KR101513988B1 - Aromatic amine derivative and organic electroluminescent device including the same - Google Patents

Abstract

[상기 화학식 1에서, 각 치환기들의 정의는 발명의 상세한 설명에서 정의한 바와 같다.]There is provided an aromatic amine derivative represented by the following formula (1).
[Chemical Formula 1]

[Wherein the definition of each substituent is as defined in the description of the invention].

Description

[0001] The present invention relates to an aromatic amine derivative and an organic electroluminescent device including the same,

The present invention relates to an aromatic amine derivative and an organic electroluminescent device including the same. More particularly, the present invention relates to an organic electroluminescent device having a high luminous efficiency and a novel aromatic amine derivative for the same.

In 1987, Tang and Van Slyke reported the characteristics of high efficiency using a multilayer thin film structure of an organic light emitting diode (OLED) [Tang, C. W., Van Slyke, S. A. Appl. Phys. Lett. 51, 91 (1987)], OLEDs have a high potential for use in LCD backlighting and lighting as well as excellent characteristics as a next generation display, and many studies have been conducted under the spotlight [Kido, J., Kimura, M., and Nagai, K., Science 267,1332 (1995)]. Especially, in order to increase the luminous efficiency, various approaches such as structural change and material development have been performed [Sun, S., Forrest, S. R., Appl. Phys. Lett. 91, 263503 (2007) / Ken-Tsung Wong, Org. Lett., 7, 2005, 5361-5364]. Especially, it is very important to study the device structure which shows the balanced emission of light by controlling the proper exciton distribution and energy transfer in the light emitting layer by optimizing the hole transporting layer.

Optimization of the hole transport layer means that the holes introduced through the hole injection layer are stably supplied to the light emitting layer. This is because the HOMO level of the hole transport layer is higher than the HOMO level of the light emitting layer to help smooth hole transport. Since the hole mobility of the hole transport layer at this time is equivalent to the charge balancing effect (the effect of achieving the high efficiency light efficiency only when the number of holes and electrons is similar to that of the light emitting layer), the performance of the device As a key factor. The materials of the hole transport layer generally include an electron donor component, which can be regarded as a p-type semiconductor, and mainly aromatic amines. In the past, aryl amine type NPB and flu- Fluorene-type TPD, and carbazole-type derivatives are also being studied variously as hole transport layer materials.

       NPB spiro-TPD spiro-TAD

The hole transporting material not only transports holes easily but also binds electrons to the light emitting region to increase the probability of forming excitons, and has a high hole mobility and a glass transition temperature (Tg) of 150 ° C or more. This is because it is preferable that the material used in the organic light emitting device has excellent thermal stability because joule heating occurs due to the movement of charges in the organic light emitting device. NPB, which is mainly used as a hole transport layer material, has a glass transition temperature of 100 Lt; 0 > C or less, there is a problem that it is difficult to use in an organic light emitting device requiring a high current. TPD was initially used as a hole transport material, but the glass transition temperature (Tg) was unstable at about 60 ° C., so that spiro-TAD, which is NPD or TPD fluorene dimer, HTL).

 In addition, it is preferable that the material used in the organic light emitting device is less deformed by moisture or oxygen. In addition, it is preferable that the density of holes and electrons is balanced in the light emitting layer of the organic light emitting device by having a suitable hole or electron mobility to maximize the formation of excitons. In addition, for the stability of the device, it is necessary to improve the interface with the electrode including the metal or the metal oxide. Therefore, research on such organic EL materials is continuously required.

The object of the present invention is to provide a novel aromatic amine derivative which is superior in luminous efficiency and durability to that of a conventional material and which contains an aromatic amine derivative in an organic material layer, And to provide a light emitting element.

According to one aspect of the present invention, there is provided an aromatic amine derivative represented by the following formula (1).

