KR102055973B1 - Hetero-cyclic compound and organic light emitting device comprising the same - Google Patents

Abstract

The present specification relates to a heterocyclic compound represented by Chemical Formula 1 and an organic light emitting device including the same.

Description

Heterocyclic compound and organic light-emitting device including the same {HETERO-CYCLIC 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.

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

According to an exemplary embodiment of the present specification provides a heterocyclic compound represented by the formula (1).

[Formula 1]

In Chemical Formula 1,

R3 and R4, or R5 and R6 are combined with the formula (2),

X1 to X4 are CR or N,

[Formula 2]

Groups R, R1, R2, and R7 to R15 which are not bound to the formula (2) in R3 to R6 are the same as or different from each other, and each independently hydrogen, deuterium, nitrile group, substituted or unsubstituted alkyl group, substituted or unsubstituted A substituted silyl group, a substituted or unsubstituted amine group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group, or combine with each other to form a substituted or unsubstituted ring,

L is a direct bond, a substituted or unsubstituted arylene group, or a substituted or unsubstituted heteroarylene group,

n is an integer from 1 to 3,

Ar is a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group, or combines with R12 to form a substituted or unsubstituted ring.

The heterocyclic compound according to the exemplary embodiment of the present specification may be used as a material of the organic material layer of the organic light emitting device, and by using the same, it is possible to improve efficiency, low driving voltage, and / or lifetime characteristics in the organic light emitting device.

1 illustrates an organic light emitting device according to an exemplary embodiment of the present specification.
2 illustrates an organic light emitting diode according to another exemplary embodiment of the present specification.
3 is a mass spectrometric result of the intermediate 2-A according to another exemplary embodiment of the present specification.
4 is a mass spectrometric result of the intermediate A according to another exemplary embodiment of the present specification.
5 is an NMR result of Intermediate A according to another exemplary embodiment of the present specification.
6 is an NMR result of intermediate C according to another exemplary embodiment of the present specification.
7 is a mass analysis result of the intermediate 3-E according to another exemplary embodiment of the present specification.
8 is a mass analysis result of the intermediate 4-E according to another exemplary embodiment of the present specification.
9 is a mass spectrometric result of the intermediate E according to another exemplary embodiment of the present specification.
10 is a mass spectrometry result of Compound A-61 according to another exemplary embodiment of the present specification.
11 is a mass spectrometry result of Compound C-3 according to another exemplary embodiment of the present specification.
12 is a mass spectrometry result of Compound C-14 according to another exemplary embodiment of the present specification.
13 is a mass spectrometry result of Compound C-59 according to another exemplary embodiment of the present specification.
14 is a mass spectrometry result of Compound C-77 according to another exemplary embodiment of the present specification.
15 is a mass spectrometry result of Compound E-3 according to another exemplary embodiment of the present specification.

Hereinafter, this specification is demonstrated in detail.

The present specification provides a heterocyclic compound represented by Chemical Formula 1.

In the present specification, when a part "includes" a certain component, this means that it may further include other components, without excluding other components unless specifically stated otherwise.

In this specification, when a member is located "on" another member, this includes not only when a member is in contact with another member but also when another member exists between the two members.

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

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

As used herein, the term "substituted or unsubstituted" is deuterium; Nitrile group; Substituted or unsubstituted alkyl group; Substituted or unsubstituted silyl group; Substituted or unsubstituted amine group; Substituted or unsubstituted aryl group; And it is substituted with one or two or more substituents selected from the group consisting of a substituted or unsubstituted heterocyclic group, or two or more of the substituents exemplified above are substituted with a substituent, or means that do not have any substituents. For example, "a substituent to which two or more substituents are linked" may be an aryl group substituted with an aryl group, an aryl group substituted with a heteroaryl group, a heterocyclic group substituted with an aryl group, an aryl group substituted with an alkyl group, or the like.

In the present specification, the alkyl group may be linear or branched chain, carbon number is not particularly limited, but is preferably 1 to 30. Specific examples 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-dimethyl Heptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl, and the like, but is not limited thereto.

In the present specification, the amine group is -NH ₂ ; Alkylamine group; N-alkylarylamine group; Arylamine group; N-aryl heteroaryl amine group; It may be selected from the group consisting of an N-alkylheteroarylamine group and a heteroarylamine group, and carbon number is not particularly limited, but is preferably 1 to 30. Specific examples of the amine group include methylamine group, dimethylamine group, ethylamine group, diethylamine group, phenylamine group, naphthylamine group, biphenylamine group, anthracenylamine group, and 9-methyl-anthracenylamine group. Diphenylamine group, N-phenylnaphthylamine group, ditolylamine group, N-phenyltolylamine group, triphenylamine group, N-phenylbiphenylamine group; N-phenylnaphthylamine group; N-biphenyl naphthylamine group; N-naphthylfluorenylamine group; N-phenylphenanthrenylamine group; N-biphenylphenanthrenylamine group; N-phenyl fluorenyl amine group; N-phenylterphenylamine group; N-phenanthrenylfluorenylamine group; N-biphenyl fluorenyl amine group and the like, but is not limited thereto.

