KR101952399B1 - Novel compound and organic light emitting device comprising the same - Google Patents

Abstract

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

Description

TECHNICAL FIELD [0001] The present invention relates to a novel compound and an organic light emitting device comprising the compound.

The present invention relates to a novel nitrogen-containing 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 nitrogen-containing 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,

A is a benzene ring fused to two adjacent pyrrol rings,

L is a bond; Substituted or unsubstituted C _6-60 arylene; Or C _2-60 heteroarylene comprising at least one of substituted or unsubstituted O, N, Si and S

이고,R is

ego,

Two of X ₁ to X ₄ are N, the other is C bonded to L and the other is CR ₂ ,

Y is S, O, or -C (CH _{3) 2} -, and

R ₁ is 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,

R ₂ is 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 substituted or unsubstituted C _2-60 heterocyclic group containing at least one of O, N, Si and S, with the proviso that phenyl is excluded.

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 the above-mentioned formula (1) can be used as luminescent, electron transport, 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 furan group, a pyrrolyl 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 pyrazinyl group, a quinolinyl group, a quinazolinyl group, a quinoxalinyl group, a phthalazinyl group, a pyridopyrimidinyl group, a pyridopyranyl group, a pyrazinopyranyl group, an isoquinoline 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, A benzyl group, a benzyl group, a benzyl group, a benzyl group, a benzyl group, a benzyl group, a benzyl group, a benzyl group, a benzyl group,

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

In Formula 1, A is a benzene ring fused with two adjacent pyrrol rings, and may be represented by any one of the following Formulas 1-1 to 1-6, depending on the fused position.

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

[Chemical Formula 1-6]

Preferably, L is a bond; Or phenylene. More preferably, L is a bond; 1,3-phenylene; Or 1,4-phenylene.

Preferably, R < ₁ > is hydrogen.

Preferably, R is any one selected from the group consisting of:

Preferably, R < ₂ > is biphenylyl, or dimethylfluorenyl. Yl, 9,9-dimethyl-9H-fluoren-1-yl, 9,9-dimethyl-9H-fluoren- , 9-dimethyl-9H-fluoren-3-yl, or 9,9-dimethyl-9H-fluoren-4-yl.

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

The compound represented by the formula (1) can be prepared, for example, by the following reaction scheme. 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 an emission layer, an electron transport layer, an electron injection layer, and the like 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.

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 dopant content may be from 1% by weight to 99% by weight relative to the host amount of the light emitting layer.

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  1-1: Synthesis of Compound of Intermediate A2

1) Preparation of Compound A1

A mixture of methyl 3-aminobenzo-thiophene-2-carboxylate (65.0 g, 313.6 mmol) and urea (84.8 g, 1.41 mol) was stirred in a 2000 mL round-bottomed flask at 200 ° C for 2 hours. After cooling to room temperature, the reaction product was poured into sodium hydroxide solution and the impurities were removed by filtration. The reaction product was acidified (HCl, 2N) and the obtained precipitate was dried to obtain Compound A1 (52.6 g, yield 77%).

(2) Production of Compound A2

A 1000 mL round flask was charged with a mixture of compound A1 (52.6 g, 0.24 mol) and phosphorus oxychloride (750 mL) under reflux for 7.5 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 A2 (51.0 g, yield 83%, white solid).

Manufacturing example  1-2: Synthesis of Compound of Intermediate B2

1) Preparation of compound B1

A mixture of methyl 3-aminobenzofuran-2-carboxylate (65.0 g, 340.0 mmol) and urea (91.9 g, 1.5 mol) was stirred in a 2000 mL round-bottomed flask at 200 ° C for 2 hours. The reaction mixture was cooled to room temperature and then poured into a sodium hydroxide solution and the impurities were removed by filtration. The reaction product was acidified (HCl, 2N) and the obtained precipitate was dried to obtain Compound B1 (49.4 g, yield 72% ≪ / RTI >

(2) Preparation of compound B2

A 1000 mL round flask was charged with a mixture of compound B1 (49.4 g, 0.24 mol) and phosphorus oxychloride (720 mL) under reflux for 7.5 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 B2 (45.1 g, yield 77%, white solid).

