthesis of Inv-33

Exc-33 (4.57, 61%) was obtained by the same procedure as in Synthesis Example 1, except that BOC-6 was used instead of PC-1.

GC-Mass (Theoretical value: 704.82 g / mol, Measured value: 704 g / mol)

Synthesis Example 34 Synthesis of Inv-34

Except for using BOC-7 and 4-Bromo-benzonitrile instead of PC-1 and 3'-Bromo-biphenyl-4-carbonitrile, the same procedure as in Synthesis Example 1 was carried out to obtain Inv-34 (4.55, 64%).

GC-Mass (Theoretical value: 668.78 g / mol, Measured value: 668 g / mol)

Synthesis Example 35 Synthesis of Inv-35

Except for using BOC-8 instead of PC-1 was carried out the same procedure as in Synthesis Example 1 to obtain the target compound Inv-35 (3.80, 48%).

GC-Mass (Theoretical value: 744.88 g / mol, Measured value: 744 g / mol)

Synthesis Example 36 Synthesis of Inv-36

Except for using BTC-1 instead of PC-1 was carried out the same procedure as in Synthesis Example 1 to obtain the target compound Inv-36 (3.25 g, 64%).

GC-Mass (Theoretical value: 477.58 g / mol, Measured value: 477 g / mol)

Synthesis Example 37 Synthesis of Inv-37

Inv, a target compound, was prepared in the same manner as in Synthesis Example 1, except that BTC-1 and 3'-Bromo-biphenyl-3-carbonitrile were used instead of PC-1 and 3'-Bromo-biphenyl-4-carbonitrile. -37 (3.81, 75%) was obtained.

GC-Mass (Theoretical value: 477.58 g / mol, Measured value: 477 g / mol)

Synthesis Example 38 Synthesis of Inv-38

Synthesis Example 1 except for using BTC-2 and 2'-bromo-9,9'-Spirobi [9H-fluorene] -2-carbonitrile instead of PC-1 and 3'-Bromo-biphenyl-4-carbonitrile Inv-38 (4.83, 71%) was obtained by the same procedure as the target compound.

GC-Mass (Theoretical value: 639.77 g / mol, Measured value: 639 g / mol)

Synthesis Example 39 Synthesis of Inv-39

Except for using BTC-2 and 3'-Bromo-biphenyl-3,5-dicarbonitrile instead of PC-1 and 3'-Bromo-biphenyl-4-carbonitrile, the same procedure as in Synthesis Example 1 was carried out. Phosphorus Inv-39 (3.10, 58%) was obtained.

GC-Mass (Theoretical value: 502.59 g / mol, Measured value: 502 g / mol)

Synthesis Example 40 Synthesis of Inv-40

Except for using BTC-3 and 4-Bromo-benzonitrile instead of PC-1 and 3'-Bromo-biphenyl-4-carbonitrile, the same procedure as in Synthesis Example 1 was carried out to obtain Inv-40 (3.55, 70%).

GC-Mass (Theoretical value: 477.58 g / mol, Measured value: 477 g / mol)

Synthesis Example 41 Synthesis of Inv-41

Inv, a target compound, was prepared in the same manner as in Synthesis Example 1, except that BTC-3 and 3'-Bromo-biphenyl-3-carbonitrile were used instead of PC-1 and 3'-Bromo-biphenyl-4-carbonitrile. -41 (4.47, 76%).

GC-Mass (Theoretical value: 553.67 g / mol, Measured value: 553 g / mol)

Synthesis Example 42 Synthesis of Inv-42

Except for using BTC-4 instead of PC-1 was carried out the same procedure as in Synthesis Example 1 to obtain the target compound Inv-42 (4.65, 79%).

GC-Mass (Theoretical value: 553.67 g / mol, Measured value: 553 g / mol)

Synthesis Example 43 Synthesis of Inv-43

Synthesis Example 1 except that BTC-4 and 9- (3-Bromo-phenyl) -9H-carbazole-3,6-dicarbonitrile were used instead of PC-1 and 3'-Bromo-biphenyl-4-carbonitrile. The same procedure was followed to obtain the target compound Inv-43 (3.41, 48%).

