WO2011108901A2

WO2011108901A2 - Spiro-carbazole compound comprising a spiro skeleton, and an organic electronic element using the same and a terminal thereof

Info

Publication number: WO2011108901A2
Application number: PCT/KR2011/001538
Authority: WO
Inventors: 김대성; 박정환; 김기원; 박용욱; 정화순; 변지훈; 박정근; 최대혁; 김동하
Original assignee: 덕산하이메탈(주)
Priority date: 2010-03-05
Filing date: 2011-03-07
Publication date: 2011-09-09
Also published as: WO2011108901A9; WO2011108901A3; KR20110100762A

Abstract

Provided are a spiro-carbazole compound comprising a spiro skeleton, and an organic electronic element using the same and a terminal thereof.

Description

Spyrocarbazole compounds comprising a spiro skeleton, organic electronic devices using the same, and terminals thereof

The present invention relates to a spiro carbazole compound containing a spiro skeleton, an organic electronic device 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 electronic device 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 to increase the efficiency and stability of the organic electronic device, for example, it may be made of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer.

Materials used as the organic material layer in the organic electronic device 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 organic electronic device described above, 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 electronic device has not been sufficiently achieved, and therefore, the development of a new material is still required.

The present inventors have found a spiro carbazole compound containing a spiro skeleton, and the compound has excellent electrical and luminescent properties, so that when applied to organic electronic devices, it has excellent hole injection and hole transport ability under low driving voltage. It has been found to be useful as a hole injection material and a hole transporting material having.

Accordingly, an object of the present invention is to provide an aromatic amine compound having various substituents, an organic electronic device using the same, and a terminal thereof.

In one aspect, the present invention provides a compound represented by the following formula.

At this time, the compound according to an embodiment of the present invention provides a spiro carbazole compound including a spiro skeleton.

The present invention has an aromatic amine compound having a variety of substituents and organic electronic device using the same, it can play a variety of roles in the terminal, and when applied to the organic electronic device and the terminal has excellent electrical characteristics and light emission characteristics excellent hole under low driving voltage It is useful as a hole injection material and a hole transport material having injection and hole transport ability. The present invention is also useful as a host material for phosphorescent dopants of various colors, depending on the compound. In the case of employing the organic film using the organic electroluminescent compound described above, an organic electronic device having high efficiency, low voltage, high brightness, and long life based on superior current density characteristics can be manufactured.

1 to 5 show examples of organic electronic devices to which the compounds 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 represented by Formula 1 below.

Formula 1

In the above formula,

(1) R ₁ , R ₂ , R ₃ and R ₄ are each independently a substituted or unsubstituted alkyl group having 1 to 60 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 60 carbon atoms, a substituted or unsubstituted carbon number 1 An alkenyl group of 60 to 60, a substituted or unsubstituted arylene group of 5 to 60 carbon atoms, a substituted or unsubstituted aryl group of 5 to 60 carbon atoms, a substituted or unsubstituted aryloxy group of 5 to 60 carbon atoms, sulfur (S), Substituted or unsubstituted alkyl group having 1 to 50 carbon atoms or at least one of nitrogen (N), oxygen (O), phosphorus (P) and silicon (Si) or sulfur (S), nitrogen (N), oxygen (O ) Substituted or unsubstituted heteroaryl group having 1 to 60 carbon atoms or at least one of phosphorus (P) and silicon (Si) or sulfur (S), nitrogen (N), oxygen (O), phosphorus (P) And it may be a substituted or unsubstituted C 1-60 heteroaryloxy group, an amine group containing at least one silicon (Si).

(2) R _a , R _b , R _c and R _d are each independently of each other a hydrogen atom, a halogen atom, a cyano group, a thiol group, a substituted or unsubstituted alkyl group having 1 to 60 carbon atoms, a substituted or unsubstituted carbon number 1 Alkoxy group of 60 to 60, substituted or unsubstituted alkenyl group of 1 to 60 carbon atoms, substituted or unsubstituted arylene group of 5 to 60 carbon atoms, substituted or unsubstituted aryl group of 5 to 60 carbon atoms, substituted or unsubstituted carbon atoms 5 Substituted or unsubstituted alkyl group having 1 to 50 carbon atoms or sulfur containing at least one aryloxy group, sulfur (S), nitrogen (N), oxygen (O), phosphorus (P) and silicon (Si) of 60 to 60 A substituted or unsubstituted heteroaryl group having 1 to 60 carbon atoms or at least one sulfur (S), nitrogen (S), nitrogen (N), oxygen (O), phosphorus (P) and silicon (Si); N), a substituted or unsubstituted heteroatom having 1 to 60 carbon atoms containing at least one of oxygen (O), phosphorus (P) and silicon (Si) It may be a ryloxy group, an amine group.

