KR102169327B1 - Heterocyclic compound and organic light emitting device comprising 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 comprising the same {HETEROCYCLIC COMPOUND AND ORGANIC LIGHT EMITTING DEVICE COMPRISING SAME}

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

An electroluminescent device is a type of self-luminous display device, and has advantages in that it has a wide viewing angle, excellent contrast, and a fast response speed.

The organic light-emitting device has a structure in which an organic thin film is disposed between two electrodes. When a voltage is applied to the organic light-emitting device having such a structure, electrons and holes injected from the two electrodes are combined in the organic thin film to form a pair and then emit light while disappearing. The organic thin film may be composed of a single layer or multiple layers as necessary.

The material of the organic thin film may have a light emitting function as needed. For example, as the organic thin film material, a compound capable of constituting an emission layer by itself may be used, or a compound capable of serving as a host or a dopant of the host-dopant-based emission layer may be used. In addition, as the material of the organic thin film, a compound capable of performing a role of hole injection, hole transport, electron blocking, hole blocking, electron transport, and electron injection may be used.

In order to improve the performance, life, or efficiency of an organic light-emitting device, development of a material for an organic thin film is continuously required.

U.S. Patent 4,356,429

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

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

[Formula 1]

In Formula 1,

X ₁ to X ₃ are the same as or different from each other, and each independently a direct bond; O; Or S,

R _a , R _b and R _c are the same as or different from each other, and each independently hydrogen; A substituted or unsubstituted alkyl group; A substituted or unsubstituted aryl group; A substituted or unsubstituted heteroaryl group; -SiRR'R";-P(=O)RR'; and NRR', or two or more groups adjacent to each other bonded to each other to form a substituted or unsubstituted aromatic hydrocarbon ring or a substituted or unsubstituted hetero ring To form,

R ₁ to R ₄ are the same as or different from each other, and each independently hydrogen; heavy hydrogen; A substituted or unsubstituted alkyl group; A substituted or unsubstituted aryl group; A substituted or unsubstituted heteroaryl group; -SiRR'R"; and -P(=O)RR',

Ar is hydrogen; A substituted or unsubstituted alkyl group; A substituted or unsubstituted monocyclic or polycyclic aryl group; A substituted or unsubstituted monocyclic or polycyclic heteroaryl group; -SiRR'R"; or -P(=O)RR',

The R, R'and R" are the same as or different from each other, and each independently hydrogen; a substituted or unsubstituted alkyl group; a substituted or unsubstituted aryl group; or a substituted or unsubstituted heteroaryl group,

p is an integer from 1 to 6,

q and r are integers from 1 to 4,

When p, q and r are integers of 2 or more, the substituents in parentheses are the same as or different from each other.

In addition, in the exemplary embodiment of the present application, the first electrode; A second electrode provided to face the first electrode; And one or more organic material layers provided between the first electrode and the second electrode, wherein at least one of the organic material layers contains a heterocyclic compound represented by Formula 1 above. Provides.

The compound described herein can be used as a material for an organic material layer of an organic light emitting device. The compound may serve as a hole injection material, a hole transport material, a light emitting material, an electron transport material, an electron injection material, a charge generation material, and the like in the organic light emitting device. In particular, the compound can be used as a material for a light emitting layer of an organic light emitting device, particularly a host material for a light emitting layer.

When the compound represented by Formula 1 is used in the organic material layer, the driving voltage of the device is lowered, the light efficiency is improved, and the lifespan characteristics of the device may be improved by thermal stability of the compound.

1 to 3 are diagrams each schematically showing a stacked structure of an organic light emitting diode according to an exemplary embodiment of the present application.

Hereinafter, the present application will be described in detail.

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

In the present specification, the halogen may be fluorine, chlorine, bromine or iodine.

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 by other substituents. The number of carbon atoms of the alkyl group may be 1 to 60, specifically 1 to 40, more specifically 1 to 20. Specific examples include methyl group, ethyl group, propyl group, n-propyl group, isopropyl group, butyl group, n-butyl group, isobutyl group, tert-butyl group, sec-butyl group, 1-methyl-butyl group, 1- Ethyl-butyl group, pentyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, hexyl group, n-hexyl group, 1-methylpentyl group, 2-methylpentyl group, 4-methyl- 2-pentyl group, 3,3-dimethylbutyl group, 2-ethylbutyl group, heptyl group, n-heptyl group, 1-methylhexyl group, cyclopentylmethyl group, cyclohexylmethyl group, octyl group, n-octyl group, tert -Octyl group, 1-methylheptyl group, 2-ethylhexyl group, 2-propylpentyl group, n-nonyl group, 2,2-dimethylheptyl group, 1-ethyl-propyl group, 1,1-dimethyl-propyl group , Isohexyl group, 2-methylpentyl group, 4-methylhexyl group, 5-methylhexyl group, and the like, but are not limited thereto.

In the present specification, the alkenyl group includes a linear or branched chain having 2 to 60 carbon atoms, and may be further substituted by other substituents. The number of carbon atoms of the alkenyl group may be 2 to 60, specifically 2 to 40, and more specifically, 2 to 20. Specific examples include vinyl group, 1-propenyl group, isopropenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 3-methyl-1 -Butenyl group, 1,3-butadienyl group, allyl group, 1-phenylvinyl-1-yl group, 2-phenylvinyl-1-yl group, 2,2-diphenylvinyl-1-yl group, 2-phenyl-2 -(Naphthyl-1-yl)vinyl-1-yl group, 2,2-bis(diphenyl-1-yl)vinyl-1-yl group, stilbenyl group, and styrenyl group, but are not limited thereto.

In the present specification, the alkynyl group includes a straight chain or branched chain having 2 to 60 carbon atoms, and may be further substituted by other substituents. The number of carbon atoms of the alkynyl group may be 2 to 60, specifically 2 to 40, and more specifically, 2 to 20.

In the present specification, the alkoxy group may be linear, branched or cyclic. The number of carbon atoms of the alkoxy group is not particularly limited, but it is preferably 1 to 20 carbon atoms. Specifically, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentyloxy, neopentyloxy, isopentyloxy, n -Hexyloxy, 3,3-dimethylbutyloxy, 2-ethylbutyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, benzyloxy, p-methylbenzyloxy, etc., but It is not limited.

In the present specification, the cycloalkyl group includes a monocyclic or polycyclic having 3 to 60 carbon atoms, and may be further substituted by other substituents. Here, the polycyclic refers to a group in which a cycloalkyl group is directly connected or condensed with another ring group. Here, the other cyclic group may be a cycloalkyl group, but may be a different type of cyclic group, such as a heterocycloalkyl group, an aryl group, or a heteroaryl group. The number of carbon atoms of the cycloalkyl group may be 3 to 60, specifically 3 to 40, and more specifically 5 to 20. Specifically, a cyclopropyl group, cyclobutyl group, cyclopentyl group, 3-methylcyclopentyl group, 2,3-dimethylcyclopentyl group, cyclohexyl group, 3-methylcyclohexyl group, 4-methylcyclohexyl group, 2 ,3-dimethylcyclohexyl group, 3,4,5-trimethylcyclohexyl group, 4-tert-butylcyclohexyl group, cycloheptyl group, cyclooctyl group, and the like, but are not limited thereto.

In the present specification, the heterocycloalkyl group includes O, S, Se, N or Si as a hetero atom, includes a monocyclic or polycyclic having 2 to 60 carbon atoms, and may be further substituted by other substituents. Here, the polycyclic means a group in which a heterocycloalkyl group is directly connected or condensed with another ring group. Here, the other cyclic group may be a heterocycloalkyl group, but may be a different type of cyclic group, such as a cycloalkyl group, an aryl group, or a heteroaryl group. The number of carbon atoms of the heterocycloalkyl group may be 2 to 60, specifically 2 to 40, and more specifically 3 to 20.

In the present specification, the aryl group includes monocyclic or polycyclic having 6 to 60 carbon atoms, and may be further substituted by other substituents. Here, the polycyclic means a group in which an aryl group is directly connected or condensed with another ring group. Here, the other cyclic group may be an aryl group, but may be another type of cyclic group such as a cycloalkyl group, a heterocycloalkyl group, a heteroaryl group, and the like. The aryl group includes a spiro group. The number of carbon atoms of the aryl group may be 6 to 60, specifically 6 to 40, and more specifically 6 to 25. Specific examples of the aryl group include phenyl group, biphenyl group, triphenyl group, naphthyl group, anthryl group, chrysenyl group, phenanthrenyl group, perylenyl group, fluoranthenyl group, triphenylenyl group, phenalenyl group, pyre Nyl group, tetrasenyl group, pentacenyl group, fluorenyl group, indenyl group, acenaphthylenyl group, benzofluorenyl group, spirobifluorenyl group, 2,3-dihydro-1H-indenyl group, condensed ring groups thereof And the like, but are not limited thereto.

In the present specification, the silyl group is a substituent including Si and the Si atom is directly connected as a radical, represented by -SiR ₁₀₄ R ₁₀₅ R ₁₀₆ , R ₁₀₄ to R ₁₀₆ are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Halogen group; Alkyl group; Alkenyl group; Alkoxy group; Cycloalkyl group; Aryl group; And it may be a substituent consisting of at least one of a heterocyclic group. Specific examples of the silyl group include trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, vinyldimethylsilyl group, propyldimethylsilyl group, triphenylsilyl group, diphenylsilyl group, phenylsilyl group, etc. It is not limited.

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

,

,

,

,

,

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

,

,

,

,

,

And the like, but is not limited thereto.

In the present specification, the heteroaryl group includes S, O, Se, N or Si as a hetero atom, and includes a monocyclic or polycyclic having 2 to 60 carbon atoms, and may be further substituted by other substituents. Here, the polycyclic means a group in which a heteroaryl group is directly connected or condensed with another ring group. Here, the other cyclic group may be a heteroaryl group, but may be another type of cyclic group such as a cycloalkyl group, a heterocycloalkyl group, an aryl group, and the like. The number of carbon atoms of the heteroaryl group may be 2 to 60, specifically 2 to 40, and more specifically 3 to 25. Specific examples of the heteroaryl group include a pyridyl group, pyrrolyl group, pyrimidyl group, pyridazinyl group, furanyl group, thiophene group, imidazolyl group, pyrazolyl group, oxazolyl group, isoxazolyl group, thiazolyl Group, isothiazolyl group, triazolyl group, furazinyl group, oxadiazolyl group, thiadiazolyl group, dithiazolyl group, tetrazolyl group, pyranyl group, thiopyranyl group, diazinyl group, oxazinyl group , Thiazinyl group, dioxynyl group, triazinyl group, tetrazinyl group, quinolyl group, isoquinolyl group, quinazolinyl group, isoquinazolinyl group, quinozolilyl group, naphthyridyl group, acridinyl group, phenanthridyl Nyl group, imidazopyridinyl group, diazanaphthalenyl group, triazaindenyl group, indolyl group, indolizinyl group, benzothiazolyl group, benzoxazolyl group, benzimidazolyl group, benzothiophene group, benzofuran group , Dibenzothiophene group, dibenzofuran group, carbazolyl group, benzocarbazolyl group, dibenzocarbazolyl group, phenazinyl group, dibenzosilol group, spirobi (dibenzosilol), dihydrophenazinyl group, Phenoxazinyl group, phenanthridyl group, imidazopyridinyl group, thienyl group, indolo[2,3-a]carbazolyl group, indolo[2,3-b]carbazolyl group, indolinyl group, 10, 11-dihydro-dibenzo[b,f]azepine group, 9,10-dihydroacridinyl group, phenanthrazinyl group, phenothiathiazinyl group, phthalazinyl group, naphthylidinyl group, phenanthrolinyl group, Benzo[c][1,2,5]thiadiazolyl group, 5,10-dihydrodibenzo[b,e][1,4]azasilinyl, pyrazolo[1,5-c]quinazolinyl group , Pyrido[1,2-b]indazolyl group, pyrido[1,2-a]imidazo[1,2-e]indolinyl group, 5,11-dihydroindeno[1,2-b ] Carbazolyl group, and the like, but are not limited thereto.

