KR102107018B1 - Heterocyclic compounds and organic light-emitting diode including the same - Google Patents

Abstract

The present invention relates to a novel heterocyclic compound and an organic electroluminescent device comprising the same as a luminescent material. Specifically, the heterocyclic compound represented by the following [Chemical Formula 1] and the organic electroluminescent device comprising the same are driven voltage, luminous efficiency It has an excellent effect in light emission characteristics.
[Formula 1]

Description

Heterocyclic compounds and organic light-emitting diode including the same}

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

Recently, the organic light emitting device capable of driving a low voltage as a self-emission type has excellent viewing angle, contrast ratio, and no backlight, and is lightweight and thin, and consumes, compared to a liquid crystal display (LCD), which is a mainstream of flat panel display devices. In terms of power, it is also attracting attention as a next-generation display device because it is advantageous and has a wide color reproduction range.

Organic light emitting diodes (OLEDs) are devices that emit light while extinguishing after pairing electrons and holes when a charge is injected into an organic light emitting layer formed between an electron injection electrode (cathode) and a hole injection electrode (anode) to be.

An organic light emitting device using an organic light emitting phenomenon usually has a structure including an anode and a cathode and an organic material layer therebetween. Here, in order to increase the efficiency and stability of the organic light emitting device, the organic material layer is often composed of a multi-layered structure composed of different materials, for example, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, etc. . When a voltage is applied between two electrodes in the structure of the organic electroluminescent device, holes are injected at the anode and electrons are injected at the cathode, and excitons are formed when the injected holes meet the electrons. When it falls to the ground again, it glows.

The organic electroluminescent device can not only form the device on a flexible transparent substrate such as plastic, but also at a voltage lower than 10 V compared to a plasma display panel or an inorganic electroluminescent (EL) display. It has the advantages of being capable of driving, relatively low power consumption, and excellent color. In addition, the organic light emitting device can display three colors of green, blue, and red, and is a target of much attention by many people as a next-generation rich color display device.

In order for the organic light emitting device to sufficiently exhibit the above-described excellent characteristics, materials constituting an organic material layer in the device, such as a hole injection material, a hole transport material, a light emitting material, an electron transport material, an electron injection material, are supported by stable and efficient materials. It should be preceded, but the development of a stable and efficient organic material layer material for an organic light emitting device has not been sufficiently made. Therefore, the development of new materials continues to be required.

The problem to be solved by the present invention is to provide a novel release ring compound having a lower driving voltage and superior luminous efficiency than a compound used in a conventional phosphorescent material and an organic electroluminescent device comprising the same.

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

[Formula 1]

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

The specific substituent of the above [Formula 1] will be described later.

The heterocyclic compound according to the present invention is more stable than conventional phosphorescent materials, and has excellent light emission characteristics in driving voltage or current efficiency, so that the organic light emitting device including the same is capable of low voltage driving and improves light emission efficiency. I can do it.

1 is a schematic diagram of an organic light emitting device according to an embodiment of the present invention.

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

The organic light emitting compound according to the present invention is a light emitting layer host material having improved light emission characteristics such as driving voltage and current efficiency of an organic light emitting device, and is characterized by being a heterocyclic compound represented by the following [Formula 1].

[Formula 1]

In the above [Formula 1],

Y ₁ to Y ₈ are each independently CR ₄ To CR ₁₁ .

L ₁ is a substituted or unsubstituted alkylene group having 1 to 30 carbon atoms, a substituted or unsubstituted 2 to 30 carbon atom; Alkenylene group, a substituted or unsubstituted alkynylene group having 2 to 30 carbon atoms, a substituted or unsubstituted 3 to 30 carbon atoms Cycloalkylene group, a substituted or unsubstituted heterocycloalkylene group having 2 to 60 carbon atoms, a substituted or unsubstituted arylene group having 5 to 50 carbon atoms, a substituted or unsubstituted heteroarylene group having 2 to 50 carbon atoms . Further, n is an integer from 0 to 3, and when n is 2, a plurality of L _{1 s} may be the same or different.

R ₁ to R ₁₁ 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 5 to 40 carbon atoms, a substituted or unsubstituted carbon number 2 to 30 alkenyl groups, substituted or unsubstituted alkynyl groups having 2 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3 to 30 carbon atoms, substituted or unsubstituted cycloalkenyl groups having 5 to 30 carbon atoms, substituted or unsubstituted A heteroaryl group having 2 to 40 carbon atoms having O, N, S or P as a substituted and heteroatom, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, substituted Or an unsubstituted alkylthio group having 1 to 30 carbon atoms, a substituted or unsubstituted arylthiooxy group having 5 to 30 carbon atoms, a substituted or unsubstituted alkylamine group having 1 to 30 carbon atoms, substituted or unsubstituted Among 5 to 30 arylamine groups, substituted or unsubstituted alkylsilyl groups having 1 to 30 carbon atoms, substituted or unsubstituted arylsilyl groups having 5 to 30 carbon atoms, cyano groups, hydroxyl groups, nitro groups and halogen groups It is one that is chosen.

In addition, the Y ₁ to Y ₈ At least one of them is a substituent represented by the following [Structural Formula A].

[Structural Formula A]

In the above [Structural Formula A],

* Means a site that binds to Y ₁ to Y ₈ in [Formula 1].

L ₂ is a substituted or unsubstituted alkylene group having 1 to 30 carbon atoms, a substituted or unsubstituted 2 to 30 carbon atom; Alkenylene group, a substituted or unsubstituted alkynylene group having 2 to 30 carbon atoms, a substituted or unsubstituted 3 to 30 carbon atoms Cycloalkylene group, substituted or unsubstituted heterocycloalkylene group having 2 to 60 carbon atoms, substituted or unsubstituted arylene group having 5 to 50 carbon atoms, substituted or unsubstituted heteroarylene group having 2 to 50 carbon atoms . In addition, m is an integer of 0 to 3, and when m is 2, a plurality of L ₂ may be the same or different, respectively.

R ₁₂ and R ₁₃ are the same 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 5 to 40 carbon atoms, a substituted or unsubstituted carbon number 2 to 30 alkenyl groups, substituted or unsubstituted alkynyl groups having 2 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3 to 30 carbon atoms, substituted or unsubstituted cycloalkenyl groups having 5 to 30 carbon atoms, substituted or unsubstituted A heteroaryl group having 2 to 40 carbon atoms having O, N, S or P as a substituted and heteroatom, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, substituted Or an unsubstituted alkylthio group having 1 to 30 carbon atoms, a substituted or unsubstituted arylthiooxy group having 5 to 30 carbon atoms, a substituted or unsubstituted alkylamine group having 1 to 30 carbon atoms, a substituted or unsubstituted carbon Among arylamine groups of 5 to 30, substituted or unsubstituted alkylsilyl groups of 1 to 30 carbon atoms, substituted or unsubstituted arylsilyl groups of 5 to 30 carbon atoms, cyano groups, hydroxyl groups, nitro groups and halogen groups It is one that is chosen.

The R ₁ to R ₁₃ , 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 method.

According to an embodiment of the present invention, the R ₁ To R ₁₃ , 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, Alkynyl group having 2 to 40 carbon atoms, alkoxy group having 1 to 40 carbon atoms, alkylamino group having 1 to 40 carbon atoms, arylamino group having 6 to 40 carbon atoms, heteroarylamino group having 3 to 40 carbon atoms, alkylsilyl group having 1 to 40 carbon atoms, At least one member 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 with.

In the present invention, the term "substituted" means substituted with one or more of the above substituents.

In addition, the range of the carbon number of the alkyl group or the aryl group in the above "substituted or unsubstituted alkyl group having 1 to 30 carbon atoms", "substituted or unsubstituted aryl group having 5 to 40 carbon atoms", etc., considers the part in which the substituent is substituted. It does not mean the total number of carbon atoms constituting the alkyl portion or the aryl portion when viewed as unsubstituted. For example, the phenyl group substituted with a butyl group in the para position means that it corresponds to an 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 [Chemical Formula 1] is not limited by the following specific examples, but more specifically, any one of compounds represented by [Chemical Formula 2] to [Chemical Formula 7] Can be

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

[Formula 6] [Formula 7]

In [Formula 2] to [Formula 7], Y ₁ to Y ₈ , R ₁ , L ₁ , L ₂ and n are the same as defined in [Formula 1].

Further, according to a preferred embodiment of the present invention, when n and m are each 1, L ₁ and L ₂ may be a single bond or any one selected from [Structural Formula A1] to [Structural Formula A8], respectively. have.

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

In addition, when n and m are 2, respectively, L ₁ and L ₂ may be any one selected from the following [Structural Formula B].

[Structural Formula B]

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

According to a preferred embodiment of the present invention, in [Structural Formula A], the R ₁₂ and R ₁₃ may each independently be any one selected from [Substituent C1] to [Substituent C46].

[Substituent C1] [Substituent C2] [Substituent C3]

[Substitution C4] [Substitution C5] [Substitution C6]

[Substituent C7] [Substituent C8] [Substituent C9]

[Substitution C10] [Substitution C11] [Substitution C12]

[Substitution C13] [Substitution C14] [Substitution C15]

[Substitution C16] [Substitution C17] [Substitution C18]

[Substituent C19] [Substituent C20] [Substituent C21]

[Substitution C22] [Substitution C23] [Substitution C24]

[Substitution C25] [Substitution C26] [Substitution C27]

[Substitution C28] [Substitution C29] [Substitution C30]

[Substitution C31] [Substitution C32] [Substitution C33]

[Substitution C34] [Substitution C35] [Substitution C36]

[Substitution C37] [Substitution C38] [Substitution C39]

[Substitution C40] [Substitution C41] [Substitution C42]

[Substitution C43] [Substitution C44] [Substitution C45]

[Substituent C46]

In the above [Substituents C1] to [Substituent C46],

R is hydrogen, deuterium, cyano group, halogen group, alkyl group having 1 to 6 carbon atoms, aryl group having 6 to 18 carbon atoms, arylalkyl group having 6 to 18 carbon atoms, heteroaryl group having 3 to 18 carbon atoms, alkyl having 1 to 12 carbon atoms A silyl group, an arylsilyl group having 6 to 18 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 6 carbon atoms, and a substituted or unsubstituted aryloxy group having 6 to 18 carbon atoms.

