KR101622822B1 - Organic compounds and organic electro luminescence device comprising the same - Google Patents

Abstract

The present invention relates to a novel compound and an organic electroluminescent device including the same, and the compound according to the present invention is used for an organic compound layer, preferably a light emitting layer, of an organic electroluminescent device, And the like can be improved.

Description

TECHNICAL FIELD [0001] The present invention relates to an organic compound and an organic electroluminescent device including the organic compound.

The present invention relates to a novel organic compound and an organic electroluminescent device including the same.

In the organic electroluminescent device, when a voltage is applied between two electrodes, holes are injected into the organic layer in the anode, and electrons are injected into the organic layer in the cathode. When the injected holes and electrons meet, an exciton is formed. When the exciton falls to the ground state, light is emitted. The material contained in the organic material layer may be classified into a light emitting material, a hole injecting material, a hole transporting material, an electron transporting material, an electron injecting material, or the like depending on its function.

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

The dopant material can be divided into a fluorescent dopant using an organic material and a phosphorescent dopant using a metal complex compound containing heavy atoms such as Ir and Pt. Since the phosphorescent dopant can theoretically improve the luminous efficiency up to 4 times as compared with the fluorescent dopant, studies on the phosphorescent dopant as well as the phosphorescent host have been conducted.

Currently, anthracene derivatives are known as fluorescent dopant / host materials used in the light emitting layer. As phosphorescent dopant materials used for the light emitting layer, metal complex compounds including Ir such as Firpic, Ir (ppy) ₃ , (acac) Ir (btp) ₂ and the like are known. As phosphorescent host materials, 4,4-dicarbazolybiphenyl (CBP) is known.

However, existing materials have advantages in terms of light emission characteristics, but their thermal stability is lowered due to their low glass transition temperature, which is not satisfactory in terms of lifetime of the organic electroluminescent device.

It is an object of the present invention to provide a novel organic compound having a high glass transition temperature and excellent thermal stability.

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

The present invention provides a compound represented by the following formula (1).

In 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 );

L is a single bond or a substituted or unsubstituted C ₆ -C ₆₀ arylene group and a substituted or unsubstituted heteroarylene group having 5 to 60 nucleus atoms,

In this case, L is connected to one carbon selected from the R ₇ to R ₁₀ positions, and at the same time, connected to one carbon or nitrogen selected from the R ₁₁ to R ₂₁ positions, but there is no substituent at a position connected to L ;

Ar ₁ to Ar ₅ are the same or different, each independently represent a substituted or unsubstituted C ₁ ~ C ₄₀ alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted of C ₂ ~ C ₄₀ unsubstituted C ₂ ~ of aryl of C ₄₀ alkynyl group, a substituted or unsubstituted C ₆ ~ C ₄₀ aryl group, a substituted or unsubstituted nuclear atoms of 5 to 40 heteroaryl group, a substituted or unsubstituted in the ring C ₆ ~ C ₄₀ of the oxy group , A substituted or unsubstituted C ₁ to C ₄₀ alkyloxy group, a substituted or unsubstituted C ₆ to C ₄₀ arylamine group, a substituted or unsubstituted C ₃ to C ₄₀ cycloalkyl group, a substituted or unsubstituted A substituted or unsubstituted C ₁ to C ₄₀ alkylsilyl group, a substituted or unsubstituted C ₁ to C ₄₀ alkylboron group, a substituted or unsubstituted C ₆ to C ₄₀ of the arylboronic group, a substituted or unsubstituted C ₆ ~ C ₄₀ aryl phosphine group, aryl phosphine oxide substituted or unsubstituted C ₆ ~ C ₄₀ group and A substituted or unsubstituted C ₆ to C ₄₀ arylsilyl group;

R ₁ to R ₂₁ are the same or different from each other and each independently represents hydrogen, deuterium (D), halogen, cyano group, substituted or unsubstituted C ₁ to C ₄₀ alkyl group, substituted or unsubstituted C ₂ to C ₄₀ A substituted or unsubstituted C ₂ to C ₄₀ alkynyl group, a substituted or unsubstituted C ₆ to C ₄₀ aryl group, a substituted or unsubstituted heteroaryl group having 5 to 40 nucleus atoms, a substituted or unsubstituted C ₂ to C ₄₀ alkynyl group, An unsubstituted C ₆ to C ₄₀ aryloxy group, a substituted or unsubstituted C ₁ to C ₄₀ alkyloxy group, a substituted or unsubstituted C ₆ to C ₄₀ arylamine group, a substituted or unsubstituted C ₃ to C ₄₀ aryloxy group, ~ C ₄₀ cycloalkyl group, a substituted or unsubstituted nuclear atoms of 3 to 40 heterocycloalkyl group, a substituted or unsubstituted C ₁ ~ C ₄₀ alkyl silyl group, a substituted or unsubstituted C for ₁ ~ C ₄₀ alkyl boron group, a substituted or unsubstituted C ₆ ~ C ₄₀ aryl boron group, a substituted or unsubstituted C ₆ ~ C ₄₀ aryl phosphine group, a substituted or unsubstituted C ₆ of ring ~ C ₄₀ aryl phosphine oxide group, and a substituted or unsubstituted C ₆ ~ selected from the group consisting of C ₄₀ or aryl silyl, or adjacent groups to be bonded to form a condensed ring;

The alkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group, aryloxy group, alkyloxy group, arylamine group of Ar ₁ to Ar ₅ and R ₁ to R ₂₁ of L, , a cycloalkyl group, a heterocycloalkyl group, alkylsilyl group, an alkyl boron group, an aryl boron group, an aryl phosphine group, aryl phosphine oxide group and an aryl silyl group each independently selected from deuterium, halogen, a cyano group, an alkyl group of C ₁ ~ C ₄₀ , A C ₂ to C ₄₀ alkenyl group, a C ₂ to C ₄₀ alkynyl group, a C ₆ to C ₄₀ aryl group, a heteroaryl group having 5 to 40 nuclear atoms, a C ₆ to C ₄₀ aryloxy group, a C _A C ₁ to C ₄₀ alkyloxy group, a C ₆ to C ₄₀ arylamine group, a C ₃ to C ₄₀ cycloalkyl group, a heterocyclic cycloalkyl group having 3 to 40 nuclear atoms, a C ₁ to C ₄₀ alkylsilyl group, a C ₁ ~ C ₄₀ group of an alkyl boron, C ₆ ~ C ₄₀ group of the arylboronic, C ₆ ~ C ₄₀ aryl phosphine group, C ₆ ~ C ₄₀ aryl phosphine oxide group, and a C ₆ ~ C ₄₀ aryl silyl group of the When substituted by one or more substituent species selected from the group true or lure is unsubstituted, wherein the substituent is a plurality, they may be the same or different from each other.

In addition, the present invention is characterized in that it includes a cathode, a cathode, and at least one organic layer interposed between the anode and the cathode, wherein at least one of the one or more organic layers includes a compound represented by the above formula An organic electroluminescent device is provided.

According to an embodiment of the present invention, the one or more organic layers include a hole injecting layer, a hole transporting layer, a light emitting layer, an electron transporting layer, and an electron injecting layer. Is a phosphorescent light-emitting layer).

According to another example of the present invention, the one or more organic layers may include a hole injecting layer, a hole transporting layer, a light emitting auxiliary layer, a light emitting layer, an electron transporting layer, and an electron injecting layer. At this time, the one or more organic layers including the compound represented by Formula 1 is a light-emitting auxiliary layer.

According to another embodiment of the present invention, the one or more organic layers may include a hole injection layer, a hole transport layer, a light emitting layer, a life improving layer, an electron transport layer, and an electron injection layer. At this time, one or more organic layers including the compound represented by Formula 1 is a life improving layer.

The compound represented by the general formula (1) of the present invention is excellent in thermal stability and phosphorescence properties and can be used as a material for an organic material layer of an organic electroluminescent device. In particular, when the compound represented by Formula 1 of the present invention is used as a phosphorescent host material, it is possible to produce an organic electroluminescent device having excellent light emitting performance, low driving voltage, high efficiency and long life time as compared with conventional host materials, And a full color display panel having an improved life span can also be manufactured.

Hereinafter, the present invention will be described in detail.

<New Organic Compound>

The novel compounds of the present invention are prepared by reacting dibenzo [b, f] azepine moiety with dibenzo [b, f] azepine, dibenzo [b, f] azepine moiety, dibenzo [b, f] thiepine, dibenzo [b, f] silepine, or dibenzo [a, d] cycloheptene, Or a linker (for example, an arylene group or a heteroarylene group) to form a basic skeleton, and is represented by the general formula (1).

Generally, in the phosphorescent light emitting layer of the organic electroluminescent device, the host material should have a triplet energy gap of higher than the dopant of the host. That is, in order to effectively provide phosphorescent emission from the dopant, the lowest excitation state of the host must be higher energy than the lowest emission state of the dopant. However, the compound of Formula 1 has a high triplet energy of 2.3 eV or more. In addition, since the substituent is introduced into the dibenzoazepine derivative having a broad singlet energy level and a high triplet energy level, the energy level of the compound represented by the formula (1) can be controlled to be higher than that of the dopant, .

Further, since the compound of the present invention has a high triplet energy as described above, it is possible to prevent the excitons generated in the light emitting layer from diffusing into the electron transporting layer or the hole transporting layer adjacent to the light emitting layer. Therefore, when an organic layer (hereinafter, referred to as 'light emission-assisting layer') is formed between the hole transporting layer and the light emitting layer using the compound of Formula 1, the diffusion of the excitons is prevented by the compound, Unlike the conventional organic electroluminescent device not including the blocking layer, the number of the excitons contributing to light emission in the light emitting layer substantially increases, and the light emitting efficiency of the device can be improved. Also, when an organic material layer (hereinafter, referred to as a 'life improving layer') is formed between the light emitting layer and the electron transporting layer by using the compound of Formula 1, the diffusion of the exciton is prevented by the compound of Formula 1, The durability and stability of the light emitting element can be improved, and the half life of the element can be efficiently increased. Thus, the compound represented by the formula (1) may be used as a light-emitting auxiliary layer material or a life improving layer material other than the host of the light emitting layer.

Since the dibenzo [b, f] azepine moiety has excellent hole-transporting ability in the compound of Formula 1, the compound represented by Chemical Formula 1 may be used in an organic material layer of an organic electroluminescent device , Hole transport layer), the performance of the device can be improved.

In addition, the compound of formula (1) can control the HOMO and LUMO energy levels according to the type of substituent introduced into the basic skeleton, and can have a wide band gap and a high carrier transporting property. For example, when the electron donor (EWG) having a high electron absorbing property is bonded to the basic skeleton of the compound of Formula 1, since the entire molecule has bipolar characteristics, the binding force between holes and electrons can be enhanced . As described above, the compound of Formula 1 having EWG introduced into the basic skeleton can exhibit excellent carrier transporting and luminescent properties, and thus can be applied to an electron injection / transport layer material or a life improving layer material of an organic electroluminescent device have. On the other hand, when the electron donor (EDG) of the electron donor is bonded to the basic skeleton of the compound of Formula 1, it can be effectively used as a hole injecting / transporting layer material or a light emitting auxiliary layer material.

In addition, the compound represented by the above formula (1) has various substituents, especially an aryl group and / or a heteroaryl group, introduced into the basic skeleton and the molecular weight of the compound is significantly increased to thereby improve the glass transition temperature, Can have higher thermal stability than the organic layer material (e.g., CBP). The compound represented by the above formula (1) also has an effect of inhibiting the crystallization of the organic material layer.

Thus, when the compound represented by Formula 1 of the present invention is applied to an organic material layer of an organic electroluminescent device, the performance and lifetime characteristics of the organic electroluminescent device can be greatly improved. Further, such lifetime enhancement of the organic electroluminescent device can maximize the performance of the full color organic luminescent panel.

In the compound represented by the general formula (I) of the present invention, 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} ) , Preferably N (Ar &_lt; ₁ &gt;).

Wherein Ar ₁ to Ar ₅ are the same or different, each independently represent a substituted or unsubstituted alkenyl group, a substituted or unsubstituted of C ₁ ~ C ₄₀ alkyl group, a substituted or unsubstituted C ₂ ~ C ₄₀ of the unsubstituted C ₂ to each other ~ C ₄₀ of the alkynyl group, a substituted or unsubstituted C ₆ ~ C ₄₀ aryl group, a substituted or unsubstituted nuclear atoms of 5 to 40 heteroaryl group, a substituted or unsubstituted C ₆ ~ aryloxy of C ₄₀ A substituted or unsubstituted C ₁ to C ₄₀ alkyl group, a substituted or unsubstituted C ₆ to C ₄₀ arylamine group, a substituted or unsubstituted C ₃ to C ₄₀ cycloalkyl group, a substituted or unsubstituted aryl group, A substituted or unsubstituted C ₁ to C ₄₀ alkylsilyl group, a substituted or unsubstituted C ₁ to C ₄₀ alkylboron group, a substituted or unsubstituted C ₆ to C ₄₀ alkylsulfonyl group, C ₄₀ aryl boron group, a substituted or unsubstituted C ₆ ~ C ₄₀ aryl phosphine group, a substituted or unsubstituted aryl phosphine oxide of a C ₆ ~ C ₄₀ ring And it is selected from the group consisting of aryl silyl substituted or unsubstituted C ₆ ~ C _40.

Preferably, Ar ₁ to Ar ₅ are the same or different and each independently represents a substituted or unsubstituted C ₁ to C ₄₀ alkyl group, a substituted or unsubstituted C ₆ to C ₄₀ aryl group, and a substituted or unsubstituted nucleus And a heteroaryl group having 5 to 40 atoms.

In the compound represented by Formula 1, L is a divalent linker and may be a single bond or a substituted or unsubstituted C ₆ to C ₄₀ arylene group and a substituted or unsubstituted nuclear atom And a heteroarylene group having a number of 5 to 40.

Examples of the arylene group and the heteroarylene group include a phenylene group, a biphenylene group, a naphthylene group, an anthracenylene group, an indenylene group, a pyranthrenylene group, a carbazolylene group, a thiophenylene group, An imidazolylene group, an oxazolylene group, a thiazolylene group, a triazolylene group, a pyridinylene group, a pyrimidinylene group and the like.

Preferably, L is a single bond, or may be a phenylene group, or a biphenylene group.

In this case, L is connected to one carbon selected from the R ₇ to R ₁₀ positions in Formula (1), and is linked to one carbon or nitrogen selected from R ₁₁ to R _{21 in} Formula (1). However, there is no substituent at the position connected to L.

For example, when L is connected to one carbon selected from the R ₇ to R ₁₀ positions in Formula (1) and is linked to one carbon selected from R ₁₁ to R _{14 in} Formula (1), the compound of Formula (1) May be a compound represented by the general formula (2).

In Formula 2,

X ₁ , L, and R ₁ to R ₂₁ are each as defined in formula (1)

In this case, L is connected to one carbon selected from the R ₇ to R ₁₀ positions, and at the same time, connected to one carbon selected from the R ₁₁ to R ₁₄ positions, but there is no substituent at the position connected to L.

In another example, when L is connected to one carbon selected from the R ₇ to R ₁₀ positions in Formula (1) and is linked to one carbon or nitrogen selected from R ₁₅ , R _16, and R _{21 in} Formula (1) The compound represented by the formula (1) may be a compound represented by the following formula (3).

In Formula 3,

X ₁ , L, and R ₁ to R ₂₁ are each as defined in formula (1)

In this case, L is connected to one carbon selected from the R ₇ to R ₁₀ positions, and at the same time, connected to one carbon or nitrogen selected from the R ₁₅ , R _16, and R ₂₁ positions, does not exist.

The compound of Formula 1 may be represented by the following Formula 4 to Formula 9, but is not limited thereto.

In the formulas (4) to (9)

X ₁ , L and R ₁ to R ₂₁ are the same as defined in the above formula (1).

R ₁ to R ₂₁ are the same or different from each other and each independently represent hydrogen, deuterium, a halogen, a cyano group, a substituted or unsubstituted C ₁ to C ₄₀ alkyl group, a substituted or unsubstituted C ₂ ~ C ₄₀ alkenyl group, a substituted or unsubstituted C ₂ ~ C ₄₀ of the alkynyl group, a substituted or unsubstituted C ₆ ~ C ₄₀ aryl group, a substituted or unsubstituted number of 5 to 40 heteroaryl unsubstituted nucleus atoms aryl A substituted or unsubstituted C ₆ to C ₄₀ aryloxy group, a substituted or unsubstituted C ₁ to C ₄₀ alkyloxy group, a substituted or unsubstituted C ₆ to C ₄₀ arylamine group, hwandoen C ₃ ~ C ₄₀ cycloalkyl group, a substituted or unsubstituted 3 to 40 nuclear atoms of a heterocycloalkyl group, a substituted or unsubstituted C ₁ ~ C ₄₀ alkyl silyl group, a substituted or non-substituted of unsubstituted C ₁ ~ C ₄₀ alkyl group of boron, a substituted or unsubstituted C ₆ ~ C ₄₀ aryl boron group, a substituted or unsubstituted C ₆ ~ C ₄₀ aryl phosphine Group, a substituted or unsubstituted C ₆ ~ C ₄₀ aryl phosphine oxide group, and a substituted or unsubstituted selected from the group consisting arylsilyl of a C ₆ ~ C ₄₀ ring, or, or adjacent groups combine to form a condensed ring .

Preferably, R ₁ to R ₂₁ are the same or different and each independently represents hydrogen, a substituted or unsubstituted C ₆ to C ₄₀ aryl group, a substituted or unsubstituted heteroaryl group having 5 to 40 nucleus atoms, and combining a substituted or unsubstituted C ₆ ~ selected from the group consisting of C ₄₀ aryl amine, or, or adjacent groups which may form a condensed ring.

