KR20180076357A - Novel hetero-cyclic compound and organic light emitting device comprising the same - Google Patents

Abstract

Provided are a novel hetero-cyclic compound and an organic light emitting device comprising the same. The hetero-cyclic compound is represented by chemical formula 1. The hetero-cyclic compound can be used as a material for an organic material layer of an organic light emitting device, for improving the efficiency, the low driving voltage and/or the lifetime characteristics in the organic light emitting device.

Description

[0001] The present invention relates to novel heterocyclic compounds and organic light emitting devices using the same. More particularly,

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

In general, organic light emission phenomenon refers to a phenomenon in which an organic material is used to convert electric energy into light energy. The organic light emitting device using the organic light emitting phenomenon has a wide viewing angle, excellent contrast, fast response time, excellent characteristics of luminance, driving voltage and response speed, and much research has been conducted.

The organic light emitting device generally has a structure including an anode and a cathode, and an organic layer between the anode and the cathode. The organic material layer may have a multilayer structure composed of different materials in order to improve the efficiency and stability of the organic light emitting device. For example, the organic material layer may include a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer. When a voltage is applied between the two electrodes in the structure of such an organic light emitting device, holes are injected in the anode, electrons are injected into the organic layer in the cathode, excitons are formed when injected holes and electrons meet, When it falls back to the ground state, the light comes out.

There is a continuing need for the development of new materials for the organic materials used in such organic light emitting devices.

Korean Patent Publication No. 10-2000-0051826

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

The present invention provides a compound represented by the following formula (1).

[Chemical Formula 1]

In Formula 1,

X ₁ , X ₂ and X ₃ are each independently N or CH,

Y ₁ and Y ₂ are each independently _{O, S, C (R 1} ) (R 2), Si (R 1) (R 2), or N (Ar _3),

L ₁ and L ₂ are each independently a bond; Substituted or unsubstituted C _6-60 arylene; Or C _2-60 heteroarylene containing at least one of substituted or unsubstituted O, N, Si and S,

Ar ₁ , Ar ₂ and Ar ₃ are each independently substituted or unsubstituted C _6-60 aryl; Or substituted or unsubstituted C _2-60 heteroaryl comprising at least one of O, N, Si and S,

R ₁ and R ₂ are each independently substituted or unsubstituted C _1-60 alkyl.

The present invention also provides a plasma display panel comprising: a first electrode; A second electrode facing the first electrode; And at least one organic layer disposed between the first electrode and the second electrode, wherein at least one of the organic layers includes a compound represented by Formula 1 do.

The compound represented by the general formula (1) can be used as a material of an organic material layer of an organic light emitting device and can improve the efficiency, the driving voltage and / or the lifetime of the organic light emitting device. In particular, the compound represented by Formula 1 can be used as a hole injecting, hole transporting, hole injecting and transporting, light emitting, electron transporting, or electron injecting material.

Fig. 1 shows an example of an organic light-emitting device comprising a substrate 1, an anode 2, a light-emitting layer 3 and a cathode 4. Fig.
2 shows an example of an organic light emitting element comprising a substrate 1, an anode 2, a hole injecting layer 5, a hole transporting layer 6, a light emitting layer 7, an electron transporting layer 8 and a cathode 4 It is.

Hereinafter, the present invention will be described in detail in order to facilitate understanding of the present invention.

는 다른 치환기에 연결되는 결합을 의미한다. In the present specification,

Quot; means a bond connected to another substituent.

As used herein, the term " substituted or unsubstituted " A halogen group; A nitrile group; A nitro group; A hydroxy group; A carbonyl group; An ester group; Imide; An amino group; Phosphine oxide groups; An alkoxy group; An aryloxy group; An alkyloxy group; Arylthioxy group; An alkylsulfoxy group; Arylsulfoxy group; Silyl group; Boron group; An alkyl group; Cycloalkyl groups; An alkenyl group; An aryl group; Aralkyl groups; An aralkenyl group; An alkylaryl group; An alkylamine group; An aralkylamine group; A heteroarylamine group; An arylamine group; Arylphosphine groups; Or a heterocyclic group containing at least one of N, O and S atoms, or a substituted or unsubstituted group in which at least two of the above-exemplified substituents are connected to each other . For example, the "substituent group to which two or more substituents are connected" may be a biphenyl group. That is, the biphenyl group may be an aryl group, and may be interpreted as a substituent in which two phenyl groups are connected.

In the present specification, the carbon number of the carbonyl group is not particularly limited, but it is preferably 1 to 40 carbon atoms. Specifically, it may be a compound having the following structure, but is not limited thereto.

In the present specification, the ester group may be substituted with a straight-chain, branched or cyclic alkyl group having 1 to 25 carbon atoms or an aryl group having 6 to 25 carbon atoms in the ester group. Specifically, it may be a compound of the following structural formula, but is not limited thereto.

In the present specification, the number of carbon atoms of the imide group is not particularly limited, but is preferably 1 to 25 carbon atoms. Specifically, it may be a compound having the following structure, but is not limited thereto.

In the present specification, the silyl group specifically includes a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group, a vinyldimethylsilyl group, a propyldimethylsilyl group, a triphenylsilyl group, a diphenylsilyl group, But are not limited thereto.

In the present specification, the boron group specifically includes, but is not limited to, a trimethylboron group, a triethylboron group, a t-butyldimethylboron group, a triphenylboron group, and a phenylboron group.

In the present specification, examples of the halogen group include fluorine, chlorine, bromine or iodine.

In the present specification, the alkyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 40. According to one embodiment, the alkyl group has 1 to 20 carbon atoms. According to another embodiment, the alkyl group has 1 to 10 carbon atoms. According to another embodiment, the alkyl group has 1 to 6 carbon atoms. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a tert-butyl group, But are not limited to, pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, , n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, But are not limited to, dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl and 5-methylhexyl.

