KR102191024B1 - 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 including the same, wherein the heterocyclic compound is represented by the following [Chemical Formula 1], and the organic electroluminescent device including the same is a driving voltage, light emission The efficiency and life characteristics are very good.
[Formula 1]

Description

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 including the same as a light emitting material, and more particularly, to a heterocyclic compound having excellent and stable light emission characteristics such as driving voltage and luminous efficiency, and organic electroluminescence containing the same. It relates to the device.

Recently, organic light emitting devices capable of low voltage driving by self-luminous type have superior viewing angles and contrast ratios, compared to LCD (liguid crystal displays), which are the mainstream of flat panel display devices, do not require a 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 while electrons and holes form a pair and then disappear when 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 electroluminescent device using the organic light emitting phenomenon has a structure including an anode, a cathode, and an organic material layer therebetween. Here, the organic material layer is often made of a multi-layered structure composed of different materials in order to increase the efficiency and stability of the organic light emitting device. For example, it may be formed of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, etc. . In the structure of such an organic light emitting device, when a voltage is applied between the two electrodes, holes are injected from the anode and electrons from the cathode are injected into the organic material layer, and excitons are formed when the injected holes and electrons meet. It glows when it falls back to the ground.

The organic electroluminescent device not only can form the device on a flexible transparent substrate such as plastic, but also at a voltage lower than 10V 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 target of many people's interest as a next-generation rich color display device.

In order for the organic electroluminescent device to fully exhibit the above-described excellent features, materials that form the organic material layer in the device, such as hole injection materials, hole transport materials, light-emitting materials, electron transport materials, and electron injection materials, are supported by stable and efficient materials. Although this should be preceded, the development of a stable and efficient organic material layer material for an organic light emitting device has not been sufficiently achieved. Therefore, the development of new materials continues to be required.

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

The present invention provides a heterocyclic compound represented by the following [Chemical 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 a heterocyclic compound represented by [Chemical Formula 1].

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

Since the heterocyclic compound represented by [Chemical Formula 1] according to the present invention is stable compared to conventional materials and has excellent luminescence characteristics in driving voltage or current efficiency, an organic electroluminescent device including the same can be driven at a low voltage, The luminous efficiency can be improved.

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 device, and is characterized in that it is a heterocyclic compound represented by the following [Formula 1].

[Formula 1]

In the above [Formula 1],

X ₁ To X ₁₄ is the same as or different from each other, and each independently hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 40 carbon atoms, a substituted or unsubstituted carbon number of 2 to 30 Heteroaryl group, halogen atom, hydroxyl group, cyano group, nitro group, amino group, amidino group, hydrazine, hydrazone, carboxyl group or salt thereof, sulfonic acid group or salt thereof, phosphoric acid or salt thereof, substituted or unsubstituted carbon number 2 to 60 alkenyl group, substituted or unsubstituted C 2 to C 60 alkynyl group, substituted or unsubstituted C 1 to C 60 alkoxy group, substituted or unsubstituted C 3 to C 60 cycloalkyl group, 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 alkyl thioxy group having 1 to 30 carbon atoms, a substituted or unsubstituted arylthioc having 5 to 30 carbon atoms It may be selected from the group consisting of a time period, a substituted or unsubstituted arylthio group having 5 to 60 carbon atoms, -SiR ₃ R ₄ R ₅ and -NR ₆ R ₇ .

In addition, the X ₁₁ to X ₁₄ may each be connected with a substituent adjacent to each other to form an alicyclic, aromatic monocyclic or polycyclic ring, and carbon atoms of the formed alicyclic, aromatic monocyclic or polycyclic ring are N, It may be substituted with any one or more heteroatoms selected from S and O.

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

Y may be selected from the group consisting of CX ₂₁ X ₂₂ , NX ₂₃ , O, S, SiX ₂₄ X ₂₅ , and X ₂₁ to X ₂₅ are the same as defined in X ₁ to X ₁₄ .

Ar ₁ and Ar ₂ are the same as or different from each other, and each may be independently selected from the group consisting of a substituted or unsubstituted aryl group having 6 to 40 carbon atoms and a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms.

L is a linking group, a single bond, a substituted or unsubstituted alkylene group having 1 to 60 carbon atoms, a substituted or unsubstituted C2 to C60 Alkenylene group, substituted or unsubstituted C2-C60 alkynylene group, substituted or unsubstituted C3-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 Can be.

n is an integer between 1 and 3, and p+q may be an integer between 1 and 6.

In addition, the R ₁ to R ₇ , X ₁₁ to X ₁₄ , X ₂₁ to X ₂₅ , L, Ar ₁ and Ar ₂ are each independently a deuterium atom, a cyano group, a halogen atom, a hydroxy group, a nitro group, a carbon number of 1 to 40 Alkyl group, C 1 to C 40 alkoxy group, C 1 to C 40 alkylamino group, C 6 to C 40 arylamino group, C 3 to C 40 heteroarylamino group, C 1 to C 40 alkylsilyl group, C 6 to C 40 It may be substituted with one or more selected from the group consisting of an arylsilyl group, a C6-C40 aryl group, a C3-C40 aryloxy group, a C3-C40 heteroaryl group, a germanium group, phosphorus and boron, and , The substituents may be bonded to each other with adjacent substituents to form a saturated or unsaturated ring, or may be attached or fused together in a pendant manner.

On the other hand, the aryl group as a substituent used in the present invention is an organic radical derived from an aromatic hydrocarbon by one hydrogen removal, 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 neighboring substituents 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, pyre And aromatic groups such as anyl group, indenyl, fluorenyl group, tetrahydronaphthyl group, pyrenyl, peryleneyl, chrysenyl, naphthacenyl, fluoranthenyl, and the like.

At least one hydrogen atom in the aryl group is a deuterium atom, a halogen atom, a hydroxy group, a nitro group, a cyano group, a silyl group, an amino group (-NH ₂ , -NH(R), -N(R')(R"), R 'And R'are 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, 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, carbon number It may be substituted with a 2 to 24 heteroaryl group or a C 2 to 24 heteroarylalkyl group.

The heteroaryl group used in the present invention may be a substituent selected from the following [Structural Formula 1] to [Structure 6] when Ar ₁ and Ar ₂ are heteroaryl groups.

[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 hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 5 to 50 carbon atoms, a substituted or unsubstituted Any one selected from a cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted aryl group having 5 to 50 carbon atoms, and a substituted or unsubstituted heteroaryl group having 2 to 50 carbon atoms having O, N or S as a hetero atom In each of the [Structural Formula 1] to [Structural Formula 6], the R ₃₁ to R ₄₄ One of them may form a single bond by bonding with nitrogen in [Chemical Formula 1].

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 the [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 at least one X May form a single bond by bonding with nitrogen in the [Chemical Formula 1].

Specific examples of the alkyl group as a substituent used in the present invention include methyl group, ethyl group, propyl 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 at least one hydrogen atom in the alkyl group is a deuterium atom, a halogen atom, a hydroxy 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 a C 1 It is an alkyl group of to 24 (referred to as an "alkylamino group" in this case), 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, a halogenated alkyl group having 1 to 24 carbon atoms, Alkenyl group having 2 to 24 carbon atoms, alkynyl group having 2 to 24 carbon atoms, heteroalkyl group having 1 to 24 carbon atoms, aryl group having 5 to 24 carbon atoms, arylalkyl group having 6 to 24 carbon atoms, heteroaryl group having 3 to 24 carbon atoms or carbon number It may be substituted with 3 to 24 heteroarylalkyl groups.

Specific examples of the alkoxy group as a substituent used in 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, and the like. May be substituted with the same substituent as in the case of the alkyl group.

Specific examples of the halogen group that is 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, fluorenyl Oxy, indenyloxy, and the like, and one or more hydrogen atoms contained 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 And dimethylfurylsilyl.

Specific examples of the alkenyl group used in the present invention represent 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'substituted' 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, 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, heteroaryl group having 2 to 24 carbon atoms or carbon number 2 to 24 heteroarylalkyl group, C 1 to C 24 alkoxy group, C 1 to C 24 alkylamino group, C 1 to C 24 arylamino group, C 1 to C 24 hetero arylamino group, C 1 to C 24 alkylsilyl group, It means 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 range of carbon atoms of the alkyl group or aryl group in the "substituted or unsubstituted alkyl group having 1 to 30 carbon atoms", "substituted or unsubstituted aryl group having 5 to 50 carbon atoms", etc. considers the portion where the substituent is substituted It does not mean the total number of carbon atoms constituting the alkyl moiety or the aryl moiety when viewed as unsubstituted. For example, a phenyl group in which a butyl group is substituted at the para position means that it corresponds to an aryl group having 6 carbon atoms substituted with a butyl group having 4 carbon atoms.

