KR102372231B1 - Heterocyclic com pounds 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, wherein the heterocyclic compound is represented by the following [Formula 1], and an organic electroluminescent device comprising the same is a driving voltage, light emission Efficiency and lifespan characteristics are very good.
[Formula 1]

Description

Heterocyclic compound and organic electroluminescent device including same {Heterocyclic com pounds 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 light emitting material, and more particularly, to a heterocyclic compound having excellent and stable light emitting characteristics such as driving voltage and luminous efficiency, and organic electroluminescence including the same It's about the little ones.

Recently, organic light emitting diodes that are self-luminous and can be driven at a low voltage have better viewing angles and contrast ratio compared to liquid crystal displays (LCDs), which are the mainstream of flat panel display devices, do not require backlight, and are lightweight and thin. 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.

Organic light emitting diodes (OLEDs) are devices that emit light when electrons and holes are paired and then disappear when electric charges are injected into an organic light emitting layer formed between an electron injection electrode (cathode) and a hole injection electrode (anode). am.

An organic light emitting diode using an organic light emitting phenomenon usually has a structure including an anode and a cathode and an organic material layer therebetween. Here, the organic material layer is often formed of a multi-layered structure composed of different materials in order to increase the efficiency and stability of the organic electroluminescent device, 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 the two electrodes in the structure of the organic light emitting device, holes are injected into the organic material layer from the anode and electrons from the cathode are injected into the organic material layer. When the injected holes and electrons meet, excitons are formed, and these excitons It will glow when it falls back to the ground state.

The organic electroluminescent device can be formed on a flexible transparent substrate such as plastic, as well as at a lower voltage of 10V or less compared to a plasma display panel or an inorganic electroluminescent (EL) display. It can be driven, consumes relatively little power, and has the advantage of excellent color. In addition, since the organic light emitting diode can display three colors of green, blue, and red, it is a next-generation rich color display element, which attracts a lot of attention from many people.

In order for the organic electroluminescent device to sufficiently exhibit the above-mentioned excellent characteristics, the material constituting the 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, etc., is supported by stable and efficient materials. However, the development of a stable and efficient organic material for an organic light emitting device has not yet been sufficiently developed. Accordingly, the development of new materials continues to be demanded.

Therefore, the problem to be solved by the present invention is a novel heterocyclic compound having a lower driving voltage and superior luminous efficiency than a compound used in a conventional phosphorescent material when employed in an organic electroluminescent device, and an organic electroluminescent device including the same will provide

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

[Formula 1]

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

Specific substituents of the [Formula 1] will be described later.

Since the heterocyclic compound represented by [Formula 1] according to the present invention is stable compared to conventional materials, and has excellent light emitting characteristics in terms of driving voltage or current efficiency, the organic electroluminescent device including the same can be driven at a low voltage, It is possible to improve the luminous efficiency.

1 is a schematic diagram of an organic electroluminescent device according to an 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 having improved light emitting characteristics such as driving voltage and current efficiency of an organic light emitting diode, and is characterized in that it is a heterocyclic compound represented by the above [Formula 1].

[Formula 1]

In the above [Formula 1],

X ₁ to X ₁₂ is the same as or different from each other, and each independently represents hydrogen, deuterium, a substituted or unsubstituted C 1 to C 30 alkyl group, a substituted or unsubstituted C 6 to C 40 aryl group, a substituted or unsubstituted C 2 to C 30 of heteroaryl group, halogen atom, hydroxyl group, cyano group, nitro group, amino group, amidino group, hydrazine, hydrazone, carboxyl group or its salt, sulfonic acid group or its salt, phosphoric acid or its salt, substituted or unsubstituted carbon number A 2 to 60 alkenyl group, a substituted or unsubstituted C2 to C60 alkynyl group, a substituted or unsubstituted C1 to C60 alkoxy group, a substituted or unsubstituted C3 to C60 cycloalkyl group, a substituted or unsubstituted A cycloalkenyl group having 5 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 5 to 60 carbon atoms, a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms, or a substituted or unsubstituted arylthiox group having 5 to 30 carbon atoms It may be selected from the group consisting of a group, a substituted or unsubstituted C5 to C60 arylthio group, -SiR ₃ R ₄ R ₅ and -NR ₆ R ₇ .

In addition, each of X ₁ to X ₂ and X ₁₁ to X ₁₂ may be connected to an adjacent substituent to form an alicyclic or aromatic monocyclic or polycyclic ring, and the formed alicyclic, aromatic monocyclic or polycyclic ring A carbon atom of the ring may be substituted with any one or more heteroatoms selected from N, S, and O.

In addition, the R ₁ to R ₇ is the same as or different from each other, and each independently represents a substituted or unsubstituted C 1 to C 30 alkyl group, a substituted or unsubstituted C 6 to C 40 aryl group, or a substituted or unsubstituted C 2 to C 30 heteroaryl group And it may be selected from the group consisting of hydrogen and deuterium.

Ar ₁ and Ar ₂ may be the same or different from each other, and each independently may be selected from the group consisting of a substituted or unsubstituted C 6 to C 40 aryl group and a substituted or unsubstituted C 2 to C 30 heteroaryl group, p +q is an integer between 1 and 6, and when p and q are each an integer of 2 or more, a plurality of Ar ₁ and Ar ₂ may be the same as or different from each other.

L is a linking group, a single bond, a substituted or unsubstituted C1-C60 alkylene group, a substituted or unsubstituted C2-C60 alkylene group An alkenylene group, a substituted or unsubstituted C2 to C60 alkynylene group, a substituted or unsubstituted C3 to C60 Selected from the group consisting of a cycloalkylene group, a substituted or unsubstituted heterocycloalkylene group having 2 to 60 carbon atoms, a substituted or unsubstituted arylene group having 6 to 60 carbon atoms, and a substituted or unsubstituted heteroarylene group having 2 to 60 carbon atoms may be, n is an integer between 1 and 3, and when n is 2 or more, a plurality of Ls may be the same or different from each other.

According to an embodiment of the present invention, the X ₁ to X _12,, R ₁ to R ₇ , Ar ₁ , Ar ₂ and L 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, 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, 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, may be further substituted with one or more substituents selected from the group consisting of phosphorus and boron, wherein the substituents are bonded to adjacent substituents to form saturated or unsaturated rings, or may be attached or fused together in a pendant manner.

On the other hand, the aryl group, which is a substituent used in the present invention, is an organic radical derived from an aromatic hydrocarbon by removal of one hydrogen, and includes a single or fused ring system containing 5 to 7 members, preferably 5 or 6 members, In addition, when the aryl group has a substituent, it may be fused with a neighboring substituent to further form a ring.

Specific examples of the aryl group 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- Ethylbiphenyl 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, pyrethyl group and aromatic groups such as nyl group, indenyl, fluorenyl group, tetrahydronaphthyl group, pyrenyl, peryleneyl, chrysenyl, naphthacenyl, fluoranthenyl, and the like.

At least one hydrogen atom of the aryl group 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 an "alkylamino group"), an amidino group, 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, 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, carbon number It may be substituted with a heteroaryl group having 2 to 24 carbon atoms or a heteroarylalkyl group having 2 to 24 carbon atoms.

A heteroaryl group as a substituent used in the present invention, in particular, when Ar ₁ and Ar ₂ is a heteroaryl group, it may be any one substituent 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 [Structural Formula 1] to [Structural Formula 6],

T ₁ to T ₈ are the same as or different from each other and each independently may be any one selected from C(R ₄₁ ), C(R ₄₂ )(R ₄₃ ), N, N(R ₄₄ ), O and S, and , wherein R ₃₁ to R ₄₄ are the same as or different from each other, and each independently represents hydrogen, deuterium, a substituted or unsubstituted C 1 to C 30 alkyl group, a substituted or unsubstituted C 3 to C 30 cycloalkyl group, substituted or unsubstituted may be any one selected from an aryl group having 5 to 50 carbon atoms and a heteroaryl group having 2 to 50 carbon atoms and a substituted or unsubstituted heteroaryl group having O, N or S as a heteroatom, In 6], one of R ₃₁ to R ₄₄ may be combined with nitrogen in [Formula 1] to form a single bond.

In addition, the [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 the [Structural Formula 3-1], T ₁ to T ₅ and R ₃₃ and R ₃₄ are the same as defined above.

In addition, according to a preferred embodiment of the present invention, the [Structural Formula 1] to [Structural Formula 6] may be selected from the following [Structural Formula 7].

[Structural Formula 7]

In [Structural Formula 7], X is the same as X ₁ to X ₁₄ , 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 X may be combined with nitrogen in the [Formula 1] to form a single bond.