For example, R ₁ and R ₂ , R ₂ and R ₃ , R ₃ and R ₄ , R ₅ and R ₆ , R ₇ and R ₈ , R ₈ and R ₉ , R ₉ and R ₁₀ , R ₁₁ and R ₁₂ , R ₁₂ and R ₁₃ , R ₁₃ and R ₁₄ , R ₁₅ and R ₁₆ , R ₁₇ and R ₁₈ , R ₁₈ and R ₁₉ , and R ₁₉ and R ₂₀ are bonded to each other to form a condensed aromatic ring . According to one example, R ₅ and R ₆ may combine with each other to form a condensed aromatic ring of C ₆ to C ₂₀ , and may preferably form a condensed benzene ring.

The condensed aromatic ring may be substituted with at least one substituent selected from the group consisting of deuterium, halogen, cyano, C ₁ to C ₄₀ alkyl, C ₂ to C ₄₀ alkenyl, C ₂ to C ₄₀ alkynyl, C ₆ to C ₄₀ aryl, A heteroaryl group having 5 to 40 atoms, a C ₆ to C ₄₀ aryloxy group, a C ₁ to C ₄₀ alkyloxy group, a C ₆ to C ₄₀ arylamine group, a C ₃ to C ₄₀ cycloalkyl group, a nucleus A heterocyclic alkyl group having 3 to 40 atoms, a C ₁ to C ₄₀ alkylsilyl group, a C ₁ to C ₄₀ alkylboron group, a C ₆ to C ₄₀ arylboron group, a C ₆ to C ₄₀ arylphosphine group, C ₆ ~ C ₄₀ aryl phosphine oxide group, and a C ₆ ~ C is substituted by one substituent at least one selected from the group consisting arylsilyl ₄₀ or is unsubstituted, wherein when the above substituent plurality, all of which are the same or be different from each other .

When R ₅ and R ₆ are bonded to each other to form a substituted or unsubstituted condensed aromatic ring, the compound of Formula 1 may be represented by Formula 10 below.

In Formula 10,

X ₁ , L, and R ₁ to R ₂₁ are each as defined in formula (1)

In this case, L is connected to one carbon selected from the R ₇ to R ₁₀ positions, and at the same time, connected to one carbon or nitrogen selected from the R ₁₁ to R ₂₁ positions, but there is no substituent at a position connected to L ;

a is an integer of 0 to 4, and when a is 0, hydrogen is not substituted with a substituent R, and when a is an integer of 1 to 3, R is deuterium (D), halogen, cyano, a C ₁ ~ C ₄₀ alkyl group, a substituted or unsubstituted C ₂ ~ C ₄₀ alkenyl group, a substituted or unsubstituted C ₂ ~ C ₄₀ alkynyl group, a substituted or unsubstituted C ₆ ~ C ₄₀ aryl group , A substituted or unsubstituted heteroaryl group having 5 to 40 nuclear atoms, a substituted or unsubstituted C ₆ to C ₄₀ aryloxy group, a substituted or unsubstituted C ₁ to C ₄₀ alkyloxy group, hwandoen C ₆ ~ C ₄₀ aryl amine group, a substituted or unsubstituted C ₃ ~ C ₄₀ cycloalkyl group, a substituted or unsubstituted 3 to 40 nuclear atoms of a heterocycloalkyl group, a substituted or unsubstituted C ₁ ~ alkylsilyl group of C _40, a substituted or unsubstituted C ₁ ~ C ₄₀ alkyl group of boron, a substituted or unsubstituted C ₆ ~ C ₄₀ aryl boron group, a substituted or unsubstituted C ₆ ~ C ₄₀ aryl phosphine group, a substituted or unsubstituted C ₆ ~ C ₄₀ aryl phosphine oxide group, and a substituted or unsubstituted C ₆ ~ selected from the group consisting arylsilyl of C ₄₀ or, or adjacent groups of To form a condensed ring,

Provided that when R is plural, they are the same or different from each other;

The alkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group, aryloxy group, alkyloxy group, arylamine group, cycloalkyl group, heterocycloalkyl group, alkylsilyl group, alkylboron group, arylboron group , Arylphosphine group, arylphosphine oxide group and arylsilyl group are each independently selected from the group consisting of deuterium, halogen, cyano group, C ₁ to C ₄₀ alkyl group, C ₂ to C ₄₀ alkenyl group, C ₂ to C ₄₀ alkynyl group, A C ₆ to C ₄₀ aryl group, a heteroaryl group having 5 to 40 nuclear atoms, a C ₆ to C ₄₀ aryloxy group, a C ₁ to C ₄₀ alkyloxy group, a C ₆ to C ₄₀ arylamine group, A C ₃ to C ₄₀ cycloalkyl group, a heterocycloalkyl group having 3 to 40 nuclear atoms, a C ₁ to C ₄₀ alkylsilyl group, a C ₁ to C ₄₀ alkylboron group, a C ₆ to C ₄₀ arylboron group, C ₆ ~ C ₄₀ aryl phosphine group, C ₆ ~ C ₄₀ aryl phosphine oxide group, and a C ₆ ~ C ₄₀ aryl silyl group substituted with one substituent at least one selected from the group consisting of or When substituted, and, in this case a plurality of the substituents, they may be the same or different from each other.

Preferably in the above formula (10), when a is from 1 to 3 is an integer, R is a substituted or unsubstituted C ₆ ~ C ₄₀ aryl group, a substituted or unsubstituted number of 5 to 40 heteroaryl unsubstituted nucleus atoms an aryl group, and a substituted Or an unsubstituted C ₆ to C ₄₀ arylamine group, wherein the aryl, heteroaryl and arylamine groups of R are each independently selected from the group consisting of deuterium, halogen, cyano, C ₁ to C ₄₀ alkyl, C ₂ ~ alkenyl group of C _40, C ₂ ~ C ₄₀ alkynyl group, an aryloxy group of a heteroaryl group of C ₆ ~ C ₄₀ aryl group, the number of nuclear atoms of 5 to _40, C ₆ ~ C 40 of, C ₁ ~ C ₄₀ alkyloxy group of, C ₆ ~ C ₄₀ aryl amine group, C ₃ ~ C ₄₀ cycloalkyl group, a nuclear atom number of 3 to 40 heterocycloalkyl group, C ₁ ~ C ₄₀ alkyl silyl group, C ₁ ~ C ₄₀ alkyl boron group, C ₆ ~ C ₄₀ aryl boron group, C ₆ ~ C ₄₀ aryl phosphine group, C ₆ ~ C ₄₀ aryl phosphine oxide group, and a C ₆ ~ C ₄₀ aryl silyl group consisting of In the army And when the substituent is plural, they may be the same or different from each other.

A specific example, the R ₅ and R ₆ are bonded to each other to form a condensed condensed benzene ring, wherein L is at the same time one of the carbon-linked and selected from the group consisting of R ₇ to R ₁₀ position in formula 1, to R ₁₁ of the formula R ₁₄ position, the compound of Formula 1 may be a compound represented by Formula 11 below.

In Formula 11,

X ₁ , L, and R ₁ to R ₂₁ are each as defined in Formula 1,

R and a are each as defined in Formula 10,

In this case, L is connected to one carbon selected from the R ₇ to R ₁₀ positions, and at the same time, connected to one carbon selected from the R ₁₁ to R ₁₄ positions, but there is no substituent at the position connected to L.

In another specific example, R ₅ and R ₆ are bonded to each other to form a condensed condensed benzene ring, and L is linked to one carbon selected from the R ₇ to R ₁₀ positions in Formula (1), and R ₁₅ , R ₁₆ and R ₂₁ , the compound of Formula 1 may be a compound represented by Formula 12 below.

In Formula 12,

X ₁ , L, and R ₁ to R ₂₁ are each as defined in formula (1)

R and a are each as defined in Formula 10,

In this case, L is connected to one carbon selected from the R ₇ to R ₁₀ positions, and at the same time, connected to one carbon or nitrogen selected from the R ₁₅ , R _16, and R ₂₁ positions, does not exist.

In the general formula (1), an aryl group, a heteroaryl group, Ar ₁ to Ar ₅ and R ₁ to the alkyl group of R _21, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, an aryloxy group, an alkyloxy group of the L, an arylamine group, a cycloalkyl group, a heterocycloalkyl group, alkylsilyl group, an alkyl boron group, an aryl boron group, an aryl phosphine group, aryl phosphine oxide group and an aryl silyl group each independently selected from deuterium, halogen, cyano group, C ₁ ~ C ₄₀ alkyl group, C ₂ ~ C ₄₀ alkenyl group, C ₂ ~ C ₄₀ of the alkynyl group, C ₆ ~ C ₄₀ aryl group, nuclear atoms aryl of from 5 to 40 heteroaryl group, a C ₆ ~ C ₄₀ of aryloxy A C ₁ to C ₄₀ alkyloxy group, a C ₆ to C ₄₀ arylamine group, a C ₃ to C ₄₀ cycloalkyl group, a heterocyclic cycloalkyl group having 3 to 40 nuclear atoms, a C ₁ to C ₄₀ alkylsilyl of the group, C ₁ ~ C ₄₀ group of an alkyl boron, C ₆ ~ C ₄₀ aryl boron group, C ₆ ~ C ₄₀ aryl phosphine group, C ₆ ~ C ₄₀ aryl phosphine oxide group, and a C ₆ ~ C ₄₀ of It may be substituted by one or more substituents selected from the group consisting of a silyl reel. At this time, when there are a plurality of substituents, they may be the same or different.

Preferably, Ar ₁ to Ar ₅ and R ₁ to R ₂₁ may be the same or different from each other, and each independently selected from the group consisting of hydrogen or the substituents S1 to S204 shown below, but is not limited thereto.

More preferably, at least one of Ar ₁ and R ₂₁ may be a substituent represented by the following formula (13). In this case, the compound of formula (1) may further improve the performance of the organic electroluminescent device.

In Formula 13,

An asterisk (*) means a site to be bonded with nitrogen (N)

L ₁ is a single bond or a substituted or unsubstituted C ₆ to C ₁₈ arylene group and a substituted or unsubstituted heteroarylene group having 5 to 18 nucleus atoms and is preferably a single bond or a , Or a phenylene group, or a biphenylene group;

Y ₁ to Y ₅ are the same or different from each other and each independently N or C (R ₂₂ ), preferably at least one of Y ₁ to Y ₅ is N and the others may be C (R ₂₂ ) When plural R &lt; ₂₂ &gt; are the same or different from each other;

R ₂₂ is selected from the group consisting of hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C ₁ -C ₄₀ alkyl, substituted or unsubstituted C ₂ -C ₄₀ alkenyl, substituted or unsubstituted C ₂ -C ₄₀ A substituted or unsubstituted C ₆ to C ₄₀ aryl group, a substituted or unsubstituted heteroaryl group having 5 to 40 nucleus atoms, a substituted or unsubstituted C ₆ to C ₄₀ aryloxy group, a substituted or unsubstituted C ₆ to C ₄₀ aryl group, An unsubstituted C ₁ to C ₄₀ alkyloxy group, a substituted or unsubstituted C ₆ to C ₄₀ arylamine group, a substituted or unsubstituted C ₃ to C ₄₀ cycloalkyl group, a substituted or unsubstituted nucleus atom number A substituted or unsubstituted C ₁ to C ₄₀ alkylsilyl group, a substituted or unsubstituted C ₁ to C ₄₀ alkylboron group, a substituted or unsubstituted C ₆ to C ₄₀ aryl boron group, a substituted or unsubstituted C ₆ ~ C ₄₀ aryl phosphine group, a substituted or unsubstituted C ₆ ~ C ₄₀ aryl phosphine oxide group, and a substituted or unsubstituted C _An arylsilyl group having ₆ to ₄₀ carbon atoms, or may be bonded to an adjacent group to form a condensed ring;

The L aryl group, a heteroaryl group of the alkylene group, R ₂₂ of Figure _1, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, an aryloxy group, an alkyloxy group, an arylamine group, a cycloalkyl group, a heterocycloalkyl group, an alkyl The silyl group, the alkylboron group, the arylboron group, the arylphosphine group, the arylphosphine oxide group and the arylsilyl group are each independently selected from the group consisting of deuterium, halogen, cyano group, C ₁ to C ₄₀ alkyl group, C ₂ to C ₄₀ alkenyl group , A C ₂ to C ₄₀ alkynyl group, a C ₆ to C ₄₀ aryl group, a heteroaryl group having 5 to 40 nuclear atoms, a C ₆ to C ₄₀ aryloxy group, a C ₁ to C ₄₀ alkyloxy group, C ₆ ~ C ₄₀ aryl amine group, a C ₃ ~ C ₄₀ cycloalkyl group, the nuclear atoms of 3 to 40 heterocycloalkyl group, C ₁ ~ C ₄₀ alkyl silyl group, C ₁ ~ C ₄₀ alkyl boronic group, group C ₆ to C ₄₀ aryl boron, C ₆ to C ₄₀ aryl phosphine group, C ₆ to C ₄₀ aryl phosphine oxide group, and a C ₆ to C ₄₀ aryl silyl group selected from the group consisting of 1 If more it substituted with a substituent or is unsubstituted, wherein, in said plurality of substituents, they may be the same or different from each other.

Examples of the substituent represented by the formula (13) include substituents represented by the following formulas (A-1) to (A-15), but are not limited thereto. .

In the above A-1 to A-15,

L ₁ is a single bond or a substituted or unsubstituted C ₆ -C ₁₈ arylene group and a substituted or unsubstituted heteroarylene group having 5 to 18 nucleus atoms,

When a plurality of R &lt; ₂₂ &gt; s are the same or different from each other,

R ₂₂ is selected from the group consisting of hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C ₁ -C ₄₀ alkyl, substituted or unsubstituted C ₂ -C ₄₀ alkenyl, substituted or unsubstituted C ₂ -C ₄₀ A substituted or unsubstituted C ₆ to C ₄₀ aryl group, a substituted or unsubstituted heteroaryl group having 5 to 40 nucleus atoms, a substituted or unsubstituted C ₆ to C ₄₀ aryloxy group, a substituted or unsubstituted C ₆ to C ₄₀ aryl group, An unsubstituted C ₁ to C ₄₀ alkyloxy group, a substituted or unsubstituted C ₆ to C ₄₀ arylamine group, a substituted or unsubstituted C ₃ to C ₄₀ cycloalkyl group, a substituted or unsubstituted nucleus atom number A substituted or unsubstituted C ₁ to C ₄₀ alkylsilyl group, a substituted or unsubstituted C ₁ to C ₄₀ alkylboron group, a substituted or unsubstituted C ₆ to C ₄₀ aryl boron group, a substituted or unsubstituted C ₆ ~ C ₄₀ aryl phosphine group, a substituted or unsubstituted C ₆ ~ C ₄₀ aryl phosphine oxide group, and a substituted or unsubstituted C _An arylsilyl group having ₆ to ₄₀ carbon atoms, or may be bonded to an adjacent group to form a condensed ring,

n is an integer of 0 to 4, and when n is 0, hydrogen is not substituted by substituent R ₂₃ ; when n is 1 to 4, R ₂₃ is deuterium, halogen, cyano, a C ₁ ~ C ₄₀ alkyl group, a substituted or unsubstituted C ₂ ~ C ₄₀ alkenyl group, a substituted or unsubstituted C ₂ ~ C ₄₀ alkynyl group, a substituted or unsubstituted C ₆ ~ C ₄₀ aryl group , A substituted or unsubstituted heteroaryl group having 5 to 40 nuclear atoms, a substituted or unsubstituted C ₆ to C ₄₀ aryloxy group, a substituted or unsubstituted C ₁ to C ₄₀ alkyloxy group, hwandoen C ₆ ~ C ₄₀ aryl amine group, a substituted or unsubstituted C ₃ ~ C ₄₀ cycloalkyl group, a substituted or unsubstituted 3 to 40 nuclear atoms of a heterocycloalkyl group, a substituted or unsubstituted C ₁ ~ for C ₄₀ alkylsilyl group, a substituted or unsubstituted C ₁ ~ C ₄₀ alkyl boron group, a substituted or unsubstituted C ₆ ~ C ₄₀ aryl boron group, a substituted or An unsubstituted C ₆ to C ₄₀ arylphosphine group, a substituted or unsubstituted C ₆ to C ₄₀ arylphosphine oxide group, and a substituted or unsubstituted C ₆ to C ₄₀ arylsilyl group, Or may be bonded to adjacent groups to form a condensed ring,

Aryl aryl group, a heterocyclic of the above L ₁ alkylene group, R ₂₂ and the alkyl group of R _23, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, an aryloxy group, an alkyloxy group, an arylamine group, a cycloalkyl group, a heterocycloalkyl alkyl group, an alkylsilyl group, an alkyl boron group, an aryl boron group, an aryl phosphine group, aryl phosphine oxide group and an aryl silyl group each independently selected from deuterium, halogen, cyano, C alkyl group of _{1 ~ C 40, C 2 ~} C 40 A C ₂ to C ₄₀ alkynyl group, a C ₆ to C ₄₀ aryl group, a heteroaryl group having 5 to 40 nuclear atoms, a C ₆ to C ₄₀ aryloxy group, a C ₁ to C ₄₀ alkyl oxy group, C ₆ ~ C ₄₀ aryl amine group, a C ₃ ~ C ₄₀ cycloalkyl group, the nuclear atoms of 3 to 40 heterocycloalkyl group, C ₁ ~ C ₄₀ alkyl silyl group, an alkyl of C ₁ ~ C ₄₀ boron group, C ₆ ~ C ₄₀ aryl boron group, C ₆ ~ C ₄₀ aryl phosphine group, C ₆ ~ C ₄₀ aryl phosphine oxide group, and a C ₆ ~ line from the group consisting of C ₄₀ aryl silyl And when the substituent is plural, they may be the same or different from each other.

