KR102254134B1 - An electroluminescent compound and an electroluminescent device comprising the same - Google Patents

Abstract

The present invention relates to an organic light emitting compound represented by the following [Chemical Formula 1-1] to [Chemical Formula 1-2], and an organic light emitting device employing the same has excellent luminous efficiency and can be driven at a low voltage at the same time, resulting in improved power efficiency and It has long life characteristics.
[Formula 1-1] [Formula 1-2]

Description

An electroluminescent compound and an electroluminescent device comprising the same}

The present invention relates to an organic light emitting compound and an organic electroluminescent device comprising the same.

Recently, organic light emitting devices capable of low voltage driving by self-luminous type have superior viewing angles and contrast ratios compared to liquid crystal displays, which are the mainstream of flat panel display devices, and do not require a backlight, are lightweight and thin, and are advantageous in terms of power consumption and color reproduction. Due to its wide range, it is attracting attention as a next-generation display device.

An organic electroluminescent device is a device that emits light while dissipating after electrons and holes form a pair when electric charges are injected into the organic light emitting layer formed between the electron injection electrode (cathode) and the hole injection electrode (anode). In addition to being able to form a device on a substrate, it is possible to drive at a lower voltage of 10 V or less compared to a plasma display panel or an inorganic electroluminescent display, and has the advantage of relatively low power consumption and excellent color. In addition, the organic electroluminescent device can display three colors of green, blue, and red, and thus has been a subject of much interest as a next-generation rich color display device.

The most important factor in determining the luminous efficiency in an organic electroluminescent device is a light-emitting material. Currently, a fluorescent material is widely used as a light emitting material, but the development of a phosphorescent material is one of the methods that can theoretically improve luminous efficiency more due to the light emitting mechanism, and accordingly, various phosphorescent materials have been developed up to now. In particular, as a phosphorescent host material, CBP (4,4'-N,N'-dicarbazolbiphenyl) is the most widely known until now, and materials in which various substituents are introduced into carbazole are (Japanese Patent Publication 2008-214244, Japanese Patent Publication). 2003-133075) or an organic electroluminescent device using a BALq derivative as a host is known.

However, organic electroluminescent devices using phosphorescent materials have significantly higher current efficiency compared to devices using fluorescent materials, but when materials such as BAlq and CBP are used as the host of phosphorescent materials, they are driven compared to devices using fluorescent materials. Since the voltage is high, there is no great advantage in terms of power efficiency, and it is not satisfactory in terms of the life of the device. Therefore, development of a more stable and high-performance host material is required.

Accordingly, the problem to be solved by the present invention is to provide an organic light-emitting compound having superior luminous efficiency compared to conventional materials and at the same time low voltage driving and improved power efficiency and long lifespan characteristics.

In addition, the present invention is to provide an organic electroluminescent device having a low voltage driving, excellent luminous efficiency, and a long lifespan by employing the organic light emitting compound as a light emitting material.

The present invention provides an organic light emitting compound represented by the following [Chemical Formula 1-1] to [Chemical Formula 1-2] in order to solve the above problems.

[Formula 1-1] [Formula 1-2]

Each substituent of [Chemical Formula 1-1] to [Chemical Formula 1-2] will be described later.

In addition, the present invention provides an organic electroluminescent device including a first electrode, a second electrode, and one or more organic layers interposed between the first electrode and the second electrode, wherein the organic layer is the [Chemical Formula 1-1] And at least one organic light-emitting compound represented by [Chemical Formula 1-2].

In addition, the organic layer may include at least one selected from a hole injection layer, a hole transport layer, an emission layer, an electron transport layer, and an electron injection layer, and organic light emission represented by [Formula 1-1] to [Formula 1-2] The compound is employed in the light emitting layer to be used as a host, and may further include one or more dopant compounds.

In addition, the organic light-emitting device according to the present invention may be an organic light-emitting device that emits white light by including at least one organic light-emitting layer emitting blue, red, or green light.

The organic light-emitting device employing the organic light-emitting compound according to the present invention can have a lower driving voltage than a device employing a conventional phosphorescent light-emitting host material, and thus has excellent power efficiency and light emission efficiency and long lifespan.

1 is a conceptual diagram showing a multi-layered organic light emitting device according to an embodiment of the present invention.

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

One aspect of the present invention relates to an organic light emitting compound represented by the following [Chemical Formula 1-1] to [Chemical Formula 1-2].

[Formula 1-1] [Formula 1-2]

In the above [Formula 1-1] to [Formula 1-2],

A ₁ to A ₁₆ are each independently CX or N, and two adjacent A of _{A 1 to A 16} are bonded to L to form a condensed ring ([*] means a bonding site).

Y, Z, W and Q are each independently CR ₁ R ₂ , NR ₃ , O, S, SiR ₄ R ₅ , GeR ₆ R ₇ , BR ₈ , PR ₉ , C=O, Se, Te or Po, At least one of Y, Z, W, and Q is NR ₃ (wherein n is an integer of 0 to 3).

The R ₁ to R ₉ are the same as or different from each other, and each independently hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 40 carbon atoms, and a substituted or unsubstituted It is selected from a C2-C30 heteroaryl group.

Each of X is 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 heteroaryl group having 2 to 30 carbon atoms, and a 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 alkenyl group having 2 to 60 carbon atoms , A substituted or unsubstituted alkynyl group having 2 to 60 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 60 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 60 carbon atoms, a substituted or unsubstituted carbon number of 5 to 60 It is selected from an aryloxy group, a substituted or unsubstituted arylthio group having 5 to 60 carbon atoms, -SiR ₁₀ R ₁₁ R ₁₂ and -NR ₁₃ R ₁₄ .

The R ₁₀ to R ₁₄ are 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 heteroaryl group having 2 to 30 carbon atoms, 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 C2-C60 alke Nyl group, substituted or unsubstituted alkynyl group having 2 to 60 carbon atoms, substituted or unsubstituted alkoxy group having 1 to 60 carbon atoms, substituted or unsubstituted cycloalkyl group having 3 to 60 carbon atoms, substituted or unsubstituted 5 to 60 carbon atoms It is selected from an aryloxy group of and a substituted or unsubstituted arylthio group having 5 to 60 carbon atoms.

According to a preferred embodiment of the present invention, when at least one of Y, Z, W, and Q is NR ₃ , R ₃ may be any one selected from the following [Structural Formula 1] to [Structural Formula 10]. .

[Structural Formula 1] [Structural Formula 2] [Structural Formula 3] [Structural Formula 4]

[Structural Formula 5] [Structural Formula 6] [Structural Formula 7]

[Structural Formula 8] [Structural Formula 9] [Structural Formula 10]

In the [Structural Formula 1] to [Structural Formula 10],

T ₁ to T ₁₂ are the same as or different from each other, and each independently, is selected from C (R ₄₁ ), C (R ₄₂ ) (R ₄₃ ), N, N (R ₄₄ ), O and S, and the R ₄₁ To R ₄₄ are the same as or different from each other, and each independently hydrogen, deuterium, a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C3-C30 cycloalkyl group, a substituted or unsubstituted C5-C5 It is selected from an aryl group of 30 and a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms having O, N, S or P as a hetero atom.

More preferably, R ₃ may be any one selected from the following [Structural Formula 11].

[Structural Formula 11]

In the [Structural Formula 11],

X is hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 5 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted carbon number 2 to 20 alkynyl group, substituted or unsubstituted C 3 to C 30 cycloalkyl group, substituted or unsubstituted C 5 to C 30 cycloalkenyl group, substituted or unsubstituted C 1 to C 30 alkoxy group, substituted or unsubstituted A substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted alkyl thioxy group having 1 to 30 carbon atoms, a substituted or unsubstituted arylthioxy group having 5 to 30 carbon atoms, a substituted or unsubstituted alkyl having 1 to 30 carbon atoms Selected from an amine group, a substituted or unsubstituted aryl group having 5 to carbon atoms, a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms having O, N, S or P as a hetero atom, a cyano group, a nitro group, and a halogen group And m is an integer of 1 to 11, and when m is 2 or more, a plurality of Xs are the same as or different from each other.

