KR20100108904A - Anthracene chemiclal and organic electroric element using the same, terminal thererof - Google Patents

Abstract

PURPOSE: An anthracene compound and an organic electric device and terminal using the same are provided to lower driving voltage and to improve light efficiency, lifetime, and device stability. CONSTITUTION: An anthracene compound is denoted by chemical formula 1. An organic electric device contains one or more organic layers having the compound of chemical formula 1. The compound of chemical formula 1 forms an organic layer by a soluble process. The organic electric device is an organic electroluminescence device. The organic layer comprises a hole an injection/transport layer, a light emitting layer, and an electron injection layer. A terminal comprises a display device having the organic electric device and a controller driving the display device.

Description

Anthracene compound, organic electroluminescent device using same, and terminal thereof {ANTHRACENE CHEMICLAL AND ORGANIC ELECTRORIC ELEMENT USING THE SAME, TERMINAL THEREROF}

The present invention relates to an anthracene compound, an organic electric device using the same, 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. In this case, the organic material layer is often formed of a multi-layered structure composed of different materials in order to increase the efficiency and stability of the organic electric device, for example, it may be made of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer.

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

On the other hand, when only one material is used as 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 the light emitting material in order to increase the light emitting efficiency through the light emitting layer. The principle is that when a small amount of 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 shifts to the wavelength of the dopant, light having a desired wavelength can be obtained according to the type of dopant to be used.

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

The present inventors have found an anthracene derivative having a novel structure, and also found that when the compound is applied to an organic electric device, the luminous efficiency, stability and lifetime of the device can be greatly improved.

Accordingly, an object of the present invention is to provide a novel anthracene compound, an organic electric device using the same, and a terminal thereof.

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

The present invention provides anthracene derivatives in which five-membered hetero rings are condensed.

This compound can be used as hole injection, hole transport, electron injection, electron transport and light emitting materials in organic electronic devices. In addition, the anthracene compound may be used alone or as a host or dopant in a luminescent material and a host / dopant.

The inventors have found that the organic electronic device containing the compound exhibits an effect of increasing efficiency, lowering driving voltage, increasing lifetime, and increasing stability.

The compound of the present invention may play various roles in the organic electric device and the terminal, and when applied to the organic electric device and the terminal, it is possible to lower the driving voltage of the device, improve light efficiency and lifespan, and stability of the device.

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

The present invention provides a compound of Formula 1 below.

In Chemical Formula 1,

(1) R ¹ and R ² are the same as or different from each other, and each independently halogen, amino group, nitrile group, nitro group, C ₁ -C ₂₀ alkyl group, C ₁ -C ₂₀ alkoxy group, C ₁ -C ₂₀ Alkylamine groups, C ₁ to C ₂₀ alkyl thiophene groups, C ₆ to C ₂₀ aryl thiophene groups, C ₂ to C ₂₀ alkenyl groups, C ₂ to C ₂₀ alkynyl groups, C ₃ to C ₂₀ a cycloalkyl, C ₆ ~ C ₂₀ aryl group, of a C ₆ ~ C ₂₀ substituted with a heavy hydrogen aryl, C ₈ ~ C ₂₀ arylalkenyl group, a substituted or unsubstituted silane group, a substituted or unsubstituted boron group, a substituted or unsubstituted germanium group, and a substituted or unsubstituted C ₅ ~ C ₂₀ heteroaryl and Rigi substituted or unsubstituted by at least one group selected from the group C ₆ ~ C ₂₀ aryl group, a halogen, CN consisting of , NO ₂ , C ₁ to C ₂₀ alkyl group, C ₁ to C ₂₀ alkoxy group, C ₁ to C ₂₀ alkylamine group, C ₁ to C ₂₀ alkylthio group, C ₂ to C ₂₀ alkenyl group, Alkynyl groups of C ₂ to C ₂₀ , C ₃ to C ₂ A cycloalkyl group of _0, C ₆ ~ C ₂₀ aryl group, of a C ₆ ~ C ₂₀ substituted with deuterium aryl group, a substituted or unsubstituted silane group, a substituted or unsubstituted boron group, a substituted or unsubstituted germanium group And C ₅ ~ C ₂₀ heterocyclic group unsubstituted or substituted with one or more groups selected from the group consisting of a substituted or unsubstituted C ₅ ~ C ₂₀ heterocyclic group; Or a condensed ring group of a C ₆ to C ₂₀ aromatic ring and a C ₄ to C ₂₀ aliphatic ring, each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aryl group , And any group selected from substituted and unsubstituted hetero aryl groups. On the other hand, R ¹ and R ² may not be a hydrogen atom at the same time. Wherein R ¹ and R ² may be substituted or unsubstituted if possible.

