KR20120140603A - New material for transporting electron and organic electroluminescent device using the same - Google Patents

Abstract

PURPOSE: A organic light-emitting device electron transporting are provided by using electron transporting material which have high light emission and strengthen driving voltage, which induces the enhancement of power efficiency so that organic light-emitting devices with high energy efficiency are manufactured. CONSTITUTION: An electron transporting material is marked structural formula 1. An electron transporting material is marked from structural formula 2 to structural formula 8. An organic light-emitting device comprises an electron transporting material. The electron transporting material comprises the first electrode, the second electrode and more than one layer of organic between the first electrode and the second electrode. The organic layer comprises electron transport layer with electron transporting materials.

Description

Novel electron transport material and organic light emitting device using the same {NEW MATERIAL FOR TRANSPORTING ELECTRON AND ORGANIC ELECTROLUMINESCENT DEVICE USING THE SAME}

The present invention relates to a novel electron transport material and an organic light emitting device using the same.

An organic light emitting device is a device that emits light by dissipating electrons and holes after pairing when an electric charge is injected into an organic film formed between an electron injection electrode (cathode) and a hole injection electrode (anode). The device can be formed on a flexible transparent substrate such as plastic, and can be driven at a lower voltage (less than 10V) compared to a plasma display panel or an inorganic EL display, and also consumes power. It is relatively small and has the advantage of excellent color.

The structure of a general organic electroluminescent device includes a substrate, an anode, a hole injection layer that receives holes from an anode, a hole transport layer that transports holes, a light emitting layer that combines holes and electrons to emit light, and receives electrons from a cathode and transfers them to the light emitting layer. It consists of an electron carrying layer and a cathode. In some cases, a light emitting layer may be formed by doping a small amount of fluorescent or phosphorescent dye into an electron transporting layer or a hole transporting layer without a separate light emitting layer, and in the case of using a polymer, it generally serves as a hole transporting layer, a light emitting layer, and an electron transporting layer. The polymer can be carried out simultaneously. The organic thin film layers between the two electrodes are formed by vacuum deposition or spin coating, inkjet printing, roll coating, or the like, and a separate electron injection layer may be inserted to efficiently inject electrons from the cathode.

Stabilizing the interface between the electrode and the organic material, or in the case of the organic material, the hole and electron movement speed is significantly different, so using the appropriate hole transport layer and electron transport layer can be effectively transferred holes and electrons to the light emitting layer and holes in the light emitting layer The organic light emitting device is manufactured in a multi-layered thin film structure in order to balance the density of electrons with the electrons to increase luminous efficiency.

Representative examples of existing electron transport materials include aluminum complexes such as Alq3 (tris (8-hydroxyquinoline) aluminum (III)) and Bebq (bis (10-hydroxybenzo- [h] quinolinato) beryllium) and beryllium complexes. However, these materials have a problem of poor color purity due to light emission due to exciton diffusion when used in blue light emitting devices.

In addition, TPBI (see structure below), published by Kodak in 1996 and disclosed in US Pat. No. 5,645,948, is known as a representative electron transport layer material having an imidazole group, and is located at the 1,3,5-substituted position of benzene. It contains N-phenyl benzimidazole groups and functionally blocks electrons from the light emitting layer as well as the ability to transfer electrons, but has a problem of low stability for practical application.

In the conventional electron transporting material, it is particularly noteworthy that compared to what is disclosed, there are problems such as a simple improvement in driving voltage only, a significant reduction in device driving life, and a variation in device life and thermal stability by color. Side effects.

In addition, although the conventional organic light emitting device uses a fluorescent light emitting material, it is gradually changing to a tendency to employ a phosphorescent light emitting material. Therefore, the electron transport layer material, which is a common material, also requires appropriate electron mobility, low driving voltage, and hole blocking property suitable for phosphorescent materials.

Accordingly, an object of the present invention is to provide a novel electron transport material capable of greatly improving luminous efficiency, stability, and device life, in consideration of the problems of the prior art.

Another object of the present invention is to provide an organic light emitting device having excellent light emission characteristics by using the novel electron transport material and inducing power efficiency by increasing driving voltage to improve power consumption.

The present invention relates to an electron transporting material represented by the following Chemical Formula 1 and an organic light emitting device including the same, wherein the electron transporting material according to the present invention not only has excellent luminescence properties but also enhances driving voltage to increase power efficiency. Induction has an advantage of manufacturing an organic light emitting device with improved power consumption.

[Formula 1]

In Formula 1,

Ar is (C6-C30) arylene or (C3-C30) heteroarylene;

L ₁ and L ₂ are independently of each other a single bond, (C1-C30) alkylene, (C6-C30) arylene, (C3-C30) cycloalkylene or (C3-C30) heteroarylene;

,

또는

이고;R ₁ and R ₂ independently of one another are hydrogen, (C1-C30) alkyl, (C3-C30) cycloalkyl, -CR '= CR''R''', (C6-C30) aryl or (C3-C30) Heteroaryl, provided that at least one of R ₁ and R ₂ is

,

or

ego;

L ₃ and L ₄ are independently of each other a single bond or (C6-C30) arylene;

R ', R'',R''', R ₃ to R ₅ independently of one another are hydrogen, (C1-C30) alkyl, (C3-C30) cycloalkyl, (C6-C30) aryl or (C3-C30) Heteroaryl;

X is O or S;

The arylene and heteroarylene of Ar, alkylene, arylene, cycloalkylene and heteroarylene of L ₁ and L ₂ , and alkyl, cycloalkyl, aryl and heteroaryl of R ₁ to R ₅ are (C1- C30) alkyl, halo (C1-C30) alkyl, halogen, cyano, (C3-C30) cycloalkyl, (C1-C30) alkoxy, (C6-C30) aryloxy, (C6-C30) aryl, (C1- C30) alkyl (C6-C30) aryl, (C6-C30) ar (C1-C30) alkyl, (C3-C30) heteroaryl, (C1-C30) alkyl substituted (C3-C30) heteroaryl, (C6 (C3-C30) heteroaryl, mono or di (C1-C30) alkylamino, mono or di (C6-C30) arylamino, tri (C1-C30) alkylsilyl, di (C1-) C30) alkyl (C6-C30) arylsilyl, tri (C6-C30) arylsilyl, nitro and hydroxy may be further substituted with one or more selected from the group consisting of;

The heteroarylene and heteroaryl include one or more heteroatoms selected from B, N, O, S, P (= 0), Si and P.

Substituents including the "alkyl", "alkoxy" and other "alkyl" moieties described herein include all linear or pulverized forms, and "cycloalkyl" is not only a monocyclic system but also substituted or unsubstituted adamantyl Or several ring-based hydrocarbons such as substituted or unsubstituted (C7-C30) bicycloalkyl. "Aryl" described in the present invention is an organic radical derived from an aromatic hydrocarbon by one hydrogen removal, and a single or fused ring containing 4 to 7, preferably 5 or 6 ring atoms in each ring as appropriate. It includes a system, including a form in which a plurality of aryl is connected by a single bond. Specific examples include phenyl, naphthyl, biphenyl, terphenyl, anthryl, indenyl, fluorenyl, phenanthryl, triphenylenyl, pyrenyl, peryleneyl, chrysenyl, naphthacenyl, fluoranthenyl and the like. There is this. "Heteroaryl" described in the present invention contains 1 to 4 heteroatoms selected from B, N, O, S, P (= O), Si and P as aromatic ring skeleton atoms, and the remaining aromatic ring skeleton atoms are carbon. Means an aryl group, 5-6 membered monocyclic heteroaryl, and polycyclic heteroaryl condensed with one or more benzene rings, which may be partially saturated. In addition, heteroaryl in the present invention also includes a form in which one or more heteroaryl is connected by a single bond. Such heteroaryl groups include divalent aryl groups in which heteroatoms in the ring are oxidized or quaternized to form, for example, N-oxides or quaternary salts. Specific examples include furyl, thiophenyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl, triazolyl, Monocyclic heteroaryl such as tetrazolyl, furazanyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, benzofuranyl, benzothiophenyl, isobenzofuranyl, benzoimidazolyl, benzothiazolyl, benzoiso Thiazolyl, benzoisoxazolyl, benzoxazolyl, isoindolyl, indolyl, indazolyl, benzothiadiazolyl, quinolyl, isoquinolyl, cinnaolinyl, quinazolinyl, quinoxalinyl, carbazolyl, phenantri Polycyclic heteroaryls such as dinyl, benzodioxyl, dibenzofuranyl, dibenzothiophenyl and their corresponding N-oxides (e.g. pyridyl N-oxides, quinolyl N-oxides), Quaternary salts;

Further, the '(C1-C30) alkyl' group described in the present invention is preferably (C1-C20) alkyl, more preferably (C1-C10) alkyl, and the '(C6-C30) aryl' group is preferred. Preferably (C6-C20) aryl. The '(C3-C30) heteroaryl' group is preferably (C3-C20) heteroaryl. The '(C3-C30) cycloalkyl' group is preferably (C3-C20) cycloalkyl, more preferably (C3-C7) cycloalkyl.

In the electron transporting material of Chemical Formula 1, Ar is preferably selected from the following structures.

[The above R ₁₁ to R ₂₁ are independently of each other hydrogen, (C1-C30) alkyl, halo (C1-C30) alkyl, halogen, cyano, (C3-C30) cycloalkyl, (C1-C30) alkoxy, (C6 -C30) aryloxy, (C6-C30) aryl, (C1-C30) alkyl (C6-C30) aryl, (C6-C30) ar (C1-C30) alkyl, (C3-C30) heteroaryl, (C1- (C3-C30) heteroaryl substituted with alkyl, (C3-C30) heteroaryl substituted with (C3-C30) aryl, mono or di (C1-C30) alkylamino, mono or di (C6-C30) Arylamino, tri (C1-C30) alkylsilyl, di (C1-C30) alkyl (C6-C30) arylsilyl, tri (C6-C30) arylsilyl, nitro or hydroxy; a to d are each independently an integer of 1 to 4; e is an integer of 1 or 2.]

More specifically, the electron transporting material of the present invention may be represented by the following Chemical Formulas 2 to 8.

[Formula 2]

(3)

[Formula 4]

[Chemical Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

이고, 상기 R₁의 알킬, 아릴 및 헤테로아릴은 (C1-C30)알킬 또는 (C6-C30)아릴로 더 치환될 수 있고; R₁₁ 내지 R₂₀은 서로 독립적으로 수소, (C1-C30)알킬, (C6-C30)아릴, (C1-C30)알킬(C6-C30)아릴 또는 (C3-C30)헤테로아릴이고, 단, R₁₁과 R₁₂가 동시에 수소인 경우는 제외되고; R₂는

,

또는

이고; L₃ 및 L₄는 서로 독립적으로 단일결합 또는 (C6-C30)아릴렌이고; R', R'', R''', R₃ 내지 R₅는 서로 독립적으로 수소, (C6-C30)아릴 또는 (C3-C30)헤테로아릴이고; X는 O 또는 S이고; a 내지 d는 서로 독립적으로 1 내지 4의 정수이다.]
[Formula 2 to In 8, L ₁ and L ₂ are each independently a single bond, (C6-C30) arylene or (C3-C30) heteroarylene, wherein the arylene and heteroarylene of L ₁ and L ₂ are (C1- C 30) alkyl or (C 6 -C 30) aryl; R ₁ is hydrogen, (C1-C30) alkyl, -CR '= CR``R''', (C6-C30) aryl, (C3-C30) heteroaryl or

Wherein the alkyl, aryl and heteroaryl of R ₁ may be further substituted with (C ₁ -C 30) alkyl or (C 6 -C 30) aryl; R ₁₁ to R ₂₀ are each independently hydrogen, (C 1 -C 30) alkyl, (C 6 -C 30) aryl, (C 1 -C 30) alkyl (C 6 -C 30) aryl or (C 3 -C 30) heteroaryl, provided that Except when ₁₁ and R ₁₂ are hydrogen at the same time; R ₂ is

,

or

ego; L ₃ and L ₄ are independently of each other a single bond or (C6-C30) arylene; R ', R'',R''', R ₃ to R ₅ are independently of each other hydrogen, (C6-C30) aryl or (C3-C30) heteroaryl; X is O or S; a to d are each independently an integer of 1 to 4.]

The electron transporting material according to the present invention may be exemplified by the following compounds, but is not limited thereto.

The electron transporting material according to the present invention may be prepared as shown in the following scheme, but is not limited thereto, and may be prepared through known organic reactions.

[Reaction Scheme 1]

[In Reaction Scheme 1, L ₁ , L ₂ , Ar, R ₁ and R ₂ are the same as defined in Formula 1, and Hal is halogen.]

In addition, the present invention provides an organic light emitting device, the organic light emitting device according to the present invention comprises: a first electrode; A second electrode; And at least one organic material layer interposed between the first electrode and the second electrode, wherein the organic material layer includes an electron transport layer including the electron transport material of Chemical Formula 1. When the electron transporting material of Chemical Formula 1 according to the present invention is used in the electron transporting layer, the driving voltage is enhanced to induce an increase in power efficiency, thereby improving power consumption.