In the present invention, the'substituted' in the'substituted or unsubstituted' means that the substituents such as R ₁ to R ₁₄ , X and R ₄₁ to R ₄₄ are each independently deuterium, a cyano group, a halogen group, a hydroxy group, a nitro group, C1-C20 alkyl group, C1-C20 alkenyl group, C1-C20 alkynyl group, C1-C20 halogenated alkyl group, C5-C24 aryl group, C2-C24 heteroaryl group, C1 A to 20 alkoxy group, a C 5 to C 24 aryloxy group, a C 1 to C 20 alkylsilyl group, a C 5 to C 24 arylsilyl group, a C 1 to C 20 alkylamine group and a C 6 to C 24 arylamine group It means that it is further substituted with one or more substituents selected from and the like.

In addition, the R ₁ to R ₁₄ , X and their substituents may be connected to each other or with adjacent substituents to form an alicyclic ring, a monocyclic or polycyclic aromatic ring or a hetero ring.

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' and'substituted or unsubstituted aryl group having 6 to 40 carbon atoms' consider the portion where the substituent is substituted It does not mean the total number of carbon atoms constituting the alkyl moiety or 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.

In addition, the aryl group included in the organic light-emitting compound according to the present invention is an organic radical derived from an aromatic hydrocarbon by the removal of one hydrogen, and has 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.

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 the 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 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, And aromatic groups such as pyrenyl, indenyl, fluorenyl, tetrahydronaphthyl, 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, a C 2 to 24 heteroarylalkyl group, and the like.

The organic light-emitting compound represented by [Chemical Formula 1-1] to [Chemical Formula 1-2] according to the present invention is not limited in its range in the following specific compounds, but more specifically, to [Chemical Formula 2] to [Chemical Formula 261] It may be selected from among the displayed compounds.

[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]

[Chemical Formula 38] [Chemical Formula 39] [Chemical Formula 40] [Chemical Formula 41]

[Formula 42] [Formula 43] [Formula 44] [Formula 45]

[Chemical Formula 46] [Chemical Formula 47] [Chemical Formula 48] [Chemical Formula 49]

[Chemical Formula 50] [Chemical Formula 51] [Chemical Formula 52] [Chemical 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] [Formula 72] [Formula 73]

[Chemical Formula 74] [Chemical 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] [Formula 88] [Formula 89]

[Formula 90] [Formula 91] [Formula 92] [Formula 93]

[Chemical Formula 94] [Chemical Formula 95] [Chemical Formula 96] [Chemical Formula 97]

[Chemical Formula 98] [Chemical Formula 99] [Chemical Formula 100] [Chemical 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]

[Chemical Formula 114] [Chemical Formula 115] [Chemical Formula 116] [Chemical Formula 117]

[Chemical Formula 118] [Chemical Formula 119] [Chemical Formula 120] [Chemical Formula 121]

[Chemical Formula 122] [Chemical Formula 123] [Chemical Formula 124] [Chemical Formula 125]

[Formula 126] [Formula 127] [Formula 128] [Formula 129]

[Chemical Formula 130] [Chemical Formula 131] [Chemical Formula 132] [Chemical Formula 133]

[Chemical Formula 134] [Chemical 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] [Chemical Formula 144] [Chemical Formula 145]

[Formula 146] [Formula 147] [Formula 148] [Formula 149]

[Chemical Formula 150] [Chemical Formula 151] [Chemical Formula 152] [Chemical Formula 153]

[Formula 154] [Formula 155] [Formula 156] [Formula 157]

[Formula 158] [Formula 159] [Formula 160] [Formula 161]

[Formula 162] [Formula 163] [Formula 164] [Formula 165]

[Formula 166] [Formula 167] [Formula 168] [Formula 169]

[Chemical Formula 170] [Chemical Formula 171] [Chemical Formula 172] [Chemical Formula 173]

[Chemical Formula 174] [Chemical Formula 175] [Chemical Formula 176] [Chemical Formula 177]

[Chemical Formula 178] [Chemical Formula 179] [Chemical Formula 180] [Chemical Formula 181]

[Chemical Formula 182] [Chemical Formula 183] [Chemical Formula 184] [Chemical Formula 185]

[Formula 186] [Formula 187] [Formula 188] [Formula 189]

[Chemical Formula 190] [Chemical Formula 191] [Chemical Formula 192] [Chemical Formula 193]

[Formula 194] [Formula 195] [Formula 196] [Formula 197]

[Formula 198] [Formula 199] [Formula 200] [Formula 201]

[Formula 202] [Formula 203] [Formula 204] [Formula 205]

[Formula 206] [Formula 207] [Formula 208] [Formula 209]

[Formula 210] [Formula 211] [Formula 212] [Formula 213]

[Formula 214] [Formula 215] [Formula 216] [Formula 217]

[Chemical Formula 218] [Chemical Formula 219] [Chemical Formula 220] [Chemical Formula 221]

[Formula 222] [Formula 223] [Formula 224] [Formula 225]

[Formula 226] [Formula 227] [Formula 228] [Formula 229]

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

[Formula 234] [Formula 235] [Formula 236] [Formula 237]

[Formula 238] [Formula 239] [Formula 240] [Formula 241]

[Formula 242] [Formula 243] [Formula 244] [Formula 245]

[Formula 246] [Formula 247] [Formula 248] [Formula 249]

[Chemical Formula 250] [Chemical Formula 251] [Chemical Formula 252] [Chemical Formula 253]

[Formula 254] [Formula 255] [Formula 256] [Formula 257]

[Formula 258] [Formula 259] [Formula 260] [Formula 261]

In addition, another aspect of the present invention relates to an organic electroluminescent device comprising a first electrode, a second electrode, and one or more organic layers interposed between the first electrode and the second electrode, wherein the organic layer includes the [Formula 1] It may contain at least one or more organic light-emitting compounds according to the present invention represented by -1] to [Chemical Formula 1-2].

In addition, the organic layer containing the organic light emitting compound of the present invention may include at least one of a hole injection layer, a hole transport layer, a functional layer having a hole injection function and a hole transport function at the same time, a light emitting layer, an electron transport layer, and an electron injection layer. .

In this case, the organic layer interposed between the first electrode and the second electrode may include an emission layer, the emission layer is formed of a host and a dopant, and the organic emission 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.

Hereinafter, an embodiment of an organic light emitting diode according to the present invention will be described in more detail with reference to FIG. 1 below.

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. It includes (80), and may further include a hole injection layer 30 and an electron injection layer 70 if necessary, and in addition to that, it is possible to further form an intermediate layer of one or two layers, and a hole blocking layer Alternatively, an electron blocking layer may be further formed, and an organic layer having various functions may be further included according to the characteristics of the device.

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 typical organic electroluminescent device is used, and an organic substrate or a transparent plastic substrate having excellent 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), and the like, which are transparent and have excellent conductivity, are used.

The hole injection layer 30 is formed by vacuum thermal evaporation or spin coating of a hole injection layer material on the anode 20 electrode. Thereafter, 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 may be used without particular limitation as long as it is commonly used in the art, and as a specific 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, as long as the material for 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 a vacuum deposition method or a spin coating method. 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 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 a light-emitting compound, and representatively, BAlq, BCP, TPBI, and the like may be used.

As the material used for the hole blocking layer, any one selected from BAlq, BCP, Bphen, TPBI, NTAZ, BeBq ₂ , OXD-7, Liq, and [Formula 301] to [Formula 307] may be used, but limited thereto It does not become.

BAlq BCP Bphen

TPBI NTAZ BeBq ₂

OXD-7 Liq

[Chemical Formula 301] [Chemical Formula 302] [Chemical Formula 303]

[Chemical Formula 304] [Chemical Formula 305] [Chemical Formula 306]

[Chemical Formula 307]

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 metals include lithium (Li), magnesium (Mg), aluminum (Al), aluminum-ridium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), and magnesium-silver ( Mg-Ag) or the like can be used, and in order to obtain a top light emitting device, a transmissive cathode using ITO or IZO can be used.

As the material for the electron transport layer, a known electron transport material may be used as it 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, [Chemical Formula 401], [Chemical Formula 402], and oxadiazole derivatives such as PBD, BMD, BND, and the like may be used.

TAZ BAlq

[Compound 401] [Compound 402] 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, which satisfies 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, the 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, but is not limited thereto.

[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 C3-C30 heteroaryl group, a substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C3-C30 cycloalkyl group, a substituted or unsubstituted C2-C30 alkenyl group, 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 C1-C30 alkyl group, a substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C5-C30 alkyl group. It is 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.