Specific examples of the alkyl group as a substituent used in the present invention include a methyl group, an ethyl group, a propyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an iso-amyl group, a hexyl group, a heptyl group, an octyl group, stearyl group, trichloromethyl group, trifluoromethyl group, etc., wherein at least one hydrogen atom of the alkyl group is a deuterium atom, a halogen atom, a hydroxyl group, a nitro group, a cyano group, a trifluoromethyl group, a silyl group (in this case, " Alkylsilyl group"), a substituted or unsubstituted amino group (-NH ₂ , -NH(R), -N(R')(R"), wherein R, R' and R" are each independently C 1 to 24 alkyl group (referred to as "alkylamino group" in this case), amidino group, hydrazine group, hydrazone group, carboxyl group, sulfonic acid group, phosphoric acid group, C1-C24 alkyl group, C1-C24 halogenated alkyl group, An alkenyl group having 2 to 24 carbon atoms, an alkynyl group having 2 to 24 carbon atoms, 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 carbon number It may be substituted with 3 to 24 heteroarylalkyl groups.

Specific examples of the alkoxy group as a substituent used in the compound of the present invention include a methoxy group, an ethoxy group, a propoxy group, an isobutyloxy group, a sec-butyloxy group, a pentyloxy group, an iso-amyloxy group, a hexyloxy group, etc. and may be substituted with the same substituents as in the case of the alkyl group.

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

* The aryloxy group used in the present invention refers to an -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 included in the aryloxy group may be further substituted.

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

Specific examples of the alkenyl group used in the present invention include a linear 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.

In addition, in the present invention, the 'substitution' in the 'substituted or unsubstituted' is deuterium, a cyano group, a halogen group, a hydroxy group, a nitro group, an alkyl group having 1 to 24 carbon atoms, a halogenated alkyl group having 1 to 24 carbon atoms, C1-C24 alkenyl group, C1-C24 alkynyl group, C1-C24 heteroalkyl group, C6-C24 aryl group, C6-C24 arylalkyl group, C2-C24 heteroaryl group or carbon number A heteroarylalkyl group having 2 to 24 carbon atoms, an alkoxy group having 1 to 24 carbon atoms, an alkylamino group having 1 to 24 carbon atoms, an arylamino group having 1 to 24 carbon atoms, a heteroarylamino group having 1 to 24 carbon atoms, an alkylsilyl group having 1 to 24 carbon atoms, It means to be substituted with one or more substituents selected from the group consisting of an arylsilyl group having 1 to 24 carbon atoms, an aryloxy group having 1 to 24 carbon atoms, germanium, phosphorus, and boron.

In addition, the carbon number range of the alkyl group or aryl group in the "substituted or unsubstituted C1 to C30 alkyl group", "substituted or unsubstituted C5 to C50 aryl group", etc., considers the portion in which the substituent is substituted. It refers to the total number of carbon atoms constituting the alkyl part or the aryl part when viewed as unsubstituted. For example, a phenyl group substituted with a butyl group at the para-position corresponds to an aryl group having 6 carbon atoms substituted with a butyl group having 4 carbon atoms.

The heterocyclic compound represented by [Formula 1] according to the present invention may be more specifically selected from compounds represented by the following [Formula 2] to [Formula 123].

[Formula 2] [Formula 3]

[Formula 4] [Formula 5]

[Formula 6] [Formula 7]

[Formula 8] [Formula 9]

[Formula 10] [Formula 11]

[Formula 12] [Formula 13]

[Formula 14] [Formula 15]

[Formula 16] [Formula 17]

[Formula 18] [Formula 19]

[Formula 20] [Formula 21]

[Formula 22] [Formula 23]

[Formula 24] [Formula 25]

[Formula 26] [Formula 27]

[Formula 28] [Formula 29]

[Formula 30] [Formula 31]

[Formula 32] [Formula 33]

[Formula 34] [Formula 35]

[Formula 36] [Formula 37]

[Formula 38] [Formula 39]

[Formula 40] [Formula 41]

[Formula 42] [Formula 43]

[Formula 44] [Formula 45]

[Formula 46] [Formula 47]

[Formula 48] [Formula 49]

[Formula 50] [Formula 51]

[Formula 52] [Formula 53]

[Formula 54] [Formula 55]

[Formula 56] [Formula 57]

[Formula 58] [Formula 59]

[Formula 60] [Formula 61]

[Formula 62] [Formula 63]

[Formula 64] [Formula 65]

[Formula 66] [Formula 67]

[Formula 68] [Formula 69]

[Formula 70] [Formula 71]

[Formula 72] [Formula 73]

[Formula 74] [Formula 75]

[Formula 76] [Formula 77]

[Formula 78] [Formula 79]

[Formula 80] [Formula 81]

[Formula 82] [Formula 83]

[Formula 84] [Formula 85]

[Formula 86] [Formula 87]

[Formula 88] [Formula 89]

[Formula 90] [Formula 91]

[Formula 92] [Formula 93]

[Formula 94] [Formula 95]

[Formula 96] [Formula 97]

[Formula 98] [Formula 99]

[Formula 100] [Formula 101]

[Formula 102] [Formula 103]

[Formula 104] [Formula 105]

[Formula 106] [Formula 107]

[Formula 108] [Formula 109]

[Formula 110] [Formula 111]

[Formula 112] [Formula 113]

[Formula 114] [Formula 115]

[Formula 116] [Formula 117]

[Formula 118] [Formula 119]

[Formula 120] [Formula 121]

[Formula 122] [Formula 123]

In addition, the present invention includes a first electrode, a second electrode opposite to the first electrode, and an organic layer interposed between the first electrode and the second electrode, wherein the organic layer is a release type represented by the [Formula 1] It may include one or more cyclic compounds.

In addition, the organic layer containing the heterocyclic 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 at the same time, a light emitting layer, an electron transport layer, and an electron injection layer there is. 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 made of a host and a dopant, and the heterocyclic compound of the present invention may be used as a host.

Meanwhile, in the present invention, in addition to the host, a dopant material may be used for the emission 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.

Also, as the material for the electron transport layer in the present invention, a known electron transport material may be used as it functions to stably transport electrons injected from an electron injection electrode (Cathode). Examples of known electron transport materials include quinoline derivatives, in particular tris(8-quinolinolate)aluminum (Alq3), TAZ, Balq, beryllium bis(benzoquinolin-10- Materials such as olate: Bebq2), ADN, [Compound 201], [Compound 202], and oxadiazole derivatives PBD, BMD, BND, etc. may be used.

TAZ BALQ

[Compound 201] [Compound 202] BCP

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

[Formula C]

In the [Formula C],

Y represents a portion in which any one selected from C, N, O and S is directly bonded to M to form a single bond, and a portion in which any one selected from C, N, O and S forms a coordination bond to M It is a ligand chelated by the single bond and the coordination bond.

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

OA is a monovalent ligand capable of single or coordinate bonding with M, wherein O is oxygen, and A is a substituted or unsubstituted C 1 to C 30 alkyl group, a substituted or unsubstituted C 5 to C 50 aryl group, A substituted or unsubstituted C 2 to C 30 alkenyl group, a substituted or unsubstituted C 2 to C 20 alkynyl group, a substituted or unsubstituted C 3 to C 30 cycloalkyl group, a substituted or unsubstituted C 5 to C 30 cyclo Any one selected from an alkenyl group and a heteroaryl group having 2 to 50 carbon atoms which is substituted or unsubstituted and has O, N or S as a hetero atom.

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

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

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

[Structural formula C1] [Structural formula C2] [Structural formula C3]

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

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

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

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

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

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

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

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

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

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

[Structural formula C37] [Structural formula C38] [Structural formula C39]

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

R is the same as or different from each other, and each independently represents hydrogen, deuterium, halogen, a cyano group, a substituted or unsubstituted C 1 to C 30 alkyl group, a substituted or unsubstituted C 6 to C 30 aryl group, a substituted or unsubstituted A heteroaryl group having 3 to 30 carbon atoms, 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, substituted or An unsubstituted C1-C30 alkylamino group, a substituted or unsubstituted C1-C30 alkylsilyl group, a substituted or unsubstituted C6-C30 arylamino group, and a substituted or unsubstituted C6-C30 arylsilyl group It is selected from the group and may be connected to an adjacent substituent with alkylene or alkenylene to form a spiro ring or a fused ring.

L is a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C5 to C30 selected from a heteroaryl group and a substituted or unsubstituted cycloalkyl group having 5 to 30 carbon atoms, wherein 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 of a heteroaryl group, a cyano group, a halogen group, and one or more substituents selected from deuterium and hydrogen, and may be connected to an adjacent substituent by alkylene or alkenylene to form a spiro ring or a fused ring.