The heterocyclic compound represented by [Chemical Formula 1] according to the present invention may be more specifically selected from compounds represented by [Chemical Formula 2] to [Chemical Formula 145].

[Chemical Formula 2] [Chemical Formula 3]

[Chemical Formula 4] [Chemical Formula 5]

[Formula 6] [Formula 7]

[Chemical Formula 8] [Chemical Formula 9]

[Formula 10] [Formula 11]

[Formula 12] [Formula 13]

[Formula 14] [Formula 15]

[Formula 16] [Formula 17]

[Chemical Formula 18] [Chemical Formula 19]

[Formula 20] [Formula 21]

[Formula 22] [Formula 23]

[Formula 24] [Formula 25]

[Formula 26] [Formula 27]

[Formula 28] [Formula 29]

[Chemical Formula 30] [Chemical Formula 31]

[Formula 32] [Formula 33]

[Formula 34] [Formula 35]

[Chemical Formula 36] [Chemical Formula 37]

[Chemical Formula 38] [Chemical Formula 39]

[Formula 40] [Formula 41]

[Formula 42] [Formula 43]

[Formula 44] [Formula 45]

[Chemical Formula 46] [Chemical Formula 47]

[Chemical Formula 48] [Chemical Formula 49]

[Formula 50] [Formula 51]

[Formula 52] [Formula 53]

[Chemical Formula 54] [Chemical Formula 55]

[Chemical Formula 56] [Chemical Formula 57]

[Chemical Formula 58] [Chemical Formula 59]

[Chemical Formula 60] [Chemical Formula 61]

[Formula 62] [Formula 63]

[Formula 64] [Formula 65]

[Chemical Formula 66] [Chemical Formula 67]

[Chemical Formula 68] [Chemical Formula 69]

[Formula 70] [Formula 71]

[Chemical Formula 72] [Chemical Formula 73]

[Formula 74] [Formula 75]

[Chemical Formula 76] [Chemical Formula 77]

[Chemical Formula 78] [Chemical Formula 79]

[Chemical Formula 80] [Chemical Formula 81]

[Formula 82] [Formula 83]

[Formula 84] [Formula 85]

[Formula 86] [Formula 87]

[Chemical Formula 88] [Chemical Formula 89]

[Formula 90] [Formula 91]

[Formula 92] [Formula 93]

[Formula 94] [Formula 95]

[Chemical Formula 96] [Chemical Formula 97]

[Chemical Formula 98] [Chemical Formula 99]

[Chemical Formula 100] [Chemical Formula 101]

[Formula 102] [Formula 103]

[Chemical Formula 104] [Chemical Formula 105]

[Formula 106] [Formula 107]

[Chemical Formula 108] [Chemical Formula 109]

[Chemical Formula 110] [Chemical Formula 111]

[Chemical Formula 112] [Chemical Formula 113]

[Chemical Formula 114] [Chemical Formula 115]

[Chemical Formula 116] [Chemical Formula 117]

[Chemical Formula 118] [Chemical Formula 119]

[Chemical Formula 120] [Chemical Formula 121]

[Formula 122] [Formula 123]

[Chemical Formula 124] [Chemical Formula 125]

[Chemical Formula 126] [Chemical Formula 127]

[Chemical Formula 128] [Chemical Formula 129]

[Chemical Formula 130] [Chemical Formula 131]

[Chemical Formula 132] [Chemical Formula 133]

[Formula 134] [Formula 135]

[Chemical Formula 136] [Chemical Formula 137]

[Chemical Formula 138] [Chemical Formula 139]

[Chemical Formula 140] [Chemical Formula 141]

[Chemical Formula 142] [Chemical Formula 143]

[Formula 144] [Formula 145]

In addition, the present invention includes a first electrode, a second electrode facing the first electrode, and an organic layer interposed between the first electrode and the second electrode, wherein the organic layer is represented by the above [Formula 1] It may contain 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. have. In this case, the organic layer interposed between the first electrode and the second electrode may include an emission layer, the emission layer is composed 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, a dopant material may be used in addition to a host for the emission layer. When the emission 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.

In addition, in the present invention, a known electron transport material may be used as the material for the electron transport layer, which has a function of stably transporting electrons injected from an 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-). olate: Bebq2), ADN, [Compound 201], [Compound 202], and oxadiazole derivatives such as PBD, BMD, BND, and the like may be used.

TAZ BAlq

[Compound 201] [Compound 202] BCP

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

[Formula C]

In [Chemical Formula C],

Y is a portion in which any one selected from C, N, O, and S is directly bonded to the 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 the M. It includes, and 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 a single bond or coordination bond with 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, A substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 5 to 30 carbon atoms 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.

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

'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 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 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 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, a substituted or Unsubstituted C1-C30 alkylamino group, substituted or unsubstituted C1-C30 alkylsilyl group, substituted or unsubstituted C6-C30 arylamino group, and substituted or unsubstituted C6-C30 arylsilyl It is selected from groups, 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 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 C 5 to 30 carbon atom 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, and 3 to 20 carbon atoms It is further substituted with one or more substituents selected from a heteroaryl group, a cyano group, a halogen group, 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 light emitting 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, the hole injection layer 30 and An electron injection layer 70 may be further included, and in addition to that, a first or second intermediate layer may be further formed, and a hole blocking layer or an electron blocking layer may be further formed.

Referring to FIG. 1, an organic light emitting device of the present invention and a method of manufacturing the same will be described 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, and an organic substrate or a transparent plastic substrate excellent in transparency, surface smoothness, ease of handling and waterproofness 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.

The hole injection layer 30 is formed by vacuum thermal evaporation or spin coating on the anode 20 electrode. Then, a hole transport layer material is vacuum thermally evaporated or spin coated on the hole injection layer 30 to form the hole transport layer 40.

The hole injection layer material is not particularly limited as long as it is commonly used in the art, and may be used, 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, 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), and 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 formed on the organic light-emitting layer 50 by vacuum deposition or spin coating to form a thin film. can do. The hole blocking layer plays a role of preventing such a problem by using a material having a very low HOMO (Highest Occupied Molecular Orbital) level because when holes pass through the organic light emitting layer and flow into the cathode, the life and efficiency of the device are reduced. . In this case, the hole blocking material to be used is not particularly limited, but must have an electron transport ability and an ionization potential higher than that of the light emitting compound, and representatively, BAlq, BCP, TPBI, etc. 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 does not become.

BAlq BCP Bphen

TPBI NTAZ BeBq ₂

OXD-7 Liq

Formula 101 Formula 102 Formula 103

Formula 104 Formula 105 Formula 106

Chemical 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 cathode-forming metal is vacuum-heated on the electron injection layer 70. The organic EL device is completed by vapor deposition to form the cathode 80 electrode. Here, the cathode-forming metal is lithium (Li), magnesium (Mg), aluminum (Al), aluminum-ridium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), and magnesium-silver ( Mg-Ag) or the like 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 emission layer may be formed of a host and a dopant, and according to a specific example of the present invention, the thickness of the emission layer is preferably 50 to 2,000 Å.

In this case, the dopant used in the light emitting layer 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]

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

[Structural Formula D]

In the [Structural 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 carbon number 5 to 50 heteroaryl group, substituted or unsubstituted C 1 to C 30 alkoxy group, substituted or unsubstituted C 3 to C 30 cycloalkyl group, substituted or unsubstituted C 2 to C 30 alkenyl group, substituted or unsubstituted A substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, and a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms It may be any one selected from, and 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, a halogen Group, deuterium and hydrogen may be further substituted with one or more substituents selected from, and the R is connected to each of the adjacent substituents by alkylene or alkenylene to form an alicyclic ring and a monocyclic or polycyclic aromatic ring. I can.

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 C 5 to 30 carbon atom 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, and 3 to 20 carbon atoms It is further substituted with one or more substituents selected from a heteroaryl group, a cyano group, a halogen group, deuterium and hydrogen, 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 [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 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 represent a linking group such as L ₁ , L ₂ and L ₃ defined in [General Formula A-1], and Q ^A11 and Q ^A12 represent an atom bonded to M ^A1 It shows the partial structure to contain.

According to an embodiment of the present invention, the compound represented by [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], Y ^B11 , Y ^B14 , Y ^B15 and Y ^B18 each independently represent a carbon atom or a nitrogen atom, and 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, and a sulfur atom, L ^B11 , L ^B12 , L ^B13 , L ^B14 represent a linking group, Q ^B11 , Q ^B12 represents a partial structure containing an atom bonded to M ^B1 .

