WO2011149284A2 - Hetero-atom-containing compound in which carbazole and fluorene are fused, an organic electrical element using the same and a terminal thereof - Google Patents

Abstract

Provided are a hetero-atom-containing compound in which carbazole and fluorene are fused, an organic electrical element using the same and a terminal thereof

Description

Compound in which carbazole and fluorene are fused including a hetero atom, an organic electric device using the same, and a terminal thereof

The present invention relates to a compound in which carbazole and fluorene are fused including a hetero atom, an organic electric element using the same, and a terminal thereof.

In general, organic light emitting phenomenon refers to a phenomenon of converting electrical energy into light energy using an organic material. An organic electric element using an organic light emitting phenomenon usually has a structure including an anode, a cathode, and an organic material layer therebetween. In this case, the organic material layer is often formed of a multi-layered structure composed of different materials in order to increase the efficiency and stability of the organic electric device, for example, it may be made of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer.

Materials used as the organic material layer in the organic electric element may be classified into light emitting materials and charge transport materials, such as hole injection materials, hole transport materials, electron transport materials, electron injection materials, and the like, depending on their functions. The light emitting material may be classified into a polymer type and a low molecular type according to molecular weight, and may be classified into a fluorescent material derived from a singlet excited state of electrons and a phosphorescent material derived from a triplet excited state of electrons according to a light emitting mechanism. Can be. In addition, the light emitting material may be classified into blue, green, and red light emitting materials and yellow and orange light emitting materials required to achieve a better natural color according to the light emitting color.

On the other hand, when only one material is used as the light emitting material, the maximum emission wavelength is shifted to a long wavelength due to the intermolecular interaction, and the color purity decreases or the efficiency of the device decreases due to the emission attenuation effect. In order to increase the light emitting efficiency through the light emitting material, a host / dopant system may be used. The principle is that when a small amount of a dopant having an energy band gap smaller than that of a host forming the light emitting layer is mixed in the light emitting layer, excitons generated in the light emitting layer are transported to the dopant, thereby producing high efficiency light. At this time, since the wavelength of the host is shifted to the wavelength of the dopant, light having a desired wavelength can be obtained according to the type of dopant to be used.

In order to fully exhibit the excellent characteristics of the above-described organic electroluminescent device, a material forming the organic material layer in the device, such as a hole injection material, a hole transport material, a light emitting material, an electron transport material, an electron injection material, etc., is supported by a stable and efficient material. Although this should be preceded, the development of a stable and efficient organic material layer for an organic electric element has not yet been made sufficiently, and therefore, the development of new materials is continuously required.

Embodiments of the present invention to solve the problems of the above-described background, a compound fused with carbazole and fluorene containing a hetero atom having a novel structure, and also applied to the organic electronic device It has been found that the light emitting efficiency, stability and lifetime of the device can be greatly improved.

Accordingly, an object of the present invention is to provide a compound in which carbazole and fluorene are fused including a novel hetero atom, an organic electric device using the same, and a terminal thereof.

In one aspect, the present invention provides a compound of the formula:

The present invention is a compound in which carbazole and fluorene are fused with a hetero atom, and can be used as a hole injection, hole transport, electron injection, electron transport, light emitting material and passivation material in organic electronic devices. It can be used as a host or a dopant in a light emitting material and a host / dopant, can be used as a hole injection, a hole transport layer, and the effect of increasing the efficiency of the organic electronic device including the same, lowering the driving voltage, increasing the lifetime and stability Revealed.

Accordingly, the present invention provides a compound in which carbazole and fluorene are fused including a hetero atom, an organic electronic device using the same, and a terminal including the organic electronic device.

The present invention is a compound in which carbazole and fluorene are fused with a hetero atom, and are useful as a hole injection, hole transport, electron injection, electron transport, light emitting material and passivation (kepping) material, and in particular as a host or dopant alone. Do.

1 to 6 show examples of the organic light emitting display device to which the compound of the present invention can be applied.

Hereinafter, some embodiments of the present invention will be described in detail through exemplary drawings. In adding reference numerals to the components of each drawing, it should be noted that the same reference numerals are assigned to the same components as much as possible even though they are shown in different drawings. In addition, in describing the present invention, when it is determined that the detailed description of the related well-known configuration or function may obscure the gist of the present invention, the detailed description thereof will be omitted.

In addition, in describing the component of this invention, terms, such as 1st, 2nd, A, B, (a), (b), can be used. These terms are only for distinguishing the components from other components, and the nature, order or order of the components are not limited by the terms. If a component is described as being "connected", "coupled" or "connected" to another component, that component may be directly connected to or connected to that other component, but there may be another configuration between each component. It is to be understood that the elements may be "connected", "coupled" or "connected".

The present invention provides a compound of Formula 1 as follows.

