KR101408514B1 - New diamine derivatives, preparation method thereof and organic electronic device using the same - Google Patents

Abstract

The present invention relates to a novel diamine derivative, a process for producing the same, and an organic electronic device using the same. The diamine derivative according to the present invention can serve as a hole injecting, hole transporting, electron injecting, electron transporting, or luminescent material in an organic electronic device including an organic light emitting device, It can act as a dopant, in particular a blue dopant. The organic electronic device according to the present invention exhibits excellent characteristics in terms of efficiency, driving voltage, lifetime, and stability.

Description

TECHNICAL FIELD [0001] The present invention relates to a novel diamine derivative, a method for producing the same, and an organic electronic device using the same. BACKGROUND ART < RTI ID = 0.0 >

The present invention relates to a novel diamine derivative, a process for producing the same, and an organic electronic device using the same.

An organic electronic device means a device requiring charge exchange between an electrode and an organic substance by using holes and electrons. The organic electronic device can be roughly classified into two types according to the operating principle as described below. First, an exciton is formed in an organic material layer by a photon introduced into an element from an external light source. The exciton is separated into an electron and a hole, and the electrons and holes are transferred to different electrodes to be used as a current source Type electronic device. The second type is an electronic device that injects holes and / or electrons into an organic semiconductor that interfaces with an electrode by applying a voltage or current to two or more electrodes, and operates by injected electrons and holes.

Examples of the organic electronic device include an organic light emitting device, an organic solar cell, an organic photoconductor (OPC), an organic transistor, and the like. These devices may be used as a hole injecting or transporting material, an electron injecting or transporting material, need.

Hereinafter, the organic light emitting device will be described in detail. However, in the organic electronic devices, hole injecting or transporting materials, electron injecting or transporting materials, or light emitting materials act on a similar principle.

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 light emitting device using an organic light emitting phenomenon generally has a structure including an anode, a cathode, and an organic material layer therebetween. Here, in order to enhance the efficiency and stability of the organic light emitting device, the organic material layer may have a multi-layered structure composed of different materials and may include a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer. When a voltage is applied between the two electrodes in the structure of such an organic light emitting device, holes are injected in the anode, electrons are injected into the organic layer in the cathode, excitons are formed when injected holes and electrons meet, When it falls back to the ground state, the light comes out. Such an organic light emitting device is known to have characteristics such as self-emission, high luminance, high efficiency, low driving voltage, wide viewing angle, high contrast, and high speed response.

A material used as an organic material layer in an organic light emitting device can be classified into a light emitting material and a charge transporting material such as a hole injecting material, a hole transporting material, an electron transporting material, and an electron injecting material depending on functions. The light emitting material can be classified into a polymer type and a low molecular type depending on the molecular weight and can be classified into a phosphorescent material derived from a singlet excited state of electrons and a phosphorescent material derived from an electron triplet excited state have. Further, the light emitting material can be classified into blue, green, and red light emitting materials and yellow and orange light emitting materials required to realize better natural color depending on the luminescent color.

On the other hand, when only one material is used as a light emitting material, there arises a problem that the maximum light emission wavelength shifts to a long wavelength due to intermolecular interaction, the color purity decreases, or the efficiency of the device decreases due to the light emission attenuating effect. A host / dopant system may be used as the light emitting material in order to increase the light emitting efficiency through the light emitting layer. When the dopant having a smaller energy band gap than the host forming the light emitting layer is mixed with a small amount of the light emitting layer, the excitons generated in the light emitting layer are transported to the dopant to emit light with high efficiency. At this time, since the wavelength of the host is shifted to the wavelength band of the dopant, the desired wavelength light can be obtained depending on the type of the dopant used.

In order for the organic luminescent device to sufficiently exhibit the above-described excellent characteristics, a material constituting the organic material layer in the device, such as a hole injecting material, a hole transporting material, a luminescent material, an electron transporting material and an electron injecting material is supported by a stable and efficient material However, development of a stable and efficient organic material layer material for an organic light emitting device has not yet been sufficiently developed. Therefore, development of new materials is continuously required, and the necessity of developing such materials is the same in other organic electronic devices described above.

The present inventors have uncovered a novel diamine derivative. In addition, when the diamine derivative can be used as a hole injection, a hole transport, an electron injection, an electron transport or a luminescent material in an organic electronic device and the organic material layer of the organic electronic device is formed, the efficiency of the organic electronic device, Rise and stability are superior.

The present invention provides a novel diamine derivative, a method for producing the same, and an organic electronic device using the same.

The present invention provides a diamine derivative represented by the following general formula (1).

