KR20120009984A - Novel organic light emitting compound and organic electroluminescent device comprising same - Google Patents

Abstract

PURPOSE: An organic electroluminescent compound is provided to excellent luminous efficiency and life time properties, thereby using for manufacturing an organic electroluminescent device of which driving life time is very superior. CONSTITUTION: An organic electroluminescent compound is in chemical formula 1. An organic electroluminescent device comprises the organic electroluminescent compound, the organic electroluminescent compound is using as material for hole injection or hole transport. The organic electroluminescent compound comprises a first electrode, a second electrode, and one or more organic material layer between the first electrode and the second electrode. The organic layer comprises the organic electroluminescent compound in chemical formula 1. The organic layer comprises a light emitting layer and a charge generating layer at the same time.

Description

Novel organic electroluminescent compounds and organic electroluminescent device using the same

The present invention relates to a novel organic light emitting compound and an organic electroluminescent device comprising the same, and more particularly to a novel organic light emitting compound used as a hole transport material or a hole injection material and an organic electroluminescent device employing the same. It is about.

Liquid crystal display (LCD), which is the most widely used at present, is a non-light emitting display device, which consumes little power and is light. However, the device driving system is complicated and characteristics such as response time and contrast are not satisfactory. Therefore, research on organic electroluminescent devices, which are recently attracting attention as a next-generation flat panel display, is being actively conducted.

Among the display elements, an electroluminescence device (EL device) is a self-luminous display element that has a wide viewing angle, excellent contrast, and high response speed.Eastman Kodak Co., Ltd. in 1987 An organic EL device using a low molecular aromatic diamine and an aluminum complex as a light emitting layer formation material was first developed [Appl. Phys. Lett. 51, 913, 1987].

In the light emitting mechanism of the organic EL device, when charge is injected into the organic film formed between the electron injection electrode (cathode) and the hole injection electrode (anode), electrons and holes are paired and then disappear to emit light. 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 has a relatively low power consumption. It has a small and excellent color.

Organic materials in organic EL devices can be roughly divided into light emitting materials and charge transport materials. The luminescent material is directly related to the emission color and the luminous efficiency. Some of the required properties are that the fluorescence quantum yield should be high in the solid state, the mobility of electrons and holes should be high, and not easily decomposed during vacuum deposition. It should be stable, forming a uniform thin film.

Hole injection and transport materials include copper phthalocyanine (CuPc), NPB, TPD, MTDATA (4, 4 ', 4 "-tris (3-methylphenylphenylamino) triphenylamine), etc. These materials are included in the hole injection and transport layer. The device has a problem in that the efficiency and lifespan are lowered, because when the organic EL device is driven at a high current, thermal stress is generated between the anode and the hole injection layer. In addition, since the organic material used in the hole injection layer has a very high hole mobility, the hole-electron charge balance between the holes and the electrons is broken, and thus the quantum efficiency (cd / A) becomes low.

In order to increase the durability of the organic EL device, it is reported that the compound having good thin film stability and the compound having high amorphousness have higher thin film stability. At this time, the glass transition point (Tg) is used as an index of amorphousness. MTDATA's glass transition temperature is 76 ℃, which means that its amorphousness is not high. These materials did not obtain satisfactory characteristics in terms of durability of the organic EL element and also in luminous efficiency due to the characteristics of hole injection and transport.

Accordingly, an object of the present invention is to provide an organic light emitting compound having an excellent luminescence efficiency and device life better than the existing hole injection or hole transport material in order to solve the above problems, and to provide a novel organic light emitting compound in the hole injection layer or An organic electroluminescent element employed in a hole transport layer is provided.

The present invention relates to an organic light emitting compound represented by Chemical Formula 1, and an organic electroluminescent device comprising the same, wherein the organic light emitting compound according to the present invention is included in the hole injection layer or the hole transport layer of the organic electroluminescent device The luminous efficiency can be improved while lowering the driving voltage.

[Formula 1]

[In Formula 1,

Y ₁ is —O—, —S—, —C (R ₁₁ R ₁₂ ) — or —Si (R ₁₃ R ₁₄ ) —;

Y ₂ is —O—, —S—, —C (R ₁₁ R ₁₂ ) —, —Si (R ₁₃ R ₁₄ ) — or —N (R ₁₅ );

이며;Ring A and Ring C are each independently

Is;

이고;B ring

ego;

Y ₃ and Y ₄ are each independently CH or N;

Y ₅ and Y ₆ are each independently a chemical bond, —O—, —S—, —C (R ₁₁ R ₁₂ ) —, —Si (R ₁₃ R ₁₄ ) — or —N (R ₁₅ ) — Unless Y ₅ and Y ₆ are chemical bonds at the same time;

R ₁ to R ₄ are each independently hydrogen, deuterium, halogen, substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl, substituted or unsubstituted (C3-C30) hetero Aryl, substituted or unsubstituted (C3-C30) cycloalkyl, substituted or unsubstituted (C1-C30) alkylsilyl group, substituted or unsubstituted 5- to 7-membered heterocycloalkyl, substituted or unsubstituted ( C6-C30) Ar (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl, fused with one or more cycloalkyl, 5- to 7-membered hetero, fused with one or more substituted or unsubstituted aromatic rings (C3-C30) cycloalkyl which is cycloalkyl or has one or more substituted or unsubstituted aromatic rings, -N (R ₁₆ R ₁₇ ), -Si (R ₁₈ R ₁₉ R ₂₀ ), -SR ₂₁ , -OR _{22 ,} Cyano, nitro or hydroxy, and when there are a plurality of R ₁ to R ₄ , may combine with each other to form a cyclic structure;

L ₁ and L ₂ are each independently a chemical bond, a substituted or unsubstituted (C6-C30) arylene, a substituted or unsubstituted (C3-C30) heteroarylene or a substituted or unsubstituted (C3-C30) cyclo Alkylene, adjacent L ₁ and L ₂ may be bonded to each other to form a cyclic structure, except that L ₁ and L ₂ are at the same time a chemical bond;

Ar is substituted or unsubstituted (C6-C30) aryl, substituted or unsubstituted (C3-C30) heteroaryl, substituted or unsubstituted (C6-C30) aryl in which at least one cycloalkyl is fused;

R ₁₁ to R ₂₂ are each independently hydrogen, deuterium, halogen, substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl, substituted or unsubstituted (C3-C30) hetero Aryl, substituted or unsubstituted 5- to 7-membered heterocycloalkyl, substituted or unsubstituted (C3-C30) cycloalkyl or substituted or unsubstituted (C3-C30) with or without fused ring with adjacent substituents Alkylene or substituted or unsubstituted (C3-C30) alkenylene to form an alicyclic ring and a monocyclic or polycyclic aromatic ring, and the alicyclic ring and the monocyclic or polycyclic aromatic ring The carbon atom may be substituted with one or more heteroatoms selected from nitrogen, oxygen and sulfur;

l, m, n and p are each independently integers of 0 to 4, and when l, m, n or p is an integer of 2 or more, each of R ₁ , R ₂ , R ₃ and R ₄ may be the same or different from each other. Adjacent substituents may combine with each other to form a ring;

Wherein said heterocycloalkyl and heteroaryl include one or more heteroatoms selected from B, N, O, S, P (= 0), Si and P.]

Substituents comprising the 'alkyl' and other 'alkyl' moieties described herein include both straight and pulverized forms, and 'cycloalkyl' is substituted or unsubstituted adamantyl or substituted or unsubstituted as well as a single ring system It also includes several ring-based hydrocarbons such as cyclic (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, anthryl, indenyl, fluorenyl, phenanthryl, triphenylenyl, pyrenyl, peryleneyl, chrysenyl, naphthacenyl, fluoranthenyl, and the like. It is not limited to this. Said naphthyl includes 1-naphthyl and 2-naphthyl, anthryl includes 1-anthryl, 2-anthryl and 9-anthryl, and fluorenyl is 1-fluorenyl, 2- Fluorenyl, 3-fluorenyl, 4-fluorenyl and 9-fluorenyl. "Heteroaryl" described in the present invention contains 1 to 4 heteroatoms selected from B, N, O, S, P, P (= O), Si and Se as aromatic ring skeleton atoms, and the remaining aromatic ring skeletons. Means an aryl group whose atoms are carbon, 5-6 membered monocyclic heteroaryl, and polycyclic heteroaryl condensed with one or more benzene rings, which may be partially saturated. 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, thienyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl, triazolyl, tetrazolyl Monocyclic heteroaryl such as furazanyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, benzofuryl, benzothienyl, isobenzofuryl, benzoimidazolyl, benzothiazolyl, benzoisothiazolyl, benzoy Soxazolyl, Benzoxazolyl, Isoindoleyl, Indolyl, Indazolyl, Benzothiadiazolyl, Quinolyl, Isoquinolyl, Cinolinyl, Quinazolinyl, Quinolizinyl, Quinoxalinyl, Carbazolyl, Phenantri Polycyclic heteroaryls such as diyl, benzodioxyl, naphthyridinyl, dibenzofuryl, dibenzothiophenyl and their corresponding N-oxides (e.g. pyridyl N-oxides, quinolyl N-oxides) , Quaternary salts thereof, and the like, No.

