CN116874494A - Novel heterocyclic compound and organic electronic device comprising same - Google Patents

Novel heterocyclic compound and organic electronic device comprising same Download PDF

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CN116874494A
CN116874494A CN202310749546.6A CN202310749546A CN116874494A CN 116874494 A CN116874494 A CN 116874494A CN 202310749546 A CN202310749546 A CN 202310749546A CN 116874494 A CN116874494 A CN 116874494A
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aryl
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heteroaryl
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阴盛镇
金圣珉
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Suzhou Shentong New Material Co ltd
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    • C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
    • C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
    • C07D491/04—Ortho-condensed systems
    • C07D491/044—Ortho-condensed systems with only one oxygen atom as ring hetero atom in the oxygen-containing ring
    • C07D491/048—Ortho-condensed systems with only one oxygen atom as ring hetero atom in the oxygen-containing ring the oxygen-containing ring being five-membered
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    • H10K50/14—Carrier transporting layers
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    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
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    • H10K85/633—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising polycyclic condensed aromatic hydrocarbons as substituents on the nitrogen atom
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    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • H10K85/636—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising heteroaromatic hydrocarbons as substituents on the nitrogen atom
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    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
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Abstract

The present invention relates to a novel heterocyclic compound, which is a polycyclic compound in which three cyclic compounds having different structures are condensed to a central skeleton of benzene and a specific substituent, and an organic electronic element including the same, and the heterocyclic compound is represented by the following chemical formula 1. An organic layer material that can be used for an organic light-emitting element. [ chemical formula 1 ]]

Description

Novel heterocyclic compound and organic electronic device comprising same
Technical Field
The present invention relates to a novel heterocyclic compound and an organic electronic device comprising the same.
Background
In general, an organic light emitting phenomenon refers to a phenomenon in which an organic substance is used to convert electric energy into light energy. An organic electronic element utilizing an organic light emitting phenomenon generally has a structure including an anode and a cathode and an organic layer between the anode. Among them, the organic layer is mostly composed of a multi-layered structure composed of different substances to improve efficiency and stability of the organic electronic element, and may be composed of, for example, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer.
In the organic electronic element, materials used as the organic layer may be classified into a light emitting material and a charge transporting material, such as a hole injecting material, a hole transporting material, an electron injecting material, and the like, according to functions. Further, the light emitting material may be classified into a high molecular type and a low molecular type according to molecular weight, and may be classified into a fluorescent material of a singlet excited state derived from electrons and a phosphorescent material of a triplet excited state derived from electrons according to a light emitting mechanism. In addition, the light emitting materials can be classified into blue, green and red light emitting materials, and yellow and orange light emitting materials required for achieving better natural colors, according to the light emitting colors.
In particular, in order for an organic electronic element to have excellent lifetime characteristics, various studies are being made on an organic substance inserted into a hole transport layer or a buffer layer (buffer layer), and for this purpose, a hole injection layer material is required which imparts high hole movement characteristics from an anode to an organic layer, and at the same time, has high uniformity and low crystallinity when a thin film is formed after vapor deposition.
There is a need to develop a hole injection layer material that can delay permeation and diffusion of a metal oxide from an anode electrode (ITO) into an organic layer, which is one of the causes of a reduction in the lifetime of an organic electronic element, and also has stable characteristics, i.e., a high glass transition temperature, with respect to Joule heat (Joule heating) occurring during element driving. In addition, it is reported that the low glass transition temperature of the hole transport layer material greatly affects the element lifetime according to the property that uniformity of the thin film surface is reduced when the element is driven. In addition, in forming OLED elements, a vapor deposition method is the mainstream, and therefore, a material having strong heat resistance characteristics that can withstand such a vapor deposition method for a long period of time is required.
On the other hand, when only one species is used as a light emitting material, a shift of the maximum emission wavelength to a long wavelength occurs due to an intermolecular interaction, and a problem of a decrease in efficiency of an element occurs due to a decrease in color purity or a light emission attenuation effect, and therefore, in order to improve light emitting efficiency by an increase in color purity and energy transfer, a host/dopant system may be used as a light emitting material. The principle is that when a small amount of dopant having a smaller energy band gap than the host forming the light emitting layer is mixed in the light emitting layer, excitons generated in the light emitting layer are transferred to the dopant, thereby generating light with high efficiency. At this time, since the wavelength of the host is shifted to the wavelength range of the dopant, light of a desired wavelength can be obtained according to the kind of the dopant used.
In order to sufficiently exhibit the excellent characteristics of the organic electronic element, first, a substance constituting an organic layer in the element, for example, a hole injecting substance, a hole transporting substance, a light emitting substance, an electron transporting substance, an electron injecting substance, or the like should be supported by a stable and effective material, but development of a stable and effective organic layer material for an organic electronic element has not been sufficiently carried out, and therefore, development of a new material has been continued.
Prior art literature
Patent literature
Patent document 1 korean laid-open patent publication No. 2016-0002408
Disclosure of Invention
Problems to be solved by the invention
The present invention provides a heterocyclic compound of a novel structure which can be used as an organic material for an organic light-emitting element.
The present invention also provides an organic electronic device comprising the heterocyclic compound of the present invention as an organic material.
Means for solving the problems
The present invention relates to a novel heterocyclic compound and an organic electronic device comprising the same, the heterocyclic compound according to the present invention is a polycyclic compound in which three different cyclic compounds are condensed with benzene, represented by the following chemical formula 1,
[ chemical formula 1]
(in the chemical formula 1 described above,
R a 、R b r is R c Each independently is hydrogen, deuterium, C1-C60 alkyl, C3-C60 cycloalkyl, C6-C60 aryl or C3-C60 heteroaryl;
L 1 to L 3 Each independently is a single bond, a C6-C60 arylene group, or a C3-C60 heteroarylene group;
R 1 to R 6 Each independently is C1-C60 alkyl, C2-C60 alkenyl, C2-C60 alkynyl, C3-C60 cycloalkyl, C3-C60 heterocycloalkyl, C6-C60 aryl, C3-C60 heteroaryl or-L 11 -R 11 Or R is 1 And R is 2 、R 3 And R is 4 R is R 5 And R is 6 Can be independently connected with each other to form an aromatic ring condensed or unfused heterocycle;
L 11 is a C6-C60 arylene group or a C3-C60 heteroarylene group;
R 11 is C6-C60 aryl, C3-C60 heteroaryl or-NR 12 R 13 ，R 12 R is R 13 Each independently is hydrogen, C1-C60 alkyl, C6-C60 aryl, or C3-C60 heteroaryl;
the R is 1 To R 6 Alkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, and heterocycle, R 11 Aryl and heteroaryl, R 12 To R 13 The alkyl, aryl and heteroaryl of (a) may be further substituted with one or more selected from the group consisting of C1-C60 alkyl, halogenated C1-C60 alkyl, deuterium, halogeno, cyano, C3-C60 cycloalkyl, C1-C60 alkoxy, C6-C60 aryl, C6-C60 aryloxy, C6-C60 arylC 1-C60 alkyl, C1-C60 alkylC 6-C60 aryl, C3-C60 heteroaryl, nitro and hydroxy;
p, q and r are each independently an integer from 0 to 4, and p, q and r are not simultaneously 0;
the heteroarylene, heteroaryl and heterocycloalkyl group comprise one or more heteroatoms selected from N, O, S and Se. )
Preferably, in chemical formula 1 according to an embodiment of the present invention,
R a 、R b r is R c Each independently is hydrogen, C1-C30 alkyl or C6-C30 aryl;
L 1 to L 3 Each independently is a single bond, a C6-C30 arylene group, or a C3-C30 heteroarylene group;
R 1 to R 6 Each independently is C6-C30 aryl, C3-C30 heteroaryl or-L 11 -R 11 Or R is 1 And R is 2 、R 3 And R is 4 R is R 5 And R is 6 Can be independently connected with each other to form an aromatic ring condensed heterocyclic ring;
L 11 is a C6-C30 arylene group or a C3-C30 heteroarylene group;
R 11 is C6-C30 aryl, C3-C30 heteroaryl or-NR 12 R 13 ，R 12 R is R 13 Each independently is a C6-C30 aryl group;
the R is 1 To R 6 Aryl, heteroaryl, and heterocyclic ring, R 11 Aryl and heteroaryl, R 12 To R 13 Is further substituted with one or more selected from the group consisting of C1-C30 alkyl, deuterium, C6-C30 aryl, and C3-C30 heteroaryl;
p, q and r are each independently integers from 0 to 2, and p, q and r are not simultaneously 0;
the heteroarylene, heteroaryl and heterocycloalkyl group may include one or more heteroatoms selected from N, O, S and Se.
From the standpoint of obtaining an organic electronic element more excellent in characteristics, it is preferable that the heterocyclic compound according to an embodiment of the present invention can be represented by any one of the following chemical formulas 2 to 4.