[Chemical Formula 1]

[In the formula 1,

R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are each independently selected from the group consisting of hydrogen, halogen, amino, nitro, cyano, hydroxy, substituted or unsubstituted C ₁ -C ₃₀ alkyl, hwandoen C ₃ -C ₃₀ cycloalkyl, substituted or unsubstituted C ₆ -C ₃₀ aryl, substituted or unsubstituted C ₆ -C ₃₀ aralkyl (aralkyl), substituted or unsubstituted C ₁ -C ₃₀ heteroalkyl , Substituted or unsubstituted C ₂ -C ₃₀ heterocycloalkyl, substituted or unsubstituted C ₅ -C ₃₀ heteroaryl, substituted or unsubstituted C ₅ -C ₃₀ heteroaralkyl, substituted or unsubstituted tr C ₁ -C ₃₀ alkyl silyl group, a substituted or unsubstituted di-C ₁ -C ₃₀ alkyl, C ₆ -C ₃₀ aryl silyl group, a substituted or unsubstituted C ₆ -C ₃₀ aryl tree silyl, substituted or unsubstituted adamantyl ring, - ^{_{(CH 2) j OR a,}} - (CH 2) j C (O) R a, - (CH 2) j C (O) OR a, - (CH 2) j OC (O) R a, - (CH _{2) j OM, - (CH} 2) j C (O) M, - (CH 2) j C (O) OM, - (CH 2) j OC (O) M, - (CH 2) j NR b R ^{_{c, - (CH 2) j}} c (O) NR b R c, - (CH 2) ^{_{j OC (O) NR b R}} c, - (CH 2) j NR d C (O) R b, - (CH 2) j NR d C (O) OR b, - (CH 2) j NR d C ( O) NR ^b R ^c , - (CH ₂ ) _j S (O) _m R ^e , or - (CH ₂ ) _j NR ^d S (O) _m M; Wherein j is an integer from 0 to 12 and m is an integer from 0 to 2; ^{R a, R b, R c} , R d and R ^e are each independently hydrogen, halogen, amino, nitro, cyano, hydroxy, substituted or unsubstituted C ₁ -C ₃₀ alkyl, substituted or unsubstituted C ₃ -C ₃₀ cycloalkyl, substituted or unsubstituted C ₆ -C ₃₀ aryl, substituted or unsubstituted C ₆ -C ₃₀ aralkyl (aralkyl), substituted or unsubstituted C ₁ -C ₃₀ heteroalkyl, substituted or Unsubstituted C ₂ -C ₃₀ heterocycloalkyl, substituted or unsubstituted C ₅ -C ₃₀ heteroaryl, substituted or unsubstituted C ₅ -C ₃₀ heteroaralkyl,

X ₁ , X ₂ and X ₃ are each independently selected from carbon (C) or nitrogen (N), at least one of which is nitrogen.

According to another aspect of the present invention, there is provided an organic electroluminescent device comprising the above-described aromatic amine derivative.

According to another aspect of the present invention, there is provided an organic electroluminescent device including a first electrode, a second electrode, and at least one organic film disposed between the electrodes, wherein the organic film includes the above-described aromatic amine derivative do.

An aromatic amine derivative according to an embodiment of the present invention may be included in an organic material layer of an organic electroluminescent device, preferably, a hole injecting layer or a hole transporting layer, thereby lowering the driving voltage of the device and improving the luminous efficiency. In particular, the thermal stability of the compound can improve the lifetime of the device.

1 is a schematic cross-sectional view of an organic electroluminescent device according to an embodiment of the present invention.
2 shows NMR analysis results of Compound 3-1 (DC1A-pd-C3).
3 shows NMR analysis results of the compound 3-2 (C1A-pd-DC3).
4 shows NMR analysis results of Compound 3-3 (C3A-pd-DC3).
5 shows NMR analysis results of compound 3-9 (DPAA-BP-pdBeC3).
6 is a PL (photoluminescence) spectrum at low temperature (77 K) measured using a Jasco FP-8500 instrument for the OLED compound of the present invention and conventional CBP.

As used herein, the term "alkyl" includes straight chain, branched or cyclic hydrocarbon radicals or combinations thereof, optionally including one or more double bonds, triple bonds or combinations thereof in the chain. E., "Alkyl" includes alkenyl or alkynyl.