In addition, the alkyl of the '(C1-C30) alkyl or (C6-C30) ar (C1-C30) alkyl' group described in the present invention includes (C1-C20) alkyl or (C1-C10) alkyl, Aryl of the '(C6-C30) aryl and (C6-C30) ar (C1-C30) alkyl' groups includes (C6-C20) aryl or (C6-C12) aryl. '(C3-C30) heteroaryl' group includes (C3-C20) heteroaryl or (C3-C12) heteroaryl, and the '(C3-C30) cycloalkyl' group is (C3-C20) cycloalkyl or (C3- C7) cycloalkyl. '(C3-C30) alkylene or alkenylene' groups include (C3-C20) alkylene or alkenylene, (C3-C10) alkylene or alkenylene.

In addition, in the description of "substituted or unsubstituted" described in the present invention, "substituted" means a case where is further substituted with an unsubstituted substituent, the R ₁ To R ₄ , R ₁₁ to R ₂₂ , L ₁ , L _2, and Ar are further substituted with each other independently of deuterium, halogen, halogen-substituted or unsubstituted (C1-C30) alkyl, (C6-C30) aryl (C3-C30) heteroaryl substituted or unsubstituted (C6-C30) aryl, 5- to 7-membered heterocycloalkyl, 5- to 7-membered heterocycloalkyl fused with one or more aromatic rings, (C3 -C30) cycloalkyl, (C6-C30) cycloalkyl fused with one or more aromatic rings, R ₃₁ R ₃₂ R ₃₃ Si-, (C2-C30) alkenyl, (C2-C30) alkynyl, cyano, carba Zolyl, -NR ₃₄ R ₃₅ , (C6-C30) ar (C1-C30) alkyl, (C1-C30) alkyl (C6-C30) aryl, R ₃₆ S-, R ₃₇ O-, nitro or hydroxy At least one selected from the group consisting of R ₃₁ to R ₃₇ independently of one another is (C 1 -C 30) alkyl, (C 6 -C 30) aryl, (C 3 -C 30) heteroaryl, or (C 3 -C 30) cycloalkyl it means.

은 하기 구조에서 선택되나, 이에 한정되지는 않는다.Also of Formula 1

Is selected from the following structures, but is not limited thereto.

[R ₃ , R ₄ , R ₁₁ to R ₁₅ , l and p are the same as defined in Formula 1 above.]

The organic light emitting compound according to the present invention may be more specifically exemplified as the following compound, but the following compound does not limit the present invention.

The organic light emitting compound according to the present invention may be prepared, for example, as shown in Scheme 1 below, but is not limited thereto.

Scheme 1

[Scheme 1, A, B, C, R ₁ to R ₃ , Y ₁ , Y ₂ , L ₁ , L ₂ , Ar, l, m, n and p are the same as defined in Formula 1 above.]

In another aspect, the present invention provides an organic electroluminescent device, characterized in that the organic light emitting compound according to the invention is used as a hole injection material or a hole transport material.

The organic electroluminescent 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 at least one organic light emitting compound of Formula 1.

In the organic electroluminescent device of the present invention, it may include one or more compounds selected from the group consisting of an organic light emitting compound of formula (1), and at the same time an arylamine compound or a styrylarylamine compound, an arylamine compound Or specific examples of the styrylarylamine-based compound are exemplified in the identification number <212> to <224> of Patent Application No. 10-2008-0060393, but is not limited thereto.

In addition, in the organic electroluminescent device of the present invention, in the organic material layer, in addition to the organic light emitting compound of Chemical Formula 1, a group consisting of Group 1, Group 2, 4 cycle, 5 cycle transition metal, lanthanide series metal and organic metal of d-transition element It may further comprise one or more metals or complex compounds selected from, the organic material layer may include a light emitting layer and a charge generating layer.

An organic electroluminescent device comprising an organic light emitting compound of Formula 1 of the present invention is a subpixel, and includes Ir, Pt, Pd, Rh, Re, Os, Tl, Pb, Bi, In, Sn, Sb, Te, Au, and An organic electroluminescent device having an independent light emitting pixel structure in which at least one subpixel including at least one metal compound selected from the group consisting of Ag is simultaneously patterned in parallel may be implemented.

In addition, an organic light emitting device that emits white light may be formed by simultaneously including one or more organic light emitting layers including red, green, or blue light emitting compounds in addition to the organic electroluminescent compound. The compound emitting blue, green, or red light is exemplified in Application Nos. 10-2008-0123276, 10-2008-0107606, or 10-2008-0118428, but is not limited thereto.

In the organic electroluminescent device of the present invention, one layer selected from a chalcogenide layer, a metal halide layer and a metal oxide layer (hereinafter referred to as "surface layer &quot;) is formed on the inner surface of at least one of the pair of electrodes, Or more. Concretely, it is preferable to dispose a halogenated metal layer or a metal oxide layer on the surface of the anode on the side of the light emitting medium layer and on the surface of the cathode on the side of the light emitting medium layer, with a chalcogenide (including oxide) layer of a metal of silicon and aluminum Do. Thus, stabilization of the drive can be obtained. Examples of the chalcogenide include SiO _x (1 ≦ _X ≦ ₂ ), AlO _X (1 ≦ _X ≦ 1.5), SiON, SiAlON, and the like, and examples of the metal halide include LiF, MgF ₂ , CaF ₂ , and fluoride. Rare earth metals and the like are preferable. Examples of the metal oxides include Cs ₂ O, Li ₂ O, MgO, SrO, BaO, CaO and the like.

Further, in the organic electroluminescent device of the present invention, disposing a mixed region of an electron transfer compound and a reducing dopant or a mixed region of a hole transfer compound and an oxidative dopant on at least one surface of the pair of electrodes thus produced desirable. In this way, the electron transfer compound is reduced to an anion, thereby facilitating injection and transfer of electrons from the mixed region into the light emitting medium. In addition, since the hole transport compound is oxidized to become a cation, it is easy to inject and transfer holes from the mixed region to the light emitting medium. Preferred oxidative dopants include various Lewis acids and acceptor compounds. Preferred reducing dopants include alkali metals, alkali metal compounds, alkaline earth metals, rare earth metals and mixtures thereof. In addition, a white organic electroluminescent device having two or more light emitting layers may be manufactured using a reducing dopant layer as a charge generation layer.

The organic electroluminescent device using the organic light emitting compound according to the present invention as a hole transporting material or a hole injection material has an advantage of producing an OLED device having excellent luminous efficiency and excellent material life characteristics and excellent driving life of the device.

Hereinafter, the organic light emitting compound according to the present invention, a method for preparing the same and a light emitting property of the device are described for the detailed understanding of the present invention, but the present invention is only intended to illustrate the embodiments of the present invention. It does not limit the scope of the invention.

Preparation Example 1 Preparation of Compound 2

compound 1-1 Manufacture

25 g (0.22 mol) of cyclohexane-1,2-dione was added to 1 L of 2-neck-RBF, and 70.9 g (0.49 mol) of phenylhydrazine, 1.18 mL (0.02 mol) of H ₂ SO _{4, and} 720 mL (0.3 M) of MeOH were added. After addition, it is heated to 100 ° C. and stirred for 4 hours. After the reaction is completed, the reaction mixture is cooled to room temperature, and the resulting solid is filtered and washed with methanol. The washed solid was put into 1L two-ball-RBF, TFA 60g, AcOH 600mL was added and heated to 100 ℃ and stirred for 12 hours. After completion of the reaction, the mixture was washed with distilled water, extracted with EA, the organic layer was dried over MgSO ₄ , and the solvent was removed using a rotary evaporator, and purified by column chromatography to obtain compound 1-1 17g (29%).

compound 1-2 Manufacture

15 g (0.058 mol) of compound 1-1 was added to 1 L of two-ball-RBF, 47 g (0.23 mol) of iodobenzene, 33 g (0.17 mol) of CuI, 76 g (0.23 mol) of Cs ₂ CO ₃ , and 650 mL of quinoline were added. Heat to 190 ° C. and stir for 12 hours. After the reaction, the solvent was removed using a distillation apparatus, washed with distilled water, extracted with EA, dried over MgSO ₄ , dried over MgSO _4, and then removed with a rotary evaporator, and then purified by column chromatography to obtain a compound 1-2 15g (65 %) Was obtained.

compound 1-3 Manufacture

6.6 g (0.016 mol) of Compound 1-2 was added to 1 L of two-ball-RBF, NBS 3.3 g (0.018 mol) and THF 300 mL were added, followed by stirring at room temperature for 12 hours. After the reaction, the mixture was washed with distilled water, extracted with EA, dried over MgSO ₄ , dried over MgSO ₄ , solvent was removed by rotary evaporation, and washed with hexane to obtain compound 1-3 7.2g (92%).

compound 1-4 Manufacture

Add 10 g (0.020 mol) of compound 1-3 to 1000 mL 2-neck-RBF, add 2.4 g (0.026 mol) of naphthalene-1-amine, 375 mg (0.4 mmol) of Pd ₂ (dba) ₃ , 229 mg (0.8 mmol) of P (cy) ₃ ), Naot-Bu 5.9g (0.06mol) and dried under vacuum and filled with argon gas. After adding 300 mL of toluene, it heated at 120 degreeC and stirred for 12 hours. After the reaction, the mixture was washed with distilled water, extracted with EA, dried over MgSO ₄ , dried over MgSO ₄ , solvent was removed by rotary evaporation, and purified by column chromatography to obtain compound 1-4 7.8g (76%).

