KR20160091735A - Organic light-emitting compound and organic electroluminescent device using the same - Google Patents

Abstract

The present invention relates to a novel compound with excellent light-emitting ability. The present invention further relates to an organic electroluminescent device which includes the same in at least one organic material layer and exhibits characteristics such as high luminous efficiency, low driving voltage, and long lifespan.

Description

TECHNICAL FIELD [0001] The present invention relates to an organic electroluminescent compound, and an organic electroluminescent device using the same. BACKGROUND ART [0002]

The present invention relates to a novel organic light emitting compound and an organic electroluminescent device using the same. More particularly, the present invention relates to a novel organic compound having excellent hole injecting and transporting ability, electron injecting and transporting ability, The present invention relates to an organic electroluminescent device having improved characteristics such as high luminous efficiency, low driving voltage and long life.

A study on electroluminescent (EL) devices (hereinafter, simply referred to as "organic EL devices") which led to blue electroluminescence using anthracene single crystals in 1965 based on observation of organic thin film emission of Bernanose in the 1950s A layered organic EL device was proposed in 1987 by Tang divided into a hole layer and a functional layer of a light emitting layer. In order to produce high efficiency and high number of organic EL devices, the organic EL device has been developed to introduce each characteristic organic material layer in the device, leading to the development of specialized materials used therefor.

In the organic EL device, when a voltage is applied between two electrodes, holes are injected into the anode, and electrons are injected into the organic layer from 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 used as the organic material layer may be classified into a light emitting material, a hole injecting material, a hole transporting material, an electron transporting material, and an electron injecting material depending on its function.

The light emitting layer forming material of the organic EL device can be classified into blue, green and red light emitting materials depending on the luminescent color. In addition, yellow and orange light emitting materials are also used as light emitting materials for realizing better color. Further, in order to increase the color purity and increase the luminous efficiency through energy transfer, a host / dopant system can be used as a light emitting material. The dopant material can be divided into a fluorescent dopant using an organic material and a phosphorescent dopant using a metal complex compound containing heavy atoms such as Ir and Pt. The development of such a phosphorescent material can theoretically improve luminous efficiency up to four times that of fluorescence, and attention is focused on phosphorescent host materials as well as phosphorescent dopants.

Up to now, hole injecting layer, hole transporting layer. As the hole blocking layer and the electron transporting layer, NPB, BCP, Alq ₃ and the like represented by the following formulas are widely known. Anthracene derivatives as a light emitting material have been reported as a fluorescent dopant / host material. Particularly, as a phosphorescent material having a great advantage in improving the efficiency of a light emitting material, a metal complex compound containing Ir such as Firpic, Ir (ppy) ₃ , (acac) Ir (btp) ₂ and the like is used as a blue, green and red dopant material . Up to now, 4,4-dicarbazolylbiphenyl (CBP) has shown excellent properties as a phosphorescent host material.

However, existing materials have advantages in terms of light emitting properties, but their glass transition temperature is low and their thermal stability is not very good, which is not satisfactory in terms of lifetime in organic EL devices.

An object of the present invention is to provide a novel organic compound which can be applied to an organic electroluminescent device and which is excellent in hole injection and transport ability, electron injection and transport ability, and light emission ability.

Another object of the present invention is to provide an organic electroluminescent device including the novel organic compound and exhibiting a low driving voltage and a high luminous efficiency and having an improved lifetime.

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

[Chemical Formula 1]

In Formula 1,

Y ₁ and Y ₂ , Y ₂ and Y ₃ , Y ₃ and Y ₄ , Y ₅ and Y ₆ , Y ₆ and Y ₇ , Y ₇ and Y ₈ , and Y ₉ and Y ₁₀ , Y ₁₀ and Y ₁₁ and Y ₁₁ and Y ₁₂ is condensed with a ring represented by the following formula (2) to form a condensed ring;

(2)

In Formula 2,

The dotted line is the part where the condensation occurs;

In the above Formulas 1 and 2,

X ₁ and X ₂ are the same or different and are each independently selected from _{O, S, N (Ar 1} ), C (Ar 2) (Ar 3), and Si (Ar ₄₎ selected from the group consisting of (Ar ₅₎ And at least one of X ₁ and X ₂ is N (Ar ₁ );

Y ₁ to Y _{12 which} are condensed with the ring represented by the general formula (2) and do not form a condensed ring are the same as or different from each other, and are each independently N or C (R ₁ );

When plural Y ₁₃ to Y ₁₆ are present, they are the same as or different from each other, and Y ₁₃ to Y ₁₆ are each independently N or C (R ₁ );

When R ₁ is plural, they are the same as or different from each other and each R ₁ is independently selected from the group consisting of hydrogen, deuterium, halogen, cyano, nitro, C ₁ to C ₄₀ alkyl, C ₃ to C ₄₀ cycloalkyl, A cycloalkyl group having 3 to 40 nuclear atoms, an aryl group having ₆ to ₆₀ carbon atoms, a heteroaryl group having 5 to 60 nuclear atoms, a C ₁ to C ₄₀ alkyloxy group, a C ₆ to C ₆₀ aryloxy group , A C ₁ to C ₄₀ alkylsilyl group, a C ₆ to C ₆₀ arylsilyl group, a C ₁ to C ₄₀ alkylboron group, a C ₆ to C ₆₀ arylboron group, a C ₆ to C ₆₀ arylphosphine group , C ₆ ~ C ₆₀ mono or diaryl phosphine of the blood selected from the group and a C ₆ ~ C ₆₀ aryl group consisting of an amine group, or by combining adjacent groups may form a condensed ring;

If the Ar ₁ to Ar ₅ multiple individuals, all of which are the same or different, wherein Ar ₁ to Ar ₅ is independently hydrogen, C alkyl group of ₁ ~ C _40, a cycloalkyl group of C ₃ ~ C _40, nuclear atomic 3 to 40 heterocycloalkyl group, an aryloxy group of a C ₆ ~ C ₆₀ aryl group, the number of nuclear atoms of 5 to 60 heteroaryl group, C ₁ ~ C ₄₀ alkyloxy group _{of, C 6 ~ C 60, C} 1 ~ C ₄₀ alkylsilyl group, a group C ₆ ~ C ₆₀ aryl silyl, C ₁ ~ C ₄₀ group of an alkyl boron, C ₆ ~ C group ₆₀ arylboronic of, C ₆ ~ C ₆₀ aryl phosphine group, C ₆ ~ selected from mono or diaryl phosphine blood group and a C ₆ ~ C ₆₀ aryl group consisting of the C ₆₀ amine, or by combining adjacent groups may form a condensed ring;

R ₁ and an alkyl group of Ar ₁ to Ar _5, a cycloalkyl group, a heterocycloalkyl group, an aryl group, a heteroaryl group, an alkyloxy group, an aryloxy group, an alkylsilyl group, an arylsilyl group, an alkyl boron group, an aryl boron group, an aryl phosphine group, a mono- or diaryl phosphine blood group and the arylamine groups are each independently selected from deuterium, halogen, cyano, C ₁ ~ C ₄₀ alkyl group, C of ₃ ~ C ₄₀ cycloalkyl group, the number of nuclear atoms of 3 to 40 heterocycloalkyl An alkyl group, a C ₆ to C ₆₀ aryl group, a heteroaryl group having 5 to 60 nuclear atoms, a C ₁ to C ₄₀ alkyloxy group, a C ₆ to C ₆₀ aryloxy group, a C ₁ to C ₄₀ alkylsilyl A C ₆ to C ₆₀ arylsulfonyl group, a C ₁ to C ₄₀ alkylboron group, a C ₆ to C ₆₀ arylboron group, a C ₆ to C ₆₀ arylphosphine group, a C ₆ to C ₆₀ mono or diaryl phosphine blood group and a C ₆ ~ substituted by one or more substituents selected from the group consisting of an aryl amine of the C ₆₀ or may be unsubstituted, being substituted by the substituents Case, the substituent groups bonded to adjacent, may form a condensed ring, when it is substituted with a plurality of substituents, they may be the same or different from each other.

The present invention also provides an organic electroluminescent device comprising (i) a positive electrode, (ii) a negative electrode, and (iii) at least one organic material layer interposed between the positive electrode and the negative electrode, One is an organic electroluminescent device comprising a compound represented by the general formula (1).

According to a preferred embodiment of the present invention, the organic material layer containing the compound represented by Formula 1 is selected from the group consisting of a light emitting layer, an electron transporting layer, an electron injecting layer, a hole transporting layer, a hole injecting layer, And preferably, the light emitting layer containing the compound represented by Formula 1 can be used as a phosphorescent host.

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

"Alkenyl" in the present invention means 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 double bond. Examples thereof include, but are not limited to, vinyl, allyl, isopropenyl, 2-butenyl, and the like.

The term "alkynyl" in the present invention means 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, but are not limited to, ethynyl, 2-propynyl, and the like.

"Aryl" in the present invention means a monovalent substituent derived from a C6-C60 aromatic hydrocarbon having a single ring or a combination of two or more rings. 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, a form in which two or more rings are pendant or condensed with each other may be included, and further, a condensed form with an aryl group may be included. Examples of such heteroaryls include 6-membered monocyclic rings such as pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, triazinyl, phenoxathienyl, indolizinyl, indolyl indolyl), purinyl, quinolyl, benzothiazole, carbazolyl, and heterocyclic rings such as 2-furanyl, N-imidazolyl, 2- , 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 5 to 60 carbon atoms. Examples of such aryloxy include, but are not limited to, phenyloxy, naphthyloxy, diphenyloxy, and the like.

In the present invention, "alkyloxy" means a monovalent substituent group represented by R'O-, wherein R 'represents alkyl having 1 to 40 carbon atoms, and may be a linear, branched or cyclic structure . ≪ / RTI > Examples of alkyloxy include, but are not limited to, methoxy, ethoxy, n-propoxy, 1-propoxy, t-butoxy, n-butoxy and pentoxy.

"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 of the ring, preferably 1 to 3 carbons, Or < RTI ID = 0.0 > Se. ≪ / RTI > Examples of such heterocycloalkyl include, but are not limited to, morpholine, piperazine, and the like.

In the present invention, "alkylsilyl" is silyl substituted with alkyl having 1 to 40 carbon atoms, and "arylsilyl" means silyl substituted with aryl having 5 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 represented by the general formula (1) of the present invention has excellent thermal stability and luminescent properties and can be used as a material of 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, A full color display panel having improved performance and lifetime can be manufactured.

Hereinafter, the present invention will be described in detail.

1. New organic compounds

The novel organic compounds according to the present invention include dibenzo [b, f] azepine, dibenzo [b, f] oxepine, dibenzo [b, thiepine, 5H-dibenzo [b, f] silepine, or 5H-dibenzo [a, d] cycloheptene) with a naphthyl-condensed 5-membered heteroaromatic ring moiety Or an indene moiety or an indole moiety is condensed to form a basic skeleton or a benzo naphtho [1,2-f] azepine (7H-benzo [b] Benzo [b] naphtho [1,2-f] oxepine, benzo [b] naphtho [1,2-f] thiepine, benznaphthosilepin benzo [b] naphtho [1,2-f] silepine, or benzenaphtho [1,2-f] cycloheptene) Or an indene moiety or an indole moiety is condensed to form a basic It can achieve price.

More specifically, the novel organic compound according to the present invention is characterized by being represented by the following general formula (1).

[Chemical Formula 1]

In Formula 1,

Y ₁ and Y ₂ , Y ₂ and Y ₃ , Y ₃ and Y ₄ , Y ₅ and Y ₆ , Y ₆ and Y ₇ , Y ₇ and Y ₈ , and Y ₉ and Y ₁₀ , Y ₁₀ and Y ₁₁ and Y ₁₁ and Y ₁₂ , preferably Y ₁ and Y ₂ , Y ₇ and Y ₈ , At least one of Y ₁₁ and Y ₁₂ is condensed with a ring represented by the following formula (2) to form a condensed ring;

(2)

In Formula 2,

The dotted line is the part where the condensation occurs;

In the above Formulas 1 and 2,

X ₁ and X ₂ are the same or different and are each independently selected from _{O, S, N (Ar 1} ), C (Ar 2) (Ar 3), and Si (Ar ₄₎ selected from the group consisting of (Ar ₅₎ At least one of X ₁ and X ₂ is N (Ar ₁ ), preferably X ₁ is selected from the group consisting of O, S and N (Ar ₁ ), X ₂ is N (Ar ₁ ) ;

Y ₁ to Y _{12 which} are condensed with the ring represented by the general formula (2) and do not form a condensed ring are the same as or different from each other, and are each independently N or C (R ₁ );

When plural Y ₁₃ to Y ₁₆ are present, they are the same as or different from each other, and Y ₁₃ to Y ₁₆ are each independently N or C (R ₁ );

When R ₁ is plural, they are the same as or different from each other and each R ₁ is independently selected from the group consisting of hydrogen, deuterium, halogen, cyano, nitro, C ₁ to C ₄₀ alkyl, C ₃ to C ₄₀ cycloalkyl, A cycloalkyl group having 3 to 40 nuclear atoms, an aryl group having ₆ to ₆₀ carbon atoms, a heteroaryl group having 5 to 60 nuclear atoms, a C ₁ to C ₄₀ alkyloxy group, a C ₆ to C ₆₀ aryloxy group , A C ₁ to C ₄₀ alkylsilyl group, a C ₆ to C ₆₀ arylsilyl group, a C ₁ to C ₄₀ alkylboron group, a C ₆ to C ₆₀ arylboron group, a C ₆ to C ₆₀ arylphosphine group , C ₆ ~ C ₆₀ mono or diaryl phosphine of the blood selected from the group and a C ₆ ~ C ₆₀ aryl group consisting of an amine group, or by combining adjacent groups may form a condensed ring;

