KR101996648B1 - New compounds and organic light-emitting diode including the same - Google Patents

Abstract

The present invention relates to a novel 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.
[Chemical Formula 1]

Description

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

The present invention relates to a novel compound and an organic electroluminescent device including the same as a light emitting material. More particularly, the present invention relates to a novel compound having excellent light emitting properties such as a driving voltage and a current efficiency, 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, an organic light emitting diode (OLED), which is a new flat display device, is a display using a self-luminous phenomenon and has a wide viewing angle and can be made thinner and thinner than a liquid crystal display, And in recent years, 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, a first object of the present invention is to provide a novel compound having low driving voltage and excellent light emitting efficiency.

A second object of the present invention is to provide an organic electroluminescent device comprising the novel 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 plurality of Rs are each independently selected from the group consisting of 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 alkenyl 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 of 6 to 30 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, A substituted or unsubstituted aryl 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, An aryl group, 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 hydroxyl group, a nitro group, a halogen group, Group, < / RTI >

A condensed ring of an aliphatic, aromatic, aliphatic hetero or aromatic hetero with an adjacent group can be formed.

According to one embodiment of the present invention, the above-mentioned formula (1) may be any one selected from the group consisting of the following formulas (2) to (6).

[Chemical Formula 2] < EMI ID =

[Chemical Formula 4]

[Chemical Formula 6]

In the above formulas 2 to 4,

Wherein the plural Rs are the same as defined in the formula (1)

The plurality of Ar's may be the same or different from each other and selected from substituted or unsubstituted aryl groups having 6 to 40 carbon atoms and substituted or unsubstituted heteroaryl groups having 2 to 40 carbon atoms.

또는

일 수 있다.According to another embodiment of the present invention,

or

Lt; / RTI >

According to another aspect of the present invention,

An anode, a cathode, and an organic electroluminescent device interposed between the anode and the cathode, the organic electroluminescent device comprising a compound represented by Formula 1 below.

According to the present invention, the novel compound represented by the formula (1) has stable and excellent luminescent characteristics as compared with the existing materials, so that the organic electroluminescent device including the novel compound can be operated at a low voltage and improve the luminous efficiency.

1 is a schematic view of an organic electroluminescent device according to one embodiment of the present invention.
FIG. 2 is a graph showing TGA and DSC of formula (72) according to an embodiment of the present invention.
FIG. 3 is a graph showing TGA and DSC of Formula 100 according to an embodiment of the present invention.
FIG. 4 illustrates TGA and DSC of Formula 137 according to an embodiment of the present invention. FIG.
FIG. 5 is a graph showing TGA and DSC of Formula 155 according to an embodiment of the present invention. Referring to FIG.
6 is a graph showing an EL spectrum of Formula 137 and Comparative Example (rubrene) according to an embodiment of the present invention.

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

The present invention is a novel compound contained in the light emitting layer of an organic electroluminescent device, which is a compound represented by the following formula (1), wherein the substituent is more specifically described below.

[Chemical Formula 1]

In Formula 1, each of the plurality of Rs is independently selected from the group consisting of a hydrogen atom, a heavy hydrogen 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 cycloalkyl group having 3 to 30 carbon atoms, A substituted or unsubstituted aryloxy group having 6 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 aryloxy group having 1 to 30 carbon atoms An alkylamine 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 carbon having a substituted or unsubstituted heteroatom, 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.

The above-mentioned formula (1) may be any one selected from the group consisting of the following formulas (2) to (6).

[Chemical Formula 2] < EMI ID =

[Chemical Formula 4]

[Chemical Formula 6]

In the above Chemical Formulas 2 to 4, the plurality of R's are the same as defined in Chemical Formula 1, and the plurality of Ar's are the same or different and each represents a substituted or unsubstituted aryl group having 6 to 40 carbon atoms And a substituted or unsubstituted heteroaryl group having 2 to 40 carbon atoms.

또는

인 것을 특징으로 한다.In the above formulas (2) to (6), the plurality of R, X and Ar are the same as defined in the formula (1)

or

.

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 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.