In addition, n is an integer of 0 to 12, and when n is 2 or more, a plurality of Rs are the same or different from each other, and may be fused to adjacent substituents to form a ring.

On the other hand, the aryl group included in the organic light emitting compound according to the present invention is an organic radical derived from an aromatic hydrocarbon by removal of one hydrogen, and a single or fused ring system comprising 5 to 7 members, preferably 5 or 6 members. In addition, if there is a substituent in the aryl group, the adjacent substituents may be fused with each other to form a ring.

Specific examples of such aryl are 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, pyrene And aromatic groups such as nil group, indenyl, fluorenyl group, tetrahydronaphthyl group, pyrenyl, peryleneyl, chrysenyl, naphthacenyl, fluoranthenyl, and the like.

In addition, at least one hydrogen atom among the aryl groups is a deuterium atom, a halogen atom, a hydroxyl group, a nitro group, a cyano group, a silyl group, an amino group (-NH ₂ , -NH (R), -N (R ') (R ") , R 'and R "are each independently 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, halogenated alkyl group having 1 to 24 carbon atoms, alkenyl group having 1 to 24 carbon atoms, alkynyl group having 1 to 24 carbon atoms, heteroalkyl group having 1 to 24 carbon atoms, aryl group having 6 to 24 carbon atoms, arylalkyl group having 6 to 24 carbon atoms , It may be substituted with a heteroaryl group having 2 to 24 carbon atoms or a heteroaryl alkyl 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 [Structural Formula 1] to [Structural Formula 6].

[Structural Formula 1] [Structural Formula 2] [Structural Formula 3]

[Structural Formula 4] [Structural Formula 5] [Structural Formula 6]

In the above [Structural Formula 1] to [Structural Formula 6],

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

In addition, [Structural Formula 3] may include a compound represented by the following [Structural Formula 3-1] by a resonance structure according to the movement of electrons.

[Structural Formula 3-1]

In [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 Formula 1] to [Structural Formula 6] may be selected from the following [Structural Formula 7].

[Structural Formula 7]

In the above [Formula 7],

X is hydrogen, deuterium, substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, substituted or unsubstituted aryl group having 5 to 30 carbon atoms, substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, substituted or unsubstituted carbon number 2 to 20 alkynyl groups, substituted or unsubstituted cycloalkyl groups having 3 to 30 carbon atoms, substituted or unsubstituted cycloalkenyl groups having 5 to 30 carbon atoms, substituted or unsubstituted alkoxy groups having 1 to 30 carbon atoms, substituted or unsubstituted Substituted aryloxy group having 6 to 30 carbon atoms, substituted or unsubstituted alkylthioxy group having 1 to 30 carbon atoms, substituted or unsubstituted arylthiooxy group having 5 to 30 carbon atoms, substituted or unsubstituted alkyl having 1 to 30 carbon atoms Amine group, substituted or unsubstituted aryl group having 5 to 5 carbon atoms, substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms having O, N, S or P, cyano group, nitro group, halogen group It is one which is selected from the group consisting of.

m is an integer of 1 to 11, and when m is 2 or more, a plurality of Xs are the same or different from each other, and any one of the one or more Xs may form a single bond with a substituent or nitrogen in [Chemical Formula 1].

Specific examples of the alkyl group which is a substituent used in the present invention are methyl group, ethyl group, propyl group, isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, iso-amyl group, hexyl group, heptyl group , Octyl group, stearyl group, trichloromethyl group, trifluoromethyl group, and the like, and one or more hydrogen atoms of the alkyl group include deuterium atom, halogen atom, hydroxy group, nitro group, cyano group, trifluoromethyl group, and silyl group. (In this case referred to as “alkylsilyl group”), a substituted or unsubstituted amino group (-NH ₂ , -NH (R), -N (R ') (R "), wherein R, R' and R" are each Independently an alkyl group having 1 to 24 carbon atoms (in this case, referred to as an "alkylamino group"), amidino group, hydrazine group, hydrazone group, carboxyl group, sulfonic acid group, phosphoric acid group, alkyl group having 1 to 24 carbon atoms, carbon group having 1 to 24 carbon atoms Halogenated alkyl group, alkenyl group having 2 to 24 carbon atoms, alky having 2 to 24 carbon atoms It may be substituted with a nil group, a heteroalkyl 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, etc. And a substituent similar to that of the 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), and bromine (Br).

The aryloxy group used in the present invention refers to the -O- aryl radical, wherein the aryl group is as defined above, and specific examples include phenoxy, naphthoxy, anthracenyloxy, phenanthrenyloxy, fluorenyloxy, Indenyloxy and the like, and one or more hydrogen atoms contained in the aryloxy group can be further substituted.

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

Specific examples of the alkenyl group used in the present invention represent a straight-chain or branched alkenyl group, 3-pentenyl group, 4-hexenyl group, 5-heptenyl group, 4-methyl-3-pentenyl group, 2,4 -Dimethyl-pentenyl group, 6-methyl-5-heptenyl group, 2,6-dimethyl-5-heptenyl group, etc. are mentioned.

The present invention is not limited by the specific example of the heterocyclic compound according to [Formula 1] having the structure as described above, but specifically, any one of the compounds represented by the following [Formula 8] to [Formula 423] Can be

[Formula 416] [Formula 417] [Formula 418] [Formula 419]

[Formula 420] [Formula 421] [Formula 422] [Formula 423]

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 is the [Formula 1] in the present invention It may include at least one heterocyclic compound represented by.

In addition, the organic layer containing the organic light emitting compound of the present invention may include at least one of a hole injection layer, a hole transport layer, a functional layer having a hole injection function and a hole transport function simultaneously, a light emitting layer, an electron transport layer, and an electron injection layer have. At this time, the organic layer interposed between the first electrode and the second electrode may include a light emitting layer, the light emitting layer is made of a host and a dopant, and the organic light emitting compound of the present invention can be used as a host.

Meanwhile, in the present invention, a dopant material may be used together with the host in 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 electroluminescent 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 device of the present invention. The organic light emitting device according to the present invention includes an anode 20, a hole transport layer 40, an organic light emitting layer 50, an electron transport layer 60 and a cathode 80, and a hole injection layer 30, if necessary The electron injection layer 70 may be further included, and in addition, an intermediate layer of one or two layers may be further formed, and 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. 1 as follows.

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

A hole injection layer 30 is formed by vacuum-evaporating or spin-coating a hole injection layer material on the anode 20 electrode. Next, a hole transport layer 40 is formed by vacuum thermal evaporation or spin coating of a hole transport layer material on the hole injection layer 30.

The hole injection layer material can be used without particular limitation as long as it is commonly used in the art, for example, 2-TNATA [4,4 ', 4 "-tris (2-naphthylphenyl-phenylamino) -triphenylamine] , NPD [N, N'-di (1-naphthyl) -N, N'-diphenylbenzidine)], TPD [N, N'-diphenyl-N, N'-bis (3-methylphenyl) -1,1'- biphenyl-4,4'-diamine], DNTPD [N, N'-diphenyl-N, N'-bis- [4- (phenyl-m-tolyl-amino) -phenyl] -biphenyl-4,4'-diamine ] Etc. can be used.

In addition, it is not particularly limited as long as it is a material commonly used in the art as the material for the hole transport layer, for example, N, N'-bis (3-methylphenyl) -N, N'-diphenyl- [1, 1-biphenyl] -4,4'-diamine (TPD) or N, N'-di (naphthalen-1-yl) -N, N'-diphenylbenzidine (α-NPD) or the like can be used.

Subsequently, an organic light emitting layer 50 is stacked on the hole transport layer 40 and a hole blocking layer (not shown) is selectively deposited on the organic light emitting layer 50 to form a thin film as a vacuum deposition method or a spin coating method. can do. The hole blocking layer serves to prevent such a problem by using a material having a very low level of HOMO (Highest Occupied Molecular Orbital) because the life and efficiency of the device is reduced when holes pass through the organic light emitting layer and enter the cathode. . In this case, the hole blocking material used is not particularly limited, but has an electron transporting ability and has a higher ionization potential than the light emitting compound, and typically BAlq, BCP, TPBI, etc. can be used.

As the material used for the hole blocking layer, any one selected from BAlq, BCP, Bphen, TPBI, NTAZ, BeBq ₂ , OXD-7, Liq and [Formula 101] to [Formula 107] may be used, but is not limited thereto. It does not work.