(3) Ar ₁ is a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 60 carbon atoms, a substituted or unsubstituted alkenyl group having 1 to 60 carbon atoms, a substituted or unsubstituted arylene group having 5 to 60 carbon atoms, substituted or unsubstituted A substituted or unsubstituted alkyl group having 1 to 50 carbon atoms containing at least one aryl group having 5 to 60 carbon atoms, sulfur (S), nitrogen (N), oxygen (O), phosphorus (P) and silicon (Si). Or a substituted or unsubstituted heteroaryl group having 1 to 60 carbon atoms or sulfur (S) containing at least one of sulfur (S), nitrogen (N), oxygen (O), phosphorus (P) and silicon (Si), It may be a substituted or unsubstituted heteroaryloxy group having 1 to 60 carbon atoms, an amine group containing at least one of nitrogen (N), oxygen (O), phosphorus (P) and silicon (Si).

(3) n is an integer of 1-4.

(4) R ₁ and R ₂ , R ₂ and R ₃ , R ₃ and R ₄ may combine with adjacent groups to form a substituted or unsubstituted saturated or unsaturated ring.

Compounds having the above structure may be used in a soluble process. That is, the organic material layer of the organic electric device, which will be described later, may be formed by the soluble process using the compound. In other words, the organic material layer of the organic electronic device is made by using a variety of polymer materials, and less by a solvent process (e.g., spin coating, dip coating, doctor blading, screen printing, inkjet printing or thermal transfer method) rather than deposition. It can be prepared in a number of layers.

The compound described above may be represented by the following formula (2). The compounds represented by Formula 2 may correspond to specific examples substituted with hydrogen atoms except for a specific position among the compounds represented by Formula 1.

Formula 2

In the above formula,

Ar ₁ is as defined above, Ar ₂ is a substituted or unsubstituted alkyl group having 1 to 60 carbon atoms, a substituted or unsubstituted alkenyl group having 1 to 60 carbon atoms, a substituted or unsubstituted arylene group having 5 to 60 carbon atoms, substituted or Substituted or unsubstituted C1 to 50 containing at least one or more unsubstituted aryl group having 5 to 60 carbon atoms, sulfur (S), nitrogen (N), oxygen (O), phosphorus (P) and silicon (Si) Or a substituted or unsubstituted heteroaryl group having 1 to 60 carbon atoms or sulfur (S) containing at least one alkyl group or sulfur (S), nitrogen (N), oxygen (O), phosphorus (P) and silicon (Si) ), Nitrogen (N), oxygen (O), phosphorus (P) and silicon (Si) may be a substituted or unsubstituted C1-C60 heteroaryloxy group, an amine group containing at least one.

In addition, the compound described above may be represented by the following formula (3).

Formula 3

In the above formula,

Ar ₁ is as defined above, and R ₈ and R ₉ are each independently a hydrogen atom, a halogen atom, a cyano group, a thiol group, a substituted or unsubstituted alkyl group having 1 to 60 carbon atoms, a substituted or unsubstituted carbon number 1 to Alkoxy group of 60, substituted or unsubstituted alkenyl group having 1 to 60 carbon atoms, substituted or unsubstituted arylene group having 5 to 60 carbon atoms, substituted or unsubstituted aryl group having 5 to 60 carbon atoms, substituted or unsubstituted carbon atoms 5 to 60 A substituted or unsubstituted alkyl group having 1 to 50 carbon atoms or sulfur containing at least one aryloxy group of 60, sulfur (S), nitrogen (N), oxygen (O), phosphorus (P) and silicon (Si); S), nitrogen (N), oxygen (O), phosphorus (P) and silicon (Si) substituted or unsubstituted heteroaryl group having 1 to 60 carbon atoms or sulfur (S), nitrogen (N ) Substituted or unsubstituted carbon number containing at least one, oxygen (O), phosphorus (P) and silicon (Si) 1 It may be from 60 to heteroaryloxy group, an amine group.

In addition, the compound described above may be represented by the following formula (4).

Formula 4

In the above formula,

Ar ₁ is as defined above, R ₈ and R ₉ are each independently a hydrogen atom, a halogen atom, a cyano group, a thiol group, a substituted or unsubstituted alkyl group having 1 to 60 carbon atoms, substituted or unsubstituted C 1 to 60 An alkoxy group, a substituted or unsubstituted C1-C60 alkenyl group, a substituted or unsubstituted C5-C60 arylene group, a substituted or unsubstituted C5-C60 aryl group, a substituted or unsubstituted C5-C60 A substituted or unsubstituted C1-C50 alkyl group or sulfur (S) containing at least one or more of an aryloxy group, sulfur (S), nitrogen (N), oxygen (O), phosphorus (P) and silicon (Si) ), A substituted or unsubstituted heteroaryl group having 1 to 60 carbon atoms or at least one of nitrogen (N), oxygen (O), phosphorus (P) and silicon (Si) or sulfur (S), nitrogen (N) , Substituted or unsubstituted carbon atoms containing at least one, oxygen (O), phosphorus (P) and silicon (Si) 1 to 60 heteroaryloxy group, may be an amine group.