In the present specification, the N-alkylarylamine group means an amine group in which an alkyl group and an aryl group are substituted for N of the amine group.

In the present specification, the N-arylheteroarylamine group means an amine group in which an aryl group and a heteroaryl group are substituted for N in the amine group.

In the present specification, the N-alkylheteroarylamine group means an amine group in which an alkyl group and a heteroarylamine group are substituted for N of the amine group.

In the present specification, the alkyl group in the alkylamine group, the N-arylalkylamine group, the alkylthioxy group, the alkyl sulfoxy group, and the N-alkylheteroarylamine group is the same as the example of the alkyl group described above.

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

In the present specification, the aryl group is not particularly limited, but preferably has 6 to 30 carbon atoms, and the aryl group may be monocyclic or polycyclic.

When the aryl group is a monocyclic aryl group, carbon number is not particularly limited, but is preferably 6 to 30 carbon atoms. Specifically, the monocyclic aryl group may be a phenyl group, a biphenyl group, a terphenyl group, etc., but is not limited thereto.

Carbon number is not particularly limited when the aryl group is a polycyclic aryl group. It is preferable that it is C10-30. Specifically, the polycyclic aryl group may be a naphthyl group, anthracenyl group, phenanthryl group, triphenyl group, pyrenyl group, penalenyl group, perrylenyl group, chrysenyl group, fluorenyl group, etc., but is not limited thereto. no.

In the present specification, the fluorenyl group may be substituted, and adjacent groups may combine with each other to form a ring.

,

,

,

,

및

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

,

,

,

,

And

And so on. However, the present invention is not limited thereto.

In the present specification, examples of the arylamine group include a substituted or unsubstituted monoarylamine group, a substituted or unsubstituted diarylamine group, or a substituted or unsubstituted triarylamine group. The aryl group in the arylamine group may be a monocyclic aryl group, may be a polycyclic aryl group. The arylamine group including two or more aryl groups may simultaneously include a monocyclic aryl group, a polycyclic aryl group, or a monocyclic aryl group and a polycyclic aryl group. For example, the aryl group in the arylamine group may be selected from the examples of the aryl group described above.

In the present specification, the aryl group in the N-arylalkylamine group and the N-arylheteroarylamine group is the same as the examples of the aryl group described above.

In the present specification, the heteroaryl group includes one or more atoms other than carbon and heteroatoms, and specifically, the heteroatoms may include one or more atoms selected from the group consisting of O, N, Se, and S, and the like. Although carbon number is not particularly limited, it is preferably 2 to 30 carbon atoms, the heteroaryl group may be monocyclic or polycyclic. Examples of the heterocyclic group include thiophene group, furanyl group, pyrrole group, imidazolyl group, thiazolyl group, oxazolyl group, oxadiazolyl group, pyridyl group, bipyridyl group, pyrimidyl group, triazinyl group, tria Sleepyl group, acridil group, pyridazinyl group, pyrazinyl group, quinolinyl group, quinazolinyl group, quinoxalinyl group, phthalazinyl group, pyrido pyrimidyl group, pyrido pyrazinyl group, pyrazino pyrazinyl group , Isoquinolinyl group, indolyl group, carbazolyl group, benzoxazolyl group, benzimidazolyl group, benzothiazolyl group, benzocarbazolyl group, benzothiophene group, dibenzothiophene group, benzofuranyl group, pe Nanthrolinyl group (phenanthroline), thiazolyl group, isooxazolyl group, oxadiazolyl group, thiadiazolyl group, benzothiazolyl group, phenothiazinyl group and dibenzofuranyl group and the like, but are not limited thereto.

In the present specification, examples of the heteroarylamine group include a substituted or unsubstituted monoheteroarylamine group, a substituted or unsubstituted diheteroarylamine group, or a substituted or unsubstituted triheteroarylamine group. The heteroarylamine group including two or more heteroaryl groups may simultaneously include a monocyclic heteroaryl group, a polycyclic heteroaryl group, or a monocyclic heteroaryl group and a polycyclic heteroaryl group. For example, the heteroaryl group in the heteroarylamine group may be selected from the examples of the heteroaryl group described above.

In the present specification, examples of the heteroaryl group in the N-arylheteroarylamine group and the N-alkylheteroarylamine group are the same as the examples of the heteroaryl group described above.

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

In the present specification, the description about the heteroaryl group described above may be applied except that the heteroarylene group is a divalent group.

According to one embodiment of the present specification, the heterocyclic compound represented by Chemical Formula 1 may be represented by the following Chemical Formula 3 or 4.

[Formula 3]

[Formula 4]

In Formulas 3 and 4, the definitions of R1 to R15, X1 to X4, n, L, and Ar are the same as defined in Formula 1 above.

In one embodiment of the present specification, X1 to X4 are CR or N.

