KR102155883B1 - 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 an organic light emitting device including the same TECHNICAL FIELD [0002] 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.

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

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

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

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

U.S. Patent 4,356,429

The present 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 Formula 1 is provided.

[Formula 1]

In Formula 1,

X ₁ to X ₃ are the same as or different from each other, and each independently N; P; Or CR _x, and at least one of X ₁ to X ₃ includes N,

X is O or S,

L ₁ is a direct bond; A substituted or unsubstituted arylene group; Or a substituted or unsubstituted heteroarylene group,

R ₁ and R ₂ are the same as or different from each other, and each independently hydrogen; heavy hydrogen; -CN; A substituted or unsubstituted alkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,

Ar ₁ is deuterium; Halogen group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,

R _a , R _b and R _x 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 selected from the group consisting of a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or an amine group unsubstituted or substituted with 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, 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 unsubstituted aryl group; or substituted or It is an unsubstituted heteroaryl group,

m is an integer from 0 to 4,

n is an integer from 0 to 2,

k is an integer from 0 to 5,

When m is 2 or more, 2 or more R _a are the same as or different from each other,

When n is 2, two R _b are the same as or different from each other,

When k is 2 or more, 2 or more L _1s are the same as or different from each other.

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

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

Specifically, the compound may be used alone as a light-emitting material, or as a host material or a dopant material for the light-emitting layer. When the compound represented by Formula 1 is used in the organic material layer, the driving voltage of the device is lowered, the light efficiency is improved, and the lifespan characteristics of the device may be improved by thermal stability of the compound.

1 to 3 are diagrams each schematically showing a stacked structure of an organic light emitting diode according to an exemplary embodiment of the present application.
4 is a diagram of a heterocyclic compound represented by Chemical Formula 2 according to an exemplary embodiment of the present application.

Hereinafter, the present application will be described in detail.

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

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

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

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

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

In the present specification, the alkoxy group may be linear, branched or cyclic. The number of carbon atoms of the alkoxy group is not particularly limited, but it is preferably 1 to 20 carbon atoms. Specifically, methoxy, ethoxy, n-propoxy, isopropoxy, 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 having 3 to 60 carbon atoms, and may be further substituted by other substituents. Here, the polycyclic refers to a group in which a cycloalkyl group is directly connected or condensed with another ring group. Here, the other cyclic group may be a cycloalkyl group, but may be a different type of cyclic group, such as a heterocycloalkyl group, an aryl group, or a heteroaryl group. The number of carbon atoms of the cycloalkyl group may be 3 to 60, specifically 3 to 40, and more specifically 5 to 20. Specifically, a cyclopropyl group, cyclobutyl group, cyclopentyl group, 3-methylcyclopentyl group, 2,3-dimethylcyclopentyl group, cyclohexyl group, 3-methylcyclohexyl group, 4-methylcyclohexyl group, 2 ,3-dimethylcyclohexyl group, 3,4,5-trimethylcyclohexyl group, 4-tert-butylcyclohexyl group, cycloheptyl group, cyclooctyl group, and the like, but are not limited thereto.

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

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

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

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

,

,

,

,

,

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

,

,

,

,

,

And the like, but is not limited thereto.

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

In the present specification, the amine group is a monoalkylamine group; Monoarylamine group; Monoheteroarylamine group; -NH ₂ ; Dialkylamine group; Diarylamine group; Diheteroarylamine group; Alkylarylamine group; Alkylheteroarylamine group; And it may be selected from the group consisting of an arylheteroarylamine group, carbon number is not particularly limited, but is preferably 1 to 30. Specific examples of the amine group include methylamine group, dimethylamine group, ethylamine group, diethylamine group, phenylamine group, naphthylamine group, biphenylamine group, dibiphenylamine group, anthracenylamine group, 9- Methyl-anthracenylamine group, diphenylamine group, phenylnaphthylamine group, ditolylamine group, phenyltolylamine group, triphenylamine group, biphenylnaphthylamine group, phenylbiphenylamine group, biphenylfluore There are nilamine group, phenyltriphenylenylamine group, biphenyltriphenylenylamine group, and the like, but are not limited thereto.

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

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

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

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

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

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

In the exemplary embodiment of the present application, X ₁ to X ₃ are the same as or different from each other, and each independently N; P; Or CR _x, and at least one of X ₁ to X ₃ includes N.

In the exemplary embodiment of the present application, R _x is 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 selected from the group consisting of a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or an amine group unsubstituted or substituted with a substituted or unsubstituted heteroaryl group Or, two or more groups adjacent to each other may be bonded to each other to form a substituted or unsubstituted aliphatic or aromatic hydrocarbon ring.

In another exemplary embodiment, R _x is hydrogen; Or deuterium.

In the exemplary embodiment of the present application, X ₁ is N; Or it can be CH.

In the exemplary embodiment of the present application, X ₂ is N; Or it can be CH.

In the exemplary embodiment of the present application, X ₃ is N; Or it can be CH.

In the exemplary embodiment of the present application, at least two or more of X ₁ to X ₃ may be N.

In the exemplary embodiment of the present application, L ₁ is a direct bond; A substituted or unsubstituted arylene group; Or it may be a substituted or unsubstituted heteroarylene group.

In another exemplary embodiment, L ₁ is a direct bond; A substituted or unsubstituted C6 to C60 arylene group; Or it may be a substituted or unsubstituted C2 to C60 heteroarylene group.

In another exemplary embodiment, L ₁ is a direct bond; C6 to C40 arylene group; Or it may be a C2 to C40 heteroarylene group.

In another exemplary embodiment, L ₁ is a direct bond; C6 to C20 arylene group; Or it may be a C2 to C20 heteroarylene group.

In another exemplary embodiment, L ₁ is a direct bond; Or it may be a C6 to C20 arylene group.

In another exemplary embodiment, L ₁ is a direct bond; Phenylene group; Biphenylene group; Or it may be a naphthylene group.

In the exemplary embodiment of the present application, Ar ₁ is deuterium; Halogen group; 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, Ar ₁ is a substituted or unsubstituted C1 to C60 alkyl group; A substituted or unsubstituted C6 to C60 aryl group; Or it may be a substituted or unsubstituted C2 to C60 heteroaryl group.

In another exemplary embodiment, Ar ₁ is a substituted or unsubstituted C1 to C40 alkyl group; A substituted or unsubstituted C6 to C40 aryl group; Or it may be a substituted or unsubstituted C2 to C40 heteroaryl group.

In the exemplary embodiment of the present application, Ar ₁ is -(L ₂ ) _a -(Z ₁ ) _b ,

L ₂ is a direct bond; A substituted or unsubstituted arylene group; Or a substituted or unsubstituted heteroarylene group,

Z ₁ is deuterium; Halogen group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,

a is an integer from 0 to 4,

b is an integer of 1 to 3,

When a is 2 or more, L ₂ is the same as or different from each other,

When b is 2 or more, Z ₁ may be the same as or different from each other.

In the exemplary embodiment of the present application, L ₂ is a direct bond; A substituted or unsubstituted arylene group; Or it may be a substituted or unsubstituted heteroarylene group.

In another exemplary embodiment, L ₂ is a direct bond; A substituted or unsubstituted C6 to C60 arylene group; Or it may be a substituted or unsubstituted C2 to C60 heteroarylene group.

In another exemplary embodiment, L ₂ is a direct bond; C6 to C40 arylene group; Or it may be a C2 to C40 heteroarylene group.

In another exemplary embodiment, L ₂ is a direct bond; C6 to C20 arylene group; Or it may be a C2 to C20 heteroarylene group.

In another exemplary embodiment, L ₂ is a direct bond; Phenylene group; Biphenylene group; Or it may be a naphthylene group.

In the exemplary embodiment of the present application, Z ₁ is deuterium; Halogen group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted aryl group; Or it may be a substituted or unsubstituted heteroaryl group.

In another exemplary embodiment, Z ₁ is a substituted or unsubstituted C1 to C60 alkyl group; A substituted or unsubstituted C6 to C60 aryl group; Or it may be a substituted or unsubstituted C2 to C60 heteroaryl group.

In another exemplary embodiment, Z ₁ is a substituted or unsubstituted C6 to C60 aryl group; Or it may be a substituted or unsubstituted C2 to C60 heteroaryl group.

In another exemplary embodiment, Z ₁ is a C6 to C60 aryl group; Or it may be a C2 to C60 heteroaryl group unsubstituted or substituted with a C6 to C60 aryl group.

In another exemplary embodiment, Z ₁ may be any one of the following structures.

In the exemplary embodiment of the present application, R ₁ and R ₂ are the same as or different from each other, and each independently hydrogen; heavy hydrogen; -CN; 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 ₁ and R ₂ are the same as or different from each other, and each independently 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 ₁ and R ₂ are the same as or different from each other, and each independently a C6 to C60 aryl group unsubstituted or substituted with a C2 to C60 heteroaryl group; Or it may be a C2 to C60 heteroaryl group.

In another exemplary embodiment, R ₁ and R ₂ are the same as or different from each other, and each independently a dibenzofuran group or a phenyl group unsubstituted or substituted with a carbazole group; Biphenyl group; Carbazole; Dibenzofuran group; Or it may be a naphthyl group.

In another exemplary embodiment, R ₁ and R ₂ may be the same as or different from each other, and each independently may have any one of the following structures.

의 의미는 다른 치환기와 연결되는 위치를 의미한다.In an exemplary embodiment of the present specification, the

The meaning of means a position connected with another substituent.

In the exemplary embodiment of the present application, R _a and R _b 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 selected from the group consisting of a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or an amine group unsubstituted or substituted with 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.

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

In another exemplary embodiment, R _a and R _b are hydrogen.

In the exemplary embodiment of the present application, Formula 1 provides a heterocyclic compound, characterized in that represented by any one of the following Formulas 2 to 7.

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

In Formulas 2 to 7,

The definitions of R _a, R _{b ,} L ₁ , X, X ₁ to X _3, R ₁ , R ₂ , m, n and k are the same as those of Formula 1,

L ₂ is a direct bond; A substituted or unsubstituted arylene group; Or a substituted or unsubstituted heteroarylene group,

Z ₁ is hydrogen; heavy hydrogen; Halogen group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,

a is an integer from 0 to 4,

b is an integer of 1 to 3,

When a is 2 or more, L ₂ is the same as or different from each other,

When b is 2 or more, Z ₁ is the same as or different from each other.

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

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

[General Formula 1]

의 정의와 동일할 수 있다.In General Formula 1, R ₁₀₁ is the same as the definition of Ar ₁ in Formula 1, and R ₁₀₂ in Formula 1 is

May be the same as the definition of

의 정의와 동일하며, 상기 일반식 1에서 R₁₀₂는, 상기 화학식 1의 Ar₁의 정의와 동일할 수 있다.In addition, in the general formula 1, R ₁₀₁ is in the formula 1

It is the same as the definition of, and R ₁₀₂ in the general formula 1 may be the same as the definition of Ar ₁ of the formula 1.

In addition, by introducing various substituents into the structures of Formulas 1 to 7, a compound having the inherent characteristics of the introduced substituent can be synthesized. For example, a hole injection layer material, a hole transport material, a light emitting layer material, an electron transport layer material, and a substituent mainly used for the charge generation layer material used in manufacturing an organic light emitting device are introduced into the core structure to meet the conditions required by each organic material layer. It is possible to synthesize a material that makes you want

In addition, by introducing various substituents into the structures of Formulas 1 to 7, it is possible to finely control the energy band gap, on the other hand, to improve the properties at the interface between organic substances, and to diversify the use of the material. .

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

In addition, in the exemplary embodiment of the present application, the first electrode; A second electrode provided to face the first electrode; And one or more organic material layers provided between the first electrode and the second electrode, wherein at least one of the organic material layers comprises a heterocyclic compound according to 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.

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 of an organic light-emitting device, except for forming one or more organic material layers using the above-described heterocyclic compound.

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

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

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

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

As another example, the organic material layer including the heterocyclic compound includes the heterocyclic compound represented by Chemical Formula 1 as a host, and may be used together with a phosphorescent dopant.

As another example, the organic material layer including the heterocyclic compound includes the heterocyclic compound represented by Formula 1 as a host, and may be used together with an iridium-based dopant.

As the phosphorescent dopant material, those known in the art may be used.

For example, phosphorescent dopant materials represented by LL'MX', LL'L"M, LMX'X", L2MX' and L3M may be used, but the scope of the present invention is not limited by these examples.

Here, L, L', L", X'and X" are different bidentate ligands, and M is a metal forming an eight-sided complex.

M can be iridium, platinum, osmium, etc.

L is an anionic bidentate ligand coordinated to M with the iridium-based dopant by sp2 carbon and a hetero atom, and X'may function to trap electrons or holes. Non-limiting examples of L include 2-(1-naphthyl)benzoxazole, (2-phenylbenzoxazole), (2-phenylbenzothiazole), (2-phenylbenzothiazole), (7,8 -Benzoquinoline), (thiophene group pyridine), phenylpyridine, benzothiophene group pyridine, 3-methoxy-2-phenylpyridine, thiophene group pyridine, tolyl pyridine, and the like. Non-limiting examples of X'include acetylacetonate (acac), hexafluoroacetylacetonate, salicylidene, picolinate, 8-hydroxyquinolinate, and the like.

More specific examples are shown below, but are not limited to these examples.

In the exemplary embodiment of the present application, as the iridium-based dopant, Ir(ppy) ₃ may be used as a green phosphorescent dopant.

In the exemplary embodiment of the present application, the content of the dopant may have a content of 1% to 15%, preferably 3% to 10%, and more preferably 5% to 10% based on the entire emission layer.