In Formula 1,

R 1, R 2, R 3, R 4, R 5, R 6, R 7 and R 8 are the same or different from each other and each independently represents a hydrogen atom, a deuterium atom, a substituted or unsubstituted C ₁ to C ₂₀ alkyl group, A substituted or unsubstituted C ₃ to C ₂₅ cycloalkyl group, a substituted or unsubstituted C ₁ to C ₂₀ alkoxy group, a substituted or unsubstituted C ₅ to C ₂₅ substituted or unsubstituted C ₆ to C ₃₀ aryl group, An aryloxy group, a substituted or unsubstituted C ₆ to C ₂₀ arylthiophene group, a substituted or unsubstituted C ₅ to C ₂₀ heterocyclic group, a substituted or unsubstituted C ₈ to C ₂₀ arylalkenyl group, A substituted or unsubstituted C ₅ -C ₂₀ arylamine group, -OR, -SR, -SeR, -TeR, -BRR ', -AlRR', -SiRR'R ", -GeRR'R" R ", or cyano group,

Wherein R, R 'and R "are the same or different, and are each independently selected from hydrogen, and C ₁ ~ C ₂₀ alkyl group, C ₃ ~ C ₂₀ cycloalkyl group, C ₆ ~ C ₂₀ aryl group or a C ₅ ~ C to each other _Lt ; RTI ID = 0.0 >

Ar 1, Ar 2, Ar 3 and Ar 4 are the same or different and each independently represents a substituted or unsubstituted C ₁ to C ₂₀ alkyl group, a substituted or unsubstituted C ₆ to C ₃₀ aryl group, ₅ ~ C and a heterocyclic group of C _20, which may form a cyclic group which are adjacent to each other.

The present invention also provides a process for preparing a diamine derivative represented by the above formula (1), comprising the step of reacting a dibromoaryl compound with an arylamine compound in the presence of a palladium catalyst.

The present invention also provides an organic electronic device comprising a first electrode, a second electrode, and at least one organic material layer disposed between the first electrode and the second electrode, wherein at least one of the organic material layers is represented by Formula 1 And a diamine derivative which is a diamine derivative.

The diamine derivative according to the present invention can serve as a hole injecting, hole transporting, electron injecting, electron transporting, or luminescent material in an organic electronic device including an organic light emitting device, It can act as a dopant, in particular a blue dopant. The organic electronic device according to the present invention exhibits excellent characteristics in terms of efficiency, driving voltage, lifetime, and stability.

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

The diamine derivative according to the present invention is characterized by being represented by the above formula (1).

In the diamine derivative according to the present invention, the substituents of the above formula (1) will be described in more detail as follows.

Examples of the C ₁ -C ₂₀ alkyl group include, but are not limited to, methyl, ethyl, tertiary-butyl and the like.

Examples of the C ₆ -C ₃₀ aryl group include, but are not limited to, a phenyl group, a biphenyl group, a naphthyl group, a phenanthrenyl group, and a fluorenyl group.

Examples of the C ₃ -C ₂₅ cycloalkyl group include, but are not limited to, a cyclopentyl group and a cyclohexyl group.

Examples of the C ₅ -C ₂₀ heteroaryl group include a carbazolyl group, a pyridyl group, a quinolinyl group, an isoquinoline group, a thiophenyl group, a furanyl group, an imidazole group, an oxazolyl group, a thiazolyl group and a triazine group , But is not limited thereto.

Examples of the C ₁ -C ₂₀ alkoxy group include, but are not limited to, a methoxy group, an ethoxy group, a phenyloxy group, and a cyclohexyloxy group.

Examples of the C ₅ -C ₂₀ arylamine group include a deuterium atom; An alkyl group having ₁ to ₆ carbon atoms; Cyano; A fluorine group; A C ₆ to C ₂₀ aryl group; A cycloalkyl group of C ₅ ~ C _12; Or an arylamine group substituted or unsubstituted with a C ₃ to C ₃₀ heteroaryl group containing N, O or S, but is not limited thereto.

In the present invention, 'substituted or unsubstituted' refers to a group selected from the group consisting of deuterium, a halogen group, a C ₁ to C ₂₀ alkyl group, a C ₂ to C ₂₀ alkenyl group, a C ₂ to C ₂₀ alkynyl group, a C ₃ to C ₂₀ cyclo At least one selected from the group consisting of an alkyl group, a C ₃ to C ₂₀ heterocycloalkyl group, a C ₆ to C ₅₀ aryl group, a C ₅ to C ₅₀ heteroaryl group, an arylamine group, a cyano group, a silyl group and a germanium group Substituted or unsubstituted.

Specific examples of the diamine derivatives represented by the above formula (1) include, but are not limited to, the following compounds.

The present invention also provides a process for preparing a diamine derivative represented by the above formula (1).