If the Ar ₁ to Ar ₅ multiple individuals, all of which are the same or different, wherein Ar ₁ to Ar ₅ is independently hydrogen, C alkyl group of ₁ ~ C _40, a cycloalkyl group of C ₃ ~ C _40, nuclear atomic 3 to 40 heterocycloalkyl group, an aryloxy group of a C ₆ ~ C ₆₀ aryl group, the number of nuclear atoms of 5 to 60 heteroaryl group, C ₁ ~ C ₄₀ alkyloxy group _{of, C 6 ~ C 60, C} 1 ~ C ₄₀ alkylsilyl group, a group C ₆ ~ C ₆₀ aryl silyl, C ₁ ~ C ₄₀ group of an alkyl boron, C ₆ ~ C group ₆₀ arylboronic of, C ₆ ~ C ₆₀ aryl phosphine group, C ₆ ~ mono or diaryl phosphine of C ₆₀ blood group and a C ₆ ~ selected from the group consisting of aryl amine group of C _60, or by combining adjacent groups may form a condensed ring;

R ₁ and an alkyl group of Ar ₁ to Ar _5, a cycloalkyl group, a heterocycloalkyl group, an aryl group, a heteroaryl group, an alkyloxy group, an aryloxy group, an alkylsilyl group, an arylsilyl group, an alkyl boron group, an aryl boron group, an aryl phosphine group, a mono- or diaryl phosphine blood group and the arylamine groups are each independently selected from deuterium, halogen, cyano, C ₁ ~ C ₄₀ alkyl group, C of ₃ ~ C ₄₀ cycloalkyl group, the number of nuclear atoms of 3 to 40 heterocycloalkyl An alkyl group, a C ₆ to C ₆₀ aryl group, a heteroaryl group having 5 to 60 nuclear atoms, a C ₁ to C ₄₀ alkyloxy group, a C ₆ to C ₆₀ aryloxy group, a C ₁ to C ₄₀ alkylsilyl A C ₆ to C ₆₀ arylsulfonyl group, a C ₁ to C ₄₀ alkylboron group, a C ₆ to C ₆₀ arylboron group, a C ₆ to C ₆₀ arylphosphine group, a C ₆ to C ₆₀ mono or diaryl phosphine blood group and a C ₆ ~ substituted by one or more substituents selected from the group consisting of an aryl amine of the C ₆₀ or may be unsubstituted, being substituted by the substituents Case, the substituent groups bonded to adjacent, may form a condensed ring, when it is substituted with a plurality of substituents, they may be the same or different from each other.

 Since the compound represented by Chemical Formula 1 has higher molecular weight than conventional organic EL device materials such as 4,4-dicarbazolylbiphenyl (hereinafter referred to as 'CBP'), glass transition It is excellent in thermal stability due to its high temperature, and excellent in carrier transporting ability and light emitting ability. Accordingly, when the compound of Formula 1 is included in the organic electroluminescent device, the driving voltage of the device may be lowered, and the efficiency and lifetime may be improved.

Generally, in a phosphorescent light emitting layer of an organic electroluminescent device, the host material should have a triplet energy gap higher than the triplet energy gap of the dopant. That is, when the lowest excitation state of the host is higher in energy than the lowest emission state of the dopant, the phosphorescence efficiency can be improved. The compound of Formula 1 has a triplet energy of 2.3 eV or higher. In addition, the compound represented by the formula (1) can be controlled to have a higher energy level than the dopant by introducing a specific substituent to the basic skeleton in which the indole derivative having a broad singlet energy level and a high triplet energy level are condensed Can be used as a host material.

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.

In addition, the compound of Formula 1 can control the HOMO and LUMO energy levels according to the type of the substituent introduced into the basic skeleton, and can have a wide band gap and a high carrier transporting property. For example, when the electron donating group (EWG) having a high electron absorbing property such as a nitrogen-containing heterocycle (for example, a pyridine group, a pyrimidine group, a triazine group, etc.) is bonded to the basic skeleton, Since it has the property of bipolar, the bonding force between holes and electrons can be increased. As described above, the compound of Formula 1 in which EWG is introduced into the basic skeleton has excellent carrier transporting property and light emitting property. Therefore, the compound of Formula 1 can be used as an electron injection / transport layer material or a life improving layer material other than the light emitting layer material of the organic electroluminescence device Can be used. On the other hand, when the electron donor compound (EDG) is bonded to the basic skeleton of the compound of Formula 1 such as an arylamine group, a carbazole group, a terphenyl group, a triphenylene group, etc., , It can be usefully used as a hole injecting / transporting layer or a light emitting auxiliary layer material other than the light emitting layer material.

As described above, the compound represented by Formula 1 can improve the luminescent characteristics of the organic electroluminescent device and improve the hole injecting / transporting ability, the electron injecting / transporting ability, the light emitting efficiency, the driving voltage, . Accordingly, the compound of formula (I) according to the present invention is useful as an organic electroluminescent device, preferably an organic layer material, preferably a light emitting layer material (blue, green and / or red phosphorescent host material), an electron transport / injection layer material and a hole transport / Emitting layer material, a light-emitting auxiliary layer material, a life-improving layer material, and more preferably a light-emitting layer material, an electron injection layer material, a light-

In addition, the compound of formula (1) may have various substituents, especially an aryl group and / or a heteroaryl group, introduced into the basic skeleton to significantly increase the molecular weight of the compound, thereby improving the glass transition temperature, And may have a higher thermal stability than the material (e.g., CBP). The compound represented by the above formula (1) is also effective for inhibiting crystallization of the organic material layer. Accordingly, the organic electroluminescent device including the compound of Formula 1 according to the present invention can greatly improve performance and lifetime characteristics, and the full-color organic luminescent panel to which such an organic electroluminescent device is applied can also maximize the performance.

The compound represented by the formula (1) of the present invention may be represented by any one of the following formulas (M-1) to (M-12).

In the above formulas (M-1) to (M-12), X ₁ , X ₂ and Y ₁ to Y ₁₆ are as defined in the above formula (1).

Preferably, X ₁ is selected from the group consisting of O, S and N (Ar ₁ ), and X ₂ may be N (Ar ₁ ).

Preferably, Y ₁ to Y ₁₆ are the same or different and each may be C (R ₁ ) or 1 to 3 N, wherein R _{1 s} are the same or different.

The compound represented by the formula (1) of the present invention may be represented by any one of the following formulas (N-1) to (N-12).

In the above formulas (N-1) to (N-12), X ₁ , Ar ₁ and R ₁ are as defined in the above formula (1).

However, preferably X ₁ may be selected from the group consisting of O, S and N (Ar ₁ ).

According to a preferred embodiment of the present invention, the compound represented by the formula (1) is a compound represented by any one of the following formulas (3) to (7).

(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

(7)

In the above Chemical Formulas 3 to 7,

If the Ar ₁ multiple individuals, all of which are the same or different, wherein Ar ₁ is each independently hydrogen, C ₁ ~ C ₄₀ alkyl group, C ₃ ~ C ₄₀ cycloalkyl group, the number of nuclear atoms of 3 to 40 heterocycloalkyl group of , C ₆ ~ C ₆₀ aryl group, the number of nuclear atoms of 5 to 60 heteroaryl group, C ₁ ~ C ₄₀ of the alkyloxy group, C ₆ ~ aryloxy C _60, C ₁ ~ C ₄₀ alkyl silyl group , An arylsilyl group of C ₆ to C ₆₀ , a C ₁ to C ₄₀ alkylboron group, a C ₆ to C ₆₀ arylboron group, a C ₆ to C ₆₀ arylphosphine group, a C ₆ to C ₆₀ mono or di Reel Phosphinicosuccinic group and a C ₆ ~, or selected from the group consisting of aryl amine group of C _60, by combining adjacent groups may form a condensed ring;

Y ₁ to Y ₁₂ are the same or different from each other and each independently N or C (R ₁ );

When plural Y ₁₃ to Y ₁₆ are present, they are the same as or different from each other, and Y ₁₃ to Y ₁₆ are each independently N or C (R ₁ );

When R ₁ is plural, they are the same as or different from each other and each R ₁ is independently selected from the group consisting of hydrogen, deuterium, halogen, cyano, nitro, C ₁ to C ₄₀ alkyl, C ₃ to C ₄₀ cycloalkyl, A cycloalkyl group having 3 to 40 nuclear atoms, an aryl group having ₆ to ₆₀ carbon atoms, a heteroaryl group having 5 to 60 nuclear atoms, a C ₁ to C ₄₀ alkyloxy group, a C ₆ to C ₆₀ aryloxy group , A C ₁ to C ₄₀ alkylsilyl group, a C ₆ to C ₆₀ arylsilyl group, a C ₁ to C ₄₀ alkylboron group, a C ₆ to C ₆₀ arylboron group, a C ₆ to C ₆₀ arylphosphine group , C ₆ ~ C ₆₀ mono or diaryl phosphine of the blood selected from the group and a C ₆ ~ C ₆₀ aryl group consisting of an amine group, or by combining adjacent groups may form a condensed ring;

Ar ₁ and the alkyl group of R _1, a cycloalkyl group, a heterocycloalkyl group, an aryl group, a heteroaryl group, an alkyloxy group, an aryloxy group, an alkylsilyl group, an arylsilyl group, an alkyl boron group, an aryl boron group, an aryl phosphine group, mono or diaryl phosphine blood group and the arylamine groups are each independently selected from deuterium, halogen, cyano, C ₁ ~ C ₄₀ alkyl group, C ₃ ~ C ₄₀ cycloalkyl group, the number of nuclear atoms of 3 to 40 hetero cycloalkyl group, C An aryl group having ₆ to ₆₀ carbon atoms, a heteroaryl group having 5 to 60 nuclear atoms, a C ₁ to C ₄₀ alkyloxy group, a C ₆ to C ₆₀ aryloxy group, a C ₁ to C ₄₀ alkylsilyl group, a C _A C ₆ to C ₆₀ aryl group, a C ₆ to C ₆₀ aryl group, a C ₁ to C ₄₀ alkylboron group, a C ₆ to C ₆₀ arylboron group, a C ₆ to C ₆₀ aryl phosphine group, a C ₆ to C ₆₀ mono or diarylphosphine If blood group and substituted with one or more substituents selected from the group consisting of a C ₆ ~ C ₆₀ aryl amine, or may be unsubstituted, it substituted by the above substituent, Substituent group are bound to the adjacent group may form a condensed ring, when it is substituted with a plurality of substituents, they may be the same or different from each other.

In the above formulas (3) to (7), Ar ₁ may be a C ₆ to C ₆₀ aryl group, and in particular, when Ar ₁ is plural, at least one may be a C ₆ to C ₆₀ aryl group, The aryl group may be substituted or unsubstituted with at least one C ₆ -C ₆₀ aryl group, and when they are substituted with a plurality of substituents, they may be the same or different from each other.

Preferably, Y ₈ in the formula (4) is C (R ₁ ), and R ₁ is a C ₆ to C ₆₀ aryl group, more preferably a phenyl group.

According to a preferred embodiment of the present invention, when at least one of Y ₁ to Y ₁₂ which does not form a condensed ring with the ring represented by Formula 2 is C (R ₁ ), at least one of R ₁ is a phenyl group .

According to a preferred embodiment of the present invention, at least one of R ₁ and Ar ₁ to Ar ₅ may be a phenyl group or a substituent represented by the following general formula (8).

[Chemical Formula 8]

In Formula 8,

* Represents a moiety bonded to Formula 1;

L ₁ is selected from the group consisting of a single bond, a C ₆ ~ C ₁₈ arylene group and a nuclear atoms of 5 to 18 groups heteroarylene, preferably a single bond, phenylene group, biphenyl group or a carbazolyl group;

Z ₁ to Z ₅ are the same or different and are each independently N or C (R ₁₁ ), at least one of Z ₁ to Z ₅ is N;

R ₁₁ is the same or different and each R ₁₁ is independently selected from the group consisting of hydrogen, deuterium, halogen, cyano, nitro, C ₁ to C ₄₀ alkyl, C ₂ to C ₄₀ alkenyl, C ₂ ~ C ₄₀ alkynyl group, C ₆ ~ C ₆₀ aryl group, the number of nuclear atoms of 5 to 40 heteroaryl group, C ₆ ~ C ₆₀ aryloxy group, alkyloxy group of C ₁ ~ C ₄₀ of, C ₃ ~ C ₄₀ cycloalkyl group, the nuclear atoms of 3 to 40 heterocycloalkyl group, C ₆ ~ C ₆₀ aryl amine group, C ₁ ~ C ₄₀ alkylsilyl group, C ₁ ~ C ₄₀ group of an alkyl boron, C ₆ ~ C group ₆₀ arylboronic of, C ₆ ~ C ₆₀ aryl phosphine group, C ₆ ~ C ₆₀ mono or diaryl the Phosphinicosuccinic group and a C ₆ ~ C ₆₀ selected from an aryl silyl group the group consisting of or a neighboring tile that To form a condensed ring;

Alkyl group of the R _11, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, an aryloxy group, an alkyloxy group, a cycloalkyl group, a heterocycloalkyl group, an arylamine group, an alkylsilyl group, an alkyl boron group, an aryl boron group, an aryl phosphine group, a mono- or diaryl phosphine blood group and an aryl silyl group, arylene group and heteroarylene group each independently selected from deuterium, halogen, cyano group, nitro group, C ₁ ~ C ₄₀ alkyl group of the L _1, C ₂ ~ C ₄₀ alkenyl group, C ₂ ~ C ₄₀ of the alkynyl group, C ₆ ~ C ₆₀ aryl group, the number of nuclear atoms of 5 to 40 heteroaryl group, C ₆ ~ aryloxy C _60, C ₁ ~ C _A C ₃ to C ₄₀ cycloalkyl group, a cyclohexyl group having 3 to 40 nuclear atoms, a C ₁ to C ₄₀ alkylsilyl group, a C ₁ to C ₄₀ alkyl group, a C ₆ to C ₆₀ arylamine group, a C ₃ to C ₄₀ cycloalkyl group, ₄₀ alkyl group of boron, C ₆ ~ C ₆₀ aryl group of boron, C ₆ ~ C ₆₀ aryl phosphine group, C ₆ ~ C ₆₀ mono or diaryl phosphine of blood group and a C ₆ ~ C ₆₀ aryl group When substituted by one or more substituents selected from the group consisting of a reel or unsubstituted and ring, which is substituted with plural substituents, they may be the same or different from each other.