In the present invention, the term "substituted or unsubstituted" means a group selected from the group consisting of a cyano group, a halogen group, a hydroxyl group, a nitro group, an alkyl group, an alkoxy group, an alkylamino group, an arylamino group, a heteroarylamino group, an alkylsilyl group, Substituted or unsubstituted with at least one substituent selected from the group consisting of an oxygen atom, an aryl group, a heteroaryl group, germanium, phosphorus, boron, hydrogen and deuterium.

The formula 1 according to the present invention may be more specifically selected from the group consisting of the following formulas (7) to (260). However, the scope of the present invention is not limited thereto.

[Chemical Formula 8] < EMI ID =

[Chemical Formula 12] [Chemical Formula 13] [Chemical Formula 14]

[Chemical Formula 14] [Chemical Formula 15] [Chemical Formula 16]

[Chemical Formula 18] [Chemical Formula 19] [Chemical Formula 20]

[Chemical Formula 21] [Chemical Formula 22] [Chemical Formula 23] [Chemical Formula 24]

[Chemical Formula 26] [Chemical Formula 27] [Chemical Formula 28]

[Chemical Formula 30] [Chemical Formula 31] [Chemical Formula 32]

[Chemical Formula 35] [Chemical Formula 35]

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

[Chemical Formula 41] [Chemical Formula 41]

[Chemical Formula 48] [Chemical Formula 47] [Chemical Formula 48]

[Chemical Formula 50] [Chemical Formula 51] [Chemical Formula 52]

[Chemical Formula 55] [Chemical Formula 55] [Chemical Formula 56]

[Chemical Formula 60] [Chemical Formula 60] [Chemical Formula 60]

[Chemical Formula 62] [Chemical Formula 63] [Chemical Formula 64]

[Formula 67] < EMI ID = 67.1 >

[Chemical Formula 70] [Chemical Formula 71] [Chemical Formula 72]

[Formula 75] [Formula 75] [Formula 75]

[Chemical Formula 79] [Chemical Formula 79] [Chemical Formula 80]

[Chemical Formula 81] [Chemical Formula 83] [Chemical Formula 84]

[Chemical Formula 86] [Chemical Formula 87] [Chemical Formula 88]

[Chemical Formula 90] [Chemical Formula 91] [Chemical Formula 92]

[Chemical Formula 95] [Chemical Formula 95]

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

(101), (102), (103)

[Formula 107] [Formula 107] [Formula 108]

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

[Formula 115] < EMI ID = 116.1 >

[Formula 119] [Formula 119] [Formula 120]

[124] [124] [124] [124]

[Formula 125] [Formula 125]

[Formula 131] [Formula 131] [Formula 132]

[Chemical Formula 135] [Chemical Formula 135] [Chemical Formula 135]

[Formula 140] < EMI ID = 139.0 >

[Chemical Formula 141] [Chemical Formula 143] [Chemical Formula 144]

[Chemical Formula 145] [Chemical Formula 145] [Chemical Formula 148]

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

[Chemical Formula 155] [Chemical Formula 155]

[Formula 15] [Formula 15] [Formula 15] [Formula 15]

[Chemical Formula 161]

[Formula 166] [Formula 166]

[Formula 17] [Formula 17] [Formula 17]

[Formula 174] [Formula 176] [Formula 176]

[Formula 177] [Formula 179] [Formula 180]

[Formula 181] [Formula 182] [Formula 184] [Formula 184]

[Formula 186] [Formula 188] [Formula 188] [Formula 188]

[Formula 19] [Formula 19] [Formula 19] [Formula 19] [Formula 19]

[Formula 19] [Formula 19] [Formula 19] [Formula 196]

[197] [198] [198]

[Chemical Formula 201]

[Chemical Formula 20] [Chemical Formula 20]

[Chemical Formula 210] [Chemical Formula 211] [Chemical Formula 212]

[Chemical Formula 215] [Chemical Formula 215]

[Formula 21] [Formula 21] [Formula 21] [Formula 21]

[223] [223] [223]

[228] [228] [228]

[Formula 230] < EMI ID =

[233] [233] [233] [233]

[238] [238]

[243] [243] [243] [244]

[248] [248] [248] [248] [248]

[Formula 252] [Formula 252] [Formula 252]

[Formula 25] [Formula 25] [Formula 25] [Formula 25]

[Chemical Formula 259] [Chemical Formula 259]

The present invention also provides an organic electroluminescent device comprising an anode, a cathode, and a novel compound represented by the above formula (1) interposed between the anode and the cathode.