In addition, the organic material layer is characterized in that it comprises at least one electron transport layer containing the electron transport material of Formula 1 and at least one light emitting layer consisting of a fluorescent host-fluorescent dopant or a phosphorescent host-phosphorescent dopant, the organic light emitting of the present invention The fluorescent host, fluorescent dopant, phosphorescent host or phosphorescent dopant applied to the device is not particularly limited.

The electron transporting material according to the present invention has an advantage in that an organic light emitting device having excellent light emission characteristics and inducing power efficiency by inducing a driving voltage to increase power consumption can be manufactured.

1-Graph of efficiency (cd / A) -luminance (cd / m 2) of organic light emitting diodes manufactured in Examples 14 to 24 and Comparative Example 2

Hereinafter, the electron transport compound according to the present invention, a method for producing the same and a light emitting property of the device for the detailed understanding of the present invention for the detailed understanding of the present invention, the following examples are for the purpose of illustrating the present invention as It is not intended to limit the scope of protection of the present invention.

Preparation Example 1 Preparation of Compound 1

compound 1-1 Manufacturing

Methylene chloride (MC, 31 mL) and 3-bromobenzoyl chloride (25 g, 0.1139 mol) were mixed and stirred at -10 ° C. After 3-bromobenzoyl chloride was completely dissolved, a mixed solution of pyridine (106 mL) and 2-chloropyridin-3-amine (13.2 g) was slowly added dropwise and stirred. After 2 hours and 30 hours, water (1250 mL) was added, and the resulting solid compound was filtered and washed with methanol. After drying, a white solid compound 1-1 (28.0 g, yield 87%) was obtained.

compound  1-2 Manufacturing

Mix 1,3-dimethyl-3,4,5,6-tetrahydro-2 (1H) -pyrimidinone (DMPU, 110 mL), compound 1-1 (27 g, 0.0866 mol) and Lawson reagent (35.1 g) And reflux was stirred. After 2 hours 30 minutes, the mixture was extracted with ethyl acetate (EA) and concentrated to give a pale yellow solid compound 1-2 (20 g, yield 80%).

¹ H NMR (CDCl ₃ ) δ [ppm]: 8.61 (dd, 1H), 8.33 (d, 1H), 8.30 (t, 1H), 8.02 (m, 1H), 7.67 (m, 1H), 7.48 (q , 1H), 7.41 (t, 1H)

compound One Manufacturing

4,4,5,5-tetramethyl-2- (10- (naphthalen-1-yl) anthracene-9-yl) -1,3,2-dioxabo in a mixed solvent of THF / water (490 mL / 246 mL) Lane (9.8 g, 0.0227 mol), compound 1-2 (7.3 g, 0.025 mol), Pd (PPh ₃ ) ₄ (2.7 g, 0.00233 mol) and K ₂ CO ₃ (6.3 g, 0.0456 mol) are mixed and refluxed Stirred. After 12 h extracted with methylene chloride (MC) and concentrated. The concentrated residue was dissolved in ethyl acetate (EA) and recrystallized by dropwise adding methanol. The product was filtered to give a yellow solid Compound 1 (5 g, yield 43%).

¹ H NMR (CDCl ₃ ) δ [ppm]: 8.61 (m, 1H), 8.34 (m, 3H), 8.11 (d, 1H), 8.06 (d, 1H), 7.80 (m, 5H), 7.63 (m , 1H), 7.51 (m, 4H), 7.38 (t, 2H), 7.28 (m, 3H), 7.20 (t, 1H); MALDI-TOF MS: m / z 514.34, cal. 514.64

Preparation Example 2 Preparation of Compound 2

4,4,5,5-tetramethyl-2- (10- (naphthalen-3-yl) anthracene-9-yl) -1,3,2-dioxabo in a mixed solvent of THF / water (425 mL: 213 mL) Lanes (8.5 g, 0.0197 mol), compounds 1-2 (6.14 g, 0.021 mol), Pd (PPh ₃ ) ₄ (2.3 g, 0.00198 mol) and K ₂ CO ₃ (5.44 g, 0.0394 mol) was mixed and stirred at reflux. After 12 h extracted with methylene chloride (MC) and concentrated. The concentrated residue was dissolved in ethyl acetate (EA) and recrystallized by dropwise adding methanol. The product was filtered to give a yellow solid Compound 2 (5.01 g, yield 50%).

¹ H NMR (DMSO-d ₆ ) δ [ppm]: 8.65 (dd, 1H), 8.45 (m, 1H), 8.40 (m, 1H), 8.23 (m, 2H), 8.15 (m, 1H), 8.08 (m, 2H), 7.95 (t, 1H), 7.79 (m, 1H), 7.66 (m, 8H), 7.47 (m, 4H); MALDI-TOF MS: m / z 514.14, cal. 514.64

Preparation Example 3 Preparation of Compound 3

compound  3-1 Manufacturing

CuBr ₂ (60.03 g, 0.27 mol), t-butyl nitrate (39.96 mL, 0.34 mol) and acetonitrile (825 mL) were mixed and heated to 65 ° C. 2-aminoanthraquinone (50 g, 0.22 mol) was added to the reaction and stirred at 65 ° C. for 5 hours. After stirring was completed, the mixture was cooled to room temperature, 20 wt% aqueous hydrochloric acid solution (2856 mL) was added thereto, stirred for 1 hour, and filtered under pressure. The obtained solid was extracted with methylene chloride (MC), and then concentrated under reduced pressure. The solid obtained by concentrating under reduced pressure was dissolved in a mixed solvent of MC / Hexane (volume ratio: 4/1), filtered through silica gel, and the filtrate was concentrated under reduced pressure and washed with acetone to obtain compound 3-1 (yield 45%).

compound  3-2 Manufacturing

2-bromonaphthalene (49.83 g, 0.24 mol) was added to THF (453 mL) purified under a nitrogen atmosphere, and stirred at -78 ° C for 30 minutes. T-butyllithium (212.03mL, 2.16mol) was slowly added to the reaction solution, stirred for 1 hour, and then Compound 3-1 (28.78g, 0.10mol) was added rapidly and stirred for 24 hours. When stirring was completed, a saturated aqueous ammonium chloride solution was added, the organic layer was extracted with methylene chloride (MC), filtered through silica gel, and the filtrate was concentrated under reduced pressure. The resulting solid was dissolved in ethyl ether and recrystallized from petroleum ether to give compound 3-2 (yield 91%).

compound  3-3 Manufacturing

Acetic acid (650 mL) was added to Compound 3-2 (50.00 g, 0.09 mol), and KI (152.74 g, 0.92 mol) and NaH ₂ PO ₂ ㆍ H ₂ O (165.95 g, 1.89 mol) were added and refluxed under stirring. . After 24 hours, cooled to room temperature, water (650 mL) was added and stirred for 1 hour. After stirring was complete, the mixture was filtered under reduced pressure and washed with methanol to obtain compound 3-3 (yield 61%).

compound  3-4 Manufacturing

Compound 3-3 (25.00g, 0.05mol), KOAc (14.45g, 0.15mol), Bis (pinacolato) diboron (16.20g, 0.06mol), PdCl ₂ (dppf) ( 2.40 g, 0.003 mol) and dioxane (250 mL) were mixed and stirred under reflux. After 24 hours, the organic layer was extracted with MC, concentrated under reduced pressure, and washed with acetone to obtain compound 3-4 (yield 72%).

compound  3 Manufacturing

Compound 3-4 (17.00g, 0.03mol), Compound 1-2 (11.12g, 0.04mol), Pd ₂ (dba) ₃ (1.40g, 0.0015mol), PPh ₃ (0.88g, 0.003mol), K ₂ CO ₃ (8.44 g, 0.06 mol), THF (51 mL) and water (17 mL) were mixed and stirred under reflux. After 24 hours, the organic layer was extracted with MC, concentrated under reduced pressure, and washed with acetone to obtain compound 3 (yield 57%).

¹ H NMR (CDCl ₃ ) δ [ppm]: 8.59 (dd, 1H), 8.33 (d, 1H), 8.28 (m, 1H), 8.17 (q, 2H), 8.05 (m, 7H), 7.90 (m) , 2H), 7.81 (m, 1H), 7.72 (m, 2H), 7.65 (m, 4H), 7.53 (m, 2H), 7.48 (m, 1H), 7.37 (m, 2H), 7.26 (m, 2H); MALDI-TOF MS: m / z 639.86, cal. 640.20

Preparation Example 4 Preparation of Compound 4

compound 4-1 Manufacturing

IPA (Isopropyl alcohol, 90 mL) was added to 2-amino-5-bromopyridine (30.00 g, 0.17 mol), followed by stirring. Dimethylformamide-dimethylacetal (DMF-DMA, 29.85mL, 0.23mol) was added to the reaction solution, and the mixture was stirred under reflux. After 3 hours, the mixture was cooled to 50 ° C, NH ₂ OH.HCl (15.67 g, 0.23 mol) was added thereto, and stirred for 24 hours. After stirring was complete, the mixture was washed with IPA to give compound 4-1 (yield 62%).

¹ H NMR (DMSO-d ₆ ) δ [ppm]: 10.20 (s, 1H), 9.57 (d, 1H), 8.23 (d, 1H), 8.81 (dd, 1H), 7.78 (d, 1H), 7.04 (d, 1H)

compound 4-2 Manufacturing

THF (230 mL) was added to Compound 4-1 (23.00 g, 0.11 mol), trifluoroacetic anhydride (22.22 mL, 0.16 mol) was added at 0 ° C., and stirred at room temperature for 24 hours. Saturated aqueous sodium bicarbonate solution was added to the reaction solution and stirred for 1 hour. After stirring was complete, the organic layer was extracted with MC, concentrated under reduced pressure, and washed with ethyl ether to obtain compound 4-2 (yield 46%).

¹ H NMR (DMSO-d ₆ ) δ [ppm]: 9.42 (s, 1 H), 9.54 (s, 1 H), 7.84 (m, 2 H)

compound 4 Manufacturing

Compound 3-4 (30.00 g, 0.05 mol), compound 4-2 (12.81 g, 0.06 mol), Pd (pph ₃ ) ₄ (1.87 g, 0.0016 mol), K ₂ CO ₃ (14.89 g, 0.11 mol), THF (90 mL) and water (30 mL) were mixed and stirred under reflux. After 24 hours, the organic layer was extracted with EA, concentrated under reduced pressure and washed with acetone to obtain compound 4 (yield 52%).

¹ H NMR (DMSO-d ₆ ) δ [ppm]: 8.27 (d, 1H), 8.14 (d, 2H), 8.05 (m, 4H), 7.96 (m, 2H), 7.84 (m, 2H), 7.78 (m, 2H), 7.67 (m, 6H), 7.57 (m, 3H), 7.34 (q, 2H), 6.49 (d, 1H); MALDI-TOF MS: m / z 547.82, cal. 547.65

Preparation Example 5 Preparation of Compound 5

compound 5-1 Manufacturing

9-bromophenanthrene (40 g, 155.6 mmol) was added to THF (500 mL) purified under a nitrogen atmosphere. 2.5M butyllithium (68.4 mL, 171.1 mmol) was slowly added while maintaining the temperature of the reaction at -78 ° C, stirred for 1 hour, and then B (Oi-Pr) ₃ (42.9 mL, 186.7 mmol) was added. . The temperature was raised to room temperature, 2N hydrochloric acid aqueous solution (250 mL) was added, and the mixture was stirred for 3 hours. After stirring was complete, the organic layer was extracted with saturated aqueous NaCl solution and ethyl acetate (EA), dried over MgSO ₄ , filtered, and concentrated under reduced pressure. The solid obtained by concentrating under reduced pressure was suspended and stirred in a nucleic acid, filtered and washed with a nucleic acid to obtain compound 5-1 (28 g, yield 81%).

¹ H NMR (DMSO-d ₆ ) δ [ppm]: 8.82 (t, 2H), 8.50 (s, 2H), 8.40-8.38 (d, 1H), 8.04 (s, 1H), 7.99-7.97 (d, 1H), 7.71-7.66 (m, 4H)

compound  5-2 Manufacturing

2,4-dichloropyrimidine (15.00g, 0.10mol), compound 5-1 (24.59g, 0.11mol), Pd (PPh ₃ ) ₄ (3.49g, 0.003mol), K ₂ CO ₃ (27.81 g, 0.2 mol), THF (45 mL) and water (15 mL) were mixed and stirred under reflux. After 24 hours, the organic layer was extracted with MC, concentrated under reduced pressure, and washed with acetone to obtain compound 5-2 (yield 76%).

compound  5-3 Manufacturing

Compound 1-2 (27.47g, 103mmol), Bis (pinacolato) diboron (27.47g, 108mmol), 1,4-dioxane (450mL), 1,1'-bis (di Phenylphosphino) ferrocene-palladium (II) dichloride dichloromethane complex (1,1'-Bis (diphenylphosphino) ferrocene-palladium (II) dichloride dichloromethane complex) (1.68 g, 2.1 mmol) and CH ₃ CO ₂ K (20.22 g, 206.1 mmol) were mixed and stirred under reflux for 12 hours, and then cooled to room temperature. Saturated NaCl solution and ethyl acetate (EA) were added to the reaction mixture, the organic layer was extracted, dried over MgSO ₄ , and treated with activated carbon and filtered through Celite. The obtained filtrate was concentrated under reduced pressure, and the obtained solid was suspended and stirred in nucleic acid, filtered and washed with nucleic acid to obtain compound 5-3 (41.8 g, 89% yield).

