KR20230055222A - Novel carbazole compound, organic light emitting device comprising the same and composition for organic layer of organic light emitting device - Google Patents

Abstract

The present specification relates to a novel carbazole compound, an organic light emitting device containing the same, and a composition for an organic material layer of the organic light emitting device. A heterocyclic compound using a novel carbazole compound structure according to one embodiment has an improved hole transport ability by using conjugation expansion, and has an effect of improving the efficiency and lifespan of the organic light emitting device due to structural stability.

Description

A novel carbazole compound, an organic light emitting device including the same, and a composition for an organic layer of an organic light emitting device

The present invention relates to a novel carbazole compound, an organic light emitting device including the same, and a composition for an organic material layer of the organic light emitting device.

An organic light emitting device is a type of self-luminous display device, and has advantages such as a wide viewing angle, excellent contrast, and fast response speed.

The organic light emitting device has a structure in which an organic thin film is disposed between two electrodes. When 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 needed.

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 the light emitting layer by itself may be used, or a compound capable of serving as a host or dopant of the host-dopant type light emitting layer may be used. In addition, as a material for the organic thin film, a compound capable of performing functions such as hole injection, hole transport, electron blocking, hole blocking, electron transport, and electron injection may be used.

In order to improve the performance, lifespan or efficiency of organic light emitting devices, the development of materials for organic thin films is continuously required.

US Patent No. 4,356,429

The present invention is to provide a novel carbazole compound, an organic light emitting device including the same, and a composition for an organic material layer of the organic light emitting device.

The present invention provides a heterocyclic compound represented by Formula 1 below:

[Formula 1]

In Formula 1,

X and Y are each independently O, S, CR13R14 or a single bond;

W is N or CR6;

R13 and R14 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen; cyano group; A substituted or unsubstituted C1 to C60 alkyl group; A substituted or unsubstituted C6 to C60 aryl group; And it is selected from the group consisting of a substituted or unsubstituted C2 to C60 heteroaryl group,

R1 to R12 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen; cyano group; A substituted or unsubstituted C1 to C60 alkyl group; A substituted or unsubstituted C2 to C60 alkenyl group; A substituted or unsubstituted C2 to C60 alkynyl group; A substituted or unsubstituted C1 to C60 alkoxy group; A substituted or unsubstituted C3 to C60 cycloalkyl group; A substituted or unsubstituted C2 to C60 heterocycloalkyl group; A substituted or unsubstituted C6 to C60 aryl group; A substituted or unsubstituted C2 to C60 heteroaryl group; And a C6 to C60 aromatic hydrocarbon ring selected from the group consisting of a group represented by Formula 1-1, or substituted or unsubstituted by combining two or more groups adjacent to each other; or a substituted or unsubstituted C2 to C60 heterocycle; forming;

L is a single bond, a substituted or unsubstituted C6 to C60 arylene group; Or a substituted or unsubstituted C2 to C60 heteroarylene group;

m is an integer from 0 to 3;

Ar1 is a group represented by Formula 1-1 below,

[Formula 1-1]

In Formula 1-1,

X1 is N or CRa;

X2 is N or CRb;

X3 is N or CRc;

X4 is N or CRd;

X5 is N or CRe;

Ra to Re are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen; cyano group; A substituted or unsubstituted C1 to C60 alkyl group; A substituted or unsubstituted C2 to C60 alkenyl group; A substituted or unsubstituted C2 to C60 alkynyl group; or a substituted or unsubstituted C1 to C60 alkoxy group; A substituted or unsubstituted C6 to C60 aryl group; and a substituted or unsubstituted C2 to C60 heteroaryl group, or a substituted or unsubstituted C6 to C60 aromatic hydrocarbon ring by combining two or more groups adjacent to each other; Or a substituted or unsubstituted C2 to C60 heterocycle; to form.

In addition, the present invention is 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 includes the heterocyclic compound according to the present invention. .

In addition, the present invention provides a composition for an organic material layer of an organic light emitting device comprising two or more kinds of heterocyclic compounds according to the present invention.

The heterocyclic compound using the novel carbazole compound structure according to an embodiment has improved hole transport ability by using conjugation expansion and improved efficiency and lifespan of an organic light emitting device due to structural stability.

More specifically, when the heterocyclic compound according to one embodiment is used as a light emitting layer or an auxiliary light emitting layer, hole transport and electron transport properties are enhanced, and band gap and triplet Through the control of the energy level (T1 level) value, the hole transfer ability is improved, the stability of the molecule is increased, the driving voltage of the organic light emitting device is lowered, the light efficiency is improved, and the thermal stability of the compound is improved. improve life characteristics;

1 to 3 are diagrams schematically illustrating a stacked structure of an organic light emitting device according to an exemplary embodiment of the present invention.

Hereinafter, the present invention will be described in more detail.

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

As used herein, "substituted or unsubstituted" means heavy hydrogen; halogen; cyano; C1 to C60 straight chain or branched chain alkyl; C2 to C60 straight chain or branched chain alkenyl; C2 to C60 straight chain or branched chain; chain 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 heteroarylamines. It means substituted or unsubstituted with one or more substituents selected from the group consisting of, or substituted or unsubstituted with substituents in which two or more substituents selected from the above exemplified substituents are connected.

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

In the present specification, the alkyl group includes a straight or branched chain having 1 to 60 carbon atoms, and may be further substituted by other substituents. The number of carbon atoms of the alkyl group may be 1 to 60, specifically 1 to 40, and 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-dimethyl heptyl group, 1-ethyl-propyl group, 1,1-dimethyl-propyl group , Isohexyl group, 2-methylpentyl group, 4-methylhexyl group, 5-methylhexyl group, etc., but is not limited thereto.

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

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

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

In the present specification, the cycloalkyl group includes a monocyclic or polycyclic group having 3 to 60 carbon atoms, and may be further substituted by other substituents. Here, the polycyclic means a group in which a cycloalkyl group is directly connected or condensed with another ring group. Here, the other ring group may be a cycloalkyl group, but may also be another type of ring group, such as a heterocycloalkyl group, an aryl group, a heteroaryl group, and the like. The number of carbon atoms in the cycloalkyl group may be 3 to 60, specifically 3 to 40, and more specifically 5 to 20. Specifically, cyclopropyl group, cyclobutyl group, cyclopentyl group, 3-methylcyclopentyl group, 2,3-dimethylcyclopentyl group, cyclohexyl group, 3-methylcyclohexyl group, 4-methylcyclohexyl group, 2 ,3-dimethylcyclohexyl group, 3,4,5-trimethylcyclohexyl group, 4-tert-butylcyclohexyl group, cycloheptyl group, cyclooctyl group, etc., 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 ring 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 ring group may be a heterocycloalkyl group, but may also be another type of ring group, such as a cycloalkyl group, an aryl group, a heteroaryl group, and the like. The heterocycloalkyl group may have 2 to 60, specifically 2 to 40, and more specifically 3 to 20 carbon atoms.

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

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

,

,

,

,

,

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

,

,

,

,

,

etc., 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 group 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 ring group may be a heteroaryl group, but may also be another type of ring group, such as a cycloalkyl group, a heterocycloalkyl group, an aryl group, and the like. The heteroaryl group may have 2 to 60 carbon atoms, specifically 2 to 40, and more specifically 3 to 25 carbon atoms. Specific examples of the heteroaryl group include a pyridyl group, a pyrrolyl group, a pyrimidyl group, a pyridazinyl group, a furanyl group, a thiophene group, an imidazolyl group, a pyrazolyl group, an oxazolyl group, an isoxazolyl group, and a thiazolyl group. group, isothiazolyl group, triazolyl group, furazanyl group, oxadiazolyl group, thiadiazolyl group, dithiazolyl group, tetrazolyl group, pyranyl group, thiopyranyl group, diazinyl group, oxazinyl group , thiazinyl group, dioxynyl group, triazinyl group, tetrazinyl group, quinolyl group, isoquinolyl group, quinazolinyl group, isoquinazolinyl group, quinozolilyl group, naphthyridyl group, acridinyl group, phenanthridi Nyl group, imidazopyridinyl group, diazanaphthalenyl group, triazaindene group, indolyl group, indolizinyl group, benzothiazolyl group, benzoxazolyl group, benzimidazolyl group, benzothiophene group, benzofuran group , Dibenzothiophene group, dibenzofuran group, carbazolyl group, benzocarbazolyl group, dibenzocarbazolyl group, phenazinyl group, dibenzosilol group, spirobi (dibenzosilol), dihydrophenazinyl group, A phenoxazinyl group, a phenanthridyl group, an imidazopyridinyl group, a thienyl group, an indolo[2,3-a]carbazolyl group, an indolo[2,3-b]carbazolyl group, an indolinyl group, 10, 11-dihydro-dibenzo[b,f]azepine group, 9,10-dihydroacridinyl group, phenantrazinyl group, phenothiathiazinyl group, phthalazinyl group, naphthyridinyl group, phenanthrolinyl group, Benzo [c] [1,2,5] thiadiazolyl group, 5,10-dihydrodibenzo [b, e] [1,4] azasilinyl group, 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 is not limited thereto.

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

In the present specification, the arylene group means that the aryl group has two bonding sites, that is, a divalent group. The description of the aryl group described above can be applied except that each is a divalent group. In addition, the heteroarylene group means a heteroaryl group having two bonding sites, that is, a divalent group. The above description of the heteroaryl group may be applied except that each is a divalent group.

As used herein, "adjacent" refers to a substituent substituted on an atom directly connected to the atom on which the substituent is substituted, a substituent located sterically closest to the substituent, or another substituent substituted on the atom on which the substituent is substituted. can For example, two substituents substituted at ortho positions 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 invention, "when no substituent is shown in the chemical formula or compound structure" means that a hydrogen atom is bonded to a carbon atom. However, since deuterium (2H) is an isotope of hydrogen, some hydrogen atoms may be deuterium.

In one embodiment of the present invention, "when a substituent is not indicated in the chemical formula or compound structure" may mean that all positions where the substituent can occur are hydrogen or deuterium. That is, deuterium is an isotope of hydrogen, and some hydrogen atoms may be an isotope of deuterium, and in this case, the content of deuterium may be 0% to 100%.

In one embodiment of the present invention, in the case of “when no substituent is indicated in the chemical formula or compound structure”, “the content of deuterium is 0%”, “the content of hydrogen is 100%”, “all substituents are hydrogen”, etc. When deuterium is not explicitly excluded, hydrogen and deuterium may be mixed and used in a compound.

In one embodiment of the present invention, deuterium is one of the isotopes of hydrogen and is an element having a deuteron composed of one proton and one neutron as an atomic nucleus, hydrogen- It can be expressed as 2, and the element symbol can also be written as D or 2H.

In one embodiment of the present invention, isotopes, which mean atoms having the same atomic number (Z) but different mass numbers (A), have the same number of protons, but have neutrons. It can also be interpreted as an element with a different number of neutrons.

In one embodiment of the present invention, the meaning of the content T% of a specific substituent is when the total number of substituents that a base compound can have is defined as T1, and the number of specific substituents among them is defined as T2. T2 It can be defined as /T1×100 = T%.

