KR101891263B1 - Novel hetero-cyclic compound and organic light emitting device comprising the same - Google Patents

Abstract

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

Description

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

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 and X ₂ are each independently NR ₁ , CR ₂ R ₃ , SiR ₄ R ₅ , S, or O,
A is a pyrimidine ring,

L is a single 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 is hydrogen; heavy hydrogen; halogen; Substituted or unsubstituted C _1-40 alkyl; Substituted or unsubstituted C _3-60 cycloalkyl; Substituted or unsubstituted C _2-40 alkenyl; 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,

Ar ₂ is any one selected from the group consisting of:

X ₃ and X ₄ are each independently NR ₁ , CR ₂ R ₃ , SiR ₄ R ₅ , S, or O,

R ₁ to R ₇ are each independently hydrogen; heavy hydrogen; halogen; Nitrile; Nitro; Amino; Substituted or unsubstituted C _1-6 alkyl; Substituted or unsubstituted C _3-60 cycloalkyl; A substituted or unsubstituted C _2-60 alkenyl group; Substituted or unsubstituted C _6-60 aryl; Or a C _2-60 heterocyclic group containing at least one of substituted or unsubstituted O, N, Si and S,

n and m each independently represent an integer of 0 to 4;

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.

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

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.

Preferably, the compound represented by the formula (1) is a compound represented by any one of the following formulas (1-1) to (1-4).

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

The compound represented by the formula 1 may be a compound represented by any one of the following formulas 2-1 to 2-4, depending on the bonding position of each substituent in the formula 1:

[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

[Chemical Formula 2-4]

Further, the substitution position of L is 1, 2, 3 or 4, preferably 3,

Preferably, X ₁ is N- (phenyl), C (CH ₃ ) ₂ , S, or O.

Preferably, X ₂ is S, or O.

Preferably, Ar ₁ is phenyl, biphenyl, naphthyl, phenanthrenyl, or triphenylenyl.

Preferably, L is a single bond.

Preferably, Ar < ₂ > is any one selected from the group consisting of:

Preferably, X ₃ is selected from the group consisting of N- (phenyl), N- (biphenylyl), N- (naphthyl), N- (triphenylenyl), N- (9,9-dimethylfluorenyl) , N- - a _{(9-phenyl-carbazolyl), C (CH 3) 2} , C ( phenyl) _2, S, or O. Also preferably, X ₄ is N- (phenyl), C (CH ₃ ) ₂ , S, or O. Also preferably, R ₆ is hydrogen, phenyl, (3,5-diphenyl) phenyl, dibenzo [b, d] furanyl, or dibenzo [b, d] thiophenyl.

The compound represented by Formula 1 may be selected from the group consisting of the following compounds.

The compound represented by the formula (1) can be prepared, for example, according to the following reaction scheme 1.

[Reaction Scheme 1]

The reaction is a step of reacting the compound represented by the formula (1-a) with the compound represented by the formula (1-b) to prepare the compound represented by the formula (1). The reaction is preferably carried out in the presence of a palladium catalyst and a base as a Suzuki coupling reaction, and the reactor for the Suzuki coupling reaction can be modified as known in the art. The above production method can be more specific in the production example to be described later.

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 material is a layer for injecting holes from the electrode. The hole injecting material has a hole injecting effect, a hole injecting effect in the anode, and an excellent hole injecting effect in the light emitting layer or the light emitting material. A compound which prevents the exciton from migrating to the electron injection layer or the electron injection 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 material 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. Is suitable. Specific examples include an Al complex of 8-hydroxyquinoline; Complexes containing Alq ₃ ; Organic radical compounds; Hydroxyflavone-metal complexes, and the like, but are not limited thereto. The 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 preparation of the compound represented by Formula 1 and the organic light emitting device comprising the same will be described in detail in the following examples. However, the following examples are intended to illustrate the present invention, and the scope of the present invention is not limited thereto.