The compounds represented by formula (1) of the present invention can be exemplified by the following exemplified compounds, but are not limited thereto.

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

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

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

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

"Heteroaryl" in the present invention means a monovalent substituent derived from a monoheterocyclic or polyheterocyclic aromatic hydrocarbon having 5 to 40 nuclear atoms. Wherein at least one of the carbons, preferably one to three carbons, is replaced by a heteroatom such as N, O, S or Se. In addition, it is understood that a form in which two or more rings are pendant or condensed with each other may be included, and further includes a condensed form with an aryl group. Examples of such heteroaryls include 6-membered monocyclic rings such as pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, and triazinyl; Such as phenoxathienyl, indolizinyl, indolyl, purinyl, quinolyl, benzothiazole, carbazolyl, and the like. ring; Imidazolyl, 2-isoxazolyl, 2-pyridinyl, 2-pyrimidinyl, and the like, but are not limited thereto.

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

The term "alkyloxy" in the present invention means a monovalent substituent group represented by R'O-, wherein R 'represents 1 to 40 alkyl, and may have a linear, branched or cyclic structure . Examples of such alkyloxy include, but are not limited to, methoxy, ethoxy, n-propoxy, 1-propoxy, t-butoxy, n-butoxy, pentoxy and the like.

"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 cycloalkyls 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, preferably 1 to 3 carbons, of the ring is replaced by N, O, S or Se. &Lt; / RTI &gt; Examples of such heterocycloalkyls 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, and "arylsilyl" means silyl substituted with aryl having 6 to 40 carbon atoms.

In the present invention, "alkylboron group" means a boron group substituted with alkyl having 1 to 40 carbon atoms, "arylboron group" means a boron group substituted with aryl having 6 to 60 carbon atoms, Means a phosphine group substituted with aryl of 1 to 60, and the term "arylphosphine oxide group" means a phosphine oxide group substituted with aryl having 1 to 60 carbon atoms.

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

The compound of formula (I) of the present invention can be synthesized according to a general synthesis method. The compounds represented by formula (1) of the present invention can be synthesized in various ways with reference to the following Synthesis Examples.

&Lt; Organic electroluminescent device &

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

Specifically, the organic electroluminescent device according to the present invention includes an anode, a cathode, and at least one organic layer sandwiched between the anode and the cathode, wherein at least one of the one or more organic layers includes Include compounds represented by the above formula (1). At this time, the compounds may be used alone or in combination of two or more.

According to an example, the at least one organic material layer may be at least one of a hole injecting layer, a hole transporting layer, a light emitting auxiliary layer, a light emitting layer, an electron transporting layer and an electron injecting layer. . &Lt; / RTI &gt; Preferably, the organic compound layer containing the compound of Formula 1 may be a light emitting layer or a hole transporting layer, and more preferably a light emitting layer. For example, the light emitting layer of the organic electroluminescent device may include a host material, The host material may include the compound of formula (1). When the compound of Formula 1 is included in the light emitting layer material of the organic electroluminescent device, preferably blue, green, and red phosphorescent host materials, the bonding strength between holes and electrons in the light emitting layer increases, Efficiency (luminous efficiency and power efficiency), lifetime, luminance, driving voltage, and the like can be improved.

According to another example, the at least one organic material layer may include a hole injection layer, a hole transport layer, a light emission auxiliary layer, a light emitting layer, an electron transport layer, and an electron injection layer. At least one organic material layer, (1). &Lt; / RTI &gt;

According to another example, the at least one organic material layer may include a hole injection layer, a hole transporting layer, a light emitting layer, a life improving layer, an electron transporting layer and an electron injection layer. At least one organic material layer, The compound of formula (1).

The structure of the organic electroluminescent device according to the present invention is not particularly limited. For example, an anode, one or more organic material layers and a cathode are sequentially laminated on a substrate, and an insulating layer or an adhesive layer is interposed between the electrode and the organic material layer Structure.

Specifically, the structure of the organic electroluminescent device may be a structure in which an anode, a hole injecting layer, a hole transporting layer, a light emitting layer, an electron transporting layer, and a cathode are sequentially laminated on a substrate. Alternatively, a light-emission-assisting layer may be interposed between the hole transporting layer and the light-emitting layer, or a life-improving layer may be interposed between the light-emitting layer and the electron-transporting layer. At least one of the hole injecting layer, the hole transporting layer, the light emitting auxiliary layer, the light emitting layer, the electron transporting layer, and the electron injecting layer may include a compound represented by Formula 1, and preferably includes a hole transporting layer, May include a compound represented by the above formula (1). On the other hand, an electron injection layer may be further stacked on the electron transport layer.

The organic electroluminescent device of the present invention may be formed by forming an organic material layer and an electrode by using materials and methods known in the art, except that at least one layer (preferably a light emitting layer) of the organic material layer includes the compound represented by the general formula .

The organic material layer 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.

Substrates usable in the present invention are not particularly limited, and examples thereof include silicon wafers, quartz, glass plates, metal plates, plastic films, and sheets.

Examples of the positive electrode material include metals such as vanadium, chromium, copper, zinc, and gold, or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); ZnO: Al or SnO _2: a combination of a metal and an oxide such as Sb; Conductive polymers such as polythiophene, poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (PEDT), polypyrrole or polyaniline; And carbon black, but are 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; And multi-layer structure materials such as LiF / Al or LiO ₂ / Al, but are not limited thereto.

The hole injecting layer, the hole transporting layer, the electron injecting layer and the electron transporting layer are not particularly limited, and ordinary materials known in the art can be used.

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

[Preparation Example 1] Synthesis of CAz-1

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

1-chloro-4-iodobenzene (244.3 g, 1024.8 mmol), Cu (27.2 g, 427.0 mmol), K ₂ CO ₃ (236.1 g, 1.70 mol) and nitrobenzene (3000 ml) were mixed and stirred at 210 占 폚 for 12 hours.

After the reaction was completed, the organic layer was extracted with ethyl acetate, the water was removed with MgSO ₄ , and the residue was purified by column chromatography (Hexane: EA = 8: 1 (v / v)) to obtain 1- (4-chlorophenyl) -indole (163.3 g, yield 84%).

^{1 H-NMR: δ 6.52 (} d, 1H), 6.87 (dd, 1H), 7.33-7.37 (m, 3H), 7.49 (d, 2H), 7.60 (d, 1H), 7.93-7.94 (m, 2H )

<Step 2> Synthesis of CAz-1

1- (4-chlorophenyl) -1H-indole (163.3 g, 717.4 mmol) and polyphosphoric acid (817 g) obtained in the above Step 1 were mixed under a nitrogen stream and stirred at 100 ° C for 12 hours. After the reaction was completed, organic matter was extracted from water and then filtered to obtain CAz-1 (49 g, yield 30%).

¹ H-NMR of CAz-1:? 6.57 (d, 1H), 6.81 (dd, 1H), 6.99-7.09 (m, 4H), 7.17 , &Lt; / RTI &gt; 1H), 8.42 (b, 1H)

[Preparation Example 2] Synthesis of CAz-2 and CAz-3

<Step 1> Synthesis of 1- (3-chlorophenyl) -1H-indole

1-chloro-3-iodobenzene (244.3 g, 1024.8 mmol), Cu (27.2 g, 427.0 mmol), K ₂ CO ₃ (236.1 g, 1.70 mol) and nitrobenzene (3000 ml) were mixed and stirred at 210 占 폚 for 12 hours. After the reaction was completed, the organic layer was extracted with ethyl acetate, the water was removed with MgSO ₄ , and the residue was purified by column chromatography (Hexane: EA = 8: 1 (v / v)) to obtain 1- (3-chlorophenyl) 1H-indole (171.0 g, yield 88%).

¹ H-NMR:? 6.52 (d, 1H), 6.87 (dd, 1 H), 7.33-7.39 (m, 3H), 7.49 7.93-7. 94 (m, 2H)

<Step 2> Synthesis of CAz-2 and CAz-3

1- (3-chlorophenyl) -1H-indole (171.0 g, 751.2 mmol) and polyphosphoric acid (855.2 g) obtained in the above <Step 1> were mixed under a nitrogen stream and stirred at 100 ° C for 12 hours. After the reaction was completed, the organic layer was extracted from water and then filtered to obtain CAz-2 (21.6 g, yield 12.6%) and CAz-3 (8.4 g, 14.4%).

¹ H-NMR of CAz-2: δ 6.81-6.85 (m , 3H), 6.99-7.05 (m, 3H), 7.19-7.25 (m, 2H), 8.21 (d, 1H), 8.42 (b, 1H)

Of ^{CAz-3 1 H-NMR:} δ 6.81-6.85 (m, 2H), 6.99-7.05 (m, 4H), 7.25 (d, 1H), 8.09 (d, 1H), 8.21 (d, 1H), 8.42 (b, 1H)

[Preparation Example 3] Synthesis of CAz-4

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

1-chloro-3-iodobenzene (244.3 g, 1024.8 mmol), Cu (27.2 g, 427.0 mmol), K ₂ CO ₃ (236.1 g, 1.70 mol) and nitrobenzene (3000 ml) were mixed and stirred at 210 占 폚 for 12 hours. After the reaction was completed, the organic layer extracted with ethyl acetate, dried with MgSO ₄ and purified by column chromatography (Hexane: EA = 7: 1 (v / v)) to give a 1- (2-chlorophenyl) - 1H-indole (167.1 g, yield 86%).

^{1 H-NMR: δ 6.52 (} d, 1H), 6.87 (dd, 1H), 7.33-7.60 (m, 6H), 7.93-7.94 (m, 2H)

<Step 2> Synthesis of CAz-4

1- (2-chlorophenyl) -1H-indole (171.0 g, 751.2 mmol) and polyphosphoric acid (855.2 g) obtained in the above Step 1 were mixed under a nitrogen stream and stirred at 100 ° C for 12 hours. After the reaction was completed, the organic layer was extracted from water and then filtered to obtain CAz-4 (51.8 g, 31%).

¹ H-NMR of 4-CAz: δ 6.75-6.81 (m, 2H) , 6.99-7.05 (m, 4H), 7.25-7.26 (m, 2H), 8.21 (d, 1H), 8.42 (b, 1H)

[ Preparation Example  4] CAZ - 5 of  synthesis

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

Under nitrogen gas stream, 5-bromo-1H-indole ( 100 g, 439.2 mmol), phenylboronic acid (64.3 g, 527.0 mmol), Pd (PPh 3) 4 (25.4 g, 22.0 mmol), K 2 CO 3 (121.4 g, 878 mmol) and 1,4-dioxane / H ₂ O (200 ml / 50 ml) were mixed and stirred at 120 ° C for 4 hours. After the reaction was completed, the organic layer was extracted with methylene chloride, and then MgSO ₄ was added thereto, followed by filtration. The solvent was removed from the obtained organic layer and then purified by column chromatography (Hexane: EA = 5: 1 (v / v)) to obtain 5-phenyl-1H-indole (70.4 g, yield 83%).

¹ H-NMR:? 6.45 (d, 1H), 7.27 (d, 1H), 7.41-7.52 (m, 5H), 7.69 10.1 (b, 1 H)

<Step 2> Synthesis of 1- (4-chlorophenyl) -5-phenyl-1H-indole

In a nitrogen atmosphere <Step 1> 5-phenyl-1H- indole (70.4g, 364.0 mmol) obtained in, 1-chloro-4-iodobenzene (104.3 g, 437.4 mmol), Cu (11.6 g, 182.2 mmol), K 2 CO ₃ (100.8 g, 729.1 mmol) and nitrobenzene (2000 ml) were mixed and stirred at 210 ° C for 12 hours. After the reaction was completed, the organic layer was extracted with ethyl acetate, the water was removed with MgSO ₄ , and the residue was purified by column chromatography (Hexane: EA = 6: 1 (v / v)) to give 1- (4-chlorophenyl) -5 -phenyl-1H-indole (88.6 g, yield 80%).

¹ H-NMR:? 6.52 (d, 1H), 7.37-7.52 (m, 9H), 7.60 (d,

<Step 3> Synthesis of CAz-5

1- (4-chlorophenyl) -5-phenyl-1H-indole (88.6 g, 291.6 mmol) and polyphosphoric acid (442.9 g) obtained in Step 2 were mixed under a nitrogen stream and stirred at 100 ° C for 12 hours. After the reaction was completed, the organic layer was extracted from water and then filtered to obtain CAz-5 (29 g, yield 33%).

Of ^{CAz-5 1 H-NMR:} δ 6.57 (d, 1H), 6.69 (d, 1H), 6.99-7.00 (m, 2H), 7.09 (d, 1H), 7.17 (s, 1H), 7.39-7.52 (m, 6 H), 7.82 (s, 1 H), 8.42 (b, 1 H)

[Preparation Example 5] Synthesis of BAz-1

<Step 1> Synthesis of 2-chloro-5-phenyl-5H-dibenzo [b, f] azepine

(49 g, 215.2 mmol), iodobenzene (52.7 g, 258.1 mmol), Cu (6.8 g, 107.6 mmol) and K ₂ CO ₃ (59.5 g, 430 mmol) synthesized in Preparation Example 1 under a nitrogen stream, And nitrobenzene (1000 ml) were mixed and stirred at 210 占 폚 for 12 hours. After the reaction was completed, the organic layer was extracted with ethyl acetate, the water was removed with MgSO ₄ and the residue was purified by column chromatography (Hexane: EA = 7: 1 (v / v)) to obtain 2-chloro-5-phenyl- dibenzo [b, f] azepine (52.3 g, yield 80%).

^{1 H-NMR: δ 6.57-6.63 (} m, 4H), 6.80-6.81 (m, 2H), 6.99-7.09 (m, 4H), 7.17-7.25 (m, 4H)

Synthesis of 5-phenyl-2- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -5H-dibenzo [b, f] azepine

5-phenyl-5H-dibenzo [b, f] azepine (52.3 g, 172.2 mmol), 4,4,4 ' (48.1 g, 189.4 mmol), Pd (dppf) Cl ₂ (15.1 g, 17.2 mmol), KOAc (48.6 g, 516.5 mmol), 5'-octamethyl-2,2'- ) And 1,4-dioxane (500 ml) were mixed and stirred at 130 ° C for 12 hours. After the reaction was completed, the organic layer was extracted with ethyl acetate, the water was removed with MgSO ₄ , and the residue was purified by column chromatography (Hexane: EA = 6: 1 (v / v) , 4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -5H-dibenzo [b, f] azepine (48.3 g, yield 71%).

^{1 H-NMR: δ 1.24 (} s, 12H), 6.61-6.63 (m, 4H), 6.81-6.83 (m, 2H), 6.99-7.05 (m, 3H), 7.20-7.25 (m, 3H), 7.35 -7.36 &lt; / RTI &gt; (m, 2H)

<Step 3> Synthesis of BAz-1

(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -5H-dibenzo [b, f] azepine 48.3 g, 122.2 mmol), CAz -1 (33.4 g, 146.7 mmol), Pd (PPh 3) 4 (7.1 g, 6.1 mmol), K 2 CO 3 (33.8 g, 244.5 mmol), 1,4-dioxane / H ₂ O (400 ml / 100 ml) were mixed and stirred at 120 ° C for 4 hours. After the reaction was completed, the organic layer was extracted with methylene chloride, and then MgSO ₄ was added thereto. The solvent was removed from the obtained organic layer and then purified by column chromatography (Hexane: EA = 3: 1 (v / v)) to obtain BAz-1 (42.2 g, yield 75%).

^{1 H-NMR: δ 6.63-6.69 (} m, 5H), 6.80-6.81 (m, 3H), 6.99-7.05 (m, 6H), 7.20-7.25 (m, 4H), 7.39-7.40 (m, 2H) , 7.80-7.82 (m, 2H), 8.12 (d, 1H), 8.43 (b, 1H)

[Preparation Example 6] Synthesis of BAz-2

(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -5H-dibenzo [b , f] azepine (48.3 g, 122.2 mmol), synthesized in preparation example 2 CAz-2 (33.4 g, 146.7 mmol), Pd (PPh 3) 4 (7.1 g, 6.1 mmol), K 2 CO 3 (33.8 g , 244.5 mmol) and 1,4-dioxane / H ₂ O (400 ml / 100 ml) were mixed and stirred at 120 ° C for 4 hours. After the reaction was completed, the organic layer was extracted with methylene chloride, and then MgSO ₄ was added thereto, followed by filtration. The solvent was removed from the obtained organic layer and then purified by column chromatography (Hexane: EA = 3: 1 (v / v)) to obtain BAz-2 (40.0 g, yield 71%).

^{1 H-NMR: δ 6.63-6.69 (} m, 4H), 6.80-6.81 (m, 3H), 6.89 (s, 1H), 6.99-7.05 (m, 7H), 7.20-7.31 (m, 5H), 7.39 (d, IH), 7.82 (s, IH), 8.21 (d, IH), 8.43

[Preparation Example 7] Synthesis of BAz-3

(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -5H-dibenzo [b, f] azepine (48.3 g, 122.2 mmol), synthesized in preparation example 2 CAz-3 (33.4 g, 146.7 mmol), Pd (PPh 3) 4 (7.1 g, 6.1 mmol), K 2 CO 3 (33.8 g, 244.5 mmol) and 1,4-dioxane / H ₂ O (400 ml / 100 ml) were mixed and stirred at 120 ° C for 4 hours. After the reaction was completed, the organic layer was extracted with methylene chloride, and then MgSO ₄ was added thereto, followed by filtration. The solvent was removed from the obtained organic layer and then purified by column chromatography (Hexane: EA = 3: 1 (v / v)) to obtain BAz-3 (36.6 g, yield 65%).