로 표시되는 페닐기에 있어서 중수소의 함량 20%라는 것은 페닐기가 가질 수 있는 치환기의 총 개수는 5(식 중 T1)개이고, 그 중 중수소의 개수가 1(식 중 T2)인 경우를 의미할 수 있다. 즉, 페닐기에 있어서 중수소의 함량 20%라는 것인 하기 구조식으로 표시될 수 있다.That is, in one example,

In the phenyl group represented by 20% of the deuterium content may mean that the total number of substituents that the phenyl group may have is 5 (T1 in the formula), and the number of deuterium is 1 (T2 in the formula) . That is, it can be represented by the following structural formula that the content of deuterium in the phenyl group is 20%.

In addition, in one embodiment of the present invention, in the case of “a phenyl group having a deuterium content of 0%”, it may mean a phenyl group that does not contain deuterium atoms, that is, has 5 hydrogen atoms.

In the present invention, the C6 to C60 aromatic hydrocarbon ring means a compound containing an aromatic ring composed of C6 to C60 carbons and hydrogen, for example, benzene, biphenyl, triphenyl, triphenylene, naphthalene, Anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, azulene, etc. may be mentioned, but is not limited thereto, and an aromatic hydrocarbon ring compound known in the art as having the above number of carbon atoms may be used. All inclusive.

The present invention provides a heterocyclic compound represented by Formula 1 below:

[Formula 1]

In Formula 1,

X and Y are each independently O, S, CR13R14 or a single bond;

W is N or CR6;

R13 and R14 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen; cyano group; A substituted or unsubstituted C1 to C60 alkyl group; A substituted or unsubstituted C6 to C60 aryl group; And it is selected from the group consisting of a substituted or unsubstituted C2 to C60 heteroaryl group,

R1 to R12 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen; cyano group; A substituted or unsubstituted C1 to C60 alkyl group; A substituted or unsubstituted C2 to C60 alkenyl group; A substituted or unsubstituted C2 to C60 alkynyl group; A substituted or unsubstituted C1 to C60 alkoxy group; A substituted or unsubstituted C3 to C60 cycloalkyl group; A substituted or unsubstituted C2 to C60 heterocycloalkyl group; A substituted or unsubstituted C6 to C60 aryl group; A substituted or unsubstituted C2 to C60 heteroaryl group; And a C6 to C60 aromatic hydrocarbon ring selected from the group consisting of a group represented by Formula 1-1, or substituted or unsubstituted by combining two or more groups adjacent to each other; or a substituted or unsubstituted C2 to C60 heterocycle; forming;

L is a single bond, a substituted or unsubstituted C6 to C60 arylene group; Or a substituted or unsubstituted C2 to C60 heteroarylene group;

m is an integer from 0 to 3;

Ar1 is a group represented by Formula 1-1 below,

[Formula 1-1]

In Formula 1-1,

X1 is N or CRa;

X2 is N or CRb;

X3 is N or CRc;

X4 is N or CRd;

X5 is N or CRe;

Ra to Re are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen; cyano group; A substituted or unsubstituted C1 to C60 alkyl group; A substituted or unsubstituted C2 to C60 alkenyl group; A substituted or unsubstituted C2 to C60 alkynyl group; or a substituted or unsubstituted C1 to C60 alkoxy group; A substituted or unsubstituted C6 to C60 aryl group; and a substituted or unsubstituted C2 to C60 heteroaryl group, or a substituted or unsubstituted C6 to C60 aromatic hydrocarbon ring by combining two or more groups adjacent to each other; Or a substituted or unsubstituted C2 to C60 heterocycle; to form.

In one embodiment of the present invention, in the heterocyclic compound represented by Formula 1, X and Y are each independently O, S, CR13R14 or a single bond, and any one of X and Y may be a single bond.

In another embodiment of the present invention, the heterocyclic compound represented by Formula 1 may be any one of Formula 1-a and Formula 1-b, but is not limited to these examples:

[Formula 1-a]

[Formula 1-b]

In Formulas 1-a and 1-b,

Z is O, S or CR13R14;

W is N or CR6;

R13 and R14 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen; cyano group; A substituted or unsubstituted C1 to C60 alkyl group; And a substituted or unsubstituted C6 to C60 aryl group; selected from the group consisting of

R1 to R12, Ar1, L and m are as defined in Formula 1 above.

In one embodiment of the present invention, Ar1 is a group represented by Formula 1-1, and in the group represented by Formula 1-1, at least one of X1 to X5 is N, or X1 to X5 are each independently CRa to CRe.

In another embodiment of the present invention, the group represented by Formula 1-1 may be any one of the following Formulas 1-1-a to 1-1-h, but is not limited to these examples:

[Formula 1-1-a]

[Formula 1-1-b]

[Formula 1-1-c]

[Formula 1-1-d]

[Formula 1-1-e]

[Formula 1-1-f]

[Formula 1-1-g]

[Formula 1-1-h]

In Formulas 1-1-a to 1-1-h, Ra to Re are as defined in Formula 1-1.

In another embodiment of the present invention, in Formulas 1-1-a to 1-1-h, Ra to Re are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen; cyano group; A substituted or unsubstituted C1 to C40 alkyl group; A substituted or unsubstituted C2 to C40 alkenyl group; A substituted or unsubstituted C2 to C40 alkynyl group; or a substituted or unsubstituted C1 to C40 alkoxy group; A substituted or unsubstituted C6 to C40 aryl group; and a substituted or unsubstituted C2 to C40 heteroaryl group, or a substituted or unsubstituted C6 to C40 aromatic hydrocarbon ring by combining two or more groups adjacent to each other; Or a substituted or unsubstituted C2 to C40 heterocycle; may be formed.

In another embodiment of the present invention, in Formulas 1-1-a to 1-1-h, Ra to Re are the same as or different from each other, and each independently hydrogen; heavy hydrogen; A substituted or unsubstituted C6 to C30 aryl group; and a substituted or unsubstituted C2 to C30 heteroaryl group, or a substituted or unsubstituted C6 to C30 aromatic hydrocarbon ring by combining two or more groups adjacent to each other; Or a substituted or unsubstituted C2 to C30 heterocycle; may be formed.

In one embodiment of the present invention, R1 to R12 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen; cyano group; A substituted or unsubstituted C1 to C60 alkyl group; A substituted or unsubstituted C2 to C60 alkenyl group; A substituted or unsubstituted C2 to C60 alkynyl group; A substituted or unsubstituted C1 to C60 alkoxy group; A substituted or unsubstituted C3 to C60 cycloalkyl group; A substituted or unsubstituted C2 to C60 heterocycloalkyl group; A substituted or unsubstituted C6 to C60 aryl group; A substituted or unsubstituted C2 to C60 heteroaryl group; And a C6 to C60 aromatic hydrocarbon ring selected from the group consisting of a group represented by Formula 1-1, or substituted or unsubstituted by combining two or more groups adjacent to each other; Or a substituted or unsubstituted C2 to C60 heterocycle; may be formed.

In another embodiment of the present invention, R1 to R12 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; A substituted or unsubstituted C6 to C60 aryl group; A substituted or unsubstituted C2 to C60 heteroaryl group; And a C6 to C60 aromatic hydrocarbon ring selected from the group consisting of a group represented by Formula 1-1, or substituted or unsubstituted by combining two or more groups adjacent to each other; Or a substituted or unsubstituted C2 to C60 heterocycle; may be formed.

In another embodiment of the present invention, R1 to R12 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; A substituted or unsubstituted C6 to C30 aryl group; A substituted or unsubstituted C2 to C30 heteroaryl group; And a C6 to C30 aromatic hydrocarbon ring selected from the group consisting of a group represented by Formula 1-1, or substituted or unsubstituted by combining two or more groups adjacent to each other; Or a substituted or unsubstituted C2 to C30 heterocycle; may be formed.

In another embodiment of the present invention, R1 to R12 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; A substituted or unsubstituted C6 to C20 aryl group; A substituted or unsubstituted C2 to C20 heteroaryl group; And a C6 to C20 aromatic hydrocarbon ring selected from the group consisting of a group represented by Formula 1-1, or substituted or unsubstituted by combining two or more groups adjacent to each other; Or a substituted or unsubstituted C2 to C20 heterocycle; may be formed.

In one embodiment of the present invention, L is a single bond; A substituted or unsubstituted C6 to C30 arylene group; Alternatively, it may be a substituted or unsubstituted C2 to C30 heteroarylene group, and m may be an integer of 0 to 3.

In another embodiment of the present invention, L is a single bond; A substituted or unsubstituted C6 to C20 arylene group; Or it may be a substituted or unsubstituted C2 to C20 heteroarylene group, m may be an integer of 0 to 3.

In one embodiment of the present invention, the content of deuterium based on the total number of hydrogen atoms and deuterium atoms in the heterocyclic compound represented by Formula 1 may be 0% to 100%.

In another embodiment of the present invention, the content of deuterium based on the total number of hydrogen atoms and deuterium atoms in the heterocyclic compound represented by Formula 1 may be 1% to 100%.

In another embodiment of the present invention, the content of deuterium based on the total number of hydrogen atoms and deuterium atoms in the heterocyclic compound represented by Formula 1 may be 10% to 90%.

In another embodiment of the present invention, the content of deuterium based on the total number of hydrogen atoms and deuterium atoms in the heterocyclic compound represented by Formula 1 may be 20% to 80%.

For example, the content of deuterium based on the total number of hydrogen atoms and deuterium atoms in the heterocyclic compound represented by Formula 1 is 0% or more, 1% or more, 5% or more, 10% or more, 15% or more, 20% or more Can be greater than, 25% or more, 30% or more, 35% or more, 40% or more, 45% or more, or 50% or more, and can be 100% or less, 95% or less, 90% or less, 85% or less, 80% or less, 75 % or less, 70% or less, 65% or less or 60% or less.

In one embodiment of the present invention, the heterocyclic compound represented by Formula 1 may be any one selected from the group consisting of the following compounds:

.

.

In addition, by introducing various substituents into the structure of Chemical Formula 1, compounds having unique characteristics of the introduced substituents can be synthesized. For example, a substituent mainly used in hole injection layer materials, hole transport layer materials, electron blocking layer materials, light emitting layer materials, electron transport layer materials, hole blocking layer materials, and electron injection layer materials used in the manufacture of organic light emitting devices is introduced into the core structure. By doing so, it is possible to synthesize a material that satisfies the conditions required by each organic layer.

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

In addition, the present invention is 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 includes the heterocyclic compound according to the present invention.

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

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

In one embodiment of the present invention, the organic light emitting device may be a red organic light emitting device, and the heterocyclic compound represented by Chemical Formula 1 may be used as a material for the red organic light emitting device.

In another embodiment of the present invention, the organic light emitting device may be a green organic light emitting device, and the heterocyclic compound represented by Chemical Formula 1 may be used as a material for the green organic light emitting device.

In another embodiment of the present invention, the organic light emitting device may be a blue organic light emitting device, and the heterocyclic compound represented by Chemical Formula 1 may be used as a material for the blue organic light emitting device.

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

In one embodiment of the present invention, the organic light emitting device may be a red organic light emitting device, and the heterocyclic compound represented by Chemical Formula 1 may be used as a material for a light emitting layer or a light emitting auxiliary layer of the red organic light emitting device.

In another embodiment of the present invention, the organic light emitting device may be a green organic light emitting device, and the heterocyclic compound represented by Chemical Formula 1 may be used as a material for a light emitting layer or an auxiliary light emitting layer of the green organic light emitting device.