[Formula 1]

(1) R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ and R ₁₂ are each independently of each other a hydrogen atom, a halogen atom, a cyan No group, alkoxy group, thiol group, substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, substituted or unsubstituted alkoxy group having 1 to 50 carbon atoms, substituted or unsubstituted alkenyl group having 1 to 50 carbon atoms, substituted or unsubstituted carbon number 5 to 60 arylene groups, substituted or unsubstituted aryl groups having 5 to 60 carbon atoms, substituted or unsubstituted aryloxy groups having 5 to 60 carbon atoms, sulfur (S), nitrogen (N), oxygen (O), phosphorus Substituted or unsubstituted alkyl group having 1 to 50 carbon atoms or at least one (P) and silicon (Si) or sulfur (S), nitrogen (N), oxygen (O), phosphorus (P) and silicon (Si) At least one substituted or unsubstituted heteroaryl group having 5 to 60 carbon atoms containing at least one or at least one containing sulfur (S), nitrogen (N), oxygen (O), phosphorus (P) and silicon (Si) Or a substituted or unsubstituted heteroaryloxy group having 5 to 60 carbon atoms.

(2) R ₁ and R ₂ , R ₂ and R ₃ , R ₃ and R ₄ , R ₅ and R ₆ , R ₆ and R ₇ , R ₇ and R ₈ , R ₈ and R ₉ , R ₉ and R ₁₀ , R ₁₀ and R ₁₁ , R ₁₁ and R ₁₂ may be bonded to adjacent groups, respectively, to form a substituted or unsubstituted saturated or unsaturated aliphatic ring, or a heterocycle having N, O, S as a heteroatom.

(3) at least one of X ₁ , X ₂ , X ₃ and X ₄ represents nitrogen (N) and the other represents carbon (C), and all of X ₁ , X ₂ , X ₃ and X ₄ are nitrogen (N); Can be.

(4) Y represents a hydrogen atom, a halogen atom, a cyano group, an alkoxy group, a thiol group, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted alkenyl group having 1 to 50 carbon atoms, a substituted or unsubstituted carbon number 5 To 60 arylene group, substituted or unsubstituted aryl group having 5 to 60 carbon atoms, substituted or unsubstituted aryloxy group having 5 to 60 carbon atoms, sulfur (S), nitrogen (N), oxygen (O), phosphorus ( A substituted or unsubstituted alkyl group having 1 to 50 carbon atoms or at least one of P) and silicon (Si) or sulfur (S), nitrogen (N), oxygen (O), phosphorus (P) and silicon (Si); Substituted or unsubstituted heteroaryl group having 5 to 60 carbon atoms containing at least one or at least one containing sulfur (S), nitrogen (N), oxygen (O), phosphorus (P) and silicon (Si) Or an unsubstituted heteroaryloxy group having 5 to 60 carbon atoms.

(5) n is an integer of 1-3.

(6) The compound having the above structural formula can be used in a soluble process.

Specific examples of the compound belonging to Formula 1 that is a compound in which carbazole and fluorene are fused with a hetero atom according to an embodiment of the present invention may be compounds represented by the following Formulas 2 to 5, but the present invention is limited thereto. It is not.

In another aspect, the present invention provides a compound of Formula 2 below.

[Formula 2]

In another aspect, the present invention provides a compound of Formula 3 below.

[Formula 3]

In another aspect, the present invention provides a compound of Formula 4 below.

[Formula 4]

In another aspect, the present invention provides a compound of Formula 5 below.

[Formula 5]

In Formula 5, Z is a single bond, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted alkenyl group having 1 to 50 carbon atoms, a substituted or unsubstituted arylene group having 5 to 60 carbon atoms, substituted or unsubstituted At least one aryl group having 5 to 60 carbon atoms, a substituted or unsubstituted aryloxy group having 5 to 60 carbon atoms, sulfur (S), nitrogen (N), oxygen (O), phosphorus (P) and silicon (Si) Substituted or unsubstituted carbon atoms containing at least one substituted or unsubstituted carbon group having 1 to 50 carbon atoms or sulfur (S), nitrogen (N), oxygen (O), phosphorus (P) and silicon (Si) 5 to 60 heteroaryl groups or substituted or unsubstituted C 5 to 60 heteroaryl containing at least one or more sulfur (S), nitrogen (N), oxygen (O), phosphorus (P) and silicon (Si) It is oxygen.

In addition, the compound of Formula 2 to 5 may be implemented in one form selected from the group consisting of Formula 6. However, the present invention is not limited to these.

[Formula 6]

The compound represented by Formula 1 to Formula 5 may be one of the compounds represented by Formula 6, but is not limited thereto. Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , X ₁ , of the compounds represented by Formula 1 to Formula 5 Each substituent of X ₂ , X ₃ , X ₄ , Y, and Z is illustrative of exemplary compounds because it is practically difficult to exemplify all compounds in a broad relationship, but Chemical Formulas 1 to 5 not shown in Chemical Formula 6 above Compounds represented by may also form part of the present specification.

