KR102374517B1 - Heterocyclic compound and organic light emitting device comprising the same - Google Patents

Abstract

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

Description

Heterocyclic compound and organic light-emitting device comprising the same

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

The electroluminescent device is a type of self-luminous display device, and has advantages of a wide viewing angle, excellent contrast, and 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 combine in the organic thin film to form a pair, and then disappear and emit light. The organic thin film may be composed of a single layer or multiple layers, if necessary.

The material of the organic thin film may have a light emitting function if necessary. For example, as the organic thin film material, a compound capable of forming the light emitting layer by itself may be used, or a compound capable of serving as a host or dopant of the host-dopant light emitting layer may be used. In addition, as a material of the organic thin film, a compound capable of performing the roles of hole injection, hole transport, electron blocking, hole blocking, electron transport, electron injection, and the like may be used.

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

U.S. Patent No. 4,356,429

An object of the present invention is to provide a novel heterocyclic compound and an organic light emitting device including the same.

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

[Formula 1]

In Formula 1,

R ₂ To R ₅ Are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; -CN; a substituted or unsubstituted alkyl group; a substituted or unsubstituted alkenyl group; a substituted or unsubstituted alkynyl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted heterocycloalkyl group; a substituted or unsubstituted aryl group; a substituted or unsubstituted heteroaryl group; -SiRR'R";-P(=O)RR'; and an amine group unsubstituted or substituted with a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group. Or, two or more groups adjacent to each other are bonded to each other to form a substituted or unsubstituted aliphatic or aromatic hydrocarbon ring,

R _a is hydrogen; a substituted or unsubstituted alkyl group; a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,

Ar ₁ is represented by -(L1)p-(Z1)q,

Ar ₂ is represented by -(L2)r-(Z2)s,

L1 and L2 are the same as or different from each other, and each independently a substituted or unsubstituted arylene group; Or a substituted or unsubstituted heteroarylene group,

Wherein Z1 and Z2 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; -CN; a substituted or unsubstituted alkyl group; a substituted or unsubstituted alkenyl group; a substituted or unsubstituted alkynyl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted heterocycloalkyl group; a substituted or unsubstituted aryl group; a substituted or unsubstituted heteroaryl group; -SiRR'R"; -P(=O)RR'; and an amine group unsubstituted or substituted with a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group. becomes,

Wherein R, R' and R" are the same as or different from each other, and each independently represents hydrogen; deuterium; -CN; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted aryl group; or substituted Or an unsubstituted heteroaryl group,

p and r are integers from 1 to 4,

q and s are integers from 1 to 3,

n is an integer from 0 to 4.

In addition, in an exemplary embodiment of the present application, the first electrode; a second electrode provided to face the first electrode; and at least one organic material layer provided between the first electrode and the second electrode, wherein at least one of the organic material layers includes a heterocyclic compound according to an exemplary embodiment of the present application. A light emitting device is provided.

The compound described herein can be used as 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, etc. in the organic light emitting device. In particular, the compound can be used as an electron transport layer material, a hole blocking layer material or a charge generating layer material of an organic light emitting device.

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

1 to 4 are views schematically showing a stacked structure of an organic light emitting device according to an exemplary embodiment of the present application, respectively.

Hereinafter, the present application will be described in detail.

The term "substitution" means that a hydrogen atom bonded to a carbon atom of a compound is replaced with another substituent, and the position to be substituted is not limited as long as the position at which the hydrogen atom is substituted, that is, a position where the substituent is substitutable, is substituted. , two or more substituents may be the same as 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 or branched chain having 1 to 60 carbon atoms, and may be further substituted by other substituents. The number of carbon atoms in 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 is not limited thereto.

In the present specification, the alkenyl group includes a straight or branched chain having 2 to 60 carbon atoms, and may be further substituted by other substituents. The carbon number of the alkenyl group may be 2 to 60, specifically 2 to 40, more specifically, 2 to 20. Specific examples include a 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, styrenyl group, etc., but are not limited thereto.

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

In the present specification, the alkoxy group may be a straight chain, branched chain or cyclic chain. Although carbon number of an alkoxy group is not specifically limited, It is preferable that it is C1-C20. Specifically, methoxy, ethoxy, n-propoxy, isopropoxy, i-propyloxy, 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. may be, but is not limited thereto.

In the present specification, the cycloalkyl group includes a monocyclic or polycyclic ring having 3 to 60 carbon atoms, and may be further substituted by other substituents. Here, polycyclic means a group in which a cycloalkyl group is directly connected to another ring group or condensed. Here, the other ring group may be a cycloalkyl group, but may be a different type of ring group, for example, a heterocycloalkyl group, an aryl group, a heteroaryl group, or the like. The carbon number of the cycloalkyl group may be 3 to 60, specifically 3 to 40, more specifically 5 to 20. Specifically, 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 is 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 ring having 2 to 60 carbon atoms, and may be further substituted by other substituents. Here, polycyclic refers to a group in which a heterocycloalkyl group is directly connected or condensed with another ring group. Here, the other ring group may be a heterocycloalkyl group, but may be a different type of ring group, for example, a cycloalkyl group, an aryl group, a heteroaryl group, or the like. The heterocycloalkyl group may have 2 to 60 carbon atoms, specifically 2 to 40 carbon atoms, and more specifically 3 to 20 carbon atoms.

In the present specification, the aryl group includes a monocyclic or polycyclic ring having 6 to 60 carbon atoms, and may be further substituted by other substituents. Here, polycyclic means a group in which an aryl group is directly connected or condensed with another ring group. Here, the other ring group may be an aryl group, but may be another type of ring group, such as a cycloalkyl group, a heterocycloalkyl group, a heteroaryl group, and the like. The aryl group includes a spiro group. The carbon number of the aryl group may be 6 to 60, specifically 6 to 40, more specifically 6 to 25. Specific examples of the aryl group include a phenyl group, a biphenyl group, a triphenyl group, a naphthyl group, an anthryl group, a chrysenyl group, a phenanthrenyl group, a perylenyl group, a fluoranthenyl group, a triphenylenyl group, a phenalenyl group, a pyrethyl group Nyl group, tetracenyl 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 is 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, and is represented by -SiR ₁₀₄ R ₁₀₅ R ₁₀₆ , R ₁₀₄ to R ₁₀₆ are the same or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; an 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 a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group, a vinyldimethylsilyl group, a propyldimethylsilyl group, a triphenylsilyl group, a diphenylsilyl group, a phenylsilyl group, etc. It is not limited.

In the present specification, the fluorenyl group may be substituted, and adjacent substituents may combine with 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 ring having 2 to 60 carbon atoms, and may be further substituted by other substituents. Here, the polycyclic refers to a group in which a heteroaryl group is directly connected or condensed with another ring group. Here, the other ring group may be a heteroaryl group, but may be a different type of ring group, for example, a cycloalkyl group, a heterocycloalkyl group, an aryl group, or the like. The heteroaryl group may have 2 to 60 carbon atoms, specifically 2 to 40 carbon atoms, and more specifically 3 to 25 carbon atoms. Specific examples of the heteroaryl group include a pyridyl group, a pyrrolyl group, a pyrimidyl group, a pyridazinyl group, a furanyl group, a thiophene group, an imidazolyl group, a pyrazolyl group, an oxazolyl group, an isoxazolyl group, a thiazolyl group group, isothiazolyl group, triazolyl group, furazanyl group, oxadiazolyl group, thiadiazolyl group, dithiazolyl group, tetrazolyl group, pyranyl group, thiopyranyl group, diazinyl group, oxazinyl group , thiazinyl group, deoxynyl group, triazinyl group, tetrazinyl group, quinolyl group, isoquinolyl group, quinazolinyl group, isoquinazolinyl group, quinazolylyl group, naphthyridyl group, acridinyl group, phenanthridyl group Nyl group, imidazopyridinyl group, diazanaphthalenyl group, triazaindene 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, phenothiazinyl 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 ] a carbazolyl group, and the like, but is 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; an alkylarylamine group; an alkyl heteroarylamine group; And it may be selected from the group consisting of an aryl heteroarylamine group, and the number of carbon atoms is not particularly limited, but is preferably 1 to 30. Specific examples of the amine group include a methylamine group, a dimethylamine group, an ethylamine group, a diethylamine group, a phenylamine group, a naphthylamine group, a biphenylamine group, a dibiphenylamine group, an anthracenylamine group, 9- Methyl-anthracenylamine group, diphenylamine group, phenylnaphthylamine group, ditolylamine group, phenyltolylamine group, triphenylamine group, biphenylnaphthylamine group, phenylbiphenylamine group, biphenylfluorene There is a nylamine group, a phenyltriphenylenylamine group, a biphenyltriphenylenylamine group, and the like, but is not limited thereto.

In the present specification, the 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 means that the heteroaryl group has two bonding positions, that is, a divalent group. Except that each of these is a divalent group, the description of the heteroaryl group described above may be applied.

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

As used herein, the "adjacent" group means a substituent substituted on an atom directly connected to the atom in which the substituent is substituted, a substituent sterically closest to the substituent, or another substituent substituted on the atom in which the substituent is substituted. 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" groups.

In the present specification, the term "substitution" means that a hydrogen atom bonded to a carbon atom of the compound is changed to another substituent, and the position to be substituted is not limited as long as the position at which the hydrogen atom is substituted, that is, the position where the substituent is substitutable, When two or more substituents are substituted, two or more substituents may be the same as or different from each other.

In the present specification, "substituted or unsubstituted" means C1 to C60 straight-chain 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 that it is substituted or unsubstituted with one or more substituents, or substituted or unsubstituted with a substituent to which two or more substituents selected from the above-exemplified substituents are connected.

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

Formula 1 has a structure in which a quinoline group is condensed to an indole group. When Formula 1 has an indole group, it does not have an sp2 lone pair but has an sp3 lone pair in the structure. Therefore, the hole transport property is particularly excellent compared to the case of having benzothiophene or benzofuran having sp2 non-covalent bond. This affects the formation of excitons in the light emitting layer when used as an organic material layer of an organic light emitting device in the future, so that the efficiency of the device increases the lifespan.

In an exemplary embodiment of the present application, R ₂ to R ₅ of Formula 1 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; -CN; a substituted or unsubstituted alkyl group; a substituted or unsubstituted alkenyl group; a substituted or unsubstituted alkynyl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted heterocycloalkyl group; a substituted or unsubstituted aryl group; a substituted or unsubstituted heteroaryl group; -SiRR'R";-P(=O)RR'; and an amine group unsubstituted or substituted with a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group. Alternatively, two or more groups adjacent to each other may combine with each other to form a substituted or unsubstituted aliphatic or aromatic hydrocarbon ring.

In another exemplary embodiment, R ₂ to R ₅ of Formula 1 are the same as or different from each other, and each independently hydrogen; a substituted or unsubstituted C1 to C60 aryl group; and a substituted or unsubstituted C2 to C60 heteroaryl group, or two or more groups adjacent to each other may combine with each other to form a substituted or unsubstituted aromatic hydrocarbon ring.

In another exemplary embodiment, R ₂ to R ₅ of Formula 1 are the same as or different from each other, and each independently hydrogen, or two or more groups adjacent to each other are bonded to each other to form a substituted or unsubstituted C2 to C60 aromatic hydrocarbon. rings can be formed.

In another exemplary embodiment, R ₂ to R ₅ in Formula 1 are the same as or different from each other, and each independently hydrogen, or two or more groups adjacent to each other may combine with each other to form a C2 to C40 aromatic hydrocarbon ring. there is.

In another exemplary embodiment, R ₂ to R ₅ in Formula 1 may be the same as or different from each other, each independently hydrogen, or two or more groups adjacent to each other may combine with each other to form a benzene ring.

In the exemplary embodiment of the present application, R ₂ and R ₃ of R ₂ to R ₅ in Formula 1 may be combined with each other to form a benzene ring, and the remainder may be hydrogen.

In the exemplary embodiment of the present application, R ₃ and R ₄ of R ₂ to R ₅ in Formula 1 may be combined with each other to form a benzene ring, and the remainder may be hydrogen.

In the exemplary embodiment of the present application, R ₄ and R ₅ of R ₂ to R ₅ in Formula 1 may be combined with each other to form a benzene ring, and the remainder may be hydrogen.

In an exemplary embodiment of the present application, R _a of Formula 1 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, R _a of Formula 1 is hydrogen; 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, R _a of Formula 1 is hydrogen; C6 to C40 aryl group; Or it may be a C2 to C40 heteroaryl group.

In another exemplary embodiment, R _a in Formula 1 may be hydrogen.

In the exemplary embodiment of the present application, Ar ₁ may be expressed as -(L1)p-(Z1)q, and Ar ₂ may be expressed as -(L2)r-(Z2)s.

Ar ₁ of Formula 1 of the present application and Ar ₂ is substituted with each substituent, so that thermal stability is superior to that of single substitution, and structurally, the introduction of a substituent that controls the hole transport properties of the indole structure can be introduced more diversely than when a single substituted, Controlling the properties of the structure can be excellent.

In an exemplary embodiment of the present application, L1 and L2 are the same as or different from each other, and each independently a substituted or unsubstituted arylene group; Or it may be a substituted or unsubstituted heteroarylene group.

In another exemplary embodiment, L1 and L2 are the same as or different from each other, and each independently 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, L1 and L2 are the same as or different from each other, and each independently a C6 to C40 arylene group; Or it may be a C2 to C40 heteroarylene group.

In another exemplary embodiment, L1 and L2 are the same as or different from each other, and each independently a C6 to C40 arylene group; Or it may be a C2 to C40 heteroarylene group.

In another exemplary embodiment, L1 and L2 are the same as or different from each other, and each independently a phenylene group; biphenylene group; naphthalene group; phenanthrenylene group; triphenylenylene group; fluoranthenylene group; pyrenylene group; a divalent pyridine group; a divalent pyrimidine group; Or it may be a divalent triazine group.

In an exemplary embodiment of the present application, L1 is 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, L1 is 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, L1 is a C6 to C40 arylene group; Or it may be a C2 to C40 heteroarylene group.

In another exemplary embodiment, L1 is a phenylene group; biphenylene group; naphthalene group; phenanthrenylene group; a divalent pyridine group; a divalent pyrimidine group; Or it may be a divalent triazine group.

In an exemplary embodiment of the present application, L2 is 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, L2 is 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, L2 is a C6 to C40 arylene group; Or it may be a C2 to C40 heteroarylene group.

In another exemplary embodiment, L2 is a phenylene group; biphenylene group; naphthalene group; phenanthrenylene group; triphenylenylene group; fluoranthenylene group; pyrenylene group; a divalent pyridine group; a divalent pyrimidine group; Or it may be a divalent triazine group.

In an exemplary embodiment of the present application, Z1 and Z2 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; -CN; a substituted or unsubstituted alkyl group; a substituted or unsubstituted alkenyl group; a substituted or unsubstituted alkynyl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted heterocycloalkyl group; a substituted or unsubstituted aryl group; a substituted or unsubstituted heteroaryl group; -SiRR'R"; -P(=O)RR'; and an amine group unsubstituted or substituted with a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group. can be

In another exemplary embodiment, Z1 and Z2 are the same as or different from each other, and each independently hydrogen; a substituted or unsubstituted aryl group; a substituted or unsubstituted heteroaryl group; or P(=O)RR'.

In another exemplary embodiment, Z1 and Z2 are the same as or different from each other, and each independently hydrogen; a substituted or unsubstituted C6 to C60 aryl group; a substituted or unsubstituted C2 to C60 heteroaryl group; or P(=O)RR'.

In another exemplary embodiment, Z1 and Z2 are the same as or different from each other, and each independently hydrogen; a substituted or unsubstituted C6 to C40 aryl group; a substituted or unsubstituted C2 to C40 heteroaryl group; or P(=O)RR'.

In another exemplary embodiment, Z1 and Z2 are the same as or different from each other, and each independently hydrogen; a C6 to C40 aryl group unsubstituted or substituted with one or more substituents selected from the group consisting of a C6 to C40 aryl group, a C2 to C40 heteroaryl group, a C1 to C40 alkyl group, and -CN; a C2 to C40 heteroaryl group unsubstituted or substituted with a C6 to C40 aryl group; Or it may be P(=O)RR', and the substituent is again a C1 to C40 alkyl group; Or it may be unsubstituted or substituted with a C6 to C40 aryl group.