According to an embodiment of the present invention, the compound represented by [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], and R ^C11 and R ^C12 each independently represent a hydrogen atom, a substituent that is connected to each other to form a 5-membered ring, and a substituent that is not connected to each other. , R ^C11 and R ^C12 each independently represent a hydrogen atom, a substituent that is connected to each other to form a 5-membered ring, and a substituent that is not connected to each other, and R ^C13 and R ^C14 are each independently a hydrogen atom, each of which is a 5-membered ring Represents a substituent that forms a substituent, a substituent that is 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 bonded to M ^C1 .

According to an embodiment of the present invention, the compound represented by [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 [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 each independently represent an atomic group required to form 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 [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], and J ^E11 and J ^E12 each independently represent 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, a substituted or unsubstituted carbon atom.

According to an embodiment of the present invention, the compound represented by [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], L ^F11 , L ^F12 and L ^F13 represent a linking group, R ^F11 , R ^F12 , R ^F13 and R ^F14 represent a substituent, and R ^F11 and R ^F12 , R ^F12 And R ^F13 , R ^F13 and R ^F14 may be 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 bonded to M ^F1 .

According to an embodiment of the present invention, the compound represented by [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 and 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 of 0 to 4, preferably 0 to 2. Also, 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, a halogen ligand, and more preferably an ortho metal. ) 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, and m ¹ is 1 or 2, preferably 2.

In addition, it is preferable that n ¹ and m ¹ make the metal complex represented by the above [General Formula H-1] 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 , L ³ are the same as R ¹¹ , n ¹ , m ¹ , and L ¹ , respectively, and q ³¹ represents an integer of 0 to 8, preferably 0 to 2, and more than 0 desirable.

According to an embodiment of the present invention, the compound represented by [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 of the rings A to D may have a substituent, and the other two rings are an aryl ring or heteroaryl which may have a substituent. Represents a ring, and can 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 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 (term) or a bond, but Q ¹ , Q ² and Q ³ do not represent a bond at the same time. Z ¹ , Z ² , Z ³ and Z ⁴ are any two representing 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 [General Formula I-1] may be any one selected from the following compounds.

[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-) bonded to the M In ), the nitrogen atom (N) is each bonded 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. In addition, 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 monodentate ligand.

The M is preferably Pt, and Ar1 is preferably selected from a 5-membered ring, a 6-membered ring, and a condensed ring group thereof.

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

In addition, the emission layer may further include various hosts 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 in a vacuum or low pressure state, and the solution process is used as a material for forming each layer It refers to a method of forming a thin film through a method such as inkjet printing, roll-to-roll coating, screen printing, spray coating, dip coating, spin coating, and the like by mixing a material to be formed with a solvent.

In addition, the organic electroluminescent device according to the present invention may 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 single color 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 explaining 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 thereto.

<Example>

<Synthesis Example 1> Synthesis of a compound represented by [Chemical Formula 2]

(1) Synthesis of a compound represented by [Formula 2-a]

A compound represented by [Chemical Formula 2-a] was synthesized by the following [Scheme 1].

[Scheme 1]

[Formula 2-a]

In a 2L round bottom flask, methylaminobenzoate 50.0g (330mmol), bromobenzene 43.2g (276mmol), palladium acetate 1.2g (5.6mmol), Xantfos 6.4g (11.02mmol), cesium carbonate 126g (386mmol), toluene 1000 mL was added and refluxed for 24 hours. After the reaction is completed, the reaction mixture is cooled to room temperature, filtered, toluene is concentrated under reduced pressure to remove the solvent, and the concentrated solution is purified by column chromatography using ethyl acetate and hexane as developing solvents, and 57 g of the compound represented by [Formula 2-a] (yield: 91.2%) was obtained.

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

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

[Scheme 2]

[Formula 2-a] [Formula 2-b]

[Chemical Formula 2-a] 57g (250mmol) obtained from [Scheme 1] and 800 mL of isopropyl ether were added to a 2L round bottom flask, cooled to 10 ℃, and then methylmagnesium bromide (1.0M in diethyl ether) 875 mL (875 mmol) ) Was added dropwise for 1 hour and then refluxed for 2 hours to terminate the reaction. After cooling the reaction solution to room temperature, 400 mL of a 10% ammonium chloride aqueous solution was added and stirred for 2 hours to separate layers to obtain an organic layer and concentrated under reduced pressure to obtain 30 g of a compound represented by [Formula 2-b] (yield: 53%). Got it.

(3) Synthesis of a compound represented by [Formula 2-c]

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

[Scheme 3]

[Formula 2-b] [Formula 2-c]

In a 250 mL round-bottom flask, 30 g (130 mol) of [Chemical Formula 2-b] obtained from [Scheme 2] was dissolved in 60 mL of phosphoric acid and reacted for 6 hours. After the reaction was completed, the reaction solution was added to an excess of water to form a solid, and then filtered to obtain 20g (yield: 73.5%) of a compound represented by [Chemical Formula 2-c].

(4) Synthesis of a compound represented by [Formula 2-d]

A compound represented by [Chemical Formula 2-d] was synthesized by the following [Scheme 4].

[Scheme 4]

[Formula 2-c] [Formula 2-d]

In a 1L round-bottom flask, 20g (96mmol) of [Chemical Formula 2-c] obtained from [Scheme 3] and 100g of silica gel were dissolved in 200 mL of methylene chloride, cooled to 0℃, and then 17.1g (96mmol) of N-bromosuscinimide. A solution dissolved in 200 mL of methylene chloride was added dropwise, followed by stirring at room temperature for 5 hours. After completion of the reaction, the reaction solution was washed 3 times with 600 mL of water, and the solvent was removed to obtain 9.7 g (yield: 35.1%) of the compound represented by [Chemical Formula 2-d].

(5) Synthesis of a compound represented by [Formula 2-e]

A compound represented by [Chemical Formula 2-e] was synthesized by the following [Scheme 5].

[Scheme 5]

[Formula 2-d] [Formula 2-e]

[Chemical Formula 2-d] obtained from [Scheme 4] in a 250 mL round-bottom flask, 9.7 g (34 mmol), iodobenzene 20.6 g (101 mmol), copper 6.4 g (101 mmol), 18-crown-6 1.8 g (7 mmol) , Potassium carbonate 18.6 g (135 mmol), 1,2-dichlorobenzene 100 mL was added and refluxed for 72 hours. After completion of the reaction, the reaction solution was cooled to room temperature and an excess of methanol was added to form a solid, which was then filtered and purified by column chromatography using ethyl acetate and hexane as developing solvents, and compound 6.5 represented by [Formula 2-e] g (yield: 53.0%) was obtained.

(6) Synthesis of a compound represented by [Formula 2-f]

A compound represented by [Chemical Formula 2-f] was synthesized by the following [Scheme 6].

[Scheme 6]

[Formula 2-e] [Formula 2-f]

In a 100 mL round-bottom flask, 6.5 g (18 mmol) of [Formula 2-e] obtained from [Scheme 5] was dissolved in 230 mL of tetrahydrofuran, and 13.4 mL (21 mmol, 1.6M in hexane) of normal-butyllithium was added at -78 °C. It was added slowly. After stirring for an hour, 2.6g (25mmol) of trimethylborate was added, and the mixture was slowly raised to room temperature and stirred for 12 hours. 2-Normal hydrochloric acid aqueous solution was added until it became an acid, followed by extraction with water and ethyl acetate. The obtained extract was dried over magnesium sulfate and recrystallized to obtain 5.4 g (yield: 91.9%) of a compound represented by [Chemical Formula 2-f].

(7) Synthesis of a compound represented by [Formula 2-g]

A compound represented by [Chemical Formula 2-g] was synthesized by the following [Scheme 7].

[Scheme 7]

[Formula 2-g]

To a 1000 mL round-bottom flask, 24.3 g (935 mmol) of magnesium, 1 g of iodine, and 150 mL of tetrahydrofuran were added to dissolve it, and then 155.3 g (985 mmol) of bromobenzene was added and refluxed for 2 hours to prepare a solution (A). I did. Meanwhile, 70 g (380 mmol) of cyanuric chloride was dissolved in 300 mL of tetrahydrofuran in a 1 L round bottom flask, cooled to 10° C., and then solution (A) was slowly added for 1 hour and refluxed for 4 hours. After the reaction was completed, the solid was filtered off, the filtrate was distilled under reduced pressure, and recrystallized with hexane to obtain 46.1g (yield: 45%) of a compound represented by [Chemical Formula 2-g].