According to a preferred embodiment of the present invention, the substituent represented by the formula (8) may be a substituent represented by any one of the following O-1 to O-15.

In the above formulas O-1 to O-15,

n is an integer of 0 to 4, and when n is 0, hydrogen is not substituted by substituent R ₁₂ ; when n is an integer of 1 to 4, R ₁₂ is each independently selected from the group consisting of deuterium, A nitro group, a C ₁ to C ₄₀ alkyl group, a C ₂ to C ₄₀ alkenyl group, a C ₂ to C ₄₀ alkynyl group, a C ₃ to C ₄₀ cycloalkyl group, a heterocyclic cycloalkyl group having 3 to 40 nuclear atoms , C ₆ ~ C ₆₀ aryl group, the number of nuclear atoms of 5 to 40 heteroaryl group, C ₆ ~ C ₆₀ of the aryloxy group, C ₁ ~ C ₄₀ of the alkyloxy group, an arylamine group of C ₆ ~ C ₆₀ , A C ₁ to C ₄₀ alkylsilyl group, a C ₁ to C ₄₀ alkylboron group, a C ₆ to C ₆₀ arylboron group, a C ₆ to C ₆₀ arylphosphine group, a C ₆ to C ₆₀ mono or di Reel Phosphinicosuccinic group and a C ₆ ~ C ₆₀ aryl selected from the group consisting of silyl group, or a, combination group adjacent to form a condensed ring;

Alkyl group of the R _12, an alkenyl group, an alkynyl group, a cycloalkyl group, a heterocycloalkyl group, an aryl group, a heteroaryl group, an aryloxy group, an alkyloxy group, an arylamine group, an alkylsilyl group, an alkyl boron group, an aryl boron group, A halogen atom, a cyano group, a nitro group, a C ₁ to C ₄₀ alkyl group, a C ₂ to C ₄₀ alkenyl group, a C ₂ to C ₄₀ alkenyl group, a substituted or unsubstituted aryl group, C ₆ to C ₆₀ aryl groups, 5 to 40 heteroaryl groups, C ₆ to C ₆₀ aryloxy groups, C ₁ to C ₄₀ alkyloxy groups, C ₆ to C ₆₀ An 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 to C ₄₀ alkylboron group, a C ₆ to C ₆₀ aryl boron group, C ₆ ~ C ₆₀ aryl phosphine group, C ₆ ~ C ₆₀ mono or diaryl phosphine blood group and a C ₆ ~ at least one selected from the group consisting of C ₆₀ arylsilyl of And when they are substituted with a plurality of substituents, they may be the same or different from each other;

L ₁ and R ₁₁ are the same as defined in the above formula (8).

According to a preferred embodiment of the present invention, Ar ₁ to Ar ₅ may be the same or different and each independently selected from the group consisting of phenyl, pyridine, pyrimidine, triazine, biphenyl and quinazoline,

The phenyl, pyridine, pyrimidine, triazine, biphenyl and quinazoline of Ar ₁ to Ar ₅ may be substituted with at least one member selected from the group consisting of cyano, phenyl, pyridine, pyrimidine, triazine, biphenyl and quinazoline Substituted or unsubstituted, and when they are substituted with a plurality of substituents, they may be the same or different.

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

The compound of formula (I) of the present invention can be synthesized according to a general synthesis method. Detailed synthesis of the compound of the present invention will be described in detail in Synthesis Examples to be described later.

2. Organic electroluminescent device

Another aspect of the present invention relates to an organic electroluminescent device (organic EL device) comprising the compound represented by the general formula (1) according to the present invention described above.

More specifically, the organic electroluminescent device according to the present invention includes one or more organic layers interposed between the anode and the cathode, (i) an anode, (ii) a cathode, and (iii) , And at least one of the one or more organic layers includes a compound represented by the general formula (1). At this time, the compounds may be used alone or in combination of two or more.

According to an embodiment of the present invention, 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, And the like. Specifically, the organic material layer containing the compound of Formula 1 is preferably selected from the group consisting of a light emitting layer, an electron transporting layer, and a hole transporting layer, and more preferably a light emitting layer.

The light emitting layer of the organic electroluminescent device of the present invention may include a host material, and may include the compound of Formula 1 as a host material. The light emitting layer of the organic electroluminescent device of the present invention may include a compound other than the compound of Formula 1 as a host.

The structure of the organic electroluminescent device of the present invention is not particularly limited, but may be a structure in which a substrate, an anode, a hole injecting layer, a hole transporting layer, a light emitting auxiliary layer, a light emitting layer, an electron transporting layer and a cathode are sequentially laminated. At this time, the electron injection layer may be further laminated on the electron transport layer. As described above, at least one of the hole injection layer, the hole transport layer, the emission auxiliary layer, the light emitting layer, the electron transport layer, ≪ / RTI > compounds.

In addition, the organic electroluminescent device may include a life improving layer or an electron transporting layer between the light emitting layer and the electron transporting layer. At this time, the compound represented by Formula 1 may also be used as a lifetime improving layer or an electron transporting auxiliary layer.

The structure of the organic electroluminescent device of the present invention may be a structure in which an insulating layer or an adhesive layer is inserted into the interface between the electrode and the organic layer.

The organic electroluminescent device of the present invention can be produced by forming an organic material layer and an electrode by materials and methods known in the art, except that at least one of the organic material layers includes the compound represented by the above formula (1).

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.

The substrate used in the fabrication of the organic electroluminescent device of the present invention is not particularly limited, but silicon wafer, quartz, glass plate, metal plate, plastic film and sheet can be used.

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 BIAz-1

Step 1 Synthesis of 1- (5H-dibenzo [b, f] azepin-5-yl)

5H-dibenzo [b, f] azepine (100.0 g, 517.5 mmol), acetyl chloride (44.3 ml, 621.0 mmol) and toluene (1000 ml) were mixed under a nitrogen stream and stirred at 80 ° C for 2 hours.

After completion of the reaction, the reaction mixture was extracted with ethyl acetate, and then concentrated and recrystallized from ethanol to obtain 113.2 g of 1- (5H-dibenzo [b, f] azepin-5-yl) ethanone (yield 93%).

^{1 H-NMR: δ 1.86 (} s, 3H), 6.92 (d, 1H), 6.98 (d, 1H), 7.26-7.45 (m, 8H)

Step 2 Synthesis of 1- (1aH-dibenzo [b, f] oxirino [2,3-d] azepin-6 (10bH)

(113.2 g, 481.3 mmol), meta -chloroperoxybenzoic acid (99.7 g, 577.5 mmol), silica (226.5 g, ), NaOCl (226.5 g) and acetonitrile (1100 ml) were mixed and stirred at 80 ° C for 2 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 recrystallized from ethanol to obtain 87.1 g of 1- (1aH-dibenzo [b, f] oxirano [2,3-d] azepin-6 (10bH) %).

¹ H-NMR:? 1.95 (s, 3H), 4.28 (s, 2H), 7.26-7.53 (m, 8H)

Step 3 Synthesis of 5-acetyl-5H-dibenzo [b, f] azepin-10 (11H)

Dibenzo [b, f] oxirino [2,3-d] azepin-6 (10bH) -yl) ethanone (87.1 g, 346.5 mmol), lithium iodide (55.7 g, 415.8 mmol) and chloroform (870 ml) were mixed and stirred at 60 ° C for 1 hour.

After the reaction was completed, the reaction mixture was extracted with ethyl acetate, the water was removed with MgSO ₄ and recrystallized in ethanol to obtain 70.5 g (yield: 81%) of 5-acetyl-5H-dibenzo [ %).

^{1 H-NMR: δ 2.10 (} s, 3H), 3.85 (d, 1H), 4.33 (d, 1H), 7.30-7.40 (m, 5H), 7.51-7.59 (m, 2H), 8.10 (d, 1H )

Step 4 Synthesis of 5-acetyl-10,11- (1H-benzo [g] indolo) -5H-dibenzo [b, f]

Dibenzo [b, f] azepin-10 (11H) -one (70.5 g, 280.7 mmol), naphthalene- 1 -ylhydrazine hydrochloride (60.1 g, 308.7 mmol), acetic acid (705 ml), and the mixture was stirred at 120 ° C for 12 hours.

After completion of the reaction, the reaction mixture was extracted with dichloromethane, added with MgSO ₄ and filtered. The solvent was removed from the resulting organic layer, and the residue was purified by column chromatography (hexane: MC = 4: 1 (v / v)) to obtain 5-acetyl-10,11- (1H- benzo [g] indole) [b, f] azepine (68.3 g, yield 65%).

^{1 H-NMR: δ 2.04 (} s, 3H), 7.25-7.39 (m, 4H), 7.56-7.87 (m, 7H), 8.16 (d, 1H), 8.51 (d, 1H), 9.06 (d, 1H ), 11.36 (b, 1 H)

Step 5 Synthesis of 5-acetyl-10,11- [1-phenylbenzo [g] indolo] -dibenzo [b, f]

5H-dibenzo [b, f] azepine (68.3 g, 350.9 mmol) and bromobenzene (66.1 g, 421.1 mmol) in a stream of nitrogen ), Cu (11.1 g, 175.5 mmol), K ₂ CO ₃ (97.0 g, 701.8 mmol) and nitrobenzene (683 ml) were mixed and stirred at 210 ° C for 12 hours.

After completion of the reaction, the reaction mixture was extracted with ethyl acetate, and then concentrated and recrystallized from ethanol to obtain 123.3 g of 5-acetyl-10,11- [1-phenylbenzo [g] indolo] -dibenzo [b, 78%).

^{1 H-NMR: δ 2.04 (} s, 3H), 7.25-7.26 (m, 2H), 7.39-7.58 (m, 9H), 7.77 (d, 1H), 7.87-7.88 (m, 2H), 8.05-8.06 (m, 2H), 8.16 (d, IH), 8.51 (d, IH), 9.06

<Step 6> Synthesis of BIAz-1

Dibenzo [b, f] azepine (123.3 g, 273.7 mmol), potassium hydroxide (16.9 g, 301.0 mmol), and a mixture of 5-acetyl-10,11- Ethylene glycol (1233 ml) was mixed and stirred at 200 &lt; 0 &gt; C for 6 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 = 6: 1 (v / v)) to obtain BIAz-1 (102.9 g, yield 92% .

^{1 H-NMR: δ 6.69-6.87 (} m, 4H), 7.16-7.17 (m, 2H), 7.45-7.67 (m, 9H), 8.05-8.06 (m, 2H), 8.16 (d, 1H), 8.51 (d, 1 H), 8.83 (d, 1 H)

[Preparation Example 2] Synthesis of BIAz-2

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

(100 g, 517.5 mmol), iodobenzene (126.7 g, 621.0 mmol), Cu (16.4 g, 258.7 mmol) and K ₂ CO ₃ (143.0 g, 1,035.0 mmol) and nitrobenzene (1000 ml) were mixed and stirred at 210 ° C for 12 hours.

After completion of the reaction, the reaction mixture was extracted with ethyl acetate, and then concentrated and recrystallized from ethanol to obtain 5-phenyl-5H-dibenzo [b, f] azepine (100.4 g, yield 72%).

^{1 H-NMR: δ 6.63-6.81 (} m, 3H), 6.92 (d, 1H), 6.98 (d, 1H), 7.20 (d, 2H), 7.26-7.45 (m, 8H)

Step 2 Synthesis of 6-phenyl-6,10b-dihydro-llaH-dibenzo [b, f] oxireno [2,3-d]

5-dibenzo [b, f] azepine (100.4 g, 372.6 mmol), meta -chloroperoxybenzoic acid (77.2 g, 447.1 mmol), silica (200.7 g), NaOCl (200.7 g) and acetonitrile (1000 ml) were mixed and stirred at 80 ° C for 2 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 the residue was recrystallized from ethanol to obtain 84.0 g (yield: 79%) of 6-phenyl-6,10b-dihydro-llaH- dibenzo [b, f] oxireno [2,3- &Lt; / RTI &gt;

¹ H-NMR:? 4.31 (s, 2H), 6.63-6.81 (m, 3H), 7.24-7.53 (m,

Step 3 Synthesis of 5-phenyl-5H-dibenzo [b, f] azepin-10 (11H)

(84.0 g, 294.3 mmol) and lithium iodide (47.3 g, 353.2 mmol) in a stream of nitrogen under a stream of nitrogen, ) And chloroform (840 ml) were mixed and stirred at 60 ° C for 1 hour.

After the reaction was completed, the reaction mixture was extracted with ethyl acetate, the water was removed with MgSO ₄ and recrystallized in ethanol to obtain 5-phenyl-5H-dibenzo [b, f] azepin-10 (11H) %).

