KR102191023B1 - An electroluminescent compound and an electroluminescent device comprising the same - Google Patents

Abstract

The present invention relates to an organic light emitting compound, characterized in that the compound represented by the following [Chemical Formula 1], and the organic light emitting device employing the organic light emitting compound according to the present invention is a device employing a conventional phosphorescent host material. Compared to that, a lower driving voltage is possible, so that power efficiency is excellent, and at the same time, it has luminous efficiency and long life.
[Formula 1]

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 including 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. Due to its wide range, it is drawing attention as a next-generation display device.

The organic electroluminescent device is a device that emits light while electrons and holes form a pair and then disappear when electric charges are injected into an organic light emitting layer formed between an electron injection electrode (cathode) and a hole injection electrode (anode).

The organic light emitting device can be formed on a transparent substrate that can bend like a plastic, and can be driven at a voltage lower than 10 V compared to a plasma display panel or an inorganic light emitting display, and consumes relatively little power. , It has the advantage of excellent color. In addition, the organic electroluminescent device can display three colors of green, blue, and red, and thus has attracted much attention 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 is the most widely known until now, and 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 than 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 the lifespan of the device is not satisfactory, and thus, development of a more stable and high-performance host material is required.

Accordingly, the problem to be solved by the present invention is to solve the above problem, and to provide an organic light-emitting compound having superior luminous efficiency and improved power efficiency and long lifespan than conventional materials.

In addition, the present invention is to provide a high-efficiency and long-life organic electroluminescent device 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] in order to solve the above problem,

It provides an organic light emitting device comprising at least one or more of the organic light emitting compound.

[Formula 1]

Each of the substituents in [Chemical Formula 1] will be described later.

In addition, the organic light-emitting device includes a first electrode, a second electrode, and one or more organic layers interposed between the first and second electrodes, and the organic layer contains at least one organic light-emitting compound. I can.

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.

In addition, the organic light-emitting compound is used as a phosphorescent host, and the organic layer may further include one or more phosphorescent dopant compounds.

In addition, it may be an organic light emitting device emitting 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 schematic diagram of an organic light emitting diode 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].

[Formula 1]

In [Chemical Formula 1], A ₁ to A ₄ are each independently CX ₁₁ , and two adjacent two of A ₁ to A ₄ combine with B to form a condensed ring, and according to a preferred embodiment, the [ Formula 1] may be any one selected from the following [Formula 1-a] to [Formula 1-f].

[Formula 1-a] [Formula 1-b]

[Formula 1-c] [Formula 1-d]

[Formula 1-e] [Formula 1-f]

In the above formula, X ₁ to X ₁₁ are 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 50 carbon atoms, and a substituted or unsubstituted carbon number 2 It is selected from a heteroaryl group of to 50, hydrogen and deuterium.

In addition, L is a chemical bond, or at least one substituted or unsubstituted aryl group having 6 to 50 carbon atoms, sulfur (S), nitrogen (N), oxygen (O), phosphorus (P), and silicon (Si). A substituted or unsubstituted heteroaryl group having 2 to 50 carbon atoms and a substituted or unsubstituted aryl group having 6 to 50 carbon atoms in which one or more substituted or unsubstituted cycloalkyls having 3 to 30 carbon atoms are fused, and the m is an integer of 0 to 3.

In addition, R is the same as or different from each other, and each independently hydrogen, deuterium, halogen group, cyano group, hydroxyl group, nitro group, substituted or unsubstituted C1 to C60 alkyl group, substituted or unsubstituted C2 to C2 A heteroaryl group of 60, a substituted or unsubstituted cycloalkyl group having 3 to 60 carbon atoms, a substituted or unsubstituted aryl group having 6 to 60 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 60 carbon atoms, a substituted or unsubstituted A C6-C60 aryloxy group, a substituted or unsubstituted C1-C30 alkylamino group, and a substituted or unsubstituted C6-C30 arylamino group. It is one or more selected from the group consisting of a substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms, and a substituted or unsubstituted alkenyl group having 2 to 60 carbon atoms. .

According to a preferred embodiment, R may be selected from the following [Structural Formula 1].

[Structural Formula 1]

In the [Structural Formula 1], Y is CR ₁ , NR ₁ , S, O or N, and at least one of the plurality of Ys in each of the structural formulas is N.

In addition, R ₁ is hydrogen, deuterium, halogen group, cyano group, hydroxyl group, nitro group, amino group, hydrazine, hydrazone, carboxyl group or salt thereof, sulfonic acid group or salt thereof, phosphoric acid or salt thereof, substituted or unsubstituted C1-C60 alkyl group, substituted or unsubstituted C3-C60 cycloalkyl group, substituted or unsubstituted C6-C60 aryl group, substituted or unsubstituted C3-C60 heteroaryl group, substituted or unsubstituted A substituted or unsubstituted alkoxy group having 1 to 60 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted alkylamino group having 1 to 20 carbon atoms, a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, A substituted or unsubstituted alkylsilyl group having 1 to 20 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms, a substituted or unsubstituted arylalkylamino group having 1 to 50 carbon atoms, a substituted or unsubstituted C 5 to carbon number It is selected from an arylthio group of 60, a substituted or unsubstituted alkenyl group having 2 to 60 carbon atoms, and a substituted or unsubstituted alkynyl group having 2 to 60 carbon atoms.

In addition, when the R ₁ is plural, the same or different from each other, and may be connected to each other with adjacent substituents to form an alicyclic, aromatic monocyclic or polycyclic ring, and the formed alicyclic, aromatic monocyclic or polycyclic ring The carbon atom of may be substituted with any one or more heteroatoms selected from N, S, and O.

When the X ₁ to X ₁₁ , L, R and R ₁ are further substituted, the substituent is hydrogen, deuterium, cyano group, halogen group, nitro group, alkyl group having 1 to 40 carbon atoms, aryl group having 6 to 40 carbon atoms, With a heteroaryl group having 2 to 40 carbon atoms, an alkylamino group having 1 to 30 carbon atoms, an aryl amino group having 1 to 30 carbon atoms, an alkoxy group having 1 to 40 carbon atoms, a cycloalkyl group having 3 to 40 carbon atoms, and an arylthio group having 6 to 40 carbon atoms. It is one or more selected from the group consisting of.