Manufacturing example

Manufacturing example  1: Preparation of compound sub 1

1) Preparation of Compound A1

A mixture of methyl 3-aminobenzo-thiophene-2-carboxylate (47.5 g, 0.23 mol) and urea (79.4 g, 1.15 mol) was stirred in a 2000 mL round-bottomed flask at 200 ° C for 2 hours. The reaction mixture was cooled to room temperature, poured into sodium hydroxide solution, the impurities were removed by filtration, the reaction product was acidified (HCl, 2N) and the resulting precipitate was dried to obtain Compound A1 (35 g, yield 75%).

(2) Preparation of compound sub 1

A 1000 mL round flask was charged with a mixture of compound A1 (35 g, 0.16 mol) and phosphorus oxychloride (600 mL) under reflux for 6 hours. The reaction mixture was cooled to room temperature and poured into ice / water with vigorous stirring to produce a precipitate. The resulting reaction product was filtered to obtain compound sub 1 (35 g, yield 85%, white solid).

Manufacturing example  2: Preparation of compound sub 2

1) Preparation of compound B1

(100 g, 333.5 mmol) and (5-chloro-2-methoxyphenyl) boronic acid (62.2 g, 333.5 mmol) were dissolved in 800 mL of tetrahydrofuran, to which was added 1-bromo-3- Melted. To this was added a 2 M solution of sodium carbonate (Na ₂ CO ₃ ) 2 (500 mL) and tetrakis (triphenylphosphine) palladium (0) (7.7 g, 6.7 mmol) and refluxed 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, and the resulting mixture was recrystallized three times using chloroform and ethanol to obtain Compound B1 (53.7 g, yield 51%; MS: [M + H] = 314).

2) Preparation of compound B2

Compound B1 (50.0 g, 158.5 mmol) was dissolved in 600 mL of dichloromethane and then cooled to 0 占 폚. Boron tribromide (15.8 mL, 166.4 mmol) was slowly added dropwise and stirred for 12 hours. It washed 3 times with water after the reaction was completed, and was evaporated under reduced pressure the filtrate was filtered and dried over magnesium sulfate and purified by column chromatography to compound B2 (47.4 g, yield: 99%; MS: [M + H] + = 300 ).

3) Preparation of compound B3

Compound B2 (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 ° C for 1 hour. After completion of the reaction, the reaction mixture was cooled to room temperature, and 100 mL of ethanol was slowly added thereto. The mixture was distilled under reduced pressure, and the resulting mixture was recrystallized from chloroform and ethyl acetate to obtain Compound B3 (30.3 g, yield 81%; MS: [M + H] ⁺ = 280).

4) Preparation of compound sub 2

Compound B3 (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 (t-BuLi) (62.7 mL, 106.6 mmol) Respectively. After stirring at the same temperature for 1 hour, triisopropyl borate (28.3 mL, 213.1 mmol) was added, and the mixture was stirred for 3 hours while gradually warming to room temperature. To the reaction mixture was added a 2 N aqueous hydrochloric acid solution (200 mL) and the mixture was stirred at room temperature for 1.5 hours. The resulting precipitate was filtered, washed with water and ethyl ether, and vacuum dried. After drying, the mixture was dispersed in ethyl ether and stirred for 2 hours, followed by filtration and drying to obtain compound sub 2 (24.4 g, yield 93%; MS: [M + H] ⁺ = 247).

Manufacturing example  3: Preparation of compound sub 3

1) Preparation of Compound C1

(62.2 g, 333.5 mmol) was used instead of (4-chloro-2-methoxyphenyl) boronic acid in place of (5-chloro-2- In the same manner, Compound C1 (65.3 g, yield 62%; MS: [M + H] ⁺ = 314) was prepared.

2) Preparation of Compound C2

Compound C 2 (43.0 g, yield 90%; MS: [M + H] < ⁺ >) was obtained in the same manner as in the preparation of Compound B2 of Production Example 2, except that Compound C1 (50.0 g, 158.5 mmol) 300).

3) Preparation of Compound C3

(30.6 g, yield 82%; MS: [M + H] < ⁺ >) was obtained in the same manner as in the preparation of the compound B3 in Production Example 2, except that Compound C2 (40.0 g, 132.7 mmol) 280).

4) Preparation of compound sub 3

(25.0 g, yield 95%; MS: [M + H] < + >) was obtained in the same manner as in the preparation of compound sub 2 of Preparation Example 2, except that Compound C3 (30.0 g, ⁺ = 247).