BAlq BCP Bphen

TPBI NTAZ BeBq ₂

OXD-7 Liq

Formula 101 Formula 102 Formula 103

Formula 104 Formula 105 Formula 106

Formula 107

After the electron transport layer 60 is deposited through the hole blocking layer through a vacuum deposition method or a spin coating method, an electron injection layer 70 is formed and a metal for forming a cathode is vacuum-heated on the electron injection layer 70. The organic EL device is completed by depositing to form the cathode 80 electrode. Here, the cathode forming metals include lithium (Li), magnesium (Mg), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), and 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 transport layer material, a known electron transport material may be used as a function of stably transporting electrons injected from the electron injection electrode (Cathode). Examples of known electron transport materials include quinoline derivatives, in particular tris (8-quinolinorate) aluminum (Alq3), TAZ, Balq, beryllium bis (benzoquinolin-10-noate) (beryllium bis (benzoquinolin-10- It is also possible to use materials such as olate: Bebq2), ADN, [Compound 201], [Compound 202], oxadiazole derivatives PBD, BMD, BND and the like.

TAZ BAlq

[Compound 201] [Compound 202] BCP

Further, in the electron transport layer used in the present invention, the organometallic compound represented by the following [Chemical Formula C] may be used alone or in combination with the electron transport layer material.

[Chemical Formula C]

In the above [Formula C],

Y is a portion selected from C, N, O, and S directly bonded to M to form a single bond, and a portion selected from C, N, O, and S forming a coordination bond to M. And a ligand chelated by the single bond and coordination bond.

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

OA is a monovalent ligand capable of single bond or coordination with the M, wherein O is oxygen, and 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 alkenyl group having 2 to 30 carbon atoms, substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, substituted or unsubstituted cycloalkyl having 5 to 30 carbon atoms It is any one selected from an alkenyl group and a substituted or unsubstituted heteroaryl group having 2 to 50 carbon atoms having O, N or S as a hetero atom.

Further, 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, n = 0, and when M is boron or aluminum, m = 1 to 3, n is any one of 0 to 2, and m + n = 3 is satisfied.

The 'substituted' in the 'substituted or unsubstituted' is deuterium, cyano group, halogen group, hydroxy group, nitro group, alkyl group, alkoxy group, alkylamino group, arylamino group, hetero arylamino group, alkylsilyl group, arylsilyl group, It means substituted with one or more substituents selected from the group consisting of aryloxy group, aryl group, heteroaryl group, germanium, phosphorus and boron.

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

[Structural Formula C1] [Structural Formula C2] [Structural Formula C3]

[Structural C4] [Structural C5] [Structural C6]

[Structural C7] [Structural C8] [Structural C9] [Structural C10]

[Structural C11] [Structural C12] [Structural C13]

[Structural C14] [Structural C15] [Structural C16]

[Structural C17] [Structural C18] [Structural C19] [Structural C20]

[Structural C21] [Structural C22] [Structural C23]

[Structural C24] [Structural C25] [Structural C26]

[Structural C27] [Structural C28] [Structural C29] [Structural C30]

[Structural C31] [Structural C32] [Structural C33]

[Structural C34] [Structural C35] [Structural C36]

[Structural Formula C37] [Structural Formula C38] [Structural Formula C39]

In the above [Structural Formula C1] to [Structural Formula C39],

R is the same or different from each other, and each independently hydrogen, deuterium, halogen, cyano group, substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, substituted or unsubstituted aryl group having 6 to 30 carbon atoms, substituted or unsubstituted Heteroaryl group having 3 to 30 carbon atoms, substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, substituted or Unsubstituted alkylamino group having 1 to 30 carbon atoms, substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, and substituted or unsubstituted arylsilyl having 6 to 30 carbon atoms. It is selected from groups, and may be connected to an adjacent substituent by alkylene or alkenylene to form a spiro ring or fused ring.

L is 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 5 to 30 carbon atoms Heteroaryl group and 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, 3 to 20 carbon atoms It is further substituted with one or more substituents selected from heteroaryl group, cyano group, halogen group, deuterium, and hydrogen, and may be connected to an adjacent substituent with alkylene or alkenylene to form a spiro ring or fused ring.

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

[General Formula A-1]

mL ₁ L ₂ L ₃

The 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. Further, the L ₁ , L ₂ and L ₃ are the same as or different from each other as a ligand, and each independently selected from the following [Structural D], but is not limited thereto.

In addition, * in the following structural formula D represents a site coordinated to the metal ion M.

[Structural Formula D]

In the above [Formula D],

R is different from each other or the same, and each independently hydrogen, deuterium, halogen, cyano group, substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, substituted or unsubstituted aryl group having 6 to 50 carbon atoms, substituted or unsubstituted Heteroaryl group having 5 to 50 carbon atoms, substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, substituted or Unsubstituted alkylamino group having 1 to 30 carbon atoms, substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, substituted or unsubstituted arylamino group having 6 to 30 carbon atoms and substituted or unsubstituted arylsilyl having 6 to 30 carbon atoms It may be any one selected from groups.

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

In addition, 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 fused ring.

As an example, the dopant represented by [General Formula A-1] may be any one selected from the following compounds.

[General Formula B-1]

In the above [General Formula B-1],

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

The exemplary structure of the compound represented by [General Formula B-1] is as follows, but is not limited thereto.

[General Formula C-1]

In the above [General Formula C-1],

M ^B1 represents the same metal ion as defined in [General Formula A-1], Y ^B11 , Y ^B14 , Y ^B15 and Y ^B18 each independently represent a carbon atom or a nitrogen atom, Y ^B12 , Y ^B13 , Y ^B16 And Y ^B17 each independently represents a substituted or unsubstituted carbon atom, a substituted or unsubstituted nitrogen atom, an oxygen atom, and a sulfur atom, and L ^B11 , L ^B12 , L ^B13 , and L ^B14 represent a linking group, and Q ^B11 , Q ^B12 represents a partial structure containing an atom that binds M ^B1 .

The exemplary structure of the compound represented by [General Formula C-1] is as follows, but is not limited thereto.

[General Formula D-1]

In the above [General Formula D-1],

M ^C1 represents a metal ion as defined in [General Formula A-1], and R ^C11 and R ^C12 are each independently a hydrogen atom, a substituent that connects to each other, and forms a five-membered ring, without any connection to each other. Represents a substituent, R ^C13 , R ^C14 each independently represents a hydrogen atom, a substituent that connects to each other to form a 5-membered ring, or a substituent that does not have anything to connect to each other, G ^C11 , G ^C12 each independently represents a nitrogen atom, a substitution Or represents an unsubstituted carbon atom, L ^C11 , L ^C12 represents a linking group, and Q ^C11 , Q ^C12 represents a partial structure containing an atom bound to M ^C1 .

The exemplary structure of the compound represented by [General Formula D-1] is as follows, but is not limited thereto.

[General Formula E-1]

In the above [General Formula E-1],

M ^D1 represents the same metal ion as defined in [General Formula A-1], and G ^D11 and G ^D12 each independently represent a nitrogen atom, a substituted or unsubstituted carbon atom, and J ^D11 , J ^D12 , J ^D13 and J ^D14 represents a group of atoms required to form a 5-membered ring on each independently, and L ^D11 and L ^D12 represent a linking group.

The exemplary structure of the compound represented by [General Formula E-1] is as follows, but is not limited thereto.

[General Formula F-1]

In the above [General Formula F-1],

M ^E1 represents the same metal ion as defined in [General Formula A-1], and J ^E11 and J ^E12 each independently represent a group of atoms necessary to form a 5-membered ring, G ^E11 , G ^E12 , G ^E13 and G ^E14 each independently represents 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.

The exemplary structure of the compound represented by [General Formula F-1] is as follows, but is not limited thereto.

[General formula G-1]

In the above [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, 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 rings formed by R ^F1 and R ^F12 , R ^F13 and R ^F14 are 5-membered rings. In addition, Q ^F11 and Q ^F12 represent partial structures containing atoms that bind to M ^F1 .

The exemplary structure of the compound represented by [General Formula G-1] is as follows, but 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 alkyl, aryl or heteroaryl substituents; In addition, it is possible to form a fused ring with a substituent 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 to 4, a plurality of R11 and R12 may be the same or different, respectively.

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

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

Moreover, it is preferable that n ¹ and m ¹ are such that the metal complex represented by the general formula H-1 is a neutral complex.

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

In the general formula H-3, R ³¹ , n ³ , m ³ , L ³ are respectively the same as R ¹¹ , n ¹ , m ¹ , L ^1, and q ³¹ represents an integer from 0 to 8, and 0 to 2 is preferable, and 0 is more preferable.

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

[Formula I-1]

In the above [General Formula I-1],

Ring A, Ring B, Ring C and Ring D represent a nitrogen-containing heterocycle in which any two rings of Rings A to D may have substituents, and the other two rings are aryl rings in which the rings may have substituents or A heteroaryl ring is represented and represented, and a condensed ring may be formed by ring A and ring B, ring A and ring C, and / or ring B and ring D. X ¹ , X ² , X ³ and X ⁴ represent a nitrogen atom in which two of them are coordinated to a platinum atom, and the other two represent a carbon atom or a nitrogen atom. Q ¹ , Q ² and Q ³ each independently represent a divalent atom (mono) or bond, but Q ¹ , Q ² and Q ³ do not simultaneously represent a bond. Z ¹ , Z ² , Z ³ and Z ⁴ , which 2 represents a coordination bond, and the other 2 represent a covalent bond, an oxygen atom or a sulfur atom.

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

[General formula J-1]

In the above [General 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 the M In, the nitrogen atom (N) each binds to the M, and as a whole forms a tridentate ligand bonded to the M at three loci.

In addition, in Ar1, C represents a carbon atom constituting the ring structure represented by Ar1. Further, R1 and R2 may be the same as or different from each other, and each represents a substituted or unsubstituted alkyl group or aryl group, and L represents a single-dentate ligand.

In the above [General Formula J-1], it is preferable that M is Pt. Moreover, as said Ar1, it is preferable to select from 5-membered ring, 6-membered ring, and these condensed ring groups.

