KR101968213B1 - Heterocyclic compound and organic light emitting device comprising the same - Google Patents

Heterocyclic compound and organic light emitting device comprising the same Download PDF

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KR101968213B1
KR101968213B1 KR1020160024321A KR20160024321A KR101968213B1 KR 101968213 B1 KR101968213 B1 KR 101968213B1 KR 1020160024321 A KR1020160024321 A KR 1020160024321A KR 20160024321 A KR20160024321 A KR 20160024321A KR 101968213 B1 KR101968213 B1 KR 101968213B1
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substituted
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차용범
조성미
허동욱
홍성길
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주식회사 엘지화학
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D279/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one sulfur atom as the only ring hetero atoms
    • C07D279/10—1,4-Thiazines; Hydrogenated 1,4-thiazines
    • C07D279/14—1,4-Thiazines; Hydrogenated 1,4-thiazines condensed with carbocyclic rings or ring systems
    • C07D279/18—[b, e]-condensed with two six-membered rings
    • C07D279/22—[b, e]-condensed with two six-membered rings with carbon atoms directly attached to the ring nitrogen atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D265/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one oxygen atom as the only ring hetero atoms
    • C07D265/28—1,4-Oxazines; Hydrogenated 1,4-oxazines
    • C07D265/34—1,4-Oxazines; Hydrogenated 1,4-oxazines condensed with carbocyclic rings
    • C07D265/38—[b, e]-condensed with two six-membered rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D279/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one sulfur atom as the only ring hetero atoms
    • C07D279/10—1,4-Thiazines; Hydrogenated 1,4-thiazines
    • C07D279/14—1,4-Thiazines; Hydrogenated 1,4-thiazines condensed with carbocyclic rings or ring systems
    • C07D279/18—[b, e]-condensed with two six-membered rings
    • C07D279/34—[b, e]-condensed with two six-membered rings with hetero atoms directly attached to the ring sulfur atom
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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    • H01L51/0071—
    • H01L51/5012—
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H05B33/14—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of the electroluminescent material, or by the simultaneous addition of the electroluminescent material in or onto the light source
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
    • C09K2211/1033—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with oxygen
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
    • C09K2211/1037—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with sulfur

Abstract

The present specification provides a heterocyclic compound of Formula 1 or 2 and an organic light emitting device including the same.

Description

Heterocyclic compound and organic light emitting device comprising the same {HeTEROCYCLIC COMPOUND AND ORGANIC LIGHT EMITTING DEVICE COMPRISING THE SAME}

The present specification relates to a heterocyclic compound and an organic light emitting device including the same.

In general, organic light emitting phenomenon refers to a phenomenon of converting electrical energy into light energy using an organic material. An organic light emitting device using an organic light emitting phenomenon usually has a structure including an anode, a cathode, and an organic material layer therebetween. The organic material layer is often made of a multi-layered structure composed of different materials to increase the efficiency and stability of the organic light emitting device, for example, it may be made of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer. When the voltage is applied between the two electrodes in the structure of the organic light emitting device, holes are injected into the organic material layer at the anode and electrons are injected into the organic material layer, and excitons are formed when the injected holes and the electrons meet each other. When it falls back to the ground, it glows.

There is a continuing need for the development of new materials for such organic light emitting devices.

Korean Patent Publication No. 2000-0051826

Described herein is a heterocyclic compound and an organic light emitting device comprising the same.

An exemplary embodiment of the present specification provides a compound represented by Formula 1:

[Formula 1]

Figure 112016019751857-pat00001

In Chemical Formula 1,

X is S, O or SO 2 ,

Ar1 is a phenyl group substituted with deuterium, an alkyl group, an aryl group or a heteroaryl group; Two or more substituted or unsubstituted aryl groups; Substituted or unsubstituted dibenzofuran group; Substituted or unsubstituted dibenzothiophene group; Substituted or unsubstituted triazine group, substituted or unsubstituted pyrimidine group; Substituted or unsubstituted pyridine group; Substituted or unsubstituted quinazoline group; Substituted or unsubstituted quinoline group; Substituted or unsubstituted benzocarbazole group; Or a substituted or unsubstituted carbazole group, R 1 and R 2 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; Substituted or unsubstituted alkoxy group; Substituted or unsubstituted aryloxy group; A substituted or unsubstituted aralkyl group; Substituted or unsubstituted alkylaryl group; Substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group, n is an integer of 0 to 3, m is an integer of 0 to 4,

L 1 is a direct bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted phenanthrene group; Or a substituted or unsubstituted fluorenylene group,

Y1 is selected from the following structural formula,

Figure 112016019751857-pat00002
Figure 112016019751857-pat00003
Figure 112016019751857-pat00004

Figure 112016019751857-pat00005
Figure 112016019751857-pat00006

Ar2 and Ar3 are the same as or different from each other, a substituted or unsubstituted aryl group, and * is a moiety bonded to L1.

In addition, an exemplary embodiment of the present specification includes a first electrode; A second electrode provided to face the first electrode; And an organic light emitting device including 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 Formula 1.

The compound described herein can be used as the material of the organic material layer of the organic light emitting device. The compound according to at least one exemplary embodiment may improve efficiency, low driving voltage, and / or lifetime characteristics in the organic light emitting diode. In particular, the compounds described herein can be used as hole injection, hole transport, hole injection and hole transport, luminescence, electron transport, or electron injection materials. In addition, the compounds described herein can be preferably used as the light emitting layer, electron transport or electron injection material. Further, more preferably, the compound described herein exhibits low voltage, high efficiency and / or long life when used as a material for hole injection, hole transport, and electron suppression layer.

FIG. 1 shows an example of an organic light emitting element composed of a substrate 1, an anode 2, a light emitting layer 3, and a cathode 4. As shown in FIG.
FIG. 2 shows an example of an organic light emitting element consisting of 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 It is.
Figure 3 illustrates one embodiment of a compound of the present invention.

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

An exemplary embodiment of the present specification provides a compound represented by Chemical Formula 1.

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

As used herein, the term "substituted or unsubstituted" is deuterium; An alkoxy group; Aryloxy group; An alkyl group; Cycloalkyl group; Aryl group; Aralkyl group; Alkylaryl group; And it is substituted or unsubstituted with one or more substituents selected from the group consisting of a heteroaryl group, or substituted or unsubstituted two or more substituents of the substituents exemplified above. For example, "a substituent to which two or more substituents are linked" may be a biphenyl group. That is, the biphenyl group may be an aryl group or may be interpreted as a substituent to which two phenyl groups are linked.

In the present specification, the alkyl group may be linear or branched chain, carbon number is not particularly limited, but is preferably 1 to 40. According to an exemplary embodiment, the alkyl group has 1 to 20 carbon atoms. According to another exemplary embodiment, the alkyl group has 1 to 10 carbon atoms. According to another exemplary embodiment, the alkyl group has 1 to 6 carbon atoms. 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, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl , n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2 -Dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 4-methylhexyl, 5-methylhexyl, and the like, but is not limited thereto.

In the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 60 carbon atoms, and according to one embodiment, the cycloalkyl group has 3 to 30 carbon atoms. According to another exemplary embodiment, the cycloalkyl group has 3 to 20 carbon atoms. According to another exemplary embodiment, the cycloalkyl group has 3 to 6 carbon atoms. Specifically 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 is not limited thereto.