Manufacturing example  1-3: Synthesis of compound of intermediate C1

(13.1 g, 51.0 mmol) and [1,1'-biphenyl] -4-ylboronic acid were dissolved in 230 mL of tetrahydrofuran, mL), tetrakis- (triphenylphosphine) palladium (0.59 g, 0.51 mmol) was added thereto, and the mixture was heated with stirring for 10 hours. The reaction mixture was cooled to room temperature and the water layer was separated and removed. The organic layer was dried over anhydrous magnesium sulfate, concentrated under reduced pressure, recrystallized from chloroform and ethanol and dried to obtain the intermediate C1 (15.8 g, yield 83% + H] < ⁺ > = 373).

Manufacturing example  1-4: Compound Synthesis of Intermediate C2

Intermediate C2 was prepared in the same manner as Intermediate C1 except for using [1,1'-biphenyl] -3-ylboronic acid in place of [1,1'-biphenyl] -4-ylboronic acid (12.9 g, yield 79%, MS: [M + H] < ⁺ > = 373).

Manufacturing example  1-5 Synthesis of Compound of Intermediate C3

The procedure of Intermediate C1 was repeated except that (9,9-dimethyl-9H-fluoren-1-yl) boronic acid was used instead of [1,1'-biphenyl] C3 (13.1 g, yield 73%, MS: [M + H] < ⁺ > = 413).

Manufacturing example  1-6: Compound Synthesis of Intermediate C4

The procedure of Intermediate C1 was repeated except that (9,9-dimethyl-9H-fluoren-2-yl) boronic acid was used instead of [1,1'-biphenyl] C4 (15.8 g, yield 77%, MS: [M + H] < ⁺ > = 413).

Manufacturing example  1-7: Compound synthesis of intermediate C5

The procedure of Intermediate C1 was repeated except that (9,9-dimethyl-9H-fluoren-3-yl) boronic acid was used instead of [1,1'-biphenyl] C5 (12.6 g, yield 75%, MS: [M + H] < ⁺ > = 413).

Manufacturing example  1-8: Compound synthesis of intermediate C6

The procedure of Intermediate C1 was repeated except that (9,9-dimethyl-9H-fluoren-4-yl) boronic acid was used instead of [1,1'-biphenyl] C6 (11.4 g, yield 73%, MS: [M + H] < ⁺ > = 413).

Manufacturing example  1-9: Compound synthesis of intermediate D1

Intermediate D1 was prepared (13.0 g, yield 79%, MS: [M + H] ⁺ = 357) in the same manner as Intermediate C1 except for using Intermediate B2 instead of Intermediate A2.

Manufacturing example  1-10: Synthesis of Intermediate D2 Compound

The same procedure as in the method for producing intermediate C1 except for using intermediate compound A2 and [1,1'-biphenyl] -4-ylboronic acid as intermediates B2 and [1,1'-biphenyl] (12.2 g, yield 77%, MS: [M + H] < ⁺ > = 357).

Manufacturing example  1-11: Synthesis of compound of intermediate D3

Intermediate C1 was prepared except that Intermediate A2 and Intermediate B2 and (9,9-dimethyl-9H-fluoren-1-yl) boronic acid were used instead of [1,1'-biphenyl] (13.3 g, yield 79%, MS: [M + H] < ⁺ > = 397).

Manufacturing example  1-12: Synthesis of Intermediate D4 Compound

Intermediate C1 was prepared except that Intermediate A2 and Intermediate B2 and (9,9-dimethyl-9H-fluoren-2-yl) boronic acid were used instead of [1,1'-biphenyl] (12.4 g, yield 75%, MS: [M + H] < ⁺ > = 397).

Manufacturing example  1-13: Synthesis of Intermediate D5 Compound

Intermediate C1 was prepared except that Intermediate A2 and Intermediate B2 and (9,9-dimethyl-9H-fluoren-3-yl) boronic acid were used instead of [1,1'- (12.1 g, yield 72%, MS: [M + H] < ⁺ > = 397).

Manufacturing example  1-14: Synthesis of Intermediate D6 Compound

Intermediate C1 was prepared except that Intermediate A2 and Intermediate B2 and (9,9-dimethyl-9H-fluoren-4-yl) boronic acid were used instead of [1,1'-biphenyl] (11.6 g, yield 70%, MS: [M + H] < ⁺ > = 397).

Manufacturing example  2-1: Synthesis of compound of intermediate E1

Dihydroindolo [2,3-a] carbazole (50.0 g, 0.19 mol), bromobenzene (15.3 g, 0.10 mol), bis (tri-tert- butylphosphine) palladium (0.99 g, 1.95 mmol) and sodium tert-butoxide (28.1 g, 0.29 mol) were added to 750 mL of xylene and the mixture was heated and stirred for 17 hours. After removing the salt by filtration cooled to room temperature, concentrated under reduced pressure, xylene and tetrahydrofuran and hexane to the column with a mixed solution was prepared in the Intermediate E1 (47.6 g, yield 73%, MS: [M + H] + = 333).