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

In addition, the light emitting layer may further include various host and various dopant materials in addition to the dopant and host.

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 mixing a substance to be a solvent and forming a thin film through methods such as inkjet printing, roll-to-roll coating, screen printing, spray coating, dip coating, spin coating, and the like.

In addition, the organic light emitting device according to the present invention can be used in a device selected from a flat panel display device, a flexible display device, a monochrome or white flat lighting device, and a monochrome or white flexible lighting device.

Hereinafter, the present invention will be described in more detail with reference to preferred embodiments. However, these examples are intended to illustrate the present invention more specifically, it will be apparent to those skilled in the art that the scope of the present invention is not limited thereby.

<Example>

<Synthesis Example 1> Synthesis of the compound represented by [Formula 17]

(1) Synthesis of compound represented by [Formula 17-a]

The compound represented by [Formula 17-a] was synthesized by the following [Scheme 1].

[Scheme 1]

[Formula 17-a]

Tertiarybutyl 4-bromo-2-iodophenyl carbamate 50.0 g (126 mmol), 2-methoxycarbonylphenylboronic acid pinacol ester 27.8 g (138 mmol), potassium carbonate 52.1 in a 2 L round bottom flask at room temperature g (377 mmol), tetrakistriphenylphosphine palladium 2.90 g (2.51 mmol), tetrahydrofuran 500 mL, distilled water 250 mL was added and refluxed for 12 hours. Upon completion of the reaction, the reaction solution was cooled to room temperature, and then ethyl acetate and distilled water were added to separate the layers, and the organic layer was extracted, and then concentrated under reduced pressure and purified by silica gel column chromatography to yield 38.7 g of the compound represented by [Formula 17-a]. 95.2mmol, yield 75.8%).

(2) Synthesis of compound represented by [Formula 17-b]

The compound represented by [Formula 17-b] was synthesized by the following [Scheme 2].

[Scheme 2]

[Formula 17-a] [Formula 17-b]

To a 1L round bottom flask purged with nitrogen at room temperature, [Formula 17-a] 38.7 g (95.3 mmol) obtained from [Scheme 1], 400 mL of tetrahydrofuran was added, cooled to 0 ° C., and 111 mL of methyl magnesium bromide (333 mmol, 3.0 M in diethyl ether) was added dropwise, and the mixture was heated to 50 ° C. and stirred for 6 hours. When the reaction was completed, the reaction solution was cooled to 0 ° C, neutralized by adding saturated aqueous ammonium chloride solution, and then ethyl acetate and distilled water were added to separate the layers, and then the organic layer was concentrated under reduced pressure. The concentrated reaction product was purified by column chromatography to obtain 30.1 g of a compound represented by [Formula 17-b] (74.1 mmol, yield 77.8%).

(3) Synthesis of compound represented by [Formula 17-c]

The compound represented by [Formula 17-c] was synthesized by the following [Scheme 3].

[Scheme 3]

[Formula 17-b] [Formula 17-c]

30.1 g (74.1 mmol) of [Formula 17-b] obtained from [Scheme 2] and 60 mL of acetic acid were added to a 1 L round bottom flask at room temperature, followed by stirring for 12 hours. When 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 16.3 g of a compound represented by [Chemical Formula 17-c] (56.6 mmol, yield 76.4%).

(4) Synthesis of compound represented by [Formula 17-d]

The compound represented by [Formula 17-d] was synthesized by the following [Scheme 4].

[Reaction Scheme 4]

[Formula 17-d]

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, cooled to 0 ° C., stirred, and 316 mL of phenylmagnesium bromide (949 mmol, 3.0 M in diethyl ether) was added. It was added dropwise for an hour and then heated to room temperature and stirred for 12 hours. After the reaction was completed, the reaction solution was cooled to 0 ° C, and then saturated aqueous ammonium chloride solution was added to neutralize it, and ethyl acetate and distilled water were added to separate the layers. 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, yield 80.5%) of the compound represented by [Formula 17-d].

(5) Synthesis of compound represented by [Formula 17-e]

The compound represented by [Formula 17-e] was synthesized by the following [Scheme 5].

[Scheme 5]

[Formula 17-c] [Formula 17-d] [Formula 17-e]

16.3g (56.6mmol), sodium hydride (60%, dispersion in paraffin liquid) 3.39g (84.8mmol), N, N obtained from [Scheme 17-c] in a 2L round bottom flask purged with nitrogen at room temperature -240 mL of dimethylformamide was added, cooled to 0 ° C, and 23.1 g (84.8 mmol) of [Formula 17-d] obtained from [Scheme 4] was added and stirred for 1 hour. When the reaction is complete, the reaction solution is allowed to stir to room temperature and stirred for 1 hour, distilled water is added to the reaction solution, the resulting solid is filtered, and purified by silica gel column chromatography to represent the compound represented by [Formula 17-e] 23.2 g (42.0 mmol, yield 74.2%) was obtained.

(6) Synthesis of compound represented by [Formula 17]

The compound represented by [Formula 17] was synthesized by the following [Scheme 6].

[Scheme 6]

[Formula 17-e] [Formula 17]

5.00 g (9.63 mmol), diphenylamine 1.79 g (10.6 mmol), palladium acetate 0.216 g (0.963 mmol), tritertylbutylphosphate obtained from [Formula 17-e] in a 250 mL round bottom flask at room temperature Pin 0.779g (1.93mmol, 50% in toluene), sodium tertiary butoxide 1.85g (19.3mmol), toluene 100mL 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 then purified by silica gel column chromatography to obtain 4.87 g (8.01 mmol, yield 79.9%) of the compound represented by [Formula 17].

MS (MALDI-TOF): m / z 607.3 [M] ⁺

Anal. Calc. for C ₄₂ H ₃₃ N ₅ C, 83.00; H, 5.47; N, 11.52. Found C, 83.01; H, 5.48; N, 11.52.

<Synthesis Example 2> Synthesis of compound represented by [Chemical Formula 49]

(1) Synthesis of compound represented by [Chemical Formula 49-a]

The compound represented by [Chemical Formula 49-a] was synthesized by the following [Scheme 7].

[Scheme 7]

[Formula 17-c] [Formula 49-a]

30.0 g (104 mmol) of iodobenzene, 31.9 g (156 mmol) of iodobenzene, 0.992 g (5.21 mmol) of copper iodide, 46.4 g of potassium phosphate from a 500 mL round bottom flask purged with nitrogen at room temperature (219mmol), 1,2-cyclohexanediamine 23.8g (208mmol), 1,4-dioxane 150mL was added and refluxed for 12 hours. Upon completion of the reaction, after cooling to room temperature, methanol was added, and the filtered solid was purified by silica gel column chromatography and recrystallization, and then 30.3 g of a compound represented by [Chemical Formula 49-a] (83.2 mmol, yield 79.9%) ).

(2) Synthesis of compound represented by [Chemical Formula 49-b]

The compound represented by [Chemical Formula 49-b] was synthesized by the following [Scheme 8].

[Scheme 8]

[Formula 49-a] [Formula 49-b]

30.3 g (83.2 mmol), aniline 8.52 g (91.5 mmol), palladium acetate 1.87 g (8.32 mmol), BINAP 5.18 g (Formula 49-a) obtained from [Scheme 7] in a nitrogen-purged 1 L round bottom flask at room temperature. 8.32 mmol), sodium tertiary butoxide 11.2 g (116 mmol), toluene 300 mL 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 then purified by silica gel column chromatography to obtain 26.1 g of a compound represented by [Chemical Formula 49-b] (69.3 mmol, yield 83.3%). .

(3) Synthesis of compound represented by [Formula 49]

A compound represented by [Chemical Formula 49] was synthesized by the following [Scheme 9].

[Scheme 9]

[Formula 49-b] [Formula 17-d] [Formula 49]

Compound represented by [Formula 49] by the same method except that [Formula 49-b] obtained from [Scheme 8] instead of [Formula 17-c] used in [Scheme 5] of Synthesis Example 1 6.90 g (11.4 mmol, yield 74.2%) was obtained.

MS (MALDI-TOF): m / z 607.3 [M] ⁺

Anal. Calc. for C ₄₂ H ₃₃ N ₅ C, 83.00; H, 5.47; N, 11.52. Found C, 83.00; H, 5.46; N, 11.54.

<Synthesis Example 3> Synthesis of compound represented by [Chemical Formula 60]

(1) Synthesis of compound represented by [Formula 60-a]

The compound represented by [Chemical Formula 60-a] was synthesized by the following [Scheme 10].

[Scheme 10]

[Formula 60-a]

In a 2 L round bottom flask at room temperature, 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, and the mixture was cooled to 0 ° C. and stirred. After the reaction was completed, 116 g (533 mmol) of dibutyl tertiary was added, and the mixture was heated to room temperature, stirred for 4 hours, cooled to 0 ° C., and neutralized by adding saturated aqueous ammonium chloride solution. After the reaction was terminated, ethyl acetate and distilled water were added to separate the layers, and then the organic layer was extracted and concentrated under reduced pressure and purified by silica gel column chromatography to yield 126 g of a compound represented by [Chemical Formula 60-a] (411 mmol, 84.9%). Got

(2) Synthesis of compound represented by [Formula 60-b]

The compound represented by [Chemical Formula 60-b] was synthesized by the following [Scheme 11].

[Scheme 11]

[Formula 64-a] [Formula 64-b]

Instead of tertiarybutyl 4-bromo-2-iodophenyl carbamate used in [Scheme 1] of Synthesis Example 1, [Formula 60-a] obtained from [Scheme 10] is used, and 2-methoxycar Compound 63.4 g (166 mmol, yield 72.6%) represented by [Formula 60-b] was obtained by synthesizing in the same manner, except that bromophenyl boronic acid was used instead of carbonylphenyl boronic acid pinacol ester.