[ chemical formula 2]
[ chemical formula 3]
[ chemical formula 4]
(in the chemical formulas 2 to 4,
R a 、R b r is R c Each independently is a C1-C30 alkyl group or a C6-C30 aryl group;
L 1 to L 3 Each independently is a single bond, a C6-C30 arylene group, or a C3-C30 heteroarylene group;
R 1 to R 6 Each independently is C6-C30 aryl, C3-C30 heteroaryl or-L 11 -R 11 Or R is 1 And R is 2 、R 3 And R is 4 R is R 5 And R is 6 Can be independently connected with each other to form an aromatic ring condensed heterocyclic ring;
L 11 is a C6-C30 arylene group or a C3-C30 heteroarylene group;
R 11 is C6-C30 aryl, C3-C30 heteroaryl or-NR 12 R 13 ，R 12 R is R 13 Each independently is a C6-C30 aryl group;
the R is 1 To R 6 Aryl, heteroaryl, and heterocyclic ring, R 11 Aryl and heteroaryl, R 12 To R 13 May be substituted with one or more selected from the group consisting of C1-C30 alkyl, deuterium, C6-C30 aryl and C3-C30 heteroaryl;
p, q and r are each independently integers from 0 to 2, and p, q and r are not simultaneously 0;
the heteroarylene, heteroaryl and heterocycloalkyl group comprise one or more heteroatoms selected from N, O, S and Se. )
Preferably, in chemical formulas 2 to 4 according to an embodiment of the present invention,
R a r is R b Each independently is a C1-C10 alkyl group;
R c is a C6-C12 aryl group;
L 1 to L 3 Each independently is a single bond, a C6-C30 arylene group, or a C3-C30 heteroarylene group;
R 1 to R 6 Each independently is C6-C30 aryl, C3-C30 heteroaryl or-L 11 -R 11 Or R is 1 And R is 2 、R 3 And R is 4 R is R 5 And R is 6 Can be independently connected with each other to form an aromatic ring condensed heterocyclic ring;
L 11 is a C6-C30 arylene group or a C3-C30 heteroarylene group;
R 11 is C6-C30 aryl, C3-C30 heteroaryl or-NR 12 R 13 ，R 12 R is R 13 Each independently is a C6-C12 aryl group;
the R is 1 To R 6 Aryl, heteroaryl, and heterocyclic ring, R 11 Aryl and heteroaryl, R 12 To R 13 May be substituted with one or more selected from the group consisting of C1-C10 alkyl, deuterium, C6-C12 aryl and C3-C12 heteroaryl;
p, q and r are each independently integers from 1 to 2, and p, q and r are not simultaneously 0;
the heteroarylene, heteroaryl and heterocycloalkyl group may include one or more heteroatoms selected from N, O, S and Se.
More preferably, the heterocyclic compound according to an embodiment of the present invention may be represented by any one of the following chemical formulas 5 to 10.
[ chemical formula 5]
[ chemical formula 6]
[ chemical formula 7]
[ chemical formula 8]
[ chemical formula 9]
[ chemical formula 10]
(in the chemical formulas 5 to 10,
R a r is R b Each independently is a C1-C10 alkyl group;
R c is a C6-C12 aryl group;
L 1 to L 3 Each independently is a single bond, a C6-C30 arylene group, or a C3-C30 heteroarylene group;
R 1 to R 6 Each independently is C6-C30 aryl, C3-C30 heteroaryl or-L 11 -R 11 ；
L 11 Is a C6-C30 arylene group or a C3-C30 heteroarylene group;
R 11 is C6-C30 aryl, C3-C30 heteroaryl or-NR 12 R 13 ，R 12 R is R 13 Each independently is a C6-C30 aryl group;
R 21 to R 26 Each independently is a C6-C30 aryl or C3-C30 heteroaryl group;
the R is 1 To R 6 Aryl and heteroaryl, R 11 Aryl and heteroaryl, R 12 To R 13 May be substituted with one or more selected from the group consisting of C1-C10 alkyl, deuterium, C6-C12 aryl and C3-C12 heteroaryl;
the heteroarylene, heteroaryl and heterocycloalkyl group comprise one or more heteroatoms selected from N, O, S and Se. )
Specifically, the heterocyclic compound of the present invention may be selected from the following compounds, but is not limited thereto.
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In addition, the present invention provides an organic electronic element comprising the heterocyclic compound of the present invention in an organic layer.
The organic layer according to an embodiment of the present invention may be any one or more selected from a light emitting layer, a hole injecting layer, a hole transporting layer, an electron injecting layer, and an electron transporting layer, and the organic electronic element may be an organic light emitting element, an organic solar cell, an organic photoreceptor, or an organic transistor.
In addition, the present invention provides an organic light emitting element including: an anode, a cathode and more than one organic layer positioned between the anode and the cathode; more than one of the organic layers comprises the heterocyclic compound of the present invention.
Effects of the invention
The heterocyclic compound of the present invention is a polycyclic compound having three different cyclic compounds of benzohydrofuran, N-substituted or N-unsubstituted indole and substituted or unsubstituted indene fused to a skeleton of benzene, and is easily used as an organic electronic material.
Further, the heterocyclic compound of the present invention has an organic electronic element for a light-emitting material, a hole-injecting material, a hole-transporting material, a light-emitting material, an electron-transporting material, an electron-injecting material, or the like, which has high efficiency, low driving voltage, and remarkably improved lifetime characteristics, by having three different cyclic compounds of benzohydrofuran, N-substituted or N-unsubstituted indole, and substituted or unsubstituted indene fused to a benzene skeleton as a central skeleton, and by introducing an amino group substituted with various functional groups as a functional group into the central skeleton.
Detailed Description
The present invention will be described in detail below, and at this time, unless otherwise defined in terms of art and science used, has meanings commonly understood by those of ordinary skill in the art to which the present invention pertains, and descriptions of well-known functions and structures that may unnecessarily obscure the gist of the present invention are omitted in the following description.
In this specification, substituents containing "alkyl", "alkoxy" and other moieties containing "alkyl" include straight or branched chain forms.
In the present specification, the alkyl group includes a straight chain or branched chain having 1 to 60 carbon atoms, and may be further substituted with other substituents. The number of carbon atoms of the alkyl group may be 1 to 60, specifically 1 to 30, more specifically 1 to 20, and preferably 1 to 10.
In the present specification, an alkenyl group contains a straight chain or branched chain having 2 to 60 carbon atoms, and may be further substituted with other substituents. The alkenyl group may have a carbon number of 2 to 60, specifically 2 to 40, more specifically 2 to 20, and preferably 2 to 10.
In the present specification, an alkynyl group includes a straight chain or branched chain having 2 to 60 carbon atoms, and may be further substituted with other substituents. The number of carbon atoms of the alkynyl group may be 2 to 60, specifically 2 to 40, more specifically 2 to 20, and preferably 2 to 10.
In the present specification, cycloalkyl groups include monocyclic or polycyclic rings having 3 to 60 carbon atoms, and may be further substituted with other substituents. Wherein polycyclic refers to a group in which the cycloalkyl group is directly linked or fused to another cyclic group. Other cyclic groups may be cycloalkyl groups, and other kinds of cyclic groups, for example, heterocycloalkyl groups, aryl groups, heterocyclic groups, and the like. The number of carbon atoms of the cycloalkyl group may be 3 to 60, specifically 3 to 40, more specifically 5 to 30.
In the present specification, the heterocycloalkyl group contains a heteroatom selected from at least one of N, O, S and Se, and contains a single ring or multiple rings of 2 to 60 carbon atoms, and may be further substituted with other substituents. Wherein polycyclic refers to a group in which the heterocycloalkyl group is directly linked or fused to other cyclic groups. Wherein, other cyclic groups can be heterocycloalkyl groups, and can also be other kinds of cyclic groups, such as cycloalkyl groups, aryl groups, heterocycle groups, and the like. The number of carbon atoms of the heterocycloalkyl group may be 2 to 60, specifically 2 to 40, more specifically 3 to 30.
In the present specification, an aryl group is an organic radical derived by removing one hydrogen from an aromatic hydrocarbon, and includes a single ring or multiple rings of 6 to 60 carbon atoms, and may be further substituted with other substituents. Wherein polycyclic refers to a group in which the aryl group is directly linked or fused to other cyclic groups. Wherein, other cyclic groups can be aryl groups, and can also be other kinds of cyclic groups, such as cycloalkyl groups, heterocycloalkyl groups, heterocycle groups, and the like. The number of carbon atoms of the aryl group may be 6 to 60, specifically 6 to 40, more specifically 6 to 35, and preferably 6 to 25. Specific examples of aryl groups are phenyl, biphenyl, triphenyl, naphthyl, anthracenyl, Examples of the fused ring include, but are not limited to, a group, phenanthryl, perylenyl, fluoranthenyl, triphenylene, phenalenyl, pyrenyl, fused tetraphenyl (tetracenyl), fused pentaphenyl, fluorenyl, indenyl, acenaphthylenyl, fluorenyl, spirobifluorenyl, and the like.
In the present specification, "arylene" refers to a divalent organic radical derived by removing one hydrogen from the aryl group, and follows the definition of the aryl group.
In the present specification, the heterocyclic group contains a heteroatom selected from at least one of N, O, S and Se, contains a single ring or multiple rings of 2 to 60 carbon atoms, and may be further substituted with other substituents. Heteroaryl groups are included within the scope of heterocyclyl groups, being heteroaromatic ring groups. Wherein polycyclic refers to a group in which the heterocyclic group is directly linked or fused to another cyclic group. Wherein, other cyclic groups can be heterocyclic groups, and can also be other kinds of cyclic groups, such as cycloalkyl, heterocycloalkyl, aryl, and the like. The number of carbon atoms of the heterocyclic group may be 2 to 60, specifically 2 to 40, more specifically 3 to 30, and preferably 3 to 25. Specific examples of the heterocyclic group are pyridyl, pyrrolyl, pyrimidinyl, pyridazinyl, furyl, thienyl, imidazolyl, pyrazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, triazolyl, furazan, oxadiazolyl, thiadiazolyl, dithiazolyl, tetrazolyl, pyranyl, thiopyranyl, diazinyl, oxazinyl, thiazinyl, dioxinyl, triazinyl, tetrazinyl, quinolinyl, isoquinolinyl, quinazolinyl, isoquinazolinyl, naphthyridinyl, acridinyl, phenanthridinyl, imidazopyridyl, naphthyridine, triazaindinyl (triazaindinyl), indole, indolizinyl, benzothiazolyl, benzoxazolyl, benzimidazolyl, benzothienyl, benzofuranyl, dibenzothienyl, dibenzofuranyl, carbazolyl, benzocarbazolyl, phenazinyl and the like or condensed rings thereof, but are not limited thereto.