In the present specification, the amine group is a monoalkylamine group; Monoarylamine group; Monoheteroarylamine group; -NH ₂ ; Dialkylamine group; Diarylamine group; Diheteroarylamine group; Alkylarylamine group; Alkylheteroarylamine group; And it may be selected from the group consisting of an arylheteroarylamine group, 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, dibiphenylamine group, anthracenylamine group, 9- Methyl-anthracenylamine group, diphenylamine group, phenylnaphthylamine group, ditolylamine group, phenyltolylamine group, triphenylamine group, biphenylnaphthylamine group, phenylbiphenylamine group, biphenylfluore There are nilamine group, phenyltriphenylenylamine group, biphenyltriphenylenylamine group, and the like, but are not limited thereto.

In the present specification, an arylene group means that the aryl group has two bonding positions, that is, a divalent group. Except that each of these is a divalent group, the description of the aryl group described above may be applied. In addition, the heteroarylene group refers to a heteroaryl group having two bonding positions, that is, a divalent group. Except that each of these is a divalent group, the description of the aforementioned heteroaryl group may be applied.

In the present specification, the phosphine oxide group specifically includes a diphenylphosphine oxide group, a dinaphthylphosphine oxide, and the like, but is not limited thereto.

In the present specification, the "adjacent" group means a substituent substituted on an atom directly connected to the atom where the corresponding substituent is substituted, a substituent positioned three-dimensionally closest to the corresponding substituent, or another substituent substituted on the atom where the corresponding substituent is substituted. I can. For example, two substituents substituted at an ortho position in a benzene ring and two substituents substituted at the same carbon in an aliphatic ring may be interpreted as "adjacent" to each other.

In the present specification, "substituted or unsubstituted" refers to C1 to C60 straight or branched alkyl; C2 to C60 linear or branched alkenyl; C2 to C60 linear or branched alkynyl; C3 to C60 monocyclic or polycyclic cycloalkyl; C2 to C60 monocyclic or polycyclic heterocycloalkyl; C6 to C60 monocyclic or polycyclic aryl; C2 to C60 monocyclic or polycyclic heteroaryl; -SiRR'R"; -P(=O)RR'; C1 to C20 alkylamine; C6 to C60 monocyclic or polycyclic arylamine; And C2 to C60 monocyclic or polycyclic heteroarylamine selected from the group consisting of It means substituted or unsubstituted with one or more substituents, or substituted or unsubstituted with a substituent to which two or more substituents selected from the aforementioned substituents are linked.

In an exemplary embodiment of the present application, a compound represented by Formula 1 is provided.

In the exemplary embodiment of the present application, Formula 1 may be represented by any one of Formulas 2 to 5 below.

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

In Formulas 2 to 5,

The definitions of R ₁ to R ₄ , X ₃ , Ar, R _a , R _b , R _c , p, q and r are the same as those in Formula 1 above.

In the exemplary embodiment of the present application, Ar is hydrogen; A substituted or unsubstituted alkyl group; A substituted or unsubstituted monocyclic or polycyclic aryl group; A substituted or unsubstituted monocyclic or polycyclic heteroaryl group; -SiRR'R"; or -P(=O)RR'.

In another exemplary embodiment, Ar is hydrogen; A substituted or unsubstituted C1 to C60 alkyl group; A substituted or unsubstituted C6 to C60 monocyclic or polycyclic aryl group; A substituted or unsubstituted C2 to C60 monocyclic or polycyclic heteroaryl group; -SiRR'R"; or -P(=O)RR'.

In another exemplary embodiment, Ar is a C6 to C40 monocyclic or polycyclic aryl group unsubstituted or substituted with a C1 to C40 alkyl group; Or it may be a C2 to C40 monocyclic or polycyclic heteroaryl group unsubstituted or substituted with a C6 to C40 aryl group.

In another exemplary embodiment, Ar is a phenyl group; Biphenyl group; Naphthyl group; Dimethylfluorene group; Dibenzofuran group; Dibenzothiophene group; A carbazole group unsubstituted or substituted with a phenyl group; Naphtho[2,1-b]benzofuran group; Or it may be a benzo[b]naphtho[1,2-d]thiophene group.

In the exemplary embodiment of the present application, Ar may be represented by -(L) _m -(Z) _n ,

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

Z is hydrogen; A substituted or unsubstituted alkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,

M is an integer of 0 to 3,

N is an integer of 1 to 5,

When m and n are integers of 2 or more, the substituents in parentheses are the same as or different from each other.

In the exemplary embodiment of the present application, L is a direct bond; A substituted or unsubstituted arylene group; Or it may be a substituted or unsubstituted heteroarylene group.

In another exemplary embodiment, L is a direct bond; A substituted or unsubstituted C6 to C60 arylene group; Or it may be a substituted or unsubstituted C2 to C60 heteroarylene group.

In another exemplary embodiment, L is a direct bond; A substituted or unsubstituted C6 to C40 arylene group; Or it may be a substituted or unsubstituted C2 to C40 heteroarylene group.

In another exemplary embodiment, L is a direct bond; C6 to C40 arylene group; Or it may be a C2 to C40 heteroarylene group.

In another exemplary embodiment, L is a direct bond; Phenylene group; Or it may be a divalent carbazole group.

In the exemplary embodiment of the present application, Z is hydrogen; A substituted or unsubstituted alkyl group; A substituted or unsubstituted aryl group; Or it may be a substituted or unsubstituted heteroaryl group.

In another exemplary embodiment, Z is hydrogen; A substituted or unsubstituted C1 to C60 alkyl group; A substituted or unsubstituted C6 to C60 aryl group; Or it may be a substituted or unsubstituted C2 to C60 heteroaryl group.

In another exemplary embodiment, Z is hydrogen; A substituted or unsubstituted C1 to C20 alkyl group; A substituted or unsubstituted C6 to C40 aryl group; Or it may be a substituted or unsubstituted C2 to C40 heteroaryl group.

In another exemplary embodiment, Z is hydrogen; C6 to C40 aryl group; Or it may be a C2 to C40 heteroaryl group unsubstituted or substituted with a C6 to C40 aryl group.

In another exemplary embodiment, Z is hydrogen; Phenyl group; Biphenyl group; Naphthyl group; Dibenzothiophene group; Dibenzofuran group; Dimethylfluorene group; A carbazole group unsubstituted or substituted with a phenyl group; Dibenzofuran group condensed with a phenyl ring; Or it may be a dibenzothiophene group condensed with a phenyl ring.

In the exemplary embodiment of the present application, X ₁ to X ₃ are the same as or different from each other, and each independently a direct bond; O; Or S.

In the exemplary embodiment of the present application, X ₁ may be a direct bond, and X ₂ may be O.

In the exemplary embodiment of the present application, X ₁ may be a direct bond, and X ₂ may be S.

In the exemplary embodiment of the present application, X ₁ may be O, and X ₂ may be a direct bond.

In the exemplary embodiment of the present application, X ₁ may be S, and X ₂ may be a direct bond.

In the exemplary embodiment of the present application, X ₃ may be O.

In the exemplary embodiment of the present application, X ₃ may be S.

In the exemplary embodiment of the present application, R _a , R _b and R _c are the same as or different from each other, and each independently hydrogen; A substituted or unsubstituted alkyl group; A substituted or unsubstituted aryl group; A substituted or unsubstituted heteroaryl group; -SiRR'R";-P(=O)RR'; and NRR', or two or more groups adjacent to each other bonded to each other to form a substituted or unsubstituted aromatic hydrocarbon ring or a substituted or unsubstituted hetero ring Can be formed.

In another exemplary embodiment, R _a , R _b and R _c may be hydrogen.

In the exemplary embodiment of the present application, R ₁ to R ₄ are the same as or different from each other, and each independently hydrogen; heavy hydrogen; A substituted or unsubstituted alkyl group; A substituted or unsubstituted aryl group; A substituted or unsubstituted heteroaryl group; -SiRR'R"; and -P(=O)RR'.

In another exemplary embodiment, R ₁ to R ₄ may be hydrogen.

In the exemplary embodiment of the present application, R, R'and R" are the same as or different from each other, and each independently hydrogen; a substituted or unsubstituted alkyl group; a substituted or unsubstituted aryl group; or a substituted or unsubstituted It may be a heteroaryl group.

In another exemplary embodiment, R, R'and R" are the same as or different from each other, and each independently a substituted or unsubstituted C1 to C60 alkyl group; Or a substituted or unsubstituted C6 to C60 aryl group. have.

In another exemplary embodiment, R, R'and R" are the same as or different from each other, and each independently a substituted or unsubstituted C1 to C40 alkyl group; Or a substituted or unsubstituted C6 to C40 aryl group. have.

In another exemplary embodiment, R, R'and R" are the same as or different from each other, and each independently a C1 to C40 alkyl group; or a C6 to C40 aryl group.

In another exemplary embodiment, R, R'and R" are the same as or different from each other, and each independently a methyl group; or a phenyl group.

In the exemplary embodiment of the present application, Ar may be a substituted or unsubstituted bicyclic or less aryl group, or may be represented by the following Formula 6 or Formula 7.

[Formula 6]

[Formula 7]

In Formulas 6 and 7,

는 상기 화학식 1에 연결되는 위치를 의미하며,

Means a position connected to Formula 1,

R ₁₁ to R ₁₄ are the same as or different from each other, and each independently hydrogen; A substituted or unsubstituted alkyl group; A substituted or unsubstituted aryl group; And selected from the group consisting of a substituted or unsubstituted heteroaryl group, or two or more groups adjacent to each other combine with each other to form a substituted or unsubstituted aromatic hydrocarbon ring or a substituted or unsubstituted hetero ring,

Y is O; S; NR; Or CRR',

The definitions of R and R'are the same as those in Chemical Formula 1.

In the exemplary embodiment of the present application, R ₁₁ to R ₁₄ are the same as or different from each other, and each independently, hydrogen, or two or more groups adjacent to each other may be bonded to each other to form a substituted or unsubstituted aromatic hydrocarbon ring. .

In another exemplary embodiment, R ₁₁ to R ₁₄ are the same as or different from each other, and each independently, hydrogen, or two or more groups adjacent to each other combine with each other to form a substituted or unsubstituted C6 to C60 aromatic hydrocarbon ring. can do.

In another exemplary embodiment, R ₁₁ to R ₁₄ are the same as or different from each other, and each independently, hydrogen, or two or more groups adjacent to each other combine with each other to form a substituted or unsubstituted C6 to C40 aromatic hydrocarbon ring. can do.

In another exemplary embodiment, R ₁₁ to R ₁₄ are the same as or different from each other, and each independently, hydrogen, or two or more groups adjacent to each other may be bonded to each other to form a C6 to C40 aromatic hydrocarbon ring.