The organic light-emitting compound represented by [Chemical Formula 1] according to the present invention may more specifically be a compound represented by [Chemical Formula 2] to [Chemical Formula 163].

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

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

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

[Formula 14] [Formula 15] [Formula 16] [Formula 17]

[Formula 18] [Formula 19] [Formula 20] [Formula 21]

[Formula 22] [Formula 23] [Formula 24] [Formula 25]

[Formula 26] [Formula 27] [Formula 28] [Formula 29]

[Formula 30] [Formula 31] [Formula 32] [Formula 33]

[Formula 34] [Formula 35] [Formula 36] [Formula 37]

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

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

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

[Formula 50] [Formula 51] [Formula 52] [Formula 53]

[Formula 54] [Formula 55] [Formula 56] [Formula 57]

[Chemical Formula 58] [Chemical Formula 59] [Chemical Formula 60] [Chemical Formula 61]

[Formula 62] [Formula 63] [Formula 64] [Formula 65]

[Formula 66] [Formula 67] [Formula 68] [Formula 69]

[Formula 70] [Formula 71] [Formula 72] [Formula 73]

[Formula 74] [Formula 75] [Formula 76] [Formula 77]

[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]

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

[Formula 98] [Formula 99] [Formula 100] [Formula 101]

[Formula 102] [Formula 103] [Formula 104] [Formula 105]

[Formula 106] [Formula 107] [Formula 108] [Formula 109]

[Formula 110] [Formula 111] [Formula 112] [Formula 113]

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

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

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

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

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

[Formula 134] [Formula 135] [Formula 136] [Formula 137]

[Formula 138] [Formula 139] [Formula 140] [Formula 141]

[Formula 142] [Formula 143] [Formula 144] [Formula 145]

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

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

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

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

[Formula 162] [Formula 163]

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 is provided according to the present invention. It is characterized in that it contains at least one or more organic light emitting compounds represented by [Formula 1].

In addition, the organic layer includes at least one selected from a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer, and the organic light emitting compound according to the present invention is included in the light emitting layer and used as a phosphorescent host compound.

In addition, the light-emitting layer is characterized in that it further comprises at least one phosphorescent dopant compound in addition to the organic light-emitting compound represented by [Chemical Formula 1], and the phosphorescent dopant compound applied to the organic electroluminescent device according to the present invention is not particularly limited. , It may be a compound represented by the following [Chemical Formula I].

[Chemical Formula Ⅰ]

In the above [Formula I],

M is selected from the group consisting of metals of groups 7, 8, 9, 10, 11, 13, 14, 15, and 16, and ligands L ₁ , L ₂ And L ₃ are each independently selected from the following [Structural Formula 2].

[Structural Formula 2]

In the above [Structural Formula 2],

R are different from each other or are 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 30 carbon atoms, substituted or unsubstituted A heteroaryl group having 5 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 chosen from among group.

In addition, each R is independently selected from an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 40 carbon atoms, a heteroaryl group having 3 to 20 carbon atoms, a cyano group, a halogen group, deuterium and hydrogen It is further substituted with one or more selected substituents, and may be connected to an adjacent substituent with alkylene or alkenylene to form an alicyclic ring and a monocyclic or polycyclic aromatic ring.

In addition, L is selected from the following [Structural Formula 3].

[Structural Formula 3]

In [Structural Formula 3], X is independently of each other hydrogen, deuterium, halogen, cyano, 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 It is selected from a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 5 to 30 carbon atoms, and a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms.

In addition, L is 1 selected from a C1-C20 alkyl group, a C3-C20 cycloalkyl group, a C6-C40 aryl group, a C3-C20 heteroaryl group, a cyano group, a halogen group, deuterium and hydrogen It is further substituted with more than one kind of substituent, and may be connected to an adjacent substituent with alkylene or alkenylene to form a spiro ring or a fused ring.

Further, according to a preferred embodiment of the present invention, the [Chemical Formula I] may be selected from compounds represented by the following [Chemical Formula II].

[Chemical Formula Ⅱ]

The organic electroluminescent device according to the present invention may further include one or more layers selected from the group consisting of a hole injection layer, a hole transport layer, an electron blocking layer, a hole blocking layer, an electron transport layer, and an electron injection layer in addition to the emission layer. In addition to the light emitting layer, the organic light emitting compound may be used for a hole injection layer, a hole transport layer, an electron injection layer, and an electron transport layer.

As a specific example, a hole transport layer (HTL) may be additionally stacked, and an electron transport layer (ETL) may be additionally stacked between the cathode and the organic light-emitting layer. The hole transport layer Silver is laminated to make it easier to inject holes from the anode, and an electron donating molecule having a small ionization potential is used as a material for the hole transport layer. It is used a lot.

In the present invention, 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.

A hole injection layer (HIL) may be additionally stacked under the hole transport layer, and the hole injection layer material is not particularly limited as long as it is commonly used in the art. For example, CuPc (copper phthalocyanine) or Starburst-type amines TCTA (4,4',4"-tri(N-carbazolyl)triphenyl-amine), m-MTDATA(4,4',4"-tris- (3-methylphenylphenylamino)triphenylamine) can be used.

In addition, the electron transport layer used in the organic light emitting device according to the present invention smoothly transports electrons supplied from the cathode to the organic light emitting layer and inhibits the movement of holes that could not be combined in the organic light emitting layer, thereby recombining in the light emitting layer. It serves to increase.

The electron transport layer material is not particularly limited and may be used as long as it is commonly used in the art. For example, an oxadiazole derivative such as PBD, BMD, BND, or Alq ₃ may be used.

On the other hand, on the top of the electron transport layer, an electron injecting layer (EIL) that facilitates electron injection from the cathode and ultimately improves power efficiency may be further stacked. The material of the electron injection layer Also, as long as it is commonly used in the art, it may be used without particular limitation, and for example, materials such as LiF, NaCl, CsF, Li ₂ O, and BaO may be used.

The organic electroluminescent device according to the present invention may be used in a display device, a display device, and a single color or white lighting device.