(3) Synthesis of compound represented by [Formula 60-c]

The compound represented by [Chemical Formula 60-c] was synthesized by the following [Scheme 12].

[Scheme 12]

[Formula 60-b] [Formula 60-c]

To a 2L round bottom flask purged with nitrogen at room temperature, 63.4 g (166 mmol) obtained from [Scheme 11] and 440 mL of tetrahydrofuran were added, cooled to -78 ° C, and 124 mL of normal butyl lithium (1.6M in n-hexane) was added dropwise and stirred for 1 hour. Upon completion of the reaction, 1.5 g (199 mmol) of acetone was dissolved in 63 mL of tetrahydrofuran, added dropwise to the reaction solution, heated to room temperature, stirred for 1 hour, cooled to 0 ° C., and then distilled water and ethyl acetate were added. The separated organic layer was extracted and concentrated under reduced pressure and purified by silica gel column chromatography to obtain 39.8 g (110 mmol, yield 66.4%) of the compound represented by [Chemical Formula 60-c].

(4) Synthesis of compound represented by [Formula 60-d]

The compound represented by [Chemical Formula 60-d] was synthesized by the following [Scheme 13].

[Scheme 13]

[Formula 60-c] [Formula 60-d]

It was synthesized in the same manner as [Formula 60-d] except that [Formula 60-c] obtained from [Scheme 12] was used instead of [Formula 17-b] used in [Scheme 3] of Synthesis Example 1 Obtained 20.1 g (82.5 mmol, 74.8% yield) of the compound.

(5) Synthesis of compound represented by [Formula 60-e]

A compound represented by [Chemical Formula 60-e] was synthesized by the following [Scheme 14].

[Scheme 14]

[Formula 60-d] [Formula 17-d] [Formula 60-e]

Synthesis in the same manner as shown in [Formula 60-e], except that [Formula 60-d] obtained from [Scheme 13] instead of [Formula 17-c] used in [Scheme 5] of Synthesis Example 1 7.93 g (16.7 mmol, yield 74.2%) of the resulting compound were obtained.

(6) Synthesis of compound represented by [Formula 60-f]

The compound represented by [Chemical Formula 60-f] was synthesized by the following [Scheme 15].

[Scheme 15]

[Formula 60-f]

It was synthesized by the same method except that 2-bromo-9,9'-dimethylfluorene was used instead of [Formula 49-a] used in [Scheme 8] of Synthesis Example 2 [Formula 60-f] Compound 46.7g (164mmol, yield 89.4%) was obtained.

(7) Synthesis of compound represented by [Formula 60]

A compound represented by [Chemical Formula 60] was synthesized by the following [Scheme 16].

[Scheme 16]

[Formula 60-e] [Formula 60-f] [Formula 60]

[Formula 60-e] obtained from [Scheme 14] is used instead of [Formula 17-e] used in [Scheme 6] of Synthesis Example 1, and [Formula 60-f] obtained from [Scheme 15] instead of diphenylamine ] Was synthesized in the same manner, except that 6.89 g (9.52 mmol, yield 90.4%) of the compound represented by [Chemical Formula 60] was obtained.

MS (MALDI-TOF): m / z 723.3 [M] ⁺

Anal. Calc. for C ₅₁ H ₄₁ N ₅ C, 84.62. H, 5.71; N, 9.67. Found C, 84.60; H, 5.71; N, 9.68.

<Synthesis Example 4> Synthesis of compound represented by [Formula 64]

(1) Synthesis of compound represented by [Formula 64-a]

A compound represented by [Chemical Formula 64-a] was synthesized by the following [Scheme 17].

[Scheme 17]

[Formula 64-a]

Instead of tertiary butyl 4-bromo-2-iodophenyl carbamate used in [Scheme 1] of Synthesis Example 1, 1-bromo-4-chloro-2-iodobenzene was used, and 2-me 53.2 g (139 mmol, yield) of a compound represented by [Chemical Formula 64-a] by synthesizing in the same manner, except that (2-Boc-aminophenyl) boronic acid pinacol ester was used instead of methoxycarbonylphenylboronic acid pinacol ester. 88.2%).

(2) Synthesis of compound represented by [Formula 64-b]

A compound represented by [Chemical Formula 64-b] was synthesized by the following [Scheme 18].

[Reaction Scheme 18]

[Formula 64-a] [Formula 64-b]

Synthesis was carried out in the same manner as [Formula 64-b], except that [Formula 64-a] obtained from [Scheme 17] was used instead of [Formula 60-b] used in [Scheme 12] of Synthesis Example 3 Obtained compound 39.8g (110mmol, 79.1% yield).

(3) Synthesis of compound represented by [Formula 64-c]

A compound represented by [Chemical Formula 64-c] was synthesized by the following [Scheme 19].

[Scheme 19]

[Formula 64-b] [Formula 64-c]

Synthesis was carried out in the same manner as [Formula 64-c] except that [Formula 64-b] obtained from [Scheme 18] was used instead of [Formula 17-b] used in [Scheme 3] of Synthesis Example 1 Obtained compound 23.7g (97.2mmol, yield 88.4%).

(4) Synthesis of compound represented by [Formula 64-d]

The compound represented by [Chemical Formula 64-d] was synthesized by the following [Scheme 20].

[Scheme 20]

[Formula 64-c] [Formula 17-d] [Formula 64-d]

Synthesis was carried out in the same manner as [Formula 64-d], except that [Formula 64-c] obtained from [Scheme 19] instead of [Formula 17-c] used in [Scheme 5] of Synthesis Example 1 was represented as [Formula 64-d] Obtained compound 39.6g (83.4mmol, yield 83.4%).

(5) Synthesis of compound represented by [Formula 64]

The compound represented by [Chemical Formula 64] was synthesized by the following [Scheme 21].

[Scheme 21]

[Formula 64-d] [Formula 60-f] [Formula 64]

Compound represented by [Formula 64] by synthesis in the same manner, except that [Formula 64-d] obtained from [Scheme 20] instead of [Formula 60-e] used in [Scheme 16] of Synthesis Example 3 5.87 g (8.11 mmol, yield 77.0%) was obtained.

MS (MALDI-TOF): m / z 723.3 [M] ⁺

Anal. Calc. for C ₅₁ H ₄₁ N ₅ C, 84.62. H, 5.71; N, 9.67. Found C, 84.63; H, 5.69; N, 9.67.

<Synthesis Example 5> Synthesis of the compound represented by [Chemical Formula 85]

(1) Synthesis of compound represented by [Formula 85-a]

The compound represented by [Chemical Formula 85-a] was synthesized by the following [Scheme 22].

[Scheme 22]

[Formula 17-a] [Formula 85-a]

Compound 28.9 g (54.5 mmol, yield 73.8%), synthesized in the same manner, except for using phenyl magnesium bromide instead of methyl magnesium bromide used in [Scheme 2] of Synthesis Example 1 Got

(2) Synthesis of compound represented by [Formula 85-b]

A compound represented by [Chemical Formula 85-b] was synthesized by the following [Scheme 23].

[Scheme 23]

[Formula 85-a] [Formula 85-b]

Synthesis was carried out in the same manner as [Formula 85-b], except that [Formula 85-a] obtained from [Scheme 22] was used instead of [Formula 17-b] used in [Scheme 3] of Synthesis Example 1 Obtained compound 19.7g (47.8mmol, yield 87.7%).

(3) Synthesis of compound represented by [Formula 85-c]

The compound represented by [Chemical Formula 85-c] was synthesized by the following [Scheme 24].

[Scheme 24]

[Formula 85-b] [Formula 17-d] [Formula 85-c]

Synthesis in the same manner as shown in [Formula 85-c], except that [Formula 85-b] obtained from [Scheme 23] instead of [Formula 17-c] used in [Scheme 5] of Synthesis Example 1 Obtained compound 26.3g (40.9mmol, yield 85.5%).

(4) Synthesis of compound represented by [Formula 85]

A compound represented by [Chemical Formula 85] was synthesized by the following [Scheme 25].

[Scheme 25]

[Formula 85-c] [Formula 85]

Compound represented by [Formula 85] by the same method except that [Formula 85-c] obtained from [Scheme 24] instead of [Formula 17-e] used in [Scheme 6] of Synthesis Example 1 4.13 g (5.64 mmol, yield 72.6%) was obtained.

MS (MALDI-TOF): m / z 731.3 [M] ⁺

Anal. Calc. for C ₅₂ H ₃₇ N ₅ C, 85.34. H, 5.10; N, 9.57. Found C, 85.34; H, 5.09; N, 9.57.

<Synthesis Example 6> Synthesis of the compound represented by [Formula 101]

(1) Synthesis of compound represented by [Formula 101-a]

The compound represented by [Chemical Formula 101-a] was synthesized by the following [Scheme 26].

[Scheme 26]

[Formula 101-a]

Compound represented by [Formula 101-a] by synthesizing in the same manner except that 3-bromo- N -phenylcarbazole was used instead of [Formula 49-a] used in [Scheme 8] of Synthesis Example 2 44.7 g (134 mmol, yield 86.1%) was obtained.

(2) Synthesis of Compound Represented by [Formula 101]

A compound represented by [Chemical Formula 101] was synthesized by the following [Scheme 27].