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 electroluminescent device of the present invention. The organic electroluminescent 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 if necessary, a hole injection layer 30 and The electron injection layer 70 may be further included, and in addition to that, it is possible to further form an intermediate layer of one or two layers, and a hole blocking layer or an electron blocking layer may be further formed.

Referring to FIG. 1, the organic electroluminescent device and the manufacturing method thereof of the present invention are as follows.

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

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

The hole injection layer material may 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 ] can be used.

In addition, the material of the hole transport layer is not particularly limited as long as it is commonly used in the art, 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), etc. can be used.

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

As a 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 limited thereto it's not going to be

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 depositing the electron transport layer 60 on 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 . By vapor deposition to form the cathode 80 electrode, the organic EL device is completed. Here, as the metal for forming the cathode, lithium (Li), magnesium (Mg), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), magnesium-silver ( Mg-Ag) may be used, and in order to obtain a top light emitting device, a transmissive cathode using ITO or IZO may be used.

In addition, the light emitting layer may be made of a host and a dopant, and according to a specific example of the present invention, the light emitting layer preferably has a thickness of 50 to 2,000 Å.

In this case, the dopant used in the light emitting layer may be at least one compound selected from compounds represented by the following [General Formula A-1] to [General Formula J-1].

[General Formula A-1]

In the above [general formula A-1],

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 are the same as or different from each other as a ligand and may each independently be any one selected from the following [Structural Formula D], and “*” in the following Structural Formula D is coordinated to the metal ion M represents the site.

[Structural Formula D]

In the [Structural Formula D],

R is different from or the same as each other, and each independently represents hydrogen, deuterium, halogen, cyano group, a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C6-C50 aryl group, a substituted or unsubstituted carbon number A 5 to 50 heteroaryl group, 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 A substituted or unsubstituted C 1 to C 30 alkylamino group, a substituted or unsubstituted C 1 to C 30 alkylsilyl group, a substituted or unsubstituted C 6 to C 30 arylamino group, and a substituted or unsubstituted C 6 to C 30 arylsilyl group may be any one selected from, wherein R is each independently 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, halogen It may be further substituted with one or more substituents selected from a group, deuterium and hydrogen, and wherein R is connected to each adjacent substituent with alkylene or alkenylene to form an alicyclic ring and a monocyclic or polycyclic aromatic ring. can

L is a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C5 to C30 selected from a heteroaryl group and a substituted or unsubstituted cycloalkyl group having 5 to 30 carbon atoms, wherein 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 of a heteroaryl group, a cyano group, a halogen group, deuterium and hydrogen, which is further substituted with one or more substituents selected from the group consisting of, and may be connected to an adjacent substituent by alkylene or alkenylene to form a spiro ring or a fused ring.

According to an embodiment of the present invention, the dopant represented by the [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 the above [General Formula A-1], and Y ^A11 , Y ^A14 , Y ^A15 and Y ^A18 each independently represent a carbon atom or a nitrogen atom, and 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, or a sulfur atom, and L ^A11 , L ^A12 , L ^A13 , L ^A14 are each independently A-1] represents a linking group such as L ₁ , L ₂ and L ₃ , and Q ^A11 , Q ^A12 represents a partial structure containing an atom bonded to M ^A1 .

According to an embodiment of the present invention, the compound represented by the [general formula B-1] may be any one selected from the following compounds.

[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] above, 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, or a sulfur atom, L ^B11 , L ^B12 , L ^B13 , L ^B14 represents a linking group, Q ^B11 , Q ^B12 represents a partial structure containing an atom bonding to M ^B1 .

According to an embodiment of the present invention, the compound represented by the [general formula C-1] may be any one selected from the following compounds.

*

[General formula D-1]

In the above [general formula D-1],

M ^C1 represents the same metal ion as defined in [General Formula A-1] above, R ^C11 , R ^C12 each independently represents a hydrogen atom, a substituent connected to each other to form a 5-membered ring, and a substituent not connected to each other , R ^C11 , R ^C12 are each independently a hydrogen atom, a substituent connected to each other to form a 5-membered ring, or a substituent not connected to each other, R ^C13 , R ^C14 are each independently a hydrogen atom, a 5-membered ring linked to each other A substituent forming a substituent, represents a substituent not connected to each other, G ^C11 , G ^C12 each independently represents a nitrogen atom, a substituted or unsubstituted carbon atom, L ^C11 , L ^C12 represents a linking group, Q ^C11 , Q ^C12 represents a partial structure containing an atom bonding to M ^C1 .

According to an embodiment of the present invention, the compound represented by the [general formula D-1] may be any one selected from the following compounds.

[General formula E-1]

In the above [general formula E-1],

M ^D1 represents the same metal ion as defined in the above [General Formula A-1], G ^D11 , G ^D12 each independently represents a nitrogen atom, a substituted or unsubstituted carbon atom, J ^D11 , J ^D12 , J ^D13 and J ^D14 each independently represent an atomic group necessary for forming a 5-membered ring, and L ^D11 and L ^D12 represent a linking group.

According to an embodiment of the present invention, the compound represented by the [general formula E-1] may be any one selected from the following compounds.

[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] above, J ^E11 , J ^E12 each independently represents an atomic group required 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 or a substituted or unsubstituted carbon atom.

According to an embodiment of the present invention, the compound represented by the [general formula F-1] may be any one selected from the following compounds.

[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] above, 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 , and R ^F13 and R ^F14 may be linked 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 bonding to M ^F1 .

According to an embodiment of the present invention, the compound represented by the [general formula G-1] may be any one selected from the following compounds.

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

In the above [general formula H-1],

R ¹¹ , R ¹² are an alkyl group, an aryl group, or a heteroaryl group, and may form a fused ring with a substituent adjacent to each other, and q11 and q12 are integers from 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 from each other.

L ¹ is a ligand binding to platinum, preferably a ligand capable of forming an ortho metalized platinum complex, a nitrogen-containing heterocyclic ligand, a diketone ligand, or a halogen ligand, more preferably an ortho metal (ortho metal). ) is a ligand that forms 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, preferably 2;

In addition, n ¹ , m ¹ is preferably such that the metal complex represented by the [general formula H-1] becomes a neutral complex.

In the above [general formula H-2],

R ²¹ , R ²² , n ² , m ² , q ²² , L ² are the same as R ¹¹ , R ¹² , n ¹ , m ¹ , q ¹² , and L ¹ , respectively, and q ²¹ is an integer of 0 to 2 , 0 is preferred.

In the above [general formula H-3],

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

According to an embodiment of the present invention, the compound represented by the [General Formula H-1] to [General Formula H-3] may be any one selected from the following compounds.

[General 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 a substituent, and the other two rings are an aryl ring or heteroaryl ring which may have a substituent. It represents a ring, and may form a condensed ring with 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 any 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 (provided) or a bond, but Q ¹ , Q ² and Q ³ do not simultaneously represent a bond. Any two of Z ¹ , Z ² , Z ³ and Z ⁴ represent a coordination bond, and the other two represent a covalent bond, an oxygen atom or a sulfur atom.

According to an embodiment of the present invention, the compound represented by the [General Formula I-1] may be any one selected from the following compounds.

[General formula J-1]

In the [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 bonded to M (-C=N- ), each nitrogen atom (N) is bonded to the above-mentioned M, and forms a tridentate ligand bonded to the above-mentioned M at 3 positions as a whole.

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

Preferably, M is Pt, and Ar1 is preferably selected from a 5-membered ring, a 6-membered ring, and condensed cyclic groups thereof.

According to an embodiment of the present invention, the compound represented by the [general formula J-1] may be any one selected from the following compounds.

*

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

In addition, at least one layer 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 under vacuum or low pressure, etc., and the solution process is used as a material for forming each layer It refers to a method of mixing a material to be used with a solvent and forming a thin film through a method such as inkjet printing, roll-to-roll coating, screen printing, spray coating, dip coating, spin coating, and the like.

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

Hereinafter, the present invention will be described in more detail with reference to preferred embodiments. However, these examples are for illustrating the present invention in more detail, and it will be apparent to those of ordinary skill 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 3]

(1) Synthesis of the compound represented by [Formula 3-a]

The compound represented by [Formula 3-a] was synthesized by the following [Scheme 1].

