KR20190087281A - Organic compound and organic electroluminescent device using the same - Google Patents

Abstract

The present invention relates to a novel organic compound and an organic electroluminescent device using the same. More specifically, the present invention relates to: a novel compound having excellent light emitting capability; and the organic electroluminescent device having improved characteristics such as high luminous efficiency, low driving voltage, long lifespan and the like by comprising the same in at least one of organic matter layers.

Description

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

The present invention relates to a novel organic compound and an organic electroluminescent device using the same. More particularly, the present invention relates to a novel compound having excellent thermal stability and light emitting ability, and a novel compound containing the same in one or more organic layers to improve characteristics such as luminous efficiency, And an organic electroluminescent device.

A study on organic electroluminescent devices that resulted in blue electroluminescence using anthracene single crystals in 1965 based on observation of organic thin film emission of Bernanose in the 1950s was conducted by Tang in 1987 divided by the functional layer of the hole layer and the light emitting layer An organic electroluminescent device having a laminated structure has been proposed. Since then, in order to make high efficiency and high number of organic electroluminescent devices, each organic material layer has been developed into a form of introducing a characteristic organic material layer in the device, leading to the development of specialized materials used therefor.

In the organic electroluminescent 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 electroluminescent device can be classified into blue, green and red light emitting materials according to 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 the luminous efficiency up to 4 times as compared with that of fluorescence, and attention is focused on phosphorescent host materials as well as phosphorescent dopants.

NPB, BCP, Alq ₃ and the like are widely known as materials used for the hole injecting layer, the hole transporting layer, the hole blocking layer and the electron transporting layer, and the anthracene derivatives as a luminescent material have been reported as a fluorescent dopant / host material . In particular Firpic, Ir as a phosphorescent material that has a great advantage in improving the efficiency aspects of the light-emitting material _{(ppy) 3, (acac)} Ir (btp) 2 Ir metal complex compound is a blue, green and red host material that includes such as . So far, CBP has shown excellent properties as a phosphorescent host material.

However, conventional luminescent materials are advantageous in terms of luminescence properties, but they are not satisfactory in terms of lifetime in an organic electroluminescent device because the glass transition temperature is low and the thermal stability is not very good. Therefore, development of a luminescent material having excellent performance is required.

Japanese Patent Application Laid-Open No. 2001-160489

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and it is an object of the present invention to provide an organic electroluminescent device which can be applied to an organic electroluminescent device and which has excellent thermal stability, hole injection ability, hole transport ability, All aimed at providing excellent novel organic compounds.

Another object of the present invention is to provide an organic electroluminescent device including the above-described novel organic compound and exhibiting thermal stability, 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).

In Formula 1,

X ₁ and X ₂ are the same as or different from each other and each independently O or S,

Y ₁ to Y ₁₆ are the same as or different from each other, and each independently CR ₈ or N, provided that when there are a plurality of CR _{8 s} , the plurality of R _{8 s} are the same as or different from each other,

Z ₁ to Z ₃ are the same or different and each independently CR ₅ or N, at least one of them is N,

Ar ₁ is 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 to C ₄₀ alkynyl, C ₃ to C ₄₀ cycloalkyl, A C ₆ to C ₆₀ aryl group,

Provided that the X ₁ containing ring and the X ₂ containing ring are asymmetrically bonded to each other based on the Z ₁ to Z ₃ containing ring,

m and n are each an integer of 0 to 3, m + n? 1,

A and B are the same or different from each other, and are each independently any one of substituents represented by the following formula (2) or (3);

(2)

(3)

In the general formula (2) or (3)

* Represents a moiety bonded to Formula 1,

X ₃ is a single bond,

Ar ₂ represents 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 C ₆ to C ₆₀ aryl group, 5 to 60 heteroaryl groups and C ₆ to C ₆₀ arylamine groups, or may be bonded to adjacent groups to form a condensed ring,

a, c, and f are each an integer of 0 to 3,

b, d and e are each an integer of 0 to 4, wherein b + m? 4, d + n? 4,

R ₁ to R ₈ are the same or different from each other and each independently represents hydrogen, deuterium, halogen, cyano, nitro, C ₁ to C ₄₀ alkyl, C ₂ to C ₄₀ alkenyl, C ₂ to C ₄₀ An alkynyl group, a C ₃ to C ₄₀ cycloalkyl group, a heteroaryl group having 3 to 40 nuclear atoms, a C ₆ to C ₆₀ aryl group, a heteroaryl group having 5 to 60 nuclear atoms, a C ₁ to C ₄₀ alkyl 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 aryl boron group, C ₆ ~ C ₆₀ aryl phosphine group, C ₆ ~ C ₆₀ aryl phosphine oxide group, and a C ₆ ~, or selected from the group consisting of an aryl amine of the C ₆₀ of, or adjacent groups combine to form a condensed ring And when R ₁ to R ₇ are each plural, they may be the same or different from each other,

Alkyl group of said Ar ₁ to Ar _2, and R ₁ to R _8, an alkenyl group, an alkynyl group, a cycloalkyl group, a heterocycloalkyl group, an aryl group, a heteroaryl group, an alkyloxy group, an aryloxy group, an alkylsilyl group, an arylsilyl A halogen atom, a cyano group, a nitro group, a C ₂ to C ₄₀ alkenyl group, a C ₂ to C ₄₀ alkenyl group, an aryloxy group, an aryloxy group, A cycloalkyl group having ₃ to ₄₀ carbon atoms, a heterocycloalkyl group having 3 to 40 nuclear atoms, a C ₁ to C ₄₀ 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 group, a C ₆ to C ₆₀ arylsilyl group, a C ₁ to C ₄₀ alkyl boron group, C ₆ ~ C ₆₀ aryl group of boron, C ₆ ~ C ₆₀ aryl phosphine group, C ₆ ~ C ₆₀ aryl phosphine oxide group, and a C ₆ ~ selected from the group consisting of an arylamine C in ₆₀ If the first plural number, and wherein said substituent is substituted by at least one substituent, these may be the same or different from each other.

The present invention also provides an organic electroluminescent device comprising a cathode, a cathode, and at least one organic layer sandwiched between the anode and the cathode, wherein at least one of the one or more organic layers includes a compound represented by the general formula An electroluminescent device is provided.

At least one of the organic compound layers including the compound represented by Formula 1 may be selected from the group consisting of a hole injection layer, a hole transport layer, a light emission assist layer, a light emitting layer, an electron transport layer, and an electron injection layer, . At this time, the compound represented by Formula 1 may be used as a phosphorescent host of the light emitting layer.

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, an organic electroluminescent device having a lower driving voltage, higher efficiency, and longer lifetime than conventional host materials can be manufactured. Further, This improved full color display panel can also be manufactured.

Hereinafter, the present invention will be described in detail.

<Organic compounds>

The novel compounds according to the invention are prepared by reacting a nitrogen-containing heteroaromatic ring (for example azine) with two dibenzo-based moieties (for example dibenzofuran or dibenzothiophene) non-symmetrically bonded to both sides thereof And a carbazole group, which is a kind of electron donating group (EDG) having an electron donor group, is bonded to at least one phenyl group of the two dibenzo series moieties, Is the basic skeleton.

Specifically, the compound of Chemical Formula 1 has dibenzo-type moieties (eg, dibenzofuran (DBF), dibenzothiophene (DBT)) having both physicochemical properties with respect to holes and electrons, (Such as pyridine, pyrazine, and triazine) which is a kind of azine group, which is a large electron withdrawing group (EWG), and at least one carbazole group is connected to the dibenzo series moiety. Since the compound of Formula 1 is a bipolar compound, the recombination of holes and electrons is high, so that the hole injecting / transporting ability, luminous efficiency, driving voltage, lifetime characteristics, durability and the like can be improved. In particular, when the compound of formula (1) is used as a green phosphorescent material, not only excellent luminous efficiency characteristics but also low voltage driving ability can be obtained and lifetime can be increased, and thermal stability, high glass transition temperature characteristics and uniform morphology morphology). Since the organic EL device is also effective in inhibiting crystallization of the organic material layer, the performance and lifetime characteristics of the organic EL device including the compound can be greatly improved.

In the present invention, the planarity and stereoscopic property of the compound can be realized according to the bonding positions of two dibenzofurans or dibenzothiophene moieties bonded to azine groups. As a result, the electron transporting ability is improved, and the driving and efficiency of the device to which these compounds are applied can be expected to be increased. Furthermore, since the dibenzofuran moiety or the dibenzothiophene moiety is more excellent in electron and hole stability than an aryl group, lifetime characteristics of a device to which such a compound is applied can be further improved. In particular, in the present invention, two dibenzo-based moieties bonded to an azine group exhibit an asymmetric structure. This asymmetric structure compound is easier to control the HOMO-LUMO value than a symmetric structure compound. For example, in the case of an asymmetric structural compound having a dibenzo-based moiety, it is relatively easy to control the intermolecular distance as compared with a compound having a symmetric structure. That is, due to the nature of the dibenzo-based moiety capable of bonding at the 1,2,3,4-position, a structural disorder between the hydrogen of triazine and the dibenzo-based moiety occurs at the 1,4-bond, The distance will be farther away, which will also increase the T1 value. By using the above-mentioned characteristics, it is possible to adjust the HOMO-LUMO and T1 and S1 values of the organic material layer through the asymmetry of the chemical structure.

In the present invention, at least one carbazole group in the form of a non-fused ring is introduced as an electron donor (EDG). This carbazole group is electrochemically stable and has a deep HOMO level by conjugation with other amines EDG. The carbazole group is also excellent in thermal stability and electrochemical stability, and has a high glass transition temperature (Tg) and excellent carrier transporting ability. Particularly, the electron and hole transport mobility is very excellent, and the balance of the carriers in the light emitting layer is very excellent.

On the other hand, in the phosphorescent light emitting layer of the organic electroluminescent device, the host material should have a triplet energy gap higher than the dopant of the host. That is, in order to effectively provide phosphorescent emission from the dopant, the lowest excitation state of the host must be higher energy than the lowest emission state of the dopant. The compound represented by Formula 1 has a high triplet energy and can be used as a host material because the energy level can be controlled higher than that of the dopant. The compound represented by the formula (1) can 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. Accordingly, the luminous efficiency of the device can be improved by increasing the number of the excitons contributing to the light emission in the light emitting layer, the durability and stability of the device can be improved, and the lifetime of the device can be efficiently increased.

