KR20180115638A - Novel hetero-cyclic compound and organic light emitting device comprising the same - Google Patents

Abstract

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

R ₁ and R ₆ are each independently hydrogen; C _2-60 heteroaryl containing substituted or unsubstituted N; Or a _{-N (Ar 1) (Ar 2} ),

R ₂ to R ₅ are each independently hydrogen; C _2-60 heteroaryl containing substituted or unsubstituted N; Or _{-N (Ar 3) (Ar 4} ) and;

Provided that when R ₁ to R ₆ are both hydrogen,

Ar ₁ and Ar ₂ are each independently a substituted or unsubstituted C _6-60 aryl; Substituted or unsubstituted _C7-60 arylalkyl; Substituted or unsubstituted _C7-60 alkylaryl; Or substituted or unsubstituted C _2-60 heteroaryl comprising one or more of O, N, and S, wherein at least one of Ar ₁ and Ar ₂ contains only one aryl or heteroaryl ring,

Ar ₃ and Ar ₄ are each independently a substituted or unsubstituted C _6-60 aryl; Substituted or unsubstituted _C7-60 arylalkyl; Substituted or unsubstituted _C7-60 alkylaryl; Or C _2-60 heteroaryl comprising at least one of substituted or unsubstituted O, N, and S.

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.

In applying an organic EL device to a display device, the lifetime of an organic light emitting material is required. However, a device using the compound proposed so far as a hole injection layer or a hole transport layer has insufficient electron durability, and accordingly, it is required to improve the lifetime of the device. The above problem of lifetime of the organic EL element is that the electrons which could not be recombined when the holes and electrons recombine in the vicinity of the interface between the light emitting layer and the hole transporting layer enter the hole transporting layer to damage the hole transporting material, . The present invention has been made in order to solve the above-mentioned problems, and according to the present invention, it is possible to provide an organic EL device having improved device lifetime by suppressing a deterioration mechanism of an element caused by electrons entering a hole transporting layer.

및

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

And

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 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 heteroaryl group is a heteroaryl group containing at least one of O, N, 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 heteroaryl 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, an isoquinolinyl group, an isoquinolinyl group, an isoquinolinyl group, an isoquinolinyl group, an isoquinolyl 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 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 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 description of the aryl group described above can be applied except that arylene is a divalent group. In this specification, the description of the above-mentioned heteroaryl 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.

The compounds of the present invention can be represented by the following formula (1)

[Chemical Formula 1]

In Formula 1,

R ₁ and R ₆ are each independently hydrogen; C _2-60 heteroaryl containing substituted or unsubstituted N; Or a _{-N (Ar 1) (Ar 2} ),

R ₂ to R ₅ are each independently hydrogen; C _2-60 heteroaryl containing substituted or unsubstituted N; Or _{-N (Ar 3) (Ar 4} ) and;

Provided that when R ₁ to R ₆ are both hydrogen,

Ar ₁ and Ar ₂ are each independently a substituted or unsubstituted C _6-60 aryl; Substituted or unsubstituted _C7-60 arylalkyl; Substituted or unsubstituted _C7-60 alkylaryl; Or substituted or unsubstituted C _2-60 heteroaryl comprising one or more of O, N, and S, wherein at least one of Ar ₁ and Ar ₂ contains only one aryl or heteroaryl ring,

Ar ₃ and Ar ₄ are each independently a substituted or unsubstituted C _6-60 aryl; Substituted or unsubstituted _C7-60 arylalkyl; Substituted or unsubstituted _C7-60 alkylaryl; Or C _2-60 heteroaryl comprising at least one of substituted or unsubstituted O, N, and S.

In Formula 1, preferably, C _2-60 heteroaryl wherein at least one of R ₁ and R ₆ is substituted or unsubstituted N; Or -N (Ar ₁ ) (Ar ₂ ), or C _2-60 heteroaryl containing at least one of R ₂ to R ₅ substituted or unsubstituted; Or a _{-N (Ar 3) (Ar 4} ).

In Formula 1, Formula 1 may be represented by Formula 2 or Formula 3 according to the bonding position of dibenzofurane:

(2)

In Formula 2,

R ₁ to R ₆ are as defined in the above formula (1).

(3)

In Formula 3,

R ₁ to R ₆ are as defined in the above formula (1).

