KR101891432B1 - Amine based compound and organic electronic device using the same - Google Patents

Abstract

The present application relates to compounds and organic electronic devices comprising them.

Description

(AMINE BASED COMPOUND AND ORGANIC ELECTRONIC DEVICE USING THE SAME)

The present application claims the benefit of Korean Patent Application No. 10-2016-0013520 filed on Feb. 03, 2016, the entire contents of which are incorporated herein by reference.

The present application relates to amine-based compounds and organic electronic devices containing them.

An organic electronic device means an element requiring charge exchange between an electrode and an organic material using holes and / or electrons. The organic electronic device can be roughly classified into two types according to the operating principle as described below. First, an exciton is formed in an electron or optoelectronic structure by a photon introduced into an element from an external light source. The exciton is separated into an electron and a hole, and the electron and the hole are transferred to different electrodes, Is an electrical device of the type used. The second type is an electronic device that injects holes and / or electrons into an organic semiconductor that interfaces with an electrode by applying a voltage or current to two or more electrodes, and operates by injected electrons and holes.

Examples of organic electronic devices include organic light emitting devices, organic solar cells, and organic transistors, all of which require hole injecting or transporting materials, electron injecting or transporting materials, or light emitting materials for driving the devices.

International Patent Application Publication No. 2003-012890

The present invention provides an amine compound and an organic electronic device including the same, and in particular, when used as a hole transport material, it can lower the driving voltage of the device, improve the light efficiency, and improve the lifetime characteristics of the device by the thermal stability of the compound have.

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

 [Chemical Formula 1]

In Formula 1,

Ar 1 and Ar 2 are the same or different and are each independently a substituted or unsubstituted aryl group, or Ar 1 and Ar 2 are bonded to each other to form a substituted or unsubstituted ring;

At least one of R 1 to R 4 is a substituted or unsubstituted aryl group and the rest is hydrogen or deuterium, R 5 and R 6 are the same or different and are each independently a substituted or unsubstituted aryl group, And R7 and R8 are the same or different from each other and each independently represents hydrogen; heavy hydrogen; A substituted or unsubstituted aryl group; Or combine with each other to form a substituted or unsubstituted ring;

n and m are integers, and the sum of n and m is 1 or more.

The present application also includes a first electrode; A second electrode facing the first electrode; And at least one organic compound layer disposed between the first electrode and the second electrode, wherein at least one of the organic compound layers includes the compound described above.

The present invention provides an organic light emitting device wherein the organic compound layer containing the compound is a hole injection layer, a hole transport layer, or a layer simultaneously injecting holes and transporting holes.

The compound according to one embodiment of the present application is used in an organic light emitting device to lower the driving voltage of the organic light emitting device, improve the light efficiency, and improve the lifetime characteristics of the device by the thermal stability of the compound.

1 shows an example of an organic light emitting device in which a substrate 1, an anode 2, a light emitting layer 3, and a cathode 4 are sequentially laminated.
2 shows an organic light emitting device in which a substrate 1, an anode 2, a hole injecting layer 5, a hole transporting layer 6, a light emitting layer 3, an electron transporting layer 7 and a cathode 4 are sequentially laminated FIG.

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

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

Examples of substituents herein are described below, but are not limited thereto.

The term "substituted" means that the hydrogen atom bonded to the carbon atom of the compound is replaced with another substituent, and the substituted position is not limited as long as the substituent is a substitutable position, , Two or more substituents may be the same as or different from each other.

As used herein, the term " substituted or unsubstituted " A halogen group; Cyano; A nitro group; A hydroxy group; An alkyl group; An aryl group; And a heterocyclic group, or that two or more of the substituents in the above-exemplified substituents are substituted with a substituent to which they are linked, or have no substituent. For example, "a substituent to which at least two 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, 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 50. Specific examples include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec- N-pentyl, 3-dimethylbutyl, 2-ethylbutyl, heptyl, n-hexyl, Cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethyl Heptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl and the like.

In the present specification, when the aryl group is a monocyclic aryl group, the number of carbon atoms is not particularly limited, but is preferably 6 to 25 carbon atoms. Specific examples of the monocyclic aryl group include a phenyl group, a biphenyl group, a terphenyl group, and the like, but are not limited thereto.

When the aryl group is a polycyclic aryl group, the number of carbon atoms is not particularly limited. And preferably has 10 to 24 carbon atoms. Specific examples of the polycyclic aryl group include naphthyl, anthracenyl, phenanthryl, pyrenyl, perylenyl, klychenyl, fluorenyl, and the like.

In the present specification, the fluorenyl group may be substituted, and adjacent substituents may be bonded to each other to form a ring.

,

,

,

,

,

등이 될 수 있으나, 이에 한정되는 것은 아니다.When the fluorenyl group is substituted,

,

,

,

,

,

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

In the present specification, the heterocyclic group includes at least one non-carbon atom or hetero atom, and specifically, the hetero atom may include at least one atom selected from the group consisting of O, N, Se and S, and the like. The number of carbon atoms of the heterocyclic group is not particularly limited, but is preferably 2 to 60 carbon atoms.

