KR100857652B1 - New organic compound and organic light emitting device using the same - Google Patents

Abstract

A new organic compound is provided to improve luminous efficiency, stability and lifetime of an organic light emitting device by containing a naphthalene core and a substitution group having electron transport ability. A new organic compound represented by the formula(2) is useful for an organic layer of an organic light emitting device, wherein X^1 is N-R^7, S or O; R^1, R^2, R^3, R^4 and R^6 are each independently H, C1-C30 alkyl group, C2-C30 alkenyl group, C3-C30 cycloalkyl group, C2-C30 heterocycloalkyl group, C5-C30 arylalkyl group, C5-C30 aryloxy group, C5-C30 aryl group or C5-C30 heteroaryl group; R^7 is C5-C30 aryl group or C5-C30 heteroaryl group; Ar^1 is single bond, C5-C30 aryl group, C5-C30 heteroaryl group or triphenyl amine; R^5 is H, C1-C30 aryl group, C2-C30 alkenyl group, C3-C30 cycloalkyl group, C2-C30 heterocycloalkyl group, C5-C30 arylalkyl group, C5-C30 aryloxy group, C5-C30 aryl group, or C5-C30 heteroaryl group. An organic light emitting device contains a cathode, at least one organic layer containing the organic compound represented by the formula(2) and an anode, sequentially. Further, the organic layer containing the organic compound is an electron transporting layer.

Description

New organic compound and organic light emitting device using the same {NEW ORGANIC COMPOUND AND ORGANIC LIGHT EMITTING DEVICE USING THE SAME}

1 is a cross-sectional view showing an example of an organic light emitting device structure according to the present invention.

The present invention relates to a novel organic compound and an organic light emitting device using the same.

In general, organic light emitting phenomenon refers to a phenomenon of converting electrical energy into light energy using an organic material. That is, when the organic material layer is positioned between the anode and the cathode, a voltage is applied between the two electrodes, and holes are injected into the organic material and electrons are injected into the cathode. When the injected holes and electrons meet, excitons are formed, and when the excitons fall back to the ground, they shine.

As a method for making an organic light emitting device efficiently, research has been conducted to manufacture an organic material layer in the device in a multilayer structure instead of a single layer. Most organic light emitting devices used in the present invention have a structure in which an electrode and an organic material layer are deposited, and the organic material layer has a multilayer structure including a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer.

Since the first development of EL devices by vacuum deposition in 1987, many people have been developing materials for decades, but there is still much room for improvement due to insufficient luminance and deterioration of durability after long time use. Remains.

The electron transport layer is a good candidate for the organic monomolecular materials such as organometallic complexes having relatively high electron stability and electron transfer speed. Among them, Alq3 having excellent stability and high electron affinity has been reported to be the most excellent, but when used in a blue light emitting device, there is a problem in that color purity is poor due to light emission due to exciton diffusion. In addition, conventionally known materials for electron transport include flavon derivatives published by Sanyo, germanium and silicon cyclopetadiene derivatives from Chiso. (Japanese Laid-Open Patent Publication No. 1998-017860, Japanese Laid-Open Patent Publication No. 1999-087067).

In addition, many organic monomolecular materials having imidazole group, oxazole group, and thiazole group have been reported as materials for the electron injection and transport layer. However, before these materials were reported as electron transport materials, it was previously reported in Motorola EU 0700917 A2 that metal complex compounds of these materials were applied to a blue light emitting layer or a cyan light emitting layer of an organic light emitting device.

TPBI, published by Kodak in 1996 and described in US Pat. No. 5,645,948, is known as a representative material for electron transport layers with imidazole groups, and its structure has three N-phenyl benzs at the 1,3,5 substitution positions of benzene. It contains an imidabol group and functionally blocks electrons from the light emitting layer as well as the ability to transfer electrons, but has a problem of low stability for practical application.

In addition, the electron transport materials disclosed in Japanese Patent Application Laid-Open No. 11-345686 report that they contain oxazole groups and thiazole groups and can be applied to the light emitting layer, but have reached practical use in terms of driving voltage, luminance, and lifetime of the device. I can't.

Therefore, in order to overcome the problems of the prior art as described above and further improve the characteristics of the organic light emitting device, development of a more stable and efficient material that can be used as an electron transporting material in the organic light emitting device is continuously required.

The present invention is to provide a novel compound that can improve the luminous efficiency, stability and device life by applying to an organic light emitting device as a compound comprising a naphthalene core and a substituent having an electron transfer capability.