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 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 an electron transport layer, an emission layer, or a hole blocking layer, and the electron transport layer, the emission layer, or the hole blocking layer may include the heterocyclic compound.

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

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

Referring to FIG. 1, an organic light-emitting device in which an anode 200, an organic material layer 300, and a cathode 400 are sequentially stacked on a substrate 100 is shown. However, 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 a multilayer. 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 lamination structure, and other layers other than the light emitting layer may be omitted, or other necessary functional layers may be further added as necessary.

The organic material layer including Formulas 1 to 7 may further include other materials as necessary.

In the organic light-emitting device according to an exemplary embodiment of the present application, materials other than the compounds of Formulas 1 to 7 are exemplified below, but these are for illustration only and are not intended to limit the scope of the present application. It can be replaced with materials known in.

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

Materials having a relatively low work function may be used as the cathode material, and metal, metal oxide, or conductive polymer may be used. Specific examples of the negative electrode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead, or alloys thereof; There are multi-layered materials such as LiF/Al or LiO ₂ /Al, but are not limited thereto.

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

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

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

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

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

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

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

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

< Manufacturing example >

< Manufacturing example 1> Preparation of compound 2

1) Preparation of compound 2-1

After dissolving dibenzo[b,d]furan-2-ol (150g, 814.37mmol) in 900ml of acetic acid, iodine monochloride (132.22g, 814.37mmol) , HCl 195ml, Acetic acid 345ml mixed solution was added and stirred at room temperature for 24 hours. After completion of the reaction, 3L of water was added to the reaction solution, and the solid was filtered and recrystallized from toluene to obtain compound 2-1 (155g, 61%) .

2) Preparation of compound 2-2

Compound 2-1 (17g, 54.82mmol) and [1,1'-biphenyl]-4-ylboronic acid ([1,1'-biphenyl]-4-ylboronic acid) (11.4g, 57.56mmol) were added to 170ml of Tol And after dissolving in 40ml of EtOH, 40ml of H2O (N ₂ condition) Pd(PPh ₃ ) ₄ (3.17g, 2.74mmol) and K ₂ CO ₃ (18.94g, 137.05mmol) were added and stirred under reflux for 3 hours. After completion of the reaction, MC was added to the reaction solution to dissolve it, extracted with distilled water, dried the organic layer with anhydrous MgSO ₄ , and then removed the solvent with a rotary evaporator, and then purified by column chromatography with dichloromethane and hexane as a developing solvent, and compound 2- 2 (13g, 70%) was obtained.

3) Preparation of compound 2-3

After dissolving compound 2-2 (13g, 38.65mmol) in MC, K ₂ CO ₃ (16.02g, 115.94mmol) and pyridine (6.11g, 77.29 mmol) were added thereto, and trifluoromethanesulfonic anhydride was added. ) (14.17g, 50.24mmol) was slowly added dropwise at 0°C, followed by stirring for 1 hour. After completion of the reaction, extract with MC and distilled water, dry the organic layer with anhydrous MgSO ₄ , remove the solvent with a rotary evaporator, and purify dichloromethane and hexane with a developing solvent by column chromatography, and compound 2-3 (16g, 88%) Got it.

4) Preparation of compound 2

Compound 2-3 (10g, 21.35mmol) and 2,4-diphenyl-6-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaboran-2-yl)phenyl )-1,3,5-triazine (2,4-diphenyl-6-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-1, 3,5-triazine) (9.76g, 22.41mmol) was dissolved in 100ml of Tol, 20ml of EtOH, and 20ml of H2O (N ₂ condition) Pd(PPh ₃ ) ₄ (1.23g, 1.07mmol) and K ₂ CO ₃ (7.38 g, 53.37mmol) was added and stirred under reflux for 16 hours. After the reaction was completed, the mixture was cooled to room temperature, a solid was generated, filtered, and washed with EA and MeOH. After that, the solid was completely dissolved in an excess of dichloromethane and filtered through silica gel to obtain compound 2 (9.1g, 67%) .

In Preparation Example 1, [1,1'-biphenyl]-4-ylboronic acid ([1,1'-biphenyl]-4-ylboronic acid) was used instead of the intermediate A of Table 1, and 2,4-di Phenyl-6-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaboran-2-yl)phenyl)-1,3,5-triazine (2,4-diphenyl -6-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-1,3,5-triazine) instead of the intermediate B in Table 1 Except for using the compound, it was prepared in the same manner as in Preparation Example 1 to synthesize the target compound.

< Manufacturing example 2> Preparation of compound 419

1) Preparation of compound 419-1

Compound 2-1 (30g, 96.75mmol) and Bis (pinacolato) diboron (36.85g, 145.12mmol) dissolved in 300ml 1,4-dioxane (1,4-dioxane) After (N ₂ condition) Pd(dppf)Cl ₂ (3.54g, 4.84mmol) and KOAc (28.48g, 290.24mmol) were added and stirred under reflux for 4 hours. After completion of the reaction, the mixture was extracted with MC and water, and the organic layer was dried over anhydrous MgSO ₄ and filtered with silica gel. It was precipitated with MC/MeOH. The precipitate was filtered to obtain 22.1 g of compound 491-1 in a yield of 73% .

2) Preparation of compound 419-2

Compound 419-1 (22g, 70.93mmol) and 2-chloro-4,6-diphenyl-1,3,5-triazine (2-chloro-4,6-diphenyl-1,3,5-triazine) ( 19.94g, 74.48mmol) was dissolved in 220ml THF and 50ml H2O (N ₂ condition) Pd(PPh ₃ ) ₄ (4.10g, 3.55mmol) and K ₂ CO ₃ (24.51g, 177.33mmol) were added thereto for 9 hours. Stir at reflux. After completion of the reaction, MC was added to the reaction solution to dissolve it, extracted with distilled water, dried the organic layer with anhydrous MgSO ₄ , and then removed the solvent with a rotary evaporator, and then purified by column chromatography using dichloromethane and hexane as a developing solvent, and compound 419- 2 (21g, 71%) was obtained.

3) Preparation of compound 419-3

After dissolving compound 419-2 (21g, 50.55mmol) in MC, K ₂ CO ₃ (20.96g, 151.65mmol) and pyridine (8g, 101.10 mmol) were added thereto and trifluoromethanesulfonic anhydride. (18.54g, 65.71mmol) was slowly added dropwise at 0 °C and stirred for 3 hours. After completion of the reaction, extract with MC and distilled water, dry the organic layer with anhydrous MgSO ₄ , remove the solvent with a rotary evaporator, and purify dichloromethane and hexane with a developing solvent by column chromatography, and compound 419-3 (19g, 68%) Got it.

4) Preparation of compound 419

Compound 419-3 (10g, 18.26mmol) and triphenylen-2-ylboronic acid (5.22g, 19.18mmol) were dissolved in 100ml of Tol, 20ml of EtOH, and 20ml of H ₂ O (N ₂ condition) Pd(PPh ₃ ) ₄ (1.06g, 0.91mmol) and K ₂ CO ₃ (6.31g, 45.66mmol) were added and stirred under reflux for 14 hours. After the reaction was completed, the mixture was cooled to room temperature, a solid was generated, filtered, and washed with EA and MeOH. Thereafter, the solid was completely dissolved in an excess of dichloromethane and filtered through silica gel to obtain compound 419 (7.2g, 63%) .

In Preparation Example 2, instead of 2-chloro-4,6-diphenyl-1,3,5-triazine (2-chloro-4,6-diphenyl-1,3,5-triazine) Intermediate C of Table 2 below A target compound was synthesized by preparing in the same manner as in Preparation Example 2, except that the compound represented by is used.

< Manufacturing example 3> Preparation of compound 436

1) Preparation of compound 436-1

Compound 2-1 (30g, 96.75mmol) and triphenylen-2-ylboronic acid (27.64g, 101.58mmol) were dissolved in 300ml of THF and 60ml of H ₂ O (N ₂ condition) Pd(PPh ₃ ) ₄ (5.59g, 4.84mmol) and K ₂ CO ₃ (33.43g, 241.87mmol) were added and stirred under reflux for 11 hours. After completion of the reaction, MC was added to the reaction solution to dissolve it, extracted with distilled water, dried the organic layer with anhydrous MgSO ₄ , and then removed the solvent with a rotary evaporator, and then purified by column chromatography using dichloromethane and hexane as a developing solvent, and compound 436- 1 (28g, 70%) was obtained.

2) Preparation of compound 436-2

Compound 436-1 (28g, 68.22mmol) was dissolved in MC, K ₂ CO ₃ (28.28g, 204.65mmol) and pyridine (10.79g, 136.43 mmol) were added thereto, and trifluoromethanesulfonic anhydride was added. ) (25.02g, 88.68mmol) was slowly added dropwise at 0 °C, followed by stirring for 4 hours. After completion of the reaction, extract with MC and distilled water, dry the organic layer with anhydrous MgSO ₄ , remove the solvent with a rotary evaporator, and purify dichloromethane and hexane with a developing solvent by column chromatography, and compound 436-2 (31g, 83%) Got it.

3) Preparation of compound 436-3

Compound 436-2 (31g, 57.14mmol) and Bis (pinacolato) diboron (21.77g, 85.71mmol) dissolved in 300ml of 1,4-dioxane (1,4-dioxane) After (N ₂ condition) Pd(dppf)Cl ₂ (2.09g, 2.86mmol) and KOAc (16.82g, 171.42mmol) were added and stirred under reflux for 18 hours. After completion of the reaction, the mixture was extracted with MC and water, and the organic layer was dried over anhydrous MgSO ₄ and filtered with silica gel. It was precipitated with MC/MeOH. The precipitate was filtered to obtain 18 g of compound 463-3 in a yield of 60% .

4) Preparation of compound 436

Compound 436-3 (9g, 17.29mmol) and 2-chloro-4,6-diphenyl-1,3,5-triazine (2-chloro-4,6-diphenyl-1,3,5-triazine) ( 4.86g, 18.16mmol) was dissolved in 100ml of Tol, 20ml of EtOH, and 20ml of H ₂ O (N ₂ condition) Pd(PPh ₃ ) ₄ (1.0g, 0.86mmol) and K ₂ CO ₃ (5.98g, 43.23mmol) And stirred under reflux for 13 hours. After the reaction was completed, the mixture was cooled to room temperature, a solid was generated, filtered, and washed with EA and MeOH. After that, the solid was completely dissolved in an excess of dichloromethane and filtered through silica gel to obtain compound 436 (6.82g, 62%).

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

<Production Example 4>

Dibenzo[b,d]furan-2-ol in Preparation Example 1 instead of dibenzo[b,d]thiophen-2-ol (dibenzo[b,d ]thiophen-2-ol), and instead of [1,1'-biphenyl]-4-ylboronic acid ([1,1'-biphenyl]-4-ylboronic acid), intermediate E of Table 4 was used, and , 2,4-diphenyl-6-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaboran-2-yl)phenyl)-1,3,5-triazine Intermediate F instead of (2,4-diphenyl-6-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-1,3,5-triazine) Except for using, the target compound was synthesized by preparing in the same manner as in Preparation Example 1.

< Manufacturing example 5>

Dibenzo[b,d]furan-2-ol instead of dibenzo[b,d]furan-2-ol in Preparation Example 2, dibenzo[b,d]thiophen-2-ol (dibenzo[b,d ]thiophen-2-ol), and instead of 2-chloro-4,6-diphenyl-1,3,5-triazine (2-chloro-4,6-diphenyl-1,3,5-triazine) Except for the use of the intermediate G in Table 5, it was prepared in the same manner as in Preparation Example 2 to synthesize the target compound.

< Manufacturing example 6>

Dibenzo[b,d]furan-2-ol in Preparation Example 3 instead of dibenzo[b,d]thiophen-2-ol (dibenzo[b,d ]thiophen-2-ol), and 2-chloro-4,6-diphenyl-1,3,5,-triazine (2-chloro-4,6-diphenyl-1,3,5-triazine) Instead, the target compound was synthesized in the same manner as in Preparation Example 3, except that the intermediate H of Table 6 was used.

Other compounds other than the compounds shown in Tables 1 to 6 were also prepared in the same manner as in the method described in Preparation Examples described above.

Tables 7 and 8 below are 1H NMR data and FD-MS data of the synthesized compound, and through the following data, it can be confirmed that the target compound was synthesized.