In the present specification, an "adjacent" group may mean a substituent in which the substituent is substituted with an atom directly connected to the substituted atom, or another substituent in which the substituent is substituted with a substituted atom. For example, two substituents substituted at the ortho position in the benzene ring and two substituents substituted at the same carbon in the aliphatic ring may be interpreted as "adjacent" groups to each other.

In the present specification, the adjacent groups bonded to each other to form a ring means that adjacent groups are bonded to each other to form a 5-membered to 8-membered hydrocarbon ring or a 5-to 8-membered heterocyclic ring as described above , Monocyclic or polycyclic, and may be aliphatic, aromatic, or condensed forms thereof, but is not limited thereto.

According to one embodiment of the present application, Ar1 and Ar2 are the same or different and each independently a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, or Ar1 and Ar2 are bonded to each other to form a substituted or unsubstituted ring .

According to one embodiment of the present application, Ar1 and Ar2 are the same or different and are each independently a substituted or unsubstituted phenyl group; A substituted or unsubstituted biphenyl group; Or a substituted or unsubstituted fluorenyl group, or a substituted or unsubstituted carbazole group bonded to each other; Or a substituted or unsubstituted benzocarbazole.

According to one embodiment of the present application, Ar 1 and Ar 2 are the same or different and are each independently a phenyl group substituted or unsubstituted with an alkyl group or an aryl group; A biphenyl group substituted or unsubstituted with an alkyl group or an aryl group; Or a fluorenyl group substituted or unsubstituted with an alkyl group or an aryl group, or a carbazolyl group substituted or unsubstituted with an alkyl group or an aryl group to combine with each other; Or a benzocarbazole group substituted or unsubstituted with an alkyl group or an aryl group.

According to one embodiment of the present application, Ar1 and Ar2 are the same or different and are each independently a phenyl group substituted or unsubstituted with an aryl group; A biphenyl group substituted or unsubstituted with an aryl group; Or a fluorenyl group substituted or unsubstituted with an aryl group, or a carbazolyl group substituted or unsubstituted with an aryl group to combine with each other; Or a benzocarbazole group substituted or unsubstituted with an aryl group.

According to one embodiment of the present application, Ar1 and Ar2 are the same or different and are each independently a phenyl group substituted or unsubstituted with a naphthyl group; Biphenyl group; Or a dimethylfluorenyl group or a carbazole group substituted or unsubstituted with a phenyl group by bonding to each other; Or a benzocarbazole group.

According to one embodiment of the present application, at least one of R 1 to R 4 is a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, and the remainder is hydrogen or deuterium.

According to one embodiment of the application, at least one of R 1 to R 4 is a substituted or unsubstituted phenyl group; A substituted or unsubstituted biphenyl group; A substituted or unsubstituted naphthalene group; A substituted or unsubstituted phenanthrenyl group; A substituted or unsubstituted terphenyl group; A substituted or unsubstituted anthracene group; A substituted or unsubstituted triphenylene group; A substituted or unsubstituted fluorene group; A substituted or unsubstituted phenylene group; A substituted or unsubstituted pyrene group; Or a substituted or unsubstituted tetracene group, and the remainder is hydrogen or deuterium.

According to one embodiment of the present application, at least one of R 1 to R 4 is a phenyl group; A biphenyl group; A naphthalene group; A phenanthrenyl group; A terphenyl group; Anthracene group; Triphenylene group; A fluorene group; Phenylene; Pyrene; Or tetracene group, and the remainder is hydrogen or deuterium.

According to one embodiment of the present application, at least one of R 1 to R 4 is a phenyl group; A biphenyl group; A naphthalene group; Phenanthrenyl group; And the remainder is hydrogen or deuterium.

According to one embodiment of the present application, at least one of R1 to R4 is selected from the following formulas, and the remainder is hydrogen or deuterium.

According to one embodiment of the present application, R5 and R6 are the same or different and each independently an aryl group having 6 to 50 carbon atoms, or each of R5 and R6 is bonded to an adjacent group to form a substituted or unsubstituted ring.

According to one embodiment of the present application, R5 and R6 are the same or different and each independently a substituted or unsubstituted phenyl group; A substituted or unsubstituted biphenyl group; A substituted or unsubstituted naphthalene group; A substituted or unsubstituted phenanthrenyl group; A substituted or unsubstituted terphenyl group; A substituted or unsubstituted anthracene group; A substituted or unsubstituted triphenylene group; A substituted or unsubstituted fluorene group; A substituted or unsubstituted pyrene group; Or a substituted or unsubstituted tetracene group, or each is bonded to an adjacent group to form a substituted or unsubstituted ring.

According to one embodiment of the present application, R5 and R6 are the same or different and are each independently a substituted or unsubstituted phenyl group; A substituted or unsubstituted naphthyl group, or a substituted or unsubstituted benzene ring bonded to adjacent groups; Or a substituted or unsubstituted hydroindene ring.