[Scheme 27]

[Formula 85-c] [Formula 101-a] [Formula 101]

[Formula 85-c] obtained from [Scheme 24] was used instead of [Formula 17-e] used in [Scheme 6] of Synthesis Example 1, and [Formula 101-a obtained from [Scheme 26] instead of diphenylamine ] Was synthesized in the same manner, except that 5.77 g (6.43 mmol, yield 82.8%) of the compound represented by [Chemical Formula 101] was obtained.

MS (MALDI-TOF): m / z 896.4 [M] ⁺

Anal. Calc. for C ₆₄ H ₄₄ N ₆ C, 85.69; H, 4.94; N, 9.37. Found C, 85.70; H, 4.95; N, 9.37.

<Synthesis Example 7> Synthesis of compound represented by [Chemical Formula 155]

(1) Synthesis of compound represented by [Formula 155-a]

A compound represented by [Chemical Formula 155-a] was synthesized by the following [Scheme 28].

[Scheme 28]

[Formula 17-a] [Formula 155-a]

32.7 g (58.6 mmol) of the compound represented by [Formula 155-a] by synthesizing in the same manner except that instead of methyl magnesium bromide used in [Scheme 2] of Synthesis Example 1 and p-tolyl magnesium bromide were used. 77.8%).

(2) Synthesis of compound represented by [Formula 155-b]

The compound represented by [Chemical Formula 155-b] was synthesized by the following [Scheme 29].

[Scheme 29]

[Formula 155-a] [Formula 155-b]

Synthesis was carried out in the same manner as [Formula 155-b], except that [Formula 155-a] obtained from [Scheme 28] was used instead of [Formula 17-b] used in [Scheme 3] of Synthesis Example 1 Obtained 21.2 g (48.1 mmol, yield 82.2%).

(3) Synthesis of compound represented by [Formula 155-c]

A compound represented by [Chemical Formula 155-c] was synthesized by the following [Scheme 30].

[Scheme 30]

[Formula 155-c]

Compound 47.9g (179mmol, yield 66.0%) synthesized by the same method except that fluorophenylmagnesium bromide was used instead of phenylmagnesium bromide used in [Scheme 4] of Synthesis Example 1 ).

(4) Synthesis of compound represented by [Formula 155-d]

The compound represented by [Chemical Formula 155-d] was synthesized by the following [Scheme 31].

[Scheme 31]

[Formula 155-b] [Formula 155-c] [Formula 155-d]

Instead of [Formula 17-c] used in [Scheme 5] of Synthesis Example 1, [Formula 155-b] obtained from [Scheme 29] is used, and [Formula 17] obtained from [Scheme 30] instead of [Formula 17-d] 155-c] to obtain a compound 27.1g (38.3mmol, yield 79.6%) represented by [Formula 155-d] was synthesized in the same manner.

(5) Synthesis of compound represented by [Formula 155]

A compound represented by [Chemical Formula 155] was synthesized by the following [Scheme 32].

[Scheme 32]

[Formula 155-d] [Formula 155]

Compound represented by [Formula 155] by the same method except that [Formula 155-d] obtained from [Scheme 31] instead of [Formula 17-e] used in [Scheme 6] of Synthesis Example 1 4.01 g (5.04 mmol, yield 71.3%) was obtained.

MS (MALDI-TOF): m / z 795.3 [M] ⁺

Anal. Calc. for C ₅₄ H ₃₉ F ₂ N ₅ C, 81.49; H, 4.94; F, 4.77; N, 8.80. C, 81.49; H, 4.93; F, 4.79; N, 8.78.

<Synthesis Example 8> Synthesis of compound represented by [Chemical Formula 264]

(1) Synthesis of compound represented by [Formula 264-a]

The compound represented by [Chemical Formula 264-a] was synthesized by the following [Reaction Scheme 33].

[Reaction Scheme 33]

[Formula 60-b] [Formula 264-a]

It was synthesized by the same method except that cyclohexanone was used instead of acetone used in [Scheme 12] of Synthesis Example 3 to obtain 18.6 g (65.5 mmol, yield 87.8%) of the compound represented by [Chemical Formula 264-a]. .

(2) Synthesis of Compound Represented by [Formula 264-b]

The compound represented by [Chemical Formula 264-b] was synthesized by the following [Scheme 34].

[Scheme 34]

[Formula 264-a] [Formula 264-b]

Synthesis was carried out in the same manner as [Formula 264-b], except that [Formula 264-a] obtained from [Scheme 33] was used instead of [Formula 17-b] used in [Scheme 3] of Synthesis Example 1 Obtained compound 10.7g (37.7mmol, yield 81.5%).

(3) Synthesis of compound represented by [Formula 264-c]

The compound represented by [Chemical Formula 264-c] was synthesized by the following [Scheme 35].

[Scheme 35]

[Formula 264-b] [Formula 17-d] [Formula 264-c]

Synthesis was carried out in the same manner as [Formula 264-c], except that [Formula 264-b] obtained from [Scheme 34] was used instead of [Formula 17-c] used in [Scheme 5] of Synthesis Example 1 14.3 g (27.8 mmol, yield 73.6%) of the resulting compound were obtained.

(4) Synthesis of compound represented by [Formula 264]

A compound represented by [Chemical Formula 264] was synthesized by the following [Scheme 36].

[Scheme 36]

[Formula 264-c] [Formula 60-f] [Formula 264]

Compound represented by [Formula 264] by synthesizing in the same manner except that [Formula 264-c] obtained from [Scheme 35] instead of [Formula 60-e] used in [Scheme 16] of Synthesis Example 3 5.98 g (7.83 mmol, yield 80.6%) was obtained.

MS (MALDI-TOF): m / z 763.4 [M] ⁺

Anal. Calc. for C ₅₄ H ₄₅ N ₅ C, 84.90; H, 5.94; N, 9.17. Found C, 84.88; H, 5.94; N, 9.18.

<Synthesis Example 9> Synthesis of compound represented by [Chemical Formula 336]

(1) Synthesis of compound represented by [Formula 336-a]

The compound represented by [Chemical Formula 336-a] was synthesized by the following [Reaction Scheme 37].

[Scheme 37]

[Formula 64-a] [Formula 336-a]

Compound 23.1 g (59.6 mmol, yield 76.0%) of compound represented by [Formula 336-a] was obtained by synthesizing in the same manner, except that cyclopentanone was used instead of acetone used in [Scheme 18] of Synthesis Example 4 .

(2) Synthesis of Compound Represented by [Formula 336-b]

The compound represented by [Chemical Formula 336-b] was synthesized by the following [Scheme 38].

[Scheme 38]

[Formula 336-a] [Formula 336-b]

It was synthesized in the same manner as in [Formula 336-b], except that [Formula 336-a] obtained from [Scheme 37] was used instead of [Formula 17-b] used in [Scheme 3] of Synthesis Example 1 Obtained compound 12.7g (47.1mmol, yield 79.1%).

(3) Synthesis of compound represented by [Formula 336-c]

The compound represented by [Chemical Formula 336-c] was synthesized by the following [Scheme 39].

[Scheme 39]

[Formula 336-b] [Formula 17-d] [Formula 336-c]

Synthesis was carried out in the same manner as [Formula 336-c], except that [Formula 336-b] obtained from [Scheme 38] was used instead of [Formula 17-c] used in [Scheme 5] of Synthesis Example 1 Obtained compound 20.4g (40.7mmol, yield 86.5%).

(4) Synthesis of compound represented by [Formula 336]

A compound represented by [Chemical Formula 336] was synthesized by the following [Scheme 40].

[Reaction Scheme 40]

[Formula 336-c] [Formula 60-f] [Formula 336]

Compound represented by [Formula 336] by the same method as the [Formula 336-c] obtained from [Scheme 39] instead of [Formula 60-e] used in [Scheme 16] of Synthesis Example 3 6.17 g (8.23 mmol, yield 82.4%) was obtained.

MS (MALDI-TOF): m / z 749.4 [M] ⁺

Anal. Calc. for C ₅₃ H ₄₃ N ₅ C, 84.88. H, 5.78; N, 9.34. Found C, 84.87; H, 5.78; N, 9.33.

<Synthesis Example 10> Synthesis of compound represented by [Chemical Formula 401]

(1) Synthesis of compound represented by [Formula 401-a]

The compound represented by [Chemical Formula 401-a] was synthesized by the following [Scheme 41].

[Scheme 41]

[Formula 60-b] [Formula 401-a]

It was synthesized in the same manner except that fluorenone was used instead of acetone used in [Scheme 12] of Synthesis Example 3 to obtain 28.5 g of a compound represented by [Chemical Formula 401-a] (58.9 mmol, yield 75.1%).

(2) Synthesis of compound represented by [Formula 401-b]

The compound represented by [Chemical Formula 401-b] was synthesized by the following [Scheme 42].

[Reaction Scheme 42]

[Formula 401-a] [Formula 401-b]

It was synthesized in the same manner as [Formula 401-b], except that [Formula 401-a] obtained from [Scheme 41] was used instead of [Formula 17-b] used in [Scheme 3] of Synthesis Example 1 19.2 g (52.5 mmol, yield 89.1%) of the obtained compound were obtained.

(3) Synthesis of compound represented by [Formula 401-c]

A compound represented by [Chemical Formula 401-c] was synthesized by the following [Scheme 43].

[Scheme 43]

[Formula 401-b] [Formula 17-d] [Formula 401-c]

It was synthesized in the same manner as [Formula 401-c], except that [Formula 401-b] obtained from [Scheme 42] was used instead of [Formula 17-c] used in [Scheme 5] of Synthesis Example 1 Obtained compound 24.0g (40.2mmol, yield 76.6%).

(4) Synthesis of compound represented by [Formula 401]

A compound represented by [Chemical Formula 401] was synthesized by the following [Scheme 44].