¹ H NMR (CDCl ₃ ) δ [ppm]: 8.60-8.58 (d, 1H), 8.50 (s, 1H), 8.32-8.30 (d, 1H), 8.25-8.22 (d, 1H), 7.99-7.97 ( d, 1H), 7.55 (t, 1H), 7.48-7.44 (q, 1H), 1.40 (s, 12H)

compound  5 Manufacturing

Compound 5-2 (22.00g, 0.08mol), Compound 5-3 (33.65g, 0.10mol), Pd (PPh ₃ ) ₄ (2.65g, 0.002mol), K ₂ CO ₃ (21.14 g, 0.15 mol), THF (66 mL) and water (22 mL) were mixed and stirred under reflux. After 24 hours, the organic layer was extracted with MC, concentrated under reduced pressure, and washed with acetone to obtain compound 5 (yield 82%).

¹ H NMR (CDCl ₃ ) δ [ppm]: 9.30 (s, 1H), 9.05 (d, 1H), 8.86 (d, 1H), 8.78 (t, 2H), 8.60 (dd, 1H), 8.38 (d , 1H), 8.32 (t, 2H), 8.07 (s, 1H), 8.02 (d, 1H), 7.78 (t, 2H), 7.68 (m, 4H), 7.47 (q, 1H); MALDI-TOF MS: m / z 467.08, cal. 466.56

Preparation Example 6 Preparation of Compound 6

compound 6-1 Manufacturing

After completely dissolving N ¹ -phenylbenzene-1,2-diamine (48 g, 260 mmol) in DMAC (N, N-dimethyl acetamide) (100 mL) at 0 ° C., 4-bromobenzoyl chloride (63 g, 287 mmol) was added dropwise. And stirred. After 2 hours and 30 minutes, pyridine (60 mL) and water (100 mL) were added thereto. After further stirring for 30 minutes, the resulting solid was filtered with washing with methanol to obtain a white solid compound 6-1 (95 g, yield 95%).

compound  6-2 Manufacturing

Compound 6-1 (95g, 258mmol), PTSA (p-Toluene solfonic acid) (89g, 516mmol) and toluene (1144mL) were mixed and stirred under reflux using a solvent recovery device (Dean-stark trap) in a nitrogen atmosphere. After 6 hours the reaction was concentrated and the organic layer was extracted with methylene chloride (MC). The resulting reaction was concentrated after silica filter, sonicated under Hexane: MC = 8: 2 solution, crystallized and filtered to give a yellow solid Compound 6-2 (85 g, yield 94%).

¹ H NMR (CDCl ₃ ) δ [ppm]: 8.24 (d, 1H), 7.66 (m, 3H), 7.62-7.46 (m, 6H), 7.40 (m, 2H), 7.32 (d, 2H)

compound  6-3 Manufacturing

Compound 6-2 (38.6g, 110mmol), KOAc (32.4g, 330mmol), bis (pinacolato) diboron (Bis (pinacolato) diboron) (36.5g, 143mmol), dioxane (390mL) and PdCl ₂ (dppf ) (1.8 g, 2 mmol) was mixed and stirred at 80 ° C. for 3 hours and then cooled to 20 ° C. Water (400 mL) was added to the reaction and stirred. After stirring was complete, the organic layer was extracted with MC, concentrated under reduced pressure, and the obtained residue was completely dissolved in EA, and crystallized by dropwise addition of petroleum ether to obtain a yellow solid compound 6-3 (36 g, yield 82%).

¹ H NMR (CDCl ₃ ) δ [ppm]: 7.92 (d, 1H), 7.76 (d, 2H), 7.59 (d, 2H), 7.56-7.45 (m, 3H), 7.41-7.29 (m, 4H) , 7.27 (s, 1H), 1.35 (s, 12H)

compound  6 Manufacturing

Compound 6-3 (18g, 1.045mol), 9-bromo-6b, 12a-dihydroacenaphtho [1,2-b] quinoxaline (13.6g, 0.0408mol), Pd ₂ (dba) ₃ (0.8 g, 0.00087 mol), PPh ₃ (1.1 g, 0.00419 mol), K ₂ CO ₃ (11.5 g, 0.0833 mol), THF (200 mL) and water (100 mL) were mixed and refluxed. When the reaction was completed, the organic layer was extracted with MC and concentrated under reduced pressure to recrystallize the yellow product obtained to give a yellow solid compound 6 (17.9g, 84% yield).

¹ H NMR (CDCl ₃ ) δ [ppm]: 8.48 (m, 3H), 8.30 (d, 1H), 8.17 (dd, 2H), 8.06 (dd, 1H), 7.95 (s, 1H), 7.89 (t , 2H), 7.79 (q, 4H), 7.64-7.53 (m, 3H), 7.47-7.37 (m, 3H), 7.32 (m, 2H); MALDI-TOF MS: m / z 522.18, cal. 523.16

Preparation Example 7 Preparation of Compound 7

compound  7-1 Manufacturing

2,4,6-trichloropyrimidine (26g, 0.1417 mol), 1-naphthylboronic acid (24.4g, 0.1421 mol), Pd (PPh ₃ ) ₄ (0.001 mol, 1.65g), 2M K ₂ CO ₃ Aqueous solution (200 mL) and THF (390 mL) were mixed and stirred under reflux for 12 hours. After completion of the reaction, the organic layer was extracted with EA, washed with ether, sonicated (Sonicate) and crystallized to obtain a white solid compound 7-1 (23.2g, 61% yield).

¹ H NMR (CDCl ₃ ) δ [ppm]: 8.18 (m, 1 H), 8.04 (d, 1 H), 7.97 (m, 1 H), 7.73 (dd, 1 H), 7.65 (s, 1 H), 7.64-7.56 (m, 3 H)

compound  7-2 Manufacturing

Compound 7-1 (16.5g, 0.0599 mol), 9,9-dimethyl-9H-fluoren-2-yl-2-boronic acid (15g, 0.0629 mol), Pd (PPh ₃ ) ₄ (0.7g, 0.000605mol ), 2M K ₂ CO ₃ aqueous solution (124 mL) and THF (248 mL) were mixed and stirred under reflux for 12 hours. After completion of the reaction, the organic layer was extracted with EA, washed with ether, sonicated (Sonicate) and crystallized to obtain a white solid compound 7-2 (22.8g, yield 88%).

¹ H NMR (CDCl ₃ ) δ [ppm]: 8.29 (d, 1H), 8.22 (t, 1H), 8.16 (dd, 1H), 8.04 (d, 1H), 8.01 (s, 1H), 7.98 (t , 1H), 7.88 (d, 1H), 7.83 (m, 1H), 7.79 (dd, 1H), 7.65 (m, 1H), 7.60 (m, 2H), 7.51 (m, 1H), 7.62 (m, 2H), 1.59 (s, 6H)

compound  7-3 Manufacturing

Compound 4-2 (40g, 202mmol), Bis (pinacolato) diboron (53.86g, 212mmol), 1,4-dioxane (480mL), 1,1'-bis (diphenyl Phosino) ferrocene-palladium (II) dichloride dichloromethane complex (1.65 g, 2 mmol) and CH ₃ CO ₂ K (39.65 g, 404 mmol) were mixed and refluxed. After 9 hours, the mixture was cooled to 20 ° C., saturated aqueous NaCl solution and ethyl acetate (EA) were added, the organic layer was extracted, dried over MgSO ₄ , treated with activated carbon, and filtered through Celite. The obtained filtrate was concentrated under reduced pressure, and the obtained solid was dissolved in nucleic acid, filtered and concentrated again. The concentrated residue was dissolved in EA again, filtered through silica gel, and concentrated. The resulting brown liquid was left at room temperature to obtain a brown solid compound 7-3 (49.5 g, 99% yield).

¹ H NMR (CDCl ₃ ) δ [ppm]: 8.97 (s, 1 H), 8.37 (s, 1 H), 7.79 (q, 2 H)

compound  7 Manufacturing

Compound 7-2 (21.2 g, 0.0489 mol), Compound 7-3 (19.3 g, 0.0787 mol), Pd (PPh ₃ ) ₄ (0.66 g, 0.000571 mol), 2M K ₂ CO ₃ aqueous solution (133 mL) and THF ( 265 mL) were stirred and refluxed for 12 h. After completion of the reaction, the organic layer was extracted with EA, washed with ether, sonicated (Sonicate) and crystallized to obtain a white solid compound 7 (18.2g, 72% yield).

¹ H NMR (CDCl ₃ ) δ [ppm]: 10.00 (s, 1H), 8.85 (dd, 1H), 8.48 (s, 1H), 8.39-8.31 (m, 3H), 8.09-8.01 (m, 3H) , 7.93 (q, 2H), 7.87 (m, 2H), 7.71 (t, 1H), 7.62 (m, 2H), 7.54 (m, 1H), 7.42 (m, 2H), 1.64 (s, 6H); MALDI-TOF MS: m / z 515.64, cal. 515.21

Preparation Example 8 Preparation of Compound 8

compound  8-1 Manufacturing

2,4,6-trichloropyrimidine (50 g, 272.6 mmol), 9,9-dimethyl-9H-fluoren-2-yl2-boronic acid (129.81 g, 545.2 mmol), THF (750 mL), Pd ( PPh ₃ ) ₄ (6.3 g, 5.5 mol) and 2M K ₂ CO ₃ aqueous solution (375 mL) were mixed and stirred under reflux for 18 hours. After the reaction was completed, the mixture was cooled to room temperature, saturated aqueous NaCl solution and ethyl acetate (EA) were added, the organic layer was extracted, dried over MgSO ₄ , and treated with activated charcoal and filtered through Celite. The obtained filtrate was concentrated under reduced pressure, and the oil thus obtained was vacuum dried to obtain a solid compound 8-1 (136 g, yield 100%) in the form of a foam.

¹ H NMR (CDCl ₃ ) δ [ppm]: 8.29 (d, 2H), 8.18-8.16 (d, 2H), 8.12 (s, 1H), 7.9 (d, 2H), 7.84-7.82 (m, 2H) , 7.53-7.51 (m, 2H), 7.44-7.41 (m, 4H), 1.62 (s, 12H)

compound  8 Manufacturing

Compound 8-1 (30 g, 60.1 mmol), Compound 7-3 (22.1 g, 90 mmol), THF (450 mL), Pd (PPh ₃ ) ₄ (1.39 g, 1.2 mol) with 2M K ₂ CO ₃ aqueous solution (225 mL) Were mixed and stirred at reflux for 18 hours. After the reaction was completed, the mixture was cooled to room temperature, saturated aqueous NaCl solution and ethyl acetate (EA) were added, the organic layer was extracted, dried over MgSO ₄ , and treated with activated charcoal and filtered through Celite. The obtained filtrate was concentrated under reduced pressure, and the obtained solid was suspended while heating with ethyl acetate, and then filtered to obtain compound 8 (20.3 g, yield 58%).

¹ H NMR (CDCl ₃ ) δ [ppm]: 10.04 (s, 1H), 8.97-8.94 (d, 1H), 8.49 (s, 1H), 8.39 (s, 2H), 8.32-8.30 (d, 2H) , 8.18 (s, 1H), 7.93 (t, 3H), 7.88-7.85 (m, 2H), 7.55-7.52 (m, 2H), 7.45-7.43 (m, 4H), 1.67 (s, 12H); LC-MS: m / z 581.92, cal. 581.71

Preparation Example 9 Preparation of Compound 9

compound  9- One of  Produce

2,4,6-trichloropyrimidine (18g, 98.1mmol), 4- (naphthalen-4-yl) phenylboronic acid (24.35g, 98mmol), THF (270mL), Pd (PPh ₃ ) ₄ (1.13g , 1 mol) and 2M K ₂ CO ₃ aqueous solution (135 mL) were mixed and refluxed for 18 hours. After the reaction was completed, the mixture was cooled to room temperature, saturated aqueous NaCl solution and ethyl acetate (EA) were added, the organic layer was extracted, dried over MgSO ₄ , and concentrated under reduced pressure. The obtained solid was recrystallized (EA / Hexane) Compound 9-1 (21 g, yield 60 %) Was obtained.

¹ H NMR (CDCl ₃ ) δ [ppm]: 8.24-8.22 (d, 2H), 7.97-7.88 (m, 3H), 7.78 (s, 1H), 7.71-7.69 (d, 2H), 7.60-7.53 ( m, 2H), 7.51-7.47 (m, 2H)

compound  9- 2 of  Produce

Compound 9-1 (20g, 55.4mmol), 9,9-dimethyl-9H-fluoren-2-yl-2-boronic acid (13.84g, 98mmol), THF (300mL), Pd (PPh ₃ ) ₄ (0.64 g, 0.55 mol) and 2M K ₂ CO ₃ aqueous solution (150 mL) were mixed and stirred under reflux for 18 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, saturated aqueous NaCl solution and ethyl acetate (EA) were added, the organic layer was extracted, dried over MgSO ₄ , and concentrated under reduced pressure. Ethyl acetate was added to the resulting oil to precipitate a solid. The resulting solid was filtered and washed with ethyl acetate to give compound 9-2 (19g, 67% yield).