^{1 H-NMR: δ 3.42 (} d, 1H), 4.21 (d, 1H), 6.62-6.74 (m, 3H), 7.25-7.40 (m, 7H), 7.51-7.59 (m, 2H), 8.10 (d , 1H)

<Step 4> Synthesis of BIAz-2

Dibenzo [b, f] azepin-10 (11H) -one (68.0 g, 238.4 mmol) and naphthalene-1-ylhydrazine hydrochloride (51.1 g, 262.3 mmol) and acetic acid (700 ml), and the mixture was stirred at 120 ° C for 12 hours.

After completion of the reaction, the reaction mixture was extracted with dichloromethane, added with MgSO ₄ and filtered. The solvent was removed from the obtained organic layer and then purified by column chromatography (hexane: MC = 3: 1 (v / v)) to obtain BIAz-2 (59.4 g, yield 61%).

^{1 H-NMR: δ 6.63-6.69 (} m, 4H), 6.81-6.87 (m, 3H), 7.16-7.20 (m, 4H), 7.54-7.56 (m, 3H), 7.65-7.67 (m, 2H) , 8.16 (d, IH), 8.51 (d, IH), 8.83

[Preparation Example 3] Synthesis of 13BAz

<Step 1> Synthesis of 1- (naphthalen-1-yl) -1H-indole

(100 g, 854.0 mmol), 1-bromonaphthalene (212.1 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 캜 for 12 hours.

After the reaction was completed, the reaction mixture 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- (naphthalen- Indole (182.8 g, yield 88%).

^{1 H-NMR: δ 6.52 (} d, 1H), 6.87 (dd, 1H), 7.33 (dd, 1H), 7.55-7.60 (m, 5H), 7.93-7.94 (m, 2H), 8.06-8.07 (m , 3H)

<Step 2> Synthesis of 13BAz

1- (naphthalen-1-yl) -1H-indole (182.8 g, 751.2 mmol) and polyphosphoric acid (914 g) were mixed under a nitrogen stream and stirred at 100 ° C for 12 hours.

After the reaction was completed, it was extracted from water and then filtered to obtain 13BAz (58.5 g, yield 32%).

^{1 H-NMR: δ 6.81 (} dd, 1H), 6.99-7.05 (m, 3H), 7.25-7.29 (m, 2H), 7.53-7.54 (m, 2H), 7.73 (d, 1H), 8.02-8.07 (m, 2H), 8.21 (d, IH), 8.42 (b, IH)

[Preparation Example 4] Synthesis of BIAz-3

Step 1 Synthesis of 1- (13H-benzo [f] naphtho [1,2-b] azepin-13-yl)

13BAz (100.0 g, 411.0 mmol), acetyl chloride (35.2 ml, 493.2 mmol) and toluene (1000 ml) were mixed under a nitrogen stream and stirred at 80 ° C for 2 hours.

After the reaction was completed, the reaction mixture was extracted with ethyl acetate and then concentrated and recrystallized from ethanol to obtain 102.0 g (yield: 87%) of 1- (13H-benzo [f] naphtho [ ).

^{1 H-NMR: δ 2.04 (} s, 3H), 6.99-7.00 (m, 2H), 7.19-7.28 (m, 3H), 7.48-7.54 (m, 3H), 7.73 (d, 1H), 7.81 (d , &Lt; / RTI &gt; 1H), 8.02-8.07 (m, 2H)

Step 2 Synthesis of 1- (1aH-benzo [f] naphtho [1,2-b] oxirano [2,3-d] azepin-6 (12bH)

(102.0 g, 357.6 mmol) and meta -chloroperoxybenzoic acid (74.0 g, 429.1 mmol) in a stream of nitrogen under nitrogen atmosphere at -78 [deg. ), Silica (204.1 g), NaOCl (204.1 g) and acetonitrile (1000 ml) were mixed and stirred at 80 ° C for 2 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 recrystallized from ethanol to obtain 1- (1aH-benzo [f] naphtho [1,2-b] oxirano [2,3- d] azepin- (76.5 g, yield 71%).

¹ H-NMR: δ 2.04 (s, 3H), 4.19-4.20 (m, 2H), 6.91 (d, 1H), 7.12 (dd, 1H), 7.34-7.36 (m, 2H), 7.49-7.53 , 3H), 7.74 (d, IH), 8.03-8.04 (m, 2H)

Step 3 Synthesis of 13-acetyl-8,13-dihydro-7H-benzo [f] naphtho [1,2-b] azepin-

Benzo [f] naphtho [1,2-b] oxirano [2,3-d] azepin-6 (12bH) -yl) ethanone (76.5 g, 253.9 mmol) Lithium iodide (40.8 g, 304.7 mmol) and chloroform (750 ml) were mixed and stirred at 60 ° C for 1 hour.

After the reaction was completed, the reaction mixture was extracted with ethyl acetate, the water was removed with MgSO ₄ and recrystallized in ethanol to obtain 13-acetyl-8,13-dihydro-7H-benzo [f] naphtho [ -7-one (57.4 g, yield 75%).

^{1 H-NMR: δ 2.04 (} s, 3H), 3.81 (s, 2H), 7.07 (dd, 1H), 7.21-7.24 (m, 2H), 7.37 (d, 1H), 7.65-7.69 (m, 3H ), 8.10-8.23 (m, 3H)

Step 4 Synthesis of 13-acetyl-7,8- (7-phenyl-1H-indolo) -benzo [f] naphtho [1,2- b]

Benzo [f] naphtho [1,2-b] azepin-7-one (57.4 g, 190.4 mmol) and biphenyl-2-ylhydrazine Hydrochloride (46.2 g, 209.5 mmol) and acetic acid (600 ml) were added thereto, followed by stirring at 120 ° C for 12 hours.

After completion of the reaction, the reaction mixture was extracted with dichloromethane, added with MgSO ₄ and filtered. The solvent was removed from the obtained organic layer and then the residue was purified by column chromatography (hexane: MC = 4: 1 (v / v)) to obtain 13-acetyl-7-8- Naphtho [l, 2-b] azepine (52.3 g, yield 61%).

^{1 H-NMR: δ 2.04 (} s, 3H), 7.14-7.25 (m, 4H), 7.39-7.54 (m, 8H), 7.77-7.87 (m, 4H), 8.02-8.07 (m, 2H), 11.36 (b, 1H)

Step 5 Synthesis of 13-acetyl-7,8- (7-phenyl-1- (3,5-diphenylbenzene) -indolo) -benzo [f] naphtho [1,2- b]

Benzo [f] naphtho [l, 2-b] azepine (52.3 g, 237.1 mmol), 1-bromo- (7.5 g, 118.6 mmol), K ₂ CO ₃ (65.5 g, 474.2 mmol) and nitrobenzene (500 ml) were mixed and reacted at 210 ° C. for 12 hours Lt; / RTI &gt;

After the reaction was completed, the reaction mixture was extracted with ethyl acetate and then concentrated and recrystallized from ethanol to obtain 13-acetyl-7,8- (7-phenyl-1- (3,5-diphenylbenzene) Tol [1,2-b] azepine (112.7 g, yield 70%).

^{1 H-NMR: δ 2.04 (} s, 3H), 7.19-7.25 (m, 3H), 7.39-7.54 (m, 17H), 7.63 (d, 1H), 7.77-7.78 (m, 2H), 7.87-7.88 (m, 2H), 8.02-8.13 (m, 5H), 8.39 (d, IH)

<Step 6> Synthesis of BIAz-3

Benzo [f] naphtho [l, 2-b] azepine (112.7 g, , 166.0 mmol), potassium hydroxide (10.2 g, 182.6 mmol) and ethylene glycol (1100 ml) were mixed and stirred at 200 ° C for 6 hours.

After completion of the reaction, the reaction mixture was extracted with ethyl acetate, the water was removed with MgSO ₄ and purified by column chromatography (hexane: EA = 6: 1 (v / v)) to obtain BIAz-3 (93.0 g, yield 88% .

^{1 H-NMR: δ 6.69 (} d, 1H), 6.87 (dd, 1H), 7.16-7.19 (m, 3H), 7.41-7.54 (m, 18H), 7.63 (d, 1H), 7.78 (d, 1H ), 7.88 (s, 1 H), 8.02-8.13 (m, 5 H), 8.39 (d,

[Preparation Example 5] Synthesis of BIAz-4

<Step 1> Synthesis of 13-phenyl-13H-benzo [f] naphtho [1,2-b]

(100 g, 411.0 mmol), iodobenzene (100.6 g, 493.2 mmol), Cu (13.1 g, 205.5 mmol), K ₂ CO ₃ (113.6 g, 822.0 mmol) and nitrobenzene (1000 ml) And the mixture was stirred at 210 DEG C for 12 hours.

After completion of the reaction, the reaction mixture was extracted with ethyl acetate, followed by concentration and recrystallization from ethanol to obtain 13-phenyl-13H-benzo [f] naphtho [1,2-b] azepine (85.3 g, yield 68%).

^{1 H-NMR: δ 6.63-6.65 (} m, 3H), 6.80-6.81 (m, 2H), 6.99-7.05 (m, 3H), 7.20-7.29 (m, 4H), 7.53-7.54 (m, 2H) , 7.73 (d, 1 H), 8.02 - 8.07 (m, 2 H)

Step 2 Synthesis of 6-phenyl-6,12b-dihydro-1 aH-benzo [f] naphtho [1,2- b] oxireno [2,3- d]

Benzo [f] naphtho [1,2-b] azepine (85.3 g, 267.2 mmol), meta -chloroperoxybenzoic acid (55.3 g, 320.6 mmol), silica ), NaOCl (170.7 g) and acetonitrile (850 ml) were mixed and stirred at 80 ° C for 2 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 recrystallized from ethanol to obtain 6-phenyl-6,12b-dihydro-1 aH-benzo [f] g, yield 68%).

^{1 H-NMR: δ 4.20 (} s, 2H), 6.56-6.63 (m, 3H), 6.74-6.81 (m, 2H), 6.91 (d, 1H), 7.11-7.20 (m, 4H), 7.49-7.53 (m, 3 H), 8.03 - 8.04 (m, 2 H)

Step 3 Synthesis of 13-phenyl-8,13-dihydro-7H-benzo [f] naphtho [1,2-b] azepin-

Benzo [f] naphtho [l, 2-b] oxireno [2,3-d] azepine (60.9 g, 181.7 mmol), lithium iodide (29.2 g, 218.0 mmol) and chloroform (600 ml) were mixed and stirred at 60 ° C for 1 hour.

After the reaction was completed, the reaction mixture was extracted with ethyl acetate, the water was removed with MgSO ₄ and recrystallized in ethanol to obtain 13-phenyl-8,13-dihydro-7H-benzoff naphtho [ -7-one (45.7 g, yield 75%).

^{1 H-NMR: δ 3.81 (} s, 2H), 6.51 (d, 1H), 6.63-6.69 (m, 3H), 6.81 (dd, 1H), 6.98-7.01 (m, 2H), 7.20-7.21 (m 2H), 7.37 (d, 1 H), 7.65-7.69 (m, 2H), 8.10-8.23 (m, 3H)

<Step 4> Synthesis of BIAz-4

Benzo [f] naphtho [l, 2-b] azepin-7-one (45.7 g, 136.3 mmol) and naphthalene-1-ylhydrazine hydro- Chloride (29.2 g, 149.9 mmol) and acetic acid (450 ml) were added thereto, followed by stirring at 120 ° C for 12 hours.

After completion of the reaction, the reaction mixture was extracted with dichloromethane, added with MgSO ₄ and filtered. The solvent was removed from the obtained organic layer and then purified by column chromatography (hexane: MC = 3: 1 (v / v)) to obtain BIAz-4 (42.5 g, yield 68%).

¹ H-NMR:? 6.63-6.69 (m, 3H), 6.81-6.87 (m, 2H), 7.16-7.20 (m, 3H), 7.53-7.67 -8.16 (m, 3H), 8.51 (d, IH), 11.36 (b, IH)

[Preparation Example 6] Synthesis of BIAz-5

<Step 1> Synthesis of 1a, 10b-dihydrodibenzo [b, f] oxireno [2,3-d]

Dibenzo [b, f] oxepine (100.0 g, 514.9 mmol), meta -chloroperoxybenzoic acid (106.6 g, 617.8 mmol), silica (200.0 g), NaOCl (200.0 g) and acetonitrile (1000 ml) were mixed and stirred at 80 ° C for 2 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 recrystallized with ethanol to obtain 1a, 10b-dihydrodibenzo [b, f] oxireno [2,3-d] oxepin (87.7 g, yield 81%).

¹ H-NMR:? 4.30 (s, 2H), 7.10 (d, 2H), 7.26-7.34 (m, 6H)

<Step 2> Synthesis of dibenzo [b, f] oxepin-10 (11H) -one

(87.7 g, 417.0 mmol), lithium iodide (67.0 g, 500.4 mmol), and chloroform (900 ml, ) Were mixed and stirred at 60 ° C for 1 hour.

After the reaction was completed, the reaction mixture was extracted with ethyl acetate, the water was removed with MgSO ₄ and recrystallized in ethanol to obtain dibenzo [b, f] oxepin-10 (11H) -one (69.3 g, yield 79%).

^{1 H-NMR: δ 3.51 (} d, 1H), 4.42 (d, 1H), 7.05 (t, 1H), 7.19-7.28 (m, 4H), 7.43-7.44 (m, 2H), 7.60 (t, 1H )

<Step 3> Synthesis of BIAz-5

Oxazin-10 (11H) -one (69.3 g, 329.5 mmol) and naphthalene-1-ylhydrazine hydrochloride (70.5 g, 362.4 mmol) and acetic acid (700 ml), and the mixture was stirred at 120 ° C for 12 hours.