Moreover, an object of this invention is to provide the organic light emitting element using the said compound.

The present invention provides a compound represented by Formula 1, a compound represented by Formula 2, a compound represented by Formula 3, a compound represented by Formula 4, and a compound represented by Formula 5.

[Formula 1]

In Formula 1, X ¹ is selected from NR ⁷ , S and O;

R ¹ to R ⁷ are each independently selected from H, C ₁ to C ₃₀ alkyl, alkenyl, cycloalkyl, heterocycloalkyl, arylalkyl, aryloxy, aryl and heteroaryl groups.

[Formula 2]

In Formula 2, X ¹ is selected from NR ⁷ , S and O;

R ¹ to R ⁷ are each independently selected from H, C ₁ to C ₃₀ alkyl, alkenyl, cycloalkyl, heterocycloalkyl, arylalkyl, aryloxy, aryl and heteroaryl groups;

Ar ¹ is selected from C ₅ to C ₃₀ aryl group, heteroaryl group, and triphenyl amine.

[Formula 3]

In Formula 3, X ¹ is selected from NR ⁷ , S, and O; X ² is selected from NR ⁸ , S and O;

R ¹ to R ⁸ are each independently selected from H, C ₁ to C ₃₀ alkyl, alkenyl, cycloalkyl, heterocycloalkyl, arylalkyl, aryloxy, aryl and heteroaryl groups.

[Formula 4]

In Formula 4, X ¹ is selected from NR ⁷ , S, and O; X ² is selected from NR ⁸ , S and O;

R ¹ to R ⁸ are each independently selected from H, C ₁ to C ₃₀ alkyl, alkenyl, cycloalkyl, heterocycloalkyl, arylalkyl, aryloxy, aryl and heteroaryl groups;

Ar ¹ and Ar ² are each independently selected from C ₅ to C ₃₀ aryl groups, heteroaryl groups, and triphenyl amines.

[Formula 5]

In Formula 5, X ¹ is selected from NR ⁷ , S, and O; X ² is selected from NR ⁸ , S and O;

R ¹ to R ⁸ are each independently selected from H, C ₁ to C ₃₀ alkyl, alkenyl, cycloalkyl, heterocycloalkyl, arylalkyl, aryloxy, aryl and heteroaryl groups;

Ar ¹ is selected from C ₅ to C ₃₀ aryl group, heteroaryl group, and triphenyl amine.

In addition, the present invention is an organic light emitting device comprising an anode, one or more organic material layer and a cathode sequentially,

At least one layer of the at least one organic material layer is a compound represented by Formula 1, a compound represented by Formula 2, a compound represented by Formula 3, a compound represented by Formula 4, and a compound represented by Formula 5 It provides an organic light emitting device characterized in that it comprises at least one compound selected from the group consisting of.

Hereinafter, the present invention will be described in detail.

Compounds represented by Formula 1 to Formula 5 according to the present invention each have a naphthalene group as a core, and as a substituent having an electron transfer ability, a benzimidazole group, a benzothiazole group and a benz It is characterized by including one or more substituents selected from benzoxazole groups.

More specifically, the compound represented by Formula 1 has a naphthalene group as a core, a benzimidazole group, benzothiazine at one carbon position of carbon 2, carbon 3, carbon 6 and carbon 7 of the naphthalene group It is characterized by having a structure in which a sol group or a benzoxazole group is substituted.

Compound represented by the formula (2) is a naphthalene group as a core, C ₅ ~ C ₃₀ arylene group, heteroarylene group on one of carbon 2, carbon 3, carbon 6 and carbon 7 of the naphthalene group And an aromatic group selected from triphenyl amine, and the aromatic group has a structure in which a benzimidazole group, a benzothiazole group, or a benzoxazole group is substituted.

The compound represented by the formula (3) is a naphthalene group as a core, the carbon 2 and 6 (or carbon 3 and carbon 7) of the naphthalene group is independently a benzimidazole group, benzothiazole group, or benz It is characterized by having a structure in which an oxazole group is substituted.

The compound represented by the formula (4) is a naphthalene group as a core, and the carbon 2 and 6 carbon (or carbon 3 and carbon 7) of the naphthalene group are each independently C ₅ ~ C ₃₀ arylene group, heteroaryl An aromatic group selected from a rene group and a triphenyl amine is introduced, and each of the aromatic groups has a structure in which a benzimidazole group, a benzothiazole group, or a benzoxazole group is substituted independently.