(2) X represents -CR _X , -NR, -O, -S, SO ₂ , -PR, PO ₂ , SiR ₂ , and (3) L represents a single bond, a substituted or unsubstituted arylene group, a substituted or And a group selected from an unsubstituted hetero arylene group and a divalent substituted or unsubstituted aliphatic hydrocarbon, and (4) HAr is a substituted or unsubstituted aryl group having 6 to 60 carbon atoms or a substituted or unsubstituted carbon number 3 to Group selected from a 60 aryl group.

(5) n represents 0,1,2.

As a result, the anthracene compound according to the embodiment has an anthracene structure in which an five-membered hetero ring is condensed.

The present invention provides a compound of Formulas 2 to 10 below.

In Formula 2 to 10 below R ¹ to R ⁴ may be the same as R ¹ and R ² defined in Formula 1. Meanwhile, in Formulas 2 to 10, L and HAr may be the same as L and HAr defined in Formula 1.

, ,

,

,

,

,

,

,

,

으로 구성된 그룹으로부터 선택된 하나일 수 있다. Meanwhile, in Formulas 2 to 10, R ¹ to R ² are

, ,

,

,

,

,

,

,

,

It may be one selected from the group consisting of.

,

,

,

,

,

,

으로 구성된 그룹으로부터 선택된 하나일 수 있다. In Formula 2 to 10 L is

,

,

,

,

,

,

It may be one selected from the group consisting of.

으로 구성된 그룹으로부터 선택된 하나일 수 있다. In Formula 2 to 10 HAr is

It may be one selected from the group consisting of.

In the above formulas, the atoms in each heterocycle are substituted or unsubstituted aryl groups having 6 to 60 carbon atoms, substituted or unsubstituted heteroaryl groups having 3 to 60 carbon atoms, substituted or unsubstituted carbon atoms 1 to 20 The bonding group consisting of an alkyl group or a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms may be bonded, or in the case where there are many bond groups, they may be the same as or different from each other. Specific examples of the anthracene derivatives in which five-membered hetero rings are condensed from the above formula are described below, but are not limited thereto.

Specific examples of the anthracene according to an embodiment of the present invention, as an example of the anthracene belonging to the general formula (2), but the compounds of the formula (11) below, but the present invention is not limited thereto.

Specific examples of anthracene according to an embodiment of the present invention, there are compounds of the formula (12) below as a specific example of anthracene belonging to formula (3), the present invention is not limited to these.

Specific examples of the anthracene according to an embodiment of the present invention, as an example of the anthracene belonging to the general formula (4), there are compounds of the formula (13) below, but the present invention is not limited thereto.

Specific examples of the anthracene according to an embodiment of the present invention, as an example of the anthracene belonging to the formula (5), there are compounds of the formula (14) below, but the present invention is not limited thereto.

Specific examples of the anthracene according to an embodiment of the present invention, there are compounds of the formula (15) as a specific example of the anthracene belonging to the formula (6), but the present invention is not limited thereto.