In another embodiment of the present invention, the organic light emitting device may be a blue organic light emitting device, and the heterocyclic compound represented by Chemical Formula 1 may be used as a material for a light emitting layer or an auxiliary light emitting layer of the blue organic light emitting device.

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

The organic light emitting diode of the present invention may be manufactured by conventional organic light emitting diode manufacturing methods and materials, except for forming one or more organic material layers using the aforementioned heterocyclic compound.

The heterocyclic compound may form 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 means spin coating, dip coating, inkjet printing, screen printing, spraying, roll coating, etc., but is not limited to these.

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

In one embodiment of the present invention, the organic light emitting device may include one or more organic material layers, and the organic material layer may include a light emitting layer or an auxiliary light emitting layer, and the light emitting layer or the auxiliary light emitting layer is represented by Chemical Formula 1 above. A heterocyclic compound may be included.

In another embodiment of the present invention, the organic material layer may include a light emitting layer or an auxiliary light emitting layer, the light emitting layer or the auxiliary light emitting layer may include a host material, the host material may include the heterocyclic compound there is.

In another embodiment of the present invention, the organic light emitting element is a light emitting layer, a light emitting auxiliary layer, a hole injection layer, a hole transport layer, an electron injection layer, an electron transport layer, a layer selected from the group consisting of a battery blocking layer and a hole blocking layer, or It may further include two or more layers.

One embodiment of the present invention provides a composition for an organic material layer of an organic light emitting device including two or more kinds of heterocyclic compounds represented by Formula 1 above. For example, the heterocyclic compound represented by Chemical Formula 1 may include a first compound and a second compound. In addition, the heterocyclic compound represented by Formula 1 may include a first compound, a second compound, and a third compound, but is not limited to these examples, and may include an nth compound (n is 1 or more). essence).

The first compound, the second compound, the third compound, and the n-th compound may be heterocyclic compounds represented by Chemical Formula 1 that are different from each other.

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

In another embodiment of the present invention, when the heterocyclic compound represented by Chemical Formula 1 in the composition for the organic layer of the organic light emitting device includes a first compound and a second compound, the weight ratio of the first compound and the second compound is 1:10 to 10:1, or 1:8 to 8:1, or 1:6 to 6:1, or 1:4 to 4:1, or 1:3 to 3:1, or 1:2 to It may be 2:1, but is not limited thereto.

The composition for the organic material layer of the organic light emitting device can be used when forming the organic material layer of the organic light emitting device, and can be more preferably used when forming the host of the light emitting layer.

1 to 3 illustrate the stacking order of the electrode and the organic material layer of the organic light emitting device according to an embodiment of the present invention. However, it is not intended that the scope of the present application be limited by these drawings, and structures of organic light emitting devices known in the art may be applied to the present application as well.

According 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 where the organic material layer is multi-layered. The organic light emitting device according to FIG. 3 includes a hole injection layer 301, a hole transport layer 302, an emission layer 303, a hole blocking layer 304, an electron transport layer 305, and an electron injection layer 306. However, the scope of the present application is not limited by such a laminated structure, and layers other than the light emitting layer may be omitted as necessary, and other necessary functional layers may be further added.

In the organic light emitting device according to an embodiment of the present invention, materials other than the heterocyclic compound represented by Formula 1 are exemplified below, but these are for illustrative purposes only and are not intended to limit the scope of the present application. Materials known in the art may be substituted.

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

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

As the hole injection layer material, a known hole injection layer 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). Starburst amine derivatives described, 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, a soluble conductive polymer, 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) and the like can be used.

As the material for the hole transport layer, pyrazoline derivatives, arylamine derivatives, stilbene derivatives, triphenyldiamine derivatives, and the like may be used, and low-molecular or high-molecular materials may also be used.

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

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

A red, green or blue light emitting material may be used as a material for the light emitting layer, and if necessary, two or more light emitting materials may be mixed and used. At this time, two or more light emitting materials may be deposited and used as separate sources or may be pre-mixed and deposited as one source. In addition, a fluorescent material may be used as a material for the light emitting layer, but it may also be used as a phosphorescent material. As the material for the light emitting layer, a single material that emits light by combining holes and electrons injected from the anode and the cathode may be used, but materials in which a host material and a dopant material are involved in light emission may also be used.

In one embodiment of the present invention, the organic material layer includes a heterocyclic compound represented by Formula 1 and may be used together with a phosphorescent 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", L ₂ MX' and L ₃ M may be used, but the scope of the present invention is not limited by these examples. .

The M may be iridium, platinum, osmium, or the like.

L is an anionic bidentate ligand coordinated to M by sp2 carbon and a hetero atom, and X may function to trap electrons or holes. Non-limiting examples of L, L' and L" include 2-(1-naphthyl)benzoxazole, (2-phenylbenzoxazole), (2-phenylbenzothiazole), (2-phenylbenzothiazole). ), (7,8-benzoquinoline), (thiophenepyrizine), phenylpyridine, benzothiophenepyridine, 3-methoxy-2-phenylpyridine, thiophenepyrizine, tolylpyridine, etc. X' and X″ include, but are not limited to, acetylacetonate (acac), hexafluoroacetylacetonate, salicylidene, picolinate, 8-hydroxyquinolinate, and the like.

Specific examples of the phosphorescent dopant are shown below, but are not limited to these examples:

In one embodiment of the present invention, the organic material layer includes the heterocyclic compound represented by Chemical Formula 1 and may be used together with an iridium-based dopant.

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

In one embodiment of the present invention, the content of the dopant may have a content of 1% to 15%, preferably 2% to 10%, more preferably 3% to 7% based on the total weight of the light emitting layer. .

In the case of mixing and using hosts of the light emitting layer material, hosts of the same series may be mixed and used, or hosts of different series may be mixed and used. For example, two or more materials selected from among n-type host materials and p-type host materials may be selected and used as host materials for the light emitting layer.

An organic light emitting device according to an embodiment of the present invention may be a top emission type, a bottom emission type, or a double side emission type depending on the material used.

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

Hereinafter, preferred embodiments are presented to aid understanding of the present invention, but the following examples are provided to more easily understand the present invention, but the present invention is not limited thereto.

<Production Example>

Preparation Example 1: Preparation of Compound A

1) Preparation of compound A-1

Compound A-2 (25g, 69.8_mol), bromophenylboronic acid (A') (bromophenylboronic acid) (14.7g, 73.3 mol), potassium carbonate (K ₂ CO ₃ ) (19.3g, 139.6 mol) and tetrakis(triphenylphosphine)palladium(0) (tetrakis(triphenylhosphine)palladium(0), Pd(PPh ₃ ) ₄ ) (4.0 g, 3.5 mol) in dimethylformamide (DMF) (250 mL). Put and stirred at 140 ℃ for 2 hours. Then, after the reaction was terminated by adding distilled water, the reaction solution was extracted with dichloromethane (DCM) and distilled water. Thereafter, water was removed from the organic layer using magnesium sulfate (MgSO ₄ ), and then the solvent was removed using a rotary evaporator. The reaction product was separated by a silica gel column to obtain 17.7 g of compound A-1 (yield: 78%).

2) Preparation of Compound A

The compound A-1 (17.6g, 53.7mol) and triphenylphosphine (PPh ₃ ) (35g, 134mol) were put in 1,2-dichlorobenzene (120mL) and heated at 180°C. Stir for 12 hours. Then, after the reaction was terminated by adding distilled water, the reaction solution was extracted with dichloromethane (DCM) and distilled water. Thereafter, water was removed from the organic layer using magnesium sulfate (MgSO ₄ ), and then the solvent was removed using a rotary evaporator. The reactant was separated by a silica gel column to obtain 7.8 g of compound A (yield: 49%).

In Preparation Example 1, using Intermediate Compound A-2, Intermediate Compound A' and Intermediate Compound A-1 in the Table below instead of Compound A-2, Compound A' and Compound A-1, in the same manner as in Preparation Example 1. The target compounds in the table below were synthesized.

Intermediate compound A-2 intermediate compound A' Intermediate compound A-1 (yield %) Target compound (yield %)

(78%)

1A
(49%)

(69%)

2A
(38%)

(70%)

3A
(34%)

(67%)

4A
(29%)

Preparation Example 2. Preparation of Compound G3

1) Preparation of Compound C

Compound A (11-bromo-7H-benzo [c] carbazole, 11-bromo-7H-benzo [c] carbazole) (30 g, 101.3 mmol) was added to a 1000 mL round-bottom flask, and tetrakis (triphenylphosphine) ) Palladium (Pd(PPh ₃ ) ₄ ) (5 g, 5 mmol), potassium carbonate (K ₂ CO ₃ ) (28 g, 202.6 mmol) and Compound B ((2-chlorobenzofuran-3-yl)boron An acid (2-chlorobenzofuran-3-yl)boronic acid) (24g, 121.5 mmol) was dissolved in toluene (150mL) solvent. Ethanol:water (EtOH:H ₂ O (30mL:10mL)) was added to the reaction vessel, and then stirred at a reaction temperature of 110 ^° C for 16 hours. After completion of the reaction, water (H ₂ O) and ethyl acetate (Ethyl acetate, EA 100mL x 3times) were used to extract the reactants, and then the solvent was concentrated by pressing. The concentrated compound was separated and purified through a silica-gel column to obtain 31.3 g (85 mmol) of Compound C as a white solid.

2) Preparation of Compound D

In a 1000 mL round bottom flask, compound C (31.3 g, 85 mmol), cesium carbonate (CS ₂ CO ₃ ) (27.7 g, 170 mmol) and palladium (II) acetate (Pd(OAc) ₂ ) 3.8 g (17 mmol) was added, replaced with a nitrogen atmosphere, and xylene (250mL) was added to dissolve the reaction mixture. Then, it was stirred for 24 hours at a reaction temperature of 120°C. After the reaction was completed, the reaction temperature was lowered to room temperature, and the organic matter was extracted using water (H ₂ O) and dichloromethane (CH ₂ Cl ₂ , 200mL x 2 times) solvent. The extracted organic matter was concentrated and then separated and purified using a silica-gel column to obtain 19.1 g (57.8 mmol) of Compound D as a white solid compound.

In Preparation Example 2, Intermediate Compound D in Table 2 was synthesized in the same manner as in Preparation Example 2, using Intermediate Compounds A, B and C in Table 2 instead of Compounds A, B and C.

intermediate compound A intermediate compound B Intermediate compound C (yield %) Intermediate compound D (yield %)

1A

1A

1B

1C
(84%)

1D
(68%)

1A

2B

2C
(82%)

2D
(66%)

1A

3B

3C
(55%)

3D
(24%)

1A

4B

4C
(55%)

4D
(36%)

2A

5B

5C
(79%)

5D
(49%)

3A

6B

6C
(66%)

6D
(62%)

1A

7B

7C
(80%)

7D
(66%)

1A

8B

8C
(80%)

8D
(58%)

4A

9B

9C
(82%)

9D
(23%)

1A

10B

10C
(77%)

10D
(27%)

3) Preparation of Compound G3

In a 250mL round bottom flask, compound D (4.2g, 12.7mmol), Tris(dibenzylideneacetone)dipalladium, Pd ₂ (dba) ₃ ) (0.5g, 0.6mmol), dicyclohexyl ( 2',4',6'-triisopropyl-[1,1'-biphenyl]-2-yl)phosphine (Dicyclohexyl(2',4',6'-triisopropyl-[1,1'-biphenyl ]-2-yl)phosphine, Xphos) (1.2g, 1.3mmol), sodium hydroxide (NaOH) (1.5g, 40mmol) and compound E (3.7g, 14mmol) were added, and dimethylacetamide (dimethylacetamide, DMA) was added and refluxed at 160° C. for 2 hours. After the reaction was completed, the reaction temperature was lowered to room temperature, and extracted with water and dichloromethane (CH ₂ Cl ₂ , 100mL x 2times). After concentrating the extracted organic solvent under reduced pressure, it was separated and recrystallized using a silica-gel column to obtain 6 g (10.7 mmol, yield 84%) of yellow solid compound G3.

