KR101497127B1 - Compound Containing At Least Two 5-Membered Heterocycle And Organic Electronic Element Using The Same, Terminal Thereof - Google Patents

Abstract

The present invention provides a compound having at least two heteroatom hetero rings, and an organic electric device using the same, and a terminal thereof.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a compound having at least two heteroatoms and at least one heteroatom having at least two heteroatoms,

TECHNICAL FIELD The present invention relates to a compound having at least two heteroatom-containing heterocyclic rings, and an organic electronic device using the compound and a terminal thereof.

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 electric device using an organic light emitting phenomenon generally has a structure including an anode, an anode, and an organic material layer therebetween. Here, in order to increase the efficiency and stability of the organic electronic device, the organic material layer may have a multi-layer structure composed of different materials, and may be formed of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer.

A material used as an organic material layer in an organic electric device may 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 phosphorescent material derived from singlet excited state of electrons and a phosphorescent material derived from the triplet excited state of electrons . 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 may 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, the desired wavelength light can be obtained depending on the type of the dopant used.

In order to sufficiently exhibit the excellent characteristics of the organic electroluminescent device described above, a material 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 is supported by a stable and efficient material However, stable and efficient development of an organic material layer for an organic electric device has not yet been sufficiently developed, and therefore development of a new material is continuously required.

The present inventors have discovered a compound having two or more heteroatom hetero rings having a novel structure and have found that the application of this compound to an organic electric device can greatly improve the luminous efficiency, stability and lifetime of the device.

Accordingly, it is an object of the present invention to provide a novel compound having two or more heteroatom-containing heterocyclic rings, an organic electric device using the compound, and a terminal thereof.

In one aspect, the invention provides compounds represented by the formula:

The present invention is useful as a hole injecting material, a hole transporting material, a light emitting material and / or an electron transporting material suitable for the fluorescence of all colors such as red, green, blue and white and phosphorescent devices according to compounds having two or more heteroatoms. And is useful as a host material for phosphorescent dopants of various colors.

The present invention also provides an organic electronic device using a compound having the above formula and a terminal including the organic electronic device.

The compound according to embodiments of the present invention can play various roles in an organic electric device and a terminal and can lower the driving voltage of a device when applied to an organic electric device and a terminal and improve the light efficiency, have.

1 to 6 show examples of organic electroluminescent devices to which the compounds of the present invention can be applied.

Hereinafter, some embodiments of the present invention will be described in detail with reference to exemplary drawings. It should be noted that, in adding reference numerals to the constituent elements of the drawings, the same constituent elements are denoted by the same reference numerals even though they are shown in different drawings. In the following description of the present invention, a detailed description of known functions and configurations incorporated herein will be omitted when it may make the subject matter of the present invention rather unclear.

In describing the components of the present invention, the terms first, second, A, B, (a), (b), and the like can be used. These terms are intended to distinguish the constituent elements from other constituent elements, and the terms do not limit the nature, order or order of the constituent elements. When a component is described as being "connected", "coupled", or "connected" to another component, the component may be directly connected to or connected to the other component, It should be understood that an element may be "connected," "coupled," or "connected."

The present invention provides a compound of formula (1).

In Formula 1,

(1) R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀ independently represent a hydrogen atom, a halogen atom, a cyano group, , A substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted alkoxy 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 aryloxy 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) Substituted or unsubstituted alkyl group having 1 to 50 carbon atoms or at least one substituent containing at least one or more of sulfur (S), nitrogen (N), oxygen (O), phosphorus (P) and silicon (Si) Or an unsubstituted heteroaryl group having 5 to 60 carbon atoms or a substituted or nonsubstituted group containing at least one of sulfur (S), nitrogen (N), oxygen (O), phosphorus (P) And a substituted 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, and R ₉ and R ₁₀ are bonded to adjacent groups to form A ring can be formed.

(3) X is sulfur (S), oxygen (O) or silicon (Si).