According to one embodiment of the present application, R5 and R6 are the same or different and are each independently a substituted or unsubstituted phenyl group; Or a substituted or unsubstituted naphthyl group, or a benzene ring substituted with an adjacent alkyl group or an aryl group to form a benzene ring; Or a hydroindene ring substituted or unsubstituted with an alkyl group or an aryl group.

According to one embodiment of the present application, R5 and R6 are the same as or different from each other, and are each independently a phenyl group; Or a naphthyl group, or may combine with adjacent groups to form a benzene ring; Or a hydroindene ring substituted with an alkyl group.

According to one embodiment of the present application, R5 and R6 are the same as or different from each other, and are each independently a phenyl group; Or a naphthyl group, or may combine with adjacent groups to form a benzene ring; Or a hydroindene ring substituted with a methyl group.

According to one embodiment of the present application, R7 and R8 are the same or different and are each independently hydrogen or deuterium, or directly bonded to each other to form a substituted or unsubstituted ring.

According to one embodiment of the present application, R7 and R8 are hydrogen.

According to one embodiment of the present application, R7 and R8 are directly bonded to each other to form a carbazole group.

구조에서 R5 또는 R6는 인접한 기와 결합하여 벤젠고리를 형성하고, R7과 R8은 서로 직접결합하여, 벤조카바졸기를 형성한다. According to one embodiment of the present application,

In the structure, R5 or R6 combine with adjacent groups to form a benzene ring, and R7 and R8 directly bond to each other to form a benzocarbazole group.

According to one embodiment of the present application, m + n is 1

According to one embodiment of the present application, m is 0 and n is 1

According to one embodiment of the present application, m is 1 and n is 1

According to one embodiment of the present application, m is 2 and n is 0

According to one embodiment of the present application, the compound represented by Formula 1 may be any one selected from the following structural formulas.

The compound according to one embodiment of the present application can be produced by a production method described below.

(1,1 ': 3', 1 "-terphenyl] -4,4'-diamine (solution) or [1,1 ': 3' -Quaterphenyl] -4 '', 6'-diamine and aryl halide (2 equivalents) are completely dissolved in toluene, the base (1.2 equivalents) is added and the mixture is stirred at reflux temperature. Once reflux begins, slowly drop the palladium catalyst (0.01 equiv). After 6 to 12 hours, the reaction was terminated, the temperature was lowered to room temperature, the reaction mixture was concentrated under reduced pressure, and the column was purified to prepare Intermediate A.

Compound A was prepared by proceeding in the same manner as in the above synthesis process except that the intermediate A obtained in the above reaction was used and the other aryl halide was used.

및

는 아릴기를 의미하며, 구체적으로 치환 또는 비치환된 아릴기를 의미하며, X는 I, Br, Cl의 할라이드를 의미하나 이에 한정되는 것은 아니다.In this reaction

And

Means an aryl group, specifically a substituted or unsubstituted aryl group, and X means a halide of I, Br or Cl, but is not limited thereto.

The compounds represented by the formula (1) may have properties suitable for being used as organic layers used in organic electronic devices by introducing various substituents into the core structure represented by the above formula.

In one embodiment of the present disclosure, the first electrode; A second electrode facing the first electrode; And at least one organic material layer provided between the first electrode and the second electrode, wherein at least one of the organic material layers includes the compound of the formula (1).

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

In one embodiment of the present invention, the organic material layer includes a hole injecting layer, a hole transporting layer, or a layer simultaneously injecting and transporting holes, and the hole injecting layer, the hole transporting layer, (1).

In one embodiment of the present application, the organic layer includes an electron blocking layer, and the electron blocking layer includes the compound of the above formula (1).

In one embodiment of the present application, the organic layer includes a hole transporting layer, and the hole transporting layer includes the compound of the above formula (1).

In one embodiment of the present application, the organic light emitting element is a hole injecting layer, a hole transporting layer. An electron transport layer, an electron injection layer, an electron blocking layer, and a hole blocking layer.

In another embodiment, the organic electronic device 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 another embodiment, the organic electronic device may be an inverted type organic light emitting device in which a cathode, at least one organic layer, and an anode are sequentially stacked on a substrate.

The organic electronic device according to the present embodiment may have the structure as shown in Figs. 1 and 2, but the present invention is not limited thereto.

1 shows a structure of an organic electronic device in which a substrate 1, an anode 2, a light emitting layer 3, and a cathode 4 are sequentially laminated.

2 shows an organic electronic device in which a substrate 1, an anode 2, a hole injecting layer 5, a hole transporting layer 6, a light emitting layer 3, an electron transporting layer 7 and a cathode 4 are sequentially stacked Structure is illustrated.

The organic electronic device of the present invention can be manufactured by materials and methods known in the art, except that one or more of the organic layers includes the compound of the present invention, i.e., the compound of the above formula (1).

When the organic electronic device includes a plurality of organic layers, the organic layers may be formed of the same material or another material.

The organic electronic device of the present invention can be manufactured by materials and methods known in the art, except that one or more of the organic layers include the compound of the above formula (1), that is, the compound represented by the above formula (1).