Various organic electric devices exist in which compounds in which carbazole and fluorene are fused including heteroatoms described with reference to Chemical Formulas 1 to 6 are used as the organic material layer. Examples of organic electroluminescent devices in which carbazole and fluorene-fused compounds including hetero atoms described with reference to Chemical Formulas 1 to 6 may be used include, for example, organic light emitting diodes (OLEDs), organic solar cells, and organic photoconductors (OPCs). ) And organic transistors (organic TFTs).

An organic electroluminescent device (OLED) will be described as an example of an organic electroluminescent device to which compounds in which carbazole and fluorene fused including heteroatoms described with reference to Chemical Formulas 1 to 6 can be applied, but the present invention is not limited thereto. And a compound in which carbazole and fluorene containing a hetero atom described above are fused to various organic electric devices.

Another embodiment of the present invention is an organic electric device comprising a first electrode, a second electrode and an organic material layer disposed between the electrodes, wherein at least one of the organic material layer of the organic electric field comprising the compounds of Formula 1 to 6 Provided is a light emitting device.

1 to 6 show examples of the organic light emitting display device to which the compound of the present invention can be applied.

In an organic light emitting display device according to another embodiment of the present invention, at least one layer of an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer is formed to include the compounds of Formulas 1 to 6 above. Except for the above, it may be manufactured in a structure known in the art using conventional manufacturing methods and materials in the art.

The structure of the organic light emitting display device according to another embodiment of the present invention is illustrated in FIGS. 1 to 6, but is not limited thereto. 1, reference numeral 101 is a substrate, 102 is an anode, 103 is a hole injection layer (HIL), 104 is a hole transport layer (HTL), 105 is a light emitting layer (EML), 106 is an electron injection layer (EIL) ), 107 represents an electron transport layer (ETL), and 108 represents a cathode. Although not shown, the organic light emitting diode may further include a hole blocking layer (HBL) for blocking the movement of holes, an electron blocking layer (EBL) for preventing the movement of electrons, and a protective layer. The protective layer may be formed to protect the organic material layer or the cathode at the uppermost layer.

In this case, the compound in which the carbazole and fluorene containing the hetero atom described with reference to Chemical Formulas 1 to 6 are fused may be included in one or more of an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer. Specifically, the compound in which carbazole and fluorene containing a hetero atom described with reference to Chemical Formulas 1 to 6 are fused to a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, a hole blocking layer, an electron blocking layer, It may be used in place of one or more of the protective layers or in combination with them. Of course, not only used in one layer of the organic layer, but may be used in two or more layers.

In particular, a compound in which carbazole and fluorene containing a hetero atom described with reference to Chemical Formulas 1 to 6 are fused to a hole injection material, a hole transport material, an electron injection material, an electron transport material, a light emitting material, and a passivation (kepping) material It can be used, in particular alone as a light emitting material and a host or dopant.

For example, the organic light emitting device according to another embodiment of the present invention is a metal having a metal or conductivity on a substrate by using a physical vapor deposition (PVD) method such as sputtering or e-beam evaporation An oxide or an alloy thereof is deposited to form an anode, an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer is formed thereon, and then a material that can be used as a cathode is deposited thereon. Can be prepared.

In addition to the above method, an organic electronic device may be fabricated by sequentially depositing a cathode material, an organic material layer, and an anode material on a substrate. The organic material layer may have a multilayer structure including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer, but is not limited thereto and may have a single layer structure. In addition, the organic material layer may be formed by using a variety of polymer materials, and by using a process such as spin coating, dip coating, doctor blading, screen printing, inkjet printing, or thermal transfer, rather than a deposition method. It can be prepared in layers.

An organic light emitting display device according to another embodiment of the present invention is a solution process (soluble process such as spin coating or ink jet process of a carbazole and fluorene fused compound including the hetero atom described above) May be used.

The substrate is a support of the organic light emitting device, and a silicon wafer, quartz or glass plate, metal plate, plastic film or sheet, or the like can be used.

An anode is positioned over the substrate. This anode injects holes into the hole injection layer located thereon. As the anode material, a material having a large work function is usually preferred to facilitate hole injection into the organic material layer. Specific examples of the positive electrode material that can be used in the present invention include metals such as vanadium, chromium, copper, zinc and gold or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO); Combinations of metals and oxides such as ZnO: Al or SnO ₂ : Sb; Conductive polymers such as poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (PEDT), polypyrrole and polyaniline, and the like, but are not limited thereto.

The hole injection layer is located on the anode. The conditions required for the material of the hole injection layer are high hole injection efficiency from the anode, it should be able to transport the injected holes efficiently. This requires a small ionization potential, high transparency to visible light, and excellent hole stability.