(8) Synthesis of a compound represented by [Formula 2-h]

A compound represented by [Chemical Formula 2-h] was synthesized by the following [Scheme 8].

[Scheme 8]

[Formula 2-g] [Formula 2-h]

To a 250 mL round-bottom flask, 5 g (26 mmol) of 5-bromoindole and 75 mL of dimethylformamide were added, stirred, and 1.7 g (43 mmol) of 60% sodium hydride was added, followed by stirring for 1 hour. [Chemical Formula 2-g] obtained from [Scheme 7] was dissolved in 50 mL of dimethylformamide, and then slowly added to the reaction solution for 1 hour and stirred for 2 hours. When the reaction was completed, 100 mL of water was poured into the reaction solution, filtered, dissolved in tetrahydrofuran, and recrystallized with acetone to obtain 9.8g (yield: 89.9%) of a compound represented by [Chemical Formula 2-h].

(9) Synthesis of a compound represented by [Formula 2]

A compound represented by [Chemical Formula 2] was synthesized by the following [Scheme 9].

[Scheme 9]

[Formula 2-h] [Formula 2-f] [Formula 2]

In a 100 mL round-bottom flask, [Formula 2-h] obtained from [Scheme 8] 5.4g (13mmol), [Formula 2-f] obtained from [Scheme 6] 5.4g (16mmol), tetrakistriphenylphosphine palladium 0.3 g (0.3 mmol), potassium carbonate 3.5 g (25 mmol), water 10 mL, toluene 30 mL, and 1,4-dioxane 30 mL were added and refluxed for 12 hours. After completion of the reaction, the reaction product was separated into layers, the organic layer was concentrated under reduced pressure, recrystallized with hexane, filtered and dried to obtain 5.6g (yield: 54.0%) of the compound represented by [Chemical Formula 2].

MS (MALDI-TOF): m/z= 632 [M] ⁺

<Synthesis Example 2> Synthesis of a compound represented by [Chemical Formula 16]

(1) Synthesis of a compound represented by [Formula 16-a]

A compound represented by [Chemical Formula 16-a] was synthesized by the following [Scheme 10].

[Scheme 10]

[Formula 2-d] [Formula 16-a]

[Chemical Formula 2-d] obtained from [Scheme 4] in a 250 mL round bottom flask, 9.7g (34mmol), 9-(4-bromophenyl)carbazole 32.5g (101mmol), copper 6.4g (101mmol), 18- Crown-6 1.8g (7mmol), potassium carbonate 18.6g (135mmol), 1,2-dichlorobenzene 100 mL was added and refluxed for 72 hours. After completion of the reaction, the mixture was cooled to room temperature, and an excess of methanol was added to form a solid, filtered, and purified by column chromatography using ethyl acetate and hexane as developing solvents, and 8.5g of the compound represented by [Formula 16-a] (yield: 47.7%) was obtained.

(2) Synthesis of a compound represented by [Formula 16-b]

A compound represented by [Chemical Formula 16-b] was synthesized by the following [Scheme 11].

[Scheme 11]

[Formula 16-a] [Formula 16-b]

Except for using [Chemical Formula 16-a] obtained from [Scheme 10] instead of [Chemical Formula 2-e] used in [Scheme 6] of Synthesis Example 1, it was synthesized in the same manner and represented as [Chemical Formula 16-b] 6.3g (yield: 79.4%) of the resulting compound was obtained.

(3) Synthesis of a compound represented by [Formula 16-c]

A compound represented by [Chemical Formula 16] was synthesized by the following [Scheme 12].

[Scheme 12]

[Formula 2-h] [Formula 16-b] [Formula 16]

A compound represented by [Chemical Formula 16] synthesized in the same manner except for using [Chemical Formula 16-b] obtained from [Scheme 11] instead of [Chemical Formula 2-f] used in [Scheme 9] of Synthesis Example 1 5.2g (yield: 53.7%) was obtained.

MS (MALDI-TOF): m/z= 797 [M] ⁺

<Synthesis Example 3> Synthesis of a compound represented by [Chemical Formula 31]

(1) Synthesis of a compound represented by [Chemical Formula 31-a]

A compound represented by [Chemical Formula 31-a] was synthesized by the following [Scheme 13].

[Scheme 13]

[Formula 2-f] [Formula 31-a]

Compound 17 g represented by [Chemical Formula 31-a] by synthesizing by the same method except for using 5-bromoindole instead of [Chemical Formula 2-h] used in [Scheme 9] of Synthesis Example 1 (yield: 69%).

(2) Synthesis of a compound represented by [Chemical Formula 31-b]

A compound represented by [Chemical Formula 31-b] was synthesized by the following [Scheme 14].

[Scheme 14]

[Formula 31-a] [Formula 31-b]

Except for using 1-bromo-4-iodobenzene instead of iodobenzene used in [Scheme 5] of Synthesis Example 1, 13.9g of a compound represented by [Chemical Formula 31-b] was synthesized in the same manner (yield : 59%) was obtained.

(3) Synthesis of a compound represented by [Chemical Formula 31-c]

A compound represented by [Chemical Formula 31-c] was synthesized by the following [Scheme 15].

[Scheme 15]

[Formula 31-b] [Formula 31-c]

Except for using [Chemical Formula 31-b] obtained from [Scheme 14] instead of [Chemical Formula 2-e] used in [Scheme 6] of Synthesis Example 1, it was synthesized by the same method and represented by [Chemical Formula 31-c] To obtain 11.8g of the compound (yield: 90.6%).

(4) Synthesis of a compound represented by [Chemical Formula 31-d]

A compound represented by [Chemical Formula 31-d] was synthesized by the following [Scheme 16].

[Scheme 16]

[Chemical Formula 31-d]

In a 1000 mL round-bottom flask, 20 g (109 mmol) of 2,4,6-trichloropyrimidine, 29.2 g (239 mmol) of phenylboronic acid, 6.3 g (5 mmol) of tetrakistriphenylphosphine palladium, and sodium carbonate (2M) After adding 160 mL, 160 mL of ethanol, and 320 mL of toluene, the mixture was heated to 120° C. and stirred for 3 hours. When the reaction was completed, the reaction solution was extracted with water and ethyl acetate, the organic layer was dried over magnesium sulfate, concentrated under reduced pressure, and purified by column chromatography to obtain 25g (yield: 86%) of the compound represented by [Chemical Formula 31-d]. .

(5) Synthesis of the compound represented by [Chemical Formula 31]

A compound represented by [Chemical Formula 31] was synthesized by the following [Scheme 17].

[Scheme 17]

[Formula 31-d] [Formula 31-c] [Formula 31]

[Chemical Formula 31-d] 2.7g (10.1mmol) synthesized from [Scheme 16], [Chemical Formula 31-c] 5g (10.1mmol) synthesized from [Scheme 15] in a 1000 mL round-bottom flask, tetrakistriphenylphos Fin palladium 0.6g (0.5 mmol), potassium carbonate (2M) 15 mL, and ethanol 15 mL were dissolved in 30 mL of toluene, 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 by column chromatography to obtain 5.1 g (yield: 71.3%) of the compound represented by [Chemical Formula 31].

MS (MALDI-TOF): m/z= 707 [M] ⁺

<Synthesis Example 4> Synthesis of a compound represented by [Chemical Formula 84]

(1) Synthesis of a compound represented by [Formula 84-a]

A compound represented by [Chemical Formula 84-a] was synthesized by the following [Scheme 18].

[Scheme 18]

[Formula 2-d] [Formula 84-a]

[Chemical Formula 84-a] was synthesized by the same method except that [Chemical Formula 2-d] obtained from [Scheme 4] of Synthesis Example 1 was used instead of the 5-bromoindole used in [Scheme 8] of Synthesis Example 1 13g of the compound represented by] (yield: 74.4%) was obtained.

(2) Synthesis of the compound represented by [Formula 84-b]

A compound represented by [Chemical Formula 84-b] was synthesized by the following [Scheme 19].

[Scheme 19]

[Formula 84-b]

In a 500 mL round bottom flask, 25 g (128 mmol) 5-bromoindole and 78 g (383 mmol) iodobenzene, 24.3 g (383 mmol) copper, 70.5 g (510 mmol) potassium carbonate, 6.7 g (26 mmol) of 18-crown-6, 250 mL of 1,2-dichlorobenzene was added and refluxed for 72 hours. After the reaction is completed, the reaction solution is cooled to room temperature, and an excess of methanol is added to generate a solid, which is filtered, and purified by column chromatography using ethyl acetate and hexane as developing solvents to obtain a compound represented by [Formula 84-b]. (Yield 43.2%) was obtained.