compound 1-5 Manufacture

7.8 g (0.015 mol) of Compound 1-4 in 1 L 2-neck-RBF, 6.6 g (0.023 mol) of 1-bromo-4-iodobenzene, 175 mg (0.7 mmol) of Pd (oAc) ₂ , P (t- Bu) ₃ 508mg (1.56mmol), Naot-Bu 4.5g (0.046mol) and vacuum dried and filled with nitrogen gas. 200 mL of toluene is added and then heated to 120 ° C. and stirred for 12 hours. After the reaction was washed with distilled water and extracted with EA, the organic layer was dried with MgSO ₄ and the solvent was removed by rotary evaporator to obtain a compound 1-5 6.8g (66%).

compound 1-6 Manufacture

6.8g (0.010mol) of Compound 1-5 was added to 500 mL RBF, and the mixture was dried in vacuo and filled with nitrogen gas. 100 mL of THF is added and then cooled to -78 ° C. 6.2 mL (0.015 mol) of n-BuLi (2.5M) was added slowly, followed by stirring while maintaining a low temperature for 1 hour. 1.7 mL (0.015 mmol) of B (OMe) ₃ was added at -78 ° C, followed by stirring for 12 hours. After the reaction was completed, 1M HCl was added, washed with distilled water after 10 minutes, extracted with EA, and the organic layer was dried over MgSO ₄ , and the solvent was removed using a rotary evaporator to purify the column to obtain Compound 1-6 5.2g (81%). .

compound  2 Manufacture

1.8 g (7.0 mmol) of Compound 1-6 were added to 100 mL 2-neck-RBF, and 5.2 g (8.0 mmol) of _4- bromodibenzo [b, d] thiophene, Pd (PPh ₃ ) ₄ 395 mg (0.3 mmol), K 10 mL of ₂ CO ₃ (2M), 10 mL of EtOH, and 20 mL of toluene were added, followed by heating to 120 ° C. and stirring for 4 hours. After the reaction, the mixture was washed with distilled water, extracted with EA, dried over MgSO ₄ , dried over MgSO ₄ , solvent was removed on a rotary evaporator, and purified by column chromatography to obtain Compound 2 4.5g (88%).

1 H NMR (CDCl 3, 200 MHz) δ = 0.23 (1H, m), 5.93 (1H, m), 6.69 (2H, m), 6.98 (1H, m), 7.25 (1H, m), 7.33-7.38 (2H , m), 7.45-7.53 (20H, m), 7.69 (1H, m), 7.94-8.12 (5H, m), 8.2 (1H, m), 8.41-8.45 (2H, m), 8.55 (1H, m) ); MS / FAB found 822, calculated 821.02

Preparation Example 2 Preparation of Compound 4

compound 2-1 Manufacture

10 g (43.84 mmol) of 4-biphenylboronic acid, 8.85 g (43.84 mmol) of bromonitrobenzene, 70 mL of 2M Na ₂ CO ₃ aqueous solution, 200 mL of toluene and 70 mL of ethanol were mixed and stirred under reflux. After 5 hours, the mixture was cooled to room temperature, extracted with EA, and washed with distilled water. The organic layer was dried over MgSO ₄ , distilled under reduced pressure, and separated by column chromatography to obtain 10 g (32.74 mmol, 74.68%) of Compound 2-1 .

compound 2-2 Manufacture

10 g (32.74 mmol) of Compound 2-1 were mixed with 100 mL of triethyl phosphite and stirred at 150 ° C. for 7 hours. Cooled to room temperature and distilled under reduced pressure. Recrystallization from EA yielded Compound 2-2 7g (25.60 mmol, 78.19%).

compound 2-3 Manufacture

Compound 2-2 7g (25.60mmol), iodobenzene 10.44g (51.21mmol), CuI 2.5g (12.80mmol), K ₃ PO ₄ 16.30g (76.82mmol), toluene 200mL was added and heated to 50 ℃ and ethylenediamine 1.72 mL (25.60 mmol) was added and stirred under reflux for 12 hours. Cooled to room temperature, extracted with EA and washed with NaHCO ₃ aqueous solution. It was dried over magnesium sulfate and distilled under reduced pressure. Separated by column chromatography to give compound 2-3 to give a 8g (22.89mmol, 89.41%).

compound 2-4 Manufacture

Compound 2-3 was dissolved in 8 g (22.89 mmol), NBS 4.07 g (22.89 mmol), and 200 mL of chloroform, followed by stirring at room temperature for 12 hours. Distilled water was added and extracted with dichloromethane. Distillation under reduced pressure and recrystallization with EA yielded 8 g (18.67 mmol, 81.56%) of compound 2-4 .

compound 2-5 Manufacture

Compound 2-4 8 g (18.67 mmol), 4-aminobiphenyl 4.7 g (28.01 mmol), Pd (OAc) ₂ 0.209 g (0.933 mmol), P (t-bu) ₃ 0.92 mL (1.867 mmol, 50% in xylene), 15.21 g (46.69 mmol) of Cs ₂ CO ₃ , and 300 mL of toluene were mixed and stirred under reflux. After 12 hours, the mixture was cooled to room temperature, extracted with EA, and washed with distilled water. It was dried over magnesium sulfate and distilled under reduced pressure. Separation by column chromatography yielded 6 g (11.61 mmol, 62.18%) of compound 2-5 .

compound 2-6 Manufacture

10 g (43.84 mmol) of 4-dibenzothiophenboronic acid, 24.8 g (87.69 mmol) of 1-bromo-4-iodobenzene, PdCl ₂ (PPh ₃ ) ₄ 0.61 g (0.87 mmol), 2M Na ₂ CO ₃ 43 mL and 300 ml of toluene were mixed and stirred at 90 ° C. for 5 hours. Cooled to room temperature, extracted with EA and washed with distilled water. Drying with magnesium sulfate and separation by column chromatography yielded 5.2 g (15.53 mmol, 35.42%) of compound 2-6 .

compound 4 Manufacture

Compound 2-5 6 g (11.61 mmol), Compound 2-6 3.9 g (11.61 mmol), Pd (OAc) ₂ 0.13 g (0.58 mmol), P (t-bu) ₃ 0.52 ml (1.16 mmol, 50% in xylene ), NaOt-bu 2.79 g (29.03 mmol) and toluene 100 mL were mixed and stirred for 5 hours. Cooled to room temperature, extracted with EA and washed with distilled water. It was dried over magnesium sulfate and distilled under reduced pressure. Separation by column chromatography and recrystallization with EA yielded 4.2 g (5.42 mmol, 46.68%) of compound 4 .

1 H NMR (CDCl 3, 200 MHz) δ = 5.93 (1H, m), 6.69 (4H, m), 7.33 (1H, m), 7.41-7.51 (20H, m), 7.69 (1H, m), 7.98 (2H , m), 8.05 (1H, m), 8.2 (1H, m), 8.41-8.45 (3H, m); MS / FAB found 775, calculated 774.99

Preparation Example 3 Preparation of Compound 13

compound 3-1 Manufacture

15 g (0.074 mol) of 1-bromo-2-nitrobenzene was added to 1 L 2-neck-RBF, and 23 g (0.096 mol) of 9,9-dimethyl-9H-fluoren-2-ylboronic acid and Pd (PPh ₃ ) ₄ 4.2 g (0.003 mol), 111 mL of Na ₂ CO ₃ (2M), 111 mL of EtOH, and 200 mL of toluene were added, followed by heating to 120 ° C. and stirring for 3 hours. After the reaction, the mixture was washed with distilled water, extracted with EA, dried over MgSO ₄ , dried over MgSO ₄ , solvent was removed on a rotary evaporator, and purified by column to obtain compound 3-1 22g (95%).

compound 3-2 Manufacture

24 g (0.076 mol) of Compound 3-1 was added to 1 L two-ball-RBF, 200 mL of triethylphosphite and 200 mL of 1,2-dichlorobenzene were added, followed by heating to 140 ° C. Stir for 12 hours. After the reaction, the solvent was distilled off, washed with distilled water, extracted with EA, the organic layer was dried over MgSO ₄ , the solvent was removed with a rotary evaporator, and purified by column chromatography to obtain a compound 3-2 7g (33%).

compound 3-3 Manufacture

8.1 g (0.028 mol) of Compound 3-2 was added to 1 L two-ball-RBF, 300 mL of DMF was added thereto, and the mixture was stirred at 0 ° C. for 10 minutes. 5.08 g (0.028 mol) of NBS was added to 300 mL of DMF, and then slowly added to the reaction. Stir at 0 ° C. for 6 hours. Upon completion of the reaction, neutralize with distilled water and extract with ethyl acetate. The organic layer was dried over MgSO ₄ , and the solvent was removed using a rotary evaporator. Then, ethyl acetate was used as a developing solvent and purified by column chromatography to obtain compound 3-3 9g (87%).

compound 3-4 Manufacture

9 g (0.024 mol) of compound 3-3 was added to 3 L 2-gut-RBF, 6 g (0.029 mol) of iodobenzene, 123 mg (0.0005 mol) of Pd (OAc) ₂ , P (t-Bu) ₃ 50% 0.5 mL ( 0.002 mmol) and 4.7 g (0.049 mol) of NaOt-Bu are added to a vacuum and then placed in a nitrogen atmosphere. Add 200 mL of toluene and stir at 120 ° C. for 12 hours. Upon completion of the reaction, neutralize with distilled water and extract with ethyl acetate. The organic layer was dried over MgSO ₄ , the solvent was removed using a rotary evaporator, and ethyl acetate was used as a developing solvent to purify the mixture by column chromatography, obtaining 8 g (74%) of the compound 3-4 .