In an exemplary embodiment of the present specification, groups R, R1, R2, and R7 to R15 which are not bonded with Formula 2 in R3 to R6 are each independently hydrogen or an aryl group, or are bonded to each other to form a substituted or unsubstituted ring. Can be formed.

In an exemplary embodiment of the present specification, groups R, R1, R2, and R7 to R15 each of R3 to R6 which are not bonded to Formula 2 are each independently hydrogen or a phenyl group, or are bonded to each other to form a substituted or unsubstituted ring. Can be formed.

In one embodiment of the present specification, R8 and R9, or R10 and R11 are each independently hydrogen or combine with each other to form a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group.

In one embodiment of the present specification, R8 and R9, or R10 and R11 are each independently hydrogen, or combine with each other to form an aryl group or an N-containing heteroaryl group substituted with an aryl group.

In one embodiment of the present specification, R8 and R9, or R10 and R11 are each independently hydrogen or combine with each other to form a pyrazine group substituted with a phenyl group.

In one embodiment of the present specification, at least one of R8 to R11 is a substituted or unsubstituted N-containing heteroaryl group.

In one embodiment of the present specification, at least one of R8 to R11 is an N-containing heteroaryl group unsubstituted or substituted with an aryl group.

In one embodiment of the present specification, at least one of R8 to R11 is a monocyclic N-containing heteroaryl group unsubstituted or substituted with an aryl group.

In one embodiment of the present specification, at least one of R8 to R11 is a triazine group unsubstituted or substituted with a phenyl group, or a pyrimidine group unsubstituted or substituted with a phenyl group.

In one embodiment of the present specification, L is a direct bond, a substituted or unsubstituted arylene group, or a substituted or unsubstituted heteroarylene group.

In one embodiment of the present specification, L is a direct bond, a substituted or unsubstituted monocyclic or polycyclic arylene group, or a heteroarylene group containing a substituted or unsubstituted N, O, or S.

In an exemplary embodiment of the present specification, L is a phenylene group, a naphthylene group, a pyridinylene group, a pyrimidinylene group, a triazinylene group, a quinazolinylene group, a carbazolylene group, a pyrazinylene group, a pyridazinylene group, a benzo A puro [3,2-d] pyrimidine group or a benzothieno [3,2-d] pyrimidine group.

In one embodiment of the present specification, Ar is a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group, or combines with R12 to form a substituted or unsubstituted ring.

In one embodiment of the present specification, Ar is a substituted or unsubstituted aryl group; Or a heteroaryl group including substituted or unsubstituted N, O, or S; Or combine with R12 to form a substituted or unsubstituted ring.

In one embodiment of the present specification, Ar is an aryl group unsubstituted or substituted with an aryl group or heteroaryl group; Or a heteroaryl group containing N, O, or S unsubstituted or substituted with an aryl group or heteroaryl group; Or combine with R12 to form a substituted or unsubstituted ring.

In one embodiment of the present specification, Ar is a fluoranthene group; Dibenzofuran group; Dibenzothiophene group; Benzofuro [3,2-d] pyrimidine groups unsubstituted or substituted with a phenyl group or a naphthyl group; A benzothieno [3,2-d] pyrimidine group unsubstituted or substituted with a phenyl group or a naphthyl group; A phenyl group unsubstituted or substituted with a phenyl group or a naphthyl group; Pyridazine groups; Pyrazine groups; Naphthyl group; Triazine group unsubstituted or substituted with a phenyl group or a naphthyl group; Triphenylene group; A pyridine group unsubstituted or substituted with a phenyl group or a naphthyl group; Pyrimidine groups unsubstituted or substituted with a phenyl group, a naphthyl group, a thibenzofuran group, or dibenzothiophenic; A phenyl group, a naphthyl group, a dibenzofuran group, a dibenzothiophene group, a quinoline group, or a triazine group unsubstituted or substituted with a substituted or unsubstituted quinazoline group, or combines with R12 to form a substituted or unsubstituted ring .

In one embodiment of the present specification, the substituted or unsubstituted quinazoline group is a dibenzothiophene, dibenzofuran, or a quinazolin group unsubstituted or substituted with a carbazole, phenyl group or naphthyl group unsubstituted or substituted with phenyl. to be.

According to an exemplary embodiment of the present specification, the compounds of Formulas 1, 3 and 4 may be represented by the following structural formula.

The compound is not limited to the compound examples claimed by this patent.

According to an exemplary embodiment of the present specification, the compound of Formula 1, 3 or 4 may be prepared according to the following scheme, but is not limited thereto. In the following schemes, the type and number of substituents can be determined by appropriate selection of known starting materials. Reaction type and reaction conditions may be used those known in the art.

Scheme 1

Intermediate A Formula A-1

The compound represented by Chemical Formula A-1 may synthesize the compound represented by Chemical Formula 1 by Ullmann reaction with benzene iodide from intermediate A as in Scheme 1.

In addition, the present specification provides an organic light emitting device comprising the compound represented by the formula (1).

According to an exemplary embodiment of the present specification, the 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 includes the aforementioned heterocyclic compound.