NO ^One H NMR( CDCl ₃ , 300Mz ) 2 7.25-7.52 (m, 19H), 7.66-7.68 (t, 2H), 7.85-7.89 (m, 4H), 8.28 (d, 4H) 4 7.29-7.51 (m, 14H), 7.63-7.68 (m, 5H), 7.79-7.94 (m, 7H), 8.12 (d, 1H), 8.28 (d, 4H), 8.55 (d, 1H) 5 7.25-7.51 (m, 13H), 7.66-7.68 (m, 3H), 7.85-7.89 (m, 7H), 8.28 (d, 4H) 7 7.25 (d, 2H), 7.32-7.51 (m, 8H), 7.66-6.68 (d, 2H), 7.782-7.89 (m, 8H), 8.10-8.12 (t, 3H), 8.28-8.34 (m, 5H) ), 8.93-8.99 (m, 3H) 9 7.25-7.68 (m, 13H), 7.85-7.96 (m, 8H), 8.10 (t, 2H), 8.28 (d, 4H), 8.42 (d, 2H) 11 7.25-7.53 (m, 16H), 7.63 (d, 4H), 7.85-7.89 (m, 4H), 8.12 (d, 2H), 8.28 (d, 4H) 13 7.25-7.51 (m, 10H), 7.66-7.71 (m, 4H), 7.85-7.89 (m, 6H), 8.04 (d, 1H), 8.12-8.18 (m, 2H), 8.28 (d, 4H), 8.95 (d, 1H), 9.15 (s, 1H) 15 7.25-7.68 (m, 28H), 7.85-7.92 (m, 4H), 8.28-8.30 (m, 6H) 16 7.25-7.68 (m, 18H), 7.78-7.98 (m, 7H), 8.06 (d, 1H), 8.16 (d, 1H), 8.28 (d, 4H), 8.54 (d, 1H), 8.81 (d, 2H) 17 7.25-7.68 (m, 17H), 7.78-7.89 (m, 5H), 7.98-8.06 (m, 3H), 8.28 (d, 4H), 8.45 (d, 1H), 8.81 (d, 2H) 18 7.25-7.68 (m, 18H), 7.78-7.89 (m, 6H), 7.98 (d, 1H), 8.06 (d, 1H), 8.28 (d, 4H), 8.81 (d, 2H) 19 7.25-7.68 (m, 17H), 7.78-7.89 (m, 5H), 7.98 (d, 2H), 8.06 (d, 1H), 8.28 (d, 4H), 8.45 (d, 1H), 8.81 (d, 2H) 20 7.25-7.68 (m, 18H), 7.78-7.89 (m, 6H), 7.98 (d, 1H), 8.06 (d, 1H), 8.28 (d, 4H), 8.81 (d, 2H) 21 7.25-7.98 (m, 27H), 8.28-8.30 (m, 6H), 8.55 (d, 1H) 22 7.25-7.51 (m, 15H), 7.64-7.68 (m, 5H), 7.79-7.89 (m, 6H), 7.98-7.99 (m, 2H), 8.16 (d, 1H), 8.28 (d, 4H), 8.54 (d, 1H), 8.81 (d, 2H) 24 7.25-7.51 (m, 19H), 7.66-7.68 (t, 2H), 7.85-7.89 (m, 4H), 8.28 (d, 4H) 27 7.25-7.51 (m, 13H), 7.66-7.68 (m, 3H), 7.85-7.89 (m, 7H), 8.28 (d, 4H) 29 7.25-7.51 (m, 10H), 7.66-7.68 (m, 2H), 7.82-7.89 (m,8H), 8.10-8.12 (m, 3H), 8.28-8.34 (m, 5H), 8.93-8.99 (m , 3H) 31 7.25-7.68 (m, 13H), 7.85-7.90 (m, 8H), 8.10 (t, 2H), 8.28 (d, 4H), 8.42 (d, 2H) 33 7.25-7.53 (m, 16H), 7.63-7.68 (m, 4H), 7.85-7.89 (m, 4H), 8.12 (d, 2H), 8.28 (d, 4H) 35 7.25-7.51 (m, 10H), 7.66-7.71 (m, 4H), 7.82-7.88 (m, 6H), 8.04 (d, 1H), 8.12-8.18 (m, 2H), 8.28 (d, 4H), 8.93 (d, 1H), 9.15 (d, 1H) 37 7.25-7.68 (m, 28H), 7.85-7.92 (m, 5H), 8.28-8.30 (m, 5H) 38 7.25-7.68 (m, 18H), 7.78-7.87 (m, 7H), 8.06 (d, 1H), 8.16 (d, 1H), 8.28 (d, 4H), 8.54 (d, 1H), 8.81 (d, 2H) 39 7.25-7.68 (m, 17H), 7.78-7.89 (m, 5H), 7.98-8.06 (m, 3H), 8.28 (d, 4H), 8.45 (d, 1H), 8.81 (d, 2H) 41 7.25-7.68 (m, 17H), 7.78-7.89 (m, 5H), 7.98-8.06 (m, 3H), 8.28 (d, 4H), 8.45 (d, 1H), 8.81 (d, 2H) 42 7.25-7.68 (m, 18H), 7.78-7.89 (m, 6H), 7.98 (d, 1H), 8.06 (d, 1H), 8.28 (d, 4H), 8.81 (d, 2H) 44 7.25-7.51 (m, 15H), 7.64-7.68 (m, 5H), 7.79-7.87 (m, 6H), 7.98-7.99 (m, 2H), 8.16 (d, 1H), 8.28 (d, 4H), 8.54 (d, 1H), 8.81 (d, 2H) 46 7.25-7.52 (m, 19H), 7.66-7.68 (m, 2H), 7.79 (d, 2H), 7.87-7.89 (m, 2H), 8.23-8.30 (m, 5H) 48 7.25-7.51 (m, 14H), 7.63-7.68 (m, 5H), 7.79-7.94 (m, 7H), 8.12 (d, 1H), 8.23-8.30 (m, 5H), 8.55 (d, 1H) 49 7.25-7.51 (m, 13H), 7.66-7.68 (m, 3H), 7.79-7.89 (m, 7H), 8.23-8.30 (m, 5H) 51 7.25-7.51 (m, 10H), 7.66-7.68 (m, 2H), 7.79-7.89 (m, 8H), 8.10-8.12 (m, 3H), 8.23-8.34 (m, 6H), 8.93-8.99 (m , 3H) 53 7.25-7.68 (m, 13H), 7.79-7.96 (m, 8H), 8.10 (t, 2H), 8.23-8.30 (m, 5H), 8.42 (d, 2H) 55 7.25-7.53 (m, 16H), 7.63-7.68 (m, 4H), 7.79 (d, 2H), 7.87-7.89 (m, 2H), 8.12 (d, 2H), 8.23-8.30 (m, 6H) 57 7.25-7.51 (m, 10H), 7.66-7.89 (m, 10H), 8.04-8.28 (m, 8H), 8.93 (d, 1H), 9.15 (s, 1H) 59 7.25-7.68 (m, 28H), 7.79 (d, 2H), 7.87-7.92 (m, 3H), 8.23-8.30 (m, 7H) 60 7.25-7.98 (m, 26H), 8.16-8.30 (m, 6H), 8.54 (d, 1H), 8.81 (d, 2H) 61 7.25-7.68 (m, 17H), 7.78-7.89 (m, 5H), 7.98-8.06 (m, 3H), 8.23-8.30 (m, 5H), 8.45 (d, 1H), 8.81 (d, 2H) 62 7.25-7.68 (m, 18H), 7.78-7.89 (m, 6H), 7.98-8.06 (m, 2H), 8.23-8.30 (m, 5H), 8.81 (d, 2H) 63 7.25-7.68 (m, 17H), 7.78-7.89 (m, 5H), 7.98-8.06 (m, 3H), 8.23-8.30 (m, 5H), 8.45 (d, 1H), 8.81 (d, 2H) 64 7,25-7.68 (m, 18H), 7.78-7.89 (m, 6H), 7.98-8.06 (m, 2H), 8.23-8.30 (m, 5H), 8.81 (d, 2H) 66 7.25-7.51 (m, 15H), 7.64-7.68 (m, 5H), 7.79-7.89 (m, 6H), 7.98-7.99 (m, 2H), 8.16 (d, 1H), 8.23-8.30 (m, 5H) ), 8.54 (d, 1H), 8.81 (d, 2H) 68 7.25-7.51 (m, 19H), 7.66-7.68 (m, 2H), 7.79 (d, 2H), 7.87-7.89 (m, 2H), 8.23-8.30 (m, 5H) 70 7.25-7.51 (m, 14H), 7.63-7.68 (m, 5H), 7.79-7.94 (m, 7H), 8.12 (d, 1H), 8.23-8.30 (m, 5H), 8.55 (d, 1H) 71 7.25-7.51 (m, 13H), 7.66-7.68 (m, 3H), 7.79-7.89 (m, 7H), 8.23-8.30 (m, 5H) 73 7.25-7.51 (m, 10H), 7.66-7.68 (d, 2H), 7.79-7.89 (m, 8H), 8.10-8.12 (m, 3H), 8.28-8.34 (m, 6H), 8.93-8.99 (m , 3H) 75 7.25-7.68 (m, 13H), 7.79-7.96 (m, 8H), 8.10 (t, 2H), 8.23-8.30 (m, 5H), 8.42 (d, 2H) 77 7.25-7.51 (m, 16H), 7.63-7.68 (m, 4H), 7.79 (d, 2H), 7.87-7.89 (m, 2H), 8.12 (d, 2H), 8.23-8.30 (m, 5H) 79 7.25-7.51 (m, 10H), 7.66-7.88 (m, 10H), 8.12-8.30 (m, 8H), 8.93 (d, 1H), 9.15 (s, 1H) 81 7.25-7.68 (m, 28H), 7.79 (d, 2H), 7.87-7.92 (m, 3H), 8.23-8.30 (m, 7H) 82 7.25-7.98 (m, 26H), 8.16-8.30 (m, 6H), 8.54 (d, 1H), 8.81 (d, 2H) 83 7.25-7.68 (m, 17H), 7.79-7.89 (m, 5H), 7.98-8.06 (m, 3H), 8.23-8.30 (m, 5H), 8.45 (d, 1H), 8.81 (d, 2H) 84 7.25-7.68 (m, 18H), 7.78-7.89 (m, 6H), 7.98-8.06 (m, 2H), 8.23-8.30 (m, 5H), 8.81 (d, 2H) 85 7.25-7.68 (m, 17H), 7.78-7.89 (m, 5H), 7.98-8.06 (m, 3H), 8.23-8.30 (m, 5H), 8.45 (d, 1H), 8.81 (d, 2H) 86 7.25-7.68 (m, 18H), 7.78-7.89 (m, 6H), 7.98-8.0 (m, 2H), 8.23-8.30 (m, 5H), 8.81 (d, 2H) 88 7.25-7.51 (m, 15H), 7.64-7.68 (m, 5H), 7.79-7.87 (m, 6H), 7.98-7.99 (m, 2H), 8.16 (d, 1H), 8.23-8.30 (m, 5H) ), 8.54 (d, 1H), 8.81 (d, 2H) 90 7.25-7.52 (m, 19H), 7.66-7.68 (m, 2H), 7.79-7.89 (m, 8H), 8.23 (s, 1H) 92 7.25-7.51 (m, 14H), 7.63-7.68 (m, 5H), 7.79-7.89 (m, 11H), 8.12 (d, 1H), 8.23 (s, 1H), 8.55 (d, 1H) 93 7.25-7.51 (m, 13H), 7.66-7.68 (m, 3H), 7.79-7.89 (m, 11H), 8.23 (s, 1H) 95 7.25-7.51 (m, 10H), 7.66-7.68 (m, 2H), 7.79-7.89 (m, 12H), 8.10-8.12 (m, 3H), 8.23 (s, 1H), 8.34 (s, 1H), 8.93-8.99 (m, 3H) 97 7.25-7.68 (m, 13H), 7.79-7.96 (m, 12H), 8.10 (t, 2H), 8.23 (s, 1H), 8.42 (d, 2H) 99 7.25-7.53 (m, 16H), 7.63-7.68 (m, 4H), 7.79-7.89 (m, 8H), 8.12 (d, 2H), 8.23 (s, 1H) 101 7.25-7.51 (m, 10H), 7.66-7.89 (m, 14H), 8.04 (d, 1H), 8.12-8.23 (m, 3H), 8.95 (d, 1H), 9.15 (s, 1H) 103 7.25-7.68 (m, 28H), 7.79-7.89 (m, 9H), 8.23 (s, 1H), 8.30 (d, 2H) 104 7.25-7.68 (m, 18H), 7.79-7.98 (m, 11H), 8.06 (d, 1H), 8.16 (d, 1H), 8.23 (s, 1H), 8.54 (d, 1H), 8.81 (d, 2H) 105 7.25-7.68 (m, 17H), 7.78-7.89 (m, 9H), 7.98-8.06 (m, 3H), 8.23 (s, 1H), 8.45 (d, 1H), 8.81 (d, 2H) 106 7.25-7.68 (m, 18H), 7.78-7.89 (m, 10H), 7.98 (d, 1H), 8.06 (d, 1H), 8.23 (s, 1H), 8.81 (d, 2H) 107 7.25-7.68 (m, 17H), 7.78-7.89 (m, 9H), 7.98-8.06 (m, 3H), 8.23 (s, 1H), 