Manufacturing example  4: Preparation of compound sub 4

1) Preparation of compound D1

After dissolving 1-bromo-3-chloro-2-methoxybenzene (113.2 g, 426.4 mmol) in tetrahydrofuran (1000 mL), the temperature was lowered to -78 ° C, 1.7M tert- BuLi) (251.7 mL, 426.4 mmol) was added slowly. After stirring at the same temperature for 1 hour, triisopropylborate (B (OiPr) ₃ ) (113.2 mL, 852.4 mmol) was added and stirred for 3 hours while gradually warming to room temperature. To the reaction mixture was added a 2 N aqueous hydrochloric acid solution (800 mL) and the mixture was stirred at room temperature for 1.5 hours. The resulting precipitate was filtered, washed with water and ethyl ether, and vacuum dried. After drying, the product was recrystallized from chloroform and ethyl acetate and dried to obtain (3-chloro-2-methoxyphenyl) boronic acid (89.6 g, yield 91%; MS: [M + H] ⁺ = 230).

Subsequently, to a solution of the compound B1 of Preparation Example 2 (3-chloro-2-methoxyphenyl) boronic acid (77.0 g, 333.5 mmol) (55.8 g, yield 53%; MS: [M + H] < ⁺ > = 314) was prepared in the same manner as the preparation of compound D1.

2) Preparation of compound D2

(39.7 g, yield 83%; MS: [M + H] < ⁺ >) was obtained in the same manner as in the preparation of Compound B2 of Preparation Example 2, except that Compound D1 (50.0 g, 158.5 mmol) 300).

3) Preparation of compound D3

Compound D3 (31.4 g, yield 84%; MS: [M + H] < ⁺ >) was obtained in the same manner as in the preparation of compound B3 in Production Example 2, except that Compound D2 (40.0 g, 132.7 mmol) 280).

4) Preparation of compound sub 4

(25.5 g, yield 97%; MS: [M + H]) was obtained in the same manner as in the preparation of compound sub 2 of Preparation Example 2, except that Compound D3 (30.0 g, 106.6 mmol) ⁺ = 247).

Manufacturing example  5: Preparation of compound sub 5

1) Preparation of compound E1

Compound 2 (30 g, 118 mmol) and phenylboronic acid (16 g, 129 mmol) were dispersed in tetrahydrofuran (300 mL), and a 2M aqueous potassium carbonate solution (aq. K ₂ CO ₃ ) It was added to mL, 352 mmol) and placed tetrakis triphenyl phosphino palladium _{[Pd (PPh 3) 4]} (4 g, 1 mol%) was refluxed with stirring for 12 hours. The temperature was lowered to room temperature and the resulting solid was filtered. The filtered solid was recrystallized from tetrahydrofuran and ethyl acetate, filtered and then dried to give Compound E1 (28 g, yield 81%; MS: [M + H] ⁺ = 297).

2) Preparation of compound sub 5

A solution of 2M potassium carbonate aqueous solution (aq. K ₂ CO ₃ ) (105 mL, 210 mmol) was added to a solution of compound E1 (20 g, 70 mmol) and compound sub 2 (19 g, 77 mmol) in tetrahydrofuran was added to the mmol), insert tetrakis triphenyl phosphino palladium _{[Pd (PPh 3) 4]} (2 g, 1 mol%) was refluxed with stirring for 12 hours. 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 sub 5 (29 g, yield 91%; MS: [M + H] ⁺ = 463).

Manufacturing example  6: Preparation of compound sub 6

The compound sub 6 (28 g, yield 88%; MS: [M + H] +) was prepared in the same manner as in the preparation of compound sub 5 of Preparation Example 5, H] < ⁺ > = 463).

Manufacturing example  7: Preparation of compound sub7

Compound 27 (27 g, yield 84%; MS: [M + H] +) was prepared in the same manner as in the preparation of compound sub 5 of Preparation Example 5, except that compound sub 4 (19 g, 77 mmol) H] < ⁺ > = 463).