The hole injection material is a material capable of well injecting holes from the anode at low voltage, and the highest occupied molecular orbital (HOMO) of the hole injection material is preferably between the work function of the positive electrode material and the HOMO of the surrounding organic material layer. Specific examples of hole injection materials include metal porphyrine, oligothiophene, arylamine-based organics, hexanitrile hexaazatriphenylene, quinacridone-based organics, perylene-based organics, Anthraquinone, polyaniline and polythiophene-based conductive polymers, but are not limited thereto.

The hole transport layer is positioned on the hole injection layer. The hole transport layer receives holes from the hole injection layer and transports the holes to the organic light emitting layer located thereon, and serves to prevent high hole mobility, hole stability, and electrons. In addition to these general requirements, when applied for vehicle body display, heat resistance to the device is required, and a material having a glass transition temperature (Tg) of 70 ° C. or higher is preferable. Materials satisfying these conditions include NPD (or NPB), spiro-arylamine compounds, perylene-arylamine compounds, azacycloheptatriene compounds, bis (diphenylvinylphenyl) anthracene, silicon germanium oxide Compound, a silicon-based arylamine compound, and the like.

The organic light emitting layer is positioned on the hole transport layer. The organic light emitting layer is a layer for emitting light by recombination of holes and electrons injected from the anode and the cathode, respectively, and is made of a material having high quantum efficiency. The light emitting material is a material capable of emitting light in the visible region by transporting and combining holes and electrons from the hole transport layer and the electron transport layer, respectively, and a material having good quantum efficiency with respect to fluorescence or phosphorescence is preferable.

Substances or compounds that satisfy these conditions include Alq3 for green, Balq (8-hydroxyquinoline beryllium salt) for blue, DPVBi (4,4'-bis (2,2-diphenylethenyl) -1,1'- biphenyl) series, Spiro material, Spiro-DPVBi (Spiro-4,4'-bis (2,2-diphenylethenyl) -1,1'-biphenyl), LiPBO (2- (2-benzoxazoyl) -phenol lithium salt), bis (diphenylvinylphenylvinyl) benzene, aluminum-quinoline metal complex, metal complexes of imidazole, thiazole and oxazole, and the like, perylene, and BczVBi (3,3 ') to increase blue light emission efficiency. [(1,1'-biphenyl) -4,4'-diyldi-2,1-ethenediyl] bis (9-ethyl) -9H-carbazole; DSA (distrylamine) can be used by doping in small amounts. In the case of red, DCJTB ([2- (1,1-dimethylethyl) -6- [2- (2,3,6,7-tetrahydro-1,1,7,7-tetramethyl-1H, 5H Small amounts of doping such as -benzo (ij) quinolizin-9-yl) ethenyl] -4H-pyran-4-ylidene] -propanedinitrile) can be used. When the light emitting layer is formed using a process such as inkjet printing, roll coating, or spin coating, an organic light emitting layer is formed of a polymer of polyphenylene vinylene (PPV) or a polymer such as poly fluorene. Can be used for

The electron transport layer is positioned on the organic light emitting layer. The electron transport layer needs a material having high electron injection efficiency from the cathode positioned thereon and capable of efficiently transporting the injected electrons. To this end, it must be made of a material having high electron affinity and electron transfer speed and excellent stability to electrons. Examples of the electron transport material that satisfies such conditions include Al complexes of 8-hydroxyquinoline; Complexes including Alq ₃ ; Organic radical compounds; Hydroxyflavone-metal complexes and the like, but are not limited thereto.

The electron injection layer is stacked on the electron transport layer. The electron injection layer is an aromatic (aromatic) having an imidazole ring, a metal complex compound such as Balq, Alq3, Be (bq) 2, Zn (BTZ) 2, Zn (phq) 2, PBD, spiro-PBD, TPBI, Tf-6P, etc. It can be produced by using low molecular materials containing compounds, boron compounds, etc. In this case, the electron injection layer may be formed in a thickness range of 100 kPa to 300 kPa.

The cathode is positioned on the electron injection layer. This cathode serves to inject electrons. As the material used as the cathode, it is possible to use the material used for the anode, and a metal having a low work function is more preferable for efficient electron injection. In particular, a suitable metal such as tin, magnesium, indium, calcium, sodium, lithium, aluminum, silver, or a suitable alloy thereof can be used. In addition, an electrode having a two-layer structure such as lithium fluoride and aluminum, lithium oxide and aluminum, strontium oxide and aluminum having a thickness of 100 μm or less may also be used.

The organic light emitting device according to the present invention may be a top emission type, a bottom emission type or a double-sided emission type according to the material used.

