KR20130142968A - Heterocyclic compounds and organic light-emitting diode including the same - Google Patents

Abstract

The present invention relates to a new heterocyclic compound and an organic electroluminescent device including the same as a light emitting material, particularly a heterocyclic compound denoted by chemical formula 1, and an organic electroluminescent device having excellent luminance properties including driving voltage and luminance efficiency.

Description

Heterocyclic compounds and organic light-emitting diodes including the same

The present invention relates to a novel heterocyclic compound and an organic electroluminescent device comprising the same as a light emitting material, and more particularly to a heterocyclic compound having excellent luminescent properties such as driving voltage and luminous efficiency, and an organic electroluminescent device comprising the same. It is about.

In recent years, organic light emitting devices capable of being driven by a low voltage in a self-emission type have superior viewing angles and contrast ratios as compared with liquid crystal displays (LCDs), which are the mainstream of flat panel display devices, and require no backlight, It is attracting attention as a next-generation display device because it is advantageous in terms of power and has a wide color reproduction range.

In organic light emitting diodes (OLEDs), when electrons are injected into an organic light emitting layer formed between an electron injection electrode (cathode) and a hole injection electrode (anode), electrons and holes are paired, to be.

An organic electroluminescent device using an organic light emitting phenomenon usually has a structure including an anode, an anode, and an organic material layer therebetween. Here, in order to increase the efficiency and stability of the organic electroluminescent device, the organic material layer may have a multi-layer structure composed of different materials and may include a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, . When a voltage is applied between the two electrodes in the structure of the organic electroluminescent device, holes are injected into the anode, electrons are injected into the organic layer, and excitons are formed when injected holes and electrons meet. When it falls back to the ground state, the light comes out.

Organic electroluminescent devices can not only form devices on flexible transparent substrates such as plastics, but also at lower voltages of 10V or less than plasma display panels or inorganic electroluminescent (EL) displays. It has the advantage of being able to drive, relatively low power consumption, and excellent color. In addition, organic electroluminescent devices can display three colors of green, blue, and red, making them an object of interest for a large number of people as a next-generation rich color display device.

In order for the organic electroluminescent device to sufficiently exhibit the above-described excellent characteristics, materials constituting the organic material layer in the device, such as a hole injecting material, a hole transporting material, a light emitting material, an electron transporting material, and an electron injecting material are supported by a stable and efficient material However, the development of a stable and efficient organic material layer material for an organic electroluminescence device has not been sufficiently developed yet. Therefore, the development of new materials continues to be demanded.

Accordingly, the problem to be solved by the present invention is to provide a novel heterocyclic compound having a lower driving voltage and excellent luminous efficiency than the compound used in the conventional phosphorescent material and an organic light emitting device including the same.

Accordingly, the present invention provides a heterocyclic compound represented by the following [Formula 1] to solve the above problems.

[Formula 1]

In addition, the present invention provides an organic light emitting display device having an organic material layer interposed between a first electrode, a second electrode, and the first electrode and the second electrode, and including a heterocyclic compound represented by the above [Formula 1]. do.

The specific substituent of the said Formula (1) is mentioned later.

The heterocyclic compound according to the present invention is more stable than the conventional phosphorescent material, and has an excellent luminescent property in driving voltage or current efficiency, so that the organic light emitting device including the low voltage can be driven and improve the luminous efficiency. You can.

1 is a schematic view of an organic electroluminescent device according to one embodiment of the present invention.

Hereinafter, the present invention will be described in more detail.

The present invention is a light emitting layer host material that improves the light emission characteristics such as driving voltage, current efficiency of the organic light emitting device, characterized in that the heterocyclic compound represented by the following [Formula 1].

[Formula 1]

In the above formula (1)

Y ₁ to Y ₈ are each independently CR ₇ To CR ₁₄ , and two adjacent Y's of Y ₁ to Y ₈ combine with Q to form a condensed ring.

R ₁ to R ₁₄ are the same as or different from each other, and each independently hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 40 carbon atoms, a substituted or unsubstituted carbon number 2 to 30 heteroaryl groups, halogen atoms, hydroxyl groups, cyano groups, nitro groups, amidino groups, hydrazines, hydrazones, carboxyl groups or salts thereof, sulfonic acid groups or salts thereof, phosphoric acid or salts thereof, substituted or unsubstituted Alkenyl group having 2 to 60 carbon atoms, substituted or unsubstituted alkynyl group having 2 to 60 carbon atoms, substituted or unsubstituted alkoxy group having 1 to 60 carbon atoms, substituted or unsubstituted cycloalkyl group having 3 to 60 carbon atoms, substituted or unsubstituted A substituted aryloxy group having 5 to 60 carbon atoms, a substituted or unsubstituted arylthio group having 5 to 60 carbon atoms, a substituted or unsubstituted alkylamine group having 1 to 30 carbon atoms, substituted or unsubstituted carbon Can be selected from a 5 to 60 arylamine group, a substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms of the ring group and a substituted or unsubstituted arylsilyl group consisting of a ring having 5 to 60.

L ₁ and L ₂ are each a single bond or a substituted or unsubstituted alkylene group having 1 to 30 carbon atoms, a substituted or unsubstituted carbon group having 2 to 30 carbon atoms, respectively. Alkenylene group, substituted or unsubstituted C2-C30 alkynylene group, substituted or unsubstituted C3-C30 It is selected from a cycloalkylene group, a substituted or unsubstituted arylene group having 5 to 50 carbon atoms, and a substituted or unsubstituted heteroarylene group having 2 to 50 carbon atoms. In addition, n and m are integers between 0 and 3, and when n and m are 2 or more, a plurality of L ₁ and L ₂ may be each independently the same or different.

R ₁ to R ₁₄ , L ₁ , L ₂ And their substituents may be bonded to each other or adjacent substituents to form a saturated or unsaturated ring or attached or fused together in a pendant manner.

According to an embodiment of the present invention, the R ₁ To R ₁₄ , L ₁ and L ₂ are each independently a deuterium atom, a cyano group, a halogen atom, a hydroxy group, a nitro group, an alkyl group having 1 to 40 carbon atoms, a cycloalkyl group having 3 to 40 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, An alkynyl group having 2 to 40 carbon atoms, an alkoxy group having 1 to 40 carbon atoms, an alkylamino group having 1 to 40 carbon atoms, an arylamino group having 6 to 40 carbon atoms, a heteroarylamino group having 3 to 40 carbon atoms, an alkylsilyl group having 1 to 40 carbon atoms, At least one selected from the group consisting of an arylsilyl group having 6 to 40 carbon atoms, an aryl group having 6 to 40 carbon atoms, an aryloxy group having 3 to 40 carbon atoms, a heteroaryl group having 3 to 40 carbon atoms, a germanium group, phosphorus and boron It may be substituted by.

In addition, the carbon number range of the alkyl group or the aryl group in the "substituted or unsubstituted alkyl group having 1 to 30 carbon atoms", "substituted or unsubstituted carbon group having 6 to 40 carbon atoms", and the like may be considered in the substituent-substituted portion. It means the total carbon number constituting the alkyl moiety or aryl moiety when viewed as unsubstituted without. For example, a phenyl group substituted with a butyl group in the para position means a aryl group having 6 carbon atoms substituted with a butyl group having 4 carbon atoms.

According to a preferred embodiment of the present invention, the heterocyclic compound according to [Formula 1] is not limited by the following specific compounds, but may be specifically any one of the compounds represented by the following [Formula 2] to [Formula 13]. .

[Formula 2] [Formula 3] [Formula 4] [Formula 5]

[Formula 6] [Formula 7] [Formula 8] [Formula 9]

[Formula 10] [Formula 11] [Formula 12] [Formula 13]

In [Formula 2] to [Formula 13], R ₁ to R ₆ , L ₁ and L ₂ , n and m are the same as the definition in [Formula 1].

In addition, according to a preferred embodiment of the present invention, when n is 1, L ₁ and L ₂ may be any one selected from the following [formula A1] to [formula A8], respectively.

[Structural formula A1] [Structural formula A2] [Structural formula A3] [Structural formula A4]

[Structural formula A5] [Structural formula A6] [Structural formula A7] [Structural formula A8]

In the above Structural Formula A1 to Structural Formula A8, hydrogen or deuterium may be bonded to the carbon of the aromatic ring in each structural formula.

In addition, when n is 2, L ₁ and L ₂ may be any one selected from the following [formula B].

[Formula B]

In [Formula B], hydrogen or deuterium may be bonded to the carbon of the aromatic ring in each formula. In addition, in the case of a substituent other than hydrogen, it may be combined with adjacent substituents to form a saturated or unsaturated ring.

On the other hand, the aryl group contained in the organic light emitting compound according to the present invention is an organic radical derived from an aromatic hydrocarbon by the removal of one hydrogen, and is a single or fused ring system containing 5 to 7 atoms, preferably 5 or 6 atoms And when a substituent is present in the aryl group, it may be fused with an adjacent substituent to further form a ring.

Specific examples of such aryl include phenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 4-ethylphenyl group, o-biphenyl group, m-biphenyl group, p-biphenyl group, 4-methylbiphenyl group, 4- Ethyl biphenyl group, o-terphenyl group, m-terphenyl group, p-terphenyl group, 1-naphthyl group, 2-naphthyl group, 1-methylnaphthyl group, 2-methylnaphthyl group, anthryl group, phenanthryl group, pyre And aromatic groups such as a silyl group, indenyl, fluorenyl group, tetrahydronaphthyl group, pyrenyl, peryleneyl, chrysenyl, naphthacenyl, fluoranthenyl and the like.

Further, at least one hydrogen atom of the aryl group may be a deuterium atom, a halogen atom, a hydroxy group, a nitro group, a cyano group, a silyl group, an amino group (-NH ₂ , -NH (R), -N (R ') (R ") , R 'and R "are independently of each other an alkyl group having 1 to 10 carbon atoms, in this case referred to as" alkylamino group "), amidino group, hydrazine group, hydrazone group, carboxyl group, sulfonic acid group, phosphoric acid group, 1 to 24 carbon atoms Alkyl group, C1-C24 halogenated alkyl group, C1-C24 alkenyl group, C1-C24 alkynyl group, C1-C24 heteroalkyl group, C6-C24 aryl group, C6-C24 arylalkyl group It may be substituted with a heteroaryl group having 2 to 24 carbon atoms or a heteroarylalkyl group having 2 to 24 carbon atoms.

The heteroaryl group which is a substituent used in the present invention may be any one selected from the following [formula 1] to [formula 6].

[Structural formula 1] [Structural formula 2] [Structural formula 3]

[Structural formula 4] [Structural formula 5] [Structural formula 6]

In the above Structural Formulas 1 to 6,

T ₁ to T ₈ may be the same or different and each independently selected from C (R ₄₁ ), C (R ₄₂ ) (R ₄₃ ), N, N (R ₄₄ ) , R ₃₁ to R ₄₄ are the same or different from each other and each independently represents hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, An aryl group having 5 to 30 carbon atoms, and a heteroaryl group having 2 to 30 carbon atoms and having a substituted or unsubstituted heteroatom, O, NS, and P, and each of [Structural Formula 1] to [Structural Formula 6], R ₃₁ to R ₄₄ One of them may form a single bond by combining with nitrogen or a substituent in the above [Formula 1].

The above-mentioned [formula 3] may include a compound represented by the following formula [3] by a resonance structure according to the movement of electrons.

[Structural Formula 3-1]

In the above structural formula 3-1, T ₁ to T ₅ and R ₃₃ and R ₃₄ are the same as defined above.

Further, according to a preferred embodiment of the present invention, the above Structural Formulas 1 to 6 can be selected from the following Structural Formula 7.

