KR20120027600A - Compound containing quinoline derivatives and organic electronic element using the same, terminal thereof - Google Patents

Abstract

PURPOSE: A compound containing quinoline derivatives is provided to perform various functions in an organic electric device and terminal. CONSTITUTION: A compound containing quinoline derivatives is denoted by chemical formula 1. An organic electric device contains one or more organic layers containing the compounds. The organic electric device is an organic electroluminescence device containing a first electrode, one or more organic layers, and a second electrode. A terminal contains an electronic device containing the organic electric device and a control unit for driving the electronic device.

Description

Compound Containing Quinoline Derivatives And Organic Electronic Element Using The Same, Terminal Thereof}

The present invention relates to a compound comprising a quinoline derivative, 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 element using an organic light emitting phenomenon has a structure including an anode, a cathode, and an organic material layer positioned between the anode and the cathode. The organic material layer may have a multi-layered structure composed of different materials in order to increase the efficiency and stability of the organic electric device. For example, the organic material layer may include a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer.

The material used as the organic material layer may be classified into a light emitting material and a charge transporting material according to a function. For example, the material used as the organic material layer may be classified into a hole injection material, a hole transport material, an electron transport material, and an electron injection material.

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. 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, a problem may occur in that the maximum light emission wavelength is shifted to a long wavelength due to intermolecular interaction, color purity is reduced, or the efficiency of the device is reduced due to the light emission attenuation effect. Accordingly, a host / dopant-based material may be used as the light emitting material in order to increase the color purity and the light emission efficiency through energy transfer.

When a small amount of dopant having a smaller energy band gap than the 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 emitting 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, an electron injection material, an electron transport material, a light emitting material, and a passivation material, is stable and Supported by an efficient material should be preceded, but development of a stable and efficient organic material layer for an organic electric device has not yet been made sufficiently, and development of a new material is still required.

The present inventors have found a compound containing a quinoline derivative having a novel structure, and the fact that applying the compound to an organic electric device can increase the luminous efficiency of the device, lower the driving voltage, increase the lifetime, and increase the safety. Revealed.

Accordingly, an object of the present invention is to provide a compound comprising a novel quinoline derivative, 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 may be useful as a hole injecting material, a hole transporting material, an electron injecting material, an electron transporting material, a light emitting material and a passivation material depending on the compound including the quinoline derivative. In addition, the compound containing the quinoline derivative of the present invention may be used alone as a light emitting material or as a host or dopant.

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

The compound including the quinoline derivative of the present invention may play various roles in the organic electronic device and the terminal, and may be useful as hole injection, hole transport, electron injection, electron transport, a light emitting material, and a passivation material.

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

Hereinafter, some embodiments of the present invention will be described in detail through exemplary drawings. In adding reference numerals to the components of each drawing, it should be noted that the same reference numerals are assigned to the same components as much as possible even though they are shown in different drawings. In 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 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 should be understood that the elements may be "connected", "coupled" or "connected".

In one aspect, the present invention provides a compound of Formula 1 below.

In the above formula, A in Formula 1 may be the same or different from each other and each independently a halogen group, cyano group, nitrile group, C ₁ ~ C ₆₀ Alkyl group, C ₁ ~ C ₆₀ Alkoxy group, C ₁ ~ C ₆₀ Alkylamine group, C ₁ ~ C ₆₀ arylamine group, C ₁ ~ C ₆₀ alkylthiophene group, C ₆ ~ C ₆₀ arylthiophene 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, of a C ₆ ~ C ₆₀ substituted by deuterium aryl group, a C ₈ ~ arylalkenyl group, a substituted or unsubstituted of C ₆₀ At least one substituted or unsubstituted C ₆ -C selected from the group consisting of a substituted silane group, a substituted or unsubstituted boron group, a substituted or unsubstituted germanium group, a substituted or unsubstituted C ₅ -C ₆₀ heterocyclic group An aryl group of ₆₀ or a heterocyclic group of C ₅ to C ₆₀ ; An amino group substituted with one or more substituents selected from the group consisting of a substituted or unsubstituted aryl group, a substituted or unsubstituted arylalkyl group, and a substituted or unsubstituted arylalkenyl group; A condensed cyclic group of an aromatic ring of C ₆ to C ₆₀ and an aliphatic ring of C ₄ to C ₆₀ , each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, a substituted or unsubstituted C ₆ ~ C ₆₀ aliphatic hydrocarbon It may be any group selected from the group, a substituted or unsubstituted aryl group, a substituted or unsubstituted hetero aryl group, but is not limited thereto. When any group of A in Formula 1 is substituted, the substituent may be substituted.