In addition, the compound represented by the formula (5) has a naphthalene group as a core, one of carbon 2 and carbon 6 (or carbon 3 and carbon 7) of the naphthalene group is a benzimidazole group, benzothiazole group Or an aromatic group in which a benzoxazole group is substituted, and a benzimidazole group, a benzothiazole group, or a benzoxazole group is substituted for the remaining carbon among carbons 2 and 6 (or carbon 3 and 7). It is characterized by having a structure. In this case, the aromatic group may be selected from C ₅ ~ C ₃₀ arylene group, heteroarylene group and triphenyl amine.

In addition, in the compounds represented by Formula 1 to Formula 5 according to the present invention, the naphthalene group includes a C ₁ to C ₃₀ alkyl group, alkenyl group, cycloalkyl group, heterocycloalkyl group, arylalkyl group, One or more substituents of the aryloxy group, the aryl group and the heteroaryl group may be introduced. In addition, the benzimidazole group, the benzothiazole group, and the benzoxazole group each independently represent an alkyl group, an alkenyl group, a cycloalkyl group, a heterocycloalkyl group, an arylalkyl group, an aryloxy group, an aryl group, and a heteroaryl of C ₁ to C ₃₀ . One or more substituents in the group may be substituted.

In addition, in Formulas 1 to 5, Ar ¹ and Ar ² are not particularly limited as long as they are each independently an aromatic ring group selected from C ₅ to C ₃₀ arylene groups, heteroarylene groups, and triphenyl amines. Examples thereof include, but are not limited to, phenylene, naphthalenylene, biphenylene, anthracenylene, triphenyl amine, and the like.

If the compound represented by the formula (1) to the compound represented by the formula (5) in more detail as shown in the following compounds, the compounds according to the present invention is not limited to those illustrated below.

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

[Formula 2-4]

[Formula 2-5]

[Formula 2-6]

[Formula 3-1]

[Formula 3-2]

[Formula 3-3]

[Formula 3-4]

[Formula 3-5]

[Formula 3-6]

[Formula 4-1]

[Formula 4-2]

[Formula 4-3]

[Formula 4-4]

[Formula 4-5]

[Formula 5-1]

[Formula 5-2]

[Formula 5-3]

[Formula 5-4]

[Formula 5-5]

The method of preparing the compound represented by Chemical Formula 1 to the compound represented by Chemical Formula 5 according to the present invention is not particularly limited, and reactions known in the art may be appropriately applied. For example and non-limiting examples, the compounds represented by Formula 1 to Formula 5 according to the present invention may be a diaminobenzene derivative, an aminobenzenethiol derivative, or a naphthalene derivative substituted with one or two aldehyde groups. It can be prepared by reaction with an aminophenol derivative.

Further, by way of non-limiting example, naphthalene derivatives in which one or two aldehyde groups are substituted may be prepared from alcohol derivatives using conventional oxidizing agents known in the art such as PCC, and the alcohol derivatives may be prepared from a ester derivative. It can be prepared using, but is not particularly limited to the above route. In addition, the naphthalene derivative in which one or two aldehyde groups are substituted can also be directly reduced from an ester derivative to an aldehyde derivative by appropriately selecting a reducing agent. In addition, the introduction of an aromatic group to the naphthalene group may be carried out through conventional reactions known in the art, and may be introduced through a reaction using an organometallic compound as a non-limiting example.

The manufacturing method exemplified above is not limited to the manufacturing method exemplified above, which is only an example of the method for preparing the compound represented by Formula 1 to the compound represented by Formula 5 according to the present invention.

The present invention is an organic light emitting device comprising an anode, at least one organic layer and a cathode sequentially, at least one layer of the at least one organic layer is a compound represented by the formula (1), a compound represented by the formula (2), the formula Provided is an organic light-emitting device comprising at least one compound selected from the group consisting of a compound represented by 3, a compound represented by Formula 4, and a compound represented by Formula 5.

The organic material layer may be a hole injection layer, a hole transport layer, a light emitting layer, and / or an electron transport layer in the organic light emitting device.

Preferably, the material selected from the group consisting of the compound represented by Formula 1 to the compound represented by Formula 5 may be included in the organic light emitting device as a material for the electron transport layer, in this case, luminous efficiency, stability and device life is improved Can be. Therefore, preferably, it is selected from the group consisting of the compound represented by the formula (1), the compound represented by the formula (2), the compound represented by the formula (3), the compound represented by the formula (4) and the compound represented by the formula (5) The organic material layer containing at least one compound to be may be an electron transport layer.