In the present specification, "heteroaryl" means an aryl group having at least one heteroatom selected from N, O, S and Se as an aromatic ring skeleton atom and the remaining aromatic ring skeleton atoms being carbon, and is a 5-to 6-membered monocyclic heteroaryl group or a polycyclic heteroaryl group fused to one or more benzene rings, and may be partially saturated. In addition, heteroaryl groups in the present invention also include forms in which more than one heteroaryl group is linked by a single bond. As specific examples, it includes: monocyclic heteroaryl groups such as furyl, thienyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, isothiazolyl, isoxazolyl, oxazolyl, triazinyl, pyridyl, pyrazinyl, pyrimidinyl, and pyridazinyl; benzofuranyl, benzothienyl, isobenzofuranyl, benzimidazolyl, benzothiazolyl, benzisothiazolyl, benzisoxazolyl, benzoxazolyl, isoindolyl, indolyl (indazolyl), indazolyl (indazolyl), quinolinyl, isoquinolinyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, benzocarbazolyl, and the like.
In this specification, "heteroarylene" refers to a divalent organic radical derived by removing one hydrogen from the heteroaryl, and follows the definition of heteroaryl.
The present invention relates to a novel heterocyclic compound and an organic electronic device including the same, and more particularly, to a novel heterocyclic compound which is a polycyclic compound having a skeleton in which a benzohydrofuran, an N-substituted or unsubstituted indole, and a substituted or unsubstituted indene are condensed to benzene, and an organic electronic device including the same.
The heterocyclic compound according to the present invention may be represented by the following chemical formula 1:
[ chemical formula 1]
(in the chemical formula 1 described above,
R a 、R b r is R c Each independently is hydrogen, deuterium, C1-C60 alkyl, C3-C60 cycloalkyl, C6-C60 aryl or C3-C60 heteroaryl;
L 1 to L 3 Each independently is a single bond, a C6-C60 arylene group, or a C3-C60 heteroarylene group;
R 1 to R 6 Each independently is C1-C60 alkyl, C2-C60 alkenyl, C2-C60 alkynyl, C3-C60 cycloalkyl, C3-C60 heterocycloalkyl, C6-C60 aryl, C3-C60 heteroaryl or-L 11 -R 11 Or R is 1 And R is 2 、R 3 And R is 4 R is R 5 And R is 6 Can be independently connected with each other to form an aromatic ring condensed or unfused heterocycle;
L 11 is a C6-C60 arylene group or a C3-C60 heteroarylene group;
R 11 is C6-C60 aryl, C3-C60 heteroaryl or-NR 12 R 13 ，R 12 R is R 13 Each independently is hydrogen, C1-C60 alkyl, C6-C60 aryl, or C3-C60 heteroaryl;
The R is 1 To R 6 Alkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, and heterocycle, R 11 Aryl and heteroaryl, R 12 To R 13 The alkyl, aryl and heteroaryl groups of (a) may be further substituted with one or more selected from the group consisting of C1-C60 alkyl, halogenated C1-C60 alkyl, deuterium, halogeno, cyano, C3-C60 cycloalkyl, C1-C60 alkoxy, C6-C60 aryl, C6-C60 aryloxy, C6-C60 arylC 1-C60 alkyl, C1-C60 alkylC 6-C60 aryl, C3-C60 heteroaryl, nitro and hydroxy;
p, q and r are each independently an integer from 0 to 4, and p, q and r are not simultaneously 0;
the heteroarylene, heteroaryl and heterocycloalkyl group comprise one or more heteroatoms selected from N, O, S and Se. )
The heterocyclic compound represented by chemical formula 1 of the present invention is a polycyclic compound having an oxygen atom and a nitrogen atom, three kinds of cyclic compounds (a benzohydrofuran, an N-substituted or unsubstituted indole, a substituted or unsubstituted indene) having different structures are condensed to the central skeleton of benzene, and a compound having a substituted amino group with or without a linker as a specific substituent on one or more benzene rings of the benzohydrofuran, indole, and indene as three kinds of cyclic compounds condensed to benzene can be effectively used for an organic electronic element.
Specifically, the heterocyclic compound of the present invention hasAt least one or more than one of the free radicals on the benzene ring simultaneously with the central skeleton of (C)>The represented substituted amino group, thereby being used as a material for an organic electronic element, significantly improves the characteristics of the organic electronic element.
That is, the heterocyclic compound of chemical formula 1 of the present invention, due to the structural characteristics of a specific substituent on a specific central skeleton, reduces driving voltage and increases light emitting efficiency and color purity and exhibits significantly improved lifetime characteristics when used as an organic layer of an organic electronic element, particularly as a hole transporting substance of an organic light emitting element.
Preferably, in chemical formula 1 according to an embodiment of the present invention, R a 、R b R is R c Each independently is hydrogen, C1-C30 alkyl or C6-C30 aryl;
L 1 to L 3 Each independently is a single bond, a C6-C30 arylene group, or a C3-C30 heteroarylene group;
R 1 to R 6 Each independently is C6-C30 aryl, C3-C30 heteroaryl or-L 11 -R 11 Or R is 1 And R is 2 、R 3 And R is 4 R is R 5 And R is 6 Can be independently connected with each other to form an aromatic ring condensed heterocyclic ring;
L 11 is a C6-C30 arylene group or a C3-C30 heteroarylene group;
R 11 is C6-C30 aryl, C3-C30 heteroaryl or-NR 12 R 13 ，R 12 R is R 13 Each independently is a C6-C30 aryl group;
The R is 1 To R 6 Aryl, heteroaryl, and heterocyclic ring, R 11 Aryl and heteroaryl, R 12 To R 13 May be substituted with one or more selected from the group consisting of C1-C30 alkyl, deuterium, C6-C30 aryl and C3-C30 heteroaryl;
p, q and r are each independently integers from 0 to 2, and p, q and r are not simultaneously 0;
the heteroarylene, heteroaryl and heterocycloalkyl group may include one or more heteroatoms selected from N, O, S and Se.
From the standpoint of achieving further improved characteristics of the organic electronic element employing the heterocyclic compound of the present invention, the heterocyclic compound is preferably represented by any one of the following chemical formulas 2 to 4.
[ chemical formula 2]
[ chemical formula 3]
[ chemical formula 4]
(in the chemical formulas 2 to 4,
R a 、R b r is R c Each independently is a C1-C30 alkyl group or a C6-C30 aryl group;
L 1 to L 3 Each independently is a single bond, a C6-C30 arylene group, or a C3-C30 heteroarylene group;
R 1 to R 6 Each independently is C6-C30 aryl, C3-C30 heteroaryl or-L 11 -R 11 Or R is 1 And R is 2 、R 3 And R is 4 R is R 5 And R is 6 Can be independently connected with each other to form an aromatic ring condensed heterocyclic ring;
L 11 is a C6-C30 arylene group or a C3-C30 heteroarylene group;
R 11 is C6-C30 aryl, C3-C30 heteroaryl or-NR 12 R 13 ，R 12 R is R 13 Each independently is a C6-C30 aryl group;
The R is 1 To R 6 Aryl, heteroaryl, and heterocyclic ring, R 11 Aryl and heteroaryl and R 12 To R 13 Aromatic of (C)The group may be substituted with one or more selected from the group consisting of C1-C30 alkyl, deuterium, C6-C30 aryl and C3-C30 heteroaryl;
p, q and r are each independently integers from 0 to 2, and p, q and r are not simultaneously 0;
the heteroarylene, heteroaryl and heterocycloalkyl group comprise one or more heteroatoms selected from N, O, S and Se. )
Preferably, in chemical formulas 2 to 4 according to an embodiment of the present invention,
R a r is R b Each independently is a C1-C10 alkyl group;
R c is a C6-C12 aryl group;
L 1 to L 3 Each independently is a single bond, a C6-C30 arylene group, or a C3-C30 heteroarylene group;
R 1 to R 6 Each independently is C6-C30 aryl, C3-C30 heteroaryl or-L 11 -R 11 Or R is 1 And R is 2 、R 3 And R is 4 R is R 5 And R is 6 Can be independently connected with each other to form an aromatic ring condensed heterocyclic ring;
L 11 is a C6-C30 arylene group or a C3-C30 heteroarylene group;
R 11 is C6-C30 aryl, C3-C30 heteroaryl or-NR 12 R 13 ，R 12 R is R 13 Each independently is a C6-C12 aryl group;
the R is 1 To R 6 Aryl, heteroaryl, and heterocyclic ring, R 11 Aryl and heteroaryl, R 12 To R 13 May be substituted with one or more selected from the group consisting of C1-C10 alkyl, deuterium, C6-C12 aryl and C3-C12 heteroaryl;
p, q and r are each independently integers from 0 to 2, and p, q and r are not simultaneously 0;
the heteroarylene, heteroaryl and heterocycloalkyl may include more than one heteroatom selected from N, O, S and Se.