For example, the organic electronic device of the present specification can be manufactured by sequentially laminating a first electrode, an organic material layer, and a second electrode on a substrate. At this time, a PVD (Physical Vapor Deposition) method such as sputtering or e-beam evaporation is used to deposit a metal or a metal oxide having conductivity or an alloy thereof on a substrate to form a positive electrode Forming an organic material layer including a hole injecting layer, a hole transporting layer, a light emitting layer and an electron transporting layer thereon, and depositing a material usable as a cathode thereon. In addition to such a method, an organic electronic device can be formed by sequentially depositing a negative electrode material, an organic material layer, and a positive electrode material on a substrate.

In addition, the compound of Formula 1 may be formed into an organic material layer by a solution coating method as well as a vacuum evaporation method in the production of an organic electronic 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 electronic device may be fabricated by sequentially depositing an organic material layer and a cathode material on a substrate from a cathode material (International Patent Application Publication No. 2003/012890). However, the manufacturing method is not limited thereto.

In one embodiment of the present invention, the first electrode is an anode and the second electrode is a cathode.

In another embodiment, 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 into the organic material layer. Specific examples of the cathode material that can be used in the present invention 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 preferable 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. The hole transport material is a material capable of transporting holes from the anode or the hole injection layer to the light emitting layer. The material is suitable. Specific examples include arylamine-based organic materials, conductive polymers, and block copolymers having a conjugated portion and a non-conjugated portion together, but are not limited thereto.

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

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

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

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

The electron injection layer is a layer for injecting electrons from the electrode. The electron injection layer has the ability to transport electrons, has an electron injection effect from the cathode, and has an excellent electron injection effect with respect to the light emitting layer or the light emitting material. A compound which prevents migration to a layer and is excellent in a thin film forming ability is preferable. Specific examples thereof include fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preorenylidene methane, A complex compound and a nitrogen-containing five-membered ring derivative, 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 electronic device according to the present invention may be a top emission type, a back emission type, or a both-sided emission type, depending on the material used.

In one embodiment of the present invention, the compound of Formula 1 may be included in an organic solar cell or an organic transistor in addition to an organic electronic device.

Hereinafter, the present invention will be described in detail by way of examples with reference to the drawings. However, the embodiments according to the present disclosure can be modified in various other forms, and the scope of the present specification is not construed as being limited to the embodiments described below. Embodiments of the present disclosure are provided to more fully describe the present disclosure to those of ordinary skill in the art.

[Synthesis of compound 1]

10 g (31.14 mmol) of N - ([1,1'-biphenyl] -4-yl) - [1,1'-biphenyl] -2-amine are dissolved in 80 ml of DMF at room temperature. The completely dissolved solution is cooled to 0 ° C and then 5.51 g (31.14 mmol) of N-bromosuccinimide dissolved in DMF is slowly added dropwise thereto. After stirring for 3 hours, the temperature is raised to room temperature and the solution is quenched into water. (74%) of N - ([1,1'-biphenyl] -4-yl) -5-bromo- [1,1'- biphenyl] -2-amine, Intermediate 1A was synthesized .

9.2 g (23.05 mmol) of Intermediate 1A obtained in the above reaction and 10.2 g (23.05 mmol) of (4- (di ([1,1'-biphenyl] -4-yl) amino) phenyl) boronic acid were added to 60 ml of THF, . To this is added an aqueous solution of 6.4 g (46.1 mmol) of potassium carbonate and the temperature is raised to reflux. 0.5 g (2 mol%) of tetrakis (triphenylphosphine) palladium (TTP) (Tetrakis (triphenylphosphine) palladium) was added thereto, and the reaction was terminated by stirring for 5 hours. After separation of water and organic layer, column purification yielded 11.9 g (72%) of N4, N4, N4'-tri ([1,1'- biphenyl] -4-yl) - [1,1 ': 3', 1 '' -terphenyl] -4,4'-diamine, Intermediate 1B was synthesized.

11.9 g (16.61 mmol) of Intermediate 1B obtained in the above reaction, 3.4 g (16.61 mmol) of iodobenzene and 1.9 g (19.93 mmol) of sodium t-butoxide are placed in 40 ml of toluene and the temperature is raised to reflux. 0.09 g (1 mol%) of bis (tri-tert-butylphosphine) palladium (0), that is, BTP (tri-tert-butylphosphine) palladium (0) is slowly added dropwise. After completion of the reaction for 3 hours, the reaction mixture was subjected to column purification to obtain 8.9 g (68%) of the compound 1.

MS [M + H] < ⁺ > = 793

[Synthesis of Compound 2]

10 g (31.14 mmol) of N - ([1,1'-biphenyl] -4-yl) - [1,1'- (75%) of N - ([1,1'-biphenyl] -4-yl) -N-phenyl- [1,1'- biphenyl] -2-amine, Intermediate 2A was synthesized.

(81%) of N - ([1,1'-biphenyl] -4- (4-fluorophenyl) -4- yl) -5-bromo-N-phenyl- [1,1'-biphenyl] -2-amine, intermediate 2B.

