阅读说明：本技术 新的杂环化合物和包含其的有机发光器件 (Novel heterocyclic compound and organic light-emitting device comprising same ) 是由 徐尚德 洪玩杓 洪性佶 于 2018-05-31 设计创作，主要内容包括：本发明提供了新的杂环化合物和包含其的有机发光器件。(The present invention provides a novel heterocyclic compound and an organic light emitting device comprising the same.)

1. A compound represented by the following chemical formula 1:

[ chemical formula 1]

Wherein, in chemical formula 1,

A is a benzene ring fused with two adjacent rings,

R₁And R₂Each independently is substituted or unsubstituted C_1-60Alkyl, or substituted or unsubstituted C_6-60Aryl, and

Ar₁Is phenyl, biphenyl, naphthyl, or any one of the following chemical formulas 2-1 to 2-5:

[ chemical formula 2-1]

[ chemical formula 2-2]

[ chemical formulas 2-3]

[ chemical formulas 2-4]

[ chemical formulas 2 to 5]

Wherein, in chemical formulas 2-1, 2-2, 2-3, 2-4 and 2-5,

R₃、R₄、R₅、R₆And R₇Each independently of the other is phenyl, biphenyl or naphthyl,

X₁Is O or S, and is a compound of,

L is a single bond or a phenylene group,

Ar₂Is composed of

Ar₃And Ar₄Each independently is substituted or unsubstituted C_6-60Aryl, and

n is 0 or 1.

2. The compound according to claim 1, wherein the compound represented by chemical formula 1 is represented by the following chemical formula 1-1, 1-2, 1-3, 1-4, 1-5, or 1-6:

[ chemical formula 1-1]

[ chemical formulas 1-2]

[ chemical formulas 1-3]

[ chemical formulas 1 to 4]

[ chemical formulas 1 to 5]

[ chemical formulas 1 to 6]

Wherein, in chemical formulas 1-1, 1-2, 1-3, 1-4, 1-5 and 1-6,

R₁、R₂、Ar₁、Ar₂And n is as defined in claim 1.

3. The compound of claim 1, wherein R₁And R₂Is methyl or phenyl.

4. The compound of claim 1, wherein Ar₃And Ar₄Is phenyl, biphenyl, terphenyl or dimethylfluorenyl.

5. The compound according to claim 1, wherein the compound represented by chemical formula 1 is any one selected from the group consisting of:

6. An organic light emitting device comprising: a first electrode; a second electrode disposed opposite to the first electrode; and one or more organic material layers disposed between the first electrode and the second electrode, wherein one or more of the organic material layers comprises the compound according to any one of claims 1 to 5.

Technical Field

Cross Reference to Related Applications

This application claims the benefit of the application date of korean patent application No. 10-2017-.

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

Background

In general, the organic light emitting phenomenon is a phenomenon of converting electric energy into light energy by using an organic material. An organic light emitting device using an organic light emitting phenomenon has characteristics such as a wide viewing angle, excellent contrast, a fast response time, and excellent brightness, driving voltage, and response speed, and thus many studies have been made thereon.

An organic light emitting device generally has a structure including an anode, a cathode, and an organic material layer interposed between the anode and the cathode. The organic material layer generally has a multi-layer structure including different materials to improve efficiency and stability of the organic light emitting device, and for example, the organic material layer may be formed of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and the like. In the structure of the organic light emitting device, if a voltage is applied between two electrodes, holes are injected from an anode into an organic material layer and electrons are injected from a cathode into the organic material layer, excitons are formed when the injected holes and electrons meet each other, and light is emitted when the excitons fall from an excited state to a ground state.

There is a continuing need to develop new materials for organic materials in these organic light emitting devices.

Disclosure of Invention

Technical problem

An object of the present invention is to provide a novel heterocyclic compound and an organic light emitting device comprising the same.

Technical scheme

In one aspect of the present invention, there is provided a compound represented by the following chemical formula 1.

[ chemical formula 1]

In the chemical formula 1, the first and second,

A is a benzene ring fused with two adjacent rings,

R₁And R₂Each independently is substituted or unsubstituted C_1-60Alkyl, or substituted or unsubstituted C_6-60Aryl, and

Ar₁is phenyl, biphenyl, naphthyl, or any one of the following chemical formulas 2-1 to 2-5:

[ chemical formula 2-1]

[ chemical formula 2-2]

[ chemical formulas 2-3]

[ chemical formulas 2-4]

[ chemical formulas 2 to 5]

Wherein, in chemical formulas 2-1, 2-2, 2-3, 2-4 and 2-5,

R₃、R₄、R₅、R₆And R₇Each independently of the other is phenyl, biphenyl or naphthyl,

X₁Is O or S, and is a compound of,

L is a single bond or a phenylene group,

Ar₂Is composed of

Ar₃And Ar₃each independently is substituted or unsubstituted C_6-60Aryl, and

n is 0 or 1.

In another aspect of the present invention, there is provided an organic light emitting device including: a first electrode; a second electrode disposed opposite to the first electrode; and one or more organic material layers disposed between the first electrode and the second electrode, wherein one or more of the organic material layers include the compound represented by chemical formula 1.