In the present specification, the alkoxy group is not particularly limited, but is preferably 1 to 40 carbon atoms. According to an exemplary embodiment, the alkoxy group has 1 to 10 carbon atoms. According to another exemplary embodiment, the alkoxy group has 1 to 6 carbon atoms. Specific examples of the alkoxy group include, but are not limited to, methoxy group, ethoxy group, propoxy group, isobutyloxy group, sec-butyloxy group, pentyloxy group, iso-amyloxy group, hexyloxy group, and the like.

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 an exemplary embodiment, the aryl group has 6 to 30 carbon atoms. According to an exemplary embodiment, the aryl group has 6 to 20 carbon atoms. The aryl group may be a monocyclic aryl group, but may be a phenyl group, a biphenyl group, a terphenyl group, etc., but is not limited thereto. The polycyclic aryl group may be a naphthyl group, anthracenyl group, phenanthryl group, pyrenyl group, peryleneyl group, chrysenyl group, fluorenyl group, triphenylene group, etc., but is not limited thereto.

In the present specification, the fluorenyl group may be substituted, and two substituents may be bonded to each other to form a spiro structure.

When the fluorenyl group is substituted,

Figure 112016019751857-pat00007
,
Figure 112016019751857-pat00008
,
Figure 112016019751857-pat00009
,
Figure 112016019751857-pat00010
,
Figure 112016019751857-pat00011
,
Figure 112016019751857-pat00012
,
Figure 112016019751857-pat00013
And
Figure 112016019751857-pat00014
And so on. However, the present invention is not limited thereto.

In the present specification, the heteroaryl group is a heteroaryl group containing one or more of N, O, S, Si, and Se as hetero atoms, and the carbon number is not particularly limited, but is preferably 2 to 60 carbon atoms. Examples of the heteroaryl group include thiophene group, furan group, pyrrole group, imidazole group, thiazole group, oxazole group, oxadiazole group, triazole group, pyridine group, bipyridine group, pyrimidine group, triazine group, triazole group, Acridil group, pyridazine group, pyrazine group, quinoline group, quinazoline group, quinoxaline group, phthalazinyl group, pyrido pyrimidine group, pyrido pyrazine group, pyrazino pyrazine group, isoquinoline group, indole group, Carbazole group, benzoxazole group, benzimidazole group, benzothiazole group, benzocarbazole group, Benzothiophene group, dibenzothiophene group, benzofuran group, phenanthroline group, thiazole group, isoxoxazole group, oxadiazole group, thiadiazole group, benzothiazole group, and dibenzofuran group, It is not limited only to these.

In the present specification, the aryl group in the aryloxy group, aralkyl group, aralkenyl group, alkylaryl group can be applied to the description of the aryl group described above.

In the present specification, the alkyl group of the aralkyl group and the alkylaryl group may be applied to the description of the aforementioned alkyl group.

In the present specification, the description of the aryl group described above may be applied except that the arylene is a divalent group.

In the present specification, except that the heteroarylene is a divalent group, the description of the aforementioned heteroaryl group may be applied.

According to an exemplary embodiment of the present specification, Formula 1 may be represented by the following formula (2).

[Formula 2]

Figure 112016019751857-pat00015

In Chemical Formula 2,

Ar 1, R 1, n, R 2, Y 1, L 1 and X are as defined in Formula 1, p is an integer of 0 to 3,

L2 is the same as or different from L1, and is as defined in L1,

Y2 is the same as or different from Y1, and is the same as the definition of Y1.

According to an exemplary embodiment of the present specification, Chemical Formula 1 may be represented by one of the following Chemical Formulas 3 to 5.

[Formula 3]

Figure 112016019751857-pat00016

[Formula 4]

Figure 112016019751857-pat00017

[Formula 5]

Figure 112016019751857-pat00018

In Chemical Formulas 3 to 5, the definition of the substituent is the same as that of Chemical Formula 1.

According to an exemplary embodiment of the present specification, Chemical Formula 1 may be represented by one of the following Chemical Formulas 6 to 8.

[Formula 6]

Figure 112016019751857-pat00019

[Formula 7]

Figure 112016019751857-pat00020

[Formula 8]

Figure 112016019751857-pat00021

In Chemical Formulas 6 to 8, the definition of a substituent is the same as that of Chemical Formula 2.

According to an exemplary embodiment of the present specification, Ar1 is a substituted or unsubstituted aryl group of two or more rings; Substituted or unsubstituted dibenzofuran group; Substituted or unsubstituted dibenzothiophene group; Substituted or unsubstituted triazine group; Substituted or unsubstituted pyrimidine group; Substituted or unsubstituted pyridine group; Substituted or unsubstituted quinazoline group; Substituted or unsubstituted quinoline group; Substituted or unsubstituted benzocarbazole group; Or a substituted or unsubstituted carbazole group.

According to an exemplary embodiment of the present specification, Ar1 is a bicyclic or more aryl group unsubstituted or substituted with an aryl group or a heterocyclic group; Dibenzofuran group unsubstituted or substituted with an aryl group or a heterocyclic group; Dibenzothiophene group unsubstituted or substituted with an aryl group or a heterocyclic group; Triazine group unsubstituted or substituted with an aryl group or a heterocyclic group; Pyrimidine groups unsubstituted or substituted with an aryl group or a heterocyclic group; A pyridine group unsubstituted or substituted with an aryl group or a heterocyclic group; A quinazoline group unsubstituted or substituted with an aryl group or a heterocyclic group; A quinoline group unsubstituted or substituted with an aryl group or a heterocyclic group; Benzocarbazole groups unsubstituted or substituted with an aryl group or a heterocyclic group; Or a carbazole group unsubstituted or substituted with an aryl group or a heterocyclic group.

According to an exemplary embodiment of the present specification, Ar1 is biphenyl, terphenyl, quarterphenyl, naphthyl, anthryl, fluorenyl, phenanthrenyl, pyrenyl, triphenylenyl or chrysenyl unsubstituted or substituted with an alkyl group. to be. According to an exemplary embodiment of the present specification, Ar1 may be represented as in the following structural formula.

Figure 112016019751857-pat00022

According to an exemplary embodiment of the present specification, Ar1 is a phenyl group substituted with deuterium, a fluorine group, a nitrile group, an alkyl group, an aryl group or a heteroaryl group.

According to an exemplary embodiment of the present specification, Ar1 is tria unsubstituted or substituted with deuterium, halogen, nitrile group, alkyl group, naphthyl, triphenylenyl, phenanthrenyl, dibenzofuran group, dibenzothiophene group, aryl group It is a phenyl substituted by the base group, the pyrimidine group, the pyridine group, the quinazoline group, the quinoline group, the carbazole group unsubstituted or substituted by the aryl group, or the benzocarbazole group unsubstituted or substituted by the aryl group.

According to an exemplary embodiment of the present specification, Ar1 is phenyl substituted with deuterium.

According to an exemplary embodiment of the present specification, Ar1 is phenyl substituted with fluorine.

According to an exemplary embodiment of the present specification, Ar1 is phenyl substituted with an alkyl group.

According to an exemplary embodiment of the present specification, Ar1 is phenyl substituted with naphthyl, triphenylenyl or phenanthrenyl.

According to an exemplary embodiment of the present specification, Ar1 is phenyl substituted with a triazine group, a pyrimidine group or a pyridine group.

According to an exemplary embodiment of the present specification, Ar1 is phenyl substituted with a pyridine group.