In another exemplary embodiment, Z1 and Z2 are the same as or different from each other, and each independently hydrogen; P(=O)RR'; a phenyl group unsubstituted or substituted with one or more substituents selected from the group consisting of 9,9'-dimethylfluorene group, -CN, triphenylene group, phenanthrene group, phenyl group, dibenzofuran group and dibenzothiophene group; a phenyl group unsubstituted or substituted with a carbazole group substituted or unsubstituted with a phenyl group; biphenyl group; triphenylene group; a fluorene group unsubstituted or substituted with a methyl group; phenanthrene group; spirobifluorene group; pyridine group; a carbazole group; dibenzofuran group; dibenzothiophene group; Or it may be a phenanthroline group unsubstituted or substituted with a phenyl group.

In an exemplary embodiment of the present application, Z1 is hydrogen; P(=O)RR'; a phenyl group unsubstituted or substituted with one or more substituents selected from the group consisting of a carbazole group substituted or unsubstituted with a phenyl group, a dibenzofuran group, and a dibenzothiophene group; biphenyl group; spirobifluorene group; a fluorene group unsubstituted or substituted with a methyl group; pyridine group; dibenzofuran group; dibenzothiophene group; Or it may be a phenanthroline group unsubstituted or substituted with a phenyl group.

In an exemplary embodiment of the present application, Z2 is hydrogen; P(=O)RR'; a phenyl group unsubstituted or substituted with one or more substituents selected from the group consisting of a phenyl group, a phenanthrene group, a triphenylene group, -CN, 9,9'-dimethylfluorene group, a carbazole group, and a dibenzofuran group; biphenyl group; triphenylene group; a fluorene group unsubstituted or substituted with a methyl group; phenanthrene group; pyridine group; a carbazole group; Or it may be a dibenzofuran group.

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

In another exemplary embodiment, R, R' and R" may be the same as or different from each other, and may each independently be a substituted or unsubstituted aryl group.

In another exemplary embodiment, R, R' and R" may be the same as or different from each other, and each independently a substituted or unsubstituted C6 to C60 aryl group.

In another exemplary embodiment, R, R′ and R″ may be the same as or different from each other, and each independently a substituted or unsubstituted C6 to C40 aryl group.

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

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

In an exemplary embodiment of the present application, Chemical Formula 1 provides a heterocyclic compound, characterized in that it is represented by any one of the following Chemical Formulas 2 to 9.

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

In Formulas 2 to 9,

Definitions of R _{a ,} Ar ₁ , Ar ₂ , R ₂ to R ₅ and n are the same as those of Formula 1 above.

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

The compound according to an exemplary embodiment of the present application may be prepared according to the following general formula (1).

In Formula 1, R ₁₀ or R ₁₁ is the same as Ar ₁ or Ar ₂ in Formula 1 above.

In addition, by introducing various substituents into the structures of Chemical Formulas 1 to 9, compounds having intrinsic properties of the introduced substituents can be synthesized. For example, by introducing a substituent mainly used for a hole injection layer material, a hole transport material, a light emitting layer material, an electron transport layer material, and a charge generation layer material used in manufacturing an organic light emitting device into the core structure, the conditions required for each organic material layer are satisfied substances can be synthesized.

In addition, by introducing various substituents into the structures of Chemical Formulas 1 to 9, it is possible to finely control the energy band gap, while improving the properties at the interface between organic materials and diversifying the use of the material. .

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

The heterocyclic compound according to an exemplary embodiment of the present application may be prepared by a multi-step chemical reaction. Some intermediate compounds are prepared first, and the compound of Formula 1 can be prepared from the intermediate compounds. More specifically, the heterocyclic compound according to an exemplary embodiment of the present application may be prepared based on Preparation Examples to be described later.

In addition, in an exemplary embodiment of the present application, the first electrode; a second electrode provided to face the first electrode; and at least one organic material layer provided between the first electrode and the second electrode, wherein at least one layer of the organic material layer comprises a heterocyclic compound according to Chemical Formula 1; to provide.

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.

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 Chemical 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 Chemical 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 Chemical Formula 1 may be used as a material of the red organic light emitting device.

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

The organic light emitting device of the present invention may be manufactured by a conventional method and material for manufacturing 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, spraying, 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 multi-layer 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, etc. 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 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, a light emitting layer, or a hole blocking layer, and the electron transport layer, the light emitting layer or the hole blocking layer may include the heterocyclic compound.

The organic light emitting device of the present invention includes a light emitting layer, a hole injection layer, and a hole transport layer. It may further include one 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 the stacking order of the electrode and the organic material layer of the 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 also 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 illustrated. However, it is not limited to such a structure, and as shown in FIG. 2 , an organic light emitting device in which a cathode, an organic material layer, and an anode are sequentially stacked on a substrate may be implemented.

3 illustrates a case in which the organic material layer is multi-layered. The organic light emitting diode 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 laminated structure, and if necessary, the remaining layers except for the light emitting layer may be omitted, and other necessary functional layers may be further added.

The organic material layer including Chemical Formulas 1 to 9 may further include other materials as needed.

In addition, the organic light emitting device according to an exemplary embodiment of the present application includes an anode, a cathode, and two or more stacks provided between the anode and the cathode, wherein the two or more stacks each independently include a light emitting layer, and the two or more stacks A charge generation layer is included between the liver, and the charge generation layer includes the heterocyclic compound represented by Formula 1 above.

In addition, the organic light emitting device according to an exemplary embodiment of the present application includes an anode, a first stack provided on the anode and including a first light emitting layer, a charge generating layer provided on the first stack, and a charge generating layer on the charge generating layer and a second stack provided on and including a second light emitting layer, and a cathode provided on the second stack. In this case, the charge generating layer may include a heterocyclic compound represented by Formula 1 above. In addition, the first stack and the second stack may each independently further include one or more of the aforementioned hole injection layer, hole transport layer, hole blocking layer, electron transport layer, electron injection layer, and the like.

The charge generating layer may be an N-type charge generating layer, and the charge generating layer may further include a dopant known in the art in addition to the heterocyclic compound represented by Chemical Formula 1.

As an organic light emitting device according to an exemplary embodiment of the present application, an organic light emitting device having a two-stack tandem structure is schematically shown in FIG. 4 below.

In this case, the first electron blocking layer, the first hole blocking layer and the second hole blocking layer described in FIG. 4 may be omitted in some cases.

In the organic light emitting device according to an exemplary embodiment of the present application, materials other than the compounds of Chemical Formulas 1 to 9 are exemplified below, but these are only for illustration and not for limiting the scope of the present application. may be substituted with known materials.

Materials having a relatively large work function may be used as the anode material, and transparent conductive oxides, metals, conductive polymers, or the like may be used. Specific examples of the anode material include metals such as vanadium, chromium, copper, zinc, 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 : Combination of metals and oxides such as Sb; conductive polymers such as poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene](PEDOT), polypyrrole, and polyaniline, but are not limited thereto.

Materials having a relatively low work function may be used as the anode material, and a metal, metal oxide, conductive polymer, or the like may be used. Specific examples of the anode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin and lead, or alloys thereof; and a multi-layered material such as LiF/Al or LiO ₂ /Al, but is 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 Advanced Material, 6, p.677 (1994). starburst-type amine derivatives such as tris(4-carbazolyl-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 or poly( 3,4-ethylenedioxythiophene)/poly(4-styrenesulfonate) (Poly(3,4-ethylenedioxythiophene)/Poly(4-styrenesulfonate)), polyaniline/Camphor sulfonic acid or polyaniline/ Poly(4-styrenesulfonate) (Polyaniline/Poly(4-styrene-sulfonate)) and the like may be used.

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

Examples of the electron transport material include oxadiazole derivatives, anthraquinodimethane and its derivatives, benzoquinone and its derivatives, naphthoquinone and its derivatives, anthraquinone and its derivatives, tetracyanoanthraquinodimethane and its derivatives, and fluorenone. Derivatives, diphenyldicyanoethylene and derivatives thereof, diphenoquinone derivatives, metal complexes of 8-hydroxyquinoline and derivatives thereof, etc. may be used, and polymer materials as well as low molecular weight materials 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.

A red, green, or blue light emitting material 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 and used as individual sources, or may be premixed and deposited as a single source for use. In addition, although a fluorescent material can be used as a light emitting material, it can 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 alone, but materials in which a host material and a dopant material together participate in light emission may be used.

When mixing and using a host of a light emitting material, a host of the same series may be mixed and used, or a host of different series may be mixed and used. For example, any two or more types of n-type host material and 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 back emission type, or a double side emission type depending on a material used.

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

Hereinafter, the present specification will be described in more detail through examples, but these are only for illustrating the present application and not for limiting the scope of the present application.

< production example >

< production example 1> Preparation of compound 1

1) Preparation of compound 1-1

(1H-indol-2-yl) boronic acid ((1H-indol-2-yl) boronic acid) (100 g, 0.621 mol), 2-bromoaniline (2-bromoaniline) (96 g, 0.558 mol) Toluene, EtOH, H ₂ O 1000 mL: 200 mL: After dissolving in 200 mL, Pd(PPh ₃ ) ₄ (35.8 g, 0.031 mol) and NaHCO ₃ (156.5 g, 1.863 mol) were added and 100 for 3 hours ℃ stir. After completion of the reaction, MC and distilled water are added to the reaction solution for extraction. After drying over anhydrous MgSO ₄ and removing the solvent by a rotary evaporator, compound 1-1 (94 g, 72%) in liquid form was obtained.

2) Preparation of compound 1-2

Compound 1-1 (94 g, 0.451 mol) and triethyl amine (42 mL, 0.451 mol) are dissolved in MC 1200 mL. After dissolving 4-bromobenzoyl chloride (108.9 g, 0.496 mol) in 300 mL of MC, it is slowly added dropwise to the mixture at 0°C. After completion of the reaction, MC and distilled water are added to the reaction solution for extraction. After drying over anhydrous MgSO ₄ and removing the solvent by a rotary evaporator, compound 1-2 (150 g, 85%) in liquid form was obtained.

3) Preparation of compound 1-3

Compound 1-2 (150 g, 0.383 mol) is dissolved in nitrobenzene (Nitrobenzene 1500) mL, and POCl ₃ (35 mL, 0.383 mol) is slowly added dropwise. React at 140° C. for 15 hours. After completion of the reaction, the solution in which NaHCO ₃ was dissolved in distilled water was slowly added to the reaction solution and stirred. The solid formed thereafter is collected by filtration. The collected solid was recrystallized in MC and MeOH to obtain compound 1-3 (68 g, 48%) in a solid form.

4) Preparation of compound 1-4

Compound 1-3 (10 g, 0.026 mol), Bis(pinacolato)diboron) (9.9 g, 0.039 mol), KOAc (7.6 g, 0.078 mol), PdCl ₂ (dppf) ( 0.9 g, 0.0013 mol) was dissolved in 200 mL of 1,4-dioxane and reacted at 90° C. for 5 hours. After completion of the reaction, MC and distilled water are added to the reaction solution for extraction. After drying over anhydrous MgSO ₄ , the solvent was removed using a rotary evaporator to obtain compound 1-4 (10 g, 91%).

5) Preparation of compound 1-5

Compound 1-4 (10 g, 0.023 mol), 2-bromo4,6-diphenyl-1,3,5-triazine (2-bromo-4,6-diphenyl-1,3,5-triazine) (7 g, 0.023 mol) was dissolved in toluene, EtOH, H ₂ O 100 mL: 20 mL: 20 mL, and then Pd(PPh ₃ ) ₄ (1.3 g, 0.0011 mol) and K ₂ CO ₃ (9.5 g) , 0.069 mol) and stirred at 100° C. for 5 hours. After completion of the reaction, MC and distilled water are added to the reaction solution for extraction. After drying over anhydrous MgSO ₄ and removing the solvent using a rotary evaporator, Compound 1-5 (9 g, 74%) was obtained.

6) Preparation of compound 1

Compound 1-5 (9 g, 0.017 mol), bromobenzene (3.2 g, 0.021 mol) was dissolved in 100 mL of toluene, and then Pd ₂ (dba) ₃ (1.5 g, 0.0017 mol), tri -Tri-tert-butylphosphine (0.6 g, 0.034 mol) and sodium tert-butoxide (4.9 g, 0.051 mol) are added and stirred at 100° C. for 15 hours. After completion of the reaction, the solid formed after cooling to room temperature was filtered to obtain Compound 1 (7.5 g, 73%) after drying.

Intermediate of Table 1 instead of 2-bromo-4,6-diphenyl-1,3,5-triazine in Preparation Example 1 (2-bromo-4,6-diphenyl-1,3,5-triazine) A target compound was synthesized in the same manner as in Preparation Example 1, except that A was used.

Intermediate B of Table 2 below was used instead of 4-bromobenzoyl chloride in Preparation Example 1, and 2-bromo-4,6-diphenyl-1,3,5-triazine (2 -bromo-4,6-diphenyl-1,3,5-triazine) was prepared in the same manner as in Preparation Example 1, except that Intermediate C of Table 2 was used, and the target compound was synthesized.

Intermediate D of Table 3 below was used instead of 2-bromoaniline in Preparation Example 1, and 2-bromo-4,6-diphenyl-1,3,5-triazine (2-bromo -4,6-diphenyl-1,3,5-triazine) was prepared in the same manner as in Preparation Example 1, except that Intermediate E of Table 3 was used, and the target compound was synthesized.

< production example 2> Preparation of compound 135

1) Preparation of compound 135-1

(1H-indol-2-yl) boronic acid ((1H-indol-2-yl) boronic acid) (100 g, 0.621 mol), 2-bromoaniline (2-bromoaniline) (96 g, 0.558 mol) Toluene, EtOH, H ₂ O 1000 mL: 200 mL: After dissolving in 200 mL, Pd(PPh ₃ ) ₄ (35.8 g, 0.031 mol) and NaHCO ₃ (156.5 g, 1.863 mol) were added and 100 for 3 hours ℃ stir. After completion of the reaction, MC and distilled water are added to the reaction solution for extraction. After drying over anhydrous MgSO ₄ and removing the solvent by a rotary evaporator, compound 135-1 (94 g, 72%) in liquid form was obtained.

2) Preparation of compound 135-2

Compound 135-1 (94 g, 0.451 mol) and triethyl amine (42 mL, 0.451 mol) are dissolved in MC 1200 mL. After dissolving benzoyl chloride (69.7 g, 0.496 mol) in MC 300 mL, it is slowly added dropwise to the mixture at 0°C. After completion of the reaction, MC and distilled water are added to the reaction solution for extraction. After drying over anhydrous MgSO ₄ and removing the solvent by a rotary evaporator, compound 135-2 (112 g, 80%) in liquid form was obtained.

3) Preparation of compound 135-3

Compound 135-2 (112 g, 0.358 mol) was dissolved in 1000 mL of nitrobenzene, and then POCl ₃ (33 mL, 0.358 mol) was slowly added dropwise. React at 140° C. for 15 hours. After completion of the reaction, the solution in which NaHCO ₃ was dissolved in distilled water was slowly added to the reaction solution and stirred. The solid formed thereafter is collected by filtration. The collected solid was recrystallized in MC and MeOH to obtain compound 135-3 (54 g, 51%) in a solid form.

4) Preparation of compound 135

Compound 135-3 (9 g, 0.030 mol), 4- (4-bromophenyl) -2,6-diphenylpyrimidine (4- (4-bromophenyl) -2,6-diphenylpyrimidine) (11.8 g, 0.030 mol) was dissolved in 100 mL of toluene and then Pd ₂ (dba) ₃ (2.8 g, 0.003 mol), Tri-tert-butylphosphine (1.2 g, 0.006 mol), sodium tert -Butoxide (Sodium tert-butoxide) (5.7 g, 0.062 mol) is added and stirred at 100°C for 15 hours. After completion of the reaction, the solid formed after cooling to room temperature was filtered to obtain compound 135 (9.4 g, 52%) after drying.