The term "heteroalkyl ", by itself or in combination with other terms, unless otherwise indicated, includes one or more carbon atoms and one or more heteroatoms selected from the group consisting of O, N, P, Si and S Means a stable straight or branched or cyclic hydrocarbon radical or combination thereof, wherein the nitrogen, phosphorus and sulfur atoms may optionally be oxidized, and the nitrogen heteroatom may optionally be quaternized.

The terms "cycloalkyl" and "heterocycloalkyl ", by themselves or in conjunction with another term, refer to a cyclic version of" alkyl "and" heteroalkyl ", respectively,

The term "aryl" means a polyunsaturated, aromatic, hydrocarbon substituent which may be a single ring or multiple rings (one to three rings) fused or covalently bonded together unless otherwise specified. The term "heteroaryl" means an aryl group (or a ring) comprising one to four heteroatoms selected from N, O and S (in each case on a separate ring in the case of multiple rings) Optionally oxidized, and the nitrogen atom (s) are optionally quaternized. Heteroaryl groups can be attached to the remainder of the molecule through carbon or heteroatoms.

The aryl includes a single or fused ring system, suitably containing from 4 to 7, preferably 5 or 6, ring atoms in each ring. Also included are structures in which one or more aryls are attached through a chemical bond. Specific examples of the aryl include phenyl, naphthyl, biphenyl, anthryl, indenyl, fluorenyl, phenanthryl, triphenylenyl, pyreneyl, perylenyl, But is not limited thereto.

The heteroaryl includes 5- to 6-membered monocyclic heteroaryl and polycyclic heteroaryl fused with one or more benzene rings, and may be partially saturated. Also included are structures in which one or more heteroaryls are attached via a chemical bond. The heteroaryl groups include divalent aryl groups in which the heteroatoms in the ring are oxidized or trisubstituted to form, for example, an N-oxide or a quaternary salt. Specific examples of the heteroaryl include furyl, thiophenyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl, Monocyclic heteroaryl such as pyridyl, pyridyl, pyrazinyl, pyridazinyl and the like, benzofuranyl, benzothiophenyl, isobenzofuranyl, benzoimidazolyl, benzothiazolyl , Benzoisothiazolyl, benzoisoxazolyl, benzoxazolyl, isoindolyl, indolyl, indazolyl, benzothiadiazolyl, quinolyl, isoquinolyl, cinnolinyl, quinazolinyl, quinoxalinyl, (Such as pyridyl N-oxide, quinolyl N-oxide), quaternary salts thereof, and the like, but are not limited thereto. But is not limited thereto.

The term "aralkyl" refers to an alkyl group substituted with aryl and aryl, wherein the alkyl and aryl moieties are independently optionally substituted.

The term "heteroaralkyl" refers to an alkyl group substituted with aryl and heteroaryl, respectively, wherein the alkyl and heteroaryl moieties are independently optionally substituted.

"Substituted" in the expression " substituted or unsubstituted ", as used herein, means that at least one hydrogen atom in the hydrocarbon is each independently replaced with the same or different substituents. Useful substituents include, but are not limited to:

Such substituents include, but are not limited to, -F; -Cl; -Br; -CN; -NO ₂ -OH; A C ₁ -C ₂₀ alkyl group which is unsubstituted or substituted by -F, -Cl, -Br, -CN, -NO ₂ or -OH; A C ₁ -C ₂₀ alkoxy group unsubstituted or substituted with -F, -Cl, -Br, -CN, -NO ₂ or -OH; A C ₆ -C ₃₀ aryl group which is unsubstituted or substituted by a C ₁ -C ₂₀ alkyl group, a C ₁ -C ₂₀ alkoxy group, -F, -Cl, -Br, -CN, -NO ₂ or -OH; A C ₆ -C ₃₀ heteroaryl group which is unsubstituted or substituted by a C ₁ -C ₂₀ alkyl group, a C ₁ -C ₂₀ alkoxy group, -F, -Cl, -Br, -CN, -NO ₂ or -OH; C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ alkoxy group, -F, -Cl, -Br, -CN , -NO 2 , or substituted by -OH or unsubstituted C ₅ -C ₂₀ cycloalkyl group; C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ alkoxy group, -F, -Cl, -Br, -CN , -NO 2 , or substituted by -OH or unsubstituted C ₅ -C ₃₀ heterocycloalkyl group; And a group represented by -N (G ₁ ) (G ₂ ). Wherein G ₁ and G ₂ are each independently selected from the group consisting of hydrogen; A C ₁ -C ₁₀ alkyl group; Or a C ₆ -C ₃₀ aryl group substituted or unsubstituted with a C ₁ -C ₁₀ alkyl group.