In another exemplary embodiment, R ₁₁ to R ₁₄ are the same as or different from each other, and each independently hydrogen, or two or more groups adjacent to each other may be bonded to each other to form a benzene ring.

In the exemplary embodiment of the present application, Formula 1 provides a heterocyclic compound represented by any one of the following compounds.

In addition, by introducing various substituents into the structure of Formula 1, a compound having the inherent characteristics of the introduced substituent can be synthesized. For example, a hole injection layer material, a hole transport material, a light emitting layer material, an electron transport layer material, and a substituent mainly used for the charge generation layer material used in manufacturing an organic light emitting device are introduced into the core structure to meet the conditions required by each organic material layer It is possible to synthesize a material that makes it possible.

In addition, by introducing various substituents to the structure of Chemical Formula 1, the energy band gap can be finely adjusted, while the properties at the interface between organic substances can be improved, and the use of the material can be varied.

On the other hand, the compound has excellent thermal stability due to its high glass transition temperature (Tg). This increase in thermal stability becomes an important factor providing driving stability to the device.

In addition, in the exemplary embodiment of the present application, the first electrode; A second electrode provided to face the first electrode; And one or more organic material layers provided between the first electrode and the second electrode, wherein at least one of the organic material layers contains a heterocyclic compound represented by Formula 1 above. Provides.

In the exemplary embodiment of the present application, the first electrode may be an anode, and the second electrode may be a cathode.

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

Details of the heterocyclic compound represented by Formula 1 are the same as described above.

In the exemplary embodiment of the present application, the organic light-emitting device may be a blue organic light-emitting device, and the heterocyclic compound according to Formula 1 may be used as a material of the blue organic light-emitting device.

In the exemplary embodiment of the present application, the organic light-emitting device may be a green organic light-emitting device, and the heterocyclic compound according to Formula 1 may be used as a material of the green organic light-emitting device.

In the exemplary embodiment of the present application, the organic light-emitting device may be a red organic light-emitting device, and the heterocyclic compound according to Formula 1 may be used as a material of the red organic light-emitting device.

The organic light-emitting device of the present invention may be manufactured by a conventional method and material of an organic light-emitting device, except for forming one or more organic material layers using the above-described heterocyclic compound.

The heterocyclic compound may be formed as an organic material layer by a solution coating method as well as a vacuum deposition method when manufacturing an organic light emitting device. Here, the solution coating method refers to spin coating, dip coating, inkjet printing, screen printing, spray method, roll coating, and the like, but is not limited thereto.

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

In the organic light-emitting device of the present invention, the organic material layer may include an emission layer, and the emission layer may include the heterocyclic compound.

In another organic light emitting device, the organic material layer may include an emission layer, the emission layer may include a host material, and the host material may include the heterocyclic compound.

In the organic light emitting device of the present invention, the organic material layer may include an electron injection layer or an electron transport layer, and the electron injection layer or the electron transport layer may include the heterocyclic compound.

In the organic light-emitting device of the present invention, the organic material layer may include an electron transport layer, and the electron transport layer may include the heterocyclic compound.

In another organic light-emitting device, the organic material layer may include an electron blocking layer or a hole blocking layer, and the electron blocking layer or the hole blocking layer may include the heterocyclic compound.

In another organic light-emitting device, the organic material layer may include a hole blocking layer, and the hole blocking layer may include the heterocyclic compound.

In another organic light-emitting device, the organic material layer may include an electron transport layer, an emission layer, or a hole blocking layer, and the electron transport layer, the emission layer, or the hole blocking layer may include the heterocyclic compound.

The organic light emitting device of the present invention is a light emitting layer, a hole injection layer, a hole transport layer. It may further include one or two or more layers selected from the group consisting of an electron injection layer, an electron transport layer, an electron blocking layer, and a hole blocking layer.

1 to 3 illustrate a stacking sequence of an electrode and an organic material layer of an organic light emitting device according to an exemplary embodiment of the present application. However, it is not intended that the scope of the present application be limited by these drawings, and the structure of an organic light emitting device known in the art may be applied to the present application.

Referring to FIG. 1, an organic light-emitting device in which an anode 200, an organic material layer 300, and a cathode 400 are sequentially stacked on a substrate 100 is shown. However, the structure is not limited thereto, and an organic light-emitting device in which a cathode 400, an organic material layer 300, and an anode 200 are sequentially stacked on the substrate 100 may be implemented as shown in FIG. 2.

3 illustrates a case in which the organic material layer is a multilayer. The organic light emitting device according to FIG. 3 includes a hole injection layer 301, a hole transport layer 302, a light emitting layer 303, a hole blocking layer 304, an electron transport layer 305, and an electron injection layer 306. However, the scope of the present application is not limited by such a lamination structure, and other layers other than the light emitting layer may be omitted, or other necessary functional layers may be further added as necessary.

The organic material layer including Formula 1 may further include the following other materials as needed.

In the organic light-emitting device according to an exemplary embodiment of the present application, materials other than the compound of Formula 1 are exemplified below, but these are for illustration only and are not intended to limit the scope of the present application, and are known in the art. Can be replaced with old materials.

Materials having a relatively large work function may be used as the cathode material, and transparent conductive oxides, metals, or conductive polymers may be used. Specific examples of the anode material include metals such as vanadium, chromium, copper, zinc, and gold, or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); ZnO: Al or SnO _2: a combination of a metal and an oxide such as Sb; Poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene] (PEDOT), conductive polymers such as polypyrrole and polyaniline, and the like, but are not limited thereto.

Materials having a relatively low work function may be used as the cathode material, and metal, metal oxide, or conductive polymer may be used. 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; There are multi-layered materials such as LiF/Al or LiO ₂ /Al, but are not limited thereto.

As the hole injection material, a known hole injection material may be used. For example, a phthalocyanine compound such as copper phthalocyanine disclosed in U.S. Patent No. 4,356,429, or a phthalocyanine compound disclosed in Advanced Material, 6, p.677 (1994) is described. Starburst type amine derivatives, such as tris(4-carbazoyl-9-ylphenyl)amine (TCTA), 4,4',4"-tri[phenyl(m-tolyl)amino]triphenylamine (m- MTDATA), 1,3,5-tris[4-(3-methylphenylphenylamino)phenyl]benzene (m-MTDAPB), polyaniline/dodecylbenzenesulfonic acid (Polyaniline/Dodecylbenzenesulfonic acid) or poly( 3,4-ethylenedioxythiophene)/poly(4-styrenesulfonate) (Poly(3,4-ethylenedioxythiophene)/Poly(4-styrenesulfonate)), polyaniline/camphor sulfonic acid or polyaniline Poly(4-styrene-sulfonate) (Polyaniline/Poly(4-styrene-sulfonate)) can be used.

As the hole transport material, pyrazoline derivatives, arylamine derivatives, stilbene derivatives, triphenyldiamine derivatives, etc. may be used, and low molecular weight or high molecular weight materials may be used.

Electron transport materials include oxadiazole derivatives, anthraquinodimethane and derivatives thereof, benzoquinone and derivatives thereof, naphthoquinone and derivatives thereof, anthraquinone and derivatives thereof, tetracyanoanthraquinodimethane and derivatives thereof, fluorenone Derivatives, diphenyl dicyanoethylene and derivatives thereof, diphenoquinone derivatives, metal complexes of 8-hydroxyquinoline and derivatives thereof, and the like may be used, and not only low-molecular substances but also high-molecular substances may be used.

As the electron injection material, for example, LiF is typically used in the art, but the present application is not limited thereto.

Red, green, or blue light-emitting materials may be used as the light-emitting material, and if necessary, two or more light-emitting materials may be mixed and used. In this case, two or more light-emitting materials may be deposited as separate sources and used, or premixed and deposited as one source. Further, a fluorescent material may be used as the light emitting material, but may also be used as a phosphorescent material. As the light emitting material, a material that emits light by combining holes and electrons respectively injected from the anode and the cathode may be used, but materials in which the host material and the dopant material are both involved in light emission may be used.

When a host of light-emitting materials is mixed and used, hosts of the same series may be mixed and used, or hosts of different types may be mixed and used. For example, any two or more of an n-type host material or a p-type host material may be selected and used as the host material of the light emitting layer.

The organic light emitting device according to the exemplary embodiment of the present application may be a top emission type, a bottom emission type, or a double-sided emission type depending on the material used.

The heterocyclic compound according to the exemplary embodiment of the present application may function in an organic electronic device including an organic solar cell, an organic photoreceptor, an organic transistor, etc. in a similar principle to that applied to an organic light emitting device.

Hereinafter, the present specification will be described in more detail through examples, but these are only intended to illustrate the present application and are not intended to limit the scope of the present application.

< Manufacturing example >

[ Manufacturing example 1] Synthesis of C1 compound

Add A1 (20g, 142.9 mmol), B1 (31.9g, 142.9 mmol), Pd(PPh ₃ ) ₄ (8.2g, 7.15 mmol), K ₂ CO ₃ (30.3g, 285.8 mmol) to 500 mL of a round bottom flask. , dioxane (200 mL), EtOH (40 mL), and H ₂ O (40 mL) were added and dissolved, and then refluxed at 120°C. After the reaction was completed, the temperature was lowered to room temperature (25° C.), washed with water, and extracted with MC (Methylene Chloride). The organic layer was dried over Mg ₂ SO ₄ , concentrated, and purified by Silica-gel column to obtain a C1 compound (30g, 108.6 mmol, 76%).

In Preparation Example 1, the compounds of A2 to A4 of Table 1 were used instead of the compound A1, and the compounds of B2 to B24 of Table 1 were used instead of the compound B1. A compound of C50 was synthesized.

A B C C yield A B C C yield A1 B1 C1 76% A1 B2 C2 88% A1 B3 C3 82% A1 B4 C4 74% A1 B5 C5 80% A1 B6 C6 80% A1 B7 C7 69% A1 B8 C8 77% A1 B9 C9 74% A1 B10 C10 62% A2 B1 C11 80% A2 B11 C12 79% A2 B12 C13 80% A2 B2 C14 89% A2 B13 C15 76% A2 B14 C16 85% A2 B15 C17 76% A2 B6 C18 74% A2 B7 C19 90% A2 B8 C20 74% A2 B7 C21 80% A2 B8 C22 77% A2 B9 C23 80% A2 B10 C24 76% A2 B19 C25 88% A3 B11 C26 90% A3 B12 C27 90% A3 B3 C28 90% A3 B13 C29 74% A3 B14 C30 69% A3 B15 C31 72% A3 B20 C32 69% A3 B15 C33 80% A3 B21 C34 84% A3 B17 C35 88% A3 B22 36 68% A3 B7 C37 79% A4 B2 C38 88% A4 B3 C39 77% A4 B5 C40 74% A4 B6 C41 76% A4 B13 C42 68% A4 B14 C43 75% A4 B15 C44 59% A4 B23 C45 80% A4 B7 C46 70% A4 B8 C47 72% A4 B9 C48 88% A4 B24 C49 88% A4 B19 50 82%

[ Manufacturing example 2] Synthesis of D1 compound

Synthesis of D1-3 compound

D1-4 (20g, 74.8 mmol) was added to a 500 mL round bottom flask and dissolved in 200 mL of CH ₂ Cl ₂ . After lowering the internal temperature of the reaction vessel to 0 ℃, Br ₂ (12.5g, 4mL, 78.3 mmol) was slowly added dropwise. After the reaction was completed, 150 mL of MeOH was added, the solid was washed, dried, and D1-3 (28.9g, 91%) was obtained and used in the next reaction.