In Preparation Example 2, the target compound G of Table 2 was synthesized in the same manner as in Preparation Example 2, using intermediate compounds D and E of Table 3 instead of Compounds D and E.

compound intermediate compound D intermediate compound E Target compound G (yield %) G3

(84%)
G4

(90%)
G5

(85%)
G6

(86%)
G8

(81%)
G11

(88%)
G13

(77%)
G16

(79%)
G19

(80%)
G27

(58%)
G31

(80%)
G35

(76%)
G37

(88%)
G44

(84%)
G49

(84%)
G52

(87%)
G53

(82%)
G55

(84%)
G56

(87%)
G66

(92%) G67

(94%)
G68

(89%)
G69

(92%)
G71

(81%)
G72

(86%)
G74

(88%)
G76

(91%)
G83

(91%)
G88

(72%)
G91

(92%)
G98

(72%)
G102

(92%)
G114

(91%)
G120

(92%)
G122

(88%)
G132

(84%)
G135

(79%)
G151

(83%)
G171

(79%)
G178

(94%)
G179

(92%)
G184

(84%)
G225

(89%)
G227

(86%)

Preparation Example 3: Preparation of compound G174

1) Preparation of Compound G174-P2

In a 250mL round bottom flask, compound D (12g, 32.8mmol), copper(I) iodide (Cul) (6.2g, 32.8mmol), iodobenzene (8.7g, 42.6mmol), (1S, 2S)-cyclohexane-1,2-diamine ((1S,2S)-cyclohexane-1,2-diamine) (3.7g, 32.8 mmol) and sodium tert-butoxide ( t -BuONa) (6.3g, 65.6mmol) was dissolved in 120mL of dioxane and then refluxed at 120°C for 2 hours. After the reaction was completed, the reaction temperature was lowered to room temperature, and extracted with water and dichloromethane (CH ₂ Cl ₂ , 100mL x 2times). The extracted organic solvent was concentrated under reduced pressure, separated and recrystallized using a silica-gel column to obtain 12.4 g (28.2 mmol, yield 86%) of yellow solid compound G174-P2.

2) Preparation of Compound G174-P1

Compound G174-P2 (12.4g, 28.2mmol), [1,1'-bis(diphenylphosphino)ferrocene]palladium(II) dichloride ([1,1'-Bis(diphenylphosphino) ferrocene]palladium(II) dichloride, PdCl ₂ (Dppf)) (0.7g, 1 mmol), potassium acetate (KOAc) (28g, 202.6 mmol) and 4,4,4',4',5,5,5',5'-octamethyl-2,2'-bi(1,3,2-dioxaborane)(4,4,4',4',5,5,5',5'-octamethyl-2,2'-bi(1,3,2-dioxa borolane)) (17.9g, 70.5 mmol) was dissolved in a solvent of dioxane (150mL), and stirred at a reaction temperature of 110 ^° C for 12 hours. Then, it was extracted with water and dichloromethane (dichloromethane, CH ₂ Cl ₂ , 100mL x 2times). After concentrating the extracted organic solvent under reduced pressure, it was separated and recrystallized using a silica-gel column to obtain 12.3 g (28.2 mmol, yield 82%) of white solid compound G174-P1.

3) Preparation of Compound G174

Solid compound G174-P1 (12.3g, 28.2mmol) was put in a 250mL round bottom flask, tetrakis(triphenylphosphine)palladium (Pd(PPh ₃ ) ₄ ) (1.6g, 1.41 mmol), potassium carbonate , K ₂ CO ₃ ) (7.8 g, 56.4 mmol)) and 2-chloro-4,6-diphenyl-1,3,5-triazine (2-chloro-4,6-diphenyl-1,3,5 -triazine) (9g, 33.8 mmol) was dissolved in toluene (150mL) solvent. Ethanol:water (EtOH:H ₂ O (30mL:10mL)) was added to the reaction vessel, and then stirred at a reaction temperature of 110 ^° C for 16 hours. After completion of the reaction, the reactants were extracted using water (H ₂ O) and a solvent (Ethyl acetate, EA 100mL x 3times), and then the solvent was concentrated under pressure. The concentrated compound was separated and purified through a silica-gel column to obtain 15.8 g (24.8 mmol) of G174 as a white solid.

Production Example 4. Production of deuterium-substituted compounds G206 and G207

1) Compound D ^d manufacture of

Compound D (4.2g, 12.7 mmol) was placed in a 100mL round bottom flask, substituted with a nitrogen atmosphere, dissolved in Benzene-d ⁶ solvent (40mL), and triflic acid (TfOH) (7 mL, 46 mmol) was slowly added dropwise. After stirring at 60° C. for 2 hours, the solvent was removed under reduced pressure. The concentrated organic matter was washed with water and extracted with dichloromethane (CH ₂ Cl ₂ ). The extracted organic solvent was dried with magnesium sulfate (Mg ₂ SO ₄ ) and then concentrated. Separation and recrystallization using a silica-gel column gave 3.6 g (10.4 mmol, yield 82%) of white solid compound ^Dd .

2) Preparation of compound G206

In a 100mL round bottom flask, add compound ^Dd compound (3.6g, 10.4mmol), Tris(dibenzylideneacetone)dipalladium (Pd ₂ (dba) ₃ ) (0.5g, 0.6mmol), dicyclo Hexyl (2',4',6'-triisopropyl-[1,1'-biphenyl]-2-yl)phosphine (Dicyclohexyl(2',4',6'-triisopropyl-[1,1' -biphenyl] -2-yl)phosphine, Xphos) (1.2 g, 1.3 mmol), sodium hydroxide (NaOH) (0.9 g, 23 mmol) and compound E (3.0 g, 12.4 mmol) in dimethylacetamide (dimethylacetamide, DMA) (50mL) and dissolved, and then refluxed at 160°C for 2 hours. After the reaction was completed, the reaction temperature was lowered to room temperature, and extracted with water and dichloromethane (CH ₂ Cl ₂ , 100mL x 2times). After concentrating the extracted organic solvent under reduced pressure, it was separated and recrystallized with a silica-gel column to obtain 5.1 g of yellow solid compound G206. (9.3 mmol, yield 90%) was obtained.

3) Preparation of compound 207

Compound G206 (5.1g, 9.3mmol) was put in a 100mL round bottom flask, substituted with a nitrogen atmosphere, dissolved in Benzene-d ⁶ solvent (40mL), and triflic acid (TfOH) (7 mL, 46 mmol) was slowly added dropwise. After stirring at 60° C. for 2 hours, the solvent was removed under reduced pressure. The concentrated organic matter was washed with water and extracted with dichloromethane (CH ₂ Cl ₂ ). The extracted organic solvent was dried with magnesium sulfate (Mg ₂ SO ₄ ) and then concentrated. Separation and recrystallization using a silica-gel column gave 4.4 g (8.0 mmol, yield 82%) of white solid compound G207.

In Preparation Example 4, the target compound G in Table 4 was synthesized in the same manner as in Preparation Example 4, using intermediate compounds D ^d and E in Table 4 instead of compounds D ^d and E.

compound intermediate compound D ^d intermediate compound E target compound G G217

Preparation Example 5: Preparation of deuterium-substituted compound G210

1) Preparation of compound G210-P3

Compound D (6g, 18.1 mmol), Tris(dibenzylideneacetone)dipalladium, Pd ₂ (dba) ₃ ) (0.75g, 0.9mmol), dicyclohexyl (2 ',4',6'-triisopropyl-[1,1'-biphenyl]-2-yl)phosphine (Dicyclohexyl(2',4',6'-triisopropyl-[1,1'-biphenyl] -2-yl)phosphine, Xphos) (1.6 g, 1.8 mmol), sodium hydroxide (NaOH) (1.4 g, 36 mmol) and the compound 1-bromo-4-iodonaphthalene (1-bromo-4-iodonaphthalene) ( 6.6 g, 20 mmol) was dissolved in dimethylacetamide (DMA) (80 mL), and then refluxed at 160° C. for 2 hours. After the reaction was completed, the reaction temperature was lowered to room temperature, and extracted with water and dichloromethane (CH ₂ Cl ₂ , 100mL x 2times). After concentrating the extracted organic solvent under reduced pressure, it was separated and recrystallized using a silica-gel column to obtain 8.9 g (16.6 mmol, yield 92%) of yellow solid compound G210-P3.

2) Compound G210-P2 ^d manufacture of

Compound G210-P3 (8.9g, 16.6mmol) was put in a 100mL round bottom flask, substituted with a nitrogen atmosphere, and then dissolved in 80mL of Benzene-d ⁶ solvent, followed by triflic acid (tfOH) 14 mL (92 mmol) ) was slowly added dropwise. After stirring at 60° C. for 2 hours, the solvent was removed under reduced pressure. The concentrated organic matter was washed with water and extracted with dichloromethane (CH ₂ Cl ₂ ). The extracted organic solvent was dried with magnesium sulfate (Mg ₂ SO ₄ ) and then concentrated. Separation and recrystallization using a silica-gel column gave 7.9 g (14.2 mmol, yield 86%) of white solid compound G210-P2 ^d .

3) Preparation of compound G210-P1

In a 250 mL round bottom flask, compound G210-P2 ^d (7.9 g, 14.2 mmol), [1,1'-bis(diphenylphosphino)ferrocene]palladium(II) dichloride ([1,1'-Bis(diphenyl phosphino) )ferrocene]palladium(II) dichloride, PdCl ₂ (Dppf) (0.5g, 0.7 mmol), potassium acetate (KOAc) (2.7g, 28.4 mmol) and 4,4,4',4',5,5,5 ',5'-octamethyl-2,2'-bi(1,3,2-dioxaborane) (4,4,4',4',5,5,5',5'-octamethyl-2 ,2'-bi(1,3,2-dioxa borolane)) (5.4g, 21.3 mmol) was dissolved in a solvent of dioxane (60mL), and stirred at a reaction temperature of 110 ^° C for 12 hours. After that, it was extracted with water and dichloromethane (dichloromethane, CH ₂ Cl ₂ , 100mL x 2times) After concentrating the extracted organic solvent under reduced pressure, it was separated and recrystallized with a silica-gel column to obtain a white color. 6.8 g (11.3 mmol, yield 80%) of solid compound G210-P1 was obtained.