In the present specification, the alkenyl group may be straight-chain or branched, and the number of carbon atoms is not particularly limited, but is preferably 2 to 40. According to one embodiment, the alkenyl group has 2 to 20 carbon atoms. According to another embodiment, the alkenyl group has 2 to 10 carbon atoms. According to another embodiment, the alkenyl group has 2 to 6 carbon atoms. Specific examples include vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, Butenyl, allyl, 1-phenylvinyl-1-yl, 2-phenylvinyl-1-yl, (Diphenyl-1-yl) vinyl-1-yl, stilbenyl, stilenyl, and the like.

In the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 60 carbon atoms. According to one embodiment, the cycloalkyl group has 3 to 30 carbon atoms. According to another embodiment, the cycloalkyl group has 3 to 20 carbon atoms. According to another embodiment, the cycloalkyl group has 3 to 6 carbon atoms. Specific examples include cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3- 4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, and the like, but are not limited thereto.

In the present specification, the aryl group is not particularly limited, but preferably has 6 to 60 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. According to one embodiment, the aryl group has 6 to 30 carbon atoms. According to one embodiment, the aryl group has 6 to 20 carbon atoms. The aryl group may be a phenyl group, a biphenyl group, a terphenyl group or the like as the monocyclic aryl group, but is not limited thereto. Examples of the polycyclic aryl group include, but are not limited to, a naphthyl group, an anthracenyl group, a phenanthryl group, a pyrenyl group, a perylenyl group, a klycenyl group and a fluorenyl group.

등이 될 수 있다. 다만, 이에 한정되는 것은 아니다.In the present specification, a fluorenyl group may be substituted, and two substituents may be bonded to each other to form a spiro structure. When the fluorenyl group is substituted,

And the like. However, the present invention is not limited thereto.

In the present specification, the heterocyclic group is a hetero ring group containing at least one of O, N, Si and S as a hetero atom, and the number of carbon atoms is not particularly limited, but is preferably 2 to 60 carbon atoms. Examples of the heterocyclic group include a thiophene group, a furane group, a furyl group, an imidazole group, a thiazole group, an oxazole group, an oxadiazole group, a triazole group, a pyridyl group, a bipyridyl group, a pyrimidyl group, A pyridazinyl group, a pyrazinopyrazinyl group, an isoquinoline group, a pyrazinyl group, a pyrazinyl group, a pyrazinyl group, a pyrazinyl group, a quinolinyl group, a quinazolinyl group, a quinoxalinyl group, a phthalazinyl group, a pyridopyrimidinyl group, , An indole group, a carbazole group, a benzoxazole group, a benzoimidazole group, a benzothiazole group, a benzocarbazole group, a benzothiophene group, a dibenzothiophene group, a benzofuranyl group, a phenanthroline, An isoxazolyl group, an oxadiazolyl group, a thiadiazolyl group, a benzothiazolyl group, a phenothiazinyl group, and a dibenzofuranyl group, but is not limited thereto.

In the present specification, the aryl group in the aralkyl group, the aralkenyl group, the alkylaryl group and the arylamine group is the same as the aforementioned aryl group. In the present specification, the alkyl group in the aralkyl group, the alkylaryl group, and the alkylamine group is the same as the alkyl group described above. In the present specification, the heteroaryl among the heteroarylamines can be applied to the aforementioned heterocyclic group. In the present specification, the alkenyl group in the aralkenyl group is the same as the above-mentioned alkenyl group. In the present specification, the description of the aryl group described above can be applied except that arylene is a divalent group. In the present specification, the description of the above-mentioned heterocyclic group can be applied except that the heteroarylene is a divalent group. In the present specification, the description of the above-mentioned aryl group or cycloalkyl group can be applied except that the hydrocarbon ring is not a monovalent group and two substituents are bonded to each other. In the present specification, the description of the above-mentioned heterocyclic group can be applied except that the heterocyclic ring is not a monovalent group and two substituents are bonded to each other.

In Formula 1, Formula 1 may be represented by Formula 2 according to the bonding position of L ₂ :

(2)

Preferably, in the above formulas (1) and (2), X ₁ , X ₂ and X ₃ are N.

Also preferably, Y ₁ and Y ₂ are each independently O, S, C (CH ₃ ) ₂ , Si (CH ₃ ) ₂ , or N- (phenyl). More preferably, Y ₁ is O and Y ₂ is O, S, C (CH ₃ ) ₂ , Si (CH ₃ ) ₂ , or N- (phenyl); Y ₁ is S, Y ₂ is S, C (CH ₃ ) ₂ , Si (CH ₃ ) ₂ , or N- (phenyl); Y ₁ is C (CH ₃ ) ₂ and Y ₂ is C (CH ₃ ) ₂ ; Y ₁ is Si (CH ₃ ) ₂ , Y ₂ is C (CH ₃ ) ₂ , or Si (CH ₃ ) ₂ ; Or Y ₁ is N- (phenyl) and Y ₂ is C (CH ₃ ) ₂ , Si (CH ₃ ) ₂ , or N- (phenyl).

Also preferably, L ₁ and L ₂ are each independently a bond or phenylene. More preferably, L ₁ and L ₂ are both a bond, or one of L ₁ and L ₂ is a bond and one is phenylene.

Also preferably, Ar ₁ , Ar ₂ and Ar ₃ are each independently phenyl or biphenyl.

Representative examples of the compound represented by the above formula (1) are as follows:

The compound represented by the formula (1) can be prepared, for example, according to the following reaction scheme (1). The above production method can be more specific in the production example to be described later.

[Reaction Scheme 1]

The description of X ₁ , X ₂ , X ₃ , Y ₁ , Y ₂ , L ₁ , L ₂ , Ar ₁ and Ar ₂ in the above Reaction Scheme is the same as that of Formula 1.