In this case, the layer containing the novel 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, ≪ RTI ID = 0.0 > and / or < / RTI >

In addition, 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 various phosphorescent host materials.

As a specific example, a hole transport layer (HTL) may be further stacked, and an electron transport layer (ETL) may be further stacked between the cathode and the organic emission layer. An electron donor molecule having a low ionization potential is used as the material of the hole transport layer. A diamine, triamine or tetraamine derivative having a basic skeleton of triphenylamine is used as the hole transport layer. It is widely used.

In the present invention, the material for the hole transport layer is not particularly limited as long as it is commonly used in the art. For example, N, N'-bis (3-methylphenyl) -N, N'- , 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 additionally 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. For example, (4,4 ', 4 "-tri (N-carbazolyl) triphenylamine), m-MTDATA (4,4', 4" -tris- (3-methylphenylphenyl amino) triphenylamine) can be used.

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 understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims. It will be clear to those who have knowledge.

<Examples>

Synthesis Example 1 Synthesis of Compound Represented by Formula 64

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

The compound represented by the formula (1-a) was synthesized by the following Reaction Scheme 1.

[Reaction Scheme 1]

[Chemical Formula 1-a]

50.0 g (0.292 mol) of 1-bromo-3-methylbenzene and 500 mL of tetrahydrofuran are placed in a 1 L round bottom flask and the temperature is cooled to -78 deg. After 97.3 g (0.358 mol) of normal butyl lithium was slowly added dropwise, the mixture was stirred at the same temperature for 1 hour, and 37.2 g (0.358 mol) of trimethyl borate was slowly added dropwise. The temperature was raised to room temperature and stirred for 2 hours. After completion of the reaction, the reaction was terminated with 2 molar hydrochloric acid aqueous solution and extraction. The organic layer was concentrated under reduced pressure, recrystallized with hexane and dried to obtain 30.6 g (77.1%) of the compound represented by the formula 1-a.

2) Synthesis of the compound represented by the formula 1-b

A compound represented by the formula 1-b was synthesized by the following Reaction Scheme 2.

[Reaction Scheme 2]

[Chemical Formula 1-b]

In a 5 L round bottom flask, 170 g (0.72 mol) of 1,4-dibromobenzene and 200.44 ml (1.59 mol) of chlorotrimethylsilane were charged and 1500 ml of tetrahydrofuran was added. The mixture was stirred for 30 minutes under a nitrogen atmosphere, . 792.72 ml (1.585 mol) of 2.0 molar lithium diisopropylamine was slowly added dropwise. After stirring at the same temperature for 1 hour, the temperature was raised to room temperature and stirred for 2 hours. After completion of the reaction, the reaction was terminated with an aqueous sulfuric acid solution and extracted. The organic layer was concentrated under reduced pressure, recrystallized from methanol, and dried to obtain 220 g (80.3%) of a compound represented by the formula 1-b.

3) Synthesis of the compound represented by the formula 1-c

The compound represented by the formula 1-c was synthesized by the following Reaction Scheme 3.

[Reaction Scheme 3]

[Chemical Formula 1-c]

(0.39 mol) of the compound represented by the formula 1-b obtained in the reaction formula 2 was added to a 5 L round bottom flask, 115.4 (0.95 mol) of phenyl boronic acid, 22.81 g (0.02 mol) of tetrakis (triphenylphosphine) palladium, 750 ml of toluene, 750 ml of tetrahydrofuran and 375 ml of water were added, and the mixture was refluxed for 12 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and extracted. The organic layer was concentrated under reduced pressure, and then separated by column chromatography using hexane. The solid was dried to obtain 136.1 g (92.1%) of the compound represented by the formula 1-c.

4) Synthesis of the compound represented by the formula (1-d)

The compound represented by the formula 1-d was synthesized by the following Reaction Scheme 4.

