KR101548686B1 - New material for transporting electron and organic electroluminescent device using the same - Google Patents

Abstract

The present invention relates to a novel electron transport material and an organic light emitting device comprising the same. The present invention provides a novel electron transport material using the electron transport material according to the present invention, There is an advantage that the improved organic light emitting device can be manufactured.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a novel electron transport material and an organic light emitting device using the same. BACKGROUND ART < RTI ID = 0.0 &

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

An organic light emitting device is a device that injects electric charge into an organic film formed between an electron injection electrode (cathode) and a hole injection electrode (anode) to form an electron and a hole. It is possible to form a device on a flexible transparent substrate such as a plastic substrate and to operate at a lower voltage (10 V or less) than a plasma display panel or an inorganic EL display, It is relatively small and has an advantage of excellent color.

The structure of a general organic electroluminescent device includes a substrate, a cathode, a hole injecting layer for receiving holes from the anode, a hole transporting layer for transporting holes, a light emitting layer for emitting light by combining holes and electrons, An electron transport layer, and a cathode. In some cases, a light emitting layer may be formed by doping a small amount of a fluorescent or phosphorescent dye to an electron transporting layer or a hole transporting layer without a separate light emitting layer. In the case of using a polymer, a hole transporting layer, a light emitting layer, and an electron transporting layer Can be performed simultaneously. The organic thin film layers between the two electrodes are formed by a vacuum deposition method, a spin coating method, an ink jet printing method, a roll coating method, or the like, and a separate electron injection layer may be inserted to efficiently inject electrons from the cathode.

Since the interface between the electrode and the organic material is stabilized, or the organic material has a large difference in moving speed between the hole and the electron, if a suitable hole transporting layer and electron transporting layer are used, holes and electrons can be effectively transferred to the light emitting layer. And the electron density are balanced so as to increase the luminous efficiency, the organic light emitting device is fabricated as a multilayer thin film structure.

On the other hand, typical examples of conventional electron transporting materials include aluminum complexes such as Alq3 (tris (8-hydroxyquinoline) aluminum (III)) and Bebq (bis (10-hydroxybenzo- [h] quinolinato) beryllium) and beryllium complexes. However, in the case of using these materials, there is a problem that the color purity is lowered due to the light emission by exciton diffusion when used for a blue light emitting device.

In addition, TPBI (see structure below) disclosed by Kodak in 1996 and disclosed in U.S. Patent No. 5,645,948 is known as a typical electron transport layer material having an imidazole group. Phenylbenzimidazole group and functions not only to block electrons from the luminescent layer but also to lower the stability of the device.

Particularly noteworthy in the conventional electron transporting material is that the driving voltage is merely slightly improved or the driving life of the device is remarkably lowered compared to the contents to be announced. In addition, variations in the lifetime of the devices and deterioration of thermal stability Side effects.

In addition, although the conventional organic light emitting element uses a fluorescent light emitting material, the organic light emitting element is gradually changing to adopt a phosphorescent light emitting material. Therefore, the electron transporting layer material, which is a common material, is also required to have suitable electron mobility, low driving voltage, and hole blocking property suitable for the phosphorescent material.

U.S. Patent No. 5,645,948

SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a novel electron transport material capable of significantly improving luminous efficiency, stability, and lifetime of devices.

It is another object of the present invention to provide an organic light emitting device in which power consumption is improved by inducing an increase in power efficiency by enhancing a driving voltage as well as an emission characteristic using the novel electron transport material.

The present invention relates to an electron transporting material represented by the following formula (1) and an organic light emitting device comprising the same: the electron transporting material according to the present invention is excellent in luminescence characteristics, And thus an organic light emitting device having improved power consumption can be manufactured.

[Chemical Formula 1]

[In the above formula (1)

L is (C1-C20) alkylene or (C2-C20) alkenylene, and the carbon atom of the L alkylene -CH ₂ - may be substituted with a hetero atom selected from N, O and S, the L The carbon atom of the alkenylene = CH- may be replaced by N;

R ₁ to R ₄ are, independently of each other, hydrogen, (C 1 -C 30) alkyl, (C 3 -C 30) cycloalkyl, (C 6 -C 30) aryl or (C 3 -C 30) heteroaryl;

L ₂ and L ₃ independently of one another are a single bond, (C 6 -C 30) arylene or (C 3 -C 30) heteroarylene;

x and y are independently an integer of 1 to 3, and when x is an integer of 2 or more, each L ₂ may be the same or different, and when y is an integer of 2 or more, each L ₃ may be the same or different ;

Ar ₂ and Ar ₃ independently represent hydrogen, (C1-C30) alkyl, (C6-C30) aryl or (C3-C30) heteroaryl;

Wherein R ₁ alkyl of 1 to R _4, cycloalkyl, aryl, heteroaryl, L of the alkylene or alkenylene, L _2, L ₃ of arylene and heteroarylene, Ar _2, alkyl, aryl and heteroaryl of Ar ₃ (C6-C30) alkyl, halo (C1-C30) alkyl, halogen, cyano, (C3- C30) cycloalkyl, (C3-C30) heteroaryl, (C3-C30) alkyl (C1-C30) alkyl substituted by (C3-C30) heteroaryl, mono or di (C1-C30) alkylamino, mono or di (C6-C30) arylamino, tri (C6-C30) arylsilyl, tri (C6-C30) arylsilyl, nitro, and hydroxy;

Wherein said heteroarylene and said heteroaryl comprise at least one heteroatom selected from B, N, O, S, P (= O), Si and P,

Provided that - (L ₂ ) _x -Ar ₂ and - (L ₃ ) _y -Ar ₃ are hydrogen at the same time.