(3) Synthesis of a compound represented by [Formula 84-c]

A compound represented by [Chemical Formula 84-c] was synthesized by the following [Scheme 20].

[Scheme 20]

[Formula 84-b] [Formula 84-c]

Except for using [Chemical Formula 84-b] obtained from [Scheme 19] instead of [Chemical Formula 2-e] used in [Scheme 6] of Synthesis Example 1, it was synthesized by the same method and represented by [Chemical Formula 84-c] To obtain 11.2g of the compound (yield: 85.7%).

(4) Synthesis of the compound represented by [Chemical Formula 84]

A compound represented by [Chemical Formula 84] was synthesized by the following [Scheme 21].

[Scheme 21]

[Formula 84-a] [Formula 84-c] [Formula 84]

In a 250 mL round bottom flask, [Chemical Formula 84-a] 13.0g (25mmol) obtained from [Scheme 18], [Chemical Formula 84-c] 7.7g (33mmol) obtained from [Scheme 20], potassium carbonate 6.9g (50mmol), 0.6 g (1 mmol) of tetrakistriphenylphosphine palladium, 30 mL of water, 70 mL of toluene, and 70 mL of tetrahydrofuran were added and refluxed for 12 hours. When the reaction was completed, the reaction solution was separated into layers to remove the aqueous layer, the organic layer was separated and concentrated under reduced pressure, and crystals were precipitated using methanol and filtered to obtain 11.0g (yield 69.6%) of the compound represented by [Chemical Formula 84]. .

MS (MALDI-TOF): m/z= 632 [M] ⁺

<Synthesis Example 5> Synthesis of a compound represented by [Chemical Formula 63]

(1) Synthesis of a compound represented by [Formula 63-a]

A compound represented by [Chemical Formula 63-a] was synthesized by the following [Scheme 22].

[Scheme 22]

[Formula 63-a]

Compound 22.3g represented by [Chemical Formula 63-a] by synthesizing in the same manner except that 2,4,6-trichloropyridine was used instead of the cyanuric chloride used in [Scheme 7] of Synthesis Example 1 ( Yield: 78%).

(2) Synthesis of a compound represented by [Chemical Formula 63-b]

A compound represented by [Chemical Formula 63-b] was synthesized by the following [Scheme 23].

[Scheme 23]

[Formula 2-d] [Formula 63-a] [Formula 63-b]

[Chemical Formula 63] was synthesized by the same method except that [Chemical Formula 63-a] obtained from [Scheme 22] was used instead of 9-(4-bromophenyl)carbazole used in [Scheme 10] of Synthesis Example 2 Compound 10.5g (yield: 78.2%) represented by -b] was obtained.

(3) Synthesis of a compound represented by [Chemical Formula 63]

A compound represented by [Chemical Formula 63] was synthesized by the following [Scheme 24].

[Scheme 24]

[Formula 63-b] [Formula 84-c] [Formula 63]

A compound represented by [Chemical Formula 63] synthesized in the same manner except for using [Chemical Formula 63-b] obtained from [Scheme 23] instead of [Chemical Formula 84-a] used in [Scheme 21] of Synthesis Example 4 5.2g (yield: 48.6%) was obtained.

MS (MALDI-TOF): m/z= 630 [M] ⁺

<Synthesis Example 6> Synthesis of a compound represented by [Chemical Formula 68]

(1) Synthesis of the compound represented by [Chemical Formula 68-a]

A compound represented by [Chemical Formula 68-a] was synthesized by the following [Scheme 25].

[Scheme 25]

[Formula 68-a]

Carbazole 26.0g (155mmol) and 390 mL of dimethylformamide were added to a 1000 mL round bottom flask, stirred, and then 60% sodium hydride 9.6g (239 mmol) was added and stirred for 1 hour. After dissolving 31.5 g (171 mmol) of cyanuric chloride in 260 mL of dimethylformamide, it was added to the reaction solution for 1 hour, followed by stirring for 2 hours. When the reaction was completed, the reaction solution was poured into 500 mL of water, filtered, dissolved in tetrahydrofuran, and recrystallized with acetone to obtain 32.4g (yield: 66.1%) of the compound represented by [Chemical Formula 68-a].

(2) Synthesis of a compound represented by [Chemical Formula 68-b]

A compound represented by [Chemical Formula 68-b] was synthesized by the following [Scheme 26].

[Scheme 26]

[Formula 68-a] [Formula 68-b]

[Chemical Formula 68-a] 13.0g (41mmol) obtained from [Scheme 25], phenylboronic acid 5.5g (45mmol), tetrakistriphenylphosphine palladium 1.0g (1mmol), potassium carbonate in a 250 mL round bottom flask 11.4 g (82 mmol), 25 mL of water, 65 mL of toluene, and 65 mL of 1,4-dioxane were added and refluxed for 12 hours. After completion of the reaction, the reaction solution was separated into layers, the organic layer was concentrated under reduced pressure, recrystallized with hexane, filtered and dried to obtain 10.6g (yield: 72%) of the compound represented by [Chemical Formula 68-b].

(3) Synthesis of a compound represented by [Chemical Formula 68-c]

A compound represented by [Chemical Formula 68-c] was synthesized by the following [Scheme 27].

[Scheme 27]

[Formula 2-d] [Formula 68-b] [Formula 68-c]

[Chemical Formula 68] was synthesized by the same method except for using [Chemical Formula 68-b] obtained from [Scheme 26] instead of 9-(4-bromophenyl)carbazole used in [Scheme 10] of Synthesis Example 2 12.1g (yield: 86.8%) of the compound represented by -c] was obtained.

(4) Synthesis of the compound represented by [Chemical Formula 68]

A compound represented by [Chemical Formula 68] was synthesized by the following [Scheme 28].

[Scheme 28]

[Formula 68-c] [Formula 84-c] [Formula 68]

A compound represented by [Chemical Formula 68] synthesized by the same method except for using [Chemical Formula 68-c] obtained from [Scheme 27] instead of [Chemical Formula 84-a] used in [Scheme 21] of Synthesis Example 4 8.1g (yield: 56.5%) was obtained.

MS (MALDI-TOF): m/z= 721 [M] ⁺

<Synthesis Example 7> Synthesis of a compound represented by [Chemical Formula 103]

(1) Synthesis of a compound represented by [Chemical Formula 103-a]

A compound represented by [Chemical Formula 103-a] was synthesized by the following [Scheme 29].

[Scheme 29]

[Formula 103-a]

Except for using 2,3-dimethylindole instead of [Chemical Formula 2-c] used in [Scheme 4] of Synthesis Example 1, 13.5g of a compound represented by [Chemical Formula 103-a] ( Yield: 72.8%).

(2) Synthesis of a compound represented by [Chemical Formula 103-b]

A compound represented by [Chemical Formula 103-b] was synthesized by the following [Scheme 30].

[Scheme 30]

[Formula 103-a] [Formula 103-b]

[Chemical Formula 103-a] 13.5g (60mmol) synthesized in [Scheme 29], iodobenzene 36.9g (181mmol), copper 11.5g (181mmol), potassium carbonate 33.3g (241mmol), 18 in a 500 mL round bottom flask -Crown-6 3.2g (12mmol), 140 mL of 1,2-dichlorobenzene was added and refluxed for 72 hours. After completion of the reaction, the mixture was cooled to room temperature, and an excess of methanol was added to generate a solid, which was then filtered and purified by column chromatography using ethyl acetate and hexane as developing solvents, thereby obtaining 9.5 g of the compound represented by [Formula 103-a] (yield : 52.5%) was obtained.

(3) Synthesis of a compound represented by [Chemical Formula 103-c]

A compound represented by [Chemical Formula 103-c] was synthesized by the following [Scheme 31].

[Scheme 31]

[Formula 103-b] [Formula 103-c]

Except for using [Chemical Formula 103-b] obtained from [Scheme 30] instead of [Chemical Formula 2-e] used in [Scheme 6] of Synthesis Example 1, it was synthesized by the same method and represented by [Chemical Formula 103-c] 7.2 g of the resulting compound (yield: 85.8%) was obtained.

(4) Synthesis of a compound represented by [Chemical Formula 103]

A compound represented by [Chemical Formula 103] was synthesized by the following [Scheme 32].