^{1 H-NMR: δ 6.63-6.69 (} m, 4H), 6.80-6.81 (m, 3H), 6.99-7.05 (m, 6H), 7.20-7.29 (m, 5H), 7.39 (d, 1H), 7.70 (d, IH), 7.82 (s, IH), 8.17-8.21 (m, 2H), 8.43

[Preparation Example 8] Synthesis of BAz-4

<Step 1> Synthesis of 4-chloro-5-phenyl-5H-dibenzo [b, f] azepine

(45 g, 197.6 mmol), iodobenzene (48.4 g, 237.2 mmol), Cu (6.3 g, 98.8 mmol), K ₂ CO ₃ (54.6 g, 395.3 mmol) synthesized in Preparation Example 3 and nitrobenzene (1000 ml) were mixed and stirred at 210 占 폚 for 12 hours. After the reaction was completed, the organic layer was extracted with ethyl acetate, the water was removed with MgSO ₄ and the residue was purified by column chromatography (Hexane: EA = 6: 1 (v / v)) to obtain 4-chloro-5-phenyl- 5H-dibenzo [b, f] azepine (49.2 g, yield 82%).

¹ H-NMR:? 6.58-6.62 (m, 3H), 6.75-6.81 (m, 3H), 6.99-7.25 (m, 8H)

Synthesis of 5-phenyl-4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -5H-dibenzo [b, f] azepine

5-phenyl-5H-dibenzo [b, f] azepine (49.2 g, 162.1 mmol) obtained in the above Step 1, 4,4,4 ' (45.2 g, 486.2 mmol), Pd (dppf) Cl ₂ (14.2 g, 16.2 mmol), KOAc (45.8 g, 17.2 mmol), 5'-octamethyl-2,2'- mmol) and 1,4-dioxane (500 ml) were mixed and stirred at 130 ° C for 12 hours.

After the reaction was completed, the organic layer was extracted with ethyl acetate, the water was removed with MgSO ₄ and the residue was purified by column chromatography (Hexane: EA = 5: 1 (v / v) , 4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -5H-dibenzo [b, f] azepine (47.4 g, yield 74%).

¹ H-NMR:? 1.24 (s, 12H), 6.61-6.63 (m, 3H), 6.81-6.83 (m, 3H), 6.99-7.05 (d, 1 H)

<Step 3> Synthesis of BAz-4

(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -5H-dibenzo [b, f] azepine obtained in the above Step 2 47.4 g, 119.9 mmol), synthesized in preparation example 1 CAz-1 (32.8 g, 143.9 mmol), Pd (PPh 3) 4 (6.9 g, 6.0 mmol), K 2 CO 3 (33.2 g, 239.9 mmol), 1,4-dioxane / H ₂ O (400 ml / 100 ml) were mixed and stirred at 120 ° C for 4 hours. After the reaction was completed, the organic layer was extracted with methylene chloride, and then MgSO ₄ was added thereto, followed by filtration. The solvent was removed from the obtained organic layer and then purified by column chromatography (Hexane: EA = 4: 1 (v / v)) to obtain BAz-4 (38.1 g, yield 69%).

^{1 H-NMR: δ 6.63-6.69 (} m, 4H), 6.81-6.87 (m, 4H), 6.99-7.05 (m, 6H), 7.20-7.25 (m, 5H), 7.39-7.40 (m, 2H) , 7.82 (s, IH), 8.21 (d, IH), 8.43 (b, IH)

[Preparation Example 9] Synthesis of BAz-5

<Step 1> Synthesis of 3-chloro-5-phenyl-5H-dibenzo [b, f] azepine

(35.9 g, 157.7 mmol), iodobenzene (38.6 g, 189.3 mmol), Cu (5.0 g, 78.9 mmol), K ₂ CO ₃ (43.6 g, 315.5 mmol) synthesized in Preparation Example 2 and nitrobenzene (1000 ml) were mixed and stirred at 210 占 폚 for 12 hours. After the reaction was completed, the organic layer was extracted with ethyl acetate, the water was removed with MgSO ₄ , and the residue was purified by column chromatography (Hexane: EA = 6: 1 (v / v) 5H-dibenzo [b, f] azepine (35.9 g, yield 75%).

¹ H-NMR:? 6.60-6.63 (m, 3H), 6.81-6.83 (m, 4H), 6.99-7.05 (m, 3H), 7.19-7.24

Synthesis of 5-phenyl-3- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -5H-dibenzo [b, f] azepine

3-chloro-5-phenyl-5H-dibenzo [b, f] azepine (35.9 g, 118.3 mmol), 4,4,4 ' Pd (dppf) Cl ₂ (10.4 g, 11.8 mmol), KOAc (33.4 g, 354.8 mmol), 5'-octamethyl-2,2'-bi (1,3,2-dioxaborolane) mmol) and 1,4-dioxane (400 ml) were mixed and stirred at 130 ° C for 12 hours. After the reaction was completed, the organic layer was extracted with ethyl acetate, the water was removed with MgSO ₄ , and the residue was purified by column chromatography (Hexane: EA = 5: 1 (v / v) , 4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -5H-dibenzo [b, f] azepine (36.5 g, yield 78%).

^{1 H-NMR: δ 1.24 (} s, 12H), 6.61-6.69 (m, 4H), 6.81-6.83 (m, 2H), 6.99-7.11 (m, 4H), 7.20-7.25 (m, 4H)

<Step 3> Synthesis of BAz-5

(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -5H-dibenzo [b, f] azepine obtained in the above Step 2 36.5 g, 92.2 mmol), CAz-1 (25.2 g, mmol 110.7), Pd ₍₃ PPh) ₄ (g 5.3, 4.6 mmol), K ₂ CO ₃ (25.5 g, mmol 184.5), dioxane-1,4 / H ₂ O (300 ml / 70 ml) were mixed and stirred at 120 ° C for 4 hours.

After the reaction was completed, the organic layer was extracted with methylene chloride, and then MgSO ₄ was added thereto, followed by filtration. The solvent was removed from the obtained organic layer and then purified by column chromatography (Hexane: EA = 3: 1 (v / v)) to obtain BAz-5 (28.5 g, yield 67%).

^{1 H-NMR: δ 6.61-6.69 (} m, 4H), 6.81-6.83 (m, 3H), 6.89 (s, 1H), 6.99-7.05 (m, 7H), 7.20-7.31 (m, 5H), 7.39 (d, IH), 7.82 (s, IH), 8.21 (d, IH), 8.43

[Preparation Example 10] Synthesis of BAz-6

<Step 1> Synthesis of 1-chloro-5-phenyl-5H-dibenzo [b, f] azepine

(32 g, 140.5 mmol), iodobenzene (34.4 g, 168.7 mmol), Cu (4.5 g, 70.3 mmol), K ₂ CO ₃ (38.8 g, 281.1 mmol) synthesized in Preparation Example 2 and nitrobenzene (500 ml) were mixed and stirred at 210 캜 for 12 hours.

After the reaction was completed, the organic layer was extracted with ethyl acetate, the water was removed with MgSO ₄ , and the residue was purified by column chromatography (Hexane: EA = 7: 1 (v / v) 5H-dibenzo [b, f] azepine (34.6 g, yield 81%).

^{1 H-NMR: δ 6.51 (} d, 1H), 6.61-6.63 (m, 3H), 6.81-6.85 (m, 3H), 6.99-7.05 (m, 4H), 7.20-7.25 (m, 3H)

Synthesis of 5-phenyl-1- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -5H-dibenzo [b, f] azepine

5-phenyl-5H-dibenzo [b, f] azepine (34.6 g, 113.8 mmol) obtained in the above Step 1, 4,4,4 ' (31.8 g, 125.2 mmol), Pd (dppf) Cl ₂ (10.0 g, 11.4 mmol), KOAc (32.2 g, 341.5 mmol), 5'-octamethyl-2,2'- mmol) and 1,4-dioxane (300 ml) were mixed and stirred at 130 ° C for 12 hours.

After the reaction was completed, the organic layer was extracted with ethyl acetate, the water was removed with MgSO ₄ , and the residue was purified by column chromatography (Hexane: EA = 6: 1 (v / v) , 4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -5H-dibenzo [b, f] azepine (48.3 g, yield 71%).

^{1 H-NMR: δ 1.24 (} s, 12H), 6.61-6.63 (m, 4H), 6.81-6.82 (m, 2H), 6.99-7.11 (m, 5H), 7.20-7.25 (m, 3H)

<Step 3> Synthesis of BAz-6

(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -5H-dibenzo [b, f] azepine obtained in the above Step 2 33.8 g, 85.4 mmol), CAz -1 (23.3 g, 102.5 mmol), Pd (PPh 3) 4 (4.9 g, 4.3 mmol), K 2 CO 3 (23.6 g, 170.1 mmol), 1,4-dioxane / H ₂ O (300 ml / 70 ml) were mixed and stirred at 120 ° C for 4 hours. After the reaction was completed, the organic layer was extracted with methylene chloride, and then MgSO ₄ was added thereto, followed by filtration. The solvent was removed from the obtained organic layer and then purified by column chromatography (Hexane: EA = 3: 1 (v / v)) to obtain BAz-6 (24.8 g, yield 63%).

^{1 H-NMR: δ 6.63-6.69 (} m, 5H), 6.80-6.81 (m, 3H), 6.99-7.05 (m, 6H), 7.20-7.29 (m, 5H), 7.39 (d, 1H), 7.70 (d, IH), 7.82 (s, IH), 8.20 (d, IH), 8.43

[Preparation Example 11] Synthesis of BAz-7

<Step 1> Synthesis of 2-chloro-5,8-diphenyl-5H-dibenzo [b, f] azepine

(50 g, 164.6 mmol), iodobenzene (40.3 g, 197.5 mmol), Cu (5.2 g, 82.3 mmol), K ₂ CO ₃ (45.5 g, 329.2 mmol) obtained in Preparation Example 4 and nitrobenzene (500 ml) were mixed and stirred at 210 占 폚 for 12 hours. After the reaction was completed, the organic layer was extracted with ethyl acetate, the water was removed with MgSO ₄ , and the residue was purified by column chromatography (Hexane: EA = 6: 1 (v / v) diphenyl-5H-dibenzo [b, f] azepine (46.9 g, yield 75%).

^{1 H-NMR: δ 6.57-6.69 (} m, 4H), 6.81 (t, 1H), 6.99-7.00 (m, 2H), 7.09 (d, 1H), 7.17-7.20 (m, 3H), 7.39-7.52 (m, 6 H), 7.82 (s, 1 H)

Synthesis of 2,5-diphenyl-8- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -5H-dibenzo [b, f] azepine

5,8-diphenyl-5H-dibenzo [b, f] azepine (46.9 g, 123.4 mmol) obtained in the above Step 1, 4,4,4 ' (34.5 g, 135.8 mmol), Pd (dppf) Cl ₂ (10.8 g, 12.3 mmol), KOAc (34.9 g, 12.8 mmol), 5 ', 5'-octamethyl-2,2'- , 370.3 mmol) and 1,4-dioxane (500 ml) were mixed and stirred at 130 ° C for 12 hours. After the reaction was completed, the organic layer was extracted with ethyl acetate, the water was removed with MgSO ₄ , and the residue was purified by column chromatography (Hexane: EA = 6: 1 (v / v)) to obtain 2,5-diphenyl- 4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -5H-dibenzo [b, f] azepine (41.3 g, yield 71%).

^{1 H-NMR: δ 1.24 (} s, 12H), 6.61-6.69 (m, 4H), 6.81-6.99 (m, 3H), 7.20 (t, 2H), 7.35-7.41 (m, 4H), 7.51-7.52 (m, 4 H), 7.82 (s, 1 H)

<Step 3> Synthesis of BAz-7

5,4'-tetramethyl-1,3,2-dioxaborolan-2-yl) -5H-dibenzo [b, f] azepine (41.3 g, 87.6 mmol) , CAz-1 (23.9 g, 105.2 mmol), Pd (PPh 3) 4 (5.1 g, 4.4 mmol), K 2 CO 3 (24.2 g, 175.3 mmol), 1,4- dioxane / H ₂ O (400 ml / 100 ml) were mixed and stirred at 120 ° C for 4 hours. After the reaction was completed, the organic layer was extracted with methylene chloride, and then MgSO ₄ was added thereto, followed by filtration. The solvent was removed from the obtained organic layer and then purified by column chromatography (Hexane: EA = 3: 1 (v / v)) to obtain BAz-7 (29.2 g, yield 62%).

^{1 H-NMR: δ 6.63-6.69 (} m, 5H), 6.80-6.81 (m, 2H), 6.99-7.05 (m, 5H), 7.20-7.25 (m, 3H), 7.39-7.52 (m, 8H) , 7.79-7.82 (m, 3H), 8.21 (d, IH), 8.43 (b, IH)

[Preparation Example 12] Synthesis of BAz-8

Synthesis of 5- (biphenyl-4-yl) -2-chloro-8-phenyl-5H-dibenzo [b, f] azepine

(50 g, 164.6 mmol), 4-iodobiphenyl (55.3 g, 197.5 mmol), Cu (5.2 g, 82.3 mmol) and K ₂ CO ₃ (45.5 g, 329.2 mmol) obtained in Preparation Example 4, And nitrobenzene (500 ml) were mixed and stirred at 210 占 폚 for 12 hours. After the reaction was completed, the organic layer was extracted with ethyl acetate, the water was removed with MgSO ₄ , and the residue was purified by column chromatography (hexane: EA = 6: 1 (v / v)) to obtain 5- (biphenyl- ) -2-chloro-8-phenyl-5H-dibenzo [b, f] azepine (53.3 g, yield 71%).

^{1 H-NMR: δ 6.57 (} d, 1H), 6.67-6.69 (m, 3H), 6.99-7.01 (m, 2H), 7.09 (d, 1H), 7.17 (s, 1H), 7.39-7.54 (m , 13 H), 7.82 (s, 1 H)

Biphenyl-4-yl) -2-phenyl-8- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -5H-dibenzo [b, f] azepine

Biphenyl-4-yl) -2-chloro-8-phenyl-5H-dibenzo [b, f] azepine (53.3 g, 116.9 mmol) obtained in the above Step 1, (32.6 g, 128.5 mmol), Pd (dppf) CI ₂ (10.2 g, 128.5 mmol), 4 ', 5,5,5', 5'-octamethyl-2,2'- 11.7 mmol), KOAc (33.0 g, 350.6 mmol) and 1,4-dioxane (500 ml) were mixed and stirred at 130 ° C for 12 hours. After the reaction was completed, the organic layer was extracted with ethyl acetate, the water was removed with MgSO ₄ , and the residue was purified by column chromatography (hexane: EA = 6: 1 (v / v)) to obtain 5- (biphenyl- B-f] azepine (47.3 g, yield 74%) was obtained as a colorless oil from the fraction eluted with ethyl acetate-hexane .

¹ H-NMR:? 1.24 (s, 12H), 6.63-6.69 (m, 4H), 6.97-6.99 (m, 2H), 7.35-7.41 (m, 5H), 7.51-7.54 (s, 1 H)

<Step 3> BAz - 8 of  synthesis

(Biphenyl-4-yl) -2-phenyl-8- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2- 5H-dibenzo [b, f] azepine (47.3 g, 86.4 mmol), CAz-1 (23.6 g, 103.8 mmol), Pd (PPh 3) 4 (5.0 g, 4.3 mmol), K 2 CO 3 (23.9 g, 173.0 mmol) and 1,4-dioxane / H ₂ O (400 ml / 100 ml) were mixed and stirred at 120 ° C for 4 hours. After the reaction was completed, the organic layer was extracted with methylene chloride, and then MgSO ₄ was added thereto, followed by filtration. The solvent was removed from the obtained organic layer and then purified by column chromatography (Hexane: EA = 3: 1 (v / v)) to obtain BAz-8 (33.4 g, yield 63%).

¹ H-NMR:? 6.65-6.68 (m, 5H), 6.81 (t, IH), 6.99-7.05 (m, 5H), 7.25 (d, IH), 7.39-7.54 (m, 3H), 8.21 (d, IH), 8.43 (b, IH)

[Preparation Example 13] Synthesis of BAz-9

Synthesis of 2-chloro-5- (9,9-dimethyl-9H-fluoren-2-yl) -8-phenyl-5H-dibenzo [b, f] azepine

(50 g, 164.6 mmol), 2-bromo-9,9-dimethyl-9H-fluorene (54.0 g, 197.5 mmol), Cu (5.2 g, 82.3 mmol) synthesized in Preparation Example 4, K ₂ CO ₃ (45.5 g, 329.2 mmol) and nitrobenzene (500 ml) were mixed and stirred at 210 ° C for 12 hours. After the reaction was completed, the organic layer was extracted with ethyl acetate, the water was removed with MgSO ₄ , and the residue was purified by column chromatography (Hexane: EA = 6: 1 (v / v) , 9-dimethyl-9H-fluoren-2-yl) -8-phenyl-5H-dibenzo [b, f] azepine (61.2 g, yield 75%).

^{1 H-NMR: δ 1.72 (} s, 6H), 6.57-6.58 (m, 2H), 6.69 (d, 1H), 6.75 (s, 1H), 6.99-7.00 (m, 2H), 7.09 (d, 1H ), 7.17 (s, 1 H), 7.28 (t, 1 H), 7.38-7.41 (m, 3H), 7.51-7.55

Step 2: Synthesis of 5- (9,9-dimethyl-9H-fluoren-2-yl) -2-phenyl-8- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan- ) -5H-dibenzo [b, f] azepine

2-yl) -8-phenyl-5H-dibenzo [b, f] azepine (61.2 g, 123.4 mmol), 4,4,4 ', 4,5,5,5,5-octamethyl-2,2'-bi (1,3,2-dioxaborolane) (34.5 g, 135.8 mmol), Pd dppf) Cl ₂ (10.8 g, 12.3 mmol), KOAc (34.9 g, 370.3 mmol) and 1,4-dioxane (500 ml) were mixed and stirred at 130 ° C for 12 hours. After the reaction was completed, the organic layer was extracted with ethyl acetate, the water was removed with MgSO ₄ , and the residue was purified by column chromatography (Hexane: EA = 6: 1 (v / v) -9H-fluoren-2-yl) -2-phenyl-8- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -5H-dibenzo [b, f] azepine 52.2 g, yield 72%).