The substituents comprising the "alkyl", "alkoxy" and other "alkyl" moieties described in the present invention include both linear and branched forms, and "cycloalkyl" includes both single ring systems as well as substituted or unsubstituted adamantyl Or a plurality of cyclic hydrocarbons such as substituted or unsubstituted (C7-C30) bicycloalkyl. &Quot; Aryl " in the present invention means an organic radical derived from an aromatic hydrocarbon by one hydrogen elimination and is a single or fused ring containing 4 to 7, preferably 5 or 6 ring atoms, And includes a form in which a plurality of aryls are connected by a single bond. Specific examples include phenyl, naphthyl, biphenyl, terphenyl, anthryl, indenyl, fluorenyl, phenanthryl, triphenylenyl, pyrenyl, perylenyl, . Heteroaryl " as used in the present invention includes 1 to 4 hetero atoms selected from B, N, O, S, P (= O), Si and P as aromatic ring skeletal atoms and the remaining aromatic ring skeletal atoms are carbon An aryl group, a 5- to 6-membered monocyclic heteroaryl, and a polycyclic heteroaryl condensed with one or more benzene rings, and may be partially saturated. The heteroaryl in the present invention also includes a form in which one or more heteroaryl is connected to a single 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 include furyl, thiophenyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl, triazolyl, Monocyclic heteroaryl such as tetrazolyl, furazanyl, pyridyl, pyrazinyl, pyrimidinyl and pyridazinyl, benzofuranyl, benzothiophenyl, isobenzofuranyl, benzoimidazolyl, benzothiazolyl, benzoiso Benzothiazolyl, benzothiazolyl, benzooxazolyl, isoindolyl, indolyl, indazolyl, benzothiadiazolyl, quinolyl, isoquinolyl, cinnolinyl, quinazolinyl, quinoxalinyl, (Such as pyridyl N-oxide, quinolyl N-oxide), polycyclic heteroaryls such as benzyloxycarbonyl, benzyloxycarbonyl, benzyloxycarbonyl, benzyloxycarbonyl, Quaternary salts and the like.

The '(C 1 -C 30) alkyl' group described in the present invention is preferably (C 1 -C 20) alkyl, more preferably (C 1 -C 10) alkyl, and the ' Is (C6-C20) aryl. The '(C3-C30) heteroaryl' group is preferably (C3-C20) heteroaryl. The '(C3-C30) cycloalkyl' group is preferably (C3-C20) cycloalkyl, more preferably (C3-C7) cycloalkyl.

Specifically, the electron transporting material of the present invention can be represented by the following formulas (2) to (4).

(2)

(3)

[Chemical Formula 4]

[In the above formulas 2 to 4,

R ₁ to R ₆ are independently of each other hydrogen, (C 1 -C 30) alkyl, (C 3 -C 30) cycloalkyl, (C 6 -C 30) aryl or (C 3 -C 30) heteroaryl;

L ₂ and L ₃ independently of one another are a single bond, (C 6 -C 30) arylene or (C 3 -C 30) heteroarylene;

x and y are independently an integer of 1 to 3, and when x is an integer of 2 or more, each L ₂ may be the same or different, and when y is an integer of 2 or more, each L ₃ may be the same or different ;

Ar ₂ and Ar ₃ are each independently hydrogen, (C1-C30) alkyl, (C6-C30) aryl or (C3-C30) heteroaryl;

Wherein L _2, and aryl and heteroaryl of L ₃ arylene group and Ar ₂ and Ar ₃ in the (C1-C30) alkyl, (C6-C30) aryl, (C6-C30) aralkyl (C1-C30) alkyl, (C1 (C6-C30) aryl, and (C3-C30) heteroaryl, each of which may optionally be substituted with one or more substituents selected from the group consisting of

Provided that - (L ₂ ) _x -Ar ₂ and - (L ₃ ) _y -Ar ₃ are hydrogen at the same time.

In the electron transporting material of Formula 1, L ₂ and L ₃ independently represent a single bond, phenylene, biphenylene, 9,9-dimethylfluoreneylene, naphthylene, anthrylene, thienylene, Lt; / RTI > or pyrimidinyl;

Ar < _{2 >} and Ar < ₃ > independently from each other are hydrogen or (C1-C30) alkyl or are selected from the following structures;

(C6-C30) aryl, (C3-C30) heteroaryl or (C1-C30) alkyl (C6-C30) alkyl, wherein R ', R "and R'" are independently of each other hydrogen, ) ≪ / RTI >

The alkyl, aryl, heteroaryl and alkylaryl of R ', R "and R'" may be further substituted with (C6-C30) aryl.

The electron transport materials according to the present invention can be exemplified by the following compounds, but are not limited thereto.

Among the electron transport materials according to the present invention, the process for preparing an electron transport material having x and y of 1 in the above formula (1) is illustrated in Scheme 1 below, but the present invention is not limited thereto.

[Reaction Scheme 1]

또는

이며, X₁과 X₂는 동일하지 않다.][Wherein R ₁ to R ₄ , L, L ₂ , L ₃ , Ar ₂ and Ar ₃ are the same as defined in the above formula (2), X ₁ and X ₂ are halogen,

or

And X ₁ and X ₂ are not the same.]

In addition, the present invention provides an organic light emitting device, wherein the organic light emitting device according to the present invention includes a first electrode; A second electrode; And at least one organic material layer interposed between the first electrode and the second electrode, wherein the organic material layer includes an electron transporting layer including the electron transporting material of Formula 1. When the electron transporting material of Formula 1 according to the present invention is used in an electron transporting layer, the driving voltage is increased to increase the power efficiency, thereby improving power consumption.