The material for the electron transport layer has a higher electron density in a molecule, the better the result, and generally a heteroamine-based compound may correspond to this. Among them, conventional benzimidazole derivatives known as substituents for electron transport have a problem of stability of molecules. Accordingly, in the present invention, the thermal stability of the molecule is increased by using a conjugated aromatic derivative, preferably a naphthalene derivative, in which the core portion is conjugated to increase the thermal stability of the organic material for electron transport, thereby increasing efficiency and lifespan. Intended.

1 is a cross-sectional view showing an example of the structure of an organic light emitting device according to the present invention, the substrate 101, the anode 102, the hole injection layer 103, the hole transport layer 104, the light emitting layer 105, the electron transport layer 106 and the cathode 107 are sequentially stacked. The electron injection layer may be positioned on the electron transport layer 106.

As described above, the organic light emitting device of the present invention may not only have a structure in which an anode, one or more organic material layers, and a cathode are sequentially stacked, but an insulating layer or an adhesive layer may be inserted at an interface between the electrode and the organic material layer.

In the organic light emitting device of the present invention, the organic material layer including at least one compound selected from the group consisting of compounds represented by Formula 1 to compound represented by Formula 5 may be formed by a vacuum deposition method or a solution coating method. have. Examples of the solution coating method include, but are not limited to, spin coating, dip coating, doctor blading, inkjet printing, or thermal transfer.

The thickness of the organic material layer including one or more compounds selected from the group consisting of compounds represented by Formula 1 to compounds represented by Formula 5 may be 50 to 1000 mm. If the thickness exceeds 1000 mW, the color purity of the light passing through is reduced due to the thickness and the driving voltage is increased, thereby reducing the premise efficiency. If the thickness is less than 50 mW, the electron mobility is lowered. .

The organic light emitting device of the present invention may be manufactured by forming an organic material layer and an electrode using materials and methods known in the art, except that at least one layer of the organic material layer is formed to include the compound of the present invention.

For example, the substrate 101 may be a silicon wafer, quartz or glass plate, metal plate, plastic film or sheet.

The anode 102 material may be a metal such as vanadium, chromium, copper, zinc, gold, or an alloy thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO); Combinations of metals and oxides such as ZnO: Al or SnO ₂ : Sb; Conductive polymers such as polythiophene, poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (PEDT), polypyrrole and polyaniline; Or carbon black, but is not limited thereto.

Cathode materials include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin and lead or alloys thereof; Multilayer structure materials such as LiF / Al or LiO ₂ / Al, and the like, but are not limited thereto.

In addition, the hole injection layer 103, the hole transport layer 104 and the light emitting layer 105 is not particularly limited, conventional materials known in the art may be used.

Hereinafter, the present invention will be described in detail with reference to the following Examples. However, the following examples are merely to illustrate the present invention and the present invention is not limited by the following examples.

Example 1 Synthesis of Compound Represented by Chemical Formula 3-6

Example 1-1

50 g (0.2 mol) of dimethyl 2,6-naphthalenedicarboxylate was dissolved in 1.5 L of THF. Then, 16.2 g (35.95 mol) of lithium aluminum hydride was slowly added under an ice bath at 0 ° C., and the reaction mixture was stirred at room temperature for 6 hours. It was confirmed by TLC whether the reaction was terminated, and when the reaction was completed, saturated sodium bicarbonate solution was slowly added again at 0 ° C. The reaction solution was filtered under reduced pressure, the filtrate was distilled under reduced pressure to remove the solvent, and then chromatographed using EA: Hex = 1: 1 (v: v) solution to obtain 35 g of a desired white solid product in a yield of 75.2%.

Example 1-2

82.4 g (0.382 mol) of pyridinium chlorochromate and 20 g of molecular sieve 4x were added and dissolved in 1.5 L of MC. Here, 30 g (0.159 mol) of 2,6-dimethylalcohol naphthalene synthesized in Example 1-1 was added slowly and stirred for 5 hours. After the reaction was performed with a short silica gel filter, the filtrate was distilled under reduced pressure. Chromatography with MC: n-Hex = 1: 4 (v: v) afforded 17 g of a white solid in a yield of 57.9%.

Example 1-3

1.5 g (8.14 mmol) of 2,6-dicarbonylaldehyde naphthalene obtained in Example 1-2 and 3.3 g (17.91 mmol) of N-phenylbenzene-1,2-diamine were added to 10 ml of acetic acid and 40 ml of toluene (1: 4). ) Was dissolved in the mixed solution, followed by stirring under reflux for 3 days. The toluene layer was extracted, washed with water, dried over anhydrous magnesium sulfate, passed through a silica gel layer, and the solvent was removed to obtain a solid compound. Column chromatography gave 0.37 g of ETL-1 (27% yield). The maximum absorption wavelength was 342 nm and the maximum emission wavelength was 410 nm.