[Structural Formula 7]

In the above formula 7,

X is hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 5 to 30 carbon atoms, an unsubstituted or substituted alkenyl group having 2 to 30 carbon atoms, A substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C3-C30 cycloalkyl group, a substituted or unsubstituted C5-C30 cycloalkenyl group, a substituted or unsubstituted C1-C30 alkoxy group, A substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms, a substituted or unsubstituted arylthioxy group having 5 to 30 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms An amino group, a substituted or unsubstituted aryl group having 5 or more carbon atoms, a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms having O, N, S, or P as a hetero atom, a cyano group, It may be any one selected from the group consisting of.

m is an integer of 1 to 11, when m is 2 or more, a plurality of X is the same or different from each other, any one of the at least one X may form a single bond with a substituent or the nitrogen in the formula [1].

Specific examples of the alkyl group as the substituent used in the present invention include a methyl group, an ethyl group, a propyl group, an isopropyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, , An octyl group, a stearyl group, a trichloromethyl group, and a trifluoromethyl group, and at least one hydrogen atom of the alkyl group may be substituted with a substituent selected from the group consisting of a deuterium atom, a halogen atom, a hydroxyl group, a nitro group, a cyano group, a trifluoromethyl group, (in this case, "alkylsilyl group" hereinafter), a substituted or unsubstituted amino group (-NH _2, -NH (R), -N (R ') (R "), where R, R' and R" are each A hydrazine group, a hydrazone group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, an alkyl group having 1 to 24 carbon atoms, an alkyl group having 1 to 24 carbon atoms (preferably an alkyl group having 1 to 24 carbon atoms) A halogenated alkyl group, an alkenyl group having 2 to 24 carbon atoms, an alkoxy group having 2 to 24 carbon atoms A heteroaryl group having 1 to 24 carbon atoms, an aryl group having 5 to 24 carbon atoms, an arylalkyl group having 6 to 24 carbon atoms, a heteroaryl group having 3 to 24 carbon atoms, or a heteroarylalkyl group having 3 to 24 carbon atoms.

Specific examples of the alkoxy group which is a substituent used in the compound of the present invention include methoxy group, ethoxy group, propoxy group, isobutyloxy group, sec-butyloxy group, pentyloxy group, iso-amyloxy group, hexyloxy group and the like. These can be mentioned and can substitute by the same substituent as the case of the said alkyl group.

Specific examples of the halogen group which is a substituent used in the compound of the present invention include fluorine (F), chlorine (Cl), bromine (Br) and the like.

Specific examples of the silyl group which is a substituent used in the present invention include trimethylsilyl, triethylsilyl, triphenylsilyl, trimethoxysilyl, dimethoxyphenylsilyl, diphenylmethylsilyl, silyl, diphenylvinylsilyl and methylcyclobutylsilyl , Dimethyl furyl silyl, and the like.

Specific examples of the alkenyl group used in the present invention include straight chain or branched chain alkenyl groups and include 3-pentenyl, 4-hexenyl, 5-heptenyl, 4-methyl- Dimethyl-pentenyl group, 6-methyl-5-heptenyl group and 2,6-dimethyl-5-heptenyl group.

Although the present invention is not limited by the specific examples of the heterocyclic compound according to [Formula 1] having the structure as described above, specifically, any one of the compounds represented by the following [Formula 14] to [Formula 237] Can be.

[Formula 230] [Formula 231] [Formula 232] [Formula 233]

[237] [237] [237]

In addition, the present invention includes a first electrode, a second electrode opposed to the first electrode and an organic layer interposed between the first electrode and the second electrode, wherein the organic layer in the present invention [Formula 1] It may include one or more organic light emitting compounds represented by.

The organic layer containing the organic luminescent compound of the present invention may include at least one of a hole injecting layer, a hole transporting layer, a functional layer having both a hole injecting function and a hole transporting function, a light emitting layer, an electron transporting layer, have. In this case, the organic layer interposed between the first electrode and the second electrode may include a light emitting layer, the light emitting layer is composed of a host and a dopant, the organic light emitting compound of the present invention may be used as a host.

Meanwhile, in the present invention, a dopant material together with a host may be used as the light emitting layer. When the light emitting layer includes a host and a dopant, the content of the dopant may be generally selected from about 0.01 to about 20 parts by weight based on about 100 parts by weight of the host.

Hereinafter, the organic light emitting display device of the present invention will be described with reference to FIG. 1.

1 is a cross-sectional view showing the structure of an organic light emitting display device according to the present invention. The organic electroluminescent device according to the present invention includes an anode 20, a hole transport layer 40, an organic emission layer 50, an electron transport layer 60 and a cathode 80, The electron injecting layer 70 may be further formed. In addition, one or two intermediate layers may be further formed, or a hole blocking layer or an electron blocking layer may be further formed.

The organic electroluminescent device of the present invention and its manufacturing method will be described with reference to FIG.

First, the anode 20 is formed by coating an anode electrode material on the substrate 10. Here, as the substrate 10, an organic substrate or a transparent plastic substrate which is excellent in transparency, surface smoothness, ease of handling, and waterproofness is used as a substrate used in a conventional organic EL device. As the material for the anode electrode, indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO ₂ ), zinc oxide (ZnO) and the like which are transparent and excellent in conductivity are used.

The hole injection layer 30 is formed by vacuum-heat deposition or spin coating of the hole injection layer material on the anode 20 electrode. Subsequently, a hole transport layer 40 is formed by vacuum thermal deposition or spin coating on the hole transport layer 30 above the hole injection layer 30.

The hole injection layer material is not particularly limited as long as it is conventionally used in the art. For example, 2-TNATA [4,4 ', 4 "-tris (2-naphthylphenyl-phenylamino) -triphenylamine] , NPD [N, N'-diphenyl-N, N'-bis (3-methylphenyl) -1,1'- biphenyl-4,4'-diamine], DNTPD [N, N'-diphenyl-N, N'-bis- [4- ] Can be used.

The material for the hole transport layer is not particularly limited as long as it is commonly used in the art and includes, for example, N, N'-bis (3-methylphenyl) -N, N'- -Biphenyl] -4,4'-diamine (TPD) or N, N'-di (naphthalene-1-yl) -N, N'-diphenylbenzidine (? -NPD).

A hole blocking layer (not shown) is selectively formed on the organic light emitting layer 50 by a vacuum deposition method or a spin coating method to form a thin film on the organic light emitting layer 50 can do. In the case where holes are injected into the cathode through the organic light-emitting layer, the lifetime and the efficiency of the device are reduced, and thus the hole blocking layer plays a role of preventing such a problem by using a material having a very low HOMO (Highest Occupied Molecular Orbital) level . In this case, the hole blocking material to be used is not particularly limited, but should have an ionization potential higher than the light emitting compound while having an electron transport ability, and typically BAlq, BCP, TPBI, and the like may be used.

Wherein as material used for the hole blocking layer, BAlq, BCP, Bphen, TPBI, NTAZ, BeBq _2, OXD-7, Liq and [Formula 101] to [Chemical Formula 107] either, but one that can be used is selected from, this limited It is not.

BAlq BCP Bphen

TPBI NTAZ BeBq ₂

OXD-7 Liq

(101)

≪ RTI ID = 0.0 >

Formula 107

After the electron transport layer 60 is deposited on the hole blocking layer by a vacuum deposition method or a spin coating method, an electron injection layer 70 is formed, and a cathode forming metal is deposited on the electron injection layer 70 in a vacuum heat- And the cathode 80 is formed by vapor deposition to complete the organic EL device. The metal for forming the cathode may be lithium (Li), magnesium (Mg), aluminum (Al), aluminum-lidium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), magnesium-silver ( Mg-Ag), and the like, and a transmissive cathode using ITO and IZO can be used to obtain a front light emitting device.

As the electron transporting layer material, a known electron transporting material can be used as a material that stably transports electrons injected from an electron injection electrode (cathode). Examples of known electron transporting materials include quinoline derivatives, especially tris (8-quinolinolate) aluminum (Alq3), TAZ, Balq, beryllium bis (benzoquinolin-10- olate: Bebq2), ADN, [Compound 201], [Compound 202], oxadiazole derivative PBD, BMD, BND and the like may be used.

TAZ BAlq

[Compound 201] [Compound 202] BCP

Further, the electron transporting layer used in the present invention can be used as the organometallic compound represented by the following formula (C) alone or in combination with the electron transporting layer material.

≪ RTI ID = 0.0 &

In [Formula C],

Y is a moiety selected from C, N, O and S, which is directly bonded to M to form a single bond, and any moiety selected from C, N, O and S is a moiety coordinating to M And is a ligand chelated by coordination bond with the single bond.

M is an alkali metal, an alkaline earth metal, an aluminum (Al), or a boron (B) atom.

OA is a monovalent ligand capable of single bond or coordination bond with M, O is oxygen, A is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 5 to 50 carbon atoms, Substituted or unsubstituted C2-C30 alkenyl, substituted or unsubstituted C2-C20 alkynyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C5-C30 cycloalkyl, An alkenyl group, and a substituted or unsubstituted heteroaryl group having 2 to 50 carbon atoms having a hetero atom O, N, or S.

In addition, when M is one metal selected from alkali metals, m = 1, n = 0, and when M is one metal selected from alkaline earth metals, m = 1, n = 1, or m = 2 and n = 0, and when M is boron or aluminum, any one of m = 1 to 3, and n satisfies m + n = 3 as any one of 0 to 2.

The 'substituted' in the 'substituted or unsubstituted' may be a substituent selected from the group consisting of deuterium, cyano, halogen, hydroxy, nitro, alkyl, alkoxy, alkylamino, arylamino, heteroarylamino, alkylsilyl, An aryl group, an aryl group, a heteroaryl group, germanium, phosphorus, and boron.

In addition, each Y is the same or different, and may be any one selected from the following [formula C1] to [formula C39] independently of each other.

[Structure C1] [Structure C2] [Structure C3]

[Structure C4] [Structure C5] [Structure C6]

[Structure C7] [Structure C8] [Structure C9] [Structure C10]

[Formula C11] [Formula C12] [Formula C13]

[Formula C14] [Formula C15] [Formula C16]

[Structure C17] [Structure C18] [Structure C19] [Structure C20]

[Structure C21] [Structure C22] [Structure C23]

[Structure C24] [Structure C25] [Structure C26]

[Structure C27] [Structure C28] [Structure C29] [Structure C30]

[Structure C31] [Structure C32] [Structure C33]

[Structure C34] [Structure C35] [Structure C36]

[Structure C37] [Structure C38] [Structure C39]

In the above Structural Formula C1 to Structural Formula C39,

R is the same or different and is each independently selected from the group consisting of hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-30 alkyl, substituted or unsubstituted C6-30 aryl, A substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, A substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, and a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms And may be connected to an adjacent substituent by alkylene or alkenylene to form a spiro ring or a fused ring.

L represents a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted group having 5 to 30 carbon atoms A substituted or unsubstituted cycloalkyl group having 5 to 30 carbon atoms, L is an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 40 carbon atoms, an aryl group having 3 to 20 carbon atoms, A heteroaryl group, a cyano group, a halogen group, deuterium, and hydrogen, and may be connected to an adjacent substituent by an alkylene or an alkenylene to form a spiro ring or a fused ring.

The organic light emitting device according to the present invention is characterized in that the organic layer includes a light emitting layer, and the light emitting layer further includes one or more phosphorescent dopants in addition to one or more heterocyclic compounds represented by the above [Formula 1], The light emitting dopant applied to the organic light emitting device is not particularly limited, but may be one or more compounds selected from compounds represented by the following [formula A-1] to [formula J-1].

[Formula A-1]

mL ₁ L ₂ L ₃

M is selected from the group consisting of metals of Groups 7, 8, 9, 10, 11, 13, 14, 15 and 16, preferably Ir, Pt, Pd, Rh, Re , Os, Tl, Pb, Bi, In, Sn, Sb, Te, Au and Ag. In addition, the L ₁ , L ₂ and L ₃ may be any one selected from the following [formula D], which is the same as or different from each other as a ligand, but is not limited thereto.

* In the following [structural formula D] represents a site coordinated to the metal ion M.