According to an exemplary embodiment of the present specification, 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 blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer, an electron electron injection layer as an organic material layer. However, the structure of the organic light emitting device is not limited thereto and may include fewer or more organic layers.

For example, the structure of the organic light emitting device of the present specification may have a structure as shown in FIGS. 1 and 2, but is not limited thereto.

1 illustrates a structure of an organic light emitting device in which a first electrode 2, a light emitting layer 3, and a second electrode 4 are sequentially stacked on a substrate 1. 1 is an exemplary structure of an organic light emitting device according to an exemplary embodiment of the present specification, and may further include another organic material layer.

2 shows a first electrode 2, a hole injection layer 5, a hole transport layer 6, a light emitting layer 3, an electron transport layer 7, an electron injection layer 8 and a second electrode on a substrate 1. The structure of the organic light emitting element 4) is sequentially illustrated. 2 is an exemplary structure according to an exemplary embodiment of the present specification, and may further include another organic material layer.

According to the exemplary embodiment of the present specification, the organic material layer includes a hole injection layer, a hole transport layer or an electron blocking layer, and the hole injection layer, the hole transport layer or the electron blocking layer is a hetero represented by Chemical Formula 1, 3 or 4 Cyclic compounds.

According to an exemplary embodiment of the present specification, the organic material layer includes a light emitting layer, and the light emitting layer includes a heterocyclic compound represented by Chemical Formula 1, 3 or 4.

According to an exemplary embodiment of the present specification, the organic material layer includes a light emitting layer, and the light emitting layer includes a compound represented by Chemical Formula 1, 3 or 4 as a host of the light emitting layer.

According to an exemplary embodiment of the present specification, the organic material layer includes a hole blocking layer, an electron transport layer or an electron injection layer, and the hole blocking layer, the electron transport layer or the electron injection layer is a hetero represented by Chemical Formula 1, 3 or 4 Cyclic compounds.

According to an exemplary embodiment of the present specification, the organic material layer may further include one or more layers selected from the group consisting of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer.

The organic light emitting device of the present specification is a material known in the art, except that at least one layer of the organic material layer includes a heterocyclic compound of the present specification, that is, a heterocyclic compound represented by Formula 1, 3 or 4 It can be prepared by the method.

When the organic light emitting device includes a plurality of organic material layers, the organic material layers may be formed of the same material or different materials.

For example, the organic light emitting device of the present specification may be manufactured by sequentially stacking a first electrode, an organic material layer, and a second electrode on a substrate. At this time, by using a physical vapor deposition (PVD: physical vapor deposition), such as sputtering (e-beam evaporation), by depositing a metal or conductive metal oxide or an alloy thereof on the substrate It can be prepared by forming a first electrode, forming 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 second electrode thereon. In addition to the above method, an organic light emitting device may be manufactured by sequentially depositing a second electrode material, an organic material layer, and a first electrode material on a substrate. In addition, the heterocyclic compound represented by Chemical Formulas 1 to 3 may be formed as 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.

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

According to another exemplary embodiment of the present specification, 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, 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, Mg / Ag, and the like, but are not limited thereto.

The hole injection layer is a layer for injecting holes from an electrode with a hole injection material, and has a capability of transporting holes with a hole injection material, and thus has a hole injection effect at an anode, and an excellent hole injection effect with respect to a light emitting layer or a light emitting material. The compound which prevents the movement of the excitons produced | generated in the light emitting layer 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 of the light emitting layer is a material capable of emitting light in the visible region by transporting and combining holes and electrons from the hole transporting layer and the electron transporting 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, benzothiazole 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 hetero ring-containing compound. Specifically, the condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, and fluoranthene compounds, and heterocyclic-containing compounds include carbazole derivatives, dibenzofuran derivatives and ladder types. 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. Specifically, the aromatic amine derivatives include condensed aromatic ring derivatives having a substituted or unsubstituted arylamino group, and include pyrene, anthracene, chrysene and periplanthene having an arylamino group, and styrylamine compounds may be substituted or unsubstituted. At least one arylvinyl group is substituted with the above-mentioned arylamine, and one or two or more substituents selected from the group consisting of aryl group, silyl group, alkyl group, cycloalkyl group and arylamino 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 of the electron transporting layer is a layer for receiving electrons from the electron injection layer and transporting electrons to the light emitting layer. The electron transporting material is a material capable of injecting electrons well from the cathode and transferring them to the light emitting layer. This large material 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 according to 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 an aluminum layer or silver layer 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 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 light emitting layer includes the compound of Formula 1, 3 or 4, such as Formula A-1, as a host, and includes a phosphorescent dopant compound as a dopant.

In one embodiment of the present specification, the phosphorescent dopant compound is any one of the following compounds.

The structures specified above are not limited to the dopant compounds.

Hereinafter, the present invention will be described in detail with reference to Examples. However, embodiments according to the present disclosure may be modified in various other forms, and the scope of the present disclosure is not interpreted to be limited to the embodiments described below. The embodiments of the present specification are provided to more fully describe the present specification to those skilled in the art.