The reaction was carried out in the same manner as in the synthesis of Intermediate 1B except that 9.0 g (18.94 mmol) of Intermediate 2B obtained in the above reaction and 5.4 g (18.94 mmol) of (4- (9H-carbazol-9-yl) phenyl) boronic acid were used Purification yielded 7.9 g (65%) of compound 2.

MS [M + H] < ⁺ > = 639

[Synthesis of Compound 3]

The reaction and purification were carried out in the same manner as in the synthesis of Intermediate 1B except that 5 g (24.40 mmol) of 2-bromo-4-chloroaniline and 6.6 g (24.40 mmol) of triphenylen-2-ylboronic acid were used and 6.5 g (75% -chloro-2- (triphenylen-2-yl) aniline, intermediate 3A.

The reaction and purification were performed in the same manner as in the synthesis of intermediate 2A except that 6.5 g (18.41 mmol) of Intermediate 3A obtained in the above reaction and 4.3 g (18.41 mmol) of 2-bromo-1,1'- %) Of N- (4-chloro-2- (triphenylen-2-yl) phenyl) - [1,1'-biphenyl] -2-amine.

The reaction and purification were performed in the same manner as in the synthesis of Intermediate 2A except that 6.3 g (12.47 mmol) of Intermediate 3B obtained in the above reaction and 2.5 g (12.47 mmol) of Iodobenzene were used and 5.6 g (77%) of N- 2- (triphenylen-2-yl) phenyl) -N-phenyl- [1,1'-biphenyl] -2-amine. Intermediate 3C was synthesized.

(11.52 mmol) of bis (pinacolato) diboron, 1.2 g (12.48 mmol) of potassium acetate and 0.05 g (2 mol%) of PCy3 were dissolved in 25 ml of 1,4- And the temperature is raised to reflux condition with stirring. 0.2 g (2 mol%) of Pd (dba) 2 was slowly added thereto and stirred, and the reaction was terminated after 5 hours. The column was purified to obtain 4.5 g (69%) of N-phenyl-N- (4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan- yl) phenyl) - [1,1'-biphenyl] -2-amine, Intermediate 3D.

(4-bromophenyl) -3-phenyl-9H-carbazole was used instead of 4.5 g (6.68 mmol) of Intermediate 3D obtained in the above reaction, ) Was synthesized.

MS [M + H] < ⁺ > = 866

[Synthesis of Compound 4]

5 g (10.5 mmol) of N - ([1,1'-biphenyl] -4-yl) -5-bromo-N-phenyl- [1,1'- biphenyl] ° C. Add 7.3 ml (12.6 mmol) of n-BuLi (2.5 M in Hexane) slowly dropwise thereto. After stirring for 0.5 hr, 3.4 ml (14.7 mmol) of (iPrO 3B) was further added thereto, followed by stirring at room temperature. After 1 hour, NH4Cl aqueous solution was added to quench the reaction, and the reaction was terminated and purified to obtain 3.8 g (82%) of [(1,1'-biphenyl) -4-yl (phenyl) amino) - [1,1'-biphenyl] -yl) boronic acid, intermediate 4A.

(8.6 mmol) of Intermediate 4A obtained in the above reaction and N - ([1,1'-biphenyl] -4-yl) -5-bromo-N-phenyl- [ Was reacted and purified in the same manner as in the synthesis of Intermediate B, except that 4.8 g (71%) of Compound 4 was synthesized

MS [M + H] < ⁺ > = 794

[Synthesis of compound 5]

5 g (23.03 mmol) of 11H-benzo [a] carbazole and 7.3 g (23.03 mmol) of 2-bromo-4-chloro-1-iodobenzene are dissolved in 60 ml of xylene and stirred. 2.6 g (46.06 mmol) of KOH and 0.8 g (4.61 mmol) of 1,10-phenanthroline were added thereto, and the mixture was heated under reflux conditions. After that, 0.9 g (4.61 mmol) of CuI was slowly added dropwise, stirred, and then terminated after 5 hours. After cooling to room temperature, the mixture was filtered through a celite pad and purified by column. 6.2 g (66%) of 11- (2-bromo-4-chlorophenyl) -11H-benzo [a] carbazole and intermediate 5A were synthesized.

The reaction and purification were performed in the same manner as in the synthesis of Intermediate 1B except that 6.2 g (15.31 mmol) of Intermediate 5A obtained in the above reaction and 2.6 g (15.31 mmol) of naphthalen-1-ylboronic acid were used and 5.1 g (74% - (4-chloro-2- (naphthalen-1-yl) phenyl) -11H-benzo [a] carbazole. Intermediate 5B was synthesized.

Except that 5.1 g (11.25 mmol) of Intermediate 5B obtained in the above reaction and (4 - ([1,1'-biphenyl] -4-yl (phenyl) amino) phenyl) boronic acid were used. The reaction was carried out in the same manner and purified to obtain 6.4 g (77%) of Compound 5.

MS [M + H] < ⁺ > = 739

[Synthesis of Compound 6]

The reaction and purification were performed in the same manner as in the synthesis of Compound 1 except that 10 g (13.96 mmol) of Intermediate 1B and 3.9 g (13.96 mmol) of 4-iodo-1,1'-biphenyl were used and 9.3 g (77% 6 was synthesized.