¹ H NMR (CDCl ₃ ) δ [ppm]: 8.34-8.32 (d, 2H), 8.3 (d, 1H), 8.2-8.18 (d, 2H), 7.97-7.93 (m, 3H), 7.91-7.89 ( d, 1H), 7.85-7.82 (m, 1H), 7.74-7.77 (d, 2H), 7.61-7.57 (t, 1H), 7.56-7.47 (m, 4H), 7.43-7.41 (m, 2H), 1.62 (s, 6 H)

compound 9 of  Produce

Compound 9-2 (18 g, 35.4 mmol), Compound 7-3 (22.10 g, 90 mmol), THF (450 mL), Pd (PPh ₃ ) ₄ (1.39 g, 1.2 mol) with 2M K ₂ CO ₃ aqueous solution (225 mL ) Was mixed and refluxed for 18 hours. After the reaction was completed, the mixture was cooled to room temperature, saturated aqueous NaCl solution and ethyl acetate (EA) were added, the organic layer was extracted, dried over MgSO ₄ , and treated with activated charcoal and filtered through Celite. The obtained filtrate was concentrated under reduced pressure, and the obtained solid was suspended with ethyl acetate, filtered and washed with ethyl acetate to obtain compound 9 (14.8 g, yield 70%).

¹ H NMR (CDCl ₃ ) δ [ppm]: 10.05 (s, 1H), 8.98-8.95 (d, 1H), 8.49 (s, 2H), 8.48-4.46 (d, 1H), 8.39 (s, 1H) , 8.31 (d, 1H), 8.23 (s, 1H), 7.99-7.93 (m, 5H), 7.90-7.81 (m, 1H), 7.78-7.76 (d, 2H), 7.61-7.44 (m, 5H) , 7.43-7.38 (m, 2 H), 1.67 (s, 6 H); MALDI-TOF MS: m / z 591.5, cal. 591.7

Preparation Example 10 Preparation of Compound 10

Compound 8-1 (60.1 mmol), Compound 5-3 (20.94 g, 62 mmol), THF (450 mL), Pd (PPh ₃ ) ₄ (1.39 g, 1.2 mol) and 2M K ₂ CO ₃ aqueous solution (225 mL) The mixture was stirred at reflux for 18 hours. After the reaction was completed, the mixture was cooled to room temperature, saturated aqueous NaCl solution and ethyl acetate (EA) were added, the organic layer was extracted, dried over MgSO ₄ , and treated with activated charcoal and filtered through Celite. The obtained filtrate was concentrated under reduced pressure, and ethyl acetate was added to the oil obtained to precipitate a solid. The resulting solid was recrystallized (dichloromethane: ethyl acetate) to give compound 10 (20 g, yield 50%).

¹ H NMR (CDCl ₃ ) δ [ppm]: 8.48 (t, 1H), 8.97-8.95 (d, 1H), 8.64-8.62 (d, 1H), 8.4 (s, 2H), 8.37 (t, 1H) , 8.35 (t, 3H), 8.17 (s, 1H), 7.95-7.93 (d, 2H), 7.86-7.84 (m, 2H), 7.76 (t, 1H), 7.55-7.53 (m, 2H), 7.51 -7.48 (q, 1 H), 7.45-7.41 (m, 4 H), 1.68 (s, 12 H); MALDI-TOF MS: m / z 675.37, cal. 674.85.

Preparation Example 11 Preparation of Compound 11

compound  11- One of  Produce

2,4,6-trichloropyrimidine (50 g, 272.6 mmol), 9,9-dimethyl-9H-fluoren-2-yl-2-boronic acid (64.9 g, 273 mmol), THF (750 mL), Pd ( PPh ₃ ) ₄ (3.15 g, 2.7 mmol) and 2M K ₂ CO ₃ aqueous solution (375 mL) were mixed and stirred under reflux for 18 hours. After the reaction was completed, the mixture was cooled to room temperature, saturated aqueous NaCl solution and ethyl acetate (EA) were added, the organic layer was extracted, dried over MgSO ₄ , and treated with activated charcoal and filtered through Celite. The obtained filtrate was concentrated under reduced pressure, and ethyl acetate was added to the oil obtained to precipitate a solid. The resulting solid was recrystallized to give compound 11-1 (109 g, 100% yield).

¹ H NMR (CDCl ₃ ) δ [ppm]: 8.18 (d, 1 H), 8.09-8.07 (d, 1 H), 7.87-7.85 (d, 1 H), 7.83-7.80 (m, 1 H), 7.75 (s, 1H), 7.52-7.50 (m, 1H), 7.43-7.41 (m, 2H)

compound  11- 2 of  Produce

Mix compound 5-1 (30.9 g, 90.6 mmol), compound 11-1 (91 mmol), THF (500 mL), Pd (PPh ₃ ) ₄ (1.05 g, 0.91 mmol) with 2M K ₂ CO ₃ aqueous solution (250 mL) And refluxed for 18 hours. After the reaction was completed, the mixture was cooled to room temperature, saturated aqueous NaCl solution and ethyl acetate (EA) were added, the organic layer was extracted, dried over MgSO ₄ , and treated with activated charcoal and filtered through Celite. The resulting filtrate was concentrated under reduced pressure to give compound 11-2 (44 g, yield 100%) in the form of an oil.

¹ H NMR (CDCl ₃ ) δ [ppm]: 9.44 (s, 1 H), 8.93-8.87 (q, 2 H), 8.82-8.80 (d, 1 H), 8.43-8.41 (d, 2H), 8.14 (s, 1H), 8.10 (s, 1H), 8.07-8.05 (d, 1H), 7.86-7.84 (m, 1H), 7.81-7.76 (q, 2H), 7.74-7.70 (m, 3H), 7.43-7.41 ( m, 2H), 1.65 (s, 6H)

compound 11 of  Produce

Compound 11-2 (40 g, 82.8 mmol), Compound 5-3 (28.01 g, 83 mmol), THF (600 mL), Pd (PPh ₃ ) ₄ (1.91 g, 1.66 mmol) and 2M K ₂ CO ₃ aqueous solution (300 mL) The mixture was stirred and refluxed for 18 hours. After the reaction was completed, the mixture was cooled to room temperature, saturated aqueous NaCl solution and ethyl acetate (EA) were added, the organic layer was extracted, dried over MgSO ₄ , and treated with activated charcoal and filtered through Celite. The filtrate was concentrated under reduced pressure, suspended in an oil obtained by heating with ethyl acetate, filtered and washed with ethyl acetate to obtain compound 11 (28 g, yield 51%).

¹ H NMR (CDCl ₃ ) δ [ppm]: 9.44 (s, 1 H), 8.93-8.87 (q, 2 H), 8.82-8.80 (d, 1 H), 8.62-8.61 (d, 1H), 8.46 (s, 1H), 8.43-8.33 (m, 4H), 8.14 (s, 1H), 8.10 (s, 1H), 8.07-8.05 (d, 1H), 7.96-7.94 (d, 1H), 7.86-7.84 (m, 1H), 7.81-7.76 (q, 2H), 7.74-7.70 (m, 3H), 7.53-7.49 (m, 1H), 7.48-7.44 (q, 1H), 7.43-7.41 (m, 2H), 1.65 ( s, 6H); MALDI-TOF MS: m / z 658.12, cal. 658.81

Preparation Example 12 Preparation of Compound 12

1-bromopyrene (20g, 0.07mol), compound 5-3 (37.21g, 0.11mol), THF (380mL), Pd (PPh ₃ ) ₄ (0.97g, 0.84mmol) and 2M K ₂ CO ₃ aqueous solution (188 mL) was mixed and stirred at reflux for 18 hours. After the reaction was completed, the mixture was cooled to room temperature, saturated aqueous NaCl solution and ethyl acetate (EA) were added, the organic layer was extracted, dried over MgSO ₄ , and treated with activated charcoal and filtered through Celite. The resulting filtrate was concentrated under reduced pressure, ethyl acetate was added to the oil, and the resulting filtrate was dissolved in silica gel. The filtrate was concentrated under reduced pressure. The solid obtained by concentration was suspended with heating with ethyl acetate, filtered and washed with ethyl acetate to obtain compound 12 (14.5 g, yield 50%).

¹ H NMR (CDCl ₃ ) δ [ppm]: 8.68 (dd, 1H), 8.46 (d, 1H), 8.31-8.04 (d, 1H), 7.78-7.61 (m, 4H), 7.86-7.54 (m, 5H), 7.38 (m, 2 H), 7.16 (m, 2 H); MALDI-TOF MS: m / z 412.34, cal. 412.51

Preparation Example 13 Preparation of Compound 13

compound 13-1 Manufacturing

Methylene chloride (64 mL) and 4-bromobenzoyl chloride (50 g, 0.2278 mol) were mixed and stirred at -10 ° C. After 4-bromobenzoyl chloride was completely dissolved, a mixed solution of pyridine (220 mL) and 2-chloropyridin-3-amine (26.6 g, 0.2069 mol) was slowly added dropwise. After stirring for 2 hours 30, water (2500 mL) was added thereto, and the resulting solid was filtered and washed with methanol to obtain a white solid compound 13-1 (54.8 g, yield 85%).

compound 13-2 Manufacturing

1,3-dimethyl-3,4,5,6-tetrahydro-2 (1H) -pyrimidinone (DMPU) (45 mL), compound 13-1 (9 g, 0.0288 mol) and Lawson reagent (11.7 g) Mix and stir at reflux for 2 hours 30 minutes. When the reaction was completed, the organic layer was extracted with ethyl acetate (EA) and concentrated to give a pale yellow solid compound 13-2 (24g, 80% yield).

compound 13-3 Manufacturing

Compound 13-2 (27.47 g, 103 mmol), bis (pinacolato) diboron (27.47 g, 108 mmol), 1,4-dioxane (450 mL), 1,1'-bis (di Phenylphosphino) ferrocene-palladium (II) dichloride dichloromethane complex (1.68 g, 2.1 mmol and CH ₃ CO ₂ K (20.22 g, 206.1 mmol) was mixed and stirred under reflux. After 12 h, cooled to room temperature and saturated NaCl Aqueous solution and ethyl acetate (EA) were added, the organic layer was extracted, dried over MgSO ₄ , activated charcoal treatment, and filtered through Celite, the resulting filtrate was concentrated under reduced pressure, suspended and stirred with nucleic acid, filtered and washed with nucleic acid. Compound 13-3 (41.8g, yield 89%) was obtained.

compound 13 Manufacturing

Compound 13-3 (27.70 g, 55.5 mmol), Compound 8-1 (19.4 g, 57.3 mmol), Pd (PPh ₃ ) ₄ (1.32 g, 1.14 mmol), 2M K ₂ CO ₃ aqueous solution (204 mL), THF ( 408 mL) and water (136 mL) were mixed and stirred under reflux. After 24 hours, the organic layer was extracted with MC, concentrated under reduced pressure, and washed with acetone to obtain compound 13 (21 g, yield 57%).

¹ H NMR (CDCl ₃ ) δ [ppm]: 9.24 (t, 1H), 8.96 (m, 1H), 8.58-8.45 (m, 4H), 8.38 (m, 3H), 8.26 (s, 1H), 8.04 (d, 2H), 7.86 (m, 2H), 7.73 (m, 1H), 7.64-7.51 (m, 3H), 7.45-7.41 (m, 4H), 1.67 (s, 12H); MALDI-TOF MS: m / z 674.61, cal. 674.85

Preparation Example 14 Preparation of Compound 14

compound 14-1 Manufacturing

2,4,6-trichloropyrimidine (15 g, 81.8 mmol), compound 5-1 (36.3 g, 163 mmol), THF (450 mL), Pd (PPh ₃ ) ₄ (0.95 g, 0.8 mmol) and 1 M K ₂ Aqueous CO ₃ solution (200 mL) was mixed and stirred under reflux for 18 hours, then cooled to room temperature. The reaction was filtered and the filtered white solid was washed with distilled water. The washed solid was suspended while heating with ethyl acetate and filtered to give compound 14-1 (25 g, yield 68%).

¹ H NMR (DMSO-d ₆ ) δ [ppm]: 9.01 (d, 2H) 8.95 (d, 2H) 8.43 (d, 2H) 8.34 (d, 2H) 8.15 (d, 2H) 7.84-7.77 (m, 9H)

compound 14 Manufacturing

Compound 14-1 (24g, 53.7mmol), Compound 5-3 (21.8g, 64.4mmol), Pd (PPh ₃ ) ₄ (1.86g, 1.6 mmol), 2M K ₂ CO ₃ aqueous solution (350mL), toluene (700mL) and THF (400mL) were mixed and stirred under reflux for 18 hours, and then cooled to room temperature. The reaction was filtered and the filtered solid was washed with distilled water. The washed solid was suspended with heating with toluene and then filtered to give compound 14 (21.6 g, yield 62%).