Due to the above-mentioned matters, the compound represented by the above formula (1) can improve the phosphorescence characteristics of the organic electroluminescent device and improve the electron injection / transport ability, luminous efficiency, driving voltage and lifetime characteristics. Therefore, the compound of Chemical Formula (1) according to the present invention can be used as a material of any one of a hole injection layer, a hole transporting layer, a light emitting layer, an electron transporting layer and an electron injecting layer which is an organic material layer of an organic electroluminescent device, , Green and / or red phosphorescent host material). In particular, when the compound represented by formula (1) of the present invention is used as a blue, green and / or red phosphorescent host material, preferably phosphorescent green n-type host and / or phosphor red host, For example, a full color display panel having a low driving voltage, a high efficiency and a long lifetime compared with the organic electroluminescent device can be manufactured, and a high efficiency and a long life can be improved.

Specifically, the compound represented by the general formula (1) according to the present invention is a compound represented by the general formula (1), which comprises an azine group and two dibenzo-based moieties (dibenzofuran or dibenzothiophene moiety) At least one carbazole group, which is a kind of electron donor (EDG), is bonded to any one of six-membered rings (e.g., phenyl group) in the core.

In the compound represented by the general formula (1), X ₁ and X ₂ are the same as or different from each other and each independently O or S. At this time, when d is 0, dibenzofuran moiety is formed, and in case of S, dibenzothiophene moiety can be formed.

Y ₁ to Y ₁₆ are the same as or different from each other, and each independently CR ₈ or N; In this case, when there are a plurality of CR _{8 s} , the plurality of R _{8 s} may be the same or different. For example, when at least one of Y ₁ to Y ₄ is N, the remaining is CR ₈ ; When at least one of Y ₁₃ to Y ₁₆ is N, the remaining is CR ₈ ; At least one of Y ₁ to Y ₄ is N, and at least one of Y ₉ to Y ₁₂ is N, the remainder is CR ₈ ; At least one of Y ₅ to Y ₈ is N, and at least one of Y ₁₃ to Y ₁₆ is N, the remainder is CR ₈ ; At least one of Y ₁ to Y ₄ is N, and when one of Y ₁₃ to Y ₁₆ is N, the remaining is CR ₈ ; Y ₁ to Y ₁₆ may all be CR ₈ (see the following formulas 9 to 13).

Wherein, R ₈ is hydrogen, heavy hydrogen, a halogen group, a cyano group, a nitro group, an amino group, an alkynyl group of C ₁ ~ C ₄₀ alkyl group, C ₂ ~ C ₄₀ alkenyl group, C ₂ ~ C ₄₀ of, C ₃ ~ C ₄₀ cycloalkyl group, the number of nuclear atoms of 3 to 40 heterocycloalkyl group, C ₆ ~ C ₆₀ aryl group, nuclear atoms aryl of from 5 to 60 heteroaryl group, a C ₁ ~ alkyloxy group of C _40, C ₆ ~ C ₆₀ aryloxy group, C group ₁ ~ C ₄₀ alkyl silyl, C ₆ ~ C ₆₀ aryl silyl group, a alkyl boronic of C ₁ ~ C _40, an aryl boronic a _{C 6 ~ C 60, C 1} ~ C ₄₀ phosphine groups, C ₁ to C ₄₀ phosphine oxide groups, and C ₆ to C ₆₀ arylamine groups. Specifically, R ₈ is a hydrogen, a deuterium, a halogen, a cyano group, a nitro group, C ₁ ~ C ₄₀ alkyl group, C ₂ ~ C ₄₀ alkenyl group, C ₂ ~ C ₄₀ alkynyl group, C ₃ ~ C ₄₀ of the A cycloalkyl group, and a C ₆ to C ₆₀ aryl group.

Z ₁ to Z ₃ are the same or different and are each independently CR ₅ or N, and at least one of them is N. In one preferred embodiment, from ₁ to ₃ of Z ₁ to Z ₃ may be N, for example, pyridine, pyrimidine, triazine. More preferably, all of Z ₁ to Z ₃ are N and triazine is electron-withdrawing.

Ar ₁ is 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 to C ₄₀ alkynyl, C ₃ to C ₄₀ cycloalkyl, A C ₆ to C ₆₀ aryl group, and the like. Specifically, Ar ₁ is preferably an aryl group of C ₆ to C ₆₀ , and may be, for example, a phenyl group, a biphenyl group, a naphthyl group, a triphenyl group, an anthryl group, a phenanthryl group and the like.

In one embodiment of the present invention, Ar ₁ can be selected from the group of substituents represented by the following structural formulas.

At this time, although not shown in the above-mentioned structural formula, Ar ₁ may be substituted with at least one substituent group known in the art (for example, the same definition as R ₆ ).

a and c are each an integer of 0 to 3, and b and d are an integer of 0 to 4, respectively. When a to d are 0, hydrogen means not substituted with R ₁ to R ₄ , and when a to d are each an integer of 1 or more, one or more hydrogen atoms are substituted with R ₁ to R ₄ . it means.

R ₁ to R ₅ are the same or different, each independently represent hydrogen, deuterium, a halogen, a cyano group, a nitro group, C ₁ ~ C ₄₀ alkyl group, C ₂ ~ C ₄₀ alkenyl group, C ₂ ~ C ₄₀ of the An alkynyl group, a C ₃ to C ₄₀ cycloalkyl group, a heteroaryl group having 3 to 40 nuclear atoms, a C ₆ to C ₆₀ aryl group, a heteroaryl group having 5 to 60 nuclear atoms, a C ₁ to C ₄₀ alkyl 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 aryl boron group, C ₆ ~ C ₆₀ aryl phosphine group, C ₆ ~ C ₆₀ aryl phosphine oxide group, and a C ₆ ~, or selected from the group consisting of an aryl amine of the C ₆₀ of, or adjacent groups combine to form a condensed ring . Here, when R ₁ to R ₅ each are plural, they are the same as or different from each other. Specifically, R ₁ to R ₅ are the same or different and each independently represents hydrogen, deuterium, halogen, cyano, nitro, C ₁ to C ₄₀ alkyl, C ₂ to C ₄₀ alkenyl, C ₂ An alkynyl group of C ₄₀ to C ₄₀ , a cycloalkyl group of C ₃ to C ₄₀ , and an aryl group of C ₆ to C ₆₀ .

m and n are each an integer of 0 to 3, and m + n? 1. When m or n is 0, it means that hydrogen is not substituted with A or B. When m and n are each an integer of 1 or more, it means that at least one hydrogen is substituted with A and B, respectively. Preferably, m and n may each be an integer of 0 to 2. For example, m = 1, n = 0; m = 0, n = 1; m = 1, n = 1; m = 2, n = 0; m = 0, n = 2. More preferably, m = 1, n = 0 or m = 1 and n = 1. That is, at least one of A and B described later may exist.

And b + m and d + n may be an integer of 0 to 4, respectively. Preferably, when b + m = 1, d + n = 0 or d + n = 1.

In the formula (1) of the present invention, A and B are electron donating substituents each of which serves to provide electrons. In the present invention, as a kind of electron donating group (EDG), at least one carbazole group may be introduced. Specifically, A and B are the same as or different from each other, and each independently may be any of the substituents represented by the above-described formulas (2) and (3).

In the substituents represented by the above formulas (2) and (3), X ₃ is a single bond.

e is an integer of 0 to 4, and f is an integer of 0 to 3. When e and f are each 0, hydrogen means not substituted by R ₆ and R ₇ , and when e and f are each an integer of 1 or more, at least one hydrogen is substituted with R ₆ and R ₇ respectively .

Wherein, R ₆ and R ₇ are the same or different, each independently represent hydrogen, deuterium, a halogen, a cyano group, a nitro group, C ₁ ~ alkenyl group of the C ₄₀ alkyl group, C ₂ ~ C ₄₀ of, C ₂ ~ C _A C ₃ to C ₄₀ cycloalkyl group, a heteroaryl group having 3 to 40 nuclear atoms, a C ₆ to C ₆₀ aryl group, a heteroaryl group having 5 to 60 nuclear atoms, a C ₁ to C ₄₀ alkenyl group, C ₆ -C ₆₀ aryloxy groups, C ₁ -C ₄₀ alkylsilyl groups, C ₆ -C ₆₀ arylsilyl groups, C ₁ -C ₄₀ alkylboron groups, C ₆ -C ₆₀ a group of the arylboronic, C ₆ ~ C ₆₀ aryl phosphine group, C ₆ ~ C ₆₀ aryl phosphine oxide group, and a C ₆ ~ selected from the group consisting of an aryl amine of the C ₆₀ or, or in adjacent groups combine a condensed ring . When R ₆ and R ₇ are plural, they may be the same as or different from each other. , For one preferred embodiment, R ₆ and R ₇ are each independently hydrogen, deuterium, a halogen, a cyano group, a nitro group, C ₁ ~ alkenyl group of the C ₄₀ alkyl group, C ₂ ~ C ₄₀ of, C ₂ ~ C ₄₀ A C ₃ to C ₄₀ cycloalkyl group, and a C ₆ to C ₆₀ aryl group, or may be bonded to adjacent groups to form a condensed ring. At this time, adjacent groups may be one R ₆ and one R ₆ , one R ₆ and one Ar ₂ , one R ₇ and another R ₇ , one R _7, and one Ar ₂ .

In the substituent represented by the general formula (2) or (3), Ar ₂ represents 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, ₆ ~ C ₆₀ aryl group, the number of nuclear atoms of 5 to 60 heteroaryl group, and a C ₆ ~, or selected from the group consisting of an aryl amine of the C _60, or adjacent groups condensed in combination with (for example, R _6, R ₇₎ A ring can be formed. Specifically, the Ar ₂ may be selected from the group consisting of an aryl amine of the C ₆ ~ C ₆₀ aryl group, the number of nuclear atoms of 5 to 60 heteroaryl group, and a C ₆ ~ C _60.

In an embodiment of the present invention, A and B are the same as or different from each other, and each independently can be any one selected from the group of substituents represented by the following structural formulas.

In the above formulas,

* Represents a moiety bonded to Formula 1,

Ar ₂ is the same as defined in formula (1). Although not specifically shown, the above-mentioned structural formula may be substituted with at least one substituent group known in the art (for example, the same definition as R ₆ ).