After completion of the reaction, the reaction mixture was extracted with dichloromethane, added with MgSO ₄ and filtered. The solvent was removed from the obtained organic layer and then purified by column chromatography (hexane: MC = 3: 1 (v / v)) to obtain BIAz-5 (56.0 g, yield 51%).

^{1 H-NMR: δ 7.20-7.23 (} m, 4H), 7.36-7.37 (m, 2H), 7.55-7.56 (m, 2H), 7.67-7.75 (m, 3H), 8.16 (d, 1H), 8.39 (d, IH), 8.51 (d, IH), 11.36 (b, IH)

[Preparation Example 7] Synthesis of BAz-6

<Step 1> Synthesis of 1a, 10b-dihydrodibenzo [b, f] oxirano [2,3-d] thiepine

(100.0 g, 475.5 mmol), meta -chloroperoxybenzoic acid (98.5 g, 570.6 mmol), silica (200.0 g), NaOCl (200.0 g) and acetonitrile (1000 ml) were mixed and stirred at 80 ° C for 2 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 recrystallized with ethanol to obtain 1a, 10b-dihydrodibenzo [b, f] oxireno [2,3-d] thiepine (80.7 g, yield 75%).

^{1 H-NMR: δ 4.40 (} s, 2H), 7.12-7.16 (m, 4H), 7.45 (t, 2H), 7.70 (d, 2H)

Step 2 Synthesis of dibenzo [b, f] thiepin-10 (11H) -one

Dihydrodibenzo [b, f] oxireno [2,3-d] thiepine (80.7 g, 356.7 mmol), lithium iodide (57.3.0 g, 428.0 mmol) and chloroform 800 ml) were mixed and stirred at 60 ° C for 1 hour.

After the reaction was completed, the reaction mixture was extracted with ethyl acetate, the water was removed with MgSO ₄ and recrystallized in ethanol to obtain dibenzo [b, f] thiepin-10 (11H) -one (59.7 g, yield 74%).

^{1 H-NMR: δ 3.61 (} d, 1H), 4.47 (d, 1H), 7.03-7.07 (m, 2H), 7.30-7.33 (m, 2H), 7.44-7.52 (m, 2H), 7.65 (d , &Lt; / RTI &gt; 1H), 7.74 (d, 1H)

<Step 3> Synthesis of BIAz-6

10 (11H) -one (59.7 g, 263.9 mmol) and naphthalene-1-ylhydrazine hydrochloride (56.5 g, 290.3 mmol) and acetic acid (600 ml) were added thereto, followed by stirring at 120 ° C for 12 hours.

After completion of the reaction, the reaction mixture was extracted with dichloromethane, added with MgSO ₄ and filtered. The solvent was removed from the obtained organic layer, and the residue was purified by column chromatography (hexane: MC = 3: 1 (v / v)) to obtain BIAz-6 (50.7 g, yield 55%).

¹ H-NMR:? 7.21-7.25 (m, 4H), 7.47-7.67 (m, 8H), 8.16 (d,

[Synthesis Example 1] Synthesis of A-1

In a nitrogen atmosphere BIAz-1 (2.7 g, 6.7 mmol), 2- bromo-4, 6-diphenyl-pyridine (2.5 g, 8.0 mmol), Pd (OAc) 2 (0.08 g, 0.34 mmol), P (t -Bu) ₃ (0.16 ml, 0.67 mmol), NaO ( t- Bu) (1.29 g, 13.4 mmol) and toluene (70 ml) were mixed and stirred at 110 ° C for 5 hours. After completion of the reaction, the toluene was concentrated, and the solid salt was filtered and then purified by recrystallization to obtain objective compound A-1 (2.7 g, yield 64%).

Mass (theory: 637.58, found: 637 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- Compound A-2 (2.9 g, yield 68%) was obtained.

Mass (theory: 638.57, measurement: 638 g / mol)

[Synthesis Example 3] Synthesis of A-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-diphenylpyridine The same procedure was followed to obtain the target compound A-3 (2.8 g, yield 65%).

Mass (theory: 638.57, measurement: 638 g / mol)

[Synthesis Example 4] Synthesis of A-4

Was obtained in the same manner as in Synthesis Example 1, except that 4- (4-bromophenyl) -2,6-diphenylpyrimidine (3.1 g, 8.0 mmol) was used instead of 2- To obtain the target compound A-4 (3.0 g, yield 63%).

Mass (theory value: 714.6, measurement value: 714 g / mol)

[Synthesis Example 5] Synthesis of A-5

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-diphenylpyridine , The target compound A-5 (3.2 g, yield 67%) was obtained by carrying out the same procedure as in Synthesis Example 1.

Mass (theory: 715.6, measured: 715 g / mol)

[Synthesis Example 6] Synthesis of A-6

Diphenyl-1,3,5-triazine (3.7 g, 8.0 mmol) instead of 2-bromo-4,6-diphenylpyridine The procedure of Synthesis Example 1 was repeated to obtain the target compound A-6 (2.9 g, yield 61%).

Mass (theory: 715.6, measured: 715 g / mol)

[Synthesis Example 7] Synthesis of A-7

(3.7 g, 8.0 mmol) instead of 2- (3'-bromobiphenyl-3-yl) -4,6-diphenyl-1,3,5- (3.5 g, yield 66%) was obtained by carrying out the same procedure as in Synthesis Example 1, except that the compound A-7 was used.

Mass (theory: 792.64, found: 792 g / mol)

[Synthesis Example 8] Synthesis of A-8

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- The target compound A-8 (3.2 g, yield 64%) was obtained.

Mass (theory: 738.6, measured: 738 g / mol)

[Synthesis Example 9] Synthesis of A-9

The procedure of Synthesis Example 1 was repeated except that 2- (3-bromophenyl) triphenylene (3.1 g, 8.0 mmol) was used instead of 2-bromo-4,6-diphenylpyridine, To obtain phosphorus A-9 (3.0 g, yield 63%).

Mass (theory: 710.60, measurement: 710 g / mol)

[Synthesis Example 10] Synthesis of A-10

The procedure of Synthesis Example 1 was repeated except for using 4'-bromobiphenyl-3-carbonitrile (2.1 g, 8.0 mmol) instead of 2-bromo-4,6-diphenylpyridine, A-10 (2.7 g, yield 70%) was obtained.

Mass (theory: 585.6, measurement: 585 g / mol)

[Synthesis Example 11] Synthesis of B-1

In a nitrogen atmosphere BIAz-2 (2.7 g, 6.7 mmol), 2- bromo-4, 6-diphenyl-pyridine (2.5 g, 8.0 mmol), Pd (OAc) 2 (0.08 g, 0.34 mmol), P (t -Bu) ₃ (0.16 ml, 0.67 mmol), NaO ( t- Bu) (1.29 g, 13.4 mmol) and toluene (70 ml) were mixed and stirred at 110 ° C for 5 hours. After the reaction was completed, the toluene was concentrated, and the solid salt was filtered and then purified by recrystallization to obtain the objective compound B-1 (2.9 g, yield 68%).

Mass (theory: 637.58, found: 637 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- To obtain compound B-2 (3.0 g, yield 71%).

Mass (theory: 638.57, measurement: 638 g / mol)

[Synthesis Example 13] Synthesis of B-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-diphenylpyridine. The same procedure was followed to obtain the target compound B-3 (2.7 g, yield 63%).

Mass (theory: 638.57, measurement: 638 g / mol)

[Synthesis Example 14] Synthesis of B-4

The same procedure as in Synthesis Example 11 was carried out except that 4- (4-bromophenyl) -2,6-dipyrimidine (3.1 g, 8.0 mmol) was used instead of 2- To obtain the target compound B-4 (3.2 g, yield 66%).

Mass (theory value: 714.6, measurement value: 714 g / mol)

[Synthesis Example 15] Synthesis of B-5

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-diphenylpyridine , The target compound B-5 (3.4 g, yield 70%) was obtained by carrying out the same procedure as in Synthesis Example 11.

Mass (theory: 715.6, measured: 715 g / mol)

[Synthesis Example 16] Synthesis of B-6

Except that 2- (3-bromophenyl) -4,6-diphenyl-1,3,5-triazine (3.7 g, 8.0 mmol) was used instead of 2-bromo-4,6-diphenylpyridine , The target compound B-6 (3.1 g, yield 65%) was obtained in the same manner as in Synthesis Example 11.

Mass (theory: 715.6, measured: 715 g / mol)

[Synthesis Example 17] Synthesis of B-7

(3.7 g, 8.0 mmol) instead of 2- (3'-bromobiphenyl-3-yl) -4,6-diphenyl-1,3,5- , The target compound B-7 (3.3 g, yield 62%) was obtained by carrying out the same procedure as in Synthesis Example 11.

Mass (theory: 792.64, found: 792 g / mol)

[Synthesis Example 18] Synthesis of B-8

The title compound was synthesized in the same manner as in Synthesis Example 11 (2) except for using 2-chloro-4- (4- (naphthalen-1-yl) phenyl) quinazoline (2.9 g, 8.0 mmol) instead of 2- The target compound B-8 (3.4 g, yield 70%) was obtained.

Mass (theory: 738.6, measured: 738 g / mol)

[Synthesis Example 19] Synthesis of B-9

The procedure of Synthesis Example 11 was repeated except for using 2- (3-bromophenyl) triphenylene (3.1 g, 8.0 mmol) instead of 2-bromo-4,6-diphenylpyridine, B-9 (3.0 g, yield 64%).

Mass (theory: 710.60, measurement: 710 g / mol)

[Synthesis Example 20] Synthesis of B-10

The procedure of Synthetic Example 11 was repeated except that 4'-bromobiphenyl-3-carbonitrile (2.1 g, 8.0 mmol) was used instead of 2-bromo-4,6-diphenylpyridine, B-10 (2.7 g, yield 68%).

Mass (theory: 585.6, measurement: 585 g / mol)

[Synthesis Example 21] Synthesis of C-1

In a nitrogen atmosphere BIAz-3 (2.7 g, 6.7 mmol), 2- bromo-4, 6-diphenyl-pyridine (2.5 g, 8.0 mmol), Pd (OAc) 2 (0.08 g, 0.34 mmol), P (t -Bu) ₃ (0.16 ml, 0.67 mmol), NaO ( t- Bu) (1.29 g, 13.4 mmol) and toluene (70 ml) were mixed and stirred at 110 ° C for 5 hours. After completion of the reaction, the toluene was concentrated, and the solid salt was filtered and then purified by recrystallization to obtain the target compound C-1 (3.8 g, yield 66%).

Mass (theory: 865.87, found: 865 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- To obtain compound C-2 (3.5 g, yield 61%).

Mass (theory: 866.86, measurement: 866 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-diphenylpyridine The same procedure was followed to obtain the target compound C-3 (3.8 g, yield 65%).

Mass (theory: 866.86, measurement: 866 g / mol)

[Synthesis Example 24] Synthesis of C-4

Was obtained in the same manner as in Synthesis Example 11, except that 4- (4-bromophenyl) -2,6-diphenylpyrimidine (3.1 g, 8.0 mmol) was used instead of 2- To obtain the target compound C-4 (4.3 g, yield 68%).

Mass (theory: 942.89, measurement: 942 g / mol)

[Synthesis Example 25] Synthesis of C-5

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-diphenylpyridine , The target compound C-5 (3.9 g, yield: 61%) was obtained in the same manner as in Synthesis Example 21.

Mass (theory: 943.89, measurement: 943 g / mol)

[Synthesis Example 26] Synthesis of C-6

Except that 2- (3-bromophenyl) -4,6-diphenyl-1,3,5-triazine (3.7 g, 8.0 mmol) was used instead of 2-bromo-4,6-diphenylpyridine , The target compound C-6 (4.5 g, yield 71%) was obtained by carrying out the same procedure as in Synthesis Example 21.

Mass (theory: 943.89, measurement: 943 g / mol)

[Synthesis Example 27] Synthesis of C-7

(3.7 g, 8.0 mmol) instead of 2- (3'-bromobiphenyl-3-yl) -4,6-diphenyl-1,3,5- (C-7) (4.9 g, yield 72%) was obtained by carrying out the same procedure as in Synthesis Example 21.

Mass (theory: 1020.93, measurement: 1020 g / mol)

 [Synthesis Example 28] Synthesis of C-8

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- The target compound C-8 (4.2 g, yield 65%) was obtained.

Mass (theory: 966.89, measurement: 966 g / mol)

[Synthesis Example 29] Synthesis of C-9

The procedure of Synthesis Example 21 was repeated except that 2- (3-bromophenyl) triphenylene (3.1 g, 8.0 mmol) was used instead of 2-bromo-4,6-diphenylpyridine, C-9 (4.2 g, yield 66%).

Mass (theory: 938.89, measurement: 938 g / mol)

[Synthesis Example 30] Synthesis of C-10

The procedure of Synthetic Example 21 was repeated except that 4'-bromobiphenyl-3-carbonitrile (2.1 g, 8.0 mmol) was used instead of 2-bromo-4,6-diphenylpyridine, C-10 (3.3 g, yield 61%) was obtained.

Mass (theory: 813.8, measured: 813 g / mol)

[Synthesis Example 31] Synthesis of D-1

In a nitrogen atmosphere BIAz-4 (2.7 g, 6.7 mmol), 2- bromo-4, 6-diphenyl-pyridine (2.5 g, 8.0 mmol), Pd (OAc) 2 (0.08 g, 0.34 mmol), P (t -Bu) ₃ (0.16 ml, 0.67 mmol), NaO ( t- Bu) (1.29 g, 13.4 mmol) and toluene (70 ml) were mixed and stirred at 110 ° C for 5 hours. After the reaction was completed, the toluene was concentrated, and the solid salt was filtered and then purified by recrystallization to obtain the target compound D-1 (3.0 g, yield 65%).