Meanwhile, the present invention includes a display device including the organic electric element described above, and a terminal including a control unit for driving the display device. This terminal means a current or future wired or wireless communication terminal. The terminal according to the present invention described above may be a mobile communication terminal such as a mobile phone, and includes all terminals such as a PDA, an electronic dictionary, a PMP, a remote control, a navigation device, a game machine, various TVs, various computers, and the like.

EXAMPLE

Hereinafter, the present invention will be described in more detail with reference to Preparation Examples and Experimental Examples. However, the following Preparation Examples and Experimental Examples are for illustrating the present invention, and the scope of the present invention is not limited thereto.

Production Example

Hereinafter, preparation examples or synthesis examples of compounds in which carbazole and fluorene are fused including a hetero atom belonging to Chemical Formula 1 will be described. However, since the number of compounds in which carbazole and fluorene are fused with a hetero atom belonging to Formula 1 is large, one or two of compounds in which carbazole and fluorene are fused with a hetero atom belonging to Formula 1 are exemplified. Explain. Those skilled in the art, that is, those skilled in the art, can prepare a compound in which carbazole and fluorene are fused including heteroatoms belonging to the present invention, which are not illustrated. have.

Synthetic

Step 1) Synthesis of Intermediate A

 Scheme 1

With reference to Scheme 1, the production method of intermediate A will be described.

Dissolve 1-Iodo-9,9-dimethyl-9 H- fluorene in anhydrous tetrahydrofuran, lower the temperature of the reaction to -78 ° C, slowly add dropwise n-BuLi (2.5 M in hexane), and then add the reaction to 0. Stir at 1 ° C. for 1 h. Lower the temperature of the reaction to -78 ° C,

After triisopropyl borate was added dropwise, the mixture was stirred at room temperature for 12 hours. When the reaction was terminated, 2N hydrochloric acid aqueous solution was added, stirred for 30 minutes, and extracted with CH ₂ Cl ₂ . After removal of a small amount of water with anhydrous magnesium sulfate (MgSO ₄ ), and filtration under reduced pressure, the product produced by concentrating the organic solvent was recrystallized using CH ₂ Cl ₂ and hexane solvent to give the desired intermediate A yield 78% Got it.

Step 2) Synthesis of Intermediate B-1

 Scheme 2

With reference to Scheme 2, a method for preparing intermediate B-1 will be described.

Intermediate A, 4-chloro-5-nitropyrimidine, Pd (PPh ₃ ) ₄ and potassium carbonate (K ₂ CO ₃ ) obtained in Scheme 1 were dissolved in tetrahydrofuran and a small amount of water, and then refluxed for 24 hours. After the reaction was completed, the temperature of the reactant was cooled to room temperature, extracted with CH ₂ Cl ₂ , and washed with water. A small amount of water was removed with anhydrous magnesium sulfate, filtered under reduced pressure, and the organic solvent was concentrated and the resulting product was separated using column chromatography to give the desired intermediate B-1 or B-2 in yield 68%.

Step 3) Synthesis of Intermediate B-2

 Scheme 3

With reference to Scheme 3, the method for preparing intermediate B-2 will be described.

After dissolving intermediate A, 2,4-dichloro-5-nitropyrimidine, Pd (PPh ₃ ) ₄ and potassium carbonate (K ₂ CO ₃ ) obtained in Scheme 1 in tetrahydrofuran (THF) and a small amount of water, 24 It was refluxed for time. After the reaction was completed, the temperature of the reactant was cooled to room temperature, extracted with CH ₂ Cl ₂ , and washed with water. A small amount of water was removed with anhydrous magnesium sulfate, filtered under reduced pressure, and then the organic solvent was concentrated and the resulting product was separated using column chromatography to give the desired intermediate B-2 in 70% yield.

Step 4) Synthesis of Intermediate C-1

 Scheme 4

With reference to Scheme 1, the production method of intermediate C-1 will be described.

Intermediate B-1 and triphenylphosphine obtained in Scheme 2 were dissolved in o -dichlorobenzene and refluxed for 24 hours. After completion of the reaction, the solvent was removed using distillation under reduced pressure, and the concentrated product was separated using column chromatography to obtain the desired intermediate C-1 in 61% yield.

Step 5) Synthesis of Intermediate C-2

 Scheme 5

Referring to Scheme 5, a method for preparing intermediate C-2 will be described.

Intermediate B-2 and triphenylphosphine obtained in Scheme 3 were dissolved in o-dichlorobenzene and refluxed for 24 hours. After completion of the reaction, the solvent was removed using distillation under reduced pressure, and the concentrated product was separated using column chromatography to obtain the desired intermediate C-2 in a yield of 58%.

Step 6) Synthesis of Intermediate D

 Scheme 6

With reference to Scheme 6, a method for preparing intermediate D will be described.