[Formula D]

In [Formula D],

A substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C6-C50 aryl group, a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C1- A substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C2 to C30 alkenyl group, a substituted or unsubstituted C2 to C30 heteroaryl group, A substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, and a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms And the like.

Each R is independently selected from an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 40 carbon atoms, a heteroaryl group having 3 to 20 carbon atoms, a cyano group, a halogen group, deuterium, and hydrogen; It may be further substituted with one or more substituents.

The R may be connected to each adjacent substituent by alkylene or alkenylene to form an alicyclic ring and a monocyclic or polycyclic aromatic ring.

The L may be connected to an adjacent substituent by alkylene or alkenylene to form a spiro ring or a fused ring.

As one example, the dopant represented by the above-mentioned [formula A-1] may be any one selected from the following compounds.

[Formula B-1]

In [Formula B-1],

M ^A1 represents the same metal ion as defined in [General Formula A-1], and Y ^A11 , Y ^A14 , Y ^A15 and Y ^A18. Each independently represent a carbon atom or a nitrogen atom, Y ^A12, Y ^A13, Y ^A16 and Y ^A17 each independently represents a substituted or unsubstituted carbon atoms, a substituted or unsubstituted nitrogen atom, an oxygen atom, a sulfur atom, the L ^A11 , L ^A12 , L ^A13 and L ^A14 each represent a linking group as defined above, and Q ^A11 and Q ^A12 represent a partial structure containing an atom bonding to M ^A1 .

Exemplary structures of the compound represented by the above-mentioned general formula B-1 are shown below, but the present invention is not limited thereto.

[Formula C-1]

In [Formula C-1],

M ^B1 represents the same metal ion as defined from the following formula ^{A-1], Y B11,} Y B14, Y B15 and Y ^B18 each independently represents a carbon atom or a nitrogen ^{atom, Y B12, Y B13, Y} B16 And Y ^B17 each independently represent a substituted or unsubstituted carbon atom, a substituted or unsubstituted nitrogen atom, an oxygen atom, a sulfur atom, L ^B11 , L ^B12 , L ^B13 and L ^B14 represent a linking group, Q ^B11 and Q ^B12 represents a partial structure containing an atom bonding to M ^B1 .

Exemplary structures of the compound represented by the above-mentioned general formula C-1 are shown below, but the present invention is not limited thereto.

[Formula D-1]

In [Formula D-1],

M ^C1 represents a metal ion as defined in [formula A-1], R ^C11 and R ^C12 each independently represent a hydrogen atom, a substituent which is connected to each other to form a 5-membered ring, Each of R ^C13 and R ^C14 independently represents a hydrogen atom, a substituent which is connected to each other to form a 5-membered ring, or a substituent which does not have any one to be connected to each other, and G ^C11 and G ^C12 each independently represent a nitrogen atom, a substituent Or an unsubstituted carbon atom, L ^C11 and L ^C12 represent a linking group, and Q ^C11 and Q ^C12 represent a partial structure containing an atom bonding to M ^C1 .

Exemplary structures of the compound represented by the above-mentioned general formula (D-1) are shown below, but the present invention is not limited thereto.

[Formula E-1]

In [Formula E-1],

M ^D1 represents a metal ion as defined in [Formula A-1], G ^D11 and G ^D12 each independently represent a nitrogen atom, a substituted or unsubstituted carbon atom, and J ^D11 , J ^D12 , J ^D13 , J ^D14 each independently represents an atomic group necessary for forming a five-membered ring, and L ^D11 and L ^D12 represent a linking group.

Exemplary structures of the compound represented by the above-mentioned [formula E-1] are shown below, but the present invention is not limited thereto.

[Formula F-1]

In [Formula F-1],

M ^E1 represents the same metal ion as defined in [Formula A-1], J ^E11 and J ^E12 each independently represent an atom group necessary for forming a 5-membered ring, and G ^E11 , G ^E12 , G ^E13 and G ^E14 each independently represent a nitrogen atom, a substituted or unsubstituted carbon atom, and Y ^E11 , Y ^E12 , Y ^E13 and Y ^E14 each independently represent a nitrogen atom, a substituted or unsubstituted carbon atom.

Exemplary structures of the compound represented by the above-mentioned general formula F-1 are shown below, but the present invention is not limited thereto.

[General Formula G-1]

In [General Formula G-1],

M ^F1 represents the same metal ion as defined in [General Formula A-1].

L ^F11 , L ^F12 and L ^F13 represent a linking group, R ^F11 , R ^F12 , R ^F13 and R ^F14 represent a substituent, and R ^F11 and R ^F12 , R ^F12 And R ^F13 , R ^F13 and R ^F14 may be connected to each other to form a ring, wherein the ring formed by R ^F1 and R ^F12 , R ^F13 and R ^F14 is a 5-membered ring. In addition, Q ^F11 and Q ^F12 represent a partial structure containing an atom bonded to M ^F1 .

Exemplary structures of the compound represented by the above-mentioned general formula G-1 are shown below, but the present invention is not limited thereto.

[General Formula H-1] [General Formula H-2] [General Formula H-3]

In the above general formula H-1,

R ¹¹ , R ¹² are substituents of alkyl, aryl or heteroaryl; It is also possible to form a fused ring with substituents adjacent to each other, q11, q12 is an integer of 0 to 4, preferably 0 to 2.

In addition, when q11 and q12 are 2-4, some R11 and R12 may be the same or different, respectively.

L ¹ is a ligand which binds to platinum and is preferably a ligand capable of forming an ortho metal platinum complex, a nitrogen-containing heterocyclic ligand, a diketone ligand, or a halogen ligand, more preferably an ortho metal ) Ligand forming a platinum complex, a bipyridyl ligand, or a phenanthroline ligand.

n ¹ is an integer of 0 to 3, preferably 0, m ¹ is 1 or 2, and preferably 2.

Further, the n ^1, m ¹ is preferably a metal complex represented by the general formula H-1 so that the neutral complex.

R ²¹ , R ²² , n ² , m ² , q ²² and L ² are the same as R ¹¹ , R ¹² , n ¹ , m ¹ , q ¹² and L ¹ in the general formula H-2, q ²¹ is an integer of 0 to 2, preferably 0.

Wherein R ³¹ , n ³ , m ³ and L ³ are the same as R ¹¹ , n ¹ , m ¹ and L ¹ , q ³¹ is an integer of 0 to 8, 2 is preferable, and 0 is more preferable.

Examples of the specific compounds of the above-mentioned general formulas H-1 to H-3 are as follows, but are not limited thereto.

[Formula I-1]

In [Formula I-1],

Ring A, ring B, ring C and ring D represents a nitrogen-containing heterocyclic ring which may have a substituent, and the remaining two rings are an aryl ring which may have a substituent And may form a condensed ring with ring A and ring B, ring A and ring C and / or ring B and ring D, respectively. X ¹ , X ² , X ³ and X ⁴ represent a nitrogen atom in which two of them coordinate to a platinum atom, and the remaining two represent a carbon atom or a nitrogen atom. Q ¹ , Q ² and Q ³ each independently represent a divalent atom (bond) or a bond, but Q ¹ , Q ² and Q ³ do not simultaneously represent a bond. ^{Two of} Z ¹ , Z ² , Z ³ and Z ⁴ represent coordinate bond, and the remaining two represent a covalent bond, an oxygen atom or a sulfur atom.

Examples of the specific compounds of the above-mentioned general formula I-1 include, but are not limited to, the following.

[Formula J-1]

In [formula J-1],

M represents the same metal ion as defined in [General Formula A-1], Ar1 represents a substituted or unsubstituted ring structure, and two azomethine bonds (-C = N-) that bind to M In the above, the nitrogen atom (N) is each bonded to the M, and forms a tridentate ligand which is bonded to the M at the trident as a whole.

In Ar1, C represents a carbon atom constituting the ring structure represented by Ar1. In addition, said R1 and R2 may mutually be same or different, and represent a substituted or unsubstituted alkyl group or an aryl group, respectively, and L represents a monodentate ligand.

In said general formula J-1, it is preferable that said M is Pt. In addition, as said Ar1, it is preferable to select from 5-membered ring, 6-membered ring, and these condensed cyclic groups.

Examples of the specific compound of [General Formula J-1] are as follows, but are not limited thereto.

In addition to the dopant and the host, the emission layer may further include various hosts and various dopant materials.

In addition, one or more layers selected from the hole injection layer, the hole transport layer, the electron blocking layer, the light emitting layer, the hole blocking layer, the electron transport layer and the electron injection layer may be formed by a single molecule deposition method or a solution process, wherein the deposition method Means a method of forming a thin film by evaporating a material used as a material for forming each layer through heating or the like in a vacuum or low pressure state, and the solution process is used as a material for forming each layer. It refers to a method of forming a thin film through a method such as mixing the material with a solvent and inkjet printing, roll-to-roll coating, screen printing, spray coating, dip coating, spin coating and the like.

Further, the organic light emitting display device according to the present invention can be used in a device selected from a flat panel display device, a flexible display device, a flat or white flat illumination device and a single or white flexible illumination device.

Hereinafter, the present invention will be described in more detail with reference to preferred embodiments. It will be apparent, however, to those skilled in the art that these embodiments are for further explanation of the present invention and that the scope of the present invention is not limited thereby.

<Examples>

Synthesis Example 1 Synthesis of Compound Represented by Formula 15

(1) Synthesis of Compound Represented by [Formula 15-a]

The compound represented by [Formula 15-a] was synthesized by the following [Scheme 1].

[Reaction Scheme 1]

[Formula 15-a]

100 g (484 mmol) of 2-bromo-5-chloroaniline, 500 mL of saturated aqueous sodium hydrogen carbonate solution and 500 mL of 1,4-dioxane were added to a 2 L round bottom flask at room temperature, and cooled to 0 ° C. and stirred. After the reaction was completed, 116 g (533 mmol) of dibutyl carbonate was added thereto, the mixture was warmed to room temperature, stirred for 4 hours, cooled to 0 ° C., and neutralized by adding a saturated ammonium chloride solution. Ethyl acetate and distilled water were added to the reaction solution to separate the layers, and the organic layer was extracted, concentrated under reduced pressure, and purified by silica gel column chromatography. Compound 126 g (411 mmol, yield 84.9%) represented by [Formula 15-a] Got.

(2) Synthesis of Compound Represented by [Formula 15-b]

The compound represented by [Formula 15-b] was synthesized by the following [Scheme 2].

[Reaction Scheme 2]

[Formula 15-a] [Formula 15-b]

70.0 g (228 mmol) obtained from [Scheme 1], 20.4 bromophenylboronic acid 50.4 g (251 mmol), potassium carbonate 94.7 g (685 mmol) and tetrakistriphenyl in a 2 L round bottom flask at room temperature 5.30 g (4.57 mmol) of phosphine palladium, 700 mL of tetrahydrofuran and 350 mL of distilled water were added thereto, and the mixture was refluxed for 12 hours. After the reaction was completed, the reaction solution was cooled to room temperature, ethyl acetate and distilled water were added to separate the layers, and the organic layer was extracted, concentrated under reduced pressure, purified by silica gel column chromatography, and the compound represented by [Formula 15-b] 63.4g (166 mmol, yield 72.6%).

(3) Synthesis of Compound Represented by [Formula 15-c]

The compound represented by [Formula 15-c] was synthesized by the following [Scheme 3].

Scheme 3

[Formula 15-b] [Formula 15-c]

63.4 g (166 mmol) of [Formula 15-b] obtained from [Scheme 2] and 440 mL of tetrahydrofuran were added to a 2 L round-bottomed flask purged with nitrogen at room temperature, cooled to -78 ° C, and 124 mL of normalbutyllithium (1.6 M in n-hexane) was added dropwise and stirred for 1 hour. After the reaction was completed, 1.5 g (199 mmol) of acetone was dissolved in 63 mL of tetrahydrofuran and added dropwise thereto. Then, the mixture was warmed to room temperature, stirred for 1 hour, cooled to 0 ° C., and distilled water and ethyl acetate were added to separate layers. Next, the organic layer was extracted, concentrated under reduced pressure, and purified by silica gel column chromatography to obtain 39.8 g (110 mmol, 66.4%) of a compound represented by [Formula 15-c].