Except for using the intermediate F of Table 4 below instead of 4-(4-bromophenyl)-2,6-diphenylpyrimidine (4-(4-bromophenyl)-2,6-diphenylpyrimidine) in Preparation Example 2 The target compound was synthesized in the same manner as in Preparation Example 2.

In Preparation Example 2, the intermediate G of Table 5 was used instead of benzoyl chloride, and 4-(4-bromophenyl)-2,6-diphenylpyrimidine (4-(4-bromophenyl)-2 ,6-diphenylpyrimidine) was prepared in the same manner as in Preparation Example 2, except that the intermediate H of Table 5 was used to synthesize the target compound.

Intermediate I of Table 6 was used instead of 2-bromoaniline in Preparation Example 2, and 4-(4-bromophenyl)-2,6-diphenylpyrimidine (4-(4- The target compound was synthesized in the same manner as in Preparation Example 2, except that Intermediate J of Table 6 was used instead of bromophenyl)-2,6-diphenylpyrimidine).

< production example 3> Preparation of compound 237

1) Preparation of compound 237-1

(1H-indol-3-yl)boronic acid ((1H-indol-3-yl)boronic acid) (100 g, 0.621 mol), 2-bromoaniline (2-bromoaniline) (96 g, 0.558 mol) Toluene, EtOH, H ₂ O 1000 mL: 200 mL: After dissolving in 200 mL, Pd(PPh ₃ ) ₄ (35.8 g, 0.031 mol) and NaHCO ₃ (156.5 g, 1.863 mol) were added and 100 for 3 hours ℃ stir. After completion of the reaction, MC and distilled water are added to the reaction solution for extraction. After drying over anhydrous MgSO ₄ and removing the solvent by a rotary evaporator, compound 237-1 (94 g, 72%) in liquid form was obtained.

2) Preparation of compound 237-2

Compound 237-1 (94 g, 0.451 mol) and triethyl amine (42 mL, 0.451 mol) are dissolved in MC 1200 mL. After dissolving 4-bromobenzoyl chloride (108.9 g, 0.496 mol) in 300 mL of MC, it is slowly added dropwise to the mixture at 0°C. After completion of the reaction, MC and distilled water are added to the reaction solution for extraction. After drying over anhydrous MgSO ₄ and removing the solvent by a rotary evaporator, compound 237-2 (150 g, 85%) in liquid form was obtained.

3) Preparation of compound 237-3

Compound 237-2 (150 g, 0.383 mol) was dissolved in 1500 mL of nitrobenzene, and then POCl ₃ (35 mL, 0.383 mol) was slowly added dropwise. React at 140° C. for 15 hours. After completion of the reaction, the solution in which NaHCO ₃ was dissolved in distilled water was slowly added to the reaction solution and stirred. The solid formed thereafter is collected by filtration. The collected solid was recrystallized in MC and MeOH to obtain compound 237-3 (68 g, 48%) in a solid form.

4) Preparation of compound 237-4

Compound 237-3 (10 g, 0.026 mol), Bis(pinacolato)diboron) (9.9 g, 0.039 mol), KOAc (7.6 g, 0.078 mol), PdCl ₂ (dppf) ( 0.9 g, 0.0013 mol) was dissolved in 200 mL of 1,4-dioxane and reacted at 90° C. for 5 hours. After completion of the reaction, MC and distilled water are added to the reaction solution for extraction. After drying over anhydrous MgSO ₄ , the solvent was removed using a rotary evaporator to obtain compound 237-4 (10 g, 91%).

5) Preparation of compound 237-5

Compound 237-4 (8 g, 0.019 mol), 2-bromo-4,6-diphenyl-1,3,5-triazine (2-bromo-4,6-diphenyl-1,3,5-triazine) ) (5.9 g, 0.019 mol) in toluene, EtOH, H ₂ O 80 mL: 10 mL: 10 mL Pd(PPh ₃ ) ₄ (1.1 g, 0.0009 mol) and K ₂ CO ₃ (7.8 g, 0.057 mol) and stirred at 100° C. for 5 hours. After completion of the reaction, MC and distilled water are added to the reaction solution for extraction. After drying over anhydrous MgSO ₄ and removing the solvent using a rotary evaporator, compound 237-5 (7.4 g, 75%) was obtained.

6) Preparation of compound 237

Compound 237-5 (7.4 g, 0.014 mol), bromobenzene (3.2 g, 0.021 mol) was dissolved in 100 mL of toluene, and then Pd ₂ (dba) ₃ (1.2 g, 0.0014 mol), tri -Tri-tert-butylphosphine (0.5 g, 0.0028 mol) and sodium tert-butoxide (2.7 g, 0.028 mol) are added and stirred at 100° C. for 15 hours. After completion of the reaction, the solid formed after cooling to room temperature was filtered to obtain compound 237 (6.5 g, 77%) after drying.

Intermediate of Table 7 instead of 2-bromo-4,6-diphenyl-1,3,5-triazine in Preparation Example 3 (2-bromo-4,6-diphenyl-1,3,5-triazine) A target compound was synthesized in the same manner as in Preparation Example 3, except that K was used.

In Preparation Example 3, the intermediate L of Table 8 was used instead of 4-bromobenzoyl chloride, and 2-bromo-4,6-diphenyl-1,3,5-triazine (2 -bromo-4,6-diphenyl-1,3,5-triazine) was prepared in the same manner as in Preparation Example 3 except for using the intermediate M shown in Table 8 below to synthesize the target compound.

Intermediate N of Table 9 was used instead of 2-bromoaniline in Preparation Example 3, and 2-bromo-4,6-diphenyl-1,3,5-triazine (2-bromo -4,6-diphenyl-1,3,5-triazine) was prepared in the same manner as in Preparation Example 3, except that the intermediate O of Table 9 was used to synthesize the target compound.

< production example 4> Preparation of compound 345

1) Preparation of compound 345-1

(1H-indol-3-yl)boronic acid ((1H-indol-3-yl)boronic acid) (100 g, 0.621 mol), 2-bromoaniline (2-bromoaniline) (96 g, 0.558 mol) Toluene, EtOH, H ₂ O 1000 mL: 200 mL: After dissolving in 200 mL, Pd(PPh ₃ ) ₄ (35.8 g, 0.031 mol) and NaHCO ₃ (156.5 g, 1.863 mol) were added and 100 for 3 hours ℃ stir. After completion of the reaction, MC and distilled water are added to the reaction solution for extraction. After drying over anhydrous MgSO ₄ and removing the solvent by a rotary evaporator, compound 345-1 (94 g, 72%) in liquid form was obtained.

2) Preparation of compound 345-2

Compound 345-1 (94 g, 0.451 mol) and triethyl amine (42 mL, 0.451 mol) are dissolved in MC 1200 mL. After dissolving benzoyl chloride (69.7 g, 0.496 mol) in MC 300 mL, it is slowly added dropwise to the mixture at 0°C. After completion of the reaction, MC and distilled water are added to the reaction solution for extraction. After drying over anhydrous MgSO ₄ and removing the solvent by a rotary evaporator, compound 345-2 (112 g, 80%) in liquid form was obtained.

3) Preparation of compound 345-3

Compound 345-2 (112 g, 0.358 mol) was dissolved in 1000 mL of nitrobenzene, and then POCl ₃ (33 mL, 0.358 mol) was slowly added dropwise. React at 140° C. for 15 hours. After completion of the reaction, the solution in which NaHCO ₃ was dissolved in distilled water was slowly added to the reaction solution and stirred. The solid formed thereafter is collected by filtration. The collected solid was recrystallized in MC and MeOH to obtain compound 345-3 (54 g, 51%) in a solid form.

4) Preparation of compound 345

Compound 345-3 (9 g, 0.030 mol), 2,4-di([1,1']-biphenyl)-4-yl)-6-(4-bromophenyl)pyrimidine (2,4- After dissolving di([1,1'-biphenyl]-4-yl)-6-(4-bromophenyl)pyrimidine) (4.7 g, 0.030 mol) in 100 mL of toluene, Pd ₂ (dba) ₃ (2.8 g, 0.003 mol), tri-tert-butylphosphine (1.2 g, 0.006 mol), sodium tert-butoxide (5.7 g, 0.062 mol) was added and 15 hours while stirring at 100 °C. After completion of the reaction, the solid formed after cooling to room temperature was filtered to obtain compound 345 (15 g, 60%) after drying.

In Preparation Example 4, 2,4-di([1,1']-biphenyl)-4-yl)-6-(4-bromophenyl)pyrimidine (2,4-di([1,1' -biphenyl]-4-yl)-6-(4-bromophenyl)pyrimidine) was prepared in the same manner as in Preparation Example 4, except that the intermediate P of Table 10 was used to synthesize the target compound.

In Preparation Example 4, the intermediate Q of Table 11 was used instead of benzoyl chloride, and 2,4-di([1,1']-biphenyl)-4-yl)-6-(4-bromo Phenyl) pyrimidine (2,4-di([1,1'-biphenyl]-4-yl)-6-(4-bromophenyl)pyrimidine) in Preparation Example 4 except for using the intermediate R of Table 11 below The target compound was synthesized by preparing in the same manner as described above.

In Preparation Example 4, the intermediate S of Table 12 was used instead of 2-bromoaniline, and 2,4-di([1,1']-biphenyl)-4-yl)-6-( 4-bromophenyl) pyrimidine (2,4-di ([1,1'-biphenyl] -4-yl) -6- (4-bromophenyl) pyrimidine) instead of using the intermediate T in Table 12 below except that The target compound was synthesized in the same manner as in Preparation Example 4.

The remaining compounds other than the compounds described in Tables 1 to 12 were prepared in the same manner as in the above-described Preparation Examples.

Tables 13 and 14 below are 1H NMR data and FD-MS data of the synthesized compound, and it can be confirmed that the desired compound was synthesized through the following data.