[Scheme 1]

[Formula 3-a]

In a 1L round bottom flask, 50 g (255 mmol) of 5-bromoindole, 156.1 g (765 mmol) of iodobenzene, 48.6 g (765 mmol) of copper, 13.5 g (51 mmol) of 18-crown-6, 141 g (1020 mmol) of potassium carbonate, 1 500 mL of ,2-dichlorobenzene was added and refluxed for 72 hours. Upon completion of the reaction, after cooling to room temperature, an excess of methanol was added to produce a solid. The resulting solid was filtered and purified by column chromatography using ethyl acetate and hexane as developing solvents to obtain 39.5 g (yield: 56.9%) of the compound represented by [Formula 3-a].

(2) Synthesis of the compound represented by [Formula 3-b]

A compound represented by [Formula 3-b] was synthesized by the following [Scheme 2].

[Scheme 2]

[Formula 3-a] [Formula 3-b]

In a 1L round-bottom flask, 39.5 g (145 mmol) of [Formula 3-a] obtained from [Scheme 1] was dissolved in 400 mL of tetrahydrofuran, and 108.8 mL (174 mmol, 1.6M in hexane) of n-butyllithium was slowly added at -78 ° C. did After stirring for one hour, 21.1 g (203 mmol) of trimethyl borate was added, and the mixture was slowly raised to room temperature and stirred for another 12 hours. 2-Normal hydrochloric acid aqueous solution was added until it became acid, extracted with water and ethyl acetate, dried over magnesium sulfate, and recrystallized to obtain 29.1 g (yield: 84.6%) of the compound represented by [Formula 3-b].

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

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

[Scheme 3]

[Formula 3-b] [Formula 3-c]

In a 500 mL round-bottom flask, 18.5 g (94 mmol) of 5-bromoindole, 29.1 g (123 mmol) of [Formula 3-b] obtained from [Scheme 2], 2.2 g (2 mmol) of tetrakistriphenylphosphine palladium, potassium carbonate 26.1 g (189 mmol), 40 mL of water, 100 mL of toluene and 100 mL of 1,4-dioxane were added and refluxed for 12 hours. After completion of the reaction, the reactant was layer-separated, the organic layer was concentrated under reduced pressure, recrystallized from hexane, and filtered and dried to obtain 22.5 g (yield: 59.5%) of the compound represented by [Formula 3-c].

(4) Synthesis of the compound represented by [Formula 3-d]

A compound represented by [Formula 3-d] was synthesized by the following [Scheme 4].

[Scheme 4]

[Formula 3-c] [Formula 3-d]

17.2 g of a compound represented by [Formula 3-d] synthesized in the same manner except that 1-bromo-4-iodobenzene was used instead of iodobenzene used in [Scheme 1] of Synthesis Example 1 ( Yield: 50.9%) was obtained.

(5) Synthesis of the compound represented by [Formula 3-e]

The compound represented by [Formula 3-e] was synthesized by the following [Scheme 5].

[Scheme 5]

[Formula 3-d] [Formula 3-e]

It was synthesized in the same manner and expressed as [Formula 3-e] except that [Formula 3-d] obtained from [Scheme 4] was used instead of [Formula 3-a] used in [Scheme 2] of Synthesis Example 1 14.1 g of the compound used (yield: 88.7%) was obtained.

(6) Synthesis of the compound represented by [Formula 3-f]

A compound represented by [Formula 3-f] was synthesized by the following [Scheme 6].

[Scheme 6]

[Formula 3-f]

In a 1L round-bottom flask, 24.3 g (935 mmol) of magnesium, 1 g of iodine, and 150 mL of tetrahydrofuran were added and dissolved, and then 155.3 g (985 mmol) of bromobenzene was added and refluxed for 2 hours to prepare solution A. In another 1L round-bottom plaque, 70 g (380 mmol) of cyanuric chloride was dissolved in 300 mL of tetrahydrofuran, cooled to 10° C., and solution A was slowly added thereto for 1 hour, followed by stirring at room temperature. Upon completion of the reaction, the solid was filtered, the filtrate was distilled under reduced pressure, and recrystallized from hexane to obtain 46.1 g (yield: 45%) of the compound represented by [Formula 3-f].

(7) Synthesis of the compound represented by [Formula 3]

The compound represented by [Formula 3] was synthesized by the following [Scheme 7].

[Scheme 7]

[Formula 3-e] [Formula 3-f] [Formula 3]

[Formula 3-e] obtained in [Scheme 5] 14.1g (33mmol), [Formula 3-f] obtained in [Scheme 6] 8.8g (33mmol), tetrakistriphenylphosphine palladium 0.8g (1mmol), potassium 50 mL of carbonate (2M) and 50 mL of ethanol were dissolved in 50 mL of toluene, and then heated at 120° C. and stirred for 3 hours. Upon completion of the reaction, extraction was performed with water and ethyl acetate, and the organic layer was dried over magnesium sulfate, concentrated under reduced pressure, and purified with hexane to obtain 13.5 g (yield: 66.7%) of the compound represented by [Formula 3].

MS(MALDI-TOF): m/z = 616 [M] ⁺

¹³ C NMR (75 MHz, CDCl3) δ:

104.8 111.6 114.1 116.8 119.4 121.3 125.5 127.5 128.1 128.3 129.2 129.3 131.1 131.5 133.6 134.7 138.7 143.7 170.7 172.2 [43C]

<Synthesis Example 2> Synthesis of the compound represented by [Formula 59]

(1) Synthesis of the compound represented by [Formula 59-a]

The compound represented by [Formula 59-a] was synthesized by the following [Scheme 8].

[Scheme 8]

[Formula 59-a]

60.0 g (413 mmol) of 2,3-dimethylindole was dissolved in 400 mL of dimethylformamide, followed by stirring at 0°C. After that, 73.5 g (413 mmol) of N-bromosuccinimide was dissolved in 200 mL of dimethylformamide and slowly added dropwise to the reaction solution while maintaining 0° C. for 1 hour. After the reaction solution was added dropwise to room temperature and stirred for 12 hours, when the reaction was completed, distilled water was added dropwise at room temperature to form brown crystals. The resulting crystals were filtered and recrystallized from toluene and methanol to obtain 50 g of a compound represented by [Formula 59-a] (yield: 54%).

(2) Synthesis of the compound represented by [Formula 59-b]

A compound represented by [Formula 59-b] was synthesized by the following [Scheme 9].

[Scheme 9]

[Formula 59-a] [Formula 59-b]

It was synthesized in the same manner as [Formula 59-b] except that [Formula 59-a] obtained from [Scheme 8] was used instead of 5-bromoindole used in [Scheme 1] of Synthesis Example 1. Compound 51g (yield: 76.1%) was obtained.

(3) Synthesis of the compound represented by [Formula 59-c]

A compound represented by [Formula 59-c] was synthesized by the following [Scheme 10].

[Scheme 10]

[Formula 59-b] [Formula 59-c]

It was synthesized in the same manner and expressed as [Formula 59-c] except that [Formula 59-b] obtained from [Scheme 9] was used instead of [Formula 3-a] used in [Scheme 2] of Synthesis Example 1 39.3 g of the compound used (yield: 87.3%) was obtained.

(4) Synthesis of the compound represented by [Formula 59-d]

The compound represented by [Formula 59-d] was synthesized by the following [Scheme 11].

[Scheme 11]

[Formula 59-a] [Formula 59-c] [Formula 59-d]

Use [Formula 59-a] obtained from [Scheme 8] instead of 5-bromoindole used in [Scheme 3] of Synthesis Example 1, and [Formula 3-b] instead of [Formula 3-b] used in [Scheme 3] 10], except that [Formula 59-c] obtained from [Formula 59-c] was synthesized in the same manner to obtain 47.8 g (Yield: 57.5%) of the compound represented by [Formula 59-d].

(5) Synthesis of the compound represented by [Formula 59-e]

A compound represented by [Formula 59-e] was synthesized by the following [Scheme 12].

[Scheme 12]

[Formula 59-d] [Formula 59-e]

35 g of the compound represented by [Formula 59-e] synthesized in the same manner except that 1-bromo-4-iodobenzene was used instead of iodobenzene used in [Scheme 1] of Synthesis Example 1 (yield : 51.4%) was obtained.

(6) Synthesis of the compound represented by [Formula 59-f]

A compound represented by [Formula 59-f] was synthesized by the following [Scheme 13].

[Scheme 13]

[Formula 59-e] [Formula 59-f]

It was synthesized in the same manner and expressed as [Formula 59-f] except that [Formula 59-e] obtained from [Scheme 12] was used instead of [Formula 3-a] used in [Scheme 2] of Synthesis Example 1 28.2 g of the compound used (yield: 86.4%) was obtained.

(7) Synthesis of the compound represented by [Formula 59]

The compound represented by [Formula 59] was synthesized by the following [Scheme 14].