Preferably, R ₁ , R ₂ , R ₅ , and R ₆ are hydrogen, and one of R ₃ and R ₄ is hydrogen and the other is C _2-60 heteroaryl containing substituted or unsubstituted N ; Or a _{-N (Ar 3) (Ar 4} ). More preferably, one of R ₃ and R ₄ is hydrogen and the other is any one of the following:

In the above,

X ₁ to X ₃ are each independently CH or N, with the proviso that at least one of X ₁ to X ₃ is N,

Ar < ₁ > is phenyl, or biphenyl,

Ar ' ₂ is phenyl, phenyl substituted with trimethylsilyl, phenyl substituted with triphenylsilyl, biphenylyl, dimethylfluorenyl, dibenzofuranyl, (dibenzofuranyl) phenyl, dibenzothiophenyl, or Dibenzothiophenyl) phenyl,

Ar ' ₃ and Ar ' ₄ are each independently phenyl or biphenyl,

Ar 'to Ar _{5' 8} are each independently hydrogen, phenyl, biphenyl, and the reel, or carbazolyl,

Ar < ₉ > is phenyl, or biphenyl.

Also preferably, R ₂ , R ₃ , R ₄ , and R ₅ are hydrogen, and one of R ₁ and R ₆ is hydrogen and the other is C _2-60 Hetero containing a substituted or unsubstituted N Aryl; Or a _{-N (Ar 3) (Ar 4} ). More preferably, one of R ₁ and R ₆ is hydrogen and the other is any one of the following:

In the above,

X ₁ to X ₃ are each independently CH or N, with the proviso that at least one of X ₁ to X ₃ is N,

Ar < ₁ > is phenyl, or biphenyl,

Ar ' ₂ is phenyl, phenyl substituted with trimethylsilyl, phenyl substituted with triphenylsilyl, biphenylyl, dimethylfluorenyl, dibenzofuranyl, (dibenzofuranyl) phenyl, dibenzothiophenyl, or Dibenzothiophenyl) phenyl, provided that at least one of Ar ' ₁ and Ar' ₂ is phenyl,

Ar ' ₃ and Ar ' ₄ are each independently phenyl or biphenyl,

Ar 'to Ar _{5' 8} are each independently hydrogen, phenyl, biphenyl, and the reel, or carbazolyl,

Ar < ₉ > is phenyl, or biphenyl.

Also preferably, Ar ₁ , Ar ₂ , Ar ₃ , and Ar ₄ each independently may be a compound having the following structure, but is not limited thereto:

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

The compound represented by the formula (1) can be prepared by using bromo-dibenzofuran as a starting material and substituting tertiary amine groups through a known Grignard or Buchwald-Hartwig reaction. 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 an organic material layer. 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 with a low work function followed by an aluminum layer or 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 the 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.

[ Example ]

Example  1: Preparation of compound 1

1-1. Synthesis of intermediate A

(Grimard) reaction was carried out in 400 mL of an anhydrous tetrahydrofuran solvent in a nitrogen atmosphere, to which 9.4 g (38 mmol) of 2-bromodibenzo [b, d] furan was added. 3.1 g (19 mmol) of 1,1'-carbonyldiimidazole was dissolved in anhydrous tetrahydrofuran solution, and the mixture was slowly added to the product of the Grignard reaction using a cannula. The mixture was stirred at room temperature for 4 hours and at reflux for 4 hours Respectively. After completion of the reaction, the organic layer was extracted with an aqueous solution of ammonium chloride and ethyl acetate, dried over magnesium sulfate, and the solvent was removed under reduced pressure. Purification was carried out by column chromatography using ethyl acetate and n-hexane as developing solvents. After vacuum drying, 10.1 g (yield: 73.6%) of the desired intermediate A was obtained

1-2. Synthesis of intermediate B

20.0 g (64 mmol) of 2,2'-dibromo-1,1'-biphenyl was dissolved in 200 mL of THF, and the mixture was cooled to -78 ° C and stirred. 28.5 mL (2.5 M in hexane) of n-BuLi was slowly added dropwise thereto, followed by stirring at -78 ° C for 30 minutes. Next, 21.0 g of Intermediate A (58 mmol) was dissolved in 100 mL of dry THF and slowly added dropwise, followed by stirring at -70 ° C for 30 minutes. After stirring, NH4 + Cl- aqueous solution was added to terminate the reaction and extracted twice with 400 mL of ethyl acetate. The organic layer was washed with water and aqueous sodium hydrogen carbonate, dried and then the obtained organic layer over anhydrous sodium sulfate (MgSO _4). After filtration, the solvent was removed by distillation under reduced pressure. To the concentrated liquid was added 100 mL of acetic acid and 1 mL of concentrated hydrochloric acid, and the mixture was stirred for 5 hours. Next, after cooling to room temperature, 200 mL of ethanol was added, stirred for 30 minutes, and then filtered. The filtered solid was washed with methanol to give 29.5 g (51 mmol) of intermediate B.