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 typical 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 (SnO2), 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 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.

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.

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, according to another embodiment of the present invention, 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 is a monomolecular deposition method or a solution process. The organic electroluminescent device according to the present invention may be used in a display device, a display device, and a single color or white lighting device.

Hereinafter, the present invention will be described in more detail with reference to preferred embodiments. However, these examples are for describing the present invention in more detail, and the scope of the present invention is not limited thereto, and various changes and modifications are possible within the scope and spirit of the present invention. It will be self-evident to those who have knowledge.

<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]

Nitrogen was charged to the dried 2 L reactor, 100.0 g (510 mmol) of xanthone and 600 mL of toluene were added, and the mixture was lowered to 0 °C. After slowly dropping 612 mL (1223 mmol) of 2 M trimethylaluminum, the mixture was stirred at 0° C. for 2 hours and then stirred at room temperature for 4 hours.

When the reaction was completed, 300 mL of hydrochloric acid was diluted with 2 L of water, and the reaction was poured little by little at low temperature. Extracted with ethyl acetate, dried over anhydrous sodium sulfate, filtered, concentrated, and separated by column chromatography to obtain 53.8 g of a compound represented by [Chemical Formula 1-a]. (Yield 52%)

(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-a] [Formula 1-b]

After dissolving 53.8 g (256 mmol) of the compound represented by [Chemical Formula 1-a] obtained from [Scheme 1] in 540 mL of tetrahydrofuran under a stream of nitrogen, 160 mL of 1.6 M normal-butyllithium while stirring at -78 °C ( 256 mmol) was slowly added dropwise, and when the dropwise addition was completed, the mixture was stirred for 1 hour while maintaining -78°C. Thereafter, 31.9 g (307 mmol) of trimethylborate was slowly added dropwise, and then raised to room temperature and stirred for 1 hour.

Upon completion of the reaction, 200 mL of 1 M hydrochloric acid aqueous solution was added dropwise at room temperature, followed by stirring for 30 minutes. Thereafter, extraction was performed with ethyl acetate and water, and the organic layer was concentrated under reduced pressure and recrystallized from methylene chloride and hexane to obtain 15 g of a compound represented by [Chemical Formula 1-b]. (Yield 23%)

(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-b] [Formula 1-c]

Compound 19.4 g (76 mmol) of the compound represented by [Chemical Formula 1-b] obtained from [Scheme 2], 2-bromonite 14 g (69 mmol), tetrakis (triphenylphosphine) palladium 1.6 g ( 1.38 mmol), potassium carbonate 19.2 g (139 mmol), 1,4-dioxane 100 mL, toluene 100 mL, distilled water 40 mL, and stirred at 100° C. for 12 hours.

When the reaction is completed, extraction is performed using methylene chloride and distilled water. The organic layer was concentrated under reduced pressure to obtain 5.8 g of a compound represented by [Chemical Formula 1-c]. (Yield 25%)

(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-c] [Formula 1-d]

7.0 g (13 mmol) of the compound represented by [Chemical Formula 1-c] obtained from [Scheme 3] and 10 g (42 mmol) of triphenylphosphine were added to 100 mL of dichlorobenzene, and stirred for 12 hours and refluxed. When the reaction was completed, the mixture was concentrated and separated by column chromatography to obtain 4 g of a compound represented by [Chemical Formula 1-d]. (Yield 49%)

(5) Synthesis of the 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 6 g (20.04 mmol) represented by [Chemical Formula 1-d] obtained from [Scheme 4] and 0.72 g (30.063 mmol) of 60% sodium hydride were added to 60 mL of dimethylformamide and stirred at room temperature for 30 minutes. . Then, 6.44 g (24.05 mmol) of chlorodiphenyltriazine was dissolved in 60 mL of dimethylformamide, slowly added dropwise, and stirred for 1 hour.

When the reaction was completed, 60 mL of distilled water was added, filtered, and recrystallized to obtain 5.5 g of a compound represented by [Chemical Formula 2]. (Yield 51%)

<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]

Chlorodiphenyltriazine 20.0 g (74.7 mmol), 3-bromophenylboronic acid 18.0 g (89.7 mmol), tetrakis (triphenylphosphine) palladium 1.7 g (1.5 mmol), potassium carbonate 20.7 g (149.4 mmol) ), 1,4-dioxane 100 mL, toluene 100 mL, distilled water 50 mL, and stirred at 100° C. for 12 hours.

When the reaction is completed, extraction is performed using ethyl acetate and distilled water. The organic layer was dried over anhydrous sodium sulfate, concentrated under reduced pressure, and recrystallized from methylene chloride and acetone to obtain 23.2 g of a compound represented by [Chemical Formula 2-a]. (Yield 80%)

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

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

[Scheme 7]

[Formula 1-d] [Formula 2-a] [Formula 3]

Compound 20.0 g (55.80 mmol) represented by [Chemical Formula 1-d] obtained from [Scheme 4], 36.43 g (88.7 mmol) compound represented by [Chemical Formula 2-a] obtained from [Scheme 6], and copper powder 7.09 g (111.6 mmol), 18-crown-6 2.95 g (11.16 mmol), potassium carbonate 123.14 g (167.4 mmol) were added in that order, and 1,2-dichlorobenzene 200 mL was added, followed by 1 day at 180°C. Reflux and stir.

When the reaction was completed, the solution was concentrated under reduced pressure after a high-temperature filter, and the organic layer solution was recrystallized from methylene chloride and acetone to obtain 27.3 g of a compound represented by [Chemical Formula 3]. (Yield 73.5%)

<Synthesis Example 3> Synthesis of a compound represented by [Chemical Formula 4]

(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 8].

[Scheme 8]

[Formula 3-a]

Dichloroquinazoline 20.0 g (100.5 mmol), 4-biphenylboronic acid 23.88 g (120.6 mmol), tetrakis (triphenylphosphine) palladium 2.3 g (2.0 mmol), potassium carbonate 27.78 g (200.9 mmol) were added. Put in a mixed solvent of 600 mL of tetrahydrofuran, 400 mL of toluene, and 400 mL of distilled water, stirred for 9 hours, and refluxed.