4) Preparation of Compound G210

In a 250mL round bottom flask, solid compound G210-P1 (6.8g, 11.3mmol) was added, tetrakis(triphenylphosphine)palladium (Pd(PPh3)4) (0.6g, 0.56 mmol), potassium carbonate (K2CO3, 3.1 g (22.6 mmol)) and 3.6 g (13.5 mmol) of 2-chloro-4,6-diphenyl-1,3,5-triazine was dissolved in toluene (80mL) solvent.Ethanol:water (EtOH:H2O (15mL:15mL)) was added to the reaction container, and then stirred at a reaction temperature of 110oC for 12 hours. After the reaction was completed, water The reactants were extracted using (H2O) and (Ethyl acetate, EA 100mL x 3times) solvent, and then the solvent was concentrated under pressure. 15.8 g (7.1 mmol, 89%) were obtained.

Other compounds other than the compounds described in Preparation Examples 1 to 5 and Tables 1 to 4 were also prepared in the same manner as described in the above Preparation Examples, and the synthesis results are shown in Tables 5 and 6 below. Table 5 below is a measurement value of ¹ H NMR (CDCl ₃ , 200 Mz), and Table 6 below is a measurement value of FD-mass spectrometer (FD-MS: Field desorption mass spectrometry).

compound ^One H NMR (CDCl ₃ , 200 Mz) G3 δ = 9.26 (d, 1H), 9.01 (d, 2H), 8.87 (d, 4H), 8.26 (dd, 2H), 8.03 to 7.99 (m, 2H), 7.70 (d, 1H), 7.64 to 7.61 ( m, 2H), 7.59~7.56(m, 3H), 7.51~7.47(m, 2H), 7.36~7.35(m, 2H), 7.27(t, 1H). G4 δ = 9.12 (d, 1H), 8.77 (d, 2H), 8.26 to 8.25 (m, 2H), 8.05 to 8.03 (m, 2H), 7.84 to 7.79 (m, 2H), 7.74 (d, 1H), 7.71~7.67(m, 3H), 7.66~7.55(m, 4H), 7.54(d, 1H), 7.36(d, 1H), 7.32(t, 1H), 7.27(t, 1H). G5 δ = 9.14 (d, 1H), 8.77 (d, 2H), 8.31 to 8.27 (m, 2H), 8.07 to 8.05 (m, 2H), 7.86 to 7.83 (m, 2H), 7.81 (d, 1H), 7.72~7.69(m, 3H), 7.66~7.55(m, 4H), 7.54(d, 1H), 7.42(d, 1H), 7.36(t, 1H), 7.33(t, 1H). G6 δ = 9.15 (d, 1H), 8.76 (d, 2H), 8.19 (d, 2H), 8.01 to 7.94 (m, 5H), 7.73 (d, 1H), 7.69 to 7.67 (m, 3H), 7.64 to 7.53 (m, 5H), 7.52 (d, 1H), 7.34 (d, 1H), 7.22 (t, 1H). G8 δ = 9.18 (d, 1H), 8.76 (d, 2H), 8.19 (d, 2H), 8.01 (s, 1H), 7.98 (d, 1H), 7.69 to 7.63 (m, 5H), 7.63 to 7.57 ( m, 4H), 7.64~7.52 (m, 5H), 7.46 (t, 1H), 7.34 (d, 2H), 7.19 (t, 1H). G11 δ = 9.26 (d, 1H), 9.01 (d, 2H), 8.87 (d, 4H), 8.26 (dd, 2H), 8.04 to 7.99 (m, 2H), 7.70 (d, 1H), 7.64 to 7.60 ( m, 2H), 7.59–7.56 (m, 3H), 7.51–7.47 (m, 2H), 7.37 (t, 1H), 7.35 (d, 1H), 7.29 (t, 1H). G13 δ = 8.86 (d, 1H), 8.76 (d, 2H), 8.19 (d, 2H), 7.91 to 7.90 (m, 2H), 7.73 (d, 1H), 7.69 to 7.67 (m, 3H), 7.48 to 7.21 (m, 9H), 6.84 (t, 1H), 1.72 (s, 6H). G16 δ = 9.19 (d, 1H), 9.01 (d, 2H), 8.87 (d, 4H), 8.28 (d, 2H), 8.03 to 7.99 (m, 2H), 7.70 (d, 1H), 7.64 to 7.61 ( m, 2H), 7.59–7.47 (m, 5H), 7.38–7.35 (m, 3H), 7.27 (t, 1H), 6.84 (d, 1H). G19 δ = 9.08 (d, 1H), 8.86 (d, 2H), 8.82 (d, 2H), 8.19 (d, 2H), 7.88 (d, 2H), 7.73 (d, 1H), 7.69-7.67 (m, 2H), 7.48~7.21 (m, 7H), 6.84 (t, 1H), 1.59 (s, 6H). G27 δ = 9.06 (s, 1H), 8.92 (d, 2H), 8.81 (d, 1H), 8.68 (d, 1H), 8.19 (d, 2H), 7.88 (d, 2H), 7.73 (d, 1H) , 7.69–7.67 (m, 2H), 7.2 (d, 2H), 6.90–6.84 (m, 2H), 6.44–6.19 (m, 7H), 6.88 (d, 1H), 6.49 (d, 1H). G31 δ = 9.11 (s, 2H), 9.02 (d, 2H), 8.87 (d, 2H), 8.36 (d, 2H), 8.03 to 7.99 (m, 2H), 7.70 (d, 1H), 7.64 to 7.61 ( m, 4H), 7.49–7.46 (m, 3H), 7.36–7.35 (m, 6H), 7.04 (t, 1H), 6.94 (d, 1H). G35 δ = 9.26 (d, 1H), 9.01 (d, 2H), 8.96 (d, 2H), 8.87 (d, 2H), 8.27 (dd, 2H), 8.03 to 7.99 (m, 2H), 7.70 (d, 1H), 7.66~7.63(m, 2H), 7.59~7.56(m, 2H), 7.51~7.47(m, 2H), 7.36~7.35(m, 2H), 7.27(t, 1H). G37 δ = 9.28 (d, 1H), 9.02 to 9.01 (m, 4H), 8.87 (d, 2H), 8.30 (d, 2H), 8.03 to 7.99 (m, 2H), 7.70 (d, 1H), 7.66 to 7.63(m, 2H), 7.59~7.56(m, 3H), 7.36~7.35(m, 2H), 7.27(t, 1H). G44 δ = 9.27 (d, 1H), 9.0 (d, 2H), 8.87 (d, 4H), 8.24 (d, 2H), 8.03 to 7.99 (m, 2H), 7.70 (d, 1H), 7.64 to 7.61 ( m, 2H), 7.59–7.56 (m, 3H), 7.51–7.47 (m, 2H), 7.36–7.34 (m, 3H), 7.01 (s, 1H), 7.09 (t, 1H). G49 δ = 9.19 (d, 1H), 9.03 (d, 2H), 8.87 (d, 4H), 8.28 (d, 2H), 8.03 to 7.01 (m, 2H), 7.76 (d, 1H), 7.64 to 7.62 ( m, 2H), 7.59~7.52(m, 5H), 7.51~7.43(m, 8H), 7.36~7.33(m, 4H), 7.22(t, 1H). G52 δ = 9.27 (d, 1H), 9.03 (s, 1H), 8.87 (d, 4H), 8.26 (d, 2H), 8.03 to 7.99 (m, 2H), 7.70 (d, 1H), 7.64 to 7.61 ( m, 2H), 7.59~7.56(m, 6H), 7.51~7.46(m, 4H), 7.36~7.35(m, 2H), 7.27(t, 1H). G53 δ = 9.22 (s, 1H), 9.01 (d, 2H), 8.87 (d, 4H), 8.26 (d, 2H), 8.03 to 7.99 (m, 2H), 7.70 (d, 1H), 7.64 to 7.61 ( m, 2H), 7.59~7.56(m, 6H), 7.49~7.44(m, 3H), 7.35~7.33(m, 2H), 7.24(t, 1H). G55 δ = 9.23 (d, 1H), 9.02 (d, 2H), 8.89 (d, 4H), 8.30 (d, 2H), 8.03 to 7.99 (m, 2H), 7.72 (d, 1H), 7.64 to 7.61 ( m, 2H), 7.59–7.47 (m, 5H), 7.38–7.35 (m, 3H), 7.33 (t, 1H), 6.89 (d, 1H). G56 δ = 9.24 (d, 1H), 9.05 (d, 2H), 8.91 (d, 4H), 8.29 (d, 2H), 8.06 to 8.03 (m, 2H), 7.72 (d, 1H), 7.64 to 7.61 ( m, 2H), 7.55–7.45 (m, 5H), 7.38–7.34 (m, 4H), 6.86 (d, 1H). G66 δ = 9.03 (d, 1H), 8.82 (d, 4H), 7.78 (d, 2H), 7.64 to 7.51 (m, 7H), 7.49 (d, 2H), 7.16 to 7.11 (m, 5H), 7.01 ( d, 2H), 6.86–6.84 (m, 2H), 6.52 (d, 1H). G67 δ = 9.05 (d, 1H), 8.90 (s, 1H), 8.82 (d, 4H), 7.73 (d, 1H), 7.63 to 7.51 (m, 7H), 7.49 (d, 2H), 7.16 to 7.11 ( m, 5H), 7.01 (d, 2H), 6.86~6.84 (m, 2H), 6.52 (d, 1H). G68 δ = 9.01 (d, 1H), 8.79 (d, 4H), 7.76 (d, 2H), 7.64 to 7.51 (m, 9H), 7.49 (d, 2H), 7.16 to 7.09 (m, 5H), 7.01 ( d, 2H), 6.86–6.84 (m, 2H), 6.54 (d, 1H). G69 δ = 9.22 (d, 1H), 8.79 (d, 4H), 8.71 (d, 2H), 7.76 (d, 2H), 7.64 to 7.51 (m, 8H), 7.49 (d, 2H), 7.14 to 7.09 ( m, 4H), 7.01 (d, 2H), 6.86~6.84 (m, 2H), 6.52 (d, 1H). G71 δ = 8.83 (d, 1H), 8.81 (d, 4H), 8.47 (d, 1H), 7.89 to 7.86 (m, 3H), 7.87 (d, 2H), 7.75 to 7.68 (m, 3H), 7.52 ( d, 1H), 7.46–7.35 (m, 11H), 7.29 (t, 1H). G72 δ = 8.87 (d, 1H), 8.84 (d, 4H), 8.51 (d, 1H), 7.89 to 7.85 (m, 3H), 7.87 (d, 2H), 7.75 to 7.68 (m, 3H), 7.52 to 7.50(m, 2H), 7.46~7.35(m, 12H), 7.29(t, 1H). G74 δ = 9.26 (d, 1H), 8.85 (d, 4H), 8.71 to 8.70 (m, 2H), 8.36 (d, 1H), 8.11 to 8.10 (m, 2H), 7.91 (d, 1H), 7.77 to 7.61(m, 8H), 7.47~7.38(m, 8H), 7.08(d, 1H). G76 δ = 9.28 (d, 1H), 9.11 (s, 1H), 8.87 (d, 4H), 8.72 (d, 1H), 8.13 to 7.99 (m, 4H), 7.73 (d, 1H), 7.66 to 7.61 ( m, 2H), 7.59~7.56(m, 4H), 7.51~7.47(m, 3H), 7.42~7.37(m, 5H), 7.33(t, 1H). G83 δ = 9.61 (s, 1H), 9.21 (d, 1H), 8.84 (d, 1H), 8.52 (d, 2H), 8.32 to 8.16 (m, 4H), 8.08 to 7.94 (m, 6H), 7.89 ( d, 1H), 7.52–7.39 (m, 9H), 7.18 (d, 1H). G88 δ = 9.17 (s, 1H), 9.03 to 8.98 (m, 5H), 8.72 to 8.70 (m, 1H), 8.67 to 8.65 (m, 1H), 8.42 (d, 2H), 8.09 to 8.02 (m, 2H) ), 8.87~7.80 (m, 5H), 7.69~7.51 (m, 8H), 7.18 (d, 1H). G91 δ = 9.13 (d, 1H), 8.78 (d, 2H), 8.30 to 8.26 (m, 2H), 8.07 to 8.05 (m, 2H), 7.86 to 7.83 (m, 2H), 7.81 (d, 1H), 7.72~7.69(m, 3H), 7.66~7.55(m, 6H), 7.54~7.52(m, 3H), 7.42(d, 1H), 7.36(t, 1H), 7.29(t, 1H) G98 δ = 9.02 (d, 1H), 8.74 (d, 2H), 8.58 to 8.50 (m, 5H), 7.87 to 7.68 (m, 8H), 7.64 to 7.63 (m, 1H), 7.56 to 7.48 (m, 4H) ), 7.29 (t, 1H), 7.18 (d, 1H). G102 δ = 9.11 (d, 1H), 8.73 (d, 2H), 8.31 to 8.28 (m, 2H), 8.07 to 8.05 (m, 2H), 7.86 to 7.83 (m, 2H), 7.81 (d, 1H), 7.72~7.69(m, 3H), 7.66~7.60(m, 4H), 7.58(d, 1H), 7.46(d, 1H), 7.37(t, 1H), 7.28(t, 1H). G114 δ = 9.29 (d, 1H), 8.87 (d, 4H), 8.48 (d, 1H), 8.29 (d, 2H), 8.03 to 8.02 (m, 2H), 7.77 (d, 1H), 7.67 to 7.64 ( m, 4H), 7.62~7.57(m, 6H), 7.51~7.47(m, 3H), 7.37~7.35(m, 3H), 7.23(t, 1H). G120 δ = 9.18 (d, 1H), 8.84 (d, 2H), 8.33 to 8.29 (m, 2H), 8.13 to 8.09 (m, 2H), 7.88 to 7.83 (m, 2H), 7.81 (d, 1H), 7.75~7.69(m, 3H), 7.67~7.60(m, 4H), 7.57(d, 1H), 7.49(d, 1H), 7.36(t, 1H), 7.27(t, 1H). G122 δ = 9.11 (d, 1H), 8.83 (s, 1H), 8.78 (d, 2H), 8.61 to 8.50 (m, 6H), 7.89 to 7.76 (m, 6H), 7.65 to 7.63 (m, 1H), 7.56~7.48(m, 5H), 7.32(t, 1H). G132 δ = 9.16 (d, 1H), 8.74 (d, 2H), 8.20 (d, 2H), 8.01 to 7.95 (m, 5H), 7.73 (d, 1H), 7.69 to 7.67 (m, 3H), 7.63 to 7.57(m, 4H), 7.52(d, 1H), 7.39~7.34(m, 3H), 7.14(t, 1H), 6.98(d, 1H). G135 δ = 9.26 (d, 1H), 9.01 (d, 2H), 8.87 (d, 4H), 8.26 (dd, 2H), 8.03 to 7.99 (m, 2H), 7.70 (d, 1H), 7.64 to 7.61 ( m, 2H), 7.59~7.56(m, 3H), 7.51~7.47(m, 2H), 7.36~7.35(m, 2H), 7.27(t, 1H). G147 δ = 9.22 (d, 1H), 8.89 (d, 4H), 8.72 (d, 1H), 8.03 to 7.99 (m, 3H), 7.64 to 7.57 (m, 5H), 7.51 to 7.42 (m, 5H), 7.36~7.35 (m, 3H), 7.27 (t, 1H), 7.11 (t, 1H), 6.83 (d, 1H). G151 δ = 9.28 (d, 1H), 8.86 (d, 4H), 7.78 (d, 1H), 7.64 to 7.51 (m, 7H), 7.49 (d, 2H), 7.16 to 7.11 (m, 5H), 7.01 ( d, 2H), 6.86–6.83 (m, 2H), 6.50 (d, 1H). G171 δ = 9.08 (d, 1H), 9.01 (d, 2H), 8.86 (d, 4H), 8.28 (d, 2H), 7.99 (dd, 1H), 7.76 (d, 1H), 7.64~7.56 (m , 5H), 7.51–7.46 (m, 2H), 7.37–7.35 (m, 2H), 7.27 (t, 1H). G174 δ = 9.22 (d, 1H), 8.91 (d, 1H), 8.86 (d, 4H), 8.69 (s, 1H), 7.72 to 7.66 (m, 3H), 7.64 to 7.57 (m, 5H), 7.51 to 7.47(m, 3H), 7.36~7.35(m, 3H), 7.29(t, 1H), 7.22(d, 1H), 7.13(t, 1H), 6.88~6.86(m, 2H). G178 δ = 8.11 to 8.08 (m, 3H), 7.63 to 7.51 (m, 9H), 7.47 (d, 1H), 7.39 to 7.29 (m, 6H), 7.22 (s, 1H), 7.12 to 7.09 (m, 2H) ), 6.83 (d, 2H), 6.54 (d, 1H), 1.57 (s, 6H). G179 δ = 8.5 to 8.03 (m, 3H), 7.60 to 7.55 (m, 7H), 7.47 to 7.46 (m, 2H), 7.39 to 7.29 (m, 7H), 7.13 (t, 1H), 7.11 to 7.08 (m , 2H), 7.01 (d, 1H), 6.77 (d, 2H), 6.52 (d, 1H). G184 δ = 9.32 (s, 1H), 9.23 (d, 1H), 8.76 (d, 2H), 8.19 (d, 2H), 8.01 to 7.94 (m, 5H), 7.73 (d, 1H), 7.69 to 7.67 ( m, 3H), 7.64–7.53 (m, 5H), 7.52 (d, 1H), 7.34 (d, 1H), 7.22 (t, 1H). G206 δ = 8.19 (d, 2H), 8.01 to 7.98 (m, 2H), 7.69 (d, 1H), 7.60 to 7.58 (m, 3H), 7.34 (d, 1H). G207 Full D-substitution structure G210 δ = 8.87 (d, 4H) G217 δ = 8.01 (s, 1H), 7.98 (d, 1H), 7.69 to 7.67 (m, 3H), 7.64 to 7.59 (m, 3H), 7.52 (d, 1H), 7.46 (t, 1H), 7.34 ( d, 2H), 7.19 (t, 1H). G220 Full D-substitution structure G225 δ = 9.26 (d, 1H), 9.12 (d, 1H), 8.92 (d, 2H), 8.89 (d, 2H), 8.79 (d, 2H), 8.31 (d, 2H), 8.03 to 7.98 (m, 2H), 7.72(d, 1H), 7.66~7.62(m, 2H), 7.60~7.55(m, 3H), 7.49~7.44(m, 3H), 7.39(d, 1H), 7.36(t, 1H) , 7.27(t, 1H). G227 δ = 9.26 (d, 1H), 9.12 (d, 1H), 8.92 (d, 2H), 8.89 (d, 2H), 8.79 (d, 2H), 8.27 (dd, 2H), 8.03 to 7.98 (m, 2H), 7.72(d, 1H), 7.64~7.60(m, 2H), 7.59~7.55(m, 3H), 7.49~7.44(m, 3H), 7.36~7.35(m, 2H), 7.27(t, 1H).