The compound represented by the formula (1) can be prepared by appropriately substituting the starting material in accordance with the structure of the compound to be prepared with reference to Reaction Scheme 1.

Also, the present invention provides an organic light emitting device including the compound represented by Formula 1. In one embodiment, the present invention provides a liquid crystal display comprising: a first electrode; A second electrode facing the first electrode; And at least one organic layer disposed between the first electrode and the second electrode, wherein at least one of the organic layers includes a compound represented by Formula 1 do.

The organic material layer of the organic light emitting device of the present invention may have a single layer structure, but may have a multilayer structure in which two or more organic material layers are stacked. For example, the organic light emitting device of the present invention may have a structure including a hole injecting layer, a hole transporting layer, a light emitting layer, an electron transporting layer, and an electron injecting layer as organic layers. However, the structure of the organic light emitting device is not limited thereto and may include a smaller number of organic layers.

The organic material layer may include a hole injecting layer, a hole transporting layer, or a layer simultaneously injecting and transporting holes, and the hole injecting layer, the hole transporting layer, And a compound to be displayed.

In addition, the organic layer may include a light emitting layer, and the light emitting layer includes a compound represented by the general formula (1).

The organic material layer may include an electron transporting layer or an electron injecting layer, and the electron transporting layer or the electron injecting layer includes the compound represented by the above formula (1).

Further, the electron transporting layer, the electron injecting layer, or the layer which simultaneously transports electrons and injects electrons includes the compound represented by the above formula (1).

The organic material layer may include a light emitting layer and an electron transporting layer, and the electron transporting layer may include a compound represented by the general formula (1).

In addition, the organic light emitting device according to the present invention may be a normal type organic light emitting device in which an anode, one or more organic layers, and a cathode are sequentially stacked on a substrate. In addition, the organic light emitting device according to the present invention may be an inverted type organic light emitting device in which a cathode, at least one organic material layer, and an anode are sequentially stacked on a substrate. For example, the structure of an organic light emitting diode according to an embodiment of the present invention is illustrated in FIGS.

Fig. 1 shows an example of an organic light-emitting device comprising a substrate 1, an anode 2, a light-emitting layer 3 and a cathode 4. Fig. In such a structure, the compound represented by Formula 1 may be included in the light emitting layer.

2 shows an example of an organic light emitting element comprising a substrate 1, an anode 2, a hole injecting layer 5, a hole transporting layer 6, a light emitting layer 7, an electron transporting layer 8 and a cathode 4 It is. In such a structure, the compound represented by Formula 1 may be contained in at least one of the hole injecting layer, the hole transporting layer, the light emitting layer, and the electron transporting layer.

The organic light emitting device according to the present invention can be manufactured by materials and methods known in the art, except that at least one of the organic material layers includes the compound represented by the above formula (1). In addition, when the organic light emitting diode includes a plurality of organic layers, the organic layers may be formed of the same material or different materials.

For example, the organic light emitting device according to the present invention can be manufactured by sequentially laminating a first electrode, an organic material layer, and a second electrode on a substrate. At this time, a metal or a metal oxide having conductivity or an alloy thereof is deposited on the substrate using a PVD (physical vapor deposition) method such as sputtering or e-beam evaporation to form an anode Forming an organic material layer including a hole injection layer, a hole transporting layer, a light emitting layer and an electron transporting layer thereon, and then depositing a material usable as a cathode on the organic material layer. In addition to such a method, an organic light emitting device can be formed by sequentially depositing a cathode material, an organic material layer, and a cathode material on a substrate.

In addition, the compound represented by Formula 1 may be formed into an organic layer by a solution coating method as well as a vacuum deposition method in the production of an organic light emitting device. Here, the solution coating method refers to spin coating, dip coating, doctor blading, inkjet printing, screen printing, spraying, roll coating and the like, but is not limited thereto.

In addition to such a method, an organic light emitting device can be manufactured by sequentially depositing an organic material layer and a cathode material from a cathode material on a substrate (WO 2003/012890). However, the manufacturing method is not limited thereto.

In one example, the first electrode is an anode, the second electrode is a cathode, or the first electrode is a cathode and the second electrode is a cathode.

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

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

The hole injecting layer is a layer for injecting holes from an electrode. The hole injecting material has a hole injecting effect, and has a hole injecting effect on the light emitting layer or a light emitting material. A compound which prevents the migration of excitons to the electron injecting layer or the electron injecting material and is also excellent in the thin film forming ability is preferable. It is preferred that the highest occupied molecular orbital (HOMO) of the hole injecting material be between the work function of the anode material and the HOMO of the surrounding organic layer. Specific examples of the hole injecting material include metal porphyrin, oligothiophene, arylamine-based organic materials, hexanitrile hexaazatriphenylene-based organic materials, quinacridone-based organic materials, and perylene- , Anthraquinone, polyaniline and polythiophene-based conductive polymers, but the present invention is not limited thereto.

The hole transport layer is a layer that transports holes from the hole injection layer to the light emitting layer and transports holes from the anode or the hole injection layer to the light emitting layer by using a hole transport material. Is suitable. Specific examples include arylamine-based organic materials, conductive polymers, and block copolymers having a conjugated portion and a non-conjugated portion together, but are not limited thereto.

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

The light emitting layer may include a host material and a dopant material. The host material is a condensed aromatic ring derivative or a heterocyclic compound. Specific examples of the condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, and fluoranthene compounds. Examples of the heterocycle-containing compounds include carbazole derivatives, dibenzofuran derivatives, Furan compounds, pyrimidine derivatives, and the like, but are not limited thereto.