Intermediate C-2, phenylboronic acid, Pd (PPh ₃ ) ₄ and potassium carbonate obtained in Scheme 5 were dissolved in anhydrous tetrahydrofuran and a small amount of water, and then refluxed for 24 hours. After the reaction was completed, the temperature of the reactant was cooled to room temperature, extracted with CH ₂ Cl ₂ , and washed with water. A small amount of water was removed with anhydrous magnesium sulfate, filtered under reduced pressure, and then the organic solvent was concentrated and the resulting product was separated using column chromatography to give the desired intermediate D in 91% yield.

Step 7) Synthesis of Intermediate E

 Scheme 7

Referring to Scheme 7, the method for preparing Intermediate E will be described.

Intermediate C-2, bromobenzene, Pd ₂ (dba) ₃ , P ( ^t Bu) ₃ and NaO ^t Bu obtained in Scheme 5 were dissolved in toluene solvent and stirred at 110 ° C. for 6 hours. After the reaction was completed, the reaction was cooled to room temperature, extracted with CH ₂ Cl ₂ , and washed with water. After removing a small amount of water with anhydrous magnesium sulfate, and filtered under reduced pressure, the organic solvent was concentrated to give the resulting intermediate E in 65% yield by column chromatography.

Step 8) Synthesis of Intermediate F

 Scheme 8

With reference to Scheme 8, a method for preparing intermediate F will be described.

The intermediate E obtained in Scheme 7 was dissolved in anhydrous tetrahydrofuran, the temperature of the reaction was lowered to -78 ° C, n-BuLi (2.5 M in hexane) was slowly added dropwise, and the reaction was stirred at 0 ° C for 1 hour. I was. Then, the temperature of the reaction was lowered to -78 ℃, triisopropyl borate (triisopropyl borate) was added dropwise, and stirred at room temperature for 12 hours. After the reaction was completed, into a 2N-HCl aqueous solution, stirred for 30 minutes, CH ₂ and extracted with Cl ₂ and after removing a small amount of water over anhydrous magnesium sulfate and filtered under reduced pressure, and the resulting concentrated the organic solvent the product CH ₂ Recrystallization with Cl ₂ and hexane solvents afforded the desired intermediate F in 55% yield.

Synthesis Example Synthesis of Compound 30

 Scheme 9

With reference to Scheme 9, a method for preparing Compound 30 will be described.

Intermediate D and bromobiphenyl, Pd ₂ (dba) ₃ , P ( ^t Bu) ₃ and NaO ^t Bu synthesized in Scheme 4 were dissolved in toluene and then stirred at 110 ° C. for 6 hours. After the reaction was completed, the reaction was cooled to room temperature, extracted with CH ₂ Cl ₂ , and washed with water. After removing a small amount of water with anhydrous magnesium sulfate, and filtered under reduced pressure, the organic solvent was concentrated to give the desired compound 30 in 81% yield using column chromatography.

Synthesis Example) Synthesis of Compound 89

 Scheme 10

With reference to Scheme 10, the method for preparing compound 89 will be described.

Intermediate C-1 and 4,4′-dibromobiphenyl, Pd ₂ (dba) ₃ , P ( ^t Bu) ₃ and NaO ^t Bu synthesized in Scheme 3 above were dissolved in toluene solvent, and then 110 ° C. Stirred for 3 days. After the reaction was completed, the reaction was cooled to room temperature, extracted with CH ₂ Cl ₂ , and washed with water. After removing a small amount of water with anhydrous magnesium sulfate, and filtered under reduced pressure, the organic solvent was concentrated to give the desired compound 89 in 48% yield using column chromatography.

Synthesis Example) Synthesis Method of Compound 101

 Scheme 11

With reference to Scheme 11, the method for preparing Compound 101 will be described.

Intermediate C-1 and 1,3,5-tribromobenzene, Pd ₂ (dba) ₃ , P ( ^t Bu) ₃ and NaO ^t Bu synthesized in Scheme 3 above were dissolved in toluene solvent and then, 110 It was stirred for 2 days at ℃. After the reaction was completed, the reaction was cooled to room temperature, extracted with CH ₂ Cl ₂ , and washed with water. After removing a small amount of water with anhydrous magnesium sulfate and filtered under reduced pressure, the organic solvent was concentrated to give the resulting compound 101 in 48% yield using column chromatography.

Synthesis Example) Synthesis of Compound 129

 Scheme 12

With reference to Scheme 12, the method for the preparation of compound 129 will be described.

The intermediates E and F obtained in Schemes 7 to 8 were dissolved in Pd (PPh ₃ ) ₄ and potassium carbonate in anhydrous tetrahydrofuran and a small amount of water, and then refluxed for 24 hours. After the reaction was completed, the temperature of the reactant was cooled to room temperature, extracted with CH ₂ Cl ₂ , and washed with water. A small amount of water was removed with anhydrous magnesium sulfate, filtered under reduced pressure, and the resulting product was concentrated by separating an organic solvent. The desired product 129 was obtained in a yield of 62% by column chromatography.