(4) Synthesis of Compound Represented by [Formula 15-d]

The compound represented by [Formula 15-d] was synthesized by the following [Scheme 4].

[Reaction Scheme 4]

[Formula 15-c] [Formula 15-d]

39.8 g (110 mmol) of [Formula 15-c] obtained from [Scheme 3] and 200 mL of acetic acid were added to a 2 L round bottom flask at room temperature, followed by stirring for 12 hours. After the reaction was completed, distilled water was added to the reaction solution, and the resulting solid was filtered and purified by silica gel column chromatography to obtain 20.1 g (82.5 mmol, 75.0%) of a compound represented by [Formula 15-d].

(5) Synthesis of Compound Represented by [Formula 15-e]

The compound represented by [Formula 15-e] was synthesized by the following [Scheme 5].

[Reaction Scheme 5]

[Formula 15-e]

50.0 g (271 mmol) of cyanuric acid chloride and 500 mL of tetrahydrofuran were added to a 2 L round bottom flask purged with nitrogen at room temperature, and the mixture was cooled to 0 ° C. and stirred. Then, 316 mL (949 mmol, 3.0 M in diethyl ether) of phenylmagnesium bromide was added dropwise for 1 hour, and then heated to room temperature, stirred for 12 hours, cooled to 0 ° C., and neutralized by adding saturated aqueous ammonium chloride solution. Next, ethyl acetate and distilled water were added to separate the layers, and the organic layer was concentrated under reduced pressure, and then purified by silica gel column chromatography and recrystallization to obtain 58.4 g (218 mmol, 80.5%) of the compound represented by Chemical Formula 15-e.

(6) Synthesis of Compound Represented by [Formula 15-f]

The compound represented by [Formula 15-f] was synthesized by the following [Scheme 6].

[Reaction Scheme 6]

[Formula 15-d] [Formula 15-e] [Formula 15-f]

20.1 g (82.5 mmol) of [Formula 15-d] obtained from [Scheme 4], 4.9 g (124 mmol) of sodium hydride (60%, dispersion in paraffin liquid) obtained from Scheme 4 in a nitrogen purged 2 L round bottom flask, N, N -800 mL of dimethylformamide was added thereto, cooled to 0 ° C., and 33.1 g (124 mmol) of [Formula 15-e] obtained from [Scheme 5] was added and stirred for 1 hour. After completion of the reaction, the mixture was stirred at room temperature for 1 hour, further stirred, and distilled water was added to the reaction solution. The resulting solid was filtered and purified by silica gel column chromatography to obtain 34.5 g of a compound represented by [Formula 15-f] (73.5). mmol, yield 89.1%).

(7) Synthesis of Compound Represented by [Formula 15-g]

The compound represented by [Formula 15-g] was synthesized by the following [Scheme 7].

[Reaction Scheme 7]

[Formula 15-f] [Formula 15-g]

34.5 g (72.6 mmol) of benzophenonehydrazone, 15.7 g (79.9 mmol) of benzophenonehydrazone, 1.60 g (7.26 mmol) of palladium acetate, 4.50 g (7.26 mmol) of BINAP, 8.40 g (87.2 mmol) of sodium tert-butoxide, and toluene (350 mL) were added thereto, and the mixture was refluxed for 12 hours. After filtering the reaction solution using Celite, the filtrate was concentrated under reduced pressure and purified by silica gel column chromatography to obtain 37.9g (59.7mmol, Yield 82.2%) of the compound represented by [Formula 15-g].

(8) Synthesis of Compound Represented by Formula 15-h

A compound represented by [Formula 15-h] was synthesized by the following [Scheme 8].

[Reaction Scheme 8]

[Formula 15-g] [Formula 15-h]

37.9 g (59.7 mmol) [Formula 15-g] obtained from Scheme 7, 10.8 g (89.6 mmol) phenylacetaldehyde, 20.6 g (119 mmol) paratoluene sulfonic acid, ethanol, were purged at room temperature with nitrogen purged at room temperature. 380 mL was added and refluxed for 12 hours. After the reaction was completed, the reaction solution was cooled to room temperature, and then concentrated under reduced pressure and purified by silica gel column chromatography to obtain 25.7 g (46.3 mmol, Yield 77.5%) of the compound represented by [Formula 15-h].

(9) Synthesis of Compound Represented by Formula 15

The compound represented by [Formula 15] was synthesized by the following [Scheme 9].

[Reaction Scheme 9]

[Formula 15-h] [Formula 15]

In a 100 mL round bottom flask purged with nitrogen at room temperature, 5.0 g (9.00 mmol) of [Formula 15-h] obtained from [Scheme 8], 2.80 g (13.5 mmol) of iodobenzene, 0.10 g (0.450 mmol) of copper iodide, and phosphoric acid 4.0 g (18.9 mmol) of potassium, 2.10 g (18.0 mmol) of 1,2-cyclohexanediamine, and 25 mL of 1,4-dioxane were added and refluxed for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, methanol was added, and the reaction solution was filtered. The solid obtained was purified by silica gel column chromatography and recrystallization to obtain 4.63 g (7.33 mmol, 81.4%) of the compound represented by [Formula 15]. .

MS (MALDI-TOF): m / z 631.3 [M] ⁺

Anal. Calc. for C ₄₄ H ₃₃ N ₅ C, 83.65; H, 5. 26; N, 11.09. Found C, 83.64; H, 5. 24; N, 11.10.

Synthesis Example 2 Synthesis of Compound Represented by Formula 20

(1) Synthesis of Compound Represented by Formula 20-a

The compound represented by [Formula 20-a] was synthesized by the following [Scheme 10].

[Reaction Scheme 10]

[Formula 20-a]

500 g (2710 mmol) of cyanuric chloride and 5000 mL of tetrahydrofuran were added to a 10 L round-bottomed flask at room temperature, cooled to 0 ° C, and 994 mL (2980 mmol, 3.0 M in diethyl ether) of phenylmagnesium was added dropwise. Then stirred for 6 hours. After the reaction was completed, neutralized by adding saturated aqueous ammonium chloride solution, ethyl acetate and distilled water were added to separate the layers, and the organic layer was purified by concentration under reduced pressure and recrystallization to yield 431 g (1907 mmol) of a compound represented by [Formula 20-a]. 70.3%).

(2) Synthesis of Compound Represented by [Formula 20-b]

The compound represented by [Formula 20-b] was synthesized by the following [Scheme 11].

[Reaction Scheme 11]

[Formula 20-a] [Formula 20-b]

81.4 g (487 mmol) of carbazole and 600 mL of tetrahydrofuran were added to a 2 L round-bottomed flask at room temperature, followed by cooling to -78 ° C to add 304 mL of normal butyllithium (487 mmol, 1.6 M in n-hexane). After stirring for 1 hour. After the reaction was completed, 100 g (442 mmol) of [Formula 20-a] obtained from [Scheme 10] was added dropwise with 200 mL of tetrahydrofuran, and then added dropwise, and the mixture was stirred at room temperature for 1 hour. Next, after cooling to 0 ° C., distilled water and ethyl acetate were added thereto to separate the layers, and then the organic layer was concentrated under reduced pressure and purified by silica gel column chromatography. The compound represented by [Formula 20-b] was 98.3 g (276 mmol, 62.3% yield). )

(3) Synthesis of Compound Represented by Formula 20-c

The compound represented by [Formula 20-c] was synthesized by the following [Scheme 12].

[Reaction Scheme 12]

[Formula 15-d] [Formula 20-b] [Formula 20-c]

Except for using [Formula 20-b] obtained from [Scheme 11] instead of [Formula 15-e] used in [Scheme 6] of Synthesis Example 1 synthesized in the same manner and represented by the formula [20-c] 25.3 g (44.9 mmol, yield 79.4%) were obtained.

(4) Synthesis of Compound Represented by [Formula 20-d]

The compound represented by [Formula 20-d] was synthesized by the following [Scheme 13].

[Reaction Scheme 13]

[Formula 20-c] [Formula 20-d]

Except for using [Formula 20-c] obtained from [Scheme 12] instead of [Formula 15-f] used in [Scheme 7] of Synthesis Example 1 synthesized in the same manner and represented by the formula [20-d] 24.8 g (34.3 mmol, yield 76.4%) of the compound was obtained.

(5) Synthesis of Compound Represented by [Formula 20-e]

The compound represented by [Formula 20-e] was synthesized by the following [Scheme 14].

[Reaction Scheme 14]

[Formula 20-d] [Formula 20-e]

Except for using [Formula 20-d] obtained from [Scheme 13] instead of [Formula 15-g] used in [Scheme 8] of Synthesis Example 1 synthesized in the same manner and represented by the formula [20-e] Obtained compound 19.6 g (30.4 mmol, yield 88.7%).

(6) Synthesis of Compound Represented by Formula 20

The compound represented by [Formula 20] was synthesized by the following [Scheme 15].

[Reaction Scheme 15]

[Formula 20-e] [Formula 20]

Compound represented by [Formula 20] synthesized in the same manner except for using [Formula 20-e] obtained from [Scheme 14] instead of [Formula 15-h] used in [Scheme 9] of Synthesis Example 1 4.35 g (6.03 mmol, yield 77.8%) were obtained.

MS (MALDI-TOF): m / z 720.3 [M] ⁺

Anal. Calc. for C ₅₀ H ₃₆ N ₆ C, 83.31; H, 5.03; N, 11.66. Found C, 83.33; H, 5.02; N, 11.67.

Synthesis Example 3 Synthesis of Compound Represented by Chemical Formula 27

(1) Synthesis of Compound Represented by [Formula 27-a]

The compound represented by [Formula 27-a] was synthesized according to Reaction Scheme 16 below.

[Reaction Scheme 16]

[Formula 15-b] [Formula 27-a]

Except for using cyclohexanone instead of ethyl acetate used in [Scheme 3] of Synthesis Example 1 Compound 12.5g (31.1mmol, yield 79.3%) represented by the formula [Formula 27-a] Got it.

(2) Synthesis of Compound Represented by [Formula 27-b]

The compound represented by [Formula 27-b] was synthesized by the following [Scheme 17].

[Reaction Scheme 17]

[Formula 27-a] [Formula 27-b]

Except for using [Formula 27-a] obtained from [Scheme 16] instead of [Formula 15-c] used in [Scheme 4] of Synthesis Example 1 synthesized in the same manner and represented by the formula [27-b] 5.70 g (20.1 mmol, Yield 64.6%) were obtained.

(2) Synthesis of Compound Represented by Formula 27-c

The compound represented by [Formula 27-c] was synthesized by the following [Scheme 18].

[Reaction Scheme 18]

[Formula 27-b] [Formula 15-e] [Formula 27-c]

Except for using [Formula 27-b] obtained from [Scheme 17] instead of [Formula 15-d] used in [Scheme 6] of Synthesis Example 1 synthesized in the same manner and represented by the formula [Formula 27-c] 7.89 g (15.3 mmol, yield 76.3%) of the compound was obtained.

(3) Synthesis of Compound Represented by Formula 27-d

The compound represented by [Formula 27-d] was synthesized according to Reaction Scheme 19 below.

Scheme 19

[Formula 27-c] [Formula 27-d]

Except for using [Formula 27-c] obtained from [Scheme 18] instead of [Formula 15-f] used in [Scheme 7] of Synthesis Example 1 synthesized in the same manner and represented by the formula [27-d] 7.89 g (15.3 mmol, yield 76.3%) of the compound was obtained.

(4) Synthesis of Compound Represented by [Formula 27-e]

The compound represented by [Formula 27-e] was synthesized by the following [Scheme 20].