compound 3-5 Manufacture

Add 9 g (0.026 mol) of compound 2-6 to 500 mL 2-neck-RBF, add 2.9 g (0.032 mol) of aniline, 179 mg (0.0008 mol) of Pd (OAc) ₂ , P (t-Bu) ₃ 50% 1.7 mL (0.002 mmol) ), Cs ₂ CO ₃ 17.3g (0.053mol) and put in a vacuum to make a nitrogen atmosphere. Add 200 mL of toluene and stir at 120 ° C. for 4 hours. Upon completion of the reaction, neutralize with distilled water and extract with ethyl acetate. The organic layer was dried over MgSO ₄ , and the solvent was removed using a rotary evaporator. Then, ethyl acetate was used as a developing solvent and purified by column chromatography to obtain compound 3-5 (7 g, 75%).

compound 13 Manufacture

5 g (0.011 mol) of Compound 3-4 was added to 500 mL 2-neck-RBF, 4.8 g (0.013 mol) of Compound 3-5 , 127 mg (0.0005 mol) Pd (OAc) ₂ , P (t-Bu) ₃ 50% 0.76 Put mL (0.001mmol) and 3.2g (0.034mol) of Naot-Bu, make it in vacuum and make it into nitrogen atmosphere. Add 200 mL of toluene and stir at 120 ° C. for 4 hours. Upon completion of the reaction, neutralize with distilled water and extract with ethyl acetate. The organic layer was dried over MgSO ₄ , the solvent was removed using a rotary evaporator, and purified by column chromatography using ethyl acetate as a developing solvent to obtain compound 13 (5 g, 62%).

1 H NMR (CDCl 3, 200 MHz) δ = 1.72 (6H, s), 6.58 (1H, m), 6.69-6.75 (3H, m), 7.04 (1H, m), 7.28 (1H, m), 7.38-7.41 (2H, m), 7.5-7.53 (11H, m), 7.78-7.79 (3H, m), 7.87 (1H, m), 7.98 (1H, m), 8.07 (1H, m), 8.2 (1H, m) ), 8.41-8.49 (3H, m); MS / FAB found 709, calculated 708.91

Preparation Example 4 Preparation of Compound 17

compound 4-1 Manufacture

50 g (271.3 mmol) of dibenzothiophene was dissolved in 1000 mL of CHCl ₃ , and 30 mL (596.9 mmol) of Br ₂ was slowly added at 0 ° C. After stirring at room temperature for 12 hours, an aqueous sodium thiosulfate solution was added thereto. When the reaction solution turned yellow, the mixture was extracted with dichloromethane and the organic layer was neutralized with an aqueous KOH solution. The organic layer was dried over magnesium sulfate and distilled under reduced pressure. 74 g (216.3 mmol, 79.70%) of Compound 4-1 was obtained by recrystallization with EA and methanol.

compound 4-2 Manufacture

74 g (216.3 mmol) of Compound 4-1 were dissolved in THF, and 86.5 mL (216.3 mmol, 2.5 M in hexane) of n-buLi was slowly added at -78 ° C. After one hour 28.9 mL (259.6 mmol) of trimethylborate was added. After stirring for 12 hours at room temperature, distilled water was added. Extracted with EA and dried over magnesium sulfate. Distillation under reduced pressure and recrystallization with EA and hexane gave 40 g (136.8 mmol, 62.96%) of compound 4-2 .

compound 4-3 Manufacture

Compound 4-2 40g (136.8mmol), iodonitrobenzene 37.4g (150.5mmol), Pd (PPh ₃ ) ₄ 6.32g (5.47mmol), 2M Na ₂ CO ₃ 170mL, toluene was added and stirred for 4 hours at 100 ℃. . After cooling to room temperature, distilled water was added and extracted with EA. It was dried over magnesium sulfate and distilled under reduced pressure. Compound 4-3 28g (72.86mmol, 52.94%) was obtained by column chromatography.

compound 4-4 Manufacture

28 g (72.86 mmol) of Compound 4-3 were mixed with 300 mL of triethyl phosphite and stirred at 150 ° C. for 12 hours. Cooled to room temperature and distilled under reduced pressure. Extracted with EA and washed with distilled water. It was dried over magnesium sulfate and distilled under reduced pressure. Compound chromatography ( 4-4) 11g (31.22mmol, 43.05%) was obtained by column chromatography.

compound 4-5 Manufacture

Compound 4-4 11g (31.22mmol), iodobenzene 12.7g (62.45mmol), CuI 2.9g (15.61mmol), K ₃ PO ₄ 19.8g (93.68mmol), toluene 300mL was added and heated to 50 ℃ and ethylene diamond 2.1 mL (31.22 mmol) was added. Stirring at reflux for 12 hours. Cooled to room temperature, extracted with EA and washed with NaHCO ₃ aqueous solution. It was dried over magnesium sulfate and distilled under reduced pressure. Separation by column chromatography gave 12 g (28.01 mmol, 90.32%) of compound 4-5 .

compound 4-6 Manufacture

Compound 4-5 12 g (28.01 mmol), 9-aminoanthracene 8.1 g (42.02 mmol), Pd (OAc) ₂ 0.25 g (1.12 mmol), P (t-bu) ₃ 1.38 mL (2.80 mmol , 50% in xylene), 22.8 g (70.03 mmol) of Cs ₂ CO ₃ , and 500 mL of toluene were mixed and stirred under reflux. After 12 hours, the mixture was cooled to room temperature, extracted with EA, and washed with distilled water. Drying over magnesium sulfate and distillation under reduced pressure yielded 9 g (16.64 mmol, 59.42%) of compound 4-6 .

compound 17 Manufacture

Compound 4-6 7 g (12.94 mmol), Compound 2-6 5.2 g (15.53 mmol), Pd (OAc) ₂ 0.11 g (0.51 mmol), P (t-bu) ₃ 0.63 mL (1.29 mmol, 50% in xylene ), NaOt-bu 3.1 g (32.36 mmol) and toluene 100 mL were mixed and stirred for 5 hours. Cooled to room temperature, extracted with EA and washed with distilled water. It was dried over magnesium sulfate and distilled under reduced pressure. Separation by column chromatography and recrystallization with EA yielded Compound 17 (4 g, 5.00 mmol, 38.68%).

1 H NMR (CDCl 3, 200 MHz) δ = 6.69 (2H, m), 6.86-6.61 (2H, m), 7.29 (1H, m), 7.4-7.63 (13H, m), 7.73 (1H, m), 7.78 (1H, s), 7.82 (2H, m), 7.86 (1H, s), 7.88 (2H, m), 7.98 (1H, m), 8.12 (3H, m), 8.2 (1H, m), 8.41- 8.45 (2H, m), 8.93 (2H, m); MS / FAB found 800, calculated 799.01

Preparation Example 5 Preparation of Compound 19

compound 5-1 Manufacture

50 g (271.3 mmol) of dibenzofuran was dissolved in 1000 mL of CHCl ₃ , and 30 mL (596.9 mmol) of Br ₂ was slowly added at 0 ° C. After stirring for 12 hours at room temperature was added sodium thiosulfate aqueous solution. When the reaction solution turned yellow, the mixture was extracted with dichloromethane and the organic layer was neutralized with an aqueous KOH solution. The organic layer was dried over magnesium sulfate and distilled under reduced pressure. 74 g (216.3 mmol, 79.70%) of Compound 5-1 was obtained by recrystallization with EA and methanol.

compound 5-2 Manufacture

74 g (216.3 mmol) of Compound 5-1 were dissolved in THF, and 86.5 mL (216.3 mmol, 2.5 M in hexane) of n-buLi was slowly added at -78 ° C. After an hour, 28.9 mL (259.6 mmol) of trimethylborate was added. After stirring for 12 hours at room temperature, distilled water was added. Extracted with EA and dried over magnesium sulfate. Distillation under reduced pressure and recrystallization with EA and hexane gave Compound 5-2 40 g (136.8 mmol, 62.96%).

compound 5-3 Manufacture

Compound 5-2 40g (136.8mmol), iodonitrobenzene 37.4g (150.5mmol), Pd (PPh ₃ ) ₄ 6.32g (5.47mmol), 2M Na ₂ CO ₃ 170mL, toluene was added and stirred for 4 hours at 100 ℃. . After cooling to room temperature, distilled water was added and extracted with EA. It was dried over magnesium sulfate and distilled under reduced pressure. Compound 5-3 28g (72.86mmol, 52.94%) was obtained by column chromatography.

compound 5-4 Manufacture

28 g (72.86 mmol) of Compound 5-3 were mixed with 300 mL of triethyl phosphite and stirred at 150 ° C. for 12 hours. Cooled to room temperature and distilled under reduced pressure. Extracted with EA and washed with distilled water. It was dried over magnesium sulfate and distilled under reduced pressure. Column chromatography was performed to give compound 5-4 11g (31.22mmol, 43.05%).

compound 5-5 Manufacture

Compound 5-4 11g (31.22mmol), iodobenzene 12.7g (62.45mmol), CuI 2.9g (15.61mmol), K ₃ PO ₄ 19.8g (93.68mmol), toluene 300mL was added and heated to 50 ℃ and ethylenediamine 2.1 mL (31.22 mmol) was added. Stirring at reflux for 12 hours. Cooled to room temperature, extracted with EA and washed with NaHCO ₃ aqueous solution. It was dried over magnesium sulfate and distilled under reduced pressure. Column chromatography was performed to give compound 5-5 12g (28.01mmol, 90.32%).

compound 5-6 Manufacture

10 g (24.25 mmol) of Compound 5-5 , 9.47 g (36.36 mmol) of 4-aminonitrophenylamine, 0.21 g (0.97 mmol) of Pd (OAc) ₂ , 1.1 mL (2.42 mmol, 50%) of P (t-bu) ₃ in xylene), 19.75 g (60.63 mmol) of Cs ₂ CO ₃ , and 500 mL of toluene were mixed and stirred under reflux. After 12 hours, the mixture was cooled to room temperature, extracted with EA, and washed with distilled water. It was dried over magnesium sulfate and distilled under reduced pressure. Column chromatography was performed to give compound 5-6 8g (13.52mmol, 55.75%).

compound 19 Manufacture

Compound 5-6 7.6 g (12.94 mmol), Compound 2-6 5.2 g (15.53 mmol), Pd (OAc) ₂ 0.11 g (0.51 mmol), P (t-bu) ₃ 0.63 mL (1.29 mmol, 50% in xylene), NaOt-bu 3.1 g (32.36 mmol) and toluene 100 mL were mixed and stirred for 5 hours. Cooled to room temperature, extracted with EA and washed with distilled water. It was dried over magnesium sulfate and distilled under reduced pressure. Separation by column chromatography and recrystallization with EA yielded Compound 19 (5 g, 5.88 mmol, 45.45%).