8.45 (d, 1H), 8.81 (d, 2H) 108 7.25-7.68 (m, 18H), 7.79-7.89 (m, 10H), 7.98 (d, 1H), 8.06 (d, 1H), 8.23 (s, 1H), 8.81 (d, 2H) 110 7.25-7.51 (m, 15H), 7.64-7.68 (m, 5H), 7.79-7.89 (m, 10H), 7.98-7.99 (m, 2H), 8.16 (d, 1H), 8.23 (s, 1H), 8.54 (d, 1H), 8.81 (d, 2H) 112 7.25-7.52 (m, 19H), 7.66-7.68 (m, 2H), 7.79-7.89 (m, 8H), 8.23 (s, 1H) 114 7.25-7.51 (m, 14H), 7.66-7.68 (m, 5H), 7.79-7.94 (m, 11H), 8.12 (d, 1H), 8.23 (s, 1H), 8.55 (d, 1H) 115 7.25-7.51 (m, 13H), 7.66-7.68 (m, 3H), 7.79-7.89 (m, 11H), 8.23 (s, 1H) 117 7.25-7.51 (m, 10H), 7.66-7.68 (m, 2H), 7.79-7.89 (m, 12H), 8.10-8.12 (m, 3H), 8.23 (s, 1H), 8.34 (s, 1H), 8.93-8.99 (m, 3H) 119 7.25-7.68 (m, 13H), 7.79-7.96 (m, 12H), 8.10 (t, 2H), 8.23 (s, 1H), 8.42 (d, 2H) 121 7.25-7.51 (m, 16H), 7.63-7.68 (m, 4H), 7.79-7.89 (m, 8H), 8.12 (d, 2H), 8.23 (s, 1H) 123 7.25-7.51 (m, 10H), 7.66-7.88 (m, 14H), 8.04 (d, 1H), 8.12-8.23 (m, 3H), 8.93 (d, 1H), 9.15 (s, 1H) 125 7.25-7.68 (m, 28H), 7.79-7.92 (m, 9H), 8.23 (s, 1H), 8.30 (d, 2H) 126 7.25-7.68 (m, 18H), 7.79-7.98 (m, 11H), 8.06 (d, 1H), 8.16 (d, 1H), 8.23 (s, 1H), 8.54 (d, 1H), 8.81 (d, 2H) 127 7.25-7.68 (m, 17H), 7.78-7.89 (m, 9H), 7.98-8.06 (m, 3H), 8.23 (s, 1H), 8.45 (d, 1H), 8.81 (d, 2H) 128 7.25-7.68 (m, 18H), 7.78-7.89 (m, 10H), 7.98 (d, 1H), 806 (d, 1H), 8.23 (s, 1H), 8.81 (d, 2H) 129 7.25-7.68 (m, 17H), 7.78-7.89 (m, 9H), 7.98-8.06 (m, 3H), 8.23 (s, 1H), 8.45 (d, 1H), 8.81 (d, 2H) 130 7.25-7.68 (m, 18H), 7.78-7.89 (m, 10H), 7.98 (d, 1H), 8.06 (d, 1H), 8.23 (s, 1H), 8.81 (d, 2H) 132 7.25-7.51 (m, 15H), 7.64-7.68 (m, 5H), 7.79-7.87 (m, 10H), 7.98-7.99 (m, 2H), 8.16 (d, 1H), 8.23 (s, 1H), 8.54 (d, 1H), 8.81 (d, 2H) 222 7.25-7.55 (m, 19H), 7.66-7.68 (m, 2H), 7.87-7.89 (m, 2H), 8.01 (d, 2H), 8.28 (d, 4H), 8.55 (d, 2H) 224 7.25-7.68 (m, 19H), 7.79-7.94 (m, 7H), 8.12 (d, 1H), 8.28 (d, 4H), 8.55 (m, 3H) 225 7.25-7.55 (m, 13H), 7.66-7.68 (m, 3H), 7.81-7.89 (m, 5H), 8.01 (d, 2H), 8.28 (d, 4H), 8.55 (d, 2H) 227 7.32-7.55 (m, 10H), 7.66-7.68 (m, 2H), 7.82-7.89 (m, 6H), 8.01 (d, 2H), 8.10-8.12 (m, 3H), 8.28-8.34 (m, 5H) ), 8.55 (d, 2H), 8.93-8.99 (m, 3H) 229 7.32-7.68 (m, 13H), 7.79-8.01 (m, 8H), 8.10 (d, 2H), 8.28 (d, 4H), 8.42 (d, 2H), 8.55 (d, 2H) 230 7.32-7.68 (m, 20H), 7.87-7.89 (m, 2H), 8.01 (d, 2H), 8.12 (d, 2H), 8.28 (d, 4H), 8.55 (d, 2H) 231 7.32-7.55 (m, 10H), 7.66-7.71 (m, 4H), 7.82-7.89 (m, 4H), 8.04-8.18 (m, 5H), 8.28 (d, 4H), 8.55 (d, 2H), 8.93 (d, 1H), 9.15 (s, 1H) 233 7.25-7.51 (m, 19H), 7.66-7.68 (m, 2H), 7.87-7.89 (m, 2H), 8.01 (d, 2H), 8.28 (d, 4H), 8.55 (d, 1H) 235 7.25-7.68 (m, 19H), 7.79-8.01 (m, 7H), 8.12 (d, 1H), 8.28 (d, 4H), 8.55 (d, 3H) 236 7.32-7.55 (m, 13H), 7.66-7.68 (m, 3H), 7.85-7.89 (m, 5H), 8.01 (d, 2H), 8.28 (d, 4H), 8.55 (d, 2H) 238 7.32-7.55 (m, 10H), 7.66-7.68 (m, 2H), 7.72-7.88 (m, 6H), 8.01 (d, 2H), 8.10-8.12 (m, 3H), 8.28-8.34 (m, 5H) ), 8.55 (d, 2H), 8.93-8.99 (m, 3H) 240 7.32-7.68 (m, 13H), 7.79-8.01 (m, 8H), 8.10 (d, 2H), 8.28 (d, 4H), 8.42 (d, 2H), 8.55 (d, 2H) 241 7.32-7.68 (m, 20H), 8.87-8.89 (m, 2H), 8.01 (d, 2H), 8.12 (d, 2H), 8.28 (d, 4H), 8.55 (d, 2H) 242 7.32-7.55 (m, 10H), 7.66-7.71 (m, 4H), 7.82-7.89 (m, 4H), 8.01-8.18 (m, 5H), 8.28 (d, 4H), 8.55 (d, 2H), 8.93 (d, 1H), 9.15 (s, 1H) 244 7.25-7.52 (m, 20H), 7.63-7.68 (m, 5H), 7.79-7.94 (m, 7H), 8.12 (d, 1H), 8.28 (d, 2H), 8.55 (d, 1H) 246 7.25-7.51 (m, 15H), 7.63-7.68 (m, 8H), 7.79-7.94 (m, 10H), 8.12 (d, 2H), 8.28 (d, 2H), 8.55 (d, 2H) 247 7.25-7.51 (m, 14H), 7.63-7.68 (m, 6H), 7.79-7.94 (m, 10H), 8.12 (d, 1H), 8.28 (d, 2H), 8.55 (d, 1H) 249 7.25-7.51 (m, 11H), 7.63-7.68 (m, 5H), 7.79-7.94 (m, 11H), 8.10-8.12 (m, 3H), 8.28-8.34 (m, 3H), 8.55 (d, 1H) ), 8.93-8.99 (m, 3H) 251 7.25-7.66 (m, 17H), 7.79-7.94 (m, 11H), 8.10 (d, 2H), 8.28 (d, 2H), 8.42 (d, 2H), 8.55 (d, 1H) 252 7.25-7.51 (m, 17H), 7.63-7.68 (m, 7H), 7.79-7.94 (m, 7H), 8.12 (d, 2H), 8.28 (d, 2H), 8.55 (d, 2H) 253 7.25-7.51 (m, 11H), 7.63-7.94 (m, 16H), 8.04-8.18 (m, 4H), 8.28 (d, 2H), 8.55 (d, 1H), 8.93 (d, 1H), 9.25 ( s, 1H) 255 7.25-7.51 (m, 20H), 7.63-7.68 (m, 5H), 7.79-7.94 (m, 7H), 8.12 (d, 1H), 8.28 (d, 2H), 8.55 (d, 1H) 257 7.25-7.51 (m, 15H), 7.63-7.68 (m, 8H), 7.79-7.94 (m, 10H), 8.12 (d, 2H), 8.28 (d, 2H), 8.55 (d, 2H) 258 7.25-7.51 (m, 14H), 7.63-7.68 (m, 6H), 7.79-7.94 (m, 10H), 8.12 (d, 1H), 8.28 (d, 2H), 8.55 (d, 1H) 260 7.25-7.51 (m, 11H), 7.63-7.68 (m, 5H), 7.79-7.94 (m, 11H), 8.10-8.12 (m, 4H), 8.25-8.28 (m, 3H), 8.55 (d, 1H) ), 8.93-8.99 (m, 3H) 262 7.25-7.68 (m, 17H), 7.79-7.94 (m, 11H), 8.10-8.12 (m, 3H), 8.28 (d, 2H), 8.42 (d, 2H), 8.55 (d, 1H) 263 7.25-7.51 (m, 17H), 7.63-7.68 (m, 7H), 7.79-7.94 (m, 7H), 8.12 (d, 3H), 8.28 (d, 2H), 8.55 (d, 1H) 264 7.25-7.51 (m, 11H), 7.63-7.94 (m, 16H), 8.12-8.18 (m, 4H), 8.28 (d, 2H), 8.55 (d, 1H), 8.93 (d, 1H), 9.15 ( s, 1H) 310 7.25-7.51 (m, 21H), 7.66-7.68 (m, 3H), 7.85-7.89 (m, 9H), 8.28 (d, 2H) 312 7.25-7.51 (m, 16H), 7.63-7.68 (m, 6H), 7.79-7.94 (m, 12H), 8.12 (d, 1H), 8.28 (d, 2H), 8.55 (d, 1H) 313 7.25-7.41 (m, 13H), 7.51 (t, 2H), 7.66-7.68 (m, 4H), 7.85-7.89 (m, 12H), 8.28 (d, 2H) 315 7.25-7.41 (m, 10H), 7.51 (t, 2H), 7.66-7.68 (m, 3H), 7.81-7.89 (m, 13H), 8.10-8.12 (m, 3H), 8.28 (d, 2H), 8.93-8.99 (m, 3H) 317 7.25-7.41 (m, 10H), 7.51-7.68 (m, 6H), 7.79-7.90 (m, 13H), 8.10 (t, 2H), 8.28 (d, 2H), 8.42 (d, 2H) 318 7.25-7.51 (m, 18H), 7.63-7.68 (m, 5H), 7.81-7.89 (m, 9H), 8.12 (d, 2H), 8.28 (d, 2H) 319 7.25-7.41 (m, 10H), 7.51 (t, 2H), 7.66-7.71 (m, 5H), 7.81-7.89 (m, 11H), 8.04 (d, 1H), 8.12-8.18 (m, 2H), 8.28 (d, 2H), 8.93 (d, 1H), 9.25 (s, 1H) 321 7.25-7.51 (m, 21H), 7.66-7.68 (m, 3H), 7.81-7.89 (m, 9H), 8.28 (d, 2H) 323 7.25-7.51 (m, 16H), 7.63-7.68 (m, 6H), 7.79-7.89 (m, 12H), 8.12 (d, 1H), 8.28 (d, 2H), 8.55 (d, 1H) 324 7.25-7.41 (m, 13H), 7.51 (t, 2H), 7.66-7.68 (m, 4H), 7.81-7.89 (m, 12H), 8.28 (d, 2H) 326 7.25-7.41 (m, 10H), 7.51 (t, 2H), 7.66-7.68 (m, 3H), 7.81-7.89 (m, 13H), 8.10-8.12 (m, 3H), 8.25-8.28 (m, 3H) ), 8.93-8.99 (m, 3H) 328 7.25-7.41 (m, 10H), 7.51-7.68 (m, 6H), 7.79-7.96 (m, 13H), 8.10 (t, 2H), 8.28 (d, 2H), 8.42 (d, 2H) 329 7.25-7.51 (m, 18H), 7.63-7.68 (m, 5H), 7.81-7.89 (m, 9H), 8.12 (d, 2H), 8.28 (d, 2H) 330 7.25-7.41 (m, 10H), 7.51 (t, 2H), 7.66-7.71 (m, 5H), 7.81-7.89 (m, 11H), 8.04 (d, 1H), 8.12-8.18 (m, 2H), 8.28 (d, 2H), 8.93 (d, 1H), 9.45 (s, 1H) 332 7.25-7.68 (m, 21H), 7.85-7.95 (m, 5H), 8.04-8.08 (m, 2H), 8.28 (d, 2H), 8.55 (d, 1H) 334 7.25-7.68 (m, 19H), 7.85-7.95 (m, 8H), 8.04-8.12 (m, 3H), 8.28 (d, 2H), 8.55 (d, 2H) 335 7.25-7.68 (m,16H), 7.85-7.95 (m, 8H), 8.04-8.08 (d, 2H), 8.28 (d, 2H), 8.55 (d, 1H) 337 7.25-7.68 (m, 