Preferably, in chemical formulas 2 to 4 according to an embodiment of the present invention,
R a r is R b Each independently is a C1-C10 alkyl group;
R c is a C6-C12 aryl group;
L 1 to L 3 Each independently is a single bond, a C6-C30 arylene group, or a C3-C30 heteroarylene group;
R 1 to R 6 Each independently is C6-C30 aryl, C3-C30 heteroaryl or-L 11 -R 11 Or R is 1 And R is 2 、R 3 And R is 4 R is R 5 And R is 6 Can be independently connected with each other to form an aromatic ring condensed heterocyclic ring;
L 11 is a C6-C30 arylene group or a C3-C30 heteroarylene group;
R 11 is C6-C30 aryl, C3-C30 heteroaryl or-NR 12 R 13 ，R 12 R is R 13 Each independently is a C6-C12 aryl group;
the R is 1 To R 6 Aryl, heteroaryl, and heterocyclic ring, R 11 Aryl and heteroaryl, R 12 To R 13 May be substituted with one or more selected from the group consisting of C1-C10 alkyl, deuterium, C6-C12 aryl and C3-C12 heteroaryl;
p, q and r are each independently integers from 0 to 2, and p, q and r are not simultaneously 0;
the heteroarylene, heteroaryl and heterocycloalkyl group comprise one or more heteroatoms selected from N, O, S and Se.
More preferably, in chemical formulas 2 to 4,
R a r is R b Each independently is a C1-C20 alkyl group;
R c is a C6-C20 aryl group;
L 1 to L 3 Each independently is a single bond, a C6-C20 arylene group, or a C3-C20 heteroarylene group;
R 1 to R 6 Each independently is C6-C20 aryl, C3-C20 heteroaryl or-L 11 -R 11 Or R is 1 And R is 2 、R 3 And R is 4 R is R 5 And R is 6 Can be independently and mutually connected to form an aromatic ring condensedA C3 to C10 heterocycle of (C);
L 11 is a C6-C20 arylene or C3-C20 heteroarylene;
R 11 is C6-C25 aryl, C3-C25 heteroaryl or-NR 12 R 13 ，R 12 R is R 13 Each independently is a C6-C25 aryl group;
the R is 1 To R 6 Aryl, heteroaryl, and heterocyclic ring, R 11 Aryl and heteroaryl, R 12 To R 13 May be substituted with one or more selected from the group consisting of C1-C20 alkyl, deuterium, C6-C20 aryl and C3-C20 heteroaryl;
p, q and r are each independently integers from 0 to 1, and p, q and r are not simultaneously 0;
the heteroarylene, heteroaryl and heterocycloalkyl may include more than one heteroatom selected from N, O, S and Se.
More preferably, the heterocyclic compound according to an embodiment of the present invention may be represented by any one of the following chemical formulas 5 to 10.
[ chemical formula 5]
[ chemical formula 6]
[ chemical formula 7]
[ chemical formula 8]
[ chemical formula 9]
[ chemical formula 10]
(in the chemical formulas 5 to 10,
R a r is R b Each independently is a C1-C10 alkyl group;
R c is a C6-C12 aryl group;
L 1 to L 3 Each independently is a single bond, a C6-C30 arylene group, or a C3-C30 heteroarylene group;
R 1 to R 6 Each independently is C6-C30 aryl, C3-C30 heteroaryl or-L 11 -R 11 ；
L 11 Is a C6-C30 arylene group or a C3-C30 heteroarylene group;
R 11 is C6-C30 aryl, C3-C30 heteroaryl or-NR 12 R 13 ，R 12 R is R 13 Each independently is a C6-C30 aryl group;
R 21 to R 26 Each independently is a C6-C30 aryl or C3-C30 heteroaryl group;
the R is 1 To R 6 Aryl and heteroaryl, R 11 Aryl and heteroaryl and R 12 To R 13 May be substituted with one or more selected from the group consisting of C1-C10 alkyl, deuterium, C6-C12 aryl and C3-C12 heteroaryl;
the heteroarylene, heteroaryl and heterocycloalkyl group comprise one or more heteroatoms selected from N, O, S and Se. )
Preferably, in formulas 5 to 10 according to an embodiment of the present invention,
R a r is R b Each independently is a C1-C5 alkyl group;
R c is a C6-C12 aryl group;
L 1 to L 3 Each independently is a single bond or a C6-C10 arylene group;
R 1 to R 6 Each independently is C6-C25 aryl, C3-C25 heteroaryl or-L 11 -R 11 ；
L 11 Is a C6-C20 arylene or C3-C20 heteroarylene;
R 11 is C6-C25 aryl, C3-C25 heteroaryl or-NR 12 R 13 ，R 12 R is R 13 Each independently is a C6-C25 aryl group;
R 21 to R 26 Each independently is a C6-C25 aryl or C3-C25 heteroaryl group;
the R is 1 To R 6 Aryl and heteroaryl, R 11 Aryl and heteroaryl, R 12 To R 13 May be substituted with one or more selected from the group consisting of C1-C10 alkyl, deuterium, C6-C12 aryl and C3-C12 heteroaryl;
the heteroarylene, heteroaryl and heterocycloalkyl group comprise one or more heteroatoms selected from N, O, S and Se.
The heterocyclic compound according to an embodiment of the present invention may be selected from the following compounds, but is not limited thereto.
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The heterocyclic compound according to an embodiment of the present invention may be used for an organic layer of an organic light-emitting element, particularly, may be used as a hole transport layer due to its structural specificity.
The foregoing compounds may be prepared based on the examples described below. Representative examples are described in the examples below, but substituents may be added or removed, and the positions of the substituents may be changed, as required. In addition, starting materials, reaction conditions, and the like may be changed based on techniques well known in the art. The variety or position of substituents at other positions can be altered as desired by those skilled in the art using techniques well known in the art.
In addition, the present invention provides an organic electronic element including the heterocyclic compound of chemical formula 1 in an organic layer.
The organic layer of the organic electronic element according to the present invention may be any one or two or more selected from the group consisting of a light-emitting layer, a hole-injecting layer, a hole-transporting layer, an electron-injecting layer, and an electron-transporting layer. The organic electronic element according to an embodiment of the present invention may be an organic light emitting element, an organic solar cell, an organic photoreceptor, or an organic transistor, and particularly may be an organic light emitting element.
In addition, the present invention provides an organic light emitting element including: an anode, a cathode, and one or more organic layers between the anode and the cathode, one or more of the organic layers comprising the heterocyclic compound according to any one of claims 1 to 6.
The heterocyclic compound of the present invention may be contained in one or more organic layers of the organic light-emitting element, and preferably, may be contained in a hole transport layer of the organic layers.
However, the structure of the organic light emitting element known in the art may also be applied to the present invention. The scope of the present invention is not limited to such a laminated structure, and other layers other than the light-emitting layer may be omitted, and other functional layers may be added as needed, as required.
The organic light emitting element according to the present invention may be prepared in materials and methods well known in the art, except that one or more layers in the organic layer include the heterocyclic compound of formula 1.
The heterocyclic compound of chemical formula 1 may constitute one or more layers among organic layers of the organic light-emitting element alone. However, the organic layer may be formed by mixing with other substances according to need.
The heterocyclic compound of chemical formula 1 is useful as a hole injecting material, a hole transporting material, a light emitting material, an electron transporting material, an electron injecting material, or the like in an organic light emitting element. The heterocyclic compound of chemical formula 1 can be used as a material for at least one of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer. As an example, the heterocyclic compound of chemical formula 1 may be used as an electron injection and transport layer material of an organic light emitting device. As another example, the heterocyclic compound of chemical formula 1 may be used as a light-emitting layer material of an organic light-emitting element. As yet another example, the heterocyclic compound of chemical formula 1 may be used as a host material of a phosphorescent light-emitting layer of an organic light-emitting element.
In the organic light emitting element according to the present invention, materials other than the heterocyclic compound of the chemical formula 1 are illustrated below, but these are only examples, not intended to limit the scope of the present invention, and may be replaced with materials well known in the art.
As the anode material, a material having a large work function can be used, and as a specific example, a metal such as vanadium, chromium, copper, zinc, gold, or an alloy thereof, a metal oxide such as zinc oxide, indium Tin Oxide (ITO), indium Zinc Oxide (IZO), such as ZnO: al or SnO 2 : combinations of metals and oxides of Sb, e.g. poly (3-methylthiophene), poly [3,4- (ethylene-1, 2-dioxy) thiophene](PEDT), a conductive polymer of polypyrrole and polyaniline, etc., but is not limited thereto. In addition, the anode layer can be formed by the following stepsOne of the materials may be formed, or a mixture of materials may be formed, and a multilayer structure composed of a plurality of layers of the same composition or different compositions may be formed.
As the cathode material, a material having a low work function can be used, and as a specific example, metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin and lead or alloys thereof such as LiF/Al or LiO can be used 2 Multi-layer structure of Al, etc.
As the hole injecting material, a publicly known hole injecting material can be used, and for example, phthalocyanine compounds such as copper phthalocyanine (copper phthalocyanine, cuPc) and the like disclosed in U.S. Pat. No. 4,356,429 and star-burst amine derivatives such as tris (4-carbazolyl-9-ylphenyl) amine (tris (4-carbazolyl-9-ylphenyl) amine, TCTA), 4 '-tris (3-methylphenyl) triphenylamine (4, 4' -tris (3-methylphenyl) triphenylamine, m-MTDATA), 1,3,5-tris [4- (3-methylphenyl amino) phenyl ] benzene (1, 3,5-tris [4- (3-methylphenyl amino) phenyl ] benzene, m-MTB), a soluble polymer Polyaniline/dodecyl benzene/polystyrene sulfonate (4-dodecyl benzene/Poly (PSS) or Poly (4-phenylene sulfide) (35) or the like, and a polymer (4-phenylene sulfide/4, 35) can be used.