[Reaction Scheme 4]

[Chemical formula 1-d]

100 g (0.27 mol) of the compound represented by the formula 1-c obtained from the reaction formula 3 and 1000 ml of chloroform were added to a 5 L round bottom flask and stirred under a nitrogen atmosphere for 30 minutes, and the temperature of the reaction product was cooled to -78 ° C. 1067 ml (1.07 mol) of 1.0 mole of iodine monochloride was slowly added dropwise. After stirring at the same temperature for 1 hour, the temperature was raised to room temperature and stirred for 2 hours. After completion of the reaction, the reaction is terminated with an aqueous solution of sodium thiosulfite, the crystals are filtered off and washed with water and methanol. Recrystallization from hexane and drying yielded 119 g (92.5%) of the compound represented by the formula (1-d).

5) Synthesis of the compound represented by the formula 1-e

The compound represented by the formula 1-e was synthesized according to the following Reaction Scheme 5.

[Reaction Scheme 5]

[Formula 1-e]

(0.19 mol) of 2-phenylethynylphenylboronic acid, 0.14 g (0.19 mol) of tetrakis (triphenylphosphine) palladium (0) in a 1 L round bottomed flask was charged with 37.4 g (0.08 mol) ), 53.61 g (0.39 mol) of potassium carbonate, 320 ml of dioxane and 80 ml of water were added, and the mixture was refluxed for 12 hours. After the reaction is completed, the temperature is lowered to room temperature, and the crystals are filtered and washed with methanol. Recrystallization from methanol was carried out and dried to obtain 39.8 g (88.0%) of the compound represented by the formula (1-e).

6) Synthesis of the compound represented by the formula 1-f

The compound represented by the formula 1-f was synthesized according to the following Reaction Scheme 6.

[Reaction Scheme 6]

[Chemical Formula 1-f]

12 g (0.02 mol) of the compound represented by the formula 1-e obtained in the reaction formula 5 and 120 ml of methylene chloride were added to a 500 ml round-bottom flask and stirred under nitrogen for 30 minutes, and the temperature of the reaction product was cooled to -78 ° C. 49.4 ml (0.05 mol) of 1.0 mole of iodine monochloride was slowly added dropwise. After stirring at the same temperature for 1 hour, the temperature was raised to room temperature and stirred for 2 hours. After completion of the reaction, the reaction is terminated with an aqueous solution of sodium thiosulfite, the crystals are filtered off and washed with water and methanol. The residue was recrystallized from methanol and dried to obtain 11.7 g (67.9%) of a compound represented by the formula (1-f)

7) Synthesis of compound represented by formula (64)

The compound represented by the general formula (64) was synthesized by the following Reaction Scheme (7).

[Reaction Scheme 7]

                                 &Lt; EMI ID =

To a solution of 11.0 g (0.017 mol) of the compound represented by the formula 1-f obtained from the reaction formula 6, 5.8 g (0.040 mol) of the compound represented by the formula 1-a obtained from the reaction formula 1, 0.96 g (0.85 mmol) of palladium (0), 9.4 g (0.068 mol) of potassium carbonate, 120 ml of dioxane and 30 ml of water were added and refluxed for 12 hours. After completion of the reaction, add celite and silica gel in a hot state, filter, and wash with hot toluene. The filtrate was concentrated under reduced pressure, recrystallized from methanol and dried to obtain 7.2 g (52.5%) of a compound represented by the formula (64).

MS: m / z Anal. Calcd 762.33 [M] + Found: 763 [M] &lt; + &gt;; Anal. Calcd. C ₆₀ H ₄₂ : C, 94.45; H, 5.55. Found: C, 94.12; H, 5.69.

&Lt; Synthesis Example 2 > Preparation of the compound represented by the formula (72)

1) Synthesis of Compound Represented by Chemical Formula 72

The compound represented by the formula (72) was synthesized by the following Reaction Scheme 8.

[Reaction Scheme 8]

(72)

(0.04 mol) of diphenylamine, 0.1 g (0.14 mmol) of copper and 6.25 g (0.03 mol) of potassium phosphate were added to a 250 mL round-bottomed flask, , 0.35 g (1.00 mmol) of 3,5-ditertbutyl salicylic acid and 100 ml of xylene were added and refluxed for 24 hours. Cover with celite and silica gel in hot state, filter and wash with hot toluene. The filtrate was concentrated under reduced pressure, recrystallized from methanol and dried to obtain 7.3 g (55.1%) of a compound represented by the formula (72).