In addition, the organic material layer may include at least one electron transport layer containing an electron transport material of Formula 1 and at least one light emitting layer comprising a fluorescent host-fluorescent dopant or a phosphorescent host-phosphorescent dopant. The fluorescent host, fluorescent dopant, phosphorescent host or phosphorescent dopant applied to the device is not particularly limited.

The electron transporting material according to the present invention has an advantage of being able to manufacture an organic light emitting device in which power consumption is improved by inducing an increase in power efficiency by enhancing a driving voltage as well as a light emitting property.

FIG. 1 is a graph showing the efficiency (cd / A) - luminance (cd / m 2) of the organic light emitting device manufactured in Examples 8 to 13 and Comparative Example 1.

Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings. In the following, exemplary embodiments of the present invention will be described with reference to the accompanying drawings. And does not intend to limit the scope of protection of the present invention.

[Example 1] Preparation of Compound 1

compound  1-1 Manufacturing

159.06 g (859 mmol) of 4-bromobenzaldehyde and 108 g (817 mmol) of 2,3-dihydroindene-1-one were placed in a 3000 mL three-necked round bottom flask and dissolved in 1728 mL of ethanol. 40.86 g (1021 mmol) of sodium was slowly added thereto, and the mixture was stirred at room temperature for 12 hours. The precipitated solid was separated by filtration under reduced pressure and washed with methanol to obtain 150 g of a pale yellow solid compound (yield: 91%).

_{^{1 H NMR (CDCl 3) δ}} [ppm]: 7.75-7.74 (q, 1H), 7.59-7.52 (m, 5H), 7.48-7.45 (m, 1H), 7.40-7.39 (d, 2H), 1.97 ( s, 2H)

compound  1-2 Manufacturing

Add 3000 mL of pyridine to a 5000 mL 3-neck round bottom flask and slowly add 300 g (1507 mmol) of 4-bromophenacyl bromide while stirring. After stirring at room temperature for 2 hours, the precipitated solid was separated by filtration under reduced pressure and washed with methanol. 150 g (501 mmol) of Compound 1-1 and 77.3 g (1002 mmol) of ammonium acetate were added to 278.92 g (1002 mmol) of the obtained compound, dissolved in 1950 mL of methanol, and refluxed for 12 hours. The precipitated solid was separated by filtration under reduced pressure and washed with methanol to obtain 99.9 g of a white solid compound (yield: 50%).

_{^{1 H NMR (CDCl 3) δ}} [ppm]: 8.00-7.98 (d, 2H), 7.90-7.88 (q, 1H), 7.76 (s, 1H), 7.65-7.64 (d, 2H), 7.54-7.52 ( (d, 2H), 7.47-7.44 (t, 2H), 7.41-7.33 (m, 4H), 3.82

compound  1-3 Manufacturing

99 g (247 mmol) of Compound 1-2 is dissolved in 2970 ml of THF under ice bath conditions, and 58.42 g (520 mmol) of t-butoxide is slowly added to a 5000 ml three-necked round bottom flask. After stirring for 1.5 hours, after confirming TLC, 87.98 g (619 mmol) of iodomethane is added at room temperature. After stirring for 2 hours or more, TLC is confirmed. After completion of the reaction, water is added. Extraction is carried out with saturated aqueous sodium chloride solution and dichloromethane. Dried with magnesium sulfate, treated with activated charcoal, filtered through celite, and concentrated under reduced pressure. The solid obtained after concentration was recrystallized from hexane to obtain 31.7 g (yield: 31%) of a pale yellow solid compound.

_{^{1 H NMR (CDCl 3) δ}} [ppm]: 8.00-7.98 (d, 2H), 7.91-7.90 (q, 1H), 7.70 (s, 1H), 7.65-7.63 (d, 2H), 7.51-7.50 ( (d, 2H), 7.47-7.44 (t, 2H), 7.41-7.32 (m, 4H), 1.65

compound  1-4 Manufacturing

31.7 g (74.4 mmol) of Compound 1-3 is added to a 1000 mL three-necked round bottom flask, 20.77 g (82 mmol) of bis (pinacolato) diboron is added, and 476 mL of 1,4-dioxane is added. (1.5 mmol) of 1,1'-bis [(diphenylphosphino) ferrocene] dichloropalladium (II) and chloromethane complex was added, 14.59 g (148.7 mmol) of potassium acetate was added and the mixture was heated and stirred under reflux . After about 12 hours of reaction, the reaction is cooled to room temperature. Extraction is carried out with a saturated aqueous solution of sodium chloride and ethyl acetate. Dried with magnesium sulfate, treated with activated charcoal, filtered through celite, and concentrated under reduced pressure. The solid obtained after concentration was suspended in hexane, filtered, and washed with hexane to obtain 23.5 g (yield: 73%) of a solid compound.

_{^{1 H NMR (CDCl 3) δ}} [ppm]: 8.00-7.98 (d, 2H), 7.91-7.90 (q, 1H), 7.70 (s, 1H), 7.55-7.53 (d, 2H), 7.47-7.44 ( t, 2H), 7.45-7.43 (d, 2H), 7.41-7.32 (m, 4H), 1.65 (s, 6H), 1.40

compound  1-5 Manufacturing

80 g (311 mmol) of 9-bromophenanthrene is added to a 2000 mL three-necked round bottom flask, 86.91 g (342 mmol) of bis (pinacolato) diboron are added and then 1,200 mL of 1,4-dioxane is added. Dichloropalladium (II) and 5.08 g (6.2 mmol) of a chloromethane complex were added, 61.07 g (662.2 mmol) of potassium acetate was added, and the mixture was heated and stirred while refluxing . After about 12 hours of reaction, the reaction is cooled to room temperature. Extraction is carried out with a saturated aqueous solution of sodium chloride and ethyl acetate. Dried with magnesium sulfate, treated with activated charcoal, filtered through celite, and concentrated under reduced pressure. The solid obtained after concentration was suspended in hexane, followed by filtration and washing with hexane to obtain 68.9 g of a solid compound (yield = 73%).