The diamine derivative according to the present invention can be produced by reacting a dibromoaryl compound with an arylamine compound under a palladium catalyst.

The diamine derivative represented by the formula (1) according to the present invention can control the energy bandgap finely by introducing the appropriate substituent as described above, while improving the property at the interface between the organic materials, It can be used in various ways.

On the other hand, the diamine derivative represented by the above formula (1) has a high glass transition temperature (Tg) and is excellent in thermal stability. This increase in thermal stability is an important factor in providing drive stability to the device.

Further, the organic electronic device according to the present invention is an organic electronic device comprising a first electrode, a second electrode, and at least one organic layer disposed between the first electrode and the second electrode, wherein at least one of the organic layers And a diamine derivative represented by the above formula (1).

The organic electronic device of the present invention can be produced by a conventional method and materials for producing an organic electronic device, except that one or more organic compound layers are formed using the above-described compounds.

Hereinafter, the organic light emitting device will be described.

The compounds of the present invention can act as hole-injecting, hole-transporting, electron-injecting, electron-transporting or luminescent materials in organic light emitting devices, Together with a luminescent host, or a suitable luminescent host, can serve as a luminescent dopant, in particular a blue dopant.

In one embodiment of the present invention, the organic light emitting device may have a structure including a first electrode, a second electrode, and an organic material layer interposed therebetween, and the above- The organic light emitting device can be manufactured using a conventional method and materials for manufacturing an organic light emitting device,

The structure of the organic light emitting device according to the present invention is illustrated in FIG.

For example, the organic light emitting device according to the present invention may be formed by using a PVD (physical vapor deposition) method such as sputtering or e-beam evaporation to form a metal oxide or a metal oxide having conductivity on the substrate, A hole transporting layer, a light emitting layer, and an electron transporting layer, and then depositing a material usable as a cathode thereon. In addition to such a method, an organic light emitting device may be manufactured by sequentially depositing a cathode material, an organic material layer, and a cathode material on a substrate.

The organic material layer may have a multi-layer structure including a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer, but is not limited thereto and may have a single layer structure. The organic material layer may be formed using a variety of polymer materials by a method such as a solvent process such as spin coating, dip coating, doctor blading, screen printing, inkjet printing, Layer.

As the anode material, a material having a large work function is preferably used so that hole injection can be smoothly conducted into the organic material layer. Specific examples of the cathode material that can be used in the present invention include metals such as vanadium, chromium, copper, zinc, and gold, or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); ZnO: Al or SnO _2: a combination of a metal and an oxide such as Sb; Conductive polymers such as poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (PEDT), polypyrrole and polyaniline.

The negative electrode material is preferably a material having a low work function to facilitate electron injection into the organic material layer. Specific examples of the negative electrode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin and lead or alloys thereof; Layer structure materials such as LiF / Al or LiO ₂ / Al, but are not limited thereto.

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

As the hole transporting material, a material capable of transporting holes from the anode or the hole injecting layer to the light emitting layer and having high mobility to holes is suitable. Specific examples include arylamine-based organic materials, conductive polymers, and block copolymers having a conjugated portion and a non-conjugated portion together, but the present invention is not limited thereto.

The light emitting material is preferably a material capable of emitting light in the visible light region by transporting and receiving holes and electrons from the hole transporting layer and the electron transporting layer, respectively, and having good quantum efficiency for fluorescence or phosphorescence. Specific examples include 8-hydroxy-quinoline aluminum complex (Alq ₃ ); Carbazole-based compounds; Dimerized styryl compounds; BAlq; 10-hydroxybenzoquinoline-metal compounds; Compounds of the benzoxazole, benzothiazole and benzimidazole series; Polymers of poly (p-phenylenevinylene) (PPV) series; Spiro compounds; Polyfluorene, rubrene, and the like, but are not limited thereto.

As the electron transporting material, a material capable of transferring electrons from the cathode well into the light emitting layer, which is suitable for electrons, is suitable. Specific examples include an Al complex of 8-hydroxyquinoline; Complexes containing Alq ₃ ; Organic radical compounds; Hydroxyflavone-metal complexes, and the like, but are not limited thereto.

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

The compound according to the present invention may act on a principle similar to that applied to organic light emitting devices in organic electronic devices including organic solar cells, organic photoconductors, organic transistors and the like.

Hereinafter, preferred embodiments of the present invention will be described in order to facilitate understanding of the present invention. However, the following examples are provided only for the purpose of easier understanding of the present invention, and the present invention is not limited thereto.