As the hole transporting material, the heterocyclic compound according to an embodiment of the present invention may be contained alone or in combination with a known hole transporting material.
Specifically, the hole transporting material may contain the heterocyclic compound according to an embodiment of the present invention, and be used together with pyrazoline derivatives, arylamine derivatives, stilbene derivatives, triphenylamine derivatives, and the like, and also may be used together with a low-molecular or high-molecular material. As specific examples, N ' -Bis (naphthalen-1-yl) -N, N ' -Bis (phenyl) -benzidine (N, N ' -Bis (naphthalen-1-yl) -N, N ' -Bis (phenyl) -benzodine, NPB), N ' -Bis (naphthalen-1-yl) -N, N ' -Bis (phenyl) -2,2' -dimethylbenzidine (N, N ' -Bis (phenyl) -2,2' -dimethylbenzidine, NPD), 1,3-Bis (N-carbazolyl) benzene (1, 3-Bis (N-carbazolyl) benzozene, mCP), N, N ' -Bis (3-methylphenyl) -N, N ' -diphenylbenzidine (N, N ' -Bis (3-methylphenyl) -N, N ' -diphenylbenzidine, TPD), N, N, N ', N ' -tetrakis (4-methylphenyl) - (1, 1' -biphenyl) -4,4-diamine (N, N, N ', N ' -tetrakis (4-methylphenyl) - (1, 1' -biphen yl) -4,4-diamine, TTB), N1, N4-diphenyl-N1, N4-di-m-tolylbenzene-1,4-diamine (N1, N4-diphenyl-N1, N4-di-m-tollbenzene-1, 4-diamine, TTP), N ' -bis (4-methylphenyl) -N, N ' -bis (4-ethylphenyl) - [1,1' - (3, 3' -dimethyl) biphenyl ] -4,4' -diamine (N, N ' -bis (4-methylphenyl) -N, N ' -bis (4-ethylphenyl) - [1,1' - (3, 3' -dimethyl) biphenyl ] -4,4' -diamine, ETPD), N4' -bis (naphthalen-1-yl) -N4, N4' -bis (4-vinyl phenyl) biphenyl-4,4' -diamine (N4, N4' -di (naphthalen-1-yl) -N4, N4' -bis (4-vinylphenyl) biphen-4, 4' -diamine, VNPB), N4' -bis (4- (6- ((3-ethyloxetan-3-yl) methoxy) hexyl) phenyl) -N4, N4' -diphenyl biphenyl-4,4' -diamine (N4, N4' -bis (4- (6- ((3-ethyloxetan-3-yl) method) phenyl) -N4, N4' -diphenylbiphenyl-4,4' -diamine, ONPB), N4' -bis (4- (6- ((3-ethyloxetan-3-yl) methoxy) hexyl) phenyl) -N4, low molecular hole-transporting substances such as N4, N4' -diphenyl biphenyl-4,4' -diamine (OTPD) and N4, N4' -bis (4- (6- ((3-ethyl-3-yl) method) phenyl) -N4, N4' -diphenylbiphenyl-4,4' -diamine; and polymer hole transport substances such as poly-N-vinylcarbazole (PVK), polyaniline, and (phenylmethyl) polysilane.
Examples of the electron transporting material include oxadiazole derivatives, anthraquinone-dimethane and derivatives thereof, benzoquinone and derivatives thereof, naphthoquinone and derivatives thereof, anthraquinone and derivatives thereof, tetracyanoanthraquinone-dimethane and derivatives thereof, fluorenone derivatives, diphenyldicyanoethylene and derivatives thereof, diphenoquinone derivatives, and metal complexes of 8-hydroxyquinoline and derivatives thereof, and not only low-molecular substances but also high-molecular substances can be used. As a specific example, diphenyl [4- (triphenylsilyl) phenyl ] can be used]Phosphine oxide (diphenyl [4- (triphenyl) silyl)phenyl]phospho-oxide, TSPO 1), 1,3,5-tris (N-phenylbenzimidazol-2-yl) benzene (1, 3,5-tris (N-phenylbenzoimidazol-2-yl) benzene, TPBI), tris (8-hydroxyquinoline) aluminum (tris (8-hydroxyquinoline) aluminum, alq 3 ) 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (2, 9-dimethyl-4,7-diphenyl-1, 10-phenanthrine, BCP), 2- (4-diphenyl) -5- (4-tert-butylphenyl) -1,3, 4-oxadiazole (2- (4-biphenyl) -5- (4-tert-butyl-phenyl) -1,3, 4-oxadazole, PBD), 3- (4-diphenyl) -4-phenyl-5- (4-tert-butylphenyl) -1,2,4-triazole (3- (4-biphenyl) -4-phenyl-5- (4-tert-butyl-phenyl) -1,2,4-triazo, TAZ), 1, 3-bis [2- (4-tert-butylphenyl) -1,3, 4-oxadiazol-5-yl ]Benzene (1, 3-bis [2- (4-tert-butyl-phenyl) -1,3, 4-oxazo-5-yl)]benzone, OXD-7) and the like; tris (phenylquinoxaline) (tris (phenylquinoxaline), TPQ), (3, 3'- [5' - [3- (3-pyridinyl) phenyl)][1,1':3', 1' -terphenyl group]-3, 3' -diyl]Bipyridine) (3, 3'- [5' - [3- (3-Pyridinyl) phenyl)][1,1'：3',1”-terphenyl]-3,3”-diyl]bispyridine, tmppb), and the like, but is not limited thereto.
As the electron injecting material, for example, LIF or Liq (lithium quinolate) is representatively used in the art, but not limited thereto.
As the light-emitting material, a red, green, or blue light-emitting material may be used, and if necessary, two or more light-emitting materials may be used in combination. Further, a fluorescent material or a phosphorescent material may be used as the light-emitting material. As the light-emitting material, a material that emits light by combining holes and electrons injected from the anode and the cathode, respectively, may be used, but a host material and a dopant material may be used together to participate in light emission.
The light-emitting layer may be formed from a light-emitting material by a method such as a vacuum evaporation method, a spin coating method, a casting method, an LB method, or the like, and more specifically, when the light-emitting layer is formed by a vacuum evaporation method, the evaporation conditions thereof differ depending on the compound used, but may be generally selected within the almost same condition range as the formation of the hole injection layer. In addition, the light-emitting layer material may use a known compound as a host or a dopant.
In addition, as an example, as a material of the light-emitting layerThe fluorescent dopant can be IDE102 or IDE105, BD-331 or BD-142 (N) of the light-emitting and light-producing company (Idemitsu) 6 ,N 12 -bis (3, 4-dimethylphenyl) -N 6 ,N 12 -diyl-6, 12-diamine) as phosphorescent dopant, a green phosphorescent dopant Ir (ppy) can be co-vacuum evaporated (doped) 3 (tris (2-phenylpyridine) iridium), blue dopant F2Irpic (iridium (III) bis [4, 6-difluorophenyl) -pyridinyl-N, C2']Picolinate), red phosphorescent dopant RD61 from UDC corporation, and the like.
In addition, when phosphorescent dopants are used together in the light-emitting layer, a hole-suppressing material (HBL) may be further laminated by a vacuum evaporation method or a spin coating method in order to prevent a phenomenon in which triplet excitons or holes diffuse into the electron-transporting layer. At this time, the hole-inhibiting substance that can be used is not particularly limited, but any known material used as a hole-inhibiting material can be selected for use. For example, oxadiazole derivatives or triazole derivatives, phenanthroline derivatives, specifically, balq (bis (8-hydroxy-2-methylquinoline) -biphenoxyaluminum), phenanthroline (phenanthrolines) type compounds (: BCP (bathocuproine) from UDC corporation), and the like can be used.
The phosphorescent dopant is a compound capable of emitting light from triplet excitons, and is not particularly limited as long as it is capable of emitting light from triplet excitons. As a specific example, a metal complex containing one or more metals selected from the group consisting of Ir, ru, pd, pt, os, re, and the like may be used, or a porphyrin metal complex or an orthometalated metal complex may be used.
The porphyrin metal complex can be specifically a porphyrin platinum complex.
The orthometalated metal complex may contain 2-phenylpyridine (2-phenylpyridine, ppy) derivative, 7, 8-benzoquinoline derivative, 2- (2-thienyl) pyridine (2- (2-thienyl) pyridine, tp) derivative, 2- (1-naphthyl) pyridine (2- (1-naphthalenyl) pyridine, npy) derivative, 2-phenylquinoline (2-phenylquinoline, pq) derivative, and the like as ligands therein. In this case, these derivatives may have a substituent as required. As auxiliary ligands, there may be further mentioned other ligands than the above-mentioned ligands, such as acetylacetone(acrylic acid) and picric acid, etc. Specific examples thereof include iridium bithiophene acetylacetonate (bisthienylpyridine acetylacetonate Iridium) and bis (2-benzo [ b ]]Thiophene-2-ylpyridine) (acetylacetonate) iridium (III) (bis (2-benzob)]thiophen-2-yl-pyridine)(acetylacetonato)iridium(III)，Ir(btp) 2 (acac)), bis (2-phenylbenzothiazole) (acetylacetonate) iridium (III), ir (bt), bis (2-phenylbenzothiolate) iridium (III) 2 (acac)), bis (1-phenylisoquinoline) (acetylacetonate) Iridium (III) (bis (1-phenylisoquinoline) (acetoacetonato) Iridium (III), ir (piq) 2 (acac)), tris (1-phenylisoquinoline) iridium (III), ir (piq) 3 ) Tris (2-phenylpyridine) iridium (III), ir (ppy) 3 ) Tris (2-biphenylpyridine) iridium (tris (2-biphenylpyridine) iridium), tris (3-biphenylpyridine) iridium (tris (3-biphenylpyridine) iridium), tris (4-biphenylpyridine) iridium (tris (4-biphenylpyridine) iridium), and the like, but are not limited thereto.