^{1 H-NMR: δ 1.24 (} s, 12H), 1.72 (s, 6H), 6.58-6.69 (m, 3H), 6.75 (s, 1H), 6.97-6.99 (m, 2H), 7.28-7.41 (m , 6H), 7.51-7.55 (m, 5H), 7.62 (d, 1H), 7.82-7.87

<Step 3> Synthesis of BAz-9

(9,9-dimethyl-9H-fluoren-2-yl) -2-phenyl-8- (4,4,5,5-tetramethyl-1,3,2 -dioxaborolan-2-yl) -5H- dibenzo [b, f] azepine (52.2 g, 88.9 mmol), CAz-1 (24.3 g, 106.7 mmol), Pd (PPh 3) 4 (5.1 g, 4.4 mmol), K ₂ CO ₃ (24.6 g, 177.8 mmol) and 1,4-dioxane / H ₂ O (500 ml / 125 ml) were mixed and stirred at 120 ° C for 4 hours. After the reaction was completed, the organic layer was extracted with methylene chloride, and then MgSO ₄ was added thereto, followed by filtration. The solvent was removed from the obtained organic layer and then purified by column chromatography (Hexane: EA = 3: 1 (v / v)) to obtain BAz-9 (38.3 g, yield 66%).

H-NMR ^1: δ 1.72 (s, 6H), 6.58 (d, 1H), 6.69-6.81 (m, 5H), 6.99-7.05 (m, 5H), 7.25-7.28 (m, 2H), 7.39-7.55 (m, 11H), 7.82-7.87 (m, 4H), 8.21 (d,

[Preparation Example 14] Synthesis of BAz-10

<Step 1> Synthesis of 6-chloro-9-phenyl-9H-tribenzo [b, d, f] azepine

(40 g, 144.0 mmol), iodobenzene (35.3 g, 172.8 mmol), Cu (4.5 g, 72.0 mmol), K ₂ CO ₃ (39.8 g, 288.0 mmol) and nitrobenzene (400 ml) were mixed and stirred at 210 ° C for 12 hours.

After the reaction was completed, the reaction mixture was extracted with ethyl acetate, the water was removed with MgSO ₄ , and purified by column chromatography (Hexane: EA = 5: 1 (v / v)) to obtain 6-chloro-9-phenyl-9H-tribenzo [ b, d, f] azepine (35.2 g, yield 69%).

¹ H-NMR:? 6.63-6.69 (m, 4H), 6.81-6.87 (m, 2H), 7.16-7.20 (m, 4H), 7.47-7.54 -7.84 (m, 2 H)

Synthesis of 9-phenyl-6- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -9H-tribenzo [b, d, f] azepine

B-dibenzo [b, d, f] azepine (35.2 g, 99.4 mmol) obtained in the above Step 1, 4,4,4 ', 4', 5,5 (27.8 g, 109.3 mmol), Pd (dppf) Cl ₂ (8.7 g, 9.9 mmol), KOAc (28.1 g, 9.9 mmol), 5'-octamethyl-2,2'- , 298.1 mmol) and 1,4-dioxane (300 ml) were mixed and stirred at 130 ° C for 12 hours.

After the reaction was completed, the reaction mixture was extracted with ethyl acetate, the water was removed with MgSO ₄ and purified by column chromatography (Hexane: EA = 5: 1 (v / v)) to obtain 9-phenyl-6- , 5-tetramethyl-1,3,2-dioxaborolan-2-yl) -9H-tribenzo [b, d, f] azepine (32.7 g, yield 74%).

¹ H-NMR:? 1.24 (s, 12H), 6.63-6.69 (m, 4H), 6.81-6.87 (m, 2H), 7.16-7.20 (m, 3H), 7.41-7.47 (d, 1 H), 7.83-7.85 (m, 2 H)

<Step 3> Synthesis of BAz-10

B, d, f] of the 9-phenyl-6- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) azepine (32.7 g, 73.5 mmol) , CAz-1 (20.1 g, 88.2 mmol), Pd (PPh 3) 4 (4.2 g, 3.7 mmol), K 2 CO 3 (20.3 g, 147.1 mmol), 1,4- dioxane / H ₂ O (400 ml / 100 ml) were mixed and stirred at 120 ° C for 4 hours.

After the reaction was completed, the reaction mixture was extracted with methylene chloride, added with MgSO ₄ and filtered. The solvent was removed from the obtained organic layer and then purified by column chromatography (Hexane: EA = 4: 1 (v / v)) to obtain BAz-10 (27.4 g, yield 73%).

^{1 H-NMR: δ 6.69-6.87 (} m, 8H), 6.99-7.05 (m, 3H), 7.16-7.25 (m, 4H), 7.39-7.54 (m, 6H), 7.82-7.85 (m, 3H) , 8.21 (d, 1 H), 8.43 (b, 1 H)

[Synthesis Example 1] Synthesis of A-1

(3.1 g, 6.7 mmol), 2-bromo-4,6-diphenylpyrimidine (2.5 g, 8.0 mmol), CuI (0.13 g, 0.67 mmol) synthesized in Preparation Example 5, 1,10- phenanthroline (0.24 g, 1.34 mmol), Cs ₂ CO ₃ (4.37 g, 13.4 mmol) and nitrobenzene (25 ml) were mixed and stirred at 210 ° C for 3 hours. After completion of the reaction, the solid salt was filtered and then purified by column chromatography to obtain the object compound A-1 (3.0 g, yield 65%).

Mass (theory: 690.27, measurement: 690 g / mol)

[Synthesis Example 2] Synthesis of A-2

The procedure of Synthesis Example 1 was repeated except that 4-bromo-2,6-diphenylpyrimidine (2.5 g, 8.0 mmol) was used instead of 2-bromo-4,6-diphenylpyrimidine used in Synthesis Example 1, Compound A-2 (3.1 g, yield 66%) was obtained.

Mass (theory: 690.27, measurement: 690 g / mol)

[Synthesis Example 3] Synthesis of A-3

Except that 2-chloro-4,6-diphenyl-1,3,5-triazine (2.14 g, 8.0 mmol) was used instead of 2-bromo-4,6-diphenylpyrimidine used in Synthesis Example 1, 1, the target compound A-3 (2.9 g, yield 63%) was obtained.

Mass (theory value: 691.27, measurement: 691 g / mol)

[Synthesis Example 4] Synthesis of A-4

Except that 2- (4-bromophenyl) -4,6-diphenyl-1,3,5-triazine (3.1 g, 8.0 mmol) was used instead of 2-bromo-4,6-diphenylpyrimidine used in Synthesis Example 1 , The target compound A-4 (3.5 g, yield 68%) was obtained by carrying out the same procedure as in Synthesis Example 1.

Mass (calc .: 767.30, found: 767 g / mol)

[Synthesis Example 5] Synthesis of A-5

Except that 2- (3-bromophenyl) -4,6-diphenyl-1,3,5-triazine (3.1 g, 8.0 mmol) was used instead of 2-bromo-4,6-diphenylpyrimidine used in Synthesis Example 1 , The target compound A-5 (3.7 g, yield 71%) was obtained by carrying out the same procedure as in Synthesis Example 1.

Mass (calc .: 767.30, found: 767 g / mol)

[Synthesis Example 6] Synthesis of A-6

Except that 2- (3-bromophenyl) dibenzo [b, d] thiophene (2.7 g, 8.0 mmol) was used in place of 2-bromo-4,6-diphenylpyrimidine used in Synthesis Example 1 To obtain the target compound A-6 (2.9 g, yield 61%).

Mass (theory: 718.24, measurement: 718 g / mol)

[Synthesis Example 7] Synthesis of A-7

Except that 2-bromodibenzo [b, d] furan (2.0 g, 8.0 mmol) was used instead of 2-bromo-4,6-diphenylpyrimidine used in Synthesis Example 1, Compound A-7 (2.8 g, yield 67%) was obtained.

Mass (theory: 626.23, measurement: 626 g / mol)

[Synthesis Example 8] Synthesis of A-8

The procedure of Synthesis Example 1 was repeated except that 2- (4-bromophenyl) triphenylene (3.1 g, 8.0 mmol) was used instead of 2-bromo-4,6-diphenylpyrimidine used in Synthesis Example 1, In A-8 (3.3 g, yield 64%).

Mass (calc .: 762.30, found: 762 g / mol)

[Synthesis Example 9] Synthesis of A-9

The procedure of Synthesis Example 1 was repeated except that 2-chloro-4-phenylquinazoline (1.9 g, 8.0 mmol) was used instead of 2-bromo-4,6-diphenylpyrimidine used in Synthesis Example 1, A-9 (2.9 g, yield 66%).

Mass (theory: 664.26, found: 664 g / mol)

[Synthesis Example 10] Synthesis of A-10

Except that 2-chloro-4- (4- (naphthalen-1-yl) phenyl) quinazoline (2.9 g, 8.0 mmol) was used in place of 2-bromo-4,6-diphenylpyrimidine used in Synthesis Example 1, The procedure of Synthesis Example 1 was repeated to obtain the target compound A-10 (3.9 g, yield 73%).

Mass (theory: 790.30, measurement: 790 g / mol)

[Synthesis Example 11] Synthesis of B-1

(3.1 g, 6.7 mmol), 2-bromo-4,6-diphenylpyrimidine (2.5 g, 8.0 mmol), CuI (0.13 g, 0.67 mmol) synthesized in Preparation Example 6, 1,10- phenanthroline (0.24 g, 1.34 mmol), Cs ₂ CO ₃ (4.37 g, 13.4 mmol) and nitrobenzene (25 ml) were mixed and stirred at 210 ° C for 3 hours. After completion of the reaction, the solid salt was filtered and purified by column chromatography to obtain the target compound B-1 (3.1 g, yield 66%).

Mass (theory: 690.27, measurement: 690 g / mol)

[Synthesis Example 12] Synthesis of B-2

The procedure of Synthesis Example 11 was repeated except that 4-bromo-2,6-diphenylpyrimidine (2.5 g, 8.0 mmol) was used instead of 2-bromo-4,6-diphenylpyrimidine used in Synthesis Example 11, To obtain compound B-2 (3.0 g, yield 64%).

Mass (theory: 690.27, measurement: 690 g / mol)

[Synthesis Example 13] Synthesis of B-3

Except that 2-chloro-4,6-diphenyl-1,3,5-triazine (2.14 g, 8.0 mmol) was used instead of 2-bromo-4,6-diphenylpyrimidine used in Synthesis Example 11 11, the target compound B-3 (2.8 g, yield 61%) was obtained.

Mass (theory value: 691.27, measurement: 691 g / mol)

[Synthesis Example 14] Synthesis of B-4

Except that 2- (4-bromophenyl) -4,6-diphenyl-1,3,5-triazine (3.1 g, 8.0 mmol) was used instead of 2-bromo-4,6-diphenylpyrimidine used in Synthesis Example 11 , The objective compound B-4 (3.5 g, yield 69%) was obtained by carrying out the same procedure as in Synthesis Example 11.

Mass (calc .: 767.30, found: 767 g / mol)

[ Synthetic example  15] Synthesis of B-5

Except that 2- (3-bromophenyl) -4,6-diphenyl-1,3,5-triazine (3.1 g, 8.0 mmol) was used instead of 2-bromo-4,6-diphenylpyrimidine used in Synthesis Example 11 , The target compound B-5 (3.3 g, yield 65%) was obtained by carrying out the same procedure as in Synthesis Example 11.

Mass (calc .: 767.30, found: 767 g / mol)

[Synthesis Example 16] Synthesis of B-6

Was obtained in the same manner as in Synthesis Example 11, except that 2- (3-bromophenyl) dibenzo [b, d] thiophene (2.7 g, 8.0 mmol) was used in place of 2-bromo-4,6-diphenylpyrimidine used in Synthesis Example 11 To obtain the target compound B-6 (3.2 g, yield 66%).

Mass (theory: 718.24, measurement: 718 g / mol)

[Synthesis Example 17] Synthesis of B-7

The procedure of Synthesis Example 11 was repeated except that 2-bromodibenzo [b, d] furan (2.0 g, 8.0 mmol) was used instead of 2-bromo-4,6-diphenylpyrimidine used in Synthesis Example 11, To obtain compound B-7 (2.7 g, yield 64%).

Mass (theory: 626.23, measurement: 626 g / mol)

[Synthesis Example 18] Synthesis of B-8

The procedure of Synthesis Example 11 was repeated except that 2- (4-bromophenyl) triphenylene (3.1 g, 8.0 mmol) was used instead of 2-bromo-4,6-diphenylpyrimidine used in Synthesis Example 11, Of B-8 (3.5 g, yield 68%).

Mass (calc .: 762.30, found: 762 g / mol)

[Synthesis Example 19] Synthesis of B-9

The procedure of Synthesis Example 11 was repeated except that 2-chloro-4-phenylquinazoline (1.9 g, 8.0 mmol) was used instead of 2-bromo-4,6-diphenylpyrimidine used in Synthesis Example 11, B-9 (3.1 g, yield 69%).

Mass (theory: 664.26, found: 664 g / mol)

[Synthesis Example 20] Synthesis of B-10

Except that 2-chloro-4- (4- (naphthalen-1-yl) phenyl) quinazoline (2.9 g, 8.0 mmol) was used instead of 2-bromo-4,6-diphenylpyrimidine used in Synthesis Example 11, The procedure of Synthesis Example 11 was repeated to obtain the target compound B-10 (3.7 g, yield 70%).

Mass (theory: 790.30, measurement: 790 g / mol)

[Synthesis Example 21] Synthesis of C-1

(3.1 g, 6.7 mmol), 2-bromo-4,6-diphenylpyrimidine (2.5 g, 8.0 mmol), CuI (0.13 g, 0.67 mmol) synthesized in Preparation Example 7, 1,10- phenanthroline (0.24 g, 1.34 mmol), Cs ₂ CO ₃ (4.37 g, 13.4 mmol) and nitrobenzene (25 ml) were mixed and stirred at 210 ° C for 3 hours. After completion of the reaction, the solid salt was filtered and purified by column chromatography to obtain the desired compound C-1 (3.0 g, yield 64%).

Mass (theory: 690.27, measurement: 690 g / mol)

[Synthesis Example 22] Synthesis of C-2

The procedure of Synthesis Example 21 was repeated except that 4-bromo-2,6-diphenylpyrimidine (2.5 g, 8.0 mmol) was used instead of 2-bromo-4,6-diphenylpyrimidine used in Synthesis Example 21 To obtain compound C-2 (3.1 g, yield 67%).

Mass (theory: 690.27, measurement: 690 g / mol)

[Synthesis Example 23] Synthesis of C-3

Except that 2-chloro-4,6-diphenyl-1,3,5-triazine (2.1 g, 8.0 mmol) was used instead of 2-bromo-4,6-diphenylpyrimidine used in Synthesis Example 21 21, the target compound C-3 (3.4 g, yield 73%) was obtained.

Mass (theory value: 691.27, measurement: 691 g / mol)

[Synthesis Example 24] Synthesis of C-4

Except that 2- (4-bromophenyl) -4,6-diphenyl-1,3,5-triazine (3.1 g, 8.0 mmol) was used instead of 2-bromo-4,6-diphenylpyrimidine used in Synthesis Example 21 , The target compound C-4 (3.6 g, yield 70%) was obtained by carrying out the same procedure as in Synthesis Example 21.

Mass (calc .: 767.30, found: 767 g / mol)

[Synthesis Example 25] Synthesis of C-5

Except that 2- (3-bromophenyl) -4,6-diphenyl-1,3,5-triazine (3.1 g, 8.0 mmol) was used in place of 2-bromo-4,6-diphenylpyrimidine used in Synthesis Example 21 , The target compound C-5 (3.1 g, yield 61%) was obtained by carrying out the same procedure as in Synthesis Example 21.

Mass (calc .: 767.30, found: 767 g / mol)

[Synthesis Example 26] Synthesis of C-6

Dibenzo [b, d] thiophene (2.7 g, 8.0 mmol) instead of 2-bromo-4,6-diphenylpyrimidine used in Synthesis Example 21 was used in place of (3.3 g, yield 68%) as a target compound C-6.

Mass (theory: 718.24, measurement: 718 g / mol)

[Synthesis Example 27] Synthesis of C-7

The procedure of Synthetic Example 21 was repeated except that 2-bromodibenzo [b, d] furan (2.0 g, 8.0 mmol) was used instead of 2-bromo-4,6-diphenylpyrimidine used in Synthesis Example 21, Compound C-7 (2.7 g, yield 65%) was obtained.

Mass (theory: 626.23, measurement: 626 g / mol)

[Synthesis Example 28] Synthesis of C-8

The procedure of Synthetic Example 21 was repeated except that 2- (4-bromophenyl) triphenylene (3.1 g, 8.0 mmol) was used instead of 2-bromo-4,6-diphenylpyrimidine used in Synthesis Example 21, C-8 (3.1 g, yield 61%) was obtained.

Mass (calc .: 762.30, found: 762 g / mol)

[Synthesis Example 29] Synthesis of C-9

The procedure of Synthetic Example 21 was repeated except that 2-chloro-4-phenylquinazoline (1.9 g, 8.0 mmol) was used instead of 2-bromo-4,6-diphenylpyrimidine used in Synthesis Example 21, C-9 (3.1 g, yield 67%).