1-3. Synthesis of Compound 1

8.8 g (26 mmol) of di [(1,1'-biphenyl) -4-yl) amine and 100 mL of toluene were placed in a 500 mL flask and stirred for 30 minutes. After stirring, 7.8 g of t-BuONa (sodium tert-butoxide) was added and the mixture was heated to 90 ° C. and stirred for 10 minutes. Then, 0.28 g (1.25 mmol) of Pd (OAc) 2 and 0.05 g (2.5 mmol) of tributylphosphine And the mixture was stirred at 90 占 폚 for 6 hours. After the reaction, the reaction mixture was filtered, and 200 mL of water was added thereto. The layers were separated, and the toluene layer was dehydrated with anhydrous magnesium sulfate (MgSO ₄ ) and the solvent was removed under reduced pressure. The resulting solid was filtered, washed with methanol, and then vacuum-dried to obtain 13.9 g (yield: 68%) of Compound 1.

MS: [M + H] < ⁺ > = 818.

Example  2: Preparation of compound 2

9.4-dimethyl-9H-fluoren-2-amine) (14.4 g, 25 mmol) obtained in Synthesis Example 1-2 and N- 9.8 g (26 mmol) of toluene and 100 mL of toluene were placed in a 500 mL flask and stirred for 30 minutes. After stirring, 7.8 g of t-BuONa (sodium tert-butoxide) was added and the mixture was heated to 90 ° C. and stirred for 10 minutes. Then, 0.28 g (1.25 mmol) of Pd (OAc) ₂ and 0.05 g (2.5 mmol) of tributylphosphine And the mixture was stirred at 90 占 폚 for 6 hours. After the reaction, the reaction mixture was filtered, and 200 mL of water was added thereto. The layers were separated, and the toluene layer was dehydrated with anhydrous magnesium sulfate (MgSO ₄ ) and the solvent was removed under reduced pressure. The obtained solid was filtered, washed with methanol, and then vacuum-dried to obtain 12.9 g (yield: 60%) of Compound 2. [

MS: [M + H] < ⁺ > = 858.

Example  3: Preparation of compound 3

3-1. Synthesis of intermediate C

In the same manner as in Synthesis Example 1-1 except that 9.4 g (38 mmol) of 4-bromodibenzo [b, d] furan was used instead of 9.4 g of 2-bromodibenzo [b, 10.0 g (yield: 72.6%) of Intermediate C was obtained.

3-2. Synthesis of intermediate D

27.2 g (Yield: 81.2%) of Intermediate Compound D was obtained in the same manner as in Preparation Example 1-2, except that 21.0 g (58 mmol) of Intermediate C was used instead of 21.0 g of Intermediate A in Synthesis Example 1-2.

3-3. Synthesis of Compound 3

8.8 g (26 mmol) of di [(1,1'-biphenyl) -4-yl) amine and 100 mL of toluene were placed in a 500 mL flask and stirred for 30 minutes. After stirring, 7.8 g of t-BuONa (sodium tert-butoxide) was added and the mixture was heated to 90 ° C. and stirred for 10 minutes. Then, 0.28 g (1.25 mmol) of Pd (OAc) 2 and 0.05 g (2.5 mmol) of tributylphosphine And the mixture was stirred at 90 占 폚 for 12 hours. After the reaction, the reaction mixture was filtered, and 200 mL of water was added thereto. The layers were separated, and the toluene layer was dehydrated with anhydrous magnesium sulfate (MgSO ₄ ) and the solvent was removed under reduced pressure. The resulting solid was filtered, washed with methanol, and then vacuum-dried to obtain 11.9 g (yield: 58.2%) of Compound 3.

MS: [M + H] < ⁺ > = 818.