In addition, X ₁ to X ₄ of Formula 1 is one of carbon or nitrogen, but is not limited thereto. X ₁ to X ₄ One may have a nitrogen atom, but is not limited thereto.

In addition, Y in Formula 1 may be the same as A, but is not limited thereto. In this case, Y may combine with adjacent groups to form an aliphatic or hetero condensed ring, This is not restrictive. Meanwhile, n may be an integer of 1 to 3, but is not limited thereto.

In addition, Ar ₁ and Ar ₂ of Formula 1 may be the same or different from each other, and each independently a halogen group, an alkyl group, an alkenyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted arylalkyl group, a substituted or unsubstituted Unsubstituted or substituted with one or more substituents selected from the group consisting of an arylalkenyl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted fluorenyl group, a nitrile group, and an acetylene group C ₁ ~ C ₆₀ Alkyl group, C ₁ ~ C ₆₀ Alkoxy group C ₁ ~ C ₆₀ An aryl group, carbazolyl group, fluorenyl group or halogen group, alkyl group, alkenyl group, alkoxy group, substituted or unsubstituted Substituted or unsubstituted with one or more substituents selected from the group consisting of an arylamine group, a substituted or unsubstituted aryl group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted fluorenyl group, a nitrile group, an acetylene group, Heterocyclic group containing O, N, S as a hetero atom; Hydroxyl group; Carboxyl groups; Nitrile group, nitro group, halogen group, -N (R ') (R "); -CO-N (R ') (R "); It can be selected from the group consisting of 'COOR'. Here, Ar ₁ and Ar ₂ may form a condensed ring of an aliphatic or hetero group with adjacent groups, but is not limited thereto. Ar ₁ and Ar ₂ may be substituted when substituted. R ′ and R ″ may be the same as A in Formula 1, but are not limited thereto.

In addition, L is a substituted or unsubstituted arylene group having 6 to 60 carbon atoms, a substituted or unsubstituted florenylene group, a hetero arylene group having 5 to 60 nuclear atoms, a divalent or trivalent substituted or unsubstituted aliphatic carbonization. Groups selected from hydrogen and divalent linking groups may be represented, but are not limited thereto. m may be an integer of 0 to 3, but is not limited thereto.

The compound represented by Chemical Formula 1 may be used in a solution process (soluble process) but may be applied to the organic electric device described below, but is not limited thereto.

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

Formula 2 is a case where X ₁ or X ₄ in Formula 1 is nitrogen (N). In this case, R ₁ , R ₂ and R ₃ of Formula 2 may be the same as A of Formula 1, but are not limited thereto. Since A of Formula 1 has been described above, a detailed description thereof will be omitted.

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

Formula 3 is a case where the X ₂ or X ₃ of the formula (1) nitrogen (N). In this case, R ₁ , R ₂ and R ₃ of Formula ₃ may be the same as A of Formula 1, but are not limited thereto. Since A of Formula 1 has been described above, a detailed description thereof will be omitted.

In this case, the compounds represented by Formulas 2 and 3 may also be used in the solution process (soluble process).

Although a compound having a quinoline derivative according to one embodiment of the present invention has been described with respect to Chemical Formulas 1 to 3, the present invention is not limited thereto.

Various organic electric devices exist in which compounds including quinoline derivatives described with reference to Chemical Formulas 1 to 3 are used as organic material layers. Organic electroluminescent devices that may be used include compounds including quinoline derivatives described with reference to Formulas 1 to 3, an organic electroluminescent device (OLED), an organic solar cell, an organic photoconductor (OPC) drum, an organic transistor (organic TFT), a photo Photodiodes, organic lasers, laser diodes, and the like.

As an example of the organic electroluminescent device to which the compounds including the quinoline derivatives described with reference to Chemical Formulas 1 to 3 may be applied, the present invention is not limited thereto. Compounds comprising the quinoline derivatives described can be applied.

Another embodiment of the present invention is an organic electroluminescent 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 electroluminescent device comprising a compound of formula 1 to 3 To provide.

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

The organic light emitting device according to another embodiment of the present invention, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer And a structure known in the art using conventional manufacturing methods and materials in the art, except that at least one layer of the organic material layer including the electron injection layer is formed to include the compounds of Formulas 1 to 3. It can be prepared as.