[Scheme 44]

[Formula 401-c] [Formula 101-a] [Formula 401]

A compound represented by [Formula 401] by synthesizing in the same manner except that [Formula 401-c] obtained from [Scheme 43] was used instead of [Formula 85-c] used in [Scheme 27] of Synthesis Example 6 6.32g (7.06mmol, Yield 84.3%) was obtained.

MS (MALDI-TOF): m / z 894.4 [M] ⁺

Anal. Calc. for C ₆₄ H ₄₂ N ₆ C, 85.88; H, 4.73; N, 9.39. Found C, 85.89; H, 4.74; N, 9.39.

<Synthesis Example 11> Synthesis of the compound represented by [Chemical Formula 416]

(1) Synthesis of compound represented by [Formula 416-a]

The compound represented by [Chemical Formula 416-a] was synthesized by the following [Scheme 45].

[Scheme 45]

[Formula 416-a]

97 g (0.56 mol) of 1-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. Next, 970 mL of dimethylformamide was added and stirred at 60 ° C overnight. After removing the solvent by concentrating under reduced pressure at room temperature, 500 mL of 10% aqueous sodium hydroxide solution was added and refluxed for about 1 hour. After extraction with ethyl acetate, separated by column chromatography, and recrystallized with toluene and heptane to obtain 50.8 g of a compound represented by [Formula 416-a] (yield 54%).

(2) Synthesis of compound represented by [Formula 416-b]

The compound represented by [Chemical Formula 416-b] was synthesized by the following [Scheme 46].

[Scheme 46]

[Formula 416-a] [Formula 416-b]

25.0 g (149 mmol) of [Formula 416-a] obtained from [Scheme 45] 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. 19.4 g (179 mmol) of ethyl chloroformate was added dropwise and refluxed for about 1 hour. The aqueous ammonium chloride solution was added until it became weakly acidic, and washed with water and heptane to obtain 32.4 g of a compound represented by [Chemical Formula 416-b] (yield 80%).

(3) Synthesis of compound represented by [Formula 416-c]

The compound represented by [Chemical Formula 416-c] was synthesized by the following [Scheme 47].

[Scheme 47]

[Formula 416-b] [Formula 416-c]

30 g (110 mmol) of [Formula 416-b] obtained from [Scheme 46] was put in about 80 mL of oxychloride and refluxed overnight. After cooling the temperature to -20 ° C, distilled water was slowly added to about 400 mL. Washed with water, methanol, and heptane, and recrystallized with toluene and heptane to obtain 14.1 g of a compound represented by [Formula 416-c] (yield 44%).

(4) Synthesis of compound represented by [Formula 416-d]

The compound represented by [Chemical Formula 416-d] was synthesized by the following [Scheme 48].

[Scheme 48]

[Formula 17-c] [Formula 416-c] [Formula 416-d]

Synthesis was carried out in the same manner as [Formula 416-d], except that [Formula 416-c] obtained from [Scheme 47] was used instead of [Formula 17-d] used in [Scheme 5] of Synthesis Example 1 Obtained compound (yield 72%) was obtained.

(5) Synthesis of compound represented by [Formula 416]

A compound represented by [Chemical Formula 416] was synthesized by the following [Reaction Scheme 49].

[Reaction Scheme 49]

[Formula 416-d] [Formula 416]

Compound represented by [Formula 416] by synthesizing in the same manner except that [Formula 416-d] obtained from [Scheme 48] instead of [Formula 17-e] used in [Scheme 6] of Synthesis Example 1 (Yield 78%).

MS (MALDI-TOF): m / z 630.28 [M] ⁺

Anal. Calc. for C ₄₅ H ₃₄ N ₄ C, 85.68; H, 5.43; N, 8.88. Found C, 85.70; H, 5.42; N, 8.87.

<Synthesis Example 12> Synthesis of the compound represented by [Formula 417]

(1) Synthesis of compound represented by [Formula 417-a]

The compound represented by [Chemical Formula 417-a] was synthesized by the following [Scheme 50].

[Reaction Scheme 50]

[Formula 417-a]

Synthesis in the same manner as in [Scheme 45] to [Scheme 47] except that 2-nitronaphthalene was used instead of 1-nitronaphthalene used in [Scheme 45] of Synthesis Example 11 to [Formula 417-a] The indicated compound (yield 44%) was obtained.

(2) Synthesis of compound represented by [Formula 417-b]

The compound represented by [Chemical Formula 417-b] was synthesized by the following [Scheme 51].

[Scheme 51]

[Formula 417-a] [Formula 417-b]

Instead of tertiarybutyl 4-bromo-2-iodophenylcarbamate used in [Scheme 1] of Synthesis Example 1, [Formula 417-a] obtained from [Scheme 50] was used, and 2-methoxy It was synthesized in the same manner except that 4-iodophenylboronic acid was used instead of the carbonylphenylboronic acid pinacol ester to obtain a compound represented by [Formula 417-b] (yield 78%).

(3) Synthesis of compound represented by [Formula 417-c]

The compound represented by [Chemical Formula 417-c] was synthesized by the following [Scheme 52].

[Scheme 52]

[Formula 60-d] [Formula 417-b] [Formula 417-c]

[Formula 60-d] obtained from [Scheme 13] was used instead of [Formula 17-c] used in [Scheme 5] of Synthesis Example 1, and [Formula 417] obtained from [Scheme 51] instead of [Formula 17-d] -b] was synthesized in the same manner, except that a compound represented by [Formula 417-c] (yield 74%) was obtained.

(4) Synthesis of compound represented by [Formula 417-d]

The compound represented by [Chemical Formula 417-d] was synthesized by the following [Scheme 53].

[Scheme 53]

[Formula 417-d]

In the same manner, except that 1-chloro-4-phenylbenzene was used instead of [Formula 49-a] used in [Scheme 8] of Synthesis Example 2, and 1-amino-4-methylbenzene was used instead of aniline. Synthesis to obtain a compound (yield 75%) represented by [Formula 417-d].

(5) Synthesis of Compound Represented by [Formula 417]

A compound represented by [Chemical Formula 417] was synthesized by the following [Scheme 54].

[Scheme 54]

[Formula 417-c] [Formula 417-d] [Formula 417]

[Formula 417-c] obtained from [Scheme 52] instead of [Formula 17-e] used in [Scheme 6] of Synthesis Example 1 is used, and [Formula 417-d] obtained from [Scheme 53] instead of diphenylamine ] Was synthesized in the same manner except for using to obtain a compound represented by [Formula 417] (yield 74%).

MS (MALDI-TOF): m / z 796.36 [M] ⁺

Anal. Calc. for C ₅₈ H ₄₄ N ₄ C, 87.41. H, 5.56; N, 7.03. Found C, 87.43; H, 5.54; N, 7.03.

<Synthesis Example 13> Synthesis of compound represented by [Chemical Formula 418]

(1) Synthesis of Compound Represented by [Formula 418-a]

The compound represented by [Chemical Formula 418-a] was synthesized by the following [Scheme 55].

[Scheme 55]

[Formula 418-a]

Synthesis in the same manner as in [Scheme 46] to [Scheme 47] except that 3-aminonaphthalene-2-carbonitrile was used instead of [Chemical Formula 416-a] used in [Scheme 46] of Synthesis Example 11 Compound 418-a] (yield 71%) was obtained.

(2) Synthesis of compound represented by [Formula 418-b]

The compound represented by [Chemical Formula 418-b] was synthesized by the following [Scheme 56].

[Scheme 56]

[Formula 64-c] [Formula 418-a] [Formula 418-b]

Instead of [Formula 17-c] used in [Scheme 5] of Synthesis Example 1, [Formula 64-c] obtained from [Scheme 19] is used, and [Formula 17] obtained from [Scheme 55] instead of [Formula 17-d] 418-a] was synthesized in the same manner, except that the compound represented by [Chemical Formula 418-b] (yield 83%).

(3) Synthesis of compound represented by [Formula 418-c]

The compound represented by [Chemical Formula 418-c] was synthesized by the following [Scheme 57].

[Reaction Scheme 57]

[Formula 418-c]

Compound represented by [Formula 418-c] by the same method except for using 3-chloro-6 methylpyridine instead of [Formula 49-a] used in [Scheme 8] of Synthesis Example 2 (Yield 72 %).

(4) Synthesis of compound represented by [Formula 418]

A compound represented by [Chemical Formula 418] was synthesized by the following [Scheme 58].

[Reaction Scheme 58]

[Formula 418-b] [Formula 418-c] [Formula 418]

[Formula 418-b] obtained from [Scheme 56] is used instead of [Formula 17-e] used in [Scheme 6] of Synthesis Example 1, and [Formula 418-c] obtained from [Scheme 57] instead of diphenylamine. ] Was synthesized in the same manner, except that a compound represented by [Chemical Formula 418] (yield 75%) was obtained.

MS (MALDI-TOF): m / z 645.29 [M] ⁺

Anal. Calc. for C ₄₅ H ₃₅ N ₅ C, 83.69. H, 5.46; N, 10.84. Found C, 83.67; H, 5.46; N, 10.85.

<Synthesis Example 14> Synthesis of the compound represented by [Formula 419]

(1) Synthesis of compound represented by [Formula 419-a]

The compound represented by [Chemical Formula 419-a] was synthesized by the following [Scheme 59].

[Scheme 59]

[Formula 419-a]

The above except that 9-nitrophenanthrene was used instead of 1-nitronaphthalene used in [Scheme 45] of Synthesis Example 11, and pentadeutereo phenylmagnesium bromide was used instead of phenylmagnesium bromide used in [Scheme 46]. It was synthesized in the same manner as in [Scheme 45] to [Scheme 47] to obtain a compound represented by [Chemical Formula 419-a] (yield 56%).