[Scheme 14]

[Formula 59-f] [Formula 3-f] [Formula 59]

The compound represented by [Formula 59] synthesized in the same manner except that [Formula 59-f] obtained from [Scheme 13] was used instead of [Formula 3-e] used in [Scheme 7] of Synthesis Example 1 18.3 g (yield: 46.7%) was obtained.

MS(MALDI-TOF): m/z = 672 [M] ⁺

¹³ C NMR (75 MHz, CDCl3) δ:

9.5 10.7 110 111.6 114.1 116.8 119.4 121.3 125.5 127.5 128.1 129.2 129.3 130.2 131.1 131.5 134.7 136.3 143.7 145 151 170.7 172.2 [47C]

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

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

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

[Scheme 15]

[Formula 60-a]

In a 2L round bottom flask, 220 g (984 mmol) of 4-bromophenylhydrazine hydrochloride, 128 g (656 mmol) of benzyl phenyl ketone and 1100 mL of ethanol were added and refluxed for 12 hours. After neutralization with a base, extraction was performed with water and ethyl acetate, and the organic material was concentrated under reduced pressure and recrystallized from hexane. The crystals were filtered and dried to obtain 136.6 g (yield 39.8%) of the compound represented by [Formula 60-a].

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

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

[Scheme 16]

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

It was synthesized in the same manner as [Formula 60-b] except that [Formula 50-a] obtained from [Scheme 15] was used instead of 5-bromoindole used in [Scheme 1] of Synthesis Example 1. Compound 57g (yield: 68.5%) was obtained.

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

A compound represented by [Formula 60-c] was synthesized by the following [Scheme 17].

[Scheme 17]

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

[Formula 60-c] was synthesized in the same manner except that [Formula 60-b] obtained from [Scheme 16] was used instead of [Formula 3-a] used in [Scheme 2] of Synthesis Example 1 and expressed as [Formula 60-c] 45.5 g of the compound used (yield: 87%) was obtained.

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

The compound represented by [Formula 60-d] was synthesized by the following [Scheme 18].

[Scheme 18]

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

31.3 g (90 mmol) of [Formula 60-a] obtained from [Scheme 15], 45.5 g (117 mmol) of [Formula 60-c] obtained from [Scheme 17], 2.1 g of tetrakistriphenylphosphine palladium in a 100 mL round-bottom flask (2mmol), 24.8g (180mmol) of potassium carbonate, 65 mL of water, 160 mL of toluene and 1600 mL of 1,4-dioxane were added and refluxed for 12 hours. Upon completion of the reaction, the reactant was layer-separated, the organic layer was concentrated under reduced pressure, recrystallized from hexane, and filtered and dried to obtain 41.7 g of a compound represented by [Formula 60-d] (yield: 58.2%).

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

A compound represented by [Formula 60-e] was synthesized by the following [Scheme 19].

[Scheme 19]

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

[Formula 60-e] was synthesized in the same manner except that [Formula 60-d] obtained from [Scheme 18] was used instead of [Formula 59-d] used in [Scheme 12] of Synthesis Example 2 and expressed as [Formula 60-e] 28.2 g of the compound used (yield: 54%) was obtained.

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

A compound represented by [Formula 60-f] was synthesized by the following [Scheme 20].

[Scheme 20]

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

It was synthesized in the same manner and expressed as [Formula 60-f] except that [Formula 60-e] obtained from [Scheme 19] was used instead of [Formula 3-a] used in [Scheme 2] of Synthesis Example 1 23.5 g of the compound used (yield: 87.3%) was obtained.

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

A compound represented by [Formula 60] was synthesized by the following [Scheme 21].

[Scheme 21]

[Formula 60-f] [Formula 3-f] [Formula 60]

The compound represented by [Formula 60] synthesized in the same manner except that [Formula 60-f] obtained from [Scheme 20] was used instead of [Formula 3-e] used in [Scheme 7] of Synthesis Example 1 15.2 g (yield: 51.4%) was obtained.

MS(MALDI-TOF): m/z= 920 [M] ⁺

¹³ C NMR (75 MHz, CDCl3) δ:

111.6 114.1 116.8 119.2 125.5 126.6 127.4 127.5 128.1 128.7 129.2 129.3 131.1 131.5 133 134.7 136.1 136.8 143.7 145.1 170.7 172.2 [67C]

<Synthesis Example 4> Synthesis of the compound represented by [Formula 61]

(1) Synthesis of the compound represented by [Formula 61-a]

A compound represented by [Formula 61-a] was synthesized by the following [Scheme 22].

[Scheme 22]

[Formula 61-a]

Compound 44.2g (yield: 52.3%) was obtained.

(2) Synthesis of the compound represented by [Formula 61-b]

A compound represented by [Formula 61-b] was synthesized by the following [Scheme 23].

[Scheme 23]

[Formula 61-a] [Formula 61-b]

It was synthesized in the same manner as [Formula 61-b] except that [Formula 61-a] obtained from [Scheme 22] was used instead of 5-bromoindole used in [Scheme 1] of Synthesis Example 1 Compound 41g (yield: 72.5%) was obtained.

(3) Synthesis of the compound represented by [Formula 61-c]

The compound represented by [Formula 61-c] was synthesized by the following [Scheme 24].

[Scheme 24]

[Formula 61-b] [Formula 61-c]

It was synthesized in the same manner and expressed as [Formula 61-c] except that [Formula 61-b] obtained from [Scheme 23] was used instead of [Formula 3-b] used in [Scheme 2] of Synthesis Example 1 29g (yield: 78.7%) of the compound used was obtained.

(4) Synthesis of the compound represented by [Formula 61-d]

A compound represented by [Formula 61-d] was synthesized by the following [Scheme 25].

[Scheme 25]

[Formula 61-a] [Formula 61-c] [Formula 61-d]

[Formula 61-a] obtained from [Scheme 22] is used instead of [Formula 60-a] used in [Scheme 18] of Synthesis Example 3, and [Formula 60-c] used in [Scheme 18] is used instead of [Formula 60-c] 21g (yield: 49.2%) of the compound represented by [Formula 61-d] was obtained by synthesizing in the same manner except that [Formula 61-c] obtained in Scheme 24] was used.

(5) Synthesis of the compound represented by [Formula 61-e]

A compound represented by [Formula 61-e] was synthesized by the following [Scheme 26].

[Scheme 26]

[Formula 61-d] [Formula 61-e]

It was synthesized in the same manner and expressed as [Formula 61-e] except that [Formula 61-d] obtained from [Scheme 25] was used instead of [Formula 59-d] used in [Scheme 12] of Synthesis Example 2 17g (yield: 60.6%) of the compound used was obtained.

(6) Synthesis of the compound represented by [Formula 61-f]

A compound represented by [Formula 61-f] was synthesized by the following [Scheme 27].

[Scheme 27]

[Formula 61-e] [Formula 61-f]

It was synthesized in the same manner and expressed as [Formula 61-f] except that [Formula 61-e] obtained from [Scheme 26] was used instead of [Formula 3-a] used in [Scheme 2] of Synthesis Example 1 13 g of the compound used (yield: 81.8%) was obtained.

(7) Synthesis of the compound represented by [Formula 61]

A compound represented by [Formula 61] was synthesized by the following [Scheme 28].

[Scheme 28]

[Formula 61-f] [Formula 3-f] [Formula 61]

The compound represented by [Formula 61] synthesized in the same manner except that [Formula 61-f] obtained from [Scheme 27] was used instead of [Formula 3-e] used in [Scheme 7] of Synthesis Example 1 12.5 g (yield: 50.7%) was obtained.

MS(MALDI-TOF): m/z= 768 [M] ⁺

¹³ C NMR (75 MHz, CDCl3) δ:

102.4 111.6 114.1 116.8 119.2 125.5 126.6 127.5 128.1 128.7 129.2 129.3 131.1 131.5 134 134.7 136.8 139.6 143.7 144.3 170.7 172.2 [55C]

<Synthesis Example 5> Synthesis of the compound represented by [Formula 58]

(1) Synthesis of the compound represented by [Formula 58-a]

The compound represented by [Formula 58-a] was synthesized by the following [Scheme 29].

[Scheme 29]

[Formula 58-a]

In a 2L round-bottom flask, 7.9 g (325 mmol) of magnesium, 1 g of iodine, and 600 mL of tetrahydrofuran were added and dissolved, and then 75.8 g (325 mmol) of 4-bromobiphenyl was added and refluxed for 2 hours to prepare solution A. In another 2L round-bottom flask, 50 g (271 mmol) of cyanuric chloride was dissolved in 600 mL of tetrahydrofuran, cooled to 0° C., and solution A was slowly added for 1 hour, followed by stirring for 2 hours. When the reaction was completed, the organic layer was dried over magnesium sulfate, concentrated under reduced pressure, and purified with hexane to obtain 45 g of the compound represented by [Formula 58-a] (yield: 54.9%).