[Scheme 32]

[Formula 84-a] [Formula 103-c] [Formula 103]

Except for using [Chemical Formula 103-c] obtained from [Scheme 31] instead of [Chemical Formula 84-c] used in [Scheme 21] of Synthesis Example 4, synthesized by the same method and represented by [Chemical Formula 103] Compound 4.0g (yield: 43.7%) was obtained.

MS (MALDI-TOF): m/z= 660 [M] ⁺

<Synthesis Example 8> Synthesis of a compound represented by [Chemical Formula 104]

(1) Synthesis of a compound represented by [Formula 104-a]

A compound represented by [Chemical Formula 104-a] was synthesized by the following [Scheme 33].

[Scheme 33]

[Formula 104-a]

To a 1000 mL round-bottom flask, 110 g (492 mmol) of 4-bromophenylhydrazine hydrochloride, 64 g (328 mmol) of benzylphenyl ketone, and 550 mL of ethanol were added and refluxed for 12 hours. After neutralization with a base, it is extracted with water and ethyl acetate. The organic material was concentrated under reduced pressure, recrystallized with hexane, filtered, and dried to obtain 68.3 g (yield: 39.8%) of the compound represented by [Chemical Formula 104-a].

(2) Synthesis of a compound represented by [Formula 104-b]

A compound represented by [Chemical Formula 104-b] was synthesized by the following [Scheme 34].

[Scheme 34]

[Formula 104-a] [Formula 104-b]

[Chemical Formula 104-a] 25g (72mmol) synthesized in [Scheme 33], iodobenzene 58.6g (287mmol), copper 13.7g (215mmol), potassium carbonate 49.6g (359mmol), 18- in a 500 mL round bottom flask Crown-6 3.8 g (14 mmol) and 125 mL of 1,2-dichlorobenzene were added and refluxed for 72 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, and an excess of methanol was added to generate a solid, which was then filtered and purified by column chromatography using ethyl acetate and hexane as developing solvents. 11.3g of the compound represented by [Formula 104-b] (yield : 37%) was obtained.

(3) Synthesis of a compound represented by [Formula 104-c]

A compound represented by [Chemical Formula 104-c] was synthesized by the following [Scheme 35].

[Scheme 35]

[Formula 104-b] [Formula 104-c]

Except for using [Chemical Formula 104-b] obtained from [Scheme 34] instead of [Chemical Formula 2-e] used in [Scheme 6] of Synthesis Example 1, it was synthesized by the same method and represented by [Chemical Formula 104-c] To obtain a compound 14.5g (yield: 73.6%).

(4) Synthesis of the compound represented by [Chemical Formula 104]

A compound represented by [Chemical Formula 104] was synthesized by the following [Scheme 36].

[Scheme 36]

[Formula 84-a] [Formula 104-c] [Formula 104]

Except for using [Chemical Formula 104-c] obtained from [Scheme 35] instead of [Chemical Formula 84-c] used in [Scheme 21] of Synthesis Example 4, synthesized by the same method and represented by [Chemical Formula 104] Compound 5.5g (yield: 30.7%) was obtained.

MS (MALDI-TOF): m/z= 784 [M] ⁺

<Synthesis Example 9> Synthesis of a compound represented by [Chemical Formula 105]

(1) Synthesis of a compound represented by [Chemical Formula 105-a]

A compound represented by [Chemical Formula 105-a] was synthesized by the following [Scheme 37].

[Scheme 37]

[Formula 105-a]

Except for using acetophenone instead of the benzylphenyl ketone used in [Scheme 33] of Synthesis Example 8, it was synthesized in the same manner to obtain 8.5g (yield: 82.5%) of the compound represented by [Chemical Formula 105-a].

(2) Synthesis of a compound represented by [Chemical Formula 105-b]

A compound represented by [Chemical Formula 105-b] was synthesized by the following [Scheme 38].

[Scheme 38]

[Formula 105-a] [Formula 105-b]

Except for using [Chemical Formula 105-a] obtained from [Scheme 37] instead of [Chemical Formula 104-a] used in [Scheme 34] of Synthesis Example 8, it was synthesized by the same method and represented as [Chemical Formula 105-b] 5.2g (yield: 47.8%) of the resulting compound was obtained.

(3) Synthesis of a compound represented by [Chemical Formula 105-c]

A compound represented by [Chemical Formula 105-c] was synthesized by the following [Scheme 39].

[Scheme 39]

[Formula 105-b] [Formula 105-c]

Except for using [Chemical Formula 105-b] obtained from [Scheme 34] instead of [Chemical Formula 2-e] used in [Scheme 6] of Synthesis Example 1, it was synthesized by the same method and represented by [Chemical Formula 105-c] 3.9 g (yield: 83.4%) of the resulting compound was obtained.

(4) Synthesis of the compound represented by [Chemical Formula 105]

A compound represented by [Chemical Formula 105] was synthesized by the following [Scheme 40].

[Scheme 40]

[Formula 84-a] [Formula 105-c] [Formula 105]

A compound represented by [Chemical Formula 105] synthesized by the same method except for using [Chemical Formula 105-c] obtained from [Scheme 39] instead of [Chemical Formula 84-c] used in [Scheme 21] of Synthesis Example 4 2.8g (yield: 52.7%) was obtained.

MS (MALDI-TOF): m/z= 708 [M] ⁺

<Synthesis Example 10> Synthesis of a compound represented by [Chemical Formula 106]

(1) Synthesis of a compound represented by [Chemical Formula 106-a]

A compound represented by [Chemical Formula 106-a] was synthesized by the following [Scheme 41].

[Scheme 41]

[Formula 106-a]

Except for using ethylphenyl ketone instead of the benzylphenyl ketone used in [Scheme 33] of Synthesis Example 8, it was synthesized in the same manner to obtain 11.2g (yield: 79.3%) of the compound represented by [Chemical Formula 106-a] .

(2) Synthesis of a compound represented by [Chemical Formula 106-b]

A compound represented by [Chemical Formula 106-b] was synthesized by the following [Scheme 42].

[Scheme 42]

[Formula 106-a] [Formula 106-b]

Synthesized by the same method except for using [Chemical Formula 106-a] obtained from [Scheme 41] instead of [Chemical Formula 104-a] used in [Scheme 34] of Synthesis Example 8 and represented by [Chemical Formula 106-b] 7.6 g of the resulting compound (yield: 53.6%) was obtained.

(3) Synthesis of a compound represented by [Chemical Formula 106-c]

A compound represented by [Chemical Formula 106-c] was synthesized by the following [Scheme 43].

[Scheme 43]

[Formula 106-b] [Formula 106-c]

Except for using [Chemical Formula 106-b] obtained from [Scheme 42] instead of [Chemical Formula 2-e] used in [Scheme 6] of Synthesis Example 1, it was synthesized by the same method and represented by [Chemical Formula 106-c] 5.5g (yield: 80.1%) of the compound was obtained.

(4) Synthesis of the compound represented by [Chemical Formula 106]

A compound represented by [Chemical Formula 106] was synthesized by the following [Scheme 44].

[Scheme 44]

[Formula 84-a] [Formula 106-c] [Formula 106]

A compound represented by [Chemical Formula 106] synthesized in the same manner except for using [Chemical Formula 106-c] obtained from [Scheme 43] instead of [Chemical Formula 84-c] used in [Scheme 21] of Synthesis Example 4 3.4g (yield: 44.5%) was obtained.

MS (MALDI-TOF): m/z= 722 [M] ⁺

<Synthesis Example 11> Synthesis of a compound represented by [Chemical Formula 140]

(1) Synthesis of a compound represented by [Chemical Formula 140-a]

A compound represented by [Chemical Formula 140-a] was synthesized by the following [Scheme 45].

[Scheme 45]

[Formula 140-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, followed by stirring. 112.9 mL (339 mmol) of phenyl magnesium bromide (3.0 M in Et ₂ O) was added dropwise. After stirring at reflux for about 1 hour, the temperature was set to 0°C. Ethyl chloroformate (22.0g, 203mmol) was added dropwise and stirred under reflux for about 1 hour. An aqueous ammonium chloride solution was added until it became slightly acidic, and the resulting solid was filtered and washed with water and heptane to obtain 30.1 g of [Chemical Formula 140-a]. (Yield: 80%)

(2) Synthesis of a compound represented by [Chemical Formula 140-b]

A compound represented by [Chemical Formula 140-b] was synthesized by the following [Scheme 46].