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. In this case, reference numeral 101 denotes a substrate, 102 an anode, 103 a hole injection layer (HIL), 104 a hole transport layer (HTL), 105 a light emitting layer (EML), 106 an electron injection layer (EIL), 107 an electron transport layer ( ETL), 108 represents a negative electrode. 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 including the quinoline derivative described with reference to Formulas 1 to 3 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 containing the quinoline derivative described with reference to Formulas 1 to 3 may be substituted for one or more of 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, a protective layer It may be used 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.

Compounds containing quinoline derivatives described with reference to Formulas 1 to 3 may play various roles in organic electronic devices and terminals, and may be used as hole injection materials, hole transport materials, electron injection materials, electron transport materials, light emitting materials, and passivation materials. Can be useful. In addition, the compound comprising a quinoline derivative according to an embodiment of the present invention may be used alone as a light emitting material or as a host or dopant.

An organic light emitting display device according to another embodiment of the present invention is a metal oxide having a metal or conductivity on a substrate by using a physical vapor deposition (PVD) method, such as sputtering or e-beam evaporation These alloys are deposited to form an anode, and 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 on the anode, and then a material that can be used as a cathode is deposited on the organic material layer. Can be.

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 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 or a hole transport layer, by a soluble process of a compound including the quinoline derivative 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), 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 material of the hole injection layer can increase the 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, NPB, spiro-arylamine compounds, perylene-arylamine compounds, azacycloheptatriene compounds, bis (diphenylvinylphenyl) anthracene, silicon germanium oxide compounds, and silicon-based aryls. Amine 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 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 a metal complex compound such as Balq, Alq3, Be (bq) 2, Zn (BTZ) 2, Zn (phq) 2, PBD, spiro-PBD, TPBI, Tf-6P, aromatic compound with imidazole ring, It can be produced using a low molecular weight material containing boron compounds and the like. At this time, the electron injection layer may be formed in a thickness range of 100 ~ 300Å.

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.

As described above, the compound including the quinoline derivative described with reference to Chemical Formulas 1 to 3 may be useful as a hole injection material, a hole transport material, an electron injection material, an electron transport material, a light emitting material, and a passivation material. In addition, when the compound containing the quinoline derivative of the present invention is used alone, the compound according to the embodiment of the present invention may be used as a light emitting material or as a host or dopant.

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.

The compounds described above may be modified in various embodiments as follows.

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.

Because of the large number of compounds based on quinoline derivatives belonging to the formulas (1) to (3), one or two of the compounds based on quinoline derivatives will be exemplarily described.

The technical field to which the present invention pertains can be prepared by those skilled in the art, that is, those skilled in the art, based on the preparation examples described below, to prepare compounds based on indole derivatives belonging to the present invention, which are not illustrated.

Synthesis of Starting Material (3-1)

1.6- bromo -2,4- diphenylquinoline Synthesis of

Step 1) Synthesis of 5-bromo-3-phenylbenzo [c] isoxazole

[Scheme 1]

100 g (1782 mmol) of potassium hydroxide was dissolved in 400 mL methyl alcohol at 0 ° C. in a round flask in a nitrogen gas atmosphere. 20 g (99 mmol) of 1-bromo-4-nitrobenzene dissolved in 150 mL THF was added to the dissolved potassium hydroxide solution, and stirred at 0 ° C. for 30 minutes. 14 g of benzyl cyanide was added to the mixture and stirred at 0 ° C. for 5 hours. The reaction mixture was poured into cold 2 L of water and the resulting solid was filtered under reduced pressure. The solid obtained by filtration was recrystallized using methyl alcohol to give 20 g (yield 73.7%) of the title compound.

Step 2) Synthesis of (2-amino-5-bromophenyl) (phenyl) methanone

[Scheme 2]

Acetic acid was dissolved in 20 g (72.963 mmol) of 5-bromo-3-phenylbenzo [c] isoxazole obtained in step 1). To the dissolved solution was added 32.6 g (583.71 mmol) of iron and stirred at 95 ° C for 3 hours. The mixture was neutralized and extracted with an aqueous sodium bicarbonate solution and ether, dried with MgSO ₄ , and filtered. The obtained residue was recrystallized using ether / hexane (1: 8) to give 19g (yield: 94.3%) of the title compound as a yellow solid.