When the reaction is complete, the organic layer is washed with a saturated aqueous sodium chloride solution after extraction and dried over anhydrous sodium sulfate. The organic solvent was distilled off under reduced pressure, and then recrystallized from toluene to obtain 26.7 g of a compound represented by [Chemical Formula 3-a]. (Yield 83%)

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

A compound represented by [Chemical Formula 4] was synthesized by the following [Scheme 9].

[Scheme 9]

[Formula 1-d] [Formula 3-a] [Formula 4]

7.0 g (23.382 mmol) of the compound represented by [Chemical Formula 1-d] obtained from [Scheme 4], and 0.84 g (35.074 mmol) of 60% sodium hydride were added to 70 mL of dimethylformamide and stirred at room temperature for 30 minutes. . Then, 8.89 g (28.059 mmol) of [Chemical Formula 3-a] was dissolved in 100 mL of dimethylformamide, slowly added dropwise, and stirred for 1 hour.

When the reaction was completed, 200 mL of distilled water was added, filtered, and recrystallized to obtain 6.0 g of a compound represented by [Chemical Formula 4]. (Yield 44%)

<Synthesis Example 4> Synthesis of a compound represented by [Chemical Formula 36]

(1) Synthesis of a compound represented by [Chemical Formula 36]

A compound represented by [Chemical Formula 36] was synthesized by the following [Scheme 10].

[Scheme 10]

[Formula 1-d] [Formula 36]

7.0 g (23.382 mmol) of the compound represented by [Chemical Formula 1-d] obtained from [Scheme 4], and 0.84 g (35.074 mmol) of 60% sodium hydride were added to 70 mL of dimethylformamide and stirred at room temperature for 30 minutes. . Then, 7.48 g (28.059 mmol) of chlorodiphenylpyrimidine was dissolved in 100 mL of dimethylformamide, slowly added dropwise, and stirred for 1 hour.

When the reaction was completed, 200 mL of distilled water was added, filtered, and recrystallized to obtain 8.3 g of a compound represented by [Chemical Formula 36]. (Yield 67%)

<Synthesis Example 5> Synthesis of a compound represented by [Chemical Formula 38]

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

A compound represented by [Chemical Formula 5-a] was synthesized by the following [Scheme 11].

[Scheme 11]

[Formula 5-a]

Dichloroquinazoline 20.0 g (100.5 mmol), phenylboronic acid 14.70 g (120.6 mmol), tetrakis (triphenylphosphine) palladium 2.3 g (2.0 mmol), potassium carbonate 27.78 g (200.9 mmol) in tetrahydrofuran Put in a mixed solvent of 600 mL, 400 mL of toluene, and 400 mL of distilled water, stirred for 9 hours, and refluxed.

When the reaction is complete, the organic layer is washed with a saturated aqueous sodium chloride solution after extraction and dried over anhydrous sodium sulfate. The organic solvent was distilled off under reduced pressure, and then recrystallized from toluene to obtain 18.54 g of a compound represented by [Chemical Formula 5-a]. (Yield 77%)

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

A compound represented by [Chemical Formula 5-b] was synthesized by the following [Scheme 12].

[Scheme 12]

[Formula 5-a] [Formula 5-b]

Compound 10.0 g (41.55 mmol), 4-bromophenylboronic acid 10.0 g (49.86 mmol), tetrakis (triphenyl phosphine) palladium 0.97 g of the compound represented by [Chemical Formula 5-a] obtained from [Scheme 11] (0.83 mmol), potassium carbonate 11.48 g (83.09 mmol), 1,4-dioxane 100 mL, toluene 100 mL, distilled water 50 mL, and stirred at 100 °C for 12 hours.

When the reaction is completed, extraction is performed using ethyl acetate and distilled water. The organic layer was dried over anhydrous sodium sulfate, concentrated under reduced pressure, and recrystallized from methylene chloride and acetone to obtain 9.6 g of a compound represented by [Chemical Formula 5-b]. (Yield 64%)

(3) Synthesis of a compound represented by [Chemical Formula 38]

A compound represented by [Chemical Formula 38] was synthesized by the following [Scheme 13].

[Scheme 13]

[Formula 1-d] [Formula 5-b] [Formula 38]

Compound 5 g (16.702 mmol) represented by [Chemical Formula 1-d] obtained from [Scheme 4], [Chemical Formula 5-b] 6.8 g (16.702 mmol) obtained from [Scheme 12], and copper powder 3.18 g (50.105) mmol), 18-crown-6 0.88 g (3.34 mmol), potassium carbonate 11.54 g (83.509 mmol) were added in that order, and 1,2-dichlorobenzene 50 mL was added, followed by refluxing and stirring at 180° C. for 1 day. .

When the reaction was completed, the solution was concentrated under reduced pressure after high-temperature filtering, and the organic layer solution was recrystallized from methylene chloride and acetone to obtain 4.3 g of a compound represented by [Chemical Formula 38]. (Yield 42%)

<Synthesis Example 6> Synthesis of a compound represented by [Chemical Formula 39]

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

A compound represented by [Chemical Formula 6-a] was synthesized by the following [Scheme 14].

[Scheme 14]

[Formula 5-a] [Formula 6-a]

Compound 10.0 g (41.55 mmol), 3-bromophenylboronic acid 10.0 g (49.86 mmol), tetrakis (triphenyl phosphine) palladium 0.97 g of the compound represented by [Chemical Formula 5-a] obtained from [Scheme 11] (0.83 mmol), potassium carbonate 11.48 g (83.09 mmol), 1,4-dioxane 100 mL, toluene 100 mL, distilled water 50 mL, and stirred at 100 °C for 12 hours.

When the reaction is completed, extraction is performed using ethyl acetate and distilled water. The organic layer was dried over anhydrous sodium sulfate, concentrated under reduced pressure, and recrystallized from methylene chloride and acetone to obtain 11.0 g of a compound represented by [Chemical Formula 6-a]. (Yield 73%)

(2) Synthesis of the compound represented by [Chemical Formula 39]

A compound represented by [Chemical Formula 39] was synthesized by the following [Scheme 15].