(2) Synthesis of the compound represented by [Formula 58-b]

A compound represented by [Formula 58-b] was synthesized by the following [Scheme 30].

[Scheme 30]

[Formula 58-a] [Formula 58-b]

In a 500 mL round-bottom flask, 4.3 g (179 mmol) of magnesium, 1 g of iodine, and 230 mL of tetrahydrofuran were added and dissolved, and then 28.1 g (179 mmol) of bromobenzene was added and refluxed for 2 hours to prepare solution A. In a 1L round bottom flask, 45 g (149 mmol) of [Formula 58-a] obtained from [Reaction Scheme 29] was dissolved in 180 mL of tetrahydrofuran, cooled to 0 ° C, and solution A was slowly added for 1 hour, followed by stirring for 2 hours. . When the reaction was completed, the filtrate was distilled under reduced pressure and recrystallized from methanol to obtain 26 g of a compound represented by [Formula 58-b] (yield: 50.8%).

(3) Synthesis of the compound represented by [Formula 58]

A compound represented by [Formula 58] was synthesized by the following [Scheme 31].

[Scheme 31]

[Formula 59-f] [Formula 58-b] [Formula 58]

The compound represented by [Formula 58] synthesized in the same manner except that [Formula 58-b] obtained from [Scheme 30] was used instead of [Formula 3-f] used in [Scheme 14] of Synthesis Example 2 31 g (yield: 54.8%) was obtained.

MS(MALDI-TOF): m/z= 748 [M] ⁺

¹³ C NMR (75 MHz, CDCl3) δ:

9.5 10.7 110 111.6 114.1 116.8 119.4 121.3 125.5 127.2 127.5 127.6 127.9 128 128.1 129.2 129.3 130.2 131.1 131.5 133.6 134.7 136.3 140.8 143.7 145 151 170.7 171.7 172.7 [53C]

<Synthesis Example 6> Synthesis of the compound represented by [Formula 56]

(1) Synthesis of the compound represented by [Formula 56-a]

The compound represented by [Formula 56-a] was synthesized by the following [Scheme 32].

[Scheme 32]

[Formula 56-a]

In a 1000mL round bottom flask, 20g (109mmol) of 2,4,6-trichloropyrimidine, 29.2g (239mmol) of phenylboronic acid, 6.3g (5mmol) of tetrakistriphenylphosphine palladium, 160mL of sodium carbonate (2M) , 160 mL of ethanol, and 320 mL of toluene were added, and then heated at 120° C. and stirred for 3 hours. Upon completion of the reaction, the reaction solution was extracted with water and ethyl acetate, and the organic layer was dried over magnesium sulfate, concentrated under reduced pressure, and purified with hexane to obtain 25 g (yield: 86%) of the compound represented by [Formula 56-a].

(2) Synthesis of the compound represented by [Formula 56]

A compound represented by [Formula 56] was synthesized by the following [Scheme 33].

[Scheme 33]

[Formula 59-f] [Formula 56-a] [Formula 56]

A compound represented by [Formula 56] synthesized in the same manner except that [Formula 56-a] obtained from [Scheme 32] was used instead of [Formula 3-f] used in [Scheme 14] of Synthesis Example 2 32 g (yield: 50.9%) was obtained.

MS(MALDI-TOF): m/z = 671 [M] ⁺

¹³ C NMR (75 MHz, CDCl3) δ:

9.5 10.7 108.8 110 111.6 114.1 116.8 119.4 121.3 125.5 127.5 128.1 128.7 129.2 129.3 130.2 131.5 135.8 136.3 143.7 145 151 155 164.6 [48C]

<Synthesis Example 7> Synthesis of the compound represented by [Formula 57]

(1) Synthesis of the compound represented by [Formula 57-a]

A compound represented by [Formula 57-a] was synthesized by the following [Scheme 34].

[Scheme 34]

[Formula 57-a]

17.8 g of a compound represented by [Formula 57-a] synthesized in the same manner except that 2,4,6-trichloropyridine was used instead of cyanuric chloride used in [Scheme 6] of Synthesis Example 1 ( Yield: 56%) was obtained.

(2) Synthesis of the compound represented by [Formula 57]

The compound represented by [Formula 57] was synthesized by the following [Scheme 35].

[Scheme 35]

[Formula 59-f] [Formula 57-a] [Formula 57]

The compound represented by [Formula 57] synthesized in the same manner except that [Formula 57-a] obtained from [Scheme 34] was used instead of [Formula 3-f] used in [Scheme 14] of Synthesis Example 2 28 g (yield: 62.4%) was obtained.

MS(MALDI-TOF): m/z= 670 [M] ⁺

¹³ C NMR (75 MHz, CDCl3) δ:

9.5 10.7 110 111.6 114.1 115.6 116.8 119.4 121.3 125.5 127.3 127.6 128 129.2 129.3 130.2 136.3 139 139.1 143.7 145 151 151.5 152 153.6 [49C]

<Synthesis Example 8> Synthesis of the compound represented by [Formula 97]

(1) Synthesis of the compound represented by [Formula 97-a]

The compound represented by [Formula 97-a] was synthesized by the following [Scheme 36].

[Scheme 36]

[Formula 97-a]

40.2 g of the compound represented by [Formula 97-a] synthesized in the same manner except that 6-bromoindole was used instead of 5-bromoindole used in [Scheme 1] of Synthesis Example 1 (Yield: 57.9 %) was obtained.

(2) Synthesis of the compound represented by [Formula 97-b]

A compound represented by [Formula 97-b] was synthesized by the following [Scheme 37].

[Scheme 37

[Formula 97-a] [Formula 97-b]

[Formula 97-b] was synthesized in the same manner except that [Formula 97-a] obtained from [Scheme 36] was used instead of [Formula 3-a] used in [Scheme 2] of Synthesis Example 1 and expressed as [Formula 97-b] 28.5 g of the compound used (yield: 81.4%) was obtained.

(3) Synthesis of the compound represented by [Formula 97-c]

The compound represented by [Formula 97-c] was synthesized by the following [Scheme 38].

[Scheme 38]

[Formula 97-b] [Formula 97-c]

[Formula 97-c] was synthesized in the same manner except that [Formula 97-b] obtained from [Scheme 37] was used instead of [Formula 3-b] used in [Scheme 3] of Synthesis Example 1 and expressed as [Formula 97-c] 21g (yield: 56.7%) of the compound used was obtained.

(4) Synthesis of the compound represented by [Formula 97-d]

A compound represented by [Formula 97-d] was synthesized by the following [Scheme 39].

[Scheme 39]

[Formula 97-c] [Formula 97-d]

[Formula 97-d] was synthesized in the same manner except that [Formula 97-c] obtained from [Scheme 38] was used instead of [Formula 3-c] used in [Scheme 4] of Synthesis Example 1 and expressed as [Formula 97-d] 15.5 g of the compound used (yield: 49.1%) was obtained.

(5) Synthesis of the compound represented by [Formula 97-e]

A compound represented by [Formula 97-e] was synthesized by the following [Scheme 40].

[Scheme 40]

[Formula 97-d] [Formula 97-e]

[Formula 97-e] was synthesized in the same manner except that [Formula 97-d] obtained from [Scheme 39] was used instead of [Formula 3-d] used in [Scheme 5] of Synthesis Example 1 11.4 g of the compound used (yield: 79.6%) was obtained.

(6) Synthesis of the compound represented by [Formula 97]

A compound represented by [Formula 97] was synthesized by the following [Scheme 41].

[Scheme 41]

[Formula 97-e] [Formula 3-f] [Formula 97]

The compound represented by [Formula 97] synthesized in the same manner except that [Formula 97-e] obtained from [Scheme 40] was used instead of [Formula 3-e] used in [Scheme 7] of Synthesis Example 1 12.2 g (yield: 74.7%) was obtained.

MS(MALDI-TOF): m/z = 616 [M] ⁺

¹³ C NMR (75 MHz, CDCl3) δ:

104.8 109.9 111.6 114.1 116.8 118.9 119.3 119.4 121.3 125.5 127.5 128.1 128.3 129.2 129.3 131.1 131.5 133.6 134.7 138.7 141.6 143.7 145.9 170.7 172.2 [43C]

<Synthesis Example 9> Synthesis of the compound represented by [Formula 118]

(1) Synthesis of the compound represented by [Formula 118-a]

A compound represented by [Formula 118-a] was synthesized by the following [Scheme 42].