Synthesis of D1-2 compound

D1-3 (28.9g, 68 mmol), PdCl ₂ (dppf) (2.5g, 3.4 mmol), KOAc (13.4g, 136 mmol), 4,4,4',4',5,5,5', 5'-octamethyl-2,2'-ratio (1,3,2-dioxaborolane) (4,4,4',4',5,5,5',5'-octamethyl-2, 2'-bi(1,3,2-dioxaborolane)) (22.4g, 88.4 mmol) compound was added to a 250 mL round bottom flask, followed by dioxane/H ₂ O and refluxed. After the reaction was completed, the temperature was lowered to room temperature, washed with water, and extracted with MC. The extracted organic solvent was dried over Mg ₂ SO ₄ and then concentrated. Silica-gel column and recrystallization to obtain a compound D1-2 (17.6g, 49mmol, 72%).

Synthesis of D1-1 compound

D1-2 (17.6 g, 49 mmol), B1 (11.2 g, 44.5 mmol), Pd(PPh ₃ ) ₄ (2.6 g, 2.3 mmol), K ₂ CO ₃ (12.3 g, 89 mmol) in a 500 mL round bottom flask Then, it was dissolved in dioxane (120 mL)/H ₂ O (30 mL) and refluxed. After the reaction was completed, the temperature was lowered to room temperature, washed with water, and extracted with Mc. The extracted organic solvent was dried over Mg ₂ SO ₄ and then concentrated. Silica-gel column and recrystallization to obtain a D1-1 (14.7g, 85%, 36.5 mmol) compound.

Synthesis of D1 compound

D1-1 (14.7g, 36.5 mmol) and PPh ₃ (19g, 73 mmol) were added to a 250 mL round bottom flask, dissolved in DCB (Dichlorobenzene) (100 mL), and then refluxed. After the reaction was completed, the reaction temperature was lowered to room temperature and purified by silica-gel column to obtain a compound D1 (9.4g, 69%, 25.2 mmol).

[ Manufacturing example 3] Synthesis of D2 compound

In Preparation Example 2, it proceeded in the same manner as the synthesis method of D1, and reacted in the same manner as in Preparation Example 2, except that D2-4 was used as a starting material, to prepare a D2 compound.

[ Manufacturing example 4] Synthesis of E6 compound

Put C4 (4g, 10.8 mmol), D1 (4g, 10.8 mmol) in a 250 mL round bottom flask, dissolve in 60 mL of toluene, and then Pd ₂ dba ₃ (0.5g, 0.54mmol), NaOtBu (2g, 21.6 mmol) ), P(t-Bu) ₃ (4.32 mmol) was added dropwise and then refluxed. After the reaction was completed, it was washed with water and extracted with Mc. The extracted organic solvent was dried with Mg ₂ SO ₄ , concentrated, and purified by silica-gel column to obtain an E6 compound (6.5g, 85%) in yield.

In Preparation Example 4, prepared in the same manner as in Preparation Example 4, except that the compounds of C1 to C50 of Table 2 below were used instead of C4, and the compounds of D1 or D2 of Table 2 below were used instead of D1. Thus, the target compound (E) was synthesized.

number C D E E yield number C D E E yield One C1 D2 E1 86% 2 C4 D2 E6 85% 3 C5 D2 E8 92% 4 C7 D2 E18 90% 5 C8 D2 E19 83% 6 C9 D2 E20 79% 7 C11 D2 E25 87% 8 C12 D2 E26 85% 9 C14 D2 E28 92% 10 C17 D2 E35 80% 11 C18 D2 E38 85% 12 C19 D2 E40 90% 13 C20 D2 E41 85% 14 C21 D2 E42 92% 15 C22 D2 E43 86% 16 C26 D2 E50 87% 17 C27 D2 E51 87% 18 C32 D2 E61 80% 19 C33 D2 E62 88% 20 C34 D2 E63 86% 21 C35 D2 E64 79% 22 C36 D2 E65 90% 23 C37 D2 E66 84% 24 C42 D2 E81 85% 25 C43 D2 E82 87% 26 C44 D2 E83 84% 27 C45 D2 E84 88% 28 C46 D2 E90 86% 29 C47 D2 E91 94% 30 C3 D1 E101 94% 31 C6 D1 E105 90% 32 C9 D1 E116 87% 33 C10 D1 E118 85% 34 C11 D1 E121 77% 35 C13 D1 E123 87% 36 C14 D1 E124 84% 37 C15 D1 E129 88% 38 C16 D1 E130 90% 39 C19 D1 E136 85% 40 C20 D1 E137 79% 41 C23 D1 E140 78% 42 C24 D1 E142 86% 43 C25 D1 E143 85% 44 C29 D1 E153 77% 45 C30 D1 E154 88% 46 C31 D1 E155 85% 47 C33 D1 E158 94% 48 C34 D1 E159 87% 49 C38 D1 E172 88% 50 C39 D1 E173 86% 51 C40 D1 E175 85% 52 C42 D1 E177 88% 53 C45 D1 E180 89% 54 C47 D1 E187 86% 55 C48 D1 E188 90% 56 C50 D1 E192 83%

Compounds other than the compounds described in Table 2 were also prepared in the same manner as the compounds described in Preparation Examples 1 to 4, and the synthesis confirmation results are shown in Tables 3 and 4 below.