In Formulas 1 to 4, the substituents of R ₁ , R ₂ , R ₃ , R ₄ , R _a , R _b , R _c and R _d , Ar ₁ , Ar ₂ , R ₈ , R ₉ may be substituted or unsubstituted. If substituted, each independently hydrogen atom, halogen atom, cyano group, thiol group, substituted or unsubstituted C1-C60 alkyl group, substituted or unsubstituted C1-C60 alkoxy group, substituted or unsubstituted carbon number Alkenyl group of 1 to 60, substituted or unsubstituted arylene group of 5 to 60 carbon atoms, substituted or unsubstituted aryl group of 5 to 60 carbon atoms, substituted or unsubstituted aryloxy group of 5 to 60 carbon atoms, sulfur (S) , A substituted or unsubstituted alkyl group having 1 to 50 carbon atoms or at least one of nitrogen (N), oxygen (O), phosphorus (P) and silicon (Si) or sulfur (S), nitrogen (N), oxygen ( O), a substituted or unsubstituted heteroaryl group having 1 to 60 carbon atoms or at least one phosphorus (P) and silicon (Si) or sulfur (S), quality It may be substituted with one selected from the group consisting of a substituted or unsubstituted heteroaryloxy group having 1 to 60 carbon atoms, an amine group containing at least one of (N), oxygen (O), phosphorus (P) and silicon (Si). .

As a result, the compounds according to the examples provide spiro carbazole compounds comprising a spiro backbone.

As a specific example of a compound according to an embodiment of the present invention, there are compounds of the formula (5) belonging to the formulas (1) to 4, but the present invention is not limited thereto. Wherein the compounds represented by Formulas 1 to 4 are substituted with substituents of R ₁ , R ₂ , R ₃ , R ₄ , R _a , R _b , R _c and R _d , Ar ₁ , Ar ₂ , R ₈ , R ₉ or Since unsubstituted substituents are practically difficult to exemplify all compounds in a broad relationship, representative compounds are exemplarily described, but the compounds represented by Formulas 1 to 4 not described in Formula 5 may also form part of the present specification. .

Formula 5

Various organic electronic devices exist in which the compounds described with reference to Chemical Formulas 1 to 5 are used as the hole injection material and the hole transport material. Organic electronic devices in which the compounds described with reference to Chemical Formulas 1 to 5 may be used include, for example, an organic light emitting diode (OLED), an organic solar cell, an organic photoconductor (OPC) drum, an organic transistor (organic TFT), and a photo. It may be used in organic semiconductor materials such as diodes, organic lasers, and laser diodes.

As an example, among the organic electronic devices to which the compounds described with reference to Chemical Formulas 1 to 5 may be applied, organic light emitting diodes (OLEDs) will be described below. However, the present invention is not limited thereto and the compounds described above may be applied to various organic electronic devices. Can be.

Another embodiment of the present invention is an organic electronic device comprising a first electrode, a second electrode and an organic material layer disposed between the electrodes, wherein at least one layer of the organic material layer comprises an organic electric field comprising the compounds of Formulas 1 to 5 Provided is a light emitting device.

The organic electroluminescent device according to another embodiment of the present invention, except that at least one layer of the organic material layer including a hole injection layer, a hole transport layer, a light emitting layer and an electron transport layer to form the compound of Formula 1 to 5 It can be prepared 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 the present invention is illustrated in FIGS. 1 to 5, but is not limited thereto. In this case, reference numeral 101 denotes a substrate, 110 denotes an anode, 103 denotes a hole injection layer, 104 denotes a hole transport layer, 105 denotes a light emitting layer, 106 denotes an electron injection layer, and 107 denotes a cathode.

Compounds described with reference to Formulas 1 to 5 may be included on one or more of a hole injection layer and a hole transport layer. Specifically, the compounds described with reference to Formulas 1 to 5 may be used in place of one or more of the hole injection material and hole transport material described below, or may be used by forming a layer with them. Of course, not only used in one layer of the organic layer, but may be used in two or more layers.

The organic electroluminescent device according to another embodiment of the present invention is a metal or conductive metal acid on a substrate by using a physical vapor deposition (PVD) method such as sputtering or e-beam evaporation It can be prepared by depositing a cargo or an alloy thereof to form an anode, forming an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer and an electron transport layer thereon, and then depositing a material that can be used as a cathode thereon. have.

In addition to the above method, an organic electronic device may be manufactured 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, and an electron transport 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, but not by a deposition process (solvent process) such as spin coating, dip coating, doctor blading, screen printing, inkjet printing or thermal transfer method, etc. It can be prepared as a 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 the soluble process of the compounds described above.