[Reaction Scheme 20]

[Formula 27-d] [Formula 27-e]

Except for using [Formula 27-d] obtained from [Scheme 19] instead of [Formula 15-g] used in [Scheme 8] of Synthesis Example 1 synthesized in the same manner and represented by the formula [27-e] Obtained compound 8.11 g (12.0 mmol, yield 78.5%).

(5) Synthesis of Compound Represented by Formula 27

The compound represented by [Formula 27] was synthesized by the following [Scheme 21].

[Reaction Scheme 21]

[Formula 27-e] [Formula 27]

Compound represented by [Formula 27] synthesized in the same manner except for using [Formula 27-e] obtained from [Scheme 20] instead of [Formula 15-h] used in [Scheme 9] of Synthesis Example 1 7.14 g (10.6 mmol, yield 78.5%) were obtained.

MS (MALDI-TOF): m / z 671.3 [M] ⁺

Anal. Calc. for C ₄₇ H ₃₇ N ₅ C, 84.02; H, 5.55; N, 10.42. Found C, 84.02; H, 5.54; N, 10.41.

Synthesis Example 4 Synthesis of Compound Represented by Chemical Formula 71

(1) Synthesis of Compound Represented by [Formula 71-a]

The compound represented by [Formula 71-a] was synthesized by the following [Scheme 22].

[Reaction Scheme 22]

[Formula 71-a]

Tertiarybutyl 4-bromo-2-iodophenyl carbamate was used in place of [Formula 15-a] used in [Scheme 2] of Synthesis Example 1, and 2-methoxycarboxe instead of bromophenylboronic acid A compound 39.2 g (96.5 mmol, yield 76.8%) was obtained by synthesizing in the same manner except that carbonylphenylboronic acid pinacol ester was used.

(2) Synthesis of Compound Represented by [Formula 71-b]

The compound represented by [Formula 71-b] was synthesized by the following [Scheme 23].

[Reaction Scheme 23]

[Formula 71-a] [Formula 71-b]

39.2 g (96.5 mmol) of [Formula 71-a] obtained from [Scheme 22] and 400 mL of tetrahydrofuran were added to a 1 L round-bottomed flask purged at room temperature, cooled to 0 ° C., and 113 mL of methylmagnesium bromide ( 338mmol, 3.0M in diethyl ether) was added dropwise and the temperature was raised to 50 ℃ and stirred for 6 hours. After the reaction was completed, the reaction solution was cooled to 0 ° C., neutralized by adding saturated aqueous ammonium chloride solution, ethyl acetate and distilled water were added to separate the layers, and the organic layer was concentrated under reduced pressure and purified by column chromatography. 31.1 g (76.5 mmol, yield 79.3%) of the compound represented by b] were obtained.

(3) Synthesis of Compound Represented by [Formula 71-c]

The compound represented by [Formula 71-c] was synthesized by the following [Scheme 24].

Scheme 24

[Formula 71-b] [Formula 71-c]

Except for using [Formula 71-b] obtained from [Scheme 23] instead of [Formula 15-c] used in [Scheme 4] of Synthesis Example 1 synthesized in the same manner and represented by the formula [71-c] Obtained compound 15.7 g (54.5 mmol, yield 71.2%).

(4) Synthesis of Compound Represented by [Formula 71-d]

The compound represented by [Formula 71-d] was synthesized by the following [Scheme 25].

[Reaction Scheme 25]

[Formula 71-c] [Formula 15-e] [Formula 71-d]

Except for using [Formula 71-c] obtained from [Scheme 24] instead of [Formula 15-d] used in [Scheme 6] of Synthesis Example 1 synthesized in the same manner and represented by the formula [71-d] Obtained compound 21.8 g (42.0 mmol, yield 77.0%).

(5) Synthesis of Compound Represented by [Formula 71-e]

The compound represented by [Formula 71-e] was synthesized by the following [Scheme 26].

[Reaction Scheme 26]

[Formula 71-d] [Formula 71-e]

Except for using [Formula 71-d] obtained from [Scheme 25] instead of [Formula 15-f] used in [Scheme 7] of Synthesis Example 1 synthesized in the same manner and represented by the formula (71-e) 22.7 g (35.8 mmol, Yield 85.2%) were obtained.

(6) Synthesis of Compound Represented by [Formula 71-f]

The compound represented by [Formula 71-f] was synthesized by the following Reaction Scheme 27.

[Reaction Scheme 27]

[Formula 71-e] [Formula 71-f]

Except for using [Chemical Formula 71-e] obtained from [Scheme 26] instead of [Chemical Formula 15-g] used in [Scheme 8] of Synthesis Example 1 synthesized in the same manner and represented by the formula [Formula 71-f] Obtained compound 13.7 g (24.7 mmol, yield 68.9%).

(7) Synthesis of Compound Represented by Formula 71

The compound represented by [Formula 71] was synthesized by the following Reaction Scheme 28.

[Reaction Scheme 28]

[Formula 71-f] [Formula 71]

Compound represented by [Formula 71] synthesized in the same manner except for using [Formula 71-f] obtained from [Scheme 27] instead of [Formula 15-h] used in [Scheme 9] of Synthesis Example 1 3.76 g (5.95 mmol, yield 66.1%) were obtained.

MS (MALDI-TOF): m / z 631.3 [M] ⁺

Anal. Calc. for C ₄₄ H ₃₃ N ₅ C, 83.65; H, 5. 26; N, 11.09. Found C, 83.65; H, 5. 28; N, 11.09.

Synthesis Example 5 Synthesis of Compound Represented by Chemical Formula 99

(1) Synthesis of Compound Represented by [Formula 99-a]

The compound represented by [Formula 99-a] was synthesized by the following [Scheme 29].

[Reaction Scheme 29]

[Formula 71-c] [Formula 99-a]

Except for using [Chemical Formula 71-c] obtained from [Scheme 24] instead of [Chemical Formula 15-h] used in [Scheme 9] of Synthesis Example 1 and synthesized in the same manner as [Formula 99-a] 31.3 g (85.9 mmol, yield 82.5%) of the resulting compound was obtained.

(2) Synthesis of Compound Represented by [Formula 99-b]

The compound represented by [Formula 99-b] was synthesized by the following [Scheme 30].

[Reaction Scheme 30]

[Formula 99-a] [Formula 99-b]

Except for using [Formula 99-a] obtained from [Scheme 29] instead of [Formula 15-f] used in [Scheme 7] of Synthesis Example 1 synthesized in the same manner and represented by the formula [99-b] 31.2 g (65.1 mmol, yield 75.7%) of the resulting compound was obtained.

(3) Synthesis of Compound Represented by [Formula 99-c]

The compound represented by [Formula 99-c] was synthesized by the following [Scheme 31].

[Reaction Scheme 31]

[Formula 99-b] [Formula 99-c]

Except for using [Formula 99-b] obtained from [Scheme 30] instead of [Formula 15-g] used in [Scheme 8] of Synthesis Example 1 synthesized in the same manner and represented by the formula [99-c] 18.4 g (45.9 mmol, yield 70.6%) was obtained.

(4) Synthesis of Compound Represented by Formula 99

The compound represented by [Formula 99] was synthesized by the following [Scheme 32].

[Reaction Scheme 32]

[Formula 99-c] [Formula 15-e] [Formula 99-c]

Compound represented by [Formula 99] synthesized in the same manner except for using [Formula 99-c] obtained from [Scheme 31] instead of [Formula 15-d] used in [Scheme 6] of Synthesis Example 1 5.70 g (9.02 mmol, yield 72.3%) were obtained.

MS (MALDI-TOF): m / z 631.3 [M] ⁺

Anal. Calc. for C ₄₄ H ₃₃ N ₅ C, 83.65; H, 5. 26; N, 11.09. Found C, 83.64; H, 5. 26; N, 11.10.

Synthesis Example 6 Synthesis of Compound Represented by Chemical Formula 136

(1) Synthesis of Compound Represented by [Formula 136-a]

The compound represented by [Formula 136-a] was synthesized by the following Reaction Scheme 33.

[Reaction Scheme 33]

[Formula 136-a]

In a 1 L round-bottomed flask at room temperature, 50.0 g (147 mmol) of methyl 5-bromo-2-iodobenzoate, 41.0 g (161 mmol) of bis (pinacolato) diboron, 31.7 g (323 mmol) of potassium acetate, 500 mL of toluene was added and refluxed for 12 hours. After the reaction was completed, the reaction solution was filtered using Celite, the filtrate was concentrated under reduced pressure and purified by silica gel column chromatography to obtain 37.8 g (111 mmol, yield 75.6%) of the compound represented by [Formula 136-a].

(2) Synthesis of Compound Represented by Formula 136-b

The compound represented by [Formula 136-b] was synthesized by the following Reaction Scheme 34.

[Reaction Scheme 34]

[Formula 136-a] [Formula 136-b]

N -Boc-2-iodoaniline was used instead of [Formula 15-a] used in [Scheme 2] of Synthesis Example 1, and [Formula 136-a] obtained from [Scheme 33] instead of bromophenylboronic acid Synthesis was carried out in the same manner except that 38.7 g (95.3 mmol, yield 85.9%) of the compound represented by [Formula 136-b] was obtained.

(3) Synthesis of Compound Represented by Formula 136-c

The compound represented by [Formula 136-c] was synthesized by the following Reaction Scheme 35.

[Reaction Scheme 35]

[Formula 136-b] [Formula 136-c]

Except for using [Formula 136-b] obtained from [Scheme 34] instead of [Formula 71-a] used in [Scheme 23] of Synthesis Example 4 synthesized in the same manner and represented by the formula [136-c] 23.1 g (56.9 mmol, yield 59.7%) of the resulting compound was obtained.

(4) Synthesis of Compound Represented by Formula 136-d

The compound represented by [Formula 136-d] was synthesized by the following Reaction Scheme 36.

[Reaction Scheme 36]

[Formula 136-c] [Formula 136-d]

Except for using [Formula 136-c] obtained from [Scheme 35] instead of [Formula 15-c] used in [Scheme 4] of Synthesis Example 1 synthesized in the same manner represented by the formula [136-d] Obtained compound 10.3 g (35.7 mmol, yield 62.9%).

(5) Synthesis of Compound Represented by Formula 136-e

The compound represented by [Formula 136-e] was synthesized by the following [Scheme 37].

[Reaction Scheme 37]

[Formula 15-e] [Formula 136-e]

Into a 2 L round bottomed flask with nitrogen purge at room temperature, 118 g (448 mmol) of 1,4-dibromo-2,5-dimethylbenzene and 600 mL of tetrahydrofuran were added, followed by cooling to -78 ° C and 257 mL of normal butyllithium ( 411 mmol, 1.6 M in n-hexane) was added dropwise and stirred for 1 hour. After the reaction was completed, 100 g (374 mmol) of [Chemical Formula 15-e] obtained from [Scheme 5] of Synthesis Example 1 was added dropwise to 200 mL of tetrahydrofuran, and then added dropwise thereto. After cooling to 0 ° C., distilled water and ethyl acetate were added thereto. The layers were separated and the organic layer was concentrated under reduced pressure, and then purified by silica gel column chromatography to obtain 124 g (297 mmol, yield 79.5%) of the compound represented by [Formula 136-e].

(6) Synthesis of Compound Represented by Formula 136-f

The compound represented by [Formula 136-f] was synthesized by the following [Scheme 38].

[Reaction Scheme 38]

[Formula 136-d] [Formula 136-e] [Formula 136-f]

In a 250 mL round bottom flask purged with nitrogen at room temperature, 10.0 g (34.7 mmol) of [Formula 136-d] obtained from [Scheme 36], 15.9 g (38.2 mmol) of [Formula 136-e] obtained from [Scheme 37], palladium 0.800 g (3.47 mmol) of acetate, 1.40 g (6.94 mmol) of tributylbutylphosphine, 6.70 g (69.4 mmol) of sodium tert-butoxide, and 100 mL of toluene were added and refluxed for 12 hours. After the reaction was completed, the reaction solution was filtered using Celite, the filtrate was concentrated under reduced pressure and purified by silica gel column chromatography to obtain 14.3 g (22.9 mmol, 66.1%) of the compound represented by [Formula 136-f]. .