Synthesis of Intermediate

Synthesis of Intermediate A

SM-1 중간체 1-A 중간체 2-A 중간체 A

SM-1 Intermediate 1-A Intermediate 2-A Intermediate A

Synthesis of Intermediate 1-A

5, 12-dihydro-5-phenyl indolo [3, 2-a-carbazole (5, 12-dihydro-5-phenyl indolo [3, 2-a] carbazole, hereinafter SM-1, CAS # 1247053- 55-9, 33g, 0. 100 mol) was dissolved in 150 ml of N, N-dimethylformamide (N, N-dimethylformamide, hereinafter referred to as DMF, CAS # 68-12-2) and lowered to 0 ° C. using an ice bath. N-bromo succinimide (Nbromosuccimide, hereinafter NBS, CAS # 128-08-5, 17. 8 g, 0. 100 mol) was dissolved in 100 ml of DMF and slowly added dropwise to the indolo carbazole reaction solution over 30 minutes. . After the addition, the precipitate precipitated was filtered and extracted with ethyl acetate (EA, CAS # 141-78-6). The extracted organic layer was dried over anhydrous magnesium sulfate (MgSO ₄ , CAS # 7487-). 88-9), followed by filtration and recrystallization while removing the solvent with a rotary concentrator to obtain 38.9 g of intermediate 1-A (94.5%). [M + H] = 411

Synthesis of Intermediate 2-A

Obtained intermediate 1-A 21g (0.051mol) and 2-chlorophenyl boronic acid (CAS # 3900-89-8) 8. 8g (0.056mol) in 150ml of toluene and ethanol (hereinafter referred to as EtOH) An aqueous solution was dissolved in 100 ml and dissolved in 26 g (0.119 mol) of potassium carbonate (hereinafter referred to as K ₂ CO ₃ , CAS # 584-08-7) in water.

[1, 1'-Bis (diphenylphosphino) ferrocene] dichloropalladium (0) (hereinafter Pd (dppf) Cl ₂ , CAS # 72287-26-4) 0.75 g (0.80 mmol) was added to the reaction solution for 8 hours. Heat stirring. After the completion of the reaction, the mixture was cooled to room temperature, and the solvent was removed using a rotary concentrator, and the intermediate 2-A 17.9 g (yield 78.8%) was obtained in the same manner as the extraction of intermediate 1-A. [M] = 442

3 is MS data of Intermediate 2-A. It can be seen that the highest peak was recorded at 443.2.

Synthesis of Intermediate A

14 g (0.033 mol) of the obtained intermediate 2-A was dissolved in 100 ml of dimethylacetamide (DMAc, CAS # 127-19-5), and potassium phosphate (hereinafter, K ₃ PO ₄ , CAS # 7778-). 53-2) 21 g (.0.99 mol) was added, followed by tetrakistriphenylphosphine palladium (0), hereinafter TTP, CAS # 14221-01-3) 0.76 g (0. 65 mmol) was added and stirred under heat for one day. After the completion of the reaction, the mixture was cooled to room temperature, poured with a large amount of water to form a precipitate, filtered, and the obtained precipitate was prepared in the same manner as the extraction of Intermediate 1-A. Got it. [M + H] = 407

4 is a result of mass analysis of intermediate A. FIG. It can be seen that the highest peak was recorded at 407.2.

5 is a result of NMR analysis of intermediate A.

Synthesis of Intermediate B

Intermediate 1-A Intermediate 1-B Intermediate B

Synthesis of Intermediate 1-B

Obtained intermediate 1-A 10g (0.024mol) and 3-chloropyridinyl-2-boronic acid (CAS # 1448866-17-8) 4. 3g (0.027mol) to intermediate 2 In the same manner as in the synthesis of -A, intermediate 1-B 3. 8 g (yield 35%) was obtained. [M + H] = 443

Synthesis of Intermediate B

3 g (6.75 mmol) of Intermediate 1-B obtained above were obtained in the same manner as in the synthesis of Intermediate A, to obtain 3 g of Intermediate B (49% yield). [M + H] = 408

Synthesis of Intermediate C

SM-1 중간체 1-C 중간체 C

SM-1 Intermediate 1-C Intermediate C

Synthesis of Intermediate 1-C

Bioorg. & Med. Chem. 6. Synthesis method as described in 2012, 20, 1711 was used to convert 6 g (0.050 mmol) into 1, 2-dichloroethane (Aluminium chloride, AlCl ₃ , CAS # 7446-70-0). , DCE, CAS # 107-06-2) into 50 ml, and stirred at room temperature for 30 minutes, followed by 9 g (0.45 mol) of 2,3-dichloroquinoxaline (2,3-dichloroquinoxaline, CAS # 2213-63-0). Added. After stirring the reaction solution for 45 minutes and further 30 minutes, 15 g (0.45 mol) of SM-1 was slowly added dropwise to the reaction solution. After completion of the reaction, the extraction and purification of Intermediate 1-A were carried out in the same manner to obtain 19.7 g of Intermediate 1-C (yield 88.4%). [M + H] = 495

Synthesis of Intermediate C

The obtained intermediate 1-C 15g (0.030 mol) was used in the same manner as the synthesis of Intermediate A, to obtain 10.7 g of Intermediate C (yield 77%). [M + H] = 459

6 is a result of NMR analysis of intermediate C.