NO ^One H NMR ( CDCl ₃ , 300Mz ) One δ = 8.69 (2H, d), 8.55 (1H, d), 8.42 (1H, d), 8.36 (4H, d), 7.96 to 7.85 (6H, m), 7.62 to 7.50 (11H, m), 7.35 ( 1H, t), 7.16 (1H, t) 2 δ = 8.69 (2H, d), 8.55 (1H, d), 8.42 to 8.30 (5H, m), 7.94 to 7.87 (6H, m), 7.62 to 7.50 (11H, m), 7.35 (1H, t), 7.16(1H, t) 4 δ = 8.69 (2H, d), 8.55 (1H, d), 8.42 to 8.36 (3H, m), 7.96 to 7.85 (8H, m), 7.75 (2H, d), 7.62 to 7.35 (12H, m), 7.25 (2H, d), 7.16 (1H, t) 6 δ = 8.69(2H, d), 8.55(1H, d), 8.42(1H, d), 8.30(2H, d), 8.23(1H, s), 7.94~7.85(10H, m), 7.75(1H, d), 7.62 to 7.49 (12H, m), 7.16 (1H, t) 7 δ = 8.69 (2H, d), 8.55 (1H, d), 8.42 (1H, d), 7.96 (10H, m), 7.75 (4H, d), 7.62 to 7.41 (12H, m), 7.25 (4H, m), 7.16 (1H, t) 8 δ = 8.69 (2H, d), 8.55 (1H, d), 8.42 (d, 1H), 8.30 (4H, d), 8.23 (1H, s), 7.94 to 7.75 (14H, m), 7.62 to 7.41 ( 12H, m), 7.16 (1H, t) 16 δ = 8.97 (2H, d), 8.68 (1H, d), 8.55 (1H, d), 8.42 (1H, d), 8.29 (1H, d), 8.23 (1H, s), 7.94 to 7.85 (7H, m), 7.62 to 7.49 (13H, m), 7.35 (1H, t), 7.16 (1H, t) 21 δ = 8.97(2H, d), 8.68(1H, d), 8.55(1H, d), 8.42(1H, d), 8.30(4H, d), 8.29(1H, d), 8.23(1H, s) , 7.94~7.75(12H, m), 7.62~7.41(14H, m), 7.16(1H, t) 26 δ = 8.69 (2H, d), 8.55 (1H, d), 8.42 (1H, d), 8.23 (1H, s), 7.94 to 7.85 (12H, m), 7.62 to 7.49 (11H, m), 7.35 ( 1H, t), 7.25 (2H, d), 7.16 (1H, t) 28 δ = 8.69 (2H, d), 8.55 (1H, d), 8.42 (1H, d), 8.35 to 8.30 (6H, m), 7.94 to 7.85 (10H, m), 7.75 (2H, d), 7.62 to 7.35 (12H, m), 7.16 (1H, t) 31 δ = 8.69(2H, d), 8.55(1H, d), 8.42(1H, d), 8.30(4H, d), 8.23(1H, s), 7.96~7.85(12H, m), 7.75(4H, d), 7.62 to 7.41 (12H, m), 7.25 (2H, d), 7.16 (1H, t) 33 δ = 9.18 (2H, d), 8.14 (2H, d), 8.69 (2H, d), 8.55 (2H, d), 8.42 (1H, d), 7.94 (2H, d), 7.85 (4H, d) , 7.74 (2H, t), 7.62 to 7.50 (5H, m), 7.35 (1H, t), 7.25 to 7.16 (7H, m) 35 δ = 8.55 (1H, d), 8.42 to 8.33 (8H, m), 7.94 to 7.85 (4H, m), 7.73 (1H, t), 7.62 to 7.50 (11H, m), 7.35 (1H, t), 7.16(1H, t) 37 δ = 8.55 (1H, d), 8.42 to 8.33 (4H, m), 8.23 (1H, s), 7.94 to 7.85 (8H, m), 7.73 (1H, t), 7.62 to 7.49 (11H, m), 7.35 (1H, t), 7.16 (1H, t) 39 δ = 8.55 (1H, d), 8.42 to 8.30 (7H, m), 8.23 (1H, s), 7.94 to 7.85 (7H, m), 7.75 (2H, d), 7.73 (1H, t), 7.62 to 7.35 (12H, m), 7.16 (1H, t) 41 δ = 8.55(1H, d), 8.42~8.33(4H, m), 7.96~7.85(8H, m), 7.75~7.73(5H, m), 7.62~7.35(12H, m), 7.25(4H, d) ), 7.16(1H, t) 42 δ=8.55 (1H, d), 8.42 to 8.30 (8H, m), 8.23 (1H, s), 7.94 to 7.75 (13H, m), 7.62 to 7.35 (12H, m), 7.16 (1H, t) 45 δ = 8.69(2H, d), 8.51(2H, d), 8.36(4H, d), 8.20(1H, d), 8.11(1H, d), 7.96(2H, d), 7.94(1H, d) , 7.90 (1H, d), 7.72 to 7.50 (13H, m), 7.35 (1H, t), 7.16 (1H, t) 59 δ = 8.69 (2H, d), 8.55 (1H, d), 8.28 (1H, d), 8.11 (1H, d), 8.03 (1H, s), 7.96 to 7.94 (7H, m), 7.79 to 7.41 ( 23H, m), 7.16 (1H, t) 65 δ = 8.69 (2H, d), 8.55 (2H, d), 8.35 (2H, d), 8.30 (2H, d), 8.23 (1H, s), 8.09 to 7.85 (10H, m), 7.62 to 7.49 ( 13H, m), 7.35 (1H, t), 7.25 (2H, d), 7.16 (1H, t) 66 δ = 8.79 (1H, d), 8.69 (2H, d), 8.55 (1H, d), 8.42 to 8.30 (6H, m), 8.15 (1H, d), 7.96 to 7.85 (6H, m), 7.70 to 7.50 (13H, m), 7.35 (1H, t), 7.16 (1H, t) 68 δ = 8.79 (1H, d), 8.69 (2H, d), 8.55 (1H, d), 8.42 (1H, d), 8.33 (2H, d), 8.30 (1H, d), 8.23 (1H, s) , 8.15 (1H, d), 7.96 to 7.85 (8H, m), 7.70 to 7.49 (13H, m), 7.35 (1H, t), 7.16 (1H, t) 70 δ = 8.69 (2H, d), 8.55 (1H, d), 8.42 (1H, d), 8.38 (2H, d), 7.94 to 7.85 (8H, m), 7.75 to 7.73 (4H, m), 7.61 to 7.35 (14H, m), 7.16 (1H, t) 73 δ = 8.69(2H, d), 8.55(1H, d), 8.42(1H, d), 8.23(1H, s), 7.96~7.85(10H, m), 7.75(2H, d), 7.73(1H, t), 7.62~7.35 (13H, m), 7.16 (1H, t) 74 δ = 8.69 (2H, d), 8.55 (1H, d), 8.42 (1H, d), 8.38 (1H, t), 8.30 (2H, d), 8.23 (1H, s), 7.94 to 7.87 (7H, m), 7.75 (2H, d), 7.73 (1H, t), 7.62 to 7.41 (13H, m), 7.16 (1H, t) 77 δ = 8.69 (2H, d), 8.55 (2H, d), 8.42 (1H, d), 8.36 (2H, d), 8.19 (1H, d), 7.96 to 7.85 (7H, m), 7.62 to 7.50 ( 10H, m), 7.35 (2H, t), 7.20 (1H, t), 7.16 (2H, t) 78 δ = 8.69 (2H, d), 8.55 (1H, d), 8.42 (1H, d), 8.36 (2H, d), 8.19 (1H, d), 7.94 to 7.85 (11H, m), 7.62 to 7.50 ( 10H, m), 7.35 (1H, t), 7.20 to 7.16 (3H, t) 88 δ = 8.69 (2H, d), 8.55 (1H, d), 8.42 (1H, d), 8.36 (2H, d), 8.09 (1H, d), 7.94 to 7.78 (9H, m), 7.62 to 7.50 ( 9H, m), 7.38 (1H, t), 7.35 (1H, t), 7.28 (1H, t), 1.69 (6H, s) 93 δ = 8.69(2H, d), 8.55(1H, d), 8.42(1H, d), 8.35(2H, d), 8.30(2H, d), 8.23(1H, s), 8.09(1H, d) , 7.94 to 7.73 (10H, m), 7.62 to 7.50 (10H, m), 7.38 to 7.28 (3H, m), 7.16 (1H, t), 1.69 (6H, s) 96 δ = 8.69 (2H, d), 8.55 (1H, d), 8.42 (1H, d), 8.36 (2H, d), 7.96 to 7.82 (10H, m), 7.62 to 7.50 (8H, m), 7.35 ( 1H, t), 7.16 (1H, t) 100 δ = 8.69 (2H, d), 8.55 (1H, d), 8.42 (1H, d), 7.96 to 7.75 (14H, m), 7.62 to 7.35 (9H, m), 7.25 (2H, d), 7.16 ( 1H, t) 101 δ = 8.69 (2H, d), 8.55 (1H, d), 8.42 (1H, d), 7.94 to 7.75 (14H, m), 7.62 to 7.35 (10H, m), 7.16 (1H, t) 104 δ = 9.08(1H, d), 8.84(1H, d), 8.69(2H, d), 8.55(1H, d), 8.42(1H, d), 8.36(2H, d), 8.27(1H, d) , 8.05(1H, s), 7.96-7.85(9H, m), 7.70-7.50(12H, m), 7.35(1H, t), 7.25(2H, d), 7.16(1H, t) 105 δ = 9.27(1H, d), 8.85(1H, d), 8.69(2H, d), 8.55(1H, d), 8.42(1H, d), 8.36(2H, d), 8.15(1H, d) , 7.96~7.85(7H, m), 7.75~7.50(12H, m), 7.35(1H, t), 7.16(1H, t) 108 δ = 8.69 (2H, d), 8.55 (1H, d), 8.42 (1H, d), 8.36 (2H, d), 8.04 (3H, s), 7.96 to 7.85 (6H, m), 7.75 (4H, d), 7.62~7.35 (15H, m), 7.16 (1H, t) 115 δ = 8.95 (1H, d), 8.55 (1H, d), 8.45 to 8.42 (2H, d), 8.30 to 8.20 (5H, m), 7.94 to 7.85 (10H, m), 7.62 to 7.35 (14H, m) ), 7.25(2H, d), 7.16(1H, t) 117 δ = 8.93 (1H, d), 8.69 (2H, d), 8.55 (1H, d), 8.42 to 8.23 (8H, m), 7.94 to 7.85 (6H, m), 7.72 (1H, d), 7.62 to 7.35 (14H, m), 7.25 (4H, m), 7.16 (1H, t) 120 δ=8.95(1H, d), 8.55(1H, d), 8.45(1H, d), 8.42(1H, d), 8.25(1H, d), 8.23(1H, s), 8.20(1H, d) , 7.94~7.85(10H, m), 7.75(4H, d), 7.73(2H, d), 7.62~7.35(16H, m), 7.25(2H, d), 7.16(1H, t) 131 δ = 9.02(1H, d), 8.95(1H, d), 8.69(2H, d), 8.55(1H, d), 8.42(1H, d), 8.36(4H, d), 8.06(1H, d) , 7.94 to 7.84 (5H, m), 7.62 to 7.46 (13H, m), 7.35 (1H, t), 7.25 (2H, d), 7.16 (1H, t) 132 δ = 9.02(1H, d), 8.95(1H, d), 8.69(2H, d), 8.55(1H, d), 8.42(1H, d), 8.35(2H, d), 8.23(1H, s) , 8.06(1H, d), 7.94~7.84(7H, m), 7.62~7.49(13H, m), 7.35(1H, t), 7.25(2H, d), 7.16(1H, t) 134 δ = 8.55 (1H, d), 8.42 to 8.36 (5H, m), 8.19 (2H, d), 7.94 to 7.85 (8H, m), 7.65 (2H, d), 7.50 to 7.49 (7H, m), 7.35 (1H, t), 7.16 (1H, t) 135 δ = 8.55(1H, d), 8.42(1H, d), 8.35(2H, d), 8.23(1H, s), 8.19(2H, d), 7.94~7.87(10H, m), 7.65(2H, t), 7.55~7.49(7H, m), 7.35(1H, t), 7.16(1H, t) 137 δ = 8.55 (1H, d), 8.42 to 8.36 (3H, d), 8.19 (2H, d), 7.96 to 7.85 (10H, m), 7.75 (2H, d), 7.65 (2H, t), 7.50 to 7.35 (8H, m), 7.25 (2H, d), 7.16 (1H, t) 139 δ = 8.55(1H, d), 8.42(1H, d), 8.30(2H, d), 8.23(1H, s), 8.19(2H, d), 7.94~7.85(12H, m), 7.75(2H, d), 7.65 (2H, t), 7.55 to 7.35 (8H, m), 7.16 (1H, t) 141 δ = 8.55 (1H, d), 8.42 (1H, d), 8.30 to 8.19 (7H, m), 7.94 to 7.75 (16H, m), 7.65 (2H, t), 7.49 to 7.35 (8H, m), 7.16(1H, t) 143 δ = 8.97 (1H, d), 8.55 (1H, d), 8.42 to 8.36 (5H, m), 8.24 to 8.12 (4H, m), 7.94 to 7.79 (5H, m), 7.65 to 7.49 (11H, m) ), 7.35(1H, t), 7.16(1H, t) 148 δ = 8.97 (1H, d), 8.55 (1H, d), 8.42 (1H, d), 8.30 to 8.12 (7H, m), 7.94 to 7.35 (23H, m), 7.16 (1H, t) 149 δ = 8.97 (1H, d), 8.55 (1H, d), 8.42 (1H, d), 8.24 to 8.19 (3H, d), 7.94 to 7.35 (25H, m), 7.25 (4H, d), 7.16 ( 1H, t) 152 δ = 8.80(1H, d), 8.71(1H, d), 8.55(1H, d), 8.45(1H, d), 8.42(1H, d), 8.30(2H, d), 8.20(1H, d) , 8.19(2H, d), 7.94~7.85(7H, m), 7.65~7.49(4H, m), 7.35(1H, t), 7.29(1H, d), 7.16(1H, t) 155 δ = 8.55(1H, d), 8.42(1H, d), 8.23(1H, s), 8.19(2H, d), 7.94~7.85(14H, m), 7.65(2H, t), 7.55~7.49( 7H, m), 7.35 (1H, t), 7.25 (2H, d), 7.16 (1H, t) 156 δ = 8.71(2H, d), 8.55(1H, d), 8.42(1H, d), 8.33(2H, d), 8.30(2H, d), 8.20(1H, d), 8.19(2H, d) , 7.94~7.85(7H, m), 7.65~7.49(6H, m), 7.35(1H, t), 7.29(2H, d), 7.16(1H, t) 157 δ = 8.71 (2H, d), 8.69 (2H, d), 8.55 (1H, d), 8.42 (1H, d), 8.33 (2H, d), 8.19 (2H, d), 7.94 to 7.85 (11H, m), 7.65 to 7.49 (6H, m), 7.35 (1H, t), 7.29 (2H, d), 7.16 (1H, t) 158 δ = 8.71 (2H, d), 8.55 (1H, d), 8.42 (1H, d), 8.33 (4H, d), 8.19 (2H, d), 7.94 to 7.85 (9H, m), 7.73 to 7.49 ( 8H, m), 7.35 to 7.29 (3H, m), 7.16 (1H, t) 159 δ = 8.55(1H, d), 8.42(1H, d), 8.19(2H, d), 7.96~7.85(14H, m), 7.75(4H, d), 7.65(2H, t), 7.49~7.35( 8H, m), 7.25~7.16 (7H, m), 161 δ = 9.18 (2H, d), 9.14 (2H, s), 8.55 (3H, d), 8.42 (1H, d), 8.19 (2H, d), 7.94 to 7.85 (8H, m), 7.74 to 7.65 ( 4H, d), 7.49 (1H, t), 7.35 (1H, t), 7.25 to 7.16 (7H, m) 165 δ = 8.55 (1H, d), 8.42 to 8.36 (5H, m), 8.24 (2H, d), 8.19 (2H, d), 7.94 to 7.85 (4H, m), 7.68 to 7.60 (4H, m), 7.50 (7H, t), 7.35 (1H, t), 7.16 (1H, t) 168 δ = 8.55 (1H, d), 8.42 to 8.36 (3H, d), 8.24 to 8.19 (4H, d), 7.96 to 7.85 (6H, m), 7.75 to 7.60 (6H, m), 7.50 to 7.35 (8H) , m), 7.25 (2H, d), 7.16 (1H, t) 169 δ = 8.55 (1H, d), 8.42 to 8.30 (5H, m), 8.23 to 8.19 (4H, m), 7.94 to 7.65 (13H, m), 7.50 to 7.35 (8H, m), 7.16 (1H, t) ) 187 δ = 8.55 (2H, d), 8.51 (1H, d), 8.36 (2H, d), 8.24 to 8.11 (6H, m), 7.99 to 7.90 (9H, m), 7.77 to 7.60 (9H, m), 7.50~7.35 (9H, m), 7.16 (1H, t) 192 δ = 8.55 (1H, d), 8.35 to 7.91 (18H, m), 7.75 to 7.65 (5H, m), 7.50 to 7.25 (11H, m), 7.16 (1H, t) 195 δ = 8.55 (2H, d), 8.35 (2H, d), 8.23 (1H, s), 8.19 (2H, d), 8.06 to 7.91 (10H, m), 7.65 to 7.49 (11H, m), 7.35 ( 1H, t), 7.16 (1H, t) 203 δ = 8.55 (1H, d), 8.42 to 8.36 (3H, d), 8.19 (2H, d), 7.98 to 7.79 (12H, m), 7.65 (2H, t), 7.54 to 7.49 (5H, m), 7.39(1H, t), 7.35(1H, t), 7.31(1H, t), 7.16(1H, t) 205 δ = 8.55(1H, d), 8.42(1H, d), 8.35(2H, d), 8.30(2H, d), 8.23(1H, s), 8.19(2H, d), 7.98~7.82(10H, m), 7.69 to 7.49 (9H, m), 7.39 to 7.25 (5H, m), 7.16 (1H, t) 209 δ = 8.55(2H, d), 8.45~8.36(4H, d), 8.19(2H, d), 7.94~7.85(10H, m), 7.70~7.49(9H, m), 7.35(1H, t), 7.16(1H, t) 212 δ = 8.55(2H, d), 8.45~8.32(5H, m), 8.23(1H, s), 8.19(2H, d), 7.94~7.85(11H, m), 7.73~7.49(11H, m), 7.35 (1H, t), 7.16 (1H, t) 213 δ = 855(1H, d), 8.42(2H, d), 8.36(4H, d), 8.21(1H, d), 8.10(2H, t), 7.94-7.80(10H, m), 7.69(1H, d), 7.55 to 7.50 (7H, m), 7.35 (1H, t), 7.16 (1H, t) 218 δ = 9.08 (1H, d), 8.84 (1H, d), 8.55 (1H, d), 8.44 (1H, s), 8.42 to 8.36 (3H, d), 8.17 (1H, d), 7.96 to 7.85 ( 11H, m), 7.75 to 7.62 (6H, m), 7.50 to 7.35 (7H, m), 7.25 (2H, d), 7.16 (1H, s) 219 δ = 9.08 (1H, d), 8.84 (1H, d), 8.55 (1H, d), 8.44 to 8.30 (6H, m), 8.23 (1H, s), 8.17 (1H, d), 7.94 to 7.85 ( 11H, m), 7.75 to 7.62 (6H, m), 7.50 to 7.35 (7H, m), 7.16 (1H, d) 222 δ = 9.08 (1H, d), 8.84 (1H, d), 8.55 (1H, d), 8.44 to 8.42 (2H, d), 8.30 (4H, d), 8.23 (1H, s), 8.17 (1H, s) d), 7.94 to 7.63 (21H, m), 7.49 to 7.35 (7H, m), 7.16 (1H, t) 228 δ = 9.08(1H, d), 8.84(1H, d), 8.55(1H, d), 8.44(1H, s), 8.42(1H, d), 8.36(2H, d) 8.17(1H, d), 7.96 to 7.85 (14H, m), 7.75 to 7.62 (6H, m), 7.50 to 7.35 (7H, m), 7.25 (4H, d), 7.16 (1H, t) 229 δ = 9.08 (1H, d), 8.84 (1H, d), 8.55 (1H, d), 8.44 (1H, s), 8.42 to 8.17 (10H, m), 7.94 to 7.85 (9H, m), 7.75 to 7.60(8H, m), 7.50~7.35(8H, m), 7.16(1H, t) 234 δ = 9.02(1H, d), 8.95(1H, d), 8.55(1H, d), 8.42(1H, d), 8.36(2H, d), 8.19(2H, d), 8.06(1H, d) , 7.96~7.84(11H, m), 7.75(2H, d), 7.65(2H, t), 7.50~7.35(10H, m), 7.25(2H, d), 7.16(1H, t) 236 δ = 9.02(1H, d), 8.95(1H, d), 8.55(1H, d), 8.42(1H, d), 8.30(2H, d), 8.19(2H, d), 8.06(1H, d) , 7.94 to 7.85 (13H, m), 7.75 (2H, d), 7.65 to 7.35 (12H, m), 7.16 (1H, t) 237 δ = 8.69 (2H, d), 8.55 (1H, d), 8.36 (4H, d), 8.20 (1H, d), 7.96 to 7.94 (4H, d), 7.85 (1H, t), 7.70 to 7.50 ( 12H, m), 7.35 (1H, t), 7.16 (1H, t) 238 δ = 8.69(2H, d), 8.55(1H, d), 8.35(2H, d), 8.30(2H, d), 8.23(1H, s), 8.20(1H, d), 7.94(4H, d) , 7.70~7.49(12H, m), 7.35(1H, t), 7.16(1H, t) 240 δ = 8.69(2H, d), 8.55(1H, d), )8.36(2H, d), 8.20(1H, d), 7.96~7.94(6H, m), 7.85(1H, t), 7.70~7.35 (15H, m), 7.25 (2H, d), 7.16 (1H, t) 242 δ = 8.69 (2H, d), 8.55 (1H, d), 8.30 (2H, d), 8.23 (1H, s), 8.20 (1H, d), 7.96 to 7.85 (9H, m), 7.70 to 7.35 ( 15H, m), 7.16 (1H, t) 248 δ = 8.97 (2H, d), 8.68 (1H, d), 8.55 (1H, d), 8.35 to 8.20 (5H, m), 7.94 to 7.85 (5H, m), 7.62 to 7.50 (14H, m), 7.35 (1H, t), 7.16 (1H, t) 250 δ = 8.97 (2H, d), 8.89 (1H, d), 8.55 (1H, d), 8.36 to 8.29 (3H, d), 8.20 (1H, d), 7.94 (4H, d), 7.85 (1H, t), 7.70~7.35 (17H, m), 7.25 (2H, d), 7.16 (1H, t) 251 δ = 8.97 (2H, d), 8.68 (1H, d), 8.55 (1H, d), 8.35 to 8.20 (7H, m), 7.94 (2H, d), 7.85 (2H, d), 7.75 to 7.35 ( 17H, m), 7.16 (1H, t) 253 δ = 8.97 (2H, d), 8.68 (1H, d), 8.55 (1H, d), 8.29 (1H, d), 8.20 (1H, d), 7.96 to 7.94 (7H, m), 7.70 to 7.35 ( 19H, m), 7.25 (4H, d), 7.16 (1H, t) 259 δ = 8.69 (2H, d), 8.55 (1H, d), 8.23 (1H, s), 8.20 (1H, d), 7.94 to 7.85 (11H, m), 7.70 to 7.49 (12H, m), 7.35 ( 1H, t), 7.25 (2H, d), 7.16 (1H, t) 263 δ = 8.69 (2H, d), 8.55 (1H, d), 8.20 (1H, d), 7.96 to 7.85 (11H, m), 7.70 to 7.41 (17H, m), 7.25 (6H, d), 7.16 ( 1H, t) 264 δ = 8.69 (2H, d), 8.55 (1H, d), 8.30 (4H, d), 8.23 (1H, s), 8.20 (1H, d), 7.96 to 7.41 (28H, m), 7.25 (2H, d), 7.16 (1H, t) 267 δ = 8.55(1H, d), 8.38(1H, s), 8.36(4H, d), 8.33(2H, s), 8.20(1H, d), 7.94(2H, d), 7.85(1H, t) , 7.70 to 7.50 (13H, m), 7.35 (1H, d), 7.16 (1H, t) 270 δ = 8.55(1H, d), 8.38(1H, s), 8.36(4H, d), 8.20(1H, d), 7.96(4H, d), 7.70~7.35(16H, m), 7.25(2H, d), 7.16 (1H, t) 273 δ = 855 (1H, d) 8.38 (1H, s), 8.33 (3H, d), 8.20 (1H, d), 7.96 to 7.94 (7H, m), 7.70 to 7.35 (18H, m), 7.25 (4H) , d), 7.16 (1H, t) 277 δ = 9.60(1H, d), 9.27(1H, s), 8.69(2H, d), 8.55(1H, d), 8.30(3H, d), 8.20~8.15(2H, d), 7.96~7.85( 7H, m), 7.70 to 7.50 (15H, m), 7.35 (1H, t), 7.25 (2H, d), 7.16 (1H, t) 278 δ = 9.60 (1H, d), 9.27 (1H, s), 8.69 (2H, d), 8.55 (1H, d), 8.37 to 8.30 (5H, m), 8.20 (1H, d), 7.96 to 7.85 ( 9H, m), 7.70 to 7.50 (15H, m), 7.35 (1H, t), 7.25 to 7.16 (5H, m) 282 δ = 9.60(1H, d), 9.27(1H, s), 8.69(2H, d), 8.55(1H, d), 8.37~8.30(3H, d), 8.23(1H, s), 8.20(1H, d), 7.96 to 7.85 (11H, m), 7.70 to 7.49 (16H, m), 7.35 (1H, t), 7.25 (2H, d), 7.16 (1H, t) 283 δ = 9.02(1H, d), 8.95(1H, d), 8.69(2H, d), 8.55(1H, d), 8.36(2H, d), 8.20(1H, d), 8.08(1H, d) , 8.06 (1H, d), 7.98 to 7.84 (6H, m), 7.70 to 7.35 (18H, m), 7.16 (1H, t) 284 δ = 8.69 (2H, d), 8.55 (1H, d), 8.36 (2H, d), 8.20 (1H, d), 8.09 (1H, d), 7.94 to 7.50 (20H, m), 7.38 to 7.25 ( 5H, m), 7.16 (1H, t), 1.69 (6H, s) 288 δ = 8.69 (2H, d), 8.55 (1H, d), 8.36 (2H, d), 8.20 (1H, d), 7.96 to 7.82 (11H, m), 7.70 to 7.50 (9H, m), 7.35 ( 1H, t), 7.25 (2H, d), 7.16 (1H, t) 290 δ = 8.69 (1H, d), 8.55 (1H, d), 8.23 (1H, s), 8.20 (1H, d), 8.12 (1H, d), 8.02 to 7.85 (11H, m), 7.70 to 7.49 ( 10H, m), 7.35 (1H, t), 7.25 (2H, d), 7.16 (1H, t) 292 δ = 8.69 (2H, d), 8.55 (1H, d), 8.20 (1H, d), 7.96 to 7.35 (25H, m), 7.25 (4H, d), 7.16 (1H, t) 293 δ = 8.69(2H, d), 8.55(1H, d), 8.38(1H, d), 8.20(1H, d), 7.95~7.35(26H, m), 7.25(2H, d), 7.16(1H, t) 296 δ = 9.08(1H, d), 8.84(1H, d), 8.69(2H, d), 8.55(1H, d), 8.36(2H, d), 8.27~8.20(2H, dd), 8.05(1H, s), 7.96 to 7.85 (10H, m), 7.70 to 7.50 (13H, m), 7.35 (1H, t), 7.25 (2H, d), 7.16 (1H, t) 299 δ = 9.27(1H, s), 8.85(1H, d), 8.69(2H, d), 8.55~8.52(2H, d), 8.23~8.15(3H, m), 7.96~7.85(10H, m), 7.75 to 7.49 (13H, m), 7.35 (1H, t), 7.25 (2H, d), 7.16 (1H, t) 300 δ = 8.69 (2H, d), 8.55 (1H, d), 8.36 (2H, d), 8.20 (1H, d), 8.04 (3H, s), 7.96 to 7.94 (4H, d), 7.85 (3H, t), 7.70~7.35 (20H, m), 7.25 (2H, d), 7.16 (1H, t) 303 δ = 9.02(1H, d), 8.95(1H, d), 8.69(2H, d), 8.55(1H, d), 8.30~8.20(6H, m), 8.06(1H, d), 7.95~7.35( 27H, m), 7.25 (2H, d), 7.16 (1H, t) 304 δ = 9.02((1H, d), 8.95(1H, d), 8.69(2H, d), 8.55(1H, d), 8.38(2H, d), 8.20(1H, d), 8.06(1H, d) ), 7.94~7.41 (29H, m), 7.25 (2H, d), 7.16 (1H, t) 305 δ = 9.60(1H, d), 9.27(1H, s), 8.97(2H, d), 8.68(1H, d), 8.55(1H, d), 8.38~8.30(7H, m), 8.20(1H, m) d), 7.94 (3H, d), 7.85 (1H, t), 7.73 to 7.50 (19H, m), 7.35 (1H, t), 7.16 (1H, t) 306 δ = 9.02(1H, d), 8.95(1H, d), 8.69(2H, d), 8.55(1H, d), 8.35(2H, d), 8.23(1H, s), 8.20(1H, d) , 8.08(1H, d), 8.06(1H, d), 7.98~7.94(3H, d), 8.85~8.84(2H, t), 7.74~7.39(19H, m), 7.16(1H, t) 308 δ = 8.95 (1H, d), 8.69 (2H, d), 8.55 (1H, d), 8.36 (2H, d), 8.20 (3H, d), 8.06 (1H, d), 7.96 to 7.94 (4H, m), 7.85 (1H, d), 7.70 to 7.50 (13H, m), 7.39 to 7.16 (9H, m) 313 δ = 8.55 (1H, d), 8.35 to 8.30 (7H, m), 8.23 (1H, s), 8.20 (1H, d), 7.94 (3H, d), 7.85 (3H, d), 7.60 to 7.35 ( 17H, m), 7.25 (2H, d), 7.16 (1H, t) 321 δ = 8.55(1H, d), 8.23(1H, s), 8.20(1H, d), 7.94~7.85(12H, m), 7.70(1H, t), 7.55~7.49(7H, m), 7.35( 1H, t), 7.28 (2H, t), 7.16 (1H, t) 324 δ = 8.55(1H, d), 8.30(2H, d), 8.23(1H, s), 8.20(1H, d), 7.94~7.85(13H, m), 7.75(2H, d), 7.70(1H, t), 7.55~7.28 (10H, m), 7.16 (1H, t) 325 δ = 8.55 (1H, d), 8.20 (1H, d), 7.96 to 7.85 (13H, m), 7.75 (4H, d), 7.70 (1H, t), 7.49 to 7.28 (14H, m), 7.16 ( 1H, t) 332 δ = 8.97 (1H, d), 8.55 (1H, d), 8.36 (2H, d), 8.28 to 8.20 (2H, d), 8.12 (1H, d), 7.96 to 7.70 (11H, m), 7.50 to 7.16 (15H, m) 336 δ = 8.97(1H, d), 8.55(1H, d), 8.30~8.20(7H, m), 8.12(1H, d), 7.94~7.70(15H, m), 7.59~7.28(12H, m), 7.16(1H, t) 339 δ = 8.55 (1H, d), 8.36 (4H, d), 8.20 (1H, d), 7.96 to 7.85 (11H, m), 7.70 (1H, t), 7.50 (7H, m), 7.35 to 7.28 ( 5H, m), 7.16 (1H, t) 343 δ = 8.55 (1H, d), 8.35 to 8.30 (6H, d), 8.23 (1H, s), 8.20 (1H, d), 7.94 to 7.86 (13H, m), 7.75 (3H, t), 7.50 to 7.28 (10H, m), 7.16 (1H, t) 345 δ = 8.55 (1H, d), 8.20 (1H, d), 7.96 to 7.85 (15H, m), 7.75 (4H, d), 7.70 (1H, t), 7.49 to 7.16 (17H, m) 352 δ=8.55(1H, d), 8.36(2H, d), 8.24~8.20(3H, m), 7.96~7.85(7H, m), 7.75(5H, d), 7.50~7.28(12H, m), 7.16(1H, t) 353 δ = 8.55 (1H, d), 8.35 to 8.30 (4H, d), 8.23 to 8.20 (3H, m), 7.94 to 7.75 (13H, m), 7.50 to 7.28 (10H, m), 7.16 (1H, t) ) 363 δ = 8.55 (1H, d), 8.51 (1H, d), 8.23 (1H, s), 8.20 (1H, d), 8.11 (1H, d), 7.94 to 7.86 (12H, m), 7.72 to 7.67 ( 2H, t), 7.55 to 7.49 (7H, m), 7.35 to 7.28 (3H, t), 7.16 (1H, t) 365 δ=8.55(1H, d), 8.35~8.23(4H, m), 8.11(1H, d), 8.03(1H, s), 7.94~7.86(9H, m), 7.75~7.69(3H, m), 7.55 to 7.49 (7H, m), 7.35 to 7.28 (3H, m), 7.16 (1H, t) 367 δ = 8.55 (1H, d), 8.44 (1H, d), 8.36 (4H, d), 8.06 to 7.86 (10H, m), 7.61 to 7.50 (9H, m), 7.35 to 7.28 (3H, m), 7.16(1H, t) 370 δ = 8.80 (1H, d), 8.71 (1H, d), 8.55 (1H, d), 8.45 (1H, d), 8.30 (2H, d), 8.20 (2H, d), 7.94 to 7.85 (8H, m), 7.70 (1, t), 7.56 to 7.49 (2H, t), 7.35 to 7.28 (4H, d), 7.16 (1H, t) 372 δ = 8.71 (2H, d), 8.55 (1H, d), 8.33 to 8.30 (4H, d), 8.20 (2H, d), 7.94 to 7.85 (8H, m), 7.70 (1H, t), 7.55 to 7.49(4H, m), 7.35~7.29(5H, m), 7.16(1H, t) 373 δ = 8.71 to 8.69 (4H, d), 8.55 (1H, d), 8.33 (2H, d), 8.20 (2H, d), 7.94 to 7.86 (12H, m), 7.70 (1H, t), 7.55 to 7.49 (4H, m), 7.35 to 7.28 (5H, m), 7.16 (1H, t) 374 δ = 8.71 (2H, d), 8.55 (1H, d), 8.33 (4H, d), 8.20 (2H, d), 7.94 to 7.85 (10H, m), 7.73 to 7.70 (2H, t), 7.61 to 7.49 (5H, m), 7.35 to 7.28 (5H, m), 7.16 (1H, t) 376 δ = 8.55 (1H, d), 8.20 (1H, d), 8.09 (1H, d), 7.94 to 7.70 (17H, m), 7.61 to 7.28 (15H, m), 7.16 (1H, t) 379 δ = 8.55 (1H, d), 8.36 (2H, d), 8.20 (1H, d), 7.96 to 7.86 (11H, m), 7.75 to 7.70 (3H, t), 7.50 to 7.16 (17H, m) 380 δ = 8.55 (1H, d), 8.35 to 8.30 (4H, d), 8.23 to 8.20 (3H, d), 7.94 to 7.85 (11H, m), 7.75 to 7.70 (3H, t), 7.50 to 7.28 (14H) , m), 7.16 (1H, t) 381 δ = 8.55(1H, d), 8.23(1H, s), 8.20(1H, d), 7.94~7.85(15H, m), 7.70(1H, t), 7.55~7.49(7H, m), 7.49~ 7.25 (9H, m), 7.16 (1H, t) 382 δ = 8.55 (1H, d), 8.36 (4H, d), 8.20 (1H, d), 7.96 to 7.85 (11H, m), 7.70 (1H, t), 7.50 (7H, m), 7.25 to 7.16 ( 10H, m) 384 δ = 9.00(2H, d), 8.55(1H, d), 8.36(4H, d), 8.20(1H, d), 7.96~7.85(11H, m), 7.70(1H, t), 7.61(2H, d), 7.50 to 7.49 (7H, m), 7.39 to 7.28 (7H, m), 7.16 (1H, t) 388 δ = 8.55~8.52(3H, d), 8.36~8.31(5H, d), 8.20(1H, d), 8.08~8.04(4H, m), 7.94~7.85(8H, m), 7.70(2H, d) ), 7.50(6H, s), 7.35(1H, t), 7.16(1H, t) 391 δ = 9.66 (1H, s), 8.79 (1H, d), 8.54 (2H, d), 8.36 to 8.33 (4H, d), 8.20 (1H, d), 7.96 to 7.85 (9H, m), 7.75 to 7.64 (7H, m), 7.50 to 7.35 (8H, m), 7.25 (2H, d), 7.16 (1H, t) 395 δ = 9.66 (1H, s), 8.85 (1H, d), 8.55 (3H, d), 8.30 to 8.20 (6H, m), 7.94 to 7.63 (21H, m), 7.49 to 7.35 (7H, m), 7.16(1H, t) 396 δ = 9.02(1H, d), 8.95(1H, d), 8.55(1H, d), 8.45(1H, d), 8.36~8.32(3H, d), 8.20(1H, d), 8.06(1H, d), 7.96 to 7.85 (13H, m), 7.70 (2H, t), 7.52 to 7.46 (8H, m), 7.35 to 7.25 (5H, m), 7.16 (1H, t) 397 δ = 9.02(1H, d), 8.95(1H, d), 8.55(1H, d), 8.20(1H, d), 8.06(1H, d), 7.94~7.84(13H, m), 7.70(1H, t), 7.55 to 7.49 (8H, m), 7.35 to 7.16 (8H, m) 398 δ = 9.02(1H, d), 8.95(1H, d), 8.55(1H, d), 8.23(1H, s), 8.20(1H, d), 8.18(1H, s), 8.06(1H, d) , 7.94 to 7.86 (13H, m), 7.74 to 7.64 (3H, d), 7.55 to 7.28 (12H, m), 7.16 (1H, t) 399 δ = 8.69 (2H, d), 8.55 (2H, d), 8.36 (4H, d), 8.06 to 7.94 (6H, m), 7.85 (2H, d), 7.63 to 7.50 (13H, m), 7.35 ( 1H, t), 7.25 (2H, d), 7.16 (1H, t) 400 δ = 9.02(1H, d), 8.95(1H, d), 8.69(2H, d), 8.55(1H, d), 8.35(2H, d), 8.23(1H, s), 8.28(1H, d) , 8.11(1H, d), 8.03(1H, s), 8.06(1H, d), 7.94(1H, d), 7.84(1H, d), 7.75~7.46(16H, m), 7.35(1H, t) ), 7.25(2H, d), 7.16(1H, t) 401 δ = 8.69(2H, d), 8.55(1H, d), 8.51(1H, d), 8.23(1H, s), 8,20(1H, d), 8.11(1H, d), 7.96 to 7.90( 8H, m), 7.72 to 7.49 (13H, m), 7.35 (1H, t), 7.16 (1H, t)