Advantageous effects

The compound represented by chemical formula 1 described above may be used as a material of an organic material layer of an organic light emitting device, and may improve efficiency, achieve a low driving voltage, and/or improve life characteristics of the organic light emitting device. In particular, the above-described compound represented by chemical formula 1 may be used as a material for hole injection, hole transport, hole injection and transport, light emission, electron transport, or electron injection.

Drawings

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 device including a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, a light emitting layer 7, an electron transport layer 8, and a cathode 4.

Detailed Description

Hereinafter, the present invention will be described in more detail to help understanding the present invention.

As used herein, the symbols a-andMeaning a bond to another substituent.

As used herein, the term "substituted or unsubstituted" means unsubstituted or substituted with one or more substituents selected from the group consisting of: deuterium; a halogen group; a nitrile group; a nitro group; a hydroxyl group; a carbonyl group; an ester group; an imide group; an amino group; a phosphine oxide group; an alkoxy group; an aryloxy group; an alkylthio group; an arylthio group; an alkylsulfonyl group; an arylsulfonyl group; a silyl group; a boron group; an alkyl group; a cycloalkyl group; an alkenyl group; an aryl group; aralkyl group; an aralkenyl group; an alkylaryl group; an alkylamino group; an aralkylamino group; a heteroaryl amino group; an arylamine group; an aryl phosphine group; and a heterocyclic group containing at least one of N, O and S atoms, or a substituent unsubstituted or linked by two or more of the substituents exemplified above. For example, "a substituent to which two or more substituents are attached" may be a biphenyl group. That is, biphenyl can also be an aryl group, and can be interpreted as a substituent with two phenyl groups attached.

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

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

In the present specification, the silyl group specifically includes, but is not limited to, a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group, a vinyldimethylsilyl group, a propyldimethylsilyl group, a triphenylsilyl group, a diphenylsilyl group, a phenylsilyl group and the like.

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

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

In the present specification, the alkyl group may be linear or branched, and the number of carbon atoms thereof is not particularly limited, but is preferably 1 to 40. According to one embodiment, the number of carbon atoms of the alkyl group is from 1 to 20. According to another embodiment, the number of carbon atoms of the alkyl group is from 1 to 10. According to another embodiment, the number of carbon atoms of the alkyl group is from 1 to 6. Specific examples of the alkyl group include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3-dimethylbutyl, 2-ethylbutyl, heptyl, n-heptyl, 1-methylhexyl, cyclopentylmethyl, cycloheptylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2-dimethylheptyl, 1-ethyl-propyl, 1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl, and the like, but are not limited thereto.

In the present specification, the alkenyl group may be linear or branched, and the number of carbon atoms thereof is not particularly limited, but is preferably 2 to 40. According to one embodiment, the number of carbon atoms of the alkenyl group is from 2 to 20. According to another embodiment, the number of carbon atoms of the alkenyl group is from 2 to 10. According to yet another embodiment, the number of carbon atoms of the alkenyl group is from 2 to 6. Specific examples thereof include: vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-methyl-1-butenyl, 1, 3-butadienyl, allyl, 1-phenylvinyl-1-yl, 2-diphenylvinyl-1-yl, 2-phenyl-2- (naphthalen-1-yl) vinyl-1-yl, 2-bis (biphenyl-1-yl) vinyl-1-yl, stilbene, styryl and the like, but are not limited thereto.

In the present specification, the cycloalkyl group is not particularly limited, but the number of carbon atoms thereof is preferably 3 to 60. According to one embodiment, the number of carbon atoms of the cycloalkyl group is from 3 to 30. According to another embodiment, the number of carbon atoms of the cycloalkyl group is from 3 to 20. According to yet another embodiment, the number of carbon atoms of the cycloalkyl group is from 3 to 6. Specific examples thereof include: cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2, 3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2, 3-dimethylcyclohexyl, 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 number of carbon atoms of the aryl group is from 6 to 30. According to one embodiment, the number of carbon atoms of the aryl group is from 6 to 20. As the monocyclic aryl group, the aryl group may be phenyl, biphenyl, terphenyl, etc., but is not limited thereto. Examples of polycyclic aromatic groups include naphthyl, anthryl, phenanthryl, pyrenyl, perylenyl, perylene,A phenyl group, a fluorenyl group, and the like, but are not limited thereto.

In the present specification, fluorenyl groupMay be substituted, and two substituents may be bonded to each other to form a spiro ring structure. In the case of substituted fluorenyl radicals, may formAnd the like. However, the structure is not limited thereto.

In the present specification, the heterocyclic group is a heterocyclic group containing one or more of O, N, Si and S as a heteroatom, and the number of carbon atoms thereof is not particularly limited, but is preferably 2 to 60. Examples of heterocyclic groups include thienyl, furyl, pyrrolyl, imidazolyl, thiazolyl, and the like,Azolyl group,Oxadiazolyl, triazolyl, pyridyl, bipyridyl, pyrimidinyl, triazinyl, acridinyl, pyridazinyl, pyrazinyl, quinolyl, quinazolinyl, quinoxalinyl, phthalazinyl, pyridopyrimidinyl, pyridopyrazinyl, pyrazinopyrazinyl, isoquinolyl, indolyl, carbazolyl, benzobenzoxazinylAzolyl, benzimidazolyl, benzothiazolyl, benzocarbazolyl, benzothienyl, dibenzothienyl, benzofuranyl, phenanthrolinyl, isoquinoylOxazolyl, thiadiazolyl, phenothiazinyl, dibenzofuranyl, and the like, but is not limited thereto.