[Scheme 46]

[Formula 140-b]

At room temperature, the synthesized [Intermediate 140-a] (30.0 g, 135 mmol) and about 80 mL of phosphorus oxychloride were added to a round bottom flask under a nitrogen stream, followed by stirring. After reflux stirring overnight, the temperature was cooled to -20℃ the next day, and water was slowly added dropwise to about 400 mL. The resulting solid was filtered and washed with water, methanol, and heptane. 14.6g of [Chemical Formula 140-b] was obtained by recrystallization from toluene and heptane. (Yield: 44.9%)

(3) Synthesis of a compound represented by [Chemical Formula 140-c]

A compound represented by [Chemical Formula 140-c] was synthesized by the following [Scheme 47].

[Scheme 47]

[Formula 2-d] [Formula 140-c]

Instead of the 5-bromoindole used in [Scheme 8] of Synthesis Example 1, the synthesized [Chemical Formula 2-d] was used, and the synthesized [Chemical Formula 140-b] was used instead of [Chemical Formula 2-g] [Chemical Formula 140-c] 13.2g (yield: 86%) was obtained by the same method.

(4) Synthesis of a compound represented by [Chemical Formula 140-d]

A compound represented by [Chemical Formula 140-d] was synthesized by the following [Scheme 48].

[Scheme 48]

[Formula 140-d]

[Chemical Formula 140-d] 11.8g (yield: 84%) in the same manner as in [Scheme 19] to [Scheme 20] using 7-bromoindole instead of 5-bromoindole used in [Scheme 19] Got it.

(5) Synthesis of a compound represented by [Chemical Formula 140]

A compound represented by [Chemical Formula 140] was synthesized by the following [Scheme 49].

[Scheme 49]

[Formula 140]

Using the synthesized [Chemical Formula 140-c] instead of [Chemical Formula 2-h] used in [Scheme 9], and using the synthesized [Chemical Formula 140-d] instead of [Chemical Formula 2-f] Synthesized to obtain [Chemical Formula 140] 3.8g (yield: 41%).

MS (MALDI-TOF): m/z= 605 [M] ⁺

<Synthesis Example 12> Synthesis of a compound represented by [Chemical Formula 141]

(1) Synthesis of a compound represented by [Formula 141-a]

A compound represented by [Chemical Formula 141-a] was synthesized by the following [Scheme 50].

[Scheme 50]

[Formula 141-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 And stirred. 100 mL of dimethylformamide was added, the temperature was raised to 60°C, and the mixture was stirred overnight. The next day, the change of TLC was checked and the temperature of the flask was set 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 5% aqueous sodium hydroxide solution was added thereto, followed by stirring. After reflux stirring for about 1 hour, the temperature was brought to room temperature. Extracted with ethyl acetate and water. It was separated by column chromatography using ethyl acetate and heptane. Recrystallized from toluene and heptane to give 24.6g (yield 50.7%) of [Chemical Formula 141-a] as a white solid.

(2) Synthesis of a compound represented by [Formula 141-b]

A compound represented by [Chemical Formula 141-b] was synthesized by the following [Scheme 51].

[Scheme 51]

[Formula 141-b]

Using the synthesized [Chemical Formula 141-a] instead of the 2-aminobenzonitrile used in [Scheme 45], it was synthesized in the same manner as in [Scheme 45] to [Scheme 46] to obtain 21g of [Formula 141-b]. (Yield: 74.5%)

(3) Synthesis of a compound represented by [Formula 141-c]

A compound represented by [Chemical Formula 141-c] was synthesized by the following [Scheme 52].

[Scheme 52]

[Formula 141-c]

[Chemical Formula 141-c] 14.5g (yield: 84%) was obtained by using the synthesized [Chemical Formula 141-b] instead of [Chemical Formula 140-b] used in [Scheme 47].

(4) Synthesis of a compound represented by [Formula 141-d]

A compound represented by [Chemical Formula 141-d] was synthesized by the following [Scheme 53].

[Scheme 53]

[Formula 141-d]

[Chemical Formula 141-d] 12.4g (yield: 82%) was obtained by the same method using 4-bromoindole instead of 7-bromoindole used in [Scheme 48].

(5) Synthesis of a compound represented by [Chemical Formula 141]

A compound represented by [Chemical Formula 141] was synthesized by the following [Scheme 54].

[Scheme 54]

[Formula 141]

Using the synthesized [Chemical Formula 141-c] instead of [Chemical Formula 140-c] used in [Scheme 49], and using the synthesized [Chemical Formula 141-d] instead of [Chemical Formula 140-d] By synthesis, [Chemical Formula 141] 4.5g (yield: 44%) was obtained.

MS (MALDI-TOF): m/z= 655 [M] ⁺

<Synthesis Example 13> Synthesis of a compound represented by [Chemical Formula 144]

(1) Synthesis of a compound represented by [Formula 144-a]

A compound represented by [Chemical Formula 144-a] was synthesized by the following [Scheme 55].

[Scheme 55]

[Formula 144-a]

[Chemical Formula 141-a] used in [Scheme 51] was synthesized in the same manner using 3-amino-2-naphtonitrile instead of [Chemical Formula 144-a] to obtain 20g. (Yield: 71%)

(2) Synthesis of a compound represented by [Formula 144-b]

A compound represented by [Chemical Formula 144-b] was synthesized by the following [Scheme 56].

[Scheme 56]

[Formula 144-b]

13.1g (yield: 83%) of [Chemical Formula 144-b] was obtained by using the synthesized [Chemical Formula 144-a] instead of [Chemical Formula 140-b] used in [Scheme 52].

(3) Synthesis of a compound represented by [Formula 144-c]

A compound represented by [Chemical Formula 144-c] was synthesized by the following [Scheme 57].

[Scheme 57]

[Formula 144-c]

[Chemical Formula 144-c] 11.4g (yield: 81%) was obtained by the same method using 6-bromoindole instead of 4-bromoindole used in [Scheme 53].

(4) Synthesis of a compound represented by [Chemical Formula 144]

A compound represented by [Chemical Formula 144] was synthesized by the following [Scheme 58].

[Scheme 58]

[Formula 144]

Using the synthesized [Formula 144-b] instead of [Formula 141-c] used in [Scheme 54], and using the synthesized [Formula 144-c] instead of [Formula 141-d] Synthesized to obtain [Chemical Formula 144] 4.3g (yield: 40%).

MS (MALDI-TOF): m/z= 655 [M] ⁺

<Examples 1 to 10> Preparation of organic electroluminescent devices including heterocyclic compounds according to Synthesis Examples 1 to 10

The ITO glass was patterned so that the light emitting area was 2 mm × 2 mm in size and washed. After mounting the substrate in the vacuum chamber, the base pressure is 1×10 ^-6 torr, and then the organic material is placed on the ITO with DNTPD (700 Å), NPD (300 Å), the compound synthesized by Synthesis Examples 1 to 10 + Ir ( ppy) ₃ (10%) (300 Å), Alq ₃ (350 Å), LiF (5 Å), and Al (1,000 Å) were formed in the order, and measured 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 fabricated in the same manner as in the device structures of Examples 1 to 10, 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 10 and Comparative Example 1, voltage, current density, luminance, color coordinates, and lifetime were measured, and the results are shown in Table 1 below.

T80 refers to the time it takes for the luminance to decrease from the initial luminance (7000nit) to 80%.

division Host Dopant Doping concentration (%) V Cd/㎡ CIEx CIEy T ₈₀ (Hr) Example 1 Formula 2 Ir(ppy) ₃ 10 4.1 5010 0.312 0.615 185 Example 2 Formula 16 Ir(ppy) ₃ 10 4.3 5120 0.312 0.613 124 Example 3 Chemical Formula 31 Ir(ppy) ₃ 10 4.5 5100 0.302 0.622 116 Example 4 Formula 84 Ir(ppy) ₃ 10 4.0 5290 0.311 0.625 197 Example 5 Formula 63 Ir(ppy) ₃ 10 4.8 5120 0.315 0.624 89 Example 6 Formula 68 Ir(ppy) ₃ 10 4.4 5210 0.317 0.622 95 Example 7 Chemical Formula 103 Ir(ppy) ₃ 10 4.0 4960 0.312 0.622 165 Example 8 Formula 104 Ir(ppy) ₃ 10 4.6 4960 0.313 0.625 133 Example 9 Formula 105 Ir(ppy) ₃ 10 4.2 5440 0.305 0.621 193 Example 10 Chemical Formula 106 Ir(ppy) ₃ 10 4.3 5440 0.308 0.625 161 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 compounds prepared according to Examples 1 to 10 of the present invention as a host material was compared to Comparative Example 1 in which the host material was CBP. ) Is low, has excellent luminous efficiency (Cd/m2) and long lifespan (T ₈₀ ), so it can be seen that it can be usefully used for display devices, display devices, and lighting.