compound FD-Mass compound FD-Mass G1 m/z = 561.64 (C ₄₀ H ₂₃ N ₃ O, 561.18) G2 m/z = 561.64 (C ₄₀ H ₂₃ N ₃ O, 561.18) G3 m/z = 562.63 (C ₃₉ H ₂₂ N ₄ O, 562.18) G4 m/z = 591.69 (C ₄₀ H ₂₁ N ₃ OS, 591.14) G5 m/z = 575.63 (C ₄₀ H ₂₁ N ₃ O ₂ , 575.16) G6 m/z = 535.61 (C ₃₈ H ₂₁ N ₃ O, 535.17) G7 m/z = 561.69 (C ₄₁ H ₂₇ N ₃ , 561.22) G8 m/z = 611.70 (C ₄₄ H ₂₅ N ₃ O, 611.20) G9 m/z = 551.67 (C ₃₈ H ₂₁ N ₃ S, 551.15) G10 m/z = 591.69 (C ₄₀ H ₂₁ N ₃ OS, 591.14) G11 m/z = 562.63 (C ₃₉ H ₂₂ N ₄ O, 562.18) G12 m/z = 585.67 (C42H23N3O, 585.18) G13 m/z = 561.69 (C ₄₁ H ₂₇ N ₃ , 561.22) G14 m/z = 575.63 (C ₄₀ H ₂₁ N ₃ O ₂ , 575.16) G15 m/z = 625.69 (C ₄₄ H ₂₃ N ₃ O ₂ , 625.18) G16 m/z = 612.69 (C ₄₃ H ₂₄ N ₄ O, 612.20) G17 m/z = 612.69 (C ₄₃ H ₂₄ N ₄ O, 612.20) G18 m/z = 662.75 (C ₄₇ H ₂₆ N ₄ O, 662.21) G19 m/z = 664.81 (C ₄₈ H ₃₂ N ₄ , 664.26) G20 m/z = 652.71 (C ₄₅ H ₂₄ N ₄ O ₂ , 652.19) G21 m/z = 667.79 (C ₄₆ H ₂₅ N ₃ OS, 667.17) G22 m/z = 612.69 (C ₄₃ H ₂₄ N ₄ O, 612.20) G23 m/z = 678.81 (C ₄₇ H ₂₆ N ₄ S, 678.19) G24 m/z = 668.77 (C ₄₅ H ₂₄ N ₄ OS, 668.17) G25 m/z = 638.73 (C ₄₅ H ₂₆ N ₄ O, 638.21) G26 m/z = 651.73 (C ₄₅ H ₂₅ N ₅ O, 651.21) G27 m/z = 701.79 (C ₄₉ H ₂₇ N ₅ O, 701.22) G28 m/z = 714.83 (C ₅₁ H ₃₀ N ₄ O, 714.24) G29 m/z = 714.83 (C ₅₁ H ₃₀ N ₄ O, 714.24) G30 m/z = 727.83 (C ₅₁ H ₂₉ N ₅ O, 727.24) G31 m/z = 742.79 (C ₅₁ H ₂₆ N ₄ O ₃ , 742.20) G32 m/z = 688.79 (C ₄₉ H ₂₈ N ₄ O, 688.23) G33 m/z = 688.79 (C ₄₉ H ₂₈ N ₄ O, 688.23) G34 m/z = 630.68 (C ₄₃ H ₂₃ FN ₄ O, 630.19) G35 m/z = 630.68 (C ₄₃ H ₂₃ FN ₄ O, 630.19) G36 m/z = 740.91 (C ₅₄ H ₃₆ N ₄ , 740.29) G37 m/z = 598.61 (C ₃₉ H ₂₀ F ₂ N ₄ O, 598.16) G38 m/z = 630.63 (C ₄₀ H ₂₁ F ₃ N ₄ O, 630.17) G39 m/z = 587.64 (C ₄₀ H ₂₁ N ₅ O, 587.17) G40 m/z = 652.71 (C ₄₅ H ₂₄ N ₄ O ₂ , 652.19) G41 m/z = 728.81 (C ₅₁ H ₂₈ N ₄ O ₂ , 728.22) G42 m/z = 612.69 (C ₄₃ H ₂₄ N ₄ O, 612.20) G43 m/z = 612.69 (C ₄₃ H ₂₄ N ₄ O, 612.20) G44 m/z = 612.69 (C ₄₃ H ₂₄ N ₄ O, 612.20) G45 m/z = 612.69 (C ₄₃ H ₂₄ N ₄ O, 612.20) G46 m/z = 662.75 (C ₄₇ H ₂₆ N ₄ O, 662.21) G47 m/z = 688.79 (C ₄₉ H ₂₈ N ₄ O, 688.23) G48 m/z = 764.89 (C ₅₅ H ₃₂ N ₄ O, 764.26) G49 m/z = 712.86 (C ₅₂ H ₃₂ N ₄ , 712.26) G50 m/z = 628.75 (C ₄₃ H ₂₄ N ₄ S, 628.17) G51 m/z = 638.73 (C ₄₅ H ₂₆ N ₄ O, 638.21) G52 m/z = 638.73 (C ₄₅ H ₂₆ N ₄ O, 638.21) G53 m/z = 638.73 (C ₄₅ H ₂₆ N ₄ O, 638.21) G54 m/z = 638.73 (C ₄₅ H ₂₆ N ₄ O, 638.21) G55 m/z = 628.75 (C ₄₃ H ₂₄ N ₄ S, 628.17) G56 m/z = 628.75 (C ₄₃ H ₂₄ N ₄ S, 628.17) G57 m/z = 704.85 (C ₄₉ H ₂₈ N ₄ S, 704.20) G58 m/z = 662.75 (C ₄₇ H ₂₆ N ₄ O, 662.21) G59 m/z = 638.73 (C ₄₅ H ₂₆ N ₄ O, 638.21) G60 m/z = 727.83 (C ₅₁ H ₂₉ N ₅ O, 727.24) G61 m/z = 638.77 (C ₄₆ H ₃₀ N ₄ , 638.25) G62 m/z = 585.67 (C42H23N3O, 585.18) G63 m/z = 611.70 (C ₄₄ H ₂₅ N ₃ O, 611.20) G64 m/z = 638.73 (C ₄₅ H ₂₆ N ₄ O, 638.21) G65 m/z = 590.69 (C ₄₁ H ₂₆ N ₄ O, 590.21) G66 m/z = 638.73 (C ₄₅ H ₂₆ N ₄ O, 638.21) G67 m/z = 638.73 (C ₄₅ H ₂₆ N ₄ O, 638.21) G68 m/z = 688.79 (C ₄₉ H ₂₈ N ₄ O, 688.23) G69 m/z = 688.79 (C ₄₉ H ₂₈ N ₄ O, 688.23) G70 m/z = 728.81 (C ₅₁ H ₂₈ N ₄ O ₂ , 728.22) G71 m/z = 728.81 (C ₅₁ H ₂₈ N ₄ O ₂ , 728.22) G72 m/z = 728.81 (C ₅₁ H ₂₈ N ₄ O ₂ , 728.22) G73 m/z = 728.81 (C ₅₁ H ₂₈ N ₄ O ₂ , 728.22) G74 m/z = 728.81 (C ₅₁ H ₂₈ N ₄ O ₂ , 728.22) G75 m/z = 728.81 (C ₅₁ H ₂₈ N ₄ O ₂ , 728.22) G76 m/z = 744.87 (C ₅₁ H ₂₈ N _{4 O} S, 744.20) G77 m/z = 728.81 (C ₅₁ H ₂₈ N ₄ O ₂ , 728.22) G78 m/z = 728.81 (C ₅₁ H ₂₈ N ₄ O ₂ , 728.22) G79 m/z = 585.67 (C ₄₂ H ₂₃ N ₃ O, 585.18) G80 m/z = 611.70 (C ₄₄ H ₂₅ N ₃ O, 611.20) G81 m/z = 700.80 (C ₅₀ H ₂₈ N ₄ O, 700.23) G82 m/z = 700.80 (C ₅₀ H ₂₈ N ₄ O, 700.23) G83 m/z = 674.76 (C ₄₈ H ₂₆ N ₄ O, 674.21) G84 m/z = 674.76 (C ₄₈ H ₂₆ N ₄ O, 674.21) G85 m/z = 625.69 (C ₄₄ H ₂₃ N ₃ O ₂ , 625.18) G86 m/z = 625.69 (C ₄₄ H ₂₃ N ₃ O ₂ , 625.18) G87 m/z = 625.69 (C ₄₄ H ₂₃ N ₃ O ₂ , 625.18) G88 m/z = 675.75 (C ₄₈ H ₂₅ N ₃ O ₂ , 675.19) G89 m/z = 675.75 (C ₄₈ H ₂₅ N ₃ O ₂ , 675.19) G90 m/z = 675.75 (C ₄₈ H ₂₅ N ₃ O ₂ , 675.19) G91 m/z = 651.73 (C ₄₆ H ₂₅ N ₃ O ₂ , 651.19) G92 m/z = 625.69 (C ₄₄ H ₂₃ N ₃ O ₂ , 625.18) G93 m/z = 665.71 (C ₄₆ H ₂₃ N ₃ O ₃ , 665.17) G94 m/z = 667.79 (C ₄₆ H ₂₅ N ₃ OS, 667.17) G95 m/z = 657.81 (C ₄₄ H ₂₃ N ₃ S ₂ , 657.13) G96 m/z = 697.83 (C ₄₆ H ₂₃ N _{3 O} S ₂ , 697.13) G97 m/z = 627.77 (C ₄₄ H ₂₅ N ₃ S, 627.18) G98 m/z = 601.73 (C ₄₂ H ₂₃ N ₃ S, 601.16) G99 m/z = 625.69 (C ₄₄ H ₂₃ N ₃ O ₂ , 625.18) G100 m/z = 677.81 (C ₄₉ H ₃₁ N ₃ O, 677.25) G101 m/z = 651.77 (C ₄₇ H ₂₉ N _{3 O} , 651.23) G102 m/z = 591.69 (C ₄₀ H ₂₁ N ₃ OS, 591.14) G103 m/z = 693.87 (C ₄₉ H ₃₁ N ₃ S, 693.22) G104 m/z = 641.75 (C ₄₄ H ₂₃ N _{3 O} S, 641.16) G105 m/z = 607.75 (C ₄₀ H ₂₁ N ₃ S ₂ , 607.12) G106 m/z = 535.61 (C ₃₈ H ₂₁ N ₃ O, 535.17) G107 m/z = 585.67 (C ₄₂ H ₂₃ N ₃ O, 585.18) G108 m/z = 591.69 (C ₄₀ H ₂₁ N ₃ OS, 591.14) G109 m/z = 585.67 (C ₄₂ H ₂₃ N ₃ O, 585.18) G110 m/z = 585.67 (C ₄₂ H ₂₃ N ₃ O, 585.18) G111 m/z = 711.82 (C ₅₂ H ₂₉ N _{3 O} , 711.23) G112 m/z = 661.76 (C ₄₈ H ₂₇ N ₃ O, 661.22) G113 m/z = 677.83 (C ₄₈ H ₂₇ N ₃ S, 677.19) G114 m/z = 688.79 (C ₄₉ H ₂₈ N _{4 O} , 688.23) G115 m/z = 650.74 (C ₄₆ H ₂₆ N _{4 O} , 650.21) G116 m/z = 509.57 (C ₃₆ H ₁₉ N ₃ O, 509.15) G117 m/z = 509.57 (C ₃₆ H ₁₉ N ₃ O, 509.15) G118 m/z = 641.75 (C ₄₄ H ₂₃ N _{3 O} S, 