In the above-described formula (1), Ar ₁ to Ar ₂ , and R ₁ to R ₈ are independently selected from the group consisting of an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a heterocycloalkyl group, an aryl group, a heteroaryl group, A halogen atom, a cyano group, a nitro group, a C ₂ to C ₄₀ alkenyl group, an aryl group, an aryl group, an aryl group, an aryl group, an aryl group, alkynyl of _{C 2 ~ C 40, C 3} ~ C 40 cycloalkyl group, a number of nuclear atoms of 3 to 40 heterocycloalkyl group, C ₁ ~ C ₄₀ alkyl group, C ₆ ~ aryl group of C _60, nuclear atoms 5 to 60 heteroaryl group, C ₁ ~ C ₄₀ alkyloxy group of, C ₆ ~ C ₆₀ aryloxy group, C ₁ ~ C ₄₀ alkylsilyl group, C ₆ ~ C aryl silyl group of _60, C ₁ ~ C ₄₀ alkyl group of boron, C ₆ ~ C ₆₀ aryl group of boron, C ₆ ~ C ₆₀ aryl phosphine group, C ₆ ~ C ₆₀ aryl phosphine oxide group, and a C ₆ ~ C ₆₀ aryl amine of achieving the If true, and it may be substituted with one or more substituent species selected from the group, wherein the substituent of the plurality, they may be the same or different from each other.

In accordance with the present invention compound represented by the formula (1), the nitrogen-containing heterocycle having an EWG properties (such as, Z ₁ ~ Z ₃ containing ring) 2 dibenzo-based moiety that is bonded to (for example, X ₁ hamyuhwan and X _2- containing rings) according to the positions of the carbon bonds of the asymmetric structure. Specifically, the bonding position of one of Y ₁ to Y ₄ of the X ₁ containing ring connected to the Z ₁ to Z ₃ containing ring and the bonding position of one of Y ₉ to Y ₁₂ of the X ₂ containing ring are asymmetric with each other . In one example, the O rare cases (for example, Z ₁ ~ Z _3-containing ring) is X ₁ containing ring carbon position coupled to Y ₁ il, X ₂ containing ring carbon position which is bonded to the azine is Y ₁₀ to the exception of Y ₉ Y ₁₂ (see Chemical Formula 4 below). The carbon bond positions of two dibenzo-based moieties respectively linked to the nitrogen-containing heterocycle may be represented by any one of the following formulas (4) to (7).

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

(7)

In the above formulas 4 to 7,

The ring containing Z ₁ to Z _{3 in} Formula 4 is bonded to any one of Y ₁₀ to Y ₁₂ (provided that the ring containing Z ₁ to Z ₃ is not bonded to Y ₉ )

The ring containing Z ₁ to Z _{3 in} Formula 5 is bonded to any one of Y ₉ and Y ₁₁ to Y ₁₂ (provided that the ring containing Z ₁ to Z ₃ is not bonded to Y ₁₀ )

The ring containing Z ₁ to Z _{3 in} Formula 6 is bonded to any one of Y ₉ , Y ₁₀ and Y ₁₂ (provided that the Z ₁ to Z ₃ containing ring is not bonded to Y ₁₁ )

The ring containing Z ₁ to Z _{3 in} the above formula (7) is bonded to any one of Y ₉ to Y ₁₁ (provided that the Z ₁ to Z ₃ containing ring is not bonded to Y ₁₂ )

X ₁ , X ₂ , Y ₁ to Y ₁₆ , Z ₁ to Z ₃ , Ar ₁ , m, n, A, B, a to d and R ₁ to R ₄ are as defined in Formula 1, respectively.

In one embodiment of the present invention, the compound represented by Formula 4 may be further represented by any one of Formulas 4a to 4c.

[Chemical Formula 4a]

(4b)

[Chemical Formula 4c]

In another embodiment of the present invention, the compound represented by Formula 5 may be further represented by any one of Formulas 5a to 5c.

[Chemical Formula 5a]

[Chemical Formula 5b]

[Chemical Formula 5c]

In another embodiment of the present invention, the compound represented by Formula 6 may be further represented by any one of Formulas 6a to 6c.

[Chemical Formula 6a]

[Formula 6b]

[Chemical Formula 6c]

In another embodiment of the present invention, the compound represented by the above formula (7) may be further represented by any one of formulas (7a) to (7c).

[Formula 7a]

[Formula 7b]

[Formula 7c]

In the compound represented by Formula 1, dibenzo-based moieties such as dibenzofurane or dibenzothiophene moiety may be further represented by any one of the following formulas (8) to (12).

[Chemical Formula 8]

[Chemical Formula 9]

[Chemical formula 10]

(11)

[Chemical Formula 12]

In Formulas 8 to 12,

X ₁ , X ₂ , Z ₁ to Z ₃ , Ar ₁ , n, A and B are as defined in the above formula (1).

More specifically, each of X ₁ and X ₂ is independently O or S, and Z ₁ to Z ₃ are each independently CR ₅ or N, a is N, Ar ₁ is an aryl group of C ₆ ~ C _60.

The carbon position of the X ₁ -containing ring and the carbon position of the X ₂ -containing ring bonded to the azine group (for example, the Z ₁ to Z ₃ -containing ring) have an asymmetric structure, and at least one of A and B is a carbazole group Lt; / RTI &gt;

The compound represented by formula (1) according to the present invention may be further represented by any one of compounds 1 to 500 shown below. However, the compounds represented by formula (1) of the present invention are not limited by the following examples.

In the present invention, "alkyl" means a monovalent substituent derived from a straight or branched saturated hydrocarbon having 1 to 40 carbon atoms. Examples of such alkyl 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 of such alkenyl 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 of such alkynyls include, but are not limited to, ethynyl, 2-propynyl, and the like.

"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 &lt; RTI ID = 0.0 &gt; Se. &Lt; / RTI &gt; Examples of such heterocycloalkyl include, but are not limited to, morpholine, piperazine, 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 60 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, "alkyloxy" means a monovalent substituent group represented by R'O-, and R 'means alkyl having 1 to 40 carbon atoms. Such alkyloxy may include linear, branched or cyclic structures. Examples of such alkyloxy include, but are not limited to, methoxy, ethoxy, n-propoxy, 1-propoxy, t-butoxy, n-butoxy and pentoxy.

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

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

In the present invention, "alkyl boron" is boron substituted with alkyl having 1 to 40 carbon atoms, and "aryl boron" means boron substituted with aryl having 6 to 60 carbon atoms.

In the present invention, "arylphosphine" means a phosphine substituted with aryl having 6 to 60 carbon atoms, and "arylphosphine oxide group" means that phosphine substituted with aryl having 6 to 60 carbon atoms includes O do.

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.

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

The compounds represented by formula (1) of the present invention can be prepared without limitation by methods known in the art. For example, various syntheses can be carried out by referring to the synthesis process of the following examples.

&Lt; Organic electroluminescent device &

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

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

The at least one organic material layer may include 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. have. Specifically, the organic compound layer containing the compound of Formula 1 is preferably a light emitting layer.

The light emitting layer of the organic electroluminescence device of the present invention may include a host material (preferably, a phosphorescent host material). The light emitting layer of the organic electroluminescent device of the present invention may contain 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, and examples thereof include 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, an electron injecting layer and a cathode sequentially stacked Structure. At least one of the hole injecting layer, the hole transporting layer, the light-emitting auxiliary layer, the light emitting layer, the electron transporting layer, and the electron injecting layer may include the compound represented by Formula 1, &Lt; / RTI &gt; compounds. Further, 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.

Meanwhile, the organic electroluminescent device of the present invention can be manufactured 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 have.

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); A combination of a metal and an oxide such as ZnO: Al or SnO2: 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.

Examples of the negative electrode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin or lead or alloys thereof; And multi-layer structure materials such as LiF / Al or LiO2 / 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 the following 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 C1

Synthesis of 3- (6-bromodibenzo [b, d] furan-1-yl) -9-phenyl-9H-carbazole

4,6-dibromodibenzo [b, d] furan (40.0 g, 122.7 mmol) and (9-phenyl-9H-carbazol -3-yl) boronic acid (35.2 g, 122.7 mmol) and Pd (PPh _{3) 4} (2.8 g, 2.5 mmol) and K ₂ CO ₃ (40.7 g, 294.5 mmol) were added to toluene (300 ml) and H ₂ O (150 ml), and the mixture was stirred at 110 ° C for 8 hours. After the completion of the reaction, the product was extracted and the solvent was removed. The solid was dissolved in toluene, filtered through silica, and recrystallized to obtain the target compound, 3- (6-bromodibenzo [b, d] furan- carbazole (44.9 g, yield 75%).

<Step 2> Synthesis of C1

A solution of Pd (dppf) Cl ₂ (0.5 g, 0.7 mmol), potassium acetate (16.8 g, 34.3 mmol) and 3- (6-bromodibenzo [b, d] furan- 5.1 g, 51.5 mmol) and 4,4,4 ', 4', 5,5,5 ', 5'-octamethyl-2,2'-bi (1,3,2-dioxaborolane (11.3 g, 44.6 mmol ) Was added to 150 ml of 1,4-dioxane and the mixture was stirred at 110 ° C for 5 hours. After completion of the reaction, the reaction mixture was extracted with methylene chloride, and the mixture was filtered with MgSO ₄ . After removing the solvent of the filtered organic layer, C1 (15.8 g, yield 86%) was obtained by column chromatography.

[Preparation Example 2] Synthesis of C2

<Step 1> Synthesis of 2,4-dichloro-2'-methoxy-1,1'-biphenyl

2-methoxyphenyl boronic acid (18.5 g , 121.7 mmol) and 1-bromo-2,4-dichlorobenzene ( 25.0 g, 110.7 mmol), Pd (PPh 3) 4 (6.4 g, 5.5 mmol) and KOH (11.1 g, 276.7 mmol) were added to DME (300 ml) and H ₂ O (150 ml), and the mixture was stirred at 85 ° C for 12 hours. After completion of the reaction, the reaction mixture was extracted with methylene chloride, and the mixture was filtered with MgSO ₄ . After removing the solvent of the filtered organic layer, 2,4-dichloro-2'-methoxy-1,1'-biphenyl (23.5 g, yield 84%) was obtained by column chromatography.