In addition, in the organic electroluminescent device according to the present invention, the organic layer includes an emission layer, and the emission layer contains at least one phosphorescent dopant in addition to the at least one organic emission compound represented by the [Chemical Formula 1-1] to [Chemical Formula 1-2]. It characterized in that it further comprises, and the light-emitting dopant applied to the organic electroluminescent device of the present invention is not particularly limited, but is selected from compounds represented by the following [General Formula A-1] to [General Formula J-1] It may be one or more compounds.

[General Formula A-1]

ML ₁ L ₂ L ₃

The M is selected from the group consisting of metals of groups 7, 8, 9, 10, 11, 13, 14, 15 and 16, preferably Ir, Pt, Pd, Rh, Re , Os, Tl, Pb, Bi, In, Sn, Sb, Te, Au and Ag. In addition, the L ₁ , L ₂ and L ₃ may be the same as or different from each other as a ligand, and may each independently include any one selected from the following [Structural Formula D], but is not limited thereto. In addition, * in the following [Structural Formula D] represents a site that binds to the metal ion M.

[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 A heteroaryl group having 5 to 50 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 may be any one selected from the group.

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

In addition, R may be connected to each of the adjacent substituents by alkylene or alkenylene to form an alicyclic ring and a monocyclic or polycyclic aromatic ring.

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

As a specific example, the dopant represented by [General Formula A-1] may be any one selected from the following compounds, but is not limited thereto.

[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 represent 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, and L ^A11 , L ^A12 , L ^A13 , L ^A14 are each a linking group as defined above. And Q ^A11 and Q ^A12 represent a partial structure containing an atom bonded to M ^A1.

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

[General Formula C-1]

In the above [general formula C-1],

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

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

[General Formula D-1]

In the above [general formula D-1],

M ^C1 represents the same metal ion as defined in [General Formula A-1], and R ^C11 and R ^C12 are each independently a hydrogen atom, a substituent that connects to each other to form a five-membered ring, and does not have any linking to each other. Represents a substituent, and R ^C13 and R ^C14 are each independently a hydrogen atom, a substituent that connects to each other to form a five-membered ring, and represents a substituent that does not have anything connected to each other, and G ^C11 and G ^C12 are each independently a nitrogen atom, substituted Or an unsubstituted carbon atom, L ^C11 and L ^C12 represent a linking group, and Q ^C11 and Q ^C12 represent a partial structure containing an atom bonded to M ^C1.

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

[General Formula E-1]

In the above [general formula E-1],

M ^D1 represents the same metal ion as defined in [General Formula A-1], 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 Each of J ^D14 represents an atomic group required to form a five-membered ring independently, and L ^D11 and L ^D12 represent a linking group.

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

[General Formula F-1]

In the above [general formula F-1],

M ^E1 represents the same metal ion as defined in [General Formula A-1], and J ^E11 and J ^E12 each independently represent an atomic group required to form a 5-membered ring, and 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.

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

[General Formula G-1]

In the above [general formula G-1],

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

L ^F11 , L ^F12 and L ^F13 represent a linking group, R ^F11 , R ^F12 , R ^F13 and R ^F14 represent a substituent, and R ^F11 and R ^F12 , R ^F12 and R ^F13 , R ^F13 and R ^F14 are connected to each other. A ring may be formed, wherein the ring formed by R ^F1 and R ^F12 and 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.

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

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

In the above [General Formula H-1] to [General Formula H-3],

R ¹¹ , R ¹² are substituents of alkyl, aryl or heteroaryl; In addition, a fused ring may be formed with a substituent adjacent to each other, and q11 and q12 are integers of 0 to 4, preferably 0 to 2.

In addition, when q11 and q12 are 2 to 4, a plurality of R11 and R12 may be the same or different, respectively.

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

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 general formula H-1 become 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.

Examples of specific compounds of [General Formula H-1] to [General Formula H-3] are as follows, but are not limited thereto.

[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 the rings A to D may have a substituent, and the other two rings are an aryl ring or a hetero ring that may have a substituent. Represents and represents an aryl ring, and a condensed ring can be formed by ring A and ring B, ring A and ring C, and/or ring B and ring D. X ¹ , X ² , X ³ and X ⁴ represent a nitrogen atom in which 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 (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.

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

[General Formula J-1]

In the above [general formula J-1],

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

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

In the above [general formula J-1], it is preferable that M is Pt. Moreover, it is preferable that Ar1 is selected from a 5-membered ring, a 6-membered ring, and a condensed ring group thereof.

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

In addition, the emission 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 monomolecular 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, etc., 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 monochromatic or white flat lighting device, and a monochromatic or white flexible lighting device.

Hereinafter, the present invention will be described in more detail with reference to preferred examples. However, these examples are intended to illustrate 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.

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

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

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

[Scheme 1]

[Formula 1-a]

In a dried reactor, 5-bromobenzothiophene 50 g (235 mmol), benzophenone hydrazone 46 g (235 mmol), tris (dibenzyrideneacetone) dipalladium 4.30 g (4.7 mmol), (2,2) '-Bis(diphenylphosphino)-1,1'-binapthyl 2.9 g (5 mmol), sodium tertiarybutoxide 45.1 g (469 mmol), and 500 mL of toluene were added and refluxed for 12 hours. When it is hot, it is filtered under reduced pressure, and the solution is dried under reduced pressure to obtain 40 g of a compound represented by [Chemical Formula 1-a] (yield 53%) using column chromatography.

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

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

[Scheme 2]

[Formula 1-b]

3,3-dimethyl-2,3-dihydro-1H-inden-1-one 29.3 g (183 mmol), 40 g (122 mmol) of a compound represented by [Chemical Formula 1-a] obtained from [Scheme 1] ), p -toluenesulfonic acid 83.9 g (487.2 mmol) was added to 400 mL of ethanol and stirred under reflux for 12 hours. When the reaction was completed, ethanol was removed as much as possible by rotary, extracted with methylene chloride and water, the organic layer was concentrated under reduced pressure and separated by column chromatography to obtain 16 g of a compound represented by [Chemical Formula 1-b]. (Yield 45%)

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

A compound represented by [Chemical Formula 1-c] was synthesized by the following [Scheme 3].

[Scheme 3]

[Formula 1-c]

After filling the dried 2 L reactor with nitrogen, 45.0 g (381 mmol) of 2-aminobenzonitrile and 405 mL of tetrahydrofuran were added, and 279 mL (838 mmol) of 3M-phenylmagnesium bromide was slowly added dropwise at 0° C. for 3 hours. Stir under reflux. When the starting material disappears, lower it to low temperature again, dissolve 62.0 g (0.571 mmol) of ethylchloroformate in 200 mL of tetrahydrofuran, slowly add dropwise, and stir under reflux for 2 hours. When the reaction was completed, an aqueous ammonium chloride solution was added to stop the reaction, extracted with ethyl acetate and water, the organic layer was concentrated under reduced pressure, and then separated by column chromatography to obtain 50 g of a compound represented by [Chemical Formula 1-c]. (Yield 58%)

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

A compound represented by [Chemical Formula 1-d] was synthesized by the following [Scheme 4].

[Scheme 4]

[Formula 1-d]

50.0 g (225 mmol) of the compound represented by [Chemical Formula 1-c] obtained from the [Scheme 3], was added to 500 mL of phosphorus oxychloride, and stirred under reflux for 5 hours. When the reaction is complete, it is slowly added dropwise to the cooled water. When the dropwise addition was completed, the mixture was filtered, extracted with methylene chloride and water, and the organic layer was concentrated under reduced pressure and separated by column chromatography to obtain 41 g of a compound represented by [Chemical Formula 1-d]. (Yield 75.1%)

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

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

[Scheme 5]

[Formula 1-d] [Formula 2]

Compound 8 g (28 mmol) represented by [Formula 1-b] obtained from [Scheme 2], 8.6 g (36 mmol) compound represented by [Formula 1-d] obtained from [Scheme 4], Tris( Dibenziridenacetone) dipalladium 0.50 g (0.6 mmol), tritertiary butylphosphonium tetrafluoroborate 0.8 g (3 mmol), sodium tertiarybutoxide 5.3 g (55 mmol), and xylene 80 mL were added. It was refluxed for 12 hours. When the reaction is finished, it is filtered under reduced pressure while hot. After the solution was dried under reduced pressure, 8.3 g of a compound represented by [Chemical Formula 2] was obtained by column chromatography. (61% yield)

MS [M] ⁺ : 494

<Synthesis Example 2> Synthesis of a compound represented by [Chemical Formula 3]

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

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

[Scheme 6]

[Formula 2-a]