Step 3) Synthesis of 6-bromo-2,4-diphenylquinoline

Scheme 3

19 g (68.81 mmol) of (2-amino-5-bromophenyl) (phenyl) methanone obtained in step 2), 13.7 g (68.81 mmol) of 4-bromoacetophenone and 17.2 g (68.81 mmol) of diphenylphosphate To the flask was added 20mL m-cresol in a nitrogen atmosphere and stirred for 8 hours at 145 ℃. The reaction mixture was extracted with aqueous sodium hydroxide solution and ethyl acetate, dried over MgSO ₄ and filtered. The obtained residue was recrystallized using ethyl acetate / hexane to give 22g (yield: 72.8%) of the title compound as a white solid.

Intermediate 2-1: N- ( biphenyl -4- yl ) -9,9- dimethyl -9H- fluoren -2- amine Synthesis of

[Scheme 4]

In a round flask, 30 g (110 mmol) of 2-bromo-9,9-dimethyl-9H-fluorene, 20.48 g (121 mmol) of 4-aminobiphenyl, 4 g of tris (dibenzylideneacetone) dipalladium (4.39) mmol) and t-BuONa 32g (329.5 mmol) were added and dissolved in 1.2 L toluene in a nitrogen atmosphere. 1.1 g (5.49 mmol) of P [C (CH ₃ ) ₃ ] ₃ was added to the solution, followed by stirring at 120 ° C. for 5 hours. The reaction mixture was extracted with methylene chloride and distilled water, dried with MgSO ₄ and filtered with water. The obtained residue was separated using column chromatography to obtain 30 g of an intermediate 2-1 compound (yield: 75.4%).

Intermediate 2-2: N- ( biphenyl -4- yl ) -N- (4- bromophenyl ) -9,9- dimethyl Synthesis of -9H-fluoren-2-amine

[Scheme 5]

In a round flask, 15 g (41.50 mmol) of N- (biphenyl-4-yl) -9,9-dimethyl-9H-fluoren-2-amine obtained in intermediate 2-1, 23.48 g of 1-bromo-4-iodinebenzene ( 83 mmol), 8.6 g (62.25 mmol) of potassium carbonate, 2.9 g (45.65 mmol) of copper, and 1.1 g (4.15 mmol) of 18-crown-6 were dissolved in 450 mL of N, N-dimethylformamide. The reaction flask was stirred at reflux for 12 hours at 165 ℃ ~ 175 ℃. After completion of the reaction, the mixture was extracted with distilled water and methylene chloride, and the obtained organic layer was washed again with 5% aqueous hydrochloric acid solution and brine. Thereafter, the resultant was dried over MgSO ₄ , concentrated, and the resulting compound was separated by column chromatography to obtain 16.4 g (70%) of an intermediate 2-2 compound.

Intermediate 2-3: dibiphenyl -4- ylamine  synthesis

Scheme 6

20 g (85.8 mmol) of 4-bromobiphenyl, 17.4 g (103 mmol) of 4-aminobiphenyl, 3.93 g (4.29 mmol) of tris (dibenzylideneacetone) dipalladium and 24.74 g of t-BuONa (257.4) mmol) was dissolved in 827 mL toluene under a nitrogen atmosphere. 1.74 g (8.58 mmol) of P [C (CH ₃ ) ₃ ] ₃ was added to the solution, followed by stirring at 120 ° C. for 7 hours. The reaction mixture was extracted with methylene chloride and distilled water, dried with MgSO ₄ and filtered with water. The obtained residue was separated using column chromatography to obtain 17.65 g (yield: 64%) of the intermediate 2-3 compound.

Intermediate 2-4: N- ( biphenyl -4- yl ) -N- (4- bromophenyl ) biphenyl -4- of amine  Synthesis

Scheme 7

In a round flask, 8 g (24.9 mmol) of dibiphenyl-4-ylamine from intermediate 2-3, 14.09 g (49.8 mmol) of 1-bromo-4-iodinebenzene, 5.16 g (37.35 mmol) of potassium carbonate, and 1.74 g of copper (27.39) mmol), 0.67 g (2.49 mmol) of 18-crown-6 was dissolved in 125 mL of N, N-dimethylformamide. The reaction flask was stirred at reflux for 12 hours at 165 ℃ ~ 175 ℃. After completion of the reaction, the mixture was extracted with distilled water and methylene chloride, and the obtained organic layer was washed again with 5% aqueous hydrochloric acid solution and brine. Thereafter, the resultant was dried over MgSO ₄ , concentrated, and the resulting compound was separated by column chromatography to obtain 7.71 g (65%) of an intermediate 2-4 compound.