12H), 7.82-7.95 (m, 9H), 8.04-8.12 (m, 5H), 8.28-8.34 (m, 3H), 8.55 (d, 1H), 8.93-8.99 (m, 3H) ) 339 7.25-7.66 (m, 13H), 7.79-8.10 (m, 13H), 8.28 (d, 2H), 8.42 (d, 2H), 8.55 (d ,1H) 340 7.25-7.68 (m, 20H), 7.85-7.95 (m, 5H), 8.04-8.12 (m, 4H), 8.28 (d, 2H), 8.55 (d, 2H) 341 7.25-7.71 (m, 14H), 7.82-7.95 (m, 7H), 8.04-8.18 (m, 5H), 8.28 (d, 2H), 8.55 (d, 1H), 8.93 (d, 1H), 9.15 ( s, 1H) 343 7.25-7.68 (m, 21H), 7.85-7.95 (m, 5H), 8.04-8.08 (m, 2H), 8.28 (d, 2H), 8.55 (d, 1H) 345 7.25-7.68 (m, 19H), 7.85-7.95 (m, 8H), 8.04-8.12 (m, 3H), 8.28 (d, 2H), 8.55 (d ,2H) 346 7.25-7.68 (m, 16H), 7.85-7.95 (m, 8H), 8.04-8.08 (m, 2H), 8.28 (d, 2H), 8.55 (d ,1H) 348 7.25-7.68 (m, 12H), 7.85-7.95 (m, 9H), 8.04-8.12 (m, 5H), 8.25-8.28 (m, 3H), 8.55 (d, 1H), 8.93-8.99 (m, 3H) ) 350 7.25-7.68 (m, 13H), 7.85-8.10 (m, 13H), 8.28 (d, 2H), 8.42 (d, 2H), 8.55 (d, 1H) 351 7.25-7.68 (m, 20H), 7.85-7.95 (m, 5H), 8.04-8.12 (m, 4H, 8.28 (d, 2H), 8.55 (d, 2H) 352 7.25-7.68 (m, 14H), 7.85-7.95 (m, 7H), 8.04-8.12 (m, 5H), 8.28 (d, 2H), 8.55 (d, 1H), 8.93 (d, 1H), 9.15 ( s, 1H) 419 7.32-7.51 (m, 8H), 7.66-7.68 (m, 2H), 7.82-7.89 (m, 6H), 8.10-8.12 (m, 3H), 8.28-8.34 (m, 5H), 8.93-8.99 (m , 3H) 421 7.32-7.51 (m, 12H), 7.66-7.70 (m, 3H), 7.82-7.89 (m, 6H), 8.10-8.12 (m, 3H), 8.24-8.34 (m, 4H), 8.93-8.99 (m , 3H) 424 7.32-7.51 (m, 8H), 7.66-7.68 (m, 2H), 7.79-7.89 (m, 8H), 8.10-8.12 (m, 3H), 8.28-8.34 (m, 4H), 8.93-8.99 (m , 3H) 429 7.32-7.51 (m, 10H), 7.66-7.68 (m, 2H), 7.82-7.89 (m, 8H), 8.10-8.12 (m, 3H), 8.23-8.34 (m, 6H), 8.93-8.99 (m , 3H), 434 7.32-7.51 (m, 12H), 7.66-7.68 (m, 2H), 7.82-7.89 (m, 10H), 8.10-8.12 (m, 3H), 8.23 (s, 1H), 8.30-8.34 (m, 5H) ), 8.93-8.99 (m, 3H) 436 7.32-7.51 (m, 8H), 7.66-7.68 (m, 2H), 7.82-7.89 (m, 6H), 8.04-8.18 (m, 4H), 8.28 (d, 4H), 8.93 (d, 2H), 9.15 (s, 1H) 438 7.32-7.57 (m, 12H), 7.66-7.70 (m, 3H), 7.82-7.89 (m, 6H), 8.04 (d, 1H), 8.12-8.24 (m,6H), 8.93 (d, 2H), 9.15 (s, 1H) 441 7.32-7.51 (m, 8H), 7.66-7.68 (m, 2H), 7.79-7.89 (m, 8H), 8.04-8.28 (m, 7H), 8.93 (d, 2H), 9.15 (s, 1H) 446 7.32-7.51 (m, 10H), 7.66-7.68 (m, 2H), 7.82-7.89 (m, 8H), 8.04 (d, 1H), 8.12-8.30 (m, 8H), 8.93 (d, 2H), 9.15 (s, 1H) 451 7.32-7.52 (m, 12H), 7.66-7.68 (m, 2H), 7.82-7.89 (m, 10H), 8.04 (s, 1H), 8.12-8.23 (m, 4H), 8.30 (d, 4H), 8.93 (d, 2H), 9.15 (s, 1H) 453 7.32-7.70 (m, 13H), 7.82-7.89 (m, 6H), 8.04-8.28 (m, 9H), 8.93 (d, 2H), 9.15 (d, 1H) 454 7.32-7.70 (m, 13H), 7.82-7.89 (m, 6H), 8.04-8.28 (m, 9H), 8.93 (d, 2H), 9.15 (d, 1H) 457 7.25-7.57 (m, 13H), 7.66-7.70 (m, 3H), 7.82-7.89 (m, 8H), 8.04-8.18 (m, 4H), 8.28 (d, 4H), 8.93 (d, 2H), 9.15 (s, 1H) 465 7.25-7.70 (m, 21H), 7.87-7.94 (m, 3H), 8.09-8.12 (m, 2H), 8.24-8.28 (m, 5H), 8.55 (d, 1H) 467 7.32-7.88 (m, 22H), 8.04-8.28 (m, 7H), 8.93 (d, 2H), 9.15 (s, 1H) 468 7.32-7.88 (m, 22H), 8.04-8.28 (m, 7H), 8.93 (d, 2H), 9.15 (s, 1H) 471 7.32-7.70 (m, 21H), 7.81-7.89 (m, 5H), 8.24-8.28 (m, 5H) 478 7.25-7.89 (m, 29H), 8.23 (s, 1H), 8.28 (d, 2H) 485 7.32-7.51 (m, 10H), 7.66-7.68 (m, 2H), 7.82-7.89 (m, 8H), 8.04-8.12 (m, 4H), 8.28 (d, 4H), 8.93 (d, 2H), 9.15 (s, 1H) 486 7.32-7.51 (m, 10H), 7.66-7.68 (m, 2H), 7.79-7.89 (m, 10H), 8.04-8.28 (m, 7H), 8.93 (d, 2H), 9.15 (s, 1H) 487 7.25-7.51 (m, 14H), 7.63-7.68 (m, 5H), 7.79-7.94 (m, 7H), 8.12 (d, 1H), 8.28 (d, 4H), 8.55 (d, 1H) 492 7.32-7.57 (m, 13H), 7.66-7.70 (m, 3H), 7.79-7.89 (m, 10H), 8.04 (d, 1H), 8.12-8.28 (m, 6H), 8.93 (d, 2H), 9.15 (s, 1H) 494 7.32-7.51 (m, 16H), 7.66-7.70 (m, 4H), 7.79-7.89 (m, 9H), 8.23-8.28 (m, 3H) 496 7.25 (d, 2H), 7.41-7.52 (m, 8H), 7.82-7.88 (m, 8H), 7.98 (d, 1H), 8.10-8.12 (m, 3H), 8.28-8.34 (m, 5H), 8.45 (d, 1H), 8.93-8.99 (m, 3H) 497 7.25 (d, 2H), 7.41-7.52 (m, 8H), 7.82-7.88 (m, 8H), 7.98 (d, 1H), 8.10-8.12 (m, 3H), 8.28-8.34 (m, 5H), 8.45 (d, 1H), 8.93-8.99 (m, 3H) 501 7.41-7.53 (m, 10H), 7.70 (s, 1H), 7.82-7.88 (m, 6H), 7.98 (d, 1H), 8.10-8.12 (m, 3H), 8.24-8.28 (m, 6H), 8.45 (d, 1H), 8.93-8.99 (m, 3H) 504 7.25 (d, 2H), 7.41-7.52 (m, 8H), 7.79-7.88 (m, 8H), 7.98 (d, 1H), 8.10-8.12 (m, 3H), 8.23-8.34 (m, 6H), 8.45 (d, 1H), 8.93-8.99 (m, 3H) 505 7.25 (d, 2H), 7.41-7.52 (m, 8H), 7.79-7.88 (m, 8H), 7.98 (d, 1H), 8.10-8.12 (m, 3H), 8.23-8.34 (m, 6H), 8.45 (d, 1H), 8.93-8.99 (m, 3H) 507 7.25 (d, 2H), 7.41-7.52 (m, 10H), 7.82-7.88 (m, 8H), 7.98 (d, 1H), 8.10-8.12 (m, 3H), 8.23-8.30 (m, 8H), 8.45 (d, 1H), 8.93-8.99 (m, 3H) 511 7.41-7.57 (m, 12H), 7.70-7.88 (m, 10H), 7.98 (d, 1H), 8.10-8.12 (m, 3H), 8.23-8.34 (m, 6H), 8.45 (d, 1H), 8.93-8.99 (m, 3H) 515 7.41-7.57 (m, 13H), 7.70 (s, 2H), 7.82-7.88 (m, 6H), 7.98 (d, 1H), 8.10-8.12 (m, 3H), 8.24-8.34 (m, 6H), 8.45 (d, 1H), 8.93-8.99 (m, 3H) 520 7.25-7.52 (m, 14H), 7.63-7.68 (m, 3H), 7.94-7.98 (m, 2H), 8.12 (d, 1H), 8.28 (d, 4H), 8.45 (d, 1H), 8.55 ( d, 1H) 521 7.25-7.52 (m, 14H), 7.63-7.68 (m, 3H), 7.94-7.98 (m, 2H), 8.12 (d, 1H), 8.28 (d, 4H), 8.45 (d, 1H), 8.55 ( d, 1H) 524 7.25-7.52 (m, 17H), 7.63 (d, 1H), 7.79-7.86 (m, 4H), 7.94-7.98 (m, 2H), 8.09-8.12 (m, 2H), 8.23-8.30 (m, 5H) ), 8.45 (d, 1H), 8.55 (d, 1H) 528 7.25-7.52 (m, 13H), 7.66 (d, 1H), 7.81-7.89 (m, 7H), 7.98 (d, 1H), 8.28 (d, 4H), 8.45 (d, 1H) 532 7.41-7.52 (m, 10H), 7.82-7.88 (m, 8H), 7.98-8.04 (m, 2H), 8.12-8.18 (m, 3H), 8.28 (d, 4H), 8.45 (d, 1H), 8.93 (d, 2H), 9.15 (s, 1H) 533 7.41-7.52 (m, 10H), 7.79-7.88 (m, 10H), 7.98-8.04 (m, 2H), 8.12-8.28 (m, 6H), 8.45 (d, 1H), 8.93 (d, 2H), 9.15 (s, 1H) 534 7.25-7.52 (m, 14H), 7.63-7.68 (m, 3H), 7.79-7.86 (m, 6H), 7.94-7.98 (m, 2H), 8.12 (d, 1H), 8.28 (d, 4H), 8.45 (d, 1H), 8.55 (d, 1H) 535 7.25-7.52 (m, 14H), 7.63-7.68 (m, 3H), 7.79-7.86 (m, 8H), 7.94-7.98 (m, 2H), 8.12 (d, 1H), 8.23-8.28 (m, 3H) ), 8.45 (d, 1H), 8.55 (d, 1H) 538 7.25 (s, 4H), 7.41-7.52 (m, 10H), 7.79-7.89 (m, 10H), 7.98-8.04 (m, 2H), 8.12-8.28 (m, 6H), 8.45 (d, 1H), 8.93 (d, 2H), 9.15 (s, 1H) 540 7.25-7.52 (m, 17H), 7.66 (d, 1H), 7.79-7.89 (m, 9H), 7.98 (d, 1H), 8.23-8.28 (m, 3H), 8.45 (d, 1H) 543 7.32-7.52 (m, 13H), 7.66 (d, 1H), 7.82-7.89 (m, 7H), 7.98 (d, 1H), 8.28 (d, 4H), 8.45 (d, 1H) 544 7.41-7.52 (m, 13H), 7.82-7.86 (m, 4H), 7.98 (d, 2H), 8.20-8.28 (m, 5H), 8.41-8.45 (m, 3H) 548 7.41-7.52 (m, 8H), 7.82-7.88 (m, 6H), 7.98 (d, 1H), 8.10-8.12 (m, 3H), 8.28-8.34 (m, 5H), 8.45 (d, 1H), 8.93-8.99 (m, 3H) 558 7.41-7.52 (m, 10H), 7.82-7.88 (m, 8H), 7.98 (d, 1H), 8.10-8.12 (m, 3H), 8.23-8.34 (m, 6H), 8.45 (d, 1H), 8.93-8.99 (m, 3H) 560 7.41-7.52 (m, 8H), 7.82-7.88 (m, 6H), 7.98 (d, 1H), 8.10-8.12 (m, 3H), 8.28-8.34 (m, 5H), 8.45 (d, 1H), 8.93-8.99 (m, 3H) 565 7.41-7.52 (m, 8H), 7.79-7.88 (m, 9H), 7.98-8.36 (m, 9H), 8.45 (d, 1H), 8.93 (d, 2H), 9.15 (s, 1H)

