KR101996647B1 - New condensed aryl compounds and organic light-emitting diode including the same - Google Patents

Abstract

The present invention relates to a novel condensed aryl compound and an organic electroluminescent device comprising the same as a light emitting material, and more particularly to a novel compound represented by the following formula (1) and an organic electroluminescent device comprising the same. The organic electroluminescent device comprising the luminescent compound of the following formula (1) according to the present invention has an excellent effect on the luminescent characteristics such as the driving voltage and the current efficiency.

Description

TECHNICAL FIELD The present invention relates to a novel condensed aryl compound and an organic electroluminescent device including the same.

The present invention relates to a novel condensed aryl compound and an organic electroluminescent device including the same as a light emitting material. More particularly, the present invention relates to a novel condensed aryl compound having excellent light emitting properties such as driving voltage and current efficiency, To an organic electroluminescent device.

In recent years, the demand for a flat display device having a small space occupation has been increasing due to the enlargement of a display device. The liquid crystal display, which is a typical flat display device, has an advantage of being lighter than a conventional CRT (cathode ray tube) angle is limited and a back light is necessarily required. On the other hand, organic light emitting diodes (OLEDs), which are new flat display devices, are displays using self-luminescence phenomenon, which have a large viewing angle and can be made thinner and smaller than liquid crystal displays, And recently, application to a full-color display or illumination is expected.

In general, organic light emission phenomenon refers to a phenomenon in which an organic material is used to convert electric energy into light energy.

An organic electroluminescent device using an organic light emitting phenomenon usually has a structure including an anode, an anode, and an organic material layer therebetween. Here, in order to enhance the efficiency and stability of the organic electroluminescent device, the organic material layer may have a multi-layer structure composed of different materials and may include a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer. When a voltage is applied between the two electrodes in the structure of the organic electroluminescent device, holes are injected into the anode, electrons are injected into the organic layer, and excitons are formed when injected holes and electrons meet. When it falls back to the ground state, the light comes out. Such an organic electroluminescent device is known to have properties such as self-emission, high luminance, high efficiency, low driving voltage, wide viewing angle, high contrast, and high speed response.

A material used as an organic material layer in an organic electroluminescent device can be classified into a light emitting material and a charge transporting material such as a hole injecting material, a hole transporting material, an electron transporting material, and an electron injecting material depending on functions. The light emitting material may be classified into a polymer type and a low molecular type depending on the molecular weight and may be classified into a fluorescent material derived from singlet excited state of electrons and a phosphorescent material derived from the triplet excited state of electrons according to an emission mechanism . Further, the light emitting material can be classified into blue, green, and red light emitting materials and yellow and orange light emitting materials required to realize better natural color depending on the luminescent color.

On the other hand, when only one material is used as a light emitting material, there arises a problem that the maximum light emission wavelength shifts to a long wavelength due to intermolecular interaction, the color purity decreases, or the efficiency of the device decreases due to the light emission attenuating effect. A host-dopant system can be used as a light-emitting material in order to increase the light-emitting efficiency through the light-emitting layer.

When the dopant having a smaller energy band gap than the host forming the light emitting layer is mixed with a small amount of the light emitting layer, the excitons generated in the light emitting layer are transported to the dopant to emit light with high efficiency. At this time, since the wavelength of the host is shifted to the wavelength band of the dopant, light of a desired wavelength can be obtained depending on the type of dopant used.

In order for the organic electroluminescent device to sufficiently exhibit the above-described excellent characteristics, materials constituting the organic material layer in the device, such as a hole injecting material, a hole transporting material, a light emitting material, an electron transporting material, and an electron injecting material are supported by a stable and efficient material However, the development of a stable and efficient organic material layer material for an organic electroluminescence device has not been sufficiently developed yet. Therefore, there is a continuing need in the art for the development of new materials.

Accordingly, it is a first object of the present invention to provide a novel condensed aryl compound having low driving voltage and high luminous efficiency.

A second object of the present invention is to provide an organic electroluminescent device comprising the novel condensed aryl compound.

In order to achieve the first technical object, the present invention provides a compound represented by the following formula (1).

[Chemical Formula 1]

In the above formula (1)

The R ₁ To R < ₁₀ > are the same or different and each independently represents a hydrogen atom, a deuterium atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted alkyl group having 7 to 30 carbon atoms, A substituted or unsubstituted C1 to C30 alkenyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C5 to C30 cycloalkenyl group, a substituted or unsubstituted C1 to C30 alkoxy group, A substituted or unsubstituted C1-C30 alkylthio group, a substituted or unsubstituted C6-C30 aryloxy group, a substituted or unsubstituted C1-C30 alkylthio group, a substituted or unsubstituted C6-C30 arylthio group, a substituted or unsubstituted C1- A substituted or unsubstituted arylamine group having 5 to 30 carbon atoms, a substituted or unsubstituted aryl group having 5 to 50 carbon atoms, a substituted or unsubstituted monovalent hydrocarbon having O, N or S A substituted or unsubstituted aryl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryl group, An amide group and an ester group, and may form a condensed ring of an aliphatic, aromatic, aliphatic hetero or aromatic hetero with an adjacent group,

N is an integer of 2,

Y ₁ and Y ₂ are the same or different and each independently represents a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted alkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted group having 2 to 30 carbon atoms A substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted cycloalkenyl group having 5 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted carbon number 6 A substituted or unsubstituted aryloxy group having 1 to 30 carbon atoms, a substituted or unsubstituted alkylthioxy group having 1 to 30 carbon atoms, a substituted or unsubstituted arylthioxy group having 5 to 30 carbon atoms, a substituted or unsubstituted alkylamine group having 1 to 30 carbon atoms, Or an unsubstituted arylamine group having 5 to 30 carbon atoms, a substituted or unsubstituted aryl group having 5 to 50 carbon atoms, a substituted or unsubstituted hetero atom having 3 to 50 carbon atoms having O, N or S A substituted or unsubstituted aryl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, Group, < / RTI >

X ₁ to X ₄ are the same or different from each other and each independently represents a hydrogen atom, a deuterium atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted alkyl group having 7 to 30 carbon atoms, A substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted cycloalkenyl group having 5 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 3 to 30 carbon atoms, A substituted or unsubstituted C1-C30 alkylthio group, a substituted or unsubstituted C1-C30 arylthio group, a substituted or unsubstituted C1-C30 alkylthio group, a substituted or unsubstituted C6-C30 aryloxy group, A substituted or unsubstituted arylamine group having 5 to 30 carbon atoms, a substituted or unsubstituted aryl group having 5 to 50 carbon atoms, a substituted or unsubstituted hetero atom, O, N or S, A substituted or unsubstituted aryl group having 3 to 50 carbon atoms, a substituted or unsubstituted silicon group, a substituted or unsubstituted boron group, a substituted or unsubstituted silane group, a carbonyl group, a phosphoryl group, an amino group, a nitrile group, a nitro group, A halogen group, an amide group and an ester group, and may form a condensed ring of aliphatic, aromatic, aliphatic hetero or aromatic hetero with groups adjacent to each other.

According to one embodiment of the present invention, the compound represented by Formula 1 may be any compound selected from the group consisting of the following Chemical Formulas 2 to 5:

[Chemical Formula 2] < EMI ID =

[Chemical Formula 4]

In the above formulas (2) to (5), R ₁ To R ₁₀ , Y ₁ , Y ₂ , X ₁ and X ₄ are as defined in the above formula (1).

According to another aspect of the present invention,

There is provided an organic electroluminescent device comprising an anode, a cathode, and a layer interposed between the anode and the cathode, the layer comprising a condensed aryl compound represented by the formula (1).

According to an embodiment of the present invention, the organic electroluminescent device may include a condensed aryl compound represented by the formula (1) in the light emitting layer between the anode and the cathode.

According to another embodiment of the present invention, the organic electroluminescent device may further comprise at least one layer selected from the group consisting of a hole injecting layer, a hole transporting layer, an electron blocking layer, a hole blocking layer, an electron transporting layer and an electron injecting layer between the anode and the cathode Layer. ≪ / RTI >

According to another embodiment of the present invention, the organic electroluminescent device includes at least one layer selected from the hole injecting layer, the hole transporting layer, the electron blocking layer, the light emitting layer, the hole blocking layer, the electron transporting layer, Or a solution process.