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 positive electrode material, a material having a large work function is generally 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, 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-methyl thiophene), 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 porphyrins, oligothiophenes, arylamine-based organics, hexanitrile hexaazatriphenylene, quinacrido ne-based organics, and perylene-based organics. Organic materials, anthraquinones and 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 positioned thereon, and serves to prevent high hole mobility, hole stability, and electrons. In addition to these general requirements, applications for vehicle body display require heat resistance to the device, and materials having a glass transition temperature (Tg) of 70 ° C. or higher are preferred. The materials satisfying these conditions include NPD (or NPB), spiro-arylamine compounds, perylene-arylamine compounds, azacycloheptatriene compounds, bis (diphenylvinylphenyl) anthracene, silicone Germanium oxide compounds, silicon arylamine compounds and the like.

The organic light emitting layer is positioned on the hole transport layer. The organic light emitting layer is a layer 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 light 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-d iphenylethenyl) -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 perylene, BczVBi (3,3) A small amount of '[(1,1'-biphenyl) -4,4'-diyldi-2,1-ethenediyl] bis (9-ethyl) -9H-carbazole (DSA) can be used. In the case of red, DCJTB ([2- (1,1-dimethylethyl) -6- [2- (2,3,6,7-tetrahydro-1,1,7,7-tetramethyl-1H, 5H A small amount of doping such as -benzo (ij) quinolizin-9-yl) etheny l] -4H-pyran-4-ylidene] -propanedinitrile) is used. When the light emitting layer is formed using a process such as inkjet printing, roll coating, or spin coating, a polymer of polyphenylene vinylene (PPV) system or a polymer such as poly fluorene may be used for the organic light emitting layer. .

As described above, the compounds described with reference to Chemical Formulas 1 to 5 may replace the hole injection layer and the hole transport layer, or may form a corresponding layer together with existing materials, and may be used as host materials of phosphorescent dopants of various colors depending on the compound. It may be formed.

The electron transport layer is positioned on the organic light emitting layer. Such an electron transport layer needs a material having high electron injection efficiency from the cathode positioned thereon and efficiently transporting the injected electrons. For this purpose, it should 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 cathode is positioned on the electron transport layer. This cathode serves to inject electrons into the electron transport layer. 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 display 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 electronic device described above, and a terminal including a control unit for driving the display device. This terminal refers to current or future wired and wireless communication terminals. 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 PDA, electronic dictionary, PMP, remote control, navigation, game machine, various TV, various computers.

실시예EXAMPLE

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

제조예Production Example

Hereinafter, the preparation or synthesis examples for the compounds belonging to the formula (5). However, since the number of compounds belonging to Formula 5 is large, one or more of the compounds belonging to Formula 5 will be exemplarily described. Those skilled in the art, that is, those skilled in the art can prepare the compounds belonging to the present invention not illustrated through the preparation examples described below.

Step 1) Synthesis of Intermediate A

Scheme 6a

2-Bromo-9H-fluorene was dissolved in Pyridine solvent, Tetrabutylammonium hydroxide was slowly added dropwise in Methanol solvent and stirred at room temperature. After the reaction was completed, the mixture was extracted with Ethyl acetate. After removing a small amount of water in the reaction with anhydrous MgSO ₄ and filtered under reduced pressure, the organic solvent was concentrated and the resulting product was recrystallized using Methanol to give the desired intermediate A (yield: 90%).

Step 2) Synthesis of Intermediate B

Scheme 6b

2-Bromobiphenyl was dissolved in anhydrous THF solvent, the reaction temperature was lowered to 78 ° C., and t-Butyllithum was slowly added dropwise and stirred for 1 hour. The intermediate B synthesized in step 1) was dissolved in THF solvent and slowly added dropwise, followed by stirring for 12 hours. After completion of the reaction, the mixture was extracted with Ethyl acetate, a small amount of water in the reaction was removed with anhydrous MgSO ₄ , filtered under reduced pressure, and the organic solvent was concentrated and separated by column chromatography to obtain the desired intermediate B (yield). : 54%).

Step 3) Synthesis of Intermediate C

Scheme 6c

Intermediate C synthesized in step 2) was dissolved in acetic acid solvent, the temperature of the reactant was lowered to 0 ° C., and HCl was slowly added dropwise. After the reaction was completed, the resulting crystals were separated by filtration under reduced pressure to give the desired intermediate C (yield: 72%).

Step 4) Synthesis of Intermediate D

Scheme 6d

The intermediate C synthesized in step 3) was dissolved in anhydrous THF, the reaction temperature was lowered to 78 ° C., n-BuLi (1.6 M in hexane) was slowly added dropwise, and the reaction was stirred for 30 minutes. The temperature of the reaction was lowered to 78 ° C. and Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane was added dropwise. After completion of the reaction, the mixture was extracted with Ethyl acetate, a small amount of water in the reaction was removed with anhydrous MgSO ₄ , filtered under reduced pressure, and the organic solvent was concentrated and the resulting product was recrystallized with Methanol to obtain the desired intermediate D (yield: 71%).