¹ H NMR (CDCl ₃ )? 8.89 (d, IH), 8.86 (d, IH), 8.11-7.78 (m, 7H)

compound  1-6 Manufacturing

31.5 g (104.5 mmol) of Compound 1-5 and 17.3 g (106.1 mmol) of 2,4-dichloro-6-methylpyrimidine are placed in a 1000 mL three-necked round bottom flask and 636 mL of tetrahydrofuran (THF) is added. 2.46 g (2.1 mmol) of tetrakis (triphenylphosphine) palladium (0) was added, 318 ml of 2M potassium carbonate aqueous solution was added, and the mixture was heated to reflux. After about 18 hours of reaction, the reaction is cooled to room temperature. Extraction is carried out with a saturated aqueous solution of sodium chloride and ethyl acetate. Dried with magnesium sulfate, treated with activated charcoal, filtered through celite, and concentrated under reduced pressure. The solid obtained after concentration was completely dissolved with acetone and then recrystallized to obtain 9.8 g (Yield = 31%) of a solid compound.

_{^{1 H NMR (CDCl 3) δ}} 8.73-8.70 (m, 2H), 8.14 (s, 1H), 8.04-8.02 (d, 2H), 7.76-7.66 (m, 4H), 7.24 (s, 1H), 2.59 (s, 3 H)

Preparation of Compound (1)

9.8 g (32.2 mmol) of the compound 1-6 and 18.27 g (38.6 mmol) of the compound 1-4 are placed in a 500 mL three-necked round bottom flask, and 196 mL of tetrahydrofuran (THF) is added. 0.37 g (0.32 mmol) of tetrakis (triphenylphosphine) palladium (0) was added thereto, 98 ml of a 1M potassium carbonate aqueous solution was added, and the mixture was heated to reflux. After about 18 hours of reaction, the reaction is cooled to room temperature. Extraction is carried out with a saturated aqueous solution of sodium chloride and ethyl acetate. Dried with magnesium sulfate, treated with activated charcoal, filtered through celite, and concentrated under reduced pressure. The solid obtained after concentration was recrystallized to obtain 14 g (yield = 71%) of Compound 1. [

_{^{1 H NMR (CDCl 3) δ}} 8.84-8.81 (t, 2H), 8.34 (s, 1H), 8.15-8.12 (t, 2H), 8.01-7.99 (d, 2H), 7.92-7.88 (m, 3H) , 7.85-7.75 (m, 7H), 7.47-7.44 (t, 2H), 7.42-7.34 (m, 4H), 7.23 (s,

[Example 2] Preparation of Compound 2

compound  2-1 Manufacturing

50 g (164.3 mmol) of Compound 1-5 and 15.07 g (82.18 mmol) of 2,4-dichloro-6-methylpyrimidine are placed in a 2000 mL three-necked round bottom flask and 1000 mL of tetrahydrofuran (THF) is added. 1.90 g (1.6 mmol) of tetrakis (triphenylphosphine) palladium (0) was added, and 50 ml of a 2M potassium carbonate aqueous solution was added and the mixture was heated to reflux. After about 18 hours of reaction, the reaction is cooled to room temperature. The reaction was filtered and the filtered white solid washed with distilled water. The washed solid was suspended in ethyl acetate while heating, followed by filtration to obtain Compound 14-1 (25 g, yield 68%).

_{^{1 H NMR (DMSO-d 6}} ) δ [ppm]: 9.01 (d, 2H) 8.95 (d, 2H) 8.43 (d, 2H) 8.34

(d, 2H) 8.15 (d, 2H) 7.84-7.77 (m, 9H)

Preparation of Compound 2

Into a 500 mL three-necked round bottom flask, 15 g (10.56 mmol) of compound 1-4 and 4.93 g (10.56 mmol) of compound 2-1 are added and 300 mL of tetrahydrofuran (THF) is added. 0.24 g (0.21 mmol) of tetrakis (triphenylphosphine) palladium (0) was added, 15 ml of a 2M potassium carbonate aqueous solution was added, and the mixture was heated to reflux. After about 18 hours of reaction, the reaction is cooled to room temperature. It is extracted with saturated aqueous sodium chloride solution and methylene chloride (MC). Dried with magnesium sulfate, treated with activated charcoal, filtered through celite, and concentrated under reduced pressure. The solid obtained after concentration was recrystallized to obtain 6.08 g of Compound 2 (yield = 74%).

_{^{1 H NMR (CDCl 3) δ}} 8.95-8.94 (d, 2H), 8.88-8.87 (d, 2H), 8.69-8.67 (d, 1H), 8.61-8.59 (d, 1H), 8.49-8.46 (t, 2H), 8.00-7.98 (d, 2H), 7.97-7.95 (q, 1H), 7.86-8.03 (d, 2H) 1H), 7.84 (t, 2H), 7.81-7.78 (m, 6H), 7.73 (s, 1H), 7.48-7.45 s, 6H)

[Example 3] Preparation of Compound 53

compound  53-1 Manufacturing

35 g (326 mmol) of picoline aldehyde and 43.19 g (327 mmol) of 1-indanone were added to a 500 mL three-neck round bottom flask and dissolved in 350 mL of ethanol. 16.34 g (408 mmol) of sodium hydroxide was slowly added at 0 ° C. Lt; / RTI > for 12 hours. The precipitated solid was separated by filtration under reduced pressure and washed with ethanol to obtain 72 g of a pale yellow solid (yield: 94%).