compound FD-MS compound FD-MS 2 m/z= 627.73 (C ₄₅ H ₂₉ N ₃ O=627.23) 4 m/z= 716.83 (C ₅₁ H ₃₂ N ₄ O=716.26) 5 m/z= 641.71 (C ₄₅ H ₂₇ N ₃ O ₂ =641.21) 7 m/z= 701.81 (C ₅₁ H ₃₁ N ₃ O=701.25) 9 m/z= 675.77 (C ₄₉ H ₂₉ N ₃ O=675.23) 11 m/z= 714.81 (C ₅₁ H ₃₀ N ₄ O=714.24) 13 m/z= 651.75 (C ₄₇ H ₂₉ N ₃ O=651.23) 15 m/z= 870.01 (C ₆₂ H ₃₉ N ₅ O=869.32) 16 m/z= 778.90 (C ₅₆ H ₃₄ N ₄ O=778.27) 17 m/z= 784.92 (C ₅₄ H ₃₂ N ₄ OS=784.23) 18 m/z= 768.86 (C ₅₄ H ₃₂ N ₄ O ₂ =768.25) 19 m/z= 784.92 (C ₅₄ H ₃₂ N ₄ OS=784.23) 20 m/z= 768.86 (C ₅₄ H ₃₂ N ₄ O ₂ =768.25) 21 m/z= 817.93 (C ₅₈ H ₃₅ N ₅ O=817.28) 22 m/z= 804.93 (C ₅₈ H ₃₆ N ₄ O=804.29) 24 m/z= 627.73 (C ₄₅ H ₂₉ N ₃ O=627.23) 27 m/z= 641.71 (C ₄₅ H ₂₇ N ₃ O ₂ =641.21) 29 m/z= 701.81 (C ₅₁ H ₃₁ N ₃ O=701.25) 31 m/z= 675.77 (C ₄₉ H ₂₉ N ₃ O=675.23) 33 m/z= 714.81 (C ₅₁ H ₃₀ N ₄ O=714.24) 35 m/z= 651.75 (C ₄₇ H ₂₉ N ₃ O=651.23) 37 m/z= 870.01 (C ₆₂ H ₃₉ N ₅ O=869.32) 38 m/z= 778.90 (C ₅₆ H ₃₄ N ₄ O=778.27) 39 m/z= 784.92 (C ₅₄ H ₃₂ N ₄ OS=784.23) 41 m/z= 784.92 (C ₅₄ H ₃₂ N ₄ OS=784.23) 42 m/z= 768.86 (C ₅₄ H ₃₂ N ₄ O ₂ =768.25) 44 m/z= 804.93 (C ₅₈ H ₃₆ N ₄ O=804.29) 46 m/z= 626.74 (C ₄₆ H ₃₀ N ₂ O=626.24) 48 m/z= 715.84 (C ₅₂ H ₃₃ N ₃ O=715.26) 49 m/z= 640.73 (C ₄₆ H ₂₈ N ₂ O ₂ =640.22) 51 m/z= 700.82 (C ₅₂ H ₃₂ N ₂ O=700.25) 53 m/z= 674.79 (C ₅₀ H ₃₀ N ₂ O=674.24) 55 m/z= 713.82 (C ₅₂ H ₃₁ N ₃ O=713.25) 57 m/z= 650.76 (C ₄₈ H ₃₀ N ₂ O=650.24) 59 m/z= 869.02 (C ₆₃ H ₄₀ N ₄ O=868.32) 60 m/z= 777.91 (C ₅₇ H ₃₅ N ₃ O=777.28) 61 m/z= 783.94 (C ₅₅ H ₃₃ N ₃ OS=783.23) 62 m/z= 767.87 (C ₅₅ H ₃₃ N ₃ O ₂ =767.26) 63 m/z= 783.94 (C ₅₅ H ₃₃ N ₃ OS=783.23) 64 m/z= 767.87 (C ₅₅ H ₃₃ N ₃ O ₂ =767.26) 66 m/z= 803.94 (C ₅₉ H ₃₇ N ₃ O=803.29) 68 m/z= 626.74 (C ₄₆ H ₃₀ N ₂ O=626.24) 70 m/z= 715.84 (C ₅₂ H ₃₃ N ₃ O=715.26) 71 m/z= 640.73 (C ₄₆ H ₂₈ N ₂ O ₂ =640.22) 73 m/z= 700.82 (C ₅₂ H ₃₂ N ₂ O=700.25) 75 m/z= 674.79 (C ₅₀ H ₃₀ N ₂ O=674.24) 77 m/z= 713.82 (C ₅₂ H ₃₁ N ₃ O=713.25) 79 m/z= 650.76 (C ₄₈ H ₃₀ N ₂ O=650.24) 81 m/z= 869.02 (C ₆₃ H ₄₀ N ₄ O=868.32) 82 m/z= 777.91 (C ₅₇ H ₃₅ N ₃ O=777.28) 83 m/z= 783.94 (C ₅₅ H ₃₃ N ₃ OS=783.23) 84 m/z= 767.87 (C ₅₅ H ₃₃ N ₃ O ₂ =767.26) 85 m/z= 783.94 (C ₅₅ H ₃₃ N ₃ OS=783.23) 86 m/z= 767.87 (C ₅₅ H ₃₃ N ₃ O ₂ =767.26) 88 m/z= 803.94 (C ₅₉ H ₃₇ N ₃ O=803.29) 90 m/z= 626.74 (C ₄₆ H ₃₀ N ₂ O=626.24) 92 m/z= 715.84 (C ₅₂ H ₃₃ N ₃ O=715.26) 93 m/z= 640.73 (C ₄₆ H ₂₈ N ₂ O ₂ =640.22) 95 m/z= 700.82 (C ₅₂ H ₃₂ N ₂ O=700.25) 97 m/z= 674.79 (C ₅₀ H ₃₀ N ₂ O=674.24) 99 m/z= 713.82 (C ₅₂ H ₃₁ N ₃ O=713.25) 101 m/z= 650.76 (C ₄₈ H ₃₀ N ₂ O=650.24) 103 m/z= 869.02 (C ₆₃ H ₄₀ N ₄ O=868.32) 104 m/z= 777.91 (C ₅₇ H ₃₅ N ₃ O=777.28) 105 m/z= 783.94 (C ₅₅ H ₃₃ N ₃ OS=783.23) 106 m/z= 767.87 (C ₅₅ H ₃₃ N ₃ O ₂ =767.26) 107 m/z= 783.94 (C ₅₅ H ₃₃ N ₃ OS=783.23) 108 m/z= 767.87 (C ₅₅ H ₃₃ N ₃ O ₂ =767.26) 110 m/z= 803.94 (C ₅₉ H ₃₇ N ₃ O=803.29) 112 m/z= 626.74 (C ₄₆ H ₃₀ N ₂ O=626.24) 114 m/z= 715.84 (C ₅₂ H ₃₃ N ₃ O=715.26) 115 m/z= 640.73 (C ₄₆ H ₂₈ N ₂ O ₂ =640.22) 117 m/z= 700.82 (C ₅₂ H ₃₂ N ₂ O=700.25) 119 m/z= 674.79 (C ₅₀ H ₃₀ N ₂ O=674.24) 121 m/z= 713.82 (C ₅₂ H ₃₁ N ₃ O=713.25) 123 m/z= 650.76 (C ₄₈ H ₃₀ N ₂ O=650.24) 125 m/z= 869.02 (C ₆₃ H ₄₀ N ₄ O=868.32) 126 m/z= 777.91 (C ₅₇ H ₃₅ N ₃ O=777.28) 127 m/z= 783.94 (C ₅₅ H ₃₃ N ₃ OS=783.23) 128 m/z= 767.87 (C ₅₅ H ₃₃ N ₃ O ₂ =767.26) 129 m/z= 783.94 (C ₅₅ H ₃₃ N ₃ OS=783.23) 130 m/z= 767.87 (C ₅₅ H ₃₃ N ₃ O ₂ =767.26) 132 m/z= 803.94 (C ₅₉ H ₃₇ N ₃ O=803.29) 222 m/z= 677.79 (C ₄₉ H ₃₁ N ₃ O=677.25) 224 m/z= 766.88 (C ₅₅ H ₃₄ N ₄ O=766.27) 225 m/z= 691.77 (C ₄₉ H ₂₉ N ₃ O ₂ =691.23) 227 m/z= 751.87 (C ₅₅ H ₃₃ N ₃ O=751.26) 229 m/z= 725.83 (C ₅₃ H ₃₁ N ₃ O=725.25) 230 m/z= 764.87 (C ₅₅ H ₃₂ N ₄ O=764.26) 231 m/z= 701.81 (C ₅₁ H ₃₁ N ₃ O=701.25) 233 m/z= 677.79 (C ₄₉ H ₃₁ N ₃ O=677.25) 235 m/z= 766.88 (C ₅₅ H ₃₄ N ₄ O=766.27) 236 m/z= 691.77 (C ₄₉ H ₂₉ N ₃ O ₂ =691.23) 238 m/z= 751.87 (C ₅₅ H ₃₃ N ₃ O=751.26) 240 m/z= 725.83 (C ₅₃ H ₃₁ N ₃ O=725.25) 241 m/z= 764.87 (C ₅₅ H ₃₂ N ₄ O=764.26) 242 m/z= 701.81 (C ₅₁ H ₃₁ N ₃ O=701.25) 244 m/z= 792.92 (C ₅₇ H ₃₆ N ₄ O=792.29) 246 m/z= 882.02 (C ₆₃ H ₃₉ N ₅ O=881.32) 247 m/z= 806.91 (C ₅₇ H ₃₄ N ₄ O ₂ =806.27) 249 m/z= 867.00 (C ₆₃ H ₃₈ N ₄ O=866.30) 251 m/z= 840.96 (C ₆₁ H ₃₆ N ₄ O=840.29) 252 m/z= 880.00 (C ₆₃ H ₃₇ N ₅ O=879.30) 253 m/z= 816.94 (C ₅₉ H ₃₆ N ₄ O=816.29) 255 m/z= 792.92 (C ₅₇ H ₃₆ N ₄ O=792.29) 257 m/z= 882.02 (C ₆₃ H ₃₉ N ₅ O=881.32) 258 m/z= 806.91 (C ₅₇ H ₃₄ N ₄ O ₂ =806.27) 260 m/z= 867.00 (C ₆₃ H ₃₈ N ₄ O=866.30) 262 m/z= 840.96 (C ₆₁ H ₃₆ N ₄ O=840.29) 263 m/z= 880.00 (C ₆₃ H ₃₇ N ₅ O=879.30) 264 m/z= 816.94 (C ₅₉ H ₃₆ N ₄ O=816.29) 310 m/z= 793.91 (C ₅₇ H ₃₅ N ₃ O ₂ =793.27) 312 m/z= 883.00 (C ₆₃ H ₃₈ N ₄ O ₂ =882.30) 313 m/z= 807.89 (C ₅₇ H ₃₃ N ₃ O ₃ =807.25) 315 m/z= 867.99 (C ₆₃ H ₃₇ N ₃ O ₂ =867.29) 317 m/z= 841.95 (C ₆₁ H ₃₅ N ₃ O ₂ =841.27) 318 m/z= 880.99 (C ₆₃ H ₃₆ N ₄ O ₂ =880.28) 319 m/z= 817.93 (C ₅₉ H ₃₅ N ₃ O ₂ =817.27) 321 m/z= 793.91 (C ₅₇ H ₃₅ N ₃ O ₂ =793.27) 323 m/z= 883.00 (C ₆₃ H ₃₈ N ₄ O ₂ =882.30) 324 m/z= 807.89 (C ₅₇ H ₃₃ N ₃ O ₃ =807.25) 326 m/z= 867.99 (C ₆₃ H ₃₇ N ₃ O ₂ =867.29) 328 m/z= 841.95 (C ₆₁ H ₃₅ N ₃ O ₂ =841.27) 329 m/z= 880.99 (C ₆₃ H ₃₆ N ₄ O ₂ =880.28) 330 m/z= 817.93 (C ₅₉ H ₃₅ N ₃ O ₂ =817.27) 332 m/z= 677.79 (C ₄₉ H ₃₁ N ₃ O=677.25) 334 m/z= 766.88 (C ₅₅ H ₃₄ N ₄ O=766.27) 335 m/z= 691.77 (C ₄₉ H ₂₉ N ₃ O ₂ =691.23) 337 m/z= 751.87 (C ₅₅ H ₃₃ N ₃ O=751.26) 339 m/z= 725.83 (C ₅₃ H ₃₁ N ₃ O=725.25) 340 m/z= 764.87 (C ₅₅ H ₃₂ N ₄ O=764.26) 341 m/z= 701.81 (C ₅₁ H ₃₁ N ₃ O=701.25) 343 m/z= 677.79 (C ₄₉ H ₃₁ N ₃ O=677.25) 345 m/z= 766.88 (C ₅₅ H ₃₄ N ₄ O=766.27) 346 m/z= 691.77 (C ₄₉ H ₂₉ N ₃ O ₂ =691.23) 348 m/z= 751.87 (C ₅₅ H ₃₃ N ₃ O=751.26) 350 m/z= 725.83 (C ₅₃ H ₃₁ N ₃ O=725.25) 351 m/z= 764.87 (C ₅₅ H ₃₂ N ₄ O=764.26) 352 m/z= 701.81 (C ₅₁ H ₃₁ N ₃ O=701.25) 419 m/z= 625.72 (C ₄₅ H ₂₇ N ₃ O=625.22) 421 m/z= 701.81 (C ₅₁ H ₃₁ N ₃ O=701.25) 424 m/z= 624.73 (C ₄₆ H ₂₈ N ₂ O=624.22) 429 m/z= 700.82 (C ₅₂ H ₃₂ N ₂ O=700.25) 434 m/z= 776.92 (C ₅₈ H ₃₆ N ₂ O=776.28) 436 m/z= 625.72 (C ₄₅ H ₂₇ N ₃ O=625.22) 438 m/z= 701.81 (C ₅₁ H ₃₁ N ₃ O=701.25) 441 m/z= 624.73 (C ₄₆ H ₂₈ N ₂ O=624.22) 446 m/z= 700.82 (C ₅₂ H ₃₂ N ₂ O=700.25) 451 m/z= 776.92 (C58H36N2O=776.28) 453 m/z= 701.81 (C51H31N3O=701.25) 454 m/z= 701.81 (C51H31N3O=701.25) 457 m/z= 777.91 (C57H35N3O=777.28) 465 m/z= 716.83 (C51H32N4O=716.26) 467 m/z= 700.82 (C52H32N2O=700.25) 468 m/z= 700.82 (C52H32N2O=700.25) 471 m/z= 717.81 (C51H31N3O2=717.24) 478 m/z= 716.82 (C52H32N2O2=716.25) 485 m/z= 701.81 (C51H31N3O=701.25) 486 m/z= 700.82 (C52H32N2O=700.25) 487 m/z= 716.83 (C51H32N4O=716.26) 492 m/z= 776.92 (C58H36N2O=776.28) 494 m/z= 716.82 (C52H32N2O2=716.25) 496 m/z= 717.88 (C51H31N3S=717.22) 497 m/z= 717.88 (C51H31N3S=717.22) 501 m/z= 717.88 (C51H31N3S=717.22) 504 m/z= 716.89 (C52H32N2S=716.23) 505 m/z= 716.89 (C52H32N2S=716.23) 507 m/z= 792.98 (C58H36N2S=792.26) 511 m/z= 792.98 (C58H36N2S=792.26) 515 m/z= 793.97 (C57H35N3S=793.26) 520 m/z= 732.89 (C51H32N4S=732.23) 521 m/z= 732.89 (C51H32N4S=732.23) 524 m/z= 731.90 (C52H33N3S=731.24) 528 m/z= 657.78 (C45H27N3OS=657.19) 532 m/z= 717.88 (C51H31N3S=717.22) 533 m/z= 716.89 (C52H32N2S=716.23) 534 m/z= 732.89 (C51H32N4S=732.23) 535 m/z= 731.90 (C52H33N3S=731.24) 538 m/z= 792.98 (C58H36N2S=792.26) 540 m/z= 732.89 (C51H32N4S=732.23) 543 m/z= 657.78 (C45H27N3OS=657.19) 544 m/z= 673.85 (C45H27N3S2=673.16) 548 m/z= 641.78 (C45H27N3S=641.19) 558 m/z= 716.89 (C52H32N2S=716.23) 560 m/z= 717.88 (C51H31N3S=717.22) 565 m/z= 640.79 (C46H28N2S=640.20)