Manufacturing example  2-2: Synthesis of compounds of intermediates E2 and E5

Except that 5,12-dihydroindolo [3,2-a] carbazole was used in place of 11,12-dihydroindolo [2,3-a] Synthesis was carried out by separating the intermediates E2 and E5 through column purification.

Manufacturing example  2-3: Synthesis of compound of intermediate E3

Except that 5,11-dihydroindolo [3,2-b] carbazole was used in place of 11,12-dihydroindolo [2,3-a] Intermediate E3 was prepared (46.2 g, 69% yield).

Manufacturing example  2-4: Compound synthesis of intermediate E4

Dihydroindolo [2,3-b] carbazole was used instead of 5,7-dihydroindolo [2,3-a] carbazole in the same manner as in the preparation of intermediate E1 Intermediate E4 was prepared (40.4 g, 69% yield).

Manufacturing example  2-5: Compound synthesis of intermediate E6

Dihydroindolo [2,3-c] carbazole was used instead of 5,8-dihydroindolo [2,3-a] carbazole in the same manner as in the preparation of intermediate E1 Intermediate E6 was prepared (37.1 g, 66% yield).

[ Example ]

Example  1: Synthesis of compound 1

Intermediate C1 (11.2 g, 30.1 mmol) and NaOt-Bu (5.78 g, 60.1 mmol) were dissolved in 150 mL of xylene and then bis (tri-tert-butylphosphine) palladium (0) (0.46 g, 0.90 mmol), which was refluxed and stirred. After 13 hours, the temperature was lowered to room temperature, filtered, and washed with water to remove the base. (10.7 g, yield 53%, MS: [M + H] ⁺ = 669) as a colorless powder.

Example  2: Synthesis of Compound 2

Compound 2 was prepared (10.1 g, yield 47%, MS: [M + H] ⁺ = 669) in the same manner as in the preparation of compound 1, except that Intermediate C2 was used instead of Intermediate C1.

Example  3: Synthesis of Compound 3

Compound 9 was prepared (9.4 g, yield 49%, MS: [M + H] ⁺ = 709) in the same manner as in the preparation of compound 1, except that Intermediate C4 was used instead of Intermediate C1.

Example  4: Synthesis of compound 4

Compound 4 was prepared (9.1 g, yield 47%, MS: [M + H] ⁺ = 709) in the same manner as in the preparation of Compound 1, except that Intermediate C5 was used instead of Intermediate C1.

Example  5: Synthesis of Compound 5

Compound 5 was prepared (8.7 g, 45% yield, MS: [M + H] ⁺ = 709) in the same manner as Compound 1 except that Intermediate C6 was used instead of Intermediate C1.

Example  6: Synthesis of Compound 6

(9.8 g, yield 49%, MS: [M + H] < ⁺ > = 669) was prepared in the same manner as in the preparation of Compound 1, except that Intermediates E2 and C2 were used instead of Intermediates E1 and C1. .

Example  7: Synthesis of Compound 7

(10.5 g, yield 52%, MS: [M + H] < ⁺ > = 709) was prepared in the same manner as in the preparation of compound 1, except that intermediates E2 and C5 were used instead of intermediates E1 and C1. .

Example  8: Synthesis of Compound 8

(9.5 g, yield 50%, MS: [M + H] < ⁺ > = 709) was prepared in the same manner as Compound 1 except that Intermediates E3 and C3 were used instead of Intermediates E1 and C1. .

Example  9: Synthesis of Compound 9

(8.8 g, yield 47%, MS: [M + H] < ⁺ > = 709) was prepared in the same manner as in the preparation of compound 1, except that intermediates E3 and C5 were used instead of intermediates E1 and C1. .

Example  10: Synthesis of Compound 10

Compound 11 was prepared (11.0 g, yield 54%, MS: [M + H] ⁺ = 668) in the same manner as in the preparation of Compound 1, except that Intermediates E4 and C2 were used instead of Intermediates E1 and C1. .

Example  11: Synthesis of Compound 11

(10.7 g, yield 52%, MS: [M + H] < ⁺ > = 709) was prepared in the same manner as in the preparation of Compound 1, except that Intermediates E4 and C4 were used instead of Intermediates E1 and C1. .