(7) Synthesis of Compound Represented by [Formula 136-g]

The compound represented by [Formula 136-g] was synthesized by the following [Scheme 39].

[Reaction Scheme 39]

[Formula 136-f] [Formula 136-g]

Except for using [Formula 136-f] obtained from [Scheme 38] instead of [Formula 15-f] used in [Scheme 7] of Synthesis Example 1 synthesized in the same manner and represented by the formula [136-g] Obtained compound 13.1 g (17.7 mmol, yield 77.3%).

(8) Synthesis of Compound Represented by Formula 136-h

The compound represented by [Formula 136-h] was synthesized by the following Reaction Scheme 40.

[Reaction Scheme 40]

[Formula 136-g] [Formula 136-h]

Except for using [Formula 136-g] obtained from [Scheme 39] instead of [Formula 15-g] used in [Scheme 8] of Synthesis Example 1 synthesized in the same manner and represented by the formula [136-h] 8.7 g (13.2 mmol, yield 74.4%) of the obtained compound was obtained.

(9) Synthesis of Compound Represented by Formula 136

The compound represented by [Formula 136] was synthesized by the following [Scheme 41].

[Reaction Scheme 41]

[Formula 136-h] [Formula 136]

Compound represented by [Formula 136] synthesized in the same manner except for using [Formula 136-h] obtained from [Scheme 40] instead of [Formula 15-h] used in [Scheme 9] of Synthesis Example 1 4.33 g (5.88 mmol, yield 77.6%) were obtained.

MS (MALDI-TOF): m / z 735.3 [M] ⁺

Anal. Calc. for C ₅₂ H ₄₁ N ₅ C, 84.87; H, 5.62; N, 9.52. Found C, 84.87; H, 5.62; N, 9.54.

Synthesis Example 7 Synthesis of Compound Represented by Chemical Formula 141

(1) Synthesis of Compound Represented by Formula 141-a

The compound represented by [Formula 141-a] was synthesized by the following [Scheme 42].

[Reaction Scheme 42]

[Formula 136-b] [Formula 141-a]

The same procedure except that [Formula 136-b] obtained from [Scheme 34] was used instead of [Formula 71-a] used in [Scheme 23] of Synthesis Example 4, except that paratolyl magnesium bromide was used instead of methylmagnesium bromide. Compound 34.9 g (62.5 mmol, yield 84.6%) of the compound represented by [Formula 141-a] was obtained by synthesis.

(2) Synthesis of Compound Represented by [Formula 141-b]

The compound represented by [Formula 141-b] was synthesized by the following [Scheme 43].

[Reaction Scheme 43]

[Formula 141-a] [Formula 141-b]

Except for using [Chemical Formula 141-a] obtained from [Scheme 42] instead of [Chemical Formula 15-c] used in [Scheme 4] of Synthesis Example 1, the compound was synthesized in the same manner and represented by [Formula 141-b] Obtained compound 19.3 g (43.8 mmol, yield 70.1%).

(3) Synthesis of Compound Represented by Formula 141-c

The compound represented by [Formula 141-c] was synthesized by the following [Scheme 44].

[Reaction Scheme 44]

[Formula 141-b] [Formula 15-c] [Formula 141-c]

Except for using [Chemical Formula 141-b] obtained from [Scheme 43] instead of [Chemical Formula 15-d] used in [Scheme 6] of Synthesis Example 1, the compound was synthesized in the same manner, and represented by [Formula 141-c] Obtained compound 24.0 g (35.7 mmol, yield 81.5%).

(4) Synthesis of Compound Represented by [Formula 141-d]

The compound represented by [Formula 141-d] was synthesized by the following [Scheme 45].

[Reaction Scheme 45]

[Formula 141-c] [Formula 141-d]

Except for using [Formula 141-c] obtained from [Scheme 44] instead of [Formula 15-f] used in [Scheme 7] of Synthesis Example 1 synthesized in the same manner and represented by the formula [141-d] 23.1 g (29.4 mmol, yield 82.1%) of the resulting compound was obtained.

(5) Synthesis of Compound Represented by Formula 141-e

The compound represented by [Formula 141-e] was synthesized by the following [Scheme 46].

[Reaction Scheme 46]

[Formula 141-d] [Formula 141-e]

Except for using [Chemical Formula 141-d] obtained from [Scheme 45] instead of [Chemical Formula 15-g] used in [Scheme 8] of Synthesis Example 1, the compound was synthesized in the same manner, and represented by [Formula 141-e] Obtained compound 14.5 g (20.5 mmol, yield 69.8%).

(6) Synthesis of Compound Represented by Formula 141

The compound represented by [Formula 141] was synthesized by the following [Scheme 47].

[Reaction Scheme 47]

[Formula 141-e] [Formula 141]

Compound represented by [Formula 141] synthesized in the same manner except for using [Formula 141-e] obtained from [Scheme 46] instead of [Formula 15-h] used in [Scheme 9] of Synthesis Example 1 4.91 g (6.26 mmol, yield 88.7%) were obtained.

MS (MALDI-TOF): m / z 783.3 [M] ⁺

Anal. Calc. for C ₅₆ H ₄₁ N ₅ C, 85.80; H, 5.27; N, 8.93. Found C, 85.79; H, 5.27; N, 8.94.

Synthesis Example 8 Synthesis of Compound Represented by Chemical Formula 145

(1) Synthesis of Compound Represented by [Formula 145-a]

The compound represented by [Formula 145-a] was synthesized by the following [Scheme 48].

[Reaction Scheme 48]

[Formula 136-d] [Formula 15-e] [Formula 145-a]

Synthesis was carried out in the same manner except for using [Formula 136-d] obtained from [Scheme 36] of Synthesis Example 6 instead of [Scheme 15-d] used in [Scheme 6] of Synthesis Example 1 47.9 g (92.2 mmol, yield 88.6%) of the compound represented by a] were obtained.

(2) Synthesis of Compound Represented by Formula 145-b

The compound represented by [Formula 145-b] was synthesized by the following [Scheme 49].

[Reaction Scheme 49]

[Formula 145-a] [Formula 145-b]

Except for using [Chemical Formula 145-a] obtained from [Schematic 48] instead of [Chemical Formula 15-f] used in [Scheme 7] of Synthesis Example 1, the compound was synthesized in the same manner, and represented by [Formula 145-b] 48.6 g (76.6 mmol, yield 83.0%) of the compound was obtained.

(3) Synthesis of Compound Represented by Formula 145-c

The compound represented by [Formula 145-c] was synthesized by the following [Scheme 50].

[Reaction Scheme 50]

[Formula 145-b] [Formula 145-c]

The same method as in [Chemical Formula 15-g] instead of [Chemical Formula 15-g] used in [Scheme 8] of Synthesis Example 1, except that cyclohexanone was used instead of phenylacetaldehyde. It synthesize | combined and obtained 6.96 g (13.0 mmol, yield 82.8%) of the compound represented by [Formula 145-c].

(4) Synthesis of Compound Represented by Formula 145

The compound represented by [Formula 145] was synthesized by the following [Scheme 51].

[Reaction Scheme 51]

[Formula 145-c] [Formula 145]

Compound represented by [Formula 145] synthesized in the same manner except for using [Formula 145-c] obtained from [Scheme 50] instead of [Formula 15-h] used in [Scheme 9] of Synthesis Example 1 3.43 g (5.63 mmol, yield 75.0%) were obtained.

MS (MALDI-TOF): m / z 609.3 [M] ⁺

Anal. Calc. for C ₄₂ H ₃₅ N ₅ C, 82.73; H, 5.79; N, 11.49. Found C, 82.74; H, 5.80; N, 11.48.

Synthesis Example 9 Synthesis of Compound Represented by Chemical Formula 168

(1) Synthesis of Compound Represented by Formula 168-a

The compound represented by [Formula 168-a] was synthesized by the following [Scheme 52].

[Reaction Scheme 52]

[Formula 136-b] [Formula 168-a]

Instead of [Formula 136-b] obtained from [Scheme 34] of Synthesis Example 6 instead of [Scheme 71-a] used in [Scheme 23] of Synthesis Example 4, except that phenylmagnesium bromide was used instead of methylmagnesium bromide Then, the compound was synthesized in the same manner to obtain 31.3 g (59.0 mmol, yield 79.9%) of the compound represented by [Formula 168-a].

(2) Synthesis of Compound Represented by Formula 168-b

The compound represented by [Formula 168-b] was synthesized by the following [Scheme 53].

[Reaction Scheme 53]

[Formula 168-a] [Formula 168-b]

Except for using [Scheme 168-a] obtained from [Scheme 52] instead of [Scheme 15-c] used in [Scheme 4] of Synthesis Example 1 synthesized in the same manner and represented by the formula [168-b] Obtained compound 19.6 g (47.5 mmol, yield 80.6%).

(3) Synthesis of Compound Represented by Formula 168-c

The compound represented by [Formula 168-c] was synthesized by the following [Scheme 54].

[Reaction Scheme 54]

[Formula 168-b] [Formula 168-c]

Except for using [Chemical Formula 168-b] obtained from [Scheme 53] instead of [Chemical Formula 15-h] used in [Scheme 9] of Synthesis Example 1 synthesized in the same manner and represented by the formula [168-c] 18.7 g (38.3 mmol, yield 80.5%) of the compound was obtained.

(4) Synthesis of Compound Represented by Formula 168-d

The compound represented by [Formula 168-d] was synthesized by the following [Scheme 55].

[Reaction Scheme 55]

[Formula 168-c] [Formula 168-d]

Except for using [Chemical Formula 168-c] obtained from [Scheme 54] instead of [Chemical Formula 15-f] used in [Scheme 7] of Synthesis Example 1 synthesized in the same manner and represented by the formula [168-d] 20.0 g (33.1 mmol, yield 86.5%) of the compound was obtained.

(5) Synthesis of Compound Represented by Formula 168-e

The compound represented by [Formula 168-e] was synthesized by the following [Scheme 56].

[Reaction Scheme 56]

[Formula 168-d] [Formula 168-e]

Except for using [Chemical Formula 168-d] obtained from [Scheme 55] instead of [Chemical Formula 15-g] used in [Scheme 8] of Synthesis Example 1 and synthesized in the same manner represented by the formula [168-e] 13.2 g (25.2 mmol, yield 76.0%) of the compound was obtained.

(6) Synthesis of Compound Represented by Formula 168

The compound represented by [Formula 168] was synthesized by the following [Scheme 57].

[Reaction Scheme 57]

[Formula 168-e] [Formula 15-e] [Formula 168]

Compound represented by [Formula 168] synthesized in the same manner except for using [Formula 168-e] obtained from [Scheme 56] instead of [Formula 15-d] used in [Scheme 6] of Synthesis Example 1 4.91 g (6.50 mmol, yield 85.2%) were obtained.

MS (MALDI-TOF): m / z 755.3 [M] ⁺

Anal. Calc. for C ₅₄ H ₃₇ N ₅ C, 85.80; H, 4.93; N, 9.26. Found C, 85.79; H, 4.94; N, 9.27.

Synthesis Example 10 Synthesis of Compound Represented by Formula 183

(1) Synthesis of Compound Represented by [Formula 183-a]

The compound represented by [Formula 183-a] was synthesized by the following [Scheme 58].

[Reaction Scheme 58]

[Formula 183-a]

Instead of [Formula 15-a] used in [Scheme 2] of Synthesis Example 1, 1-bromo-4-chloro-2-iodobenzene was used, and instead of 2-bromophenylboronic acid (2-Boc- Except for using aminophenyl) boronic acid pinacol ester, and synthesized in the same manner to give 30.5g (79.7mmol, 84.3% yield) of the compound represented by the formula (183-a).

(2) Synthesis of Compound Represented by [Formula 183-b]

The compound represented by [Formula 183-b] was synthesized by the following [Scheme 59].

