KR101181264B1 - Condensed Compound Containing Cyclized Aryl, Acrydine Derivatives And Organic Electronic Element Using The Same, Terminal Thereof - Google Patents

Abstract

The present invention provides a compound in which an aryl ring and an acridine derivative are condensed, an organic electric device using the same, and a terminal thereof.

Description

Condensed Compound Containing Cyclized Aryl, Acrydine Derivatives And Organic Electronic Element Using The Same, Terminal Thereof}

The present invention relates to a compound in which an aryl ring and an acridine derivative are condensed, 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 and an electron injection layer.

Materials used as the organic material layer in the organic electric element may be classified into light emitting materials and charge transport materials, such as hole injection materials, hole transport materials, electron transport materials, electron injection materials, and the like, depending on their functions. The light emitting material may be classified into a polymer type and a low molecular type depending on the molecular weight, and may be classified into a phosphorescent material derived from singlet excited state of electrons and a phosphorescent material derived from the triplet excited state of electrons . 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 is shifted to the wavelength band of the dopant, the desired wavelength light can be obtained depending on the type of the dopant used.

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

Embodiments of the present invention to solve the problems of the above-described background, a compound having a condensed aryl ring and acridine derivative having a novel structure has been found, and when the compound is applied to an organic electronic device It has been found that the luminous efficiency, stability and lifetime can be greatly improved.

Accordingly, an object of the present invention is to provide a compound in which a novel aryl ring and an acridine derivative are condensed, an organic electric device using the same, and a terminal thereof.

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

The present invention is a compound in which an aryl ring and an acridine derivative are condensed, and may be used as a hole injection, hole transport, electron injection, electron transport, light emitting material, and passivation (kepping) material in an organic electronic device. It can be used as a host or a dopant in the host / dopant, it can be used as a hole injection, a hole transport layer, it has been found that the effect of increasing the efficiency of the organic electronic device including the same, lowering the driving voltage, increasing the life and stability.

Accordingly, the present invention provides a compound having a structure in which an aryl ring and an acridine derivative are condensed, an organic electronic device using the same, and a terminal including the organic electronic device.

The present invention is a compound in which an aryl ring and an acridine derivative are condensed, and are useful as hole injection, hole transport, electron injection, electron transport, a light emitting material and a passivation (kepping) material, and are particularly useful as a host or a dopant.

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

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

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

(1) In Formula 1, A is represented by Formula 2, and may be configured as in Formulas 3 to 5. Ar is a group represented by a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group independently of one another.

(2) R ₁ to R ₇ are the same as or different from each other, and each independently
Hydrogen atom; Halogen atom;
Hydrogen, a halogen group, a C ₁ to C ₆₀ alkyl group, a C ₁ to C ₆₀ alkoxy group, a C ₁ to C ₆₀ alkylamine group, a C ₆ to C ₆₀ arylamine group, a C ₁ to C ₆₀ alkyl tee Opene group, C ₆ -C ₆₀ aryl thiophene group, C ₂ -C ₆₀ alkenyl group, C ₂ -C ₆₀ alkynyl group, C ₃ -C ₆₀ cycloalkyl group, C ₆ -C ₆₀ aryl group, C ₆ ~ C ₆₀ aryl group substituted with deuterium, C ₈ ~ C ₆₀ aryl alkenyl group, substituted or unsubstituted silane group, substituted or unsubstituted boron group, substituted or unsubstituted germanium group, and substituted or C ₆ ~ C ₆₀ aryl group unsubstituted or substituted with one or more groups selected from the group consisting of an unsubstituted C ₅ ~ C ₆₀ heterocyclic group ;

Halogen, CN, NO ₂ , C ₁ ~ C ₆₀ alkyl group, C ₁ ~ C ₆₀ alkoxy group, C ₁ ~ C ₆₀ alkylamine group, C ₆ ~ C ₆₀ arylamine group, C ₁ ~ C ₆₀ the alkylthio group, C ₂ ~ C ₆₀ alkenyl group, C ₂ ~ C ₆₀ alkynyl group, C ₃ ~ C ₆₀ cycloalkyl group, C ₆ ~ C ₆₀ aryl group, a C ₆ ~ C ₆₀ substituted with a heavy hydrogen of the Substituted with one or more groups selected from the group consisting of an 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 to C ₆₀ heterocyclic group Or an unsubstituted C ₅ -C ₆₀ heterocyclic group ; And

A condensed ring group of an aromatic ring of C ₆ -C ₆₀ and an aliphatic ring of C ₄ -C ₆₀ ;
(3) R ₁ to R ₇ may combine with adjacent groups to form a saturated or unsaturated carbon ring.