1 H NMR (CDCl 3, 200 MHz) δ = 6.38 to 6.39 (5H, m), 6.63 (4H, m), 6.69 (2H, m), 6.81 (2H, m), 7.2 (4H, m), 7.29 (1H) , m), 7.41 (1H, m), 7.42 (1H, s), 7.45 (1H, m), 7.49 (1H, s), 7.5-7.75 (12H, m), 7.98 (1H, m), 8.12 ( 1H, m), 8.2 (1H, m), 8.41-8.45 (2H, m); MS / FAB found 851, calculated 850.04

Preparation Example 6 Preparation of Compound 25

compound 6-1 Manufacture

Mix 30 g (120.4 mmol) of 2-iodonitrobenzene, 26 g (132.5 mmol) of 4-bromophenylboronic acid, 6.9 g (6.02 mmol) of Pd (PPh ₃ ) ₄ , 150 mL of 2M Na ₂ CO ₃ , and mix with toluene. Heated to ° C. After 4 hours, the mixture was cooled to room temperature and extracted with EA. Washed with distilled water and dried over magnesium sulfate. Distillation under reduced pressure and separation by column chromatography yielded 28 g (100.68 mmol, 83,33%) of compound 6-1 .

compound 6-2 Manufacture

28 g (100.68 mmol) of Compound 6-1 were mixed with 300 mL of triethyl phosphite and stirred at 150 ° C. After 6 hours, the mixture was cooled to room temperature and distilled under reduced pressure. Extracted with EA and washed with distilled water. It was dried over magnesium sulfate and distilled under reduced pressure. Separation by column chromatography yielded 11 g (44.69 mmol, 44.38%) of Compound 6-2 .

compound 6-3 Manufacture

11 g (44.69 mmol) of compound 6-2 , 18.23 g (89.39 mmol) of iodobenzene, 4.25 g (22.34 mmol) of CuI, 28.4 g (134.09 mmol) of K ₃ PO ₄ , and 200 mL of toluene were mixed and heated to 50 ° C. 3.01 mL (44.69 mmol) of ethylenediamine was added thereto, and the mixture was stirred under reflux. After 14 hours, cooled to room temperature and distilled water was added. Extracted with EA and dried over magnesium sulfate. Distillation under reduced pressure and separation by column chromatography yielded 12 g (37.24 mmol, 83.32%) of compound 6-3 .

compound 6-4 Manufacture

20 g (62.07 mmol) of Compound 6-3 was dissolved in THF, and 29.79 mL (74.48 mmol, 2.5 M in Hexne) of n-buLi was slowly added at -78 ° C. After one hour, 10.38 mL (93.10 mmol) of trimethylborate was added. After stirring at room temperature for 12 hours, distilled water was added. Extracted with EA and dried over magnesium sulfate. Distillation under reduced pressure and recrystallization from EA and hexane. 12 g (41.79 mmol, 67.32%) of Compound 6-4 were obtained.

compound 6-5 Manufacture

Compound 6-4 12 g (41.79 mmol), methyl-2,5-dibromobenzoate 13.51 g (45.97 mmol), Pd (PPh ₃ ) ₄ 1.9 g (1.67 mmol), ₂ M Na ₂ CO ₃ 60 mL, toluene 200 mL Mix and stir at reflux. After 12 hours, the mixture was cooled to room temperature and distilled water was added. Extracted with EA and dried over magnesium sulfate. Distillation under reduced pressure and separation by column chromatography yielded 8 g (17.53 mmol, 41.95%) of compound 6-5 .

compound 6-6 Manufacture

8 g (17.53 mmol) of Compound 6-5 was dissolved in THF, and 14.60 mL (43.82 mmol, 3.0 M in diethyl ether) of methylmagnesium bromide was added thereto. Heated to 60 ℃ and cooled to room temperature after 6 hours. Distilled water was added and extracted with EA. It was dried over magnesium sulfate and distilled under reduced pressure. Compound 6-6 (g. 13.14 mmol, 74.95%) was obtained by column chromatography.

compound 6-7 Manufacture

6 g (13.14 mmol) of compound 6-6 , acetic acid 50mL and phosphoric acid 50mL were mixed and stirred at 50 ° C for 5 hours. Cooled to room temperature and neutralized with aqueous NaOH solution. Extracted with EA and dried over magnesium sulfate. After distillation under reduced pressure, the residue was separated by column chromatography to obtain 4.6 g (10.49 mmol, 79.83%) of Compound 6-7 .

compound 6-8 Manufacture

Compound 6-7 4.6 g (10.49 mmol), 4.09 g (15.74 mmol) 4-aminotriphenylamine, 0.11 g (0.52 mmol) Pd (OAc) ₂ , 0.51 mL (1.04 mmol, 50) P (t-bu) ₃ % in xylene), 8.54 g (26.23 mmol) Cs ₂ CO ₃ , and 100 mL of toluene were mixed and stirred under reflux. After 12 hours, the mixture was cooled to room temperature, extracted with EA, and washed with distilled water. It was dried over magnesium sulfate and distilled under reduced pressure. Separation by column chromatography afforded 4 g (6.47 mmol, 61.67%) of Compound 6-8 .

compound 25 Manufacture

Compound 6-8 4 g (6.47 mmol), Compound 2-6 2.63 g (7.76 mmol), Pd (OAc) ₂ 0.058 g (0.25 mmol), P (t-bu) ₃ 0.31 mL (0.64 mmol, 50% in xylene ), NaOt-bu 1.55 g (16.18 mmol) and toluene 70 mL were mixed and stirred for 5 hours. Cooled to room temperature, extracted with EA and washed with distilled water. It was dried over magnesium sulfate and distilled under reduced pressure. Separation by column chromatography and recrystallization with EA yielded 3.0 g (3.42 mmol, 52.92%) of compound 25 .

1 H NMR (CDCl 3, 200 MHz) δ = 1.72 (6H, s), 6.38 (4H, m), 6.63-6.69 (7H, m), 6.81 (3H, m), 7.2-7.25 (5H, m), 7.33 (1H, m), 7.45-7.58 (10H, m), 7.71 (1H, m), 7.84 (1H, m), 7.94-8 (3H, m), 8.2 (1H, m), 8.41-8.45 (2H m), 8.55 (1 H, m); MS / FAB found 877, calculated 876.12

Preparation Example 7 Preparation of Compound 28

compound 7-1 Manufacture

Compound 2,5-Dibromonitrobenzene 50g (177.99mol), 1-naphthaleneboronic acid 36.7g (213.59mmol), Pd (PPh ₃ ) ₄ 10.28g (8.89mmol), 2M Na ₂ CO ₃ 533.97 mmol) 700 mL of toluene and 200 mL of ethanol were mixed and stirred at 100 ° C. for 5 hours. Cooled to room temperature and distilled water was added. Extracted with EA and dried over magnesium sulfate. Distillation under reduced pressure and separation by column chromatography yielded 50 g (152.36 mmol, 85.60%) of Compound 7-1 .

compound 7-2 Manufacture

50 g (152.36 mmol) of Compound 7-1 and 500 mL of triethyl phosphite were mixed and stirred at 150 ° C. for 7 hours. Cooled to room temperature and distilled under reduced pressure. Extracted with EA and washed with distilled water. It was dried over magnesium sulfate and distilled under reduced pressure. Compound 7-2 30g (101.29mmol, 66.64%) was obtained by column chromatography.

compound 7-3 Manufacture

30 g (101.29 mmol) of Compound 7-2 , 41.3 g (202.59 mmol) of iodobenzene, 9.6 g (50.64 mmol) of CuI, 82.5 g (253.2 mmol) of Cs ₂ CO ₃ , and 600 mL of toluene were mixed and heated to 50 ° C. 6.8 mL (101.29 mmol) of ethylenediamine was added thereto, and the mixture was stirred under reflux. After 14 hours, cooled to room temperature and distilled water was added. Extracted with EA and dried over magnesium sulfate. Distillation under reduced pressure and separation by column chromatography gave 32 g (85.96 mmol, 84.86%) of compound 7-3 .