[Reaction Scheme 59]

[Formula 183-a] [Formula 183-b]

Except for using [Formula 183-a] obtained from [Scheme 58] instead of [Formula 15-b] used in [Scheme 3] of Synthesis Example 1 synthesized in the same manner and represented by the formula (183-b) Obtained compound 17.3 g (47.8 mmol, yield 60.0%).

(3) Synthesis of Compound Represented by [Formula 183-c]

The compound represented by [Formula 183-c] was synthesized by the following [Scheme 60].

[Reaction Scheme 60]

[Formula 183-b] [Formula 183-c]

Except for using [Formula 183-b] obtained from [Scheme 59] instead of [Formula 15-c] used in [Scheme 4] of Synthesis Example 1 synthesized in the same manner and represented by the formula (183-c) 9.68 g (39.7 mmol, yield 83.1%) of the compound was obtained.

(4) Synthesis of Compound Represented by [Formula 183-d]

The compound represented by [Formula 183-d] by the following [Scheme 61] was synthesized.

Scheme 61

[Formula 183-c] [Formula 15-e] [Formula 183-d]

Except for using [Formula 183-c] obtained from [Scheme 60] instead of [Formula 15-d] used in [Scheme 6] of Synthesis Example 1 synthesized in the same manner and represented by [Formula 183-d] Obtained compound 15.2 g (32.0 mmol, yield 80.6%).

(5) Synthesis of Compound Represented by Formula 183-e

The compound represented by [Formula 183-e] was synthesized by the following Reaction Scheme 62.

[Reaction Scheme 62]

[Formula 183-d] [Formula 183-e]

Except for using [Formula 183-d] obtained from [Scheme 61] instead of [Formula 15-f] used in [Scheme 7] of Synthesis Example 1 synthesized in the same manner and represented by [Formula 183-e] 14.9 g (23.5 mmol, yield 73.4%) of the compound was obtained.

(6) Synthesis of Compound Represented by [Formula 183-f]

The compound represented by [Formula 183-f] by the following [Scheme 63] was synthesized.

[Reaction Scheme 63]

[Formula 183-e] [Formula 183-f]

Except for using [Formula 183-e] obtained from [Scheme 62] instead of [Formula 15-g] used in [Scheme 8] of Synthesis Example 1 synthesized in the same manner and represented by the formula (183-f) Obtained compound 10.2 g (18.4 mmol, yield 78.2%).

(7) Synthesis of Compound Represented by Formula 183

The compound represented by [Formula 183] was synthesized by the following [Scheme 64].

[Reaction Scheme 64]

[Formula 183-f] [Formula 183]

Compound represented by [Formula 183] synthesized in the same manner except for using [Formula 183-f] obtained from [Scheme 63] instead of [Formula 15-h] used in [Scheme 9] of Synthesis Example 1 3.97 g (6.28 mmol, yield 69.8%) were obtained.

MS (MALDI-TOF): m / z 631.3 [M] ⁺

Anal. Calc. for C ₄₄ H ₃₃ N ₅ C, 83.65; H, 5. 26; N, 11.09. Found C, 83.66; H, 5. 25; N, 11.09.

Synthesis Example 11 Synthesis of Compound Represented by Chemical Formula 230

(1) Synthesis of Compound Represented by [Formula 230-a]

The compound represented by [Formula 230-a] was synthesized by the following [Scheme 65].

[Reaction Scheme 65]

[Formula 230-a]

97 g (0.56 mol) of 2-nitronaphthalene, 166.5 g (1.68 mol) of methyl cyanoacetate, 40.1 g (0.62 mol) of potassium cyanide, and 62.9 g (1.12 mol) of potassium hydroxide were added and stirred. 970 mL of dimethylformamide was added and stirred at 60 ° C. overnight. The mixture was concentrated under reduced pressure at room temperature to remove the solvent, and then 500 mL of 10% sodium hydroxide solution was added to reflux for about 1 hour. Extracted with ethyl acetate, separated by column chromatography, and recrystallized with toluene and heptane to give 49g (yield 75%) of the compound represented by [Formula 230-a].

(2) Synthesis of Compound Represented by [Formula 230-b]

The compound represented by [Formula 230-b] was synthesized by the following [Scheme 66].

[Reaction Scheme 66]

[Formula 230-a] [Formula 230-b]

25.0 g (149 mmol) [Formula 230-a] obtained in [Scheme 65] was added to 200 mL of tetrahydrofuran and stirred. 87.4 mL (297 mmol) of phenyl magnesium bromide (3.0 M in Et ₂ O) was added dropwise and refluxed at 0 ° C. for about 1 hour. After dropping 19.4 g (179 mmol) of ethyl chloroformate, the mixture was refluxed for about 1 hour. Aqueous ammonium chloride solution was added until weakly acidic and washed with water and heptane to obtain 32.4 g (yield 80%) of the compound represented by [Formula 230-b].

(3) Synthesis of Compound Represented by [Formula 230-c]

The compound represented by [Formula 230-c] was synthesized by the following [Scheme 67].

[Reaction Scheme 67]

[Formula 230-b] [Formula 230-c]

30 g (110 mmol) of [Formula 230-b] obtained in [Scheme 66] was added to about 80 mL of phosphorus oxychloride and refluxed overnight. After cooling to -20 ° C, approximately 400 mL of distilled water was slowly added. The mixture was washed with water, methanol and heptane and recrystallized with toluene and heptane to obtain 14.5 g (yield 45%) of the compound represented by [Formula 230-c].

(4) Synthesis of Compound Represented by [Formula 230-d]

The compound represented by [Formula 230-d] was synthesized by the following Reaction Scheme 68.

[Reaction Scheme 68]

[Formula 15-d] [Formula 230-c] [Formula 230-d]

Except for using [Formula 230-c] obtained from [Scheme 67] instead of [Formula 15-e] used in [Scheme 6] of Synthesis Example 1 synthesized in the same manner and represented by the formula [230-d] The resulting compound (yield 86%) was obtained.

(5) Synthesis of Compound Represented by Formula 230

The compound represented by [Formula 230] was synthesized by the following [Scheme 69].

[Reaction Scheme 69]

[Formula 230-d] [Formula 230]

Synthesis was carried out in the same manner as in [Scheme 7] to [Scheme 9] using [Formula 230-d] obtained from [Scheme 68] instead of [Scheme 15-f] used in [Scheme 7] of Synthesis Example 1 The compound represented by the formula (230) was obtained (yield 80%).

MS (MALDI-TOF): m / z 654.28 [M] ⁺

Anal. Calc. for C ₄₇ H ₃₄ N ₄ C, 86.21; H, 5.23; N, 8.56. Found C, 86.24; H, 5.22; N, 8.54.

Synthesis Example 12 Synthesis of Compound Represented by Chemical Formula 231

(1) Synthesis of Compound Represented by Formula 231-a

The compound represented by [Formula 231-a] was synthesized by the following [Scheme 70].

[Reaction Scheme 70]

[Formula 231-a]

Compound represented by [Formula 231-a] by synthesizing in the same manner as in [Scheme 65] to [Scheme 67] using 1-nitronaphthalene instead of 2-nitronaphthalene used in [Scheme 65] of Synthesis Example 11 (Yield 44%) was obtained.

(2) Synthesis of Compound Represented by [Formula 231-b]

The compound represented by [Formula 231-b] was synthesized by the following [Scheme 71].

[Reaction Scheme 71]

[Formula 71-c] [Formula 231-a] [Formula 231-b]

[Formula 71-c] obtained from [Scheme 24] instead of [Formula 15-d] used in [Scheme 6] of Synthesis Example 1, and [Formula 15] obtained from [Scheme 70] instead of [Formula 15-e] Except for using 231-a] to synthesize in the same manner to obtain [Formula 231-b] (yield 87%).

(3) Synthesis of Compound Represented by Formula 231

The compound represented by [Formula 231] was synthesized by the following [Scheme 72].

[Reaction Scheme 72]

[Formula 231-b] [Formula 231]

Synthesis by the same method as in [Scheme 7] to [Scheme 9] using [Chemical Formula 231-b] obtained from [Scheme 71] instead of [Chemical Formula 15-f] used in [Scheme 7] of Synthesis Example 1 The compound represented by the formula (231) was obtained (yield 65%).

MS (MALDI-TOF): m / z 654.28 [M] ⁺

Anal. Calc. for C ₄₇ H ₃₄ N ₄ C, 86.21; H, 5.23; N, 8.56. Found C, 86.23; H, 5.22; N, 8.55.

Synthesis Example 13 Synthesis of Compound Represented by Chemical Formula 232

(1) Synthesis of Compound Represented by [Formula 232-a]

The compound represented by [Formula 232-a] was synthesized by the following Reaction Scheme 73.

[Reaction Scheme 73]

[Formula 232-a]

Synthesis by the same method as in [Scheme 66] to [Scheme 67], except that 3-aminonaphthalene-2-carbonitrile was used instead of [Chemical Formula 230-a] used in [Scheme 66] of Synthesis Example 11 [ The compound represented by the formula (232-a] (yield 71%) was obtained.

(2) Synthesis of Compound Represented by [Formula 232-b]

The compound represented by [Formula 232-b] was synthesized by the following [Scheme 74].

[Reaction Scheme 74]

[Formula 232-a] [Formula 232-b]

Instead of [Chemical Formula 15-a] used in [Scheme 2] of Synthesis Example 1, [Chemical Formula 232-a] obtained from [Scheme 73], 4-bromophenylboronic acid instead of 2-bromophenylboronic acid A compound (yield 75%) represented by [Formula 232-b] was obtained in the same manner except for using.

(3) Synthesis of Compound Represented by Formula 232

The compound represented by [Formula 232] was synthesized by the following [Scheme 75].

[Reaction Scheme 75]

[Formula 99-c] [Formula 232-b] [Formula 232]

[Chemical Formula 99-c] obtained from [Scheme 31] instead of [Chemical Formula 15-d] used in [Scheme 6] of Synthesis Example 1, and [Chemical Formula 15] instead of [Chemical Formula 15-e] 232-b] was synthesized in the same manner to obtain a compound (yield 72%) represented by [Formula 232].

MS (MALDI-TOF): m / z 730.31 [M] ⁺

Anal. Calc. for C ₅₃ H ₃₈ N ₄ C, 87.09; H, 5. 24; N, 7.67. Found C, 87.12; H, 5.22; N, 7.66.

Synthesis Example 14 Synthesis of Compound Represented by Formula 233

(1) Synthesis of Compound Represented by [Formula 233-a]

The compound represented by [Formula 233-a] was synthesized by the following [Scheme 76].

[Reaction Scheme 76]

[Formula 233-a]

Synthesis by the same method as in [Scheme 65] to [Scheme 67] using 9-nitrophenanthrene instead of 2-nitronaphthalene used in [Scheme 65] of Synthesis Example 11 is represented by [Formula 233-a] Compound (yield 56%) was obtained.

(2) Synthesis of Compound Represented by [Formula 233-b]

The compound represented by [Formula 233-b] was synthesized by the following [Scheme 77].

[Reaction Scheme 77]

[Formula 136-d] [Formula 233-a] [Formula 233-b]

[Chemical Formula 136-d] obtained from [Scheme 37] instead of [Chemical Formula 15-d] used in [Scheme 6] of Synthesis Example 1, and [Chemical Formula 76] obtained from [Scheme 76] instead of [Chemical Formula 15-e] Except that 233-a] was synthesized in the same manner to obtain [Formula 233-b] (yield 86%).

(3) Synthesis of Compound Represented by Formula 233

The compound represented by [Formula 233] was synthesized by the following [Scheme 78].

[Reaction Scheme 78]

[Formula 233-b] [Formula 233]

Instead of [Chemical Formula 15-f] used in [Scheme 7] of Synthesis Example 1 by using [Chemical Formula 233-b] obtained from [Scheme 77] by the same method as in [Scheme 7] to [Scheme 9] The compound represented by the formula (233) was obtained (yield 77%).