Mass (theory: 664.26, found: 664 g / mol)

[Synthesis Example 30] Synthesis of C-10

Except that 2-chloro-4- (4- (naphthalen-1-yl) phenyl) quinazoline (2.9 g, 8.0 mmol) was used instead of 2-bromo-4,6-diphenylpyrimidine used in Synthesis Example 21, The procedure of Synthesis Example 21 was repeated to obtain the desired compound C-10 (3.7 g, yield 70%).

Mass (theory: 790.30, measurement: 790 g / mol)

[Synthesis Example 31] Synthesis of D-1

(3.1 g, 6.7 mmol), 2-bromo-4,6-diphenylpyrimidine (2.5 g, 8.0 mmol), CuI (0.13 g, 0.67 mmol) synthesized in Preparation Example 8, 1,10- phenanthroline (0.24 g, 1.34 mmol), Cs ₂ CO ₃ (4.37 g, 13.4 mmol) and nitrobenzene (25 ml) were mixed and stirred at 210 ° C for 3 hours. After completion of the reaction, the solid salt was filtered and purified by column chromatography to obtain the target compound D-1 (3.0 g, yield 65%).

Mass (theory: 690.27, measurement: 690 g / mol)

[Synthesis Example 32] Synthesis of D-2

The procedure of Synthesis Example 31 was repeated except that 4-bromo-2,6-diphenylpyrimidine (2.5 g, 8.0 mmol) was used instead of 2-bromo-4,6-diphenylpyrimidine used in Synthesis Example 31, To obtain compound D-2 (3.3 g, yield 72%).

Mass (theory: 690.27, measurement: 690 g / mol)

[Synthesis Example 33] Synthesis of D-3

Except that 2-chloro-4,6-diphenyl-1,3,5-triazine (2.1 g, 8.0 mmol) was used instead of 2-bromo-4,6-diphenylpyrimidine used in Synthesis Example 31. 31, D-3 (2.8 g, yield 61%) was obtained.

Mass (theory value: 691.27, measurement: 691 g / mol)

[Synthesis Example 34] Synthesis of D-4

Except that 2- (4-bromophenyl) -4,6-diphenyl-1,3,5-triazine (3.1 g, 8.0 mmol) was used instead of 2-bromo-4,6-diphenylpyrimidine used in Synthesis Example 31 , The target compound D-4 (3.4 g, yield 66%) was obtained in the same manner as in Synthesis Example 31.

Mass (calc .: 767.30, found: 767 g / mol)

[ Synthetic example  35] Synthesis of D-5

Except that 2- (3-bromophenyl) -4,6-diphenyl-1,3,5-triazine (3.1 g, 8.0 mmol) was used instead of 2-bromo-4,6-diphenylpyrimidine used in Synthesis Example 31 , The target compound D-5 (3.8 g, yield 75%) was obtained in the same manner as in Synthesis Example 31.

Mass (calc .: 767.30, found: 767 g / mol)

[Synthesis Example 36] Synthesis of D-6

Was obtained in the same manner as in Synthesis Example 31, except that 2- (3-bromophenyl) dibenzo [b, d] thiophene (2.7 g, 8.0 mmol) was used in place of 2-bromo-4,6-diphenylpyrimidine used in Synthesis Example 31. To obtain the target compound D-6 (2.9 g, yield 61%).

Mass (theory: 718.24, measurement: 718 g / mol)

[Synthesis Example 37] Synthesis of D-7

The procedure of Synthesis Example 31 was repeated except that 2-bromodibenzo [b, d] furan (2.0 g, 8.0 mmol) was used instead of 2-bromo-4,6-diphenylpyrimidine used in Synthesis Example 31 to obtain To obtain compound D-7 (2.8 g, yield 66%).

Mass (theory: 626.23, measurement: 626 g / mol)

[Synthesis Example 38] Synthesis of D-8

The procedure of Synthesis Example 31 was repeated except for using 2- (4-bromophenyl) triphenylene (3.1 g, 8.0 mmol) instead of 2-bromo-4,6-diphenylpyrimidine used in Synthesis Example 31 to obtain the desired compound Of D-8 (3.5 g, yield 68%).

Mass (calc .: 762.30, found: 762 g / mol)

[Synthesis Example 39] Synthesis of D-9

The procedure of Synthesis Example 31 was repeated except that 2-chloro-4-phenylquinazoline (1.9 g, 8.0 mmol) was used instead of 2-bromo-4,6-diphenylpyrimidine used in Synthesis Example 31 to obtain D-9 (2.8 g, yield 64%).

Mass (theory: 664.26, found: 664 g / mol)

[Synthesis Example 40] Synthesis of D-10

Except that 2-chloro-4- (4- (naphthalen-1-yl) phenyl) quinazoline (2.9 g, 8.0 mmol) was used in place of 2-bromo-4,6-diphenylpyrimidine used in Synthesis Example 31, The procedure of Synthetic Example 31 was repeated to give the desired compound D-10 (4.0 g, yield 76%).

Mass (theory: 790.30, measurement: 790 g / mol)

[Synthesis Example 41] Synthesis of E-1

(3.1 g, 6.7 mmol), 2-bromo-4,6-diphenylpyrimidine (2.5 g, 8.0 mmol), CuI (0.13 g, 0.67 mmol) synthesized in Preparation Example 9, 1,10- phenanthroline (0.24 g, 1.34 mmol), Cs ₂ CO ₃ (4.37 g, 13.4 mmol) and nitrobenzene (25 ml) were mixed and stirred at 210 ° C for 3 hours. After completion of the reaction, the solid salt was filtered and purified by column chromatography to obtain the desired compound E-1 (2.9 g, yield 63%).

Mass (theory: 690.27 g / mol, measurement: 690 g / mol)

[Synthesis Example 42] Synthesis of E-2

The procedure of Synthesis Example 41 was repeated except that 4-bromo-2,6-diphenylpyrimidine (2.5 g, 8.0 mmol) was used instead of 2-bromo-4,6-diphenylpyrimidine used in Synthesis Example 41, Compound E-2 (3.2 g, yield 69%) was obtained.

Mass (theory: 690.27 g / mol, measurement: 690 g / mol)

[Synthesis Example 43] Synthesis of E-3

Except that 2-chloro-4,6-diphenyl-1,3,5-triazine (2.14 g, 8.0 mmol) was used instead of 2-bromo-4,6-diphenylpyrimidine used in Synthesis Example 41. 41, the target compound E-3 (3.0 g, yield 65%) was obtained.

Mass (691.27 g / mol, measured: 691 g / mol)

[Synthesis Example 44] Synthesis of E-4

Except that 2- (4-bromophenyl) -4,6-diphenyl-1,3,5-triazine (3.15 g, 8.0 mmol) was used instead of 2-bromo-4,6-diphenylpyrimidine used in Synthesis Example 41 , The target compound E-4 (3.7 g, yield 71%) was obtained by the same procedure as Synthesis Example 41.

Mass (calculated: 767.30 g / mol, measured: 767 g / mol)

[Synthesis Example 45] Synthesis of E-5

Except that 2- (3-bromophenyl) -4,6-diphenyl-1,3,5-triazine (3.15 g, 8.0 mmol) was used instead of 2-bromo-4,6-diphenylpyrimidine used in Synthesis Example 41 , The target compound E-5 (3.8 g, yield 75%) was obtained in the same manner as in Synthesis Example 41.

Mass (calculated: 767.30 g / mol, measured: 767 g / mol)

[Synthesis Example 46] Synthesis of E-6

Was obtained in the same manner as in Synthesis Example 41, except that 2- (3-bromophenyl) dibenzo [b, d] thiophene (2.71 g, 8.0 mmol) was used in place of 2-bromo-4,6-diphenylpyrimidine used in Synthesis Example 41 (3.1 g, yield 64%) as a target compound E-6.

Mass (theory: 718.24 g / mol, measured: 718 g / mol)

[Synthesis Example 47] Synthesis of E-7

The procedure of Synthesis Example 41 was repeated except that 2-bromodibenzo [b, d] furan (1.98 g, 8.0 mmol) was used instead of 2-bromo-4,6-diphenylpyrimidine used in Synthesis Example 41, Compound E-7 (2.6 g, yield 61%) was obtained.

Mass (theory: 626.23 g / mol, measurement: 626 g / mol)

[Synthesis Example 48] Synthesis of E-8

The procedure of Synthesis Example 41 was repeated except that 2- (4-bromophenyl) triphenylene (3.07 g, 8.0 mmol) was used instead of 2-bromo-4,6-diphenylpyrimidine used in Synthesis Example 41, E-8 (3.1 g, yield 60%).

Mass (calculated: 762.3 g / mol, measured: 762 g / mol)

[Synthesis Example 49] Synthesis of E-9

The same procedure as in Synthesis Example 41 was repeated but using 2-chloro-4-phenylquinazoline (1.93 g, 8.0 mmol) instead of 2-bromo-4,6-diphenylpyrimidine used in Synthesis Example 41, E-9 (2.8 g, yield 62%).

Mass (theory: 664.26 g / mol, measurement: 664 g / mol)

[Synthesis Example 50] Synthesis of E-10

Except that 2-chloro-4- (4- (naphthalen-1-yl) phenyl) quinazoline (2.94 g, 8.0 mmol) was used in place of 2-bromo-4,6-diphenylpyrimidine used in Synthesis Example 41, The procedure of Synthesis Example 41 was repeated to obtain the desired compound E-10 (3.7 g, yield 69%).

Mass (theory: 790.30 g / mol, measurement: 790 g / mol)

[Synthesis Example 51] Synthesis of F-1

(3.1 g, 6.7 mmol), 2-bromo-4,6-diphenylpyrimidine (2.5 g, 8.0 mmol), CuI (0.13 g, 0.67 mmol) synthesized in Preparation Example 10, 1,10- phenanthroline (0.24 g, 1.34 mmol), Cs ₂ CO ₃ (4.37 g, 13.4 mmol) and nitrobenzene (25 ml) were mixed and stirred at 210 ° C for 3 hours. After completion of the reaction, the solid salt was filtered and purified by column chromatography to obtain the target compound F-1 (3.0 g, yield 65%).

Mass (theory: 690.27 g / mol, measurement: 690 g / mol)

[Synthesis Example 52] Synthesis of F-2

The procedure of Synthesis Example 51 was repeated except that 4-bromo-2,6-diphenylpyrimidine (2.5 g, 8.0 mmol) was used instead of 2-bromo-4,6-diphenylpyrimidine used in Synthesis Example 51 to obtain To obtain compound F-2 (2.9 g, yield 62%).

Mass (theory: 690.27 g / mol, measurement: 690 g / mol)

[Synthesis Example 53] Synthesis of F-3

Except that 2-chloro-4,6-diphenyl-1,3,5-triazine (2.14 g, 8.0 mmol) was used instead of 2-bromo-4,6-diphenylpyrimidine used in Synthesis Example 51 51, 3.2 g (yield 70%) of the target compound F-3 was obtained.

Mass (691.27 g / mol, measured: 691 g / mol)

[Synthesis Example 54] Synthesis of F-4

Except that 2- (4-bromophenyl) -4,6-diphenyl-1,3,5-triazine (3.15 g, 8.0 mmol) was used instead of 2-bromo-4,6-diphenylpyrimidine used in Synthesis Example 51 , The target compound F-4 (3.3 g, yield 64%) was obtained by carrying out the same procedure as in Synthesis Example 51.

Mass (calculated: 767.30 g / mol, measured: 767 g / mol)

[Synthesis Example 55] Synthesis of F-5

Except that 2- (3-bromophenyl) -4,6-diphenyl-1,3,5-triazine (3.15 g, 8.0 mmol) was used instead of 2-bromo-4,6-diphenylpyrimidine used in Synthesis Example 51 , The target compound F-5 (3.7 g, yield 71%) was obtained in the same manner as in Synthesis Example 51.

Mass (calculated: 767.30 g / mol, measured: 767 g / mol)

[Synthesis Example 56] Synthesis of F-6

Dibenzo [b, d] thiophene (2.71 g, 8.0 mmol) instead of 2-bromo-4,6-diphenylpyrimidine used in Synthesis Example 51 was used in place of To obtain the target compound F-6 (3.3 g, yield 68%).

Mass (theory: 718.24 g / mol, measured: 718 g / mol)

[Synthesis Example 57] Synthesis of F-7

The procedure of Synthesis Example 51 was repeated except that 2-bromodibenzo [b, d] furan (1.98 g, 8.0 mmol) was used instead of 2-bromo-4,6-diphenylpyrimidine used in Synthesis Example 51 to obtain To obtain compound F-7 (2.5 g, yield 60%).

Mass (theory: 626.23 g / mol, measurement: 626 g / mol)

[Synthesis Example 58] Synthesis of F-8

The procedure of Synthesis Example 51 was repeated except for using 2- (4-bromophenyl) triphenylene (3.07 g, 8.0 mmol) instead of 2-bromo-4,6-diphenylpyrimidine used in Synthesis Example 51 to obtain the desired compound F-8 (3.2 g, yield 62%).

Mass (calculated: 762.30 g / mol, measured: 762 g / mol)

[Synthesis Example 59] Synthesis of F-9

The procedure of Synthesis Example 51 was repeated except that 2-chloro-4-phenylquinazoline (3.07 g, 8.0 mmol) was used instead of 2-bromo-4,6-diphenylpyrimidine used in Synthesis Example 51, F-9 (3.2 g, yield 72%) was obtained.

Mass (theory: 664.26 g / mol, measurement: 664 g / mol)

[Synthesis Example 60] Synthesis of F-10

Except that 2-chloro-4- (4- (naphthalen-1-yl) phenyl) quinazoline (2.94 g, 8.0 mmol) was used in place of 2-bromo-4,6-diphenylpyrimidine used in Synthesis Example 51, The procedure of Synthesis Example 51 was repeated to obtain the target compound F-10 (3.6 g, yield 68%).

Mass (theory: 790.30 g / mol, measurement: 790 g / mol)

[Synthesis Example 61] Synthesis of G-1

(3.6 g, 6.7 mmol), 2-bromo-4,6-diphenylpyrimidine (2.5 g, 8.0 mmol), CuI (0.13 g, 0.67 mmol) synthesized in Preparation Example 11, 1,10- phenanthroline (0.24 g, 1.34 mmol), Cs ₂ CO ₃ (4.37 g, 13.4 mmol) and nitrobenzene (25 ml) were mixed and stirred at 210 ° C for 3 hours. After completion of the reaction, the solid salt was filtered and purified by column chromatography to obtain the target compound G-1 (3.2 g, yield 63%).

Mass (calculated: 766.31 g / mol, measured: 766 g / mol)

[Synthesis Example 62] Synthesis of G-2

The procedure of Synthesis Example 61 was repeated except that 4-bromo-2,6-diphenylpyrimidine (2.5 g, 8.0 mmol) was used instead of 2-bromo-4,6-diphenylpyrimidine used in Synthesis Example 61, To obtain compound G-2 (3.1 g, yield 61%).

Mass (calculated: 766.31 g / mol, measured: 766 g / mol)

[Synthesis Example 63] Synthesis of G-3

Except that 2-chloro-4,6-diphenyl-1,3,5-triazine (2.14 g, 8.0 mmol) was used instead of 2-bromo-4,6-diphenylpyrimidine used in Synthesis Example 61 61, the objective compound G-3 (3.3 g, yield 65%) was obtained.

Mass (theory: 767.31 g / mol, measured: 767 g / mol)

[Synthesis Example 64] Synthesis of G-4

Except that 2- (4-bromophenyl) -4,6-diphenyl-1,3,5-triazine (3.15 g, 8.0 mmol) was used instead of 2-bromo-4,6-diphenylpyrimidine used in Synthesis Example 61 , The target compound G-4 (3.7 g, yield 66%) was obtained in the same manner as in Synthesis Example 61.

Mass (theory: 843.34 g / mol, measured: 843 g / mol)

[ Synthetic example  65] Synthesis of G-5

Except that 2- (3-bromophenyl) -4,6-diphenyl-1,3,5-triazine (3.15 g, 8.0 mmol) was used instead of 2-bromo-4,6-diphenylpyrimidine used in Synthesis Example 61 , The target compound G-5 (3.6 g, yield 64%) was obtained in the same manner as in Synthesis Example 61.

Mass (theory: 843.34 g / mol, measured: 843 g / mol)

[Synthesis Example 66] Synthesis of G-6

Dibenzo [b, d] thiophene (2.71 g, 8.0 mmol) was used in place of 2-bromo-4,6-diphenylpyrimidine used in Synthesis Example 61, To obtain the target compound G-6 (3.8 g, yield 71%).

Mass (theory: 794.28 g / mol, measured: 794 g / mol)

[Synthesis Example 67] Synthesis of G-7

The procedure of Synthesis Example 61 was repeated except for using 2-bromodibenzo [b, d] furan (1.98 g, 8.0 mmol) instead of 2-bromo-4,6-diphenylpyrimidine used in Synthesis Example 61, To obtain compound G-7 (3.5 g, yield 74%).

Mass (theory: 702.27 g / mol, measurement: 702 g / mol)

[ Synthetic example  68] Synthesis of G-8

The procedure of Synthesis Example 61 was repeated except for using 2- (4-bromophenyl) triphenylene (3.07 g, 8.0 mmol) instead of 2-bromo-4,6-diphenylpyrimidine used in Synthesis Example 61 to obtain the desired compound G-8 (3.4 g, yield 60%).