Examples of the dopant material include aromatic amine derivatives, styrylamine compounds, boron complexes, fluoranthene compounds, and metal complexes. Specific examples of the aromatic amine derivatives include condensed aromatic ring derivatives having substituted or unsubstituted arylamino groups, and examples thereof include pyrene, anthracene, chrysene, and peripherrhene having an arylamino group. Examples of the styrylamine compound include substituted or unsubstituted Wherein at least one aryl vinyl group is substituted with at least one aryl vinyl group, and at least one substituent selected from the group consisting of an aryl group, a silyl group, an alkyl group, a cycloalkyl group and an arylamino group is substituted or unsubstituted. Specific examples thereof include, but are not limited to, styrylamine, styryldiamine, styryltriamine, styryltetraamine, and the like. Examples of the metal complex include iridium complex, platinum complex, and the like, but are not limited thereto.

The electron transporting layer is a layer that receives electrons from the electron injecting layer and transports electrons to the light emitting layer. The electron transporting material is a material capable of transferring electrons from the cathode well to the light emitting layer. Suitable. Specific examples include an Al complex of 8-hydroxyquinoline; Complexes containing Alq ₃ ; Organic radical compounds; Hydroxyflavone-metal complexes, and the like, but are not limited thereto. The electron transporting layer can be used with any desired cathode material as used according to the prior art. In particular, an example of a suitable cathode material is a conventional material having a low work function followed by an aluminum layer or a silver layer. Specifically cesium, barium, calcium, ytterbium and samarium, in each case followed by an aluminum layer or a silver layer.

The electron injection layer is a layer for injecting electrons from the electrode. The electron injection layer has an ability to transport electrons, has an electron injection effect from the cathode, and has an excellent electron injection effect with respect to the light emitting layer or the light emitting material. A compound which prevents migration to a layer and is excellent in a thin film forming ability is preferable. Specific examples thereof include fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preorenylidene methane, A nitrogen-containing 5-membered ring derivative, and the like, but are not limited thereto.

Examples of the metal complex compound include 8-hydroxyquinolinato lithium, bis (8-hydroxyquinolinato) zinc, bis (8-hydroxyquinolinato) copper, bis (8- Tris (8-hydroxyquinolinato) aluminum, tris (2-methyl-8-hydroxyquinolinato) aluminum, tris (8- hydroxyquinolinato) gallium, bis (10- Quinolinato) beryllium, bis (10-hydroxybenzo [h] quinolinato) zinc, bis (2-methyl-8- quinolinato) chlorogallium, bis (2-methyl-8-quinolinato) (2-naphtholato) gallium, and the like, But is not limited thereto.

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

In addition, the compound represented by Formula 1 may be included in an organic solar cell or an organic transistor in addition to an organic light emitting device.

The invention will be described in more detail in the following examples. However, the following examples are illustrative of the present invention, and the present invention is not limited by the following examples.

[Manufacturing Example]

Preparation Example 1: Preparation of Compound A-1

Chloro-2-methoxyphenylboronic acid (62.2 g, 333.5 mmol) was dissolved in tetrahydrofuran (800 mL). Here 2M solution of sodium carbonate (500 mL), tetrakis (triphenylphosphine) palladium _{(0) [Pd (PPh 3} ) 4] (7.7 g, 6.7 mmol) was placed under reflux for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, and the resulting mixture was extracted three times with water and toluene. The toluene layer was separated and dried with magnesium sulfate. The filtrate was distilled under reduced pressure. The resulting mixture was recrystallized three times using chloroform and ethanol to obtain Compound A-1 (53.7 g, yield 51%; MS: [M + ⁺ = 314).

Production Example 2: Preparation of Compound A-2

Compound A-1 (50.0 g, 158.5 mmol) was dissolved in dichloromethane (600 mL) and then cooled to 0 占 폚. Boron tribromide (15.8 mL, 166.4 mmol) was slowly added dropwise and stirred for 12 hours. After the reaction was completed, the reaction mixture was washed with water three times, dried over magnesium sulfate, and filtered. The filtrate was distilled under reduced pressure and purified by column chromatography to obtain Compound A-2 (47.4 g, yield 99%; MS: [M ⁺ = 300).

Preparation Example 3: Preparation of Compound A-3

Compound A-2 (40.0 g, 132.7 mmol) was dissolved in distilled dimethylformamide (400 mL). This was cooled to 0 < 0 > C and sodium hydride (3.5 g, 145.9 mmol) was slowly added dropwise thereto. The mixture was stirred for 20 minutes and then at 100 for 1 hour. After the reaction was completed, the reaction mixture was cooled to room temperature, and ethanol (100 mL) was slowly added thereto. The mixture was vacuum distilled, and the resulting mixture was recrystallized from chloroform and ethyl acetate to obtain Compound A-3 (30.3 g, yield 81%; MS: [M + H] ⁺ = 280).

Production Example 4: Preparation of Compound A-4

Compound A-3 (30.0 g, 106.6 mmol) was dissolved in tetrahydrofuran (300 mL), the temperature was lowered to -78 ° C and 1.7 M tert-butyllithium (62.7 mL, 106.6 mmol) was added slowly. After stirring at the same temperature for 1 hour, triisopropylborate (28.3 mL, 213.1 mmol) was added, and the mixture was stirred at room temperature for 3 hours while gradually warming to room temperature. To the reaction mixture was added a 2N aqueous hydrochloric acid solution (200 mL) and the mixture was stirred at room temperature for 1.5 hours. The resulting precipitate was filtered, washed sequentially with water and ethyl ether, and vacuum dried. After drying, the mixture was dispersed in ethyl ether, stirred for 2 hours, filtered and dried to obtain Compound A-4 (24.4 g, yield 93%; MS: [M + H] ⁺ = 247).