Specific examples of anthracene according to an embodiment of the present invention, there are compounds of the formula (16) below as a specific example of the anthracene belonging to the formula (7), but the present invention is not limited thereto.

Specific examples of the anthracene according to an embodiment of the present invention, there are compounds of the formula (17) as a specific example of the anthracene belonging to the formula (8), but the present invention is not limited thereto.

Specific examples of the anthracene according to an embodiment of the present invention, there are compounds of the formula (18) as a specific example of the anthracene belonging to the formula (9), but the present invention is not limited thereto.

Specific examples of the anthracene according to an embodiment of the present invention, as an example of the anthracene belonging to the formula (10), but the compounds of the formula (19) below, but the present invention is not limited thereto.

Various organic electronic devices exist in which the anthracene compounds described with reference to Chemical Formulas 1 to 19 are used as the organic material layer. The organic electronic device in which the anthracene compounds described with reference to Chemical Formulas 1 to 19 may be used, for example, an organic light emitting diode (OLED), an organic solar cell, an organic photoconductor (OPC) drum, an organic transistor (organic TFT), a photo Organic semiconductor materials such as diodes, organic lasers, and laser diodes may be used.

As an example of the organic electroluminescent device to which the anthracene compounds described above with reference to Chemical Formulas 1 to 19 may be applied, the present invention is not limited thereto, but the anthracene compound described above may be applied to various organic electroluminescent devices. Can be.

Another embodiment of the present invention is an organic electric device comprising a first electrode, a second electrode and an organic material layer disposed between the electrodes, wherein at least one of the organic material layer of the organic electric field comprising the compounds of Formula 1 to 19 Provided is a light emitting device.

The organic light emitting device according to another embodiment of the present invention, except that at least one layer of an 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 19 to include Can be prepared with 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, 102 an anode, 103 a hole injection layer, 104 a hole transport layer, 105 a light emitting layer, 106 an electron injection layer, and 107 a cathode.

In this case, the anthracene compound described with reference to Chemical Formulas 1 to 19 may be included in one or more of an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer. Specifically, the anthracene compound described with reference to Chemical Formulas 1 to 19 may be used instead of one or more of the hole injection layer, hole transport layer, light emitting layer, and electron transport layer described below, or may be used by forming a layer with them. Of course, the organic layer may be used not only in one layer but also in two or more layers.

In particular, the anthracene compound described with reference to Chemical Formulas 1 to 19 may form a corresponding layer with the existing materials or with the existing materials in the electron transport layer, respectively.

For example, the organic light emitting device according to another embodiment of the present invention is a metal having a metal or conductivity on a substrate by using a physical vapor deposition (PVD) method such as sputtering or e-beam evaporation It can be prepared by depositing an oxide 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. .

In addition to the above method, an organic electronic device may be fabricated by sequentially depositing a cathode material, an organic material layer, and an anode material on a substrate. The organic material layer may have a multilayer structure including a hole injection layer, a hole transport layer, a light emitting layer, 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 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 material layer, for example, a light emitting layer, by the soluble process of the anthracene compound 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 anode material, a material having a large work function is usually preferred to facilitate hole injection into the organic material layer. Specific examples of the positive electrode material that can be used in the present invention include metals such as vanadium, chromium, copper, zinc and gold or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO); 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.

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.

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 hole injection materials include metal porphyrine, oligothiophene, arylamine-based organics, hexanitrile hexaazatriphenylene, quinacridone-based organics, perylene-based organics, Anthraquinone, polyaniline and polythiophene-based conductive polymers, but are not limited thereto.