<Experimental Example 1>-Fabrication of organic light emitting device

<Comparative Example 1>

1) Fabrication of organic light emitting device

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

Next, the ITO substrate is installed in the substrate folder of the vacuum evaporation 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.

Subsequently, after evacuating until the degree of vacuum in the chamber reached 10 ^-6 torr, a current was applied to the cell to evaporate 2-TNATA to deposit a hole injection layer having a thickness of 600 Å 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 hole transport layer having a thickness of 300Å was deposited on the hole injection layer by evaporation by applying a current to the cell.

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

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

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

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

<Comparative Example 2>

An organic light-emitting device was manufactured in the same manner as in Comparative Example 1, except that the following E2 was used instead of E1 used to form the electron transport layer in Comparative Example 1.

<Examples 1 to 170>

An organic light-emitting device was manufactured in the same manner as in Comparative Example 1, except that the compound shown in Table 9 below was used instead of E1 used to form the electron transport layer in Comparative Example 1.

The driving voltage, luminous efficiency, color coordinates (CIE), and lifetime of the blue organic light-emitting device manufactured according to the present invention were measured, and the results are shown in Table 9 below.

compound Driving voltage
(V) Luminous efficiency
(cd/A) CIE
(x, y) life span
(T95) Comparative Example 1 E1 5.56 5.91 (0.134, 0.100) 28 Comparative Example 2 E2 6.9 4.4 (0.134, 0.101) 20 Example 1 2 5.44 6.47 (0.134, 0.102) 36 Example 2 4 5.41 6.44 (0.134, 0.101) 43 Example 3 5 5.34 6.38 (0.134, 0.101) 39 Example 4 7 5.38 6.20 (0.134, 0.103) 40 Example 5 9 5.60 6.12 (0.134, 0.102) 43 Example 6 11 5.45 6.21 (0.134, 0.101) 37 Example 7 13 5.44 6.22 (0.134, 0.102) 43 Example 8 15 5.62 5.95 (0.134, 0.103) 42 Example 9 16 5.40 6.12 (0.134, 0.101) 39 Example 10 17 5.50 5.89 (0.134, 0.100) 41 Example 11 18 5.44 6.01 (0.134, 0.101) 36 Example 12 19 5.34 6.58 (0.134, 0.100) 45 Example 13 20 5.38 6.93 (0.134, 0.100) 43 Example 14 21 4.91 6.32 (0.134, 0.100) 41 Example 15 22 4.98 6.44 (0.134, 0.100) 40 Example 16 24 5.62 6.38 (0.134, 0.100) 35 Example 17 27 4.72 6.20 (0.134, 0.102) 48 Example 18 29 5.45 6.44 (0.134, 0.103) 48 Example 19 31 5.44 6.34 (0.134, 0.102) 36 Example 20 33 5.62 6.20 (0.134, 0.101) 39 Example 21 35 5.40 6.12 (0.134, 0.103) 44 Example 22 37 5.60 6.21 (0.134, 0.102) 43 Example 23 38 5.45 6.22 (0.134, 0.101) 37 Example 24 39 5.39 5.95 (0.134, 0.102) 33 Example 25 41 4.96 5.95 (0.134, 0.101) 42 Example 26 42 4.91 6.13 (0.134, 0.101) 39 Example 27 44 4.91 5.85 (0.134, 0.100) 41 Example 28 46 4.98 6.38 (0.134, 0.101) 42 Example 29 48 5.62 6.20 (0.134, 0.100) 45 Example 30 49 4.72 6.12 (0.134, 0.100) 43 Example 31 51 4.91 6.21 (0.134, 0.101) 41 Example 32 53 4.98 6.22 (0.134, 0.100) 40 Example 33 55 5.62 5.95 (0.134, 0.100) 33 Example 34 57 5.44 6.13 (0.134, 0.102) 36 Example 35 59 5.44 5.89 (0.134, 0.102) 36 Example 36 60 5.44 6.41 (0.134, 0.102) 47 Example 37 61 5.34 6.44 (0.134, 0.102) 36 Example 38 62 5.38 6.38 (0.134, 0.101) 39 Example 39 63 5.38 6.20 (0.134, 0.103) 40 Example 40 64 5.39 6.62 (0.134, 0.102) 43 Example 41 66 4.96 6.21 (0.134, 0.101) 37 Example 42 68 4.91 6.22 (0.134, 0.102) 33 Example 43 70 4.91 6.12 (0.134, 0.101) 42 Example 44 71 4.98 6.51 (0.134, 0.101) 39 Example 45 73 5.62 6.21 (0.134, 0.100) 42 Example 46 75 5.39 5.95 (0.134, 0.101) 34 Example 47 77 4.96 6.88 (0.134, 0.100) 45 Example 48 79 4.91 6.93 (0.134, 0.102) 43 Example 49 81 4.91 6.95 (0.134, 0.100) 41 Example 50 82 4.98 6.22 (0.134, 0.100) 40 Example 51 83 5.62 5.68 (0.134, 0.101) 33 Example 52 84 4.72 6.53 (0.134, 0.102) 48 Example 53 85 5.44 6.63 (0.134, 0.102) 48 Example 54 86 5.34 6.13 (0.134, 0.101) 39 Example 55 88 5.38 6.88 (0.134, 0.100) 41 Example 56 90 5.60 6.93 (0.134, 0.101) 32 Example 57 92 5.45 6.95 (0.134, 0.100) 45 Example 58 93 4.91 6.93 (0.134, 0.100) 43 Example 59 95 4.91 6.95 (0.134, 0.100) 41 Example 60 97 4.98 6.23 (0.134, 0.100) 40 Example 61 99 5.62 5.98 (0.134, 0.100) 36 Example 62 101 4.72 6.51 (0.134, 0.102) 48 Example 63 103 4.91 6.93 (0.134, 0.100) 43 Example 64 104 4.91 6.95 (0.134, 0.100) 41 Example 65 105 4.98 6.26 (0.134, 0.100) 40 Example 66 106 5.62 5.98 (0.134, 0.100) 33 Example 67 107 4.72 6.53 (0.134, 0.102) 44 Example 68 108 4.72 6.53 (0.134, 0.102) 48 Example 69 110 4.91 6.43 (0.134, 0.100) 43 Example 70 112 4.91 6.93 (0.134, 0.100) 43 Example 71 114 4.98 6.95 (0.134, 0.100) 41 Example 72 115 5.62 6.22 (0.134, 0.100) 47 Example 73 117 5.62 5.98 (0.134, 0.100) 33 Example 74 119 4.72 6.55 (0.134, 0.102) 48 Example 75 121 4.72 6.20 (0.134, 0.102) 43 Example 76 123 5.40 6.12 (0.134, 0.101) 39 Example 77 125 5.44 6.21 (0.134, 0.100) 41 Example 78 126 5.39 6.20 (0.134, 0.101) 36 Example 79 127 4.96 6.88 (0.134, 0.100) 45 Example 80 128 4.91 6.93 (0.134, 0.100) 43 Example 81 129 5.39 6.95 (0.134, 0.100) 41 Example 82 130 4.96 6.22 (0.134, 0.100) 40 Example 83 132 4.91 5.98 (0.134, 0.100) 33 Example 84 222 4.72 6.53 (0.134, 0.102) 48 Example 85 224 4.72 6.53 (0.134, 0.102) 48 Example 86 225 4.91 6.98 (0.134, 0.100) 43 Example 87 227 4.91 6.93 (0.134, 0.100) 41 Example 88 229 4.98 6.22 (0.134, 0.100) 40 Example 89 230 5.62 5.98 (0.134, 0.100) 38 Example 90 231 4.72 6.53 (0.134, 0.102) 48 Example 91 233 4.72 6.33 (0.134, 0.102) 41 Example 92 235 5.40 6.13 (0.134, 0.101) 39 Example 93 236 5.44 5.89 (0.134, 0.100) 41 Example 94 238 5.39 6.01 (0.134, 0.101) 32 Example 95 240 4.96 6.55 (0.134, 0.100) 45 Example 96 241 4.91 6.93 (0.134, 0.100) 42 Example 97 242 4.92 6.91 (0.134, 0.100) 41 Example 98 244 4.98 6.22 (0.134, 0.100) 40 Example 99 246 5.62 5.98 (0.134, 0.100) 33 Example 100 247 4.72 6.53 (0.134, 0.102) 43 Example 101 249 4.63 6.53 (0.134, 0.102) 48 Example 102 251 4.91 6.82 (0.134, 0.100) 43 Example 103 252 4.99 6.95 (0.134, 0.100) 41 Example 104 253 4.98 6.22 (0.134, 0.100) 40 Example 105 255 5.62 5.98 (0.134, 0.100) 33 Example 106 257 4.72 6.53 (0.134, 0.102) 48 Example 107 258 4.88 6.89 (0.134, 0.102) 42 Example 108 260 5.40 6.12 (0.134, 0.101) 39 Example 109 262 5.41 5.89 (0.134, 0.100) 41 Example 110 263 5.39 6.01 (0.134, 0.101) 32 Example 111 264 4.96 6.88 (0.134, 0.100) 35 Example 112 310 4.91 6.93 (0.134, 0.100) 43 Example 113 312 4.77 6.95 (0.134, 0.100) 41 Example 114 313 4.98 6.22 (0.134, 0.100) 40 Example 115 315 5.62 5.98 (0.134, 0.100) 33 Example 116 317 4.71 6.51 (0.134, 0.102) 48 Example 117 318 4.72 6.53 (0.134, 0.102) 38 Example 118 319 4.91 6.78 (0.134, 0.100) 43 Example 119 321 4.90 6.95 (0.134, 0.100) 41 Example 120 323 4.98 6.22 (0.134, 0.100) 40 Example 121 324 5.62 5.98 (0.134, 0.100) 33 Example 122 326 4.72 6.53 (0.134, 0.102) 48 Example 123 328 4.74 6.59 (0.134, 0.102) 45 Example 124 329 5.42 6.13 (0.134, 0.101) 39 Example 125 330 5.44 5.89 (0.134, 0.100) 41 Example 126 332 5.36 6.01 (0.134, 0.101) 32 Example 127 334 4.96 6.82 (0.134, 0.100) 45 Example 128 335 4.91 6.93 (0.134, 0.100) 43 Example 129 337 4.95 6.95 (0.134, 0.100) 41 Example 130 339 4.98 6.22 (0.134, 0.100) 40 Example 131 340 5.62 5.98 (0.134, 0.100) 33 Example 132 341 4.75 6.53 (0.134, 0.102) 40 Example 133 343 4.72 6.35 (0.134, 0.102) 48 Example 134 345 4.91 6.93 (0.134, 0.100) 43 Example 135 346 4.93 6.95 (0.134, 0.100) 40 Example 136 348 4.98 6.21 (0.134, 0.100) 40 Example 137 350 5.62 5.98 (0.134, 0.100) 34 Example 138 351 4.72 6.53 (0.134, 0.102) 35 Example 139 352 4.79 6.55 (0.134, 0.102) 48 Example 140 419 5.55 6.13 (0.134, 0.101) 39 Example 141 421 5.44 5.89 (0.134, 0.100) 41 Example 142 424 5.41 5.89 (0.134, 0.101) 34 Example 143 429 4.96 6.88 (0.134, 0.100) 45 Example 144 434 4.88 6.93 (0.134, 0.102) 43 Example 145 436 5.52 5.87 (0.134, 0.100) 33 Example 146 438 4.98 6.23 (0.134, 0.100) 40 Example 147 441 5.62 5.98 (0.134, 0.100) 33 Example 148 446 4.72 6.22 (0.134, 0.102) 45 Example 149 451 4.73 6.53 (0.134, 0.102) 48 Example 150 453 5.21 5.82 (0.134, 0.100) 43 Example 151 454 5.34 6.11 (0.134, 0.101) 38 Example 152 457 4.86 6.76 (0.134, 0.100) 45 Example 153 467 4.94 6.73 (0.134, 0.102) 42 Example 154 468 4.91 6.55 (0.134, 0.100) 46 Example 155 471 4.91 6.29 (0.134, 0.100) 42 Example 156 478 5.22 6.11 (0.134, 0.100) 35 Example 157 487 4.79 6.24 (0.134, 0.102) 41 Example 158 492 4.75 6.57 (0.134, 0.102) 46 Example 159 496 4.98 6.63 (0.134, 0.100) 40 Example 160 497 5.11 5.98 (0.134, 0.100) 36 Example 161 504 4.78 6.12 (0.134, 0.102) 45 Example 162 505 4.73 6.58 (0.134, 0.102) 48 Example 163 507 5.07 5.82 (0.134, 0.100) 41 Example 164 511 5.14 6.15 (0.134, 0.101) 38 Example 165 515 4.86 6.76 (0.134, 0.100) 44 Example 166 521 4.74 6.63 (0.134, 0.102) 42 Example 167 524 4.91 6.55 (0.134, 0.100) 46 Example 168 528 4.91 6.39 (0.134, 0.100) 42 Example 169 532 5.22 6.16 (0.134, 0.100) 36 Example 170 548 4.75 6.24 (0.134, 0.102) 41

As can be seen from the results of Table 9, 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 lifetime compared to Comparative Example 1.