¹ H NMR (DMSO-d ₆ ) δ [ppm]: 9.30 (s, 1H) 9.06 (d, 2H) 8.99 (d, 2H) 8.78 (d, 1H) 8.64 (d, 1H) 8.57 (d, 2H) 8.48 (d, 1H) 8.41 (s, 2H) 8.32 (s, 2H) 8.19 (d, 2H) 7.86-7.83 (m, 5H) 7.80-7.75 (m, 4H) 7.61 (m, 1H); LC-MS: m / z 641, cal. 642.77

Preparation Example 15 Preparation of Compound 131

compound 15-1 Manufacturing

9-bromophenanthrene (40 g, 155.6 mmol), bis (pinacolato) diboron (43.4 g, 171 mmol), 1,4-dioxane (600 mL), 1,1'-bis (Diphenylphosphino) ferrocene-palladium (II) dichloride dichloromethane complex (1,1'-Bis (diphenylphosphino) ferrocene-palladium (II) dichloride dichloromethane complex) (2.54 g, 3.1 mmol) and CH ₃ CO ₂ K (30.5 g, 311.1 mmol) were mixed, stirred at reflux for 12 hours, and cooled to room temperature. Saturated NaCl solution and ethyl acetate (EA) were added to the reaction mixture. The organic layer was extracted, dried over MgSO ₄ , and treated with acidic clay. The filtrate was concentrated under reduced pressure, and n-hexane was added to the residue, which was then stirred. The resulting solid was filtered and washed with hexane to give compound 15-1 (32g, yield 67%).

¹ H NMR (CDCl ₃ ) δ [ppm]: 8.86 (m, 1 H) 8.74-8.69 (m, 2 H) 8.42 (S, 1 H) 7.97 (d, 1 H) 7.72-7.59 (m, 4H) 1.49 (s, 12H)

compound  15- 2 of  Produce

1-bromo-3-iodobenzene (34.2 g, 120.8 mmol), THF (560 mL), compound 15-1 (35 g, 115.1 mmol), Pd (PPh ₃ ) ₄ (1.33 g, 1.2 mmol) and 1 M K ₂ CO ₃ An aqueous solution (280 mL) was added thereto, and the mixture was stirred under reflux for 48 hours and cooled to room temperature. Saturated NaCl solution and ethyl acetate (EA) were added to the reaction mixture, the organic layer was extracted, dried over MgSO ₄ , filtered and concentrated under reduced pressure. The oil residue obtained after concentration was purified by column with n-hexane to give compound 15-2 (33.6g, 90% yield).

¹ H NMR (CDCl ₃ ) δ [ppm]: 8.81 (d, 1H) 8.76 (d, 1H) 7.93-7.87 (m, 2H) 7.74-7.73 (d, 2H) 7.71 (s, 2H) 7.69-7.52 ( m, 3H) 7.51 (d, 1H) 7.41 (t, 1H)

compound  15- 3 of  Produce

Compound 15-2 (44.9 g, 130 mmol), 1,4-dioxane (600 mL), bis (pinacolato) diboron (37.7 g, 149 mmol), 1,1'-bis ( Diphenylphosphino) ferrocene-palladium (II) dichloride dichloromethane complex (1,1'-Bis (diphenylphosphino) ferrocene-palladium (II) dichloride dichloromethane complex) (2.21 g, 2.7 mmol) and CH ₃ CO ₂ K ( 36.5 g, 270.1 mmol) were mixed and refluxed under stirring for 12 hours, and then cooled to room temperature. Saturated NaCl solution and ethyl acetate (EA) were added to the reaction mixture, the organic layer was extracted, dried over MgSO ₄ , filtered and concentrated under reduced pressure. The solid obtained after concentration was recrystallized with ethyl acetate and n-hexane. The resulting solid was filtered and washed with n-hexane to give compound 15-3 (42 g, yield 81%).

¹ H NMR (CDCl ₃ ) δ [ppm]: 8.69 (d, 1H) 8.90 (d, 1H) 8.07 (d, 1H) 7.81 (t, 3H) 7.79-7.67 (m, 5H) 7.63-7.59 (m, 2H) 1.31 (s, 12H)

compound  15- 4 of  Produce

Compound 15-3 (25 g, 65.7 mmol), 2,4-dichloro-6-methylpyrimidine (10.9 g, 67.1 mmol), THF (370 mL), Pd (PPh ₃ ) ₄ (0.76 g, 0.7 mmol) 1 M K ₂ CO ₃ aqueous solution (180 mL) was mixed and stirred at reflux for 18 h. After the reaction was completed, the mixture was cooled to room temperature, saturated aqueous NaCl solution and ethyl acetate (EA) were added, the organic layer was extracted, dried over MgSO ₄ , and concentrated under reduced pressure. The oil residue was purified by column purification with ethyl acetate and n-hexane to obtain Compound 15-4 ( 25 g, yield 100%) was obtained.

¹ H NMR (CDCl ₃ ) δ [ppm]: 8.83 (d, 1H) 8.81 (d, 1H) 8.75 (t, 1H) 8.24 (d, 1H) 7.92 (d, 1H) 7.88 (d, 1H) 7.75- 7.59 (m, 6H) 7.55 (t, 2H) 2.60 (s, 3H)

compound 131 of  Produce

Compound 15-4 (22 g, 57.8 mmol), Compound 5-3 (19.5 g, 57.8 mmol), THF (400 mL), Pd (PPh ₃ ) ₄ (1.34 g, 1.16 mmol) and 2M K ₂ CO ₃ aqueous solution (200 mL ) Was mixed and refluxed for 18 hours. After the reaction was completed, the mixture was cooled to room temperature, and the precipitated solid was filtered and washed with distilled water. The white solid obtained was suspended while heating with ethyl acetate, and then filtered to obtain compound 131 (22 g, yield 68%).

¹ H NMR (CDCl ₃ ) δ [ppm]: 9.31 (t, 1H) 8.86 (d, 1H) 8.80-8.77 (m, 2H) 8.62 (d, 1H) 8.41 (m, 2H) 8.31 (d, 1H) 8.25 (d, 1H) 8.00-7.96 (m, 2H) 7.82 (s, 1H) 7.76-7.71 (m, 4H) 7.69-7.66 (m, 2H) 7.60-7.58 (m, 2H) 7.48-7.45 (m, 1H) 2.72 (s, 3 H); MALDI-TOF MS: m / z 556.8, cal. 556.68

Preparation Example 16 Preparation of Compound 137

compound 16-1 Manufacturing

4-bromophenacyl bromide (45 g, 161.9 mmol) was slowly added to pyridine (450 mL) in small portions. After stirring for 1 hour at room temperature, the precipitated solid was filtered. The filtered solid was washed with diethyl ether to give compound 16-1 (57 g, 98% yield).

compound 16-2 Manufacturing

Compound 16-1 (12.5g, 159.4mmol), trans-Chalcone (16.6g, 79.7mmol), methanol (220mL) and ammonium acetate (12.3g, 159.4mmol) were mixed and stirred under reflux for 12 hours. . After the reaction was completed, the mixture was cooled to room temperature, and the resulting solid was filtered and washed with methanol to obtain compound 16-2 (12.5 g, yield 40%).

¹ H NMR (CDCl ₃ ) δ [ppm]: 8.22-8.20 (d, 2H) 8.19-8.10 (d, 2H) 7.93 (d, 1H) 7.88 (d, 1H) 7.77-7.75 (d, 2H) 7.68- 7.64 (d, 2H) 7.58-7.51 (m, 4H) 7.50-7.28 (m, 2H)

compound 16-3 Manufacturing

Compound 16-2 (12.5g, 32.4mmol), Bis (pinacolato) diboron (9.04g, 36mmol), 1,4-dioxane (200mL), 1,1'-bis ( Diphenylphosphino) ferrocene-palladium (II) dichloride dichloromethane complex (0.53 g, 0.6 mmol) and CH ₃ CO ₂ K (6.35 g, 64.7 mmol) were mixed and stirred under reflux for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, saturated aqueous NaCl solution and ethyl acetate (EA) were added, the organic layer was extracted, dried over MgSO ₄ , and concentrated under reduced pressure. The oil residue was purified by column purification with ethyl acetate and n-hexane to give compound 16-3 ( 11.8 g, yield 84%).

¹ H NMR (CDCl ₃ ) δ [ppm]: 8.25-8.22 (m, 4H) 7.99-7.97 (d, 2H) 7.95-7.92 (d, 2H) 7.79-7.77 (d, 2H) 7.58-7.47 (m, 6H) 1.41 (s, 12H)

compound 16-4 Manufacturing

Compound 16-3 (11.8 g, 27.2 mmol), 2,4-dichloro-6-methylpyrimidine (4.57 g, 28 mmol), THF (230 mL), Pd (PPh ₃ ) ₄ (0.31 g, 0.3 mmol) 1 M K ₂ CO ₃ aqueous solution (110 mL) was mixed and stirred at reflux for 18 h. After the reaction was completed, the mixture was cooled to room temperature, saturated aqueous NaCl solution and ethyl acetate (EA) were added, the organic layer was extracted, dried over MgSO ₄ , and concentrated under reduced pressure. The resulting oil residue was purified by column purification with ethyl acetate and n-hexane to give Compound 16-4 9.8 g, yield 83%) was obtained.

¹ H NMR (CDCl ₃ ) δ [ppm]: 8.38-8.36 (d, 2H) 8.26-8.22 (m, 4H) 7.98-7.96 (d, 2H) 7.79-7.78 (d, 2H) 7.60-7.49 (m, 7H)

compound 137 Manufacturing

Compound 16-4 (10 g, 23 mmol), Compound 5-3 (9.35 g, 27.7 mmol), THF (200 mL), Pd (PPh ₃ ) ₄ (0.27 g, 0.23 mmol) and 1M K ₂ CO ₃ aqueous solution (100 mL) The mixture was stirred and refluxed for 18 hours. After the reaction was completed, the mixture was cooled to room temperature, and the precipitated solid was filtered and washed with distilled water. The obtained white solid was suspended while heating with ethyl acetate and filtered to obtain compound 137 (8.9 g, yield 63%).

¹ H NMR (CDCl ₃ ) δ [ppm]: 9.34 (s, 1 H) 8.83 (d, 1 H) 8.63 (d, 1 H) 8.44 (s, 4 H) 8.38 (d, 1 H) 8.36-8.26 (m, 3 H) 8.03 (s, 1 H) 7.98 (s, 1 H) 7.82 (d, 2 H) 7.71 (t, 1 H) 7.65 (s, 1 H) 7.61-7.48 (m, 7 H) 2.76 (s, 3 H); LC-MS: m / z 610.4, cal. 609.74

Preparation Example 17 Preparation of Compound 127

compound 17- One of  Produce

THF (250 mL), 2,4-dichloro-6-methylpyrimidine (25 g, 153.4 mmol), 1-ethynylbenzene (16.5 g, 161.0 mmol), triethylamine (62.1 g, 613.5 mmol), Pd ( Ph ₃ P) ₂ Cl ₂ (2.15 g, 3.1 mmol) and CuI (0.58 g, 3.1 mmol) were mixed and stirred under reflux for 12 hours. After the reaction was completed, distilled water was added, the organic layer was extracted with dichloromethane, dried over MgSO ₄ , and concentrated under reduced pressure. The obtained solid was washed with hexane to obtain a white solid compound 17-1 (25.0 g, 71.3%).

¹ H NMR (CDCl ₃ ) δ [ppm]: 7.64 (d, 2H), 7.45 (d, 3H), 7.29 (s, 1H), 2.58 (s, 3H)

compound 17- 2 of  Produce

Compound 17-1 (8 g, 34.98 mmol), Compound 5-3 (13.02 g, 38.48 mmol), Pd (PPh ₃ ) ₄ (0.8 g, 0.7 mmol) and K in a mixed solvent of THF / water (80 mL: 40 mL) ₂ CO ₃ (9.7 g, 70.0 mmol) was mixed and stirred at reflux for 12 hours. After the reaction was completed, the organic layer was extracted with methylene chloride (MC), concentrated, and treated with acidic clay to obtain compound 17-2 (8.01 g, yield 56.5%) as a white solid.

¹ H NMR (DMSO-d ₆ ) δ [ppm]: 9.49 (s, 1H), 8.97 (d, 2H), 8.66 (d, 2H), 7.99 (s, 3H), 7.82 (m, 4H), 7.64 (s, 1 H), 2.88 (s, 3 H)

compound 17- 3 of  Produce

1,3-diphenyl-2-propanone (15g) and benzyl (15g) were dissolved in ethanol (105mL), potassium hydroxide (2g) was added thereto, and the mixture was stirred under reflux for 5 hours. After the reaction was completed, a black solid compound 17-3 (24.7 g, yield 89.9%) was obtained after filtration under reduced pressure.

¹ H NMR (DMSO-d ₆ ) δ [ppm]: 7.83 (d, 1 H), 7.58 (d, 1 H), 7.43 (m, 7 H), 7.34 (t, 1 H)

compound 127 of  Produce

Compound 17-2 (14 g) and compound 17-3 (13.3 g) were dissolved in diphenyl ether (70 mL) and stirred under reflux for 4 hours. After the reaction was completed, hexane (140 mL) was added, and the formed brown solid was filtered under reduced pressure, and then separated by a silica gel column (EA: Hexane = 3: 1) to obtain a compound 127 (21 g, yield 79.7%) as a white solid.