According to another embodiment of the present invention, the organic electroluminescent device can be used for a display device, a display device, or a monochromatic or white illumination device.

According to the present invention, the novel condensed aryl compound represented by the general formula (1) has stable and excellent luminescent characteristics as compared with the conventional materials, and thus the organic electroluminescent device including the novel condensed aryl compound has low voltage driving capability and can improve the luminous efficiency .

1 is a schematic view of an organic electroluminescent device according to one embodiment of the present invention.

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

The present invention relates to an organic electroluminescent device improved in luminescence characteristics such as a driving voltage and a current efficiency, wherein R ₁ to R ₁₀ , X ₁ to X ₄ , Y ₁ and Y ₂ And the like.

[Chemical Formula 1]

When R ₁ to R ₁₀ , X ₁ to X ₄ , Y ₁ and Y ₂ are substituted, the substituents are each independently selected from the group consisting of a deuterium atom, a cyano group, a halogen atom, a hydroxy group, a nitro group, an alkyl group having 1 to 40 carbon atoms, An alkoxy group having 1 to 40 carbon atoms, an alkylamino group having 1 to 40 carbon atoms, an arylamino group having 6 to 40 carbon atoms, a heteroarylamino group having 3 to 40 carbon atoms, an alkylsilyl group having 1 to 40 carbon atoms, an arylsilyl group having 6 to 40 carbon atoms, An aryl group having 6 to 40 carbon atoms, an aryloxy group having 3 to 40 carbon atoms, a heteroaryl group having 3 to 40 carbon atoms, a germanium group, phosphorus, fluoro, cyanide, silyl groups and boron. In addition, the substituents may be bonded to each other to form a saturated or unsaturated ring or may be fused together by a pendant method.

Specific examples of the alkyl group as the substituent used in the present invention include a methyl group, an ethyl group, a propyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an isoamyl group, a hexyl group, a heptyl group, A halogen atom, a hydroxyl group, a nitro group, a cyano group, a trifluoromethyl group, a silyl group (in this case, a " alkylsilyl group "hereinafter), a substituted or unsubstituted amino group _{(-NH 2, -NH (R)} , -N (R ') (R''), where R, R' and R" are each independently a carbon number A hydrazine group, a hydrazone group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, an alkyl group having 1 to 24 carbon atoms, a halogenated alkyl group having 1 to 24 carbon atoms (for example, an alkyl group having 1 to 24 carbon atoms , An alkenyl group having 2 to 24 carbon atoms, an alkynyl group having 2 to 24 carbon atoms, An aryl group having from 5 to 24 carbon atoms, an aryl group having from 5 to 24 carbon atoms, an arylalkyl group having from 6 to 24 carbon atoms, a heteroaryl group having from 3 to 24 carbon atoms, or a heteroarylalkyl group having from 3 to 24 carbon atoms.

Specific examples of the alkoxy group used as the substituent in the compound of the present invention include methoxy, ethoxy, propoxy, isobutyloxy, sec-butyloxy, pentyloxy, isoamyloxy, And can be substituted with substituents similar to those in the case of the alkyl group.

Specific examples of the halogen group which is a substituent used in the compound of the present invention include fluorine (F), chlorine (Cl), bromine (Br) and the like.

Specific examples of the aryl group as the substituent group used in the compound of the present invention include a phenyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, a 4-ethylphenyl group, Examples of the aryl group include phenyl group, 4-methylbiphenyl group, 4-ethylbiphenyl group, o-terphenyl group, m-terphenyl group, p-terphenyl group, 1-naphthyl group, , Anthryl group, phenanthryl group, pyrenyl group, fluorenyl group, tetrahydronaphthyl group and the like, which may be substituted with the same substituents as those in the case of the alkyl group.

Specific examples of the heteroaryl group used as the substituent in the compound of the present invention include pyridinyl, pyrimidinyl, triazinyl, indolinyl, quinolinyl, pyrrolidinyl, piperidinyl, An oxazolyl group, an oxadiazolyl group, a benzoxazolyl group, a thiazolyl group, a thiadiazolyl group, a benzothiazolyl group, a triazolyl group, an imidazolyl group, a benzoimidazole group, And at least one of the hydrogen atoms of the heteroaryl group may be substituted with the same substituent as the alkyl group.

Specific examples of the alkenyl group used as the substituent in the compound of the present invention include an alkenyl group to which an aryl group such as stibenyl group and styrenyl group is connected. Specific examples of the cycloalkyl group include a cyclopentyl group and a cyclohexyl group, But is not limited thereto.

The arylamine group, which is a substituent group used in the compound of the present invention, may be selected from the group consisting of a diphenylamine group, a phenylnaphthylamine group, a phenylbiphenylamine group, a naphthylbiphenylamine group, a dinaphthylamine group, a diphenylamine group, a dianthracenylamine Methyl-naphthylamine group, a 2-methyl-biphenylamine group, a 9-methyl-anthracenylamine group, a ditolylamine group, a phenyltolylamine group, Phenylamine group, phenylbiphenylaminophenylamine group, and naphthylphenylaminophenylbiphenylamine group, but the present invention is not limited thereto.

The aryloxy group used in the present invention means an -O-aryl radical, wherein the aryl group is as defined above, and specific examples include phenoxy, naphthoxy, anthracenyloxy, phenanthrenyloxy, fluorenyloxy, Indenyloxy and the like, and at least one hydrogen atom contained in the aryloxy group may be further substituted.

Specific examples of the silyl group used in the present invention include trimethylsilyl, triethylsilyl, triphenylsilyl, trimethoxysilyl, dimethoxyphenylsilyl, diphenylmethylsilyl, silyl, diphenylvinylsilyl, methylcyclobutylsilyl , Dimethyl furyl silyl and the like.

Specific examples of the alkenyl group used in the present invention include straight chain or branched chain alkenyl groups and include 3-pentenyl, 4-hexenyl, 5-heptenyl, 4-methyl- Dimethyl-pentenyl group, 6-methyl-5-heptenyl group and 2,6-dimethyl-5-heptenyl group.

In the present invention, the term "substituted" refers to a group selected from the group consisting of cyano, halogen, hydroxy, nitro, alkyl, alkoxy, alkylamino, arylamino, Substituted with at least one substituent selected from the group consisting of an aryl group, a heteroaryl group, germanium, phosphorus, boron, hydrogen and deuterium.

The present invention is not limited by the concrete examples of the condensed aryl compound according to the above-mentioned formula (1) having the above-mentioned structure, but specifically, any one of the compounds represented by the following formulas (6) to Lt; / RTI >

    [Chemical Formula 6] < EMI ID =

    [Chemical Formula 8]

  [Chemical Formula 11] [Chemical Formula 12]

    [Chemical Formula 13]

    [Chemical Formula 15]

    [Chemical Formula 17]

    [Chemical Formula 19]

    [Chemical Formula 21]

    [Chemical Formula 23]

    [Chemical Formula 25]

    [Chemical Formula 27]

    [Chemical Formula 30]

    (32)

    [Chemical Formula 33]

    [Chemical Formula 35]

    [Chemical Formula 37]

    [Chemical Formula 39]

    [Chemical Formula 41]

    [Chemical Formula 43]

    [Chemical Formula 45]

    [Chemical Formula 47]

    [Chemical Formula 49]

    [Chemical Formula 51]

    (54)

    [Chemical Formula 55]

    [Chemical Formula 57]

    [Chemical Formula 60]

    [Chemical Formula 61]

    (63)

    [Chemical Formula 65]

    [Chemical Formula 67]

    (70)

    [Chemical Formula 71]

    [Chemical Formula 73]

    [Chemical Formula 75]

    [Formula 77]

    [Formula 79]

    [Formula 81]

    [Chemical Formula 83]

    [Chemical Formula 85]

    [Chemical Formula 87]

    (90)

    [Chemical Formula 91]

    [Chemical Formula 93]

    [Chemical Formula 95]

    (98)

    (100)

    (101)

    [Chemical Formula 103]

    (106)

    (108)

    (110)

    (111)

    [Formula 113]

    (115)

    (118)

    (120)

    [Formula 121]

    (124)

    [Formula 125]

    (128)

    [Formula 130]

    [Formula 131]

    [Formula 133]

    [Chemical Formula 135]

    [Chemical Formula 137]

    [Formula 140]

    (141)

    (144)

    [Chemical Formula 145]

    [Chemical Formula 147]

    [Formula 150]

    [Formula 152]

    (154)

    [Chemical Formula 155]

    (158)

    [Formula 15]

    [Formula 161]

    (163)

    [166]

    [Formula 16]

    (170)

    (172)

    [174]

    [176]

    [178]

    [Formula 179]

    [Formula 181] [Formula 182]

    [Formula 184]

    [Formula 186]

    [Formula 188] [Formula 188]

    [Chemical Formula 189] [Chemical Formula 190]

    (191)

    [Chemical Formula 193] [Chemical Formula 194]

    [196]

 [197] [198]

    (200)

    [Formula 201]

 (203)

The method for producing the condensed aryl compound according to the present invention is specifically shown in the following Examples.