<Step 2> Synthesis of 2 ', 4'-dichloro- [1,1'-biphenyl] -2-ol

2,4-dichloro-2'-methoxy-1,1'-biphenyl (17.0 g, 67.2 mmol) and pyridine hydrochloride (38.8 g, 335.8 mmol) were mixed and stirred at 190 ° C for 12 hours. After completion of the reaction, the reaction mixture was extracted with distilled water and methylene chloride, and the mixture was filtered with MgSO ₄ . After removal of the solvent of the filtered organic layer, 2'-, 4'-dichloro- [1,1'-biphenyl] -2-ol (12.8 g, yield 80%) was obtained by column chromatography.

<Step 3> Synthesis of 3-bromo-2 ', 4'-dichloro- [1,1'-biphenyl] -2-ol

NBS (11.1 g, 62.1 mmol) was added to 150 mL of a methylene chloride mixture with 2 ', 4'-dichloro- [1,1'-biphenyl] -2-ol (13.5 g, 56.5 mmol) and Diisopropylamine ) Was slowly added thereto and stirred at 40 ° C for 12 hours. After completion of the reaction, the mixture was extracted with methylene chloride and sodium thiosulfate aqueous solution, and the mixture was filtered with MgSO ₄ . After removing the solvent of the filtered organic layer, 3-bromo-2 ', 4'-dichloro- [1,1'-biphenyl] -2-ol (13.5 g, yield 75%) .

<Step 4> Synthesis of 6-bromo-3-chlorodibenzo [b, d] furan

Sodium hydrosulfite (1.8 g, 5.7 mmol) and KOH (12.7 g, 226.4 mmol) were added to a solution of 3-bromo- And tetrabutylammonium bromide (2.0 g, 11.3 mmol) were added to DMF (200 ml), and the mixture was stirred at 155 ° C for 5 hours. After completion of the reaction, distilled water is added, and the resulting solid is filtered. After extraction with methylene chloride, the solvent was removed and the desired compound, 6-bromo-3-chlorodibenzo [b, d] furan (14.2 g, yield 89%) was obtained by column chromatography.

<Step 5> Synthesis of 3- (7-chlorodibenzo [b, d] furan-4-yl) -9-phenyl-9H-

3-chlorodibenzo [b, d] furan (11.5 g, 40.9 mmol) and Pd (PPh ₃ ) ₄ (9.9 g, 44.9 mmol) (1.4 g, 1.2 mmol) and K ₂ CO ₃ (13.6 g, 98.0 mmol) were added to toluene (150 ml) and H ₂ O (75 ml), and the mixture was stirred at 110 ° C for 8 hours. The solids formed after the reaction were filtered. The obtained solid was dissolved in toluene, filtered through a silica filter, and recrystallized to obtain 13.8 g (yield: 76%) of 3- (7-chlorodibenzo [b, d] furan- &Lt; / RTI &gt;

<Step 6> Synthesis of C2

A solution of Pd (dppf) Cl ₂ (0.6 g, 0.8 mmol), potassium acetate (8.3 g, 18.7 mmol) and 3- (7-chlorodibenzo [b, d] furan- 3.7 g, 37.5 mmol), 4,4,4 ', 4', 5,5,5,5-octamethyl-2,2'-bi (1,3,2-dioxaborolane) (6.2 g, 24.4 mmol ) And X-Phos (1.8 g, 3.8 mmol) were added to 80 ml of 1,4-dioxane and the mixture was stirred at 110 ° C for 5 hours. After completion of the reaction, the reaction mixture was extracted with methylene chloride, and the mixture was filtered with MgSO ₄ . After removing the solvent of the filtered organic layer, the desired compound C2 (8.5 g, yield 85%) was obtained by column chromatography.

[Preparation Example 3] Synthesis of C3

<Step 1> Synthesis of 2,6-dichloro-2'-methoxy-1,1'-biphenyl

2-methoxyphenyl boronic acid (18.5 g , 121.7 mmol) and 1-bromo-2,4-dichlorobenzene ( 25.0 g, 110.7 mmol), Pd (PPh 3) 4 (6.4 g, 5.5 mmol) and KOH (11.1 g, 276.7 mmol) were added to DME (300 ml) and H ₂ O (150 ml), and the mixture was stirred at 85 ° C for 12 hours. After completion of the reaction, the reaction mixture was extracted with methylene chloride, and the mixture was filtered with MgSO ₄ . After removing the solvent of the filtered organic layer, 2,6-dichloro-2'-methoxy-1,1'-biphenyl (24.6 g, yield 88%) was obtained by column chromatography.

<Step 2> Synthesis of 2 ', 6'-dichloro- [1,1'-biphenyl] -2-ol

2,6-dichloro-2'-methoxy-1,1'-biphenyl (22.5 g, 88.9 mmol) and pyridine hydrochloride (41.1 g, 355.56 mmol) were mixed and stirred at 190 ° C for 12 hours. After completion of the reaction, the reaction mixture was extracted with distilled water and methylene chloride, and the mixture was filtered with MgSO ₄ . After removing the solvent of the filtered organic layer, 2'-, 6'-dichloro- [1,1'-biphenyl] -2-ol (17.4 g, yield 82%) was obtained by column chromatography.

<Step 3> Synthesis of 3-bromo-2 ', 6'-dichloro- [1,1'-biphenyl] -2-ol

NBS (13.6 g, 76.4 mmol) was added to 200 mL of a methylene chloride mixture of 2 ', 6'-dichloro- [1,1'-biphenyl] -2-ol (16.6 g, 69.4 mmol) and Diisopropylamine ) Was slowly added thereto and stirred at 40 ° C for 12 hours. After completion of the reaction, the mixture was extracted with methylene chloride and sodium thiosulfate aqueous solution, and the mixture was filtered with MgSO ₄ . After removing the solvent of the filtered organic layer, 3-bromo-2 ', 6'-dichloro- [1,1'-biphenyl] -2-ol (17.0 g, yield 77%) .

<Step 4> Synthesis of 6-bromo-1-chlorodibenzo [b, d] furan

Sodium hydrosulfite (3.3 g, 10.4 mmol) and KOH (23.3 g, 415.1 mmol) were added to a solution of 3-bromo- And tetrabutylammonium bromide (3.6 g, 20.8 mmol) were added to DMF (200 ml), and the mixture was stirred at 155 ° C for 5 hours. After completion of the reaction, distilled water is added, and the resulting solid is filtered. After extraction with methylene chloride, the solvent was removed and the desired compound, 6-bromo-1-chlorodibenzo [b, d] furan (24.8 g, yield 85%) was obtained by column chromatography.

<Step 5> Synthesis of 3- (9-chlorodibenzo [b, d] furan-4-yl) -9-phenyl-9H-carbazole

B, d] furan (13.0 g, 46.8 mmol) and Pd (PPh ₃ ) ₄ (14.8 g, 50.8 mmol) (1.6 g, 1.4 mmol) and K ₂ CO ₃ (15.3 g, 110.8 mmol) were added to toluene (150 ml) and H ₂ O (75 ml), and the mixture was stirred at 110 ° C for 8 hours. The solids formed after the reaction were filtered. The obtained solid was dissolved in toluene, filtered through silica, and recrystallized to obtain 15.2 g (yield: 74%) of 3- (9-chlorodibenzo [b, d] furan- &Lt; / RTI &gt;

<Step 6> Synthesis of C3

Pd (dppf) Cl ₂ (1.0 g, 1.36 mmol) and potassium acetate (15.1 g, 34.0 mmol) were added to a solution of 3- (9-chlorodibenzo [b, d] furan- 6.7 g, 68.0 mmol), 4,4,4 ', 4,5,5,5,5-octamethyl-2,2'-bi (1,3,2-dioxaborolane) (11.2 g, 44.2 mmol ) And X-Phos (3.2 g, 6.8 mmol) were added to 80 ml of 1,4-dioxane and the mixture was stirred at 110 ° C for 5 hours. After completion of the reaction, the reaction mixture was extracted with methylene chloride, and the mixture was filtered with MgSO ₄ . After removing the solvent of the filtered organic layer, C3 (14.6 g, yield 80%) of the target compound C3 was obtained by column chromatography.

[Preparation Example 4] Synthesis of C4

Synthesis of 4- (6-bromodibenzo [b, d] furan-4-yl) -9-phenyl-9H-carbazole

4,6-dibromodibenzo [b, d] furan (40.0 g, 122.7 mmol) and (9-phenyl-9H-carbazol -3-yl) boronic acid (35.2 g, 122.7 mmol) and Pd (PPh _{3) 4} (2.8 g, 2.5 mmol) and K ₂ CO ₃ (40.7 g, 294.5 mmol) were added to toluene (300 ml) and H ₂ O (150 ml), and the mixture was stirred at 110 ° C for 8 hours. After the completion of the reaction, the product was extracted and the solvent was removed. The solid was dissolved in toluene, filtered through silica, and recrystallized to obtain the target compound, 4- (6-bromodibenzo [b, d] furan- carbazole (38.4 g, yield 64%).

<Step 2> Synthesis of C4

Pd (dppf) Cl ₂ (0.6 g, 0.8 mmol), potassium acetate (20.0 g, 41.0 mmol) and 4- 6.0 g, 61.4 mmol) and 4,4,4 ', 4', 5,5,5 ', 5'-octamethyl-2,2'-bi (1,3,2-dioxaborolane) ) Was added to 150 ml of 1,4-dioxane and the mixture was stirred at 110 ° C for 5 hours. After completion of the reaction, the reaction mixture was extracted with methylene chloride, and the mixture was filtered with MgSO ₄ . After removing the solvent of the filtered organic layer, C4 (18.2 g, yield 83%) of the desired compound was obtained by column chromatography.

[Preparation Example 5] Synthesis of C5

Synthesis of 2- (6-bromodibenzo [b, d] furan-4-yl) -9-phenyl-9H-carbazole

4,6-dibromodibenzo [b, d] furan (40.0 g, 122.7 mmol) and (9-phenyl-9H-carbazol -3-yl) boronic acid (35.2 g, 122.7 mmol) and Pd (PPh _{3) 4} (2.8 g, 2.5 mmol) and K ₂ CO ₃ (40.7 g, 294.5 mmol) were added to toluene (300 ml) and H ₂ O (150 ml), and the mixture was stirred at 110 ° C for 8 hours. After the completion of the reaction, the product was extracted and the solvent was removed, and the solid was dissolved in toluene to remove the solvent. The residue was recrystallized to obtain 2- (6-bromodibenzo [b, d] furan- carbazole (50.3 g, yield 84%).