¹ H NMR (CDCl ₃ ) δ [ppm]: 8.69 (s, 1H), 8.61 (d, 1H), 8.34 (d, 1H), 8.21 (t, 1H), 7.50 (m, 2H), 7.28 (m , 4H), 7.19 (m, 3H), 7.10 (m, 2H), 6.92 (m, 24H), 6.64 (s, 1H); MALDI-TOF MS: m / z 760.42, cal. 760.94

Preparation Example 18 Preparation of Compound 138

compound 18-1 Manufacturing

Dissolve 1,3-diphenyl-2-propanone (10.1g) and 9,10-Phenanthrenequinone (10g) in ethanol (70mL), add potassium hydroxide (1.35g) It was stirred at reflux for 4 hours. After the reaction was completed, a black solid Compound 18-1 (10.2 g, yield 55.2%) was obtained after filtration under reduced pressure.

¹ H NMR (DMSO-d ₆ ) δ [ppm]: 7.79 (d, 1 H), 7.59 (d, 1 H), 7.40 (m, 6 H), 7.31 (t, 1 H)

compound 138 Manufacturing

Compound 17-2 (10 g) and Compound 18-1 (9.46 g) were dissolved in diphenyl ether (50 mL) and stirred under reflux for 4 hours. After completion of the reaction, hexane (100 mL) was added, and the formed brown solid was filtered under reduced pressure, and then separated by a silica gel column (EA: Hexane = 3: 1) to obtain a compound 138 (10.2 g, yield 54.4%) as a white solid.

¹ H NMR (CDCl ₃ ) δ [ppm]: 8.68 (s, 1H), 8.62 (d, 1H), 8.31 (d, 1H), 8.18 (t, 1H), 7.50 (m, 2H), 7.28 (m , 4H), 7.16 (m, 3H), 7.08 (m, 2H), 6.92 (m, 22H), 6.64 (s, 1H); MALDI-TOF MS: m / z 758.50, cal. 758.92

Preparation Example 19 Preparation of Compound 132

compound 19- One of  Produce

1,4-Dibromonaphthalene (16.7g, 58mmol), 9,9-dimethyl-9H-flowen-2-yl-boronic acid (13.9g, 58mmol), THF (300mL), Pd (PPh ₃ ) ₄ (1.34 g, 1.16 mmol) and a 2 M K ₂ CO ₃ aqueous solution (80 mL) were mixed and stirred under reflux for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, methylene chloride (300 mL) and distilled water (300 mL) were added, the organic layer was extracted, dried over MgSO ₄ , and concentrated under reduced pressure. The concentrated residue was filtered through a SiO ₂ column filter and the filtrate was concentrated in vacuo and dried to give compound 19-1 (14.5 g, yield 63%).

¹ H NMR (CDCl ₃ ) δ [ppm]: 8.42 (d, 1H) 8.05 (d, 1H) 7.92-7.83 (m, 3H) 7.70 (t, 1H) 7.59 (s, 1H) 7.54-7.39 (m, 4H) 7.34-7.29 (m, 3H) 1.60 (s, 6H)

compound 19- 2 of  Produce

Compound 19-1 (14.5g, 36.3mmol), Bis (pinacolato) diboron (13.8g, 54.4mmol), 1,4-dioxane (300mL), 1,1'-bis (Diphenylphosphino) ferrocene-palladium (II) dichloride dichloromethane complex (1.52 g, 2.1 mmol) and CH ₃ CO ₂ K (10.5 g, 108 mmol) were mixed and refluxed for 6 hours. After the reaction was completed, the mixture was cooled to room temperature, distilled water (300 mL) and ethyl acetate (300 mL) were added, the organic layer was extracted, dried over MgSO ₄ , and treated with activated carbon and filtered through Celite. The obtained filtrate was concentrated under reduced pressure, and the obtained solid was recrystallized from ethyl acetate to obtain compound 19-2 (14.7 g, yield 93%).

¹ H NMR (CDCl ₃ ) δ [ppm]: 8.91 (d, 1H) 8.19 (d, 1H) 8.11 (d, 1H) 7.87 (dd, 2H) 7.60-7.56 (m, 2H) 7.53-7.44 (m, 4H) 7.42-7.35 (m, 2H) 1.57 (s, 6H) 1.48 (s, 12H)

compound 19- 3 of  Produce

Compound 19-2 (14.7g, 33.3mmol), 2,6-dichloro-4-methylpyrimidine (6.4g, 40mmol), THF (300mL), Pd (PPh ₃ ) ₄ (0.9g, 0.78mmol) and 2M Aqueous K ₂ CO ₃ aqueous solution (80 mL) was mixed and stirred at reflux for 12 h. After the reaction was completed, the reaction mixture was cooled to room temperature, methylene chloride (300 mL) and distilled water (300 mL) were added, the organic layer was extracted, dried over MgSO ₄ , and concentrated under reduced pressure. The concentrated residue was filtered through a SiO ₂ column filter, the filtrate was concentrated in vacuo and dried to give compound 19-3 (10.4 g, yield 70%).

¹ H NMR (CDCl ₃ ) δ [ppm]: 8.50 (d, 1H) 8.44 (s, 1H) 8.15 (t, 2H) 8.11-8.076 (m, 4H) 8.042 (s, 1H) 7.98-7.92 (t, 1H) 7.92 (d, 1H) 7.81-7.77 (m, 2H) 7.77-7.64 (m, 6H) 7.45 (d, 1H) 7.41-7.37 (m, 2H) 2.07 (s, 1H)

compound 132 of  Produce

Compound 19-3 (14.4 g, 23.3 mmol), Compound 5-3 (8.7 g, 25.7 mmol), THF (300 mL), Pd (PPh ₃ ) ₄ (0.54 g, 0.47 mmol) and 2M K ₂ CO ₃ aqueous solution ( 50 mL) was stirred and refluxed for 18 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, methylene chloride (300 mL) and distilled water (300 mL) were added, the organic layer was extracted, dried over MgSO ₄ , and concentrated under reduced pressure. The obtained solid was suspended with ethyl acetate, filtered and washed with ethyl acetate to give compound 132 (5.7 g, yield 39%).

¹ H NMR (CDCl ₃ ) δ [ppm]: 9.18 (t, 1H), 8.80 (d, 1H), 8.77 (s, 1H), 8.61 (d, 1H), 8.45 (d, 1H), 8.34 (d , 1H), 8.32-8.21 (m, 2H), 8.17 (d, 1H), 8.10 (s, 1H), 8.08 (m, 3H), 7.98 (m, 2H), 7.95 (s, 1H), 7.89- 7.82 (m, 2H) 7.77 (d, 1H) 7.71-7.65 (m, 5H) 7.53 (d, 1H) 7.48-7.45 (t, 1H) 7.43 (d, 1H) 7.41-7.38 (m, 2H) 2.38 ( s, 1 H); MALDI-TOF MS: m / z 717.2 cal. 718.87

Preparation Example 20 Preparation of Compound 135

compound 20-1 Manufacturing

4,4'-dibromobiphenyl (30g, 96mmol), bis (pinacolato) diboron (66g, 260mmol), 1,4-dioxane (600mL), 1,1'- Bis (diphenylphosphino) ferrocene-palladium (II) dichloride dichloromethane complex (4.08 g, 5.6 mmol) and CH ₃ CO ₂ K (28.3 g, 288 mmol) were mixed and refluxed for 6 hours. After the reaction was completed, the mixture was cooled to room temperature, saturated aqueous NaCl solution and ethyl acetate (EA) were added, the organic layer was extracted, dried over MgSO ₄ , and treated with activated charcoal and filtered through Celite. The filtrate was concentrated under reduced pressure, and the obtained solid was recrystallized from ethyl acetate to obtain compound 20-1 (25 g, yield 76%).

¹ H NMR (CDCl ₃ ) δ [ppm]: 7.91 (d, 4H) 7.66 (d, 4H) 1.39 (s, 24H)

compound 20-2 Manufacturing

Compound 20-1 (27.1 g, 66.7 mmol), 2,6-dichloro-4-methylpyrimidine (23.92 g, 146 mmol), THF (500 mL), Pd (PPh ₃ ) ₄ (3.1 g, 2.7 mmol), 2M Aqueous K ₂ CO ₃ solution (150 mL) was mixed and stirred at reflux for 12 h. After the reaction was completed, the mixture was cooled to room temperature, methylene chloride (500 mL) and distilled water (500 mL) were added, the organic layer was extracted, dried over MgSO ₄ , and concentrated under reduced pressure. The concentrated residue was filtered through a SiO ₂ column filter, and the filtrate was concentrated under reduced pressure and dried to obtain compound 20-2 (9.36 g, yield 68%).

¹ H NMR (CDCl ₃ ) δ [ppm]: 8.23 (t, 2H) 7.82 (d, 2H) 7.77 (d, 2H) 7.74 (d, 2H) 7.58 (s, 2H) 2.65 (s, 6H)

compound 135 Manufacturing

Compound 20-2 (9.36 g, 23.3 mmol), Compound 5-3 (16.3 g, 48.3 mmol), THF (300 mL), Pd (PPh ₃ ) ₄ (0.53 g, 0.46 mmol) and 2M K ₂ CO ₃ aqueous solution ( 80 mL) was stirred and refluxed for 18 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, methylene chloride (300 mL) and distilled water (300 mL) were added, the organic layer was extracted, dried over MgSO ₄ , and concentrated under reduced pressure. The obtained solid was suspended with ethyl acetate, filtered and washed with ethyl acetate to give compound 135 (13 g, yield 74%).

¹ H NMR (CDCl ₃ ) δ [ppm]: 8.77 (d, 2H) 8.62 (d, 2H) 8.45 (d, 2H) 8.39 (d, 2H) 8.24 (m, 2H) 8.14 (d, 2H) 7.89 ( m, 6H) 7.70 (t, 2H) 7.60 (s, 2H) 7.51 (d, 2H) 2.65 (s, 6H)

Preparation Example 21 Preparation of Compound 139

compound 21- One of  Produce

2,4,6-trichloropyrimidine (33.5 g, 182.6 mmol), compound 15-1 (55.56 g, 182.6 mmol), THF (503 mL), Pd (PPh ₃ ) ₄ (2.12 g, 1.83 mmol) and 1M K ₂ CO ₃ Aqueous solutions (252 mL) were mixed and stirred at reflux for 18 h. After the reaction was completed, the mixture was cooled to room temperature, saturated aqueous NaCl solution and ethyl acetate (EA) were added, the organic layer was extracted, dried over MgSO ₄ , and treated with activated charcoal and filtered through Celite. The obtained filtrate was concentrated under reduced pressure, and the obtained solid was completely dissolved in acetone, followed by recrystallization to obtain compound 21-1 (36 g, yield 61%).

¹ H NMR (CDCl ₃ ) δ [ppm]: 8.82-8.80 (d, 1H), 8.75-8.73 (d, 1H) 114 (d, 1H), 8.00 (s, 1H), 7.98 (s, 1H), 7.81-7.67 (m, 5H)

compound 21- 2 of  Produce

Compound 21-1 (29.6g, 91.0mmol), pyridin-3-yl-3-boronic acid (11.19g, 91.0mmol), THF (592mL), Pd (PPh ₃ ) ₄ (1.06g, 0.91mmol) and 2M Aqueous K ₂ CO ₃ solution (296 mL) was mixed and stirred at reflux for 18 h. After the reaction was completed, the mixture was cooled to room temperature, saturated aqueous NaCl solution and ethyl acetate (EA) were added, the organic layer was extracted, dried over MgSO ₄ , and treated with activated charcoal and filtered through Celite. The obtained filtrate was concentrated under reduced pressure, and the obtained solid was recrystallized to obtain compound 21-2 (15.36 g, yield 47%).

¹ H NMR (DMSO-d ₆ ) δ [ppm]: 9.36-9.35 (d, 1H) 8.84-8.81 (d, 2H) 8.77-8.75 (d, 1H) 8.55-8.52 (m, 1H) 8.20-8.18 ( d, 1H) 8.05 (d, 2H) 8.01-7.99 (d, 1H) 7.80-7.76 (m, 2H) 7.71-7.65 (m, 2H) 7.54-7.50 (q, 1H)

compound 139 Manufacturing

Compound 21-2 (14 g, 38.1 mmol), Compound 5-3 (22 g, 65.0 mmol), THF (400 mL), Pd (PPh ₃ ) ₄ (0.7 g, 0.6 mmol) and 2M K ₂ CO ₃ aqueous solution (200 mL) The mixture was stirred and refluxed for 18 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, saturated aqueous NaCl solution and dichloromethane were added, the organic layer was extracted, dried over MgSO ₄ , treated with activated carbon, and filtered through Celite. The obtained filtrate was concentrated under reduced pressure, and the obtained solid was recrystallized to obtain compound 139 (9 g, yield 45%).