Manufacturing example  8: Preparation of compound sub 8

The compound 5 (20 g, 41 mmol), bis (pinacolato) diboron (12 g, 45 mmol), potassium acetate (12 g, 123 mmol), dibenzylidene acetone palladium Tricyclohexylphosphine (1 g, 2.5 mmol) was added to tetrahydrofuran (300 mL) and refluxed for 12 hours. After 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. The compound sub 8 (23 g, yield 85%; MS: [M + H] ⁺ = 556) was prepared by distillation under reduced pressure.

Manufacturing example  9: Preparation of compound sub 9

(23 g, yield 89%; MS: [M + H] < + >) was prepared in the same manner as in the preparation of compound sub 8 of Preparation Example 8, H] < ⁺ > = 555).

Manufacturing example  10: Preparation of compound sub 10

The compound sub 10 (18 g, yield 79%; MS: [M + H] +) was prepared in the same manner as in the preparation of compound sub 8 of Production Example 8, except that compound sub 7 (19 g, 77 mmol) H] < ⁺ > = 555).

Manufacturing example  11: Preparation of compound sub 11

1) Preparation of Compound A1

A mixture of methyl 3-aminobenzofuran-2-carboxylate (48 g, 0.25 mol) and urea (75 g, 1.24 mol) was stirred in a 2000 mL round-bottomed flask at 200 ° C for 2 hours. The reaction mixture was cooled to room temperature, poured into sodium hydroxide solution, the impurities were removed by filtration, the reaction product was acidified (HCl, 2N) and the obtained precipitate was dried to obtain Compound F1 (35 g, yield 70%).

(2) Preparation of compound sub 11

A 1000 mL round flask was charged with a mixture of compound F1 (35 g, 173 mmol) and phosphorus oxychloride (600 mL) under reflux for 6 hours. The reaction mixture was cooled to room temperature and poured into ice / water with vigorous stirring to produce a precipitate. The resulting reaction product was filtered to obtain compound sub 11 (32 g, yield 78%, white solid).

Manufacturing example  12: Preparation of compound sub 12

1) Preparation of compound G2

The compound sub 11 (30 g, 118 mmol) and phenylboronic acid (16 g, 129 mmol) were dispersed in tetrahydrofuran (300 mL), and a 2M aqueous potassium carbonate solution (aq. K ₂ CO ₃ ) It was added to mL, 352 mmol) and placed tetrakis triphenyl phosphino palladium _{[Pd (PPh 3) 4]} (4 g, 1 mol%) was refluxed with stirring for 12 hours. The temperature was lowered to room temperature and the resulting solid was filtered. The filtered solid was recrystallized from tetrahydrofuran and ethyl acetate, filtered and dried to give Compound G2 (28 g, yield 81%; MS: [M + H] ⁺ = 297).

2) Preparation of compound sub 12

Compound 2 (20 g, 70 mmol) and compound sub 2 (19 g, 77 mmol) were dispersed in tetrahydrofuran (300 mL), and a 2M aqueous potassium carbonate solution (aq. K ₂ CO ₃ ) was added to the mmol), insert tetrakis triphenyl phosphino palladium _{[Pd (PPh 3) 4]} (2 g, 1 mol%) was refluxed with stirring for 12 hours. 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 sub 12 (29 g, yield 91%; MS: [M + H] ⁺ = 463).

Manufacturing example  13: Preparation of compound sub 13

1) Preparation of Compound H2

Compound 2 (30 g, 118 mmol) and compound sub 2 (29 g, 118 mmol) were dispersed in tetrahydrofuran (300 mL), and a 2M aqueous potassium carbonate solution (aq. K ₂ CO ₃ ) after addition of 352 mmol) and placed tetrakis triphenyl phosphino palladium _{[Pd (PPh 3) 4]} (1.4 g, 1 mol%) was refluxed with stirring for 12 hours. The temperature was lowered to room temperature and the resulting solid was filtered. The filtered solid was recrystallized from tetrahydrofuran and ethyl acetate, filtered, and then dried to give compound H2 (35 g, yield 71%; MS: [M + H] ⁺ = 422).