(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 aryl group having 5 to 60 carbon atoms, a substituted or unsubstituted aryloxy group having 5 to 60 carbon atoms, a sulfur (S), a nitrogen (N), an oxygen (O) P) and silicon (Si), or a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms or a sulfur (S), nitrogen (N), oxygen (O), phosphorus (P) A substituted or unsubstituted heteroaryl group having 5 to 60 carbon atoms or a substituted or unsubstituted heteroaryl group containing at least one or more of sulfur (S), nitrogen (N), oxygen (O), phosphorus (P) and silicon Or an unsubstituted heteroaryloxy group having 5 to 60 carbon atoms.

(5) n is an integer of 1 to 3;

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

The present invention provides compounds of the following formulas (2) to (5).

The symbols in the following formulas (2) to (5) may be the same as those defined in formula (1).

(7) R ₁₁ represents a hydrogen atom, a halogen atom or a substituted or unsubstituted C1-C50 alkyl group, a substituted or unsubstituted C1-C50 alkenyl group, a substituted or unsubstituted C6-C60 arylene group, An unsubstituted aryl group having 5 to 60 carbon atoms or a substituted or unsubstituted group containing at least one of sulfur (S), nitrogen (N), oxygen (O), phosphorus (P) and silicon (Si) Lt; / RTI >

(8) Ar ₁ and Ar ₂ independently represent a hydrogen atom, a halogen atom, 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 5 to 60 A substituted or unsubstituted aryl group having 5 to 60 carbon atoms or a substituted or unsubstituted aryl group containing at least one of sulfur (S), nitrogen (N), oxygen (O), phosphorus (P) and silicon (Si) And a substituted heteroaryl group having 5 to 60 carbon atoms.

(9) R ₁₂ and R ₁₃ independently represent a hydrogen atom, a halogen atom, 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 5 to 60 A substituted or unsubstituted aryl group having 5 to 60 carbon atoms or a substituted or unsubstituted aryl group containing at least one of sulfur (S), nitrogen (N), oxygen (O), phosphorus (P) and silicon (Si) And a substituted heteroaryl group having 5 to 60 carbon atoms.

(10) Z denotes a single bond independently or, - O -, - S - , - CO -, - SO 2 -, - NR 14 -, - PR 15 -, - SiR 16 R 17 -, substituted or unsubstituted A substituted or unsubstituted C1 to C50 alkyl group, a substituted or unsubstituted C1 to C50 alkenyl group, a substituted or unsubstituted C6 to C60 arylene group, a substituted or unsubstituted C6 to C60 aryl group or a sulfur (S) Substituted or unsubstituted heteroaryl group having 5 to 60 carbon atoms and containing at least one of nitrogen (N), oxygen (O), phosphorus (P) and silicon (Si)

(11) R ₁₄ , R ₁₅ , R ₁₆ and R ₁₇ independently represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted alkenylene group having 1 to 50 carbon atoms, At least one of an unsubstituted arylene group having 5 to 60 carbon atoms, a substituted or unsubstituted aryl group having 5 to 60 carbon atoms or sulfur (S), nitrogen (N), oxygen (O), phosphorus (P) and silicon Or a substituted or unsubstituted heteroaryl group having 5 to 60 carbon atoms.

Specific examples of the compounds belonging to the formulas (1) to (5), which are compounds having two or more heteroatom-containing heterocyclic rings according to an embodiment of the present invention, include compounds represented by the following formula (6), but the present invention is not limited thereto.

There are various organic electric devices in which the compounds having two or more heteroatomic heterocyclic rings described with reference to Formulas 1 to 6 are used as organic layers. Organic electric devices in which the compounds having two or more heteroatoms having two or more heteroatoms as described with reference to Formulas 1 to 6 can be used include organic electroluminescent devices (OLED), organic solar cells, organic photoconductor (OPC) (Organic TFT), a photodiode, an organic laser, and a laser diode.

The organic electroluminescent device (OLED) will be described below as one example of the organic electroluminescent devices to which the compounds having two or more heteroatoms having two or more heteroatoms as described above with reference to the formulas (1) to (6) are applicable. However, A compound having at least one heteroatom hetero ring can be applied to various organic electronic devices.