compound FD-MS compound FD-MS One m/z= 601.71 (C42H27N5=601.22) 2 m/z= 600.72 (C43H28N4=600.23) 3 m/z= 600.72 (C43H28N4=600.23) 4 m/z=677.81 (C48H31N5=677.23) 5 m/z= 676.81 (C49H32N4=676.26) 6 m/z= 676.82 (C49H32N4=676.26) 7 m/z= 753.90 (C54H35N5=753.28) 8 m/z= 752.92 (C55H36N4=752.29) 9 m/z= 601.71 (C42H27N5=601.22) 10 m/z= 599.73 (C44H29N3=599.23) 11 m/z= 599.73 (C44H29N3=599.23) 12 m/z= 675.83 (C50H33N3=675.26) 13 m/z= 570.63 (C39H27N2OP=570.18) 14 m/z= 651.77 (C46H29N5=651.24) 15 m/z= 650.78 (C47H30N4-650.24) 16 m/z= 650.78 (C47H30N4=650.24) 17 m/z= 727.87 (C52H33N5=727.27) 18 m/z= 726.88 (C53H34N4=726.27) 19 m/z= 726.88 (C53H34N4=726.27) 20 m/z= 803.96 (C58H37N5=803.30) 21 m/z = 802.98 (C59H38N4=802.31) 22 m/z= 651.77 (C46H29N5=651.24) 23 m/z= 620.69 (C43H29N2OP=620.20) 24 m/z= 677.81 (C48H31N5=677.25) 25 m/z= 676.82 (C49H32N4=676.26) 26 m/z= 676.82 (C49H32N4=676.26) 27 m/z= 753.90 (C54H35N5=753.28) 28 m/z= 752.91 (C55H36N4=752.29) 29 m/z= 752.92 (C55H36N4=752.29) 30 m/z= 830.00 (C60H39N5=829.31) 31 m/z= 829.01 (C61H40N4=828.32) 32 m/z= 829.01 (C61H40N4=828.32) 33 m/z= 677/81 (C48H31N5=677.25) 34 m/z= 646.73 (C45H31N2OP=646.21) 35 m/z= 601.71 (C42H27N5=601.22) 36 m/z= 600.72 (C43H28N4=600.23) 37 m/z= 600.72 (C43H28N4=600.23) 38 m/z= 677.81 (C48H31N5=677.25) 39 m/z= 676.82 (C49H32N4=676.26) 40 m/z= 676.82 (C49H32N4=676.26) 41 m/z= 753.90 (C54H35N5=753.28) 42 m/z= 752.92 (C55H36N4=752.29) 43 m/z= 601.71 (C42H27N5=601.22) 44 m/z= 570.63 (C39H27N2OP=570.18) 45 m/z= 651.77 (C46H29N5=651.24) 46 m/z= 650.78 (C47H30N4=650.24) 47 m/z= 650.78 (C47H30N4=650.24) 48 m/z= 727.87 (C52H33N5=727.27) 49 m/z= 726.88 (C53H34N4=726.27) 50 m/z= 726.88 (C53H34N4=726.27) 51 m/z= 803.96 (C58H37N5=803.30) 52 m/z= 802.98 (C59H38N4=802.30) 53 m/z = 651.77 (c46H29N5 = 651.24) 54 m/z= 650.78 (C47H30N4=650.24) 55 m/z= 650.78 (C47H30N4=650.24) 56 m/z= 727.87 (C52H33N5=727.27) 57 m/z= 726.88 (C53H34N4=726.27) 58 m/z= 726.88 (C53H34N4=726.27) 59 m/z= 803.96 (C58H37N5=803.30) 60 m/z=802.91 (C59H38N4=802.31) 61 m/z= 651.77 (C46H29N5=651.24) 62 m/z= 650.78 (C47H30N4=650.24) 63 m/z= 650.78 (C47H30N4=650.24) 64 m/z= 803.96 (C58H37N5=803.30) 65 m/z = 802.98 (C59H38N4=802.31) 66 m/z=751.89 (C54H33N5=751.27) 67 m/z= 750.90 (C55H34N4=750.27) 68 m/z= 750.90 (C55H34N4=750.27) 69 m/z= 750.90 (C55H34N4=750.27) 70 m/z= 753.90 (C54H35N5=753.28) 71 m/z= 677.81 (C48H31N5=677.25) 72 m/z= 676.82 (C49H32N4=676.26) 73 m/z= 676.82 (C49H32N4=676.26) 74 m/z= 676.82 (C49H32N4=676.26) 75 m/z= 752.92 (C55H36N4=752.29) 76 m/z= 752.92 (C55H36N4=752.29) 77 m/z= 690.81 (C48H30N6=690.25) 78 m/z= 766.90 (C54H34N6=766.28) 79 m/z= 766.90 (C54H32N6=766.28) 80 m/z= 689.82 (C49H31N5=689.25) 81 m/z= 765.92 (C55H35N5=765.28) 82 m/z= 765.92 (C55H35N5=765.28) 83 m/z= 689.82 (C49H31N5=689.25) 84 m/z= 765.92 (C55H35N5=765.28) 85 m/z= 765.92 (C55H35N5=765.28) 86 m/z= 765.92 (C55H35N5=765.28) 87 m/z= 765.92 (C55H35N5=765.28) 88 m/z= 717.87 (C51H35N5=717.28) 89 m/z= 716.88 (C52H36N4=716.29) 90 m/z= 716.88 (C52H36N4=716.29) 91 m/z= 716.88 (C52H36N4=716.29) 92 m/z= 793.97 (C57H39N5=793.32) 93 m/z= 792.98 (C58H40N4=792.32) 94 m/z= 792.98 (C58H40N4=792.32) 95 m/z= 792.98 (C58H40N4=792.32) 96 m/z= 626.72 (C43H26N6=626.22) 97 m/z= 625.73 (C44H27N5=625.22) 98 m/z= 625.73 (C44H27N5=625.22) 99 m/z= 625.73 (C44H27N5=625.22) 100 m/z= 702.82 (C49H30N6=702.25) 101 m/z= 702.82 (C49H30N6=702.25) 102 m/z= 701.83 (C50H31N5=701.25) 103 m/z= 701.83 (C50H31N5=701.25) 104 m/z= 777.93 (C56.35N5=777.28) 105 m/z= 701.83 (C50H31N5=701.25) 106 m/z= 776.94 (C57H36N4=776.29) 107 m/z= 700.84 (C51H32N4=700.26) 108 m/z= 753.90 (C54H35N5=753.28) 109 m/z= 752.92 (C55H36N4=752.29) 110 m/z= 651.77 (C46H29N5=651.24) 111 m/z= 650.78 (C47H30N4=650.24) 112 m/z= 650.78 (C47H30N4=650.24) 113 m/z= 803.96 (C58H37N5=803.30) 114 m/z = 802.98 (C59H38N4=802.31) 115 m/z = 802.98 (C59H38N4=802.31) 116 m/z= 803.96 (C58H37N5=803.30) 117 m/z = 802.98 (C59H38N4=802.31) 118 m/z = 802.98 (C59H38N4=802.31) 119 m/z= 777.93 (C56H35N5=777.28) 120 m/z= 879.07 (C65H42N4=878.34) 121 m/z= 651.77 (C46H29H5=651.24) 122 m/z= 650.78 (C47H30N4=650.24) 123 m/z= 650.78 (C47H30N4=650.24) 124 m/z= 727.87 (C52H33N5=727.27) 125 m/z= 726.88 (C53H34N4=726.27) 126 m/z= 726.88 (C53H34N4=726.27) 127 m/z= 803.96 (C58H37N5=803.30) 128 m/z = 802.98 (C59H38N4=802.31) 129 m/z= 651.77 (C46H29N5=651.24) 130 m/z= 620.69 (C43H29N2OP=620.20) 131 m/z= 727.87 (C52H33N5=727.27) 132 m/z= 726.88 (C53H34N4=726.27) 133 m/z= 726.88 (C53H34N4=726.27) 134 m/z= 601.71 (C42H27N5=601.22) 135 m/z= 600.72 (C43H28N4=600.23) 136 m/z= 600.72 (C43H28N4=600.23) 137 m/z= 677.81 (C48H31N5=677.25) 138 m/z= 676.82 (C49H32N4=676.26) 139 m/z= 676.82 (C49H32N4=676.26) 140 m/z= 753.90 (C54H35N5=753.28) 141 m/z= 752.92 (C55H36N4=752.29) 142 m/z= 601.71 (C42H27N5=601.22) 143 m/z= 651.77 (C46H29N5=651.24) 144 m/z= 650.78 (C47H30N4=650.24) 145 m/z= 650.78 (C47H30N4=650.24) 146 m/z= 727.87 (C52H33N5=727.27) 147 m/z= 726.88 (C53H34N4=726.27) 148 m/z= 726.88 (C53H34N4=726.27) 149 m/z= 803.96 (C58H37N5=803.30) 150 m/z = 802.98 (C59H38N4=802.31) 151 m/z= 651.77 (C46H29N5=651.24) 152 m/z=548.69 (C39H24N4=548.20) 153 m/z= 677.81 (C48H31N5=677.25) 154 m/z= 676.82 (C49H32N4=676.26) 155 m/z= 676.82 (C49H32N4=676.26) 156 m/z = 624.74 (C45H28N4=624.23) 157 m/z= 700.84 (C51H32N4=700.26) 158 m/z= 700.84 (C51H32N4=700.26) 159 m/z= 830.00 (C60H39N5=829.32) 160 m/z= 829.01 (C61H40N4=828.32) 161 m/z= 677.81 (C48H31N5=677.25) 162 m/z= 675.83 (C50H33N3=675.26) 163 m/z= 751.93 (C56H37N3=751.29) 164 m/z= 646.73 (C45H31N2OP=646.21) 165 m/z= 601.71 (C42H27N5=601.22) 166 m/z= 600.72 (C43H28N4=600.23) 167 m/z= 600.72 (C43H28N4=600.23) 168 m/z= 677.81 (C48H31N5=677.25) 169 m/z= 676.82 (C49H32N4=676.26) 170 m/z= 676.82 (C49H32N4=676.26) 171 m/z= 753.90 (C54H35N5=753.28) 172 m/z= 752.92 (C55H36N4=752.29) 173 m/z= 601.71 (C42H27N5=601.22) 174 m/z= 599.73 (C44H29N3=599.23) 175 m/z= 599.73 (C44H29N3=599.23) 176 m/z= 675.83 (C50H33N3=675.26) 177 m/z= 675.83 (C50H33N3=675.26) 178 m/z= 570.63 (C39H27N2OP=570.18) 179 m/z= 651.77 (C46H29N5=651.24) 180 m/z= 650.78 (C47H30N4=650.24) 181 m/z= 650.78 (C47H30N4=650.24) 182 m/z= 727.87 (C52H33N5=727.27) 183 m/z= 726.88 (C53H34N4=726.27) 184 m/z= 726.88 (C53H34N4=726.27) 185 m/z= 816.96 (C58H36N6=816.30) 186 m/z= 816.96 (C58H36N6=816.30) 187 m/z= 893.06 (C64H40N6=892.33) 188 m/z= 651.77 (C46H29N5=651.24) 189 m/z= 650.78 (C47H30N4=650.24) 190 m/z= 650.78 (C47H30N4=650.24) 191 m/z = 817.95 (C58H35N5O=817.28) 192 m/z = 816.96 (C59H36N4O=816.28) 193 m/z = 816.96 (C59H36N4O=816.28) 194 m/a = 651.77 (C46H29N5=651.24) 195 m/z= 650.78 (C47H30N4=650.24) 196 m/z= 650.78 (C47H30N4=650.24) 197 m/z= 727.87 (C52H33N5=727.27) 198 m/z= 726.88 (C53H34N4=726.27) 199 m/z= 726.88 (C53H34N4=726.27) 200 m/z= 834.01 (C58H35N5S=833.26) 201 m/z= 833.02 (C59H36N4S=832.26) 202 m/a= 756.92 (C53H32N4S=756.23) 203 m/z = 691.79 (C48H29N5O=691.23) 204 m/z = 691.79 (C48H29N4O=691.23) 205 m/z = 766.90 (C55H34N4O=766.27) 206 m/z = 766.90 (C55H34N4O=766.27) 207 m/z= 701.83 (C50H31N5=701.25) 208 m/z= 700.84 (C51H32N4=700.26) 209 m/z= 707.85 (C48H29N5S=707.21) 210 m/z= 706.86 (C49H30N4S=706.21) 211 m/z= 782.96 (C55H34N4S=782.25) 212 m/z= 782.96 (C55H34N4S=782.25) 213 m/z= 725.85 (C52H31N5=725.25) 214 m/z= 724.86 (C53H32N4=724.26) 215 m/z= 701.83 (C50H31N5=701.25) 216 m/z= 700.84 (C51H32N4=700.26) 217 m/z= 700.84 (C51H32N4=700.26) 218 m/z= 777.93 (C56H35N5=777.28) 219 m/z= 776.94 (C57H36N4=776.29) 220 m/z= 776.94 (C57H36N4=776.29) 221 m/z= 854.02 (C62H39N5=853.32) 222 m/z= 853.04 (C63H40N4=852.32) 223 m/z= 701.83 (C50H31N5=701.25) 224 m/z= 670.75 (C47H31N2OP=670.21) 225 m/z= 777.93 (C56H35N5=777.28) 226 m/z= 776.94 (C57H36N4=776.29) 227 m/z= 827.00 (C61H38N4=826.31) 228 m/z= 854.02 (C62H39N5=853.32) 229 m/z= 853.04 (C63H40N4=852.32) 230 m/z= 903.10 (C67H42N4=902.34) 231 m/z= 854.02 (C62H39N5=853.32) 232 m/z= 853.04 (C63H40N4=852.32) 233 m/z= 777.93 (C56H35N5=777.28) 234 m/z= 803.96 (C58H37N5=803.30) 235 m/z = 802.98 (C59H38N4=802.31) 236 m/z = 802.98 (C59H38N4=802.31) 237 m/z= 601.71 (C42H27N5=601.22) 238 m/z= 600.72 (C43H28N4=600.23) 239 m/z= (600.72 (C43H28N4=600.23) 240 m/z= 677.81 (C48H31N5=677.25) 241 m/z= 676.82 (C49H32N4=676.26) 242 m/z= 676.82 (C49H32N4=676.26) 243 m/z= 753.90 (C54H35N4=753.28) 244 m/z= 752.92 (C55H36N4=752.29) 245 m/z= 601.71 (C42H27N4=601.22) 246 m/z= 570.63 (C39H27N2OP=570.18) 247 m/z= 651.77 (C46H29N5=651.24) 248 m/z= 650.78 (C47H30N4=650.24) 249 m/z= 650.78 (C47H30N4=650.24) 250 m/z= 727.87 (C52H33N5=727.27) 251 m/z= 726.88 (C53H34N4=726.27) 252 m/z= 726.88 (C53H34N4=726.27) 253 m/z= 803.96 (C58H37N5=803.30) 254 m/z = 802.98 (C59H38N4=802.31) 255 m/z= 651.77 (C46H29N5=651.24) 256 m/z= 620.69 (C43H29N2OP=620.20) 257 m/z= 677.81 (C48H31N5=677.25) 258 m/z= 676.82 (C49H32N4=676.26) 259 m/z= 676.82 (C49H32N4=676.26) 260 m/z= 753.90 (C54H35N5=753.28) 261 m/z= 752.92 (C55H36N4=752.29) 262 m/z= 752.29 (C55H36N4=752.29) 263 m/z= 830.00 (C60H39N5=829.32) 264 m/z= 829.01 (C61H40N4=828.32) 265 m/z= 677.81 (C48H31N5=677.25) 266 m/z= 646.73 (C45H31N2OP=646.21) 267 m/z= 601.71 (C42H27N5=601.22) 268 m/z= 600.72 (C43H28N4=600.23) 269 m/z= 600.72 (C43H28N4=600.23) 270 m/z= 677.81 (C48H31N5=677.25) 271 m/z= 676.82 (C49H32N4=676.26) 272 m/z= 676.82 (C49H32N4=676.26) 273 m/z= 753.90 (C54H35N5=753.28) 274 m/z= 752.92 (C55H36N4=752.29) 275 m/z= 601.71 (C42H27N5=601.22) 276 m/z= 570.63 (C39H27N2OP=570.18) 277 m/z= 827.99 (C60H37N5=827.30) 278 m/z= 904.08 (C66H41N5=903.33) 279 m/z= 904.08 (C66H41N5=903.33) 280 m/z= 827.00 (C61H38N4=826.31) 281 m/z= 903.10 (C67H42N4=902.32) 282 m/z= 903.10 (C67H42N4=902.23) 283 m/z = 817.95 (C58H35N5O=817.28) 284 m/z= 793.97 (C57H39N5=793.32) 285 m/z= 792.98 (C58H40N4=792.32) 286 m/z= 792.98 (C58H40N4=792.32) 287 m/z= 792.98 (C58H40N4=792.32) 288 m/z= 702.82 (C49H30N6=702.25) 289 m/z= 701.83 (C50H31N5=701.25) 290 m/z= 701.83 (C50H31N5=701.25) 291 m/z= 701.83 (C50H31N5=701.25) 292 m/z= 778.91 (C55H34N6=778.28) 293 m/z= 778.91 (C55H34N6=778.28) 294 m/z= 777.93 (C56H35N5=777.28) 295 m/z= 777.93 (C56H35N5=777.28) 296 m/z= 854.02 (C62H39N5=853.32) 297 m/z= 777.93 (C56H35N5=777.28) 298 m/z= 853.04 (C63H40N4=852.32) 299 m/z= 776.94 (C57H36N4=776.29) 300 m/z= 830.00 (C60H39N5=829.32) 301 m/z= 829.01 (C61H40N4=828.32) 302 m/z= 880.06 (C64H41N5=879.33) 303 m/z= 879.07 (C65H42N4=878.34) 304 m/z= 880.06 (C64H41N5=879.33) 305 m/z= 878.05 (C64H39N5=877.32) 306 m/z = 816.96 (C59H36N4O=816.28) 307 m/z = 893.06 (C65H40N4O=829.32) 308 m/z = 894.05 (C64H39N5O=893.31) 309 m/z= 601.71 (C42H27N5=601.22) 310 m/z= 600.72 (C43H28N4=600.23) 311 m/z= 600.72 (C43H28N4=600.23) 312 m/z= 677.81 (C48H31N5=677.25) 313 m/z= 752.92 (Cm55H36N4=752.29) 314 m/z= 752.92 (c55H36N4=752.29) 315 m/z= 753.90 C (54H35N5=753.28) 316 m/z= 752.92 (C55H36N4=752.29) 317 m/z= 677.82 (C48H31N5=677.25) 318 m/z= 570.63 (C39H27N2OP=570.18) 319 m/z= 601.71 (C42H27N5=601.22) 320 m/z= 600.72 (C43H28N4=600.23) 321 m/z= 600.72 (C43H28N4=600.23) 322 m/z= 677.81 (C48H31N5=677.25) 323 m/z= 676.82 (C49H32N4=676.26) 324 m/z= 676.82 (C49H32N4=676.26) 325 m/z= 753.90 (C54H35N5=753.28) 326 m/z= 752.92 (C55H36N4=752.29) 327 m/z= 601.71 (C42H27N5=601.22) 328 m/z= 570.63 (C39H27N2OP=570.18) 329 m/z= 651.77 (C46H29N5=651.24) 330 m/z= 650.78 (C47H30N4=650.24) 331 m/z=650.78 (C47H30N4=650.24). 332 m/z= 727.87 (C52H33N5=727.27) 333 m/z= 726.88 (C53H34N4=726.27) 334 m/z= 726.88 (C53H34N4=726.27) 335 m/z= 803.96 (C58H37N5=803.30) 336 m/z = 802.98 (C59H38N4=802.31) 337 m/z= 651.77 (C46H29N5=651.24) 338 m/z= 620.69 (C43H29N2OP=620.20) 339 m/z= 677.81 (C548H31N5=677.25) 340 m/z= 676.82 (C49H32N4=676.26) 341 m/z= 676.82 (C49H32N4=676.26) 342 m/z= 753.90 (C54H35N5=753.28) 343 m/z= 752.92 (C55H36NN4=752.29) 344 m/z= 752.92 (C55H36N4=752.29) 345 m/z= 830.00 (C60H39N5=829.32) 346 m/z= 829.01 (C61H40N4=828.32) 347 m/z= 677.81 (C48H31N5=677.25) 348 m/z= 646.73 (C45H31N2OP=646.21) 349 m/z= 601.71 (C42H27N5=601.22) 350 m/z= 600.72 (C43H28N4=600.23) 351 m/z= 600.72 (C43H28N4=600.23) 352 m/z= 677.81 (C48H31N5=677.25) 353 m/z= 676.82 (C49H32N4=676.26) 354 m/z= 676.82 (C49H32N4=676.26) 355 m/z= 753.90 (C54H35N5=753.28) 356 m/z= 752.92 (C55H36N4=752.29) 357 m/z= 601.71 (C42H27N5=601.22) 358 m/z= 599.73 (C44H29N3=599.23) 359 m/z= 599.73 (C44H29N3=599.23) 360 m/z= 570.63 (C39H27N2OP=570.18) 361 m/z= 651.77 (C46H29N5=651.24) 362 m/z= 650.78 (C47H30N4=650.24) 363 m/z= 650.78 (C47H30N4=650.24) 364 m/z= 651.77 (C46H29N5=651.24) 365 m/z= 650.78 (C47H30N4=6050.24) 366 m/z= 650.78 (C47H30N4=650.24) 367 m/z= 651.77 (C46H29N5=651.24) 368 m/z= 650.78 (C47H30N4=650.24) 369 m/z= 650.78 (C47H30N4=650.24) 370 m/z= 548.64 (C39H24N4=548.20) 371 m/z= 624.74 (C45H28N4=624.23) 372 m/z= 624.74 (C45H28N4=624.23) 373 m/z= 700.84 (C51H32N4=700.26) 374 m/z= 700.84 (C51H32N4=700.26) 375 m/z= 760.94 (C58H36N2=760.28) 376 m/z= 760.94 (C58H36N2=760.28) 377 m/z= 811.00 (C62H38N2=810.30) 378 m/z= 752.92 (C55H36N4=752.29) 379 m/z= 853.90 (C54H35N5=753.28) 380 m/z= 752.92 (C55H36N4=752.29) 381 m/z= 752.92 (C55H36N4=752.29) 382 m/z= 753.90 (C54H35N5=753.28) 383 m/z = 802.98 (C59H38N4=802.31) 384 m/z= 803.96 (C58H37N5=803.30) 385 m/z= 677.81 (C48H31N5=677.25) 386 m/z= 725.89 (C54H35N3=725.28) 387 m/z= 725.89 (C54H35N3=725.28) 388 m/z= 725.85 (C52H31N5=725.25) 389 m/z= 726.88 (C53H34N4=726.27) 390 m/z= 724.86 (C53H32N4=724.26) 391 m/z= 827.99 (C60H37N5=827.30) 392 m/z= 827.00 (C61H38N4=826.31) 393 m/z= 827.00 (C61H38N4=826.31) 394 m/z= 854.02 (C62H39N5=853.32) 395 m/z= 853.04 (C63H40N4=852.32) 396 m/z= 910.11 (C64H39N5S=909.29) 397 m/z= 815.98 (C59H37N5=815.30) 398 m/z= 843.04 (C62H42N4=842.34) 399 m/z= 727.87 (C52H33N5=727.27) 400 m/z= 776.94 (C57H36N4=776.29) 401 m/z= 650.78 (C47H30N4=650.24)