¹ H NMR (500 MHz, THF-d8): 7.21 (t, 2H), 7.28 (t, 2H), 7.3 (d, 4H), 7.53 (t, 2H), 7.55 (m, 4H), 7.92 (d, 2H), 9.09 (d, 2H).

Example 2 Synthesis of Compound Represented by Chemical Formula 1-2

Example 2-1

15.57 g (90.53 mmol) of 1-naphthyl boronic acid and 20 g (75.44 mmol) of methyl 6-bromo-2-naphthoate were dissolved in 150 ml of toluene under nitrogen. 2.62 g (2.26 mmol) of keystroke phenylphosphine palladium and 20.85 g of potassium carbonate were added. The mixed solution was heated and stirred at 120 ° C. for 13 hours, and then the mixed solution was filtered on a pad of celide, and the filtrate was distilled under reduced pressure to remove the solvent. The obtained solid was columned by column chromatography EA: Hex = 3: 7 (v: v) to obtain a white solid 23g, yield 97.6%.

Example 2-2

23 g (73.63 mmol) of Compound A was dissolved in 150 ml of THF. 5.59 g (147.27 mmol) of lithium aluminum hydride was slowly added under nitrogen in an ice bath at 0 ° C., and the reaction mixture was stirred at room temperature for 4 hours. It was confirmed by TLC whether the reaction was terminated, and when the reaction was completed, saturated sodium bicarbonate solution was slowly added again under 0 ° C. The reaction mixture was filtered under reduced pressure, the filtrate was distilled under reduced pressure to remove the solvent, and then chromatographed using EA: Hex = 4: 6 (v: v) solution to obtain 19.44 g of a desired white solid in 92.8% yield. .

Example 2-3

29.5 g (136.73 mmol) of pyridinium chlorochromate and 20 g of molecular sieve 4g were added, and then dissolved in 250 ml of MC. Compound B 19.44 g (68.37 mmol) was added slowly thereto, followed by stirring for 5 hours. After the reaction was performed with a short silica gel filter, the filtrate was distilled under reduced pressure. Chromatography with MC: n-Hex = 4: 6 (v: v) afforded 14.78 g of a white solid in a yield of 76.6%.

Example 2-4

7 g (24.80 mmol) of Compound C and 4.57 g (24.80 mmol) of N-phenylbenzene-1,2-diamine were dissolved in a solution of 30 ml of acetic acid and 120 ml of Toluene (1: 4), followed by stirring under reflux for 3 days. . The toluene layer was extracted, washed with water, dried over anhydrous magnesium sulfate, passed through a silica gel layer, and the solvent was removed to obtain a solid compound. Column chromatography gave 3.8 g of ETL-2 (34.3% yield).

¹ H NMR (500MHz, THF-d8): 7.21 (t, 1H), 7.28 (t, 1H), 7.3 (d, 2H), 7.32 (t, 1H), 7.46 (t, 1H) 7.53 (t, 1H ), 7.55 (m, 2H), 7.58 (d, 1H), 7.61 (t, 1H), 7.63 (t, 2H), 7.73 (d, 1H), 7.92 (d, 2H), 8.42 (d, 1H) , 8.55 (d, 1 H), 9.09 (d, 1 H).

Example 3 Synthesis of Compound Represented by Chemical Formula 2-6

Example 3-1

4.22 g (24.52 mmol) of 2-naphthyl boronic acid and 5 g (18.86 mmol) of methyl-6-bromo-2-naphthoate were dissolved in 150 ml of toluene under nitrogen, followed by 0.65 g of tetrakistriphenylphosphinepalladium ( 0.57 mmol) and 6.00 g (56.58 mmol) sodium carbonate were added. This mixed solution was heated and stirred at 120 ° C. After stirring for 13 hours, the mixed solution was filtered on a pad of celide, and the filtrate was distilled under reduced pressure to remove the solvent. The obtained solid was columned with column chromatography EA: Hex = 3: 7 (v: v) to obtain 5.3 g of a white solid, yield 90.0%.