_{^{1 H-NMR (CDCl 3)}} δ [ppm]: 8.54-8.52 (d, 1H), 8.00 (s, 1H), 7.74-7.73 (d, 1H), 7.58-7.54 (m, 3H), 7.47-7.39 (t, IH), 7.41-7.39 (d, IH), 7.25-7.22 (t, IH), 3.36

compound  53-2 Manufacturing

Add 500 mL of pyridine to a 1000 mL 3-neck round bottom flask and slowly add 50 g (179 mmol) of 4-bromophenacyl bromide while stirring. After stirring at room temperature for 2 hours, the precipitated solid was separated by filtration under reduced pressure and washed with methanol. The obtained compound (62.6 g, 175 mmol), compound (53-1) (19.4 g, 88 mmol) and ammonium acetate (27.03 g, 351 mmol) were dissolved in methanol (350 mL) and refluxed for 12 hours. The precipitated solid was separated by filtration under reduced pressure and washed with methanol to obtain 19 g of a white solid compound (yield: 50%).

¹ H-NMR (CDCl ₃ )? [Ppm]: 8.74-8.72 (d, 1H), 8.05 (s, 1H), 7.90-7.78 (m, 4H), 7.78-7.63 (d, 2H), 7.49-7.46 (t, IH), 7.41-7.35 (m, 3H), 3.99

compound  53-3 Manufacturing

17 g (43 mmol) of the compound 53-2 and 19.33 g (85 mmol) of 2,3-dichloro-5,6-dicyanobenzoquinone were placed in a 500 mL three-necked round bottom flask. To 200 mL of 1,2- After dissolving, the mixture was refluxed at 120 ° C for 12 hours. After cooling, the mixture was extracted with water and methylene chloride, and the residue was separated by silica gel column (hexane: methylene chloride = 1: 1) to obtain 8.6 g (yield: 47%) of a pale yellow solid.

_{^{1 H-NMR (CDCl 3)}} δ [ppm]: 8.78-8.76 (d, 1H), 7.95-7.84 (m, 5H), 7.71-7.69 (d, 1H), 7.65-7.63 (d, 2H), 7.49 -7.46 (t, 1 H), 7.41-7.35 (m, 3 H), 1.66 (s, 6 H)

Preparation of Compound 53

To a 2000 mL three-necked round bottom flask was added 28.79 g (177 mmol) of flowcene 3-boronic acid, 50 g (177 mmol) of compound 53-3 and 0.14 g (0.01 mmol) of tetrakis- (triphenylphosphine) Was dissolved in 1000 mL of tetrahydrofuran, 500 g (1 M) of potassium carbonate was dissolved in distilled water, added to the reactor, refluxed for 8 hours, layered on ethyl acetate, and then filtered through magnesium sulfate. The solvent was concentrated. The residue was dissolved in toluene and subjected to hexane treatment to obtain 34 g (yield: 54%) of a pale yellow solid compound.

_{^{1 H-NMR (CDCl 3)}} δ [ppm]: 8.77-8.75 (d, 1H), 8.43 (s, 1H), 8.22-8.21 (d, 1H), 8.14-8.10 (m, 2H), 8.03-8.01 (d, 1H), 7.99-7.97 (m, 1H), 7.93-7.90 (m, 2H), 7.78-7.62 (m, 7H), 7.50-7.35

[Example 4] Preparation of Compound 57

compound  57-1 Manufacturing

60 g (0.5602 mol) of picoline aldehyde and 85.59 g (0.5882 mol) of 1-tetralone were added to a 1000 mL 3-neck round bottom flask and dissolved in 600 mL of ethanol. Then, 42.05 g (0.7002 mol) of sodium hydroxide was slowly added at 0 ° C. Lt; / RTI > for 12 hours. The precipitated solid was separated by filtration under reduced pressure and washed with methanol to obtain 108 g of a pale yellow solid (yield: 82%).

_{^{1 H NMR (CDCl 3) δ}} [ppm]: 8.57-8.56 (d, 1H), 8.05 (s, 1H), 7.83-7.81 (d, 1H), 7.64-7.61 (t, 1H), 7.55-7.53 ( (t, 2H), 7.29-7.25 (t, 1H), 3.08-3.03 (m, 4H)

compound  57-2 Manufacturing

Add 1050 mL of pyridine to a 2000 mL 3-neck round bottom flask and slowly add 105 g (0.3778 mol) of 4-bromophenacyl bromide while stirring. After stirring at room temperature for 2 hours, the precipitated solid was separated by filtration under reduced pressure and washed with methanol. 94.9 g (0.2633 mol) of compound 113-1 and 40.59 g (0.5266 mol) of ammonium acetate were added to 123.9 g (0.5266 mol) of the obtained compound, and the mixture was refluxed for 12 hours. The precipitated solid was separated by filtration under reduced pressure and washed with methanol to obtain 46.8 g of a white solid compound (yield: 43%).

_{^{1 H NMR (CDCl 3) δ}} [ppm]: 8.72-8.71 (d, 1H), 7.94-7.90 (m, 2H), 7.85-7.81 (m, 3H), 7.76-7.74 (d, 1H), 7.60- 2H), 7.48-7.45 (t, 1H), 7.31-7.25 (m, 3H), 3.29-3.27 (t,

Preparation of Compound 57

To a 1000 mL three necked round bottom flask was added 20 g (0.0484 mol) of compound 57-2, 12.50 g (0.0508 mol) of fluoransen-3-yl boronic acid and 0.56 g (0.0005 mol) of tetrakis- (triphenylphosphine) palladium ), 145 ml of 2M potassium carbonate aqueous solution and 400 ml of THF are added, and the mixture is heated to reflux. After about 18 hours of reaction, the reaction is cooled to room temperature. The mixture is extracted with saturated aqueous sodium chloride solution and dichloromethane, dried over magnesium sulfate and concentrated under reduced pressure. The solid was separated by silica gel column (Hexane: M.C = 5: 1), concentrated, and washed with hexane to obtain a white solid compound 57 (19.66 g, yield: 76%).