The compound of formula (I) according to the present invention can be prepared by a multistage chemical reaction. The preparation of these compounds is described by the following examples. As shown in the examples, some intermediate compounds are prepared first, and the compounds of formula (1) are prepared from the intermediate compounds. Illustrative intermediate compounds are the following compounds A-M. In these compounds, "Br" may be substituted with any other reactive atom or functional group.

< Manufacturing example  1> Preparation of Compound A

Dibromobenzene (20 g, 84.78 mmol) was dissolved in dry tetrahydrofuran (THF, 200 mL) at room temperature under a nitrogen atmosphere. The solution was cooled to -78 &lt; 0 &gt; C. n-Butyl lithium (34 mL, 2.5M pentane solution) was added slowly to the solution at -78 &lt; 0 &gt; C and the mixture was slowly raised to 0 &lt; 0 &gt; C for about 1 hour. Thereto was added trimethylgerumanium bromide (18 ml, 101.74 mmol) and the mixture was allowed to stand at room temperature for 1 hour. After confirming that the reaction was completed, the mixture was extracted with ethyl acetate, dried over magnesium sulfate, and fractionally distilled under reduced pressure to obtain Compound A (20 g, 90%).

MS (M &lt; + &gt;) 273

< Manufacturing example  2> Preparation of compound B

Compound in a nitrogen atmosphere A (18g, 65.45mmol), aniline (6.6ml, 72mmol), Pd ( dba) 2 (0.125g, 0.13mmol), P (t-Bu) 3 (0.04g, 0.2mmol) and sodium t -Butoxide (1.80 g, 18.7 mmol) were dissolved in toluene (200 mL) and refluxed for about 3 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and the reaction mixture was poured into a mixture of THF and H ₂ O. [ The organic layer was separated, dried over magnesium sulfate and concentrated. After purification by column chromatography, Compound B (8.4 g, 45%) was obtained.

MS [M] = 286

< Manufacturing example  3> Preparation of Compound C

In the same manner as in Production Example 2, except that 5,6,7,8-tetrahydro-1-naphthylamine (10.6 g, 72 mmol) was used instead of aniline (6.6 ml, 72 mmol) Compound C (17 g, 40%) was obtained.

MS [M] = 340 &lt; RTI ID =

< Manufacturing example  4> Preparation of compound D

Dibromobenzene (20 g, 84.78 mmol) was dissolved in dry tetrahydrofuran (THF, 200 mL) at room temperature under a nitrogen atmosphere. The solution was cooled to -78 &lt; 0 &gt; C. n-Butyl lithium (34 mL, 2.5M pentane solution) was added slowly to the solution at -78 &lt; 0 &gt; C and the mixture was slowly raised to 0 &lt; 0 &gt; C for about 1 hour. To this was added chloro trimethylsilane 13 ml, 101.74 mmol) was added and the mixture was allowed to stand at room temperature for 1 hour. After confirming the completion of the reaction, the mixture was extracted with ethyl acetate, dried over magnesium sulfate, and then fractionally distilled under reduced pressure to obtain compound D (18 g, 93%).

MS (M &lt; + &gt;) = 229

< Manufacturing example  5> Preparation of Compound E

Under a nitrogen atmosphere, compound D (15g, 65.45mmol), aniline (6.6ml, 72mmol), Pd ( dba) 2 (0.125g, 0.13mmol), P (t-Bu) 3 (0.04g, 0.2mmol) and sodium t-Butoxide (1.80 g, 18.7 mmol) was added to toluene (200 mL) and refluxed for about 3 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and the reaction mixture was poured into a mixture of THF and H ₂ O. [ The organic layer was separated and concentrated layer was dried with MgSO _4. After purification by column chromatography, Compound E (3.9 g, 42%) was obtained.

MS [M] = 241

< Manufacturing example  6> Preparation of Compound F

Under nitrogen, bromophenyl (10.3g, 65.45mmol), aniline (6.6ml, 72mmol), Pd ( dba) 2 (0.125g, 0.13mmol), P (t-Bu) 3 (0.04g, 0.2mmol) And sodium t-butoxide (1.80 g, 18.7 mmol) were placed in toluene (200 mL) and refluxed for about 3 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and the reaction mixture was poured into a mixture of THF and H ₂ O. [ The organic layer was separated and concentrated layer was dried with MgSO _4. After purification by column chromatography, Compound F (9.5 g, 86%) was obtained.

MS [M] = 169

< Manufacturing example  7> Preparation of compound G

(10.3 g, 65.45 mmol), aniline (6.6 ml, 72 mmol), Pd (dba) ₂ (0.125 g, 0.13 mmol) and P (t-Bu) ₃ , 0.2 mmol) and sodium t-butoxide (1.80 g, 18.7 mmol) were placed in toluene (200 mL) and refluxed for about 3 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and the reaction mixture was poured into a mixture of THF and H ₂ O. [ The organic layer was separated and concentrated layer was dried with MgSO _4. After purification by column chromatography, Compound G (9.5 g, 86%) was obtained.