MS: m / z Anal. Calcd 945.2 [M] + Found: 944 [M] &lt; + &gt;; Anal. Calcd. C ₇₂ H ₅₂ N ₂ : C, 91.49; H, 5.55; N, 2.96. Found: C, 90.86; H, 4.98; N, 2.72.

&Lt; Synthesis Example 3 > Preparation of a compound represented by the formula (85)

1) Synthesis of Compound Represented by Formula 3-a

A compound represented by the formula 3-a was synthesized by the following Reaction Scheme 9.

[Reaction Scheme 9]

[Formula 3-a]

Synthesis was conducted in the same manner as in Reaction Scheme 1 of Preparation Example 1 to obtain 10.0 g (64.1%) of the compound represented by Formula 3-a.

2) Synthesis of the compound represented by the formula (72)

The compound represented by the general formula (85) was synthesized according to the following reaction formula (10).

[Reaction Scheme 10]

(85)

Synthesis was conducted in the same manner as in the above Reaction Scheme 7 to give 7.6 g (57.4%) of the compound represented by the formula (85).

MS: m / z Anal. Calcd 736.9 [M] + Found: 736 [M] &lt; + &gt;; Anal. Calcd. C ₅₆ H ₃₈ N ₂ : C, 91.27; H, 4.92; N, 3.80. Found: C, 89.62; H, 4.68; N, 3.56.

Synthesis Example 4: Preparation of a compound represented by the formula (100)

1) Synthesis of Compound Represented by Formula 100

The compound represented by the general formula (100) was synthesized by the following Reaction Scheme 11.

[Reaction Scheme 11]

(100)

(51.8%) was obtained by synthesizing the compound represented by the formula (100) in the same manner as in the reaction scheme 8 of the synthesis example 2.

MS: m / z Anal. Calcd 1169.45 [M] + Found: 1168 [M] &lt; + &gt;; Anal. Calcd. C ₉₀ H ₆₀ N ₂ : C, 92.43; H, 5.17; N, 2.40. Found: C, 91.83; H, 5.09; N, 2.28.

&Lt; Synthetic Example 5 > Preparation of a compound represented by the formula (115)

1) Synthesis of the compound represented by the formula (115)

The compound represented by the formula (115) was synthesized according to the following reaction scheme (12).

[Reaction Scheme 12]

(115)

Synthesis was conducted in the same manner as in Reaction Scheme 8 of Preparation Example 2 to obtain 7.5 g (52.6%) of the compound represented by Formula (115).

MS: m / z Anal. Calcd 1017.26 [M] + Found: 1016 [M] &lt; + &gt;; Anal. Calcd. C ₇₈ H ₅₂ N ₂ : C, 92.09; H, 5.15; N, 2.75. Found: C, 91.89; H, 5.24; N, 2.78.

&Lt; Synthesis Example 6 > Preparation of a compound represented by the formula (137)

1) Synthesis of the compound represented by the formula (137)

The compound represented by the formula (137) was synthesized by the following reaction scheme (13).

[Reaction Scheme 13]

(137)

Synthesis was conducted in the same manner as in Reaction Scheme 8 of Preparation Example 2 to obtain 6.7 g (52.3%) of a compound represented by the formula (137).

m / z Anal. Calcd 913.11 [M] + Found: 912 [M] +; Anal. Calcd. C ₇₀ H ₄₄ N ₂ : C, 92.08; H, 4.86; N, 3.07. Found: C, 91.82; H, 4.87; N, 2.89.

&Lt; Synthesis Example 7 > Preparation of a compound represented by the formula (153)

1) Synthesis of Compound Represented by Chemical Formula 153

The compound represented by the formula (153) was synthesized according to the following reaction scheme (14).

[Reaction Scheme 14]

[Formula 153]

Was synthesized in the same manner as Reaction Scheme 8 in Synthesis Example 2 to obtain 9.4 (58.7%) of the compound represented by the formula (153).