According to an exemplary embodiment of the present specification, Ar1 is phenyl substituted with a carbazole group unsubstituted or substituted with phenyl, biphenyl or naphthyl; Or phenyl substituted with phenyl, biphenyl or naphthyl or substituted with an unsubstituted benzocarbazole group.

According to an exemplary embodiment of the present specification, Ar1 is a dibenzofuran group unsubstituted or substituted with an aryl group or a heterocyclic group; Dibenzothiophene group unsubstituted or substituted with an aryl group or a heterocyclic group; Triazine group unsubstituted or substituted with an aryl group or a heterocyclic group; Pyrimidine groups unsubstituted or substituted with an aryl group or a heterocyclic group; A pyridine group unsubstituted or substituted with an aryl group or a heterocyclic group; A quinazoline group unsubstituted or substituted with an aryl group or a heterocyclic group; A quinoline group unsubstituted or substituted with an aryl group or a heterocyclic group; Benzocarbazole groups unsubstituted or substituted with an aryl group or a heterocyclic group; Or a carbazole group unsubstituted or substituted with an aryl group or a heterocyclic group.

According to an exemplary embodiment of the present specification, Ar1 is a dibenzofuran group unsubstituted or substituted with an aryl group; Dibenzothiophene group unsubstituted or substituted with an aryl group; Triazine group unsubstituted or substituted with an aryl group; Pyrimidine groups unsubstituted or substituted with aryl groups; A pyridine group unsubstituted or substituted with an aryl group; A quinazoline group unsubstituted or substituted with an aryl group; A quinoline group unsubstituted or substituted with an aryl group; A benzocarbazole group unsubstituted or substituted with an aryl group; Or a carbazole group unsubstituted or substituted with an aryl group.

According to an exemplary embodiment of the present specification, Ar1 is a dibenzofuran group unsubstituted or substituted with phenyl, biphenyl or naphthyl; Dibenzothiophene group unsubstituted or substituted with phenyl, biphenyl or naphthyl; Triazine groups unsubstituted or substituted with phenyl, biphenyl or naphthyl; Pyrimidine groups unsubstituted or substituted with phenyl, biphenyl or naphthyl; Pyridine groups unsubstituted or substituted with phenyl, biphenyl or naphthyl; A quinazoline group unsubstituted or substituted with phenyl, biphenyl or naphthyl; A quinoline group unsubstituted or substituted with phenyl, biphenyl or naphthyl; Benzocarbazole groups unsubstituted or substituted with phenyl, biphenyl or naphthyl; Or a carbazole group unsubstituted or substituted with an aryl group.

According to an exemplary embodiment of the present specification, Ar1 is a dibenzofuran group; Dibenzothiophene group; A quinazoline group unsubstituted or substituted with phenyl, biphenyl or naphthyl; A quinoline group unsubstituted or substituted with phenyl, biphenyl or naphthyl; Benzocarbazole groups unsubstituted or substituted with phenyl, biphenyl or naphthyl; Or a carbazole group unsubstituted or substituted with an aryl group.

According to an exemplary embodiment of the present disclosure, L1 and L2 are the same as or different from each other, and each independently a direct bond, substituted or unsubstituted phenylene, substituted or unsubstituted biphenylylene, substituted or unsubstituted naphthylene , Substituted or unsubstituted phenanthrenylene, or substituted or unsubstituted fluorenylene.

According to an exemplary embodiment of the present specification, L1 and L2 are the same as or different from each other, and each independently a direct bond, or a fluorine unsubstituted or substituted with a phenylene, biphenylylene, naphthylene, phenanthrenylene, or alkyl group. Niylene.

According to an exemplary embodiment of the present disclosure, L1 and L2 are the same as or different from each other, and each independently a direct bond or phenylene.

According to an exemplary embodiment of the present specification, Ar2 and Ar3 are the same as or different from each other, and each independently a substituted or unsubstituted monocyclic to tricyclic aryl group.

According to an exemplary embodiment of the present specification, Ar2 and Ar3 are the same as or different from each other, and each independently substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted Quarterphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthryl, fluorenyl unsubstituted or substituted with an alkyl or aryl group, or substituted or unsubstituted phenanthrenyl.

According to an exemplary embodiment of the present specification, Ar2 and Ar3 are the same as or different from each other, and each independently phenyl unsubstituted or substituted with an alkyl group or an aryl group; Biphenyl; Naphthyl; Anthryl; Or fluorenyl unsubstituted or substituted with an alkyl group or an aryl group.

According to an exemplary embodiment of the present specification, Ar2 and Ar3 are the same as or different from each other, and each independently phenyl unsubstituted or substituted with an alkyl group or naphthyl; Biphenyl; Terphenyl; Naphthyl; Anthryl; Or fluorenyl unsubstituted or substituted with an alkyl group or a phenyl group.

According to an exemplary embodiment of the present specification, Ar2 and Ar3 are the same as or different from each other, and may be selected from the following structural formulas.

Figure 112016019751857-pat00023

According to an exemplary embodiment of the present specification, Ar2 and Ar3 are the same as or different from each other, and each independently phenyl; Biphenyl; Naphthyl; Or fluorenyl unsubstituted or substituted with an alkyl group.

According to an exemplary embodiment of the present invention, the compound of Formula 1 may be any one selected from the following compounds .

Figure 112016019751857-pat00024

Figure 112016019751857-pat00025

Figure 112016019751857-pat00026

Figure 112016019751857-pat00027

According to an exemplary embodiment of the present invention, the compound of Formula 1 may be any one selected from the following compounds.

Figure 112016019751857-pat00028

Figure 112016019751857-pat00029

Figure 112016019751857-pat00030

Figure 112016019751857-pat00031

According to an exemplary embodiment of the present invention, the compound of Formula 1 may be any one selected from the following compounds.

Figure 112016019751857-pat00032

Figure 112016019751857-pat00033

According to an exemplary embodiment of the present invention, the compound of Formula 1 may be any one selected from the following compounds.

Figure 112016019751857-pat00034

Figure 112016019751857-pat00035

Figure 112016019751857-pat00036

Figure 112016019751857-pat00037

Figure 112016019751857-pat00038

Figure 112016019751857-pat00039

Figure 112016019751857-pat00040

According to an exemplary embodiment of the present invention, the compound of Formula 1 may be any one selected from the following compounds.

Figure 112016019751857-pat00041

Figure 112016019751857-pat00042

Figure 112016019751857-pat00043

According to an exemplary embodiment of the present invention, the compound of Formula 1 may be any one selected from the following compounds.

Figure 112016019751857-pat00044

Figure 112016019751857-pat00045

Figure 112016019751857-pat00046

According to an exemplary embodiment of the present invention, the compound of Formula 1 may be any one selected from the following compounds.

Figure 112016019751857-pat00047

Figure 112016019751857-pat00048

According to an exemplary embodiment of the present invention, the compound of Formula 1 may be any one selected from the following compounds.

Figure 112016019751857-pat00049

Figure 112016019751857-pat00050

According to an exemplary embodiment, the compound of Formula 1 described above may be prepared according to Scheme 1 and Scheme 2-1 or 2-2. According to another exemplary embodiment, the compound of Chemical Formula 2 described above may be prepared according to Scheme 1 and Scheme 3-1 or 3-2.

Scheme 1

Figure 112016019751857-pat00051

Scheme 2-1

Figure 112016019751857-pat00052

Scheme 2-2

Figure 112016019751857-pat00053

Scheme 3-1

Figure 112016019751857-pat00054

Scheme 3-2

Figure 112016019751857-pat00055

In the above schemes, X and Ar1 to Ar3 are the same as defined in Chemical Formula 1. Those skilled in the art may further introduce additional substituents corresponding to R 1 and R 2 of Formula 1 as necessary, based on the above schemes and the synthesis examples described below and techniques known in the art.