¹ H NMR (DMSO-d ₆ ) δ [ppm]: 9.57 (d, 1H) 9.42-9.41 (t, 2H) 8.91-8.80 (m, 4H) 8.72-8.69 (m, 1H) 8.62-8.61 (m, 1H) 8.42-8.32 (m, 3H) 8.14 (s, 1H) 8.09 (s, 1H) 8.06-8.04 (d, 1H) 7.82-7.68 (m, 5H) 7.60-7.57 (m, 1H) 7.50-7.47 ( m, 1 H); LC-MS: m / z 544.4, cal. 543.64

Preparation Example 22 Preparation of Compound 128

compound 22-1 Manufacturing

Compound 15-1 (31.8 g, 104.5 mmol), 2,4-dichloro-6-methylpyrimidine (17.3 g, 106.1 mmol), THF (636 mL), Pd (PPh ₃ ) ₄ (2.46 g, 2.1 mmol) Aqueous 2M K ₂ CO ₃ solution (318 mL) was mixed and stirred at reflux for 18 h. After the reaction was completed, the reaction mixture was cooled to room temperature, saturated aqueous NaCl solution and ethyl acetate were added, the organic layer was extracted, dried over MgSO ₄ , treated with activated carbon, and filtered through Celite. The obtained filtrate was concentrated under reduced pressure, and the obtained solid was completely dissolved in acetone, and then recrystallized to obtain compound 22-1 (9.8 g, yield 31%).

¹ H NMR (CDCl ₃ ) δ [ppm]: 8.98-8.96 (d, 1H), 8.93-8.91 (d, 1H), 8.15-8.10 (m, 3H), 7.87 (s, 1H), 7.83-7.67 ( m, 4H)

compound 128 Manufacturing

Compound 22-1 (9.8 g, 32.2 mmol), Compound 5-3 (10.88 g, 32.2 mmol), THF (196 mL), Pd (PPh ₃ ) ₄ (0.75 g, 0.64 mmol) and 1M aqueous solution of K ₂ CO ₃ ( 98 mL) was stirred and refluxed for 18 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, saturated aqueous NaCl solution and ethyl acetate were added, the organic layer was extracted, dried over MgSO ₄ , treated with activated carbon, and filtered through Celite. The obtained filtrate was concentrated under reduced pressure, and the obtained solid was recrystallized to obtain compound 128 (11 g, yield 71%).

¹ H NMR (DMSO-d ₆ ) δ [ppm]: 9.22 (s, 1H) 9.02-9.00 (d, 1H) 8.96-8.94 (d, 1H) 8.70-8.68 (d, 1H) 8.65-8.64 (d, 1H) 8.51-8.49 (d, 1H) 8.29-8.27 (m, 2H) 8.18-8.14 (m, 1H) 7.84-7.61 (m, 8H) 7.40-7.37 (m, 1H) LC-MS: m / z 480.99 , cal. 480.58

Preparation Example 23 Preparation of Compound 134

compound 23- One of  Produce

CuBr ₂ (50 g, 223.8 mmol), Al ₂ O ₃ (100 g, 980.8 mmol) and water (200 mL) were mixed and stirred for 20 minutes. After stirring was complete, the reaction mixture was concentrated and dried crystals (100 g) were placed in a 250 mL three-neck round bottom flask, 1-bromonaphthalene (25 g, 120.7 mmol) and chlorobenzene (100 mL) were added, and the mixture was stirred under reflux for 2 hours. . After the reaction was completed, the mixture was filtered and concentrated under reduced pressure. The concentrated residue was added dropwise to methanol (200 mL), and the crystals obtained by standing in a freezer for 24 hours were filtered to obtain compound 23-1 (20.7 g).

compound 23- 2 of  Produce

Compound 23-1 (20.7g, 72.4mmol), 1-naphthaleneboronic acid (12.45g, 72.4mmol), Pd (PPh ₃ ) ₄ (0.84g, 0.7mmol), 1M K ₂ CO ₃ aqueous solution (200mL) and THF (410 mL) was mixed and stirred at reflux for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, saturated aqueous NaCl solution and ethyl acetate (EA) were added, the organic layer was extracted, dried over MgSO ₄ , and treated with activated charcoal and filtered through Celite. The resulting filtrate was concentrated under reduced pressure to give compound 23-2 (14.79 g, 42.8 mmol).

compound 23-3 Manufacturing

Compound 23-2 (14.79 g, 44.4 mmol), bis (pinacolato) diboron (12.4 g, 49 mmol), 1,4-dioxane (375 mL), 1,1'-bis ( Diphenylphosphino) ferrocene-palladium (II) dichloride dichloromethane complex (0.72 g, 0.9 mmol) and CH ₃ CO ₂ K (8.71 g, 88.8 mmol) were mixed and stirred under reflux for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, saturated aqueous NaCl solution and ethyl acetate (EA) were added, the organic layer was extracted, dried over MgSO ₄ , and treated with activated charcoal and filtered through Celite. The resulting filtrate was concentrated under reduced pressure to give compound 23-3 (16.88 g) in an oil phase.

compound 23-4 Manufacturing

2,4-dichloro-6-methylpyrimidine (7.24 g, 44.4 mmol), compound 23-3 (16.88 g, 44.4 mmol), THF (340 mL), Pd (PPh ₃ ) ₄ (0.84 g, 0.7 mmol) And 1M K ₂ CO ₃ aqueous solution (207 mL) were mixed and stirred under reflux for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, saturated aqueous NaCl solution and ethyl acetate (EA) were added, the organic layer was extracted, dried over MgSO ₄ , and treated with activated charcoal and filtered through Celite. The resulting filtrate was concentrated under reduced pressure to give compound 23-4 (16.91 g) in an oil phase.

compound 134 Manufacturing

Compound 23-4 (16.91g, 44.4mmol), Compound 5-3 (15.02g, 44.4mmol), THF (340mL), Pd (PPh ₃ ) ₄ (0.51g, 0.4mmol) and 1M K ₂ CO ₃ aqueous solution ( 170 mL) was stirred and refluxed for 12 h. After the reaction was completed, the reaction mixture was cooled to room temperature and the reaction product was filtered. The white solid was suspended and stirred while heating with ethyl acetate, and then filtered to obtain Compound 134 (15.4 g, 62.5% yield).

¹ H NMR (CDCl ₃ ) δ [ppm]: 7.48 (s, 1 H) 8.25 (s, 1 H) 8.46 (d, 1 H) 8.71 (d, 1 H) 8.34 (d, 1 H) 8.26 (d, 1 H) 8.05 ( d, 2H) 7.65 (t, 1H) 7.52 (t, 2H) 7.21-7.39 (m, 9H) 7.28 (s, 1H) 7.24 (d, 2H) 7.51 (s, 1H) 2.69 (s, 3H) LC- MS: m / z 558.60, cal. 558.69

Preparation Example 24 Preparation of Compound 136

compound 24-1 Manufacturing

2- (4-bromophenyl) -1,1-diphenylethylene (25g, 74.6mmol), bis (pinacolato) diboron (20.83g, 82mmol), 1,4- Dioxane (375 mL), 1,1'-bis (diphenylphosphino) ferrocene-palladium (II) dichloride dichloromethane complex (1.22 g, 1.5 mmol) and CH ₃ CO ₂ K (14.64 g, 149.1 mmol) The mixture was refluxed for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, saturated aqueous NaCl solution and ethyl acetate (EA) were added, the organic layer was extracted, dried over MgSO ₄ , and treated with activated charcoal and filtered through Celite. The obtained filtrate was concentrated under reduced pressure to give compound 24-1 (28.5 g) in an oil phase.

compound 24-2 Manufacturing

2,4-Dichloro-6-methylpyrimidine (12.16 g, 74.6 mmol), compound 24-1 (28.5 g, 74.5 mmol), THF (570 mL), Pd (PPh ₃ ) ₄ (0.86 g, 0.7 mmol) And 1M K ₂ CO ₃ aqueous solution (285 mL) were mixed and stirred under reflux for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, saturated aqueous NaCl solution and ethyl acetate (EA) were added, the organic layer was extracted, dried over MgSO ₄ , and treated with activated charcoal and filtered through Celite. Concentrate under reduced pressure. The resulting filtrate was concentrated under reduced pressure to give compound 24-2 (28.55 g) in an oil phase.

compound 136 Manufacturing

Compound 24-2 (28.55g, 74.6mmol), Compound 5-3 (25.22g, 74.6mmol), THF (570mL), Pd (PPh ₃ ) ₄ (0.86g, 0.7mmol) and 1M K ₂ CO ₃ aqueous solution ( 286 mL) were stirred and refluxed for 12 h. After the reaction was completed, the reaction mixture was cooled to room temperature and the reaction product was filtered. The white solid was suspended and stirred while heating with ethyl acetate, and then filtered to obtain Compound 136 (30.6 g, yield 73.45%).

¹ H NMR (CDCl ₃ ) δ [ppm]: 7.28 (s, 1 H) 9.25 (s, 1 H) 8.74 (d, 1 H) 8.61 (d, 1 H) 8.34 (d, 1 H) 8.26 (d, 1 H) 8.05 ( d, 2H) 7.65 (t, 1H) 7.50 (t, 2H) 7.41-7.33 (m, 9H) 7.28 (s, 1H) 7.23 (d, 2H) 7.21 (s, 1H) 2.68 (s, 3H); LC-MS: m / z 558.60, cal. 558.69

Example 1 Fabrication of Organic Light-Emitting Device Using Compound 1 According to the Present Invention

A 40 mm × 40 mm × 0.7 mm sized glass substrate with an ITO (indium tin oxide) transparent electrode line with a thickness of 150 nm was ultrasonically cleaned in distilled water with detergent for 10 minutes and 10 minutes in distilled water. The wash was repeated twice. After the distilled water was washed, the substrate was sequentially ultrasonically cleaned for 10 minutes and dried using a solvent of isopropyl alcohol, acetone and methanol. Subsequently, after dry cleaning using oxygen / argon plasma, the glass substrate having the transparent electrode lines was mounted on the substrate holder of the vacuum deposition apparatus, and the film thickness 60 was formed so as to cover the transparent electrodes on the surface where the transparent electrode lines were formed. A nm IDE-406 (following structure, I company) film was formed as a hole injection layer. Next, a 4,4'-bis [N- (1-naphthyl) -N-phenylamino] biphenyl film (hereinafter, α-NPB film) having a thickness of 30 nm was formed on the IDE-406 film as a hole transporting layer. It was. Next, BD-1 having the following structure as a dopant was deposited on the NPB film in β-ADN (9,10-di (naphthalen-2-yl) anthracene) as a light emitting host at a weight ratio of 5%, and the film thickness was 20 nm. It formed into a film as a light emitting layer of.

Compound 1 of the present invention was deposited on the light emitting layer to form a film with an electron transporting layer having a thickness of 20 nm. Subsequently, LiF was deposited thereon to form an electron injection layer. Metal aluminum was deposited on the LiF film to form a metal cathode to fabricate an organic light emitting device.

Example 2 Fabrication of Organic Light-Emitting Device Using Compound 2 According to the Present Invention

An organic light-emitting device was manufactured in the same manner as in Example 1, except that Compound 2 was used instead of Compound 1 as the electron transporting layer material in Example 1.

Example 3 Fabrication of Organic Light-Emitting Device Using Compound 3 According to the Present Invention

An organic light-emitting device was manufactured in the same manner as in Example 1, except that Compound 3 was used instead of Compound 1 as the electron transporting layer material in Example 1.

Example 4 Fabrication of Organic Light-Emitting Device Using Compound 4 According to the Present Invention

An organic light-emitting device was manufactured in the same manner as in Example 1, except that Compound 4 was used instead of Compound 1 as an electron transporting layer material in Example 1.

Example 5 Fabrication of Organic Light-Emitting Device Using Compound 5 According to the Present Invention

An organic light-emitting device was manufactured in the same manner as in Example 1, except that Compound 5 was used instead of Compound 1 as the electron transport layer material in Example 1.

Example 6 Fabrication of Organic Light-Emitting Device Using Compound 6 According to the Present Invention

An organic light-emitting device was manufactured in the same manner as in Example 1, except that Compound 6 was used instead of Compound 1 as an electron transporting layer material in Example 1.

Example 7 Fabrication of Organic Light-Emitting Device Using Compound 7 According to the Present Invention

An organic light-emitting device was manufactured in the same manner as in Example 1, except that Compound 7 was used instead of Compound 1 as the electron transporting layer material in Example 1.

Example 8 Fabrication of Organic Light-Emitting Device Using Compound 8 According to the Present Invention

An organic light-emitting device was manufactured in the same manner as in Example 1, except that Compound 8 was used instead of Compound 1 as the electron transporting layer material in Example 1.

Example 9 Fabrication of Organic Light-Emitting Device Using Compound 9 According to the Present Invention

An organic light-emitting device was manufactured in the same manner as in Example 1, except that Compound 9 was used instead of Compound 1 as an electron transporting layer material in Example 1.

Example 10 Fabrication of Organic Light-Emitting Device Using Compound 10 According to the Present Invention

An organic light-emitting device was manufactured in the same manner as in Example 1, except that Compound 10 was used instead of Compound 1 as an electron transporting layer material in Example 1.