(2) Synthesis of compound represented by [Formula 419-b]

A compound represented by [Chemical Formula 419-b] was synthesized by the following [Scheme 60].

[Scheme 60]

[Formula 85-b] [Formula 419-a] [Formula 419-b]

Instead of [Formula 17-c] used in [Scheme 5] of Synthesis Example 1, [Formula 85-b] obtained from [Scheme 23] is used, and [Formula 17] obtained from [Scheme 59] instead of [Formula 17-d] Compound 419-a was synthesized in the same manner, except that [Formula 419-b] to obtain a compound (yield 85%) d.

(3) Synthesis of compound represented by [Formula 419-c]

The compound represented by [Chemical Formula 419-c] was synthesized by the following [Scheme 61].

[Scheme 61]

[Formula 419-c]

Compound represented by [Formula 419-c] by synthesis in the same manner except that (4-chlorophenyl) trimethylsilane was used instead of [Formula 49-a] used in [Scheme 8] of Synthesis Example 2 (yield) 75%).

(4) Synthesis of compound represented by [Formula 419]

A compound represented by [Chemical Formula 419] was synthesized by the following [Reaction Scheme 62].

[Reaction Scheme 62]

[Formula 419-b] [Formula 419-c] [Formula 419]

[Formula 419-b] obtained from [Scheme 60] is used instead of [Formula 17-e] used in [Scheme 6] of Synthesis Example 1, and [Formula 419-c] obtained from [Scheme 61] instead of diphenylamine. ] Was synthesized in the same manner, except that a compound represented by [Chemical Formula 419] (yield 72%) was obtained.

MS (MALDI-TOF): m / z 881.40 [M] ⁺

Anal. Calc. for C ₆₂ H ₄₃ D ₅ N ₄ Si C, 84.41; H, 6.05; N, 6.35, Si, 3.18. Found C, 84.39; H, 6.07; N, 6.35. Si 3.18

<Examples 1 to 20> Preparation of organic electroluminescent device

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

[DNTPD]

[NPD]

[Ir (ppy) ₃ ]

[Alq ₃ ]

<Comparative Example 1>

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

[CBP]

division Host Dopant Doping concentration (%) V Cd / ㎡ CIEx CIEy T ₉₇ (Hr) Example 1 Formula 17 Ir (ppy) ₃ 10 3.99 5435 0.295 0.622 201 Example 2 Formula 49 Ir (ppy) ₃ 10 3.87 5376 0.299 0.623 233 Example 3 Formula 60 Ir (ppy) ₃ 10 4.10 4932 0.293 0.627 210 Example 4 Formula 64 Ir (ppy) ₃ 10 4.04 4954 0.300 0.625 231 Example 5 Chemical Formula 85 Ir (ppy) ₃ 10 3.94 5146 0.296 0.628 221 Example 6 Formula 101 Ir (ppy) ₃ 10 3.78 5012 0.298 0.625 223 Example 7 Chemical Formula 155 Ir (ppy) ₃ 10 3.86 5002 0.299 0.625 194 Example 8 Chemical Formula 264 Ir (ppy) ₃ 10 3.89 5110 0.295 0.623 231 Example 9 Chemical Formula 336 Ir (ppy) ₃ 10 3.92 5010 0.297 0.624 224 Example 10 Formula 401 Ir (ppy) ₃ 10 3.96 5093 0.296 0.623 219 Example 11 Chemical Formula 34 Ir (ppy) ₃ 10 4.01 5450 0.296 0.623 240 Example 12 Chemical Formula 51 Ir (ppy) ₃ 10 3.78 5235 0.293 0.621 217 Example 13 Formula 56 Ir (ppy) ₃ 10 3.91 4981 0.295 0.627 193 Example 14 Chemical Formula 84 Ir (ppy) ₃ 10 3.88 4971 0.295 0.622 227 Example 15 Chemical Formula 89 Ir (ppy) ₃ 10 3.87 5241 0.296 0.625 223 Example 16 Formula 118 Ir (ppy) ₃ 10 3.67 4991 0.299 0.623 218 Example 17 Chemical Formula 162 Ir (ppy) ₃ 10 3.92 5111 0.300 0.622 202 Example 18 Formula 222 Ir (ppy) ₃ 10 4.10 5110 0.293 0.621 191 Example 19 Chemical Formula 230 Ir (ppy) ₃ 10 4.00 4934 0.296 0.624 199 Example 20 Chemical Formula 243 Ir (ppy) ₃ 10 3.97 5211 0.297 0.624 190 Comparative Example 1 CBP Ir (ppy) ₃ 10 7.93 3801 0.297 0.624 68

<Examples 21 to 24> Preparation of organic electroluminescent device

The organic light emitting diode devices for Examples 21 to 24 were [Compounds 416] to [Compounds 419] for the light emitting layers in the device structures of Examples 1 to 20, and instead of [Ir (ppy) ₃ ], [(piq) ₂ Ir (acac)] except that the same was used, and 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 that [(piq) ₂ Ir (acac)] was used instead of [Ir (ppy) ₃ ] in the device structure of Comparative Example 1 Did.

division Host Dopant Doping concentration (%) V Cd / ㎡ CIEx CIEy T ₉₇ (Hr) Example 21 Chemical Formula 416 [(pic) ₂ Ir (acac)] 10 3.99 5005 0.669 0.328 201 Example 22 Chemical Formula 417 [(pic) ₂ Ir (acac)] 10 3.86 4987 0.670 0.329 189 Example 23 Chemical Formula 418 [(pic) ₂ Ir (acac)] 10 4.06 4982 0.671 0.329 197 Example 24 Chemical Formula 419 [(pic) ₂ Ir (acac)] 10 3.98 4838 0.671 0.328 186 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], an organic electroluminescent device comprising a heterocyclic compound prepared according to Examples 1 to 24 of the present invention as a host material, Comparative Example 1 in which the host material is CBP, and Compared to Comparative Example 2, since the driving voltage (V) is low and exhibits characteristics with excellent luminous efficiency (Cd / m 2) and long life (T ₉₇ ), it can be seen that it can be usefully used for display devices, display devices, and lighting. have.

Claims (13)

Heterocyclic compounds represented by the following [Formula 1]:
[Formula 1]

In the above [Formula 1],
R ₁ is any _{one selected} from hydrogen, deuterium, substituted or unsubstituted aryl group having 5 to 40 carbon atoms and substituted or unsubstituted heteroaryl group having 2, 40 carbon atoms having hetero atom O, N, S or P ,
L ₁ is any one selected from 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 is an integer from 0 to 3, and n is 2) Case, a plurality of L ₁ are the same or different)
R ₂ and R ₃ are the same or different from each other, and each independently hydrogen, deuterium, an alkyl group having 1 to 30 carbon atoms, an aryl group having 5 to 40 carbon atoms, and a substituted or unsubstituted hetero atom having O, N, S or P Selected from heteroaryl groups having 2 to 40 carbon atoms (wherein R ₂ to R ₃ may combine with each other or adjacent substituents to form a saturated or unsaturated ring),
Y ₁ to Y ₈ are each independently CR ₄ to CR ₁₁ ,
R ₄ to R ₁₁ is hydrogen, deuterium or a substituent represented by the following [Structural Formula A], and at least one of R ₄ to R ₁₁ is characterized in that the following [Structural A],
[Structural Formula A]

In the above [Structural Formula A],
* Means a site that binds to Y ₁ to Y ₈ in [Formula 1],
L ₂ is any one selected from 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 (m is an integer from 0 to 1),
R ₁₂ and R ₁₃ are the same as or different from each other, and each independently a substituted or unsubstituted aryl group having 5 to 40 carbon atoms and a substituted or unsubstituted heteroatom having 2, 40 carbon atoms having O, N, S or P It is any one selected from aryl groups. According to claim 1,
R ₁ , R ₁₂ , R ₁₃ , L ₁ and L ₂ are each independently deuterium, cyano group, halogen group, alkyl group having 1 to 40 carbon atoms, alkylsilyl group having 1 to 40 carbon atoms, aryl group having 6 to 40 carbon atoms. , Heterocyclic compound characterized in that it is further substituted with one or more selected from the group consisting of a heteroaryl group having 3 to 40 carbon atoms. According to 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 7]:

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

[Formula 6] [Formula 7]
In [Formula 2] to [Formula 7], Y ₁ to Y ₈ , R ₁ , L ₁ , L ₂ and n are the same as defined in [Formula 1]. delete delete delete delete According to claim 1,
[Formula 1] is a heterocyclic compound, characterized in that any one selected from the group represented by the following [Formula 8] to [Formula 423]:

[Formula 416] [Formula 417] [Formula 418] [Formula 419]

[Formula 420] [Formula 421] [Formula 422] [Formula 423] 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 comprising at least one heterocyclic compound represented by [Formula 1] according to claim 1. The method of claim 9,
The organic layer is a hole injection layer, a hole transport layer, an organic electroluminescent device comprising at least one layer selected from a functional layer having a hole injection function and a hole transport function at the same time, a light emitting layer, an electron transport layer and an electron injection layer. The method of claim 9,
The organic electroluminescent device, characterized in that the organic layer interposed between the first electrode and the second electrode includes a light emitting layer. The method of claim 9,
The light emitting 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 electroluminescent device comprising at least one dopant compound. The method of claim 9,
The organic light emitting device is an organic light emitting device characterized in that it is used for a display element, a display element, or a monochromatic or white lighting element.

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