2) Preparation of compound sub 13

Compound 2 (20 g, 48 mmol) and phenylboronic acid (6 g, 48 mmol) were dispersed in tetrahydrofuran (300 mL), and a 2M aqueous potassium carbonate solution (aq. K ₂ CO ₃ ) after the addition of, 142 mmol) and placed tetrakis triphenyl phosphino palladium _{[Pd (PPh 3) 4]} (0.5 g, 1 mol%) was refluxed with stirring for 12 hours. 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 sub 13 (20 g, yield 89%; MS: [M + H] ⁺ = 463).

Manufacturing example  14: Preparation of compound sub 14

1) Preparation of compound I2

Compound 2 (30 g, 126 mmol) and compound sub 2 (31 g, 126 mmol) were dispersed in tetrahydrofuran (300 mL), and a 2M aqueous potassium carbonate solution (aq. K ₂ CO ₃ ) after addition of 376 mmol) and placed tetrakis triphenyl phosphino palladium _{[Pd (PPh 3) 4]} (1.4 g, 1 mol%) was refluxed with stirring for 12 hours. The temperature was lowered to room temperature and the resulting solid was filtered. The filtered solid was recrystallized from tetrahydrofuran and ethyl acetate, filtered and dried to give Compound I2 (38 g, yield 74%; MS: [M + H] ⁺ = 406).

2) Preparation of compound sub 14

Compound 2 (20 g, 49 mmol) and phenylboronic acid (7 g, 54 mmol) were dispersed in tetrahydrofuran (300 mL), and a 2M aqueous potassium carbonate solution (aq. K ₂ CO ₃ ) after the addition of, 148 mmol) and placed tetrakis triphenyl phosphino palladium _{[Pd (PPh 3) 4]} (0.6 g, 1 mol%) was refluxed with stirring for 12 hours. The temperature was lowered to room temperature and the resulting solid was filtered. The filtered solid was recrystallized from tetrahydrofuran and ethyl acetate, filtered and dried to give compound sub 14 (17 g, yield 76%; MS: [M + H] ⁺ = 447).

Example

Example  1: Preparation of compound 1

K ₂ CO ₃ (55 mL, 110 mmol) was added to a solution of the compound R1 (12 g, 37 mmol) and the compound sub 8 (20 g, 37 mmol) in tetrahydrofuran was added to the mmol), insert tetrakis triphenyl phosphino palladium _{[Pd (PPh 3) 4]} (2 g, 1 mol%) was refluxed with stirring for 12 hours. The temperature was lowered to room temperature and the resulting solid was filtered. The filtered solid was recrystallized from tetrahydrofuran and ethyl acetate, filtered and dried to give Compound 1 (19 g, yield 78%; MS: [M + H] ⁺ = 670).

Example  2: Preparation of compound 2

(16 g, yield 66%; MS: [M + H]) was obtained in the same manner as in the preparation of the compound 1 of Example 1, except that the compound sub 9 (20 g, 37 mmol) ⁺ = 670).

Example  3: Preparation of compound 3

(17 g, yield 70%; MS: [M + H]) was obtained in the same manner as in the preparation of the compound 1 of Example 1, except that the compound sub 10 (20 g, ⁺ = 670).

Example  4: Preparation of compound 4

(17 g, yield 77%; MS: [M + H] < ⁺ > = 70%) was obtained in the same manner as in the preparation of Compound 1 of Example 1, 595).

Example  5: Preparation of compound 5

Compound 5 (19 g, yield 85%; MS: [M + H] < ⁺ >) was obtained in the same manner as in the preparation of Compound 1 of Example 1, 611).

Example  6: Preparation of Compound 6

(17 g, yield 60%; MS: [M + H] < ⁺ > = 60%) was obtained in the same manner as in the preparation of the compound 1 of Example 1, 786).

Example  7: Preparation of Compound 7

(21 g, yield 71%; MS: [M + H] < ⁺ >) was obtained in the same manner as in the preparation of the compound 1 of Example 1 except that the compound R5 (17 g, 836).

Example  8: Preparation of compound 8

Compound 8 (13 g, yield 58%; MS: [M + H] < ⁺ >) was obtained in the same manner as in the preparation of Compound 1 of Example 1 except that compound R6 (11 g, 621).