Example 3-2

5.3 g (16.98 mmol) of Compound D were dissolved in 150 ml of THF. 1.42 g (37.36 mmol) of lithium aluminum hydride was slowly added under nitrogen at an ice bath, and the reaction mixture was stirred at room temperature for 4 hours. It was confirmed by TLC whether the reaction was terminated, and when the reaction was completed, saturated sodium bicarbonate solution was slowly added again at 0 ° C. The reaction solution was filtered under reduced pressure, the filtrate was distilled under reduced pressure to remove the solvent, and then chromatographed using EA: Hex = 4: 6 (v: v) solution to give 4.3 g of the desired white solid product in 89.1% yield. Got

Example 3-3

6.52g (30.27mmol) of pyridinium chlorochromate and 5g of 4L of molecular sieve were added and dissolved in 100ml of MC. Compound E 4.3g (15.13 mmol) was added slowly and stirred for 5 hours. After the reaction was performed with a short silica gel filter, the filtrate was distilled under reduced pressure. Chromatography with MC: n-Hex = 4: 6 (v: v) yielded 3.11 g of a white solid in a yield of 72.8%.

Example 3-4

3.11 g (11.02 mmol) of Compound F and 2.03 g (11.02 mmol) of N-phenylbenzene-1,2-diamine were dissolved in a mixed solution of 30 ml of acetic acid and 120 ml of Toluene (1: 4), followed by stirring under reflux for 3 days. I was. The toluene layer was extracted, washed with water, dried over anhydrous magnesium sulfate, passed through a silica gel layer, and the solvent was removed to obtain a solid compound. Column chromatography gave 1.22 g (yield 24.8%) of ETL-3 as a yellow solid.

¹ H NMR (500 MHz, THF-d8): 7.21 (t, 2H), 7.28 (t, 2H), 7.3 (d, 4H), 7.53 (t, 2H), 7.55 (m, 4H), 7.58 (d, 2H), 7.59 (m, 3H), 7.73 (d, 2H), 7.92 (t, 1H), 8.01 (t, 1H), 8.11 (t, 1H) 7.92 (d, 2H), 9.09 (d ,, 2H ).

Example 4 Synthesis of Compound Represented by Chemical Formula 4-1

Example 4-1

10 g (0.0349 mol) of dibromonaphthalene, 6.3 g (0.042 mol) of formylphenylboronic acid, 2 g (1.74 mmol) of tetrakistriphenylphosphine palladium, 4.3 g (0.042 mol) of potassium carbonate, Toluene 450 ml / H ₂ O 50 ml were dissolved in the mixed solution, followed by stirring under reflux. The toluene layer was extracted, washed with water, dried over anhydrous magnesium sulfate, passed through a silica gel layer, and the solvent was removed to obtain a solid compound. Column chromatography gave 10.43 g (yield 88.9%) of Compound G as a white solid.

Example 4-2

10 g (0.0297 mol) of Compound G and 16.41 g (0.0891 mol) of N-phenylbenzene-1,2-diamine were dissolved in a solution of 50 ml of acetic acid and 200 ml of Toluene (1: 4), followed by stirring under reflux for 3 days. . The toluene layer was extracted, washed with water, dried over anhydrous magnesium sulfate, passed through a silica gel layer, and the solvent was removed to obtain a solid compound. Column chromatography gave 5.23 g (26.5%) of ETL-4 as a yellow solid.

¹ H NMR (500 MHz, THF-d8): 7.21 (t, 2H), 7.25 (d, 2H) 7.28 (t, 2H), 7.3 (d, 4H), 7.53 (m, 4H), 7.55 (m, 4H ), 7.92 (d, 2H), 9.09 (d, 2H).

Example 5 Synthesis of Compound Represented by Chemical Formula 5-1

Example 5-1

5 g (0.0188 mol) of methyl-6-bromo-2-naphthoate was dissolved in 100 ml of THF. 0.85 g (0.0226 mol) of lithium aluminum hydride was slowly added under nitrogen in an ice bath at 0 ° C., and the reaction mixture was stirred at room temperature for 4 hours. It was confirmed by TLC whether the reaction was terminated, and when the reaction was completed, saturated sodium bicarbonate solution was slowly added again under 0 ° C. The reaction solution was filtered under reduced pressure, the filtrate was distilled under reduced pressure to remove the solvent, and then chromatographed using EA: Hex = 4: 6 (v: v) solution to give 4.05 g of a desired white solid (Compound H) as 91%. Obtained in the yield.