MS [M + H] < ⁺ > = 870

[Synthesis of Compound 7]

Except for using 10 g (31.14 mmol) of Di ([1,1'-biphenyl] -4-yl) amine and 9.8 g (31.14 mmol) of 2-bromo-4-chloro-1-iodobenzene. The reaction was carried out in the same manner and then purified to obtain 5.9 g (59%) of N - ([1,1'-biphenyl] -4-yl) -N- (2-bromo-4-chlorophenyl) - [ -4-amine, intermediate 7A.

4.1 g (70%) of the compound 5 was reacted and purified in the same manner as in the synthesis of the compound 5 except that 5.9 g (11.59 mmol) of Intermediate 7A and 2.3 g (11.59 mmol) of [1,1'-biphenyl] Synthesis of N, N-di ([1,1'-biphenyl] -4-yl) -5-chloro- [1,1 ': 4', 1 "-terphenyl] -2- Respectively.

(80%) of N, N-di ([1,1'-biphenyl] -1,3,4-thiadiazol-2-yl) benzamide was reacted and purified in the same manner as in the synthesis of Intermediate 3D, except that 4.1 g (8.1 mmol) -4-yl) -5- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) - [1,1 ': 4', 1 " amine, intermediate 7C were synthesized

4-yl) -N- (4-bromophenyl) - [1,1'-biphenyl] -4-amine Was reacted and purified in the same manner as in the synthesis of Intermediate 1B except that 3.1 g (6.5 mmol) of Intermediate 1B was used to synthesize 4.7 g (77%) of Compound 7.

MS [M + H] < ⁺ > = 946

[Synthesis of Compound 8]

The reaction and purification were performed in the same manner as in the synthesis of Intermediate 7B except that 10 g (19.64 mmol) of Intermediate 7A and 3.4 g (19.64 mmol) of naphthalen-2-ylboronic acid were used and 8.4 g (77% 4-yl) -N- (4-chloro-2- (naphthalen-2-yl) phenyl) - [1,1'-biphenyl] -4-amine.

The reaction and purification were performed in the same manner as in the synthesis of Intermediate 3D, except that 8.4 g (15.07 mmol) of Intermediate 8A obtained in the above reaction was used, yielding 7.1 g (85%) of N- (1,1'-biphenyl- yl) -N- (2- (naphthalen-2-yl) -4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan- biphenyl] -4-amine, intermediate 8B.

The reaction was carried out in the same manner as in the synthesis of Intermediate 1B except 7.1 g (12.93 mmol) of Intermediate 8B obtained in the above reaction and 5.1 g (12.93 mmol) of 9- (4-bromophenyl) 8.4 g (77%) of Compound 8 was synthesized.

MS [M + H] < ⁺ > = 842

[Synthesis of Compound 9]

9.8 g (31.14 mmol) of 2-bromo-4-chloro-1-iodobenzene and 10 g (31.14 mmol) of N - ([1,1'- biphenyl] -4-yl) - [1,1'- mmol) was reacted and purified in the same manner as in the synthesis of Intermediate 5A, except that 12.2 g (77%) of N - ([1,1'-biphenyl] -4-yl) 4-chlorophenyl) - [1,1'-biphenyl] -2-amine, Intermediate 9A was synthesized.

The reaction and purification were carried out in the same manner as in the synthesis of Intermediate 7B except that 12.2 g (23.97 mmol) of Intermediate 9A obtained in the above reaction and 5.3 g (23.97 mmol) of phenanthren-9-ylboronic acid were used and 9.9 g (68% - (1,1'-biphenyl] -4-yl) -N- (4-chloro-2- (phenanthren- Were synthesized.

The reaction and purification were performed in the same manner as in the synthesis of Intermediate 3D, except that 9.9 g (16.3 mmol) of Intermediate 9B obtained in the above reaction was used to obtain 8.8 g (77%) of N - ([1,1'-biphenyl] -4- yl) -N- (2-bromo-4-chlorophenyl) - [1,1'-biphenyl] -2-amine. Intermediate 9C was synthesized.

8.8 g (12.58 mmol) of Intermediate 9C obtained in the above reaction was reacted with N - ([1,1'-biphenyl] -4-yl) -N- (4-bromophenyl) - [ Was reacted and purified in the same manner as in the synthesis of Intermediate 1B except that 5.9 g (12.58 mmol) of Intermediate 1B was used. 8.4 g (69%) of Compound 9 was synthesized.

MS [M + H] < ⁺ > = 970

[Synthesis of Compound 10]

The reaction and purification were carried out in the same manner as in the synthesis of Compound 2 except that 10 g (25.06 mmol) of Intermediate 1A was used to obtain 11.4 g (81%) of N - ([1,1'-biphenyl] - (9H-carbazol-9-yl) - [1,1 ': 3', 1 "-terphenyl] -4'-amine, Intermediate 10A.