Another embodiment of the present invention is directed to an organic electronic device comprising a first electrode, a second electrode, and an organic material layer disposed between the first electrode and the second electrode, wherein at least one of the organic material layers contains an organic electric field A light emitting device is provided.

1 to 6 show examples of organic electroluminescent devices to which the compounds of the present invention can be applied.

An organic electroluminescent device according to another embodiment of the present invention includes a hole injecting layer, a hole transporting layer, a light emitting layer, And an organic layer including an electron injecting layer are formed so as to include the compounds of the above Chemical Formulas 1 to 6, a structure known in the art using conventional manufacturing methods and materials in the art . ≪ / RTI >

The structure of an organic electroluminescent device according to another embodiment of the present invention is illustrated in FIGS. 1 to 6, but the present invention is not limited to these structures. Reference numeral 101 denotes a substrate, 102 denotes an anode, 103 denotes a hole injection layer (HIL), 104 denotes a hole transport layer (HTL), 105 denotes a light emitting layer (EML), 106 denotes an electron injection layer (EIL) ETL), and 108 denotes a cathode. However, the organic EL device may further include a hole blocking layer (HBL) for blocking the movement of holes, an electron blocking layer (EBL) for blocking the movement of electrons, and a protective layer. In the case of the protective layer, it may be formed to protect the organic layer at the uppermost layer or to protect the cathode.

At this time, the compound having two or more heteroatom heterocyclic rings described with reference to the formulas (1) to (6) may be included in at least one of organic compound layers including a hole injecting layer, a hole transporting layer, a light emitting layer and an electron transporting layer. Specifically, the compound having two or more heteroatom hetero rings described with reference to Formulas 1 to 6 may be at least one of a hole injecting layer, a hole transporting layer, a light emitting layer, an electron transporting layer, an electron injecting layer, a hole blocking layer, May be used in place of, or in combination with, layers. Of course, it can be used in more than two layers, not only one layer of the organic material layer.

Particularly, the compound having two or more heteroatoms having two or more heteroatoms as described with reference to the formulas (1) to (6) can be used as a hole injecting material, a hole transporting material, a light emitting material and a hole injecting material suitable for the fluorescence of all colors such as red, green, And / or as an electron transporting material, are useful as host materials for phosphorescent dopants of various colors, and are particularly useful as green phosphorescent host materials.

For example, the organic electroluminescent device according to another embodiment of the present invention may be formed by depositing a metal or a metal having conductivity on a substrate by using a physical vapor deposition (PVD) method such as sputtering or e-beam evaporation Oxide or an alloy thereof to form an anode, forming an organic material layer including a hole injecting layer, a hole transporting layer, a light emitting layer, an electron transporting layer and an electron injecting layer on the anode, depositing a material usable as a cathode thereon .

In addition to such a method, the organic material may be formed by sequentially depositing a negative electrode material, an organic material layer, and a positive electrode material on a substrate. The organic material layer may have a multi-layer 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 using a variety of polymer materials by a solvent process such as a spin coating process, a dip coating process, a doctor blading process, a screen printing process, an inkjet printing process or a thermal transfer process, Layer.

The organic electroluminescent device according to another embodiment of the present invention may form an organic layer, for example, a light emitting layer, by a solution process of a compound having two or more of the above-mentioned five-membered heterocyclic rings.

The substrate may be a silicon wafer, a quartz or glass plate, a metal plate, a plastic film, a sheet, or the like, which is a support for an organic electroluminescent device.

An anode is placed on the substrate. Such an anode injects holes into the hole injection layer located thereon. As the anode material, a material having a large work function is preferably used so as to smoothly inject holes into the organic material layer. Specific examples of the cathode 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), and indium zinc oxide (IZO); ZnO: Al or SnO _2: a combination of a metal and an oxide such as Sb; Conductive polymers such as poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (PEDT), polypyrrole and polyaniline.