Example 5-2

7.3 g (0.0337 mol) of pyridinium chlorochromate and 2 g of molecular sieve 4g were added, and then dissolved in 150 ml of MC. Compound H 4g (0.0168mol) was added slowly, and stirred for 5 hours. After the reaction was performed with a short silica gel filter, the filtrate was distilled under reduced pressure. Chromatography with MC: n-Hex = 4: 6 (v: v) yielded 3.0 g of a white solid (Conpound I) with a yield of 76.2%.

Example 5-3

Compound I 5g (0.0213mol), formylphenylboronic acid 3.82g (0.0255mol), tetrakistriphenylphosphinepalladium 0.73g (0.63mmol), potassium carbonate 3.52g (0.0255mol), Toluene 150ml / H ₂ O 20 ml was dissolved in the mixed solution, followed by stirring under reflux. The toluene layer was extracted, washed with water, dried over anhydrous magnesium sulfate, passed through a silica gel layer, and the solvent was removed to obtain a solid compound. Column chromatography gave the compound J 5.1g (yield 92%) as a white solid.

Example 5-4

5 g (0.0192 mol) of Compound J and 10.61 g (0.0576 mol) of N-phenylbenzene-1,2-diamine were dissolved in a mixed solution of 40 ml of acetic acid and 160 ml (1: 4) of acetic acid, followed by stirring under reflux for 3 days. . The toluene layer was extracted, washed with water, dried over anhydrous magnesium sulfate, passed through a silica gel layer, and the solvent was removed to obtain a solid compound. Column chromatography gave 3.07 g of a yellow solid, ETL-5 (yield 27.2%).

¹ H NMR (500 MHz, THF-d8): 7.21 (t, 2H), 7.25 (d, 2H) 7.28 (t, 2H), 7.3 (d, 4H), 7.53 (m, 4H), 7.55 (m, 4H ), 7.73 (d, 2H), 7.92 (d, 2H), 8.49 (d, 2H), 9.09 (d, 2H).

Examples 6 to 8 and Comparative Example 1 Manufacture of Organic Light-Emitting Device

The glass substrate coated with ITO (Indium tin oxide) having a thickness of 1500 Å was washed with distilled water ultrasonic waves. After washing the distilled water, ultrasonic cleaning with a solvent such as isopropyl alcohol, acetone, methanol and the like was dried and then transferred to a plasma cleaner, and then the substrate was cleaned for 5 minutes using an oxygen plasma, and then the substrate was transferred to a vacuum depositor.

The arylamine derivative (product name DS-205, Doosan Corporation, hereinafter referred to as DS-205) was thermally vacuum deposited to a thickness of 600 kPa on the prepared ITO transparent electrode to form a hole injection layer. NPB, which is a material for transporting holes, was deposited thereon, and then Alq3 and C-545T, which serves as a light emitting layer, were deposited.

ETL-1 (Example 6), ETL-2 (Example 7), ETL-3 (Example 8) or Alq3 (Comparative Example 1), which are comparative materials, were respectively used as materials for injecting and transporting electrons on the emission layer. It was deposited to a thickness of 250 mm 3. The device was fabricated by depositing LiF and Al having a thickness of 2,000 mW in a thickness of 10 mW sequentially on the electron injection and transport layer to form a cathode.

Structures of the organic light emitting diodes of Examples 6 to 8 are shown in Table 1 below, and structures of the organic light emitting diodes of Comparative Example 1 are described in Table 2 below. In addition, the properties of the organic light emitting device of Example 6 are described in Table 3, the properties of the organic light emitting device of Example 7 are described in Table 4, and the properties of the organic light emitting device of Example 8 are described in Table 5 below. The characteristics of the organic light emitting device of Comparative Example 1 are described in Table 6 below.

HIL HTL EML ETL EIL Cathode Materials DS-205 NPB Alq3 + C-545T ETL-1 (Example 6) ETL-2 (Example 7) ETL-3 (Example 8) LiF Al Thickness / Å 600 150 294 + 6 250 10 2,000 Evapo. Temp. / ℃ 330-340 240 to 250 Alq3: 260 ~ 270 C-545T: 150 ~ 160 210 to 220 - - Vacuum / torr 15.5 × 10 ^-8 1.6 × 10 ^-7 1.3 × 10 ^-7 1.3 × 10 ^-7

HIL HTL EML ETL EIL Cathode Materials DS-205 NPB Alq3 + C-545T Alq3 LiF Al Thickness / Å 600 150 294 + 6 250 10 2,000 Evapo. Temp. / ℃ 330-340 240 to 250 Alq3: 240 ~ 250 C-545T: 150 ~ 160 260-270 - - Vacuum / torr 15.5 × 10 ^-8 1.6 × 10 ^-7 5.7 × 10 ^-7 5.7 × 10 ^-7