In a dried 2 L reactor under nitrogen, ethyl cyanoacetate 139.8 g (1.236 mol), potassium cyanide 29.5 g (0.453 mol), potassium hydroxide 46.2 g (0.824 mol), and 920 mL of dimethylformamide were dissolved at 10° C. Stir for 20 minutes at. Then, 1-nitronaphthalene 92 g (412 mol) was added to the reaction and stirred at 60° C. for 4 hours. After the reaction was completed, the solvent was concentrated, 600 mL of a 10% sodium hydroxide aqueous solution was added, and the mixture was stirred under reflux for 1 hour. The solid was filtered and subjected to column chromatography with methylene chloride and heptane to obtain 50 g of a compound represented by [Chemical Formula 2-a]. (Yield 60%)

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

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

[Scheme 7]

[Formula 2-b]

Except for using [Chemical Formula 2-a] instead of 2-aminobenzonitrile used in [Scheme 3] of Synthesis Example 1-3, it was synthesized in the same manner to obtain 104 g of a compound represented by [Chemical Formula 2-b]. (Yield 63%)

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

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

[Scheme 8]

[Formula 2-c]

Except for using [Chemical Formula 2-b] instead of [Chemical Formula 1-c] used in [Scheme 4] of Synthesis Example 1-4, it was synthesized in the same manner to obtain 63 g of a compound represented by [Chemical Formula 2-c] . (Yield 60%)

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

A compound represented by [Chemical Formula 3] was synthesized by the following [Scheme 9].

[Scheme 9]

[Formula 3]

Except for using [Chemical Formula 2-c] instead of [Chemical Formula 1-d] used in [Scheme 5] of Synthesis Example 1-5, it was synthesized in the same manner to obtain 9.1 g of a compound represented by [Chemical Formula 3]. (61% yield)

MS [M] ⁺ : 544

<Synthesis Example 3> Synthesis of a compound represented by [Formula 10]

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

A compound represented by [Chemical Formula 3-a] was synthesized by the following [Scheme 10].

[Scheme 10]

[Formula 3-a]

1,4-dibromo 2-nitrobenzene 50 g (178 mmol), cupacyanide 23.9 g (267 mmol), and dimethylformamide 312 mL were added to a dried 1000 mL flask and stirred at 100° C. for 1 hour. When the reaction is complete, toluene and water are added, Celite is added, stirred for 30 minutes, and filtered to remove solids. The liquid layer was washed with 1% aqueous ammonia and brine, concentrated under reduced pressure, and separated by column chromatography to obtain 30 g of a compound represented by [Chemical Formula 3-a]. (Yield 72%)

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

A compound represented by [Chemical Formula 3-b] was synthesized by the following [Scheme 11].

[Scheme 11]

[Formula 3-b]

15 g (66 mmol) of the compound represented by [Chemical Formula 3-a] obtained from [Scheme 10] and 150 mL of concentrated hydrochloric acid were added, adjusted to 0°C, and 74.55 g (330 mmol) of tin chloride was slowly added. Stir for 1 hour at room temperature. When the reaction is complete, the reactor temperature is adjusted to 0° C. and then made into a basic state with 10N sodium hydroxide. After extraction with ethyl acetate and water, the organic layer was treated with anhydrous magnesium sulfate and distilled under reduced pressure to obtain 12 g of a compound represented by [Chemical Formula 3-b]. (Yield 92%)

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

A compound represented by [Chemical Formula 3-c] was synthesized by the following [Scheme 12].

[Scheme 12]

[Formula 3-c]

Compound 12 g (60.72 mmol) represented by [Chemical Formula 3-b] obtained from [Scheme 11], phenyl boronic acid 8.88 g (72.8 mmol), tetrakis (triphenylphosphine) palladium 1.4 g (1.21 mmol), Add potassium carbonate 16.78 g (121.44 mmol), 1,4-dioxane 60 mL, toluene 60 mL, and distilled water 24 mL, and stir at 100° C. for 12 hours. When the reaction was completed, the temperature was adjusted to room temperature, extracted with ethyl acetate, and the organic layer was concentrated and then subjected to column chromatography to obtain 11.4 g of a compound represented by [Chemical Formula 3-c]. (Yield 97%)

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

A compound represented by [Chemical Formula 3-d] was synthesized by the following [Scheme 13].

[Scheme 13]

[Formula 3-d]

Synthesis was performed in the same manner except for using [Chemical Formula 3-c] instead of 2-aminobenzonitrile used in [Scheme 3] of Synthesis Example 1-3 to obtain 11.07 g of a compound represented by [Chemical Formula 3-d]. (Yield 63%)

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

A compound represented by [Chemical Formula 3-e] was synthesized by the following [Scheme 14].

[Scheme 14]

[Formula 3-e]

Except for using [Chemical Formula 3-d] instead of [Chemical Formula 1-c] used in [Scheme 4] of Synthesis Example 1-4, it was synthesized in the same manner to obtain 63 g of a compound represented by [Chemical Formula 3-e] . (Yield 60%)

(6) Synthesis of a compound represented by [Chemical Formula 10]

A compound represented by [Chemical Formula 10] was synthesized by the following [Scheme 15].

[Scheme 15]

[Formula 10]

Except for using [Chemical Formula 3-e] instead of [Chemical Formula 1-d] used in [Scheme 5] of Synthesis Example 1-5, 9.6 g of a compound represented by [Chemical Formula 10] was obtained. (61% yield)

MS [M] ⁺ : 570

<Synthesis Example 4> Synthesis of a compound represented by [Chemical Formula 11]

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

A compound represented by [Chemical Formula 4-a] was synthesized by the following [Scheme 16].

[Scheme 16]

[Formula 4-a]

After nitrogen was filled in the dried 1 L reactor, 35.1 g (297 mmol) of 2-aminobenzonitrile and 350 mL of dimethylformamide were stirred. Then, 55.56 g (312 mmol) of N-bromosuccinimide was slowly added to the reactor. After raising to room temperature, it was stirred for 4 hours. When the reaction was completed, distilled water was added dropwise at room temperature, and when brown crystals were formed, the crystals were filtered and separated by column chromatography to obtain 54.2 g of a compound represented by [Chemical Formula 4-a]. (Yield 92.6%)

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

A compound represented by [Chemical Formula 4-b] was synthesized by the following [Scheme 17].

[Scheme 17]

[Formula 4-b]

Compound 12 g (60.72 mmol) represented by [Formula 4-a] obtained from [Scheme 16], phenyl boronic acid 8.88 g (72.8 mmol), tetrakis (triphenylphosphine) palladium 1.4 g (1.21 mmol), Potassium carbonate 16.78 g (121.44 mmol), 1,4-dioxane 60 mL, toluene 60 mL, and distilled water 24 mL were added and stirred at 100° C. for 12 hours. When the reaction was completed, the temperature was adjusted to room temperature, extracted with ethyl acetate, and the organic layer was concentrated and then subjected to column chromatography to obtain 11.4 g of a compound represented by [Chemical Formula 4-b]. (Yield 97%)

(3) Synthesis of a compound represented by [Formula 4-c]

A compound represented by [Chemical Formula 4-c] was synthesized by the following [Scheme 18].

[Scheme 18]

[Formula 4-c]

Except for using [Chemical Formula 4-b] instead of 2-aminobenzonitrile used in [Scheme 3] of Synthesis Example 1-3, it was synthesized in the same manner to obtain 11.07 g of a compound represented by [Chemical Formula 4-c]. (Yield 63%)

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

A compound represented by [Chemical Formula 4-d] was synthesized by the following [Scheme 19].

[Scheme 19]

[Formula 4-d]

Except for using [Chemical Formula 4-c] instead of [Chemical Formula 1-c] used in [Scheme 4] of Synthesis Example 1-4, it was synthesized in the same manner to obtain 63 g of a compound represented by [Chemical Formula 4-d] . (Yield 60%)

(5) Synthesis of a compound represented by [Chemical Formula 11]

A compound represented by [Chemical Formula 11] was synthesized by the following [Scheme 20].

[Scheme 20]

[Formula 11]

Except for using [Chemical Formula 4-d] instead of [Chemical Formula 1-d] used in [Scheme 5] of Synthesis Example 1-5, 9.6 g of a compound represented by [Chemical Formula 11] was obtained. (61% yield)

MS [M] ⁺ : 570

<Synthesis Example 5> Synthesis of a compound represented by [Chemical Formula 19]

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

A compound represented by [Chemical Formula 5-a] was synthesized by the following [Scheme 21].