In the formula (3) it can be carried out by the following examples.

In Formula 4, it may be carried out by the following examples.

In the formula (5) it can be carried out by the following examples.

Specific examples of the compound belonging to Formula 1 that is a compound in which an aryl ring and an acridine derivative are condensed according to an embodiment of the present invention may be compounds represented by the following Formulas 2 to 8, but the present invention is not limited thereto.

Various organic electric devices exist in which compounds in which an aryl ring and an acridine derivative condensed with reference to Chemical Formulas 1 to 8 are used as an organic material layer. Examples of the organic electroluminescent device in which the compounds in which the aryl ring and the acridine derivative are condensed with reference to Chemical Formulas 1 to 8 may be used include, for example, an organic light emitting diode (OLED), an organic solar cell, an organic photoconductor (OPC) drum, Organic transistors (organic TFTs).

An organic electroluminescent device (OLED) will be described as an example of an organic electric device to which the compounds in which the aryl ring and the acridine derivative are condensed with reference to Chemical Formulas 1 to 8 can be applied, but the present invention is not limited thereto. The compound in which the aryl ring and the acridine derivative are condensed as described above may be applied to the electrical device.

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 8 Provided is a light emitting device.

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

In an organic light emitting display device according to another embodiment of the present invention, at least one layer of an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer is formed to include the compounds of Formulas 1 to 8 Except for the above, it may be manufactured in a structure known in the art using conventional manufacturing methods and materials in the art.

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

In this case, the compound in which the aryl ring and the acridine derivative condensed with reference to Chemical Formulas 1 to 8 may be included in one or more of an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer. Specifically, the compound in which the aryl ring and the acridine derivative are condensed with reference to Chemical Formulas 1 to 8 may be a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, a hole blocking layer, an electron blocking layer, or a protective layer. It may be used in place of one or more, or may be used in conjunction with them to form a layer. Of course, the organic layer may be used not only in one layer but also in two or more layers.

In particular, the compound in which the aryl ring and the acridine derivative described with reference to Chemical Formulas 1 to 8 are condensed may be used as a hole injection material, a hole transport material, an electron injection material, an electron transport material, a light emitting material, and a passivation (kepping) material. In particular alone, as a light emitting material and as a host or dopant.

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

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

According to another embodiment of the present invention, an organic light emitting display device may be used in a solution process such as spin coating or ink jet process of a compound in which the aryl ring and the acridine derivative are condensed as described above. It may be.

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), and indium zinc oxide (IZO); ZnO: Al or SnO _2: a combination of a metal and an oxide such as Sb; Conductive polymers such as poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (PEDT), polypyrrole and polyaniline.

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, silicon germanium oxide Compound, a silicon-based arylamine compound, and the like.

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

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

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

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

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

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

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

Example

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

Manufacturing example

Hereinafter, preparation or synthesis examples of the compounds in which the aryl ring and acridine derivative belonging to Chemical Formula 1 are condensed will be described. However, one or two of the compounds in which the aryl ring and the acridine derivative condensed in Formula 1 are condensed because of the large number of compounds in which the aryl ring and the acridine derivative belong to Formula 1 are condensed. Those skilled in the art, that is, those skilled in the art can prepare a compound in which the aryl ring and the acridine derivative belonging to the present invention, which are not illustrated, are condensed.

Synthetic

[Synthesis of Indenocarbazole core]

The following is an example of the preparation method of forming Formula 3 to Formula 5 by combining the formula (2) in the position of A shown in the formula (1).

Synthesis of Intermediate 2

Under argon atmosphere, 1-bromo-2-nitrobenzene (12.12 g 60 mmol), intermediate 1 (11.90 g, 50 mmol), tetrakis triphenyl phosphine palladium (0.5 g, 4.32 mmol) in THF 500 ml, water Put potassium carbonate (K ₂ CO ₃ ) in 250 ml and heated to reflux for 24 hours. The solid obtained was washed with water and methanol and then separated by silica gel column chromatography to give intermediate 2 in 78% yield.