The hole transport layer is positioned on the hole injection layer. The hole transport layer receives holes from the hole injection layer and transports the holes to the organic light emitting layer located thereon, and serves to prevent high hole mobility, hole stability, and electrons. In addition to these general requirements, when applied for vehicle body display, heat resistance to the device is required, and a material having a glass transition temperature (Tg) of 70 ° C. or higher is preferable. Materials satisfying these conditions include NPD (or NPB), spiro-arylamine compounds, perylene-arylamine compounds, azacycloheptatriene compounds, bis (diphenylvinylphenyl) anthracene and silicon germanium oxide. Compounds, silicone 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 for emitting light by recombination of holes and electrons injected from the anode and the cathode, respectively, and is made of a material having high quantum efficiency. The light emitting material is a material capable of emitting light in the visible region by transporting and combining holes and electrons from the hole transport layer and the electron transport layer, respectively, and a material having good quantum efficiency with respect to fluorescence or phosphorescence is preferable.

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

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

 As described above, the anthracene compound described with reference to Chemical Formulas 1 to 19 may replace the existing materials or form the corresponding layers with the existing materials in the electron transport layer, respectively. In this case, the anthracene compound described above may be formed by an soluble process such as spin coating, dip coating, doctor blading, screen printing, inkjet printing, or thermal transfer.

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

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

Example

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

Production Example

Hereinafter, the preparation or synthesis examples of the anthracene compounds belonging to Formula 11 to 19 will be described. However, only one or two of the anthracene compounds belonging to Chemical Formulas 11 to 19 are exemplarily described since the number of anthracene compounds belonging to Chemical Formulas 11 to 19 is large. Those of ordinary skill in the art, that is, those skilled in the art can prepare anthracene compounds belonging to the present invention, which are not illustrated through the preparation examples described below.

Comprehensive synthesis examples are expressed as the general Synthesis Examples 1 and 2 primarily expressed mainly in the reaction scheme.

Normally Synthesis Example 1

General Synthesis Example 2

의 제조) Preparation Example 1 Compound 1-1 belonging to the group of Formula 2

Manufacture)

1. Synthesis of Trimethyl-2-thiophenylstanan

Under argon atmosphere, 16.3 g (100 mmol) of 2-bromothiophene was dissolved in 100 ml of ether, cooled to −78 ^° C., and 20 ml (1.6 mol / L) of n-butyllithium was added dropwise. The mixture was stirred at -78 ^o C for 1 h and then warmed up to 0 ^o C. The mixture was cooled again at -78 ^° C. and 39 g (120 mmol) of tributyltin chloride were added and reacted at room temperature for 2 hours. After completion of the reaction, the mixture was extracted with ether and water, concentrated, dried over magnesium sulfate and concentrated again to give tributyl-2-thiophenylstannan.

2. Synthesis of 2-bromo-3- (thiophen-2-yl) naphthalene-1,4-dione

18.9 g (60 mmol) 2,3-dibromonaphthalene-1,4-dione under argon atmosphere, tributyl-3-thiophenylstanan 18.6 g (50 mmol), tetrakis triphenylphosphine palladium (0 ) 0.03 g (3 mmol) is added to 500 ml of THF and 250 ml of water and heated to reflux. After completion of the reaction, the mixture was extracted with MC and water, concentrated, dried over magnesium sulfate, and concentrated to give 2-bromo-3- (thiophen-2-yl) naphthalene-1,4-dione.

3. Synthesis of 2- (thiophen-2-yl) -3-{(trimethylsilyl) ethynyl} naphthalene-1,4-dione

6.4 g (20 mmol) of 2-bromo-3- (thiophen-2-yl) naphthalene-1,4-dione under argon atmosphere, 0.11 g (1 mmol) of tetrakistriphenylphosphine palladium (0), 0.632 g (2 mmol) of copper iodide and 1.96 g (20 mmol) of trimethylsilylacetylene were added to 100 ml of triethylamine, followed by reaction at room temperature for 8 hours. An aqueous ammonium chloride solution was added to the mixture, and the obtained solid was washed with water and methanol, followed by 2- (thiophen-2-yl) -3-{(trimethylsilyl) ethynyl} naphthalene-1,4-dione. It was.