GC-Mass (Theoretical value: 667.78 g / mol, Measured value: 667 g / mol)

Synthesis Example 44 Synthesis of Inv-44

Except for using BTC-5 and 4-Bromo-benzonitrile instead of PC-1 and 3'-Bromo-biphenyl-4-carbonitrile, the same procedure as in Synthesis Example 1 was carried out to obtain Inv-44 (4.39, 64%).

GC-Mass (Theoretical value: 644.79 g / mol, Measured value: 644 g / mol)

Synthesis Example 45 Synthesis of Inv-45

Except for using BTC-5 instead of PC-1 was carried out the same procedure as in Synthesis Example 1 to obtain the target compound Inv-45 (4.83, 63%).

GC-Mass (Theoretical value: 720.88 g / mol, Measured value: 720 g / mol)

Synthesis Example 46 Synthesis of Inv-46

Except for using BTC-6 instead of PC-1 was carried out the same procedure as in Synthesis Example 1 to obtain the target compound Inv-46 (4.75, 62%).

GC-Mass (Theoretical value: 720.88 g / mol, Measured value: 720 g / mol)

Synthesis Example 47 Synthesis of Inv-47

Except for using BOC-7 and 4-Bromo-benzonitrile instead of PC-1 and 3'-Bromo-biphenyl-4-carbonitrile, the same procedure as in Synthesis Example 1 was carried out to obtain Inv-47 (4.66, 64%).

GC-Mass (Theoretical value: 684.86 g / mol, Measured value: 684 g / mol)

Synthesis Example 48 Synthesis of Inv-48

Except for using BTC-8 instead of PC-1 was carried out the same procedure as in Synthesis Example 1 to obtain the target compound Inv-48 (3.72, 46%).

GC-Mass (Theoretical value: 760.95 g / mol, Measured value: 760 g / mol)

Examples 1 to 48 Fabrication of Green Organic Electroluminescent Devices

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

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

M-MTDATA (60 nm) / TCTA (80 nm) / 90% Inv-1 to Inv-48 compound + 10% Ir (ppy) ₃ (30 nm) / BCP (ITO transparent substrate (electrode) thus prepared) 10 nm) / Alq ₃ (30 nm) / LiF (1 nm) / Al (200 nm) was laminated in order to manufacture a device.

Comparative Example 1 Fabrication of Green Organic Electroluminescent Device

A device was manufactured in the same manner as in Example 1, except for using CBP instead of the compound Inv-1 as a light emitting host material when forming the emission layer.

The structures of m-MTDATA, TCTA, Ir (ppy) ₃ , BCP and CBP used in Examples 1 to 48 and Comparative Example 1 are as follows.

[Evaluation Example]

For each of the green organic electroluminescent devices prepared in Examples 1 to 48 and Comparative Example 1, the driving voltage, current efficiency, and emission peak at a current density of 10 mA / cm 2 were measured, and the results are shown in Table 1 below. .