compound FD-Mass compound FD-Mass E 1 m/z= 601.1790 (C42H23N3O2, 601.1790) E 2 m/z= 677.7630 (C48H27N3O2, 677.2103) E 3 m/z= 677.7630 (C48H27N3O2, 677.2103) E 4 m/z= 651.7250 (C46H25N3O2, 651.1947) E 5 m/z= 651.7250 (C46H25N3O2, 651.1947) E 6 m/z= 691.7460 (C48H25N3O3, 691.1896) E 7 m/z= 691.7460 (C48H25N3O3, 691.1896) E 8 m/z= 691.7460 (C48H25N3O3, 691.1896) E 9 m/z= 691.7460 (C48H25N3O3, 691.1896) E 10 m/z= 707.8070 (C48H25N3O2S, 707.1667) E 11 m/z= 707.8070 (C48H25N3O2S, 707.1667) E 12 m/z= 707.8070 (C48H25N3O2S, 707.1667) E 13 m/z= 707.8070 (C48H25N3O2S, 707.1667) E 14 m/z= 717.8280 (C51H31N3O2, 717.2416) E 15 m/z= 717.8280 (C51H31N3O2, 717.2416) E 16 m/z= 766.8600 (C54H30N4O2, 766.2369) E 17 m/z= 766.8600 (C54H30N4O2, 766.2369) E 18 m/z= 757.8670 (C52H27N3O2S, 757. 1824) E 19 m/z= 757.8670 (C52H27N3O2S, 757. 1824) E 20 m/z= 741.8060 (C52H27N3O3, 741.2052) E 21 m/z= 741.8060 (C52H27N3O3, 741.2052) E 22 m/z= 741.8060 (C52H27N3O3, 741.2052) E 23 m/z= 741.8060 (C52H27N3O3, 741.2052) E 24 m/z= 741.8060 (C52H27N3O3, 741.2052) E 25 m/z= 617.7260 (C42H23N3OS, 617.1562) E 26 m/z= 693.8240 (C48H27N3OS, 693.1875) E 27 m/z= 693.8240 (C48H27N3OS, 693.1875) E 28 m/z= 667.7860 (C46H25N3OS, 667.1718) E 29 m/z= 667.7860 (C46H25N3OS, 667.1718) E 30 m/z= 707.8070 (C48H25N3O2S, 707.1667) E 31 m/z= 707.8070 (C48H25N3O2S, 707.1667) E 32 m/z= 707.8070 (C48H25N3O2S, 707.1667) E 33 m/z= 707.8070 (C48H25N3O2S, 707.1667) E 34 m/z= 723.8680 (C48H25N3OS2, 723.1439) E 35 m/z= 723.8680 (C48H25N3OS2, 723.1439) E 36 m/z= 723.8680 (C48H25N3OS2, 723.1439) E 37 m/z= 723.8680 (C48H25N3OS2, 723.1439) E 38 m/z= 733.8890 (C51H31N3OS, 733.2188) E 39 m/z= 733.8890 (C51H31N3OS, 733.2188) E 40 m/z= 782.9210 (C54H30N4OS, 782.2140) E 41 m/z= 782.9210 (C54H30N4OS, 782.2140) E 42 m/z= 773.9280 (C52H27N3OS2, 773.1596) E 43 m/z= 773.9280 (C52H27N3OS2, 773.1596) E 44 m/z= 757.8670 (C52H27N3O2S, 757.1824) E 45 m/z= 757.8670 (C52H27N3O2S, 757.1824) E 46 m/z= 757.8670 (C52H27N3O2S, 757.1824) E 47 m/z= 757.8670 (C52H27N3O2S, 757.1824) E 48 m/z= 757.8670 (C52H27N3O2S, 757.1824) E 49 m/z= 601.1790 (C42H23N3O2, 601.1790) E 50 m/z= 677.7630 (C48H27N3O2, 677.2103) E 51 m/z= 677.7630 (C48H27N3O2, 677.2103) E 52 m/z= 651.7250 (C46H25N3O2, 651.1947) E 53 m/z= 651.7250 (C46H25N3O2, 651.1947) E 54 m/z= 691.7460 (C48H25N3O3, 691.1896) E 55 m/z= 691.7460 (C48H25N3O3, 691.1896) E 56 m/z= 691.7460 (C48H25N3O3, 691.1896) E 57 m/z= 691.7460 (C48H25N3O3, 691.1896) E 58 m/z= 707.8070 (C48H25N3O2S, 707.1667) E 59 m/z= 707.8070 (C48H25N3O2S, 707.1667) E 60 m/z= 707.8070 (C48H25N3O2S, 707.1667) E 61 m/z= 707.8070 (C48H25N3O2S, 707.1667) E 62 m/z= 717.8280 (C51H31N3O2, 717.2416) E 63 m/z= 717.8280 (C51H31N3O2, 717.2416) E 64 m/z= 767.7790 (C48H28N4O, 767.2263) E 65 m/z= 767.7790 (C48H28N4O, 767.2263) E 66 m/z= 757.8670 (C52H27N3O2S, 757. 1824) E 67 m/z= 757.8670 (C52H27N3O2S, 757. 1824) E 68 m/z= 741.8060 (C52H27N3O3, 741.2052) E 69 m/z= 741.8060 (C52H27N3O3, 741.2052) E 70 m/z= 741.8060 (C52H27N3O3, 741.2052) E 71 m/z= 741.8060 (C52H27N3O3, 741.2052) E 72 m/z= 741.8060 (C52H27N3O3, 741.2052) E 73 m/z= 617.7260 (C42H23N3OS, 617.1562) E 74 m/z= 693.8240 (C48H27N3OS, 693.1875) E 75 m/z= 693.8240 (C48H27N3OS, 693.1875) E 76 m/z= 667.7860 (C46H25N3OS, 667.1718) E 77 m/z= 667.7860 (C46H25N3OS, 667.1718) E 78 m/z= 707.8070 (C48H25N3O2S, 707.1667) E 79 m/z= 707.8070 (C48H25N3O2S, 707.1667) E 80 m/z= 707.8070 (C48H25N3O2S, 707.1667) E 81 m/z= 707.8070 (C48H25N3O2S, 707.1667) E 82 m/z= 723.8680 (C48H25N3OS2, 723.1439) E 83 m/z= 723.8680 (C48H25N3OS2, 723.1439) E 84 m/z= 723.8680 (C48H25N3OS2, 723.1439) E 85 m/z= 723.8680 (C48H25N3OS2, 723.1439) E 86 m/z= 733.8890 (C51H31N3OS, 733.2188) E 87 m/z= 733.8890 (C51H31N3OS, 733.2188) E 88 m/z= 782.9210 (C54H30N4OS, 782.2140) E 89 m/z= 782.9210 (C54H30N4OS, 782.2140) E 90 m/z= 773.9280 (C52H27N3OS2, 773.1596) E 91 m/z= 773.9280 (C52H27N3OS2, 773.1596) E 92 m/z= 757.8670 (C52H27N3O2S, 757.1824) E 93 m/z= 757.8670 (C52H27N3O2S, 757.1824) E 94 m/z= 757.8670 (C52H27N3O2S, 757.1824) E 95 m/z= 757.8670 (C52H27N3O2S, 757.1824) E 96 m/z= 757.8670 (C52H27N3O2S, 757.1824) E 97 m/z= 617.7260 (C42H23N3OS, 617.1562) E 98 m/z= 693.8240 (C48H27N3OS, 693.1875) E 99 m/z= 693.8240 (C48H27N3OS, 693.1875) E 100 m/z= 667.7860 (C46H25N3OS, 667.1718) E 101 m/z= 667.7860 (C46H25N3OS, 667.1718) E 102 m/z= 707.8070 (C48H25N3O2S, 707.1667) E 103 m/z= 707.8070 (C48H25N3O2S, 707.1667) E 104 m/z= 707.8070 (C48H25N3O2S, 707.1667) E 105 m/z= 707.8070 (C48H25N3O2S, 707.1667) E 106 m/z= 723.8680 (C48H25N3OS2, 723.1439) E 107 m/z= 723.8680 (C48H25N3OS2, 723.1439) E 108 m/z= 723.8680 (C48H25N3OS2, 723.1439) E 109 m/z= 723.8680 (C48H25N3OS2, 723.1439) E 110 m/z= 733.8890 (C51H31N3OS, 733.2188) E 111 m/z= 733.8890 (C51H31N3OS, 733.2188) E 112 m/z= 782.9210 (C54H30N4OS, 782.2140) E 113 m/z= 782.9210 (C54H30N4OS, 782.2140) E 114 m/z= 773.9280 (C52H27N3OS2, 773.1596) E 115 m/z= 773.9280 (C52H27N3OS2, 773.1596) E 116 m/z= 757.8670 (C52H27N3O2S, 757.1824) E 117 m/z= 757.8670 (C52H27N3O2S, 757.1824) E 118 m/z= 757.8670 (C52H27N3O2S, 757.1824) E 119 m/z= 757.8670 (C52H27N3O2S, 757.1824) E 120 m/z= 757.8670 (C52H27N3O2S, 757.1824) E 121 m/z= 633.7870 (C42H23N3S2, 633.1333) E 122 m/z= 709.8850 (C48H27N3S2, 709.1646) E 123 m/z= 709.8850 (C48H27N3S2, 709.1646) E 124 m/z= 683.8470 (C46H25N3S2, 683.1490) E 125 m/z= 683.8470 (C46H25N3S2, 683.1490) E 126 m/z= 723.8680 (C48H25N3OS2, 723.1439) E 127 m/z= 723.8680 (C48H25N3OS2, 723.1439) E 128 m/z= 723.8680 (C48H25N3OS2, 723.1439) E 129 m/z= 723.8680 (C48H25N3OS2, 723.1439) E 130 m/z= 739.9290 (C48H25N3S3, 739.1211) E 131 m/z= 739.9290 (C48H25N3S3, 739.1211) E 132 m/z= 739.9290 (C48H25N3S3, 739.1211) E 133 m/z= 739.9290 (C48H25N3S3, 739.1211) E 134 m/z= 749.9500 (C51H31N3S2, 749.1959) E 135 m/z= 749.9500 (C51H31N3S2, 749.1959) E 136 m/z= 798.9820 (C54H30N4S2, 798.1912) E 137 m/z= 798.9820 (C54H30N4S2, 798.1912) E 138 m/z= 789.9890 (C52H27N3S3, 789.1367) E 139 m/z= 789.9890 (C52H27N3S3, 789.1367) E 140 m/z= 773.9280 (C52H27N3OS2, 773.1596) E 141 m/z= 773.9280 (C52H27N3OS2, 773.1596) E 142 m/z= 773.9280 (C52H27N3OS2, 773.1596) E 143 m/z= 773.9280 (C52H27N3OS2, 773.1596) E 144 m/z= 773.9280 (C52H27N3OS2, 773.1596) E 145 m/z= 617.7260 (C42H23N3OS, 617.1562) E 146 m/z= 693.8240 (C48H27N3OS, 693.1875) E 147 m/z= 693.8240 (C48H27N3OS, 693.1875) E 148 m/z= 667.7860 (C46H25N3OS, 667.1718) E 149 m/z= 667.7860 (C46H25N3OS, 667.1718) E 150 m/z= 707.8070 (C48H25N3O2S, 707.1667) E 151 m/z= 707.8070 (C48H25N3O2S, 707.1667) E 152 m/z= 707.8070 (C48H25N3O2S, 707.1667) E 153 m/z= 707.8070 (C48H25N3O2S, 707.1667) E 154 m/z= 723.8680 (C48H25N3OS2, 723.1439) E 155 m/z= 723.8680 (C48H25N3OS2, 723.1439) E 156 m/z= 723.8680 (C48H25N3OS2, 723.1439) E 157 m/z= 723.8680 (C48H25N3OS2, 723.1439) E 158 m/z= 733.8890 (C51H31N3OS, 733.2188) E 159 m/z= 733.8890 (C51H31N3OS, 733.2188) E 160 m/z= 782.9210 (C54H30N4OS, 782.2140) E 161 m/z= 782.9210 (C54H30N4OS, 782.2140) E 162 m/z= 773.9280 (C52H27N3OS2, 773.1596) E 163 m/z= 773.9280 (C52H27N3OS2, 773.1596) E 164 m/z= 757.8670 (C52H27N3O2S, 757.1824) E 165 m/z= 757.8670 (C52H27N3O2S, 757.1824) E 166 m/z= 757.8670 (C52H27N3O2S, 757.1824) E 167 m/z= 757.8670 (C52H27N3O2S, 757.1824) E 168 m/z= 757.8670 (C52H27N3O2S, 757.1824) E 169 m/z= 633.7870 (C42H23N3S2, 633.1333) E 170 m/z= 709.8850 (C48H27N3S2, 709.1646) E 171 m/z= 709.8850 (C48H27N3S2, 709.1646) E172 m/z= 683.8470 (C46H25N3S2, 683.1490) E 173 m/z= 683.8470 (C46H25N3S2, 683.1490) E 174 m/z= 723.8680 (C48H25N3OS2, 723.1439) E 175 m/z= 723.8680 (C48H25N3OS2, 723.1439) E 176 m/z= 723.8680 (C48H25N3OS2, 723.1439) E 177 m/z= 723.8680 (C48H25N3OS2, 723.1439) E 178 m/z= 739.9290 (C48H25N3S3, 739.1211) E 179 m/z= 739.9290 (C48H25N3S3, 739.1211) E 180 m/z= 739.9290 (C48H25N3S3, 739.1211) E 181 m/z= 739.9290 (C48H25N3S3, 739.1211) E 182 m/z= 749.9500 (C51H31N3S2, 749.1959) E 183 m/z= 749.9500 (C51H31N3S2, 749.1959) E 184 m/z= 798.9820 (C54H30N4S2, 798.1912) E 185 m/z= 798.9820 (C54H30N4S2, 798.1912) E 186 m/z= 789.9890 (C52H27N3S3, 789.1367) E 187 m/z= 789.9890 (C52H27N3S3, 789.1367) E 188 m/z= 773.9280 (C52H27N3OS2, 773.1596) E189 m/z= 773.9280 (C52H27N3OS2, 773.1596) E190 m/z= 773.9280 (C52H27N3OS2, 773.1596) E 192 m/z= 773.9280 (C52H27N3OS2, 773.1596) E192 m/z= 773.9280 (C52H27N3OS2, 773.1596)