In the present specification, the aryl group of the aralkyl group, aralkenyl group, alkylaryl group, and arylamine group is the same as the foregoing examples of the aryl group. In the present specification, the alkyl group in the aralkyl group, the alkylaryl group and the alkylamino group is the same as the foregoing examples of the alkyl group. In the present specification, the heteroaryl group in the heteroarylamine may employ the aforementioned description of the heterocyclic group. In the present specification, the alkenyl group in the aralkenyl group is the same as the foregoing example of the alkenyl group. In this specification, the foregoing description of aryl groups may be applied with the exception that the arylene group is a divalent group. In this specification, the foregoing description of heterocyclyl groups may be applied, with the difference that the heteroarylene group is a divalent group. In this specification, the foregoing description of aryl or cycloalkyl groups may be applied, except that the hydrocarbon ring is not a monovalent group but is formed by the combination of two substituents. In the present specification, the foregoing description of heterocyclic group may be applied except that the heterocyclic group is not a monovalent group but is formed by combining two substituents.

In chemical formula 1, chemical formula 1 may be represented by the following chemical formula 1-1, 1-2, 1-3, 1-4, 1-5, or 1-6, based on a structure fused with a carbazolyl group and an indenyl group through a.

[ chemical formula 1-1]

[ chemical formulas 1-2]

[ chemical formulas 1-3]

[ chemical formulas 1 to 4]

[ chemical formulas 1 to 5]

[ chemical formulas 1 to 6]

In chemical formulas 1-1, 1-2, 1-3, 1-4, 1-5 and 1-6,

R₁、R₂、Ar₁、Ar₂And n is as defined in chemical formula 1.

Preferably, R₁And R₂Is methyl or phenyl.

Preferably, Ar₃And Ar₄Is phenyl, biphenyl, terphenyl or dimethylfluorenyl.

Representative examples of the compound represented by chemical formula 1 are as follows.

The compound represented by chemical formula 1 may be prepared by the method shown in the following reaction scheme 1.

The above production method can be further explained in detail in the production examples described later.

[ reaction scheme 1]

In reaction scheme 1, A, R₁、R₂、Ar₁、Ar₂And n is as defined in chemical formula 1, and R₈Is a halogen group such as fluorine, chlorine, bromine, iodine, etc.

Specifically, the above reaction uses Buchwald-Hartwig reaction, and can be carried out in a palladium-based catalyst (Pd catalyst) compound such as Pd (P-tBu)₃)₂Etc. in the presence of a catalyst.

further, the reaction may be carried out in the presence of one or more organic solvents such as dichloromethane, ethyl acetate, diethyl ether, acetonitrile, isopropanol, acetone, Tetrahydrofuran (THF), N-Dimethylformamide (DMF), dimethyl sulfoxide (DMSO), toluene, or xylene, with one or more basic activators such as NaOtBu, K, or₂CO₃、Cs₂CO₃And so on together.

In still another embodiment of the present invention, there is provided an organic light emitting device comprising the compound represented by chemical formula 1. As an example, there is provided an organic light emitting device including: a first electrode; a second electrode disposed opposite to the first electrode; and one or more organic material layers disposed between the first electrode and the second electrode, wherein one or more of the organic material layers include the compound represented by chemical formula 1.

The organic material layer of the organic light emitting device of the present invention may have a single layer structure, or 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 disclosure may have a structure including a hole injection layer, a hole transport layer, a light emitting 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 it may include a smaller number of organic layers.

In addition, the organic material layer may include a hole injection layer, a hole transport layer, or a layer simultaneously performing hole injection and hole transport, wherein the hole injection layer, the hole transport layer, or the layer simultaneously performing hole injection and hole transport includes the compound represented by chemical formula 1.

In addition, the organic material layer may include a light emitting layer, wherein the light emitting layer includes the compound represented by chemical formula 1.

In addition, the organic material layer may include an electron transport layer or an electron injection layer, wherein the electron transport layer or the electron injection layer includes the compound represented by chemical formula 1.

In addition, the electron transport layer, the electron injection layer, or the layer simultaneously performing electron transport and electron injection includes the compound represented by chemical formula 1.

In addition, the organic material layer includes a light emitting layer and an electron transport layer, wherein the electron transport layer may include the compound represented by chemical formula 1.

further, the organic light emitting device according to the present invention may be a normal type organic light emitting device in which an anode (positive electrode), one or more organic material layers, and a cathode (negative electrode) are sequentially stacked on a substrate. In addition, the organic light emitting device according to the present disclosure may be an inverted type organic light emitting device in which a cathode, one or more organic material layers, and an anode are sequentially stacked on a substrate. For example, the structure of an organic light emitting device according to one embodiment of the present disclosure is shown in fig. 1 and 2.

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. In such a structure, the compound represented by chemical formula 1 may be included in the light emitting layer.

Fig. 2 shows an example of an organic light emitting device including a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, a light emitting layer 7, an electron transport layer 8, and a cathode 4. In such a structure, the compound represented by chemical formula 1 may be contained in one or more layers among the hole injection layer, the hole transport layer, the light emitting layer, and the electron transport layer.