Synthesis of Intermediate E

중간체 1-E 중간체 2-E 중간체 3-E 중간체 4-E

Intermediate 1-E Intermediate 2-E Intermediate 3-E Intermediate 4-E

Synthesis of Intermediate 1-E

Citric acid 30 g (0.174 mol) of 5-chloro-2-nitroaniline (CAS # 1635-61-6) was synthesized according to the synthesis method described in WO 2010-020363. CAS # 64-19-7) was dissolved in 200 ml and then NBS 30.9 g (0.174 mol) was added. After stirring the reaction solution for 30 minutes, it was confirmed that the reaction was terminated, and a large amount of water was poured to form a precipitate, which was obtained in the same manner as the extraction of Intermediate 1-A to obtain Intermediate 1-E 30.6 g (63.5%). . [M + H] = 252

Synthesis of Intermediate 2-E

25 g (0. 100 mol) of the recovered intermediate 1-E was added to 400 ml of EtOH, and 139 g (0.800 mol) of sodium dithionite (hereinafter referred to as Na ₂ S ₂ O ₄ , CAS # 7775-14-6) was 300 ml of water. It was dissolved in and added to the reaction solution. The reaction solution was heated and stirred for 6 hours and then the reaction was terminated. After filtering and removing the salts floating in the reaction solution, the filtrate was removed with a rotary concentrator, and the intermediate 2-E 9. 4g (yield 43%) was obtained in the same manner as the extraction method of intermediate 1-A. [M] = 219

Synthesis of Intermediate 3-E

Cited by J. Organometall. Chem. In the same manner as in the synthesis method of 2013, 1-8, 10 g (0.45 mol) of intermediate 2-E was added to 150 ml of EtOH, and 0.1 g of lithium chloride (Lithium Chloride, hereinafter LiCl, CAS # 7447-41-8) was 0.4 g (4.5 mmol). ) Was heated. After heating and stirring for one day and the reaction was completed, the precipitate was filtered and the filtered precipitate was obtained in the same manner as the extraction of Intermediate 1-A to give 10. 2 g (Yield 57%) of Intermediate 3-E. [M] = 395

7 is a result of mass analysis of intermediate 3-E.

Synthesis of Intermediate 4-E

20 g (0.51 mol) of intermediate 3-E and Bis (boron pincolate) (4, 4, 4 ', 4', 5, 5, 5 ', 5'-octamethyl-2, 2'-bi-1, 3 , 2-dioxaborolane, B2pina2, CAS # 73183-34-3) 12.8g (0.051mol) and Potassium acetate (KOAc, CAS # 127-08-2) 9, 72g (0.101mol) To 1,4-dioxane (hereinafter referred to as dioxane) and heated. After heating and stirring for 30 minutes, Pd (dppf) Cl ₂ 0.14 g (1.0 mmol) was added thereto, and the mixture was heated and stirred for one day. After completion of the reaction, the precipitate was added to a large amount of water to precipitate and filtered. [M + H] = 443

8 is a mass spectrometry result of the intermediate 4-E.

Intermediate 1-A Intermediate 4-E Intermediate 5-E Intermediate E

Synthesis of Intermediate 5-E

15 g (0.36 mol) of Intermediate 1-A obtained above and 17 g (0.38 mol) of Intermediate 4-E were obtained in the same manner as in the synthesis of Intermediate 2-A, yielding 20 g (87% yield) of Intermediate 5-E. [M] = 647

Synthesis of Intermediate E

7 g (0.010 mol) of Intermediate 5-E obtained above was obtained in the same manner as in the synthesis of Intermediate A, to obtain 5 g of Intermediate E (yield 76%). [M + H] = 611

9 is a result of mass analysis of intermediate E. FIG.

< Production Example >

< Production Example  1> Synthesis of Compound A-1

15 g (0.37 mol) of the synthesized intermediate A was converted to 4.69 g (0.073 mol) of copper (Cu, CAS # 7440-50-8) in a solvent of iodobenzene (CAS # 591-50-4). ₃ PO ₄ 23. 5 g (0. 110 mol) l) were added together (hereinafter Ullmann conditions) and stirred by heating for one day. After the completion of the reaction, the reaction solution was cooled to room temperature, and excess ethanol (EtOH) was added to precipitate the compound, followed by extraction with CHCl ₃ , followed by water removal and recrystallization using ethyl acetate (EA), Compound A-1 12. 1 g (yield) 80%). [M] = 482

< Production Example  2> Synthesis of Compound A-61

15 g (0.37 mol) of the synthesized intermediate A was dissolved in 150 ml of anhydrous DMF, and 1.88 g (0.44 mol) of sodium hydride (NaH, CAS # 7646-69-7) was slowly added thereto. 2-chloro-4- (2-naphthyl) quinazolin (2-chloro-4- (2-naphthyl) quinazoline, hereinafter 4-CNQ, CAS # 124959-44-0) after stirring at room temperature for 1 hour 11. 8g (0.041mol) was added and stirred at room temperature for one day. After the reaction was terminated, the resulting precipitate was filtered, washed with EtOH and extracted with EA to obtain 14.3 g of Compound A-61 (yield 59%). [M + H] = 661

10 is a mass spectrometry result of Compound A-61.