4. Synthesis of 4- (trimethylsilyl) anthra [1,2-b] thiophene-6,11 (5aH, 11aH) -dione

Dissolve 6.7 g (20 mmol) of 2- (thiophen-2-yl) -3-{(trimethylsilyl) ethynyl} naphthalene-1,4-dione under argon atmosphere in 100 ml of dichloromethane. It was heated to reflux 0.34 g (0.6 mmol) RuCl ₂ (PPh ₃ ) (np-cymene). After the reaction for 24 hours, the reaction was terminated and separated by silica gel column chromatography to obtain 4- (trimethylsilyl) anthra [1,2-b] thiophene-6,11 (5aH, 11aH) -dione.

5. Synthesis of 6,11-di (naphthalen-2-yl) -4- (trimethylsilyl) -6,11-dihydroanthra [1,2-b] thiophene-6,11-diol

Under argon atmosphere, 18.63 g (90 mmol) of 2-bromonattalene and 5.4 g of Mg were dissolved in 150 ml of THF, and the mixture was stirred at −78 ^° C. for 1 hour and then heated to reflux for 3 hours. After cooling to room temperature, -78 ^° C., the mixture was purified by 4- (trimethylsilyl) anthra [1,2-b] thiophene-6,11 (5aH, 11aH) -dione and 10.2 g (30 mmol) of THF 50 It was slowly added to the solution dissolved in ml. The reaction was carried out at room temperature for 12 hours. THF was removed and the product was extracted with dichloromethane. The organic layer was dried over magnesium sulfate, the solvent was evaporated under reduced pressure, and the solid obtained was washed with ethanol to give 6,11-di (naphthalen-2-yl) -4- (trimethylsilyl) -6,11-dihydroanthra [1 , 2-b] thiophene-6,11-diol.

6. Synthesis of 6-11-di (naphthylene-2yl) anthra [1,2-b] thiophen-4-yl) trimethylsilane

17.8 g (30) of 6,11-di (naphthalen-2-yl) -4- (trimethylsilyl) -6,11-dihydroanthra [1,2-b] thiophene-6,11-diol under argon atmosphere mmol) was dissolved in acetonitrile, SnCl ₂ dihydrate (90 mmol) was added, and the mixture was heated to reflux with vigorous stirring for 3 hours. After cooling to room temperature the mixture was filtered. The obtained solid was washed with water and methanol and then dried under reduced pressure to give 6-11-di (naphthylene-2yl) anthra [1,2-b] thiophen-4-yl) trimethylsilane.

7. Synthesis of 6-11-di (naphthylene-2-yl) anthra [1,2b] thiophene

Dissolve 100 ml of THF in 11.1 g (20 mmol) of 6-11-di (naphthylene-2-yl) anthra [1,2-b] thiophen-4-yl) trimethylsilane under argon atmosphere. 5.6 g (100 mmol) of KOH was dissolved in 50 ml of methanol and slowly added thereto, followed by reaction at room temperature for 2 hours. Separation by silica gel column chromatography gave 6-11-di (naphthylene-2-yl) anthra [1,2b] thiophene.

8. Synthesis of 3- {5- (5-bromothiophen-2-yl) -2-pyridyl} quinoline

In an argon atmosphere, 17.7 g (100 mmol) of NBS, 48.6 g (100 mmol) of 6,11-di (naphthalein-2-yl) anthra [1.2-b] thiophene, 100 ml of DMF were added thereto, and the resulting mixture was dried at room temperature. The reaction was time. The organic layer was washed with water and then separated by silica gel column chromatography to obtain 2-bromo-6,11-di (naphthalein-2-yl) anthra [1.2-b] thiophene.