Example ¹ H NMR (CDCl ₃ , 200Mz) E1 δ = 9.26(d, 1H), 9.16~9.13(m, 2H), 8.79(d, 1H), 8.56(d, 1H), 8.46~8.42(m, 2H), 8.33(d, 1H), 8.06~ 8.02(m, 2H), 7.89(d, 1H), 7.77~7.70(m, 4H), 7.69~7.66(m, 1H), 7.60~7.52(m, 6H), 7.29(t, 1H). E6 δ = 9.19(d, 1H), 9.09~9.06(m, 1H), 8.77(d, 1H), 8.56(d, 1H), 8.44~8.41(m, 2H), 8.36(d, 1H), 8.28( d, 1H), 8.06~8.02(m, 2H), 7.89(d, 1H), 7.77~7.70(m, 5H), 7.69~7.66(m, 2H), 7.60~7.52(m, 5H), 7.46~ 7.42 (m, 2H). E8 δ = 9.18(d, 1H), 8.91~8.88(m, 1H), 8.82(s, 1H), 8.77(d, 1H), 8.56(d, 1H), 8.44(d, 1H), 8.37(d, 1H), 8.28(d, 1H), 8.06~8.03(m, 3H), 7.75~7.69(m, 5H), 7.68~7.66(m, 2H), 7.58~7.50(m, 5H), 7.44~7.40( m, 2H). E18 δ = 9.14 (d, 1H), 9.09 (s, 1H), 8.84 (d, 1H), 8.79 (d, 1H), 8.62 (d, 1H), 8.45 (d, 1H), 8.41 (d, 1H) , 8.28(d, 1H), 8.09~8.04(m, 3H), 7.78~7.71(m, 6H), 7.66(d, 1H), 7.61~7.59(m, 2H), 7.58~7.50(m, 5H) , 7.47~7.44 (m, 2H). E19 δ = 9.16 (s, 1H), 9.13 (d, 1H), 8.89 (d, 1H), 8.77 (d, 1H), 8.66 (d, 1H), 8.48 (d, 1H), 8.43 (d, 1H) , 8.28(d, 1H), 8.12~8.07(m, 3H), 7.76~7.67(m, 6H), 7.65(d, 1H), 7.61(d, 2H), 7.58~7.51(m, 5H), 7.48 ~7.45 (m, 2H). E20 δ = 9.09 (d, 1H), 9.04 (d, 1H), 8.79 (s, 1H), 8.77 (d, 1H), 8.59 (d, 1H), 8.46 (d, 1H), 8.43 (d, 1H) , 8.28~8.26(m, 1H), 8.07~8.02(m, 3H), 7.77~7.66(m, 7H), 7.61~7.50(m, 7H), 7.49~7.46 (m, 2H). E25 δ = 9.31(d, 1H), 9.20~9.17(m, 2H), 8.89(d, 1H), 8.60(d, 1H), 8.48(d, 1H), 8.44~8.40(m, 1H), 8.36( d, 1H), 8.09~8.04(m, 2H), 7.91(d, 1H), 7.79~7.72(m, 4H), 7.69~7.66(m, 1H), 7.62~7.53(m, 6H), 7.36( t, 1H). E26 δ = 9.24(d, 1H), 9.16(d, 2H), 8.82(d, 1H), 8.56(d, 1H), 8.51~8.48(m, 2H), 8.36(d, 1H), 8.06~8.02( m, 2H), 7.89(d, 1H), 7.77~7.70(m, 4H), 7.67(s, 1H), 7.60~7.48(m, 8H), 7.32~7.29(m, 3H). E28 δ = 9.22 (d, 1H), 9.09 (d, 2H), 8.78 (d, 1H), 8.59 (d, 1H), 8.53 (d, 1H), 8.48-8.46 (m, 1H), 8.36 (d, 1H), 8.06~8.02(m, 2H), 7.86(s, 1H), 7.77~7.70(m, 4H), 7.67(s, 1H), 7.60~7.57(m, 3H), 7.54~7.48(m, 5H), 7.32-7.29 (m, 1H). E35 δ = 9.19 (s, 1H), 9.14 (d, 1H), 9.11 (d, 1H), 8.72 (d, 2H), 8.66 (d, 1H), 8.59 (d, 1H), 8.54 (d, 1H) , 8.44~8.38(m ,4H), 8.29(d, 2H), 8.19~8.16(m, 3H), 7.82~7.76(m, 3H), 7.63~7.54(m, 5H). E38 δ = 9.14 (d, 1H), 9.11 (d, 1H), 8.89 (s, 1H), 8.65 (d, 2H), 8.61 (d, 1H), 8.57 (d, 1H), 8.54 (d, 1H) , 8.43~8.38(m ,4H), 8.32(d, 2H), 8.21~8.18(m, 3H), 7.84~7.79(m, 3H), 7.61~7.54(m, 5H), 1.39(s, 6H) . E40 δ = 9.29(d, 1H), 9.20(dd, 2H), 8.88(d, 1H), 8.63(d, 1H), 8.59(s, 1H), 8.43~8.34(m, 3H), 8.21(d, 1H), 8.02(d, 2H), 7.82(d, 1H), 7.83~7.68(m, 5H), 7.61~7.56(m, 3H), 7.47~7.42(m, 4H), 7.39~7.24(m, 5H). E41 δ = 9.27(d, 1H), 9.19(dd, 2H), 8.89(d, 1H), 8.67(d, 1H), 8.62(s, 1H), 8.47~8.39(m, 3H), 8.19(d, 1H), 7.92(d, 2H), 7.78(d, 1H), 7.76~7.65(m, 5H), 7.61~7.56(m, 3H), 7.46~7.42(m, 4H), 7.37~7.24(m, 5H). E42 δ = 9.26 (d, 1H), 9.18 (dd, 2H), 8.87 (d, 1H), 8.71 (s, 1H), 8.61 (d, 1H), 8.47 to 8.39 (m, 3H), 8.19 (d, 1H), 7.92(d, 2H), 7.78(d, 1H), 7.76~7.65(m, 5H), 7.61~7.56(m, 3H), 7.49~7.46(m, 2H), 7.38~7.31(m, 4H). E43 δ = 9.28 (d, 1H), 9.21 (d, 2H), 8.88 (s, 1H), 8.86 (d, 1H), 8.63 (d, 1H), 8.51-8.42 (m, 3H), 8.24 (d, 1H), 7.89(d, 2H), 7.79(d, 1H), 7.72~7.63(m, 5H), 7.61~7.58(m, 3H), 7.49~7.46(m, 2H), 7.38~7.31(m, 4H). E50 δ = 9.19(d, 1H), 9.11(s, 1H), 9.03(d, 1H), 8.89(d, 2H), 8.77(d, 1H), 8.66~8.63(m, 2H), 8.29~8.25( m, 3H), 7.98~7.91(m, 4H), 7.78~7.74(m, 3H), 7.71~7.66(m, 4H), 7.52(d, 2H), 7.49~7.39(m, 3H). E51 δ = 9.19(d, 1H), 9.08(d, 2H), 9.03(d, 1H), 8.89(d, 2H), 8.77(d, 1H), 8.68(d, 2H), 8.29~8.27(m, 2H), 7.94~7.89(m, 4H), 7.77~7.73(m, 3H), 7.71~7.67(m, 4H), 7.49(d, 2H), 7.47~7.38(m, 3H). E61 δ = 9.25 (d, 1H), 9.01 (d, 1H), 8.82 (d, 1H), 8.79 (d, 1H), 8.58 (d, 1H), 8.46 (d, 1H), 8.38 (d, 1H) , 8.28(d, 1H), 8.07~8.03(m, 3H), 7.75~7.69(m, 5H), 7.70~7.68(m, 2H), 7.59~7.51(m, 5H), 7.43~7.39(m, 2H). E62 δ = 9.14 (d, 1H), 9.01 (d, 1H), 8.80 (d, 1H), 8.70 (d, 1H), 8.69 (s, 1H), 8.54 (d, 1H), 8.41 (d, 1H) , 8.22(d, 1H), 8.05~8.03(m, 3H), 7.69~7.63(m, 3H), 7.60~7.55(m, 4H), 7.54~7.47(m, 5H), 7.42~7.38(m, 2H), 1.76 (s, 6H). E63 δ = 9.19 (d, 1H), 8.98 (d, 1H), 8.79 (d, 1H), 8.72 (d, 1H), 8.58 (d, 1H), 8.46 (d, 1H), 8.36 (d, 1H) , 8.22(d, 1H), 8.06~8.03(m, 3H), 7.69~7.64(m, 3H), 7.61~7.57(m, 4H), 7.54~7.49(m, 5H), 7.43~7.39(m, 2H), 1.73 (s, 6H). E64 δ = 9.22(d, 1H), 9.11(d, 2H), 8.86(d, 1H), 8.60(d, 1H), 8.57(s, 1H), 8.44(d, 1H), 8.40~8.36(m, 2H), 8.19(d, 1H), 8.01(d, 2H), 7.83(d, 1H), 7.82~7.66(m, 5H), 7.63~7.58(m, 3H), 7.47(d, 1H), 7.46 ~7.42(m, 3H), 7.39~7.24(m, 5H) . E65 δ = 9.16(d, 1H), 9.03(d, 2H), 8.88(d, 1H), 8.60(d, 1H), 8.57(d, 1H), 8.44(d, 1H), 8.40~8.36(m, 2H), 8.19(d, 1H), 8.01(d, 2H), 7.83(d, 1H), 7.82~7.66(m, 5H), 7.61~7.56(m, 3H), 7.47~7.42(m, 4H) , 7.39~7.24(m, 5H) . E66 δ = 9.15 (d, 1H), 9.05 (s, 1H), 8.87 (d, 1H), 8.79 (d, 1H), 8.60 (d, 1H), 8.46 (d, 1H), 8.38 (d, 1H) , 8.27(d, 1H), 8.10~8.06(m, 3H), 7.77~7.71(m, 6H), 7.46(d, 1H), 7.58~7.55(m, 2H), 7.53~7.47(m, 5H) , 7.46~7.44 (m, 2H). E81 δ = 9.24 (d, 1H), 9.16 (d, 1H), 8.99 (s, 1H), 8.79 (d, 1H), 8.64 (d, 1H), 8.52 (d, 1H), 8.43 (d, 1H) , 8.31~8.30(m, 1H), 8.11~8.07(m, 3H), 7.72~7.66(m, 5H), 7.65~7.63(m, 2H), 7.58~7.51(m, 5H), 7.41~7.39( m, 2H). E82 δ = 9.25(d, 1H), 9.18(d, 1H), 8.86(d, 1H), 8.81~8.77(m, 2H), 8.62(d, 1H), 8.43(d, 1H), 8.30~8.28( m, 1H), 8.14~8.08(m, 3H), 7.94(d, 1H), 7.77~7.71(m, 4H), 7.68~7.65(m, 2H), 7.62(d, 1H), 7.60~7.56( m, 4H), 7.44~7.42 (m, 2H). E83 δ = 9.24(d, 1H), 9.18(d, 1H), 8.83(s, 1H), 8.80~8.78(m, 2H), 8.64(d, 1H), 8.47(d, 1H), 8.30~8.28( m, 1H), 8.14~8.08(m, 3H), 7.96(d, 1H), 7.77~7.70(m, 4H), 7.69~7.65(m, 2H), 7.62(d, 1H), 7.60~7.56( m, 4H), 7.44~7.42 (m, 2H). E84 δ = 9.25 (d, 1H), 9.16 (d, 1H), 8.97 (s, 1H), 8.86 (d, 1H), 8.83 (d, 1H), 8.72 (d, 1H), 8.43 (d, 1H) , 8.30~8.28(m, 2H), 8.14~8.10(m, 2H), 7.95(d, 1H), 7.75~7.69(m, 4H), 7.68~7.65(m, 2H), 7.62(d, 1H) , 7.58~7.52(m, 4H), 7.45~7.43(m, 2H). E90 δ = 9.22 (d, 1H), 9.16 (d, 2H), 8.89 (d, 1H), 8.79 (s, 1H), 8.68 (d, 