Preparation Example 5: Preparation of Compound A-5

After dispersing Compound A-4 (20.0 g, 81.2 mmol) and 2-chloro-4,6-diphenyl-1,3,5-triazine (21.8 g, 81.2 mmol) in tetrahydrofuran , it was added a 2M aqueous potassium carbonate solution (33.6 mL, 243.5 mmol) and tetrakistriphenylphosphine palladium was pinot _{[Pd (PPh 3) 4]} (1.9 g, 2 mol%) was stirred for 4 hours and then put under reflux. The temperature was lowered to room temperature and the resulting solid was filtered. The filtrated solid was recrystallized from tetrahydrofuran and ethyl acetate, filtered and dried to give Compound A-5 (32.4 g, yield 92%; MS: [M + H] ⁺ = 434).

Preparation Example 6: Preparation of Compound A-6

A solution of compound A-5 (30 g, 69.2 mmol), bis (pinacolato) diboron (19.3 g, 76.1 mmol), potassium acetate (20.4 g, 207.5 mmol), tetrakis triphenylphosphinopalladium _{(PPh 3) 4] (1.6} g, 2 mol%) is put into a tetrahydrofuran (300 mL) was refluxed for 12 hours. After the completion of the reaction, the reaction mixture was cooled to room temperature and distilled under reduced pressure to remove the solvent. This was dissolved in chloroform and washed three times with water. The organic layer was separated and dried over magnesium sulfate. Compound A-6 (34.5 g, yield 95%; MS: [M + H] ⁺ = 526) was prepared by distillation under reduced pressure.

Preparation Example 7: Preparation of Compound B-1

Except that 2-methoxyphenyl) boronic acid (50.7 g, 333.5 mmol) was used in place of 5-chloro-2-methoxyphenylboronic acid (62.2 g, 333.5 mmol) B-1 (81.6 g, yield 87%; MS: [M + H] < ⁺ > = 280).

Production Example 8: Preparation of Compound B-2

Compound B-2 (71.2 g, yield 99%; MS (yield: 99%) was obtained in the same manner as in the preparation of Compound A-2 except that Compound B-1 (75.7 g, 269.4 mmol) : [M + H] < ⁺ > = 266).

Preparation Example 9: Preparation of Compound B-3

Compound B-3 (62.3 g, yield 95%; MS (yield: 95%) was obtained in the same manner as Compound A-3 except that Compound B-2 (70.9 g, 265.3 mmol) : [M + H] < ⁺ > = 246).

Production Example 10: Preparation of compound B-4

Compound B-3 (40 g, 161.9 mmol) was dissolved in acetic acid (200 mL). Iodine (4.16 g, 81.0 mmol), iodic acid (6.3 g, 36.0 mmol) and sulfuric acid (10 mL) were added thereto, followed by stirring at 65 ° C for 3 hours. After the reaction was completed, the mixture was cooled to room temperature and water was added thereto. The resulting solid was filtered, washed with water and then recrystallized with toluene and ethyl acetate to obtain 50.1 g (yield: 83%; MS: [M + H] ⁺ = 372) of compound B-4.

Preparation Example 11: Preparation of Compound B-5

Compound B-4 (30 g, 80.7 mmol) and 2-bromo-9,9-dimethyl-9H-xantin (23.2 g, 80.7 mmol) were dissolved in tetrahydrofuran (300 mL). Here 2M solution of sodium carbonate (121 mL), put the tetrakis (triphenylphosphine) palladium _{(0) [Pd (PPh 3} ) 4] (1.9 g, 2 mol%) was refluxed for 6 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, and the resulting mixture was extracted three times with water and toluene. The toluene layer was separated and dried over magnesium sulfate, and the filtrate was distilled under reduced pressure. The resulting mixture was recrystallized from chloroform and ethyl acetate to obtain Compound B-5 (28 g, yield 77%; MS: [M + H ] ⁺ = 455).

Preparation Example 12: Preparation of Compound B-6

A mixture of compound B-5 (25 g, 54.5 mmol), bis (pinacolato) diboron (20.6 g, 71.8 mmol), potassium acetate (15.5 g, 158.1 mmol), tetrakistriphenylphosphinopalladium _{(PPh 3) 4] (1.3} g, 2 mol%) is put into a tetrahydrofuran (300 mL) was refluxed for 12 hours. After the completion of the reaction, the reaction mixture was cooled to room temperature and distilled under reduced pressure to remove the solvent. This was dissolved in chloroform and washed three times with water. The organic layer was separated and dried over magnesium sulfate. This was subjected to vacuum distillation to obtain Compound B-6 (22.4 g, yield 81%; MS: [M + H] ⁺ = 503).

Production Example 13: Preparation of Compound C-1

Except that 4-chloro-2-methoxyphenylboronic acid (62.2 g, 333.5 mmol) was used instead of 5-chloro-2-methoxyphenylboronic acid (62.2 g, 333.5 mmol) (65.3 g, yield 62%; MS: [M + H] < ⁺ > = 315).

Production Example 14: Preparation of Compound C-2

Compound C-2 (43.0 g, yield 90%; MS (yield: 90%) was obtained in the same manner as Compound A-2 except that Compound C-1 (50.0 g, 158.5 mmol) : [M + H] < ⁺ > = 300).

Production Example 15: Preparation of Compound C-3

Compound C-3 (30.6 g, yield 82%; MS (M + H)) was obtained in the same manner as Compound A-3 except that Compound C-2 (40.0 g, 132.7 mmol) : [M + H] < ⁺ > = 280).

Production Example 16: Preparation of Compound C-4

Compound C-4 (25.0 g, yield 95%; MS (yield: 95%) was obtained in the same manner as Compound A-3 except that Compound C-3 (30.0 g, 106.6 mmol) : [M + H] < ⁺ > = 247).

Production Example 17: Preparation of Compound C-5

Compound C-5 (31.7 g, yield 90%; MS (yield: 90%) was obtained in the same manner as Compound A-5 except that Compound C-4 (20.0 g, 81.2 mmol) : [M + H] < ⁺ > = 434).