In addition, the present specification provides an organic light emitting device including the compound represented by Formula 1.

In one embodiment of the present specification, the first electrode; A second electrode provided to face the first electrode; And one or more organic material layers provided between the first electrode and the second electrode, wherein one or more layers of the organic material layers include the compound of Formula 1.

The organic material layer of the organic light emitting device of the present specification may be formed of a single layer structure, but may be formed of a multilayer structure in which two or more organic material layers are stacked. For example, the organic light emitting device of the present invention may have a structure including a hole injection layer, a hole transport layer, an electron suppression layer, a light emitting layer, a hole suppression layer, an electron transport layer, an electron injection layer and the like as an organic material layer. However, the structure of the organic light emitting device is not limited thereto and may include a smaller number of organic layers. At least one of the hole injection layer, the hole transport layer, the electron suppression layer, the light emitting layer, the hole suppression layer, the electron transport layer and the electron injection layer may include the compound of Formula 1.

In another exemplary embodiment, the organic material layer includes a light emitting layer, and the light emitting layer includes the compound of Formula 1.

In another exemplary embodiment, the organic material layer includes a hole suppression layer, and the hole suppression layer includes the compound of Formula 1.

In an exemplary embodiment of the present specification, the electron transport layer, the electron injection layer or the layer at the same time the electron transport and electron injection comprises a compound of the formula (1).

In another exemplary embodiment, the organic material layer includes a light emitting layer and an electron transport layer, and the electron transport layer includes the compound of Formula 1.

In one embodiment of the present specification, the first electrode; A second electrode provided to face the first electrode; And a light emitting layer provided between the first electrode and the second electrode. An organic light emitting device including two or more organic material layers provided between the light emitting layer and the first electrode or between the light emitting layer and the second electrode, wherein at least one of the two or more organic material layers includes the compound of Formula 1 . In one exemplary embodiment, two or more organic material layers may be selected from the group consisting of an electron transport layer, an electron injection layer, a layer for simultaneously transporting electrons and electron injection, and a hole suppression layer.

In one embodiment of the present specification, the organic material layer includes two or more electron transport layers, and at least one of the two or more electron transport layers includes the compound of Formula 1. Specifically, in one embodiment of the present specification, the compound of Formula 1 may be included in one layer of the two or more electron transport layers, and may be included in each of the two or more electron transport layers.

In addition, in an exemplary embodiment of the present specification, when the compound of Formula 1 is included in each of two or more electron transport layers, other materials except for the compound of Formula 1 may be the same or different from each other.

In another exemplary embodiment, the organic light emitting diode may be an organic light emitting diode having a structure in which an anode, one or more organic material layers, and a cathode are sequentially stacked on a substrate.

 In another exemplary embodiment, the organic light emitting diode may be an organic light emitting diode having an inverted type 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 diode according to one embodiment of the present specification is illustrated in FIGS. 1 and 2.

FIG. 1 shows an example of an organic light emitting element composed of a substrate 1, an anode 2, a light emitting layer 3, and a cathode 4. As shown in FIG. In such a structure, the compound may be included in the light emitting layer.

FIG. 2 shows an example of an organic light emitting element consisting of 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 It is. In such a structure, the compound may be included in one or more layers of the hole injection layer, hole transport layer, light emitting layer and electron transport layer.

The organic light emitting device of the present specification may be manufactured by materials and methods known in the art, except that at least one layer of the organic material layer includes the compound of the present specification, that is, the compound of Formula 1.

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.

 The organic light emitting device of the present specification may be manufactured by materials and methods known in the art, except that at least one layer of the organic material layer includes the compound represented by Chemical Formula 1, that is, the compound represented by Chemical Formula 1.

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

In addition, the compound of Formula 1 may be formed of an organic material layer by a solution coating method as well as a vacuum deposition method in the manufacture of the organic light emitting device. Here, the solution coating method means spin coating, dip coating, doctor blading, inkjet printing, screen printing, spray method, 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 an organic material layer and an anode material on a substrate (International Patent Application Publication No. 2003/012890). However, the manufacturing method is not limited thereto.

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

In another exemplary embodiment, the first electrode is a cathode and the second electrode is an anode.

As the anode material, a material having a large work function is usually preferred to facilitate hole injection into the organic material layer. Specific examples of the positive electrode 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), indium zinc oxide (IZO); ZnO: Al or SNO 2 : Combination of metals and oxides such as Sb; Conductive polymers such as poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (PEDOT), polypyrrole and polyaniline, and the like, but are not limited thereto.

It is preferable that the cathode material is 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; Multilayer structure materials such as LiF / Al or LiO 2 / Al, and the like, but are not limited thereto.

The hole injection material is a layer for injecting holes from an electrode, and the hole injection material has a capability of transporting holes, and thus has a hole injection effect at an anode, an excellent hole injection effect for a light emitting layer or a light emitting material, and is generated in a light emitting layer. The compound which prevents the movement of the excited excitons to the electron injection layer or the electron injection material, and is excellent in thin film formation ability is preferable. Preferably, the highest occupied molecular orbital (HOMO) of the hole injection material is between the work function of the positive electrode material and the HOMO of the surrounding organic material layer. Specific examples of the hole injection material include metal porphyrin, oligothiophene, arylamine-based organic material, hexanitrile hexaazatriphenylene-based organic material, quinacridone-based organic material, and perylene-based Organic materials, anthraquinone, and polyaniline and polythiophene-based conductive polymers, but are not limited thereto.

The hole transport layer is a layer that receives holes from the hole injection layer and transports holes to the light emitting layer. As a hole transport material, 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 thereof include an arylamine-based organic material, a conductive polymer, and a block copolymer having a conjugated portion and a non-conjugated portion together, but are not limited thereto.

The light emitting material is a material capable of emitting light in the visible region by transporting and combining holes and electrons from the hole transport layer and the electron transport layer, respectively, and a material having good quantum efficiency with respect to fluorescence or phosphorescence is preferable. Specific examples thereof include 8-hydroxyquinoline aluminum complex (Alq 3 ); Carbazole series compounds; Dimerized styryl compounds; BAlq; 10-hydroxybenzoquinoline-metal compound; Benzoxazole, benzthiazole and benzimidazole series compounds; Poly (p-phenylenevinylene) (PPV) -based polymers; 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 containing compound. Specifically, the condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, and fluoranthene compounds, and the heterocyclic containing compounds include carbazole derivatives, dibenzofuran derivatives and ladder types. Furan compounds, pyrimidine derivatives, and the like, but are not limited thereto.

Dopant materials include aromatic amine derivatives, styrylamine compounds, boron complexes, fluoranthene compounds, metal complexes, and the like. Specifically, the aromatic amine derivative is a condensed aromatic ring derivative having a substituted or unsubstituted arylamine group, and includes pyrene, anthracene, chrysene and periplanthene having an arylamine group, and the styrylamine compound is substituted or unsubstituted. At least one arylvinyl group is substituted with the arylamine, and one or two or more substituents selected from the group consisting of an aryl group, a silyl group, an alkyl group, a cycloalkyl group and an arylamine group are substituted or unsubstituted. Specifically, styrylamine, styryldiamine, styryltriamine, styryltetraamine and the like, but is not limited thereto. In addition, the metal complex includes, but is not limited to, an iridium complex, a platinum complex, and the like.