Table 1 Sample Host Driving voltage (V) Light emitting peak (nm) Current efficiency (cd / A) Example 1 Inv-1 6.66 516 42.6 Example 2 Inv-2 6.91 517 39.4 Example 3 Inv-3 6.85 516 38.8 Example 4 Inv-4 6.86 516 43.5 Example 5 Inv-5 6.91 517 42.1 Example 6 Inv-6 6.85 516 42.6 Example 7 Inv-7 6.63 515 39.4 Example 8 Inv-8 6.75 515 38.8 Example 9 Inv-9 6.85 516 40.9 Example 10 Inv-10 6.63 517 42.1 Example 11 Inv-11 6.75 516 42.6 Example 12 Inv-12 6.73 517 39.4 Example 13 Inv-13 6.75 515 38.8 Example 14 Inv-14 6.63 516 40.9 Example 15 Inv-15 6.75 517 41.2 Example 16 Inv-16 6.73 516 39.2 Example 17 Inv-17 6.75 517 41.1 Example 18 Inv-18 6.81 517 42.0 Example 19 Inv-19 6.89 517 41.1 Example 20 Inv-20 6.81 518 40.9 Example 21 Inv-21 6.64 516 41.7 Example 22 Inv-22 6.66 516 41.3 Example 23 Inv-23 6.69 516 42.2 Example 24 Inv-24 6.83 516 41.5 Example 25 Inv-25 6.69 517 39.8 Example 26 Inv-26 6.65 515 40.5 Example 27 Inv-27 6.68 516 40.9 Example 28 Inv-28 6.61 518 41.1 Example 29 Inv-29 6.73 517 40.9 Example 30 Inv-30 6.73 516 41.8 Example 31 Inv-31 6.68 518 41.3 Example 32 Inv-32 6.62 516 42.8 Example 33 Inv-33 6.61 516 41.3 Example 34 Inv-34 6.83 516 39.8 Example 35 Inv-35 6.72 517 41.3 Example 36 Inv-36 6.69 516 42.2 Example 37 Inv-37 6.65 517 41.3 Example 38 Inv-38 6.68 517 39.8 Example 39 Inv-39 6.61 518 40.5 Example 40 Inv-40 6.73 516 40.9 Example 41 Inv-41 6.68 516 40.9 Example 42 Inv-42 6.62 518 39.8 Example 43 Inv-43 6.61 516 40.5 Example 44 Inv-44 6.82 517 40.9 Example 45 Inv-45 6.85 517 38.9 Example 46 Inv-46 6.63 516 42.0 Example 47 Inv-47 6.68 517 41.3 Example 48 Inv-48 6.91 518 39.8 Comparative Example 1 CBP 6.93 516 38.1

As shown in Table 1, when the compound according to the present invention is used for the light emitting layer of the green organic electroluminescent device (Examples 1 to 48), the efficiency and driving voltage are superior to those when using the conventional CBP (Comparative Example 1). You can see that.

Since the compound of the present invention has excellent thermal stability, electron and hole transport ability, light emitting ability, and the like, it can be usefully applied as an organic material layer material of an organic EL device.

In addition, the organic electroluminescent device including the compound of the present invention in the organic material layer can be effectively applied to a full color display panel since the aspects such as light emission performance, driving voltage, lifetime, and efficiency are greatly improved.

Claims (9)

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

In Chemical Formula 1, X ₁ is selected from the group consisting of O, S, Se, N (Ar ₁ ), C (Ar ₂ ) (Ar ₃ ) and Si (Ar ₄ ) (Ar ₅ ), X ₂ and X ₃ are each independently N or C (R ₂ ), Y ₁ to Y ₄ are each independently N or C (R ₁ ), and at least one of Y ₁ and Y ₂ , Y ₂ and Y _3, and Y ₃ and Y ₄ forms a condensed ring represented by Formula 2 below. and, [Formula 2]