Example  12: Synthesis of Compound 12

(10.2 g, yield 51%, MS: [M + H] < ⁺ > = 709) was prepared in the same manner as in the preparation of Compound 1, except that Intermediates E4 and C6 were used instead of Intermediates E1 and C1. .

Example  13: Synthesis of compound 13

(12.1 g, yield 55%, MS: [M + H] < ⁺ > = 668) was prepared in the same manner as in the preparation of compound 1, except that intermediates E1 and C1 were used instead of intermediates E1 and C1. .

Example  14: Synthesis of compound 14

(11.8 g, yield 54%, MS: [M + H] < ⁺ > = 668) was prepared in the same manner as in the preparation of Compound 1, except that Intermediates E5 and C2 were used instead of Intermediates E1 and C1. .

Example  15: Synthesis of compound 15

(10.7 g, yield 50%, MS: [M + H] < ⁺ > = 709) was prepared in the same manner as Compound 1 except that Intermediates E5 and C5 were used instead of Intermediates E1 and C1. .

Example  16: Synthesis of Compound 16

(10.4 g, yield 52%, MS: [M + H] < ⁺ > = 668) was prepared in the same manner as Compound 1 except that Intermediates E6 and C2 were used instead of Intermediates E1 and C1. .

Example  17: Synthesis of Compound 17

Compound 11 was prepared (11.4 g, yield 54%, MS: [M + H] ⁺ = 653) in the same manner as in the preparation of Compound 1, except that Intermediate D1 was used instead of Intermediate C1.

Example  18: Synthesis of compound 18

Compound 11 was prepared (11.1 g, yield 53%, MS: [M + H] ⁺ = 693) in the same manner as in the preparation of compound 1, except that Intermediate D4 was used instead of Intermediate C1.

Example  19: Synthesis of Compound 19

(12.1 g, yield 54%, MS: [M + H] < ⁺ > = 653) was prepared in the same manner as in the preparation of Compound 1, except that Intermediates E2 and D1 were used instead of Intermediates E1 and C1. .

Example  20: Synthesis of Compound 20

(10.8 g, yield 51%, MS: [M + H] < ⁺ > = 693) was prepared in the same manner as Compound 1 was prepared, except that Intermediates E2 and D5 were used instead of Intermediates E1 and C1. .

Example  21: Synthesis of Compound 21

(11.2 g, yield 53%, MS: [M + H] < ⁺ > = 653) was prepared in the same manner as in the preparation of Compound 1, except that Intermediates E3 and D1 were used instead of Intermediates E1 and C1. .

Example  22: Synthesis of Compound 22

(11.3 g, yield 53%, MS: [M + H] < ⁺ > = 653) was prepared in the same manner as in the preparation of compound 1, except that intermediates E3 and D2 were used instead of intermediates E1 and C1. .

Example  23: Synthesis of Compound 23

(10.4 g, yield 50%, MS: [M + H] < ⁺ > = 693) was prepared in the same manner as the compound 1 except that Intermediates E3 and D5 were used instead of Intermediates E1 and C1. .

Example  24: Synthesis of Compound 24

(12.2 g, yield 54%, MS: [M + H] < ⁺ > = 653) was prepared in the same manner as in the preparation of Compound 1, except that Intermediates E4 and D1 were used instead of Intermediates E1 and C1. .

Example  25: Synthesis of Compound 25

(12.0 g, yield 53%, MS: [M + H] < ⁺ > = 653) was prepared in the same manner as in the preparation of Compound 1, except that Intermediates E4 and D2 were used instead of Intermediates E1 and C1. .

Example  26: Synthesis of Compound 26

(10.9 g, yield 50%, MS: [M + H] < ⁺ > = 693) was prepared in the same manner as in the preparation of Compound 1, except that Intermediates E4 and D4 were used instead of Intermediates E1 and C1. .

Example  27: Synthesis of Compound 27

(10.2 g, yield 51%, MS: [M + H] < ⁺ > = 653) was prepared in the same manner as in the preparation of Compound 1, except that Intermediates E5 and D1 were used instead of Intermediates E1 and C1. .

Example  28: Synthesis of Compound 28

(9.9 g, yield 49%, MS: [M + H] < ⁺ > = 653) was prepared in the same manner as in the preparation of Compound 1, except that Intermediates E5 and D2 were used instead of Intermediates E1 and C1. .

Example  29: Synthesis of Compound 29

(9.1 g, yield 46%, MS: [M + H] < ⁺ > = 693) was prepared in the same manner as in the preparation of Compound 1, except that Intermediates E5 and D5 were used instead of Intermediates E1 and C1. .