Mass (theory: 687.64, measurement: 687 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- Compound D-2 (3.2 g, yield 69%).

Mass (theory: 688.63, measurement: 688 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-diphenylpyridine The same procedure was carried out to obtain D-3 (3.0 g, yield 66%) as a target compound.

Mass (theory: 688.63, measurement: 688 g / mol)

[Synthesis Example 34] Synthesis of D-4

Was obtained in the same manner as in Synthesis Example 31, except that 4- (4-bromophenyl) -2,6-diphenylpyrimidine (3.1 g, 8.0 mmol) was used instead of 2- To obtain the target compound D-4 (3.4 g, yield 67%).

Mass (theory: 764.66, measured: 764 g / mol)

[Synthesis Example 35] Synthesis of D-5

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-diphenylpyridine , The target compound D-5 (3.1 g, yield 61%) was obtained by carrying out the same procedure as in Synthesis Example 31.

Mass (theory: 765.66, measured: 765 g / mol)

[Synthesis Example 36] Synthesis of D-6

Except that 2- (3-bromophenyl) -4,6-diphenyl-1,3,5-triazine (3.7 g, 8.0 mmol) was used instead of 2-bromo-4,6-diphenylpyridine , The target compound D-6 (3.1 g, yield 61%) was obtained in the same manner as in Synthesis Example 31.

Mass (theory: 765.66, measured: 765 g / mol)

[Synthesis Example 37] Synthesis of D-7

(3.7 g, 8.0 mmol) instead of 2- (3'-bromobiphenyl-3-yl) -4,6-diphenyl-1,3,5- (D-7) (3.6 g, yield 63%) was obtained by carrying out the same procedure as in Synthesis Example 31, except that

Mass (theory: 842.7, measured: 842 g / mol)

[Synthesis Example 38] Synthesis of D-8

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-diphenylpyridine. The target compound D-8 (3.5 g, yield 66%) was obtained.

Mass (theory: 788.66, measurement: 788 g / mol)

[Synthesis Example 39] Synthesis of D-9

The procedure of Synthesis Example 31 was repeated except that 2- (3-bromophenyl) triphenylene (3.1 g, 8.0 mmol) was used instead of 2-bromo-4,6-diphenylpyridine, Of D-9 (3.5 g, yield 69%).

Mass (theory: 760.66, measured: 760 g / mol)

[Synthesis Example 40] Synthesis of D-10

The procedure of Synthetic Example 31 was repeated except for using 4'-bromobiphenyl-3-carbonitrile (2.1 g, 8.0 mmol) instead of 2-bromo-4,6-diphenylpyridine, D-10 (3.1 g, yield 72%).

Mass (theory: 635.6, measured: 635 g / mol)

[Synthesis Example 41] Synthesis of E-1

In a nitrogen atmosphere BIAz-5 (2.7 g, 6.7 mmol), 2- bromo-4, 6-diphenyl-pyridine (2.5 g, 8.0 mmol), Pd (OAc) 2 (0.08 g, 0.34 mmol), P (t -Bu) ₃ (0.16 ml, 0.67 mmol), NaO ( t- Bu) (1.29 g, 13.4 mmol) and toluene (70 ml) were mixed and stirred at 110 ° C for 5 hours. After the reaction was completed, the toluene was concentrated, and the solid salt was filtered and then purified by recrystallization to obtain objective compound E-1 (2.4 g, yield 64%).

Mass (theory: 562.47, measured: 562 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- Compound E-2 (2.6 g, yield 69%) was obtained.

Mass (theory: 563.46, found: 563 g / mol)

[Synthesis Example 43] Synthesis of E-3

Synthesis Example 41 was repeated 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- The same procedure was followed to obtain the target compound E-3 (2.6 g, yield 70%).

Mass (theory: 563.46, found: 563 g / mol)

[Synthesis Example 44] Synthesis of E-4

Was obtained in the same manner as in Synthesis Example 41, except that 4- (4-bromophenyl) -2,6-diphenylpyrimidine (3.1 g, 8.0 mmol) was used instead of 2- To obtain the target compound E-4 (3.1 g, yield 73%).

Mass (theory: 639.49, measurement: 639 g / mol)

[Synthesis Example 45] Synthesis of E-5

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-diphenylpyridine , The target compound E-5 (2.8 g, yield 65%) was obtained in the same manner as in Synthesis Example 41.

Mass (theory: 640.49, measured: 640 g / mol)

[Synthesis Example 46] Synthesis of E-6

Except that 2- (3-bromophenyl) -4,6-diphenyl-1,3,5-triazine (3.7 g, 8.0 mmol) was used instead of 2-bromo-4,6-diphenylpyridine , The target compound E-6 (2.8 g, yield 65%) was obtained in the same manner as in Synthesis Example 41.

Mass (theory: 640.49, measured: 640 g / mol)

[Synthesis Example 47] Synthesis of E-7

(3.7 g, 8.0 mmol) instead of 2- (3'-bromobiphenyl-3-yl) -4,6-diphenyl-1,3,5- (3.5 g, yield 72%) was obtained by carrying out the same procedure as in Synthesis Example 41, except that the compound E-7 was used.

Mass (theory: 717.53, measured: 717 g / mol)

[Synthesis Example 48] Synthesis of E-8

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-diphenylpyridine. The target compound E-8 (3.4 g, yield 77%) was obtained.

Mass (theory: 663.49, measured: 663 g / mol)

[Synthesis Example 49] Synthesis of E-9

The procedure of Synthesis Example 41 was repeated except for using 2- (3-bromophenyl) triphenylene (3.1 g, 8.0 mmol) instead of 2-bromo-4,6-diphenylpyridine, E-9 (3.1 g, yield 73%) was obtained.

Mass (theory: 635.49, measurement: 635 g / mol)

[Synthesis Example 50] Synthesis of E-10

The procedure of Synthesis 41 was followed except that 4'-bromobiphenyl-3-carbonitrile (2.1 g, 8.0 mmol) was used instead of 2-bromo-4,6-diphenylpyridine to give the desired compound E-10 (2.4 g, yield 73%) was obtained.

Mass (theory: 510.44, measured: 510 g / mol)

[Synthesis Example 51] Synthesis of F-1

In a nitrogen atmosphere BIAz-6 (2.7 g, 6.7 mmol), 2- bromo-4, 6-diphenyl-pyridine (2.5 g, 8.0 mmol), Pd (OAc) 2 (0.08 g, 0.34 mmol), P (t -Bu) ₃ (0.16 ml, 0.67 mmol), NaO ( t- Bu) (1.29 g, 13.4 mmol) and toluene (70 ml) were mixed and stirred at 110 ° C for 5 hours. After the reaction was completed, the toluene was concentrated, and the solid salt was filtered and then purified by recrystallization to obtain the target compound F-1 (2.4 g, yield 63%).

Mass (theory: 578.54, measurement: 578 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- To obtain compound F-2 (2.7 g, yield 69%).

Mass (calc .: 579.53, found: 579 g / mol)

[Synthesis Example 53] Synthesis of F-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-diphenylpyridine The same procedure was followed to obtain the target compound F-3 (2.9 g, yield 74%).

Mass (calc .: 579.53, found: 579 g / mol)

[Synthesis Example 54] Synthesis of F-4

The same procedure as in Preparation Example 51 was repeated except for using 4- (4-bromophenyl) -2,6-diphenylpyrimidine (3.1 g, 8.0 mmol) instead of 2-bromo- To obtain the objective compound F-4 (3.3 g, yield 76%).

Mass (theory: 655.56, measurement: 655 g / mol)

[Synthesis Example 55] Synthesis of F-5

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-diphenylpyridine , The target compound F-5 (3.1 g, yield 70%) was obtained by carrying out the same procedure as in Synthesis Example 51.

Mass (theory value: 656.56, measurement: 656 g / mol)

[Synthesis Example 56] Synthesis of F-6

Except that 2- (3-bromophenyl) -4,6-diphenyl-1,3,5-triazine (3.7 g, 8.0 mmol) was used instead of 2-bromo-4,6-diphenylpyridine , The target compound F-6 (3.1 g, yield 71%) was obtained in the same manner as in Synthesis Example 51.

Mass (theory value: 656.56, measurement: 656 g / mol)

[Synthesis Example 57] Synthesis of F-7

Instead of 2- (3'-bromobiphenyl-3-yl) -4,6-diphenyl-1,3,5-triazine e (3.7 g, 8.0 mmol ), The procedure of Synthetic Example 51 was repeated to obtain the desired compound F-7 (3.6 g, yield 73%).

Mass (theory: 733.60, measurement: 733 g / mol)

[Synthesis Example 58] Synthesis of F-8

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-diphenylpyridine. The target compound F-8 (3.2 g, yield 70%) was obtained.

Mass (theory: 679.56, found: 679 g / mol)

[Synthesis Example 59] Synthesis of F-9

The procedure of Synthetic Example 51 was repeated except for using 2- (3-bromophenyl) triphenylene (3.1 g, 8.0 mmol) instead of 2-bromo-4,6-diphenylpyridine, F-9 (3.1 g, yield 72%) was obtained.

Mass (theory: 651.56, found: 651 g / mol)

[Synthesis Example 60] Synthesis of F-10

The procedure of Synthetic Example 51 was repeated except for using 4'-bromobiphenyl-3-carbonitrile (2.1 g, 8.0 mmol) instead of 2-bromo-4,6-diphenylpyridine, F-10 (2.3 g, yield 65%) was obtained.

Mass (theory: 526.51, measurement: 526 g / mol)

[Examples 1 to 54] Fabrication of green organic EL device

The compound synthesized in the above Synthesis Example 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, dried and transferred to a UV OZONE cleaner (Power Sonic 405, Hoshin Tech), the substrate was cleaned using UV for 5 minutes, The substrate was transferred.

M-MTDATA (60 nm) / TCTA (80 nm) / 90% on the prepared ITO transparent electrode + host compound + 10% Ir (ppy) ₃ (300 nm) / BCP (10 nm) / Alq ₃ nm) / LiF (1 nm) / Al (200 nm) were stacked in this order to fabricate an organic EL device.

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

[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 each of the green organic EL devices manufactured in Examples 1 to 54 and Comparative Example 1, and the results are shown in the following Table 1 .

Sample Host Driving voltage EL peak Current efficiency (V) (nm) (cd / A) Example 1 A-1 6.77 517 41.3 Example 2 A-2 6.46 515 41.3 Example 3 A-3 6.81 518 39.7 Example 4 A-4 6.68 518 38.9 Example 5 A-5 6.66 517 41.5 Example 6 A-6 6.48 518 39.2 Example 7 A-7 6.48 517 41.3 Example 8 A-9 6.86 515 39.7 Example 9 A-10 6.48 518 38.9 Example 10 B-1 6.48 518 41.3 Example 11 B-2 6.86 517 41.3 Example 12 B-3 6.77 515 41.3 Example 13 B-4 6.66 518 41.2 Example 14 B-5 6.65 518 38.9 Example 15 B-6 6.65 517 41.3 Example 16 B-7 6.64 515 41.3 Example 17 B-9 6.64 518 41.3 Example 18 B-10 6.64 518 41.2 Example 19 C-1 6.81 517 42.2 Example 20 C-2 6.66 515 42 Example 21 C-3 6.81 518 39.7 Example 22 C-4 6.68 518 38.9 Example 23 C-5 6.66 518 41.3 Example 24 C-6 6.7 517 41.3 Example 25 C-7 6.7 515 43.1 Example 26 C-9 6.51 518 43.5 Example 27 C-10 6.77 518 41.4 Example 28 D-1 6.7 515 43.1 Example 29 D-2 6.51 518 43.5 Example 30 D-3 6.77 518 41.4 Example 31 D-4 6.46 518 42.2 Example 32 D-5 6.81 517 42 Example 33 D-6 6.68 515 41.8 Example 34 D-7 6.66 515 41.3 Example 35 D-9 6.48 518 41.2 Example 36 D-10 6.66 518 41.3 Example 37 E-1 6.86 517 41.2 Example 38 E-2 6.77 515 42 Example 39 E-3 6.66 518 39.7 Example 40 E-4 6.77 518 38.9 Example 41 E-5 6.46 515 41.3 Example 42 E-6 6.81 518 41.3 Example 43 E-7 6.73 518 43.1 Example 44 E-9 6.73 517 43.5 Example 45 E-10 6.73 515 41.4 Example 46 F-1 6.48 515 43.1 Example 47 F-2 6.86 518 43.5 Example 48 F-3 6.73 518 41.4 Example 49 F-4 6.48 517 41.5 Example 50 F-5 6.86 515 39.2 Example 51 F-6 6.77 518 41.3 Example 52 F-7 6.66 517 39.7 Example 53 F-9 6.65 518 38.9 Example 54 F-10 6.65 517 41.3 Comparative Example 1 CBP 6.93 516 38.2

As shown in Table 1, when the compound according to the present invention was used for the light emitting layer of the green organic EL device (Examples 1 to 54), the efficiency and the emission efficiency of the conventional CBP compared with the case of using the green organic EL device (Comparative Example 1) It was confirmed that the driving voltage was excellent.

[Examples 55 to 60] Preparation of red organic EL device

The compound synthesized in the above Synthesis Example was subjected to high purity sublimation purification by a conventionally known method, and then 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, dried and transferred to a UV OZONE cleaner (Power Sonic 405, Hoshin Tech), the substrate was cleaned using UV for 5 minutes, The substrate was transferred.