Example 11 Fabrication of Organic Light-Emitting Device Using Compound 11 According to the Present Invention

An organic light-emitting device was manufactured in the same manner as in Example 1, except that Compound 11 was used instead of Compound 1 as an electron transporting layer material in Example 1.

Example 12 Fabrication of Organic Light-Emitting Device Using Compound 12 According to the Present Invention

An organic light-emitting device was manufactured in the same manner as in Example 1, except that Compound 12 was used instead of Compound 1 as an electron transporting layer material in Example 1.

Example 13 Fabrication of Organic Light-Emitting Device Using Compound 13 According to the Present Invention

An organic light-emitting device was manufactured in the same manner as in Example 1, except that Compound 13 was used instead of Compound 1 as an electron transporting material in Example 1.

Comparative Example 1 Fabrication of Organic Light - Emitting Device Using Compound ETM-1

An organic light-emitting device was manufactured in the same manner as in Example 1, except that Compound ETM-1 having the following structure was used instead of Compound 1 as an electron transporting layer material in Example 1.

Table 1 shows the electroluminescent properties and basic physical property measurement results of the organic light emitting diodes manufactured in Examples 1 to 13 and Comparative Example 1.

No . Voltage (V) Current density
( mA Of cm ² ) efficiency
( CD / A) Color coordinates (x, y) Luminance
( CD / ㎡) Example  One 4.49 18.65 5.36 (0.127, 0.142) 1000 Example  2 4.50 17.40 5.74 (0.127, 0.143) 1000 Example  3 4.76 20.40 4.90 (0.128, 0.147) 1000 Example  4 4.12 17.25 5.79 (0.128, 0.141) 1000 Example  5 4.30 16.23 6.16 (0.130, 0.147) 1000 Example  6 4.79 23.17 4.31 (0.138, 0.151) 1000 Example  7 4.41 18.82 5.31 (0.128, 0.143) 1000 Example  8 4.58 17.10 5.84 (0.128, 0.143) 1000 Example  9 4.21 15.40 6.49 (0.128, 0.148) 1000 Example  10 4.90 20.53 4.87 (0.128, 0.142) 1000 Example  11 4.58 19.10 5.23 (0.128, 0.143) 1000 Example  12 4.13 14.25 7.00 (0.130, 0.149) 1000 Example  13 4.20 15.50 6.45 (0.127, 0.145) 1000 Comparative example  One 4.71 21.10 4.75 (0.128, 0.146) 1000

Example 14 Fabrication of Organic Light-Emitting Device Using Compound 14 According to the Present Invention

A 25 mm × 25 mm × 0.7 mm sized glass substrate having an ITO (indium tin oxide) transparent electrode line having a thickness of 150 nm was ultrasonically cleaned for 10 minutes in distilled water. After washing the distilled water, using a solvent of acetone, distilled water, isopropyl alcohol, the substrate was sequentially ultrasonically cleaned for 10 minutes and dried. Subsequently, after dry cleaning using oxygen / nitrogen plasma, the glass substrate having the transparent electrode lines was mounted on the substrate holder of the vacuum deposition apparatus, and the film thickness 60 was formed so as to cover the transparent electrodes on the surface where the transparent electrode lines were formed. A nm IDE-406 (following structure, I company) film was formed as a hole injection layer. Next, HT320 (tetrakis-N-biphenyl-4-yl-benzidine) (hereinafter referred to as HT320 film) having a thickness of 30 nm was formed on the IDE-406 film as a hole transporting layer. Next, BD-2 having the following structure as a dopant was deposited on the HT320 film at a weight ratio of 5% to β-ADN (9,10-di (naphthalen-2-yl) anthracene) as a light emitting host, and the film thickness was 20 nm. It formed into a film as a light emitting layer of.

Compound 14 of the present invention was deposited on the emission layer to form an electron transport layer having a thickness of 20 nm. Subsequently, Liq (lithium quinolate) was deposited thereon to form an electron injection layer. Metal aluminum was deposited on the Liq film to form a metal cathode, thereby producing an organic light emitting device.

Example 15 Fabrication of Organic Light-Emitting Device Using Compound 131 According to the Present Invention

An organic light emitting device was manufactured in the same manner as in Example 14, except that Compound 131 was used instead of Compound 14 as an electron transporting material in Example 14.

Example 16 Fabrication of Organic Light-Emitting Device Using Compound 137 According to the Present Invention

An organic light-emitting device was manufactured in the same manner as in Example 14, except that Compound 137 was used instead of Compound 14 as an electron transporting layer material in Example 14.

Example 17 Fabrication of Organic Light-Emitting Device Using Compound 127 According to the Present Invention

An organic light-emitting device was manufactured in the same manner as in Example 14, except that Compound 127 was used instead of Compound 14 as an electron transporting layer material in Example 14.

Example 18 Fabrication of Organic Light-Emitting Device Using Compound 138 According to the Present Invention

An organic light emitting device was manufactured in the same manner as in Example 14, except that Compound 138 was used instead of Compound 14 as an electron transporting layer material in Example 14.

Example 19 Fabrication of Organic Light-Emitting Device Using Compound 132 According to the Present Invention

An organic light-emitting device was manufactured in the same manner as in Example 14, except that Compound 132 was used instead of Compound 14 as an electron transporting material in Example 14.

Example 20 Fabrication of Organic Light-Emitting Device Using Compound 135 According to the Present Invention

An organic light-emitting device was manufactured in the same manner as in Example 14, except that Compound 135 was used instead of Compound 14 as an electron transporting layer material in Example 14.

Example 21 Fabrication of Organic Light-Emitting Device Using Compound 139 According to the Present Invention

An organic light-emitting device was manufactured in the same manner as in Example 14, except that Compound 139 was used instead of Compound 14 as an electron transporting material in Example 14.

Example 22 Fabrication of Organic Light-Emitting Device Using Compound 128 According to the Present Invention

An organic light-emitting device was manufactured in the same manner as in Example 14, except that Compound 128 was used instead of Compound 14 as the electron transporting layer material in Example 14.

Example 23 Fabrication of Organic Light-Emitting Device Using Compound 134 According to the Present Invention

An organic light-emitting device was manufactured in the same manner as in Example 14, except that Compound 134 was used instead of Compound 14 as an electron transporting material in Example 14.

Example 24 Fabrication of Organic Light-Emitting Device Using Compound 136 According to the Present Invention

An organic light emitting device was manufactured in the same manner as in Example 14, except that Compound 136 was used instead of Compound 14 as an electron transporting layer material in Example 14.

Comparative Example 2 Fabrication of Organic Light - Emitting Device Using Compound ETM-1

An organic light-emitting device was manufactured in the same manner as in Example 14, except that Compound ETM-1 having the following structure was used instead of Compound 14 as an electron transporting material in Example 14.

The electroluminescent properties and basic physical property measurement results of the organic light emitting diodes manufactured in Examples 14 to 24 and Comparative Example 2 are shown in Table 2 below, and the organic light emitting diodes manufactured in Examples 14 to 24 and Comparative Example 2 are shown in FIG. 1. The luminance (cd / m 2) versus the efficiency (cd / A) of the device is shown.

No . Voltage (V) Current density
( mA Of cm ² ) efficiency
( CD / A) Color coordinates (x, y) Luminance
( CD / ㎡) Example  14 5.0 13.73 7.91 0.136, 0.153 1000 Example  15 4.8 22.66 4.84 0.135, 0.147 1000 Example  16 5.8 23.15 5.26 0.136, 0.152 1000 Example  17 6.8 18.48 5.64 0.135, 0.155 1000 Example  18 5.4 16.83 6.56 0.135, 0.150 1000 Example  19 6.2 20.33 5.10 0.136, 0.146 1000 Example  20 6.8 17.11 6.24 0.135, 0.153 1000 Example  21 4.8 15.07 6.87 0.138, 0.156 1000 Example  22 4.8 22.66 4.59 0.138, 0.147 1000 Example  23 7.1 27.82 3.62 0.135, 0.201 1000 Example  24 6.3 21.38 4.70 0.137, 0.149 1000 Comparative example  2 5.0 29.05 4.03 0.135, 0.143 1000

As shown in Table 1 and Table 2, it was confirmed that the light emission characteristics of the material developed in the present invention shows superior properties compared to the conventional material. In addition, the organic light emitting device using the heteroaromatic ring compound according to the present invention as the electron transporting layer not only has excellent light emission characteristics, but also enhances the driving voltage, thereby increasing power efficiency and improving power consumption.

Claims (6)

An electron transport material represented by the following formula (1).
[Formula 1]

[In the above formula (1)
Ar is (C6-C30) arylene or (C3-C30) heteroarylene;
L ₁ and L ₂ are independently of each other a single bond, (C1-C30) alkylene, (C6-C30) arylene, (C3-C30) cycloalkylene or (C3-C30) heteroarylene;
R ₁ and R ₂ independently of one another are hydrogen, (C1-C30) alkyl, (C3-C30) cycloalkyl, -CR '= CR''R''', (C6-C30) aryl or (C3-C30) Heteroaryl, provided that at least one of R ₁ and R ₂ is

,

or

ego;
L ₃ and L ₄ are independently of each other a single bond or (C6-C30) arylene;
R ', R'',R''', R ₃ to R ₅ independently of one another are hydrogen, (C1-C30) alkyl, (C3-C30) cycloalkyl, (C6-C30) aryl or (C3-C30) Heteroaryl;
X is O or S;
The arylene and heteroarylene of Ar, alkylene, arylene, cycloalkylene and heteroarylene of L ₁ and L ₂ , and alkyl, cycloalkyl, aryl and heteroaryl of R ₁ to R ₅ are (C1- C30) alkyl, halo (C1-C30) alkyl, halogen, cyano, (C3-C30) cycloalkyl, (C1-C30) alkoxy, (C6-C30) aryloxy, (C6-C30) aryl, (C1- C30) alkyl (C6-C30) aryl, (C6-C30) ar (C1-C30) alkyl, (C3-C30) heteroaryl, (C1-C30) alkyl substituted (C3-C30) heteroaryl, (C6 (C3-C30) heteroaryl, mono or di (C1-C30) alkylamino, mono or di (C6-C30) arylamino, tri (C1-C30) alkylsilyl, di (C1-) C30) alkyl (C6-C30) arylsilyl, tri (C6-C30) arylsilyl, nitro and hydroxy may be further substituted with one or more selected from the group consisting of;
Wherein said heteroarylene and heteroaryl include one or more heteroatoms selected from B, N, O, S, P (= 0), Si and P.]
The method of claim 1,
And Ar is selected from the following structures.

[The above R ₁₁ to R ₂₁ are independently of each other hydrogen, (C1-C30) alkyl, halo (C1-C30) alkyl, halogen, cyano, (C3-C30) cycloalkyl, (C1-C30) alkoxy, (C6 -C30) aryloxy, (C6-C30) aryl, (C1-C30) alkyl (C6-C30) aryl, (C6-C30) ar (C1-C30) alkyl, (C3-C30) heteroaryl, (C1- (C3-C30) heteroaryl substituted with alkyl, (C3-C30) heteroaryl substituted with (C3-C30) aryl, mono or di (C1-C30) alkylamino, mono or di (C6-C30) Arylamino, tri (C1-C30) alkylsilyl, di (C1-C30) alkyl (C6-C30) arylsilyl, tri (C6-C30) arylsilyl, nitro or hydroxy; a to d are each independently an integer of 1 to 4; e is an integer of 1 or 2.]
The method of claim 2,
An electron transport material represented by the following Chemical Formulas 2 to 8.
(2)

(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

(7)

[Chemical Formula 8]

[Formula 2 to In 8, L ₁ and L ₂ are each independently a single bond, (C6-C30) arylene or (C3-C30) heteroarylene, wherein the arylene and heteroarylene of L ₁ and L ₂ are (C1- C 30) alkyl or (C 6 -C 30) aryl; R ₁ is hydrogen, (C1-C30) alkyl, -CR '= CR``R''', (C6-C30) aryl, (C3-C30) heteroaryl or

Wherein the alkyl, aryl and heteroaryl of R ₁ may be further substituted with (C ₁ -C 30) alkyl or (C 6 -C 30) aryl; R ₁₁ to R ₂₀ are each independently hydrogen, (C 1 -C 30) alkyl, (C 6 -C 30) aryl, (C 1 -C 30) alkyl (C 6 -C 30) aryl or (C 3 -C 30) heteroaryl, provided that Except when ₁₁ and R ₁₂ are hydrogen at the same time; R ₂ is

,

or

ego; L ₃ and L ₄ are independently of each other a single bond or (C6-C30) arylene; R ', R'',R''', R ₃ to R ₅ are independently of each other hydrogen, (C6-C30) aryl or (C3-C30) heteroaryl; X is O or S; a to d are each independently an integer of 1 to 4.]
The method of claim 3,
An electron transport material selected from the following compounds.

An organic light emitting device comprising the electron transport material according to any one of claims 1 to 4.
6. The method of claim 5,
The organic light emitting diode includes a first electrode; A second electrode; And at least one organic material layer interposed between the first electrode and the second electrode, wherein the organic material layer includes an electron transport layer including the electron transport material.

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