The electron transporting material is a layer that receives electrons from the electron injection layer and transports electrons to the light emitting layer. The electron transporting material is a material that can inject electrons well from the cathode and move them to the light emitting layer. This is suitable. Specific examples thereof include Al complexes of 8-hydroxyquinoline; Complexes including Alq 3 ; Organic radical compounds; Hydroxyflavone-metal complexes and the like, but are not limited thereto. The electron transport layer can be used with any desired cathode material as used in accordance with the prior art. In particular, examples of suitable cathode materials are conventional materials having a low work function followed by an aluminum or silver layer. Specifically cesium, barium, calcium, ytterbium and samarium, followed by aluminum layers or silver layers in each case.

The electron injection layer is a layer that injects electrons from an electrode, has an ability of transporting electrons, has an electron injection effect from a cathode, an electron injection effect with respect to a light emitting layer or a light emitting material, and hole injection of excitons generated in the light emitting layer. The compound which prevents the movement to a layer and is excellent in thin film formation ability is preferable. Specifically, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preorenylidene methane, anthrone and the like and derivatives thereof, metal Complex compounds, nitrogen-containing five-membered ring derivatives, and the like, but are not limited thereto.

Examples of the metal complex compound include 8-hydroxyquinolinato lithium, bis (8-hydroxyquinolinato) zinc, bis (8-hydroxyquinolinato) copper, bis (8-hydroxyquinolinato) manganese, Tris (8-hydroxyquinolinato) aluminum, tris (2-methyl-8-hydroxyquinolinato) aluminum, tris (8-hydroxyquinolinato) gallium, bis (10-hydroxybenzo [h] Quinolinato) beryllium, bis (10-hydroxybenzo [h] quinolinato) zinc, bis (2-methyl-8-quinolinato) chlorogallium, bis (2-methyl-8-quinolinato) ( o-cresolato) gallium, bis (2-methyl-8-quinolinato) (1-naphtolato) aluminum, bis (2-methyl-8-quinolinato) (2-naphtolato) gallium, It is not limited to this.

The organic light emitting device according to the present specification may be a top emission type, a bottom emission type, or a double side emission type according to a material used.

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

Preparation of the compound represented by Chemical Formula 1 and an organic light emitting device including the same will be described in detail in the following Examples. However, the following examples are intended to illustrate the present specification, and the scope of the present specification is not limited thereto.

First, an intermediate was prepared as in the following scheme.

Figure 112016019751857-pat00056

Figure 112016019751857-pat00057

Figure 112016019751857-pat00058

Figure 112016019751857-pat00059

< Production Example  1>

1) Compound Synthesis of the Following Compound 1-1

[Compound A] [Compound 1-1]

Figure 112016019751857-pat00060

Compound A (10.0 g, 19.92 mmol), 2,4-diphenyl-6- (3- (4,4,5,5-tetramethyl-1,3,2-dioxa) in a 500 ml round bottom flask under nitrogen atmosphere Borol-2-yl) phenyl) -1,3,5-triazine (9.53 g, 21.91 mmol) was completely dissolved in 320 ml of tetrahydrofuran, followed by addition of aqueous 2M potassium carbonate solution (160 ml), followed by tetrakis- (tri Phenylphosphine) palladium (0.69 g, 0.61 mmol) was added thereto, followed by heating and stirring for 5 hours. The temperature was lowered to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized with 350 ml of ethyl acetate to obtain Compound 1-1 (8.95 g, yield: 61%).

MS [M + H] + = 732

< Production Example  2>

1) Compound Synthesis of the Following Compound 1-2

[Compound A] [Compound 1-2]

Figure 112016019751857-pat00061

Compound A (10.0 g, 19.92 mmol), 2,4-diphenyl-6- (3- (4,4,5,5-tetramethyl-1,3,2-dioxa) in a 500 ml round bottom flask under nitrogen atmosphere Borol-2-yl) phenyl) pyrimidine (9.53 g, 21.91 mmol) was completely dissolved in 320 ml of tetrahydrofuran, followed by addition of 2M aqueous potassium carbonate solution (160 ml), followed by tetrakis- (triphenylphosphine) palladium (0.69 g, 0.61 mmol), and the mixture was heated and stirred for 5 hours. The temperature was lowered to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized with 350 ml of ethyl acetate, thereby obtaining Compound 1-2 (9.84 g, yield: 67%).

MS [M + H] + = 731

< Production Example  3>

1) Compound Synthesis of the Following Compound 1-3

[Compound B] [Compound 1-3]

Figure 112016019751857-pat00062

Compound B (10.0 g, 19.31 mmol), 2,4-diphenyl-6- (3- (4,4,5,5-tetramethyl-1,3,2-dioxa) in a 500 ml round bottom flask under nitrogen atmosphere Borol-2-yl) phenyl) pyrimidine (9.22 g, 21.24 mmol) was completely dissolved in 450 ml of tetrahydrofuran, then 2M aqueous potassium carbonate solution (220 ml) was added, and tetrakis- (triphenylphosphine) palladium (0.67 g, 0.58 mmol), and the mixture was heated and stirred for 3 hours. The temperature was lowered to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure and recrystallized with 220 ml of tetrahydrofuran to prepare the compound 1-3 (11.17 g, yield: 77%).

MS [M + H] + = 747

< Production Example  4>

1) Compound Synthesis of the Following Compound 1-4

 [Compound A] [Compound 1-4]

Figure 112016019751857-pat00063

Compound A (10.0 g, 19.92 mmol), 2,4-diphenyl-6- (4- (4,4,5,5-tetramethyl-1,3,2-dioxa) in a 500 ml round bottom flask under nitrogen atmosphere Borol-2-yl) phenyl) -1,3,5-triazine (9.53 g, 21.91 mmol) was completely dissolved in 320 ml of tetrahydrofuran, followed by addition of aqueous 2M potassium carbonate solution (160 ml), followed by tetrakis- (tri Phenylphosphine) palladium (0.69 g, 0.61 mmol) was added thereto, followed by heating and stirring for 5 hours. The temperature was lowered to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized with 350 ml of ethyl acetate to obtain Compound 1-4 (10.17 g, yield: 73%).

MS [M + H] + = 732

< Production Example  5>

1) Compound Synthesis of the Following Compound 1-5

[Compound J] [Compound 1-5]

Figure 112016019751857-pat00064

Compound J (10.0 g, 24.21 mmol), 2,4-diphenyl-6- (3- (4,4,5,5-tetramethyl-1,3,2-dioxa) in 500 ml round bottom flask in nitrogen atmosphere Borol-2-yl) phenyl) -1,3,5-triazine (11.59 g, 26.63 mmol) was completely dissolved in 220 ml of tetrahydrofuran, followed by addition of aqueous 2M potassium carbonate solution (110 ml), followed by tetrakis- (tri Phenylphosphine) palladium (0.84 g, 73 mmol) was added thereto, followed by heating and stirring for 8 hours. The temperature was lowered to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized with 350 ml of ethyl acetate to obtain Compound 1-5 (12.26 g, yield: 79%).