9. Synthesis of 3- {5- (2-bromopyridyl)} quinoline

17 g (60 mmol) of 5-bromo-2-iodopyridine, 8.6 g (50 mmol) of quinoline-3-boronic acid, 0.03 g (3 mmol) of tetrakis triphenylphosphine palladium (0), under argon atmosphere, 16.4 g (120 mmol) of potassium carbonate was added to 500 ml of THF and 250 ml of water, followed by heating to reflux. The solid obtained was washed with water and methanol and then separated by silica gel column chromatography to give 3- {5- (2-bromopyridyl)} quinoline.

10. 6- (3-quinolinyl) -3 boronic acid

2.5 g (8.6 mmol) of 3- {5- (2-bromopyridyl)} quinoline under argon atmosphere was added 100 ml of THF, cooled to -78 ^o C, and then 6 ml of n-butyllithium (1.6 mol in hexane). / l) was added dropwise. The mixture was stirred at -78 ^o C for 1 h and then warmed to 0 ^o C. The mixture was again cooled to -78 ^° C. and 2.9 ml (26 mmol) of trimethoxyborate were added dropwise. The mixture was stirred at -78 ^o C for 1 hour and then at room temperature for 2 hours. 50 ml of 10 mass% hydrochloric acid was added, stirred for 1 hour, and filtered. The solid obtained was washed with toluene to give 6- (3-quinolinyl) -3 boronic acid.

11.Synthesis of 6,11-di (naphthalein-2-yl)-{3- (5-quinolinyl) pyridinyl} anthra [1.2-b] thiophene

33 g (60 mmol), 6- (3-quinolinyl) -3boron of 2-bromo-6,11-di (naphthalein-2-yl) anthra [1.2-b] thiophene under argon atmosphere 12.5 g (50 mmol) of acid, 3.46 g (3 mmol) of tetrakis triphenylphosphine palladium (0), 16.4 g (120 mmol) of potassium carbonate were added to 500 ml of THF and 250 ml of water, followed by heating to reflux. The obtained solid was washed with water and methanol, and then separated by silica gel column chromatography to give 6,11-di (naphthalin-2-yl)-{3- (5-quinolinyl) pyridinyl} anthra [1.2 -b] thiophene was obtained.

MS: m / z = 690.21 [M ⁺ ]

의 제조) Preparation 2 (compound 2-1 belong to the group of formula (3)

Manufacture)

Compounds were synthesized in the same manner as in all synthesis procedures except that 3-bromothiphene was used instead of 2-bromothiphene.

의 제조) Preparation Example 3 Compound 3-1 belonging to the group of formula 4

Manufacture)

Compounds were synthesized in the same manner as in all synthesis procedures except that 2-bromofuran was used instead of 2-bromothiphene.

의 제조) Preparation Example 4 (compound 4-1 belong to the group of formula (5)

Manufacture)

Compounds were synthesized in the same manner as in all synthesis procedures except that 3-bromofuran was used instead of 2-bromofuran.

의 제조) Preparation 5 (compound 5-1 belong to the group of formula (6)

Manufacture)

Compounds were synthesized in the same manner as in all synthesis procedures except that 5-bromo-3H-pyrrole was used instead of 2-bromothiphene.

의 제조) Preparation Example 6 Compound 6-1 belonging to the group of Formula 7

Manufacture)

Compounds were synthesized in the same manner as in all synthesis procedures except that 3-bromo-3H-pyrrole was used instead of 2-bromothiphene.

의 제조) Preparation Example 7 Compound 7-1 Belonging to Group of Formula 8

Manufacture)

Compounds were synthesized in the same manner as in all synthesis procedures except that 2-bromo-1-methyl-1H-pyrrole was used instead of 2-bromothiphene.

의 제조) Preparation Example 8 Compound 8-8 belonging to group of Formula 9

Manufacture)

Compounds were synthesized in the same manner as in all synthesis procedures except that 3-bromo-1-phenyl-1H-pyrrole was used instead of 2-bromothiphene.

의 제조) Preparation Example 9 Compound 9-9 belonging to group of Formula 10

Manufacture)

Compounds were synthesized in the same manner as in all synthesis procedures except that 1-bromocyclopenta-1,3-diene was used instead of 2-bromothiphene.