Looking at the results of Table 9, Compounds 7, 29, 73 and 436, 419, and 424 have a linker between the dibenzofuran and the heteroaryl group or form a direct bond. When there is a linker, electrons in the LUMO state are wider and distributed, reducing intramolecular stress. For this reason, it was confirmed that the lifespan was improved when there was a linker.

It was confirmed that the organic light-emitting device using the electron transport layer material of the present invention had a lower driving voltage and significantly improved luminous efficiency and lifetime compared to Comparative Examples 1 and 2.

The cause of these results is that when the invented compound having appropriate length, strength, and flat properties is used as an electron transport layer, it receives electrons under certain conditions to create an excited state, and in particular, the excited state of the heteroskeleton region of the compound. When is formed, the excited energy will be transferred to a stable state before other reactions of the excited heteroskeletal site, and it is believed that the relatively stable compound can efficiently transfer electrons without decomposition or destruction of the compound. For reference, those that have a stable state when excited are considered to be aryl or acene compounds or polycyclic hetero compounds. therefore. It is judged that the compound of the present invention has improved electron-transport characteristics or improved stability, thereby bringing excellence in all aspects of driving, efficiency, and life.

<Experimental Example 2>-Fabrication of organic light emitting device

<Comparative Example 3>

1) Fabrication of organic light emitting device

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

Next, the ITO substrate is installed in the substrate folder of the vacuum evaporation 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.

Subsequently, after evacuating until the degree of vacuum in the chamber reached 10 ^-6 torr, a current was applied to the cell to evaporate 2-TNATA to deposit a hole injection layer having a thickness of 600 Å 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 hole transport layer having a thickness of 300Å was deposited on the hole injection layer by evaporation by applying a current to the cell.

Thus, a hole injection layer and a hole transport layer were formed.

On the light emitting layer, H2 as a host and Ir(ppy)3 as a green phosphorescent dopant were doped 7% and deposited at 400 Å.

Ir(ppy) ₃

After that, 60Å of BCP was deposited as a hole blocking layer, and 200Å of Alq3 was deposited as an electron transport layer thereon. Finally, lithium fluoride (LiF) was deposited on the electron transport layer to a thickness of 10Å to form an electron injection layer, and then an aluminum (Al) cathode was deposited on the electron injection layer to a thickness of 1,200Å to form a cathode. An electroluminescent device was manufactured.

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

<Examples 171 to 207>

An organic light-emitting device was manufactured in the same manner as in Comparative Example 3, except that the compound shown in Table 10 below was used instead of H2 used for forming the host in Comparative Example 3.

Table 10 shows the results of measuring the driving voltage, luminous efficiency, color coordinates (CIE), and lifetime of the green organic light-emitting device manufactured according to the present invention.

compound Driving voltage
(V) Luminous efficiency
(cd/A) CIE
(x, y) life span
(T95) Comparative Example 3 H2 7.24 35.83 (0.266, 0.711) 63 Example 171 5 7.11 41.23 (0.266, 0.712) 92 Example 172 7 6.96 43.88 (0.265, 0.711) 79 Example 173 11 6.74 46.02 (0.265, 0.712) 89 Example 174 27 7.12 38.82 (0.266, 0.713) 92 Example 175 29 6.89 39.44 (0.266, 0.711) 93 Example 176 139 6.72 41.36 (0.267, 0.711) 77 Example 177 150 6.93 42.77 (0.266, 0.711) 76 Example 178 419 7.02 40.76 (0.265, 0.712) 88 Example 179 421 7.06 38.52 (0.265, 0.712) 91 Example 180 423 6.73 38.89 (0.266, 0.712) 90 Example 181 424 6.85 42.13 (0.265, 0.713) 81 Example 182 427 7.03 44.61 (0.266, 0.711) 85 Example 183 436 7.01 38.22 (0.267, 0.711) 79 Example 184 441 6.78 39.72 (0.265, 0.711) 96 Example 185 447 6.67 40.96 (0.264, 0.712) 92 Example 186 465 7.01 38.42 (0.265, 0.712) 92 Example 187 471 6.77 39.29 (0.266, 0.712) 89 Example 188 485 6.75 42.23 (0.265, 0.713) 85 Example 189 486 6.83 43.64 (0.266, 0.711) 82 Example 190 487 7.03 38.21 (0.267, 0.711) 88 Example 191 492 6.88 39.44 (0.265, 0.711) 94 Example 192 494 6.64 41.96 (0.264, 0.712) 92 Example 193 496 7.01 39.99 (0.267, 0.711) 81 Example 194 501 6.98 39.92 (0.265, 0.711) 94 Example 195 520 6.94 40.91 (0.264, 0.712) 99 Example 196 532 7.21 38.62 (0.265, 0.712) 92 Example 197 533 6.85 39.42 (0.266, 0.712) 89 Example 198 534 6.67 42.41 (0.265, 0.713) 85 Example 199 535 6.89 42.64 (0.266, 0.711) 78 Example 200 538 7.21 38.86 (0.267, 0.711) 88 Example 201 540 6.87 40.56 (0.264, 0.712) 91 Example 202 543 7.22 39.55 (0.265, 0.712) 92 Example 203 544 6.74 39.59 (0.266, 0.712) 89 Example 204 548 6.95 42.29 (0.265, 0.713) 86 Example 205 558 6.83 43.24 (0.266, 0.711) 82 Example 206 560 7.15 38.51 (0.267, 0.711) 89 Example 207 565 7.14 39.81 (0.267, 0.711) 88

<Experimental Example 3>-Fabrication of organic light emitting device

<Comparative Example 4>

1) Fabrication of organic light emitting device

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

Next, the ITO substrate is installed in the substrate folder of the vacuum evaporation 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.

Subsequently, after evacuating until the degree of vacuum in the chamber reached 10 ^-6 torr, a current was applied to the cell to evaporate 2-TNATA to deposit a hole injection layer having a thickness of 600 Å 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 hole transport layer having a thickness of 300Å was deposited on the hole injection layer by evaporation by applying a current to the cell.

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

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

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

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

<Comparative Example 5>

Organic electroluminescence was carried out in the same manner as in Comparative Example 4, except that the electron transport layer E1 was formed with a thickness of 250 Å and a hole blocking layer was formed on the electron transport layer with a thickness of 50 Å of the structural formula B1 below. The device was fabricated.

<Examples 208 to 231>

In Comparative Example 4, the electron transport layer E1 was formed with a thickness of 250 Å, and then the hole blocking layer was formed on the electron transport layer with the thickness of the compound shown in Table 11 at 50 Å. Thus, an organic electroluminescent device was manufactured.

Table 11 shows the results of measuring the driving voltage, luminous efficiency, color coordinate (CIE), and lifetime of the blue organic light-emitting device manufactured according to the present invention.

compound Driving voltage
(V) Luminous efficiency
(cd/A) CIE
(x, y) life span
(T95) Comparative Example 4 - 5.51 5.54 (0.134, 0.100) 31 Comparative Example 5 B1 5.33 5.92 (0.134, 0.100) 37 Example 208 2 5.23 6.67 (0.134, 0.101) 52 Example 209 7 5.14 6.89 (0.134, 0.102) 54 Example 210 10 5.34 6.58 (0.134, 0.101) 44 Example 211 25 5.38 6.51 (0.134, 0.103) 47 Example 212 26 5.11 6.75 (0.134, 0.102) 46 Example 213 29 5.42 6.21 (0.134, 0.101) 54 Example 214 30 5.13 6.63 (0.134, 0.102) 52 Example 215 48 5.05 6.66 (0.134, 0.101) 49 Example 216 156 5.42 6.13 (0.134, 0.101) 41 Example 217 381 5.44 5.94 (0.134, 0.100) 43 Example 218 384 5.27 6.17 (0.134, 0.101) 46 Example 219 453 5.32 6.25 (0.134, 0.101) 55 Example 220 454 5.14 6.46 (0.134, 0.102) 51 Example 221 457 5.04 6.62 (0.134, 0.101) 55 Example 222 467 5.22 6.34 (0.134, 0.101) 42 Example 223 468 5.53 5.95 (0.134, 0.100) 48 Example 224 478 5.33 6.47 (0.134, 0.101) 46 Example 225 496 5.38 6.51 (0.134, 0.103) 47 Example 226 497 5.11 6.75 (0.134, 0.102) 46 Example 227 504 5.42 6.21 (0.134, 0.101) 54 Example 228 520 5.13 6.63 (0.134, 0.102) 52 Example 229 521 5.05 6.66 (0.134, 0.101) 49 Example 230 532 5.42 6.13 (0.134, 0.101) 41 Example 231 548 5.44 5.94 (0.134, 0.100) 43

As can be seen from the results of Table 11, the organic light-emitting device using the hole blocking layer material of the blue organic light-emitting device of the present invention has a lower driving voltage and significantly improved luminous efficiency and lifetime compared to Comparative Examples 4 and 5. .

In particular, when compared with the compound of Comparative Example 5, the compound of Comparative Example 5 has a substituent bonded to positions 4 and 6 of dibenzofuran, whereas the compounds shown in Table 11 are 1,2 of dibenzofuran or dibenzothiophene. A substituent is bonded to position As the substituent is bonded to the 1st and 2nd positions, the structure is distorted and has a high triplet energy, and when deposited, a space is created between the molecule and the molecule, which slows electron and hole mobility, effectively confining excitons in the emission layer. It becomes. For this reason, the luminous efficiency and lifespan have been remarkably improved.

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

Claims (12)

Heterocyclic compound represented by the following Formula 2 or Formula 3:
[Formula 2]

[Formula 3]

In Formulas 2 and 3,
X ₁ to X ₃ are the same as or different from each other, and each independently N; P; Or CR _x, and at least one of X ₁ to X ₃ includes N,
X is O or S,
L ₁ is a direct bond; A substituted or unsubstituted arylene group; Or a substituted or unsubstituted heteroarylene group,
R ₁ and R ₂ are the same as or different from each other, and each independently -CN; A substituted or unsubstituted alkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,
L ₂ is a direct bond; A substituted or unsubstituted arylene group; Or a substituted or unsubstituted heteroarylene group,
Z ₁ is a fluoranthene group, or is represented by any one of the following structures,

R _a , R _b and R _x 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 selected from the group consisting of a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or an amine group unsubstituted or substituted with 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, 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 unsubstituted aryl group; or substituted or It is an unsubstituted heteroaryl group,
m is an integer from 0 to 4,
n is an integer from 0 to 2,
k is an integer from 0 to 5,
When m is 2 or more, 2 or more R _a are the same as or different from each other,
When n is 2, two R _b are the same as or different from each other,
When k is 2 or more, 2 or more L ₁ are the same as or different from each other,
a is an integer from 1 to 4,
b is an integer of 1 to 3,
When a is 2 or more, L ₂ is the same as or different from each other,
When b is 2 or more, Z ₁ is the same as or different from each other,
Z ₁ is

In the case of, L ₂ is a substituted or unsubstituted arylene group; Or a substituted or unsubstituted heteroarylene group,
X is O, and Z ₁ is

In the case of, L ₂ is a substituted or unsubstituted arylene group; Or a substituted or unsubstituted heteroarylene group, X ₁ to X ₃ are N,
When L ₁ is a direct bond, at least one of R ₁ and R ₂ is a substituted or unsubstituted C10 to C60 aryl group,
When L ₁ is a phenylene group, X ₁ to X ₃ are N, and R ₁ and R ₂ are unsubstituted phenyl groups, Z ₁ is a fluoranthene group or is represented by any one of the following structures,

When L ₁ is a phenylene group or a naphthalene group, X ₁ and X ₃ are N, X ₂ are CRx, and R ₁ and R ₂ are unsubstituted phenyl groups, Z1 is a fluoranthene group, or in the following structure It is represented by either.

The method according to claim 1, "substituted or unsubstituted" means C1 to C60 straight-chain alkyl; C2 to C60 linear alkenyl; C2 to C60 linear alkynyl; C3 to C60 monocyclic or polycyclic cycloalkyl; C2 to C60 monocyclic or polycyclic heterocycloalkyl; C6 to C60 monocyclic or polycyclic aryl; C2 to C60 monocyclic or polycyclic heteroaryl; -SiRR'R";-P(=O)RR'; C1 to C20 alkylamine; C6 to C60 monocyclic or polycyclic arylamine; And C2 to C60 monocyclic or polycyclic heteroarylamine selected from the group consisting of It means substituted or unsubstituted with one or more substituents, or substituted or unsubstituted with a substituent to which two or more substituents selected from the aforementioned substituents are linked,
The definition of R, R'and R" is the same as the definition in Formula 2 or Formula 3 above. delete delete The heterocyclic compound of claim 1, wherein R _a and R _b are hydrogen. Heterocyclic compounds represented by any of the following compounds:

A first electrode; A second electrode provided to face the first electrode; And one or more organic material layers provided between the first electrode and the second electrode, wherein at least one of the organic material layers is a heterocyclic compound according to any one of claims 1, 2, 5 and 6 The organic light emitting device comprising a. The organic light-emitting device of claim 7, wherein the organic material layer includes an emission layer, and the emission layer includes the heterocyclic compound. The organic light-emitting device of claim 7, wherein the organic material layer includes an emission layer, the emission layer includes a host material, and the host material includes the heterocyclic compound. The organic light-emitting device of claim 7, 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 7, 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 7, wherein the organic light emitting device is a light emitting layer, a hole injection layer, a hole transport layer. An organic light-emitting device further comprising one or two or more layers selected from the group consisting of an electron injection layer, an electron transport layer, an electron blocking layer, and a hole blocking layer.

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