Also, the condensed aryl compound of the present invention is an anode, a cathode, an organic electroluminescent element interposed between the anode and the cathode, and having a layer containing a condensed aryl compound represented by the formula (1).

The layer containing the condensed aryl compound is preferably a light emitting layer between the anode and the cathode, and a hole injecting layer, a hole transporting layer, an electron blocking layer, a hole blocking layer, an electron transporting layer, and an electron injecting layer are provided between the anode and the cathode And at least one layer selected from the group consisting of

According to another embodiment of the present invention, the thickness of the light emitting layer is preferably 50 to 2,000 ANGSTROM, and the light emitting layer may further include a material having the following structural formula.

[Ir (ppy) ₃ ]

[Ir (chpy) ₃ ]

[Ir (mchpy) ₃ ]

As a specific example, a hole transport layer (HTL) may be additionally stacked, and an electron transport layer (ETL) may be further stacked between the cathode and the organic emission layer. The electron transport layer is deposited to facilitate the injection of holes from the anode. As the material of the hole transport layer, an electron donor molecule having a small ionization potential is used, and diamine, triamine or tetraamine derivative having a basic skeleton of triphenylamine Is widely used.

In the present invention, the material of the hole transport layer is not particularly limited, and examples thereof include N, N'-bis (3-methylphenyl) -N, N'- 1-biphenyl] -4,4'-diamine (TPD) or N, N'-di (naphthalene-1-yl) -N, N'-diphenylbenzidine (a-NPD).

A hole injection layer (HIL) may be further formed on the lower portion of the hole transport layer. The material for the hole injection layer is not particularly limited as long as it is commonly used in the art, (4,4 ', 4' '- tri (N-carbazolyl) triphenyl-amine) or m-MTDATA (4,4', 4 ''), which is a copper phthalocyanine (CuPc) or starburst type amine, -tris- (3-methyl phenylphenylamino) triphenylamine).

In addition, the electron transport layer used in the organic electroluminescent device according to the present invention can transport electrons supplied from the cathode smoothly to the organic luminescent layer and inhibit the movement of holes which are not bonded in the organic luminescent layer, .

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

Meanwhile, an electron injection layer (EIL) may be further formed on the electron transport layer to facilitate injection of electrons from the cathode to ultimately improve power efficiency. The electron injection layer material As long as it is commonly used in the art, it can be used without any particular limitation. For example, materials such as LiF, NaCl, CsF, Li ₂ O, and BaO can be used.

The organic electroluminescent device according to the present invention can be used for a display device, a display device, an element for a single color or a white light, and the like.

1 is a cross-sectional view showing the structure of an organic electroluminescent device of the present invention. The organic electroluminescent device according to the present invention includes an anode 20, a hole transport layer 40, an organic emission layer 50, an electron transport layer 60 and a cathode 80, The electron injecting layer 70 may be further formed. In addition, one or two intermediate layers may be further formed, or a hole blocking layer or an electron blocking layer may be further formed.

The organic electroluminescent device of the present invention and its manufacturing method will be described with reference to FIG. First, an anode electrode material is coated on the substrate 10 to form an anode 20. Here, as the substrate 10, an organic substrate or a transparent plastic substrate which is excellent in transparency, surface smoothness, ease of handling, and waterproofness is used as a substrate used in a conventional organic EL device. As the material for the anode electrode, indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO ₂ ), zinc oxide (ZnO) and the like which are transparent and excellent in conductivity are used.

A hole injection layer 30 is formed on the anode 20 by vacuum thermal deposition or spin coating. Subsequently, a hole transport layer 40 is formed by vacuum thermal deposition or spin coating on the hole transport layer 30 above the hole injection layer 30.

A hole blocking layer (not shown) is selectively formed on the organic light emitting layer 50 by a vacuum deposition method or a spin coating method to form a thin film on the organic light emitting layer 50 can do. In the case where holes are injected into the cathode through the organic light-emitting layer, the lifetime and the efficiency of the device are reduced, and thus the hole blocking layer plays a role of preventing such a problem by using a material having a very low HOMO (Highest Occupied Molecular Orbital) level . In this case, the hole blocking material to be used is not particularly limited, but it is required to have an ionization potential higher than that of the light emitting compound while having electron transporting ability. Typically, BAlq, BCP, TPBI and the like can be used.

After the electron transport layer 60 is deposited on the hole blocking layer by a vacuum deposition method or a spin coating method, an electron injection layer 70 is formed, and a cathode forming metal is deposited on the electron injection layer 70 in a vacuum heat- And the cathode 80 is formed by vapor deposition to complete the organic EL device. Here, as the metal for forming the cathode, lithium, magnesium, aluminum, aluminum-lithium, calcium, magnesium-magnesium, Mg-Ag), and a transmissive cathode using ITO or IZO can be used to obtain a top light-emitting device.

According to another embodiment of the present invention, at least one layer selected from the hole injecting layer, the hole transporting layer, the electron blocking layer, the light emitting layer, the hole blocking layer, the electron transporting layer and the electron injecting layer is formed by a single molecular deposition method or a solution process And the organic electroluminescent device according to the present invention can be used for a display device, a display device, and a monochromatic or white illumination device.

Hereinafter, the present invention will be described in more detail with reference to preferred embodiments. It will be apparent, however, to those skilled in the art that these embodiments are for further illustrating the present invention and that the scope of the present invention is not limited thereby.

<Examples>

Synthesis Example 1 Synthesis of Compound Represented by Formula 13

(1) Synthesis of Compound Represented by Formula (13-a)

[Chemical Formula 13-a] was synthesized by the following Reaction Scheme 1.

[Reaction Scheme 1]

                                                  [Chemical Formula 13-a]

(97 mmol) of 9,9-diphenyl-9H-fluorene-2-ylboronic acid, 35.5 g (116 mmol) of 2,5-dibromonitrobenzene and 2.2 g of Pd (PPh3) 4 in a 1 L round bottom flask 26.7 g (193 mmol) of potassium carbonate, 175 ml of tetrahydrofuran, 175 ml of toluene and 70 ml of water were added and the mixture was stirred under reflux. After the reaction was completed, the reaction mixture was cooled to room temperature and extracted with EA / H ₂ O. The organic layer was separated, concentrated under reduced pressure, and then separated into a column. The separated solution was concentrated under reduced pressure, recrystallized with MC / MeOH, and dried to obtain 30 g (yield: 59%) of a compound represented by the formula (13-a).

(2) Synthesis of Compound Represented by Formula (13-b)

[Chemical Formula 13-b] was synthesized by the following Reaction Scheme 2.

[Reaction Scheme 2]

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

30 g (58 mmol) of [Formula 13-a], 240 ml of ethanol and 144 ml of hydrochloric acid were placed in a 1 L round bottom flask and cooled to 0 ° C or lower. 17.2 g (145 mmol) of tin powder was gradually added to the cooled reaction solution, -a] was completely dissolved. After confirming the completion of the reaction by TLC, the reaction solution was adjusted to pH 10 or higher by adding 40% sodium hydroxide solution, and then filtered through celite and then extracted with EA / H ₂ O. [ Thereafter, the organic layer was separated, concentrated under reduced pressure, and separated into a column to obtain 18 g (yield: 63.7%) of a compound represented by the formula 13-b.

(3) Synthesis of Compound Represented by Formula 13-c

[Chemical Formula 13-c] was synthesized by the following Reaction Scheme 3.