Mass (theory: 838.34 g / mol, measurement: 838 g / mol)

[Synthesis Example 69] Synthesis of G-9

The procedure of Synthesis Example 61 was repeated except that 2-chloro-4-phenylquinazoline (3.07 g, 8.0 mmol) was used instead of 2-bromo-4,6-diphenylpyrimidine used in Synthesis Example 61, G-9 (3.4 g, yield 68%).

Mass (calculated value: 740.30 g / mol, measured value: 740 g / mol)

[Synthesis Example 70] Synthesis of G-10

Except that 2-chloro-4- (4- (naphthalen-1-yl) phenyl) quinazoline (2.94 g, 8.0 mmol) was used in place of 2-bromo-4,6-diphenylpyrimidine used in Synthesis Example 61, The procedure of Synthesis Example 61 was repeated to give the target compound G-10 (4.2 g, yield 73%).

Mass (theory: 866.34 g / mol, measurement: 866 g / mol)

[Synthesis Example 71] Synthesis of H-1

(4.1 g, 6.7 mmol), 2-bromo-4,6-diphenylpyrimidine (2.5 g, 8.0 mmol), CuI (0.13 g, 0.67 mmol) synthesized in Preparation Example 12, 1,10- phenanthroline (0.24 g, 1.34 mmol), Cs ₂ CO ₃ (4.37 g, 13.4 mmol) and nitrobenzene (25 ml) were mixed and stirred at 210 ° C for 3 hours. After completion of the reaction, the solid salt was filtered and purified by column chromatography to obtain the target compound H-1 (3.7 g, yield 65%).

Mass (theory: 842.34 g / mol, measured: 842 g / mol)

[Synthesis Example 72] Synthesis of H-2

The procedure of Synthesis Example 71 was repeated except that 4-bromo-2,6-diphenylpyrimidine (2.5 g, 8.0 mmol) was used instead of 2-bromo-4,6-diphenylpyrimidine used in Synthesis Example 71, To obtain compound H-2 (3.7 g, yield 66%).

Mass (theory: 842.34 g / mol, measured: 842 g / mol)

[Synthesis Example 73] Synthesis of H-3

Except that 2-chloro-4,6-diphenyl-1,3,5-triazine (2.14 g, 8.0 mmol) was used instead of 2-bromo-4,6-diphenylpyrimidine used in Synthesis Example 71. 71, the target compound H-3 (3.5 g, yield 62%) was obtained.

Mass (theory: 843.34 g / mol, measured: 843 g / mol)

[Synthesis Example 74] Synthesis of H-4

Except that 2- (4-bromophenyl) -4,6-diphenyl-1,3,5-triazine (3.15 g, 8.0 mmol) was used instead of 2-bromo-4,6-diphenylpyrimidine used in Synthesis Example 71 , The objective compound H-4 (3.9 g, yield 64%) was obtained by carrying out the same procedure as in Synthesis Example 71.

Mass (theory: 919.37 g / mol, measured: 919 g / mol)

[Synthesis Example 75] Synthesis of H-5

Except that 2- (3-bromophenyl) -4,6-diphenyl-1,3,5-triazine (3.15 g, 8.0 mmol) was used instead of 2-bromo-4,6-diphenylpyrimidine used in Synthesis Example 71 , The target compound H-5 (4.4 g, yield 71%) was obtained in the same manner as in Synthetic Example 71.

Mass (theory: 919.37 g / mol, measured: 919 g / mol)

[Synthesis Example 76] Synthesis of H-6

Dibenzo [b, d] thiophene (2.71 g, 8.0 mmol) was used instead of 2-bromo-4,6-diphenylpyrimidine used in Synthesis Example 71. (3.8 g, yield 66%) of the desired compound, H-6, was obtained.

Mass (theory: 870.31 g / mol, measured: 870 g / mol)

[Synthesis Example 77] Synthesis of H-7

The procedure of Synthesis Example 71 was repeated except that 2-bromodibenzo [b, d] furan (1.98 g, 8.0 mmol) was used instead of 2-bromo-4,6-diphenylpyrimidine used in Synthesis Example 71, To obtain compound H-7 (3.7 g, yield 70%).

Mass (theory: 778.30 g / mol, measurement: 778 g / mol)

[Synthesis Example 78] Synthesis of H-8

The procedure of Synthesis Example 71 was repeated except that 2- (4-bromophenyl) triphenylene (3.07 g, 8.0 mmol) was used instead of 2-bromo-4,6-diphenylpyrimidine used in Synthesis Example 71, H-8 (4.0 g, yield 65%).

Mass (calculated: 914.37 g / mol, measured: 914 g / mol)

[Synthesis Example 79] Synthesis of H-9

The procedure of Synthesis Example 71 was repeated except that 2-chloro-4-phenylquinazoline (3.07 g, 8.0 mmol) was used instead of 2-bromo-4,6-diphenylpyrimidine used in Synthesis Example 71, H-9 (3.7 g, yield 67%).

Mass (theory: 816.33 g / mol, measured: 816 g / mol)

[Synthesis Example 80] Synthesis of H-10

Except that 2-chloro-4- (4- (naphthalen-1-yl) phenyl) quinazoline (2.94 g, 8.0 mmol) was used in place of 2-bromo-4,6-diphenylpyrimidine used in Synthesis Example 71, The target compound H-10 (4.5 g, yield 72%) was obtained in the same manner as in Synthetic Example 71.

Mass (theory: 942.37 g / mol, measurement: 942 g / mol)

[Synthesis Example 81] Synthesis of I-1

(4.4 g, 6.7 mmol), 2-bromo-4,6-diphenylpyrimidine (2.5 g, 8.0 mmol), CuI (0.13 g, 0.67 mmol) synthesized in Preparation Example 13, 1,10- phenanthroline (0.24 g, 1.34 mmol), Cs ₂ CO ₃ (4.37 g, 13.4 mmol) and nitrobenzene (25 ml) were mixed and stirred at 210 ° C for 3 hours. After the reaction was completed, the solid salt was filtered and then purified by column chromatography to obtain the desired compound I-1 (3.7 g, yield 63%).

Mass (theory: 882.37 g / mol, measurement: 882 g / mol)

[Synthesis Example 82] Synthesis of I-2

The procedure of Synthesis Example 81 was repeated except that 4-bromo-2,6-diphenylpyrimidine (2.5 g, 8.0 mmol) was used instead of 2-bromo-4,6-diphenylpyrimidine used in Synthesis Example 81 to obtain Compound I-2 (4.0 g, yield 67%) was obtained.

Mass (theory: 882.37 g / mol, measurement: 882 g / mol)

[Synthesis Example 83] Synthesis of I-3

Except that 2-chloro-4,6-diphenyl-1,3,5-triazine (2.14 g, 8.0 mmol) was used instead of 2-bromo-4,6-diphenylpyrimidine used in Synthesis Example 81. 81, the objective compound I-3 (3.6 g, yield 60%) was obtained.

Mass (theory: 883.37 g / mol, measurement: 883 g / mol)

[Synthesis Example 84] Synthesis of I-4

Except that 2- (4-bromophenyl) -4,6-diphenyl-1,3,5-triazine (3.15 g, 8.0 mmol) was used instead of 2-bromo-4,6-diphenylpyrimidine used in Synthesis Example 81 , The objective compound I-4 (4.4 g, yield 68%) was obtained in the same manner as in Synthesis Example 81.

Mass (theory: 959.40 g / mol, measurement: 959 g / mol)

[ Synthetic example  85] Synthesis of I-5

Except that 2- (3-bromophenyl) -4,6-diphenyl-1,3,5-triazine (3.15 g, 8.0 mmol) was used instead of 2-bromo-4,6-diphenylpyrimidine used in Synthesis Example 81 , The objective compound I-5 (4.7 g, yield 73%) was obtained by carrying out the same procedure as in Synthesis Example 81.

Mass (theory: 959.40 g / mol, measurement: 959 g / mol)

[Synthesis Example 86] Synthesis of I-6

The same procedure as in Synthesis Example 81 was repeated except for using 2- (3-bromophenyl) dibenzo [b, d] thiophene (2.71 g, 8.0 mmol) instead of 2-bromo-4,6-diphenylpyrimidine used in Synthesis Example 81 Was performed to obtain I-6 (4.6 g, yield 75%) as a target compound.

Mass (theory: 910.34 g / mol, measured: 910 g / mol)

[Synthesis Example 87] Synthesis of I-7

The procedure of Synthesis Example 81 was repeated except that 2-bromodibenzo [b, d] furan (1.98 g, 8.0 mmol) was used in place of 2-bromo-4,6-diphenylpyrimidine used in Synthesis Example 81 to obtain Compound I-7 (3.9 g, yield 72%) was obtained.

Mass (theory: 818.33 g / mol, measurement: 818 g / mol)

[Synthesis Example 88] Synthesis of I-8

The procedure of Synthesis Example 81 was repeated except for using 2- (4-bromophenyl) triphenylene (3.07 g, 8.0 mmol) instead of 2-bromo-4,6-diphenylpyrimidine used in Synthesis Example 81 to obtain the desired compound I-8 (4.2 g, yield 65%).

Mass (calculated: 954.40 g / mol, measured: 954 g / mol)

[Synthesis Example 89] Synthesis of I-9

The procedure of Synthesis Example 81 was repeated except that 2-chloro-4-phenylquinazoline (3.07 g, 8.0 mmol) was used instead of 2-bromo-4,6-diphenylpyrimidine used in Synthesis Example 81 to obtain the desired compound I-9 (3.8 g, yield 66%).

Mass (theory: 856.36 g / mol, measured: 856 g / mol)

[Synthesis Example 90] Synthesis of I-10

Except that 2-chloro-4- (4- (naphthalen-1-yl) phenyl) quinazoline (2.94 g, 8.0 mmol) was used in place of 2-bromo-4,6-diphenylpyrimidine used in Synthesis Example 81, The target compound I-10 (4.7 g, yield 71%) was obtained in the same manner as in Synthesis Example 81.

Mass (theory: 982.40 g / mol, measured: 982 g / mol)

[Synthesis Example 91] Synthesis of J-1

(3.1 g, 6.7 mmol), 5'-bromo- (1,1 ', 3', 1 ") terphenyl (2.5 g, 8.0 mmol) synthesized in Preparation Example 5 and CuI (0.27 g, 1.34 mmol), Cs ₂ CO ₃ (4.37 g, 13.4 mmol) and nitrobenzene (25 ml) were mixed and stirred at 210 ° C. for 3 hours. , The solid salt was filtered and then purified by column chromatography to obtain the target compound J-1 (3.0 g, yield 65%).

Mass (theory: 688.28, found: 688 g / mol)

[Synthesis Example 92] Synthesis of J-2

The procedure of Synthesis Example 91 was repeated except that 4-bromobiphenyl (1.90 g, 8.0 mmol) was used instead of 5'-bromo- (1,1 ', 3', 1 " To obtain the target compound J-2 (3.0 g, yield 72%).

Mass (theory: 612.25, measurement: 612 g / mol)

[Synthesis Example 93] Synthesis of J-3

The use of a 5'-bromo- (1,1 ', 3 ', 1 ") 2-bromo-9,9-dimethyl-9 H- fluorene instead terphenyl (2.18 g, 8.0 mmol) in Synthesis Example 91 , The objective compound J-3 (3.1 g, yield 70%) was obtained in the same manner as in Synthesis Example 91.

Mass (theory: 652.28, found: 652 g / mol)

[Synthesis Example 94] Synthesis of K-1

(3.6 g, 6.7 mmol), 5'-bromo- (1,1 ', 3', 1 ") terphenyl (2.5 g, 8.0 mmol) synthesized in Preparation Example 11 and CuI (0.27 g, 1.34 mmol), Cs ₂ CO ₃ (4.37 g, 13.4 mmol) and nitrobenzene (25 ml) were mixed and stirred at 210 ° C. for 3 hours. , The solid salt was filtered and then purified by column chromatography to obtain the desired compound K-1 (3.5 g, yield 68%).

Mass (calcd.: 764.32, found: 764 g / mol)

[ Synthetic example  95] Synthesis of K-2

The procedure of Synthesis Example 94 was repeated except that 4-bromobiphenyl (1.90 g, 8.0 mmol) was used instead of 5'-bromo- (1,1 ', 3', 1 " To obtain the target compound K-2 (3.0 g, yield 65%).

Mass (theory: 688.29, found: 688 g / mol)

[Synthesis Example 96] Synthesis of K-3

The use of a 5'-bromo- (1,1 ', 3 ', 1 ") 2-bromo-9,9-dimethyl-9 H- fluorene instead terphenyl (2.18 g, 8.0 mmol) in Synthesis Example 94 , The target compound K-3 (3.0 g, yield: 61%) was obtained by carrying out the same processes as in Synthesis Example 94.

Mass (theory: 728.32, measurement: 728 g / mol)

[ Synthetic example  97] Synthesis of L-1

(4.1 g, 6.7 mmol), 5'-bromo- (1,1 ', 3', 1 ") terphenyl (2.5 g, 8.0 mmol) synthesized in Preparation Example 12 and CuI (0.27 g, 1.34 mmol), Cs ₂ CO ₃ (4.37 g, 13.4 mmol) and nitrobenzene (25 ml) were mixed and stirred at 210 ° C. for 3 hours. , The solid salt was filtered and then purified by column chromatography to obtain the target compound L-1 (3.7 g, yield 65%).

Mass (theory: 840.35, measured: 840 g / mol)

[Synthesis Example 98] Synthesis of L-2

The procedure of Synthesis Example 97 was repeated except that 4-bromobiphenyl (1.90 g, 8.0 mmol) was used instead of 5'-bromo- (1,1 ', 3', 1 " To obtain the target compound L-2 (3.3 g, yield 64%).

Mass (calcd.: 764.32, found: 764 g / mol)

[Synthesis Example 99] Synthesis of L-3

The use of a 5'-bromo- (1,1 ', 3 ', 1 ") 2-bromo-9,9-dimethyl-9 H- fluorene instead terphenyl (2.18 g, 8.0 mmol) in Synthesis Example 97 , The target compound L-3 (3.3 g, yield 61%) was obtained by carrying out the same procedure as in Synthesis Example 97.

Mass (theory: 804.35, measured: 804 g / mol)

[Synthesis Example 100] Synthesis of M-1

(4.4 g, 6.7 mmol), 5'-bromo- (1,1 ', 3', 1 ") terphenyl (2.5 g, 8.0 mmol) synthesized in Preparation Example 13 and CuI (0.27 g, 1.34 mmol), Cs ₂ CO ₃ (4.37 g, 13.4 mmol) and nitrobenzene (25 ml) were mixed and stirred at 210 ° C. for 3 hours. , The solid salt was filtered and then purified by column chromatography to obtain the target compound M-1 (3.8 g, yield 64%).

Mass (theory: 880.38, measured: 880 g / mol)

[Synthesis Example 101] Synthesis of M-2

The procedure of Synthesis Example 100 was repeated except that 4-bromobiphenyl (1.90 g, 8.0 mmol) was used instead of 5'-bromo- (1,1 ', 3', 1 " To obtain the target compound M-2 (3.8 g, yield 70%).

Mass (theory: 804.35, measured: 804 g / mol)

[Synthesis Example 102] Synthesis of M-3

The use of a 5'-bromo- (1,1 ', 3 ', 1 ") 2-bromo-9,9-dimethyl-9 H- fluorene instead terphenyl (2.18 g, 8.0 mmol) synthesized in Example 100 , The target compound M-3 (4.1 g, yield 73%) was obtained by carrying out the same procedure as in Synthesis Example 100.

Mass (theory: 844.38, found: 844 g / mol)

[Synthesis Example 103] Synthesis of Q-1

(3.4 g, 6.7 mmol), 2-bromo-4,6-diphenylpyrimidine (2.5 g, 8.0 mmol), CuI (0.13 g, 0.67 mmol) synthesized in Preparation Example 14, 1,10- phenanthroline (0.24 g, 1.34 mmol), Cs ₂ CO ₃ (4.37 g, 13.4 mmol) and nitrobenzene (25 ml) were mixed and stirred at 210 ° C for 3 hours. After completion of the reaction, the solid salt was filtered and then purified by column chromatography to obtain the target compound Q-1 (3.2 g, yield 65%).

Mass (theory: 740.71, measurement: 740 g / mol)

[Synthesis Example 104] Synthesis of Q-2

The procedure of Synthesis Example 103 was repeated except that 4-bromo-2,6-diphenylpyrimidine (2.5 g, 8.0 mmol) was used instead of 2-bromo-4,6-diphenylpyrimidine used in Synthesis Example 103. Compound Q-2 (3.1 g, yield 62%).

Mass (theory: 740.71, measurement: 740 g / mol)

[Synthesis Example 105] Synthesis of Q-3

Except that 2-chloro-4,6-diphenyl-1,3,5-triazine (2.14 g, 8.0 mmol) was used instead of 2-bromo-4,6-diphenylpyrimidine used in Synthesis Example 103. 103, 3.2 g (yield 64%) of the target compound Q-3 was obtained.

Mass (theory value: 741.71, measurement: 741 g / mol)

[Synthesis Example 106] Synthesis of Q-4

Except that 2- (4-bromophenyl) -4,6-diphenyl-1,3,5-triazine (3.1 g, 8.0 mmol) was used instead of 2-bromo-4,6-diphenylpyrimidine used in Synthesis Example 103 , The target compound Q-4 (3.9 g, yield 71%) was obtained by carrying out the same processes as in Synthesis Example 103.

Mass (theory: 817.7, measurement: 817 g / mol)

[Synthesis Example 107] Synthesis of Q-5

Except that 2- (3-bromophenyl) -4,6-diphenyl-1,3,5-triazine (3.1 g, 8.0 mmol) was used in place of 2-bromo-4,6-diphenylpyrimidine used in Synthesis Example 103 , The objective compound Q-5 (4.1 g, yield 75%) was obtained by carrying out the same processes as in Synthesis Example 103.