The present invention is further illustrated by the following examples, which are merely illustrative of the present invention and are not intended to limit the scope of the present invention.
EXAMPLE 1 preparation of Compounds Com1-1 to Com-1-30
Preparation of Compound P-11
To toluene/ethanol/water (4:1:1, 200 mL) was added 10g (40.15 mmol) of 4, 5-tetramethyl-2- (2-nitrophenyl) -1,3, 2-dioxaborane, 14.5g (48.18 mmol) of 4-bromo-1-fluoro-2-iodobenzene, 11.10g (80.30 mmol) of potassium carbonate, and the mixture was stirred under nitrogen at 30℃for 10 minutes. Thereafter, 4.64g (4.02 mmol) of tetrakis (triphenylphosphine) palladium (Pd (PPh) 3 ) 4 ) Heated and refluxed at 120 ℃. After completion of the reaction, the mixture was filtered through celite (celite) and florisil, and then washed with MC (dichloromethane). Column chromatography purification using MC and Hex10.2g (86%) of the target compound P-11 were obtained.
Preparation of Compound P-10
After 10g (33.77 mmol) of P-11 were dissolved in 170mL of 1, 2-dichlorobenzene, 10.63g (40.53 mmol) of triphenylphosphine was added and stirred at 180℃under reflux. After completion of the reaction, the mixture was filtered through celite (celite) and florisil, and then washed with n-hexane (hexane) and MC. Column chromatography purification was performed using MC and Hex, thereby obtaining 7.3g (82%) of the target compound P-10.
Preparation of Compound P-9
After adding 10g (37.86 mmol) of P-10, 5.1mL (45.43 mmol) of iodobenzene, 1.44g (7.57 mmol) of Copper (I) iodide, 10.47g (75.73 mmol) of potassium carbonate (potassium carbonate), 3.41g (18.93 mmol) of 1,10-Phenanthroline (1, 10-Phenanthroline) to 420mL of DMF, they were refluxed under nitrogen atmosphere at 150 ℃. After completion of the reaction, the mixture was filtered through celite (celite) and florisil, and washed with MC. Column chromatography purification was performed using MC and Hex, thereby obtaining 9.9g (77%) of the target compound P-9.
Preparation of Compound P-8
After 10g (29.40 mmol) of Compound P-9 was dissolved in 150mL of N-methylpyrrolidone (N-Methyl pyrrolidone, NMP), 8.23g (32.33 mmol) of 2-chloro-6-iodophenol, 8.13g (58.79 mmol) of potassium carbonate (potassium carbonate) were added and stirred at 80℃for 24 hours. After completion of the reaction, MC and H were used 2 After O extraction, the solvent was removed, and column chromatography purification was performed using Hex and MC, thereby obtaining 11.99g (71%) of the target compound P-8.
Preparation of Compound P-7
To 150mL of N, N' -dimethylacetamide was added 10g (29.39 mmol) of compound P-8, 0.99g (4.41 mmol) of palladium acetate, 3.25g (8.82 mmol) of tricyclohexylphosphine tetrafluoroborate, 8.13g (58.79 mmol) of potassium carbonate (potassium carbonate), and stirred at 165℃under reflux for 24 hours. After completion of the reaction, MC and H were used 2 After O extraction, the solvent was removed, and column chromatography purification was performed using Hex and MC, thereby obtaining 9.19g (70%) of the objective compound P-7.
Preparation of Compound P-6
To toluene/ethanol/water (4:1:1, 110 mL) was added 10g (22.39 mmol) of P-7, 7.04g (26.86 mmol) of methyl2- (4, 5-tetramethyl-1,3, 2-dioxaborane-2-yl) benzoate (methyl 2- (4, 5-tetramethyl-1,3, 2-dioxaborolan-2-yl) benzoate) and 6.19g (44.77 mmol) of potassium carbonate, followed by stirring under nitrogen at 30℃for 10 minutes. Thereafter, 2.59g (2.24 mmol) of tetrakis (triphenylphosphine) palladium (Pd (PPh) 3 ) 4 ) And was refluxed at 120 ℃. After completion of the reaction, the mixture was filtered through celite (celite) and florisil, and washed with MC. Column chromatography purification was performed using MC and Hex, thereby obtaining 9.55g (85%) of the target compound P-6.
Preparation of Compound P-5
After 10g (19.92 mmol) of Compound P-6 was dissolved in 10mL of THF, the temperature was lowered to-78 ℃. After that, 15mL (43.83 mmol) of methylmagnesium bromide (1.4 m, thf: tol=1:3) was slowly added dropwise. After stirring at the same temperature for 1 hour, the temperature was gradually raised to normal temperature and stirring was performed. After completion of the reaction, MC and H were used 2 After O extraction, the solvent was removed, and column chromatography purification was performed using Hex and MC, thereby obtaining 7.20g (72%) of the target compound P-5.
Preparation of Compound P-4
To 100mL of hydrochloric acid/acetic acid (1:9) was added 10g (19.92 mmol) of P-5, and the mixture was stirred under reflux for 24 hours. After completion of the reaction, the reaction was terminated with water. The resulting solid was filtered and washed multiple times with Hex. Thereafter, purification was performed by recrystallization from Hex/EA, whereby 6.56g (68%) of the objective compound P-4 was obtained.
Preparation of Compound P-3
To toluene/ethanol/water (4:1:1, 100 mL) was added 10g (20.66 mmol) of P-4, 5.80g (24.79 mmol) of 2- (4-anisole) -4, 5-tetramethyl-1,3,2-dioxaborane (2- (4-aniole) -4, 5-tetramethy-1, 3, 2-dioxaband) and 5.71g (41.32 mmol) of potassium carbonate, followed by stirring under nitrogen at 30℃for 10 minutes. Thereafter, 2.39g (2.07 mmol) of tetrakis (triphenylphosphine) palladium (Pd (PPh) 3 ) 4 )，And refluxed at 120 ℃. After completion of the reaction, the mixture was filtered through celite (celite) and florisil, and washed with MC. Column chromatography purification was performed using MC and Hex, thereby obtaining 7.23g (68%) of the target compound P-3.
Preparation of Compound P-2
After 10g (18.00 mmol) of Compound P-3 was dissolved in 90mL of MC, the temperature was lowered to 0 ℃. Thereafter, 2.1mL (21.60 mmol) of boron tribromide (boron tribromide) was slowly added dropwise. Then, the temperature was gradually raised to room temperature, and stirring was performed. After completion of the reaction, MC and H were used 2 After O extraction, the solvent was removed, and column chromatography purification was performed using Hex and MC, thereby obtaining 8.48g (87%) of the target compound P-2.
Preparation of Compound P-1
After 10g (18.46 mmol) of Compound P-2 was dissolved in 95mL of THF, 3mL (36.92 mmol) of pyridine, 0.23g (1.85 mmol) of 4-dimethylaminopyridine (4- (dimethylaminoo) pyridine) were added and the temperature was lowered to 0 ℃. After that, 3.5mL (20.31 mmol) of trifluoromethanesulfonic anhydride (trifluoromethanesulfonic anhydride) was slowly added dropwise. After that, the temperature was gradually raised to normal temperature and stirred. After completion of the reaction, MC and H were used 2 After O extraction, the solvent was removed, and column chromatography purification was performed using Hex and MC, thereby obtaining 10.82g (87%) of the target compound P-1.
Preparation of the Compound Com.1-1 (P)
After 5g (7.42 mmol) of Compound P-1 was dissolved in 40mL of toluene, 1.51g (8.91 mmol) of diphenylamine (N, N-diphenylamine), 0.68g (0.74 mmol) of tris (dibenzylideneacetone) dipalladium (0) (tris (dibenzylideneacetone) dipalladium (0)), 2.3mL (2.23 mmol) of tris (tert-butyl) phosphine (1.0M toluene solution), 1.43g (14.84 mmol) of sodium tert-butoxide (sodium tert-butoxide) were added and refluxed at 120℃for 24 hours. After completion of the reaction, it was filtered through celite (celite). Here, 100mL of methanol was poured in to effect solidification. The resulting solid was filtered and washed with DMF, hex. After that, after once recrystallization purification in DMF/Hex1, recrystallization purification in methanol was further carried out, thereby obtaining 4.68g (91%) of the objective compound Com.1-1.
The reaction was carried out in a solvent using the existing palladium amination method (Buchwald-Hartwig amination reaction: buchwald-Hartwig amination). After the completion of the reaction, it is purified by recrystallization from DMF, n-hexane, methanol or the like to obtain the objective compound P. The amine compound used in this reaction is prepared by reacting by a typical reaction method known in the literature.
Prepared by the preparation method of the compound Com.1-1. The compounds prepared in table 1 below were prepared using various amines instead of diphenylamine. The reaction yields of the prepared heterocyclic compounds and the confirmation result data of the prepared compounds are shown in table 1 below. However, the amines used do not limit the scope of the invention.