Step 5) Synthesis of Intermediate E-1

Scheme 6e

The intermediate D synthesized in step 4), 1-Bromo-2-nitrobenzene, Pd (PPh ₃ ) ₄ , and K ₂ CO ₃ were dissolved in anhydrous THF 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 MgSO ₄ , filtered under reduced pressure, and the organic solvent was concentrated and the resulting product was separated using column chromatography to give the desired intermediate E-1 (yield: 73%).

Step 6) Synthesis of Intermediate E-2

Scheme 6f

123 The intermediate D and 2,5-Dibromonitrobenzene, Pd (PPh ₃ ) ₄ , K ₂ CO ₃ synthesized in step 4) were dissolved in anhydrous THF 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 MgSO ₄ , filtered under reduced pressure, the organic solvent was concentrated, and the resulting product was separated using column chromatography to obtain the desired intermediate E-2 (yield: 70%).

Step 7) Synthesis of Intermediate E-3

[Scheme 6g]

127

The intermediate D synthesized in step 4) and 2,4-Dibromonitrobenzene, Pd (PPh ₃ ) ₄ , K ₂ CO ₃ were dissolved in anhydrous THF 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 MgSO ₄ , filtered under reduced pressure, and the organic solvent was concentrated and the resulting product was separated using column chromatography to give the desired intermediate E-3 (yield: 75%).

Step 8) Synthesis of Intermediate F-1

[Scheme 6h]

Intermediate E-1 and triphenylphosphine synthesized in step 5) were dissolved in o -dichlorobenzene and refluxed for 24 hours. At the end 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 F-1 (yield: 58%).

Step 9) Synthesis of Intermediate F-2

Scheme 6i

Intermediate E-2 and triphenylphosphine synthesized in step 6) were dissolved in o- dichlorobenzene and refluxed for 24 hours. At the end 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 F-2 (yield: 56%).

Step 10) Synthesis of Intermediate F-3

Scheme 6j

Intermediate E-3 and triphenylphosphine synthesized in step 7) were dissolved in o- dichlorobenzene and refluxed for 24 hours. At the end 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 F-3 (yield: 59%).

Step 11) Synthesis of Intermediate G-1

[Scheme 6k]

The intermediate F-2 and Iodobenzene, Pd ₂ (dba) ₃ , P ( t -Bu) ₃ and NaO t Bu synthesized in step 9) were dissolved in a 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 removal of a small amount of water with anhydrous MgSO ₄ and filtration under reduced pressure, the organic solvent was concentrated to give the resulting product by column chromatography to give the desired intermediate G-1 (yield: 73%).

Step 12) Synthesis of Intermediate G-2

[Scheme 6l]

The intermediate F-3 and Iodobenzene, Pd ₂ (dba) ₃ , P ( t -Bu) ₃ and NaO t Bu synthesized in step 10) were dissolved in a 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 removal of a small amount of water with anhydrous MgSO ₄ and filtration under reduced pressure, the organic solvent was concentrated and the resulting product was purified by column chromatography to give the desired intermediate G-2 (yield: 77%).

Synthesis Example) Subgenuse 1 (Compound) 44 Example of)

Scheme 7

The intermediate F-1 and Iodobiphenyl, Pd ₂ (dba) ₃ , P ( t -Bu) ₃ and NaO t Bu synthesized in step 8) were dissolved in a toluene solvent and stirred at 110 ° C. for 12 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 MgSO ₄ and filtered under reduced pressure, the organic solvent was concentrated to give the desired compound 4 by column chromatography (yield: 63%).

Synthesis Example Subgenuse 2 3434 Example of)

Scheme 8

Intermediate G-1 synthesized in step 11) and 4- (1-Phenyl-1 H- benzo [ d ] imidazol-2-yl) phenylboronic acid, Pd (PPh ₃ ) ₄ , K ₂ CO ₃ After dissolving in a small amount of water, it was refluxed for 24 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 MgSO ₄ and filtered under reduced pressure, the organic solvent was concentrated to give the desired compound 34 using the column chromatography (yield: 55%).

Synthesis Example) Subgenuse 3 (Compound) 5050 Example of)

Scheme 9

The intermediate G-2 synthesized in step 12) and 2-Naphthylboronic acid, Pd (PPh ₃ ) ₄ , K ₂ CO ₃ were dissolved in anhydrous THF and a small amount of water, and then refluxed for 24 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 MgSO ₄ and filtered under reduced pressure, the organic solvent was concentrated to give the desired compound 50 by column chromatography (yield: 68%).