Among the terms indicating the number of carbon atoms, for example, "C _n -C ₃₀ " may have n to 30 carbon atoms, may have n to 20 carbon atoms, may have n to 10 carbon atoms, And may have 6 carbon atoms. Similarly, "C _n -C ₂₀ " may have n to 20 carbon atoms, may have n to 10 carbon atoms, and may have n to 6 carbon atoms (n is an integer of 1 to 6).

Hereinafter, the present invention will be described in detail.

An aromatic amine derivative according to an embodiment of the present invention may be represented by the following general formula (1).

[Chemical Formula 1]

In Formula 1,

R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are each independently selected from the group consisting of hydrogen, halogen, amino, nitro, cyano, hydroxy, substituted or unsubstituted C ₁ -C ₃₀ alkyl, hwandoen C ₃ -C ₃₀ cycloalkyl, substituted or unsubstituted C ₆ -C ₃₀ aryl, substituted or unsubstituted C ₆ -C ₃₀ aralkyl (aralkyl), substituted or unsubstituted C ₁ -C ₃₀ heteroalkyl , Substituted or unsubstituted C ₂ -C ₃₀ heterocycloalkyl, substituted or unsubstituted C ₅ -C ₃₀ heteroaryl, substituted or unsubstituted C ₅ -C ₃₀ heteroaralkyl, substituted or unsubstituted tr C ₁ -C ₃₀ alkyl silyl group, a substituted or unsubstituted di-C ₁ -C ₃₀ alkyl, C ₆ -C ₃₀ aryl silyl group, a substituted or unsubstituted C ₆ -C ₃₀ aryl tree silyl, substituted or unsubstituted adamantyl ring, - ^{_{(CH 2) j OR a,}} - (CH 2) j C (O) R a, - (CH 2) j C (O) OR a, - (CH 2) j OC (O) R a, - (CH _{2) j OM, - (CH} 2) j C (O) M, - (CH 2) j C (O) OM, - (CH 2) j OC (O) M, - (CH 2) j NR b R ^{_{c, - (CH 2) j}} C (O) NR b R c, - (CH 2) ^{_{j OC (O) NR b R}} c, - (CH 2) j NR d C (O) R b, - (CH 2) j NR d C (O) OR b, - (CH 2) j NR d C ( O) NR ^b R ^c , - (CH ₂ ) _j S (O) _m R ^e , or - (CH ₂ ) _j NR ^d S (O) _m M; Wherein j is an integer from 0 to 12 and m is an integer from 0 to 2; ^{R a, R b, R c} , R d and R ^e are each independently hydrogen, halogen, amino, nitro, cyano, hydroxy, substituted or unsubstituted C ₁ -C ₃₀ alkyl, substituted or unsubstituted C ₃ -C ₃₀ cycloalkyl, substituted or unsubstituted C ₆ -C ₃₀ aryl, substituted or unsubstituted C ₆ -C ₃₀ aralkyl (aralkyl), substituted or unsubstituted C ₁ -C ₃₀ heteroalkyl, substituted or Unsubstituted C ₂ -C ₃₀ heterocycloalkyl, substituted or unsubstituted C ₅ -C ₃₀ heteroaryl, or substituted or unsubstituted C ₅ -C ₃₀ heteroaralkyl.

Preferably, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are each independently hydrogen, substituted or unsubstituted C ₁ -C ₃₀ alkyl, substituted or unsubstituted C ₃ -C ₃₀ cycloalkyl Substituted or unsubstituted C ₆ -C ₃₀ aryl, substituted or unsubstituted C ₆ -C ₃₀ aralkyl, substituted or unsubstituted C ₁ -C ₃₀ heteroalkyl, substituted or unsubstituted C ₂ -C ₃₀ aralkyl, C ₃₀ heteroaryl is a cycloalkyl, a substituted or unsubstituted C ₅ -C ₃₀ heteroaryl group, a substituted or unsubstituted C ₅ -C ₃₀ heteroaralkyl.