Current Density (mA / cm ² ) Voltage (V) Luminance (cd / m ² ) CIE index (x, y) Peak λ (nm) Efficiency (cd / A) Efficiency (lm / W) 10 5.3 1653 0.322, 0.635 524 16.5 9.8 25 6.2 4083 0.321, 0.636 525 16.3 8.3 50 6.9 8031 0.321, 0.636 525 16.1 7.3 100 7.8 15670 0.320, 0.635 524 15.7 6.3 150 8.3 23520 0.319, 0.635 524 15.7 5.9

Current Density (mA / cm ² ) Voltage (V) Luminance (cd / m ² ) CIE index (x, y) Peak λ (nm) Efficiency (cd / A) Efficiency (lm / W) 10 5.3 1645 0.322, 0.635 524 16.1 9.6 25 6.2 4033 0.321, 0.635 524 15.9 8.2 50 6.9 7919 0.320, 0.635 524 15.7 7.2 100 7.7 15470 0.319, 0.635 524 15.5 6.3 150 8.2 23220 0.319, 0.635 524 15.5 5.9

Current Density (mA / cm ² ) Voltage (V) Luminance (cd / m ² ) CIE index (x, y) Peak λ (nm) Efficiency (cd / A) Efficiency (lm / W) 10 5.3 1645 0.322, 0.635 524 16.1 9.7 25 6.2 4033 0.321, 0.635 524 16.0 8.0 50 6.9 7919 0.320, 0.635 524 15.8 7.2 100 7.7 15470 0.319, 0.635 524 15.5 6.3 150 8.2 23220 0.319, 0.635 524 15.5 6.0

Current Density (mA / cm ² ) Voltage (V) Luminance (cd / m ² ) CIE index (x, y) Peak λ (nm) Efficiency (cd / A) Efficiency (lm / W) 10 4.6 1219 0.315, 0.639 523 12.2 8.3 25 5.4 3093 0.314, 0.639 523 12.4 7.2 50 6.2 6217 0.314, 0.639 523 12.4 6.3 100 7.0 12450 0.313, 0.638 523 12.5 5.6 150 7.4 19010 0.312, 0.638 523 12.7 5.4

As described above, the compound according to the present invention was able to obtain an efficiency improvement of about 1.3 times than that of the conventional Alq3. As a result, the compounds according to the present invention can greatly gear to improve the EL performance of the organic EL device. In particular, the improvement of the electron transport performance is expected to have a great effect in maximizing the performance in the full color organic EL panel.

Claims (7)

delete A compound represented by the following formula (2). [Formula 2]

In Formula 2, X ¹ is selected from NR ⁷ , S and O; R ¹ , R ² , R ³ , R ⁴ and R ⁶ are each independently H, C ₁ -C ₃₀ alkyl group, C ₂ -C ₃₀ alkenyl group, C ₃ -C ₃₀ cycloalkyl group, C ₂ -C ₃₀ heterocycloalkyl group of, C ₅ ~ C ₃₀ aryl group, an aryloxy group of C ₅ ~ C _30, C ₅ ~ C ₃₀ aryl group and a C ₅ ~ C ₃₀ heteroaryl is selected from aryl groups; R ⁷ is a C ₅ -C ₃₀ aryl group or a C ₅ -C ₃₀ heteroaryl group; Ar ¹ is selected from a single bond, a C ₅ -C ₃₀ aryl group, a C ₅ -C ₃₀ heteroaryl group, and triphenyl amine; R ⁵ is H, a C ₁ to C ₃₀ alkyl group, C ₂ to C ₃₀ alkenyl group, C ₃ to C ₃₀ cycloalkyl group, C ₂ to C ₃₀ heterocycloalkyl group, C ₅ to C ₃₀ arylalkyl group, an aryl group of C ₅ ~ aryloxy _{C 30, C 5 ~ C 30} ( wherein anthracene carbonyl group is excluded), and is selected from the heteroaryl group of C ₅ ~ C _30. delete delete delete An organic light emitting device including an anode, one or more organic material layers, and a cathode sequentially, At least one layer of the one or more organic material layer is an organic light emitting device, characterized in that it comprises a compound represented by the formula (2). [Formula 2]

In the above formula, X ¹ , R ¹ to R ⁶ and Ar ¹ are the same as defined in claim 2. The organic light emitting device of claim 6, wherein the organic material layer including the compound represented by Chemical Formula 2 is an electron transport layer.

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