MS: m / z Anal. Calcd 1141.57 [M] + Found: 1140 [M] +; Anal. Calcd. C ₈₆ H ₈₀ N ₂ : C, 90.48; H, 7.06; N, 2.45. Found: C, 90.02; H, 6.97; N, 2.49.

Synthesis Example 8: Preparation of a compound represented by the formula (155)

1) Synthesis of the compound represented by the formula (155)

The compound represented by the formula (155) was synthesized according to the following reaction scheme (15).

[Reaction Scheme 15]

(155)

Synthesis was conducted in the same manner as Reaction Scheme 8 in Synthesis Example 2 to obtain 9.9 g (57.8%) of the compound represented by the formula (155).

MS: m / z Anal. Calcd 1221.53 [M] + Found: 1221 [M] +; Anal. Calcd. C ₉₄ H ₆₄ N ₂ : C, 92.43; H, 5.28; N, 2.29. Found: C, 92.09; H, 5.97; N, 2.39.

Synthesis Example 9 Synthesis of Compound Represented by Formula 161

1) Synthesis of Compound Represented by Formula 161

The compound represented by the formula (161) was synthesized by the following reaction scheme (16).

[Reaction Scheme 16]

[Formula 161]

Synthesis was conducted in the same manner as Reaction Scheme 8 in Synthesis Example 2 to obtain 7.4 g (57.6%) of the compound represented by Formula 161.

MS: m / z Anal. Calcd 917.14 [M] &lt; + &gt;; Found: 916 [M] +; Anal. Calcd. C ₇₀ H ₄₈ N ₂ : C, 91.67; H, 5.28; N, 3.05. Found: C, 91.02; H, 3.97; N, 3.09.

Synthesis Example 10 Synthesis of Compound Represented by Formula (171)

1) Synthesis of Compound Represented by Formula 10-a

A compound represented by the general formula (10-a) was synthesized by the following Reaction Scheme (17).

[Reaction Scheme 17]

[Chemical Formula 10-a]

29.2 g (0.12 mol) of triphenylamine and 80 ml of dimethylformamide were added to a 500 mL round-bottomed flask, stirred under a nitrogen atmosphere for 30 minutes, and the temperature of the reaction product was cooled to 0 degree. 7.1 g (0.04 mol) of n-bromosuccinimide was dissolved in 120 ml of dimethylformamide and slowly added dropwise to the reaction mixture. After stirring at the same temperature for 1 hour, the temperature was raised to room temperature and stirred for 2 hours. After completion of the reaction, the reaction was terminated with water and the reaction mixture was extracted. The organic layer was concentrated under reduced pressure, recrystallized with hexane, and dried to obtain 30.1 g (77.2%) of a compound represented by the formula 10-a.

2) Synthesis of the compound represented by the formula 10-b

The compound represented by the formula 10-b was synthesized by the following Reaction Scheme 18.

[Reaction Scheme 18]

[Chemical Formula 10-b]

Synthesis was conducted in the same manner as in Reaction Scheme 1 of Preparation Example 1 to obtain 15.1 g (73.3%) of the compound represented by Formula 10-b.

3) Synthesis of the compound represented by the formula (171)

The compound represented by the general formula (171) was synthesized by the following reaction scheme (19).

[Reaction Scheme 19]

[171]

Synthesis was conducted in the same manner as in the above Reaction Scheme 7 of Synthesis Example 1 to obtain 10.6 g (55.1%) of the compound represented by the Formula 171.

MS: m / z Anal. Calcd 1036.34 [M] &lt; + &gt;; Found: 1068 [M] +; Anal. Calcd. C ₃₇ H ₅₆ N ₂ : C, 92.10; H, 5.28; N, 2.62. Found: C, 92.02; H, 4.97; N, 2.69.

Synthesis Example 11 Synthesis of the compound represented by the formula (257)

1) Synthesis of Compound Represented by Formula 11-a

A compound represented by the formula 11-a was synthesized by the following Reaction Scheme 20.

[Reaction Scheme 20]

[Formula 11-a]

To a 250 mL round bottom flask was added 30 g (0.26 mol) of indole, 44.8 g (0.26 mol) of 4-fluorobromobenzene, 29.8 g (0.51 mol) of potassium fluoride, 1.35 g (5 mmol) of 18- And the mixture was refluxed for 24 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and extracted. The organic layer was concentrated under reduced pressure, and then separated by column chromatography using hexane and ethyl acetate. The solid was dried to obtain 47.6 g (68.3%) of the compound represented by Formula 11-a.