A hole injection layer is located on the anode. The conditions required for the material of the hole injection layer are that the hole injection efficiency from the anode is high and the injected holes must be efficiently transported. For this purpose, the ionization potential is small, the transparency to visible light is high, and the stability against holes is excellent.

As the hole injecting material, it is preferable that the highest occupied molecular orbital (HOMO) of the hole injecting material be between the work function of the anode material and the HOMO of the surrounding organic layer. Specific examples of the hole injecting material include metal porphyrine, oligothiophene, arylamine-based organic materials, hexanitrile hexaazatriphenylene, quinacridone-based organic materials, perylene-based organic materials, Anthraquinone, polyaniline and a polythiophene-based conductive polymer, but are not limited thereto.

A hole transport layer is disposed on the hole injection layer. The hole transport layer transports holes from the hole injection layer to an organic light emitting layer disposed thereon, and has high hole mobility, stability to holes, and electrons. In addition to these general requirements, a material having a glass transition temperature (Tg) of 70 DEG C or more is preferable when heat resistance is required for a device for application to a vehicle body. Materials satisfying such conditions include NPD (or NPB), spiro-arylamine compounds, perylene-arylamine compounds, azacycloheptatriene compounds, bis (diphenylvinylphenyl) anthracene, silicon germanium oxide Compounds, silicone-based arylamine compounds, and the like.

An organic light emitting layer is disposed on the hole transporting layer. The organic light emitting layer is a layer in which holes and electrons injected from the anode and the cathode respectively recombine to emit light, and the organic light emitting layer is made of a material having high quantum efficiency. The light emitting material is preferably a material capable of emitting light in the visible light region by transporting and combining holes and electrons from the hole transporting layer and the electron transporting layer, respectively, and having a high quantum efficiency for fluorescence or phosphorescence.

Materials or compounds that satisfy these conditions include Alq3 in the case of green, Balq (8-hydroxyquinoline beryllium salt) in the case of blue, DPVBi (4,4'-bis (2,2-diphenylethenyl) biphenyl series, Spiro materials, Spiro-4,4'-bis (2,2-diphenylethenyl) -1,1'-biphenyl), LiPBO (2- (2-benzoxazoyl) -phenol lithium and metal complexes of imidazole, thiazole and oxazole, and perylene and BczVBi (3,3 ', 2', 2 ', 2'- Bis (9-ethyl) -9H-carbazole (DSA (distrylamine)) may be used as a dopant. In the case of red, the green luminescent material was doped with DCJTB ([2- (1,1-dimethylethyl) -6- [2- (2,3,6,7-tetrahydro-1,1,7,7-tetramethyl- -benzo (ij) quinolizin-9-yl) ethenyl] -4H-pyran-4-ylidene] -propanedinitrile). Polymer such as polyphenylene vinylene (PPV) -based polymer or polyfluorene (polyfluorene) can be formed on the organic light-emitting layer (light-emitting layer) when the light-emitting layer is formed using processes such as inkjet printing, roll coating, .

An electron transporting layer is disposed on the organic light emitting layer. Such an electron transporting layer requires a material capable of efficiently injecting electrons with a high electron injection efficiency from a cathode disposed thereon. For this purpose, it is required to be made of a material having high electron affinity, high electron transfer rate and excellent stability against electrons. Specific examples of the electron transporting material satisfying such conditions include an Al complex of 8-hydroxyquinoline; Complexes containing Alq ₃ ; Organic radical compounds; Hydroxyflavone-metal complexes, and the like, but are not limited thereto.

An electron injection layer is deposited on the electron transport layer. The electron injection layer may be a metal complex compound such as Balq, Alq3, Be (bq) 2, Zn (BTZ) 2, Zn (phq) 2, PBD, spiro-PBD, TPBI or Tf-6P, boron compounds, and the like. At this time, the electron injection layer may be formed in a thickness range of 100 ANGSTROM to 300 ANGSTROM.