Mass (theory: 817.7, measurement: 817 g / mol)

[Synthesis Example 108] Synthesis of Q-6

Dibenzo [b, d] thiophene (2.7 g, 8.0 mmol) instead of 2-bromo-4,6-diphenylpyrimidine used in Synthesis Example 103 was used in place of To obtain the object compound Q-6 (3.6 g, yield 70%).

Mass (theory: 768.68, measurement: 768 g / mol)

[Synthesis Example 109] Synthesis of Q-7

The procedure of Synthesis Example 103 was repeated except that 2-bromodibenzo [b, d] furan (2.0 g, 8.0 mmol) was used instead of 2-bromo-4,6-diphenylpyrimidine used in Synthesis Example 103, To obtain compound Q-7 (3.0 g, yield 67%).

Mass (theory: 676.67, found: 676 g / mol)

[Synthesis Example 110] Synthesis of Q-8

The procedure of Synthesis Example 103 was repeated except for using 2- (4-bromophenyl) triphenylene (3.1 g, 8.0 mmol) instead of 2-bromo-4,6-diphenylpyrimidine used in Synthesis Example 103, (Q-8, 3.3 g, yield 60%).

Mass (theory: 812.74, measured: 812 g / mol)

[Synthesis Example 111] Synthesis of Q-9

The procedure of Synthesis Example 103 was repeated except that 2-chloro-4-phenylquinazoline (1.9 g, 8.0 mmol) was used instead of 2-bromo-4,6-diphenylpyrimidine used in Synthesis Example 103, Q-9 (3.1 g, yield 65%).

Mass (theory: 714.7, measured: 714 g / mol)

[Synthesis Example 112] Synthesis of Q-10

Except that 2-chloro-4- (4- (naphthalen-1-yl) phenyl) quinazoline (2.9 g, 8.0 mmol) was used in place of 2-bromo-4,6-diphenylpyrimidine used in Synthesis Example 103, The procedure of Synthesis Example 103 was repeated to obtain the target compound Q-10 (3.7 g, yield 66%).

Mass (theory: 840.74, measured: 840 g / mol)

[Example 1] Production of green organic EL device

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

First, glass substrate coated with ITO (Indium tin oxide) thin film of 1500 Å thickness was cleaned with distilled water ultrasonic wave. After the distilled water was washed, the substrate was ultrasonically washed with a solvent such as isopropyl alcohol, acetone, or methanol, and dried. Then, the substrate was transferred to a UV OZONE cleaner (Power sonic 405, Hoshin Tech) And the substrate was transferred to a vacuum evaporator.

(60 nm) / TCTA (80 nm) / 90% Compound A-1 + 10% Ir (ppy) ₃ (30 nm) / BCP (10 nm) / Alq ₃ (30 nm) / LiF (1 nm) / Al (200 nm) were stacked in this order to fabricate an organic EL device.

At this time, the structures of m-MTDATA, TCTA, Ir (ppy) ₃ , and BCP used are as follows.

[ Example  2] to [ Example  80] Green organic EL  Device fabrication

A green organic EL device was fabricated in the same manner as in Example 1 except that each compound described in the following Table 1 was used in place of the compound A-1 used as a host material in forming the light emitting layer in Example 1.

[Comparative Example 1] Production of green organic EL device

A green organic EL device was fabricated in the same manner as in Example 1, except that CBP was used instead of Compound A-1 as a luminescent host material in forming the light emitting layer.

[Evaluation Example 1]

The driving voltage, current efficiency and emission peak at the current density (10) mA / cm 2 were measured for the green organic EL devices manufactured in Examples 1 to 80 and Comparative Example 1, respectively, and the results are shown in the following Table 1 .

Sample Host The driving voltage (V) EL peak (nm) Current efficiency (cd / A) Example 1 A-1 6.48 517 41.3 Example 2 A-2 6.86 518 41.3 Example 3 A-3 6.77 517 43.1 Example 4 A-4 6.66 515 43.5 Example 5 A-5 6.65 518 41.4 Example 6 A-6 6.65 518 42.2 Example 7 A-7 6.7 518 42 Example 8 A-8 6.66 515 41.8 Example 9 B-1 6.65 518 41.3 Example 10 B-2 6.65 517 41.2 Example 11 B-3 6.71 515 41.2 Example 12 B-4 6.65 518 41.4 Example 13 B-5 6.71 518 41.4 Example 14 B-6 6.72 518 41.9 Example 15 B-7 6.72 517 41.6 Example 16 B-8 6.73 518 41.5 Example 17 C-1 6.73 517 39.2 Example 18 C-2 6.73 515 41.3 Example 19 C-3 6.48 518 39.7 Example 20 C-4 6.86 518 38.9 Example 21 C-5 6.77 518 41.3 Example 22 C-6 6.66 518 39.7 Example 23 C-7 6.65 518 38.9 Example 24 C-8 6.65 515 41.3 Example 25 D-1 6.64 518 41.3 Example 26 D-2 6.64 518 41.3 Example 27 D-3 6.64 517 41.2 Example 28 D-4 6.63 518 41.2 Example 29 D-5 6.72 517 41.3 Example 30 D-6 6.73 515 41.3 Example 31 D-7 6.73 518 41.3 Example 32 D-8 6.73 518 41.2 Example 33 E-1 6.48 518 41.2 Example 34 E-2 6.86 517 41.4 Example 35 E-3 6.77 518 42.2 Example 36 E-4 6.66 517 42 Example 37 E-5 6.77 515 41.8 Example 38 E-6 6.66 518 42 Example 39 E-7 6.66 518 42.5 Example 40 E-8 6.81 517 41.3 Example 41 F-1 6.66 515 41.3 Example 42 F-2 6.81 518 39.7 Example 43 F-3 6.68 518 38.9 Example 44 F-4 6.66 518 41.3 Example 45 F-5 6.7 517 41.3 Example 46 F-6 6.7 515 43.1 Example 47 F-7 6.51 518 41.3 Example 48 F-8 6.77 518 41.3 Example 49 G-1 6.46 518 41.2 Example 50 G-2 6.81 517 41.2 Example 51 G-3 6.68 515 41.4 Example 52 G-4 6.66 518 42.2 Example 53 G-5 6.73 518 42 Example 54 G-6 6.73 517 41.2 Example 55 G-7 6.73 515 41.4 Example 56 G-8 6.48 518 43.1 Example 57 H-1 6.86 518 43.5 Example 58 H-2 6.77 517 41.4 Example 59 H-3 6.66 515 42.2 Example 60 H-4 6.77 518 41.9 Example 61 H-5 6.66 517 41.8 Example 62 H-6 6.73 515 41.4 Example 63 H-7 6.73 518 42.2 Example 64 H-8 6.48 518 42.0 Example 65 I-1 6.70 518 43.5 Example 66 I-2 6.75 517 41.4 Example 67 I-3 6.60 517 42.0 Example 68 I-4 6.70 518 42.1 Example 69 I-5 6.65 517 41.6 Example 70 I-6 6.72 515 41.4 Example 71 I-7 6.70 518 42.0 Example 72 I-8 6.50 518 41.9 Example 73 Q-1 6.66 518 41.2 Example 74 Q-2 6.60 518 42.1 Example 75 Q-3 6.60 518 41.8 Example 76 Q-4 6.60 517 42.1 Example 77 Q-5 6.70 515 42.0 Example 78 Q-6 6.64 518 41.5 Example 79 Q-7 6.50 518 41.9 Example 80 Q-8 6.55 518 42.6 Comparative Example 1 CBP 6.93 516 38.2

As shown in Table 1, the green organic EL devices of Examples 1 to 80 using the compounds (A-1 to Q-8) according to the present invention as the host of the light emitting layer were green OLEDs of Comparative Example 1 using CBP It was confirmed that the current efficiency and the driving voltage were superior to those of the device.

[Example 81] Production of red organic EL device

Compound A-9 synthesized in Synthesis Example 9 was subjected to high purity sublimation purification by a conventionally known method, and a red organic electroluminescent device was fabricated according to the following procedure.

First, glass substrate coated with ITO (Indium tin oxide) thin film of 1500 Å thickness was cleaned with distilled water ultrasonic wave. After the distilled water was washed, the substrate was ultrasonically washed with a solvent such as isopropyl alcohol, acetone, or methanol, and dried. Then, the substrate was transferred to a UV OZONE cleaner (Power sonic 405, Hoshin Tech) And the substrate was transferred to a vacuum evaporator.

(60 nm) / TCTA (80 nm) / 90% Compound A-9 + 10% (piq) ₂ Ir (acac) (30 nm) / BCP (10 nm) / Alq ₃ 30 nm) / LiF (1 nm) / Al (200 nm) were stacked in this order to fabricate an organic electroluminescent device.

At this time, the structures of m-MTDATA, TCTA and BCP used are as described in Example 1, and the structure of (piq) ₂ Ir (acac) is as follows.

[Example 82] - [Example 100] Production of red organic EL device

A red organic EL device was fabricated in the same manner as in Example 81 except that each compound described in the following Table 2 was used in place of Compound A-9 used as a host material in forming the light emitting layer in Example 81.

[ Comparative Example  2]

A red organic electroluminescent device was fabricated in the same manner as in Example 81 except that CBP was used instead of the compound A-9 used as a luminescent host material in the formation of the light emitting layer. At this time, the structure of CBP used is as described in Comparative Example 1.

[Evaluation Example 2]

The driving voltage and the current efficiency at a current density of 10 mA / cm 2 were measured for each of the organic electroluminescent devices manufactured in Examples 81 to 100 and Comparative Example 2, and the results are shown in Table 2 below.

Sample Host The driving voltage (V) Current efficiency (cd / A) Example 81 A-9 4.91 12.1 Example 82 A-10 4.55 12.4 Example 83 B-9 4.67 8.6 Example 84 B-10 4.87 13.7 Example 85 C-9 4.78 12.1 Example 86 C-10 4.91 9.1 Example 87 D-9 4.52 9.2 Example 88 D-10 4.87 13.7 Example 89 E-9 4.78 12.1 Example 90 E-10 4.55 9.1 Example 91 F-9 4.87 12.1 Example 92 F-10 4.78 9.1 Example 93 G-9 4.78 9.2 Example 94 G-10 4.91 8.9 Example 95 H-9 4.52 8.6 Example 96 H-10 4.87 12.1 Example 97 I-9 4.78 9.1 Example 98 I-10 4.91 9.2 Example 99 Q-9 4.80 10.8 Example 100 Q-10 4.90 11.0 Comparative Example 2 CBP 5.25 8.2

As shown in Table 2, the red organic electroluminescent devices of Examples 81 to 100 using the compounds (A-9 to Q-10) according to the present invention as the host of the light emitting layer were red organic It was confirmed that the current efficiency and the driving voltage were superior to those of the electroluminescent device.

[Example 101] Production of green organic EL device

Compound J-1 synthesized in Synthesis Example 91 was subjected to high purity sublimation purification by a conventional method, and a red organic electroluminescent device was fabricated according to the following procedure.

First, glass substrate coated with ITO (Indium tin oxide) thin film of 1500 Å thickness was cleaned with distilled water ultrasonic wave. After the distilled water was washed, the substrate was ultrasonically washed with a solvent such as isopropyl alcohol, acetone, or methanol, and dried. Then, the substrate was transferred to a UV OZONE cleaner (Power sonic 405, Hoshin Tech) And the substrate was transferred to a vacuum evaporator.

(60 nm) / Compound J-1 (80 nm) / 90% CBP + 10% Ir (ppy) ₃ (30 nm) / BCP (10 nm) / Alq ₃ (30 nm) / LiF (1 nm) / Al (200 nm) were stacked in this order to fabricate an organic electroluminescent device.

 [Example 102] - [Example 112] Production of green organic EL device

A green organic EL device was fabricated in the same manner as in Example 101 except that each compound described in the following Table 3 was used instead of the compound J-1 used as a hole transporting layer material in Example 101.

[ Comparative Example  3]

A green organic electroluminescent device was fabricated in the same manner as in Example 101 except that TCTA was used in place of the compound J-1 used as the hole transport layer material. At this time, the structure of the TCTA used is the same as described in Example 1.

[Evaluation Example 3]

The driving voltage and the current efficiency at a current density of 10 mA / cm 2 were measured for each of the organic electroluminescent devices manufactured in Examples 101 to 112 and Comparative Example 3, and the results are shown in Table 2 below.

Sample Hole transport layer material The driving voltage (V) Current efficiency (cd / A) Example 101 J-1 6.50 40.9 Example 102 J-2 6.45 41.9 Example 103 J-3 6.50 41.9 Example 104 K-1 6.55 41.5 Example 105 K-2 6.60 42.0 Example 106 K-3 6.45 42.3 Example 107 L-1 6.50 40.9 Example 108 L-2 6.60 41.3 Example 109 L-3 6.65 41.8 Example 110 M-1 6.60 42.1 Example 111 M-2 6.70 41.6 Example 112 M-3 6.55 41.8 Comparative Example 3 TCTA 6.93 38.2

As shown in Table 3, the green organic electroluminescent devices of Examples 101 to 112, in which the compounds (J-1 to M-3) according to the present invention were used as the hole transport layer material, It was confirmed that the current efficiency and the driving voltage were superior to those of the electroluminescent device.

Claims (12)

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

(In the formula 1,
X ₁ is N (Ar ₁ )
L is a single bond,
In this case, L is connected to one carbon selected from the R ₇ to R ₁₀ positions, and at the same time, connected to one carbon selected from the R ₁₁ to R ₂₀ positions, but there is no substituent at a position connected to L,
R ₁ to R ₂₀ are the same as or different from each other, and each independently selected from the group consisting of hydrogen and C ₆ to C ₄₀ aryl groups, or R ₅ and R _6, or R ₁₅ and R ₁₆ , May form a ring,
Ar ₁ and R ₂₁ are each independently selected from the group consisting of a C ₆ to C ₄₀ aryl group and a heteroaryl group having 5 to 40 nuclear atoms,
Provided that when Ar ₁ and R ₂₁ are both a C ₆ to C ₄₀ aryl group, at least one aryl group is substituted with a heteroaryl group having 5 to 40 nuclear atoms,
The aryl group and the heteroaryl group of Ar ₁ and R ₂₁ are each independently substituted with at least one group selected from the group consisting of a C ₁ to C ₄₀ alkyl group, a C ₆ to C ₄₀ aryl group, and a heteroaryl group having 5 to 40 nuclear atoms Wherein the substituents may be the same or different when they are plural. The method according to claim 1,
Wherein said compound is represented by the following formula (2): &lt; EMI ID =
(2)

(In the formula (2)
X ₁ , L, and R ₁ to R ₂₁ are each as defined in claim 1,
Wherein L is connected to one carbon selected from the R ₇ to R ₁₀ positions and is connected to one carbon selected from R ₁₁ to R ₁₄ at the same time, but there is no substituent at a position connected to L). The method according to claim 1,
Wherein the compound is represented by any one of the following Chemical Formulas (4) to (7):
[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

(7)

(In the formulas (4) to (7)
X ₁ , L, R ₁ to R ₂₁ are as defined in claim 1, respectively. The method according to claim 1,
Wherein R ₅ and R ₆ is The compound is characterized by forming a condensed ring of C ₆ ~ C ₂₀ bonded to each other. The method according to claim 1,
Wherein said compound is represented by Formula 10:
[Chemical formula 10]

In Formula 10,
X ₁ , L, and R ₁ to R ₄ , R ₇ to R ₂₁ are each as defined in claim 1,
Wherein L is connected at the R ₈ position and at the same time is connected to one carbon selected from the R ₁₃ or R ₁₈ position, but no substituent at the position connected to L is present;
a is an integer of 1 to 4, and R is hydrogen. delete delete delete The method according to claim 1,
Wherein at least one of Ar &lt; ₁ &gt; and R &lt; ₂₁ &gt; is a substituent represented by the following formula (13)
[Chemical Formula 13]

(In the above formula (13)
L ₁ is a single bond or a group selected from the group consisting of C ₆ to C ₁₈ arylene groups and heteroarylene groups having 5 to 18 nuclear atoms,
Y ₁ to Y ₅ are the same or different and each independently N or C (R ₂₂ ), wherein when R ₂₂ is plural, they are the same or different,
R ₂₂ is selected from the group consisting of hydrogen, a C ₆ to C ₄₀ aryl group and a heteroaryl group having 5 to 40 nuclear atoms, or may be bonded to an adjacent group to form a condensed ring,
The arylene group and heteroarylene group of L _1, the aryl group and heteroaryl group of R ₂₂ may each independently be substituted with at least one substituent selected from the group consisting of C ₆ to C ₄₀ aryl groups, , They may be the same or different from each other). The method according to claim 1,
Wherein at least one of Ar ₁ and R ₂₁ is selected from the group consisting of substituents represented by the following formulas A-1 to A-15:

(In the above formulas A-1 to A-15,
L ₁ and R ₂₂ are each as defined in claim 9,
n is an integer from 1 to 4, R ₂₃ is selected from the group consisting of hydrogen and C ₆ ~ C ₄₀ aryl,
Each of the aryl groups of R ₂₃ may be independently substituted with one or more substituents selected from the group consisting of C ₆ to C ₄₀ aryl groups, and when the substituents are plural, they may be the same or different from each other). A cathode, and at least one organic layer interposed between the anode and the cathode,
Wherein at least one of the one or more organic layers includes the compound according to any one of claims 1 to 5, 9 and 10. 12. The method of claim 11,
Wherein the one or more organic layers include a hole injection layer, a hole transport layer, a phosphorescent light emitting layer, an electron transport layer and an electron injection layer,
Wherein the organic compound layer containing the compound is a hole transport layer or a phosphorescent light-emitting layer.