R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are each independently 1 to 4 carbon atoms in the ring, and p, q, r, s, t and u are integers of 1 to 4 Quot; means the same or different types. For example, in the case of (R ₁ ) ₄ , it can be seen that four rings of the same or different R ₁ are substituted in one ring.

R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ adjacent to each other in each ring may be substituted or unsubstituted C ₃ -C ₂₀ alkylene or substituted or unsubstituted C ₃ -C ₂₀ < / RTI > alkenylene to form a fused ring.

X ₁ , X ₂ and X ₃ are each independently selected from C or N, and at least one of them is N.

The compound represented by Formula 1 may be selected from among the structures represented by Formula 2 below.

(2)

In Formula 2, R ₁ , R ₂ , R ₄ , R ₅ and R ₆ are as defined in Formula 1.

More specifically, the compound represented by Formula 1 may be selected from among the compounds represented by Formula 3, but is not limited thereto.

(3)

The aromatic amine derivative represented by Formula 1 may be synthesized using a known organic synthesis method. The method for synthesizing the amine derivative can be easily recognized by those skilled in the art with reference to the following Production Examples.

Also, according to the present invention, there is provided an organic electroluminescent device comprising the amine derivative represented by the above formula (1).

The amine derivative of Formula 1 is useful as a hole injecting material or a hole transporting material, and can also be used as a host material for blue, green, red fluorescent, and phosphorescent devices.

The organic electroluminescent device according to the present invention includes a first electrode, a second electrode, and at least one organic film disposed between the electrodes. The organic layer includes at least one amine derivative represented by the general formula (1).

The organic layer includes a hole injecting layer, a hole transporting layer, a functional layer having both a hole injecting function and a hole transporting function, a buffer layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transporting layer, And at least one layer selected from the group consisting of functional layers having at the same time.

For example, the amine derivative may be included in at least one selected from the group consisting of a light emitting layer, an organic layer disposed between the anode and the light emitting layer, and an organic layer disposed between the light emitting layer and the cathode. Preferably, the amine derivative may be contained in one or more layers selected from the group consisting of a hole injection layer, a hole transport layer, and a functional layer having both a hole injection function and a hole transport function. The amine derivative may be included in the organic film as a single substance or a combination of different substances. Alternatively, the amine derivative may be used in combination with a conventionally known compound such as a hole transport layer and a hole injection layer.

The organic electroluminescent device according to the present invention can be applied to an organic electroluminescent device including a positive electrode / a light emitting layer / a cathode, a positive electrode / a hole injecting layer / a light emitting layer / a negative electrode, an anode / a hole injecting layer / a hole transporting layer / a light emitting layer / an electron transporting layer / / Light emitting layer / electron transporting layer / electron injecting layer / cathode structure. Alternatively, the organic electroluminescent device may include a functional layer / a light emitting layer / an electron transporting layer / a cathode having both an anode / hole injecting function and a hole transporting function, or a functional layer / a light emitting layer / an electron transporting layer / Electron injecting layer / cathode structure, but the present invention is not limited thereto.

1 is a schematic cross-sectional view of an organic electroluminescent device according to an embodiment of the present invention.

The organic electroluminescent device may be manufactured using a physical vapor deposition (PVD) method such as sputtering or e-beam evaporation. For example, an anode is formed by depositing a metal or a metal oxide having conductivity or an alloy thereof on a substrate, and an organic material layer including a hole injecting layer, a hole transporting layer, a light emitting layer, an electron transporting layer, and an electron injecting layer is formed thereon And then depositing a material which can be used as a cathode thereon. In addition to such a method, an organic electroluminescent device may be formed by sequentially depositing a cathode material, an organic film, and a cathode material on a substrate.

The organic layer may be prepared by a variety of polymer materials, not by vapor deposition, but by a solvent process such as spin coating, dip coating, doctor blading, screen printing, inkjet printing, or thermal transfer.