641.16) G119 m/z = 591.69 (C ₄₀ H ₂₁ N ₃ OS, 591.14) G120 m/z = 591.69 (C ₄₀ H ₂₁ N ₃ OS, 591.14) G121 m/z = 625.69 (C ₄₄ H ₂₃ N ₃ O ₂ , 625.18) G122 m/z = 625.69 (C ₄₄ H ₂₃ N ₃ O ₂ , 625.18) G123 m/z = 641.75 (C ₄₄ H ₂₃ N ₃ OS, 641.16) G124 m/z = 700.80 (C ₅₀ H ₂₈ N ₄ O, 700.23) G125 m/z = 700.80 (C ₅₀ H ₂₈ N ₄ O, 700.23) G126 m/z = 661.76 (C ₄₈ H ₂₇ N ₃ O, 661.22) G127 m/z = 687.85 (C ₅₁ H ₃₃ N ₃ , 687.27) G128 m/z = 726.88 (C ₅₃ H ₃₄ N ₄ , 726.28) G129 m/z = 776.90 (C ₅₆ H ₃₂ N _{4 O} , 776.26) G130 m/z = 661.76 (C ₄₈ H ₂₇ N ₃ O, 661.22) G131 m/z = 661.76 (C ₄₈ H ₂₇ N ₃ O, 661.22) G132 m/z = 611.70 (C ₄₄ H ₂₅ N ₃ O, 611.20) G133 m/z = 574.64 (C ₄₀ H ₂₂ N ₄ O, 574.18) G134 m/z = 585.67 (C ₄₂ H ₂₃ N ₃ O, 585.18) G135 m/z = 611.70 (C ₄₄ H ₂₅ N ₃ O, 611.20) G136 m/z = 638.73 (C ₄₅ H ₂₆ N ₄ O, 638.21) G137 m/z = 688.79 (C ₄₉ H ₂₈ N ₄ O, 688.23) G138 m/z = 754.91 (C ₅₃ H ₃₀ N ₄ S, 754.22) G139 m/z = 688.79 (C ₄₉ H ₂₈ N ₄ O, 688.23) G140 m/z = 738.85 (C ₅₃ H ₃₀ N ₄ O, 738.24) G141 m/z = 738.85 (C ₅₃ H ₃₀ N ₄ O, 738.24) G142 m/z = 738.85 (C ₅₃ H ₃₀ N ₄ O, 738.24) G143 m/z = 788.91 (C ₅₇ H ₃₂ N ₄ O, 788.26) G144 m/z = 788.91 (C ₅₇ H ₃₂ N ₄ O, 788.26) G145 m/z = 688.79 (C ₄₉ H ₂₈ N ₄ O, 688.23) G146 m/z = 666.78 (C ₄₇ H ₃₀ N ₄ O, 666.24) G147 m/z = 638.73 (C ₄₅ H ₂₆ N ₄ O, 638.21) G148 m/z = 638.73 (C ₄₅ H ₂₆ N ₄ O, 638.21) G149 m/z = 638.73 (C ₄₅ H ₂₆ N ₄ O, 638.21) G150 m/z = 638.73 (C ₄₅ H ₂₆ N ₄ O, 638.21) G151 m/z = 639.72 (C ₄₄ H ₂₅ N ₅ O, 639.21) G152 m/z = 640.71 (C ₄₃ H ₂₄ N ₆ O, 640.20) G153 m/z = 689.78 (C ₄₈ H ₂₇ N ₅ O, 689.22) G154 m/z = 607.75 (C ₄₀ H ₂₁ N ₃ S ₂ , 607.12) G155 m/z = 551.67 (C ₃₈ H ₂₁ N ₃ S, 551.15) G156 m/z = 551.67 (C ₃₈ H ₂₁ N ₃ S, 551.15) G157 m/z = 688.79 (C ₄₉ H ₂₈ N ₄ O, 688.23) G158 m/z = 688.79 (C ₄₉ H ₂₈ N ₄ O, 688.23) G159 m/z = 688.79 (C ₄₉ H ₂₈ N ₄ O, 688.23) G160 m/z = 714.83 (C ₅₁ H ₃₀ N ₄ O, 714.24) G161 m/z = 638.73 (C ₄₅ H ₂₆ N ₄ O, 638.21) G162 m/z = 611.70 (C ₄₄ H ₂₅ N ₃ O, 611.20) G163 m/z = 585.67 (C42H23N3O, 585.18) G164 m/z = 611.70 (C ₄₄ H ₂₅ N ₃ O, 611.20) G165 m/z = 611.70 (C ₄₄ H ₂₅ N ₃ O, 611.20) G166 m/z = 625.69 (C ₄₄ H ₂₃ N ₃ O ₂ , 625.18) G167 m/z = 611.75 (C ₄₅ H ₂₉ N ₃ , 611.24) G168 m/z = 651.77 (C ₄₇ H ₂₉ N _{3 O} , 651.23) G169 m/z = 611.70 (C ₄₄ H ₂₅ N ₃ O, 611.20) G170 m/z = 638.73 (C ₄₅ H ₂₆ N ₄ O, 638.21) G171 m/z = 563.62 (C ₃₈ H ₂₁ N ₅ O, 563.17) G172 m/z = 667.79 (C ₄₆ H ₂₅ N ₃ OS, 667.17) G173 m/z = 688.79 (C ₄₉ H ₂₈ N ₄ O, 688.23) G174 m/z = 638.73 (C ₄₅ H ₂₆ N ₄ O, 638.21) G175 m/z = 688.79 (C ₄₉ H ₂₈ N ₄ O, 688.23) G176 m/z = 688.79 (C ₄₉ H ₂₈ N ₄ O, 688.23) G177 m/z = 654.79 (C ₄₅ H ₂₆ N ₄ S, 654.19) G178 m/z = 585.75 (C ₄₅ H ₃₁ N, 585.25) G179 m/z = 559.67 (C ₄₂ H ₂₅ NO, 559.19) G180 m/z = 533.63 (C ₄₀ H ₂₃ NO, 533.18) G181 m/z = 641.75 (C ₄₄ H ₂₃ N _{3 O} S, 641.16) G182 m/z = 625.69 (C ₄₄ H ₂₃ N ₃ O ₂ , 625.18) G184 m/z = 585.67 (C ₄₂ H ₂₃ N ₃ O, 585.18) G184 m/z = 675.75 (C ₄₈ H ₂₅ N ₃ O ₂ , 675.19) G185 m/z = 675.75 (C ₄₈ H ₂₅ N ₃ O ₂ , 675.19) G186 m/z = 675.75 (C ₄₈ H ₂₅ N ₃ O ₂ , 675.19) G187 m/z = 675.75 (C ₄₈ H ₂₅ N ₃ O ₂ , 675.19) G188 m/z = 715.77 (C ₅₀ H ₂₅ N ₃ O ₃ , 715.19) G189 m/z = 715.77 (C ₅₀ H ₂₅ N ₃ O ₃ , 715.19) G190 m/z = 731.83 (C ₅₀ H ₂₅ N ₃ O ₂ S, 731.17) G191 m/z = 731.83 (C ₅₀ H ₂₅ N ₃ O ₂ S, 731.17) G192 m/z = 731.83 (C ₅₀ H ₂₅ N ₃ O ₂ S, 731.17) G193 m/z = 661.76 (C ₄₈ H ₂₇ N ₃ O, 661.22) G194 m/z = 559.63 (C ₄₀ H ₂₁ N ₃ O, 559.17) G195 m/z = 584.68 (C ₄₃ H ₂₄ N ₂ O, 584.19) G196 m/z = 635.73 (C ₄₆ H ₂₅ N ₃ O, 635.20) G197 m/z = 585.67 (C42H23N3O, 585.18) G198 m/z = 661.76 (C ₄₈ H ₂₇ N ₃ O, 661.22) G199 m/z = 700.80 (C ₅₀ H ₂₈ N ₄ O, 700.23) G200 m/z = 700.80 (C ₅₀ H ₂₈ N ₄ O, 700.23) G201 m/z = 750.86 (C ₅₄ H ₃₀ N ₄ O, 750.24) G202 m/z = 624.70 (C ₄₄ H ₂₄ N ₄ O, 624.20) G203 m/z = 641.75 (C ₄₄ H ₂₃ N ₃ OS, 641.16) G204 m/z = 651.79 (C ₄₆ H ₂₅ N ₃ S, 651.79) G205 m/z = 544.66 (C ₃₈ H ₁₂ D ₉ N ₃ O, 544.22) G206 m/z = 547.68 (C ₃₈ H ₉ D ₁₂ N ₃ O, 547.24) G207 m/z = 556.73 (C ₃₈ D ₂₁ N ₃ O, 556.30) G208 m/z = 638.73 (C ₄₅ H ₂₆ N ₄ O, 638.21) G209 m/z = 702.88 (C ₄₉ H ₁₄ D ₁₄ N ₄ O, 702.31) G210 m/z = 706.90 (C ₄₉ H ₁₀ D ₁₈ N ₄ O, 706.34) G211 m/z = 638.73 (C ₄₅ H ₂₆ N ₄ O, 638.21) G212 m/z = 643.76 (C ₄₅ H ₂₁ D ₅ N ₄ O, 643.24) G213 m/z = 648.79 (C ₄₅ H ₁₆ D ₁₀ N ₄ O, 648.27) G214 m/z = 593.71 (C ₄₂ H ₁₅ D ₈ N ₃ O, 593.23) G215 m/z = 583.68 (C ₄₀ H ₁₃ D ₈ N ₃ O ₂ , 583.21) G216 m/z = 599.74 (C ₄₀ H ₁₃ D ₈ N ₃ OS, 599.19) G217 m/z = 623.78 (C ₄₄ H ₁₃ D ₁₂ N ₃ O, 623.28) G218 m/z = 587.70 (C ₄₀ H ₉ D ₁₂ N ₃ O ₂ , 587.24) G219 m/z = 603.76 (C ₄₀ H ₉ D ₁₂ N ₃ OS, 603.76) G220 m/z = 634.84 (C ₄₄ H ₂ D ₂₃ N ₃ O, 634.34) G221 m/z = 594.74 (C ₄₀ H ₂ D ₁₉ N ₃ O ₂ , 594.28) G222 m/z = 610.80 (C ₄₀ H ₂ D ₁₉ N ₃ OS, 610.26) G223 m/z = 674.76 (C ₄₈ H ₂₆ N ₄ O, 674.21) G224 m/z = 816.92 (C ₅₇ H ₃₂ N ₆ O, 816.26) G225 m/z = 652.71 (C ₄₅ H ₂₄ N ₄ O ₂ , 652.19) G226 m/z = 728.81 (C ₅₁ H ₂₈ N ₄ O ₂ , 728.22) G227 m/z = 652.71 (C ₄₅ H ₂₄ N ₄ O ₂ , 652.19) G228 m/z = 668.77 (C ₄₅ H _24N4 OS, 668.17) G229 m/z = 743.89 (C ₅₁ H ₂₉ N ₅ S, 743.21) G230 m/z = 727.83 (C ₅₁ H ₂₉ N ₅ O, 727.24) G231 m/z = 750.86 (C ₅₄ H ₃₀ N ₄ O, 750.24) G232 m/z = 590.69 (C ₄₁ H ₂₆ N ₄ O, 590.21) G233 m/z = 712.81 (C ₅₁ H ₂₈ N ₄ O, 712.23) G234 m/z = 712.81 (C ₅₁ H ₂₈ N ₄ O, 712.23)