M-MTDATA (60 nm) / TCTA (80 nm) / 90% on the prepared ITO transparent electrode + 10% (piq) ₂ Ir (acac) (300 nm) / BCP ₃ (30 nm) / LiF (1 nm) / Al (200 nm) were stacked in this order to fabricate an organic electroluminescent device.

[Comparative Example 2] Production of red organic EL device

A red organic electroluminescent device was fabricated in the same manner as in Example 55, except that CBP was used instead of the compound A-8 of Synthesis Example 8 as a luminescent host material in forming the light emitting layer.

The structures of m-MTDATA, (piq) ₂ Ir (acac), CBP and BCP used in Examples 55 to 60 and Comparative Example 2 are as follows.

[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 55 to 60 and Comparative Example 2, and the results are shown in Table 2 below.

Sample Host Driving voltage Current efficiency (V) (cd / A) Example 55 A-8 4.65 11.8 Example 56 B-8 4.74 11.5 Example 57 C-8 4.87 11.8 Example 58 D-8 4.74 11.5 Example 59 E-8 4.87 11.8 Example 60 F-8 4.56 9.6 Comparative Example 2 CBP 5.25 8.2

As shown in Table 2, when the compound according to the present invention was used for the light emitting layer of the red organic electroluminescent device (Examples 55 to 60), the efficiency and the efficiency of the conventional CBP were higher than those of the red organic electroluminescent device It was confirmed that the driving voltage was excellent.

[Example 61] Manufacture of organic EL device

Glass substrate coated with ITO (Indium tin oxide) thin film with thickness of 1500 Å was washed with distilled water ultrasonic wave. After the distilled water was washed, it was ultrasonically washed with a solvent such as isopropyl alcohol, acetone, and methanol, and dried. Then, the substrate was transferred to a UV OZONE cleaner (Power Sonic 405, Hoshin Tech), and the substrate was cleaned using UV for 5 minutes And the substrate was transferred to the back vacuum deposition machine.

 (60 nm) / Compound A-9 (80 nm) / DS-H522 + 5% DS-501 (30 nm) / BCP (10 nm) / Alq3 (80 nm) synthesized in Synthetic Example 9 on a prepared ITO transparent electrode nm) / LiF (1 nm) / Al (200 nm).

The structures of m-MTDATA, TCTA, CBP, Ir (ppy) ₃ and BCP are as follows. DS-H522 and DS-501 used in the device fabrication are products of Doosan Electronics BG.

[Examples 62 to 66] Manufacture of organic EL device

Except that the compounds B-9, C-9, D-9, E-9 and F-9 were used instead of the compound A-9 used as the hole transporting layer material in forming the hole transporting layer in Example 61, The organic EL device was fabricated in the same manner as in Example 61.

[Comparative Example 3] Production of organic EL device

An organic EL device was prepared in the same manner as in Example 61, except that NPB was used as the hole transport layer material instead of the compound A-9 used as the hole transport layer material in forming the hole transport layer in Example 61. The structure of the NPB used is as follows.

[Evaluation Example 3]

The driving voltage and current efficiency at the current density of 10 mA / cm 2 were measured for the organic EL devices manufactured in Examples 61 to 66 and Comparative Example 3, respectively, and the results are shown in Table 3 below.

Sample Hole transport layer The driving voltage (V) Current efficiency (cd / A) Example 61 A-9 4.4 19.8 Example 62 B-9 4.2 19.2 Example 63 C-9 4.3 18.9 Example 64 D-9 4.4 19.2 Example 65 E-9 4.2 18.9 Example 66 F-9 4.9 20.1 Comparative Example 3 NPB 5.2 18.1

As shown in Table 3, the organic EL devices (organic EL devices manufactured in Examples 61 to 66, respectively) using the compounds (A-9 to F-9) according to the present invention as a hole transport layer, It was found that the organic EL device exhibited better current efficiency and better driving voltage than the organic EL device (organic EL device of Comparative Example 3).

[Example 67] Production of blue organic EL device

Compound A-1 synthesized in Synthesis Example 1 was subjected to high-purity sublimation purification by a conventionally known method, and then a blue organic electroluminescent device was produced as follows.

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

(30 nm) / Compound A-1 (5 nm) / Alq3 (25 nm) / LiF (30 nm) on the ITO transparent electrode prepared as above. (1 nm) / Al (200 nm) in this order to form an organic electroluminescent device.

The structures of NPB, AND and Alq ₃ used in this case are as follows.

[Examples 68 to 108] Preparation of blue organic EL device

A blue organic EL device was produced in the same manner as in Example 67 except that each compound described in Table 4 was used in place of Compound A-1 used as the lifetime improving layer material in Example 67. [

[Comparative Example 4] Production of blue organic EL device

A blue organic electroluminescent device was fabricated in the same manner as in Example 67 except that the lifetime improving layer was not formed and Alq ₃ , which is an electron transporting layer material, was deposited at 30 nm instead of 25 nm.

[Comparative Example 5] Production of blue organic EL device

An organic electroluminescent device was fabricated in the same manner as in Example 1 except that BCP was used instead of the compound A-1 used as the lifetime improving layer material in Example 67.

The structure of the BCP used is as follows.

[Evaluation Example 4]

The driving voltage, current efficiency, emission wavelength and lifetime (T97) at current densities of 10 mA / cm 2 were measured for the organic electroluminescent devices manufactured in Examples 67 to 109 and Comparative Examples 4 and 5, respectively, Are shown in Table 4 below.

Sample Life improvement layer Driving voltage Current efficiency EL peak life span (V) (cd / A) (nm) (hr, T ₉₇ ) Example 67 A-1 4.8 5.9 463 41 Example 68 A-2 4.2 5.9 465 42 Example 69 A-3 5.0 6.0 469 43 Example 70 A-4 5.1 6.2 461 45 Example 71 A-5 5.2 6.3 462 48 Example 72 A-6 4.5 6.4 458 38 Example 73 A-7 5.3 6.0 458 37 Example 74 B-1 5.1 6.1 459 32 Example 75 B-2 5.2 6.1 460 39 Example 76 B-3 4.3 5.9 461 43 Example 77 B-4 4.2 5.9 463 45 Example 78 B-5 4.3 6.4 465 48 Example 79 B-6 4.2 6.3 469 38 Example 80 B-7 4.8 6.1 461 37 Example 81 C-1 4.9 6.1 462 32 Example 82 C-2 5.2 5.9 451 45 Example 83 C-3 5.3 5.9 457 48 Example 84 C-4 5.3 6.3 459 38 Example 85 C-5 5.2 5.9 459 37 Example 86 C-6 5.0 6.4 459 32 Example 87 C-7 5.0 6.3 451 39 Example 88 D-1 4.9 6.1 459 43 Example 89 D-2 4.9 6.1 460 45 Example 90 D-3 4.9 5.9 461 44 Example 91 D-4 5.0 5.9 463 40 Example 92 D-5 4.9 6.3 465 42 Example 93 D-6 4.9 5.9 469 40 Example 94 D-7 4.9 6.2 461 40 Example 95 E-1 4.8 6.1 462 41 Example 96 E-2 4.2 6.1 451 44 Example 97 E-3 4.2 6.0 458 38 Example 98 E-4 4.1 5.9 458 40 Example 99 E-5 4.1 5.9 461 33 Example 100 E-6 4.1 6.0 462 32 Example 101 E-7 4.1 6.2 465 38 Example 102 F-1 4.0 6.3 469 40 Example 103 F-2 5.1 6.4 461 42 Example 104 F-3 5.1 6.0 462 40 Example 105 F-4 5.3 6.1 465 40 Example 106 F-5 4.8 6.1 469 41 Example 107 F-6 4.9 6.0 458 39 Example 108 F-7 5.0 6.1 458 42 Comparative Example 4 - 4.7 5.6 458 32 Comparative Example 5 BCP 5.3 5.9 458 28

As can be seen from Table 4, in the case of the blue organic EL devices of Examples 67 to 108 in which the compounds A-1 to F-7 were used as the lifetime improving material, the blue color of Comparative Example 4 The driving voltage of the organic EL device is similar or slightly superior, but the current efficiency and lifetime are greatly improved.

In addition, the blue organic EL devices of Examples 67 to 108 are superior in driving voltage and current efficiency to those of the blue organic EL device of Comparative Example 5 using conventional CBP instead of the lifetime improving layer as the hole blocking layer material, .

[Example 109] Manufacture of blue organic EL device

Compound A-5 synthesized in Synthesis Example 5 was subjected to high purity sublimation purification by a conventionally known method, and then a blue organic electroluminescent device was produced as follows.

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

(30 nm) / LiF (1 nm) / Al (5 nm) / DS-405 (30 nm) 200 nm) were stacked in this order to fabricate an organic electroluminescent device.

[Examples 110 to 114] Preparation of blue organic EL device

A blue organic EL device was produced in the same manner as in Example 109 except that each compound described in Table 5 was used in place of Compound A-5 used as the electron transport layer material in Example 109. [

[Comparative Example 6] Production of blue organic EL device

A blue organic electroluminescent device was fabricated in the same manner as in Example 108 except that the lifetime improving layer was not included and Alq ₃ , which is an electron transporting layer material, was deposited at 30 nm instead of 25 nm.

[Evaluation Example 5]

The driving voltage, current efficiency, light emission wavelength and lifetime (T97) at a current density of 10 mA / cm 2 were measured for the organic electroluminescent devices manufactured in Examples 109 to 114 and Comparative Example 6, Respectively.

Sample Electron transport layer Driving voltage
(V) Current efficiency
(cd / A) Emission peak
(nm) Example 109 A-5 4.5 5.8 463 Example 110 B-5 4.2 6.1 462 Example 111 C-5 4.0 6.3 460 Example 112 D-5 4.2 5.8 462 Example 113 Synthesis of E-5 4.0 6.1 460 Example 114 F-5 4.7 6.0 459 Comparative Example 6 _ 4.7 5.6 458

As shown in Table 5, in the case of the blue organic EL devices of Examples 109 to 114 using the compounds A-5 to F-5 as electron transporting layer materials, the blue organic EL devices of Comparative Example 6 using Alq ₃ as the electron transporting layer The driving voltage and the current efficiency were further improved.

As described above, it was confirmed that when the compound of Chemical Formula 1 according to the present invention is used as a material for a lifetime improving layer or an electron transporting layer material, the driving voltage and the current efficiency can be improved, and the lifetime characteristics can be greatly improved.

Claims (17)

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

In Formula 1,
Y ₁ and Y ₂ , Y ₂ and Y ₃ , Y ₃ and Y ₄ , Y ₅ and Y ₆ , Y ₆ and Y ₇ , Y ₇ and Y ₈ , and Y ₉ and Y ₁₀ , Y ₁₀ and Y ₁₁ and Y ₁₁ and Y ₁₂ is condensed with a ring represented by the following formula (2) to form a condensed ring;
(2)

In Formula 2,
The dotted line is the part where the condensation occurs;
In the above Formulas 1 and 2,
X ₁ and X ₂ are the same or different and are each independently selected from _{O, S, N (Ar 1} ), C (Ar 2) (Ar 3), and Si (Ar ₄₎ selected from the group consisting of (Ar ₅₎ And at least one of X ₁ and X ₂ is N (Ar ₁ );
Y ₁ to Y _{12 which} are condensed with the ring represented by the general formula (2) and do not form a condensed ring are the same as or different from each other, and are each independently N or C (R ₁ );
When plural Y ₁₃ to Y ₁₆ are present, they are the same as or different from each other, and Y ₁₃ to Y ₁₆ are each independently N or C (R ₁ );
When R ₁ is plural, they are the same as or different from each other and each R ₁ is independently selected from the group consisting of hydrogen, deuterium, halogen, cyano, nitro, C ₁ to C ₄₀ alkyl, C ₃ to C ₄₀ cycloalkyl, A cycloalkyl group having 3 to 40 nuclear atoms, an aryl group having ₆ to ₆₀ carbon atoms, a heteroaryl group having 5 to 60 nuclear atoms, a C ₁ to C ₄₀ alkyloxy group, a C ₆ to C ₆₀ aryloxy group , A C ₁ to C ₄₀ alkylsilyl group, a C ₆ to C ₆₀ arylsilyl group, a C ₁ to C ₄₀ alkylboron group, a C ₆ to C ₆₀ arylboron group, a C ₆ to C ₆₀ arylphosphine group , C ₆ ~ C ₆₀ mono or diaryl phosphine blood group and a C ₆ ~, or selected from the group consisting of an aryl amine of the C _60, by combining the adjacent group to form a condensed ring;
Ar ₁ to Ar ₅ are the same or different from each other and each independently represents hydrogen, a C ₁ to C ₄₀ alkyl group, a C ₃ to C ₄₀ cycloalkyl group, a heteroarylalkyl group having 3 to 40 nuclear atoms, a C ₆ to C ₆₀ An aryloxy group having 5 to 60 ring atoms, a C ₁ to C ₄₀ alkyloxy group, a C ₆ to C ₆₀ aryloxy group, a C ₁ to C ₄₀ alkylsilyl group, a C ₆ to C ₆₀ aryl silyl group, C ₁ ~ C ₄₀ group of an alkyl boron, C ₆ ~ C group ₆₀ arylboronic of, C ₆ ~ C ₆₀ aryl phosphine group, C ₆ ~ C ₆₀ mono or diaryl phosphine blood group and C of An arylamine group having ₆ to ₆₀ carbon atoms, or is bonded to an adjacent group to form a condensed ring;
Wherein Ar ₁ to Ar ₅ and the alkyl group of R _1, a cycloalkyl group, a heterocycloalkyl group, an aryl group, a heteroaryl group, an alkyloxy group, an aryloxy group, an alkylsilyl group, an arylsilyl group, an alkyl boron group, an aryl boron group, A halogen atom, a cyano group, a C ₁ to C ₄₀ alkyl group, a C ₃ to C ₄₀ cycloalkyl group, a heteroaryl group having 3 to 40 hetero atoms, a heteroaryl group, A cycloalkyl group, a C ₆ to C ₆₀ aryl group, a heteroaryl group having 5 to 60 nuclear atoms, a C ₁ to C ₄₀ alkyloxy group, a C ₆ to C ₆₀ aryloxy group, a C ₁ to C ₄₀ alkyl A silyl group, a C ₆ to C ₆₀ arylsilyl group, a C ₁ to C ₄₀ alkylboron group, a C ₆ to C ₆₀ arylboron group, a C ₆ to C ₆₀ arylphosphine group, a C ₆ to C ₆₀ mono or diaryl phosphine blood group and a C ₆ ~ substituted by one or more substituents selected from the group consisting of C ₆₀ aryl amine, or is unsubstituted, substituted by the substituents Wu, when the substituent is bonded to the adjacent groups may form a condensed ring, which is substituted with plural substituents, they may be the same or different from each other.
The method according to claim 1,
The Y ₁ and Y ₂ , Y ₇ and Y ₈ , At least one of Y ₁₁ and Y ₁₂ is condensed with a ring represented by the following formula (2) to form a condensed ring:
(2)