[Scheme 15]

[Formula 1-d] [Formula 6-a] [Formula 39]

5.5 g (18.37 mmol) of the compound represented by [Chemical Formula 1-d] obtained from [Scheme 4], 8.25 g (20.21 mmol) of [Chemical Formula 6-a] obtained from [Scheme 14], 3.5 g (111.6) of copper powder mmol), 18-crown-6 0.97 g (3.67 mmol), potassium carbonate 12.70 g (91.86 mmol) were added in that order, 1,2-dichlorobenzene 555 mL was added, and then refluxed and stirred at 180° C. for 1 day. .

When the reaction was completed, the solution was concentrated under reduced pressure after high-temperature filtering, and the organic layer solution was recrystallized from methylene chloride and acetone to obtain 6.3 g of the compound represented by [Chemical Formula 39]. (Yield 59%)

<Synthesis Example 7> Synthesis of a compound represented by [Chemical Formula 62]

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

A compound represented by [Chemical Formula 7-a] was synthesized by the following [Scheme 16].

[Scheme 16]

[Formula 1-a] [Formula 7-a]

After dissolving 50 g (237.79 mmol) of the compound represented by [Formula 1-a] obtained from [Scheme 1] in 400 mL of tetrahydrofuran under a stream of nitrogen, while stirring at -78 °C, 111 mL of 1.6 M normal-butyllithium ( 285.34 mmol) was slowly added dropwise, and when the dropwise addition was completed, the mixture was stirred for 1 hour while maintaining -78°C. Then, 66.38 g (261.56 mmol) of iodine was slowly added dropwise, and the mixture was raised to room temperature and stirred for 1 hour.

When the reaction is complete, 500 mL of an aqueous sodium thiosulfate solution was added dropwise, followed by stirring for 30 minutes. Thereafter, extraction was performed with ethyl acetate and water, and the organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure to obtain 21.4 g of a compound represented by [Chemical Formula 7-a]. (Yield 26%)

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

A compound represented by [Chemical Formula 7-b] was synthesized by the following [Scheme 17].

[Scheme 17]

[Formula 7-a] [Formula 7-b]

Compound 20 g (53.58 mmol) represented by [Chemical Formula 7-a] obtained from [Scheme 16], 2-bromoaniline 9.22 g (53.58 mmol), tris(dibenzylideneacetone)dipalladium 0.9 g (1.07) mmol), sodium tertiary butoxide 10.3 g (107.17 mmol), 2,2'-bis (diphenylphosphino)-1,1'-binapthyl 1.1 g (2.14 mmol) and 200 mL of toluene were added for 12 hours. Refluxed.

When the reaction is finished, it is filtered under reduced pressure while hot. After the solution was dried under reduced pressure, 16.4 g (73%) of a compound represented by [Chemical Formula 7-b] was obtained by column chromatography.

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

A compound represented by [Chemical Formula 7-c] was synthesized by the following [Scheme 18].

[Scheme 18]

[Formula 7-b] [Formula 7-c]

Compound 20 g (39.45 mmol) represented by [Chemical Formula 7-b] obtained from [Scheme 17], tetrakistriphenylphosphine palladium 1.82 g, (1.58 mmol), potassium acetate (5.8 g, 59.167 mmol) and dimethylacetamide (150 mL) were added and then refluxed for 12 hours. After the reaction solution was filtered using Celite, the filtrate was concentrated under reduced pressure and then purified by column chromatography to obtain 5.3 g of [Chemical Formula 7-c]. (Yield 44.9%)

(4) Synthesis of the compound represented by [Chemical Formula 62]

A compound represented by [Chemical Formula 62] was synthesized by the following [Scheme 19].

[Scheme 19]

[Formula 7-c] [Formula 62]

Compound 4 g (13.36 mmol) represented by [Chemical Formula 7-c] obtained from [Scheme 18] and 0.48 g (20.04 mmol) of 60% sodium hydride were added to 60 mL of dimethylformamide and stirred at room temperature for 30 minutes. . Then, 4.29 g (24.05 mmol) of chlorodiphenyltriazine was dissolved in 40 mL of dimethylformamide, slowly added dropwise, and stirred for 1 hour.

When the reaction was completed, 50 mL of distilled water was added, filtered, and recrystallized to obtain 5.2 g of a compound represented by [Chemical Formula 62]. (Yield 73%)

<Synthesis Example 8> Synthesis of a compound represented by [Chemical Formula 64]

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

A compound represented by [Chemical Formula 64] was synthesized by the following [Scheme 20].

[Scheme 20]

[Formula 7-c] [Formula 3-a] [Formula 64]

7.0 g (23.382 mmol) of the compound represented by [Chemical Formula 7-c] obtained from [Scheme 18], and 0.84 g (35.074 mmol) of 60% sodium hydride were added to 70 ml of dimethylformamide and stirred at room temperature for 30 minutes. . Thereafter, 8.89 g (28.059 mmol) of [Chemical Formula 3-a] was dissolved in 100 mL of dimethylformamide, slowly added dropwise, and stirred for 1 hour.

When the reaction was completed, 200 mL of distilled water was added, filtered, and recrystallized to obtain 9.0 g of the compound represented by [Chemical Formula 64]. (Yield 66%)

<Synthesis Example 9> Synthesis of a compound represented by [Chemical Formula 74]

(1) Synthesis of a compound represented by [Chemical Formula 74]

A compound represented by [Chemical Formula 74] was synthesized by the following [Scheme 21].

[Scheme 21]

[Formula 7-c] [Formula 5-a] [Formula 74]

5.0 g (16.702 mmol) of the compound represented by [Chemical Formula 7-c] obtained from [Scheme 18] and 0.60 g (25.053 mmol) of 60% sodium hydride were added to 50 mL of dimethylformamide and stirred at room temperature for 30 minutes. . Thereafter, 4.82 g (20.042 mmol) of [Chemical Formula 5-a] was dissolved in 100 mL of dimethylformamide, slowly added dropwise, and stirred for 1 hour.