<Examples 11 to 13> Preparation of organic electroluminescent devices including heterocyclic compounds according to Synthesis Examples 11 to 13

The ITO glass was patterned so that the light emitting area was 2 mm × 2 mm in size and 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 with DNTPD (700 Å), NPD (300 Å), the compound synthesized by Synthesis Examples 11 to 13 + (piq ) ₂ Ir (acac) (10%) (300 Å), Alq ₃ (350 Å), LiF (5 Å), Al (1,000 Å) were formed in the order, and measured at 0.4 mA.

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

[(piq) ₂ Ir(acac)]

<Example 14> In the device structures of Examples 11 to 13, [Chemical Formula 144] was used for the light emitting layer, and [PTOEP] was used instead of [(piq) ₂ Ir(acac)], and the same was prepared [ The structure of [PTOEP] is as follows.

[PTOEP]

<Comparative Example 2>

The organic light emitting diode device for Comparative Example 2 was fabricated in the same manner as in the device structures of Examples 11 to 13, except that CBP was used instead of the compound prepared by the present invention as a host material.

For the organic electroluminescent devices prepared according to Examples 11 to 14 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 it takes for the luminance to decrease from the initial luminance (3700nit) to 90%.

division Host Dopant Doping concentration (%) V Cd/㎡ CIEx CIEy T ₉₀ (Hr) Example 11 Formula 140 (piq) ₂ Ir(acac) 10 4.2 1620 0.665 0.334 1285 Example 12 Chemical Formula 141 (piq) ₂ Ir(acac) 10 3.8 1460 0.673 0.325 1170 Example 13 Formula 144 (piq) ₂ Ir(acac) 10 3.9 1500 0.672 0.329 1205 Example 14 Formula 144 PTOEP 10 3.9 1520 0.656 0.331 1180 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 compounds prepared according to Examples 11 to 14 of the present invention as a host material was compared to Comparative Example 2 in which the host material was CBP. ) Is low, has excellent luminous efficiency (Cd/m2) and long life (T ₉₀ ), so it can be seen that it can be usefully used for display devices, display devices, and lighting.

Claims (11)

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

In the above [Formula 1],
X ₁ to X ₁₄ is the same as or different from each other, and each independently hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 40 carbon atoms, a substituted or unsubstituted carbon number of 2 to 30 Heteroaryl group, halogen atom, hydroxyl group, cyano group, nitro group, amino group, amidino group, hydrazine, hydrazone, carboxyl group or salt thereof, sulfonic acid group or salt thereof, phosphoric acid or salt thereof, substituted or unsubstituted carbon number 2 to 60 alkenyl group, substituted or unsubstituted C 2 to C 60 alkynyl group, substituted or unsubstituted C 1 to C 60 alkoxy group, substituted or unsubstituted C 3 to C 60 cycloalkyl group, substituted or unsubstituted A cycloalkenyl group having 5 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 60 carbon atoms, a substituted or unsubstituted alkyl thioxy group having 1 to 30 carbon atoms, a substituted or unsubstituted arylthioc having 6 to 30 carbon atoms It is selected from the group consisting of a time period, a substituted or unsubstituted arylthio group having 6 to 60 carbon atoms, -SiR ₃ R ₄ R ₅ and -NR ₆ R ₇ ,
Y is selected from the group consisting of CX ₂₁ X ₂₂ , NX ₂₃ , O, S and SiX ₂₄ X ₂₅ ,
Ar ₁ and Ar ₂ are the same as or different from each other, and each independently selected from the group consisting of a substituted or unsubstituted aryl group having 6 to 40 carbon atoms and a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms, p+q Is an integer between 1 and 6,
L is a single bond, a substituted or unsubstituted C1 to C60 alkylene group, a substituted or unsubstituted C2 to C60 Alkenylene group, substituted or unsubstituted C2-C60 alkynylene group, substituted or unsubstituted C3-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 And n is an integer between 1 and 3,
The R ₁ to R ₇ is the same as or different from each other, and each independently a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 40 carbon atoms, a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms , Selected from the group consisting of hydrogen and deuterium,
The X ₂₁ to X ₂₅ are the same as defined in X ₁ to X ₁₄ . delete delete The method of claim 1,
The R ₁ to R ₇ , X ₁ to X ₁₄ , X ₂₁ to X ₂₅ , L, Ar ₁ and Ar 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 , 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, arylsilyl having 6 to 40 carbon atoms Group, a C6-C40 aryl group, a C3-C40 aryloxy group, a C3-C40 heteroaryl group, a germanium group, phosphorus and boron, characterized in that substituted with at least one selected from the group consisting of Heterocyclic compounds. delete delete The method of claim 1,
[Formula 1] is a heterocyclic compound, characterized in that any one selected from the group represented by the following formula:

[Chemical Formula 2] [Chemical Formula 3]

[Chemical Formula 4] [Chemical Formula 5]

[Formula 6] [Formula 7]

[Chemical Formula 8] [Chemical Formula 9]

[Formula 10] [Formula 11]

[Formula 12] [Formula 13]

[Formula 14] [Formula 15]

[Formula 16] [Formula 17]

[Chemical Formula 18] [Chemical Formula 19]

[Formula 20] [Formula 21]

[Formula 22] [Formula 23]

[Formula 24] [Formula 25]

[Formula 26] [Formula 27]

[Formula 28] [Formula 29]

[Chemical Formula 30] [Chemical Formula 31]

[Formula 32] [Formula 33]

[Formula 34] [Formula 35]

[Chemical Formula 36] [Chemical Formula 37]

[Chemical Formula 38] [Chemical Formula 39]

[Formula 40] [Formula 41]

[Formula 42] [Formula 43]

[Formula 44] [Formula 45]

[Chemical Formula 46] [Chemical Formula 47]

[Chemical Formula 48] [Chemical Formula 49]

[Formula 50] [Formula 51]

[Formula 52] [Formula 53]

[Chemical Formula 54] [Chemical Formula 55]

[Chemical Formula 56] [Chemical Formula 57]

[Chemical Formula 58] [Chemical Formula 59]

[Chemical Formula 60] [Chemical Formula 61]

[Formula 62] [Formula 63]

[Formula 64] [Formula 65]

[Chemical Formula 66] [Chemical Formula 67]

[Chemical Formula 68] [Chemical Formula 69]

[Formula 70] [Formula 71]

[Chemical Formula 72] [Chemical Formula 73]

[Chemical Formula 74]

[Chemical Formula 77]

[Chemical Formula 78] [Chemical Formula 79]

[Chemical Formula 80] [Chemical Formula 81]

[Formula 82] [Formula 83]

[Formula 84] [Formula 85]

[Formula 86] [Formula 87]

[Chemical Formula 88] [Chemical Formula 89]

[Formula 90] [Formula 91]

[Formula 92] [Formula 93]

[Formula 94] [Formula 95]

[Chemical Formula 96] [Chemical Formula 97]

[Chemical Formula 98] [Chemical Formula 99]

[Chemical Formula 100] [Chemical Formula 101]

[Formula 102] [Formula 103]

[Chemical Formula 104] [Chemical Formula 105]

[Formula 106] [Formula 107]

[Chemical Formula 108] [Chemical Formula 109]

[Chemical Formula 110] [Chemical Formula 111]

[Chemical Formula 112] [Chemical Formula 113]

[Chemical Formula 114] [Chemical Formula 115]

[Chemical Formula 116] [Chemical Formula 117]

[Chemical Formula 118] [Chemical Formula 119]

[Chemical Formula 120] [Chemical Formula 121]

[Formula 122] [Formula 123]

[Chemical Formula 124] [Chemical Formula 125]

[Chemical Formula 126] [Chemical Formula 127]

[Chemical Formula 128] [Chemical Formula 129]

[Chemical Formula 130] [Chemical Formula 131]

[Chemical Formula 132] [Chemical Formula 133]

[Chemical Formula 134] A first electrode; A second electrode facing the first electrode; And one or more organic layers 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 [Chemical Formula 1] according to claim 1. The method of claim 8,
The organic layer comprises at least one layer selected from a hole injection layer, a hole transport layer, a functional layer having a hole injection function and a hole transport function at the same time, a light emitting layer, an electron transport layer, and an electron injection layer. The method of claim 9,
The emission layer includes at least one host compound and at least one dopant compound, and the host compound is an organic electroluminescent device, wherein the host compound is a heterocyclic compound represented by [Chemical Formula 1]. The method of claim 8,
An organic electroluminescent device, characterized in that the organic layer further includes at least one organic emission layer emitting red, green, or blue light to emit white light.

Images