< Experimental example 1> Fabrication of organic light emitting device

1) Fabrication of an organic light emitting device

The transparent electrode ITO thin film obtained from glass for OLED (manufactured by Samsung-Corning) was ultrasonically washed for 5 minutes each using trichloroethylene, acetone, ethanol, and distilled water sequentially, and then stored in isopropanol and used.

Next, the ITO substrate is installed in the substrate folder of the vacuum deposition equipment, and the following 4,4',4"-tris(N,N-(2-naphthyl)-phenylamino)triphenylamine ( 4,4',4"-tris(N,N-(2-naphthyl)-phenylamino)triphenyl amine: 2-TNATA) was added.

Then, after evacuating the chamber until the vacuum degree reached 10-6 torr, an electric current was applied to the cell to evaporate 2-TNATA, and a hole injection layer having a thickness of 600 Å was deposited on the ITO substrate.

The following N,N'-bis(α-naphthyl)-N,N'-diphenyl-4,4'-diamine (N,N'-bis(α-naphthyl)-N, N'-diphenyl-4,4'-diamine: NPB) was added, and a current was applied to the cell to evaporate and deposit a hole transport layer with a thickness of 300 Å on the hole injection layer.

After the hole injection layer and the hole transport layer were formed in this way, a blue light emitting material having the following structure was deposited as a light emitting layer thereon. Specifically, H1, a blue light-emitting host material, was vacuum-deposited to a thickness of 200 Å in one cell in the vacuum deposition equipment, and D1, a blue light-emitting dopant material, was vacuum-deposited 5% compared to the host material thereon.

Then, as an electron transport layer, one of the compounds listed in Table 15 below was deposited to a thickness of 300 Å.

As an electron injection layer, lithium fluoride (LiF) was deposited to a thickness of 10 Å, and an Al cathode was deposited to a thickness of 1,000 Å to fabricate an OLED device.

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

Table 15 shows the results of measuring the driving voltage, luminous efficiency, color coordinates (CIE), and lifespan of the blue organic light emitting diode manufactured according to the present invention.

compound drive voltage
(V) luminous efficiency
(cd/A) CIE
(x, y) life span
(T95) Comparative Example 1 E1 5.70 6.00 (0.134, 0.102) 20 Comparative Example 2 A 5.33 4.21 (0.134, 0.100) 12 Comparative Example 3 B 5.31 4.10 (0.134, 0.100) 8 Comparative Example 4 C 5.26 4.98 (0.134, 0.100) 9 Example 1 One 5.45 6.21 (0.134, 0.101) 37 Example 2 2 5.44 6.22 (0.134, 0.102) 34 Example 3 4 5.62 5.95 (0.134, 0.103) 42 Example 4 6 4.98 6.44 (0.134, 0.100) 40 Example 5 7 5.62 6.38 (0.134, 0.100) 35 Example 6 8 4.72 6.20 (0.134, 0.102) 48 Example 7 16 5.45 6.44 (0.134, 0.103) 33 Example 8 21 5.44 6.34 (0.134, 0.102) 36 Example 9 26 5.62 6.20 (0.134, 0.101) 39 Example 10 28 5.40 6.12 (0.134, 0.103) 44 Example 11 31 5.60 6.21 (0.134, 0.102) 43 Example 12 33 5.45 6.22 (0.134, 0.101) 37 Example 13 35 4.98 6.38 (0.134, 0.101) 42 Example 14 37 5.62 6.20 (0.134, 0.100) 45 Example 15 39 4.72 6.12 (0.134, 0.100) 43 Example 16 41 4.91 6.21 (0.134, 0.101) 41 Example 17 42 4.98 6.22 (0.134, 0.100) 40 Example 18 45 5.62 5.95 (0.134, 0.100) 33 Example 19 59 5.44 6.13 (0.134, 0.102) 25 Example 20 65 5.38 6.38 (0.134, 0.101) 39 Example 21 66 5.38 6.20 (0.134, 0.103) 40 Example 22 68 5.39 6.25 (0.134, 0.102) 41 Example 23 70 4.96 6.21 (0.134, 0.101) 37 Example 24 73 4.91 6.22 (0.134, 0.102) 33 Example 25 74 4.91 6.12 (0.134, 0.101) 42 Example 26 77 4.98 6.51 (0.134, 0.101) 39 Example 27 78 5.62 6.21 (0.134, 0.100) 41 Example 28 88 5.39 5.95 (0.134, 0.101) 34 Example 29 93 5.38 5.85 (0.134, 0.101) 35 Example 30 96 5.38 6.38 (0.134, 0.101) 39 Example 31 100 5.38 6.20 (0.134, 0.103) 40 Example 32 101 5.39 6.42 (0.134, 0.102) 43 Example 33 104 4.96 6.21 (0.134, 0.101) 37 Example 34 105 4.91 6.22 (0.134, 0.102) 33 Example 35 108 4.91 6.12 (0.134, 0.101) 37 Example 36 115 5.38 6.38 (0.134, 0.101) 39 Example 37 117 5.38 6.20 (0.134, 0.103) 40 Example 38 120 5.39 6.62 (0.134, 0.102) 43 Example 39 131 4.96 6.21 (0.134, 0.101) 37 Example 40 132 4.91 6.22 (0.134, 0.102) 33 Example 41 134 4.91 6.12 (0.134, 0.101) 42 Example 42 135 4.98 6.51 (0.134, 0.101) 39 Example 43 137 5.62 6.21 (0.134, 0.100) 41 Example 44 139 5.39 5.95 (0.134, 0.101) 34 Example 45 141 5.10 6.88 (0.134, 0.100) 41 Example 46 143 5.38 6.38 (0.134, 0.101) 39 Example 47 148 5.38 6.20 (0.134, 0.103) 40 Example 48 149 5.11 6.62 (0.134, 0.102) 43 Example 49 155 4.95 6.22 (0.134, 0.100) 41 Example 50 157 4.98 6.92 (0.134, 0.100) 40 Example 51 159 5.62 5.98 (0.134, 0.100) 39 Example 52 161 4.75 6.53 (0.134, 0.102) 40 Example 53 165 4.72 6.35 (0.134, 0.102) 42 Example 54 168 4.91 6.93 (0.134, 0.100) 45 Example 55 169 4.93 6.95 (0.134, 0.100) 40 Example 56 187 4.98 6.21 (0.134, 0.100) 40 Example 57 192 5.62 5.98 (0.134, 0.100) 34 Example 58 195 5.31 6.53 (0.134, 0.102) 35 Example 59 203 4.79 6.55 (0.134, 0.102) 48 Example 60 205 5.40 6.13 (0.134, 0.101) 39 Example 61 209 5.44 6.04 (0.134, 0.100) 41 Example 62 212 5.39 6.01 (0.134, 0.101) 34 Example 63 213 4.96 6.88 (0.134, 0.100) 45 Example 64 218 4.95 6.95 (0.134, 0.100) 41 Example 65 219 4.98 6.22 (0.134, 0.100) 40 Example 66 222 5.62 5.98 (0.134, 0.100) 33 Example 67 228 4.75 6.53 (0.134, 0.102) 40 Example 68 229 5.40 6.12 (0.134, 0.101) 39 Example 69 234 5.44 6.21 (0.134, 0.100) 41 Example 70 236 5.39 6.20 (0.134, 0.101) 36 Example 71 237 5.39 6.88 (0.134, 0.100) 45 Example 72 238 5.21 6.93 (0.134, 0.100) 43 Example 73 240 5.13 6.95 (0.134, 0.100) 41 Example 74 242 5.05 6.22 (0.134, 0.100) 40 Example 75 248 4.91 5.98 (0.134, 0.100) 33 Example 76 250 4.72 6.53 (0.134, 0.102) 48 Example 77 251 5.40 6.12 (0.134, 0.101) 39 Example 78 253 5.43 6.53 (0.134, 0.102) 48 Example 79 259 5.33 6.53 (0.134, 0.102) 48 Example 80 263 4.91 6.98 (0.134, 0.100) 43 Example 81 264 4.91 6.12 (0.134, 0.100) 35 Example 82 267 4.98 6.22 (0.134, 0.100) 40 Example 83 270 5.62 5.98 (0.134, 0.100) 38 Example 84 273 4.72 6.53 (0.134, 0.102) 48 Example 85 277 4.72 6.33 (0.134, 0.102) 41 Example 86 278 4.63 6.53 (0.134, 0.102) 48 Example 87 282 4.91 6.82 (0.134, 0.100) 43 Example 88 283 4.99 6.95 (0.134, 0.100) 41 Example 89 284 4.98 6.22 (0.134, 0.100) 40 Example 90 288 5.62 5.98 (0.134, 0.100) 33 Example 91 290 5.43 6.53 (0.134, 0.102) 41 Example 92 292 4.88 6.89 (0.134, 0.102) 42 Example 93 293 5.40 6.12 (0.134, 0.101) 39 Example 94 296 5.41 5.89 (0.134, 0.100) 41 Example 95 299 5.39 6.01 (0.134, 0.101) 32 Example 96 300 4.63 6.53 (0.134, 0.102) 48 Example 97 303 4.91 6.82 (0.134, 0.100) 43 Example 98 304 4.72 6.53 (0.134, 0.102) 38 Example 99 305 4.91 6.78 (0.134, 0.100) 43 Example 100 306 4.90 6.95 (0.134, 0.100) 41 Example 101 308 4.98 6.22 (0.134, 0.100) 40 Example 102 313 5.62 5.98 (0.134, 0.100) 33 Example 103 321 5.21 6.03 (0.134, 0.101) 33 Example 104 324 5.39 6.01 (0.134, 0.101) 32 Example 105 325 5.33 6.04 (0.134, 0.101) 33 Example 106 332 4.91 6.93 (0.134, 0.100) 43 Example 107 336 4.77 6.95 (0.134, 0.100) 41 Example 108 339 4.98 6.22 (0.134, 0.100) 40 Example 109 343 5.03 5.98 (0.134, 0.100) 39 Example 110 345 4.71 6.51 (0.134, 0.102) 41 Example 111 352 4.72 6.53 (0.134, 0.102) 48 Example 112 353 4.74 6.59 (0.134, 0.102) 45 Example 113 363 5.42 6.13 (0.134, 0.101) 39 Example 114 365 4.72 6.53 (0.134, 0.102) 38 Example 115 367 4.91 6.78 (0.134, 0.100) 43 Example 116 370 5.44 5.89 (0.134, 0.100) 41 Example 117 372 5.36 6.01 (0.134, 0.101) 32 Example 118 373 4.96 6.82 (0.134, 0.100) 45 Example 119 374 4.91 6.93 (0.134, 0.100) 43 Example 120 376 4.95 6.95 (0.134, 0.100) 41 Example 121 379 5.34 6.11 (0.134, 0.101) 38 Example 122 380 4.86 6.76 (0.134, 0.100) 45 Example 123 381 4.94 6.73 (0.134, 0.102) 42 Example 124 382 4.91 6.55 (0.134, 0.100) 46 Example 125 384 5.31 6.29 (0.134, 0.100) 42 Example 126 388 5.22 6.11 (0.134, 0.100) 35 Example 127 391 5.33 6.24 (0.134, 0.102) 41 Example 128 395 5.31 6.57 (0.134, 0.102) 46 Example 129 396 4.72 6.53 (0.134, 0.102) 35 Example 130 397 4.79 6.55 (0.134, 0.102) 48 Example 131 398 5.40 6.13 (0.134, 0.101) 39 Example 132 399 5.12 5.89 (0.134, 0.100) 41 Example 133 400 5.31 6.01 (0.134, 0.101) 34 Example 134 401 5.11 6.88 (0.134, 0.100) 45