Meanwhile, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , X _{1 of} the compounds represented by Formula 1 to Formula 5 Substituents of X, X ₂ , X ₃ , X ₄ , Y, and Z are represented by the general formulas (1) to (5), which exemplarily described the synthesis examples of the representative compounds in a broad relationship, but are not exemplarily described as the synthesis examples. The resulting compounds may also form part of this specification.

Manufacturing evaluation of organic electroluminescent element

Compounds 30, 89, 101, and 129 obtained through synthesis were used as light emitting host materials of the light emitting layer, respectively, to fabricate an organic light emitting diode according to a conventional method. First, a copper phthalocyanine (hereinafter abbreviated as CuPc) film was vacuum-deposited on the ITO layer (anode) formed on the glass substrate to form a thickness of 10 nm. Subsequently, 4,4-bis [ N- (1-naphthyl) -N -phenylamino] biphenyl (hereinafter abbreviated as a-NPD) was vacuum-deposited on the membrane to form a hole transport compound. A transport layer was formed. After forming the hole transporting layer, compounds 30, 89, 101 or 129 were respectively deposited on the hole transporting layer as a phosphorescent host material to form a light emitting layer, and then tris (2-phenylpyridine) iridium as a phosphorescent Ir metal complex dopant. (Hereinafter abbreviated as I r (ppy) ₃ ) was added. At this time, the concentration of I r (ppy) _{3 in} the light emitting layer was 5% by weight. As a hole blocking layer, (1,1'-bisphenyl) -4-oleito) bis (2-methyl-8-quinoline oleito) aluminum (hereinafter abbreviated as BAlq) was vacuum-deposited to a thickness of 10 nm, and electron injection was performed. Tris (8-quinolinol) aluminum (hereinafter abbreviated to Alq ₃ ) was deposited into the layer to a thickness of 40 nm. Subsequently, LiF, an alkali metal halide, was deposited to a thickness of 0.2 nm, and then Al was deposited to a thickness of 150 nm to use an Al / LiF as a cathode to prepare an organic light emitting device.

Comparative Experiment

For comparison, an organic electroluminescent device having the same structure as the test example was manufactured using a compound represented by the following formula (hereinafter abbreviated as CBP) as a light emitting host material instead of the compound of the present invention.

[Formula 7]

Table 1

	Host material of emitting layer	Voltage (V)	Current density (mA / cm 2 )	Luminance (cd / m 2 )	Luminous Efficiency (cd / A)	Chromaticity coordinates (x, y)
Example 1	Compound 30	5.3	0.31	108	48.3	(0.30, 0.60)
Example 2	Compound 89	5.7	0.33	106	55.2	(0.32, 0.61)
Example 3	Compound 101	5.5	0.32	106	50.9	(0.30, 0.60)
Example 4	Compound 129	5.4	0.31	108	51.3	(0.30, 0.60)
Comparative Example 1	CBP	6.1	0.31	101	32.6	(0.33, 0.61)

As can be seen from the results of Table 1, the organic electroluminescent device using the organic electroluminescent device material of the present invention is not only high efficiency and color purity, but also a long life green light emission is obtained green phosphorescent host material of the organic light emitting device It can be used to significantly improve the luminous efficiency and lifetime.

Even if the compounds of the present invention are used in other organic material layers of the organic light emitting device, for example, a hole transport layer as well as a light emitting layer, a light emitting auxiliary layer, an electron injection layer, an electron transport layer, and a hole injection layer, it is obvious that the same effect can be obtained. .

The terms "comprise", "comprise" or "having" described above mean that a corresponding component may be included, unless otherwise stated, and thus, excludes other components. It should be construed that it may further include other components. All terms, including technical and scientific terms, have the same meanings as commonly understood by one of ordinary skill in the art unless otherwise defined. Terms commonly used, such as terms defined in a dictionary, should be interpreted to coincide with the contextual meaning of the related art, and shall not be construed in an ideal or excessively formal sense unless explicitly defined in the present invention.

The above description is merely illustrative of the technical idea of the present invention, and those skilled in the art to which the present invention pertains may make various modifications and changes without departing from the essential characteristics of the present invention. Therefore, the embodiments disclosed in the present invention are not intended to limit the technical idea of the present invention but to describe the present invention, and the scope of the technical idea of the present invention is not limited by these embodiments. The protection scope of the present invention should be interpreted by the following claims, and all technical ideas within the equivalent scope should be interpreted as being included in the scope of the present invention.

CROSS-REFERENCE TO RELATED APPLICATION

This patent application claims priority to US Patent Application No. 10-2010-0049328, filed in Korea on May 26, 2010, pursuant to Article 119 (a) (35 USC § 119 (a)). All content is incorporated by reference in this patent application. In addition, if this patent application claims priority for the same reason as above for a country other than the United States, all the contents thereof are incorporated into this patent application by reference.