On the electron injection layer, a cathode is positioned. These cathodes serve to inject electrons. As the material used for the cathode, materials used for the anode can be used, and a metal having a low work function is more preferable for efficient electron injection. Particularly suitable metals such as tin, magnesium, indium, calcium, sodium, lithium, aluminum, silver, or their alloys may be used. Also, an electrode having a two-layer structure such as lithium fluoride and aluminum, lithium oxide and aluminum, strontium oxide and aluminum, etc., having a thickness of 100 μm or less may be used.

As described above, according to the compound having two or more heteroatoms having two or more heteroatoms as described above with reference to the formulas (1) to (6), hole injection materials, hole transport materials, and light emitting materials suitable for the fluorescence of all colors such as red, green, , An electron transporting material and an electron injecting material, and can be used as a host material for phosphorescent dopants of various colors.

The organic electroluminescent device according to the present invention may be a front emission type, a back emission type, or a both-sided emission type, depending on the material used.

Meanwhile, the present invention includes a display device including the above-described organic electronic device 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 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 controller, a navigation device, a game machine, various TVs, and various computers.

Example

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

Manufacturing example

Hereinafter, preparation examples or synthesis examples of compounds having two or more heteroatom heterocyclic rings belonging to the general formula (6) will be described. However, one or two of the compounds having two or more heteroatom heterocycles belonging to the general formula (6) are exemplarily explained because the number of the compounds having two or more heteroatom heterocyclic rings belonging to the general formula (6) is large. Those skilled in the art, that is, those skilled in the art, can prepare the compound of the present invention having at least two heteroatomic heterocyclic rings which are not illustrated through the following production examples.

Step 1) Synthesis of intermediate A

[Reaction Scheme 1]

2-fluorothiophenol, Cu ₂ O and 1-chloro-2-nitrobenzene were added to the pyridine solvent at room temperature under nitrogen, and the reaction was refluxed for 12 hours. When the reaction was completed, the temperature of the reaction mixture was cooled to room temperature, 1 M aqueous HCl solution was added, and the mixture was extracted with ether and wiped with water. A small amount of water was removed with anhydrous MgSO _4. After filtration under reduced pressure, the organic solvent was concentrated, and the resulting product was separated by column chromatography to obtain the desired intermediate A (yield: 78%).

Step 2) Synthesis of intermediate B

[Reaction Scheme 2]

The intermediate A and iron powder obtained in step 1) were placed in a mixed solvent of ethanol and HCl, and the reaction was refluxed for 6 hours. After that, the reaction product was filtered using Celite, extracted with ethyl acetate, and wiped with water. A small amount of water was removed with anhydrous MgSO _4. After filtration under reduced pressure, the organic solvent was concentrated, and the resulting product was separated by column chromatography to obtain the desired intermediate B (yield: 90%).

Step 3) Synthesis of Intermediate C

[Reaction Scheme 3]

Intermediate B obtained in step 2) is dissolved in a mixed solvent of H ₂ O and H ₂ SO ₄ , and NaNO ₂ and KI are dissolved in H ₂ O and gradually added dropwise. After the dropwise addition, the mixture was stirred at room temperature for 30 minutes, then copper powder was added and the mixture was refluxed for 30 minutes. At the end of the reaction, the reaction mixture was cooled to room temperature, extracted with CH ₂ Cl ₂ and wiped with Na ₂ S ₂ O ₃ . A small amount of water was removed with anhydrous MgSO ₄ , filtered under reduced pressure, the organic solvent was concentrated, and the resulting product was separated by column chromatography to obtain the desired intermediate C (yield: 72%).

Step 4) Synthesis of Intermediate D

[Reaction Scheme 4]

Intermediate C obtained in step 3) is dissolved in anhydrous THF (tetrahydrofuran) and the temperature of the reaction is lowered to -78 ° C. After t- BuLi (1.5 M in pentane) was slowly added dropwise, the reaction was stirred at -78 < 0 > C for 1 hour, then the temperature of the reaction was raised to 0 < 0 > C and stirred again for 30 minutes. Thereafter, the temperature of the reaction was lowered again to -78 ° C, 1,2-dibromoethane was added dropwise, and the mixture was stirred at room temperature for 1 hour.