< Production Example  3> Synthesis of Compound A-71

Compound A-71 16.3 g (yield 67%) was obtained in the same manner as in Production Example 2, 15 g (0.37 mol) of the synthesized intermediate A. [M + H] = 661

< Production Example  4> Synthesis of Compound C-3

Intermediate C 12g (0.026mol) and 2-Bromonaphthalene (CAS # 580-13-2) 5. 7g (0.027mol) was added to xylene and t-butoxy sodium (sodium) 5.0 g (0.052 mol) of t-butoxide, hereinafter NaOtBu, and CAS # 865-48-5 were added thereto, followed by heating and stirring for 30 minutes. After stirring for 30 minutes, add bis (tri-tert-butylphosphine) palladium (0) (Bis (tri-tert-butylphosphine) palladium (0), hereinafter BTP) 0.03g (0.05mmol) and heat-stirr for 4 hours It was. (Hereinafter referred to as Buchwald conditions), the reaction cooled to room temperature after termination into a large excess of EtOH after the precipitate precipitate chloroform (CHCl ₃ below) in the same manner as extraction of the intermediate compound 1-A C-3 12. 6g (yield 82%) Got. [M + H] = 585

11 is a mass spectrometry result of Compound C-3.

< Production Example  5> Synthesis of Compound C-14

Intermediate C 10g (0.22mol) and 3- (4-bromophenyl) -fluoranthene (3- (4-bromophenyl) fluoranthene, CAS # 667940-21-8) 8.6g (0.024mol) In the same manner as in the synthesis method of Preparation Example 4, 12 g (yield 75%) of compound C-14 was obtained. [M + H] = 735

12 is a mass spectrometry result of Compound C-14.

< Production Example  6> Synthesis of Compound C-59

Compound 10 g (0.022 mol) and 2-chloro-4-phenylquinazoline (hereinafter referred to as CPQ) 5. 8 g (0.023 mol) synthesized in the same manner as in Preparation Example 2 Obtained with 12 g of C-59 (yield 88%). [M + H] = 663

13 is a mass spectrometry result of Compound C-59.

< Production Example  7> Synthesis of Compound C-77

13 g (0.28 mol) of the synthesized intermediate C and 10 g (0.31 mol) of 9-phenyl-3-bromocarbazole (3-bromo-9-phenyl-9H-carbazole, CAS # 1153-85-1) were prepared. Compound C-77 14. 7 g (yield 74%) was obtained by the same method as the example 4. [M + H] = 700

14 is a mass spectrometry result of Compound C-77.

< Production Example  8> Compound E-3 Synthesis

Compound 6.7g (0.011mol) and 2-bromonaphthalene (2-Bromonaphthalene, CAS # 580-13-2) 2. 5g (0.012mol) synthesized in the same manner as in Synthesis Example 4 E-3 7g (yield 88%) was obtained. [M + H] = 737

15 is a mass spectrometry result of Compound E-3.

< Comparative example  1>

A glass substrate (corning 7059 glass) coated with ITO (Indium Tin Oxide) with a thickness of 1,000 Å was placed in distilled water in which a dispersant was dissolved, and ultrasonically washed. Fischer Co. products were used for the detergent, and Millipore Co. Secondly filtered distilled water was used as a filter of the product. After the ITO was washed for 30 minutes, the ultrasonic cleaning was repeated twice with distilled water for 10 minutes. After washing the distilled water, the ultrasonic washing in the order of isopropyl alcohol, acetone, methanol solvent and dried. Hexanitrile hexaazatriphenylene (HAT-CN) was thermally vacuum deposited to a thickness of 50 kPa on the prepared ITO transparent electrode to form a hole injection layer. HT1 (700 mW) carrying holes thereon was vacuum deposited and subsequently HT2 (200 mW) was deposited. In the light emitting layer, the host H1 and the dopant Dp-7 compound were vacuum deposited to a thickness of 300 kPa. Subsequently, E1 compound (300 kPa) was thermally vacuum deposited sequentially with an electron injection and transport layer. An organic light emitting device was manufactured by sequentially depositing 12 Å thick lithium fluoride (LiF) and 2,000 Å thick aluminum on the electron transport layer to form a cathode.

In the above process, the deposition rate of the organic material was maintained at 1 Å / sec, LiF was 0.2 Å / sec, and the aluminum was maintained at a deposition rate of 3 Å / sec to 7 Å / sec.