compound 7-4 Manufacture

32 g (85.96 mmol) of Compound 7-3 was dissolved in 300 mL of THF, and 37.8 mL (94.55 mmol, 2.5 M in hexane) of n-buLi was slowly added at -78 ° C. After 1 hour trimethyl borate 12.4 mL (111.7 mmol) was added. After stirring for 12 hours at room temperature, distilled water was added. Extracted with EA and dried over magnesium sulfate. Distillation under reduced pressure and separation by column chromatography yielded 20 g (59.31 mmol, 69.00%) of compound 7-4 .

compound 7-5 Manufacture

Compound 7-4 20g (59.31mmol), bromonitrobenzene 14.3g (71.17mmol), Pd (PPh ₃ ) ₄ 2.7g (2.37mmol), 2M Na ₂ CO ₃ 75mL, toluene 300mL, ethanol 70mL and stirred under reflux It was. After 5 hours, cooled to room temperature and distilled water was added. Extracted with EA and dried over magnesium sulfate. Distillation under reduced pressure and separation by column chromatography yielded 20 g (48.25 mmol, 81.36%) of compound 7-5 .

compound 7-6 Manufacture

20 g (48.25 mmol) of Compound 7-5 were mixed with 200 mL of triethylphosphite and stirred at 150 ° C. for 6 hours. Cooled to room temperature and distilled under reduced pressure. Extracted with EA and washed with distilled water. It was dried over magnesium sulfate and distilled under reduced pressure. Compound 7-6 (7.30 mmol, 37.93%) was obtained by column chromatography.

compound 7-7 Manufacture

Compound 7-6 7 g (18.30 mmol), 7.46 g (36.60 mmol) iodobenzene, 1.7 g (9.15 mmol) CuI, 11.6 g (54.90 mmol) K ₃ PO ₄ , and 100 mL of toluene were mixed and heated to 50 ° C. 1.2 mL (18.30 mmol) of ethylenediamine was added thereto, and the mixture was stirred under reflux. After 14 hours, cooled to room temperature and distilled water was added. Extracted with EA and dried over magnesium sulfate. Distillation under reduced pressure and separation by column chromatography yielded 8 g (17.44 mmol, 95.33%) of compound 7-7 .

compound 7-8 Manufacture

8 g (17.44 mmol) of Compound 7-7 and 3.1 g (17.44 mmol) of NBS were dissolved in 200 mL of CHCl ₃ , and the mixture was stirred at room temperature for 10 hours. Distilled water was added and extracted with dichloromethane. It was dried over magnesium sulfate and distilled under reduced pressure. Column chromatography was performed to give compound 7-8 8g (14.88mmol, 85.35%).

compound 7-9 Manufacture

Compound 7-8 8 g (14.88 mmol), 1-aminonaphthalene 3.19 g (22.32 mmol), Pd (OAc) ₂ 0.16 g (0.74 mmol), P (t-bu) ₃ 0.73 mL (1.48 mmol, 50% in xylene ), Cs ₂ CO ₃ 14.54 g (44.65 mmol) and toluene 100 mL were mixed and stirred under reflux. After 12 hours, the mixture was cooled to room temperature, extracted with EA, and washed with distilled water. It was dried over magnesium sulfate and distilled under reduced pressure. Separation by column chromatography yielded 7 g (11.67 mmol, 78.44%) of compound 7-9 .

compound 28 Manufacture

Compound 7-9 7 g (11.67 mmol), Compound 2-6 4.75 g (14.00 mmol), Pd (OAc) ₂ 0.13 g (0.25 mmol), P (t-bu) ₃ 0.57 mL (1.16 mmol, 50% in xylene ), NaOt-bu 2.8 g (29.18 mmol) and toluene 100 mL were mixed and stirred for 5 hours. Cooled to room temperature, extracted with EA and washed with distilled water. It was dried over magnesium sulfate and distilled under reduced pressure. Separation by column chromatography and recrystallization with EA yielded 4.0 g (4.66 mmol, 39.94%) of compound 28 .

1 H NMR (CDCl 3, 200 MHz) δ = 5.93 (1H, m), 6.69 (2H, m), 6.98 (1H, m), 7.38 (1H, m), 7.45 (2H, m), 7.5 (5H, m ), 7.52-7.57 (16H, m), 7.94-8.02 (8H, m), 8.41-8.45 (2H, m), 8.54 (1H, m); MS / FAB found 859, calculated 858.06

Preparation Example 8 Preparation of Compound 32

compound 8-1 Manufacture

10.2 g (59.4 mmol) of 1-naphthaleneboronic acid, 10.0 g (49.5 mmol) of 1-bromo-2-nitrobenzene, 1.7 g (1.4 mmol) of Pd (PPh ₃ ) ₄ , 2M K ₂ CO ₃ 70 mL of aqueous solution, 200 mL of toluene and 100 mL of ethanol were added thereto, and the mixture was stirred under reflux for 12 hours. The residue was washed with distilled water, extracted with EA, dried over anhydrous MgSO ₄ , and distilled under reduced pressure. The residue was separated by column chromatography to obtain 9.0 (73.7%) of Compound 8-1 .

compound 8-2 Manufacture

9.0 g (36.1 mmol) of Compound 8-1 and 7.6 g (43.3 mmol) of N-bromosuccinimide were dissolved in 300 mL of dichloromethane and stirred at room temperature for 12 hours. After distillation under reduced pressure, the obtained solid was washed sequentially with distilled water, methanol and hexane to obtain 9.6 g (81.3%) of Compound 8-2 .

compound 8-3 Manufacture

9.6 g (29.3 mmol) of Compound 8-2 and 72.2 g (175.5 mmol) of iron oxalate dihydrate (FeC ₂ O ₄ 2H ₂ O) were mixed, heated to 205 ° C. for 30 minutes, cooled to room temperature, extracted with EA, and washed with distilled water. It was. Recrystallization from toluene gave 5.2 g (60.5%) of compound 8-3 .

compound  8-4 Manufacture

Compound 8-3 5.2 g (17.6 mmol), 0.6 g (8.8 mmol) copper, 0.2 g (0.9 mmol) 18-crown-6, 4.8 g (35.1 mmol) K ₂ CO ₃ and 100 mL 1,2-dichlorobenzene The mixture was stirred and refluxed at 180 ° C. for 12 hours. After cooling to room temperature and distillation under reduced pressure, the mixture was extracted with MC and washed with distilled water. The residue obtained by drying over anhydrous MgSO ₄ and distillation under reduced pressure was separated by column chromatography to obtain 5.0 g (76.5%) of Compound 8-4 .

compound 8-5 Manufacture

23.1 g (62.07 mmol) of Compound 8-4 was dissolved in THF, and 29.79 mL (74.48 mmol, 2.5 M in Hexne) of n-buLi was slowly added at -78 ° C. After one hour, 10.38 mL (93.10 mmol) of trimethylborate was added. After stirring at room temperature for 12 hours, distilled water was added. Extracted with EA and dried over magnesium sulfate. Distillation under reduced pressure and recrystallization from EA and hexane. 14g (67%) of compound 8-5 was obtained.

compound 8-6 Manufacture

14 g (41.79 mmol) of compound 8-5 , 13.51 g (45.97 mmol) of methyl-2,5-dibromobenzoate, 1.9 g (1.67 mmol) of Pd (PPh ₃ ) ₄ , 60 mL of 2M Na ₂ CO ₃ , and 200 mL of toluene Mix and stir at reflux. After 12 hours, the mixture was cooled to room temperature and distilled water was added. Extracted with EA and dried over magnesium sulfate. Distillation under reduced pressure and separation by column chromatography yielded 8.8 g (42%) of the compound 8-6 .

compound 8-7 Manufacture

8.8 g (17.53 mmol) of Compound 8-6 was dissolved in THF, and 14.60 mL (43.82 mmol, 3.0 M in diethyl ether) of methylmagnesium bromide was added thereto. Heated to 60 ℃ and cooled to room temperature after 6 hours. Distilled water was added and extracted with EA. It was dried over magnesium sulfate and distilled under reduced pressure. Separation by column chromatography yielded 6.6 g (74%) of Compound 8-7 .

compound 8-8 Manufacture

6.6 g (13.14 mmol) of the compound 8-7 , 50 mL of acetic acid and 50 mL of phosphoric acid were mixed and stirred at 50 ° C for 5 hours. Cooled to room temperature and neutralized with aqueous NaOH solution. Extracted with EA and dried over magnesium sulfate. After distillation under reduced pressure, the residue was separated by column chromatography to obtain 5.1 g (80%) of the compound 8-8 .

compound 8-9 Manufacture

Compound 8-8 5.1 g (10.49 mmol), aniline 1.5 g (15.74 mmol), Pd (OAc) ₂ 0.11 g (0.52 mmol), P (t-bu) ₃ 0.51 mL (1.04 mmol, 50% in xylene), Cs ₂ CO ₃ 8.54 g (26.23 mmol) and 100 mL of toluene were mixed and stirred under reflux. After 12 hours, the mixture was cooled to room temperature, extracted with EA, and washed with distilled water. It was dried over magnesium sulfate and distilled under reduced pressure. 3.2 g (62%) of Compound 8-9 was obtained by column chromatography.

compound 32 Manufacture

Compound 8-9 3.2 g (6.47 mmol), Compound 2-6 2.63 g (7.76 mmol), Pd (OAc) ₂ 0.058 g (0.25 mmol), P (t-bu) ₃ 0.31 mL (0.64 mmol, 50% in xylene), NaOt-bu 1.55 g (16.18 mmol) and toluene 70 mL were mixed and stirred for 5 hours. Cooled to room temperature, extracted with EA and washed with distilled water. It was dried over magnesium sulfate and distilled under reduced pressure. Column chromatography was isolated and recrystallized with EA to give compound 32 2.6g (53%).