After the reaction was completed, the reaction mixture was extracted with ethyl acetate and wiped with water. A small amount of water was removed with anhydrous MgSO ₄ , filtered under reduced pressure, the organic solvent was concentrated, and the resulting product was separated by column chromatography to obtain the desired intermediate D (yield: 76%).

Step 5) Synthesis of intermediate E

[Reaction Scheme 5]

Intermediate D obtained in step 4) was dissolved in anhydrous THF, 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. Then, the temperature of the reaction was lowered to -78 ° C, trimethyl borate was added dropwise, and the mixture was stirred at room temperature for 12 hours. When the reaction was completed, 2N-HCl aqueous solution was added, stirred for 30 minutes, and extracted with ether.

After removing water in the reaction mixture with anhydrous MgSO ₄ , the reaction mixture was filtered under reduced pressure, the organic solvent was concentrated, and the resulting product was separated by column chromatography to obtain the desired intermediate E (yield: 81%).

Step 6) Synthesis of intermediate F

[Reaction Scheme 6]

Intermediate E, Pd (PPh ₃ ) ₄ and K ₂ CO ₃ obtained in step 5) were dissolved in anhydrous THF and a small amount of water, and refluxed for 24 hours. When the reaction was completed, the temperature of the reaction mixture was cooled to room temperature, extracted with CH ₂ Cl ₂ and wiped with water. A small amount of water was removed with anhydrous MgSO ₄ , filtered under reduced pressure, the organic solvent was concentrated, and the resulting product was separated by column chromatography to obtain the desired intermediate F (yield: 77%).

Step 7) Synthesis of intermediate G

[Reaction Scheme 7]

Intermediate F and triphenylphosphine obtained in step 6) were dissolved in o- dichlorobenzene and refluxed for 24 hours. After the reaction was completed, the solvent was removed by distillation under reduced pressure, and the concentrated product was separated by column chromatography to obtain the desired intermediate G (yield: 54%).

Synthesis Example 1 : Synthesis of Compound 1

[Reaction Scheme 8]

Intermediate G synthesized in Step 7), bromobenzene, Pd ₂ (dba) ₃ , P ( ^t Bu) ₃ and NaO ^t Bu were dissolved in toluene solvent and stirred at 110 ° C for 6 hours. When the reaction was completed, the temperature of the reaction was cooled to room temperature, then extracted with CH ₂ Cl ₂ and wiped with water. A small amount of water was removed with anhydrous MgSO ₄ , and the organic solvent was concentrated under reduced pressure. The resulting product was purified by column chromatography to obtain the desired compound 1 (yield: 81%).

Synthetic example  2: Synthesis of compound 56

[Reaction Scheme 9]

Intermediate G synthesized in Step 7), 4,4'-dibromobiphenyl, Pd ₂ (dba) ₃ , P ( ^t Bu) ₃ and NaO ^t Bu were dissolved in toluene solvent and stirred at 110 ° C for 6 hours. When the reaction was completed, the temperature of the reaction was cooled to room temperature, then extracted with CH ₂ Cl ₂ and wiped with water. A small amount of water was removed by using anhydrous MgSO ₄ , filtered under reduced pressure, and the organic solvent was concentrated. The resulting product was purified by column chromatography to obtain the desired compound 56 (yield: 59%).

Synthetic example  3: Synthesis of Compound 64

[Reaction Scheme 10]

Compound 1 obtained in the above step and NBS ( N- bromosuccinimide) and BPO (benzoyl peroxide) were dissolved in CH ₂ Cl ₂ and stirred at room temperature for 3 hours. After the reaction was completed, sodium bicarbonate aqueous solution was added, stirred for 30 minutes, and extracted with CH ₂ Cl ₂ . After removing water in the reaction mixture with anhydrous MgSO ₄ , the reaction mixture was filtered under reduced pressure, the organic solvent was concentrated, and the resulting product was separated by column chromatography to obtain the desired intermediate H (yield: 70%). Intermediate H, diphenylamine, Pd ₂ (dba) ₃ , P ( ^t Bu) ₃ and NaO ^t Bu were dissolved in toluene solvent and stirred at 110 ° C for 6 hours. When the reaction was completed, the temperature of the reaction was cooled to room temperature, then extracted with CH ₂ Cl ₂ and wiped with water. A small amount of water was removed with anhydrous MgSO ₄ , and the organic solvent was concentrated under reduced pressure. The resulting product was purified by column chromatography to obtain the desired compound 64 (yield: 57%).