[Reaction Scheme 3]

[Chemical Formula 13-b] [Chemical Formula 13-c]

18 g (37 mmol) of [Formula 13-b], 6.1 g (88 mmol) of sodium nitrite, 14.7 g (88 mmol) of potassium iodide and 180 ml of acetonitrile were placed in a 500 ml round bottom flask and cooled to 0 ° C or lower while stirring. Hydrochloric acid was slowly dropped into the cooled reaction solution, stirred at room temperature, and TLC was confirmed to complete the reaction. Water was added to the reaction solution in which the reaction was terminated, stirred, dichloromethane was added, stirred, and then treated with sodium cyanosulfate. It was then extracted with MC / H ₂ O and the organic layer was concentrated under reduced pressure and then separated into a column. The separated solution was concentrated under reduced pressure, then recrystallized with hexane and dried under reduced pressure to obtain 16.5 g (yield: 74.7%) of a compound represented by the formula 13-c.

(4) Synthesis of a compound represented by the formula (13-d)

[Chemical Formula 13-d] was synthesized by the following Reaction Scheme 4.

[Reaction Scheme 4]

[Chemical Formula 13-c] [Chemical Formula 13-d]

(1 mmol) of tetrakis (triphenylphosphine) palladium (0 mmol), 0.3 g (1 mmol) of copper (I) iodide, 1.5 g 115 ml of ethylamine was added thereto, and 2.8 ml (28 mmol) of phenylacetylene was slowly added dropwise while stirring at room temperature. Thereafter, the mixture was stirred at room temperature for about 1 hour, and hexane was added thereto to terminate the reaction. After the reaction was terminated, the reaction solution was concentrated and separated into a column. The separated solution was concentrated under reduced pressure, recrystallized and filtered to obtain 12.5 g (yield: 79.2%) of a compound represented by the formula 13-d.

(5) Synthesis of Compound Represented by Formula 13-e

[Chemical Formula 13-e] was synthesized by the following Reaction Scheme 5.

[Reaction Scheme 5]

[Chemical Formula 13-d] [Chemical Formula 13-e]

12.5 g (22 mmol) of [Formula 13-d], 1.3 g (3 mmol) of iron (III) trifluoromethanesulfonate and 500 ml of 1,2-dichloroethane were placed in a 1 L round bottom flask, And the mixture was stirred under reflux for 24 hours. After the reaction was completed, the reaction solution was cooled to room temperature and separated into a column. The separated solution was concentrated under reduced pressure and recrystallized with MC / MeOH. The resulting crystals were filtered to obtain 10.8 g of the compound represented by the formula (13-e) 86.4%).

(6) Synthesis of a compound represented by the formula (13-f)

[Chemical Formula 13-f] was synthesized by the following Reaction Scheme 6.

[Reaction Scheme 6]

[Chemical Formula 13-e] [Chemical Formula 13-f]

10.8 g (19 mmol) of [Formula 13-e] and 6.4 g (24 mmol) of methyl 2- (4,4,5,5-tetramethyl-1,3,2-dioxaborolyl) benzoate were placed in a 250 ml round- 0.4 g (1 mmol) of tetrakis (triphenylphosphine) palladium (0), 7.8 g (56 mmol) of potassium carbonate, 54 ml of 1,4-dioxane, 54 ml of toluene and 21 ml of water were added and the mixture was refluxed and stirred. TLC was confirmed and the reaction was terminated. The reaction mixture was cooled to room temperature and extracted with ethyl acetate / water. The organic layer was separated, concentrated under reduced pressure, and the concentrate was separated into a column. The separated solution was concentrated under reduced pressure, and recrystallized from methylene chloride / hexane to obtain 7.9 g (yield: 66.7%) of a compound represented by the general formula [13-f].

(7) Synthesis of Compound Represented by Formula 13

A compound represented by the formula (13) was synthesized by the following reaction scheme [7].

[Reaction Scheme 7]

[Chemical Formula 13-f] [Chemical Formula 13]

11.9 g (75 mmol) of bromobenzene and 65 ml of tetrahydrofuran were placed in a 500 ml round-bottomed flask, cooled to -78 ° C in a nitrogen atmosphere, and 44 ml (70 mmol) of n-butyl lithium was added dropwise to the cooled solution. Thereafter, the mixture was stirred at the same temperature for 1 hour, and 7.9 g (13 mmol) of [Formula 13-f] was added little by little. After completion of the reaction was confirmed by TLC, 100 ml of water was added, and the mixture was extracted with ethyl acetate / water. The organic layer was separated and concentrated under reduced pressure. The concentrate was placed in a 250 ml round bottom flask, and 70 ml of acetic acid and 0.5 ml of hydrochloric acid were added, followed by stirring under reflux. After confirming the completion of the reaction by TLC, the reaction mixture was cooled to room temperature. The resulting solid was filtered, washed with 100 ml of water and 100 ml of methanol, and then purified by column. The purified solid was recrystallized from toluene / hexane to obtain 3.2 g (yield: 34.7%) of a compound represented by the formula (13).

Synthesis Example 2 Synthesis of Compound Represented by Formula 16

(1) Synthesis of a compound represented by the formula (16-a)

A compound represented by the formula (16-a) was synthesized by the following reaction scheme (8).

[Reaction Scheme 8]

                                           [Chemical Formula 16-a]

9,9-dimethyl-9H-fluorene-2-yl boronic acid was used in place of the 9,9-diphenyl-9H-fluorene-2-yl boronic acid used in [Reaction Scheme 1] (Yield: 64.4%) of the compound represented by the formula (16-a) was obtained.

(2) Synthesis of Compound Represented by Formula 16-b

[Chemical Formula 16-b] was synthesized by the following Reaction Scheme 9.

[Reaction Scheme 9]

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

Was synthesized in the same manner as in Synthesis Example 1, except that [Formula 16-a] was used in place of [Formula 13-a] used in Reaction Formula 2 of Synthesis Example 1 to obtain 18.2 g of the compound represented by Formula 16- : 61.6%).

(3) Synthesis of Compound Represented by Formula 16-c

[Chemical Formula 16-c] was synthesized by the following Reaction Scheme 10.

[Reaction Scheme 10]

[Chemical Formula 16-b] [Chemical Formula 16-c]

Was synthesized in the same manner as in Synthesis Example 1, except that [Formula 16-b] was used instead of [Formula 13-b] used in [Reaction Scheme 3] in Synthesis Example 1 to obtain 17.5 g : 73.7%).

(4) Synthesis of a compound represented by the formula (16-d)

[Chemical Formula 16-d] was synthesized by the following Reaction Scheme 11.

[Reaction Scheme 11]

[Chemical Formula 16-c] [Chemical Formula 16-d]

Synthesis was conducted in the same manner as in Synthesis Example 1, except that [Formula 16-c] was used instead of [Formula 13-c] used in [Reaction Scheme 4] in Synthesis Example 1 to obtain 12.5 g of the compound represented by Formula 16- : 72.7%).

(5) Synthesis of Compound Represented by Formula 16-e

[Chemical Formula 16-e] was synthesized by the following Reaction Scheme 12.

[Reaction Scheme 12]

[Chemical Formula 16-d] [Chemical Formula 16-e]

Was synthesized in the same manner as in Synthesis Example 1, except that [Formula 16-d] was used instead of [Formula 13-e] used in [Reaction Scheme 6] in Synthesis Example 1 to obtain 8.6 g of a compound represented by Formula 16- : 61.3%).

(6) Synthesis of a compound represented by the formula (16-f)

[Chemical Formula 16-f] was synthesized by the following Reaction Scheme 13.

[Reaction Scheme 13]

[Chemical Formula 16-e] [Chemical Formula 16-f]

After dissolving 8.6 g (17 mmol) of [Formula 16-e] and 90 ml of dichloromethane in a 250 ml round bottom flask, the solution was cooled to -78 ° C and 20.5 ml of iodine monochloride was slowly added dropwise. The mixture was stirred at the same temperature for 1 hour, and then the temperature was raised to room temperature. Then, a saturated sodium bisulfite aqueous solution was added to terminate the reaction. The reaction solution was extracted with dichloromethane and water. The organic layer was separated and concentrated under reduced pressure. The obtained crystals were filtered through a methanol slurry and filtered to obtain 7.6 g (yield: 70.7%) of a compound represented by the formula 16-f.

(7) Synthesis of Compound Represented by Formula 16-g

[Chemical Formula 16-g] was synthesized by the following Reaction Scheme 14.