1H), 8.52-8.47 (m, 3H), 8.20 (d, 1H), 7.88(d, 2H), 7.77(d, 1H), 7.76~7.66(m, 5H), 7.61~7.58(m, 3H), 7.49~7.47(m, 2H), 7.38~7.32(m, 4H). E91 δ = 9.21(d, 1H), 9.16(s, 1H), 8.89(d, 1H), 8.74(d, 1H), 8.72(d, 1H), 8.68(d, 1H), 8.51~8.47(m, 3H), 8.22(d, 1H), 7.85(d, 2H), 7.75(d, 1H), 7.76~7.66(m, 5H), 7.61~7.58(m, 3H), 7.49~7.46(m, 2H) , 7.37~7.33 (m, 4H). E101 δ = 9.10(d, 1H), 9.01(d, 1H), 8.80(d, 1H), 8.76~8.73(m, 2H), 8.59(d, 1H), 8.48(d, 1H), 8.29(d, 1H), 8.07~8.03(m, 3H), 7.84(d, 1H), 7.79(d, 1H), 7.69~7.62(m, 5H), 7.61~7.48(m, 5H), 7.45~7.43(m, 2H). E105 δ = 9.08(d, 1H), 8.89(m, 1H), 8.70(d, 1H), 8.59(d, 1H), 8.41(d, 1H), 8.38~3.36(m, 2H), 8.28(d, 1H), 8.03~7.98(m, 2H), 7.88(d, 1H), 7.77~7.74(m, 3H), 7.73~7.71(m, 2H), 7.68~7.66(m, 2H), 7.62~7.55( m, 5H), 7.42-7.39 (m, 2H). E116 δ = 9.13 (d, 1H), 9.06 (d, 1H), 8.80 (s, 1H), 8.79 (d, 1H), 8.59 (d, 1H), 8.48 (d, 1H), 8.45 (d, 1H) , 8.29(d, 1H), 8.07~8.03(m, 3H), 7.74~7.66(m, 7H), 7.61~7.48(m, 7H), 7.47~7.45(m, 2H). E118 δ = 9.13 (d, 1H), 9.07 (d, 1H), 8.82 (d, 1H), 8.77 (d, 1H), 8.61 (d, 1H), 8.41 (d, 1H), 8.36 (d, 1H) , 8.29(d, 1H), 8.07~8.03(m, 3H), 7.74~7.71(m, 3H), 7.69~7.64(m, 4H), 7.60~7.49(m, 7H), 7.48~7.46(m, 2H). E121 δ = 9.33(d, 1H), 9.20~9.17(m, 2H), 8.89(d, 1H), 8.59(d, 1H), 8.48~8.42(m, 2H), 8.35(d, 1H), 8.09~ 8.02(m, 2H), 7.92(d, 1H), 7.79~77.70(m, 4H), 7.69~7.65(m, 1H), 7.62~7.53(m, 6H), 7.36(t, 1H). E123 δ = 9.29(d, 1H), 9.22(d, 2H), 8.88(d, 1H), 8.58(d, 1H), 8.46~8.43(m, 2H), 8.32(d, 1H), 8.11(d, 2H), 7.87(d, 1H), 7.77~7.69(m, 4H), 7.69~7.65(m, 3H), 7.62~7.53(m, 8H), 7.29(t, 1H). E124 δ = 9.44(d, 1H), 9.33~9.28(m, 2H), 9.07(s, 1H), 9.02(, d, 1H), 8.72(d, 1H), 8.62(d, 1H), 8.50(d , 1H), 8.19~8.12(m, 4H), 8.08~8.02(m, 2H), 7.89~7.7.74(m, 5H), 7.72~7.64(m, 5H), 7.44(t, 1H). E129 δ = 9.14(d, 1H), 8.96~8.94(m, 1H), 8.77(d, 1H), 8.62(d, 1H), 8.43(d, 1H), 8.41(d, 1H), 8.39(d, 1H), 8.30(d, 1H), 8.13~8.09(m, 2H), 7.89(d, 1H), 7.79~7.72(m, 5H), 7.69~7.66(m, 2H), 7.64~7.56(m, 5H), 7.44 (d, 1H), 7.42 (t, 1H). E130 δ = 9.28(d, 1H), 9.20(d, 1H), 8.92(d, 1H), 8.83~8.80(m, 2H), 8.67(d, 1H), 8.49(d, 1H), 8.33~8.30( m, 1H), 8.20~8.17(m, 3H), 7.99(d, 1H), 7.82~7.74(m, 4H), 7.69~7.66(m, 2H), 7.62(d, 1H), 7.59~7.54( m, 4H), 7.48 to 7.45 (m, 2H). E136 δ = 9.33(d, 1H), 9.21(dd, 2H), 8.91(d, 1H), 8.62(d, 1H), 8.59(s, 1H), 8.44~8.34(m, 3H), 8.21(d, 1H), 8.06(d, 2H), 7.86(d, 1H), 7.84~7.66(m, 5H), 7.63~7.56(m, 3H), 7.48~7.41(m, 4H), 7.39~7.26(m, 5H). E137 δ = 9.32(d, 1H), 9.21~9.19(m, 2H), 8.92(d, 1H), 8.69(s, 1H), 8.64(d, 1H), 8.46~8.44(m, 1H), 8.37~ 8.34(m, 2H), 8.22(d, 1H), 8.11(d, 1H), 8.07(d, 1H), 7.85~7.68(m, 6H), 7.62~7.57(m, 3H), 7.52~7.49( m, 2H), 7.48~7.45(m, 2H), 7.39~7.37(m, 2H), 7.31~7.26(m, 3H). E140 δ = 9.22(d, 1H), 9.18~9.16(m, 1H), 8.86(s, 1H), 8.82(d, 1H), 8.62(d, 1H), 8.33~8.29(m, 3H), 8.27( d, 1H), 8.15 (d, 1H). 7.74~7.71(m, 2H), 7.70~7.67(m, 2H), 7.61~7.55(m, 4H), 7.53~7.49(m, 3H), 7.49~7.46(m, 2H), 7.43~7.38(m , 4H). E142 δ = 9.26 (d, 1H), 9.18 (d, 1H), 8.84 (d, 1H), 8.66 (d, 1H), 8.59 (d, 1H), 8.31 to 8.29 (m, 3H), 8.2 (d, 1H), 8.17 (d, 1H). 7.74~7.68(m, 4H), 7.60~7.55(m, 4H), 7.53~7.49(m, 3H), 7.47~7.39(m, 6H). E143 δ = 9.35(d, 1H), 9.19(d, 2H), 8.99(d, 1H), 8.76(s, 1H), 8.62(d, 1H), 8.46~8.37(m, 7H), 8.26(d, 1H), 7.91(d, 1H), 7.81~7.62(m, 3H), 7.59~7.53(m, 3H), 7.45~7.41(m, 3H), 7.38~7.30(m, 3H). E153 δ = 9.39(d, 1H), 9.12(dd, 2H), 8.95(s, 1H), 8.65(d, 1H), 8.49~8.37(m, 6H), 8.20(d, 1H), 7.99(d, 1H), 7.82~7.65(m, 3H), 7.61~7.56(m, 2H), 7.49~7.41(m, 3H), 7.38~7.32(m, 4H). E154 δ = 9.28(d, 1H), 9.08(dd, 2H), 8.91(t, 1H), 8.75(s, 1H), 8.50~8.41(m, 5H), 8.31(d, 1H), 7.91(d, 1H), 7.80~7.67(m, 4H), 7.60~7.56(m, 2H), 7.45~7.41(m, 3H), 7.38~7.32(m, 4H). E155 δ = 9.38(d, 1H), 9.21(d, 2H), 9.05(s, 1H), 8.88(s, 1H), 8.70~8.61(m, 5H), 8.42(d, 1H), 8.02(d, 1H), 7.89~7.75(m, 4H), 7.68~7.59(m, 3H), 7.50~7.47(m, 2H), 7.40~7.35(m, 4H). E158 δ = 9.16 (d, 1H), 8.97 (d, 1H), 8.75 (s, 1H), 8.69 (d, 1H), 8.53 (d, 1H), 8.42 (d, 1H), 8.31 (d, 1H) , 8.20(d, 1H), 8.01~7.94(m, 4H), 7.76~7.69(m, 4H), 7.62~7.59(m, 3H), 7.52~7.46(m, 4H), 7.41~7.32(m, 2H), 1.70 (s, 6H). E159 δ = 9.15 (d, 1H), 8.99 (d, 1H), 8.72 (t, 1H), 8.66 (d, 1H), 8.56 (d, 1H), 8.47 (d, 1H), 8.34 (d, 1H) , 8.21(d, 1H), 8.11~7.99(m, 5H), 7.79~7.70(m, 3H), 7.63~7.57(m, 3H), 7.50~7.46(m, 3H), 7.42~7.31(m, 3H), 1.69 (s, 6H). E172 δ = 9.24 (d, 1H), 9.11 (dd, 2H), 8.79 (d, 1H), 8.60 (d, 1H), 8.52 (d, 1H), 8.47 to 8.42 (m, 2H), 8.35 (d, 1H), 8.04~7.99(m, 3H), 7.83(s, 1H), 7.75~7.70(m, 2H), 7.64(s, 1H), 7.59~7.53(m, 3H), 7.50~7.45(m, 4H), 7.31-7.29 (m, 2H). E173 δ = 9.26 (d, 1H), 9.13 (dd, 2H), 8.77 (d, 1H), 8.62 (d, 1H), 8.53 (d, 1H), 8.50 to 8.43 (m, 3H), 8.37 (d, 1H), 8.07~8.01(m, 2H), 7.84(s, 1H), 7.72~7.69(m, 2H), 7.63(s, 1H), 7.57~7.54(m, 3H), 7.49~7.46(m, 4H), 7.32-7.28 (m, 2H). E175 δ = 9.19 (d, 1H), 9.01 (d, 1H), 8.79 (s, 1H), 8.65 (d, 1H), 8.52 (d, 1H), 8.40 (d, 1H), 8.32 (d, 1H) , 8.19(d, 1H), 8.02~7.95(m, 3H), 7.77~7.69(m, 5H), 7.60~7.53(m, 3H), 7.49~7.46(m, 3H), 7.41~7.35(m, 3H). E177 δ = 9.16(d, 1H), 8.99~8.97(m, 1H), 8.76(d, 1H), 8.64(d, 1H), 8.48~4.47(m, 1H), 8.43(d, 1H), 8.40( d, 1H), 8.32(d, 1H), 8.15~8.10(m, 2H), 7.92(d, 1H), 7.82~7.79(m, 2H), 7.76~7.72(m, 3H), 7.69~7.67( m, 2H), 7.66~7.65(m, 1H), 7.64~7.56(m, 4H), 7.44~7.42(m, 1H). E180 δ = 9.23(d, 1H), 8.99~8.89(m, 2H), 8.82(s, 1H), 8.78(d, 1H), 8.61(d, 1H), 8.47(d, 1H), 8.33(d, 1H), 8.23(d, 1H), 8.02~7.98(m, 3H), 7.81~7.72(m, 4H), 7.68~7.63(m, 2H), 7.52~7.47(m, 4H), 7.40~7.37( m, 3H). E187 δ = 9.19(d, 1H), 9.17(s, 1H), 8.77(d, 1H), 8.65(d, 2H), 8.61~8.58(m, 1H), 8.54~8.52(m, 2H), 8.43( d, 1H), 8.38(d, 1H), 8.28~8.25(m, 4H), 7.91~7.86(m, 5H), 7.79~7.73(m, 4H), 7.53~7.44(m, 4H). E188 δ = 9.16 (d, 1H), 8.94 (s, 1H), 8.73 (d, 1H), 8.62 (d, 2H), 8.58 (d, 1H), 8.48-8.46 (m, 2H), 8.39 (d, 1H), 8.36(d, 1H), 8.28~8.25(m, 4H), 7.87~7.83(m, 5H), 7.76~7.71(m, 4H), 7.53~7.46(m, 4H).