Production Example 18: Preparation of Compound D-2

Compound D-2 (39.7 g, yield 83%; MS (M + H) +) was obtained in the same manner as in the preparation of Compound A-2 except that Compound D-1 (50.0 g, 158.5 mmol) : [M + H] < ⁺ > = 300).

Production Example 19: Preparation of Compound D-3

Compound D-3 (31.4 g, yield: 84%; MS (M + H) +) was obtained in the same manner as in the preparation of Compound A-3 except that Compound D-2 (40.0 g, 132.7 mmol) : [M + H] < ⁺ > = 280).

Production Example 20: Preparation of Compound D-4

Compound D-4 (25.5 g, yield 97%; MS (M + H) +) was obtained in the same manner as in the preparation of Compound A-4 except that Compound D-3 (30.0 g, 106.6 mmol) : [M + H] < ⁺ > = 247).

Production Example 21: Preparation of Compound D-5

Compound D-5 (32.4 g, yield 92%; MS (yield: 92%) was obtained in the same manner as Compound A-5 except that Compound D-4 (20.0 g, 81.2 mmol) : [M + H] < ⁺ > = 434).

[Example]

Example 1: Preparation of Compound 1

9-dimethyl-9H-xantin (7.6 g, 41.9 mmol) was dispersed in tetrahydrofuran (200 mL), and then 2M potassium carbonate aqueous _{(aq. K 2 CO 3)} (57.2 mL, 114.3 mmol) was added and tetrakis triphenyl phosphino palladium _{[Pd (PPh 3) 4]} (1.3 g, 3 mol%) was placed to stir for 5 hours, and Lt; / RTI > The temperature was lowered to room temperature and the resulting solid was filtered. The filtered solid was recrystallized from chloroform and ethyl acetate, filtered and dried to give Compound 1 (15.0 g, yield 65%; MS: [M + H] ⁺ = 608).

Example 2: Preparation of compound 2

(16.4 g, yield 74%) was obtained in the same manner as in the preparation of Compound 1, except that 2-bromopheno xatine (11.6 g, 41.9 mmol) was used instead of 2-bromo-9,9- ; MS: [M + H] < ⁺ > = 598).

Example 3: Preparation of Compound 3

Compound 11 was obtained in the same manner as in the preparation of Compound 1, except that 2-bromo-10-phenyl-10H-phenoxazine (11.6 g, 41.9 mmol) was used instead of 2-bromo-9,9- (17.0 g, yield 68%; MS: [M + H] < ⁺ > = 657).

Example 4: Preparation of compound 4

Except that 2-bromodibenzo [b, e] [1,4] dioxane (11.0 g, 41.9 mmol) was used instead of 2-bromo-9,9-dimethyl- To give compound 4 (13.1 g, yield 59%; MS: [M + H] ⁺ = 582).

Example 5: Preparation of compound 5

Compound 9 (9.6 g, yield 41%) was obtained in the same manner as in the preparation of Compound 1, except that 2-bromo-isanetracene (12.3 g, 41.9 mmol) was used instead of 2-bromo-9,9-dimethyl-9H-xanthene. MS: [M + H] < ⁺ > = 614).

Example 6: Preparation of compound 6

Compound B-6 (20.0 g, 39.8 mmol) and 2 - ([1,1'-biphenyl] -4-chloro- 39.8 mmol) of tetrahydrofuran (which, 2M potassium carbonate aqueous solution (aq then dispersed in _{300 mL). K 2 CO 3} ) (60 mL, was added 119 mmol) and tetrakis triphenyl phosphino palladium [Pd (PPh ₃ ) ₄ ] (0.9 g, 2 mol%) was added thereto, followed by stirring and refluxing for 4 hours. The temperature was lowered to room temperature and the resulting solid was filtered. The filtered solid was recrystallized from chloroform and ethyl acetate, filtered and dried to give Compound 6 (16.6 g, yield 61%; MS: [M + H] ⁺ = 684).

Example 7: Preparation of Compound 7

Chloro-4- (dibenzo [b, d] furan-2-yl) -4-chloro- (14.2 g, yield 51%; MS: [M + H] < + >) was obtained in the same manner as in the preparation of Compound 6, M + H] < ⁺ > = 698).

Example 8: Preparation of compound 8

Chloro-4- (dibenzo [b, d] pyridin-2-yl) (17.3 g, yield 61%; MS (M + H) +) was obtained in the same manner as in the preparation of Compound 6, except that thiophene- : [M + H] < ⁺ > = 714).

Example 9: Preparation of Compound 9

Instead of 2- (4-bromophenyl) -4,6-dihydro-2-phenyl-1,3,5- (13.6 g, yield 50%; MS: [M + H] ⁺ = 684 (M + H) ⁺ ) was prepared in the same manner as in the preparation of Compound 6, except that diphenyl-1,3,5- ).

Example 10: Preparation of compound 10

The compound C-5 (20.0 g, 46.2 mmol) and (9,9-dimethyl-9H-xantin-2-yl) boronic acid (10.1 g, 46.2 mmol) were dispersed in dioxane (300 mL) 2M potassium phosphate solution _{(aq. K 3 PO 4)} (69 mL, 138.5 mmol) was added and bis (dibenzylideneacetone naphthyridin-acetone) palladium (0.8 g, 1.4 mmol) and tri-cyclohexyl-phosphine (0.8 mg, 2.8 mmol) to And the mixture was stirred and refluxed for 12 hours. The temperature was lowered to room temperature and the resulting solid was filtered. The filtered solid was recrystallized from chloroform and ethyl acetate, filtered and dried to give compound 10 (12.1 g, yield 50%; MS: [M + H] ⁺ = 608).