Synthesis Example Subgenuse 4 8585 Example of)

Scheme 10

Intermediate G-1 synthesized in step 11) and N- (Biphenyl-4-yl) -9,9-dimethyl-9 H -fluoren-2-amine, Pd ₂ (dba) ₃ , P ( t -Bu) ₃ and NaO t Bu was dissolved in Toluene solvent and stirred at 110 ° C. for 24 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 MgSO ₄ and filtered under reduced pressure, the organic solvent was concentrated to give the desired compound 85 by column chromatography (yield: 61%).

Synthesis Example) Subgenuse 5 (Compound) 101101 Example of)

Scheme 11

* 175

Intermediate G-2 and Dibiphenyl-4-ylamine, Pd ₂ (dba) ₃ , P ( t -Bu) ₃ and NaO t Bu synthesized in step 12) were dissolved in a toluene solvent and stirred at 110 ° C. for 24 hours. I was. 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 MgSO ₄ and filtered under reduced pressure, the organic solvent was concentrated to give the desired compound 101 by column chromatography (yield: 66%).

Wherein the compounds represented by Formulas 1 to 4 are substituted with substituents of R ₁ , R ₂ , R ₃ , R ₄ , R _a , R _b , R _c and R _d , Ar ₁ , Ar ₂ , R ₈ , R ₉ or Unsubstituted substituents have been described a synthesis example of some of the compounds represented by the general formula (5) in a broad relationship, but compounds represented by the general formula (1) to 5 that are not illustrated by way of synthesis also part of the present specification Can be configured.

Manufacturing evaluation of organic electroluminescent element

Various compounds obtained through synthesis were used as light emitting host materials and hole transport layer materials, respectively, to fabricate an organic light emitting display device according to a conventional method. A copper phthalocyanine (hereinafter abbreviated as CuPc) film was first vacuum deposited on the ITO layer (anode) formed on the glass substrate to form a thickness of 10 nm.

When measured as a luminescent host material, 30 nm of 4,4-bis [ N- (1-naphthyl) -N -phenylamino] biphenyl (hereinafter abbreviated as a-NPD) was used as a hole transport compound on this film. The hole transport layer was formed by vacuum deposition to a thickness of. After the hole transport layer was formed, tris (2-phenylpyridine) iridium (abbreviated as I r (ppy) ₃ hereinafter) was added as a phosphorescent Ir metal complex dopant on the hole transport layer. At this time, the concentration of I r (ppy) _{3 in} the light emitting layer was 5% by weight. Into the 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, followed by electron injection. 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, Al was deposited to a thickness of 150 nm, and the organic electroluminescent device was manufactured by using this Al / LiF as a cathode.

When measuring as a hole transport layer material, a light emitting material doped with BD-052X (Idemitus) 7% doped with a thickness of 45 nm was used. In this case, BD-052X is a blue fluorescent dopant, and an organic light emitting diode was manufactured using 9,10-di (naphthalen-2-yl) anthracene (ADN) as a light emitting host material.

Comparative Experimental Example 1

Of the synthesized compounds, compounds 4, 34 and 50, respectively, were used as luminescent host materials. For comparison, an organic electroluminescent device having the same structure as the test example was manufactured by using a compound represented by Chemical Formula 6 (hereinafter abbreviated as CBP) as a light emitting host material instead of the compound of the present invention.

Formula 6

The physical properties of the organic electroluminescent device of Comparative Example 1 and the organic electroluminescent device of Experimental Example using 184CBP as a host material are summarized in Table 1 below.

Table 1

	Host material of emitting layer	Voltage (V)	Current density (mA / cm ² )	Luminous Efficiency (㏅ / A)	Chromaticity coordinates (x, y)
Example 1	Compound 4	5.2	0.30	50.5	(0.31, 0.61)
Example 2	Compound 34	5.0	0.31	55.2	(0.3 2, 0.61)
Example 3	Compound 50	5.5	0.32	48.3	(0.3 0, 0.60)
Comparative Example 1	CBP	5.1	0.31	32.6	(0.33, 0.61)

As can be seen from Table 1, the organic light emitting diodes of Experimental Examples 1 to 3 exhibit substantially the same color coordinates compared to the organic light emitting diodes using CBP as a host material and have improved luminous efficiency with critical significance. It can be seen that.

Comparative Experiment 2

Compounds 85 and 101, respectively, of the synthesized compounds were used as hole transport layer materials. For comparison, instead of the compound of the present invention, a compound represented by the following Chemical Formula 7 (hereinafter abbreviated as a-NPB) was used as a hole transport layer material, thereby fabricating an organic light emitting display device having the same structure as in the test example.

Formula 7

Table 2 summarizes the physical properties of the organic electroluminescent device of Comparative Example 2 and the organic electroluminescent device of Experimental Example using a-NPD as the hole injection layer material.