Intermediate 4-1: 2,4- diphenylquinolin -6- ylboronic acid Synthesis of

Scheme 8

After dissolving intermediate 3 in 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 aqueous hydrochloric acid solution, extracted with water and ethyl acetate, dried over MgSO ₄ and recrystallized with Hexane to give the intermediate 4 in 58% yield.

Hereinafter, synthesis examples of synthesizing some of the compounds listed in Chemical Formula 4 using intermediates in the synthesis will be described. Compounds listed in the formula (4) which do not explain the synthesis examples can also be synthesized in the same or similar manner to the synthesis examples described below.

Synthesis of Final Compounds of Formula 4

1. Synthesis of Compound A-11: N- ( biphenyl -4- yl ) -N- (9,9- dimethyl -9H- fluoren Synthesis of -2-yl) -2,4-diphenylquinolin-6-amine

Scheme 9

5 g (13.88 mmol) N- (biphenyl-4-yl) -9,9-dimethyl-9H-fluoren-2-amine as intermediate 2-1, 6.02 g as 6-bromo-2,4-diphenylquinoline as intermediate 3-1 (16.66 mmol) and 0.28 g (1.388 mmol) of Pd (t-Bu) ₃ NaOtBu 4g (41.64 mmol) was added to 50 ml of toluene and stirred at reflux for 6 hours. The obtained solid was extracted with water and ether, dried over MgSO ₄ and separated by silica gel column chromatography to obtain 6.5 g (yield: 73%) of product A-11.

FD-MS: m / z = 640.29 (C ₄₈ H ₃₆ N ₂ = 640.81)

H-NMR (CDCl 3, 400 MHz) δ (ppm) 8.89 (d, 1H), 8.30 (d, 2H), 7.87-7.80 (m, 4H), 7.62 (d, 1H), 7.55-7.47 (m, 13H) , 7.41-7.30 (m, 4H), 6.80 (s, 1H), 6.75-6.60 (m, 4H), 1.72 (s, 6H)

2. Synthesis of Compound A-24: N, N- di ( biphenyl -4- yl ) -2,4- diphenylquinolin -6- of amine  synthesis

Scheme 10

5g (15.56 mmol) dibiphenyl-4-ylamine as intermediate 2-3, 6.02g (16.66 mmol) 6-bromo-2,4-diphenylqu inoline as intermediate 3-1 and 0.28g (1.388 mmol) Pd (t-Bu) ₃ ) NaOtBu 4g (41.64 mmol) was added to 50 ml of toluene and stirred at reflux for 5 hours. The obtained solid was extracted with water and ether, dried over MgSO ₄ and separated by silica gel column chromatography to give 6.45 g (yield: 69%) of product A-24.

FD-MS: m / z = 600.26 (C ₄₅ H ₃₂ N ₂ = 600.75)

H-NMR (CDCl 3, 400 MHz) δ (ppm) 8.89 (d, 1H), 8.30 (d, 2H), 7.82-7.79 (m, 3H), 7.55-7.41 (m, 21H), 6.80 (s, 1H) , 6.70-6.68 (m, 4H)

3. Synthesis of Compound A-47: N- ( biphenyl -4- yl ) -N- (9,9- dimethyl -9H- fluoren Synthesis of -2-yl) quinolin-6-amine

Scheme 11

5g (13.88 mmol) N- (biphenyl-4-yl) -9,9-dimethyl-9H-fluoren-2-amine as intermediate 2-1, 3.47g (16.66 mmol) and Pd as 6-bromoquinoline as intermediate 3-1 (t-Bu) ₃ 0.28 g (1.388 mmol) NaOtBu 4g (41.64 mmol) was added to 50 ml of toluene and stirred at reflux for 7.5 hours. The obtained solid was extracted with water and ether, dried over MgSO ₄ and separated by silica gel column chromatography to give 5.09 g (yield: 75%) of product A-47.

FD-MS: m / z = 488.23 (C ₃₆ H ₂₈ N ₂ = 488.62)

H-NMR (CDCl 3, 400 MHz) δ (ppm) 8.89 (d, 1H), 8.60 (d, 1H), 8.15 (d, 1H), 7.87 (d, 1H), 7.82 (d, 1H), 7.62 (d , 1H), 7.55-7.49 (m, 8H), 7.41-7.30 (m, 3H), 6.80-6.60 (m, 5H), 1.72 (s, 6H)

4. Compound A-52 Synthesis: N, N- di ( biphenyl -4- yl ) quinolin-6- of amine  synthesis

Scheme 12

5 g (15.56 mmol) dibiphenyl-4-ylamine as intermediate 2-3, 3.47 g (16.66 mmol) 6-bromoquinoline as intermediate 3-1 and 0.28 g (1.388 mmol) Pd (t-Bu) ₃ NaOtBu 4g (41.64 mmol) was added to 50 ml of toluene and stirred at reflux for 6 hours. The obtained solid was extracted with water and ether, dried over MgSO ₄ and separated by silica gel column chromatography to give 6.45 g (yield: 69%) of product A-24.