The organic light emitting device according to the present invention may be manufactured by materials and methods known in the art, except that one or more layers of the organic material layer include the compound represented by chemical formula 1. In addition, when the organic light emitting device includes a plurality of organic material layers, the organic material layers may be formed of the same material or different materials.

For example, the organic light emitting device according to the present invention may be manufactured by sequentially stacking a first electrode, an organic material layer, and a second electrode on a substrate. In this case, the organic light emitting device may be manufactured by: a metal, a metal oxide having conductivity, or an alloy thereof is deposited on a substrate using a PVD (physical vapor deposition) method such as a sputtering method or an electron beam evaporation method to form an anode, an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer is formed on the anode, and then a material that can be used as a cathode is deposited on the organic material layer. In addition to such a method, the organic light emitting device may be manufactured by sequentially depositing a cathode material, an organic material layer, and an anode material on a substrate.

in addition, in manufacturing the organic light emitting device, the compound represented by chemical formula 1 may be formed into an organic layer by a solution coating method as well as a vacuum deposition method. Here, the solution coating method means spin coating, dip coating, blade coating, inkjet printing, screen printing, spray coating, roll coating, etc., but is not limited thereto.

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

As an example, the first electrode is an anode and the second electrode is a cathode, or alternatively, the first electrode is a cathode and the second electrode is an anode.

As the anode material, it is generally preferable to use a material having a large work function so that holes can be smoothly injected into the organic material layer. Specific examples of the anode material include: metals such as vanadium, chromium, copper, zinc and gold, or alloys thereof; metal oxides such as zinc oxide, Indium Tin Oxide (ITO), and Indium Zinc Oxide (IZO); combinations of metals and oxides, e.g. ZnO: Al or SNO₂Sb; conducting polymers, e.g. poly (3-methylthiophene), poly [3,4- (ethylene-1, 2-dioxy) thiophene](PEDOT), polypyrrole, polyaniline, and the like, but are not limited thereto.

As the cathode material, it is generally preferable to use a material having a small work function so that electrons can be easily injected into the organic material layer. Specific examples of the cathode material include: metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead, or alloys thereof; materials of multilayer construction, e.g. LiF/Al or LiO₂Al; and the like, but are not limited thereto.

The hole injection layer is a layer for injecting holes from the electrode, and the hole injection material is preferably a compound of: it has an ability to transport holes, and thus has an effect of injecting holes in the anode and an excellent hole injection effect to the light emitting layer or the light emitting material, prevents excitons generated in the light emitting layer from moving to the hole injecting layer or the electron injecting material, and has an excellent thin film forming ability. Preferably, the HOMO (highest occupied molecular orbital) of the hole injecting material is between the work function of the anode material and the HOMO of the surrounding organic material layer. Specific examples of the hole injection material include metalloporphyrin, oligothiophene, arylamine-based organic material, hexanenitrile-based hexaazatriphenylene-based organic material, quinacridone-based organic material, perylene-based organic material, anthraquinone, polyaniline-and polythiophene-based conductive polymer, and the like, but are not limited thereto.

The hole transport layer is a layer that receives holes from the hole injection layer and transports the holes to the light emitting layer, and is suitably a material having a large hole mobility that can receive holes from the anode or the hole injection layer and transport the holes to the light emitting layer. Specific examples thereof include arylamine-based organic materials, conductive polymers, block copolymers in which both a conjugated portion and a non-conjugated portion exist, and the like, but are not limited thereto.

The luminescent material is preferably a material that: which can receive holes and electrons respectively transported by the hole transport layer and the electron transport layer and combine the holes and the electrons to emit light in the visible light range, and has good quantum efficiency for fluorescence or phosphorescence. Specific examples of the light-emitting material include: 8-hydroxy-quinoline aluminum complex (Alq)₃) (ii) a A carbazole-based compound; a di-polystyrene based compound; BAlq; 10-hydroxybenzoquinoline-metal compounds; based on benzenecompounds of oxazole, benzothiazole and benzimidazole; polymers based on poly (p-phenylene vinylene) (PPV); a spiro compound; a polyfluorene; rubrene, and the like, but is not limited thereto.

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

Examples of the dopant material include aromatic amine derivatives, styryl amine compounds, boron complexes, fluoranthene compounds, metal complexes, and the like. Specifically, the aromatic amine derivative is a substituted or unsubstituted fused aromatic ring derivative having an arylamino group, and examples thereof include pyrene, anthracene, having an arylamino group,Diindenopyrene, and the like. Styrylamine compounds as suchA compound substituted with at least one arylvinyl group in a substituted or unsubstituted arylamine, wherein one or two or more substituents selected from the group consisting of aryl, silyl, alkyl, cycloalkyl and arylamine are substituted or unsubstituted. Specific examples thereof include, but are not limited to, styrylamine, styryldiamine, styryltrriamine, styryltretramine, and the like. Further, the metal complex includes an iridium complex, a platinum complex, and the like, but is not limited thereto.