Method of synthesis of intermediates 3a and 3b

Compound 2 (1.89 g, 5.98 mmol) and triphenylphosphinepalladium (3.92 g, 14.85 mmol) dissolved in olsodichlorobenzene were added to 2-neck and refluxed for 24 hours. The color of the solvent changed from yellow to brown. Thereafter, the mixture was heated to room temperature, concentrated and separated by silica gel column chromatography to obtain intermediates 3a and 3b in a yield of 45% and 45%, respectively.

Synthesis of Intermediate 5

In a 1000 mL two-necked round bottom flask, 1-iodo-2-nitrobenzene (102.74 mmol, 25.58 g), 2-bromophenylboronic acid (102.74 mmol, 20.63 g), tetrakistriphenylphosphine palladium (0) (3.08 mmol, 3.56 g), potassium carbonate Add (K ₂ CO ₃ ) (308.21 mmol, 42.60 g), add 300 mL of Tetrahydrofuran (THF) and 100 mL of water as a solvent, and stir at 80 ° C. The reaction solution was cooled to room temperature and extracted with dichloromethane. The obtained extract was dried over anhydrous magnesium sulfate and concentrated. The resulting mixture was separated by silica gel column chromatography to give 20.00 g of the title compound as a white solid. Intermediate 5 was obtained in yield 70%.

Synthesis of Intermediate 6

Compound 5 and triphenylphosphine palladium dissolved in oxodichlorobenzene were added to 2-neck and refluxed for 24 hours to change the color of the solvent from yellow to brown.

Thereafter, the mixture was heated to room temperature, concentrated and separated by silica gel column chromatography to obtain Intermediate 6 in a yield of 75%.

Synthesis of Intermediate 7

In a 500 mL two-necked round bottom flask, 4-bromo-9H-carbazole (67.19 mmol, 16.53 g) is charged with nitrogen. Add 300 mL of anhydrous Tetrahydrofuran (THF), dissolve it, and slowly add n-Butyllithium in Hexane 2.5M (70.55 mmol, 28.22 mL) at -78 ° C. The temperature was allowed to stand at room temperature, followed by stirring for 30 minutes. The temperature was then set to -78 ° C, and 2-bromobenzoyl chloride (67.19 mmol, 14.74 g) was diluted in anhydrous Tetrahydrofuran (THF) and slowly added. The temperature is brought to room temperature and stirred. After completion of the reaction, the mixture is extracted with dichloromethane and the extract is dried over anhydrous magnesium sulfate and concentrated. The resulting mixture was separated by silica gel column chromatography to give 18.02 g of the title compound as a yellow solid in 77% yield.

Synthesis of Intermediate 8

(2-bromophenyl) (9H-carbazol-4-yl) methanone (85.66 mmol, 27.77 g) and Pd (OAc) 2 (0.86 mmol, 0.19 g) were charged to a 1000 mL two neck round bottom flask. 500 mL of Dimethyformamide was added as a solvent, and P (o-tol) 3 (1.71 mmol, 0.52 g) was added thereto, followed by stirring at 90 ° C. After the reaction, the temperature of the reaction solution was lowered to room temperature, and ethanol was added to filter the precipitate. The resulting mixture was separated by silica gel column chromatography (eluent-dichloromethane: n-hexane = 3: 7) to give 15.0 g of the title compound as a white solid in 50% yield.

Synthesis of Intermediate 3c

Place intermediate 8 in a 500 mL two-necked round bottom flask, filled with nitrogen. Then, add 300 mL of anhydrous THF, dissolve it, and slowly add Methylmagnesium bromide 3M (63.03 mmol, 25.32 mL) at -78 ° C. Then, slowly bring the temperature to room temperature and stir. After the reaction is completed, the mixture is extracted with dichloromethane, and the extract is dried over anhydrous magnesium sulfate and concentrated. The resulting mixture was separated by silica gel column chromatography to give the title compound as a yellow solid in 80% yield.