¹ H NMR (CDCl ₃ )? [Ppm]: 8.78-8.76 (d, 1H), 8.23-8.18 (q, 3H), 8.12-8.11 2H), 7.50-7.47 (t, 1H), 7.90-7.67 (m, 2H) ), 7.45-7.43 (q, 2H), 7.38-7.3 (m, 3H), 3.22-3.20 (t, 2H), 3.09-3.07

[Example 5] Preparation of Compound 70

compound  70-1 Manufacturing

35 g (239 mmol) of 2-naphthaldehyde and 39.2 g (251 mmol) of 1-tetralone were added to a 500 mL three-neck round bottom flask and dissolved in 200 mL of ethanol. Then, 11.9 g (299 mmol) of sodium hydroxide And the mixture was stirred at room temperature for 12 hours. After cooling, the precipitated solid was separated by filtration under reduced pressure and washed with methanol to obtain 64 g of a pale yellow solid (yield: 94%).

_{^{1 H NMR (CDCl 3) δ}} [ppm]: 2.78 (t, 2H), 3.07 (t, 2H), 7.33-7.36 (m, 2H), 7.41-7.44 (m, 2H), 7.46-7.47 (d, 1H), 7.50-7.53 (m, IH), 7.62 (s, IH), 7.68

compound  70-2 Manufacturing

Add 500 mL of pyridine to a 1000 mL 3-neck round bottom flask and slowly add 50 g (179 mmol) of 4-bromophenacyl bromide while stirring. After stirring at room temperature for 2 hours, the precipitated solid was separated by filtration under reduced pressure and washed with methanol. The obtained compound (62.7 g, 175 mmol), compound 58-1 (25 g, 87.9 mmol) and ammonium acetate (13.5 g, 175 mmol) were dissolved in methanol (350 mL) and refluxed for 12 hours. After cooling, the precipitated solid was separated by filtration under reduced pressure and washed with methanol to obtain 17 g of a white solid compound (yield: 50%).

_{^{1 H NMR (CDCl 3) δ}} [ppm]: 2.86 (t, 2H), 3.03 (t, 2H), 7.26-7.31 (m, 3H), 7.40-7.44 (m, 2H), 7.58 (d, 2H) , 7.73-7.84 (m, 7H), 7.92-7.94 (d, IH), 8.04 (s, IH)

compound  70-3 Manufacturing

17 g (36.8 mmol) of the compound 58-2 and 16.6 g (8346 mmol) of 2,3-dichloro-5,6-dicyanobenzoquinone were placed in a 500 mL three-necked round bottom flask. To 200 mL of 1,2- After dissolving, the mixture was refluxed at 120 ° C for 12 hours. The reaction mixture was cooled, extracted with water and methylene chloride, and then subjected to silica gel column chromatography (hexane: methylene chloride = 1: 1) to obtain 7.96 g of a pale yellow solid compound (yield: 47%).

_{^{1 H NMR (CDCl 3) δ}} [ppm]: 7.43-7.49 (m, 2H), 7.53-7.56 (m, 2H), 7.63-7.67 (m, 3H), 7.73 (s, 1H), 7.80-7.83 ( 1H), 8.28 (s, 1H), 7.85-7.89 (m, 2H), 7.91-7.94

Preparation of Compound 70

(77.2 mmol) of 2-phenylbenzimidazole, 42.6 g (92.7 mmol) of compound 58-3 and 0.9 g (0.77 mmol) of tetrakis- (triphenylphosphine) palladium were placed in a 500 mL three- , And N-dimethylformamide (150 mL), refluxed for 3 hours, extracted with methylene chloride, and then concentrated. The residue was washed with hexane and ethyl acetate to obtain 32.3 g (yield: 73%) of a pale yellow solid compound.

¹ H NMR (CDCl ₃ )? [Ppm]: 7.31-7.39 (m, 3H), 7.43-7.47 (m, 4H), 7.52-7.54 (m, 2H), 7.63-7.68 (M, 2H), 7.85 (s, 1H), 7.89-7.92 (m, 4H), 8.01 (d, 1H), 8.08 (d, 1H), 8.33-8.35 2H)

[Example 6] Preparation of Compound 125

compound  125-1 Manufacturing

60 g (0.5602 mol) of picoline aldehyde and 85.59 g (0.5882 mol) of 1-tetralone were added to a 1000 mL 3-neck round bottom flask and dissolved in 600 mL of ethanol. Then, 42.05 g (0.7002 mol) of sodium hydroxide was slowly added at 0 ° C. Lt; / RTI > for 12 hours. The precipitated solid was separated by filtration under reduced pressure and washed with methanol to obtain 108 g of a pale yellow solid (yield: 82%).

_{^{1 H NMR (CDCl 3) δ}} [ppm]: 8.57-8.56 (d, 1H), 8.05 (s, 1H), 7.83-7.81 (d, 1H), 7.64-7.61 (t, 1H), 7.55-7.53 ( (t, 2H), 7.29-7.25 (t, 1H), 3.08-3.03 (m, 4H)

compound  125-2 Manufacturing

Add 1050 mL of pyridine to a 2000 mL 3-neck round bottom flask and slowly add 105 g (0.3778 mol) of 4-bromophenacyl bromide while stirring. After stirring at room temperature for 2 hours, the precipitated solid was separated by filtration under reduced pressure and washed with methanol. 94.9 g (0.2633 mol) of compound 113-1 and 40.59 g (0.5266 mol) of ammonium acetate were added to 123.9 g (0.5266 mol) of the obtained compound, and the mixture was refluxed for 12 hours. The precipitated solid was separated by filtration under reduced pressure and washed with methanol to obtain 46.8 g of a white solid compound (yield: 43%).