Comparative Example 1

(200 Å)/ LiF / Al로 소자를 구성하였다.An organic substrate having an ITO transparent electrode of 25 mm length 75 mm width 1.1 mm thickness was subjected to ultrasonic cleaning in isopropyl alcohol for 5 minutes, followed by UV ozone cleaning for 30 minutes. 2TNATA (600 Hz) / NPB (300 Hz) / ADN: BD052X (300 Hz: 7%) / Compound 1-1

The device was constructed with (200 mA) / LiF / Al.

(200 Å)대신에 Alq3 (200 Å)를 사용한 점을 제외하고 비교실시예1과 동일하다.The device structure of the comparative example was composed of ITO / 2TNATA (600 Hz) / NPB (300 Hz) / AND: BD052X (300 Hz: 7%) / Alq3 (200 Hz) / LiF / Al. Comparative Example is Compound 1-1 as an electron transfer material

Same as Comparative Example 1 except that Alq3 (200 Hz) was used instead of (200 Hz).

6 to 9 show spectrum and device evaluation results. 6 to 9, (1) means an embodiment, and (2) means a comparative example.

At this time, the device evaluation resulted in the emission of 450nm ~ 580nm, it was found that the effect of the efficiency increase, the driving voltage drop, the lifetime increase and the stability increase effect.

(화학식 11에 속하는 화합물)의 대신에, 표 1에 기술된 화합물을 사용하여 유사한 유기전계발광소자를 제작하고, 유사한 측정을 실시하였다. 그 결과가 표 1에 기술되어 있다. 표1에서 화학물 2-1 내지 9-1은 위 제조예들에서 제조한 화합물들을 의미한다.Compound 1-1 in Comparative Experimental Example 1

In place of (Compound 11), similar organic electroluminescent devices were manufactured using the compounds described in Table 1, and similar measurements were performed. The results are shown in Table 1. In Table 1, Chemicals 2-1 to 9-1 refer to compounds prepared in the above Preparation Examples.

@ 1000 nit Electronic transport material Driving voltage
(V) Current density
(mA / cm ² ) Luminous efficiency
(cd / A) Production Example 2 Compound 2-1 4.0  14.02 7.11 Production Example 3 Compound 3-1 6.0 14.56 7.02 Preparation Example 4 Compound 4-1 6.8 14.89 6.78 Preparation Example 5 Compound 5-1 4.2 13.20 7.55 Preparation Example 6 Compound 6-1 5.8 13.58 7.42 Preparation Example 8 Compound 7-1 5.5 13.69 7.30 Preparation Example 9 Compound 9-1 7.0 14.96 6.64

As can be seen from the results of Table 1, it can be seen that the organic EL device using the organic EL device material of the present invention has the effect of increasing efficiency, lowering driving voltage, increasing lifetime, and increasing stability.

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

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 are not limited by these embodiments.

The protection scope of the present invention should be interpreted by the following claims, and all the technologies within the equivalent scope should be interpreted as being included in the scope of the present invention.

1 to 5 show examples of the organic electric device to which the compound of the present invention can be applied.

6 to 9 are spectrum and device evaluation results of Examples and Comparative Examples.

Claims (11)

Anthracene compound represented by the following formula.