The organic electroluminescent 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.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the following examples are intended to illustrate the present invention and the scope of the present invention is not limited thereto.

Example 1: Synthesis of Compound 3-1 (DC1A-pd-C3)

The synthesis route of DC1A-pd-C3 is shown below.

(Synthesis of Intermediate 1 )

4-nitrobenzene (9.3 g, 46 mmol) and CuI (0.52 g, 3 mmol) were added to a 250 ml two-necked flask, , 1,10-phenanthroline (0.94 g, 5 mmol), K ₃ PO ₄ (22 g, 104 mmol) and dioxane (120 ml) . After completion of the reaction, the reaction mixture was dissolved in methylene chloride (MC) and filtered through a Celite filter. The filtered solution was distilled under reduced pressure and extracted with MC and distilled water. The extracted MC layer was extracted with MgSO ₄ , and the solvent was removed by distillation under reduced pressure to obtain a yellow solid. The solid was separated into a white solid ( 1 ) using a column chromatography method (8 g, 67%).

(Synthesis of intermediate 2 )

1 (10 g, 35 mmol) and 2N acetic acid (100 ml) are put in a two-neck 250 ml flask and stirred. After 30 minutes, Fe (11.6 g, 208 mmol) was added and stirred vigorously at room temperature for 5-6 hours. After the reaction was completed, it was dissolved in MC and subjected to cell light filter. The filtered solution was distilled under reduced pressure and then extracted with MC and Na ₂ CO ₃ (sat) or Na ₂ CO ₃ (sat) + NaCl (sat). The extracted MC layer was extracted with MgSO ₄ , and the solvent was removed by distillation under reduced pressure to obtain a yellow solid. The solid was separated into a white solid ( 2 ) (6.3 g, 70%) by column chromatography.

(Synthesis of final compound)

In two 250ml flasks 2 (0.6g, 2.3mmol), 9- (4- bromophenyl) -9H- carbazole (9- (4-bromophenyl) -9H -carbazole, 1.7g, 5mmol), NaO t Bu (0.67 g, 6.9 mmol) were dissolved in toluene (100 ml) and stirred under nitrogen. The reaction temperature was raised to 80 ° C and reaction was carried out for 1 hour. Pd ₂ (dba) ₃ (0.07 g, 0.07 mmol) and (tert-Bu) ₃ P (0.02 g, 0.09 mmol) were added thereto and reacted at 80 ° C for 4-5 hours. The reaction solution was filtered to remove the salt. The filtrate was distilled to remove toluene and the concentrate was separated into a column, and the yield of DC1A-pd-C3 (3-1) was 1.2 g (yield: 70%). NMR analysis results of the obtained DC1A-pd-C3 (3-1) are as follows (see Fig. 1).

NMR ^{analysis: 1 H NMR (300MHz, DMSO} ) δ 8.56 (d, 1H), 8.30 (d, 1H), 8.23 (m, 4H), 7.88 (m, 1H), 7.66 (m, 6H), 7.55 ( m, 8H), 7.45 (m, 8H), 7.37 (m,

Example 2: Synthesis of compound 3-2 (C1A-pd-DC3 compound)

The synthesis route of C1A-pd-DC3 is shown below.

(Synthesis of Intermediate 3 )

1-bromo-4-iodobenzene (37.8 g, 134 mmol), CuI (1.1 g, 5.79 mmol), 1, 10-phenanthroline (2 g, 11.13 mmol), K ₃ PO ₄ (47 g, 220 mmol) and Dioxane (300 ml) were added thereto and refluxed at 80-100 ° C under nitrogen for 24 hours. After the reaction was completed, it was melted in MC and Celite filter. The filtered solution was distilled under reduced pressure and extracted with methylene chloride and distilled water. The extracted Methylene Chloride layer was hydrated with MgSO ₄ and the solvent was removed by distillation under reduced pressure to obtain a yellow solid. The white solid ( 3 ) was isolated (18.7 g, 65%) by Column Chromatography method.