TABLE 1
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EXAMPLE 2 preparation of Compounds 2-1 to 2-23 (Com 2-1 to Com 2-23)
Preparation of Compound P-10
To toluene/ethanol/water (4:1:1, 180 mL) was added 10g (35.83 mmol) of 2- (4-methoxy-2-nitrophenyl) -4, 5-tetramethyl-1, 3, 2-dioxaborane, 14.5g (43.00 mmol) of 4-bromo-1-fluoro-2-iodobenzene, 9.90g (71.66 mmol) of potassium carbonate, and the mixture was stirred under nitrogen at 30℃for 10 minutes. Thereafter, 4.14g (3.58 mmol) of tetrakis (triphenylphosphine) palladium (Pd (PPh) 3 ) 4 ) It was refluxed at 120 ℃. After completion of the reaction, the mixture was filtered through celite (celite) and florisil, and washed with MC. Column chromatography purification was performed using MC and Hex, thereby obtaining 10.3g (88%) of the target compound P-10.
Preparation of Compound P-9
After 10g (30.66 mmol) of P-10 was dissolved in 150mL of 1, 2-dichlorobenzene, 9.65g (36.80 mmol) of triphenylphosphine was added and stirred at 180℃under reflux. After completion of the reaction, the mixture was filtered through celite (celite) and florisil, and then washed with n-hexane and MC. Column chromatography purification was performed using MC and Hex, thereby obtaining 9.02g (81%) of the target compound P-9.
Preparation of Compound P-8
After 10g (34.00 mmol) of P-9, 4.6mL (40.80 mmol) of iodobenzene, 1.30g (6.80 mmol) of Copper (I) iodide, 9.40g (68.00 mmol) of potassium carbonate (potassium carbonate) and 3.37g (17.00 mmol) of 1,10-Phenanthroline (1, 10-Phenanthroline) were added to 170mL of DMF, they were refluxed under nitrogen atmosphere at 150 ℃. After completion of the reaction, the mixture was filtered through celite (celite) and florisil, and washed with MC. Column chromatography purification was performed using MC and Hex, thereby obtaining 9.5g (75%) of the target compound P-8.
Preparation of Compound P-7
After 10g (27.01 mmol) of Compound P-8 was dissolved in 140mL of NMP, 7.13g (32.41 mmol) of 2-iodophenol, 7.47g (54.02 mmol) of potassium carbonate (potassium carbonate) were added and stirred at 80℃for 24 hours. After completion of the reaction, MC and H were used 2 After O extraction, the solvent was removed, and column chromatography purification was performed using Hex and MC, thereby obtaining 12.32g (80%) of the objective compound P-7.
Preparation of Compound P-6
To 100mL of N, N' -dimethylacetamide was added 10g (17.54 mmol) of compound P-7, 0.60g (0.26 mmol) of palladium acetate, 3.22g (8.77 mmol) of tricyclohexylphosphine tetrafluoroborate, 4.85g (35.07 mmol) of potassium carbonate (potassium carbonate), and stirred at 165℃under reflux for 24 hours. After completion of the reaction, MC and H were used 2 After O extraction, the solvent was removed and column chromatography purification was performed using Hex and MC to obtain 4.65 (60%) of the target compound P-6.
Preparation of Compound P-5
To toluene/ethanol/water (4:1:1, 110 mL) were added 10g (22.61 mmol) of P-6, 7.11g (27.13 mmol) of methyl2- (4, 5-tetramethyl-1, 3, 2-dioxaborane-2-yl) benzoate and 6.25g (45.22 mmol) of potassium carbonate, followed by stirring under a nitrogen atmosphere at 30℃for 10 minutes. Thereafter, 2.61g (2.26 mmol) of tetrakis (triphenylphosphine) palladium (Pd (PPh) 3 ) 4 ) And heated to reflux at 120 ℃. After completion of the reaction, the mixture was filtered through celite (celite) and florisil, and washed with MC. Column chromatography purification was performed using MC and Hex, thereby obtaining 9.22g (82%) of the target compound P-5.
Preparation of Compound P-4
After 10g (20.10 mmol) of Compound P-5 was dissolved in 100mL of THF, the temperature was lowered to-78 ℃. After that, 32mL (44.22 mmol) of methylmagnesium bromide (1.4 m, thf: tol=1:3) was slowly added dropwise. After stirring at the same temperature for 1 hour, the temperature was gradually raised to room temperature and stirring was performed. After completion of the reaction, MC and H were used 2 After O extraction, the solvent was removed, and column chromatography purification was performed using Hex and MC, thereby obtaining 7.0g (70%) of the target compound P-4.
Preparation of Compound P-3
To 100mL of hydrochloric acid/acetic acid (1:9) was added 10g (20.10 mmol) of P-4, and the mixture was stirred under reflux for 24 hours. After completion of the reaction, the reaction was terminated with water. The resulting solid was filtered and washed multiple times with Hex. Thereafter, purification was performed by recrystallization from Hex/EA, whereby 5.69g (59%) of the objective compound P-3 was obtained.
Preparation of Compound P-2
After 10g (20.85 mmol) of Compound P-3 was dissolved in 100mL of MC, the temperature was lowered to 0 ℃. Thereafter, 2.4mL (25.02 mmol) of boron tribromide (boron tribromide) was slowly added dropwise. After that, the temperature was gradually raised to normal temperature and stirred. After completion of the reaction, MC and H were used 2 After O extraction, the solvent was removed, and column chromatography purification was performed using Hex and MC, thereby obtaining 8.15g (84%) of the target compound P-2.
Preparation of Compound P-1
After 10g (21.47 mmol) of Compound P-2 was dissolved in 110mL of THF, 3.5mL (42.96 mmol) of pyridine, 0.26g (2.15 mmol) of 4-dimethylaminopyridine (4- (dimethyllamino) pyridine) were added and the temperature was lowered to 0 ℃. After that, 4.5mL (25.78 mmol) of trifluoromethanesulfonic anhydride (trifluoromethanesulfonic anhydride) was slowly added dropwise. After that, the temperature was gradually raised to normal temperature and stirred. After completion of the reaction, MC and H were used 2 After O extraction, the solvent was removed, and column chromatography purification was performed using Hex and MC, thereby obtaining 10.27g (80%) of the objective compound P-1.
Preparation of Compound P
According to the preparation method of the compound Com.1-1, the reaction is carried out by using the existing palladium amination reaction (Buchwald-Hartwig amination reaction: buchwald-Hartwig amination reaction) method. After the completion of the reaction, it is purified by recrystallization from DMF, n-hexane, methanol or the like to obtain the objective compound P. The amine compound used in this reaction is prepared by reacting by a typical reaction method known in the literature.
The compounds prepared in table 2 below were prepared using various amines instead of diphenylamine. The reaction yields of the prepared heterocyclic compounds and the confirmation result data of the prepared compounds are shown in table 2 below. However, the amines used do not limit the scope of the invention.
TABLE 2
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EXAMPLE 3 preparation of Compounds 3-1 to 3-20 (Com 3-1 to Com 3-20)
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Preparation of Compound P-10
To toluene/ethanol/water (4:1:1, 200 mL) was added 10g (40.15 mmol) of 4, 5-tetramethyl-2- (2-nitrophenyl) -1,3, 2-dioxaborane, 14.5g (48.18 mmol) of 4-bromo-1-fluoro-2-iodobenzene, 11.10g (80.30 mmol) of potassium carbonate, and the mixture was stirred under nitrogen at 30℃for 10 minutes. Thereafter, 4.64g (4.02 mmol) of tetrakis (triphenylphosphine) palladium (Pd (PPh) 3 ) 4 ) It was refluxed at 120 ℃. After completion of the reaction, the mixture was filtered through celite (celite) and florisil, and washed with MC. Column chromatography purification was performed using MC and Hex, thereby obtaining 10.2g (86%) of the target compound P-10.
Preparation of Compound P-9
After 10g (33.77 mmol) of P-10 was dissolved in 170mL of 1, 2-dichlorobenzene, 10.63g (40.53 mmol) of triphenylphosphine was added and stirred at 180℃under reflux. After completion of the reaction, the mixture was filtered through celite (celite) and florisil, and then washed with n-hexane and MC. Column chromatography purification was performed using MC and Hex, thereby obtaining 7.3g (82%) of the target compound P-9.
Preparation of Compound P-8
To 420mL of DMF, 10g (37.86 mmol) of P-9, 5.1mL (45.43 mmol) of iodobenzene, 1.44g (7.57 mmol) of Copper (I) iodide, 10.47g (75.73 mmol) of potassium carbonate (potassium carbonate), 3.41g (18.93 mmol) of 1,10-Phenanthroline (1, 10-Phenanthroline) were added, and the mixture was refluxed under a nitrogen atmosphere at 150 ℃. After completion of the reaction, the mixture was filtered through celite (celite) and florisil, and washed with MC. Column chromatography purification was performed using MC and Hex, thereby obtaining 9.9g (77%) of the target compound P-8.
Preparation of Compound P-7
After 10g (29.40 mmol) of Compound P-8 was dissolved in 150mL of NMP, 7.76g (35.27 mmol) of 2-iodophenol and 8.13g (58.79 mmol) of potassium carbonate (potassium carbonate) were added and stirred at 80℃for 24 hours. After completion of the reaction, MC and H were used 2 After O extraction, the solvent was removed, and column chromatography purification was performed using Hex and MC, thereby obtaining 12.07g (76%) of the target compound P-7.