In Formula 2,
And the dotted lines and Y ₁₃ to Y ₁₆ are as defined in claim 1.
The method according to claim 1,
Wherein X ₁ is selected from the group consisting of O, S and N (Ar ₁ ), and X ₂ is N (Ar ₁ ).
The method according to claim 1,
Wherein the compound represented by the formula (1) is a compound represented by any one of the following formulas (M-1) to (M-12):

In the above formulas (M-1) to (M-12), X ₁ , X ₂ and Y ₁ to Y ₁₆ are as defined in claim 1.
5. The method of claim 4,
Wherein Y ₁ to Y ₁₆ are both C (R ₁ ) or may contain 1 to 3 N, and a plurality of R _{1 s} are the same or different.
The method according to claim 1,
Wherein the compound represented by the formula (1) is a compound represented by any one of the following formulas (N-1) to (N-12)

In the above formulas N-1 to N-12, X ₁ , Ar ₁ and R ₁ are as defined in claim ₁ .
The method according to claim 1,
Wherein the compound represented by Formula 1 is a compound represented by any one of Chemical Formulas 3 to 7:
(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

(7)

In the above Chemical Formulas 3 to 7,
If the Ar ₁ multiple individuals, all of which are the same or different, wherein Ar ₁ is each independently hydrogen, C ₁ ~ C ₄₀ alkyl group, C ₃ ~ C ₄₀ cycloalkyl group, the number of nuclear atoms of 3 to 40 heterocycloalkyl group of , C ₆ ~ C ₆₀ aryl group, the number of nuclear atoms of 5 to 60 heteroaryl group, C ₁ ~ C ₄₀ of the alkyloxy group, C ₆ ~ aryloxy C _60, C ₁ ~ C ₄₀ alkyl silyl group , An arylsilyl group of C ₆ to C ₆₀ , a C ₁ to C ₄₀ alkylboron group, a C ₆ to C ₆₀ arylboron group, a C ₆ to C ₆₀ arylphosphine group, a C ₆ to C ₆₀ mono or di Reel Phosphinicosuccinic group and a C ₆ ~, or selected from the group consisting of aryl amine group of C _60, by combining adjacent groups may form a condensed ring;
Y ₁ to Y ₁₂ are the same or different from each other and each independently N or C (R ₁ );
When plural Y ₁₃ to Y ₁₆ are present, they are the same as or different from each other, and Y ₁₃ to Y ₁₆ are each independently N or C (R ₁ );
When R ₁ is plural, they are the same as or different from each other and each R ₁ is independently selected from the group consisting of hydrogen, deuterium, halogen, cyano, nitro, C ₁ to C ₄₀ alkyl, C ₃ to C ₄₀ cycloalkyl, A cycloalkyl group having 3 to 40 nuclear atoms, an aryl group having ₆ to ₆₀ carbon atoms, a heteroaryl group having 5 to 60 nuclear atoms, a C ₁ to C ₄₀ alkyloxy group, a C ₆ to C ₆₀ aryloxy group , A C ₁ to C ₄₀ alkylsilyl group, a C ₆ to C ₆₀ arylsilyl group, a C ₁ to C ₄₀ alkylboron group, a C ₆ to C ₆₀ arylboron group, a C ₆ to C ₆₀ arylphosphine group , C ₆ ~ C ₆₀ mono or diaryl phosphine of the blood selected from the group and a C ₆ ~ C ₆₀ aryl group consisting of an amine group, or by combining adjacent groups may form a condensed ring;
Ar ₁ and the alkyl group of R _1, a cycloalkyl group, a heterocycloalkyl group, an aryl group, a heteroaryl group, an alkyloxy group, an aryloxy group, an alkylsilyl group, an arylsilyl group, an alkyl boron group, an aryl boron group, an aryl phosphine group, mono or diaryl phosphine blood group and the arylamine groups are each independently selected from deuterium, halogen, cyano, C ₁ ~ C ₄₀ alkyl group, C ₃ ~ C ₄₀ cycloalkyl group, the number of nuclear atoms of 3 to 40 hetero cycloalkyl group, C An aryl group having ₆ to ₆₀ carbon atoms, a heteroaryl group having 5 to 60 nuclear atoms, a C ₁ to C ₄₀ alkyloxy group, a C ₆ to C ₆₀ aryloxy group, a C ₁ to C ₄₀ alkylsilyl group, a C _A C ₆ to C ₆₀ aryl group, a C ₆ to C ₆₀ aryl group, a C ₁ to C ₄₀ alkylboron group, a C ₆ to C ₆₀ arylboron group, a C ₆ to C ₆₀ aryl phosphine group, a C ₆ to C ₆₀ mono or diarylphosphine If blood group and substituted with one or more substituents selected from the group consisting of a C ₆ ~ C ₆₀ aryl amine, or may be unsubstituted, it substituted by the above substituent, Substituent group are bound to the adjacent group may form a condensed ring, when it is substituted with a plurality of substituents, they may be the same or different from each other.
8. The method of claim 7,
At least one of Ar ₁ and Ar ₁ may be a C ₆ to C ₆₀ aryl group, and the aryl group may be substituted with at least one C ₆ to C ₆₀ aryl group, When substituted, are the same or different from each other.
8. The method of claim 7,
Wherein in Formula 4, Y ₈ is C (R ₁ ) and R ₁ is a C ₆ to C ₆₀ aryl group.
The method according to claim 1,
Wherein at least one of R ₁ and Ar ₁ to Ar ₅ is a phenyl group or a substituent group represented by the following formula (8):
[Chemical Formula 8]

In Formula 8,
* Represents a moiety bonded to Formula 1;
L ₁ is selected from the group consisting of a single bond, a C ₆ to C ₁₈ arylene group and a heteroarylene group having 5 to 18 nuclear atoms;
Z ₁ to Z ₅ are the same or different and are each independently N or C (R ₁₁ ), at least one of Z ₁ to Z ₅ is N;
R ₁₁ is the same or different from each other and each of R ₁₁ is independently hydrogen, deuterium, halogen, cyano, nitro, C ₁ to C ₄₀ alkyl, C ₂ to C ₄₀ alkenyl, C ₂ ~ alkynyl group of C _40, C ₆ ~ C ₆₀ aryl group, the number of nuclear atoms of 5 to 40 heteroaryl group, C ₆ ~ C ₆₀ aryloxy group, alkyloxy group of C ₁ ~ C ₄₀ of, C C ₃ to C ₄₀ cycloalkyl groups, 3 to 40 nucleus atom heterocycloalkyl groups, C ₆ to C ₆₀ arylamine groups, C ₁ to C ₄₀ alkylsilyl groups, C ₁ to C ₄₀ alkylboron groups, C group _{of 6} to arylboronic of C _60, C ₆ to C ₆₀ aryl phosphine group, C ₆ to C ₆₀ mono or diaryl phosphine blood group and a C ₆ - or selected from the group consisting arylsilyl of C ₆₀ of the adjacent To form a condensed ring;
Alkyl group of the R _11, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, an aryloxy group, an alkyloxy group, a cycloalkyl group, a heterocycloalkyl group, an arylamine group, an alkylsilyl group, an alkyl boron group, an aryl boron group, an aryl phosphine group, a mono- or diaryl phosphine blood group and an aryl silyl group, arylene group and heteroarylene group each independently selected from deuterium, halogen, cyano group, nitro group, C ₁ ~ C ₄₀ alkyl group of the L _1, C ₂ ~ C ₄₀ alkenyl group, C ₂ ~ C ₄₀ of the alkynyl group, C ₆ ~ C ₆₀ aryl group, the number of nuclear atoms of 5 to 40 heteroaryl group, C ₆ ~ aryloxy C _60, C ₁ ~ C _A C ₃ to C ₄₀ cycloalkyl group, a cyclohexyl group having 3 to 40 nuclear atoms, a C ₁ to C ₄₀ alkylsilyl group, a C ₁ to C ₄₀ alkyl group, a C ₆ to C ₆₀ arylamine group, a C ₃ to C ₄₀ cycloalkyl group, ₄₀ alkyl group of boron, C ₆ ~ C ₆₀ aryl group of boron, C ₆ ~ C ₆₀ aryl phosphine group, C ₆ ~ C ₆₀ mono or diaryl phosphine of blood group and a C ₆ ~ C ₆₀ aryl group When substituted by one or more substituents selected from the group consisting of a reel or unsubstituted and ring, which is substituted with plural substituents, they may be the same or different from each other.
11. The method of claim 10,
Wherein the substituent represented by the formula (8) is a substituent represented by any one of the following formulas O-1 to O-15:

In the above formulas O-1 to O-15,
n is an integer of 0 to 4, and when n is 0, hydrogen is not substituted by substituent R ₁₂ ; when n is an integer of 1 to 4, R ₁₂ is each independently selected from the group consisting of deuterium, A nitro group, a C ₁ to C ₄₀ alkyl group, a C ₂ to C ₄₀ alkenyl group, a C ₂ to C ₄₀ alkynyl group, a C ₃ to C ₄₀ cycloalkyl group, a heterocyclic cycloalkyl group having 3 to 40 nuclear atoms , C ₆ ~ C ₆₀ aryl group, the number of nuclear atoms of 5 to 40 heteroaryl group, C ₆ ~ C ₆₀ of the aryloxy group, C ₁ ~ C ₄₀ of the alkyloxy group, an arylamine group of C ₆ ~ C ₆₀ , A C ₁ to C ₄₀ alkylsilyl group, a C ₁ to C ₄₀ alkylboron group, a C ₆ to C ₆₀ arylboron group, a C ₆ to C ₆₀ arylphosphine group, a C ₆ to C ₆₀ mono or di Reel Phosphinicosuccinic group and a C ₆ ~ C ₆₀ aryl selected from the group consisting of silyl group, or a, combination group adjacent to form a condensed ring;
Alkyl group of the R _12, an alkenyl group, an alkynyl group, a cycloalkyl group, a heterocycloalkyl group, an aryl group, a heteroaryl group, an aryloxy group, an alkyloxy group, an arylamine group, an alkylsilyl group, an alkyl boron group, an aryl boron group, A halogen atom, a cyano group, a nitro group, a C ₁ to C ₄₀ alkyl group, a C ₂ to C ₄₀ alkenyl group, a C ₂ to C ₄₀ alkenyl group, a substituted or unsubstituted aryl group, C ₆ to C ₆₀ aryl groups, 5 to 40 heteroaryl groups, C ₆ to C ₆₀ aryloxy groups, C ₁ to C ₄₀ alkyloxy groups, C ₆ to C ₆₀ An 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 to C ₄₀ alkylboron group, a C ₆ to C ₆₀ aryl boron group, C ₆ ~ C ₆₀ aryl phosphine group, C ₆ ~ C ₆₀ mono or diaryl phosphine blood group and a C ₆ ~ at least one selected from the group consisting of C ₆₀ arylsilyl of And when they are substituted with a plurality of substituents, they may be the same or different from each other;
L ₁ and R ₁₁ are as defined in claim 10, respectively.
11. The method of claim 10,
Wherein L &lt; _{1 &gt;} is a single bond, a phenylene group, a biphenylene group or a carbazolyl group.
The method according to claim 1,
Wherein Ar ₁ to Ar ₅ are the same or different and are each independently selected from the group consisting of phenyl, pyridine, pyrimidine, triazine, biphenyl, and quinazoline,
The phenyl, pyridine, pyrimidine, triazine, biphenyl and quinazoline of Ar ₁ to Ar ₅ are substituted or unsubstituted with at least one member selected from the group consisting of phenyl, pyridine, pyrimidine, triazine, biphenyl and quinazoline. And when they are substituted with a plurality of substituents, they are the same or different from each other.
The method according to claim 1,
Wherein said compound is selected from the group consisting of:

1. An organic electroluminescent device comprising: (i) an anode, (ii) a cathode, and (iii) one or more organic layers sandwiched between the anode and the cathode,
Wherein at least one of the one or more organic layers includes a compound represented by formula (1) according to any one of claims 1 to 14.
16. The method of claim 15,
Wherein the organic compound layer including the compound represented by Formula 1 is selected from the group consisting of a hole injection layer, a hole transport layer, an electron transport layer, an electron injection layer, and a light emitting layer.
17. The method of claim 16,
Wherein the light emitting layer comprising the compound represented by Formula 1 is used as a phosphorescent host.