[Reaction Scheme 14]

[Chemical Formula 16-f] [Chemical Formula 16-g]

[Chemical Formula 16-f] to a round bottom of the plaque's 250ml 7.6g (12mmol), 2- dibenzo thiophene-boronic acid 3.3g (13mmol), Pd (PPh 3) 4 0.3g (1mmol), potassium carbonate 3.3g ( 40 ml of tetrahydrofuran, 40 ml of toluene and 15 ml of water were placed, and the mixture was stirred under reflux. After the reaction was completed, the reaction mixture was cooled to room temperature and extracted with EA / H ₂ O. The organic layer was separated, concentrated under reduced pressure, and then separated into a column. The separated solution was concentrated under reduced pressure, recrystallized from MC / MeOH and dried to obtain 5.3 g (yield: 64%) of a compound represented by the formula 16-g.

(8) Synthesis of Compound Represented by Formula 16

A compound represented by the formula (16) was synthesized by the following scheme (15).

[Reaction Scheme 15]

[Chemical Formula 16-g] [Chemical Formula 16-h] [Chemical Formula 16]

15 g (22 mmol) of [Formula 16-g] was dissolved in 150 ml of tetrahydrofuran in a 500 ml round bottom flask, cooled to 0 ° C in a nitrogen atmosphere, 23.3 ml (70 mmol) of methylmagnesium bromide was added dropwise to the cooled reaction solution, Stirring and reflux stirring were performed for 2 hours each. After the completion of the reaction was confirmed by TLC, the reaction mixture was cooled to room temperature and acidified by adding 0.2N hydrochloric acid dropwise. The reaction solution was extracted with ethyl acetate and water. The organic layer was separated, concentrated under reduced pressure, and recrystallized with toluene / hexane. The resulting solid was put into a 500 ml round bottom flask, and 150 ml of acetic acid and 1 ml of hydrochloric acid were added. After completion of the reaction, the reaction mixture was extracted with ethyl acetate and water. The organic layer was separated, concentrated under reduced pressure, and recrystallized from toluene / hexane to obtain 2.8 g (yield: 41%) of a compound represented by the following formula (16).

Synthesis Example 3 Synthesis of Compound Represented by Formula 32

(1) Synthesis of Compound Represented by Formula (32-a)

A compound represented by the formula (32-a) was synthesized according to the following scheme (Scheme 16).

[Reaction Scheme 16]

[Chemical Formula 16-c] [Chemical Formula 32-a]

Except that 1-naphthylacetylene was used in place of phenylacetylene used in [Reaction Scheme 11] in Synthesis Example 2 to obtain 16.5 g (yield: 75.5%) of the compound represented by the formula (32-a) .

(2) Synthesis of a compound represented by the formula (32-b)

[Chemical Formula 32-b] was synthesized by the following Reaction Scheme 17.

[Reaction Scheme 17]

[Formula 32-a] [Formula 32-b]

Was synthesized in the same manner except that [Formula 32-a] was used in place of [Formula 13-d] used in [Reaction Scheme 5] in Synthesis Example 1 to obtain 13 g of the compound represented by Formula 32- 78.8%).

(3) Synthesis of Compound Represented by Formula (32-c)

A compound represented by the formula (32-c) was synthesized by the following scheme (Scheme 18).

[Reaction Scheme 18]

[Formula 32-b] [Formula 32-c]

Synthesis was conducted in the same manner as in Synthesis Example 1, except that [Formula 32-b] was used in place of [Formula 13-e] used in [Reaction Scheme 6] in Synthesis Example 1 to obtain 9.8 g of a compound represented by Formula 32- : 67.9%).

(4) Synthesis of Compound Represented by Formula 32

A compound represented by formula (32) was synthesized by the following reaction scheme (19).

[Reaction Scheme 19]

(32-c) (32-d)

13 g (23 mmol) of [Formula 32-c] was dissolved in 130 ml of tetrahydrofuran in a 500 ml round-bottomed flask and then cooled to 0 ° C in a nitrogen atmosphere. 25 ml (75 mmol) of methylmagnesium bromide was added dropwise to the cooled reaction solution, followed by stirring at room temperature and refluxing for 2 hours each. After the completion of the reaction was confirmed by TLC, the reaction mixture was cooled to room temperature and acidified by dropwise addition of 0.2 N hydrochloric acid, followed by extraction with ethyl acetate and water. The organic layer was separated and concentrated under reduced pressure. The concentrate was recrystallized from tetrahydrofuran / hexane, and the resulting solid was placed in a 500 ml round-bottomed flask, and 150 ml of acetic acid and 0.5 ml of hydrochloric acid were added and stirred under reflux. After completion of the reaction, the reaction mixture was extracted with ethyl acetate and water. The organic layer was separated, concentrated under reduced pressure, and then separated and purified by column. The resulting solid was recrystallized from toluene / hexane to obtain 2.3 g (yield: 31.4%).

Synthesis Example 4 Synthesis of Compound Represented by Formula 98

(1) Synthesis of Compound Represented by Formula 98-a

A compound represented by the formula (98-a) was synthesized by the following reaction scheme (20).

[Reaction Scheme 20]

[Chemical Formula 13-d] [Chemical Formula 98-a]

Was synthesized in the same manner as in Synthesis Example 1, except that [Formula 13-d] was used instead of [Formula 13-e] used in [Reaction Scheme 6] in Synthesis Example 1 to obtain 14.1 g of the compound represented by Formula 98- : 64.3%).

(2) Synthesis of Compound Represented by Formula 98-b

A compound represented by the formula (98-b) was synthesized by the following Reaction Scheme (21).

[Reaction Scheme 21]

[Formula 98-a] [Formula 98-b]

In a 500 ml round bottom flask, 14.2 g (23 mmol) of [Formula 98-a] was dissolved in 150 ml of dichloromethane, cooled to -78 ° C, and then 27.1 ml of iodine monochloride was slowly added dropwise. The mixture was stirred at the same temperature for 1 hour, the temperature was raised to room temperature, and a saturated aqueous solution of sodium bisulfite was added to terminate the reaction, followed by extraction with dichloromethane and water. The organic layer was separated from the extract and concentrated under reduced pressure to obtain crystals. The residue was filtered through a methanol slurry to obtain 14 g (yield: 82.7%) of a compound represented by the formula (98-b).

(3) Synthesis of Compound Represented by Formula 98-c

[Chemical Formula 98-c] was synthesized by the following Reaction Formula 22.

[Reaction Scheme 22]

[Chemical Formula 98-b] [Chemical Formula 98-c]

Except that 4-tert-butylphenylboronic acid was used instead of 2-dibenzothiophene boronic acid instead of [Formula 98-b], which was used in [Scheme 14] in Synthesis Example 2, instead of [Formula 16-f] To obtain 8.6 g (Yield: 60.9%) of a compound represented by the formula (98-c).

(4) Synthesis of a compound represented by the formula (98)

A compound represented by the formula (98) was synthesized by the following Reaction Scheme (23).

[Reaction Scheme 23]

98-c] [Chemical Formula 98-d] [Chemical Formula 98]

Synthesis was conducted in the same manner as in Synthesis Example 1, except that [Formula 98-c] was used instead of [Formula 13-f] used in [Reaction Scheme 7] in Synthesis Example 1 to obtain 2.5 g of the compound represented by Formula 98 %).

Synthesis Example 5 Synthesis of Compound Represented by Formula 119

(1) Synthesis of a compound represented by the formula (119-a)

A compound represented by the formula (119-a) was synthesized according to the following scheme (Scheme 24).

[Reaction Scheme 24]

[Chemical Formula 13-c] [Chemical Formula 119-a]

Synthesis was conducted in the same manner as in Synthesis Example 1, except that 4-tertiary butylphenylacetylene was used instead of phenylacetylene used in [Reaction Scheme 4] in Synthesis Example 1 to obtain 12.5 g (Yield: 66.1% ).

(2) Synthesis of a compound represented by the formula (119-b)

[Chemical Formula 119-b] was synthesized by the following Reaction Scheme 25.

[Reaction Scheme 25]

[Chemical Formula 119-a] [Chemical Formula 119-b]

Synthesis was conducted in the same manner as in Synthesis Example 1, except that [Formula 119-a] was used instead of [Formula 13-d] used in [Reaction Scheme 5] in Synthesis Example 1 to obtain 9 g of the compound represented by Formula 119- 72%).