Compound 9 was obtained by reacting and purifying in the same manner as in the synthesis of Compound 1 except that 11.4 g (20.28 mmol) of Intermediate 10A and 4-iodo-1,1'-biphenyl were used.

MS [M + H] < ⁺ > = 715

[Synthesis of compound 11]

(68%) of the compound 10, except that 10 g (17.79 mmol) of Intermediate 10A and 4.8 g (17.79 mmol) of 2-bromo-9,9-dimethyl-9H- Of Compound 11 was synthesized.

MS [M + H] < ⁺ > = 755

< Example >

< Experimental Example 1 -1>

The glass substrate coated with ITO (indium tin oxide) thin film with a thickness of 1,000 Å was immersed in distilled water containing detergent and washed with ultrasonic waves. In this case, Fischer Co. was used as a detergent, and distilled water filtered by a filter of Millipore Co. was used as distilled water. The ITO was washed for 30 minutes and then washed twice with distilled water and ultrasonically cleaned for 10 minutes. After the distilled water was washed, it was ultrasonically washed with a solvent of isopropyl alcohol, acetone, and methanol, dried, and then transported to a plasma cleaner. Further, the substrate was cleaned using oxygen plasma for 5 minutes, and then the substrate was transported by a vacuum evaporator.

On this ITO transparent electrode, hexanitrile hexaazatriphenylene (HAT) of the following chemical formula was thermally vacuum deposited to a thickness of 500 Å to form a hole injection layer.

[LINE]

Compound 1, which is a material for transporting holes, was vacuum-deposited on the hole injection layer to form a hole transport layer.

 [Compound 1]

Subsequently, EB 1 (TCTA) having a thickness of 100 Å was vacuum deposited on the hole transport layer to form an electron blocking layer.

[EB 1]

Subsequently, BH and BD were vacuum deposited on the electron blocking layer to a thickness of 300 ANGSTROM at a weight ratio of 25: 1 to form a light emitting layer.

[BH] [BD]

On the light emitting layer, the following compound ET1 and LiQ (Lithium Quinolate) were vacuum deposited at a weight ratio of 1: 1 to form an electron injection and transport layer having a thickness of 300 Å.

[ET1] [LiQ]

Lithium fluoride (LiF) and aluminum were deposited to a thickness of 2000 Å on the electron injecting and transporting layer sequentially to form a cathode.

Was maintained at the deposition rate was 0.4 ~ 0.7Å / sec for organic material in the above process, the lithium fluoride of the cathode was 0.3Å / sec, aluminum is deposited at a rate of 2Å / sec, the degree of vacuum upon deposition ⅹ10 2 ^-7 To 5 x 10 &lt; ^-6 &gt; torr, thereby fabricating an organic light emitting device.

<Experimental Example 1-2>

An organic light emitting device was fabricated in the same manner as in Experimental Example 1-1, except that Compound 2 was used instead of Compound 1 in Experimental Example 1-1.

<Experimental Example 1-3>

An organic light emitting device was fabricated in the same manner as in Experimental Example 1-1, except that Compound 3 was used instead of Compound 1 in Experimental Example 1-1.

<Experimental Example 1-4>

An organic light emitting device was fabricated in the same manner as in Experimental Example 1-1, except that Compound 4 was used instead of Compound 1 in Experimental Example 1-1.

<Experimental Example 1-5>

An organic light emitting device was fabricated in the same manner as in Experimental Example 1-1, except that Compound 5 was used instead of Compound 1 in Experimental Example 1-1.

<Experimental Example 1-6>

An organic light emitting device was fabricated in the same manner as in Experimental Example 1-1, except that Compound 6 was used instead of Compound 1 in Experimental Example 1-1.

<Experimental Example 1-7>

An organic light emitting device was fabricated in the same manner as in Experimental Example 1-1, except that Compound 7 was used instead of Compound 1 in Experimental Example 1-1.

 <Experimental Example 1-8>

An organic light emitting device was fabricated in the same manner as in Experimental Example 1-1, except that Compound 8 was used instead of Compound 1 in Experimental Example 1-1.

<Experimental Example 1-9>

An organic light emitting device was fabricated in the same manner as in Experimental Example 1-1, except that Compound 9 was used instead of Compound 1 in Experimental Example 1-1.

<Experimental Example 1-10>

An organic light emitting device was fabricated in the same manner as in Experimental Example 1-1, except that Compound 10 was used instead of Compound 1 in Experimental Example 1-1.

<Experimental Example 1-11>

An organic light emitting device was fabricated in the same manner as in Experimental Example 1-1, except that Compound 11 was used instead of Compound 1 in Experimental Example 1-1.

&Lt; Comparative Example 1-1 >

An organic light emitting device was fabricated in the same manner as in Experimental Example 1-1 except that HT 1 was used instead of Compound 1 in Experimental Example 1-1.

[HT 1]

&Lt; Comparative Example 1-2 >

An organic light emitting device was fabricated in the same manner as in Experimental Example 1-1 except that HT 2 was used instead of Compound 1 in Experimental Example 1-1.