MS [M] = 187

< Manufacturing example  8> Preparation of Compound H

Under nitrogen atmosphere, 9,10-dibromo-anthracene (2.86g, 8.5mmol), 4- chlorophenyl-boronic acid (2.9g, 18.7mmol), Pd ( PPh 3) 4 (0.29g, 0.26mmol) with 2M K ₂ CO ₃ aqueous solution (20 mL) and THF (80 mL), and the mixture was refluxed and stirred for about 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, and the organic layer was separated from the reaction mixture. The organic layer was dried over magnesium sulfate, distilled under reduced pressure, and purified by column chromatography to obtain 3.0 g (90%) of compound H.

MS [M + H] &lt; + &gt; = 398

< Manufacturing example  9> Preparation of Compound I

A nitrogen atmosphere, 9,10-dibromo-Cry sensor (3.28g, 8.5mmol), 4- chlorophenyl-boronic acid (2.9g, 18.7mmol), Pd ( PPh 3) 4 (0.29g, 0.26mmol) 2M Was added to a K ₂ CO ₃ aqueous solution (20 mL) and THF (80 mL), and the mixture was refluxed and stirred for about 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, and the organic layer was separated from the reaction mixture. The organic layer was dried over magnesium sulfate, distilled under reduced pressure, and purified by column chromatography to obtain Compound I (2.9 g, 75%).

MS [M + H] &lt; + &gt; = 448

< Manufacturing example  10> Preparation of Compound J

Under a nitrogen atmosphere bromobenzene -d ₅ (10.6g, 65.45mmol), aniline (6.6ml, 72mmol), Pd ( dba) 2 (0.125g, 0.13mmol), P (t-Bu) 3 (0.04g, 0.2 mmol) and sodium t-butoxide (1.80 g, 18.7 mmol) were placed in toluene (80 mL) and refluxed for about 3 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and the reaction mixture was poured into a mixture of THF and H ₂ O. [ The organic layer was separated, dried over magnesium sulfate and concentrated. After purification by column chromatography, Compound J (16 g, 85%) was obtained.

MS [M] = 174

< Manufacturing example  11> Preparation of compound K

Under a nitrogen atmosphere bromobenzene -d ₅ (10.6g, 65.45mmol), aniline -2,3,4,5,6-D5 (6.6ml, 72mmol) , Pd (dba) 2 (0.125g, 0.13mmol), P (t-Bu) ₃ (0.04 g, 0.2 mmol) and sodium t-butoxide (1.80 g, 18.7 mmol) were added to toluene (80 mL) and refluxed for about 3 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and the reaction mixture was poured into a mixture of THF and H ₂ O. [ The organic layer was separated, dried over magnesium sulfate and concentrated. After purification by column chromatography, Compound K (16 g, 85%) was obtained.

MS [M] = 179

< Manufacturing example  12> Preparation of Compound L

(15 g, 65.45 mmol), aniline-2,3,4,5,6-D5 (6.6 ml, 72 mmol), Pd (dba) ₂ (0.125 g, 0.13 mmol) P (t-Bu) ₃ (0.04 g, 0.2 mmol) and sodium t-butoxide (1.80 g, 18.7 mmol) were added to toluene (80 mL) and refluxed for about 3 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and the reaction mixture was poured into a mixture of THF and H ₂ O. [ The organic layer was separated, dried over magnesium sulfate and concentrated. After purification by column chromatography, Compound L (16 g, 85%) was obtained.

MS [M] = 246

< Manufacturing example  13> Preparation of Compound (M)

Compound A (18 g, 65.45 mmol), aniline-2,3,4,5,6-D5 (6.6 ml, 72 mmol), Pd (dba) ₂ (0.125 g, 0.13 mmol) P (t-Bu) ₃ (0.04 g, 0.2 mmol) and sodium t-butoxide (1.80 g, 18.7 mmol) were added to toluene (80 mL) and refluxed for about 3 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and the reaction mixture was poured into a mixture of THF and H ₂ O. [ The organic layer was separated, dried over magnesium sulfate and concentrated. After purification by column chromatography, Compound M (16 g, 85%) was obtained.

MS [M] = 291

< Manufacturing example  14> Preparation of Compound N

(20 g, 170 mmol), Pd (dba) ₂ (0.125 g, 0.13 mmol), P (t-Bu) ₃ (0.04 g, 0.2 mmol) and sodium t-butoxide (1.80 g, 18.7 mmol) were placed in toluene (80 mL) and refluxed for about 3 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and the reaction mixture was poured into a mixture of THF and H ₂ O. [ The organic layer was separated, dried over magnesium sulfate and concentrated. After purification by column chromatography, Compound N (13 g, 50%) was obtained.