<Step 2> Synthesis of C5

Pd (dppf) Cl ₂ (0.6 g, 0.8 mmol) and potassium acetate (20.0 g, 41.0 mmol) were added to a solution of 2- (6-bromodibenzo [b, d] furan- 6.0 g, 61.4 mmol) and 4,4,4 ', 4', 5,5,5 ', 5'-octamethyl-2,2'-bi (1,3,2-dioxaborolane) ) Was added to 150 ml of 1,4-dioxane and the mixture was stirred at 110 ° C for 5 hours. After completion of the reaction, the reaction mixture was extracted with methylene chloride, and the mixture was filtered with MgSO ₄ . After removing the solvent of the filtered organic layer, C5 (18.6 g, yield 85%) was obtained by column chromatography.

[Preparation Example 6] Synthesis of C6

Synthesis of 1- (6-bromodibenzo [b, d] furan-4-yl) -9-phenyl-9H-carbazole

4,6-dibromodibenzo [b, d] furan (40.0 g, 122.7 mmol) and (9-phenyl-9H-carbazol -3-yl) boronic acid (35.2 g, 122.7 mmol) and Pd (PPh _{3) 4} (2.8 g, 2.5 mmol) and K ₂ CO ₃ (40.7 g, 294.5 mmol) were added to toluene (300 ml) and H ₂ O (150 ml), and the mixture was stirred at 110 ° C for 8 hours. After the completion of the reaction, the product was extracted and the solvent was removed, and the solid was dissolved in toluene, filtered through silica, and recrystallized to obtain the desired compound, 1- (6-bromodibenzo [b, d] furan- carbazole (34.8 g, yield 58%).

<Step 2> Synthesis of C6

Pd (dppf) Cl ₂ (0.6 g, 0.8 mmol), potassium acetate (20.0 g, 41.0 mmol) and 1- 6.0 g, 61.4 mmol) and 4,4,4 ', 4', 5,5,5 ', 5'-octamethyl-2,2'-bi (1,3,2-dioxaborolane) ) Was added to 150 ml of 1,4-dioxane and the mixture was stirred at 110 ° C for 5 hours. After completion of the reaction, the reaction mixture was extracted with methylene chloride, and the mixture was filtered with MgSO ₄ . After removing the solvent of the filtered organic layer, the desired compound C6 (17.8 g, yield 81%) was obtained by column chromatography.

[Preparation Example 7] Synthesis of C7

<Step 1> Synthesis of 9- (8-chlorodibenzo [b, d] furan-4-yl) -9H-carbazole

6-bromo-2-chlorodibenzo [b, d] furan (17.3 g, 61.4 mmol) and Pd ₂ (dba) ₃ (1.7 g, 1.8 mmol), sodium tert-butoxide (8.8 g, 92.0 mmol) and toluene (150 mL) were added. Tri-tert-butylphosphine (0.9 mL, 3.7 mmol) was added and the mixture was stirred at 110 ° C for 8 hours. After completion of the reaction, the product was extracted, and the solvent was removed. The solid was dissolved in toluene to remove silica, and then the desired product, 9- (8-chlorodibenzo [b, d] furan- carbazole (11.51 g, yield 51%).

<Step 2> Synthesis of C7

Potassium acetate (3.7 g, 37.5 mmol) and Pd (dppf) Cl ₂ (0.6 g, 0.8 mmol) and 9- (8-chlorodibenzo [b, d] furan- mmol), 4,4,4 ', 4,5,5,5,5-octamethyl-2,2'-bi (1,3,2-dioxaborolane) (6.2 g, 24.4 mmol) Phos (1.8 g, 3.8 mmol) was added to 80 ml of 1,4-dioxane and the mixture was stirred at 110 ° C for 5 hours. After completion of the reaction, the reaction mixture was extracted with methylene chloride, and the mixture was filtered with MgSO ₄ . After removing the solvent of the filtered organic layer, C7 (7.3 g, yield 85%) was obtained by column chromatography.

[Preparation Example 8] Synthesis of C8

<Step 1> Synthesis of 9- (7-bromodibenzo [b, d] furan-3-yl) -9H-carbazole

(10.0 g, 61.4 mmol), 3,7-dibromodibenzo [b, d] furan (20.0 g, 61.4 mmol) and Pd ₂ (dba) ₃ (1.7 g, 1.8 mmol), sodium tert- g, 92.0 mmol) and toluene (150 mL) were added. Tri-tert-butylphosphine (0.9 mL, 3.7 mmol) was added and the mixture was stirred at 110 ° C for 8 hours. After completion of the reaction, the product was extracted and the solvent was removed, and the solid was dissolved in toluene to remove the silica filter. The desired compound, 9- (7-bromodibenzo [b, d] furan- carbazole (13.16 g, yield 52%).

<Step 2> Synthesis of C8

Potassium acetate (2.9 g, 29.7 mmol) and Pd (dppf) Cl ₂ (0.3 g, 0.4 mmol) and 9- (7-bromodibenzo [b, d] furan- mmol) and 4,4,4 ', 4', 5,5,5 ', 5'-octamethyl-2,2'-bi (1,3,2-dioxaborolane) (6.5 g, 25.8 mmol) 4-Dioxane (60 ml), and the mixture was stirred at 110 ° C for 5 hours. After completion of the reaction, the reaction mixture was extracted with methylene chloride, and the mixture was filtered with MgSO ₄ . After removing the solvent of the filtered organic layer, C8 (7.3 g, yield 80%) was obtained by column chromatography.

[Preparation Example 9] Synthesis of C9

Synthesis of 3- (8-bromodibenzo [b, d] furan-3-yl) -9-phenyl-9H-carbazole

(9-phenyl-9H-carbazol -3-yl) boronic acid (17.6 g, 61.4 mmol) and 2-bromo-7-iododibenzo [ b, d] furan (22.9 g, 61.4 mmol) and Pd (PPh _{3) 4} (1.4 g, 1.2 mmol) and K ₂ CO ₃ (20.4 g, 147.2 mmol) were added to toluene (150 ml) and H ₂ O (75 ml), and the mixture was stirred at 110 ° C for 8 hours. (8-bromodibenzo [b, d] furan-3-yl) -9-phenyl-9H-quinolinone was obtained by removing the solvent and then dissolving the solid in toluene, carbazole (22.2 g, yield 74%).

<Step 2> Synthesis of C9

(Dppf) Cl ₂ (0.3 g, 0.4 mmol), potassium acetate (9.4 g, 19.2 mmol) and 3- (8-bromodibenzo [b, d] furan- 2.8 g, 28.8 mmol) and 4,4,4 ', 4', 5,5,5 ', 5'-octamethyl-2,2'-bi (1,3,2-dioxaborolane ) Was added to 1,4-dioxane (60 ml), and the mixture was stirred at 110 ° C for 5 hours. After completion of the reaction, the reaction mixture was extracted with methylene chloride, and the mixture was filtered with MgSO ₄ . After removing the solvent of the filtered organic layer, C9 (7.8 g, yield 76%) was obtained by column chromatography.

[Preparation Example 10] Synthesis of C10

<Step 1> Synthesis of 1- (7-chlorodibenzo [b, d] furan-1-yl) -9-phenyl-9H-carbazole

(9-phenyl-9H-carbazol -1-yl) boronic acid (17.6 g, 61.4 mmol) and 1-bromo-7-chlorodibenzo [ b, d] furan (17.3 g, 61.4 mmol) and Pd (PPh _{3) 4} (1.4 g, 1.2 mmol) and K ₂ CO ₃ (20.4 g, 147.2 mmol) were added to toluene (150 ml) and H ₂ O (75 ml), and the mixture was stirred at 110 ° C for 8 hours. (7-chlorodibenzo [b, d] furan-1-yl) -9-phenyl-9H-quinolinecarboxylic acid was obtained by removing the solvent, dissolving the solid in toluene, carbazole (19.9 g, yield 73%).

<Step 2> Synthesis of C10

A solution of Pd (dppf) Cl ₂ (0.6 g, 0.8 mmol), potassium acetate (8.3 g, 18.7 mmol) and 1- (7-chlorodibenzo [b, d] furan- 3.7 g, 37.5 mmol), 4,4,4 ', 4', 5,5,5,5-octamethyl-2,2'-bi (1,3,2-dioxaborolane) (6.2 g, 24.4 mmol ) And X-Phos (1.8 g, 3.8 mmol) were added to 80 ml of 1,4-dioxane and the mixture was stirred at 110 ° C for 5 hours. After completion of the reaction, the reaction mixture was extracted with methylene chloride, and the mixture was filtered with MgSO ₄ . After removing the solvent of the filtered organic layer, C12 (6.8 g, yield 68%) was obtained by column chromatography.

[Preparation Example 11] Synthesis of C11

Synthesis of 9- (8-chlorodibenzo [b, d] furan-2-yl) -9H-carbazole

8-chlorodibenzo [b, d] furan (17.3 g, 61.4 mmol) and Pd ₂ (dba) ₃ (1.7 g, 1.8 mmol), sodium tert-butoxide (8.8 g, 92.0 mmol) and toluene (150 mL) were added. Tri-tert-butylphosphine (0.9 mL, 3.7 mmol) was added and the mixture was stirred at 110 ° C for 8 hours. After the completion of the reaction, the product was extracted and the solvent was removed. The solid was dissolved in toluene, filtered through silica, and then purified by column chromatography to obtain the target compound, 9- (8-chlorodibenzo [b, d] furan- carbazole (12.0 g, yield 53%).

<Step 2> Synthesis of C11

Potassium acetate (3.7 g, 37.5 mmol) and Pd (dppf) Cl ₂ (0.6 g, 0.8 mmol) and 9- (8-chlorodibenzo [b, d] furan- mmol), 4,4,4 ', 4,5,5,5,5-octamethyl-2,2'-bi (1,3,2-dioxaborolane) (6.2 g, 24.4 mmol) Phos (1.8 g, 3.8 mmol) was added to 80 ml of 1,4-dioxane and the mixture was stirred at 110 ° C for 5 hours. After completion of the reaction, the reaction mixture was extracted with methylene chloride, and the mixture was filtered with MgSO ₄ . After removing the solvent of the filtered organic layer, C11 (6.0 g, yield 70%) as a target compound was obtained by column chromatography.