Example  4: Preparation of compound 4

9.8 g (26 mmol) of Intermediate D (14.4 g, 25 mmol) and N - ([1,1'-biphenyl] -4-yl) -9,9- 100 mL was added to a 500 mL flask and stirred for 30 minutes. After stirring, 7.8 g of t-BuONa (sodium tert-butoxide) was added and the mixture was heated to 90 ° C. and stirred for 10 minutes. Then, 0.28 g (1.25 mmol) of Pd (OAc) 2 and 0.05 g (2.5 mmol) of tributylphosphine And the mixture was stirred at 90 占 폚 for 12 hours. After the reaction, the reaction mixture was filtered, and 200 mL of water was added thereto. The layers were separated, and the toluene layer was dehydrated with anhydrous magnesium sulfate (MgSO ₄ ) and the solvent was removed under reduced pressure. The obtained solid was filtered, washed with methanol, and then vacuum-dried to obtain 11.4 g (yield: 53.1%) of Compound 4.

MS: [M + H] < ⁺ > = 858.

Example  5: Preparation of compound 5

5-1. Preparation of intermediate E

Intermediate B (11.5 g, 20 mmol), bis (pinacolato) diboron (5.6 g, 22 mmol) and potassium acetate (8.5 g, 85 mmol) Dibenzylidene acetone palladium (0.73 g, 1.3 mmol) and tricyclohexylphosphine (0.71 g, 1.3 mmol) were added under reflux and stirring, and the mixture was refluxed and stirred for 12 hours. When the reaction is complete, the mixture is cooled to room temperature and filtered through celite. The filtrate was concentrated under reduced pressure, and the residue was dissolved in chloroform. The organic layer was washed with water, and dried over anhydrous magnesium sulfate. This was distilled off under reduced pressure, and the mixture was stirred with ethyl acetate and ethanol to obtain Intermediate E (10.0 g, yield: 80.0%).

5-2. Preparation of Compound 5

A solution of Intermediate E (12.5 g, 20 mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine (5.9 g, 22 mmol), and tetrahydrofuran And the mixture was stirred for 30 minutes. After adding 2M potassium carbonate aqueous solution (aq. K ₂ CO ₃ ) (58 mL, 115 mmol), tetrakis triphenylphosphinopalladium [Pd (PPh ₃ ) ₄ ] (0.45 g, 1 mol% 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 obtain Compound 5 (10.8 g, yield: 74.0%).

MS: [M + H] < ⁺ > = 730.

Example  6: Preparation of Compound 6

6-1. Preparation of intermediate F

Intermediate F (7.2 g, yield: 72.1%) was obtained in the same manner as in the preparation of Intermediate E, except that Intermediate D (9.4 g, 16 mmol) was used instead of Intermediate B (9.4 g).

6-2. Preparation of Compound 6

Intermediate F (12.5 g, 20 mmol), 2 - ([1,1'-biphenyl] -4-chloro-6-phenyl-1,3,5- ), And tetrahydrofuran (60 mL) were placed in a 500 mL flask and stirred for 30 minutes. After adding 2M potassium carbonate aqueous solution (aq. K ₂ CO ₃ ) (58 mL, 115 mmol), tetrakis triphenylphosphinopalladium [Pd (PPh ₃ ) ₄ ] (0.45 g, 1 mol% 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 obtain Compound 6 (9.8 g, yield: 60.8%).

MS: [M + H] < ⁺ > = 806.

[ Experimental Example ]

Experimental Example  One

The glass substrate coated with ITO (Indium tin oxide) thin film with thickness of 1,000 Å was immersed in distilled water containing detergent and washed with ultrasonic waves. In this case, Fischer Co. was used as a detergent, and distilled water filtered by 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.

On this ITO transparent electrode thus prepared, an HAT compound shown below was deposited to form an acceptor film having a film thickness of 5 nm. On the acceptor film, a HT1 compound shown below was deposited to form a first hole transporting layer having a film thickness of 100 nm. Subsequent to the film formation of the first hole transporting layer, the previously prepared Compound 1 was deposited to form a second hole transporting layer having a film thickness of 20 nm. On the hole transport layer, the following CBP compound and the following Ir (ppy) ₃ compound were co-deposited to a thickness of 40 nm to obtain a phosphorescent light emitting layer. The concentration of Ir (ppy) ₃ was 10 mass%. Subsequently, the following ET1 compound was deposited on the phosphorescent light-emitting layer to form an electron transport layer having a thickness of 20 nm. Lithium fluoride (LiF) with a thickness of 1 nm and metal Al with a thickness of 80 nm were successively laminated sequentially on the electron transporting layer to form an electron injecting layer and a cathode, thereby preparing an organic light emitting device. At this time, LiF as the electron injection layer was formed at a deposition rate of 1 A / min.