TABLE 2

	Hole transport material	Voltage (V)	Current density (mA / cm²)	Luminous Efficiency (㏅ / A)	Chromaticity coordinates (x, y)
Example 4	Compound 85	6.1	12.55	8.6	(0.15, 0.14)
Example 5	Compound 101	6.2	12.77	8.3	(0.1 5, 0.15)
Comparative Example 2	a-NPB	7.2	13.3 5	7.5	(0.15, 0 .15)

As can be seen from Table 2, the organic light emitting diodes of Experimental Examples 4 and 5 exhibit substantially the same color coordinates as the organic EL devices using a-NPB as the hole transport layer material, and have a driving voltage and a current density. Therefore, it can be seen that the luminous efficiency is improved with a critical significance.

Based on the above results, the compounds of the present invention have excellent electrical and luminescent properties, and when used in an organic light emitting device as a hole injection material and a hole transport material, based on improvements in physical characteristics such as driving voltage, current density, and luminous efficiency, High efficiency, low voltage, high brightness and long life can be expected. In addition, since green and blue light emission of long life is obtained, it is used as a green phosphorescent host material and a hole transport layer material of the organic light emitting display device, and thus it is possible to remarkably improve the luminous efficiency and lifetime. On the other hand, it is apparent that the compounds of the present invention can achieve the same effect even when used in other organic material layers of the organic light emitting device.

In this case, the compounds represented by Formulas 1 to 5 are substituted or unsubstituted of R ₁ , R ₂ , R ₃ , R ₄ , R _a , R _b , R _c and R _d , Ar ₁ , Ar ₂ , R ₈ , R ₉ The substituents described above are illustrative examples of some of the compounds represented by the formula (5) in a broad relationship, but compounds represented by the formulas (1) to (4) that are not illustrated by way of example as a comparative example It can be confirmed that the reason for having the parent-nucleus structure of 4 has the same effect as the above-described comparative examples, and the results may form part of the present specification.

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

CROSS-REFERENCE TO RELATED APPLICATION

This patent application is filed in Korea on March 5, 2010. Patent Application No. 10-2010-

Priority is issued to 0019759 under U.S. Patent Act Article 119 (a) (35 U.S.C § 119 (a)), all of which is incorporated herein by reference. In addition, if this patent application claims priority for the same reason for countries other than the United States, all its contents are incorporated into this patent application by reference.

Claims

A compound represented by the following formula;

(1) R 1 , R 2 , R 3 and R 4 are each independently a substituted or unsubstituted alkyl group having 1 to 60 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 60 carbon atoms, substituted or unsubstituted Alkenyl group having 1 to 60 carbon atoms, substituted or unsubstituted arylene group having 5 to 60 carbon atoms, substituted or unsubstituted aryl group having 5 to 60 carbon atoms, substituted or unsubstituted aryloxy group having 5 to 60 carbon atoms, sulfur (S ), A substituted or unsubstituted C1-C50 alkyl or sulfur (S), nitrogen (N) containing at least one, nitrogen (N), oxygen (O), phosphorus (P) and silicon (Si) , A substituted or unsubstituted heteroaryl group having 1 to 60 carbon atoms containing at least one oxygen (O), phosphorus (P) and silicon (Si) or sulfur (S), nitrogen (N), oxygen (O), Substituted or unsubstituted heteroaryloxy group having 1 to 60 carbon atoms containing at least one phosphorus (P) and silicon (Si).

(2) R a , R b , R c and R d are each independently a hydrogen atom, a halogen atom, a cyano group, a thiol group, a substituted or unsubstituted alkyl group having 1 to 60 carbon atoms, a substituted or unsubstituted carbon number An alkoxy group of 1 to 60, a substituted or unsubstituted alkenyl group of 1 to 60 carbon atoms, a substituted or unsubstituted arylene group of 5 to 60 carbon atoms, a substituted or unsubstituted aryl group of 5 to 60 carbon atoms, a substituted or unsubstituted carbon number A substituted or unsubstituted alkyl group having 1 to 50 carbon atoms containing at least one of 5 to 60 aryloxy groups, sulfur (S), nitrogen (N), oxygen (O), phosphorus (P) and silicon (Si); or Substituted or unsubstituted heteroaryl group having 1 to 60 carbon atoms or sulfur (S), nitrogen containing at least one of sulfur (S), nitrogen (N), oxygen (O), phosphorus (P) and silicon (Si) A substituted or unsubstituted carbon having 1 to 60 carbon atoms containing at least one of (N), oxygen (O), phosphorus (P) and silicon (Si). It is a teroaryloxy group.