_{^{1 H NMR (CDCl 3) δ}} [ppm]: 8.72-8.71 (d, 1H), 7.94-7.90 (m, 2H), 7.85-7.81 (m, 3H), 7.76-7.74 (d, 1H), 7.60- 2H), 7.48-7.45 (t, 1H), 7.31-7.25 (m, 3H), 3.29-3.27 (t,

compound  125-3 Manufacturing

45 g (0.1089 mol) of the compound 113-2 and 49.43 g (0.2178 mol) of 2,3-dichloro-5,6-dicyanobenzoquinone were placed in a 500 mL three-necked round bottom flask and 450 mL of 1,2- After dissolving, the mixture was refluxed at 120 ° C for 12 hours. After cooling, the reaction mixture was extracted with water and methylene chloride, and then subjected to silica gel column chromatography (hexane: methylene chloride = 1: 1) to obtain 21.49 g of a pale yellow solid compound (yield: 48%).

_{^{1 H NMR (CDCl 3) δ}} [ppm]: 8.75-8.74 (d, 1H), 8.19-8.18 (d, 2H), 7.95-7.92 (t, 2H), 7.88-7.84 (t, 2H), 7.79- 2H), 7.37-7.30 (m, 3H), 7.57 (d, IH)

Preparation of Compound 125

To a 1000 mL three necked round bottom flask was added 20 g (0.0486 mol) of compound 113-3, 12.56 g (0.0511 mol) of fluoransen-3-yl boronic acid and 1.124 g (0.001 mol) of tetrakis- (triphenylphosphine) palladium ), 145 ml of 2M potassium carbonate aqueous solution and 400 ml of THF are added, and the mixture is heated to reflux. After about 18 hours of reaction, the reaction is cooled to room temperature. The mixture is extracted with saturated aqueous sodium chloride solution and dichloromethane, dried over magnesium sulfate and concentrated under reduced pressure. The solid was separated by silica gel column (Hexane: M = 4: 1), concentrated and washed with hexane to obtain a white solid compound 113 (18.1 g, yield: 70%).

_{^{1 H NMR (CDCl 3) δ}} [ppm]: 8.81-8.79 (d, 1H), 8.53-8.52 (t, 1H), 8.23-8.22 (d, 1H), 8.18 (s, 1H), 8.15-8.12 ( (m, 3H), 8.03-8.01 (m, IH), 7.95-7.92 (t, IH), 7.89-7.88 (d, IH), 7.83-7.63 (m, 9H), 7.52-7.49 7.48-7.43 (m, 4H)

[Example 7] Preparation of Compound 139

compound  151-1 Manufacturing

Add 1050 mL of pyridine to a 2000 mL 3-neck round bottom flask and slowly add 105 g (0.3778 mol) of 3-bromophenacyl bromide while stirring. After stirring at room temperature for 2 hours, the precipitated solid was separated by filtration under reduced pressure and washed with methanol. 94.9 g (0.2633 mol) of compound 113-1 and 40.59 g (0.5266 mol) of ammonium acetate were added to 123.9 g (0.5266 mol) of the obtained compound, and the mixture was refluxed for 12 hours. The precipitated solid was separated by filtration under reduced pressure and washed with methanol to obtain 45.7 g (yield: 42%) of a white solid compound.

_{^{1 H NMR (CDCl 3) δ}} [ppm]: 8.72-8.71 (d, 1H), 8.17 (s, 1H), 7.95- 7.90 (m, 3H), 7.83-7.81 (q, 1H), 7.76-7.74 ( 2H), 2.97-2.94 (t, 2H), 7.30-7.30 (m, 4H)

compound  151-2 Manufacturing

40 g (0.0968 mol) of the compound 139-1 and 46.14 g (0.2032 mol) of 2,3-dichloro-5,6-dicyanobenzoquinone were placed in a 1000 mL three-necked round bottom flask and dissolved in 400 mL of 1,2- And then refluxed at 120 ° C for 12 hours. After cooling, the reaction mixture was concentrated, and the residue was purified by silica gel column chromatography (hexane: methylene chloride = 1: 1) to obtain 20.59 g of a pale yellow solid compound (yield: 46%).

_{^{1 H NMR (CDCl 3) δ}} [ppm]: 8.75-8.74 (d, 1H), 8.19-8.18 (s, 2H), 7.95-7.92 (t, 2H), 7.88-7.84 (m, 2H), 7.79- 2H), 7.37-7.30 (m, 3H), 7.77-7.67 (m, 1H)

compound  151-3 Manufacturing

40 g (87.26 mmol) of the compound 139-2 is added to a 2000 mL three-necked round bottom flask, 24.37 g (95.99 mmol) of bis (pinacolato) diboron are added, and then 800 mL of 1,4-dioxane is added. (1.74 mmol) of 1,1'-bis [(diphenylphosphino) ferrocene] dichloropalladium (II) and chloromethane complex, 17.1 g (174.52 mmol) of potassium acetate was added and the mixture was heated and stirred under reflux . After about 12 hours of reaction, the reaction is cooled to room temperature. Extraction is carried out with a saturated aqueous solution of sodium chloride and ethyl acetate. Dried with magnesium sulfate, treated with activated charcoal, filtered through celite, and concentrated under reduced pressure. The solid obtained after concentration was suspended in hexane, followed by filtration and washing with hexane to obtain 30.8 g of a solid compound (yield = 77%).