Experimental Example  2 to 4

An organic luminescent device was prepared in the same manner as in Experimental Example 1, except that the compound described in the following Table 1 was used instead of Compound 1 in the formation of the second hole transport layer.

Comparative Experimental Example  1 to 3

An organic luminescent device was prepared in the same manner as in Experimental Example 1, except that the compounds described in the following Table 1 were used instead of Compound 1 in the formation of the second hole transport layer. In the following Table 1, Compound A, Compound B, and Compound C are respectively as follows.

A current was applied to the organic light emitting device manufactured in Experimental Examples 1 to 4 and Comparative Experimental Examples 1 to 3 to measure a driving voltage, a luminous efficiency and a lifetime (T80). The results are shown in Table 1 below. In this case, the lifetime T80 represents a time required for the luminance to decrease from the initial luminance (5000 nits) to 80% after driving the organic light emitting device.

The second hole transport layer
(Hole transport material) The driving voltage (V)
(@ 10 mA / cm ² ) The luminous efficiency (Cd / A)
(@ 10 mA / cm ² ) T80
(hr) Experimental Example 1 Compound 1 4.2 62.8 168 Experimental Example 2 Compound 2 4.0 69.0 162 Experimental Example 3 Compound 3 4.1 66.4 150 Experimental Example 4 Compound 4 4.2 60.8 144 Comparative Experimental Example 1 Compound A 4.5 54.2 116 Comparative Experimental Example 2 Compound B 4.5 46.6 80 Comparative Experimental Example 3 Compound C 4.6 52.6 100

As shown in Table 1, the organic light emitting device manufactured using the compound according to the present invention as a hole transporting material has superior performance in terms of driving voltage, luminous efficiency, and lifetime in comparison with the organic light emitting devices of Comparative Experiments 1 to 3 Can be confirmed.

Experimental Example  5

A glass substrate (corning 7059 glass) coated with ITO (indium tin oxide) to a thickness of 1000 Å was placed in distilled water in which dispersant was dissolved and ultrasonically cleaned. 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 HAT compound was thermally vacuum deposited on the prepared ITO transparent electrode to a thickness of 500 Å to form a hole injection layer. The HT2 compound shown below was vacuum-deposited to a thickness of 400 Å to form a hole transport layer. The following H1 compound and the following D1 compound were vacuum-deposited at a weight ratio of 9: 1 to a thickness of 300 ANGSTROM to form a light emitting layer. Compound 5 prepared above and LiQ (Lithium Quinolate) were vacuum deposited on the light emitting layer at a weight ratio of 1: 1 to a thickness of 350 ANGSTROM to form an electron injection and transport layer. Aluminum was sequentially deposited on the electron injecting and transporting layer to a thickness of 12 Å and lithium fluoride (LiF) to a thickness of 2,000 Å to form an anode, thereby preparing an organic light emitting device.

Was maintained at a vapor deposition rate of 0.4 to 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 Example  6

An organic light emitting device was prepared in the same manner as in Experimental Example 5, except that Compound 6 was used instead of Compound 5 in electron injection and transport layer formation.

Comparative Experimental Example  4 and 5

An organic light emitting device was prepared in the same manner as in Experimental Example 5, except that the compound described in the following Table 2 was used in place of the compound 5 as the electron injecting and transporting layer material in forming the electron injecting and transporting layer. In the following Table 2, the compound D and the compound E are respectively as follows.

Of the Example 5 and 6 and Comparative Example 4, and by applying a current to the organic light emitting device prepared in 5, it was measured drive voltage and luminous efficiency at a current density of ^{10 mA / cm 2, 20 mA} / cm 2 The lifetime (T95) was measured at the current density, and the results are shown in Table 2 below. In this case, the lifetime (T95) means the time required for the current density to be reduced to 95% of the initial luminance at a current density of 20 mA / cm ² .