[Scheme 21]

[Formula 5-a]

In a dried reactor, 6-bromobenzothiophene 50 g (235 mmol), benzophenone hydrazone 46 g (235 mmol), tris (dibenziridenacetone) dipalladium 4.30 g (4.7 mmol), (2,2) '-Bis(diphenylphosphino)-1,1'-binafthyl 2.9 g (5 mmol), sodium tertiarybutoxide 45.1 g (469 mmol), and 500 mL of toluene were added and refluxed for 12 hours. When it is hot, it is filtered under reduced pressure, and the solution is dried under reduced pressure to obtain 40 g of the compound represented by [Chemical Formula 5-a] by column chromatography (yield 53%).

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

A compound represented by [Chemical Formula 5-b] was synthesized by the following [Scheme 22].

[Scheme 22]

[Formula 5-b]

3,3-dimethyl-2,3-dihydro-1H-inden-1-one 29.3 g (183 mmol), 40 g (122 mmol) of a compound represented by [Chemical Formula 5-a] obtained from [Scheme 21] ), p -toluenesulfonic acid 83.9 g (487.2 mmol) was added to 400 mL of ethanol and stirred under reflux for 12 hours. When the reaction was completed, ethanol was removed as much as possible by rotary, extracted with methylene chloride and water, the organic layer was concentrated under reduced pressure and separated by column chromatography to obtain 16 g of a compound represented by [Chemical Formula 5-b]. (Yield 45%)

(3) Synthesis of the compound represented by [Chemical Formula 19]

A compound represented by [Chemical Formula 19] was synthesized by the following [Scheme 23].

[Scheme 23]

[Formula 19]

8 g (28 mmol) of the compound represented by [Chemical Formula 5-b] obtained from [Scheme 22], 8.6 g (36) of the compound represented by [Chemical Formula 1-d] obtained from [Scheme 4] of Synthesis Example 1-4 mmol), tris(dibenziridenacetone) dipalladium 0.50 g (0.6 mmol), tritertiary butylphosphonium tetrafluoroborate 0.8 g (3 mmol), sodium tertiarybutoxide 5.3 g (55 mmol) and xyl 80 mL of len was added and refluxed for 12 hours. When the reaction is finished, it is filtered under reduced pressure while hot. After the solution was dried under reduced pressure, 8.3 g of a compound represented by [Chemical Formula 19] was obtained by column chromatography. (61% yield)

MS [M] ⁺ : 494

<Synthesis Example 6> Synthesis of a compound represented by [Chemical Formula 28]

(1) Synthesis of a compound represented by [Chemical Formula 6-a]

A compound represented by [Chemical Formula 6-a] was synthesized by the following [Scheme 24].

[Scheme 24]

[Formula 6-a]

In a dried reactor, 4-bromobenzothiophene 50 g (235 mmol), benzophenone hydrazone 46 g (235 mmol), tris (dibenziridenacetone) dipalladium 4.30 g (4.7 mmol), (2,2) '-Bis(diphenylphosphino)-1,1'-binafthyl 2.9 g (5 mmol), sodium tertiarybutoxide 45.1 g (469 mmol), and 500 mL of toluene were added and refluxed for 12 hours. When it is hot, it is filtered under reduced pressure, and the solution is dried under reduced pressure to obtain 40 g of the compound represented by [Chemical Formula 6-a] by column chromatography (yield 53%).

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

A compound represented by [Chemical Formula 6-b] was synthesized by the following [Scheme 25].

[Scheme 25]

[Formula 6-b]

3,3-dimethyl-2,3-dihydro-1H-inden-1-one 29.3 g (183 mmol), 40 g (122 mmol) of a compound represented by [Chemical Formula 6-a] obtained from [Scheme 24] ), p -toluenesulfonic acid 83.9 g (487.2 mmol) was added to 400 mL of ethanol and stirred under reflux for 12 hours. When the reaction was completed, ethanol was removed as much as possible by rotary, extracted with methylene chloride and water, the organic layer was concentrated under reduced pressure and separated by column chromatography to obtain 16 g of a compound represented by [Chemical Formula 6-b]. (Yield 45%)

(3) Synthesis of a compound represented by [Chemical Formula 28]

A compound represented by [Chemical Formula 28] was synthesized by the following [Scheme 26].

[Scheme 26]

[Formula 28]

8 g (28 mmol) of the compound represented by [Chemical Formula 6-b] obtained from [Scheme 25], 8.6 g (36) of the compound represented by [Chemical Formula 1-d] obtained from [Scheme 4] of Synthesis Example 1-4 mmol), tris(dibenziridenacetone) dipalladium 0.50 g (0.6 mmol), tritertiary butylphosphonium tetrafluoroborate 0.8 g (3 mmol), sodium tertiarybutoxide 5.3 g (55 mmol) and xyl 80 mL of len was added and refluxed for 12 hours. When the reaction is finished, it is filtered under reduced pressure while hot. After the solution was dried under reduced pressure, 8.3 g of a compound represented by [Chemical Formula 28] was obtained by column chromatography. (61% yield)

MS [M] ⁺ : 494

<Synthesis Example 7> Synthesis of a compound represented by [Chemical Formula 51]

(1) Synthesis of a compound represented by [Chemical Formula 7-a]

A compound represented by [Chemical Formula 7-a] was synthesized by the following [Scheme 27].

[Scheme 27]

[Formula 7-a]

In a dried reactor, 6-bromobenzofuran 46 g (235 mmol), benzophenone hydrazone 46 g (235 mmol), tris (dibenzyrideneacetone) dipalladium 4.30 g (4.7 mmol), (2,2' -Bis(diphenylphosphino)-1,1'-binapthyl 2.9 g (5 mmol), sodium tertiarybutoxide 45.1 g (469 mmol) and toluene 460 mL were added and refluxed for 12 hours. After drying under reduced pressure, the solution was dried under reduced pressure to obtain 38.9 g of a compound represented by [Chemical Formula 7-a] (yield 53%) by column chromatography.

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

A compound represented by [Chemical Formula 7-b] was synthesized by the following [Scheme 28].

[Scheme 28]

[Formula 7-b]

3,3-dimethyl-2,3-dihydro-1H-inden-1-one 29.3 g (183 mmol), 38.9 g (122 mmol) of the compound represented by [Chemical Formula 7-a] obtained from [Scheme 27] ), p -toluenesulfonic acid 83.9 g (487.2 mmol) was added to 400 mL of ethanol and stirred under reflux for 12 hours. When the reaction was completed, ethanol was removed as much as possible by rotary, extracted with methylene chloride and water, the organic layer was concentrated under reduced pressure and separated by column chromatography to obtain 15 g of a compound represented by [Chemical Formula 7-b]. (Yield 45%)

(3) Synthesis of a compound represented by [Chemical Formula 7-c]

A compound represented by [Chemical Formula 7-c] was synthesized by the following [Scheme 29].

[Scheme 29]

[Formula 7-c]

After filling the dried 1 L reactor with nitrogen, 50.0 g (297 mmol) of [Chemical Formula 2-a] obtained from [Scheme 6] of Synthesis Example 2-1, and 500 mL of dimethylformamide were stirred. Then, 55.56 g (312 mmol) of N-bromosuccinimide was slowly added to the reactor. After raising to room temperature, it was stirred for 4 hours. When the reaction was completed, distilled water was added dropwise at room temperature, and when brown crystals were formed, the crystals were filtered and separated by column chromatography to obtain 68 g of a compound represented by [Chemical Formula 7-c]. (Yield 92.6%)

(4) Synthesis of a compound represented by [Chemical Formula 7-d]

A compound represented by [Chemical Formula 7-d] was synthesized by the following [Scheme 30].

[Scheme 30]

[Formula 7-d]

Compound 68.0 g (275 mmol) represented by [Chemical Formula 7-c] obtained from [Scheme 29], phenylboronic acid 40.3 g (330 mmol), tetrakis (triphenylphosphine) palladium 6.36 g (6 mmol) , Potassium carbonate 76.07 g (192 mmol), 1,4-dioxane 340 mL, toluene 340 mL, and distilled water 136 mL and stirred at 100 °C for 12 hours. When the reaction is complete, extraction is performed using ethyl acetate and distilled water. The organic layer was concentrated under reduced pressure and separated by column chromatography to obtain 45 g of a compound represented by [Chemical Formula 7-d]. (Yield 66.9%)

(5) Synthesis of a compound represented by [Chemical Formula 7-e]

A compound represented by [Chemical Formula 7-e] was synthesized by the following [Scheme 31].