Synthetic example  4: Synthesis of Compound 104

[Reaction Scheme 11]

Intermediate H obtained in the above step was dissolved in anhydrous THF, 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. Then, the temperature of the reaction was lowered to -78 ° C, trimethyl borate was added dropwise, and the mixture was stirred at room temperature for 12 hours. When the reaction was completed, 2N-HCl aqueous solution was added, stirred for 30 minutes, and extracted with ether.

After removing water in the reaction mixture with anhydrous MgSO ₄ , the reaction mixture was filtered under reduced pressure, and the organic solvent was concentrated. The resulting product was separated by column chromatography to obtain the desired intermediate I (yield: 69%).

Then, Intermediate I and Intermediate H, diphenylamine, Pd ₂ (dba) ₃ , P ( ^t Bu) ₃ and NaO ^t Bu were dissolved in toluene solvent and stirred at 110 ° C for 6 hours. At the end of the reaction, the temperature of the reaction was cooled to room temperature, extracted with CH ₂ Cl ₂ and wiped with water. A small amount of water was removed with anhydrous MgSO ₄ , and the organic solvent was concentrated under reduced pressure. The resulting product was purified by column chromatography to obtain the desired compound 104 (yield: 41%).

abandonment Field  Device manufacturing evaluation

Organic electroluminescent devices were fabricated according to a conventional method using the compounds 1, 56, 64, and 104 obtained through the synthesis as the luminescent host material of the light emitting layer. First, a film of copper phthalocyanine (hereinafter referred to as CuPc) was vacuum deposited on the ITO layer (anode) formed on a glass substrate to form a hole injection layer having a thickness of 10 nm.

Then, 4,4-bis [ N - (1-naphthyl) -N -phenylamino] biphenyl (abbreviated as a-NPD hereinafter) was vacuum deposited on the film to a thickness of 30 nm Thereby forming a hole transporting layer. After the hole transporting layer was formed, Compound 1, 56, 64, or 104 was deposited as a phosphorescent host material on the hole transporting layer to form a light emitting layer.

Tris (2-phenylpyridine) iridium (hereinafter abbreviated as I r (ppy) ₃ ) was added as a phosphorescent Ir metal complex dopant. At this time, the concentration of I r (ppy) _{3 in} the light emitting layer was 5 wt%. (1, 1 '-bisphenyl) -4-oleato) bis (2-methyl-8-quinolinolato) aluminum (hereinafter abbreviated as BAlq) as a hole blocking layer was vacuum deposited to a thickness of 10 nm, Tris (8-quinolinol) aluminum (hereinafter abbreviated as Alq ₃ ) was deposited to a thickness of 40 nm as an electron injecting layer. Thereafter, LiF as an alkali metal halide was deposited to a thickness of 0.2 nm, Al was deposited to a thickness of 150 nm, and the Al / LiF was used as a cathode. Thus, an organic electroluminescent device was fabricated.

Comparative Experimental Example

For comparison, an organic electroluminescent device having the same structure as that of the test example was prepared using the compound represented by the formula (7) (hereinafter abbreviated as CBP) instead of the compound of the present invention as a luminescent host material.