(3) Synthesis of a compound represented by the formula (119-c)

[Chemical Formula 119-c] was synthesized by the following Reaction Formula 26.

[Reaction Scheme 26]

[Chemical Formula 119-b] [Chemical Formula 119-c]

Was synthesized in the same manner as in Synthesis Example 1, except that [Formula 119-b] was used in place of [Formula 13-e] used in [Reaction Scheme 6] in Synthesis Example 1 to obtain 6 g of the compound represented by Formula 119- 61.3%).

(4) Synthesis of a compound represented by the formula (119)

A compound represented by the formula (119) was synthesized by the following scheme (27).

[Reaction Scheme 27]

[Chemical Formula 119-c] [Chemical Formula 119-d]

Was synthesized in the same manner as in Synthesis Example 1, except that [Formula 119-c] was used instead of [Formula 13-f] used in [Reaction Scheme 7] in Synthesis Example 1 to obtain 2.1 g of the compound represented by Formula 119 %).

Synthesis Example 6 Synthesis of Compound Represented by Formula 146

(1) Synthesis of Compound Represented by Formula 146-a

A compound represented by the formula (146-a) was synthesized by the following reaction scheme (28).

[Reaction Scheme 28]

                                             [Chemical Formula 146-a]

Instead of methyl 2-iodobenzoate and 9,9-diphenyl-9H-fluorene-2-ylboronic acid in place of benzene in the 2,5-dibromonium used in [Reaction Scheme 1] (Yield: 65.8%) of the compound represented by the formula (146-a) was obtained, except that bromophenylboronic acid was used.

(2) Synthesis of Compound Represented by Formula 146-b

[Chemical Formula 146-b] was synthesized by the following Reaction Scheme 29.

[Reaction Scheme 29]

[Chemical Formula 146-a] [Chemical Formula 146-a '] [Chemical Formula 146-b]

Except that 4-bromotoluene was used instead of bromobenzene instead of [Formula 146-a] used in [Scheme 7] in Synthesis Example 1, and [Formula 146- 35 g (yield: 79%) of a compound represented by the formula [b] was obtained.

(3) Synthesis of Compound Represented by Formula 146-c

[Chemical Formula 146-c] was synthesized by the following Reaction Formula 30.

[Reaction Scheme 30]

[Chemical Formula 146-b] [Chemical Formula 146-c]

35 g (82 mmol) of [Formula 146-b] and 280 ml of tetrahydrofuran were placed in a 500 ml round-bottomed flask and cooled to -78 deg. C in a nitrogen atmosphere. 61.7 ml (99 mmol) of n-butyllithium was added dropwise to the cooled solution. After stirring at the same temperature for 1 hour, 12 g (115 mmol) of trimethylborate was added dropwise, and the mixture was stirred at room temperature. When the reaction was completed, 2N hydrochloric acid was added to the mixture to cause acidification. The reaction solution was extracted with ethyl acetate and water. The organic layer was separated, concentrated under reduced pressure, and hexane was added thereto to crystallize. The resulting solid was filtered to obtain 21 g (yield: 65%) of a compound represented by the formula 146-c .

(4) Synthesis of Compound Represented by Formula 146-d

A compound represented by the formula (146-d) was synthesized by the following reaction scheme [31].

[Reaction Scheme 31]

[Chemical Formula 146-c] [Chemical Formula 146-d]

Except that 9,9-ditolyl-9H-fluorene-2-yl boronic acid was used in place of 9,9-diphenyl-9H-fluorene-2-ylboronic acid used in [Reaction Scheme 1] Were synthesized in the same manner as above to give 29 g (yield: 69%) of the compound represented by the formula 146-d.

(5) Synthesis of Compound Represented by Formula 146-e

[Chemical Formula 146-e] was synthesized by the following Reaction Formula 32.

[Reaction Scheme 32]

[Chemical Formula 146-d] [Chemical Formula 146-e]

Was synthesized in the same manner as in Synthesis Example 1 except that [Formula 146-d] was used instead of [Formula 13-a] used in [Reaction Scheme 2] in Synthesis Example 1 to obtain 17.2 g of the compound represented by Formula 146- : 62.8%).

(6) Synthesis of Compound Represented by Formula 146-f

A compound represented by the following formula (146-f) was synthesized by the following reaction scheme (33).

[Reaction Scheme 33]

[Chemical Formula 146-e] [Chemical Formula 146-f]

Was synthesized in the same manner as in Synthesis Example 1, except that [Formula 146-e] was used in place of [Formula 13-b] used in [Reaction Scheme 3] in Synthesis Example 1 to obtain 16.2 g of the compound represented by Formula 146- : 73.3%).

(7) Synthesis of a compound represented by the formula (146-g)

A compound represented by the formula (146-g) was synthesized by the following Reaction Scheme (34).

[Reaction Scheme 34]

[Chemical Formula 146-f] [Chemical Formula 146-g]

Was synthesized in the same manner as in Synthesis Example 1, except that [Formula 146-f] was used in place of [Formula 13-c] used in [Reaction Scheme 4] in Synthesis Example 1 to obtain 11.7 g : 75.3%).

(8) Synthesis of Compound Represented by Formula 146-h

[Chemical Formula 146-h] was synthesized by the following Reaction Scheme 35.

[Reaction Scheme 35]

[Chemical Formula 146-g] [Chemical Formula 146-h]

Was synthesized in the same manner as in Synthesis Example 1, except that [Formula 146-g] was used in place of [Formula 13-e] used in [Reaction Scheme 6] in Synthesis Example 1 to obtain 8.6 g of a compound represented by Formula 146- : 63%).

(9) Synthesis of Compound Represented by Formula 146-i

[Chemical Formula 146-i] was synthesized according to the following Reaction Scheme 36.

[Reaction Scheme 36]

[Chemical Formula 146-h] [Chemical Formula 146-i]

Was synthesized in the same manner as in Synthesis Example 2, except that [Formula 146-h] was used in place of [Formula 16-e] used in [Reaction Scheme 13] in Synthesis Example 2 to obtain 7.6 g : 74.2%).

(10) Synthesis of a compound represented by the formula (146-j)

A compound represented by the formula (146-j) was synthesized according to the following Reaction Formula (37).

[Reaction Scheme 37]

[Chemical Formula 146-i] [Chemical Formula 146-j]

Synthesis was carried out in the same manner except that [Formula 146-i] was used in place of [Formula 16-f] used in [Reaction Formula 14] in Synthesis Example 2 to obtain 7g (yield: 65.3%).

(11) Synthesis of a compound represented by the formula (146)

A compound represented by the formula (146) was synthesized by the following scheme [Reaction formula 38].

[Reaction Scheme 38]

[Chemical Formula 144-j] [Chemical Formula 144-k] [Chemical Formula 144]

Except that 4-bromotoluene was used instead of bromobenzene instead of [Formula 146-j], which was used in [Scheme 7] in Synthesis Example 1, instead of [Formula 13-f] 2.6 g (yield: 32.1%) of the compound represented by the following formula was obtained.

Synthesis Example 7 Synthesis of Compound Represented by Formula 191

(1) Synthesis of Compound Represented by Formula 191-a

A compound represented by the formula (191-a) was synthesized by the following scheme (Scheme 39).

[Reaction Scheme 39]

                                                [Formula 191-a]

Instead of the 9,9-diphenyl-9H-fluorene-2-yl boronic acid used in [Reaction Scheme 1] in Synthesis Example 1, 2,4-dibromobutane instead of benzene 2,5- (Yield: 65.8%) of a compound represented by the formula [191-a] was obtained.

(2) Synthesis of Compound Represented by Formula 191-b

A compound represented by the formula (191-b) was synthesized by the following reaction scheme (40).

[Reaction Scheme 40]

[Formula 191-a] [Formula 191-b]

Synthesis was carried out in the same manner as in Synthesis Example 1, except that [Formula 191-a] was used in place of [Formula 13-a] used in [Reaction Scheme 2] in Synthesis Example 1 to obtain 22.5 g of the compound represented by Formula 191- : 56%).

(3) Synthesis of Compound Represented by Formula 191-c

A compound represented by the formula (191-c) was synthesized by the following reaction scheme (41).

[Reaction Scheme 41]

[Formula 191-b] [Formula 191-c]

Was synthesized in the same manner as in Synthesis Example 1, except that [Formula 191-b] was used instead of [Formula 13-b] used in [Reaction Scheme 3] in Synthesis Example 1 to obtain 20.4 g : 62.7%).