Synthesis of Intermediate 9

Add 3a and methyl 2-bromobenzoate, potassium carbonate (K ₂ CO ₃ ), sodium sulfate (Na ₂ SO ₄ ), copper (Cu), add nitrobenzene, and heat reflux at 190 ° C for 24 hours. After completion of the reaction, the mixture was extracted with MC, water, dried over MgSO 4, concentrated, and the resulting compound was separated by column chromatography to obtain intermediate 9, 65% of the desired compound.

Obtained in yield.

Synthesis of Intermediate 11

The synthesis of intermediate 11 is the same as the synthesis of intermediate 9 except that the synthesis of intermediate 9 is performed using 3b instead of intermediate 3a. Intermediate 11 was obtained with a yield of 49%.

Synthesis of Intermediate 13

The synthesis of intermediate 13 is the same as the synthesis of intermediate 9 except that the synthesis of intermediate 9 is carried out using 3c instead of intermediate 3a. Intermediate 13 was obtained in yield 72%.

Synthesis of Intermediate 10

Intermediate 9 was dissolved in benzene, diluted in ether, and slowly stirred with magnesium magnesium iodide (CH ₃ MgI) at 0 ° C. for 30 minutes while stirring. It is then heated to reflux at 70 ° C. for 2 hours. After completion of the reaction, the mixture was extracted with methyl chloride (MC) and ice water, dried over magnesium sulfate (MgSO ₄ ), concentrated, and the resulting compound was separated using column chromatography to obtain 53% of intermediate 10 as a desired compound. Obtained in the yield.

Synthesis of Intermediate 12

Synthesis of intermediate 12 is the same as the synthesis of intermediate 10 except that the synthesis of intermediate 10 is performed using 11 instead of intermediate 9. Intermediate 12 was obtained with a yield of 62%.

Synthesis of Intermediate 14

The synthesis of intermediate 14 is the same as the synthesis of intermediate 10 except that the synthesis of intermediate 10 is carried out using 13 instead of intermediate 9. Intermediate 14 was obtained with a yield of 63%.

Synthesis of Intermediate 15

Intermediate 10 was placed in trifluoroacetate (CF ₃ COOH) and heated to reflux at 80 ° C. for 2 hours. After completion of the reaction, the mixture was extracted with methyl chloride (MC) and water, dried over magnesium sulfate (MgSO ₄ ), concentrated, and the resulting compound was separated by column chromatography to obtain intermediate 15 as an intermediate compound, 61%. Obtained in yield.

Synthesis of Intermediate 17

The synthesis of intermediate 17 is the same as the synthesis of intermediate 15 except that the synthesis of intermediate 15 is carried out using 12 instead of intermediate 10. Intermediate 17 was obtained with a yield of 39%.

Synthesis of Intermediate 19

The synthesis of intermediate 19 is the same as the synthesis of intermediate 15, except that the synthesis of intermediate 15 is carried out using 14 instead of intermediate 10. Intermediate 19 was obtained with yield 68%.

Synthesis of Intermediate 16

Intermediate 15 was added to methyl chloride (MC), NBS and then reacted with trifluoroacetate (CF ₃ COOH) at room temperature for 5 hours.

After completion of the reaction, methyl chloride (MC) and sodium bicarbonate were extracted with dissolved water, dried over magnesium sulfate (MgSO ₄ ), concentrated, and the resulting compound was acetone 1: 3. Washing with (Hexane) gave the desired compound Intermediate 16 in 94% yield.

Synthesis of Intermediate 18

The synthesis of intermediate 18 is the same as the synthesis of intermediate 16 except that the synthesis of intermediate 16 is carried out using 17 instead of intermediate 15.

Synthesis of Intermediate 20

Synthesis of intermediate 20 is the same as the synthesis of intermediate 16 except that the synthesis of intermediate 16 is carried out using 19 instead of intermediate 15.

[Synthesis method of compound A-9]

The following is an example of synthesizing the A-9 compound shown in the formula (6).