Example  9: Preparation of compound 9

Compound 12 (15 g, 34 mmol) and compound R7 (11 g, 37 mmol) were added to 150 ml of dioxane in a nitrogen atmosphere and stirred and refluxed. Then, potassium phosphate (10 g, 101 mmol) was dissolved in 30 ml of water and the mixture was stirred sufficiently. Then, bis (dibenzylidineacetone) palladium (0.6 g, 3 mol%) and tricyclohexylphosphine mol%). After 24 hours of reaction, the temperature was lowered to room temperature and filtered. The filtrate was extracted with chloroform and water, and then the organic layer was dried with magnesium sulfate. The organic layer was then distilled under reduced pressure and recrystallized using ethyl acetate. The resulting solid was filtered and dried to obtain Compound 9 (15 g, yield 70%; MS: [M + H] ⁺ = 654).

Example  10: Preparation of compound 10

(17 g, yield 79%; MS: [M + H]) was obtained in the same manner as in the preparation of the compound 9 of Example 9, except that the compound sub 13 (17 g, 32 mmol) ⁺ = 670).

Example  11: Preparation of compound 11

(14 g, yield 65%; MS: [M + H]) was obtained in the same manner as in the preparation of the compound 9 of Example 9, except that the compound sub 14 (17 g, 34 mmol) ⁺ = 654).

Experimental Example  One

A glass substrate coated with ITO (indium tin oxide) having a thickness of 1300 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 filtered by a secondary filter using a filter of Millipore Co. was used as distilled water. The ITO substrate was washed for 30 minutes and then washed twice with distilled water and ultrasonically cleaned for 10 minutes. After the distilled water was washed, the ITO substrate was ultrasonically washed with a solvent of isopropyl alcohol, acetone, and methanol, dried, and then transported to a plasma cleaner. Then, the ITO substrate was cleaned using oxygen plasma for 5 minutes, and then transported by a vacuum evaporator.

On the prepared ITO electrode, the following compound HI-1 was thermally vacuum-deposited to a thickness of 50 A to form a hole injection layer. The following compound HT-1 was thermally vacuum deposited on the hole injection layer to form a hole transport layer, and the following compound HT-2 was vacuum-deposited to a thickness of 50 Å on the hole transport layer to form an electron blocking layer . Subsequently, a compound 1 prepared in Example 1 above as a host material and a phosphorescent dopant (compound GD-1 shown below) were co-deposited on the electron blocking layer in an amount of 12 wt% based on the weight of the compound 1, Thereby forming a light emitting layer. On the light emitting layer, the following compound ET-1 was vacuum deposited to a thickness of 250 ANGSTROM to form an electron transport layer, and 2 wt% of Li was co-deposited with respect to the weight of the following compound ET-2 and ET- A < / RTI > electron injection layer was formed. Aluminum was deposited on the electron injection layer to a thickness of 1000 Å to form a cathode.

In the above process, the deposition rate of the organic material was maintained at 0.4 to 0.7 A / sec, the deposition rate of aluminum was maintained at 2 A / sec, and the degree of vacuum during deposition was maintained at 1 × 10 ^-7 to 5 × 10 ^-8 torr Thereby preparing an organic light emitting device.

Experimental Example  2 to 11

An organic light emitting device was fabricated in the same manner as in Experimental Example 1, except that the compound described in Table 1 was used in place of Compound 1.

Comparative Experimental Example  1 to 3

An organic light emitting device was fabricated in the same manner as in Experimental Example 1, except that the compound described in Table 1 was used in place of Compound 1. In the following Table 1, the compounds a, b, and c are as follows.

The driving voltage, the efficiency, the color coordinate, and the lifetime were measured by applying current to the organic light emitting device manufactured in the Experimental Example and the Comparative Experimental Example, and the results are shown in Table 1 below. The lifetime (LT95) is defined as the time required for the luminance to decrease to 95% when the initial luminance is taken as 100%, and is measured at a current density of 20 mA / cm ² .