In Chemical Formula 2, Dotted line is a portion that is bonded to the compound of Formula 1, X ₄ is selected from the group consisting of O, S, Se, N (Ar ₁ ), C (Ar ₂ ) (Ar ₃ ) and Si (Ar ₄ ) (Ar ₅ ), Y ₅ to Y ₈ are each independently N or C (R ₃ ), At least one of X ₁ and X ₄ is N (Ar ₁ ), Wherein R ₁ to R ₃ and Ar ₁ to Ar ₅ are each independently, hydrogen, deuterium, halogen group, nitro group, amino group, C ₁ ~ C ₄₀ alkyl group, C ₂ ~ C ₄₀ alkenyl group, C ₂ ~ C ₄₀ alkynyl group, C ₃ to C ₄₀ cycloalkyl group, nuclear atom 3 to 40 heterocycloalkyl group, C ₆ to C ₆₀ aryl group, nuclear atom 5 to 60 heteroaryl group, C ₁ to C ₄₀ Alkyloxy group, C ₆ ~ C ₆₀ aryloxy group, C ₁ ~ C ₄₀ alkylsilyl group, C ₆ ~ C ₆₀ arylsilyl group, C ₁ ~ C ₄₀ alkyl boron group, C ₆ ~ C ₆₀ the arylboronic group, C ₁ ~ C ₄₀ of the phosphine group, is selected from the group consisting of an aryl amine of the C ₁ ~ C ₄₀ phosphine oxide group, and a C ₆ ~ C ₆₀ of the, at this time, R ₁ to R ₃ and Ar ₁ At least one of Ar ₅ is a C ₆ ~ C ₆₀ Aryl group substituted with a cyano group or a heteroaryl group having 5 to 60 nuclear atoms substituted with a cyano group, R ₁ to R ₃ form or not form a condensed ring with an adjacent group, The alkyl group, alkenyl group, alkynyl group, cycloalkyl group, heterocycloalkyl group, aryl group, heteroaryl group, alkyloxy group, aryloxy group, alkylsilyl group, arylsilyl group of R ₁ to R ₃ and Ar ₁ to Ar ₅ , Alkyl boron group, aryl boron group, phosphine group, phosphine oxide group and arylamine group are each independently deuterium, halogen group, nitro group, amino group, C ₁ ~ C ₄₀ alkyl group, C ₂ ~ C ₄₀ alkenyl group , C ₂ ~ C ₄₀ Alkynyl group, C ₃ ~ C ₄₀ Cycloalkyl group, C ₃ ~ C ₄₀ heterocycloalkyl group, C ₆ ~ C ₆₀ Aryl group, Nuclear atoms 5 to 60 heteroaryl group, C ₁ -C ₄₀ alkyloxy group, C ₆ -C ₆₀ aryloxy group, C ₁ -C ₄₀ alkylsilyl group, C ₆ -C ₆₀ arylsilyl group, C ₁ -C ₄₀ alkylboron group, C ₆ ~ C ₆₀ aryl boron group, C ₁ ~ C ₄₀ of the phosphine group, C ₁ ~ C ₄₀ phosphine oxide group, and a C ₆ ~ substituted by one or more selected from the group consisting of an aryl amine of the C ₆₀ of the Or unsubstituted. The method of claim 1, Compound represented by the formula (1) is a compound selected from the group consisting of compounds represented by the following formula 1a to 1f. [Formula 1a]

[Formula 1b]

[Formula 1c]

[Formula 1d]

[Formula 1e]

[Formula 1f]

In Chemical Formulas 1a to 1f, X ₁ to X ₄ and Y ₁ to Y ₈ are as defined in claim 1. The method of claim 1, The compound represented by Formula 1 is a compound selected from the group consisting of compounds represented by the following formulas B-1 to B-30.

In Chemical Formulas B-1 to B-30, Ar ₁ and R ₁ to R ₃ are as defined in claim 1, A plurality of R ₁ are the same or different from each other, a plurality of R ₂ are the same or different from each other, and a plurality of R ₃ are the same or different from each other. The method of claim 1, Ar ₁ is a C ₆ ~ C ₆₀ aryl group substituted with a cyano group, or a heteroaryl group having 5 to 60 nuclear atoms substituted with a cyano group. According to the first, Ar ₁ to Ar ₅ are each independently a group consisting of a C ₆ ~ C ₆₀ aryl group, a heteroaryl group of 5 to 60 nuclear atoms, a C ₆ ~ C ₆₀ arylamine group and a C ₆ ~ C ₆₀ arylsilyl group Compound selected from. The method of claim 1, R ₁ to R ₃ are each independently hydrogen, halogen, cyano group, C ₁ ~ C ₄₀ alkyl group, C ₆ ~ C ₆₀ aryl group, nuclear atoms 5 to 60 heteroaryl group and C ₆ ~ C ₆₀ A compound selected from the group consisting of arylamine groups. An organic electroluminescent device comprising an anode, a cathode, and at least one organic material layer interposed between the anode and the cathode. At least one of the one or more organic material layers is an organic electroluminescent device comprising the compound according to any one of claims 1 to 6. The method of claim 7, wherein The organic material layer containing the compound is an organic electroluminescent device selected from the group consisting of a hole injection layer, a hole transport layer, an electron transport layer, an electron injection layer and a light emitting layer. The method of claim 8, The organic material layer containing the compound is a light emitting layer, The compound is an organic electroluminescent device which is a phosphorescent host of the light emitting layer.