[Preparation Example 12] Synthesis of C12

Synthesis of 4- (8-chlorodibenzo [b, d] furan-1-yl) -9-phenyl-9H-carbazole

(9-phenyl-9H-carbazol -4-yl) boronic acid (17.6 g, 61.4 mmol) and 1-bromo-8-chlorodibenzo [ b, d] furan (17.3 g, 61.4 mmol) and Pd (PPh _{3) 4} (1.4 g, 1.2 mmol) and K ₂ CO ₃ (20.4 g, 147.2 mmol) were added to toluene (150 ml) and H ₂ O (75 ml), and the mixture was stirred at 110 ° C for 8 hours. (8-chlorodibenzo [b, d] furan-1-yl) -9-phenyl-9H-quinolinecarboxylic acid was obtained by removing the solvent from the reaction mixture, carbazole (19.6 g, yield 72%).

<Step 2> Synthesis of C12

Pd (dppf) Cl ₂ (0.6 g, 0.8 mmol), potassium acetate (8.3 g, 18.7 mmol) and 4- (8-chlorodibenzo [b, d] furan- 3.7 g, 37.5 mmol), 4,4,4 ', 4', 5,5,5,5-octamethyl-2,2'-bi (1,3,2-dioxaborolane) (6.2 g, 24.4 mmol ) And X-Phos (1.8 g, 3.8 mmol) were added to 80 ml of 1,4-dioxane and the mixture was stirred at 110 ° C for 5 hours. After completion of the reaction, the reaction mixture was extracted with methylene chloride, and the mixture was filtered with MgSO ₄ . After removing the solvent of the filtered organic layer, C12 (6.9 g, yield 69%) was obtained by column chromatography.

[Preparation Example 13] Synthesis of C13

<Step 1> Synthesis of 3,4-dichloro-2- (2-methoxyphenyl) pyridine

2,3,4-trichloropyridine (100.0 g, 548.1 mmol) and 2-methoxyphenyl boronic acid (87.5 g, 141.7 mmol) are placed in a 2-neck flask at room temperature. Of _{Pd (PPh 3) 4 (19.0} g, 16.4mmol) and KF (47.8 g, 822.2 mmol) is added. After adding 1100 ml of toluene, the mixture is stirred at 100 ° C for 5 hours. After completion of the reaction, the solution is subjected to silica filtration. After removal of the solvent, the solid compound 3,4-dichloro-2- (2-methoxyphenyl) pyridine (124.0 g, yield 89%) was obtained as a pale green solid after purification by column chromatography (MC: Hexane = 1: 1).

<Step 2> Synthesis of 2- (3,4-dichloropyridin-2-yl) phenol

3,4-dichloro-2- (2-methoxyphenyl) pyridine (40.0 g, 157.4 mmol) is dissolved in 400 ml of methylene chloride and placed in a 2-neck flask. Keep the condition at 0 ℃ in an ice bath. Of _{BBr 3 (22.7 ml, 236.1 mmol} ) was slowly added. After completion of the reaction, 400 ml of distilled water at 0 ° C is slowly added. The reaction is extracted with methylene chloride and silica filtered. After removal of the solvent, a white solid compound, 2- (3,4-dichloropyridin-2-yl) phenol (31.4 g, yield 83%) was obtained.

<Step 3> Synthesis of 4-chlorobenzofuro [3,2-b] pyridine

2-neck flask is charged with 23.0 g (95.8 mmol) of 2- (3,4-dichloropyridin-2-yl) phenol and 3.1 g of sodium hydrosulfite (21.5 g, 383.2 mmol) in KOH. Add 180 ml of DMF and add tetrabutylammonium bromide (3.3 g, 19.2 mmol). Stir 2 hours at 155 &lt; 0 &gt; C. After completion of the reaction, 400 ml of distilled water is slowly added. The reaction is extracted with methylene chloride and silica filtered. After removal of the solvent, white solid 4-chlorobenzofuro [3,2-b] pyridine (13.8 g, yield 71%) was obtained.

<Step 4> Synthesis of (4-chlorobenzofuro [3,2-b] pyridin-6-yl) boronic acid

4-chlorobenzofuro [3,2-b] pyridine (30.0 g, 147.3 mmol) and THF (300 ml) were added and n-butyllithium (70.7 ml, 176.8 mmol) was added at -78 ° C. After 2 hours, add triisopropyl borate (70.7 ml, 176.8 mmol) at -78 ° C and add HCl for 2 hours. The reaction mixture was extracted with methylene chloride and the solvent was removed to obtain 26.7 g (yield 66%) of 4-chlorobenzofuro [3,2-b] pyridin-6-yl) boronic acid.

Step 5 Synthesis of 4-chloro-6- (9-phenyl-9H-carbazol-3-yl) benzofuro [3,2-b]

9-phenyl-9H-carbazole (15.0 g, 46.6 mmol) and Pd (PPh ₃ ) were added to a solution of 4-chlorobenzofuro [3,2- b] pyridin- ) ₄ (1.6 g, 1.4 mmol) and K ₂ CO ₃ (15.4 g, 111.7 mmol) were added to toluene (150 ml) and H ₂ O (75 ml), and the mixture was stirred at 110 ° C for 8 hours. The solids formed after the reaction were filtered. The filtered solid was dissolved in toluene, filtered through silica, and recrystallized to obtain the target compound, 4-chloro-6- (9-phenyl-9H-carbazol-3-yl) benzofuro [3,2- 82%).

<Step 6> Synthesis of C12

3-yl) benzofuro [3,2-b] pyridine (15.0 g, 33.7 mmol) and Pd (dppf) Cl ₂ (1.0 g, 1.3 mmol) potassium acetate (6.6 g, 67.4 mmol), 4,4,4 ', 4', 5,5,5 ', 5'-octamethyl-2,2'-bi (1,3,2-dioxaborolane) , 40.5 mmol) and X-Phos (3.2 g, 6.7 mmol) were placed in 250 ml of 1,4-dioxane and stirred at 110 ° C for 5 hours. After completion of the reaction, the reaction mixture was extracted with methylene chloride, and the mixture was filtered with MgSO ₄ . After removing the solvent of the filtered organic layer, C12 (15.9 g, yield: 88%) was obtained by column chromatography.

[Synthesis Example 1] Synthesis of 119

Cl (6.0 g, 11.2 mmol) and 2-chloro-4- (dibenzo [b, d] furan-1-yl) -6-phenyl-1,3,5-triazine (4.0 g, 11.2 mmol) PPh ₃ ) ₄ (0.3 g, 0.2 mmol) and K ₂ CO ₃ (3.7 g, 26.9 mmol) were added to toluene 30 ml and H ₂ O 15 ml and stirred at 110 ° C for 8 hours. The solids formed after the reaction were filtered. The filtered solid was dissolved in toluene, filtered through silica, and recrystallized to obtain the desired compound 119 (7.0 g, yield 85%).

[LCMS]: 731

[Synthesis Example 2] Synthesis of 239

Cl (6.0 g, 11.2 mmol) and 2-chloro-4- (dibenzo [b, d] furan-3-yl) -6- PPh ₃ ) ₄ (0.3 g, 0.2 mmol) and K ₂ CO ₃ (3.7 g, 26.9 mmol) were added to toluene 30 ml and H ₂ O 15 ml and stirred at 110 ° C for 8 hours. The solids formed after the reaction were filtered. The filtered solid was dissolved in toluene, filtered through silica, and recrystallized to obtain the desired compound 239 (6.9 g, yield 84%).

[LCMS]: 731

[Synthesis Example 3] Synthesis of 219

Dibenzo [b, d] furan-4-yl) -6-phenyl-1,3,5-triazine (4.0 g, 11.2 mmol) and Pd PPh ₃ ) ₄ (0.3 g, 0.2 mmol) and K ₂ CO ₃ (3.7 g, 26.9 mmol) were added to toluene 30 ml and H ₂ O 15 ml and stirred at 110 ° C for 8 hours. The solids formed after the reaction were filtered. The filtered solid was dissolved in toluene, filtered through silica, and recrystallized to obtain the target compound 219 (7.0 g, yield 85%).

[LCMS]: 731

[Synthesis Example 4] Synthesis of 59

3-yl) -6-phenyl-1,3,5-triazine (4.0 g, 11.2 mmol) and Pd (2-chloro-4- PPh ₃ ) ₄ (0.3 g, 0.2 mmol) and K ₂ CO ₃ (3.7 g, 26.9 mmol) were added to toluene 30 ml and H ₂ O 15 ml and stirred at 110 ° C for 8 hours. The solids formed after the reaction were filtered. The filtered solid was dissolved in toluene, filtered through silica, and recrystallized to obtain the desired compound 59 (6.4 g, yield 78%).

[LCMS]: 731

[Synthesis Example 5] Synthesis of 99

4-yl) -6-phenyl-1,3,5-triazine (4.0 g, 11.2 mmol) and Pd (2-chloro-4- PPh ₃ ) ₄ (0.3 g, 0.2 mmol) and K ₂ CO ₃ (3.7 g, 26.9 mmol) were added to toluene 30 ml and H ₂ O 15 ml and stirred at 110 ° C for 8 hours. The solids formed after the reaction were filtered. The filtered solid was dissolved in toluene, filtered through silica, and recrystallized to obtain the target compound, 99 (6.0 g, yield 73%).

[LCMS]: 731

[Synthesis Example 6] Synthesis of 240

Dibenzo [b, d] furan-3-yl) -6-phenyl-1,3,5-triazine (4.0 g, 11.2 mmol) and Pd PPh ₃ ) ₄ (0.3 g, 0.2 mmol) and K ₂ CO ₃ (3.7 g, 26.9 mmol) were added to toluene 30 ml and H ₂ O 15 ml and stirred at 110 ° C for 8 hours. The solids formed after the reaction were filtered. The filtered solid was dissolved in toluene, filtered through silica, and recrystallized to obtain the desired compound 240 (6.7 g, yield 82%).

[LCMS]: 731

[Synthesis Example 7] Synthesis of 118

C5 (6.0 g, 11.2 mmol) and 2-chloro-4- (dibenzo [b, d] furan-1- yl) -6- PPh ₃ ) ₄ (0.3 g, 0.2 mmol) and K ₂ CO ₃ (3.7 g, 26.9 mmol) were added to toluene 30 ml and H ₂ O 15 ml and stirred at 110 ° C for 8 hours. The solids formed after the reaction were filtered. The filtered solid was dissolved in toluene, filtered through silica, and recrystallized to obtain the desired compound 118 (6.9 g, yield 84%).