Preparation of Compound P-6
To 100mL of N, N' -dimethylacetamide was added 10g (18.51 mmol) of compound P-7, 0.62g (2.78 mmol) of palladium acetate, 3.41g (9.26 mmol) of tricyclohexylphosphine tetrafluoroborate, 5.12g (37.02 mmol) of potassium carbonate (potassium carbonate), and stirred at 165℃under reflux for 24 hours. After completion of the reaction, MC and H were used 2 O extraction, removal of solvent, column with Hex and MCChromatography gave 4.9g (64%) of the title compound P-6.
Preparation of Compound P-5
To toluene/ethanol/water (4:1:1, 120 mL) were added 10g (24.26 mmol) of P-6, 8.50g (29.11 mmol) of methyl 5-methoxy-2- (4, 5-tetramethyl-1,3, 2-dioxaborane-2-yl) benzoate (methyl 5-methoxy-2- (4, 5-tetramethyl-1,3, 2-dioxabloan-2-yl) benzoate), and 6.71g (48.51 mmol) of potassium carbonate, followed by stirring under a nitrogen atmosphere at 30℃for 10 minutes. Thereafter, 2.80g (2.43 mmol) of tetrakis (triphenylphosphine) palladium (Pd (PPh) 3 ) 4 ) And was refluxed at 120 ℃. After completion of the reaction, the mixture was filtered through celite (celite) and florisil, and washed with MC. Column chromatography purification was performed using MC and Hex, thereby obtaining 9.8g (81%) of the target compound P-5.
Preparation of Compound P-4
After 10g (20.10 mmol) of Compound P-5 was dissolved in 100mL of THF, the temperature was lowered to-78 ℃. After that, 32mL (44.22 mmol) of methylmagnesium bromide (1.4 m, thf: tol=1:3) was slowly added dropwise. After stirring at the same temperature for 1 hour, the temperature was gradually raised to room temperature and stirring was performed. After completion of the reaction, MC and H were used 2 After O extraction, the solvent was removed, and column chromatography purification was performed using Hex and MC, thereby obtaining 7.8g (78%) of the target compound P-4.
Preparation of Compound P-3
To 100mL of hydrochloric acid/acetic acid (1:9) was added 10g (20.10 mmol) of P-4, and the mixture was stirred under reflux for 24 hours. After completion of the reaction, the reaction was terminated with water. The resulting solid was filtered and washed multiple times with Hex. Thereafter, purification was performed by recrystallization from Hex/EA, whereby 6.2g (64%) of the objective compound P-3 was obtained.
Preparation of Compound P-2
After 10g (20.85 mmol) of Compound P-3 was dissolved in 110mL of MC, the temperature was lowered to 0 ℃. Thereafter, 2.5mL (25.02 mmol) of boron tribromide (boron tribromide) was slowly added dropwise. Then, the temperature was gradually raised to room temperature, and stirring was performed. After completion of the reaction, MC and H were used 2 After O extractionThe solvent was removed, and column chromatography purification was performed using Hex and MC, thereby obtaining 8g (82%) of the target compound P-2.
Preparation of Compound P-1
After 10g (21.48 mmol) of Compound P-2 was dissolved in 110mL of THF, 3.5mL (42.96 mmol) of pyridine, 0.26g (2.15 mmol) of 4-dimethylaminopyridine (4- (dimethyllamino) pyridine) were added and the temperature was lowered to 0 ℃. After that, 4.5mL (25.78 mmol) of trifluoromethanesulfonic anhydride (trifluoromethanesulfonic anhydride) was slowly added dropwise. After that, the temperature was gradually raised to normal temperature and stirred. After completion of the reaction, MC and H were used 2 O extraction, removal of the solvent, and column chromatography purification with Hex and MC were performed to obtain 10.3g (80%) of the target compound P-1.
Preparation of Compound P
According to the preparation method of the compound Com.1-1, the reaction is carried out by using the existing palladium amination reaction (Buchwald-Hartwig amination reaction: buchwald-Hartwig amination reaction) method. After the completion of the reaction, it is purified by recrystallization from DMF, n-hexane, methanol or the like to obtain the objective compound P. The amine compound used in this reaction is prepared by reacting by a typical reaction method known in the literature.
The compounds prepared in table 3 below were prepared using various amines instead of diphenylamine. The reaction yields of the prepared heterocyclic compounds and the confirmation result data of the prepared compounds are shown in table 3 below. However, the amines used do not limit the scope of the invention.
TABLE 3
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Preparation and evaluation of organic electronic component
The compounds obtained in examples were used as hole transport layers, respectively, and organic electroluminescent elements were fabricated according to a conventional method. First, an ITO substrate was mounted on a substrate holder of a vacuum evaporation apparatus, and a 4,4',4"-Tris [ 2-naphthalene (phenyl) amino ] triphenylamine (4, 4',4" -Tris [2-naphthyl (phenyl) amino ] triphenylamine, 2-TNATA) film having a thickness of 10nm was vacuum-evaporated on an ITO layer (anode) formed on a glass substrate as a hole injection layer.
Then, the heterocyclic compound prepared in the examples of the present invention and the comparative example compound described below were vacuum-deposited to a thickness of 20nm as a hole transport layer. Vacuum evaporation and comparative experiments were performed. Thereafter, BD-331 (manufactured by Levonic Co.) was used as a light-emitting dopant, and 9, 10-bis- (naphthalene-2-anthracene) was used as a host material; AND (automatic AND)]The doping concentration was fixed at 4%, so that a comparative experiment was performed. Then, tris (8-quinolinolato) aluminum was formed into a film with a thickness of 40nm as an electron injection layer. Then, an alkali metal halide LiF having a thickness of 0.2nm was evaporated, followed by evaporation at a thickness of 150nmAl, this Al/LiF was used as a cathode, and an organic electroluminescent element was produced. By applying a forward bias direct current voltage to the organic electroluminescent element using the heterocyclic compound of the present invention prepared as described above, the Electroluminescent (EL) characteristics were measured by PR-650 of the company of photoesearch, and as a result of the measurement thereof, a life measuring apparatus manufactured by the company Max Science was used at 300cd/m 2 T95 lifetime was measured at the reference brightness of (c). T95 refers to the time taken for the luminance of the light emitting element to reach 95% of the initial luminance.
For comparison, the compounds of well-known α -NPD (comparative example-1), comparative example-2 and comparative example-3 were used as a hole transporting layer instead of the heterocyclic compound of the present invention, and an organic electroluminescent element having the same structure as the organic electroluminescent element using the heterocyclic compound of the present invention was produced.
Comparative example 1
Comparative example 2
Comparative example 3
The performance (driving voltage, current density, luminance, efficiency, lifetime, etc.) of the organic light-emitting element using the heterocyclic compound of the present invention and comparative examples 1 to 3 as hole transport layer substances is shown in table 4 below.
TABLE 4
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From the results of table 4, it is apparent that the organic electroluminescent element of the present invention exhibits a characteristic of a reduction in driving voltage and further exhibits a further improved characteristic when substituted with deuterium. In addition, life characteristics are also significantly increased.
Therefore, it is found that the organic electroluminescent element using the material for an organic electroluminescent element of the present invention has low driving voltage, excellent color purity, high luminous efficiency and long life when used as a hole transport layer or a light emitting layer material. It is also apparent that the same effect can be obtained by using the compound of the present invention for other organic layers of an organic electroluminescent element, for example, a hole injection layer, an electron transport layer, and the like.

Claims (3)

1. A heterocyclic compound represented by any one of the following chemical formulas 5 to 10:
[ chemical formula 5]
[ chemical formula 6]
[ chemical formula 7]
[ chemical formula 8]
[ chemical formula 9]
[ chemical formula 10]
In the chemical formulas 5 to 10 described above,
R a r is R b Each independently is a C1-C10 alkyl group;
R c is a C6-C12 aryl group;
L 1 to L 3 Each independently is a single bond or a C6-C30 arylene group;
R 1 to R 6 Each independently is C6-C30 aryl, C3-C30 heteroaryl or-L 11 -R 11 ；
L 11 Is a C6-C30 arylene group or a C3-C30 heteroarylene group;
R 11 is C6-C30 aryl, C3-C30 heteroaryl or-NR 12 R 13 ，R 12 R is R 13 Each independently is a C6-C30 aryl group;
R 21 to R 26 Each independently is a C6-C30 aryl or C3-C30 heteroaryl group;
the R is 1 To R 6 Aryl and heteroaryl, R 11 Aryl and heteroaryl, R 12 To R 13 The aryl group of (C) is further substituted with one or more selected from the group consisting of C1-C10 alkyl, deuterium, C6-C12 aryl and C3-C12 heteroaryl.
2. The heterocyclic compound according to claim 1, wherein,
the heterocyclic compound is selected from the following compounds:
3. an organic light-emitting element, wherein,
comprising the following steps:
an anode is provided with a cathode,
cathode and method for manufacturing the same
More than one organic layer positioned between the anode and the cathode;
the organic layer includes a hole transport layer, wherein the hole transport layer includes the heterocyclic compound of claim 1 or claim 2.
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KR102601598B1 (en) * 2015-09-14 2023-11-14 삼성전자주식회사 Mixture, thin film and organic light emitting device including the same
CN107973786B (en) * 2016-10-25 2021-07-09 株式会社Lg化学 Novel compound and organic light-emitting element using same
KR102611877B1 (en) * 2017-12-21 2023-12-08 덕산네오룩스 주식회사 Compound for organic electronic element, organic electronic element comprising the same, and electronic device thereof

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