< Comparative example  2>

An organic light-emitting device was manufactured in the same manner as in Comparative Example 1, except that [H2] was used instead of [H1] in Comparative Example 1.

< Comparative example  3>

An organic light-emitting device was manufactured in the same manner as in Comparative Example 1, except that [H3] was used instead of [H1] in Comparative Example 1.

< Example  1>

An organic light emitting device was manufactured in the same manner as in Comparative Example 1, except that [Compound A-61] was used instead of [H1] in Comparative Example 1.

< Example  2>

An organic light emitting device was manufactured in the same manner as in Comparative Example 1, except that [Compound A-71] was used instead of [H1] in Comparative Example 1.

< Example  3>

An organic light-emitting device was manufactured in the same manner as in Comparative Example 1, except that [Compound C-3] was used instead of [H1] in Comparative Example 1.

< Example  4>

An organic light-emitting device was manufactured in the same manner as in Comparative Example 1, except that [Compound C-14] was used instead of [H1] in Comparative Example 1.

< Example  5>

An organic light-emitting device was manufactured in the same manner as in Comparative Example 1, except that [Compound C-59] was used instead of [H1] in Comparative Example 1.

< Example  6>

An organic light-emitting device was manufactured in the same manner as in Comparative Example 1, except that [Compound C-77] was used instead of [H1] in Comparative Example 1.

< Example  7>

An organic light-emitting device was manufactured in the same manner as in Comparative Example 1, except that [Compound E-3] was used instead of [H1] in Comparative Example 1.

When the current was applied to the organic light emitting diodes produced by Comparative Examples 1 to 4 and Examples 1 to 7, the results of Table 1 were obtained.

matter Driving voltage Efficiency (cd / A) x-coordinate y-coordinate Comparative example H1 3.6 18.55 0.665 0.333 H2 4.12 21.2 0.663 0.329 H3 4.42 24.35 0.659 0.338 Example A-61 4.52 22.35 0.660 0.332 A-71 3.8 24.3 0.662 0.337 C-3 3.61 23.9 0.661 0.327 C-14 3.49 22.32 0.662 0.337 C-59 3.52 23.12 0.661 0.336 C-77 3.45 22.03 0.660 0.332 E-3 3.50 23.5 0.664 0.331

Looking at the driving voltage and the efficiency of the table, it can be seen that in the comparative example, either the driving voltage or the efficiency of the efficiency is highlighted, while the present material has both the driving voltage and the efficiency improvement.

1: substrate
2: first electrode
3: light emitting layer
4: second electrode
5: hole injection layer
6: hole transport layer
7: electron transport layer
8: electron injection layer

Claims (9)

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

In Chemical Formula 1,
R3 and R4, or R5 and R6 are combined with the formula (2),
X1 to X4 are the same as or different from each other, and each independently, CR or N,
[Formula 2]

Groups R, R1, R2, and R7 to R15 which are not bound to the formula (2) in R3 to R6 are the same as or different from each other, and each independently hydrogen, deuterium, nitrile group, substituted or unsubstituted alkyl group, substituted or unsubstituted A substituted silyl group, a substituted or unsubstituted amine group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group, or combine with each other to form a substituted or unsubstituted ring,
* Is a site that binds to R3, R4, R5, or R6,
L is a direct bond, a substituted or unsubstituted arylene group, or a substituted or unsubstituted heteroarylene group,
n is an integer of 1 to 3,
Ar is a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group, or combines with R12 to form a substituted or unsubstituted ring. The heterocyclic compound according to claim 1, wherein Formula 1 is represented by Formula 3 or 4 below:
[Formula 3]

[Formula 4]

In Formulas 3 and 4, the definitions of R1 to R15, X1 to X2, n, L, and Ar are the same as defined in Formula 1 above. The compound of claim 1, wherein R8 and R9; Or R 10 and R 11 combine with each other to form a substituted or unsubstituted benzene. The heterocyclic compound according to claim 1, wherein R14 and R15 combine with each other to form a substituted or unsubstituted aromatic hydrocarbon ring having 6 to 20 carbon atoms, or a substituted or unsubstituted hetero ring having 2 to 10 carbon atoms. The hetero of claim 1, wherein Ar is a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted quinazoline, or a substituted or unsubstituted quinoxaline Ring compounds. The heterocyclic compound according to claim 1, wherein Formula 1 is any one of the following compounds:

A first electrode; A second electrode provided to face the first electrode; And one or two 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 heterocyclic compound according to any one of claims 1 to 6. Phosphorescent organic light-emitting device. The organic light emitting device of claim 7, wherein the organic material layer includes a light emitting layer, and the light emitting layer includes the heterocyclic compound. The organic light emitting device of claim 7, wherein the organic material layer includes a hole injection layer, a hole transport layer, or an electron blocking layer, and the hole injection layer, the hole transport layer, or the electron blocking layer includes the heterocyclic compound.

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