[Scheme 31]

[Formula 7-e]

Synthesis was performed in the same manner except for using [Chemical Formula 7-d] instead of 2-aminobenzonitrile used in [Scheme 3] of Synthesis Example 1-3 to obtain 51 g of a compound represented by [Chemical Formula 7-e]. (Yield 78%)

(6) Synthesis of a compound represented by [Chemical Formula 7-f]

A compound represented by [Chemical Formula 7-f] was synthesized by the following [Scheme 32].

[Scheme 32]

[Formula 7-f]

Synthesized in the same manner except for using [Chemical Formula 7-e] instead of [Chemical Formula 1-c] used in [Scheme 4] of Synthesis Example 1-4 to obtain 31 g of a compound represented by [Chemical Formula 7-f] . (Yield 57.8%)

(7) Synthesis of a compound represented by [Chemical Formula 51]

A compound represented by [Chemical Formula 51] was synthesized by the following [Scheme 33].

[Scheme 33]

[Formula 51]

7.7 g (28 mmol) of the compound represented by [Chemical Formula 7-b] obtained from [Scheme 28], 13.2 g (36 mmol) of the compound represented by [Chemical Formula 7-f] obtained from [Scheme 32], Tris( Dibenziridenacetone) dipalladium 0.50 g (0.6 mmol), tritertiary butylphosphonium tetrafluoroborate 0.8 g (3 mmol), sodium tertiarybutoxide 5.3 g (55 mmol), and xylene 77 mL were added. It was refluxed for 12 hours. When the reaction is finished, it is filtered under reduced pressure while hot. After the solution was dried under reduced pressure, 10.3 g of a compound represented by [Chemical Formula 51] was obtained by column chromatography. (61% yield)

MS [M] ⁺ : 604

<Synthesis Example 8> Synthesis of a compound represented by [Chemical Formula 54]

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

A compound represented by [Chemical Formula 8-a] was synthesized by the following [Scheme 34].

[Scheme 34]

[Formula 8-a]

In a dried reactor, 5-bromobenzofuran 46 g (235 mmol), benzophenone hydrazone 46 g (235 mmol), tris (dibenzyrideneacetone) dipalladium 4.30 g (4.7 mmol), (2,2' -Bis(diphenylphosphino)-1,1'-binaphthyl 2.9 g (5 mmol), sodium tertiarybutoxide 45.1 g (469 mmol), and toluene 460 mL were added and refluxed for 12 hours. After drying under reduced pressure, the solution was dried under reduced pressure to obtain 38.9 g of a compound represented by [Chemical Formula 8-a] (yield 53%) by column chromatography.

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

A compound represented by [Chemical Formula 8-b] was synthesized by the following [Scheme 35].

[Scheme 35]

[Formula 8-b]

3,3-dimethyl-2,3-dihydro-1H-inden-1-one 29.3 g (183 mmol), 38.9 g (122 mmol) of the compound represented by [Chemical Formula 8-a] obtained from [Scheme 34] ), p -toluenesulfonic acid 83.9 g (487.2 mmol) was added to 400 mL of ethanol and stirred under reflux for 12 hours. When the reaction was completed, ethanol was removed as much as possible by rotary, extracted with methylene chloride and water, the organic layer was concentrated under reduced pressure and separated by column chromatography to obtain 15 g of a compound represented by [Chemical Formula 8-b]. (Yield 45%)

(3) Synthesis of the compound represented by [Chemical Formula 54]

A compound represented by [Chemical Formula 54] was synthesized by the following [Scheme 36].

[Scheme 36]

[Chemical Formula 54]

7.7 g (28 mmol) of the compound represented by [Chemical Formula 8-b] obtained from [Scheme 35], 8.6 g (36) of the compound represented by [Chemical Formula 1-d] obtained from [Scheme 4] of Synthesis Example 1-4 mmol), tris(dibenziridenacetone) dipalladium 0.50 g (0.6 mmol), tritertiary butylphosphonium tetrafluoroborate 0.8 g (3 mmol), sodium tertiarybutoxide 5.3 g (55 mmol) and xyl 77 mL of len was added and refluxed for 12 hours. When the reaction is finished, it is filtered under reduced pressure while hot. After the solution was dried under reduced pressure, 8.1 g of a compound represented by [Chemical Formula 54] was obtained by column chromatography. (61% yield)

MS [M] ⁺ : 478

<Synthesis Example 9> Synthesis of a compound represented by [Chemical Formula 66]

(1) Synthesis of a compound represented by [Chemical Formula 66]

A compound represented by [Chemical Formula 66] was synthesized by the following [Scheme 37].

[Scheme 37]

[Formula 66]

7.7 g (28 mmol) of the compound represented by [Chemical Formula 8-b] obtained from [Scheme 35] of Synthesis Example 8-2, and [Chemical Formula 4-d] obtained from [Scheme 19] of Synthesis Example 4-4 Compound 11.4 g (36 mmol), tris(dibenziridenacetone) dipalladium 0.50 g (0.6 mmol), tritertiary butylphosphonium tetrafluoroborate 0.8 g (3 mmol), sodium tertiarybutoxide 5.3 g ( 55 mmol) and 77 mL of xylene were added and refluxed for 12 hours. When the reaction is finished, it is filtered under reduced pressure while hot. After the solution was dried under reduced pressure, 9.4 g of a compound represented by [Chemical Formula 66] was obtained by column chromatography. (61% yield)

MS [M] ⁺ : 554

<Synthesis Example 10> Synthesis of a compound represented by [Chemical Formula 71]

(1) Synthesis of a compound represented by [Formula 10-a]

A compound represented by [Chemical Formula 10-a] was synthesized by the following [Scheme 38].

[Scheme 38]

[Formula 10-a]

In a dried reactor, 6-bromo- N -phenylindole 63.7 g (235 mmol), benzophenone hydrazone 46 g (235 mmol), tris (dibenzyrideneacetone) dipalladium 4.30 g (4.7 mmol), (2 ,2'-bis(diphenylphosphino)-1,1'-binapthyl 2.9 g (5 mmol), sodium tertiarybutoxide 45.1 g (469 mmol) and toluene 460 mL were added and refluxed for 12 hours. After completion of the filtration under reduced pressure in a hot state, the solution was dried under reduced pressure to obtain 48.2 g of a compound represented by [Formula 10-a] by column chromatography (yield 53%).

(2) Synthesis of a compound represented by [Formula 10-b]

A compound represented by [Chemical Formula 10-b] was synthesized by the following [Scheme 39].

[Scheme 39]

[Formula 10-b]

3,3-dimethyl-2,3-dihydro-1H-inden-1-one 29.3 g (183 mmol), 38.9 g (122 mmol) of the compound represented by [Chemical Formula 10-a] obtained from [Scheme 38] ), p -toluenesulfonic acid 83.9 g (487.2 mmol) was added to 400 mL of ethanol and stirred under reflux for 12 hours. When the reaction was completed, ethanol was removed as much as possible by rotary, extracted with methylene chloride and water, the organic layer was concentrated under reduced pressure and separated by column chromatography to obtain 19.1 g of a compound represented by [Formula 10-b]. (Yield 45%)

(5) Synthesis of the compound represented by [Chemical Formula 71]

A compound represented by [Chemical Formula 71] was synthesized by the following [Scheme 40].

[Scheme 40]

[Formula 71]

9.8 g (28 mmol) of the compound represented by [Chemical Formula 10-b] obtained from [Scheme 39], 8.6 g (36) of the compound represented by [Chemical Formula 1-d] obtained from [Scheme 4] of Synthesis Example 1-4 mmol), tris(dibenziridenacetone) dipalladium 0.50 g (0.6 mmol), tritertiary butylphosphonium tetrafluoroborate 0.8 g (3 mmol), sodium tertiarybutoxide 5.3 g (55 mmol) and xyl 98 mL of len was added and refluxed for 12 hours. When the reaction is finished, it is filtered under reduced pressure while hot. After the solution was dried under reduced pressure, 9.4 g of a compound represented by [Chemical Formula 71] was obtained by column chromatography. (61% yield)

MS [M] ⁺ : 553

<Synthesis Example 11> Synthesis of a compound represented by [Chemical Formula 72]

(1) Synthesis of a compound represented by [Formula 11-a]

A compound represented by [Chemical Formula 11-a] was synthesized by the following [Scheme 41].