[Scheme 42]

[Formula 118-a]

At room temperature, 2-aminobenzonitrile (20.0 g, 169 mmol) and 140 mL of tetrahydrofuran were added to a round bottom flask under a nitrogen stream and stirred. Phenylmagnesium bromide (3.0M in Et ₂ O) was added dropwise to 112.9 mL (339 mmol). After stirring at reflux for about 1 hour, the temperature was set to 0°C. Ethyl chloroformate (22.0 g, 203 mmol) was added dropwise, and the mixture was stirred under reflux for about 1 hour. An aqueous ammonium chloride solution was added until it became weakly acidic, and the resulting solid was filtered and washed with water and heptane to obtain 30.1 g of [Formula 118-a]. (Yield: 80%)

(2) Synthesis of the compound represented by [Formula 118-b]

A compound represented by [Formula 118-b] was synthesized by the following [Scheme 43].

[Scheme 43]

[Formula 118-b]

At room temperature, about 80 mL of the synthesized [Intermediate 118-a] (30.0 g, 135 mmol), phosphorus oxychloride, was added to a round bottom flask under a nitrogen stream and stirred. After stirring at reflux overnight, the temperature was cooled to -20 °C the next day, and then about 400 mL of water was slowly added dropwise. The resulting solid was filtered and washed with water, methanol, and heptane. 14.6 g of [Formula 118-b] was obtained by recrystallization from toluene and heptane. (Yield: 44.9%)

(3) Synthesis of the compound represented by [Formula 118]

The compound represented by [Formula 118] was synthesized by the following [Scheme 44].

[Scheme 44]

[Formula 118]

8 g (26 mmol) of the synthesized [Formula 3-c] and 100 mL of dimethylformamide were added to a round bottom flask and stirred, then 1.7 g (43 mmol) of 60% sodium hydride was added and stirred for 1 hour. After dissolving 8.5 g (33 mmol) of the synthesized [Formula 118-b] in 100 mL of dimethylformamide, it was slowly added to the reaction solution for 1 hour and stirred for 2 hours. When the reaction was completed, water was poured into the reaction solution, filtered, dissolved in toluene, and recrystallized from acetone to obtain 6 g (yield: 45%) of [Formula 118].

MS(MALDI-TOF): m/z = 513 [M] ⁺

¹³ C NMR (75 MHz, CDCl3) δ:

102.4 104.8 111.6 116.8 119.2 119.4 121.3 124.7 125.5 127.4 127.5 127.7 128.3 128.5 128.7 129.2 129.3 131.1 131.8 132.3 133.6 138.7 143.3 143.7 149.3 155.8 161 [36C]

<Synthesis Example 10> Synthesis of the compound represented by [Formula 119]

*(1) Synthesis of the compound represented by [Formula 119-a]

The compound represented by [Formula 119-a] was synthesized by the following [Scheme 45].

[Scheme 45]

[Formula 119-a]

Under a stream of nitrogen, 1-nitronaphthalene (50.0 g, 289 mmol), ethyl cyanoacetate (98.0 g, 866 mmol), potassium cyanide (20.7 g, 318 mmol), potassium hydroxide (32.4 g, 577 mmol) in a round bottom flask immersed in water was added and stirred. 100 mL of dimethylformamide was added, and the temperature was raised to 60° C., followed by stirring overnight. The next day, the change in TLC was confirmed, and the temperature of the flask was brought to room temperature. The reaction solution was concentrated under reduced pressure to remove all possible dimethylformamide. The concentrate was transferred to a reactor with a small amount of dichloromethane, and 500 mL of a 5% aqueous sodium hydroxide solution was added and stirred. After stirring under reflux for about 1 hour, the temperature was brought to room temperature. It was extracted with ethyl acetate and water. It was separated by column chromatography using ethyl acetate and heptane. It was recrystallized from toluene and heptane to obtain 24.6 g (yield 50.7%) of [Formula 119-a] as a white solid.

(2) Synthesis of the compound represented by [Formula 119-b]

A compound represented by [Formula 119-b] was synthesized by the following [Scheme 46].

[Scheme 46]

[Formula 119-b]

21 g of [Formula 119-b] was obtained by synthesizing in the same manner as in [Scheme 42] to [Scheme 43] using the synthesized [Formula 119-a] instead of the 2-aminobenzonitrile used in [Scheme 42]. (Yield: 74.5%)

(3) Synthesis of the compound represented by [Formula 119]

A compound represented by [Formula 119] was synthesized by the following [Scheme 47].

[Scheme 47]

[Formula 119]

7g (yield: 48%) of [Formula 119] was obtained in the same manner using the synthesized [Formula 119-b] instead of [Formula 118-b] used in [Scheme 44].

MS(MALDI-TOF): m/z = 563 [M] ⁺

¹³ C NMR (75 MHz, CDCl3) δ:

102.4 104.8 111.6 116.8 119.2 119.4 121.3 124.7 124.9 125.5 127.2 127.3 127.4 127.5 127.9 128.3 128.7 129.2 129.3 131.1 131.8 133 133.6 134.4 138.7 143.3 143.7 150 155.8 161 [40C]

<Synthesis Example 11> Synthesis of the compound represented by [Formula 122]

(1) Synthesis of the compound represented by [Formula 122-a]

A compound represented by [Formula 122-a] was synthesized by the following [Scheme 48].

[Scheme 48]

[Formula 122-a]

20 g of [Formula 122-a] was obtained by synthesizing in the same manner using 3-amino-2-naphthonitrile instead of [Formula 119-a] used in [Scheme 46]. (Yield: 71%)

(2) Synthesis of the compound represented by [Formula 122]

The compound represented by [Formula 122] was synthesized by the following [Scheme 49].

[Scheme 49]

[Formula 122]

[Formula 119] 6.4g (yield: 44%) was obtained in the same manner using the synthesized [Formula 122-a] instead of [Formula 119-b] used in [Scheme 47].

MS(MALDI-TOF): m/z = 563 [M] ⁺

¹³ C NMR (75 MHz, CDCl3) δ:

102.4 104.8 111.6 116.8 119.2 119.4 121.3 124.7 125.5 127.2 127.3 127.5 128.2 128.3 128.6 128.7 129.2 129.3 131.1 131.8 133.6 134.4 138.7 143.3 143.7 149.3 155.8 161 [40C]

<Examples 1 to 8> Preparation of an organic electroluminescent device including the compound synthesized in Synthesis Examples 1 to 8

After patterning so that the light emitting area of the ITO glass has a size of 2 mm × 2 mm, it was washed. After mounting the substrate in a vacuum chamber, the base pressure was set to 1×10 ^-6 torr, and then organic materials were placed on the ITO with DNTPD (700 Å), NPD (300 Å), the compound synthesized by Synthesis Examples 1 to 8 + Ir ( ppy) ₃ (10%) (300 Å), Alq ₃ (350 Å), LiF (5 Å), and Al (1,000 Å) were formed into a film in the order, and measurement was performed at 0.4 mA.

[DNTPD]

[NPD]

[Ir(ppy) ₃ ]

[Alq ₃ ]

<Comparative Example 1>

The organic light emitting diode device for Comparative Example 1 was manufactured in the same manner as in the device structures of Examples 1 to 8, except that CBP was used instead of the compound prepared by the present invention as a host material.

[CBP]

For the organic electroluminescent devices manufactured according to Examples 1 to 8 and Comparative Example 1, voltage, current density, luminance, color coordinates, and lifetime were measured, and the results are shown in Table 1 below. T80 means the time it takes for the luminance to decrease from the initial luminance (7000 nits) to 80%.

division host dopant Doping concentration (%) V Cd/m2 CIEx CIEy T ₈₀ (Hr) Example 1 Formula 3 Ir(ppy) ₃ 10 4.7 5010 0.308 0.625 131 Example 2 Formula 59 Ir(ppy) ₃ 10 4.5 5110 0.312 0.621 128 Example 3 Formula 60 Ir(ppy) ₃ 10 4.6 5100 0.313 0.621 135 Example 4 Formula 61 Ir(ppy) ₃ 10 4.5 5200 0.312 0.625 148 Example 5 Formula 58 Ir(ppy) ₃ 10 4.7 5010 0.314 0.622 110 Example 6 Formula 56 Ir(ppy) ₃ 10 4.8 5060 0.315 0.623 125 Example 7 Formula 57 Ir(ppy) ₃ 10 4.6 5000 0.315 0.621 139 Example 8 Formula 97 Ir(ppy) ₃ 10 4.6 5060 0.309 0.620 126 Comparative Example 1 CBP Ir(ppy) ₃ 10 7.9 3800 0.297 0.624 68

As shown in Table 1, the organic electroluminescent device including the heterocyclic compound prepared according to Examples 1 to 8 of the present invention as a host material has a driving voltage (V) compared to Comparative Example 1 in which the host material is CBP. ) is low, and has excellent luminous efficiency (Cd/m2) and long lifespan (T ₈₀ ).