[Experimental example]

<Experimental Example 1>

1) Fabrication of organic light emitting device

A glass substrate coated with a thin film of ITO to a thickness of 1,500 Å was washed with distilled water and ultrasonic waves. After washing with distilled water, ultrasonic cleaning was performed with a solvent such as acetone, methanol, and isopropyl alcohol, dried, and then treated with UVO (Ultraviolet Ozone) for 5 minutes using UV in a UV scrubber. After the substrate was transferred to a plasma cleaner (PT), plasma treatment was performed to remove the ITO work function and residual film in a vacuum state, and then transferred to a thermal evaporation equipment for organic deposition.

Hole injection layer 2-TNATA (4,4',4"-Tris[2-naphthyl(phenyl)amino]triphenylamine) and a hole transport layer NPB (N,N'-Di() as a common layer on the ITO transparent electrode (anode) 1-naphthyl)-N,N'-diphenyl-(1,1'-biphenyl)-4,4'-diamine) was formed.

The light emitting layer was thermally vacuum deposited thereon as follows. The light emitting layer was doped with 3% of (piq) ₂ (Ir) (acac) to the host using the compound shown in Table 5 below as a host, and a red phosphorescent dopant (piq) ₂ (Ir) (acac) was deposited at 500 Å. After that, 60Å of BCP was deposited as a hole blocking layer, and 200Å of Alq ₃ was deposited as an electron transport layer thereon. After that, 60Å of BCP was deposited as a hole blocking layer, and 200Å of Alq ₃ was deposited as an electron transport layer thereon. Finally, lithium fluoride (LiF) was deposited on the electron transport layer to a thickness of 10 Å to form an electron injection layer, and then an aluminum (Al) cathode was deposited on the electron injection layer to a thickness of 1,200 Å to form a cathode. An electroluminescent device was manufactured.

On the other hand, all organic compounds required for OLED device fabrication were vacuum-sublimated and purified under 10 ^-6 ~10 ^-8 torr for each material, and used for OLED fabrication.

2) organic Electric field Driving voltage and luminous efficiency of light-emitting elements

For the organic electroluminescent device manufactured as described above, electroluminescence (EL) characteristics were measured with the M7000 of McScience, and the reference luminance was 6,000 through the life equipment measuring equipment (M6000) manufactured by McScience. When cd/m ² , T90 was measured. The characteristics of the organic electroluminescent device of the present invention are shown in Table 5 below.

compound Driving voltage
(V) efficiency
(cd/A) Color coordinates
(x, y) life span
(T90) Comparative Example 1 A 4.65 15.9 (0.661, 0.352) 71 Comparative Example 2 B 4.62 17.1 (0.661, 0.353) 58 Comparative Example 3 C 4.46 14.8 (0.664, 0.351) 66 Comparative Example 4 D 4.75 16.6 (0.665, 0.349) 58 Comparative Example 5 E 4.66 15.9 (0.662, 0.353) 73 Comparative Example 6 F 4.56 17.8 (0.661, 0.352) 59 Comparative Example 7 G 4.38 15.9 (0.661, 0.353) 74 Comparative Example 8 H 4.49 18.9 (0.661, 0.355) 48 Comparative Example 9 I 4.37 17.1 (0.661, 0.356) 71 Comparative Example 10 J 4.44 15.8 (0.661, 0.354) 60 Comparative Example 11 K 4.52 14.9 (0.661, 0.353) 58 Example 1 E1 4.26 22.2 (0.661, 0.352) 101 Example 2 E6 4.32 22.0 (0.661, 0.352) 102 Example 3 E8 4.31 22.7 (0.661, 0.352) 110 Example 4 E18 4.27 22.2 (0.662, 0.353) 101 Example 5 E19 4.22 21.2 (0.663, 0.353) 110 Example 6 E20 4.23 22.6 (0.661, 0.353) 111 Example 7 E25 4.11 22.0 (0.659, 0.353) 112 Example 8 E26 4.00 20.2 (0.660, 0.354) 112 Example 9 E28 4.15 22.4 (0.661, 0.352) 112 Example 10 E35 4.17 22.5 (0.660, 0.354) 119 Example 11 E38 4.06 20.2 (0.659, 0.354) 133 Example 12 E40 4.09 21.2 (0.658, 0.352) 121 Example 13 E41 4.19 20.1 (0.657, 0.351) 129 Example 14 E42 3.97 21.0 (0.659, 0.353) 121 Example 15 E43 4.02 21.8 (0.663, 0.353) 124 Example 16 E50 4.13 22.0 (0.662, 0.352) 100 Example 17 E51 4.19 22.7 (0.663, 0.349) 98 Example 18 E61 4.12 23.9 (0.664, 0.352) 98 Example 19 E62 4.24 23.0 (0.663, 0.353) 89 Example 20 E63 4.10 23.5 (0.662, 0.352) 94 Example 21 E64 4.26 22.9 (0.662, 0.351) 106 Example 22 E65 4.19 22.4 (0.661, 0.351) 100 Example 23 E66 4.21 22.3 (0.661, 0.354) 110 Example 24 E81 3.97 20.9 (0.659, 0.352) 104 Example 25 E82 3.80 20.6 (0.660, 0.351) 102 Example 26 E83 3.97 22.6 (0.661, 0.352) 118 Example 27 E84 4.14 24.9 (0.661, 0.352) 82 Example 28 E90 4.01 23.9 (0.661, 0.352) 121 Example 29 E91 4.00 19.9 (0.662, 0.351) 122 Example 30 E101 4.02 22.9 (0.663, 0.351) 121 Example 31 E105 3.96 21.9 (0.663, 0.352) 112 Example 32 E105 3.93 20.9 (0.659, 0.353) 131 Example 33 E116 4.00 22.8 (0.658, 0.352) 125 Example 34 E118 3.88 23.7 (0.661, 0.353) 127 Example 35 E121 3.95 23.8 (0.657, 0.353) 137 Example 36 E123 3.92 22.5 (0.660, 0.352) 134 Example 37 E124 3.97 21.9 (0.660, 0.348) 129 Example 38 E129 3.91 22.4 (0.660, 0.350) 129 Example 39 E130 4.12 23.9 (0.662, 0.351) 112 Example 40 E136 3.82 22.8 (0.659, 0.352) 112 Example 41 E137 3.97 20.9 (0.661, 0.355) 121 Example 42 E140 3.99 21.2 (0.661, 0.354) 97 Example 43 E142 3.99 20.9 (0.660, 0.352) 98 Example 44 E143 4.11 21.6 (0.662, 0.353) 121 Example 45 E153 4.10 22.7 (0.663, 0.354) 129 Example 46 E154 3.91 21.9 (0.662, 0.352) 117 Example 47 E155 4.21 22.3 (0.663, 0.354) 105 Example 48 E158 4.11 22.1 (0.662, 0.353) 103 Example 49 E159 3.99 22.5 (0.660, 0.353) 109 Example 50 E172 4.05 22.9 (0.660, 0.353) 119 Example 51 E173 3.99 22.9 (0.659, 0.354) 112 Example 52 E175 4.24 24.3 (0.660, 0.353) 109 Example 53 E177 4.02 20.6 (0.660, 0.352) 98 Example 54 E180 3.88 22.7 (0.662, 0.353) 90 Example 55 E187 3.90 19.9 (0.662, 0.352) 98 Example 56 E188 4.30 24.9 (0.661, 0.352) 132

100: substrate
200: anode
300: organic material layer
301: hole injection layer
302: hole transport layer
303: light emitting layer
304: hole blocking layer
305: electron transport layer
306: electron injection layer
400: cathode

Claims (13)

Heterocyclic compound represented by the following Formula 1:
[Formula 1]

In Formula 1,
X ₁ to X ₃ are the same as or different from each other, and each independently a direct bond; O; Or S,
R _a , R _b and R _c are the same as or different from each other, and each independently hydrogen; A substituted or unsubstituted alkyl group; A substituted or unsubstituted aryl group; A substituted or unsubstituted heteroaryl group; -SiRR'R";-P(=O)RR'; and NRR', or two or more groups adjacent to each other bonded to each other to form a substituted or unsubstituted aromatic hydrocarbon ring or a substituted or unsubstituted hetero ring To form,
R ₁ to R ₄ are the same as or different from each other, and each independently hydrogen; heavy hydrogen; A substituted or unsubstituted alkyl group; A substituted or unsubstituted aryl group; A substituted or unsubstituted heteroaryl group; -SiRR'R"; and -P(=O)RR',
Ar is hydrogen; A substituted or unsubstituted alkyl group; A substituted or unsubstituted monocyclic or polycyclic aryl group; A substituted or unsubstituted monocyclic or polycyclic heteroaryl group; -SiRR'R"; or -P(=O)RR',
The R, R'and R" are the same as or different from each other, and each independently hydrogen; a substituted or unsubstituted alkyl group; a substituted or unsubstituted aryl group; or a substituted or unsubstituted heteroaryl group,
p is an integer from 1 to 6,
q and r are integers from 1 to 4,
When p, q and r are integers of 2 or more, the substituents in parentheses are the same as or different from each other. The method according to claim 1, "substituted or unsubstituted" means C1 to C60 linear or branched alkyl; C2 to C60 linear or branched alkenyl; C2 to C60 linear or branched alkynyl; C3 to C60 monocyclic or polycyclic cycloalkyl; C2 to C60 monocyclic or polycyclic heterocycloalkyl; C6 to C60 monocyclic or polycyclic aryl; C2 to C60 monocyclic or polycyclic heteroaryl; -SiRR'R";-P(=O)RR'; C1 to C20 alkylamine; C6 to C60 monocyclic or polycyclic arylamine; And C2 to C60 monocyclic or polycyclic heteroarylamine selected from the group consisting of It means substituted or unsubstituted with one or more substituents, or substituted or unsubstituted with a substituent to which two or more substituents selected from the aforementioned substituents are linked,
The definition of R, R'and R" is the same as the definition in Formula 1 above. The method according to claim 1,
Formula 1 is a heterocyclic compound represented by any one of the following Formulas 2 to 5:
[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

In Formulas 2 to 5,
The definitions of R ₁ to R ₄ , X ₃ , Ar, R _a , R _b , R _c , p, q and r are the same as those in Formula 1 above. The method according to claim 1,
Ar is hydrogen; A substituted or unsubstituted C1 to C60 alkyl group; A substituted or unsubstituted C6 to C60 monocyclic or polycyclic aryl group; A substituted or unsubstituted C2 to C60 monocyclic or polycyclic heteroaryl group; -SiRR'R"; or -P(=O)RR',
The definition of R, R'and R" is the same as the definition in Formula 1 above. The method according to claim 1,
R _a , R _b and R _c is a heterocyclic compound that is hydrogen. The method according to claim 1,
Wherein Ar is a substituted or unsubstituted bicyclic aryl group, or a heterocyclic compound represented by the following formula 6 or the following formula 7:
[Formula 6]

[Formula 7]

In Formulas 6 and 7,

Means a position connected to Formula 1,
R ₁₁ to R ₁₄ are the same as or different from each other, and each independently hydrogen; A substituted or unsubstituted alkyl group; A substituted or unsubstituted aryl group; And selected from the group consisting of a substituted or unsubstituted heteroaryl group, or two or more groups adjacent to each other combine with each other to form a substituted or unsubstituted aromatic hydrocarbon ring or a substituted or unsubstituted hetero ring,
Y is O; S; NR; Or CRR',
The definitions of R and R'are the same as those in Chemical Formula 1. The heterocyclic compound of claim 1, wherein the formula 1 is represented by any one of the following compounds:

. A first electrode; A second electrode provided to face the first electrode; And one or more organic material layers provided between the first electrode and the second electrode, wherein at least one of the organic material layers contains the heterocyclic compound according to any one of claims 1 to 7 Phosphorus organic light emitting device. The organic light-emitting device of claim 8, wherein the organic material layer includes an emission layer, and the emission layer includes the heterocyclic compound. The organic light-emitting device of claim 8, wherein the organic material layer includes an emission layer, the emission layer includes a host material, and the host material includes the heterocyclic compound. The organic light-emitting device of claim 8, wherein the organic material layer includes an electron injection layer or an electron transport layer, and the electron injection layer or the electron transport layer includes the heterocyclic compound. The organic light-emitting device of claim 8, wherein the organic material layer includes an electron blocking layer or a hole blocking layer, and the electron blocking layer or the hole blocking layer includes the heterocyclic compound. The method according to claim 8, wherein the organic light emitting device is a light emitting layer, a hole injection layer, a hole transport layer. An organic light-emitting device further comprising one or two or more layers selected from the group consisting of an electron injection layer, an electron transport layer, an electron blocking layer, and a hole blocking layer.

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