The electron transport layer is a layer that receives electrons from the electron injection layer and transports the electrons to the light emitting layer, and the electron transport material is suitably a material that can well receive electrons from the cathode and transport the electrons to the light emitting layer, and has a large electron mobility. Specific examples of the electron transport material include: al complexes of 8-hydroxyquinoline; comprising Alq₃The complex of (1); an organic radical compound; a hydroxyflavone-metal complex; and the like, but are not limited thereto. The electron transport layer may be used with any desired cathode material as used according to the related art. Suitable examples of cathode materials are, in particular, typical materials having a low work function, followed by an aluminum or silver layer. Specific examples thereof include cesium, barium, calcium, ytterbium and samarium, in each case followed by an aluminum or silver layer.

The electron injection layer is a layer that injects electrons from the electrode, and is preferably a compound of: it has an ability to transport electrons, has an effect of injecting electrons from a cathode and an excellent effect of injecting electrons into a light emitting layer or a light emitting material, prevents excitons generated from the light emitting layer from moving to a hole injecting layer, and also has an excellent thin film forming ability. Specific examples of the electron-injecting layer include fluorenone, anthraquinone dimethane, diphenoquinone, thiopyran dioxide, fluorine-containing compound,Azole,Oxadiazole, triazole, imidazole, perylene tetracarboxylic acid, fluorenylidene methane, anthrone, and the like, and derivatives and metal complexes thereofCompounds, nitrogen-containing 5-membered ring derivatives, and the like, but are not limited thereto.

Examples of the metal complex compounds include lithium 8-quinolinolato, zinc bis (8-quinolinolato), copper bis (8-quinolinolato), manganese bis (8-quinolinolato), aluminum tris (2-methyl-8-quinolinolato), gallium tris (8-quinolinolato), bis (10-hydroxybenzo [ h ] quinoline) beryllium, bis (10-hydroxybenzo [ h ] quinoline) zinc, bis (2-methyl-8-quinoline) chlorogallium, bis (2-methyl-8-quinoline) (o-cresol) gallium, bis (2-methyl-8-quinoline) (1-naphthol) aluminum, bis (2-methyl-8-quinoline) (2-naphthol) gallium, and the like, but are not limited thereto.

The organic light emitting device according to the present invention may be a front side emission type, a rear side emission type, or a double side emission type depending on the material used.

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

The preparation of the compound represented by chemical formula 1 and the organic light emitting device including the same will be described in detail in the following examples. However, these examples are presented for illustrative purposes only and are not intended to limit the scope of the present invention.

[ Synthesis examples ]

< Synthesis example 1>

1-1)Synthesis of Compound A-1

In a three-necked flask, (9, 9-dimethyl-9H-fluoren-2-yl) boronic acid (30.0g, 126.0mmol) and 1-bromo-4-chloro-2-nitrobenzene (31.3g, 132.3mmol) are dissolved in 450mL of THF and K is added₂CO₃(69.7g, 504.0mmol) was dissolved in 150mL of H₂And adding into the mixture. To which Pd (PPh) was added₃)₄(7.3g, 6.3mmol) and the reaction mixture was stirred under an argon atmosphere for 8 hours. After completion of the reaction, the reaction solution was cooled to room temperature, then transferred to a separatory funnel, and extracted with ethyl acetate. The extract was over MgSO₄Drying, filtering and concentratingFollowed by recrystallization from EtOH to obtain 37.5g of Compound A-1. (yield: 85%, MS [ M + H ]]⁺＝350)

1-2)Synthesis of Compound A and Compound B

Compound A-1(35.0g, 100.1mmol), triphenylphosphine (20.7g, 150.1mmol) and 350mL o-dichlorobenzene were added to a two-necked flask, and the mixture was stirred under reflux for 24 hours. After completion of the reaction, the reaction solution was cooled to room temperature, the solvent was removed by distillation under the reduced pressure, and CH was used₂Cl₂extraction is carried out. The extract was over MgSO₄Dried, filtered and concentrated. The sample was purified by silica gel column chromatography to obtain 16.2g (yield: 51%) of compound A and 11.1g (yield: 35%) of compound B. (MS [ M + H)]⁺＝318)

< Synthesis example 2>

2-1)synthesis of Compound C-1

In a two-necked flask, 9-dimethyl-9H-fluoren-2-amine (20.0g, 95.6mmol) was dissolved in 400mL of DMF at 0 ℃, N-bromosuccinimide (NBS, 17.0g, 95.6mmol) was slowly added thereto, and the mixture was stirred at room temperature for 8 hours. After completion of the reaction, the reaction solution was transferred to a separatory funnel, and water (300mL) was added thereto, followed by extraction with ethyl acetate. The sample was purified by silica gel column chromatography to obtain 22.6g of Compound C-1. (yield: 82%, MS [ M + H ]]⁺＝288)

2-2)synthesis of Compound C-2

In a three-necked flask, compound C-1(20.0g, 69.4mmol) and (2, 5-dichlorophenyl) boronic acid (14.6g, 76.3mmol) were dissolved300mL of THF, and adding K₂CO₃(38.4g, 277.6mmol) was dissolved in 150mL of H₂And adding into the mixture. To which Pd (PPh) was added₃)₄(4.0g, 3.5mmol) and the mixture was stirred under an argon atmosphere for 8 hours. After completion of the reaction, the reaction solution was cooled to room temperature, and then transferred to a separatory funnel and extracted with ethyl acetate. The extract was over MgSO₄Dried, filtered and concentrated. The sample was then purified by silica gel column chromatography to obtain 19.2g of compound C-2. (yield: 78%, MS [ M + H ]]⁺＝354)