FD-MS: m / z = 448.19 (C ₃₃ H ₂₄ N ₂ = 448.56)

H-NMR (CDCl3, 400 MHz) δ (ppm) 8.89 (d, 1H), 8.60 (d, 1H), 8.15 (d, 1H), 7.82 (d, 1H), 7.54-7.45 (m, 14H), 6.80 (s, 1H), 6.70-6.68 (m, 4H)

5. Compound B-11 Synthesis: N- ( biphenyl -4- yl ) -N- (4- (2,4- diphenylquinolin Synthesis of -6-yl) phenyl) -9,9-dimethyl-9H-fluoren-2-Amine

Scheme 13

Intermediate 2-2: 10 g (19.36 mmol) of N- (biphenyl-4-yl) -N- (4-bromophenyl) -9,9-dimethyl-9H-fluoren-2-amine, 2,4 as intermediate 4-1 -diphenylquinolin-6-ylboronic acid 6.93g (21.3 mmol), Pd [P (Ph) ₃ ] ₄ 0.67g (0.58 mmol), NaOH 2.32g (58.08 mmol), THF 100 mL, 50 mL of water, and 24 hours While stirring at reflux. After the reaction was completed, water was added, extracted with water and methylene chloride, and the organic layer was washed with 5% aqueous hydrochloric acid solution again. Thereafter, the organic layer was dried over MgSO ₄ , concentrated, and the obtained compound was separated by column chromatography to obtain 10 g (72%) of a B-11 compound.

FD-MS: m / z = 716.32 (C ₅₄ H ₄₀ N ₂ = 716.91)

H-NMR (CDCl 3, 400 MHz) δ (ppm) 8.30 (d, 2H), 8.21 (d, 1H), 8.04 (d, 1H), 7.90-7.87 (m, 2H), 7.79 (d, 2H), 7.64 -7.30 (m, 20H), 6.73-6.60 (m, 6H), 1.72 (s, 6H)

6. Tue Compound  B-52 Synthesis: N- ( biphenyl -4- yl ) -N- (4- ( quinolin Synthesis of -6-yl) phenyl) biphenyl-4-amine

Scheme 14

9.22 g (19.36 mmol) N- (biphenyl-4-yl) -N- (4-bromophenyl) biphenyl-4-amine as intermediate 2-4, 3.68 g (21.3 mmol) as Pd [6-Quinolineboronic acid, intermediate 4 P (Ph) ₃ ] ₄ 0.67g (0.58 mmol), NaOH 2.32g (58.08 mmol), THF 100mL, water 50mL were added thereto, and the mixture was stirred under reflux for 24 hours. After the reaction was completed, water was added, extracted with water and methylene chloride, and the organic layer was washed with 5% aqueous hydrochloric acid solution again. Thereafter, the organic layer was dried over MgSO ₄ , concentrated, and the obtained compound was separated by column chromatography to obtain 7.11 g (70%) of a B-52 compound.

FD-MS: m / z = 524.23 (C ₃₉ H ₂₈ N ₂ = 524.65)

H-NMR (CDCl 3, 400 MHz) δ (ppm) 8.83 (d, 1H), 8.38 (d, 1H), 8.21 (d, 1H), 8.04 (d, 1H), 7.90 (s, 1H), 7.58-7.51 (m, 15H), 7.41 (t, 2H), 6.69-6.68 (m, 6H)

7. Synthesis of Compound B-47: N- ( biphenyl -4- yl ) -9,9- dimethyl -N- (4- ( quinolin Synthesis of -6-yl) phenyl) -9H-fluoren-2-amine

Scheme 15

10 g (19.36 mmol) of N- (biphenyl-4-yl) -N- (4-bromophenyl) -9,9-dimethyl-9H-fluoren-2-amine as intermediate 2-2, 6-Quinolineboronic acid as intermediate 4 3.68 g (21.3 mmol), Pd [P (Ph) ₃ ] ₄ 0.67 g (0.58 mmol), NaOH 2.32 g (58.08 mmol), THF 100 mL, 50 mL of water were added thereto, and the mixture was stirred under reflux for 24 hours. After the reaction was completed, water was added, extracted with water and methylene chloride, and the organic layer was washed with 5% aqueous hydrochloric acid solution again. Thereafter, the organic layer was dried over MgSO ₄ , concentrated, and the obtained compound was separated by column chromatography to obtain 7.98 g (73%) of B-47 compound.