MS [M] = 199

< Manufacturing example  15> Preparation of compound O

1,2,3,6,7,8-hexahydropyrene (7.0 g, 33.6 mmol) was dissolved in acetic acid (90 mL) under nitrogen atmosphere, Br2 (11.28 g, 70.5 mmol) was slowly added dropwise and the mixture was stirred at room temperature for 12 hours Allows stirring. After the reaction was completed, the resulting precipitate was filtered, the precipitate was dissolved in chloroform, washed with water, dried over MgSO ₄ , and concentrated. After purification by THF / EtOH, Compound O (7.6 g, 62%) was obtained.

MS [M] = 366

< Manufacturing example  16> Compound P  Produce

(2.32 g, 6.9 mmol) synthesized in Preparation Example 15 was dissolved in anhydrous toluene (60 mL) and tetrachloro-0-benzoquinone (5.9 g, 24.2 mmol) was added thereto under nitrogen atmosphere. To do. After completion of the reaction, the reaction mixture was cooled to room temperature and the reaction mixture was poured into a mixture of THF and H ₂ O. [ The organic layer was separated, dried over magnesium sulfate and concentrated. After purification by column chromatography, Compound P (0.75 g, 30%) was obtained.

MS [M] = 360

< Example  1> Preparation of Compound 2

(3.0 g, 8.5 mmol), compound F (3.45 g, 20.4 mmol), Pd (dba) ₂ (0.097 g, 0.17 mmol) and P (t-Bu) ₃ (0.05 g, 0.255 mmol) and sodium t-butoxide (2.45 g, 25.5 mmol) were placed in toluene (100 mL) and refluxed for about 2 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and the reaction mixture was poured into a mixture of THF and H ₂ O. [ The organic layer was separated and concentrated layer was dried with MgSO _4. After purification by column chromatography, Compound 2 (2.82 g, 62%) was obtained.

MS [M] = 536

< Example  2> Preparation of Compound 13

(3.0 g, 8.5 mmol), compound J (3.55 g, 20.4 mmol), Pd (dba) ₂ (0.097 g, 0.17 mmol) and P (t-Bu) ₃ (0.05 g, 0.255 mmol) and sodium t-butoxide (2.45 g, 25.5 mmol) were placed in toluene (100 mL) and refluxed for about 2 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and the reaction mixture was poured into a mixture of THF and H ₂ O. [ The organic layer was separated and concentrated layer was dried with MgSO _4. After purification by column chromatography, Compound 13 (2.78 g, 60%) was obtained.

MS [M] = 546

< Example  3> Preparation of Compound 15

Under a nitrogen atmosphere 4,9- dibromo pyrene (3.0g, 8.5mmol), compound E (4.91g, 20.4mmol), Pd (dba) 2 (0.097g, 0.17mmol), P (t-Bu) 3 (0.05 g, 0.255 mmol) and sodium t-butoxide (2.45 g, 25.5 mmol) were placed in toluene (100 mL) and refluxed for about 2 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and the reaction mixture was poured into a mixture of THF and H ₂ O. [ The organic layer was separated and concentrated layer was dried with MgSO _4. After purification by column chromatography, Compound 15 (3.76 g, 65%) was obtained.

MS [M] = 680

< Example  4> Preparation of Compound 16

(3.0 g, 8.5 mmol), compound B (5.83 g, 20.4 mmol), Pd (dba) ₂ (0.097 g, 0.17 mmol) and P (t-Bu) ₃ (0.05 g, 0.255 mmol) and sodium t-butoxide (2.45 g, 25.5 mmol) were placed in toluene (100 mL) and refluxed for about 2 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and the reaction mixture was poured into a mixture of THF and H ₂ O. [ The organic layer was separated and concentrated layer was dried with MgSO _4. After purification by column chromatography, Compound 16 (4.06 g, 62%) was obtained.

MS [M] = 770

< Example  5> Preparation of Compound 18

(3.0 g, 8.5 mmol), Compound I (6.39 g, 20.4 mmol), Pd (dba) ₂ (0.097 g, 0.17 mmol), P (t-Bu) ₃ (0.05 g, 0.255 mmol) and sodium t-butoxide (2.45 g, 25.5 mmol) were placed in toluene (100 mL) and refluxed for about 2 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and the reaction mixture was poured into a mixture of THF and H ₂ O. [ The organic layer was separated and concentrated layer was dried with MgSO _4. After purification by column chromatography, Compound 18 (4.34 g, 62%) was obtained.