Synthesis of Intermediate b

Dibiphenyl-4-ylamine, 1-Bromo-4-iodobenzene, Pd ₂ (dba) ₃ , triphenylphosphine, and sodium tert-butoxide were added to a toluene solvent and stirred under reflux for 24 hours at 130 ° C. After completion of the reaction, the mixture was extracted with methyl chloride (MC) and water, dried over magnesium sulfate (MgSO ₄ ), concentrated and the resulting compound was separated by column chromatography to obtain the intermediate compound (b) as 67%. Obtained in yield.

Synthesis of Intermediate a

After dissolving intermediate 16 in tetrahydrofolate (THF), n-BuLi was slowly added dropwise at -78 ° C, followed by stirring for about 1 hour. Triisopropylborate was then slowly added dropwise at −78 ° C., stirred, acidified with 1N hydrochloric acid (HCl), extracted with water and ethyl acetate (EA), dried over magnesium sulfate (MgSO ₄ ), and dried over hexane. Recrystallization from (Hexane) afforded intermediate a in 55% yield.

Synthesis of Compound A-9

Potassium carbonate (K ₂ CO ₃ ) was added to 500 ml of tetrahydrofolate (THF) and 250 ml of water for intermediate a, intermediate b, and Pd (PPh 3) 4 and refluxed for 24 hours. The obtained solid was washed with water and methanol, and then separated by silica gel column chromatography to give a white solid product A-9 in 70% yield.

[Synthesis method of compound B-10]

The following is an example of synthesizing the B-10 compound shown in formula (7).

Synthesis of Intermediate d

Synthesis of intermediate b is the same as the synthesis of intermediate b, except that N- (biphenyl-4-yl) -9,9-dimethyl-9H-fluoren-2-amine is substituted for dibiphenyl-4-ylamine. Intermediate d was obtained with a yield of 62%.

Synthesis of Intermediate c

Synthesis of intermediate a is the same as the synthesis of intermediate a, except that intermediate 18 is substituted for intermediate 16. Intermediate c was obtained with a yield of 52%.

Synthesis of Compound B-10

Synthesis of Compound A-9 was the same as the synthesis of Compound A-9 except that Intermediate c instead of Intermediate a was replaced by Intermediate b. Compound B-10 was obtained in a yield of 73%.

[Synthesis method of compound C-9]

The following is an example of synthesizing the C-9 compound shown in formula (8).

Synthesis of Intermediate e

Synthesis of intermediate a is the same as the synthesis of intermediate a, except that intermediate 20 is substituted for intermediate 16. Intermediate e was obtained with a yield of 50%.

Synthesis of Compound C-9

Synthesis of Compound A-9 is the same as the synthesis of Compound A-9, except that Intermediate e is substituted for Intermediate a. Compound C-9 was obtained in yield 54%.

[Production Evaluation of Organic EL Device]

Various compounds obtained through the synthesis were used as the hole transport layer to manufacture an organic light emitting device according to a conventional method. First, 4,4 ', 4 "-tris (N- (2-naphthyl) -N-phenylamino) -triphenylamine (hereinafter 2T-NATA) as a hole injection layer on the ITO layer (anode) formed on the glass substrate first The film was vacuum deposited to form a thickness of 10 nm.

Subsequently, the material developed as a major transport compound was vacuum deposited to a thickness of 30 nm to form a hole transport layer. After the formation of the hole transport layer, when the developed material was measured by the hole transport layer, a light emitting layer doped with 7% of BD-052X (Idemitus) having a thickness of 45 nm on the hole transport layer (where BD-052X was a blue fluorescent dopant) 9,10-di (naphthalene-2-anthracene (AND)) was used as the light emitting host material. (1,1'-bisphenyl) -4-oleito) bis (2-methyl- 8-quinolinoleito) aluminum (hereinafter abbreviated as BAlq) was vacuum deposited to a thickness of 10 nm, and then tris (8-quinolinol) aluminum (hereinafter abbreviated as Alq3) was 40 nm thick as an electron injection layer. It was formed into a film. Thereafter, LiF, an alkali metal halide, was deposited to a thickness of 0.2 nm, and then Al was deposited to a thickness of 150 nm to use an Al / LiF as a cathode to prepare an organic light emitting device.

Comparative Example

When the compounds of the present invention were measured by the hole transport layer, an organic electroluminescent light emitting device having the same structure as in the experimental example was prepared by using a compound represented by the following formula (hereinafter abbreviated as NPB) as a hole transport material instead of the compound of the present invention for comparison. The device was produced.