2-3)Synthesis of Compound C

Mixing compound C-2(18.0g, 50.8mmol), Pd (OAc)₂(1.0g, 4.1mmol), Tricyclohexylphosphine (PCy)₃，2.3g，8.1mmol)、K₂CO₃(28.1g, 203.2mmol) and 540mL of DMAC were added to a three-necked flask and the mixture was stirred under an argon atmosphere for 10 hours. After completion of the reaction, the reaction solution was cooled to room temperature, and 200mL of H was added thereto₂O, then transferred to a separatory funnel and extracted with ethyl acetate. The extract was over MgSO₄Dried and concentrated. The sample was then purified by silica gel column chromatography to obtain 12.1g of compound C. (yield: 75%, MS [ M + H ]]⁺＝318)

<Synthesis example 3>

3-1)Synthesis of Compound D-1

In a three-necked flask, (9, 9-dimethyl-9H-fluoren-2-yl) boronic acid (20.0g, 84.0mmol) and 1-bromo-4-chloro-2-nitrobenzene (25.3g, 88.2mmol) are dissolved in 300mL of THF and K is added₂CO₃(46.4g, 336.0mmol) was dissolved in 120mL of H₂And adding into the mixture. To which Pd (PPh) was added₃)₄(4.9g, 4.2mmol) and the mixture was stirred under an argon atmosphereStirring for 8 hours. After completion of the reaction, the reaction solution was cooled to room temperature, and then transferred to a separatory funnel and extracted with ethyl acetate. The extract was over MgSO₄Dried, filtered and concentrated, then recrystallized from EtOH to obtain 28.6g of Compound D-1. (yield: 85%, MS [ M + H ]]⁺＝400)

3-2)Synthesis of Compound D

Compound D-1(27.0g, 67.5mmol), triphenylphosphine (14.0g, 101.3mmol) and o-dichlorobenzene (270mL) were added to a two-necked flask, and the reaction mixture was stirred under reflux for 24 hours. After completion of the reaction, the reaction solution was cooled to room temperature, the solvent was removed by distillation under the reduced pressure, and CH was used₂Cl₂Extraction is carried out. The extract was over MgSO₄Dried, filtered and concentrated. The sample was then purified by silica gel column chromatography to obtain 10.7g of compound D. (yield: 43%, MS [ M + H ]]⁺＝318)

< Synthesis example 4>

4-1)Synthesis of Compound E-1

In a three-necked flask, (9, 9-dimethyl-9H-fluoren-2-yl) boronic acid (20.0g, 84.0mmol) and 1-bromo-4-chloro-2-nitrobenzene (20.9g, 88.2mmol) are dissolved in 300mL of THF and K is added₂CO₃(46.4g, 336.0mmol) was dissolved in 100mL of H₂And adding into the mixture. To which Pd (PPh) was added₃)₄(4.9g, 4.2mmol) and the mixture was stirred under an argon atmosphere for 8 hours. After completion of the reaction, the reaction solution was cooled to room temperature, then transferred to a separatory funnel, and the organic layer was separated. The separated organic solution was over MgSO₄Dried, filtered and concentrated. The resulting product is then dissolved in CH₂Cl₂to this was added dropwise n-hexane to obtain 22.9g of compound E-1. (yield: 78%, MS [ M + H ]]⁺＝350)

4-2)Synthesis of Compound E

Compound E-1(20.0g, 57.2mmol) and triethyl phosphite (58.8mL, 343.0mmol) were added to a two-necked flask, and the mixture was stirred at 120 ℃ for 12 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and added dropwise to distilled water. Ethyl acetate was then added to the separatory funnel and the organic layer was separated. The separated organic solution was over MgSO₄Dried, and then the sample was purified by silica gel column chromatography to obtain 11.8g of compound E. (yield: 65%, MS [ M + H ]]⁺＝318)

< Synthesis example 5>

5-1)synthesis of Compound F-1

in a three-necked flask, 4-bromo-9, 9-dimethyl-9H-fluorene (25.0g, 91.5mmol) and 5-chloro-2-nitroaniline (17.4g, 100.7mmol) were dissolved in 500mL of toluene, and sodium tert-butoxide (13.2g, 137.3mmol) and Pd (P (t-Bu) were added₃)₂(0.9g, 1.8mmol) and then the mixture was stirred under an argon atmosphere under reflux for 6 hours. After completion of the reaction, the reaction solution was cooled to room temperature, and 200mL of H was added thereto₂O, then transferred to a separatory funnel and extracted. The extract was over MgSO₄Dried and concentrated. The sample was purified by silica gel column chromatography to obtain 22.0g of compound F-1. (yield: 66%, MS [ M + H ]]⁺＝365)

5-2)Synthesis of Compound F-2

Compound F-1(22.0g, 60.3mmol), tin (II) chloride anhydride (40.8g, 180.9mmol) and EtOH (400mL) were addedInto a two-necked flask, and the mixture was stirred under reflux for 12 hours. After completion of the reaction, ethanol was distilled under reduced pressure, and then neutralized with a 1N NaOH solution to precipitate a solid. The precipitated solid was filtered and dissolved in toluene, and then transferred to a separatory funnel, washed with water and extracted. The extract was over MgSO₄dried and concentrated to obtain 14.5g of compound F-2 as a solid. (yield: 72%, MS [ M + H ]]⁺＝335)