When the reaction was completed, 50 mL of distilled water was added, filtered, and recrystallized to obtain 5.2 g of a compound represented by [Chemical Formula 74]. (Yield 62%)

<Synthesis Example 10> Synthesis of a compound represented by [Chemical Formula 75]

(1) Synthesis of the compound represented by [Chemical Formula 75]

A compound represented by [Chemical Formula 75] was synthesized by the following [Scheme 22].

[Scheme 22]

[Formula 7-c] [Formula 5-b] [Formula 75]

Compound 5 g (16.702 mmol) represented by [Chemical Formula 7-c] obtained from [Scheme 18], [Chemical Formula 5-b] 6.8 g (16.702 mmol) obtained from [Scheme 12], and copper powder 3.18 g (50.105) mmol), 18-crown-6 0.88 g (3.34 mmol), potassium carbonate 11.54 g (83.509 mmol) were added in that order, and 1,2-dichlorobenzene 50 mL was added, followed by refluxing and stirring at 180° C. for 1 day. .

When the reaction was completed, the solution was concentrated under reduced pressure after high-temperature filtering, and the organic layer solution was recrystallized from methylene chloride and acetone to obtain 5.9 g of the compound represented by [Chemical Formula 75]. (Yield 56%)

<Synthesis Example 11> Synthesis of a compound represented by [Chemical Formula 76]

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

A compound represented by [Chemical Formula 11-a] was synthesized by the following [Scheme 23].

[Scheme 23]

[Formula 3-a] [Formula 11-a]

Compound 5 g (13.39 mmol) represented by [Chemical Formula 3-a] obtained from [Scheme 8], 4-bromophenylboronic acid 3.25 g (16.07 mmol), tetrakis (triphenylphosphine) palladium 0.31 g (0.26 mmol), potassium carbonate 3.7 g (26.78 mmol), 1,4-dioxane 50 mL, toluene 50 mL, distilled water 50 mL, and stirred at 100° C. for 12 hours.

When the reaction is completed, extraction is performed using ethyl acetate and distilled water. The organic layer was dried over anhydrous sodium sulfate, concentrated under reduced pressure, and recrystallized from methylene chloride and acetone to obtain 5.2 g of a compound represented by [Chemical Formula 11-a]. (Yield 88%)

(2) Synthesis of a compound represented by [Chemical Formula 76]

A compound represented by [Chemical Formula 76] was synthesized by the following [Scheme 24].

[Scheme 24]

[Formula 7-c] [Formula 11-a] [Formula 76]

2.1 g (7.02 mmol) of the compound represented by [Chemical Formula 7-c] obtained from [Scheme 18], 4.0 g (8.42 mmol) of [Chemical Formula 11-a] obtained from [Scheme 23], and 1.34 g (21.04 of copper powder) mmol), 18-crown-6 0.37 g (1.4 mmol), potassium carbonate 4.8 g (35.07 mmol) were added in that order, and 1,2-dichlorobenzene 50 mL was added, followed by refluxing and stirring at 180° C. for 1 day. . When the reaction was completed, the solution was concentrated under reduced pressure after a high-temperature filter, and the organic layer solution was recrystallized from methylene chloride and acetone to obtain 2.9 g of a compound represented by [Chemical Formula 76]. (Yield 63%)

<Synthesis Example 12> Synthesis of a compound represented by [Chemical Formula 158]

(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 25].

[Scheme 25]

[Formula 1-a] [Formula 12-a]

56 g (266 mmol) of the compound represented by [Chemical Formula 1-a] obtained from [Scheme 1] was dissolved in 600 mL of acetic acid under a stream of nitrogen, and then 42.56 g (266 mmol) of bromine was slowly added dropwise while stirring at 0° C. When the dropwise addition is completed, the mixture is stirred for 1 hour while maintaining 0°C. When the reaction is complete, 200 mL of a 1 M aqueous hydrochloric acid solution is added dropwise at room temperature and stirred for 30 minutes. Thereafter, extraction was performed with ethyl acetate and water, the organic layer was concentrated under reduced pressure, and recrystallized in methylene chloride and hexane to obtain 19.3 g of a compound represented by [Chemical Formula 12-a]. (Yield 32%)

(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 26].

[Scheme 26]

[Formula 12-a] [Formula 12-b]

100 g (346 mmol) of the compound represented by [Chemical Formula 12-a] obtained from [Scheme 25] was dissolved in 100 mL of tetrahydrofuran under a stream of nitrogen, and stirred at -78 °C, while 260 mL of 1.6 M normal-butyllithium ( 415 mmol) was slowly added dropwise, and when the dropwise addition was completed, the mixture was stirred for 1 hour while maintaining -78°C. Thereafter, 50.3 g (484 mmol) of trimethylborate was slowly added dropwise, and the mixture was raised to room temperature and stirred for 1 hour.

When the reaction is complete, 200 mL of a 1 M aqueous hydrochloric acid solution is added dropwise at room temperature and stirred for 30 minutes. Thereafter, extraction was performed with ethyl acetate and water, and the organic layer was concentrated under reduced pressure and recrystallized from methylene chloride and hexane to obtain 72 g of a compound represented by [Chemical Formula 12-b]. (Yield 82%)

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

A compound represented by [Chemical Formula 12-c] was synthesized by the following [Scheme 27].

[Scheme 27]

[Formula 12-b] [Formula 12-c]

50 g (196 mmol) of the compound represented by [Chemical Formula 12-b] obtained from [Scheme 26], 33 g (163 mmol) of 2-bromonite, and 3.7 g of tetrakis (triphenylphosphine) palladium ( 3.26 mmol), potassium carbonate 45.2 g (139 mmol), 1,4-dioxane 300 mL, toluene 300 mL, distilled water 120 mL, and stirred at 100° C. for 12 hours. When the reaction is completed, extraction is performed using methylene chloride and distilled water. The organic layer was concentrated under reduced pressure to obtain 43 g of a compound represented by [Chemical Formula 12-c]. (79% yield)

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

A compound represented by [Chemical Formula 12-d] was synthesized by the following [Scheme 28].