Electron injection and transport layer material The driving voltage (V)
(@ 10 mA / cm ² ) The luminous efficiency (Cd / A)
(@ 10 mA / cm ² ) T95 (hr)
(@ 20 mA / cm ² ) Experimental Example 5 Compound 5 4.2 6.9 90 Experimental Example 6 Compound 6 4.2 6.4 110 Comparative Experimental Example 4 Compound D 4.5 5.0 52 Comparative Experiment Example 5 Compound E 4.8 4.8 48

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,
R ₁ and R ₆ are each independently hydrogen; C _2-60 heteroaryl containing substituted or unsubstituted N; Or a _{-N (Ar 1) (Ar 2} ),
R ₂ to R ₅ are each independently hydrogen; C _2-60 heteroaryl containing substituted or unsubstituted N; Or _{-N (Ar 3) (Ar 4} ) and;
Provided that when R ₁ to R ₆ are both hydrogen,
Ar ₁ and Ar ₂ are each independently a substituted or unsubstituted C _6-60 aryl; Substituted or unsubstituted _C7-60 arylalkyl; Substituted or unsubstituted _C7-60 alkylaryl; Or substituted or unsubstituted C _2-60 heteroaryl comprising one or more of O, N, and S, wherein at least one of Ar ₁ and Ar ₂ contains only one aryl or heteroaryl ring,
Ar ₃ and Ar ₄ are each independently a substituted or unsubstituted C _6-60 aryl; Substituted or unsubstituted _C7-60 arylalkyl; Substituted or unsubstituted _C7-60 alkylaryl; Or C _2-60 heteroaryl comprising at least one of substituted or unsubstituted O, N, and S.
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,
R ₁ to R ₆ are as defined in claim 1.
The method according to claim 1,
The compound represented by the formula (1) is a compound represented by the following formula (3)
compound:
(3)

In Formula 3,
R ₁ to R ₆ are as defined in claim 1.
The method according to claim 1,
R ₁ , R ₂ , R ₅ , and R ₆ are hydrogen;
R < ₃ > and R < ₄ > are hydrogen and the other is C _2-60 heteroaryl containing substituted or unsubstituted N; Or _{-N (Ar 3) (Ar 4} ) a,
compound.
5. The method of claim 4,
Wherein one of R < ₃ > and R < ₄ > is hydrogen and the other is any one of the following:
compound:

In the above,
X ₁ to X ₃ are each independently CH or N, with the proviso that at least one of X ₁ to X ₃ is N,
Ar < ₁ > is phenyl, or biphenyl,
Ar ' ₂ is phenyl, phenyl substituted with trimethylsilyl, phenyl substituted with triphenylsilyl, biphenylyl, dimethylfluorenyl, dibenzofuranyl, (dibenzofuranyl) phenyl, dibenzothiophenyl, or Dibenzothiophenyl) phenyl,
Ar ' ₃ and Ar ' ₄ are each independently phenyl or biphenyl,
Ar 'to Ar _{5' 8} are each independently hydrogen, phenyl, biphenyl, and the reel, or carbazolyl,
Ar < ₉ > is phenyl, or biphenyl.
The method according to claim 1,
R ₂ , R ₃ , R ₄ , and R ₅ are hydrogen;
One of R ₁ and R ₆ is hydrogen and the other is C _2-60 heteroaryl containing substituted or unsubstituted N; Or _{-N (Ar 3) (Ar 4} ) a,
compound.
The method according to claim 6,
Wherein one of R < ₁ > and R < ₆ > is hydrogen and the other is any one of the following:
compound:

In the above,
X ₁ to X ₃ are each independently CH or N, with the proviso that at least one of X ₁ to X ₃ is N,
Ar < ₁ > is phenyl, or biphenyl,
Ar ' ₂ is phenyl, phenyl substituted with trimethylsilyl, phenyl substituted with triphenylsilyl, biphenylyl, dimethylfluorenyl, dibenzofuranyl, (dibenzofuranyl) phenyl, dibenzothiophenyl, or Dibenzothiophenyl) phenyl, provided that at least one of Ar ' ₁ and Ar' ₂ is phenyl,
Ar ' ₃ and Ar ' ₄ are each independently phenyl or biphenyl,
Ar 'to Ar _{5' 8} are each independently hydrogen, phenyl, biphenyl, and the reel, or carbazolyl,
Ar < ₉ > is phenyl, or biphenyl.
The method according to claim 1,
Ar ₁ to Ar ₄ each independently represent any one selected from the group consisting of:
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 provided between the first electrode and the second electrode, wherein at least one of the organic compound layers includes the compound according to any one of claims 1 to 9 The organic light-emitting device.

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