5-3)Synthesis of Compound F

Compound F-2(14.5g, 43.3mmol), sulfuric acid (12mL), and acetic acid (120mL) were added to a three-necked flask, and the mixture was stirred at 10 ℃ for 10 minutes. Then, sodium nitrate (3.3g, 47.6mmol) was dissolved in 70mL of distilled water and added dropwise for 15 minutes. After stirring for a further 10 minutes, the mixture was stirred at 130 ℃ for 20 minutes. After completion of the reaction, the reaction mixture was cooled to room temperature, and 100mL of H was added thereto₂And O. The precipitated solid was filtered and washed with MeOH. Dissolving the filtered solid in CH₂Cl₂then over MgSO₄And (5) drying. The sample was purified by silica gel column chromatography to obtain 9.2g of compound F. (yield: 67%, MS [ M + H ]]⁺＝318)

< Synthesis example 6>

6-1)Synthesis of Compound 1-1

In a three-necked flask, compound A (15.0g, 47.2mmol) and bromobenzene (7.8g, 49.6mmol) were dissolved in 300mL of toluene, to which were added sodium tert-butoxide (6.8g, 70.8mmol) and Pd (P (t-Bu)₃)₂(0.5g, 0.9mmol) and the mixture was stirred under an argon atmosphere at reflux for 9 hours. After completion of the reaction, the reaction solution was cooled to room temperature, and 200mL of H was added thereto₂O, then transferred to a separatory funnel and fedAnd (5) performing extraction. The extract was over MgSO₄Dried and concentrated. The sample was purified by silica gel column chromatography to obtain 12.1g of compound 1-1. (yield: 70%, MS [ M + H ]]⁺＝365)

6-2)Synthesis of Compound 1

In a three-necked flask, compound 1-1(13.0g, 47.6mmol) and bis ([1,1' -biphenyl ] e]-4-yl) amine (16.8g, 52.3mmol) was dissolved in 260mL of xylene, to which was added sodium tert-butoxide (6.9g, 71.4mmol) and Pd (P (t-Bu)₃)₂(0.5g, 1.0mmol) and the mixture was stirred under an argon atmosphere at reflux for 12 h. After completion of the reaction, the reaction solution was cooled to room temperature, and 200mL of H was added thereto₂O, then transferred to a separatory funnel and extracted. The extract was over MgSO₄Dried and concentrated. The sample was purified by silica gel column chromatography, and then purified by sublimation to obtain 11.0g of compound 1. (yield: 34%, MS [ M + H ]]⁺＝679)

< Synthesis example 7>

Compound 2 was obtained in the same manner as in synthesis example 6, except that N- ([1,1 '-biphenyl ] -3-yl) -9, 9-dimethyl-9H-fluoren-2-amine was used in place of bis ([1,1' -biphenyl ] -4-yl) amine in the preparation of synthesis example 6.

< Synthesis example 8>

8-1)Synthesis of Compound 3-1

Compound 3-1 was obtained in the same manner as in Synthesis example 6-1, except that Compound B was used in place of Compound A in the preparation of Synthesis example 6.

8-2)Synthesis of Compound 3

Compound 3 was obtained in the same manner as in Synthesis example 6-2, except that Compound 3-1 was used in place of Compound 1-1 in the preparation of Synthesis example 6.

< Synthesis example 9>

9-1)Synthesis of Compound 4-1

Compound 4-1 was obtained in the same manner as in Synthesis example 6-1, except that Compound C was used in place of Compound A and 4-bromo-1, 1' -biphenyl was used in place of bromobenzene in the preparation of Synthesis example 6.

9-2)Synthesis of Compound 4

Compound 4 was obtained in the same manner as in Synthesis example 6-2, except that in the production of Synthesis example 6, Compound 4-1 was used in place of Compound 1-1, and N- ([1,1' -biphenyl ] -4-yl) - [1,1' -biphenyl ] -3-amine was used in place of bis ([1,1' -biphenyl ] -4-yl) amine.

< Synthesis example 10>

Compound 5 was obtained in the same manner as in synthesis example 6-2, except that in the preparation process of synthesis example 6, compound 4-1 was used instead of compound 1-1 and N- ([1,1 '-biphenyl ] -4-yl) -9, 9-dimethyl-9H-fluoren-2-amine was used instead of bis ([1,1' -biphenyl ] -4-yl) amine.

< Synthesis example 11>

11-1)Synthesis of Compound 6-1

compound 6-1 was obtained in the same manner as in Synthesis example 6-1, except that Compound D was used in place of Compound A in the preparation of Synthesis example 6.

11-2)Synthesis of Compound 6

Compound 6 was obtained in the same manner as in Synthesis example 6-2, except that Compound 6-1 was used in place of Compound 1-1 in the preparation of Synthesis example 6.

< Synthesis example 12>

Compound 7 was obtained in the same manner as in synthesis example 6-2, except that in the production process of synthesis example 6, compound 6-1 was used instead of compound 1-1, and N- ([1,1 '-biphenyl ] -4-yl) -9, 9-dimethyl-9H-fluoren-2-amine was used instead of bis ([1,1' -biphenyl ] -4-yl) amine.