MS [M + H] + = 643

< Production Example  6>

1) Compound Synthesis of the Following Compound 1-6

[Compound I] [Compound 1-6]

Figure 112016019751857-pat00065

Compound I (10.0 g, 23.31 mmol), 2,4-diphenyl-6- (4- (4,4,5,5-tetramethyl-1,3,2-dioxane) in a 500 ml round bottom flask under nitrogen atmosphere Borol-2-yl) phenyl) -1,3,5-triazine (11.15 g, 25.64 mmol) was completely dissolved in 260 ml of tetrahydrofuran, followed by addition of aqueous 2M potassium carbonate solution (130 ml), followed by tetrakis- (tri Phenylphosphine) palladium (0.84 g, 73 mmol) was added thereto, followed by heating and stirring for 8 hours. The temperature was lowered to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized with 230 ml of tetrahydrofuran to prepare the compound 1-6 (13.88 g, yield: 90%).

MS [M + H] + = 659

< Production Example  7>

1) Compound Synthesis of the Following Compound 1-7

[Compound L] [Compound 1-7]

Figure 112016019751857-pat00066

Compound L (10.0 g, 21.15 mmol), 2,4-diphenyl-6- (4- (4,4,5,5-tetramethyl-1,3,2-dioxa) in a 500 ml round bottom flask in a nitrogen atmosphere Borol-2-yl) phenyl) -1,3,5-triazine (10.29 g, 23.66 mmol) was completely dissolved in 240 ml of tetrahydrofuran, followed by addition of aqueous 2M potassium carbonate solution (120 ml), followed by tetrakis- (tri Phenylphosphine) palladium (0.75g, 65mmol) was added thereto, followed by heating and stirring for 4 hours. The temperature was lowered to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized with 230 ml of tetrahydrofuran to prepare the compound 1-7 (12.22 g, yield: 82%).

MS [M + H] + = 695

< Production Example  8>

1) Compound Synthesis of the Following Compound 1-8

[Compound K] [Compound 1-8]

Figure 112016019751857-pat00067

Compound K (10.0 g, 19.23 mmol), 2,4-diphenyl-6- (4- (4,4,5,5-tetramethyl-1,3,2-dioxane) in 500 ml round bottom flask in nitrogen atmosphere Borol-2-yl) phenyl) -1,3,5-triazine (9.20 g, 21.15 mmol) was completely dissolved in 280 ml of tetrahydrofuran and 2M aqueous potassium carbonate solution (140 ml) was added, followed by tetrakis- (tri Phenylphosphine) palladium (0.75 g, 65 mmol) was added thereto, followed by heating and stirring for 6 hours. The temperature was lowered to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized with 160 ml of tetrahydrofuran to prepare the compound 1-8 (9.78 g, yield: 72%).

MS [M + H] + = 711

< Production Example  9>

1) Compound Synthesis of the Following Compound 1-9

[Compound M] [Compound 1-9]

Figure 112016019751857-pat00068

Compound M (10.0 g, 19.92 mmol), 2,4-diphenyl-6- (3- (4,4,5,5-tetramethyl-1,3,2-dioxa) in a 500 ml round bottom flask under nitrogen atmosphere Borol-2-yl) phenyl) -1,3,5-triazine (9.53 g, 21.91 mmol) was completely dissolved in 360 ml of tetrahydrofuran, followed by addition of aqueous 2M potassium carbonate solution (180 ml), followed by tetrakis- (tri Phenylphosphine) palladium (0.69 g, 0.61 mmol) was added thereto, followed by heating and stirring for 5 hours. The temperature was lowered to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized with 230 ml of ethyl acetate to obtain Compound 1-9 (9.86 g, yield: 67%).

MS [M + H] + = 732

< Production Example  10>

1) Compound Synthesis of the Following Compound 1-10

[Compound M] [Compound 1-10]

Figure 112016019751857-pat00069

Compound M (10.0 g, 19.92 mmol), 2,4-diphenyl-6- (4- (4,4,5,5-tetramethyl-1,3,2-dioxa) in a 500 ml round bottom flask in a nitrogen atmosphere Borol-2-yl) phenyl) -1,3,5-triazine (9.53 g, 21.91 mmol) was completely dissolved in 360 ml of tetrahydrofuran, followed by addition of aqueous 2M potassium carbonate solution (180 ml), followed by tetrakis- (tri Phenylphosphine) palladium (0.69 g, 0.61 mmol) was added thereto, followed by heating and stirring for 5 hours. The temperature was lowered to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized with 230 ml of ethyl acetate to prepare the compound 1-10 (9.86 g, yield: 67%).

MS [M + H] + = 732

< Production Example  11>

1) Compound Synthesis of the Following Compound 1-11

[Compound B-2] [Compound 1-11]

Figure 112016019751857-pat00070

Compound B-2 (10.0 g, 18.18 mmol), 2,4-diphenyl-6- (3- (4,4,5,5-tetramethyl-1,3,2- in a 500 ml round bottom flask in a nitrogen atmosphere Dioxaborolan-2-yl) phenyl) -1,3,5-triazine (8.71 g, 20.01 mmol) was completely dissolved in 320 ml of tetrahydrofuran and 2M aqueous potassium carbonate solution (160 ml) was added thereto, followed by tetrakis- (Triphenylphosphine) palladium (0.63 g, 0.55 mmol) was added thereto, followed by heating and stirring for 3 hours. The mixture was cooled to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized with 220 ml of tetrahydrofuran to prepare the compound 1-11 (10.25 g, yield: 72%).

MS [M + H] + = 779

< Production Example  12>

1) Compound Synthesis of the Following Compound 1-12

[Compound N] [Compound 1-12]

Figure 112016019751857-pat00071

Compound N (10.0 g, 19.31 mmol), 2,4-diphenyl-6- (3- (4,4,5,5-tetramethyl-1,3,2-dioxane) in 500 ml round bottom flask in nitrogen atmosphere Borol-2-yl) phenyl) pyrimidine (9.22 g, 21.24 mmol) was completely dissolved in 450 ml of tetrahydrofuran, then 2M aqueous potassium carbonate solution (220 ml) was added, and tetrakis- (triphenylphosphine) palladium (0.67 g, 0.58 mmol), and the mixture was heated and stirred for 3 hours. The mixture was cooled to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized with 220 ml of tetrahydrofuran to prepare the compound 1-12 (11.17 g, yield: 77%).

MS [M + H] + = 747

< Production Example  13>

1) Compound Synthesis of the Following Compound 1-13

[Compound I-2] [Compound 1-13]

Figure 112016019751857-pat00072

Compound I-2 (10.0 g, 23.31 mmol), 2,4-diphenyl-6- (4- (4,4,5,5-tetramethyl-1,3,2- in a 500 ml round bottom flask in a nitrogen atmosphere Dioxaborolan-2-yl) phenyl) -1,3,5-triazine (11.15 g, 25.64 mmol) was completely dissolved in 260 ml of tetrahydrofuran, and then 2M aqueous potassium carbonate solution (130 ml) was added thereto, followed by tetrakis- (Triphenylphosphine) palladium (0.84 g, 73 mmol) was added thereto, followed by heating and stirring for 5 hours. The mixture was cooled to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized with 230 ml of tetrahydrofuran to prepare the compound 1-13 (11.27 g, yield: 75%).

MS [M + H] + = 691

<Experimental Example 1-1>

After the compounds synthesized in the Preparation Example was subjected to high purity sublimation purification by a commonly known method, a green organic light emitting device was manufactured by the following method.