Hole transport
material Voltage
(V) Current density
(mA / cm ² ) Luminous efficiency
(cd / A) Chromaticity coordinates
(x, y) Example 1
Compound A-9 4.9 12.31 8.9 (0.15, 0.14) Example 2
Compound B-10 4.9 12.22 8.7 (0.15, 0.15) Example 3
Compound c-9 5.1 12.54 9.0 (0.15, 0.14) Comparative Example 1
NPB 6.0 13.35 7.5 (0.15, 0.15)

As can be seen from the results of the above table, the organic EL device using the organic EL device material of the present invention is used as a hole transporting material of the organic EL device because the blue light emission with improved color purity is obtained with high efficiency. The luminous efficiency and lifespan can be significantly improved.

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

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.

Claims (11)

Compound represented by the following formula.

In the above formula
(1) A is

Is,
(2) R ₁ to R ₇ are the same as or different from each other, and each independently
Hydrogen atom; Halogen atom;
Hydrogen, a halogen group, a C ₁ to C ₆₀ alkyl group, a C ₁ to C ₆₀ alkoxy group, a C ₁ to C ₆₀ alkylamine group, a C ₆ to C ₆₀ arylamine group, a C ₁ to C ₆₀ alkyl tee Opene group, C ₆ -C ₆₀ aryl thiophene group, C ₂ -C ₆₀ alkenyl group, C ₂ -C ₆₀ alkynyl group, C ₃ -C ₆₀ cycloalkyl group, C ₆ -C ₆₀ aryl group, C ₆ ~ C ₆₀ aryl group substituted with deuterium, C ₈ ~ C ₆₀ aryl alkenyl group, substituted or unsubstituted silane group, substituted or unsubstituted boron group, substituted or unsubstituted germanium group, and substituted or C ₆ ~ C ₆₀ aryl group unsubstituted or substituted with one or more groups selected from the group consisting of an unsubstituted C ₅ ~ C ₆₀ heterocyclic group ;
Halogen, CN, NO ₂ , C ₁ ~ C ₆₀ alkyl group, C ₁ ~ C ₆₀ alkoxy group, C ₁ ~ C ₆₀ alkylamine group, C ₆ ~ C ₆₀ arylamine group, C ₁ ~ C ₆₀ the alkylthio group, C ₂ ~ C ₆₀ alkenyl group, C ₂ ~ C ₆₀ alkynyl group, C ₃ ~ C ₆₀ cycloalkyl group, C ₆ ~ C ₆₀ aryl group, a C ₆ ~ C ₆₀ substituted with a heavy hydrogen of the Substituted with one or more groups selected from the group consisting of an 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 to C ₆₀ heterocyclic group Or an unsubstituted C ₅ -C ₆₀ heterocyclic group ; And
A condensed ring group of an aromatic ring of C ₆ -C ₆₀ and an aliphatic ring of C ₄ -C ₆₀ ;
(3) Ar is a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted hetero aryl group,
(4) R ₁ to R ₇ may combine with adjacent groups to form a saturated or unsaturated carbon ring. The method of claim 1,
Compound which is one of the following compounds.

,

,

The method of claim 1,
R ₁ to R ₇ are bonded to each other with adjacent groups to form a saturated or unsaturated carbon ring. The method of claim 1,
The compound is one of the following compounds.

An organic electric device comprising at least one organic material layer comprising the compound of claim 1. 6. The method of claim 5,
And forming the compound into the organic material layer by a soluble process. 6. The method of claim 5,
An organic electroluminescent device comprising a first electrode, one or more organic material layers, and a second electrode, which are sequentially stacked. 6. The method of claim 5,
The organic material layer is an organic electric element, characterized in that any one of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer. 6. The method of claim 5,
The organic material layer includes an emission layer, and the compound is an organic electric element, characterized in that used as a host or dopant material of the emission layer. A display device comprising the organic electric device of claim 5;
And a control unit for driving the display device. The method of claim 10,
The organic electroluminescent device is an organic electroluminescent device (OLED), an organic solar cell, an organic photoconductor (OPC) drum, characterized in that one of the organic transistor (organic TFT).

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