MS [M] = 824

< Example  6> Preparation of Compound 19

Under a nitrogen atmosphere 4,9- dibromo pyrene (3.0g, 8.5mmol), Compound H (5.43g, 20.4mmol), Pd (dba) 2 (0.097g, 0.17mmol), P (t-Bu) 3 (0.05 g, 0.255 mmol) and sodium t-butoxide (2.45 g, 25.5 mmol) were placed in toluene (100 mL) and refluxed for about 2 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and the reaction mixture was poured into a mixture of THF and H ₂ O. [ The organic layer was separated and concentrated layer was dried with MgSO _4. After purification by column chromatography, Compound 19 (3.72 g, 60%) was obtained.

MS [M] = 730

< Example  7> Preparation of Compound 37

(3.0 g, 8.5 mmol), compound N (4.06 g, 20.4 mmol), Pd (dba) ₂ (0.097 g, 0.17 mmol) and P (t-Bu) ₃ (0.05 g, 0.255 mmol) and sodium t-butoxide (2.45 g, 25.5 mmol) were placed in toluene (100 mL) and refluxed for about 2 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and the reaction mixture was poured into a mixture of THF and H ₂ O. [ The organic layer was separated and concentrated layer was dried with MgSO _4. After purification by column chromatography, Compound 37 (3.04 g, 60%) was obtained.

MS [M] = 596

< Example  8> Preparation of Compound 38

(3.0 g, 8.5 mmol), C (6.94 g, 20.4 mmol), Pd (dba) ₂ (0.097 g, 0.17 mmol) and P (t-Bu) ₃ (0.05 g, 0.255 mmol) and sodium t-butoxide (2.45 g, 25.5 mmol) were placed in toluene (100 mL) and refluxed for about 2 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and the reaction mixture was poured into a mixture of THF and H ₂ O. [ The organic layer was separated and concentrated layer was dried with MgSO _4. After purification by column chromatography, Compound 38 (4.62 g, 62%) was obtained.

MS [M] = 878

< Example  9> Preparation of Compound 39

(3.0 g, 8.5 mmol), compound C (3.65 g, 20.4 mmol), Pd (dba) ₂ (0.097 g, 0.17 mmol) and P (t-Bu) ₃ (0.05 g, 0.255 mmol) and sodium t-butoxide (2.45 g, 25.5 mmol) were placed in toluene (100 mL) and refluxed for about 2 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and the reaction mixture was poured into a mixture of THF and H ₂ O. [ The organic layer was separated and concentrated layer was dried with MgSO _4. After purification by column chromatography, Compound 39 (3.07 g, 65%) was obtained.

MS [M] = 556

< Example  10> Preparation of Compound 40

(3.0 g, 8.5 mmol), compound L (5.02 g, 20.4 mmol), Pd (dba) ₂ (0.097 g, 0.17 mmol) and P (t-Bu) ₃ (0.05 g, 0.255 mmol) and sodium t-butoxide (2.45 g, 25.5 mmol) were placed in toluene (100 mL) and refluxed for about 2 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and the reaction mixture was poured into a mixture of THF and H ₂ O. [ The organic layer was separated and concentrated layer was dried with MgSO _4. After purification by column chromatography, Compound 40 (3.81 g, 65%) was obtained.

MS [M] = 690

< Experimental Example  1>

A glass substrate (corning 7059 glass) coated with ITO (indium tin oxide) at a thickness of 1,000 Å was immersed in distilled water containing a dispersing agent and washed with ultrasonic waves. The dispersing agent was a product of Fischer Co., and distilled water was supplied by Millipore Co. Distilled water, which was secondly filtered with a filter of the product, was used. After the ITO was washed for 30 minutes, ultrasonic washing was repeated 10 times with distilled water twice. After the distilled water was washed, the substrate was ultrasonically cleaned in the order of isopropyl alcohol, acetone, and methanol solvent, dried, and transported by a plasma cleaner. The substrate was cleaned using oxygen plasma for 5 minutes, and then the substrate was transported by a vacuum evaporator.

Naphthylphenylamino-N- [4- (2-naphthylphenyl) aminophenyl] carbazole (800 Å) and 4,4'-bis [N- Naphthyl) -N-phenylamino] biphenyl (NPB) (300 ANGSTROM) were vapor deposited to form a hole injection layer and a hole transport layer. The compounds 2, 10, 13, 15, 16, 18, 19, 37, 38, 39 or 40 (2 wt%) was deposited (300 Å) with the following compound Q to form a light emitting layer and then 9,10- N-phenylbenzoimidazoyl) phenyl] anthracene (300 ANGSTROM) were thermally vacuum deposited to form an electron transporting layer.