Voltage (V)
(@ 10 mA / cm ² ) Efficiency (Cd / A)
(@ 10 mA / cm ² ) Color coordinates
(x, y) Lifetime (LT95, h)
(@ 20 mA / cm ² ) Experimental Example 1 Compound 1 3.25 68.5 (0.33, 0.63) 120 Experimental Example 2 Compound 2 3.33 67.9 (0.32, 0.64) 58 Experimental Example 3 Compound 3 3.31 68.0 (0.33, 0.64) 58 Experimental Example 4 Compound 4 3.25 65.1 (0.33, 0.63) 70 Experimental Example 5 Compound 5 3.22 66.2 (0.32, 0.60) 75 Experimental Example 6 Compound 6 3.38 70.2 (0.33, 0.63) 95 Experimental Example 7 Compound 7 3.35 69.8 (0.33, 0.63) 90 Experimental Example 8 Compound 8 3.2 67.8 (0.33, 0.63) 70 Experimental Example 9 Compound 9 3.21 70.2 (0.33, 0.63) 101 Experimental Example 10 Compound 10 3.27 69.1 (0.33, 0.63) 105 Experimental Example 11 Compound 11 3.23 67.9 (0.33, 0.63) 92 Comparative Experimental Example 1 Compound A 3.35 65.0 (0.34, 0.62) 38 Comparative Experimental Example 2 Compound B 3.2 64.0 (0.33, 0.62) 35 Comparative Experimental Example 3 Compound C 3.8 66.1 (0.35, 0.64) 8

As shown in Table 1, the compound represented by Formula 1 according to an embodiment of the present invention can be used as a phosphorescent host material of an organic light emitting device, and can be driven at a lower voltage than conventional compounds, and has high efficiency and long lifetime It is possible to provide an organic light emitting device.

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 (10)

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

In Formula 1,
X ₁ and X ₂ are each independently NR ₁ , CR ₂ R ₃ , S, or O,
A is a pyrimidine ring,
L is a single bond, C _6-60 arylene; Or C _2-60 heteroarylene containing one or more of O, N, Si and S,
Ar < ₁ > is C _6-60 aryl,
Ar ₂ is any one selected from the group consisting of:

X ₃ is selected from the group consisting of N- (phenyl), N- (biphenylyl), N- (naphthyl), N- (triphenylenyl) and carbazolyl), C (CH _{3) 2,} or C (phenyl) _2, phenyl
X ₄ is NR ₁ , CR ₂ R ₃ , S, or O,
R ₁ to R ₃ , R ₆ and R ₇ are each independently hydrogen; C _1-60 alkyl; C _6-60 aryl; Or a C _2-60 heterocyclic group containing at least one of O, N, Si and S,
n and m are each independently 0 or 1;
The method according to claim 1,
The compound represented by the formula (1) is a compound represented by any one of the following formulas (1-1) to (1-4)
compound:
[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

.
The method according to claim 1,
The compound represented by the formula (1) is a compound represented by any one of the following formulas (2-1) to (2-4)
compound:
[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

[Chemical Formula 2-4]

.
The method according to claim 1,
X ₁ is N- (phenyl), C (CH ₃ ) ₂ , S, or O,
compound.
The method according to claim 1,
X ₂ is S, or O,
compound.
The method according to claim 1,
Ar ₁ is phenyl, biphenyl, naphthyl, phenanthrenyl, or triphenylenyl,
compound.
The method according to claim 1,
L is a single bond,
compound.
The method according to claim 1,
Ar ₂ is any one selected from the group consisting of:
compound:

In the above,
X ₃ is selected from the group consisting of N- (phenyl), N- (biphenylyl), N- (naphthyl), N- (triphenylenyl) and carbazolyl), C (CH _{3) 2,} or C (phenyl) _2, phenyl
X ₄ is N- (phenyl), C (CH ₃ ) ₂ , S, or O,
R ₆ is hydrogen, phenyl, (3,5-diphenyl) phenyl, dibenzo [b, d] furanyl, or dibenzo [b, d] thiophenyl.
The method according to claim 1,
Wherein said compound is any one selected from the group consisting of the following compounds:
compound:

A first electrode; A second electrode facing the first electrode; And at least one organic compound layer provided 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 9 The organic light-emitting device.

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