FD-MS: m / z = 564.26 (C ₄₂ H ₃₂ N ₂ = 564.72)

H-NMR (CDCl 3, 400 MHz) δ (ppm) 8.83 (d, 1H), 8.38 (d, 1H), 8.21 (d, 1H), 8.04 (d, 1H), 7.90-7.87 (m, 2H), 7.65 -7.51 (m, 11H), 7.41-7.30 (m, 3H), 6.75-6.60 (m, 6H), 1.72 (s, 6H)

Manufacturing example

Hereinafter, the preparation or synthesis examples of the compounds containing quinoline derivatives belonging to the formula (4). However, since a large number of compounds including the quinoline derivatives belonging to the general formula (4), one or two of the compounds containing the quinoline derivatives belonging to the general formula (4) will be exemplarily described. Those skilled in the art, that is, those skilled in the art can prepare a compound comprising a quinoline derivative belonging to the present invention not illustrated through the preparation examples described below.

Of organic light emitting device  Manufacturing evaluation

Using the compound according to an embodiment of the present invention obtained through synthesis as a light emitting host material or a hole transport layer, respectively, an organic light emitting diode was manufactured according to a conventional method.

First, a 4,4 ', 4 "-tris (N- (2-naphthyl) -N-phenylamino) -triphenylamine (hereinafter abbreviated as 2T-NATA) film is formed on the ITO layer (anode) formed on the glass substrate. Evaporation was carried out to form a hole injection layer on the ITO layer with a thickness of 10 nm.

Subsequently, the hole transporting layer is formed by vacuum depositing the compound according to the embodiment of the present invention as a major transport compound to a thickness of 30 nm.

After forming the hole transport layer, when using the compound according to the embodiment of the present invention as a hole transport layer, a light emitting layer having a thickness of 45nm on the hole transport layer is used. At this time, the light emitting layer is doped with BD-052X (Idemitus) at 7%. BD-052X is a blue fluorescent dopant, and the light emitting host material may be 9,10-di (naphthalene-2-anthracene (AND)).

(1,1′-bisphenyl) -4-oleito) bis (2-methyl-8-quinolinoleito) aluminum (hereinafter abbreviated as BAlq) was vacuum deposited to a thickness of 10 nm to form a hole blocking layer. Subsequently, tris (8-quinolinol) aluminum (hereinafter abbreviated as Alq ₃ ) is deposited to a thickness of 40 nm to form an electron injection layer.

Subsequently, LiF, an alkali metal halide, is deposited to a thickness of 0.2 nm, and then Al is deposited to a thickness of 150 nm, whereby Al / LiF is used as a cathode, thereby manufacturing an organic light emitting device.

Comparative Experimental Example

When the compounds according to the embodiment of the present invention were measured by the hole transport layer, the same structure as that of the experimental example 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 An organic EL device was fabricated.

Hole transport
material Voltage
(V) Current density
(mA / cm ² ) Luminous efficiency
(cd / A) Chromaticity coordinates
(x, y) Example 1 Compound A-11 6.1 12.85 9.2 (0.15, 0.13) Example 2 Compound a -24 6.1 12.87 9.1 (0.15, 0.13) Example 3 Compound B-11 6.0 12.81 9.3 (0.15, 0.14) Example 4 Compound b-47 5.7 12.70 9.9 (0.15, 0.14) Example 5 Compound b-52 6.0 12.79 9.5 (0.15, 0.14) Comparative Example 1 NPB 7.2 13.35 7.5 (0.15, 0.15)

As can be seen from the results of Table 1, the organic electroluminescent device using the compound according to the embodiment of the present invention is used as a hole transport material of the organic electroluminescent device because it provides blue light emission with improved color purity and high efficiency. High luminous efficiency and lifetime can be significantly improved.

Compounds according to an embodiment of the present invention can obtain the same effect even when 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. have.

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)

A compound represented by the following formula.