(3) Ar 1 is a hydrogen atom, a substituted or unsubstituted C1-C60 alkyl group, a substituted or unsubstituted C1-C60 alkenyl group, a substituted or unsubstituted C5-C60 arylene group, substituted or unsubstituted Substituted or unsubstituted carbon atoms having 1 to 50 carbon atoms containing at least one or more aryl groups having 5 to 60 ring carbon atoms, sulfur (S), nitrogen (N), oxygen (O), phosphorus (P) and silicon (Si); Substituted or unsubstituted heteroaryl group having 1 to 60 carbon atoms or sulfur (S) containing at least one alkyl group or sulfur (S), nitrogen (N), oxygen (O), phosphorus (P) and silicon (Si) ), A substituted or unsubstituted heteroaryloxy group having 1 to 60 carbon atoms containing at least one of nitrogen (N), oxygen (O), phosphorus (P) and silicon (Si).

(3) Said n is an integer of 1-4.
The method of claim 1,

The compound is,

or
Is indicated by

Ar 1 is as defined above, and Ar 2 is a substituted or unsubstituted C1-C60 alkyl group, a substituted or unsubstituted C1-C60 alkenyl group, a substituted or unsubstituted C5-C60 arylene group Substituted or unsubstituted carbon atoms containing at least one substituted or unsubstituted aryl group having 5 to 60 carbon atoms, sulfur (S), nitrogen (N), oxygen (O), phosphorus (P) and silicon (Si) A substituted or unsubstituted heteroaryl group having 1 to 50 carbon atoms containing at least one alkyl group of 1 to 50 or sulfur (S), nitrogen (N), oxygen (O), phosphorus (P) and silicon (Si) or It is a substituted or unsubstituted heteroaryloxy group having 1 to 60 carbon atoms containing at least one of sulfur (S), nitrogen (N), oxygen (O), phosphorus (P) and silicon (Si).
The method of claim 1,

The compound is,

or
Is indicated by

Ar 1 is as defined above, and R 8 and R 9 are each independently a hydrogen atom, a halogen atom, a cyano group, a thiol group, a substituted or unsubstituted C1-C60 alkyl group, a substituted or unsubstituted carbon number An alkoxy group of 1 to 60, a substituted or unsubstituted alkenyl group of 1 to 60 carbon atoms, a substituted or unsubstituted arylene group of 5 to 60 carbon atoms, a substituted or unsubstituted aryl group of 5 to 60 carbon atoms, substituted or unsubstituted A substituted or unsubstituted alkyl group having 1 to 50 carbon atoms containing at least one aryloxy group having 5 to 60 carbon atoms, sulfur (S), nitrogen (N), oxygen (O), phosphorus (P) and silicon (Si). Or a substituted or unsubstituted heteroaryl group having 1 to 60 carbon atoms or sulfur (S) containing at least one of sulfur (S), nitrogen (N), oxygen (O), phosphorus (P) and silicon (Si), Substitution or not including at least one of nitrogen (N), oxygen (O), phosphorus (P) and silicon (Si) It is a hetero aryloxy group having 1 to 60 carbon atoms.
The method of claim 1,

The compound is,

Is indicated by

Ar 1 is as defined above, and R 8 and R 9 are each independently a hydrogen atom, a halogen atom, a cyano group, a thiol group, a substituted or unsubstituted alkyl group having 1 to 60 carbon atoms, a substituted or unsubstituted carbon number Alkoxy groups of 1 to 60, substituted or unsubstituted alkenyl groups of 1 to 60 carbon atoms, substituted or unsubstituted arylene groups of 5 to 60 carbon atoms, substituted or unsubstituted aryl groups of 5 to 60 carbon atoms, substituted or unsubstituted carbon atoms A substituted or unsubstituted C1-C50 alkyl group containing 5 to 60 aryloxy groups, sulfur (S), nitrogen (N), oxygen (O), phosphorus (P) and silicon (Si); Substituted or unsubstituted heteroaryl group having 1 to 60 carbon atoms or sulfur (S), nitrogen containing at least one of sulfur (S), nitrogen (N), oxygen (O), phosphorus (P) and silicon (Si) Substitution or non-containing at least one containing (N), oxygen (O), phosphorus (P) and silicon (Si) It is a hetero aryloxy group having 1 to 60 carbon atoms.
The method of claim 1,

R 1 and R 2 , R 2 and R 3 , R 3 and R 4 combine with an adjacent group to form a substituted or unsubstituted saturated or unsaturated ring.
The method of claim 1,

The compound is characterized in that one of the following compounds.
An organic electronic device comprising at least one organic material layer containing a compound of any one of claims 1 to 6.
The method of claim 7, wherein

The organic electronic 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.
The method of claim 7, wherein

The organic material layer includes a hole injection layer, a hole transport layer, a light emitting layer and an electron injection layer, wherein the compound of claim 1 is included in one or more of the hole injection layer and the hole transport layer.
The method of claim 9,

The compound is an organic electronic device, characterized in that used as a fluorescent host material containing blue, green, red, white in the light emitting layer.
The method of claim 9,

The organic electronic device of claim 1, wherein the compound of any one of claims 1 to 6 is formed by a solution process.
A display device comprising the organic electronic device of claim 7;

And a control unit for driving the display device.