[LCMS]: 731

[Synthesis Example 8] Synthesis of 117

(6.0 g, 11.2 mmol) and 2-chloro-4- (dibenzo [b, d] furan-1- yl) -6- PPh ₃ ) ₄ (0.3 g, 0.2 mmol) and K ₂ CO ₃ (3.7 g, 26.9 mmol) were added to toluene 30 ml and H ₂ O 15 ml and stirred at 110 ° C for 8 hours. The solids formed after the reaction were filtered. The filtered solid was dissolved in toluene, filtered through silica, and recrystallized to obtain the desired compound 117 (6.5 g, yield 79%).

[LCMS]: 731

[Synthesis Example 9] Synthesis of 254

Dibenzo [b, d] furan-1-yl) -1,3-dihydro- 30 ml of toluene and 15 ml of H ₂ O were added to a solution of 5-triazine (4.9 g, 11.2 mmol), Pd (PPh ₃ ) ₄ (0.3 g, 0.2 mmol) and K ₂ CO ₃ Lt; / RTI &gt; for 8 hours. The solids formed after the reaction were filtered. The filtered solid was dissolved in toluene, filtered through silica, and recrystallized to obtain the desired compound 254 (7.2 g, yield 80%).

[LCMS]: 807

[Synthesis Example 10] Synthesis of 284

4-yl) -4-chloro-6- (dibenzo [b, d] furan- 30 ml of toluene and 15 ml of H ₂ O were added to a solution of 5-triazine (4.9 g, 11.2 mmol), Pd (PPh ₃ ) ₄ (0.3 g, 0.2 mmol) and K ₂ CO ₃ Lt; / RTI &gt; for 8 hours. The solids formed after the reaction were filtered. The filtered solid was dissolved in toluene, filtered through silica, and recrystallized to obtain the desired compound 284 (6.1 g, yield 67%).

[LCMS]: 807

[Synthesis Example 11] Synthesis of 304

C7 (5.1 g, 11.2 mmol) and 2-chloro-4- (dibenzo [b, d] furan-1-yl) -6- (naphthalen- 11.2 mmol), Pd (PPh ₃ ) ₄ (0.3 g, 0.2 mmol) and K ₂ CO ₃ (3.7 g, 26.9 mmol) were added to toluene 30 ml and H ₂ O 15 ml and stirred at 110 ° C for 8 hours. The solids formed after the reaction were filtered. The filtered solid was dissolved in toluene, filtered through silica, and recrystallized to obtain the desired compound 304 (6.6 g, yield 84%).

[LCMS]: 705

[Synthesis Example 12] Synthesis of 360

Cl (6.0 g, 11.2 mmol) and 2-chloro-4- (dibenzo [b, d] furan-3-yl) -6- (naphthalen- 11.2 mmol), Pd (PPh ₃ ) ₄ (0.3 g, 0.2 mmol) and K ₂ CO ₃ (3.7 g, 26.9 mmol) were added to toluene 30 ml and H ₂ O 15 ml and stirred at 110 ° C for 8 hours. The solids formed after the reaction were filtered. The filtered solid was dissolved in toluene, filtered through silica, and recrystallized to obtain the title compound 360 (7.3 g, yield 83%).

[LCMS]: 781

[Synthesis Example 13] Synthesis of 386

C8 (5.1 g, 11.2 mmol) and 2 - ([1,1 ': 3', 1 "-terphenyl] -5'-yl) -4-chloro-6- (dibenzo [b, -yl) -1,3,5-triazine (5.7 g , 11.2 mmol) and _{Pd (PPh 3) 4 (0.3} g, 0.2 mmol), K 2 CO 3 (3.7 g, 26.9 mmol) to toluene and 60 ml H ₂ O 15 ml and the mixture was stirred at 110 ° C for 8 hours. The solids formed after the reaction were filtered. The filtered solid was dissolved in toluene, filtered through silica, and recrystallized to obtain the desired compound 386 (6.4 g, yield 71%).

[LCMS]: 807

[Synthesis Example 14] Synthesis of 259

Dibenzo [b, d] furan-3-yl) - 1, 3, 60 ml of toluene and 15 ml of H ₂ O were added to a solution of 5-triazine (4.9 g, 11.2 mmol), Pd (PPh ₃ ) ₄ (0.3 g, 0.2 mmol) and K ₂ CO ₃ Lt; / RTI &gt; for 8 hours. The solids formed after the reaction were filtered. The filtered solid was dissolved in toluene, filtered through silica, and recrystallized to obtain the target compound 259 (6.3 g, yield 70%).

[LCMS]: 807

[Synthesis Example 15] 266 Synthesis

D] benzo [b, d] furan-4-yl) -1,3- 5-triazine, Pd (PPh ₃ ) ₄ (0.3 g, 0.2 mmol) and K ₂ CO ₃ (3.7 g, 26.9 mmol) were added to toluene 60 ml and H ₂ O 15 ml and stirred at 110 ° C for 8 hours. The solids formed after the reaction were filtered. The filtered solid was dissolved in toluene, filtered through silica, and recrystallized to obtain the desired compound 266 (6.2 g, yield 69%).

[LCMS]: 807

[Synthesis Example 16] Synthesis of 290

(5.1 g, 11.2 mmol) and 2 - ([1,1'-biphenyl] -4-yl) -4-chloro-6- (dibenzo [b, d] furan- 60 ml of toluene and 15 ml of H ₂ O were added to a solution of 5-triazine (4.9 g, 11.2 mmol), Pd (PPh ₃ ) ₄ (0.3 g, 0.2 mmol) and K ₂ CO ₃ Lt; / RTI &gt; for 8 hours. The solids formed after the reaction were filtered. The filtered solid was dissolved in toluene, filtered through silica, and recrystallized to obtain the desired compound 290 (5.6 g, yield 68%).

[LCMS]: 731

[Synthesis Example 17] Synthesis of 289

4-yl) -4-chloro-6- (dibenzo [b, d] furan-3-yl) 60 ml of toluene and 15 ml of H ₂ O were added to a solution of 5-triazine (4.9 g, 11.2 mmol), Pd (PPh ₃ ) ₄ (0.3 g, 0.2 mmol) and K ₂ CO ₃ Lt; / RTI &gt; for 8 hours. The solids formed after the reaction were filtered. The filtered solid was dissolved in toluene, filtered through silica, and recrystallized to obtain the desired compound 289 (6.0 g, yield 67%).

[LCMS]: 807

[Synthesis Example 18] Synthesis of 409

C7 (4.6 g, 10 mmol) and 2,4-dichloro-6-phenyl- 1,3,5-triazine (2.3 g, 10 mmol) and _{Pd (PPh 3) 4 (0.3} g, 0.2 mmol), K 2 CO ₃ (3.7 g, 26.9 mmol) was added to toluene (60 ml) and H ₂ O (15 ml), and the mixture was stirred at 110 ° C for 8 hours. After completion of the reaction, the reaction mixture was extracted with methylene chloride, and then MgSO ₄ was added thereto. The solvent was removed from the obtained organic layer, and a solid was obtained by column chromatography. Then this was added to C8 (4.6 g, 10 mmol) to _{Pd (PPh 3) 4 (0.3} g, 0.2 mmol), K 2 CO 3 (3.7 g, 26.9 mmol) put in 15 ml toluene 60 ml and H ₂ O And the mixture was stirred at 110 DEG C for 8 hours. The target compound 409 (5.3 g, yield 65%) was obtained by purification in the same manner as above.

[LCMS]: 820

[Synthesis Example 19] Synthesis of 407

C9 (5.3 g, 10 mmol) and 2,4-dichloro-6-phenyl- 1,3,5-triazine (2.3 g, 10 mmol) and _{Pd (PPh 3) 4 (0.3} g, 0.2 mmol), K 2 CO ₃ (3.7 g, 26.9 mmol) was added to toluene (60 ml) and H ₂ O (15 ml), and the mixture was stirred at 110 ° C for 8 hours. After completion of the reaction, the reaction mixture was extracted with methylene chloride, and then MgSO ₄ was added thereto. The solvent was removed from the obtained organic layer, and a solid was obtained by column chromatography. Here the C10 was added to (5.3 g, 10 mmol) Pd (PPh 3) 4 (0.3 g, 0.2 mmol), K 2 CO 3 (3.7 g, 26.9 mmol) put in 15 ml toluene 60 ml and H ₂ O And the mixture was stirred at 110 DEG C for 8 hours. The target compound 407 (6.2 g, yield 64%) was obtained by purification in the same manner as above.

[LCMS]: 972

[Synthesis Example 20] Synthesis of 415

C1 (5.3 g, 10 mmol) and 2,4-dichloro-6-phenyl- 1,3,5-triazine (2.3 g, 10 mmol) and _{Pd (PPh 3) 4 (0.3} g, 0.2 mmol), K 2 CO ₃ (3.7 g, 26.9 mmol) was added to toluene (60 ml) and H ₂ O (15 ml), and the mixture was stirred at 110 ° C for 8 hours. After completion of the reaction, the reaction mixture was extracted with methylene chloride, and then MgSO ₄ was added thereto. The solvent was removed from the obtained organic layer, and a solid was obtained by column chromatography. Here the C12 was added to (5.3 g, 10 mmol) Pd (PPh 3) 4 (0.3 g, 0.2 mmol), K 2 CO 3 (3.7 g, 26.9 mmol) put in 15 ml toluene 60 ml and H ₂ O And the mixture was stirred at 110 DEG C for 8 hours. The target compound 415 (6.1 g, yield 63%) was obtained by purification in the same manner as above.

 [LCMS]: 972

[Synthesis Example 21] Synthesis of 481

C13 (5.36 g, 10 mmol), 2-chloro-4- (dibenzo [b, d] thiophen-3- yl) -6- PPh ₃ ) ₄ (0.34 g, 0.3 mmol) and K ₂ CO ₃ (2.76 g, 20 mmol) were added to 25 ml of toluene 100 ml / H ₂ O and the mixture was stirred at 100 ° C for 8 hours. After completion of the reaction, the reaction mixture was extracted with methylene chloride, and the mixture was filtered with MgSO ₄ . After removing the solvent of the filtered organic layer, 481 (4.63 g, yield 62%) of the target compound was obtained by column chromatography.