[Scheme 28]

[Formula 12-c] [Formula 12-d]

43 g (129 mmol) of a compound represented by [Chemical Formula 12-c] obtained from [Scheme 27] and 88 g (337 mmol) of triphenylphosphine were added to 430 mL of dichlorobenzene, and stirred for 12 hours and refluxed. When the reaction was completed, it was concentrated and separated by column chromatography to obtain 4 g. After filtration, it was recrystallized to obtain 7.1 g of a compound represented by [Chemical Formula 12-d]. (Yield 18%)

(5) Synthesis of the compound represented by [Chemical Formula 158]

A compound represented by [Chemical Formula 158] was synthesized by the following [Scheme 29].

[Scheme 29]

[Formula 12-d] [Formula 158]

7 g (23.38 mmol) of the compound represented by [Chemical Formula 12-d] obtained from [Scheme 28] and 0.85 g (28.05 mmol) of 60% sodium hydride were added to 70 mL of dimethylformamide and stirred at room temperature for 30 minutes. . Then, 7.5 g (28.06 mmol) of chlorodiphenyltriazine was dissolved in 70 mL of dimethylformamide, slowly added dropwise, and stirred for 1 hour.

When the reaction was completed, 70 ml of distilled water was added, filtered, and recrystallized to obtain 8.6 g of a compound represented by [Chemical Formula 158]. (Yield 69%)

<Synthesis Example 13> Synthesis of a compound represented by [Chemical Formula 159]

(1) Synthesis of a compound represented by [Formula 13-a]

A compound represented by [Chemical Formula 13-a] was synthesized by the following [Scheme 30].

[Scheme 30]

[Formula 12-a] [Formula 13-a]

Compound 50 g (172 mmol) 2-bromoaniline 29.74 g (172 mmol), tris(dibenziridenacetone) dipalladium 3.16 g (3.4 mmol) obtained from [Scheme 25] and represented by [Chemical Formula 12-a] ), sodium tertiary butoxide 33.23 g (345.82 mmol), 2,2'-bis(diphenylphosphino)-1,1'-binapthyl 3.8 g (6.92 mmol) and 200 mL of toluene were added and refluxed for 12 hours Made it. When the reaction is finished, it is filtered under reduced pressure while hot. After the solution was dried under reduced pressure, 45.5 g of the compound represented by [Chemical Formula 13-a] was obtained by column chromatography. (Yield 69%)

(2) Synthesis of a compound represented by [Formula 13-b]

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

[Scheme 31]

[Formula 13-a] [Formula 13-b]

Compound 45.5 g (109 mmol) represented by [Chemical Formula 13-a] obtained from [Scheme 30], tetrakistriphenylphosphine palladium 5.04 g, (4.3 mmol), potassium acetate 16.04 g (160.4 mmol) and 450 mL of dimethylacetamide were added, and then refluxed for 12 hours. After the reaction solution was filtered using Celite, the filtrate was concentrated under reduced pressure, and then purified by column chromatography to obtain 4.9 g of a compound represented by [Chemical Formula 13-b]. (Yield 13%)

(3) Synthesis of the compound represented by [Chemical Formula 159]

A compound represented by [Chemical Formula 159] was synthesized by the following [Scheme 32].

[Scheme 32]

[Formula 13-b] [Formula 159]

Compound 4 g (13 mmol) represented by [Chemical Formula 13-b] obtained from [Scheme 31] and 0.48 g (25 mmol) of 60% sodium hydride were added to 40 mL of dimethylformamide and stirred at room temperature for 30 minutes. . Thereafter, 3.8 g (16 mmol) of [Formula 5-a] was dissolved in 40 mL of dimethylformamide, slowly added dropwise, and stirred for 1 hour. When the reaction was completed, 40 mL of distilled water was added, filtered, and recrystallized to obtain 4.3 g of a compound represented by [Chemical Formula 159]. (Yield 64%)

<Synthesis Example 14> Synthesis of a compound represented by [Chemical Formula 161]

(1) Synthesis of a compound represented by [Formula 14-a]

A compound represented by [Chemical Formula 14-a] was synthesized by the following [Scheme 33].

[Scheme 33]

[Formula 13-a] [Formula 14-a]

Compound 45.5 g (109 mmol) represented by [Chemical Formula 13-a] obtained from [Scheme 30], tetrakistriphenylphosphine palladium 5.04 g (4.3 mmol), potassium acetate 16.04 g (160.4 mmol) and 450 mL of dimethylacetamide were added, and then refluxed for 12 hours. After filtering the reaction solution using Celite, the filtrate was concentrated under reduced pressure and then purified by column chromatography to obtain 3.6 g of a compound represented by [Chemical Formula 14-a]. (Yield 9.5%)

(2) Synthesis of the compound represented by [Chemical Formula 161]

A compound represented by [Chemical Formula 161] was synthesized by the following [Scheme 34].

[Scheme 34]

[Formula 14-a] [Formula 161]

3.6 g (12 mmol) of the compound represented by [Formula 14-a] obtained from [Scheme 33] and 0.43 g (18 mmol) of 60% sodium hydride were added to 35 mL of dimethylformamide and stirred at room temperature for 30 minutes. . Thereafter, 3.4 g (14 mmol) of [Formula 5-a] was dissolved in 35 mL of dimethylformamide, slowly added dropwise, and stirred for 1 hour. When the reaction was completed, 35 mL of distilled water was added, filtered, and recrystallized to obtain 2.9 g of a compound represented by [Chemical Formula 161]. (Yield 48%)

Examples 1 to 14: Preparation of organic light emitting diode

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 a vacuum chamber and making the base pressure 1 × 10 ^-6 torr, the organic material is placed on the ITO DNTPD (700 Å), NPD (300 Å), the compound prepared by the present invention + [RD-1 ] (10%) (300 Å), Alq ₃ (350 Å), LiF (5 Å), and Al (1,000 Å) were formed in the order, and the measurement was performed at 0.4 mA.