1 H NMR (CDCl 3, 200 MHz) δ = 1.78 (6H, s), 6.63-6.69 (5H, m), 6.81 (2H, m), 7.2-7.25 (3H, m), 7.33 (1H, m), 7.45 ~ 7.58 (12H, m), 7.84 (1H, m), 7.94-7.98 (2H, m), 8.2 (1H, m), 8.41-8.45 (2H, m), 8.55 (3H, m); MS / FAB found 759, calculated 758.97

Preparation Example 9 Preparation of Compound 36

compound 9-1 Manufacture

Compound 6-3 12 g (37.42 mmol), 2- (methylthio) phenylboronic acid 7.5 g (44.69 mmol), Pd (PPh ₃ ) ₄ 2.15 g (1.6 mmol), 45 mL of 2M Na ₂ CO ₃ aqueous solution and 200 mL of THF were mixed and stirred under reflux. After 5 hours, the mixture was cooled to room temperature, extracted with EA, and washed with distilled water. It was dried over magnesium sulfate and distilled under reduced pressure. Separation by column chromatography gave 10 g (27.36 mmol, 73.47%) of compound 9-1 .

compound 9-2 Manufacture

10 g (27.36 mmol) of Compound 9-1 was placed in 100 mL of acetic acid, and 2.65 mL (30.09 mmol, 35%) of H ₂ O ₂ was slowly added thereto. After stirring for 12 hours at room temperature, acetic acid was distilled under reduced pressure. Extracted with dichloromethane and neutralized with NaHCO ₃ aqueous solution. It was dried over magnesium sulfate and distilled under reduced pressure. 10g (26.21 mmol, 95.79%) of Compound 9-2 was obtained.

compound 9-3 Manufacture

10 g (26.21 mmol) of Compound 9-2 were mixed with 70 mL of trifluoromethanesulphonic acid and stirred at 100 ° C. After 5 hours, the mixture was cooled to room temperature, which was added to pyridine: distilled water = 1: 5 100 mL. It was stirred at reflux for 1 hour. Cooled to room temperature and the resulting solid was filtered under reduced pressure. Separation by column chromatography yielded 6 g (17.16 mmol, 65.47%) of compound 9-3 .

compound 9-4 Manufacture

6 g (17.16 mmol) of Compound 9-3 and 3.36 g (18.88 mmol) of NBS were dissolved in 200 mL of CHCl ₃ , and the mixture was stirred at room temperature for 12 hours. Distillation under reduced pressure and separation by column chromatography yielded 7 g (16.34 mmol, 95.22%) of compound 9-4 .

compound 9-5 Manufacture

Compound 9-4 7 g (16.34 mmol), aniline 2.28 g (24.51 mmol), Pd (OAc) ₂ 0.14 g (0.65 mmol), P (t-bu) ₃ 0.80 mL (1.63 mmol, 50% in xylene), Cs 13.31 g (40.85 mmol) of ₂ CO ₃ and 100 mL of toluene were mixed and stirred under reflux. After 12 hours, the mixture was cooled to room temperature, extracted with EA, and washed with distilled water. It was dried over magnesium sulfate and distilled under reduced pressure. Separation by column chromatography afforded 5 g of compound 9-5 (11.34 mmol, 69.40%).

compound 9-6 Manufacture

10 g (43.84 mmol) of 4-dibenzothiophenboronic acid, 27.3 g (87.69 mmol) of 4,4'-dibromophenyl, PdCl ₂ (PPh ₃ ) ₄ 0.61 g (0.87 mmol), 2M Na ₂ CO ₃ 43 mL Toluene 300mL was mixed and stirred at 90 degreeC for 5 hours. Cooled to room temperature, extracted with EA and washed with distilled water. Drying with magnesium sulfate and separation by column chromatography yielded 5.6 g (13.61 mmol, 31.04%) of compound 9-6 .

compound 36 Manufacture

5 g (11.34 mmol) of compound 9-5, 5.6 g (13.61 mmol) of compound 9-6 , 0.10 g (0.45 mmol) of Pd (OAc) ₂ , 0.56 mL (1.13 mmol, 50% in xylene) P (t-bu) 3 ), NaOt-bu 2.7 g (28.37 mmol) and toluene 100 mL were mixed and stirred for 5 hours. Cooled to room temperature, extracted with EA and washed with distilled water. It was dried over magnesium sulfate and distilled under reduced pressure. Isolation by column chromatography and recrystallization with EA yielded 3.6 g (4.64 mmol, 40.96%) of compound 36 .

1 H NMR (CDCl3, 200 MHz) δ = 5.93 (1H, m), 6.63 (2H, m), 6.69 (2H, m), 6.81 (1H, m), 7.2-7.45 (6H, m), 7.45-7.63 (14H, m), 7.69 (1H, m), 7.98 (2H, m), 8.05 (1H, m), 8.2 (1H, m), 8.41-8.45 (3H, m); MS / FAB found 775, calculated 774.99

Preparation Example 10 Preparation of Compound 48

compound 10-1 Manufacture

7.7g (0.015mol) of compound 2-5 was added to 1L 2-neck-RBF, and 6.6g (0.023mol) of 1-bromo-4-iodobenzene, 175mg (0.7mmol) of Pd (oAc) 2, P (t- Bu) 3 508mg (1.56mmol) and Naot-Bu 4.5g (0.046mol) are put in vacuum and filled with nitrogen gas. 200 mL of toluene is added and then heated to 120 ° C. Stir for 12 hours. After the reaction, the mixture was washed with distilled water, extracted with EA, dried over MgSO ₄ , dried over MgSO ₄ , solvent was removed by rotary evaporation, and purified by column chromatography to obtain 6.2 g (62%) of Compound 10-1 .

compound 10-2 Manufacture

6.8 g (0.010 mol) of Compound 10-1 was added to 500 mL RBF, followed by vacuum drying. 100 mL of THF is added and then cooled to -78 ° C. 6.2 mL (0.015 mol) of n-BuLi (2,5M) is slowly added, followed by stirring at low temperature for 1 hour. 1.7 mL (0.015 mmol) of B (OMe) ₃ was added at -78 ° C, followed by stirring for 12 hours. After the reaction was completed 10 minutes later, washed with 1M HCl was added to distilled water after purifying the organic layer was back extracted with EA by column chromatography after removal of solvent on a rotary evaporator then dried with MgSO ₄ and compound 10-2 4.3g (67 %) Was obtained.

compound  48 Manufacture

4.4 g (7.0 mmol) of Compound 10-2 was added to 100 mL 2-neck-RBF, and 5.2 g (8.0 mmol) of _4- bromodibenzo [b, d] thiophene, Pd (PPh ₃ ) ₄ 395 mg (0.3 mmol), K 10 mL of ₂ CO ₃ (2M) and 10 mL of EtOH are added thereto, and 20 mL of toluene is added thereto, followed by heating to 120 ° C. Stir for 4 hours. After the reaction was washed with distilled water, extracted with EA, the organic layer was dried with MgSO ₄ and the solvent was removed by rotary evaporation to purified by column chromatography to give the compound 48 2.9g (54%).

1 H NMR (CDCl 3, 200 MHz) δ = 5.93 (1H, m), 6.69 (4H, m), 7.33 (1H, m), 7.41 (1H, m), 7.45-7.52 (19H, m), 7.69 (1H , m), 7.82 (1H, m), 7.94-7.98 (3H, m), 8.05 (1H, m), 8.45 (2H, m); MS / FAB found 775, calculated 774.99

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

An OLED device having a structure using the light emitting material of the present invention was produced. First, a transparent electrode ITO thin film (15? It was used after. Next, the ITO substrate is installed in the substrate folder of the vacuum deposition equipment, and 2-TNATA [4,4 ', 4 "-tris (N, N- (2-naphthyl) -phenylamino) triphenylamine] is installed in the cell in the vacuum deposition equipment. And evacuated until the vacuum in the chamber reached 10 ⁻⁶ torr, followed by applying a current to the cell to evaporate 2-TNATA to deposit a 60 nm thick hole injection layer on the ITO substrate. Compounds according to the invention in other cells in deposition equipment 4 was added, a current was applied to the cell, and compound 1 was evaporated to deposit a 20 nm thick hole transport layer on the hole injection layer. After the hole injection layer and the hole transport layer were formed, the light emitting layer was deposited thereon as follows. CBP [4,4'-N, N'-dicarbazole-biphenyl] is added as a host to one cell in the vacuum deposition equipment and (piq) ₂ Ir (acac) [bis- (1-phenylisoquinolyl) as a dopant in another cell. ) iridium (III) acetylacetonate] was added, and the light emitting layer having a thickness of 30 nm was deposited on the hole transport layer by evaporating the two materials at different rates and doping at 4 to 10% by weight. Subsequently, bis (2-methyl-8-quinolinate) ( p -phenylphenolrato) aluminum (III) (BAlq) was deposited to a thickness of 10 nm on the light emitting layer with a hole blocking layer, followed by Alq [ tris (8-hydroxyquinoline)-

aluminum (III)] was deposited to a thickness of 20 nm. Next, Alq [tris (8-hydroxyquinoline) -aluminum (III)] was deposited to a thickness of 20 nm as an electron transport layer, and then Liq [lithium quinolate] was deposited to a thickness of 1 to 2 nm using an electron injection layer. An OLED was fabricated by depositing an Al cathode to a thickness of 150 nm using a vacuum deposition equipment.