The light-
Host material Voltage
(V) Current density
(mA / cm ² ) Luminance
(cd / m ² ) Luminous efficiency
(cd / A) Chromaticity coordinates
(x, y) Example 1 Compound 1 6.1 0.31 103 43.9 (0.30, 0.60) Example 2 Compound 56 6.1 0.33 112 49.2 (0.32, 0.61) Example 3 Compound 64 6.1 0.31 107 41.4 (0.30, 0.60) Example 4 Compound 104 6.1 0.32 109 48.3 (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 material for an organic electroluminescent device of the present invention has high efficiency and improved color purity as well as long-life green luminescence, To thereby remarkably improve the luminous efficiency and life span.

It is apparent that the same effects can be obtained even when the compounds of the present invention are used for other organic layers of an organic electroluminescent device, for example, a light emitting layer, an electron injecting layer, an electron transporting layer, a hole injecting layer and a hole transporting layer.

While the present invention has been described with reference to exemplary embodiments, it is to be understood that the invention is not limited to the disclosed exemplary embodiments. Accordingly, the embodiments disclosed herein are intended to be illustrative rather than limiting, and the spirit and scope of the present invention is not limited by these embodiments.

The scope of protection of the present invention should be construed according to the following claims, and all the techniques within the scope of the same should be construed as being included in the scope of the present invention.

Claims (11)

A compound represented by the formula:
≪ Formula 4 >

In Formula 4,
X is S or O,
R ₁₁ is a C ₆ -C ₃₀ aryl group; A fluorenyl group substituted or unsubstituted with an alkyl group having _{1 to 20} carbon atoms; Is selected from the group consisting of; and sulfur (S), a heteroaryl group of C ₅ -C ₃₀ containing at least one heteroatom selected from the group consisting of nitrogen (N) and oxygen (O)
Ar ₁ and Ar ₂ are each independently a C ₆ -C ₃₀ aryl group; A fluorenyl group substituted or unsubstituted with an alkyl group having _{1 to 20} carbon atoms; It is selected from the group consisting of; and sulfur (S), a heteroaryl group of C ₅ -C ₃₀ containing at least one heteroatom selected from the group consisting of nitrogen (N) and oxygen (O). delete A compound represented by the formula:
≪ Formula 5 >

In the above formula (5)
X is S or O,
R ₁₂ and R ₁₃ are independently of each other a C ₆ -C ₃₀ aryl group; A fluorenyl group substituted or unsubstituted with an alkyl group having _{1 to 20} carbon atoms; Is selected from the group consisting of; and sulfur (S), a heteroaryl group of C ₅ -C ₃₀ containing at least one heteroatom selected from the group consisting of nitrogen (N) and oxygen (O)
Z is a single bond; A C ₆ -C ₃₀ arylene group; And a C ₅ -C ₃₀ heteroarylene group containing at least one heteroatom selected from the group consisting of sulfur (S), nitrogen (N) and oxygen (O). delete An organic electrical device comprising at least one organic layer comprising a compound represented by one of the following formulas:
&Lt; Formula 4 >< EMI ID =

In the above formulas (4) and (5)
X is S,
R ₁₁ is a C ₆ -C ₃₀ aryl group;
Ar ₁ and Ar ₂ are each independently a C ₆ -C ₃₀ aryl group,
R ₁₂ and R ₁₃ are each independently a C ₆ -C ₃₀ aryl group;
Z is a single bond; 6. The method of claim 5,
Wherein the organic compound layer is formed by a solution process of the compound. 6. The method of claim 5,
Wherein the organic electroluminescent device is an organic electroluminescent device including a first electrode, at least one organic layer, and a second electrode sequentially stacked. 8. The method of claim 7,
Wherein the organic material layer is any one of a hole injecting layer, a hole transporting layer, a light emitting layer, an electron transporting layer, and an electron injecting layer. 8. The method of claim 7,
Wherein the organic layer includes a light emitting layer,
Wherein the compound in the light emitting layer is used as a green phosphorescent host material. A display device including the organic electroluminescent device of claim 5;
And a control unit for driving the display device. 11. The method of claim 10,
The organic electric device may be an organic electroluminescent (OLED), an organic solar cell, an organic photoconductor (OPC) drum, an organic TFT, a photodiode, an organic laser, a laser diode The terminal being one of the plurality of terminals.

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