(Synthesis of final compound)

(9H-carbazol-9-yl) aniline, 0.6g, 2.3mmol), 3 (1.7g, 5mmol), NaO ^t Bu (0.67 g, 6.9 mmol) were dissolved in toluene (100 ml) and stirred under nitrogen. The reaction temperature was raised to 80 ° C and reaction was carried out for 1 hour. Pd ₂ (dba) ₃ (0.07 g, 0.07 mmol) and (tert-Bu) ₃ P (0.02 g, 0.09 mmol) were added thereto and reacted at 80 ° C for 4-5 hours. The reaction solution was filtered to remove the salt. The filtrate was distilled to remove toluene and the concentrate was separated into a column, and the yield of C1A-pd-DC3 (3-2) was 1.1 g (yield: 68%) (see FIG.

NMR analysis results of the obtained C1A-pd-DC3 (3-2) are as follows.

NMR ^{analysis: 1 H NMR (300MHz, DMSO} ) δ 8.56 (m, 2H), 8.25 (m, 4H), 7.87 (m, 2H), 7.67 (m, 6H), 7.55 (m, 10H), 7.45 ( m, 6H), 7.37 (m, 2H), 7.28 (m, 2H)

Example 3: Synthesis of Compound 3-3 (C3A-pd-DC3)

The synthesis route of C3A-pd-DC3 is shown below.

In a two-necked 250ml flask 2 (0.6g, 2.3mmol), 3 (1.7g, 5mmol), with NaO ^t Bu (0.67g, 6.9mmol) into a toluene (100ml) was stirred under nitrogen and the reaction temperature 80 ℃ The mixture was heated to react for 1 hour. Pd ₂ (dba) ₃ (0.07 g, 0.07 mmol) and (tert-Bu) ₃ P (0.02 g, 0.09 mmol) were added thereto and reacted at 80 ° C for 4-5 hours. The reaction solution is filtered to remove the salt. The filtrate was distilled to remove toluene and the concentrate was separated into a column, and the yield of C3A-pd-DC3 (3-3) was 1.1 g (yield: 68%). NMR analysis results of the obtained C3A-pd-DC3 (3-3) are as follows (see FIG. 3).

NMR ^{analysis: 1 H NMR (300MHz, DMSO} ) δ 8.54 (m, 3H), 8.28 (d, 3H), 7.75 (m, 3H), 7.65 (m, 12H), 7.54 (m, 3H), 7.44 ( m, 6 H), 7.36 (m, 3 H)

Example 4: Synthesis of compound 3-9 (C1A-pd-BeDC3)

The synthesis route of C1A-pd-BeDC3 is shown below.

(Synthesis of Intermediate 4 )

Benzo δ-carboline (3 g, 14 mmol), 1-bromo-4-iodobenzene (5.8 g, 21 mmol), CuI (0.17 g, 0.89 mmol), 1,10-phenanthroline _{0.17g, 1.71mmol), K 3 PO} 4 (7.3g, 34mmol), as a put Dioxane (100ml) was refluxed for 24 hours at 80 ~ 100 ℃ under nitrogen. After the reaction was completed, it was melted in MC and Celite filter. The filtered solution was distilled under reduced pressure and extracted with MC and distilled water. The extracted MC layer was extracted with MgSO ₄ , and the solvent was removed by distillation under reduced pressure to obtain a yellow solid. The solid was separated into a white solid ( 4 ) (3.6 g, 70%) by Column Chromatography method.

(Synthesis of final compound)

In a two-necked 250 ml flask 4- (9H-carbazol-9-yl) aniline (0.5g, 2mmol), 4 ( 1.59g, 4.3mmol), put NaO ^t Bu (0.56g, 6mmol) in toluene (100ml) was stirred under nitrogen, and the temperature rise the reaction temperature to 80 ℃ was reacted for 1 hour. Pd ₂ (dba) ₃ (0.055 g, 0.059 mmol) and (tert-Bu) ₃ P (0.015 g, 0.08 mmol) were added thereto and reacted at 80 ° C for 4-5 hours. The reaction solution was filtered to remove the salt. The filtrate was distilled to remove toluene and the concentrate was separated into columns. The yield of C1A-pd-BeDC3 (3-9) was 0.9 g (yield: 60%). NMR analysis results of the obtained C1A-pd-BeDC3 (3-9) are as follows (see FIG. 4).