Example  30: Synthesis of compound 30

(10.6 g, yield 52%, MS: [M + H] < ⁺ > = 653) was prepared in the same manner as in the preparation of Compound 1, except that Intermediates E6 and D2 were used instead of Intermediates E1 and C1. .

[ Experimental Example ]

Experimental Example  One

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

The following HI-1 compound was thermally vacuum deposited on the ITO transparent electrode prepared above to form a hole injection layer. The HT-1 compound was thermally vacuum deposited to a thickness of 250 Å on the hole injection layer to form a hole transport layer And an HT-2 compound was vacuum deposited on the HT-1 vapor deposition layer to a thickness of 50 Å to form an electron blocking layer. Compound 1 and the phosphorescent dopant Dp were then co-deposited on the HT-2 deposited film at a weight ratio of 88:12 to form a 400Å thick light emitting layer. An ET-1 material was vacuum deposited on the light-emitting layer to a thickness of 250 ANGSTROM and an ET-2 material was co-deposited with a 2% weight ratio Li to a thickness of 100 ANGSTROM to form an electron transport layer and an electron injection layer. Aluminum was deposited on the electron injection layer to a thickness of 1000 Å to form a cathode, thereby preparing an organic light emitting device.

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

Experimental Example  2 to 8

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

Experimental Example  9-14

An organic light emitting device was fabricated in the same manner as in Experimental Example 1, except that the compound described in the following Table 1 was used instead of the compound 1 in Experimental Example 1. In Table 1 below, it means that the following compound H1 is used instead of compound 1, and the compound prepared above is used at a weight ratio of 1: 1.

Comparative Experimental Example  1 and 2

An organic light emitting device was fabricated in the same manner as in Experimental Example 1, except that the compound described in the following Table 1 was used instead of the compound 1 in Experimental Example 1. In the following Table 1, the compounds H1 and C1 are respectively as follows, and in the case of Comparative Experiment 2, the following compound H1 and the following C1 compound are used in a weight ratio of 1: 1, respectively, instead of the compound 1.

The driving voltage, the efficiency, the lifetime and the luminescent color were measured by applying a 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. In this case, 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 50 mA / cm ² .

compound Voltage V
(@ 10 mA / cm ² ) Efficiency cd / A
(@ 10 mA / cm ² ) Life span (h)
T95 at 50mA / cm ² Luminous color Experimental Example 1 One 2.86 63.0 60 green Experimental Example 2 4 2.87 61.0 59 green Experimental Example 3 6 2.89 63.5 63 green Experimental Example 4 13 2.87 64.1 65 green Experimental Example 5 15 2.89 63.9 61 green Experimental Example 6 17 2.91 62.8 50 green Experimental Example 7 24 2.93 63.2 53 green Experimental Example 8 28 2.93 61.7 54 green Experimental Example 9 H1, 2 3.13 70.2 182 green Experimental Example 10 H1, 10 3.16 72.5 177 green Experimental Example 11 H1, 14 3.15 70.9 175 green Experimental Example 12 H1, 17 3.34 71.8 157 green Experimental Example 13 H1, 25 3.36 72.0 156 green Experimental Example 14 H1, 29 3.39 71.5 151 green Comparative Experimental Example 1 C1 3.01 60.0 40 green Comparative Experimental Example 2 H1, C1 3.52 67.0 140 green

As shown in Table 1, it was confirmed that the compound of the present invention has an advantage over the compound C1, which is a green luminescent host material used in the past. In addition, it was confirmed that when two-component host was used, it showed better performance in terms of voltage as well as lifetime. For example, when Examples 1 to 8 and Comparative Example 1 were compared, it was confirmed that the lifetime increased from 25% to 50%. In addition, it has been confirmed that the lifetime of the two-component host is further increased, and the low-voltage driving characteristic of about 10% in terms of voltage is exhibited.

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 (7)

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

In Formula 1,
A is a benzene ring fused to two adjacent pyrrol rings,
L is a bond or phenylene,
R is any one selected from the group consisting of:

In the above,
R ₂ is biphenylyl, or dimethylfluorenyl.
The method according to claim 1,
(1) is represented by any one of the following formulas (1-1) to (1-6)
compound:
[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

[Chemical Formula 1-6]

.
delete delete delete 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 light-emitting layer provided between the first electrode and the second electrode, wherein at least one of the light-emitting layers is formed by a method according to any one of claims 1, 2, and 6 ≪ / RTI >

Images