Each compound was vacuum sublimated and purified under 10 ^-6 torr to be used as an OLED light emitting material.

As a result, a current of 16.1 mA / cm ² flowed at a voltage of 7.0 V, and red light emission of 1200 cd / m ² was confirmed.

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

An OLED device was manufactured in the same manner as in Example 1, except that Compound 13 of the present invention was used as a hole transport material.

As a result, a current of 17.1 mA / cm ² flowed at a voltage of 7.3 V, and red light emission of 1260 cd / m ² was confirmed.

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

OLED device in the same manner as in Example 1, except that Compound 30 of the present invention was used as a hole transport material, and an organic iridium complex Ir (ppy) ₃ [tris (2-phenylpyridine) iridium] was used as a light emitting dopant in the light emitting layer. Was produced.

As a result, a current of 3.2 mA / cm ² flowed at a voltage of 7.1 V, and green light emission of 1015 cd / m ² was confirmed.

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

An OLED device was manufactured in the same manner as in Example 3, except that Compound 37 of the present invention was used as the hole transport material.

As a result, a current of 3.9 mA / cm ² flowed at a voltage of 7.0 V, and green light emission of 1115 cd / m ² was confirmed.

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

2-TNATA [4,4 ', 4 "-tris (N, N- (2-naphthyl) -phenylamino) as hole injection material

triphenylamine] was manufactured in the same manner as in Example 1 except that Compound 25 of the present invention was used.

As a result, a current of 15.9 mA / cm ² flowed at a voltage of 7.2 V, and red light emission of 1095 cd / m ² was confirmed.

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

2-TNATA [4,4 ', 4 "-tris (N, N- (2-naphthyl) -phenylamino) as hole injection material

triphenylamine] was manufactured in the same manner as in Example 3, except that Compound 42 of the present invention was used.

As a result, a current of 3.0 mA / cm ² flowed at a voltage of 6.6 V, and green light emission of 990 cd / m ² was confirmed.

[Comparative Example 1] Light emission characteristics of OLED device using conventional light emitting material

Except for using NPB [N, N'-bis (α-naphthyl) -N, N'-diphenyl-4,4'-diamine] as a hole transporting material in one cell in the vacuum deposition equipment An OLED device was manufactured in the same manner as in Example 1 .

As a result, a current of 15.3 mA / cm ² flowed at a voltage of 7.5 V, and red light emission of 1000 cd / m ² was confirmed.

Comparative Example 2 Light Emitting Characteristics of OLED Devices Using Conventional Light-Emitting Materials

, Except that the - [ 'N, N -bis ( α-naphthyl)'-diphenyl-4,4'-diamine N, N] to the one cell of the vacuum vapor-deposit device as a hole-transporting material NPB instead of the compound of the invention An OLED device was manufactured in the same manner as in Example 3 .

As a result, a current of 3.8 mA / cm ² flowed at a voltage of 7.5 V, and green light emission of 1000 cd / m ² was confirmed.

The organic light emitting compounds developed in the present invention was confirmed that the light emitting properties are superior to the conventional material. In addition, the organic light emitting device using the organic light emitting compound according to the present invention as a hole transporting material or a hole injection material has the lowest unoccupied molecular orbital function (LUMO; Lowest Unoccupied Molecular Orbital), the triplet (triplet) to increase the light emitting layer By effectively blocking the triplet excitons present in the light emitting layer to effectively block the light emitting layer, the light emitting efficiency is excellent in phosphorescence, and the lifespan characteristics of the material are excellent. have.

Claims (10)

An organic light emitting compound represented by Formula 1 below.
[Formula 1]

[In the above formula (1)
Y ₁ is —O—, —S—, —C (R ₁₁ R ₁₂ ) — or —Si (R ₁₃ R ₁₄ ) —;
Y ₂ is —O—, —S—, —C (R ₁₁ R ₁₂ ) —, —Si (R ₁₃ R ₁₄ ) — or —N (R ₁₅ );
Ring A and Ring C are each independently

Is;
B ring

ego;
Y ₃ and Y ₄ are each independently CH or N;
Y ₅ and Y ₆ are each independently a chemical bond, —O—, —S—, —C (R ₁₁ R ₁₂ ) —, —Si (R ₁₃ R ₁₄ ) — or —N (R ₁₅ ) — Unless Y ₅ and Y ₆ are chemical bonds at the same time;
R ₁ to R ₄ are each independently hydrogen, deuterium, halogen, substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl, substituted or unsubstituted (C3-C30) hetero Aryl, substituted or unsubstituted (C3-C30) cycloalkyl, substituted or unsubstituted (C1-C30) alkylsilyl group, substituted or unsubstituted 5- to 7-membered heterocycloalkyl, substituted or unsubstituted ( C6-C30) Ar (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl, fused with one or more cycloalkyl, 5- to 7-membered hetero, fused with one or more substituted or unsubstituted aromatic rings (C3-C30) cycloalkyl which is cycloalkyl or has one or more substituted or unsubstituted aromatic rings, -N (R ₁₆ R ₁₇ ), -Si (R ₁₈ R ₁₉ R ₂₀ ), -SR ₂₁ , -OR _{22 ,} Cyano, nitro or hydroxy, and when there are a plurality of R ₁ to R ₄ , may combine with each other to form a cyclic structure;
L ₁ and L ₂ are each independently a chemical bond, a substituted or unsubstituted (C6-C30) arylene, a substituted or unsubstituted (C3-C30) heteroarylene or a substituted or unsubstituted (C3-C30) cyclo Alkylene, adjacent L ₁ and L ₂ may be bonded to each other to form a cyclic structure, except that L ₁ and L ₂ are at the same time a chemical bond;
Ar is substituted or unsubstituted (C6-C30) aryl, substituted or unsubstituted (C3-C30) heteroaryl, substituted or unsubstituted (C6-C30) aryl in which at least one cycloalkyl is fused;
R ₁₁ to R ₂₂ are each independently hydrogen, deuterium, halogen, substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl, substituted or unsubstituted (C3-C30) hetero Aryl, substituted or unsubstituted 5- to 7-membered heterocycloalkyl, substituted or unsubstituted (C3-C30) cycloalkyl or substituted or unsubstituted (C3-C30) with or without fused ring with adjacent substituents Alkylene or substituted or unsubstituted (C3-C30) alkenylene to form an alicyclic ring and a monocyclic or polycyclic aromatic ring, and the alicyclic ring and the monocyclic or polycyclic aromatic ring The carbon atom may be substituted with one or more heteroatoms selected from nitrogen, oxygen and sulfur;
l, m, n and p are each independently integers of 0 to 4, and when l, m, n or p is an integer of 2 or more, each of R ₁ , R ₂ , R ₃ and R ₄ may be the same or different from each other. Adjacent substituents may combine with each other to form a ring;
Wherein said heterocycloalkyl and heteroaryl include one or more heteroatoms selected from B, N, O, S, P (= 0), Si and P.] The method of claim 1,
Substituents further substituted with R ₁ to R ₄ , R ₁₁ to R ₂₂ , L ₁ , L _2, and Ar independently of each other, deuterium, halogen, (C1-C30) alkyl substituted or unsubstituted, (C6- C30) aryl, (C6-C30) aryl substituted or unsubstituted (C3-C30) heteroaryl, 5- to 7-membered heterocycloalkyl, 5- to 7-membered heterocycloalkyl fused with one or more aromatic rings , (C3-C30) cycloalkyl, (C6-C30) cycloalkyl fused with one or more aromatic rings, R ₃₁ R ₃₂ R ₃₃ Si-, (C2-C30) alkenyl, (C2-C30) alkynyl, cya No, carbazolyl, -NR ₃₄ R ₃₅ , (C6-C30) ar (C1-C30) alkyl, (C1-C30) alkyl (C6-C30) aryl, R ₃₆ S-, R ₃₇ O-, nitro or At least one selected from the group consisting of hydroxy, and R ₃₁ to R ₃₇ independently of one another are (C 1 -C 30) alkyl, (C 6 -C 30) aryl, (C 3 -C 30) heteroaryl, or (C 3 -C 30) cyclo An organic light emitting compound, characterized in that alkyl. The method of claim 1,
Of Formula 1

Is an organic light emitting compound, characterized in that selected from the following structure.

[R ₃ , R ₄ , R ₁₁ to R ₁₅ , l and p are the same as defined in Formula 1 above.] The method of claim 1,
An organic light emitting compound, which is selected from the following compounds.

An organic electroluminescent device comprising the organic light emitting compound according to any one of claims 1 to 4. 6. The method of claim 5,
The organic light emitting device is an organic electroluminescent device, characterized in that used as a hole injection or hole transport material. The method of claim 6,
The organic electroluminescent device 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 comprises at least one organic light emitting compound of Chemical Formula 1. The method of claim 7, wherein
An organic electric field further comprising at least one metal or a complex compound selected from the group consisting of Group 1, Group 2, 4, 5 cycle transition metals, lanthanum series metals and organic metals of d-transition elements in the organic layer. Light emitting element. The method of claim 7, wherein
The organic material layer is an organic electroluminescent device comprising a light emitting layer and a charge generating layer at the same time. The method of claim 7, wherein
An organic electroluminescent device for emitting white light, further comprising at least one organic light emitting layer emitting red, green, or blue light to the organic material layer.