MS (MALDI-TOF): m / z 704.29 [M] ⁺

Anal. Calc. for C ₅₁ H ₃₆ N ₄ C, 86.90; H, 5. 15; N, 7.95. Found C, 86.92; H, 5.14; N, 7.94.

Examples 1 to 20 Fabrication of Organic Light Emitting Diode

The ITO glass was patterned to have a light emitting area of 2 mm x 2 mm and then cleaned. After mounting the substrate in a vacuum chamber, the base pressure is 1 × 10 ^-6 torr and the organic material is placed on the ITO DNTPD (700 kPa), NPD (300 kPa), the compound + Ir (ppy) ₃ (prepared by the present invention) 10%) (300 mW), Alq ₃ (350 mW), LiF (5 mW), and Al (1,000 mW) were formed in this order and measured at 0.4 mA.

[DNTPD]

[NPD]

[Ir (ppy) ₃ ]

[Alq ₃ ]

&Lt; Comparative Example 1 &

The organic light emitting diode device for the comparative example was manufactured in the same manner except for using CBP instead of the compound prepared by the present invention as a host material in the device structure of the above embodiment.

[CBP]

division Host Dopant Doping concentration (%) V Cd / ㎡ CIEx CIEy T ₉₇ (Hr) Example 1 Formula 15 Ir (ppy) ₃ 10 4.31 5148 0.293 0.623 191 Example 2 20 Ir (ppy) ₃ 10 4.30 5320 0.299 0.623 183 Example 3 27 Ir (ppy) ₃ 10 4.21 5123 0.289 0.625 174 Example 4 Formula 71 Ir (ppy) ₃ 10 4.22 4910 0.300 0.622 196 Example 5 Formula 99 Ir (ppy) ₃ 10 4.27 5010 0.298 0.631 193 Example 6 Formula 136 Ir (ppy) ₃ 10 4.21 5110 0.291 0.625 182 Example 7 Formula 141 Ir (ppy) ₃ 10 4.27 5312 0.289 0.621 181 Example 8 Formula 145 Ir (ppy) ₃ 10 4.31 5210 0.301 0.631 180 Example 9 Formula 168 Ir (ppy) ₃ 10 4.20 4540 0.296 0.621 182 Example 10 Formula 183 Ir (ppy) ₃ 10 4.17 4790 0.294 0.625 165 Example 11 20 Ir (ppy) ₃ 10 4.30 5320 0.299 0.623 183 Example 12 Formula 29 Ir (ppy) ₃ 10 4.20 4976 0.289 0.631 176 Example 13 Formula 45 Ir (ppy) ₃ 10 4.18 4540 0.292 0.620 181 Example 14 Formula 76 Ir (ppy) ₃ 10 4.31 4930 0.298 0.626 196 Example 15 Formula 108 Ir (ppy) ₃ 10 4.26 4390 0.302 0.628 125 Example 16 Formula 127 Ir (ppy) ₃ 10 4.31 4942 0.289 0.625 147 Example 17 Formula 156 Ir (ppy) ₃ 10 4.38 4830 0.291 0.630 193 Example 18 Formula 161 Ir (ppy) ₃ 10 4.22 4720 0.296 0.627 190 Example 19 Formula 195 Ir (ppy) ₃ 10 4.32 5010 0.287 0.630 191 Example 20 Formula 227 Ir (ppy) ₃ 10 4.35 4993 0.296 0.632 187 Comparative Example 1 CBP Ir (ppy) ₃ 10 7.93 3801 0.297 0.624 68

Examples 21 to 24 Fabrication of Organic Light Emitting Diode

In the organic light emitting diode device of Examples 21 to 24, [Compound 230] to [Compound 233] were used as the light emitting layer in the device structure of Examples 1 to 20, and [(piq) ₂ instead of [Ir (ppy) ₃ ]. Except that the Ir (acac)] was produced in the same manner, the structure of [(pic) ₂ Ir (acac)] is as follows.

[(pic) ₂ Ir (acac)]

Comparative Example 2

The organic light emitting diode device for Comparative Example 2 was manufactured in the same manner as in Comparative Example 1 except for using [(piq) ₂ Ir (acac)] instead of [Ir (ppy) ₃ ] for the light emitting layer in the device structure of Comparative Example 1. It was.

division Host Dopant Doping concentration (%) V Cd / ㎡ CIEx CIEy T ₉₇ (Hr) Example 21 Formula 230 [(pic) ₂ Ir (acac)] 10 4.21 4889 0.670 0.328 186 Example 22 Formula 231 [(pic) ₂ Ir (acac)] 10 4.23 4692 0.671 0.328 178 Example 23 Formula 232 [(pic) ₂ Ir (acac)] 10 4.18 4986 0.669 0.329 169 Example 24 Formula 233 [(pic) ₂ Ir (acac)] 10 4.20 4793 0.670 0.328 174 Comparative Example 2 CBP [(pic) ₂ Ir (acac)] 10 7.91 3655 0.667 0.324 50

As shown in [Table 1] and [Table 2], the organic electroluminescent device comprising a heterocyclic compound prepared according to Examples 1 to 24 of the present invention as a host material is Comparative Example 1 and the host material is CBP and Compared with Comparative Example 2, the driving voltage (V) is lower, and excellent luminous efficiency (Cd / m 2) and long life (T ₉₇ ) are shown, which makes it useful for display devices, display devices, and lighting. have.

Claims (12)

A heterocyclic compound represented by the following [Formula 1]:
[Chemical Formula 1]

In [Formula 1],
Y ₁ to Y ₈ are each independently CR ₇ To CR ₁₄ , and two adjacent Y of Y ₁ to Y ₈ combine with Q to form a condensed ring,
R ₁ to R ₁₄ are the same as or different from each other, and each independently hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 40 carbon atoms, a substituted or unsubstituted carbon number 2 to 30 heteroaryl groups, halogen atoms, hydroxyl groups, cyano groups, nitro groups, amidino groups, hydrazines, hydrazones, carboxyl groups or salts thereof, sulfonic acid groups or salts thereof, phosphoric acid or salts thereof, substituted or unsubstituted Alkenyl group having 2 to 60 carbon atoms, substituted or unsubstituted alkynyl group having 2 to 60 carbon atoms, substituted or unsubstituted alkoxy group having 1 to 60 carbon atoms, substituted or unsubstituted cycloalkyl group having 3 to 60 carbon atoms, substituted or unsubstituted A substituted aryloxy group having 5 to 60 carbon atoms, a substituted or unsubstituted arylthio group having 5 to 60 carbon atoms, a substituted or unsubstituted alkylamine group having 1 to 30 carbon atoms, substituted or unsubstituted carbon Can be selected from a 5 to 60 arylamine group, a substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms of the ring group and a substituted or unsubstituted arylsilyl group consisting of a ring having 5 to 60,
L ₁ and L ₂ are a single bond or a substituted or unsubstituted alkylene group having 1 to 30 carbon atoms, a substituted or unsubstituted carbon atom having 2 to 30 carbon atoms Alkenylene group, substituted or unsubstituted C2-C30 alkynylene group, substituted or unsubstituted C3-C30 A cycloalkylene group, a substituted or unsubstituted arylene group having 5 to 50 carbon atoms, and a substituted or unsubstituted heteroarylene group having 2 to 50 carbon atoms,
n and m are integers between 0 and 3, and when n and m are 2 or more, a plurality of L ₁ and L ₂ are each independently the same or different,
The R ₁ to R ₁₄ , L ₁ , L ₂ and their substituents may be bonded to each other or adjacent substituents to form a saturated or unsaturated ring or attached or fused together by a pendant method. The method of claim 1,
The R ₁ To R ₁₄ , L ₁ and L ₂ are each independently a deuterium atom, a cyano group, a halogen atom, a hydroxy group, a nitro group, an alkyl group having 1 to 40 carbon atoms, a cycloalkyl group having 3 to 40 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, An alkynyl group having 2 to 40 carbon atoms, an alkoxy group having 1 to 40 carbon atoms, an alkylamino group having 1 to 40 carbon atoms, an arylamino group having 6 to 40 carbon atoms, a heteroarylamino group having 3 to 40 carbon atoms, an alkylsilyl group having 1 to 40 carbon atoms, At least one selected from the group consisting of an arylsilyl group having 6 to 40 carbon atoms, an aryl group having 6 to 40 carbon atoms, an aryloxy group having 3 to 40 carbon atoms, a heteroaryl group having 3 to 40 carbon atoms, a germanium group, phosphorus and boron Substituted with
Wherein said substituents are bonded to each other to form a saturated or unsaturated ring or attached or fused together by a pendant method. The method of claim 1,
[Formula 1] is a heterocyclic compound, characterized in that any one selected from the group represented by the following [Formula 2] to [Formula 13]:

[Chemical Formula 2] &lt; EMI ID =

[Chemical Formula 7] [Chemical Formula 8] [Chemical Formula 9]

[Chemical Formula 11] [Chemical Formula 12] [Chemical Formula 13]
In [Formula 2] to [Formula 13], R ₁ to R ₆ , L ₁ and L ₂ , n and m are the same as the definition in [Formula 1]. The method of claim 1,
Wherein L ₁ and L ₂ is a single bond or when n and m is 1, heterocyclic compound, characterized in that any one selected from the following [formula A1] to [formula A8]:
[Structural formula A1] [Structural formula A2] [Structural formula A3] [Structural formula A4]

[Structural formula A5] [Structural formula A6] [Structural formula A7] [Structural formula A8]

In the above Structural Formula A1 to Structural Formula A8, hydrogen or deuterium may be bonded to the carbon of the aromatic ring in each structural formula. The method of claim 1,
When n and m is 2, L ₁ and L ₂ is a heterocyclic compound, characterized in that any one selected from the following [formula B]:
[Formula B]

In the above structural formula B, hydrogen or deuterium may be bonded to the carbon of the aromatic ring in each structural formula, and when it is a substituent other than hydrogen, the aromatic ring may be bonded to adjacent substituents to form a saturated or unsaturated ring. The method of claim 1,
R ₁ to R ₁₀ are each independently a heterocyclic compound, characterized in that any one selected from [formula 1] to [formula 6]:
[Structural formula 1] [Structural formula 2] [Structural formula 3]

[Structural formula 4] [Structural formula 5] [Structural formula 6]

In the above Structural Formulas 1 to 6,
T ₁ to T ₈ are the same or different and each independently selected from C (R ₄₁ ), C (R ₄₂ ) (R ₄₃ ), N, N (R ₄₄ )
R ₃₁ to R ₄₄ are the same as or different from each other, and each independently hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted group An aryl group having 5 to 30 carbon atoms and a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms having O, NS, and P as hetero atoms, R ₃₁ to R _44; One of them may form a single bond by combining with nitrogen and carbon atoms of [Formula 1]. The method of claim 1,
[Formula 1] is a heterocyclic compound, characterized in that any one selected from the group represented by the following [Formula 14] to [Formula 237]:

[233] [232] [233]

[237] [237] [237] A first electrode; A second electrode; And at least one organic layer interposed between the first electrode and the second electrode.
The organic layer is an organic electroluminescent device, characterized in that it comprises one or more heterocyclic compounds represented by [Formula 1] according to claim 1. 9. The method of claim 8,
And the organic layer includes at least one layer selected from a hole injection layer, a hole transport layer, a functional layer having a hole injection function and a hole transport function, a light emitting layer, an electron transport layer, and an electron injection layer. 9. The method of claim 8,
The organic light emitting device according to claim 1, wherein the organic layer interposed between the first electrode and the second electrode includes a light emitting layer. 9. The method of claim 8,
The emission layer is composed of a host compound and a dopant compound, the heterocyclic compound of [Formula 1] is used as a host,
The light emitting layer is an organic light emitting device, characterized in that it further comprises one or more dopant compounds. 9. The method of claim 8,
Wherein the organic electroluminescent device is used in a display device, a display device, or a device for monochromatic or white illumination.

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