In Chemical Formula 1, (1) R ¹ and R ² are the same as or different from each other, and each independently a halogen, amino group, nitrile group, nitro group, C ₁ -C ₂₀ alkyl group, C ₁ -C ₂₀ alkoxy group, C ₁ -C ₂₀ Alkylamine group, C ₁ to C ₂₀ alkyl thiophene group, C ₆ to C ₂₀ aryl thiophene group, C ₂ to C ₂₀ alkenyl group, C ₂ to C ₂₀ alkynyl group, C ₃ to C ₂₀ Cycloalkyl group, C ₆ to C ₂₀ aryl group, C ₆ to C ₂₀ aryl group, C ₈ to C ₂₀ arylalkenyl group, substituted or unsubstituted silane group, substituted or unsubstituted boron group, substituted or unsubstituted C ₆ ~ C ₂₀ aryl group unsubstituted or substituted with one or more groups selected from the group consisting of a substituted germanium group, and a substituted or unsubstituted C ₅ ~ C ₂₀ heterocyclic group; Of _{halogen, CN, NO 2, C 1} ~ C 20 alkyl group, C ₁ ~ C ₂₀ alkoxy group, C ₁ ~ C ₂₀ alkyl amine group, C ₁ ~ C ₂₀ coming of the alkyl group, C ₂ ~ C ₂₀ of the alkenyl group, C ₂ ~ C ₂₀ of the alkynyl group, C ₃ ~ C ₂₀ cycloalkyl group, C ₆ ~ C ₂₀ aryl group, of a C ₆ ~ C ₂₀ substituted by deuterium aryl group, a substituted or unsubstituted silane group , a substituted or unsubstituted boron group, a substituted or unsubstituted germanium group, and a substituted or unsubstituted C ₅ ~ C ₂₀ by at least one group selected from the group consisting of a heterocyclic-substituted or unsubstituted C ₅ ~ C ₂₀ of the ring Heterocyclic group; Or a condensed ring group of a C ₆ to C ₂₀ aromatic ring and a C ₄ to C ₂₀ aliphatic ring, each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aryl group , Optionally selected from substituted and unsubstituted heteroaryl groups, and (2) X represents -CR _X , -NR, -O, -S, SO ₂ , -PR, PO ₂ , SiR ₂ , and (3) L represents a group selected from a single bond, a substituted or unsubstituted arylene group, a substituted or unsubstituted hetero arylene group, and a divalent substituted or unsubstituted aliphatic hydrocarbon, and (4) HAr represents a substituted or unsubstituted carbon number. The group chosen from a 6-60 aryl group or a substituted or unsubstituted C3-C60 hero aryl group is represented, (5) n represents 0,1,2. The method of claim 1, The formula is

,

,

,

,

,

,

,

,

An anthracene compound selected from the group consisting of, wherein R ³ and R ⁴ in the formulas are the same as R ¹ and R ² . The method of claim 1, R ¹ and R ² in the above formula are each independently a phenyl group, a substituted or unsubstituted C ₅ ~ C ₂₀ heterocyclic group substituted phenyl group, naphthyl group, biphenyl group, fluorenyl group, anthracenyl group, tetrasenyl group, Pentaxenyl group, terphenyl group, tetralinyl group, stilbenyl group, carbazolylene group, peryllenyl group, pyrenyl group, phenanthrenyl group, triphenylenyl group, chrysenyl group, pyridyl group, bipyridyl group, carbazole group, Anthracene compound, characterized in that one selected from the group consisting of a thiophenyl group, a quinolinyl group, or an isoquinolinyl group. The method of claim 1, L in the formula

,

,

,

,

,

,

Anthracene compound, characterized in that one selected from the group consisting of. The method of claim 1, HAr of the above formula

Anthracene compound, characterized in that one selected from the group consisting of. An organic electronic device comprising at least one organic material layer comprising the compound of any one of claims 1 to 5. The method of claim 6, The organic electronic device, characterized in that to form the organic material layer by a solution process (soluble process). The method of claim 6, 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 organic electronic device of claim 8, wherein the organic material layer includes a hole injection / transport layer, a light emitting layer, and an electron injection layer, and the compound of any one of claims 1 to 5 is used in an electron injection layer. . A display device comprising the organic electric element of claim 6; And a control unit for driving the display device. The terminal of claim 10, wherein the organic electroluminescent element is an organic light emitting diode or an organic solar cell, an organic photoconductor (OPC), or an organic transistor.

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