Lithium fluoride (LiF) having a thickness of 12 Å and aluminum having a thickness of 2,000 Å were sequentially deposited on the electron transporting layer to form a cathode, thereby preparing an organic light emitting device.

The deposition rate of the organic material was maintained at 0.4 to 0.7 Å / sec, the lithium fluoride at the cathode was maintained at a deposition rate of 0.3 Å / sec, and the deposition rate of aluminum was maintained at 2 Å / sec. ^-7 to 5 x 10 &lt; ^-8 &gt; torr.

Comparative Example 1 was carried out in the same manner as in Experimental Example except for using the following compound D1 in place of the compound prepared in the above Example.

The voltage, current, luminance and color coordinate results for the organic EL device manufactured according to the above experiment are shown in Table 1 below.

1 is a view illustrating the structure of an organic light emitting device according to one embodiment of the present invention.

Claims (10)

A diamine derivative represented by the following formula (1): [Chemical Formula 1]

In Formula 1, Wherein R 1, R 2, R 3, R 4, R 5, R 6, R 7 and R 8 are the same or different from each other and each independently represents a hydrogen atom, a deuterium atom, a substituted or unsubstituted C ₁ to C ₂₀ alkyl group, C for ₆ ~ C ₃₀ aryl group, a substituted or unsubstituted C1-C ₃ ~ C ₂₅ cycloalkyl group, a substituted or unsubstituted C ₁ ~ C ₂₀ alkoxy group, a substituted or unsubstituted C ₅ ~ C ₂₅ aryl oxy group, an arylalkenyl group of substituted or unsubstituted C ₆ ~ C ₂₀ aryl thiophene group, a substituted or unsubstituted C ₅ ~ C ₂₀ heterocyclic group, a substituted or unsubstituted C ₈ ~ C ₂₀ of, substituted Or an unsubstituted C ₅ -C ₂₀ arylamine group, -OR, -SR, -SeR, -TeR, -BRR ', -AlRR', -SiRR'R ", -GeRR'R"Quot; or a cyano group, Wherein R, R 'and R "are the same or different, and are each independently selected from hydrogen, and C ₁ ~ C ₂₀ alkyl group, C ₃ ~ C ₂₀ cycloalkyl group, C ₆ ~ C ₂₀ aryl group or a C ₅ ~ C to each other _Lt ; RTI ID = 0.0 &gt; Ar 1, Ar 2, Ar 3 and Ar 4 are the same or different and each independently represents a substituted or unsubstituted C ₁ to C ₂₀ alkyl group, a substituted or unsubstituted C ₆ to C ₃₀ aryl group, ₅ ~ C and a heterocyclic group of C _20, which may form a cyclic group which are adjacent to each other, When Ar 1 to Ar 4 are aryl groups, Ar 1 and Ar 3 are C ₆ to C ₃₀ aryl groups substituted with a nitrile group (-CN), and Ar 2 and Ar 4 are substituted or unsubstituted C ₆ to C ₃₀ aryl groups. The diamine derivative according to claim 1, wherein the C ₁ -C ₂₀ alkyl group is selected from the group consisting of a methyl group, an ethyl group, and a tertiary-butyl group. The diamine derivative according to claim 1, wherein the C ₆ -C ₃₀ aryl group is selected from the group consisting of phenyl, biphenyl, naphthyl, phenanthrenyl and fluorenyl groups. The diamine derivative according to claim 1, wherein the C ₃ -C ₂₅ cycloalkyl group is a cyclopentyl group or a cyclohexyl group. The heteroaryl group as set forth in claim 1, wherein the C ₅ -C ₂₀ heteroaryl group includes a carbazolyl group, a pyridyl group, a quinolinyl group, an isoquinoline group, a thiophenyl group, a furanyl group, an imidazole group, an oxazolyl group, a thiazolyl group, &Lt; / RTI &gt; or a pharmaceutically acceptable salt thereof. The diamine derivative according to claim 1, wherein the diamine derivative is selected from the group consisting of the following compounds:

delete 1. An organic electronic device comprising a first electrode, a second electrode, and at least one organic compound layer disposed between the first electrode and the second electrode, wherein the organic compound layer is represented by Formula 1 of any one of Claims 1 to 6 Diamine derivative. &Lt; RTI ID = 0.0 &gt; 11. &lt; / RTI &gt; The organic electronic device according to claim 8, wherein the organic material layer comprises at least one layer selected from the group consisting of a hole injection layer, a hole transport layer, a light emitting layer, an electron injection layer and an electron transport layer. The organic electronic device according to claim 8, wherein the organic electronic device is selected from the group consisting of an organic light emitting device, an organic solar cell, an organic photoconductor (OPC), and an organic transistor.

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