<Examples 9 to 11> Preparation of an organic electroluminescent device including the compound synthesized in Synthesis Examples 9 to 11

After patterning so that the light emitting area of the ITO glass has a size of 2 mm × 2 mm, it was washed. After mounting the substrate in a vacuum chamber, the base pressure was set to 1×10 ^-6 torr, and the organic material was placed on the ITO with DNTPD (700 Å), NPD (300 Å), and the compound synthesized by Synthesis Examples 9 to 11 + (piq) ) ₂ Ir (acac) (10%) (300 Å), Alq ₃ (350 Å), LiF (5 Å), Al (1,000 Å) was formed into a film in the order, and the measurement was performed at 0.4 mA.

The structure of (piq) ₂ Ir(acac) is as follows.

[(piq) ₂ Ir(acac)]

<Example 12> In the device structures of Examples 9 to 11, [Formula 122] was used for the light emitting layer, and [PTOEP] was used instead of [(piq) ₂ Ir(acac)]. PTOEP] is structured as follows.

[PTOEP]

<Comparative Example 2>

The organic light emitting diode device for Comparative Example 2 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 structures of Examples 9 to 11.

For the organic electroluminescent devices manufactured according to Examples 9 to 12 and Comparative Example 2, voltage, current density, luminance, color coordinates and lifetime were measured, and the results are shown in Table 2 below. T90 refers to the time required for the luminance to decrease from the initial luminance (3700 nit) to 90%.

division host dopant Doping concentration (%) V Cd/m2 CIEx CIEy T ₉₀ (Hr) Example 9 Formula 118 (piq) ₂ Ir(acac) 10 4.4 1380 0.671 0.325 1175 Example 10 Formula 119 (piq) ₂ Ir(acac) 10 4.1 1450 0.674 0.322 1105 Example 11 Formula 122 (piq) ₂ Ir(acac) 10 4.1 1420 0.671 0.325 1080 Example 12 Formula 122 PTOEP 10 4.1 1400 0.652 0.327 1065 Comparative Example 2 CBP (piq) ₂ Ir(acac) 10 7.5 410 0.667 0.328 140

As shown in [Table 2], the organic electroluminescent device including the heterocyclic compound prepared according to Examples 9 to 12 of the present invention as a host material has a driving voltage (V) compared to Comparative Example 2 in which the host material is CBP. ) is low, and has excellent luminous efficiency (Cd/m2) and long lifespan (T ₉₀ ).

Claims (7)

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

In the above [Formula 1],
X ₁ to X ₂ and X ₁₁ to X ₁₂ are the same as or different from each other and each independently represent hydrogen, deuterium, a carboxyl group or a salt thereof, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, and a substituted or unsubstituted carbon number 6 to 40 selected from the aryl group of
X ₃ to X ₁₀ are the same as or different from each other and each independently represent hydrogen, deuterium, a halogen group, a substituted or unsubstituted C 1 to C 30 alkyl group, a substituted or unsubstituted C 1 to C 60 alkoxy group, and a substituted or unsubstituted It is selected from an aryl group having 6 to 40 carbon atoms,
Ar ₁ and Ar ₂ are the same or different from each other and each independently is a single bond, or is selected from the group consisting of a substituted or unsubstituted arylene group having 6 to 40 carbon atoms and a substituted or unsubstituted heteroarylene group having 2 to 30 carbon atoms; , p+q is an integer between 1 and 6, and when p and q are each an integer of 2 or more, a plurality of Ar ₁ and Ar ₂ are the same as or different from each other,
R ₁ is selected from the following [Structural Formula 7],
R ₂ are the same or different from each other and are each independently a substituted or unsubstituted C 1 to C 30 alkyl group, a substituted or unsubstituted C 1 to C 30 alkylsilyl group, a substituted or unsubstituted C 6 to C 40 aryl group, and It is selected from the following [Structural Formula 7],
[Structural Formula 7]

In the [Structural Formula 7],
X is selected from hydrogen, deuterium, a substituted or unsubstituted C 1 to C 30 alkyl group, a substituted or unsubstituted C 6 to C 40 aryl group, and a substituted or unsubstituted C 2 to C 30 heteroaryl group,
m is an integer of 1 to 5, 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 is bonded through Ar ₁ and Ar ₂ at the nitrogen position in [Formula 1] forming a single bond,
L is a single bond, or is selected from the group consisting of a substituted or unsubstituted C6 to C60 arylene group and a substituted or unsubstituted C2 to C60 heteroarylene group (provided that L is a substituted or unsubstituted acry Dean is excluded), n is an integer between 1 and 3, and when n is 2 or more, a plurality of L's are the same or different from each other. According to claim 1,
X ₁ to X ₁₂ , R ₁ to R ₇ , Ar ₁ , Ar ₂ and L are each independently a deuterium atom, a cyano group, a halogen atom, an alkyl group having 1 to 40 carbon atoms, an alkoxy group having 1 to 40 carbon atoms, alkyl having 1 to 40 carbon atoms An amino group, 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, an arylsilyl group having 6 to 40 carbon atoms, an aryl group having 6 to 40 carbon atoms, an aryl group having 6 to 40 carbon atoms An aryloxy group, a substituted or unsubstituted arylthio group having 6 to 40 carbon atoms, a heteroaryl group having 3 to 40 carbon atoms, a germanium group, characterized in that it is further substituted with one or more substituents selected from the group consisting of phosphorus and boron. a heterocyclic compound. According to claim 1,
The heterocyclic compound represented by the [Formula 1] is a heterocyclic compound, characterized in that any one selected from the group represented by the following formula:

[Formula 2] [Formula 3]

[Formula 4] [Formula 5]

[Formula 6] [Formula 7]

[Formula 8] [Formula 9]

[Formula 10] [Formula 11]

[Formula 12] [Formula 13]

[Formula 14] [Formula 15]

[Formula 16] [Formula 17]

[Formula 18] [Formula 19]

[Formula 20] [Formula 21]

[Formula 22] [Formula 23]

[Formula 24] [Formula 25]

[Formula 26] [Formula 27]

[Formula 28] [Formula 29]

[Formula 30] [Formula 31]

[Formula 32] [Formula 33]

[Formula 34] [Formula 35]

[Formula 36] [Formula 37]

[Formula 38] [Formula 39]

[Formula 40] [Formula 41]

[Formula 42] [Formula 43]

[Formula 44] [Formula 45]

[Formula 46] [Formula 47]

[Formula 48] [Formula 49]

[Formula 50] [Formula 51]

[Formula 52] [Formula 53]

[Formula 54] [Formula 55]

[Formula 56] [Formula 57]

[Formula 58] [Formula 59]

[Formula 60] [Formula 61]

[Formula 62] [Formula 63]

[Formula 64] [Formula 65]

[Formula 66] [Formula 67]

[Formula 68] [Formula 69]

[Formula 70] [Formula 71]

[Formula 72] [Formula 73]

[Formula 74] [Formula 75]

[Formula 76] [Formula 77]

[Formula 78] [Formula 79]

[Formula 80] [Formula 81]

[Formula 82] [Formula 83]

[Formula 84] [Formula 85]

[Formula 86] [Formula 87]

[Formula 88] [Formula 89]

[Formula 90] [Formula 91]

[Formula 92] [Formula 93]

[Formula 94] [Formula 95]

[Formula 96] [Formula 97]

[Formula 101]

[Formula 102] [Formula 103]

[Formula 104] [Formula 105]

[Formula 106] [Formula 107]

[Formula 108] [Formula 109]

[Formula 110] [Formula 111]

[Formula 112] [Formula 113] a first electrode; a second electrode opposite the first 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. 5. The method of claim 4,
The organic layer comprises at least one layer selected from a hole injection layer, a hole transport layer, a functional layer having both a hole injection function and a hole transport function, a light emitting layer, an electron transport layer, and an electron injection layer. 6. The method of claim 5,
The light emitting layer includes at least one host compound and at least one dopant compound, wherein the host compound is a heterocyclic compound represented by the above [Formula 1]. 5. The method of claim 4,
An organic light emitting device, characterized in that the organic layer further includes at least one organic light emitting layer emitting red, green or blue light to emit white light.

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