Example 11: Preparation of compound 11

Compound 12 (12.8 g, yield 53%; MS: [M + H] ⁺ = 608) was used in the same manner as Compound D-5 (20.0 g, 46.2 mmol) .

[Experimental Example]

Experimental Example 1-1

A thin glass substrate coated with ITO (indium tin oxide) at a thickness of 1,300 Å was immersed in distilled water containing detergent and washed with ultrasonic waves. At this time, a Fischer Co. product was used as a detergent, and distilled water, which was filtered with a filter of Millipore Co., was used as distilled water. The ITO was washed for 30 minutes and then washed twice with distilled water and ultrasonically cleaned for 10 minutes. After the distilled water was washed, it was ultrasonically washed with a solvent of isopropyl alcohol, acetone, and methanol, dried, and then transported to a plasma cleaner. Further, the substrate was cleaned using oxygen plasma for 5 minutes, and then the substrate was transported by a vacuum evaporator.

The following HI-1 compound was thermally vacuum deposited on the ITO transparent electrode prepared above to a thickness of 50 Å to form a hole injection layer. The following HT-1 compound was thermally vacuum deposited on the hole injection layer to form a hole transport layer, and HT-2 compound was vacuum deposited on the HT-1 vapor deposition layer to a thickness of 50 Å to form an electron blocking layer. Compound 1, the following YGH-1 compound, and phosphorescent dopant YGD-1 prepared in Example 1 were co-deposited as a light emitting layer on the HT-2 deposited film at a weight ratio of 44:44:12 to form a 400Å thick light emitting layer. On the light emitting layer, the following ET-1 compound was vacuum deposited to a thickness of 250 ANGSTROM to form an electron transporting layer. On the electron transporting layer, the following ET-2 compound and Li were co-deposited at a weight ratio of 98: . Aluminum was deposited on the electron injecting layer to a thickness of 1000 to form a cathode.

In the above process, the deposition rate of the organic material was maintained at 0.4 to 0.7 Å / sec, the deposition rate of aluminum was maintained at 2 Å / sec, and the vacuum degree during deposition was maintained at 1 × 10 ^-7 to 5 × 10 ^-8 torr Respectively.

Experimental Examples 1-2 to 1-11

An organic light emitting device was prepared in the same manner as in Experimental Example 1-1, except that the compound described in Table 1 was used instead of the compound 1 of Example 1 in Experimental Example 1-1.

Comparative Experimental Examples 1-1 and 1-2

An organic light emitting device was prepared in the same manner as in Experimental Example 1-1, except that the compound described in the following Table 1 was used instead of the Compound 1 of Example 1 in Experimental Example 1. The compounds of CE1 and CE2 in the following Table 1 are as follows.

Experimental Example and Comparative an organic light-emitting device of Experimental Example were measured and a voltage efficiency at a current density of 10mA / cm ^2, to measure the lifetime at a current density of 50mA / cm ² and the results are shown in Table 1. In this case, LT ₉₅ means the time to reach 95% of the initial luminance.

compound Voltage (V)
(@ 10 mA / cm ² ) Efficiency (Cd / A)
(@ 10 mA / cm ² ) Color coordinates
(x, y) Life span (h)
(LT ₉₅ at ₅₀ mA / cm ² ) Experimental Example 1-1 Compound 1 4.1 73 0.46, 0.54 99 Experimental Example 1-2 Compound 2 3.9 75 0.46, 0.54 150 Experimental Example 1-3 Compound 3 3.8 80 0.46, 0.53 140 Experimental Examples 1-4 Compound 4 3.7 74 0.46, 0.53 300 Experimental Examples 1-5 Compound 5 3.9 60 0.46, 0.52 150 Experimental Example 1-6 Compound 6 3.9 74 0.46, 0.54 280 Experimental Example 1-7 Compound 7 4 70 0.46, 0.53 310 Experimental Examples 1-8 Compound 8 4 72 0.46, 0.52 300 Experimental Examples 1-9 Compound 9 3.8 72 0.46, 0.53 360 Experimental Example 1-10 Compound 10 3.7 73 0.46, 0.54 180 Experimental Example 1-11 Compound 11 3.7 66 0.46, 0.53 210 Comparative Experimental Example 1-1 CE1 4 70 0.46, 0.53 90 Comparative Experimental Example 1-2 CE2 4.5 68 0.44, 0.55 100

As shown in Table 1, when the compound of the present invention was used as a light emitting layer material, it was confirmed that the compound exhibited better efficiency and longer lifetime than the comparative example.

Experimental Example 2-1

A glass substrate (corning 7059 glass) coated with ITO (indium tin oxide) at a thickness of 1,000 Å was immersed in distilled water dissolved in a dispersant and washed with ultrasonic waves. The detergent was a product of Fischer Co. The distilled water was supplied by Millipore Co. Distilled water, which was secondly filtered with a filter of the product, was used. After the ITO was washed for 30 minutes, ultrasonic washing was repeated 10 times with distilled water twice. After the distilled water was washed, ultrasonic washing was performed in the order of isopropyl alcohol, acetone, and methanol solvent, followed by drying.

The following HI-1 compound was thermally vacuum deposited on the prepared ITO transparent electrode to a thickness of 500 Å to form a hole injection layer. The following HT-1 compound was vacuum-deposited on the hole injection layer to a thickness of 400 Å to form a hole transport layer, and a host H1 and a dopant D1 compound were vacuum-deposited to a thickness of 300 Å at a weight ratio of 97.5: 2.5. The following compound ET-A was vacuum deposited on the light emitting layer to a thickness of 50 Å to form an electron transporting layer. Compound 1 prepared in Example 1 and LiQ (Lithium Quinolate) were vacuum deposited on the electron transport layer at a weight ratio of 1: 1 to form an electron injection and transport layer having a thickness of 350 Å. Lithium fluoride (LiF) and aluminum were deposited to a thickness of 2000 Å on the electron injecting and transporting layer sequentially to form a cathode.