[Scheme 41]

[Formula 11-a]

In a dried reactor, 5-bromo- N -phenylindole 63.7 g (235 mmol), benzophenone hydrazone 46 g (235 mmol), tris(dibenziridenacetone) dipalladium 4.30 g (4.7 mmol), (2 ,2'-bis(diphenylphosphino)-1,1'-binapthyl 2.9 g (5 mmol), sodium tertiarybutoxide 45.1 g (469 mmol) and toluene 460 mL were added and refluxed for 12 hours. After completion of the filtration under reduced pressure in a hot state, the solution was dried under reduced pressure to obtain 48.2 g of a compound represented by [Formula 11-a] by column chromatography (yield 53%).

(2) Synthesis of a compound represented by [Formula 11-b]

A compound represented by [Chemical Formula 11-b] was synthesized by the following [Scheme 42].

[Scheme 42]

[Formula 11-b]

3,3-dimethyl-2,3-dihydro-1H-inden-1-one 29.3 g (183 mmol), 38.9 g (122 mmol) of the compound represented by [Chemical Formula 11-a] obtained from [Scheme 41] ), p -toluenesulfonic acid 83.9 g (487.2 mmol) was added to 400 mL of ethanol and stirred under reflux for 12 hours. When the reaction was completed, ethanol was removed as much as possible by rotary, extracted with methylene chloride and water, the organic layer was concentrated under reduced pressure and separated by column chromatography to obtain 19.1 g of a compound represented by [Chemical Formula 11-b]. (Yield 45%)

(3) Synthesis of a compound represented by [Formula 11-c]

A compound represented by [Chemical Formula 11-c] was synthesized by the following [Scheme 43].

[Scheme 43]

[Formula 11-c]

After filling the dried 1L reactor with nitrogen, 20.0 g (169 mmol) of 2-aminobenzonitrile and 200 mL of tetrahydrofuran were added, and 113 mL (339 mmol) of 3M-phenylmagnesium bromide was slowly added dropwise at 0°C and refluxed for 3 hours. Stir. When the starting material disappears, the mixture was lowered to low temperature again, and 44.58 g (0.203 mmol) of 3-bromobenzoyl chloride was dissolved in 200 mL of tetrahydrofuran, slowly added dropwise, and stirred under reflux for 2 hours. When the reaction was completed, an aqueous ammonium chloride solution was added to stop the reaction, extracted with ethyl acetate and water, the organic layer was concentrated under reduced pressure, and then separated by column chromatography to obtain 37 g of a compound represented by [Chemical Formula 11-c]. (Yield 60.3%)

(4) Synthesis of a compound represented by [Chemical Formula 72]

A compound represented by [Chemical Formula 72] was synthesized by the following [Scheme 44].

[Scheme 44]

[Formula 72]

9.8 g (28 mmol) of the compound represented by [Chemical Formula 11-b] obtained from [Scheme 42], 13 g (36 mmol) of the compound represented by [Chemical Formula 11-c] obtained from [Scheme 43], Tris( Dibenziridenacetone) dipalladium 0.50 g (0.6 mmol), tritertiary butylphosphonium tetrafluoroborate 0.8 g (3 mmol), sodium tertiarybutoxide 5.3 g (55 mmol), and xylene 98 mL were added. It was refluxed for 12 hours. When the reaction is finished, it is filtered under reduced pressure while hot. After the solution was dried under reduced pressure, 10.7 g of a compound represented by [Chemical Formula 72] was obtained by column chromatography. (61% yield)

MS [M] ⁺ : 629

<Synthesis Example 12> Synthesis of a compound represented by [Chemical Formula 91]

(1) Synthesis of a compound represented by [Chemical Formula 12-a]

A compound represented by [Chemical Formula 12-a] was synthesized by the following [Scheme 45].

[Scheme 45]

[Formula 12-a]

In a dried reactor, 4-bromo- N -phenylindole 63.7 g (235 mmol), benzophenone hydrazone 46 g (235 mmol), tris(dibenziridenacetone) dipalladium 4.30 g (4.7 mmol), (2 ,2'-bis(diphenylphosphino)-1,1'-binapthyl 2.9 g (5 mmol), sodium tertiarybutoxide 45.1 g (469 mmol) and toluene 460 mL were added and refluxed for 12 hours. After completion of the filtration under reduced pressure in a hot state, the solution was dried under reduced pressure to obtain 48.2 g of a compound represented by [Chemical Formula 12-a] by column chromatography (yield 53%).

(2) Synthesis of a compound represented by [Chemical Formula 12-b]

A compound represented by [Chemical Formula 12-b] was synthesized by the following [Scheme 46].

[Scheme 46]

[Formula 12-b]

3,3-dimethyl-2,3-dihydro-1H-inden-1-one 29.3 g (183 mmol), 38.9 g (122 mmol) of the compound represented by [Chemical Formula 12-a] obtained from [Scheme 45] ), p -toluenesulfonic acid 83.9 g (487.2 mmol) was added to 400 mL of ethanol and stirred under reflux for 12 hours. When the reaction was completed, ethanol was removed as much as possible by rotary, extracted with methylene chloride and water, the organic layer was concentrated under reduced pressure and separated by column chromatography to obtain 19.1 g of a compound represented by [Chemical Formula 12-b]. (Yield 45%)

(3) Synthesis of the compound represented by [Chemical Formula 91]

A compound represented by [Chemical Formula 91] was synthesized by the following [Scheme 47].

[Scheme 47]

[Formula 91]

9.8 g (28 mmol) of the compound represented by [Chemical Formula 12-b] obtained from [Scheme 46], 11.4 g (36) of the compound represented by [Chemical Formula 4-d] obtained from [Scheme 19] of Synthesis Example 4-4 mmol), tris(dibenziridenacetone) dipalladium 0.50 g (0.6 mmol), tritertiary butylphosphonium tetrafluoroborate 0.8 g (3 mmol), sodium tertiarybutoxide 5.3 g (55 mmol) and xyl 98 mL of len was added and refluxed for 12 hours. When the reaction is finished, it is filtered under reduced pressure while hot. After the solution was dried under reduced pressure, 10.7 g of a compound represented by [Chemical Formula 91] was obtained by column chromatography. (61% yield)

MS [M] ⁺ : 629

Example: Preparation of organic light emitting diode

The ITO glass was patterned so that the light emitting area had a size of 2 mm×2 mm, and then 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 DNTPD (700 Å), α-NPB (300 Å), the compound prepared by the present invention + RD- 1 (10%) (300 Å), compound E: Liq = 1:1 (250 Å), Liq (10 Å), Al (1,000 Å) was formed in the order of the film, and was measured at 0.4 mA.

<DNTPD> <α-NPB>

<RD-1> <Compound E> <Liq>

Comparative example

The organic light emitting diode device for the comparative example was fabricated in the same manner, except that BAlq, which is commonly used as a phosphorescent host material, was used instead of the compound prepared according to the invention in the device structure of the above example, and the structure of the BAlq is as follows.

<BAlq>

For the organic electroluminescent devices manufactured according to Examples 1 to 12 and Comparative Example 1, voltage, current density, luminance, color coordinates, and lifetime were measured, and the results are shown in Table 1 below. T ₉₅ refers to the time it takes for the luminance to decrease from the initial luminance (3000 cd/m2) to 95%.

division Host Doping concentration% V Cd/㎡ CIEx CIEy T ₉₅ (Hr) Comparative Example 1 BAlq 10 6.2 1510 0.665 0.334 45 Example 1 2 10 4.2 2200 0.664 0.335 310 Example 2 3 10 4.6 2260 0.666 0.333 250 Example 3 10 10 4.5 2150 0.665 0.334 280 Example 4 11 10 4.4 2180 0.665 0.334 330 Example 5 19 10 4.1 2220 0.664 0.335 260 Example 6 28 10 4.4 2100 0.666 0.334 240 Example 7 51 10 4.6 2160 0.664 0.335 300 Example 8 54 10 4.3 2240 0.665 0.334 270 Example 9 66 10 4.3 2120 0.664 0.335 280 Example 10 71 10 4.2 2190 0.664 0.335 320 Example 11 72 10 4.5 2210 0.665 0.334 280 Example 12 91 10 4.3 2170 0.665 0.334 290

As shown in [Table 1], the organic light-emitting device including the organic light-emitting compound according to the present invention has a lower driving voltage, higher luminous efficiency and long life than BAlq among host materials commonly used as a conventional phosphorescent host material. .