[RD-1]

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.The structure of BAlq is as follows.

division Host Dopant Current(mA) V Cd/m ² CIEx CIEy T ₅₀ (Hr) Comparative Example 1 BAlq RD-1 10 6.7 1100 0.636 0.338 2500 Example 1 2 RD-1 10 4.5 1340 0.633 0.335 4700 Example 2 3 RD-1 10 5.2 1310 0.634 0.334 5600 Example 3 4 RD-1 10 4.5 1540 0.635 0.332 9300 Example 4 36 RD-1 10 4.7 1280 0.630 0.336 4500 Example 5 38 RD-1 10 4.2 1570 0.632 0.334 9700 Example 6 39 RD-1 10 5.1 1550 0.634 0.335 9500 Example 7 62 RD-1 10 4.6 1320 0.632 0.334 4500 Example 8 64 RD-1 10 4.4 1350 0.639 0.338 5100 Example 9 74 RD-1 10 4.7 1490 0.633 0.336 9800 Example 10 75 RD-1 10 4.5 1520 0.633 0.335 9100 Example 11 76 RD-1 10 4.8 1510 0.639 0.334 8900 Example 12 158 RD-1 10 4.2 1340 0.630 0.334 4900 Example 13 159 RD-1 10 4.7 1540 0.633 0.332 9700 Example 14 161 RD-1 10 4.6 1500 0.632 0.333 8900

In the [Table 1], T ₅₀ means the time required for the luminance to be reduced to 50% compared to the initial luminance.

As shown in [Table 1], when the organic light-emitting compound embodied according to the present invention is employed as the light emitting layer host compound of the organic light-emitting device, the lifespan characteristics compared to the device employing BAlq, which is widely used as a phosphorescent host material. This remarkably improves, and not only has excellent light-emitting characteristics, but also lowers the driving voltage, thereby inducing an increase in power efficiency and improving power consumption.

10: substrate 20: anode
30: hole injection layer 40: hole transport layer
50: organic light emitting layer 60: electron transport layer
70: electron injection layer 80: cathode

Claims (16)

Organic light-emitting compound represented by the following [Formula 1]:
[Formula 1]

In the above [Formula 1],
A ₁ to A ₄ are each independently CX ₁₁ , and two adjacent two of A ₁ to A ₄ combine with B to form a condensed ring,
The X ₁ to X ₁₁ are 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 50 carbon atoms, and a substituted or unsubstituted C 2 to 50 carbon number. A heteroaryl group, selected from hydrogen and deuterium,
L is a chemical bond or a substituted or unsubstituted aryl group having 6 to 50 carbon atoms and a substituted or unsubstituted aryl group having 6 to 50 carbon atoms fused with one or more substituted or unsubstituted cycloalkyls having 3 to 30 carbon atoms And
R is the same as or different from each other, and each independently hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 60 carbon atoms, a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms, a substituted or unsubstituted carbon number 3 to 60 Is selected from a cycloalkyl group and a substituted or unsubstituted aryl group having 6 to 60 carbon atoms,
m is an integer of 0 to 3. The method of claim 1,
The X ₁ to X ₁₁ , L and R are hydrogen, deuterium, cyano group, halogen group, nitro group, alkyl group having 1 to 40 carbon atoms, aryl group having 6 to 40 carbon atoms, heteroaryl group having 2 to 40 carbon atoms, and 3 carbon atoms Organic light-emitting compound, characterized in that further substituted with one or more selected from the group consisting of a cycloalkyl group of to 40. The method of claim 1,
The organic light-emitting compound, characterized in that the X ₁ to X ₁₁ , L, R and substituents thereof are bonded to each other with adjacent substituents to form a saturated or unsaturated ring. The method of claim 1,
[Chemical Formula 1] is an organic light emitting compound, characterized in that any one selected from the following [Formula 1-a] to [Formula 1-f]:
[Formula 1-a] [Formula 1-b]

[Formula 1-c] [Formula 1-d]

[Formula 1-e] [Formula 1-f]

In the [Formula 1-a] to [Formula 1-f],
The definitions of X ₁ to X ₁₁ , L and R are the same as those in [Chemical Formula 1]. delete delete The method of claim 1,
The [Chemical Formula 1] is an organic light-emitting compound, characterized in that any one selected from compounds represented by the following [Chemical Formula 2] to [Chemical Formula 163]:

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

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

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

[Formula 14] [Formula 15] [Formula 16] [Formula 17]

[Formula 18] [Formula 19] [Formula 20] [Formula 21]

[Formula 22] [Formula 23] [Formula 24] [Formula 25]

[Formula 26] [Formula 27] [Formula 28] [Formula 29]

[Formula 30] [Formula 31] [Formula 32] [Formula 33]

[Formula 34] [Formula 35] [Formula 36] [Formula 37]

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

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

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

[Formula 50] [Formula 51] [Formula 52] [Formula 53]

[Formula 54] [Formula 55] [Formula 56] [Formula 57]

[Chemical Formula 58] [Chemical Formula 59] [Chemical Formula 60] [Chemical Formula 61]

[Formula 62] [Formula 63] [Formula 64] [Formula 65]

[Formula 66] [Formula 67] [Formula 68] [Formula 69]

[Formula 70] [Formula 71] [Formula 72] [Formula 73]

[Formula 74] [Formula 75] [Formula 76] [Formula 77]

[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]

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

[Formula 98] [Formula 99] [Formula 100] [Formula 101]

[Formula 102] [Formula 103] [Formula 104] [Formula 105]

[Formula 106] [Formula 107] [Formula 108] [Formula 109]

[Formula 110] [Formula 111] [Formula 112] [Formula 113]

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

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

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

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

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

[Formula 134] [Formula 135] [Formula 136] [Formula 137]

[Formula 138] [Formula 139] [Formula 140] [Formula 141]

[Formula 142] [Formula 143] [Formula 144] [Formula 145]

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

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

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

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

[Formula 162] [Formula 163] An organic electroluminescent device comprising at least one organic light-emitting compound selected according to claim 1. A first electrode; It consists of a second electrode and one or more organic layers interposed between the first electrode and the second electrode,
The organic electroluminescent device, characterized in that the organic layer comprises at least one organic light-emitting compound selected according to claim 1. The method of claim 9,
The organic layer comprises 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. The method of claim 9,
The organic electroluminescent device, characterized in that the organic light emitting compound is used as a phosphorescent host, and the organic layer further comprises at least one phosphorescent dopant compound. delete delete delete delete The method of claim 9,
The organic electroluminescent device, characterized in that it emits white light by including at least one organic light-emitting layer emitting blue, red, or green light.

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