_{^{1 H NMR (CDCl 3) δ}} 8.75-8.74 (d, 1H), 8.20 (s, 1H), 8.18 (s, 1H), 7.95-7.92 (t, 2H), 7.88-7.84 (m, 2H), 7.79 (D, 1H), 7.50-7.47 (t, 1H), 7.37-7.30 (m, 1H), 7.57-7.57 3H), 1.24 (s, 12H)

Preparation of Compound 151

20 g (43.63 mol) of compound 139-3, 10.46 g (43.63 mol) of 4-chloro-2-phenylquinoline and 1.01 g (0.87 mmol) of tetrakis- (triphenylphosphine) palladium were added to a 1000 mL three- 20 ml of 2M potassium carbonate aqueous solution and 400 ml of THF are added, and the mixture is heated to reflux. After about 15 hours of reaction, the reaction is cooled to room temperature. The mixture is extracted with saturated aqueous sodium chloride solution and dichloromethane, dried over magnesium sulfate and concentrated under reduced pressure. The solid was separated by silica gel column (Hexane: M.C = 4: 1), concentrated and washed with hexane to obtain a white solid compound 113 (18.46 g, yield: 79%).

¹ H NMR (CDCl ₃ )? [Ppm]: 8.88-8.78 (d, IH), 8.50 (s, IH), 8.21-8.19 (d, 2H), 8.13-8.11 (m, 3H), 7.96-7.93 (t, IH), 7.89-7.88 (d, IH), 7.82-7.76 (m, 5H), 7.72-7.70 7.59-7.56 (t, 1H), 7.52-7.38 (m, 7H)

[Example 8] Fabrication of organic light emitting device using Compound 1 according to Example 1 of the present invention A transparent electrode line of ITO (indium tin oxide) having a thickness of 150 nm and a thickness of 25 mm x 25 mm x 0.7 mm The glass substrate was ultrasonically cleaned in distilled water containing detergent for 10 minutes and washed once in distilled water for 10 minutes. After the distilled water was cleaned, the substrate was ultrasonically cleaned by using a solvent of isopropyl alcohol, acetone, and methanol for 10 minutes sequentially and dried. Subsequently, the substrate was dry-cleaned with oxygen / argon plasma, and then a glass substrate having a transparent electrode line was mounted on a substrate holder of a vacuum evaporation apparatus. On the surface where the transparent electrode line was formed, a film thickness of 60 nm of IDE-406 (the following structure, I company) film was formed as a hole injecting layer. Next, H-1 (tetrakis-N-biphenyl-4-yl-benzidine, hereinafter referred to as H-1 film) with a film thickness of 30 nm was formed as a hole transporting layer on the film of IDE-406. Next, BD-1 having the following structure as a dopant was deposited on the H-1 film at a weight ratio of 5% to β-ADN (9,10-di (naphthalene-2-yl) anthracene) Emitting layer of 20 nm in thickness.

Compound 1 of Example 1 of the present invention was deposited on the light emitting layer to form an electron transport layer having a thickness of 20 nm. Liq (lithium quinolate) was then deposited thereon to form an electron injection layer. Metal aluminum was deposited on the Liq film to form a metal cathode, thereby fabricating an organic light emitting device.

[Example 9] Fabrication of organic light emitting device using compound 2 according to the present invention

An organic light emitting device was fabricated in the same manner as in Example 7, except that the compound 2 of Example 2 was used instead of the compound 1 as the electron transporting layer material in Example 8.

[Example 10] Fabrication of organic light emitting device using compound 53 according to the present invention

An organic light emitting device was fabricated in the same manner as in Example 7, except that the compound 53 of Example 3 was used instead of the compound 1 as the electron transporting layer material in Example 8.

[Example 11] Fabrication of organic light emitting device using compound 70 according to the present invention

An organic light emitting device was fabricated in the same manner as in Example 7, except that the compound 70 of Example 4 was used instead of the compound 1 as the electron transporting layer material in Example 8.

[Example 12] Fabrication of organic light emitting device using compound 125 according to the present invention

An organic light emitting device was fabricated in the same manner as in Example 7, except that the compound 125 of Example 5 was used instead of the compound 1 as the electron transporting layer material in Example 8.

[Example 13] Fabrication of organic light emitting device using compound 151 according to the present invention

An organic light emitting device was fabricated in the same manner as in Example 7, except that the compound 151 of Example 6 was used instead of the compound 1 as the electron transport layer material in Example 8.

[Comparative Example 1] Production of organic light emitting device using compound ETM-1

An organic light emitting device was fabricated in the same manner as in Example 7, except that Compound ETM-1 having the following structure was used instead of Compound 1 as the electron transporting layer material in Example 7.

The electroluminescent characteristics and basic physical properties of the organic luminescent devices fabricated in Examples 8 to 13 and Comparative Example 1 are shown in Table 1 below. The organic luminescent characteristics of the organic luminescent devices manufactured in Examples 8 to 13 and Comparative Example 1 are shown in Table 1, (Cd / m < 2 >) relative to the efficiency (cd / A) of the device.

[Table 1]

As shown in Table 1, it was confirmed that the luminescent characteristics of the material developed in the present invention exhibited superior characteristics to those of the conventional materials. In addition, the organic light emitting device using the heteroaromatic compound according to the present invention as an electron transport layer not only excels in luminescence characteristics but also enhances the driving voltage, thereby increasing power efficiency and improving power consumption.

Claims (6)

delete delete delete Lt; RTI ID = 0.0 > of: < / RTI >

An organic light emitting device comprising an electron transporting material according to claim 4. 6. The method of claim 5,
The organic light emitting device includes a first electrode; A second electrode; And at least one organic material layer interposed between the first electrode and the second electrode, wherein the organic material layer includes an electron transporting layer containing the electron transporting material.

Images