Claims (11)

1. A compound represented by the following formula.

   

   R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ and R ₁₂ are each independently hydrogen, halogen, cyano or alkoxy. Groups, thiol groups, substituted or unsubstituted C1-C50 alkyl groups, substituted or unsubstituted C1-C50 alkoxy groups, substituted or unsubstituted C1-C50 alkenyl groups, substituted or unsubstituted C5-C60 Arylene group, substituted or unsubstituted aryl group having 5 to 60 carbon atoms, substituted or unsubstituted aryloxy group having 5 to 60 carbon atoms, sulfur (S), nitrogen (N), oxygen (O), phosphorus (P) And at least one substituted or unsubstituted alkyl group having 1 to 50 carbon atoms or sulfur (S), nitrogen (N), oxygen (O), phosphorus (P) and silicon (Si) containing at least one silicon (Si). A substituted or unsubstituted heteroaryl group having 5 to 60 carbon atoms or more containing at least one of sulfur (S), nitrogen (N), oxygen (O), phosphorus (P) and silicon (Si) Ring or unsubstituted heteroaryloxy group having 5 to 60 carbon atoms,

   At least one of X ₁ , X ₂ , X ₃ and X ₄ is nitrogen (N) and the rest represent carbon (C),

   Y is a hydrogen atom, a halogen atom, a cyano group, an alkoxy group, a thiol group, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted alkenyl group having 1 to 50 carbon atoms, a substituted or unsubstituted carbon group having 5 to 60 carbon atoms An arylene group, a substituted or unsubstituted aryl group having 5 to 60 carbon atoms, a substituted or unsubstituted aryloxy group having 5 to 60 carbon atoms, sulfur (S), nitrogen (N), oxygen (O), phosphorus (P) and At least one substituted or unsubstituted alkyl group having 1 to 50 carbon atoms or at least one of sulfur (S), nitrogen (N), oxygen (O), phosphorus (P) and silicon (Si) containing at least one silicon (Si) Substituted or unsubstituted containing at least one substituted or unsubstituted heteroaryl group having 5 to 60 carbon atoms or sulfur (S), nitrogen (N), oxygen (O), phosphorus (P) and silicon (Si) Heteroaryloxy group having 5 to 60 carbon atoms,

   n is an integer of 1-3.
2. The method of claim 1,

   R ₁ and R ₂ , R ₂ and R ₃ , R ₃ and R ₄ , R ₅ and R ₆ , R ₆ and R ₇ , R ₇ and R ₈ , R ₈ and R ₉ , R ₉ and R ₁₀ , R ₁₀ And R ₁₁ , R ₁₁ and R ₁₂ combine with an adjacent group to form a ring.
3. The method of claim 1,

   The compound is a compound represented by the following formula.

   

   

   

   

   Wherein Z is a single bond, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted alkenyl group having 1 to 50 carbon atoms, a substituted or unsubstituted arylene group having 5 to 60 carbon atoms, a substituted or unsubstituted carbon group having 5 to 50 carbon atoms Substitutes containing at least one aryl group of 60, a substituted or unsubstituted aryloxy group having 5 to 60 carbon atoms, sulfur (S), nitrogen (N), oxygen (O), phosphorus (P) and silicon (Si) Or a substituted or unsubstituted C 5 to 60 carbon atoms containing at least one unsubstituted alkyl group having 1 to 50 carbon atoms or sulfur (S), nitrogen (N), oxygen (O), phosphorus (P) and silicon (Si). Heteroaryl group or substituted or unsubstituted heteroaryloxy group having 5 to 60 carbon atoms containing at least one of sulfur (S), nitrogen (N), oxygen (O), phosphorus (P) and silicon (Si) .
4. The compound of claim 3, wherein the compound is

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   Compounds, characterized in that one selected from the group consisting of.
5. An organic electric device comprising at least one organic material layer comprising the compound of claim 1.
6. The method of claim 5,

   The organic material layer is an organic electric device, characterized in that formed by containing the compound by a solution process (soluble process).
7. The method of claim 5,

   The organic electroluminescent device is an organic electroluminescent device comprising a first electrode, the at least one organic material layer and the second electrode in a stacked form sequentially.
8. The method of claim 7, wherein

   The organic material layer is an organic electric element, characterized in that any one of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer.
9. The method of claim 7, wherein

   The organic material layer includes a light emitting layer,

   In the light emitting layer, the compound is used as a host or a dopant material.
10. A display device comprising the organic electric element of claim 7;

    And a control unit for driving the display device.
11. The method of claim 10,

    The organic electroluminescent device is one of an organic light emitting diode (OLED), an organic solar cell, an organic photoconductor (OPC) drum, an organic transistor (organic TFT).

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