NMR ^{analysis: 1 H NMR (300MHz, CD} 2 Cl 2) δ 9.66 (d, 2H), 8.78 (d, 2H), 8.18 (d, 2H), 8.04 (m, 4H), 7.96 (d, 2H) 2H), 7.75 (m, 2H), 7.62 (m, 13H), 7.55 (m, 3H), 7.48

Test Example

The UV / VIS spectra of the OLED compounds of the present invention were measured using a Jasco V-630 instrument and PL (photoluminescence) spectra were measured using a Jasco FP-8500 instrument. The PL (photoluminescence) spectrum at low temperature (77 K) was measured on a Jasco FP-8500 instrument for the OLED compound (see (a) of the present invention) and the conventional CBP compound .

[Table 1]

The OLED material of the present invention has a triplet energy of 2.6 eV or greater. Therefore, it has triplet energy equal to or higher than that of CBP used as the host material of the conventional light emitting material layer, which can prevent the energy reversal phenomenon from the host material to the dopant.

Claims (11)

An aromatic amine derivative represented by the following formula (1).
[Chemical Formula 1]

[In the formula 1,
R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are each independently hydrogen, substituted or unsubstituted C ₁ -C ₃₀ alkyl, substituted or unsubstituted C ₃ -C ₃₀ cycloalkyl, Substituted or unsubstituted C ₆ -C ₃₀ aryl, substituted or unsubstituted C ₆ -C ₃₀ aralkyl, substituted or unsubstituted C ₁ -C ₃₀ heteroalkyl, substituted or unsubstituted C ₂ -C ₃₀ hetero Cycloalkyl, substituted or unsubstituted C ₅ -C ₃₀ heteroaryl, or substituted or unsubstituted C ₅ -C ₃₀ heteroaralkyl,
R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ adjacent to each other in one ring are each a substituted or unsubstituted C ₃ -C ₂₀ alkylene or a substituted or unsubstituted C ₃ -C ₂₀ alkenylene They may be connected to each other to form a fused ring,
p, q, r, s, t and u are each an integer of 1 to 4,
X ₁ , X ₂ and X ₃ are each independently selected from CH or nitrogen (N), at least one of which is nitrogen (N) and not all of which is nitrogen (N). delete The method according to claim 1,
Wherein the compound represented by Formula 1 is selected from the structures of Formula 2 below.
(2)

[In the formula (2)
R ₁ to R ₆ are the same as defined in formula (1)
R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ adjacent to each other in one ring are each a substituted or unsubstituted C ₃ -C ₂₀ alkylene or a substituted or unsubstituted C ₃ -C ₂₀ alkenylene They may be connected to each other to form a fused ring,
p, q, r, s, t and u are each an integer of 1 to 4.] The method according to claim 1,
Wherein the compound represented by Formula 1 is selected from the structures listed in Formula 3 below.
(3)

An organic electroluminescent device comprising an aromatic amine derivative according to any one of claims 1, 3, and 4. 6. The method of claim 5,
Wherein the aromatic amine derivative is used as a hole injecting material or a hole transporting material. 6. The method of claim 5,
Wherein said amine derivative is used as a host material for blue, green, red fluorescence and phosphorescent devices. A first electrode, a second electrode, and at least one organic film disposed between the electrodes,
Wherein the organic film comprises the aromatic amine derivative of any one of claims 1, 3, and 4. 9. The method of claim 8,
The organic layer includes a hole injecting layer, a hole transporting layer, a functional layer having both a hole injecting function and a hole transporting function, a buffer layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transporting layer, And at least one functional layer having at least one functional group at the same time. 9. The method of claim 8,
Wherein the amine derivative is contained in at least one selected from the group consisting of a light emitting layer, an organic layer disposed between the anode and the light emitting layer, and an organic layer disposed between the light emitting layer and the cathode. 9. The method of claim 8,
Wherein the amine derivative is contained in at least one layer selected from the group consisting of a hole injecting layer, a hole transporting layer, and a functional layer having both a hole injecting function and a hole transporting function.

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