[HT 2]

division compound
(Hole transport layer) Voltage
(V @ 10 mA / cm ² ) efficiency
(cd / A @ 10mA / cm 2) Color coordinates
(x, y) Experimental Example 1-1 Compound 1 4.55 5.75 (0.139, 0.122) Experimental Example 1-2 Compound 2 4.52 5.78 (0.138, 0.126) Experimental Example 1-3 Compound 3 4.30 5.96 (0.138, 0.127) Experimental Examples 1-4 Compound 4 4.31 5.94 (0.137, 0.125) Experimental Examples 1-5 Compound 5 4.59 5.73 (0.136, 0.125) Experimental Example 1-6 Compound 6 4.54 5.77 (0.136, 0.127) Experimental Example 1-7 Compound 7 4.50 5.78 (0.136, 0.125) Experimental Examples 1-8 Compound 8 4.44 5.71 (0.137, 0.125) Experimental Examples 1-9 Compound 9 4.43 5.78 (0.138, 0.125) Experimental Example 1-10 Compound 10 4.44 5.72 (0.136, 0.125) Experimental Example 1-11 Compound 11 4.43 5.77 (0.137, 0.125) Comparative Example 1-1 HT 1 5.45 5.37 (0.136, 0.125) Comparative Example 1-2 HT 2 5.42 5.29 (0.138, 0.126)

As shown in Table 1, when the compound of the present invention is included in the organic material layer of the organic light emitting diode, particularly, the hole transport layer, it is confirmed that the efficiency is higher than that of Comparative Examples 1-1 and 1-2 and the driving voltage is low there was. Also, it was confirmed that the compound of the formula (1) had better efficiency and lower driving voltage than the compound of Comparative example 1-2 where n + m is 0.

1: substrate
2: anode
3: light emitting layer
4: cathode
5: Hole injection layer
6: hole transport layer
7: Electron transport layer

Claims (10)

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

In Formula 1,
Ar 1 and Ar 2 are the same or different and are each independently a substituted or unsubstituted aryl group, or Ar 1 and Ar 2 are bonded to each other to form a substituted or unsubstituted ring;
At least one of R 1 to R 4 is a substituted or unsubstituted aryl group and the rest is hydrogen or deuterium, R 5 and R 6 are the same or different and are each independently a substituted or unsubstituted aryl group, And R7 and R8 are the same or different from each other and each independently represents hydrogen; heavy hydrogen; A substituted or unsubstituted aryl group; Or combine with each other to form a substituted or unsubstituted ring;
n and m each are an integer of 0 to 4, the sum of n and m is 1 or more,
The term " substituted or unsubstituted " A halogen group; Cyano; A nitro group; A hydroxy group; An alkyl group; An aryl group; And a heterocyclic group, or wherein at least two of the substituents in the substituent are substituted with a substituent to which they are linked, or have no substituent. The compound according to claim 1, wherein at least one of R 1 to R 4 is selected from the following formulas, and the remainder is hydrogen or deuterium.

[2] The compound according to claim 1, wherein Ar1 and Ar2 are the same or different and are each independently a substituted or unsubstituted phenyl group; A substituted or unsubstituted biphenyl group; Or a substituted or unsubstituted fluorenyl group, or a substituted or unsubstituted carbazole group bonded to each other; Or a substituted or unsubstituted benzocarbazole group:
The term " substituted or unsubstituted " A halogen group; Cyano; A nitro group; A hydroxy group; An alkyl group; An aryl group; And a heterocyclic group, or wherein at least two of the substituents in the substituent are substituted with a substituent to which they are linked, or have no substituent. [4] The compound according to claim 1, wherein R5 and R6 are the same or different and each independently is a substituted or unsubstituted phenyl group; A substituted or unsubstituted naphthyl group, or a substituted or unsubstituted benzene ring bonded to adjacent groups; Or a substituted or unsubstituted hydroindenyl ring.
The term " substituted or unsubstituted " A halogen group; Cyano; A nitro group; A hydroxy group; An alkyl group; An aryl group; And a heterocyclic group, or wherein at least two of the substituents in the substituent are substituted with a substituent to which they are linked, or have no substituent. 2. The compound of claim 1, wherein R7 and R8 are independently selected from the group consisting of hydrogen; Or directly bonded to each other to form a carbazole group. The compound of claim 1, wherein the compound of formula (1) is selected from the following formulas:

A first electrode; A second electrode facing the first electrode; And at least one organic compound layer provided between the first electrode and the second electrode, wherein at least one of the organic compound layers comprises a compound according to any one of claims 1 to 6 Organic electronic device. The organic electroluminescent device according to claim 7, wherein the organic compound layer includes a hole injecting layer, a hole transporting layer, or a layer simultaneously injecting holes and transporting holes, wherein the hole injecting layer, the hole transporting layer, Organic electronic device. The organic electronic device according to claim 7, wherein the organic layer includes an electron blocking layer, and the electron blocking layer comprises the compound. The organic electroluminescent device according to claim 7, wherein the organic electronic device comprises one or more layers selected from the group consisting of a hole injection layer, a hole transport layer, an electron transport layer, an electron injection layer, an electron blocking layer and a hole blocking layer. device.

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