Was maintained at the deposition rate was 0.4 ~ 0.7Å / sec for organic material in the above process, the lithium fluoride of the cathode was 0.3Å / sec, aluminum is deposited at a rate of 2Å / sec, During the deposition, a vacuum 2 × 10 ^{- 7} To 5 x 10 < ^-6 > torr to manufacture an organic light emitting device.

Experimental Examples 2-2 to 2-11

An organic light emitting device was fabricated in the same manner as in Experimental Example 2-1 except that the compound described in the following Table 2 was used instead of the compound 1 of Example 1 in Experimental Example 2-1.

Comparative Experimental Examples 2-1 and 2-2

An organic light emitting device was fabricated in the same manner as in Experimental Example 2-1 except that the compound described in the following Table 2 was used instead of the compound 1 of Example 1 in Experimental Example 2-1. The compounds of CE3 and CE4 in Table 2 are as follows.

In the examples and comparative examples, the voltage and efficiency of the organic light emitting device were measured at a current density of 10 mA / cm ² , the lifetime was measured at a current density of 50 mA / cm ² , and the results are shown in Table 1 . In this case, LT ₉₅ means the time to reach 95% of the initial luminance.

compound Voltage (V)
(@ 10 mA / cm ² ) Efficiency (Cd / A)
(@ 10 mA / cm ² ) Color coordinates
(x, y) Life span (h)
(LT ₉₅ at ₅₀ mA / cm ² ) Experimental Example 2-1 Compound 1 4.1 6.8 0.134, 0.133 95 EXPERIMENTAL EXAMPLE 2-2 Compound 2 4.1 6.1 0.133, 0.133 185 Experimental Example 2-3 Compound 3 3.9 6.3 0.134, 0.132 225 Experimental Example 2-4 Compound 4 3.6 7.2 0.134, 0.132 255 Experimental Example 2-5 Compound 5 3.6 7.1 0.134, 0.132 180 Experimental Examples 2-6 Compound 6 3.7 6.9 0.134, 0.133 160 Experimental Example 2-7 Compound 7 3.7 6.9 0.133, 0.133 170 Experimental Examples 2-8 Compound 8 3.8 7.2 0.134, 0.132 160 Experimental Examples 2-9 Compound 9 3.8 6.8 0.134, 0.132 250 Experimental Example 2-10 Compound 10 3.7 7.2 0.134, 0.132 250 Experimental Example 2-11 Compound 11 3.7 7.0 0.134, 0.133 230 Comparative Experimental Example 2-1 CE3 3.9 5.9 0.133, 0.133 90 Comparative Experimental Example 2-2 CE4 4.1 6.6 0.134, 0.132 90

As shown in Table 2, when the compound of the present invention was used as an electron transport layer material, it was confirmed that the compound exhibited excellent efficiency and lifetime as compared with Comparative Experimental Example.

1: substrate 2: anode
3: light emitting layer 4: cathode
5: Hole injection layer 6: Hole transport layer
7: light emitting layer 8: electron transporting layer

Claims (9)

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

In Formula 1,
X ₁ , X ₂ and X ₃ are each independently N or CH,
Y ₁ and Y ₂ are each independently _{O, S, C (R 1} ) (R 2), Si (R 1) (R 2), or N (Ar _3),
L ₁ and L ₂ are each independently a bond; Substituted or unsubstituted C _6-60 arylene; Or C _2-60 heteroarylene containing at least one of substituted or unsubstituted O, N, Si and S,
Ar ₁ , Ar ₂ and Ar ₃ are each independently substituted or unsubstituted C _6-60 aryl; Or substituted or unsubstituted C _2-60 heteroaryl comprising at least one of O, N, Si and S,
R ₁ and R ₂ are each independently substituted or unsubstituted C _1-60 alkyl.
The method according to claim 1,
The compound represented by the formula (1) is a compound represented by the following formula (2)
compound:
(2)

In Formula 2,
X ₁ , X ₂ , X ₃ , Y ₁ , Y ₂ , L ₁ , L ₂ , Ar ₁ , Ar ₂ , Ar ₃ , R ₁ and R ₂ are as defined in claim 1.
The method according to claim 1,
X ₁ , X ₂ and X ₃ are N,
compound.
The method according to claim 1,
Y ₁ and Y ₂ are each independently O, S, C (CH ₃ ) ₂ , Si (CH ₃ ) ₂ , or N-
compound.
The method according to claim 1,
Y ₁ is O and Y ₂ is O, S, C (CH ₃ ) ₂ , Si (CH ₃ ) ₂ , or N- (phenyl)
Y ₁ is S and Y ₂ is S, C (CH ₃ ) ₂ , Si (CH ₃ ) ₂ , or N- (phenyl)
Y ₁ is C (CH ₃ ) ₂ , Y ₂ is C (CH ₃ ) ₂ ,
Y ₁ is Si (CH ₃ ) ₂ , Y ₂ is C (CH ₃ ) ₂ , or Si (CH ₃ ) ₂ , or
Y ₁ is N- (phenyl) and Y ₂ is C (CH ₃ ) ₂ , Si (CH ₃ ) ₂ , or N- (phenyl)
compound.
The method according to claim 1,
L ₁ and L ₂ are each independently a bond,
compound.
The method according to claim 1,
Ar ₁ , Ar ₂ and Ar ₃ are each independently phenyl or biphenyl,
compound.
The method according to claim 1,
The compound represented by the formula (1) is any one selected from the group consisting of
compound:

A first electrode; A second electrode facing the first electrode; And at least one organic compound layer disposed between the first electrode and the second electrode, wherein at least one of the organic compound layers includes a compound according to any one of claims 1 to 8 The organic light-emitting device.

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