(4) Synthesis of Compound Represented by Formula 191-d

A compound represented by the formula (191-d) was synthesized by the following reaction scheme (42).

[Reaction Scheme 42]

                                                [Chemical Formula 191-d]

30 g (114 mmol) of methyl 2-iodobenzoate and 360 ml of N, N-dimethylformamide were added to a 1 L round bottom flask, and then 22.5 g (229 mmol) of trimethylsilylacetylene and 114.9 ml 8 g (11 mmol) of dichloro (bistriphenylphosphine) palladium (II) and 2.2 g (11 mmol) of Cooper (I) iodide were placed under nitrogen bubbling for 20 minutes and the mixture was heated and stirred at 80 ° C for 3 hours. When the reaction was completed, the reaction solution was purified by column to obtain 23 g (yield: 86%) of a compound represented by the formula [191-d].

(5) Synthesis of Compound Represented by Formula 191-e

A compound represented by the formula (191-e) was synthesized by the following scheme (43).

[Reaction Scheme 43]

[Formula 191-d] [Formula 191-e]

23 g (99 mmol) of [Formula 191-d], 230 ml of acetonitrile and 50 ml of water were placed in a 1 L round bottom flask, and 45.1 g (297 mmol) of cesium fluoride was added thereto. The mixture was stirred at room temperature, After completion of the reaction, the reaction solution was extracted with ethyl acetate and 0.2N hydrochloric acid. The organic layer was separated and purified by column to obtain 18 g (yield: 82.6%) of a compound represented by the formula [191-e].

(6) Synthesis of a compound represented by the formula (191-f)

A compound represented by the formula (191-f) was synthesized by the following scheme (44).

[Reaction Scheme 44]

[Chemical Formula 191-c] [Chemical Formula 191-e] [Chemical Formula 191-f]

Was synthesized in the same manner as in Synthesis Example 1, except that [Formula 191-c] was used instead of [Formula 13-c] and [Formula 191-e] was used instead of phenylacetylene used in [Reaction Formula 4] 15 g (yield: 69%) of the compound represented by the formula [f] was obtained.

(7) Synthesis of a compound represented by the formula (191-g)

A compound represented by the formula (191-g) was synthesized by the following scheme (45).

[Reaction Scheme 45]

[Formula 191-f] [Formula 191-g]

G was synthesized except that [Formula 191-f] was used in place of [Formula 13-d] used in [Reaction Scheme 5] in Synthesis Example 1 to obtain 12 g of the compound represented by Formula 191- 79.8%).

(8) Synthesis of Compound Represented by Formula 191-h

A compound represented by the formula (191-h) was synthesized by the following scheme (46).

[Reaction Scheme 46]

[Formula 191-g] [Formula 191-g '] [Formula 191-h]

Was synthesized in the same manner as in Synthesis Example 1, except that [Formula 191-g] was used instead of [Formula 13-f] used in [Reaction Scheme 7] in Synthesis Example 1 to obtain 10 g of the compound represented by Formula 191- 65.5%).

(9) Synthesis of a compound represented by the formula (191-i)

A compound represented by the formula (191-i) was synthesized by the following reaction scheme (47).

[Reaction Scheme 47]

[Formula 191-h] [Formula 191-i]

15 g (30 mmol) of [Formula 191-h], 10 g (39 mmol) of bis (pinacolate) diboron and 1,1-bis (diphenylphosphino) ferrocene] dichloropalladium (II) were placed in a 500 ml round- , 0.59 g (1 mmol) of potassium acetate, 8.9 g (90 mmol) of potassium acetate and 150 ml of toluene were added and stirred under reflux. After the reaction was completed, the reaction mixture was filtered through silica gel / celite, concentrated under reduced pressure and separated into a column. The resulting solution was concentrated under reduced pressure, then crystallized with hexane and filtered to obtain 11 g of a compound represented by the formula (191- 67%).

(10) Synthesis of a compound represented by the formula (191-j)

[Chemical Formula 191-j] was synthesized by the following Reaction Scheme 48.

[Reaction Scheme 48]

[Formula 191-i] [Formula 191-j]

Except that [Formula 191-i] was used in place of [Formula 13-e] used in [Reaction Scheme 6] in Synthesis Example 1 to obtain 7 g of the compound represented by Formula 191- 62.7%).

(11) Synthesis of a compound represented by the formula (191-l) and (191-m)

[Chemical Formula 191-1] and [Chemical Formula 191-m] were synthesized according to the following Reaction Scheme 49.

[Reaction Scheme 49]

[Formula 191-j] [Formula 191-k] [Formula 191-1] [Formula 191-m]

Was synthesized in the same manner as in Synthesis Example 1, except that [Formula 191-j] was used instead of [Formula 13-f] used in Reaction Scheme 7 in Synthesis Example 1 to obtain 8 g of the compound represented by Formula 191-1 [ 33.6%) and 6 g (yield: 25.2%) of a compound represented by the formula 191-m.

(12) Synthesis of a compound represented by the formula (191-n)

A compound represented by the formula (191-n) was synthesized by the following reaction scheme (50).

[Reaction Scheme 50]

[Formula 191-1] [Formula 191-n]

9 g (14 mmol) of [Formula 191-1] and 75 ml of chloroform were added to a 250 ml round bottom flask, and then 1.96 ml (38 mmol) of bromine was separately added to 20 ml of chloroform and added dropwise to the reaction solution. While the reaction solution was stirred at room temperature, the reaction was terminated by TLC, and a saturated aqueous solution of sodium hydrogen carbonate was added to terminate the reaction. The resulting solid was filtered, washed with 100 ml of methanol and 100 ml of acetone, and then the solid was recrystallized from dichlorobenzene to obtain 6 g (yield: 53.8%) of a compound represented by the formula 191-n.

(13) Synthesis of Compound Represented by Formula 191

A compound represented by the formula (191) was synthesized by the following scheme (51).

[Reaction Scheme 51]

[Formula 191-n] [Formula 191]

(9 mmol) of 9-phenanthreneboronic acid, 0.2 g (1 mmol) of tetrakis (triphenylphosphine) palladium (0 mmol), and carbonic acid 2.4 g (17 mmol) of potassium, 35 ml of tetrahydrofuran, 35 ml of toluene and 15 ml of water were added and the mixture was stirred under reflux. After the reaction was completed, the reaction mixture was cooled to room temperature and extracted with EA / H ₂ O. The organic layer was separated, concentrated under reduced pressure, recrystallized from toluene and dried to obtain 3.43 g (yield: 39.2% .

Synthesis Example 8 Synthesis of Compound Represented by Formula 182

(1) Synthesis of Compound Represented by Formula 182-a

A compound represented by Formula 182-a was synthesized by the following Reaction Formula 52.

[Reaction Scheme 52]

                                               [Formula 182-a]

31 g (277 mmol) of 2-methylcyclohexanone and 170 ml of acetic acid were added to a 500 ml round bottom flask and stirred at 40 to 60 ° C. 30 g (277 mmol) of phenylhydrazine was added dropwise to the reaction solution. After completion of dropwise addition, the reaction mixture was refluxed, and the reaction was completed by TLC. When the reaction was completed, 100 ml of water and sodium hydroxide were added to make the reaction solution. The reaction solution was extracted with ethyl acetate and hexane. The organic layer was separated, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and then separated into a column and purified to obtain 42 g of a compound represented by the formula 182-a (yield: 81.7% Respectively.

(2) Synthesis of Compound Represented by Formula 182-b

A compound represented by the formula (182-b) was synthesized by the following scheme (Scheme 53).

[Reaction Scheme 53]

[Formula 182-a] [Formula 182-b]

(227 mmol) of 4a-methyl-2,3,4,4a-tetrahydro-1H-carbazole was dissolved in 420 ml of toluene in a 2 L round bottomed flask and stirred at 10 ° C under a nitrogen atmosphere. 218 ml (349 mmol) of methyllithium was added dropwise to the reaction solution, and the mixture was stirred at room temperature. After completion of the reaction, water was added to terminate the reaction. The reaction solution was extracted with ethyl acetate. The organic layer was separated, concentrated under reduced pressure, and then separated into a column and purified to obtain 30 g (yield: 65.7%) of a compound represented by the formula 182-b.