2) Synthesis of the compound represented by the formula 11-b

The compound represented by the formula 11-b was synthesized by the following Reaction Scheme 21.

[Reaction Scheme 21]

[Formula 11-b]

Synthesis was conducted in the same manner as in Reaction Scheme 1 of Synthesis Example 1 to obtain 13.9 g (77.9%) of the compound represented by Formula 11-b.

3) Synthesis of the compound represented by the formula 257

A compound represented by the formula (257) was synthesized according to the following reaction scheme (22).

[Reaction Scheme 22]

[257]

(62.3%) of the compound represented by the formula (257) was synthesized in the same manner as in the reaction scheme 7 of the synthesis example 1.

MS: m / z Anal. Calcd 1065.3 [M] + Found: 1064 [M] &lt; + &gt;; Anal. Calcd. C ₈₂ H ₅₂ N ₂ : C, 92.45; H, 4.92; N, 2.63. Found: C, 91.87; H, 5.38; N, 2.64.

&Lt; Examples 1 to 11 > Manufacture of Organic Electroluminescent Device

The ITO glass was patterned to have a light emitting area of 2 mm x 2 mm and then cleaned. After the substrate was mounted in a vacuum chamber, the substrate was adjusted to have a pressure of 1 × 10 ^-6 torr. Then, an organic material was doped with DNTPD (700 Å), NPD (300 Å), compound according to the present invention + DCJTB (1.0% (300 Å), LiF (5 Å), and Al (1,000 Å).

[DCJTB]

<Comparative Example>

The organic light emitting diode device for the comparative example was manufactured in the same manner except that rubrene was used in place of the compound prepared by the invention in the device structure of the embodiment.

[rubrene]

division Host Dopant Doping concentration (%) ETL V Cd / A CIEx CIEy Comparative Example 1 rubrene DCJTB 1.0 Alq ₃ 4.5 3.0 0.65 0.34 Example 1 (64) DCJTB 1.0 Alq ₃ 3.9 6.8 0.65 0.34 Example 2 (72) DCJTB 1.0 Alq ₃ 3.8 9.2 0.65 0.36 Example 3 Formula 85 DCJTB 1.0 Alq ₃ 4.1 7.8 0.65 0.34 Example 4 100 DCJTB 1.0 Alq ₃ 3.8 10.2 0.64 0.34 Example 5 Formula 115 DCJTB 1.0 Alq ₃ 4.2 10.1 0.65 0.35 Example 6 137 DCJTB 1.0 Alq ₃ 3.9 12.9 0.64 0.36 Example 7 Formula 153 DCJTB 1.0 Alq ₃ 4.1 11.7 0.65 0.36 Example 8 Formula 155 DCJTB 1.0 Alq ₃ 3.6 9.4 0.65 0.34 Example 9 Formula 161 DCJTB 1.0 Alq ₃ 3.7 8.7 0.65 0.36 Example 10 171 DCJTB 1.0 Alq ₃ 3.9 11.8 0.65 0.36 Example 11 257 DCJTB 1.0 Alq ₃ 4.5 8.7 0.65 0.34

As shown in Table 1, the organic compound obtained according to the present invention exhibits low driving voltage and excellent luminous efficiency as compared with rubrene, which is widely used as a conventional host material.

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 compound represented by any one of the following formulas (2) to (6):
(2)

In the above formula (2)
R ₁ to R ₈ each independently represents a hydrogen atom, a deuterium atom, a substituted or unsubstituted arylamine group having 5 to 30 carbon atoms, a substituted or unsubstituted aryl group having 5 to 50 carbon atoms, and a substituted or unsubstituted heteroatom O , A heteroaryl group having 3 to 50 carbon atoms having N or S,
Wherein R ₁ to R ₈ in the R ₃ to R ₈ all are hydrogen, or except when a heavy hydrogen, and aryl wherein R ₃ to R ₈ is a group having 5 to 30 carbon atoms both are each independently a substituted or unsubstituted amine group , A substituted or unsubstituted aryl group having 5 to 50 carbon atoms, and a substituted or unsubstituted heteroaryl group having 3 to 50 carbon atoms having a hetero atom O, N or S;