In the above formula, A may be the same or different from each other, and each independently a halogen group, cyano group, nitrile group, C ₁ ~ C ₆₀ Alkyl group, C ₁ ~ C ₆₀ Alkoxy group, C ₁ ~ C ₆₀ Alkyl Amine group, C ₁ ~ C ₆₀ arylamine group, C ₁ ~ C ₆₀ alkylthiophene group, C ₆ ~ C ₆₀ arylthiophene group, C ₂ ~ C ₆₀ alkenyl group, C ₂ ~ C ₆₀ alkynyl, C cycloalkyl group of _{3 ~ C 60, C 6 ~} C ₆₀ aryl group, of a C ₆ ~ C ₆₀ substituted by deuterium aryl group, an arylalkenyl group of C ₈ ~ C _60, a substituted or unsubstituted silane At least one substituted or unsubstituted C ₆ -C ₆₀ selected from the group consisting of a group, a substituted or unsubstituted boron group, a substituted or unsubstituted germanium group, a substituted or unsubstituted C ₅ -C ₆₀ heterocyclic group Aryl group or C ₅ ~ C ₆₀ heterocyclic group; An amino group substituted with one or more substituents selected from the group consisting of a substituted or unsubstituted aryl group, a substituted or unsubstituted arylalkyl group, and a substituted or unsubstituted arylalkenyl group; A condensed ring group of an aromatic ring of C ₆ to C ₆₀ and an aliphatic ring of C ₄ to C ₆₀ , each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, a substituted or unsubstituted aliphatic C ₆ ~ C ₆₀ Any group selected from a hydrocarbon group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, wherein X ₁ to X ₄ are one of carbon or nitrogen, and Y is the same as A, and n is an integer of 1 to 3, Ar ₁ and Ar ₂ may be the same or different from each other, and each independently a halogen group, an alkyl group, an alkenyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted arylalkyl group, At least one substituent selected from the group consisting of a substituted or unsubstituted arylalkenyl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted fluorenyl group, a nitrile group, an acetylene group Substitution Unsubstituted (C ₁ ~ C ₆₀ alkyl group, C ₁ ~ C ₆₀ alkoxy group, C ₁ ~ C ₆₀ of the aryl group, a carbazolyl group, a fluorenyl group) and a halogen group, an alkyl group, an alkenyl group, an alkoxy group, Substituted with one or more substituents selected from the group consisting of a substituted or unsubstituted arylamine group, a substituted or unsubstituted aryl group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted fluorenyl group, a nitrile group, an acetylene group Or a heterocyclic group which is unsubstituted and contains O, N, S as hetero atoms; Hydroxyl group; Carboxyl groups; Nitrile group, nitro group, halogen group, -N (R ') (R "); -CO-N (R ') (R "); Is selected from the group consisting of -COOR ', wherein R' and R "are the same as A, and L is a substituted or unsubstituted arylene group having 6 to 60 carbon atoms, a substituted or unsubstituted florenylene group, and a nuclear atom. A hetero arylene group having 5 to 60 groups, a divalent or trivalent substituted or unsubstituted aliphatic hydrocarbon group and a divalent linking group, wherein m is an integer of 0 to 3. The method of claim 1,
Compound represented by the formula shown below.

In the above formula,
X ₁ or X ₄ is nitrogen, and R ₁ , R ₂ and R ₃ of the above formula are the same as A of the above formula. The method of claim 1,
Compound represented by the formula shown below.

In the above formula,
X ₂ or X ₃ is nitrogen, and R ₁ , R _2, and R ₃ of Formula ₂ are the same as A of Formula. The compound according to any one of claims 1 to 3, wherein the compound is

Compounds, characterized in that one selected from the group consisting of. An organic electric device comprising at least one organic material layer comprising a compound of any one of claims 1 to 3. The method of claim 5,
The organic electroluminescent device according to claim 1, wherein the organic layer is formed by a solution process. The method of claim 5,
The organic electric device is
An organic electroluminescent device comprising a first electrode, one or more organic material layers and a second electrode sequentially stacked. The method of claim 7, wherein
The compound is an organic electronic device, characterized in that used as one of a hole injection material, a hole transport material, an electron injection material, an electron transport material, a light emitting material and a passivation material. The method of claim 7, wherein
The compound is an organic electroluminescent device, characterized in that used as a hole transport material. An electronic device comprising the organic electric device of claim 5;
And a control unit for driving the electronic device. The method of claim 10,
The organic electroluminescent device includes an organic light emitting diode (OLED), an organic solar cell, an organic photoconductor (OPC) drum, an organic transistor (organic TFT), a photodiode, an organic laser, and a laser diode. Terminal) characterized in that one of.

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