[LCMS]: 747

[Examples 1 to 21] Fabrication of green organic electroluminescent device

The compounds synthesized in Synthesis Examples 1 to 21 were subjected to high purity sublimation purification by a conventionally known method, and then a green organic electroluminescent device was fabricated according to the following procedure.

First, a glass substrate coated with ITO (Indium tin oxide) thin film having a thickness of 1500 Å was washed with distilled water ultrasonic waves. 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.

(60 nm) / TCTA (80 nm) / 90% of the above exemplified compound + 10% of Ir (ppy) ₃ (30 nm) / BCP (10 nm) / Alq ₃ 30 nm) / LiF (1 nm) / Al (200 nm) were stacked in this order to fabricate an organic electroluminescent device.

[Comparative Example 1] Production of green organic electroluminescent device

A green organic electroluminescent device was fabricated in the same manner as in Example 1, except that CBP was used instead of the compound 119 as a luminescent host material in forming the light emitting layer.

[Comparative Example 2] Production of green organic electroluminescent device

A green organic electroluminescent device was fabricated in the same manner as in Example 1, except that Compound I was used instead of Compound 119 as a luminescent host material in forming the light emitting layer.

[Comparative Example 3] Production of green organic electroluminescent device

A green organic electroluminescent device was fabricated in the same manner as in Example 1, except that Compound II was used instead of Compound 119 as a luminescent host material in forming the light emitting layer.

The structures of m-MTDATA, TCTA, Ir (ppy) ₃ , CBP, BCP, Compound I and Compound II used in Examples 1 to 21 and Comparative Examples 1 to 3 are as follows.

[Evaluation Example 1]

The driving voltage, current efficiency and emission peak at the current density of 10 mA / cm 2 were measured for each of the green organic electroluminescent devices manufactured in Examples 1 to 21 and Comparative Examples 1 to 3, Respectively.

Sample Host Driving voltage
(V) Emission peak
(nm) Current efficiency
(cd / A) Example 1 119 4.62 516 55.5 Example 2 239 4.55 516 62.1 Example 3 219 5.46 516 42.1 Example 4 59 5.33 516 43.0 Example 5 99 4.95 516 51.2 Example 6 240 5.01 516 53.1 Example 7 118 4.88 516 48.2 Example 8 117 4.58 516 40.2 Example 9 254 5.11 516 55.5 Example 10 284 4.76 516 42.1 Example 11 304 4.54 516 58.0 Example 12 360 4.99 516 52.7 Example 13 386 5.01 516 55.5 Example 14 259 4.21 516 56.3 Example 15 266 5.46 516 49.6 Example 16 290 4.87 516 47.2 Example 17 289 5.21 516 53.1 Example 18 409 4.77 516 52.1 Example 19 407 4.56 516 53.3 Example 20 415 4.99 516 47.7 Example 21 481 4.89 516 56.6 Comparative Example 1 CBP 6.93 516 38.2 Comparative Example 2 Compound I 5.67 516 42.1 Comparative Example 3 Compound II 5.55 516 41.2

As shown in Table 1, the green organic electroluminescent devices of Examples 1 to 21, in which the compound according to the present invention was applied to the light emitting layer, were compared with the green organic electroluminescent devices of Comparative Examples 1 to 3 in which CBP, It was found that the current efficiency and the driving voltage were superior to those of the electroluminescent device.

Claims (10)

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

In Formula 1,
X ₁ and X ₂ are the same as or different from each other and each independently O or S,
Y ₁ to Y ₁₆ are the same as or different from each other, and each independently CR ₈ or N, provided that when there are a plurality of CR _{8 s} , the plurality of R _{8 s} are the same as or different from each other,
Z ₁ to Z ₃ are the same or different and each independently CR ₅ or N, at least one of them is N,
Ar ₁ is 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 to C ₄₀ alkynyl, C ₃ to C ₄₀ cycloalkyl, A C ₆ to C ₆₀ aryl group,
Provided that the X ₁ containing ring and the X ₂ containing ring are asymmetrically bonded to each other based on the Z ₁ to Z ₃ containing ring,
m and n are each an integer of 0 to 3, m + n? 1,
A and B are the same or different from each other, and are each independently any one of substituents represented by the following formula (2) or (3);
(2)

(3)

In the general formula (2) or (3)
* Represents a moiety bonded to Formula 1,
X ₃ is a single bond,
Ar ₂ represents 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 C ₆ to C ₆₀ aryl group, 5 to 60 heteroaryl groups and C ₆ to C ₆₀ arylamine groups, or may be bonded to adjacent groups to form a condensed ring,
a, c, and f are each an integer of 0 to 3,
b, d and e are each an integer of 0 to 4, wherein b + m? 4, d + n? 4,
R ₁ to R ₈ are the same or different from each other and each independently represents hydrogen, deuterium, halogen, cyano, nitro, C ₁ to C ₄₀ alkyl, C ₂ to C ₄₀ alkenyl, C ₂ to C ₄₀ An alkynyl group, a C ₃ to C ₄₀ cycloalkyl group, a heteroaryl group having 3 to 40 nuclear atoms, a C ₆ to C ₆₀ aryl group, a heteroaryl group having 5 to 60 nuclear atoms, a C ₁ to C ₄₀ alkyl 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 aryl boron group, C ₆ ~ C ₆₀ aryl phosphine group, C ₆ ~ C ₆₀ aryl phosphine oxide group, and a C ₆ ~, or selected from the group consisting of an aryl amine of the C ₆₀ of, or adjacent groups combine to form a condensed ring And when R ₁ to R ₇ are each plural, they may be the same or different from each other,
Alkyl group of said Ar ₁ to Ar _2, and R ₁ to R _8, an alkenyl group, an alkynyl group, a cycloalkyl group, a heterocycloalkyl group, an aryl group, a heteroaryl group, an alkyloxy group, an aryloxy group, an alkylsilyl group, an arylsilyl A halogen atom, a cyano group, a nitro group, a C ₂ to C ₄₀ alkenyl group, a C ₂ to C ₄₀ alkenyl group, an aryloxy group, an aryloxy group, A cycloalkyl group having ₃ to ₄₀ carbon atoms, a heterocycloalkyl group having 3 to 40 nuclear atoms, a C ₁ to C ₄₀ 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 group, a C ₆ to C ₆₀ arylsilyl group, a C ₁ to C ₄₀ alkyl boron group, C ₆ ~ C ₆₀ aryl group of boron, C ₆ ~ C ₆₀ aryl phosphine group, C ₆ ~ C ₆₀ aryl phosphine oxide group, and a C ₆ ~ selected from the group consisting of an arylamine C in ₆₀ If the first plural number, and wherein said substituent is substituted by at least one substituent, these may be the same or different from each other. The method according to claim 1,
The compound represented by the formula (1) is represented by any one of the following formulas (4) to (7)
[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

(7)

In the above formulas 4 to 7,
The ring containing Z ₁ to Z _{3 in} Formula 4 is bonded to any one of Y ₁₀ to Y ₁₂ (provided that the ring containing Z ₁ to Z ₃ is not bonded to Y ₉ )
The ring containing Z ₁ to Z _{3 in} Formula 5 is bonded to any one of Y ₉ and Y ₁₁ to Y ₁₂ (provided that the ring containing Z ₁ to Z ₃ is not bonded to Y ₁₀ )
The ring containing Z ₁ to Z _{3 in} Formula 6 is bonded to any one of Y ₉ , Y ₁₀ and Y ₁₂ (provided that the Z ₁ to Z ₃ containing ring is not bonded to Y ₁₁ )
The ring containing Z ₁ to Z _{3 in} the above formula (7) is bonded to any one of Y ₉ to Y ₁₁ (provided that the Z ₁ to Z ₃ containing ring is not bonded to Y ₁₂ )
X ₁ , X ₂ , Y ₁ to Y ₁₆ , Z ₁ to Z ₃ , Ar ₁ , m, n, A, B, a to d and R ₁ to R ₄ are as defined in claim 1, respectively. The method according to claim 1,
The compound represented by the formula (1) is represented by any one of the following formulas (8) to (12).
[Chemical Formula 8]

[Chemical Formula 9]

[Chemical formula 10]

(11)

[Chemical Formula 12]

In Formulas 8 to 12,
X ₁ , X ₂ , Z ₁ to Z ₃ , Ar ₁ , n, A and B are as defined in claim 1, respectively. The method according to claim 1,
Wherein Z ₁ to Z ₃ are all N. The method according to claim 1,
Wherein A and B are the same or different from each other, and each independently selected from the group consisting of substituents represented by the following structural formulas.

In the above formulas,
* Represents a moiety bonded to Formula 1,
Ar &lt; ₂ &gt; is as defined in claim 1. The method according to claim 1,
Wherein Ar &lt; ₁ &gt; is any one selected from the substituent groups represented by the following structural formulas.

The method according to claim 1,
R ₁ to R ₅ and R ₈ are the same or different and each independently represents hydrogen, deuterium, halogen, cyano, nitro, C ₁ to C ₄₀ alkyl, C ₂ to C ₄₀ alkenyl, C ₂ An alkynyl group of C ₄₀ to C ₄₀ , a cycloalkyl group of C ₃ to C ₄₀ , and an aryl group of C ₆ to C ₆₀ ,
Wherein R ₆ and R ₇ are the same or different, each independently represent hydrogen, deuterium, a halogen, a cyano group, a nitro group, C ₁ ~ alkenyl group of the C ₄₀ alkyl group, C ₂ ~ C ₄₀ of, C ₂ ~ C ₄₀ A cycloalkyl group having ₃ to ₄₀ carbon atoms, an aryl group having ₆ to ₆₀ carbon atoms and a heteroaryl group having 5 to 60 nuclear atoms, or is bonded to an adjacent group to form a condensed ring. An organic electroluminescent device comprising a cathode, a cathode, and at least one organic layer interposed between the anode and the cathode,
Wherein at least one of the one or more organic layers includes a compound according to any one of claims 1 to 7. 9. The method of claim 8,
Wherein the organic compound layer containing the compound is selected from the group consisting 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. 10. The method of claim 9,
Wherein the organic compound layer containing the compound is a phosphorescent light-emitting layer.