< Synthesis example 13>

13-1)synthesis of Compound 8-1

Compound 8-1 was obtained in the same manner as in Synthesis example 6-1, except that Compound E was used in place of Compound A in the preparation of Synthesis example 6.

13-2)Synthesis of Compound 8

Compound 8 was obtained in the same manner as in Synthesis example 6-2, except that Compound 8-1 was used in place of Compound 1-1 in the preparation of Synthesis example 6.

< Synthesis example 14>

14-1)Synthesis of Compound 9-1

Compound 9-1 was obtained in the same manner as in Synthesis example 6-1, except that Compound F was used in place of Compound A in the preparation of Synthesis example 6.

14-2)Synthesis of Compound 9

Compound 9 was obtained in the same manner as in synthesis example 6-2, except that in the production process of synthesis example 6, compound 9-1 was used instead of compound 1-1, and N- ([1,1 '-biphenyl ] -4-yl) -9, 9-dimethyl-9H-fluoren-2-amine was used instead of bis ([1,1' -biphenyl ] -4-yl) amine.

< Synthesis example 15>

15-1)Synthesis of Compound 10-1

Mixing compound A (12.0g, 37.8mmol), 2-chloro-4-phenylquinazoline (9.5g, 39.6mmol), and K₃PO₄(12.0g, 56.6mmol), xylene (180mL), and DMAC (60mL) were added to a three-necked flask, and the mixture was stirred under an argon atmosphere under reflux for 8 hours. After completion of the reaction, the reaction solution was cooled to room temperature, and 200mL of H was added thereto₂O, then transferred to a separatory funnel and extracted. The extract was over MgSO₄Dried and concentrated. The sample was purified by silica gel column chromatography to obtain 13.4g of compound 10-1. (yield: 68%, MS [ M + H ]]⁺＝522)

15-2)Synthesis of Compound 10

In a three-necked flask, compound 10-1(13.0g, 24.9mmol) and 9H-carbazole (4.6g, 27.4mmol) were dissolved in 400mL of xylene, and sodium tert-butoxide (3.6g, 37.4mmol) and Pd (P (t-Bu) were added thereto₃)₂(0.3g, 0.5mmol) and the mixture was stirred under an argon atmosphere at reflux for 12 h. After completion of the reaction, the reaction solution was cooled to room temperature, and 200mL of H was added thereto₂O, then transferred to a separatory funnel and extracted. The extract was over MgSO₄Dried and concentrated. The sample was purified by silica gel column chromatography and then by sublimation to obtain 5.4g of compound 10. (yield: 32%, MS [ M + H ]]⁺＝679)

< Synthesis example 16>

Compound 11 was obtained in the same manner as in Synthesis example 15, except that 2-chloro-4- (naphthalen-2-yl) quinazoline was used in place of 2-chloro-4-phenylquinazoline in the preparation of Synthesis example 15.

< Synthesis example 17>

17-1)Synthesis of Compound 12-1

In a three-necked flask, compound A (15.0g, 47.2mmol) and 2- (4-chloronaphthalen-1-yl) -4, 6-diphenyl-1, 3, 5-triazine (13.0g, 33.0mmol) were dissolved in 250mL of toluene, to which was added sodium tert-butoxide (4.5g, 47.2mmol) and Pd (P (t-Bu)₃)₂(0.3g, 0.6mmol) and the mixture was stirred under an argon atmosphere at reflux for 7 hours. After completion of the reaction, the reaction solution was cooled to room temperature, and 150mL of H was added thereto₂O, then transferred to a separatory funnel and extracted. The extract was over MgSO₄dried and concentrated. Mixing the samplePurification by silica gel column chromatography, followed by sublimation was carried out to obtain 11.7g of compound 12-1. (yield: 55%, MS [ M + H ]]⁺＝394)

17-2)Synthesis of Compound 12

Compound 12 was obtained in the same manner as in Synthesis example 15-2, except that Compound 12-1 was used in place of Compound 10-1 in the preparation of Synthesis example 15.

< Synthesis example 18>

Compound 13 was obtained in the same manner as in synthesis example 15, except that compound B was used in place of compound a and 2-chloro-4- (dibenzo [ B, d ] furan-4-yl) quinazoline was used in place of 2-chloro-4-phenylquinazoline in the production process of synthesis example 15.

< Synthesis example 19>

Compound 14 was obtained in the same manner as in synthesis example 17 except that compound C was used in place of compound a and 2-chloro-4-phenylbenzo [4,5] thieno [3,2-d ] pyrimidine was used in place of 2- (4-chloronaphthalen-1-yl) -4, 6-diphenyl-1, 3, 5-triazine in the production process of synthesis example 17.

< Synthesis example 20>

Compound 15 was obtained in the same manner as in synthesis example 17, except that in the production process of synthesis example 17, compound D was used instead of compound a, and 2-chloro-4-phenylbenzo [4,5] furo [3,2-D ] pyrimidine was used instead of 2- (4-chloronaphthalen-1-yl) -4, 6-diphenyl-1, 3, 5-triazine.

< Synthesis example 21>

Compound 16 was obtained in the same manner as in synthesis example 15, except that compound E was used instead of compound a in the preparation of synthesis example 15.

< Synthesis example 22>

Compound 17 was obtained in the same manner as in synthesis example 15, except that compound F was used instead of compound a in the preparation of synthesis example 15.