A glass substrate coated with a thin film of ITO (indium tin oxide) at a thickness of 1,000 Å was placed in distilled water in which detergent was dissolved and ultrasonically cleaned. At this time, Fischer Co. product was used as a detergent, and distilled water filtered secondly as a filter of Millipore Co. product was used as distilled water. After ITO was washed for 30 minutes, ultrasonic washing was performed twice with distilled water for 10 minutes. After washing the distilled water, ultrasonic washing with a solvent of isopropyl alcohol, acetone, methanol, dried and transported to a plasma cleaner. In addition, the substrate was cleaned for 5 minutes using an oxygen plasma, and then the substrate was transferred to a vacuum evaporator.

Using the compound 1-1 as a host on the prepared ITO transparent electrode, m-MTDATA (60 nm) / TCTA (80 nm) / Compound 1-1 + 10% Ir (ppy) 3 (300 nm) / BCP (10 nm) The organic EL device was manufactured by constructing a light emitting device in the order of / Alq 3 (30 nm) / LiF (1 nm) / Al (200 nm).

The structures of m-MTDATA, TCTA, Ir (ppy) 3 and BCP are as follows.

[m-MTDATA] [TCTA]

Figure 112016019751857-pat00073

[Ir (ppy) 3] [BCP]

Figure 112016019751857-pat00074

[Compound 1-1]

Figure 112016019751857-pat00075

<Experimental Example 1-2>

The organic light emitting device was manufactured by the same method as Experimental Example 1-1, except that compound 1-2 was used instead of compound 1-1 in Experimental Example 1-1.

<Experimental Example 1-3>

The organic light emitting device was manufactured by the same method as Experimental Example 1-1, except that compound 1-3 was used instead of compound 1-1 in Experimental Example 1-1.

<Experimental Example 1-4>

The organic light emitting device was manufactured by the same method as Experimental Example 1-1, except that compound 1-4 was used instead of compound 1-1 in Experimental Example 1-1.

<Experimental Example 1-5>

The organic light emitting device was manufactured by the same method as Experimental Example 1-1, except that compound 1-5 was used instead of compound 1-1 in Experimental Example 1-1.

<Experimental Example 1-6>

The organic light emitting device was manufactured by the same method as Experimental Example 1-1, except that compound 1-6 was used instead of compound 1-1 in Experimental Example 1-1.

<Experimental Example 1-7>

The organic light emitting device was manufactured by the same method as Experimental Example 1-1, except that compound 1-9 was used instead of compound 1-1 in Experimental Example 1-1.

<Experimental Example 1-8>

The organic light emitting device was manufactured by the same method as Experimental Example 1-1, except that compound 1-10 was used instead of compound 1-1 in Experimental Example 1-1.

Experimental Example 1-9

The organic light emitting device was manufactured by the same method as Experimental Example 1-1, except that compound 1-12 was used instead of compound 1-1 in Experimental Example 1-1.

Experimental Example 1-10

The organic light emitting device was manufactured by the same method as Experimental Example 1-1, except that compound 1-13 was used instead of compound 1-1 in Experimental Example 1-1.

<Comparative Example 1-1>

An organic light emitting diode was manufactured according to the same method as Experimental Example 1-1 except for using GH 1 instead of compound 1-1 in Experimental Example 1-1.

[GH 1]

Figure 112016019751857-pat00076

<Comparative Example 1-2>

The organic light emitting device was manufactured by the same method as Experimental Example 1-1, except that GH 2 was used instead of compound 1-1 in Experimental Example 1-1.

[GH 2]

Figure 112016019751857-pat00077

<Comparative Example 1-3>

The organic light emitting device was manufactured by the same method as Experimental Example 1-1, except that GH 3 was used instead of compound 1-1 in Experimental Example 1-1.

[GH 3]

Figure 112016019751857-pat00078

When the current was applied to the organic light emitting devices manufactured by Experimental Examples 1-1 to 1-10 and Comparative Examples 1-1 to 1-3, voltage, efficiency, EL peak, and lifetime were measured, and the results are shown below. ]. T95 means the time taken for the luminance to be reduced to 95% from the initial luminance (5000 nits).

compound
(Host) Voltage
(V @ 10mA / cm 2 ) efficiency
(cd / A @ 10mA / cm 2 ) EL peak
(nm) T95
(hr) Experimental Example 1-1 Compound 1-1 5.18 44.83 517 170 Experimental Example 1-2 Compound 1-2 5.26 46.14 516 145 Experimental Example 1-3 Compound 1-3 5.15 45.69 518 150 Experimental Example 1-4 Compound 1-4 5.29 47.05 517 185 Experimental Example 1-5 Compound 1-5 5.28 45.21 515 175 Experimental Example 1-6 Compound 1-6 5.13 46.53 516 180 Experimental Example 1-7 Compound 1-9 5.29 46.52 516 155 Experimental Example 1-8 Compound 1-10 5.27 47.54 517 135 Experimental Example 1-9 Compound 1-12 5.24 47.58 518 195 Experimental Example 1-10 Compound 1-13 5.18 43.73 517 200 Comparative Example 1-1 GH 1 6.76 38.26 517 95 Comparative Example 1-2 GH 2 6.51 39.72 517 75 Comparative Example 1-3 GH 3 6.61 39.26 517 85

As a result, the green organic EL device of Experimental Examples 1-1 to 1-10 using the compound represented by Chemical Formula 1 according to the present invention as a host material of the green light emitting layer was compared with unsubstituted phenyl in the N direction of the core. It was confirmed that the green organic EL device of Comparative Example 1-2 and Comparative Example 1-3, in which the alkyl group was connected to the N direction of the core in Example 1-1 and Comparative Example 1-3, showed excellent performance not only in terms of current efficiency and driving voltage but also in terms of lifetime.

<Comparative Example 2-1>

A glass substrate coated with a thin film of ITO (indium tin oxide) at a thickness of 1,000 Å was placed in distilled water in which detergent was dissolved and ultrasonically cleaned. At this time, Fischer Co. product was used as a detergent, and distilled water filtered secondly as a filter of Millipore Co. product was used as distilled water. After ITO was washed for 30 minutes, ultrasonic washing was performed twice with distilled water for 10 minutes. After washing the distilled water, ultrasonic washing with a solvent of isopropyl alcohol, acetone, methanol, dried and transported to a plasma cleaner. In addition, the substrate was cleaned for 5 minutes using an oxygen plasma, and then the substrate was transferred to a vacuum evaporator.

The hexanitrile hexaazatriphenylene (HAT) of the following formula was thermally vacuum deposited to a thickness of 500 kPa on the prepared ITO transparent electrode to form a hole injection layer.

[HAT]

Figure 112016019751857-pat00079

Compound 4-4'-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (NPB) (300 Pa), which is a substance for transporting holes on the hole injection layer, was vacuum deposited to form a hole transport layer. It was.

[NPB]

Figure 112016019751857-pat00080

Subsequently, the following compound 1 was vacuum deposited to a film thickness of 100 kPa on the hole transport layer to form an electron blocking layer.

[Compound 1]

Figure 112016019751857-pat00081

Subsequently, the light emitting layer was formed by vacuum depositing the following BH and BD in a weight ratio of 25: 1 on the electron blocking layer with a film thickness of 300 GPa.

[BH]

Figure 112016019751857-pat00082

[BD]

Figure 112016019751857-pat00083

[ET1]

Figure 112016019751857-pat00084

[LiQ]

Figure 112016019751857-pat00085

The compound ET1 and the compound LiQ (Lithium Quinolate) were vacuum-deposited on the emission layer in a weight ratio of 1: 1 to form an electron injection and transport layer having a thickness of 300 kPa. On the electron injection and transport layer, lithium fluoride (LiF) and aluminum were deposited to a thickness of 12 kPa in order 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 The organic light emitting device was manufactured by maintaining ˜5 × 10 −6 torr.