(3) Synthesis of Compound Represented by Formula 182-c

A compound represented by the formula [182-c] was synthesized by the following reaction scheme [54].

[Reaction Scheme 54]

[Formula 191-m] [Formula 182-c]

The procedure of Synthesis Example 7 was repeated except that [Formula 191-m] was used instead of [Formula 191-l] used in Reaction Formula 50 of Synthesis Example 7 to obtain 5 g of the compound represented by Formula 182- 44.8%).

(4) Synthesis of Compound Represented by Formula 182

A compound represented by the formula (182) was synthesized by the following reaction scheme (55).

[Reaction Scheme 55]

[Formula 182-c] [Formula 182-b] [Formula 182]

(0.5 mmol) of tris (dibenzylideneacetone) dipalladium (0), 2 (2 mmol) of 2,2'-bipyridinium chloride , 0.3 g (0.5 mmol) of 2'- (diphenylphosphino) 1,1; -binaphthyl, 4,71 g (490 mmol) of sodium tertiary butoxide and 100 ml of toluene were placed and stirred under reflux. After completion of the reaction, the reaction mixture was filtered through silica gel and celite, and the filtrate was concentrated under reduced pressure. The filtrate was separated and purified by using a column. The eluent was concentrated under reduced pressure and recrystallized from toluene and ethyl acetate to give 3 g %).

Examples 1 to 8 Production of organic electroluminescent devices including the compounds synthesized by Synthesis Examples 1 to 8

The ITO glass was patterned to have a light emitting area of 2 mm x 2 mm and then cleaned. After the ITO glass was mounted in a vacuum chamber, the base pressure was adjusted to 1 × 0 ^-7 torr, and CuPc was deposited on the ITO to form a hole injection layer having a thickness of 800 Å. On the hole injection layer, To form a hole transporting layer having a thickness of 300 ANGSTROM. The hole of transporting the produced compound BH1 and by the invention to compound (3 wt%) of co-deposited by the formation of a 250Å thick light-emitting layer, and then depositing the Alq ₃ on the emission layer to form a 350Å thick electron transport layer . Then, a 5 Å thick LiF electron injection layer and a 500 Å thick Al electrode were sequentially formed to complete an organic light emitting device.

&Lt; Comparative Example 1 &

The compound [A] was used in place of the compound prepared by the present invention, and an organic light emitting device was completed.

[Compound A]

&Lt; Comparative Example 2 &

The compound [B] was used in place of the compound prepared by the present invention, and an organic light emitting device was completed.

[Compound B]

<Test Example>

Current, luminance (measured at 0.4 mA), color coordinates and lifetime (T97) for the organic light emitting device manufactured according to Examples 1 to 8 and Comparative Examples 1 and 2 were measured using PR650 Spectroscan Source Measurement Unit. Ltd.), and the results are shown in Table 1 below. T97 means the time required for the measured luminance to be reduced to 97% of the initial luminance and measured at 1,000 nits.

division Dopant Voltage (V) Current density (mA / cm 2) External quantum efficiency Brightness (cd / m 2) ClEx ClEy T97 (hr) Example 1 Formula 13 3.9 10 6.5 653 0.142 0.122 262 Example 2 Formula 16 3.7 10 6.4 667 0.141 0.130 222 Example 3 (32) 3.7 10 7.2 883 0.138 0.166 308 Example 4 98 3.7 10 6.0 551 0.136 0.112 111 Example 5 (119) 3.9 10 5.9 489 0.140 0.093 307 Example 6 136 4.0 10 6.0 717 0.142 0.160 181 Example 7 183 4.1 10 5.8 606 0.144 0.129 274 Example 8 (192) 3.8 10 6.2 677 0.143 0.139 78 Comparative Example 1 Compound A 4.3 10 5.06 534 0.133 0.137 45 Comparative Example 2 Compound B 4.3 10 4.59 504 0.134 0.144 35

As shown in Table 1, the organic light emitting device including the compound prepared according to Examples 1 to 8 of the present invention as a dopant has lower driving voltage (V), higher external voltage Quantum efficiency, excellent luminance, color purity and lifetime, it can be used for display devices, display devices, lighting, and the like.

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

Claims (9)

A condensed aryl compound which is any one selected from the group consisting of the following formulas (2) to (5):
(2)

(3)

[Chemical Formula 4]

[Chemical Formula 5]

In the above Chemical Formulas 2 to 5,
R ₁ to R ₄ , R ₆ to R ₁₀ and X ₁ to X ₄ are the same or different and each independently represents a hydrogen atom, a deuterium atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted An arylamine group having 5 to 30 carbon atoms, a substituted or unsubstituted aryl group having 5 to 50 carbon atoms, and a heteroaryl group having 3 to 50 carbon atoms having a substituted or unsubstituted heteroatom, O, N or S, Aromatic aliphatic, heteroaliphatic, or aromatic hetero ring,
Y ₁ and Y ₂ are the same or different and each independently represents a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms and a substituted or unsubstituted aryl group having 5 to 50 carbon atoms and a substituted or unsubstituted heteroatom such as O, Or a heteroaryl group having 3 to 50 carbon atoms with S. delete delete The method according to claim 1,
The condensed aryl compound represented by any one of formulas (2) to (5) is any one selected from the group consisting of the following formulas (6) to (203);

[Chemical Formula 6] &lt; EMI ID =

[Chemical Formula 8]

[Chemical Formula 11] [Chemical Formula 12]

[Chemical Formula 13]

[Chemical Formula 15]

[Chemical Formula 17]

[Chemical Formula 19]

[Chemical Formula 21]

[Chemical Formula 23]

[Chemical Formula 25]

[Chemical Formula 27]

[Chemical Formula 30]

(32)

[Chemical Formula 33]

[Chemical Formula 35]

[Chemical Formula 37]

[Chemical Formula 39]

[Chemical Formula 41]

[Chemical Formula 43]

[Chemical Formula 45]

[Chemical Formula 47]

[Chemical Formula 49]

[Chemical Formula 51]

(54)

[Chemical Formula 55]

[Chemical Formula 57]

[Chemical Formula 60]

[Chemical Formula 61]

(63)

[Chemical Formula 65]

[Chemical Formula 67]

(70)

[Chemical Formula 71]

[Chemical Formula 73]

[Chemical Formula 75]

[Formula 77]

[Formula 79]

[Formula 81]

[Chemical Formula 83]

[Chemical Formula 85]

[Chemical Formula 87]

(90)

[Chemical Formula 91]

[Chemical Formula 93]

[Chemical Formula 95]

(98)

(100)

(101)

[Chemical Formula 103]

(106)

(108)

(110)

(111)

[Formula 113]

(115)

(118)

(120)

[Formula 121]

(124)

[Formula 125]

(128)

[Formula 130]

[Formula 131]

[Formula 133]

[Chemical Formula 135]

[Chemical Formula 137]

[Formula 140]

(141)

(144)

[Chemical Formula 145]

[Chemical Formula 147]

[Formula 150]

[Formula 152]

(154)

[Chemical Formula 155]

(158)

[Formula 15]

[Formula 161]

(163)

[166]

[Formula 16]

(170)

(172)

[174]

[176]

[178]

[Formula 179]

[Formula 181] [Formula 182]

[Formula 184]

[Formula 186]

[Formula 188] [Formula 188]

[Chemical Formula 189] [Chemical Formula 190]

(191)

[Chemical Formula 193] [Chemical Formula 194]

[196]

[197] [198]

(200)

[Formula 201]

(203) Anode;
Cathode; And
The organic electroluminescent device according to any one of claims 1 to 5, which is interposed between the anode and the cathode. 6. The method of claim 5,
Wherein the compound is contained in the light emitting layer between the anode and the cathode. The method according to claim 6,
Wherein at least one layer selected from the group consisting of a hole injecting layer, a hole transporting layer, an electron blocking layer, a hole blocking layer, an electron transporting layer and an electron injecting layer is further interposed between the anode and the cathode. 8. The method of claim 7,
Wherein at least one layer selected from the group consisting of the hole injection layer, the hole transport layer, the electron blocking layer, the light emitting layer, the hole blocking layer, the electron transport layer and the electron injection layer is formed by a single molecular deposition method or a solution process. 6. The method of claim 5,
Wherein the organic electroluminescent device is used in a display device, a display device, or a device for monochromatic or white illumination.

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