Claims (8)

An organic light-emitting compound represented by any one of the following [Chemical Formula 1-1] to [Chemical Formula 1-2]:
[Formula 1-1] [Formula 1-2]

In the above [Formula 1-1] to [Formula 1-2],
A ₁ to A ₁₆ are each independently CX,
_{At least one or more of "two adjacent from A 1} to A ₄ " and "two adjacent from A ₅ to A ₈ " of [Formula 1-1] are bonded to L to form a condensed ring, and ([*] is Refers to the binding site),
_{At least one or more of "two adjacent among A 9} to A ₁₂ " and "two adjacent among A ₁₃ to A ₁₆ " of [Formula 1-2] are combined with L to form a condensed ring ([*] is Refers to the binding site),
In _{each of the benzene ring rings described in A 1} to A ₄ , A ₅ to A ₈ , A ₉ to A ₁₂ and A ₁₃ to A ₁₆ , the remaining two except for the two bonded to L are CH,
Y and Q are each independently CR ₁ R ₂ , NR ₃ , GeR ₆ R ₇ , O or S (however, n is an integer of 0 to 3, excluding cases _{where both Y and Q are CR 1} R ₂₎ ),
Z is CR ₁ R ₂ , NR ₃ , O or S,
W is CR ₁ R ₂ , NR ₃ , O, S, SiR ₄ R ₅ , Se or Te,
At least one or more of Y, Z, W and Q is NR ₃ ,
The R ₁ to R ₂ and R ₄ to R ₇ 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 and a substituted or unsubstituted aryl group having 6 to 40 carbon atoms Is any one selected from,
R ₃ is any one selected from a substituted or unsubstituted aryl group having 6 to 40 carbon atoms and a substituted or unsubstituted heteroaryl group having 2 to 24 carbon atoms,
When only any one of Y, Z, W and Q is NR ₃ , R ₃ is an aryl group having 6 to 40 carbon atoms substituted with a heteroaryl group having 2 to 24 carbon atoms, or a substituted or unsubstituted C 2 to 24 carbon number Is a heteroaryl group of,
When two or more of Y, Z, W and Q are NR ₃ , _{at least one of R 3} is an aryl group having 6 to 40 carbon atoms substituted with a heteroaryl group having 2 to 24 carbon atoms, or substituted or unsubstituted It is a C2-C24 heteroaryl group,
X is 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 heteroaryl group having 2 to 24 carbon atoms, a halogen atom , A cyano group, a substituted or unsubstituted alkenyl group having 2 to 60 carbon atoms, and a substituted or unsubstituted cycloalkyl group having 3 to 60 carbon atoms,
The term'substituted' in the'substituted or unsubstituted' means that _{at least one of R 1} to R ₅ and X is each independently deuterium, a cyano group, a halogen group, an alkyl group having 1 to 20 carbon atoms, and It means that it can be further substituted with one or more substituents selected from an alkenyl group having 1 to 20, a halogenated alkyl group having 1 to 20 carbon atoms, an aryl group having 5 to 24 carbon atoms, and a heteroaryl group having 2 to 24 carbon atoms,
The X and the substituents thereof may be connected to each other or with a substituent adjacent to each other to further form an alicyclic ring, a monocyclic or polycyclic aromatic ring or a hetero ring. The method of claim 1,
An organic light-emitting compound characterized in that the heteroaryl group having 2 to 24 carbon atoms described in the definition of R _{3 is any one selected from the following [Structural Formula 11]:}
[Structural Formula 11]

In the [Structural Formula 11],
X is hydrogen, deuterium, cyano group, nitro group, halogen group, substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, substituted or unsubstituted aryl group having 5 to 30 carbon atoms, and substituted or unsubstituted and heteroatoms are O, N , S or P is selected from a C2-C30 heteroaryl group, m is an integer of 1 to 11, when m is 2 or more, a plurality of X are the same or different from each other. The method of claim 1,
[Formula 1-1] to [Formula 1-2] is an organic light-emitting compound, characterized in that any one compound 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]

[Chemical Formula 38] [Chemical Formula 39] [Chemical Formula 40] [Chemical Formula 41]

[Formula 42] [Formula 43] [Formula 44] [Formula 45]

[Chemical Formula 46] [Chemical Formula 47] [Chemical Formula 48] [Chemical Formula 49]

[Chemical Formula 50] [Chemical Formula 51] [Chemical Formula 52] [Chemical 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] [Formula 72] [Formula 73]

[Chemical Formula 74] [Chemical 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] [Formula 88] [Formula 89]

[Formula 90] [Formula 91] [Formula 92] [Formula 93]

[Chemical Formula 94] [Chemical Formula 95] [Chemical Formula 96] [Chemical Formula 97]

[Chemical Formula 98] [Chemical Formula 99] [Chemical Formula 100] [Chemical 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]

[Chemical Formula 114] [Chemical Formula 115] [Chemical Formula 116] [Chemical Formula 117]

[Chemical Formula 118] [Chemical Formula 119] [Chemical Formula 120] [Chemical Formula 121]

[Chemical Formula 122] [Chemical Formula 123] [Chemical Formula 124] [Chemical Formula 125]

[Formula 126] [Formula 127] [Formula 128] [Formula 129]

[Chemical Formula 130] [Chemical Formula 131] [Chemical Formula 132] [Chemical Formula 133]

[Chemical Formula 134] [Chemical 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] [Chemical Formula 144] [Chemical Formula 145]

[Formula 146] [Formula 147] [Formula 148] [Formula 149]

[Chemical Formula 150] [Chemical Formula 151] [Chemical Formula 152] [Chemical Formula 153]

[Formula 154] [Formula 155] [Formula 156] [Formula 157]

[Formula 158] [Formula 159] [Formula 160] [Formula 161]

[Formula 162] [Formula 163] [Formula 164] [Formula 165]

[Formula 166] [Formula 167] [Formula 168] [Formula 169]

[Chemical Formula 170] [Chemical Formula 171] [Chemical Formula 172] [Chemical Formula 173]

[Chemical Formula 174] [Chemical Formula 175] [Chemical Formula 176] [Chemical Formula 177]

[Chemical Formula 178] [Chemical Formula 179] [Chemical Formula 180] [Chemical Formula 181]

[Chemical Formula 182] [Chemical Formula 183] [Chemical Formula 184] [Chemical Formula 185]

[Formula 186] [Formula 187] [Formula 188] [Formula 189]

[Chemical Formula 190] [Chemical Formula 191] [Chemical Formula 192] [Chemical Formula 193]

[Formula 194] [Formula 195] [Formula 196] [Formula 197]

[Formula 198] [Formula 199] [Formula 200] [Formula 201]

[Formula 202] [Formula 203] [Formula 204] [Formula 205]

[Formula 206] [Formula 207] [Formula 208] [Formula 209]

[Formula 210] [Formula 211] [Formula 212] [Formula 213]

[Formula 214] [Formula 215] [Formula 216] [Formula 217]

[Chemical Formula 218] [Chemical Formula 219] [Chemical Formula 220] [Chemical Formula 221]

[Formula 222] [Formula 223] [Formula 224] [Formula 225]

[Formula 226] [Formula 227] [Formula 228] [Formula 229]

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

[Formula 234] [Formula 235] [Formula 236] [Formula 237]

[Formula 238] [Formula 239] [Formula 240] [Formula 241]

[Formula 242] [Formula 243] [Formula 244] [Formula 245]

[Formula 246] [Formula 247] [Formula 248] [Formula 249]

[Chemical Formula 250] [Chemical Formula 251] [Chemical Formula 252] [Chemical Formula 253]

[Formula 254] [Formula 255] [Formula 256]

[Formula 258] [Formula 259] [Formula 260] [Formula 261] A first electrode; Consisting of a second 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 organic light emitting compound represented by any one of [Chemical Formula 1-1] to [Chemical Formula 1-2] according to claim 1. 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 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 4,
An organic electroluminescent device, characterized in that the organic layer interposed between the first electrode and the second electrode includes a light emitting layer. The method of claim 6,
The light emitting layer is made of a host compound and a dopant compound, and an organic light emitting compound represented by any one of [Chemical Formula 1-1] to [Chemical Formula 1-2] according to claim 1 is used as a host,
The organic electroluminescent device, characterized in that the emission layer further comprises at least one dopant compound. The method of claim 4,
An organic light-emitting device comprising: at least one organic light-emitting layer emitting red, green, or blue light on the organic layer to emit white light.

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