As can be seen from the results of Table 15, the organic light-emitting device using the electron transport layer material of the blue organic light-emitting device of the present invention has a lower driving voltage and significantly improved luminous efficiency and lifespan compared to Comparative Example 1.

In addition, it can be seen that the luminous efficiency and lifespan are superior to those of Comparative Examples 2 to 4. In particular, it can be seen that in the compounds B and C of Comparative Examples 3 and 4, one substituent is substituted in the core structure of the present application. When one substituent is substituted, it can be confirmed that the thermal stability is lower than that of the disubstituted compound, such as the heterocyclic compound of Formula 1, and the lifespan is particularly reduced.

< Experimental example 2> Fabrication of organic light emitting device

1) Fabrication of an organic light emitting device

The transparent electrode ITO thin film obtained from glass for OLED (manufactured by Samsung-Corning) was ultrasonically washed for 5 minutes each using trichloroethylene, acetone, ethanol, and distilled water sequentially, and then stored in isopropanol and used.

Next, the ITO substrate is installed in the substrate folder of the vacuum deposition equipment, and the following 4,4',4"-tris(N,N-(2-naphthyl)-phenylamino)triphenylamine ( 4,4',4"-tris(N,N-(2-naphthyl)-phenylamino)triphenyl amine: 2-TNATA) was added.

Then, after evacuating the chamber until the vacuum degree reached 10-6 torr, an electric current was applied to the cell to evaporate 2-TNATA, and a hole injection layer having a thickness of 600 Å was deposited on the ITO substrate.

The following N,N'-bis(α-naphthyl)-N,N'-diphenyl-4,4'-diamine (N,N'-bis(α-naphthyl)-N, N'-diphenyl-4,4'-diamine: NPB) was added, and a current was applied to the cell to evaporate and deposit a hole transport layer with a thickness of 300 Å on the hole injection layer.

After the hole injection layer and the hole transport layer were formed in this way, a blue light emitting material having the following structure was deposited as a light emitting layer thereon. Specifically, H1, a blue light-emitting host material, was vacuum-deposited to a thickness of 200 Å in one cell in the vacuum deposition equipment, and D1, a blue light-emitting dopant material, was vacuum-deposited 5% compared to the host material thereon.

Then, as an electron transport layer, a compound of the following structural formula E1 was deposited to a thickness of 300 Å.

As an electron injection layer, lithium fluoride (LiF) was deposited to a thickness of 10 Å, and an Al cathode was deposited to a thickness of 1,000 Å to fabricate an OLED device.

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

In Experimental Example 2, the same as in Experimental Example 2, except that the thickness of the electron transport layer E1 was formed at 250 Å, and then a hole blocking layer was formed with a thickness of 50 Å of the compound shown in Table 16 on the electron transport layer. to fabricate an organic electroluminescent device.

Table 16 shows the results of measuring the driving voltage, luminous efficiency, color coordinates (CIE), and lifespan of the blue organic light emitting diode manufactured according to the present invention.

compound drive voltage
(V) luminous efficiency
(cd/A) CIE
(x, y) life span
(T95) Comparative Example 5 - 5.51 5.94 (0.134, 0.100) 31 Comparative Example 6 A 5.21 4.12 (0.134, 0.101) 12 Comparative Example 7 B 5.33 4.01 (0.134, 0.100) 11 Comparative Example 8 C 5.31 4.01 (0.134, 0.100) 11 Example 135 2 5.14 6.89 (0.134, 0.102) 54 Example 136 8 5.34 6.58 (0.134, 0.101) 44 Example 137 68 5.38 6.51 (0.134, 0.103) 47 Example 138 77 5.11 6.75 (0.134, 0.102) 46 Example 139 104 5.42 6.21 (0.134, 0.101) 54 Example 140 108 5.13 6.63 (0.134, 0.102) 52 Example 141 120 5.05 6.66 (0.134, 0.101) 49 Example 142 205 5.42 6.13 (0.134, 0.101) 41 Example 143 212 5.14 6.89 (0.134, 0.102) 54 Example 144 213 5.34 6.58 (0.134, 0.101) 44 Example 145 273 5.38 6.51 (0.134, 0.103) 47 Example 146 277 5.11 6.75 (0.134, 0.102) 46 Example 147 288 5.32 6.25 (0.134, 0.101) 55 Example 148 388 5.14 6.46 (0.134, 0.102) 51 Example 149 391 5.04 6.62 (0.134, 0.101) 55 Example 150 395 5.32 6.25 (0.134, 0.101) 55

As can be seen from the results of Table 16, the organic light emitting device using the hole blocking layer material of the blue organic light emitting device of the present invention had a lower driving voltage and significantly improved luminous efficiency and lifespan compared to Comparative Example 5. In addition, compared to Comparative Examples 6 to 8, the luminous efficiency and lifespan were significantly improved. In particular, it can be seen that in the compounds B and C of Comparative Examples 7 and 8, one substituent is substituted in the core structure of the present application. When one substituent is substituted, it was confirmed that the thermal stability was lower than that of the disubstituted compound, such as the heterocyclic compound of Formula 1, and the lifespan was particularly reduced.

The reason for this result is that, since the compound of Formula 1 is a bipolar type having both p-type and n-type, hole leakage can be prevented and excitons can be effectively confined in the emission layer.

< Experimental example 3> Fabrication of organic light emitting device

1) Fabrication of an organic light emitting device

A glass substrate coated with a thin film of ITO to a thickness of 1500 Å was washed with distilled water and ultrasonic waves. After washing with distilled water, it was ultrasonically washed with a solvent such as acetone, methanol, isopropyl alcohol, etc., dried, and then UVO-treated for 5 minutes using UV in a UV washer. After transferring the substrate to a plasma cleaner (PT), plasma treatment was performed to remove the ITO work function and residual film in a vacuum state, and the substrate was transferred to a thermal deposition equipment for organic deposition.

An organic material was formed in a two-stack WOLED (White Orgainc Light Device) structure on the ITO transparent electrode (anode). In the first stack, a hole transport layer was formed by thermal vacuum deposition of TAPC to a thickness of 300 Å. After the hole transport layer was formed, a light emitting layer was deposited thereon by thermal vacuum deposition as follows. The emission layer was deposited at 300 Å by doping 8% of FIrpic with a blue phosphorescent dopant on TCz1 as a host. The electron transport layer was formed to be 400 Å using TmPyPB, and then 20% Cs ₂ CO ₃ was doped to the compound shown in Table 17 as a charge generation layer to form 100 Å.

The second stack was first formed by thermal vacuum deposition of MoO ₃ to a thickness of 50 Å to form a hole injection layer. The hole transport layer, which is a common layer, was formed by doping TAPC with 20% MoO ₃ to form 100 Å, and then depositing TAPC ₃₀₀ Å to form a light emitting layer thereon. After 300 Å deposition, 600 Å was formed using TmPyPB as an electron transport layer. Finally, lithium fluoride (LiF) is deposited on the electron transport layer to a thickness of 10 Å to form an electron injection layer, and then an aluminum (Al) cathode is deposited to a thickness of 1,200 Å on the electron injection layer to form a cathode. A light emitting device was manufactured.

On the other hand, all organic compounds required for manufacturing OLED devices were vacuum sublimated and purified under 10 ^-6 to 10 ^-8 torr for each material, respectively, and used for OLED manufacturing.

The results of measuring the driving voltage, luminous efficiency, color coordinate (CIE), and lifetime (T95) of the white organic light emitting diode manufactured according to the present invention are shown in Table 17 below.

compound drive voltage
(V) luminous efficiency
(cd/A) CIE
(x, y) life span
(T95) Comparative Example 9 TmPyPB 8.57 57.61 (0.212, 0.433) 22 Comparative Example 10 BBQB 8.43 58.11 (0.220, 0,429) 22 Comparative Example 11 TBQB 8.47 58.90 (0.222, 0,430) 26 Comparative Example 12 A 7.21 41.11 (0.201, 0.398) 9 Comparative Example 13 B 7.28 41.12 (0.189, 0.388) 6 Comparative Example 14 C 7.22 41.01 (0.188, 0.388) 6 Example 1 One 7.24 61.88 (0.209, 0.415) 23 Example 2 33 6.98 60.58 (0.224, 0.429) 30 Example 3 66 6.89 72.10 (0.243, 0.442) 38 Example 4 78 6.71 69.65 (0.205, 0.411) 41 Example 5 101 6.49 71.44 (0.243, 0.442) 39 Example 6 152 7.34 58.29 (0.209, 0.419) 30 Example 7 156 7.21 59.33 (0.210, 0.420) 29 Example 8 157 7.44 69.65 (0.205, 0.411) 33 Example 9 158 7.41 71.44 (0.243, 0.442) 35 Example 10 296 6.95 58.29 (0.209, 0.419) 34 Example 11 299 7.21 59.33 (0.210, 0.420) 29 Example 12 370 6.71 69.65 (0.205, 0.411) 41 Example 13 372 6.49 71.44 (0.243, 0.442) 39 Example 14 373 6.95 58.29 (0.209, 0.419) 34

As can be seen from the results of Table 17, the organic light-emitting device using the charge generation layer material of the two-stack white organic light-emitting device of the present invention had a lower driving voltage and improved luminous efficiency compared to Comparative Examples 9 to 11. . Also, compared to Comparative Examples 12 to 14, the driving voltage is similar, but the luminous efficiency and lifespan are significantly improved.

In particular, it can be seen that in the compounds B and C of Comparative Examples 13 and 14, one substituent is substituted in the core structure of the present application. When one substituent is substituted, it can be confirmed that the lifespan is particularly reduced due to lower thermal stability than the disubstituted compound, such as the heterocyclic compound of Formula 1 herein.

100: substrate
200: positive electrode
300: organic 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 (15)

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

In Formula 1,
R ₂ To R ₅ Are the same as or different from each other, and each independently hydrogen; or deuterium, or two or more groups adjacent to each other combine with each other to form a C2 to C40 aromatic hydrocarbon ring,
R _a is hydrogen,
Ar ₁ is represented by -(L1)p-(Z1)q,
Ar ₂ is represented by -(L2)r-(Z2)s,
L1 and L2 are the same as or different from each other, and each independently a C6 to C40 arylene group; Or a C2 to C40 heteroarylene group,
Wherein Z1 and Z2 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; -CN; a substituted or unsubstituted C6 to C40 aryl group; a substituted or unsubstituted C2 to C40 heteroaryl group; And -P(=O)RR' is selected from the group consisting of,
Wherein R and R' are the same as or different from each other, and are each independently a C6 to C40 aryl group,
p and r are integers from 1 to 3,
q and s are integers from 1 to 3,
n is an integer from 0 to 4. The method according to claim 1, "substituted or unsubstituted" means C1 to C60 straight-chain 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 that it is substituted or unsubstituted with one or more substituents, or substituted or unsubstituted with a substituent to which two or more substituents selected from the above substituents are connected,
Wherein R, R' and R" are a C6 to C40 aryl group. delete delete delete The heterocyclic compound according to claim 1, wherein Formula 1 is represented by any one of Formulas 2 to 9:
[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

In Formulas 2 to 9,
Definitions of R _{a ,} Ar ₁ , Ar ₂ , R ₂ to R ₅ and n are the same as those of Formula 1 above. The heterocyclic compound according to claim 1, wherein Formula 1 is represented by any one of the following compounds:

a first electrode; a second electrode provided to face the first electrode; and at least one organic material layer provided between the first electrode and the second electrode, wherein at least one of the organic material layers is a heterocyclic compound according to any one of claims 1, 2, 6 and 7 An organic light emitting device comprising a. 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 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 that further comprises one 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. The method according to claim 8, wherein the organic light emitting device comprises a first electrode, a first stack provided on the first electrode and including a first light emitting layer, a charge generating layer provided on the first stack, and on the charge generating layer An organic light-emitting device comprising a second stack provided in the second stack and including a second light-emitting layer, and a second electrode provided on the second stack. The organic light emitting diode of claim 13 , wherein the charge generating layer includes the heterocyclic compound. The organic light-emitting device of claim 13 , wherein the charge generation layer is an N-type charge generation layer, and the charge generation layer includes the heterocyclic compound.

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