[Chemical Formula 3]

[Chemical Formula 5]

[Chemical Formula 6]

In the formulas (3) to (6)
R ₁ to R ₁₂ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted 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,
The plurality of R's are each independently selected from the group consisting of substituted or unsubstituted aryl groups having 5 to 50 carbon atoms and heteroaryl groups having 3 to 50 carbon atoms having substituted or unsubstituted heteroatoms O, N or S,
Ar

or

to be. delete delete The method according to claim 1,
[Formula 19], [Formula 197] to [Formula 245], and [Formula 248] to [Formula 259]: [Formula 24] Wherein the organic compound is any one selected from the group consisting of:

[Chemical Formula 30] [Chemical Formula 31] [Chemical Formula 32]

[Chemical Formula 35] [Chemical Formula 35]

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

[Chemical Formula 41] [Chemical Formula 41]

[Chemical Formula 48] [Chemical Formula 47] [Chemical Formula 48]

[Chemical Formula 50] [Chemical Formula 51] [Chemical Formula 52]

[Chemical Formula 55] [Chemical Formula 55] [Chemical Formula 56]

[Chemical Formula 60] [Chemical Formula 60] [Chemical Formula 60]

[Chemical Formula 62] [Chemical Formula 63] [Chemical Formula 64]

[Formula 67] &lt; EMI ID = 67.1 &gt;

[Chemical Formula 70] [Chemical Formula 71] [Chemical Formula 72]

[Formula 75] [Formula 75] [Formula 75]

[Chemical Formula 79] [Chemical Formula 79] [Chemical Formula 80]

[Chemical Formula 81] [Chemical Formula 83] [Chemical Formula 84]

[Chemical Formula 86] [Chemical Formula 87] [Chemical Formula 88]

[Chemical Formula 90] [Chemical Formula 91] [Chemical Formula 92]

(96)

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

(101), (102), (103)

[Formula 107] [Formula 107] [Formula 108]

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

[Formula 115] &lt; EMI ID = 116.1 &gt;

[Formula 119] [Formula 119] [Formula 120]

[124] [124] [124] [124]

[Formula 125] [Formula 125]

[Formula 131] [Formula 131] [Formula 132]

[Chemical Formula 135] [Chemical Formula 135] [Chemical Formula 135]

[Formula 140] &lt; EMI ID = 139.0 &gt;

[Chemical Formula 141] [Chemical Formula 143] [Chemical Formula 144]

[Chemical Formula 147]

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

[Chemical Formula 155] [Chemical Formula 155]

[Formula 15] [Formula 15] [Formula 15] [Formula 15]

[Chemical Formula 161]

[Formula 166] [Formula 166]

[Formula 17] [Formula 17] [Formula 17]

[Formula 174] [Formula 176] [Formula 176]

[Formula 177] [Formula 179] [Formula 180]

[Formula 181] [Formula 182] [Formula 184] [Formula 184]

[Formula 186] [Formula 188] [Formula 188] [Formula 188]

[Formula 19] [Formula 19] [Formula 19] [Formula 19] [Formula 19]

[Chemical Formula 193] [Chemical Formula 194]

[197] [198] [198]

[Chemical Formula 201]

[Chemical Formula 20] [Chemical Formula 20]

[Chemical Formula 210] [Chemical Formula 211] [Chemical Formula 212]

[Chemical Formula 215] [Chemical Formula 215]

[Formula 21] [Formula 21] [Formula 21] [Formula 21]

[223] [223] [223]

[228] [228] [228]

[Formula 230] &lt; EMI ID =

[233] [233] [233] [233]

[238] [238]

[243] [243] [243] [244]

[248] [248]

[Formula 252] [Formula 252] [Formula 252]

[Formula 25] [Formula 25] [Formula 25] [Formula 25]

[Chemical Formula 259] [Chemical Formula 259] Anode;
Cathode; And
An organic electroluminescent element interposed between the anode and the cathode and comprising the compound according to claim 1. 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.

Images