Experimental Example 2-1

The same experiment was conducted except that Compound 1-1 was used instead of ET 1 as the electron transporting layer in Comparative Example 2-1.

Experimental Example 2-2

The same experiment was conducted except that Compound 1-2 was used instead of ET 1 as the electron transporting layer in Comparative Example 2-1.

Experimental Example 2-3

The same experiment was conducted except that Compound 1-3 was used instead of ET 1 as the electron transporting layer in Comparative Example 2-1.

Experimental Example 2-4

The same experiment was conducted except that Compound 1-4 was used instead of ET 1 as the electron transporting layer in Comparative Example 2-1.

Experimental Example 2-5

The same experiment was conducted except that Compound 1-5 was used instead of ET 1 in Comparative Example 2-1.

Experimental Example 2-6

Except for using the compound 1-6 instead of ET 1 in the Comparative Example 2-1 was the same experiment.

Experimental Example 2-7

Except for using the compound 1-9 instead of ET 1 in the Comparative Example 2-1 was the same experiment.

<Experimental Example 2-8>

Except for using the compound 1-10 instead of ET 1 in the Comparative Example 2-1 was the same experiment.

Experimental Example 2-9

Except for using the compound 1-12 instead of ET 1 as the electron transport layer in Comparative Example 2-1 was the same experiment.

<Comparative Example 2-2>

An organic light-emitting device was manufactured in the same manner as in Comparative Example 2-1, except that Compound ET1, instead of Compound ET1, was used as the electron transporting layer in Comparative Example 2-1.

[ET2]

Figure 112016019751857-pat00086

Comparative Example 2-3

An organic light-emitting device was manufactured in the same manner as in Comparative Example 2-1, except that Compound ET1, instead of Compound ET3, was used as the electron transporting layer in Comparative Example 2-1.

[ET3]

Figure 112016019751857-pat00087

compound Voltage
(V @ 10Ma / cm 2 ) efficiency
(cd / A @ 10mA / cm 2 ) Color coordinates
(x, y) T95
(hr) Comparative Example 2-1 ET1 4.05 4.42 (0.138, 0.127) 120 Experimental Example 2-1 Compound 1-1 3.75 4.85 (0.139, 0.122) 145 Experimental Example 2-2 Compound 1-2 3.86 4.74 (0.138, 0.126) 120 Experimental Example 2-3 Compound 1-3 3.85 4.92 (0.138, 0.127) 135 Experimental Example 2-4 Compound 1-4 3.89 4.75 (0.137, 0.129) 125 Experimental Example 2-5 Compound 1-5 3.95 4.64 (0.138, 0.128) 130 Experimental Example 2-6 Compound 1-6 3.90 4.62 (0.138, 0.129) 135 Experimental Example 2-7 Compound 1-9 3.96 4.75 (0.136, 0.128) 125 Experimental Example 2-8 Compound 1-10 3.98 4.72 (0.137, 0.127) 145 Experimental Example 2-9 Compound 1-12 3.94 4.61 (0.138, 0.129) 130 Comparative Example 2-2 ET2 4.22 4.45 (0.136, 0.130) 95 Comparative Example 2-3 ET3 4.63 4.12 (0.136, 0.128) 60

As a result, the organic light emitting diodes of Experimental Examples 2-1 to 2-9 using the compound prepared according to the present invention as the electron transporting layer are more efficient than the organic light emitting diodes of Comparative Examples 2-1, 2-2 and 2-3. It was confirmed that the excellent performance in terms of driving voltage, lifetime.

Although the preferred embodiment of the present invention has been described above, the present invention is not limited thereto, and various modifications and changes can be made within the scope of the claims and the detailed description of the invention, which also belong to the scope of the invention. .

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

Claims (13)

A compound of any one of formulas 5 to 8
[Formula 5]
Figure 112019031506717-pat00131

[Formula 6]
Figure 112019031506717-pat00132

[Formula 7]
Figure 112019031506717-pat00133

[Formula 8]
Figure 112019031506717-pat00134

In Chemical Formulas 5 to 8,
Ar1 is a phenyl group substituted with deuterium, a halogen group, a nitrile group, an alkyl group, an aryl group or a heteroaryl group; Biphenyl group; Naphthyl group; Terphenyl group; Phenanthrene group; A fluorene group unsubstituted or substituted with an alkyl group; Triphenylene group; Dibenzofuran group; Dibenzothiophene group; A quinazoline group unsubstituted or substituted with an aryl group; A quinoline group unsubstituted or substituted with an aryl group; A benzocarbazole group unsubstituted or substituted with an aryl group; Or a carbazole group unsubstituted or substituted with an aryl group,
R1 and R2 are hydrogen, n and p are 3, m is 4,
L1 is a direct bond or a phenylene group,
Y1 is selected from the following structural formula,
Figure 112019031506717-pat00089
Figure 112019031506717-pat00090
Figure 112019031506717-pat00091

Figure 112019031506717-pat00092
Figure 112019031506717-pat00093

Ar2 and Ar3 are the same as or different from each other, an aryl group having 6 to 30 carbon atoms unsubstituted or substituted with an alkyl group having 1 to 10 carbon atoms, * is a moiety bonded to L1,
L2 is the same as or different from L1, and is as defined in L1,
Y2 is the same as or different from Y1 and is the same as the definition of Y1. delete delete delete delete delete The compound of claim 1, wherein Ar 1 is a phenyl group substituted with deuterium, a fluorine group, a nitrile group, an alkyl group, an aryl group, or a heteroaryl group. delete The method according to claim 1, Ar2 and Ar3 are the same as or different from each other, each independently represent a phenyl group unsubstituted or substituted with an alkyl group having 1 to 10 carbon atoms; A biphenyl group unsubstituted or substituted with an alkyl group having 1 to 10 carbon atoms; Terphenyl group unsubstituted or substituted with an alkyl group having 1 to 10 carbon atoms; A quarterphenyl group unsubstituted or substituted with an alkyl group having 1 to 10 carbon atoms; A naphthyl group unsubstituted or substituted with an alkyl group having 1 to 10 carbon atoms; Anthryl groups unsubstituted or substituted with alkyl groups having 1 to 10 carbon atoms; A fluorenyl group unsubstituted or substituted with an alkyl group having 1 to 10 carbon atoms; Or a phenanthrenyl group unsubstituted or substituted with an alkyl group having 1 to 10 carbon atoms. The compound of claim 1, wherein any one of Formulas 5 to 8 is selected from the following structural formulas:
Figure 112019502069376-pat00110

Figure 112019502069376-pat00111

Figure 112019502069376-pat00119

Figure 112019502069376-pat00138

Figure 112019502069376-pat00121

Figure 112019502069376-pat00135

Figure 112019502069376-pat00136
 A first electrode; A second electrode provided to face 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 comprises a compound according to any one of claims 1, 7, 9, and 10. Organic light-emitting device comprising. The organic light emitting device of claim 11, wherein the organic material layer includes a light emitting layer, and the light emitting layer includes the compound. The organic light emitting device of claim 11, wherein the organic material layer includes at least one of an electron injection layer, an electron transport layer, and a hole suppression layer, and at least one of the electron injection layer, the electron transport layer, and the hole suppression layer includes the compound. .
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