<Experimental example>

Experimental Example 1

(1) Manufacture of organic light emitting device

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

4,4',4''-tris[2-naphthyl(phenyl)amino]triphenylamine(4,4',4''-Tris[ 2-naphthyl(phenyl)amino]triphenylamine): 2-TNATA) was deposited, and N,N'-bis(α-naphthyl)-N,N'-diphenyl-4,4'-diamine ( N,N'-bis(α-naphthyl)-N,N'-diphenyl-4,4'-diamine: NPB) was deposited, and cyclohexylidenebis[N,N-bis(4- Methylphenyl) benzenamine] (cyclohexylidenebis [N, N-bis (4-methylphenyl) benzenamine]: TAPC) or tris (4-carbazoyl-9-ylphenyl) amine (Tris (4-carbazoyl-9-ylphenyl) amine as an exciton blocking layer) ylphenyl)amine, TCTA) was deposited.

After the hole injection layer, the hole transport layer, and the electron blocking layer or exciton blocking layer were formed in this way, a light emitting layer was thermally vacuum deposited thereon as follows. The light emitting layer was deposited with a thickness of 400 Å through a single or two sources of the compounds listed in Table 7 as a red host, and using (piq) ₂ (Ir)(acac) as a red phosphorescent dopant, an Ir compound was applied to the host as the light emitting layer. It was deposited by doping with an amount of 3 wt% of the deposition thickness of.

Thereafter, Bphen was deposited to a thickness of 30 Å as a hole blocking layer, and TPBI was deposited to a thickness of 250 Å as an electron transport layer thereon.

Finally, lithium fluoride (LiF) is deposited on the electron transport layer to a thickness of 10 Å to form an electron injection layer, and then an aluminum (Al) cathode is deposited on the electron injection layer to a thickness of 1,200 Å to form a cathode By doing so, an organic light emitting device was manufactured.

On the other hand, all the organic compounds required for the manufacture of the organic light emitting device were purified by vacuum sublimation under 10 ⁻⁶ to 10 ⁻⁸ torr for each material, and then used for the manufacture of the organic light emitting device.

(2) Measurement of driving voltage, luminous efficiency and lifetime of organic light emitting device

The electroluminescence (EL) characteristics of the organic light emitting device manufactured as described above were measured with McSyers' M7000, and the standard luminance was 6,000 cd through the lifetime equipment measuring equipment (M6000) manufactured by McScience with the measurement result. / m ² , the lifetime T ₉₀ , which is the time to reach 90% of the initial luminance, was measured. The characteristics of the organic light emitting device of the present invention are shown in Table 7 below.

compound Driving voltage (V) Luminous efficiency (cd/A) Color coordinates (x,y) lifetime (T ₉₀ ) Comparative Example 1 A 4.62 21.6 (0.682, 0.318) 18 Comparative Example 2 B 4.82 19.2 (0.682, 0.318) 22 Comparative Example 3 C 4.71 23.8 (0.682, 0.318) 19 Comparative Example 4 D 4.73 22.1 (0.682, 0.318) 22 Comparative Example 5 E 4.54 23.4 (0.684, 0.316) 16 Comparative Example 6 F 4.53 22.1 (0.684, 0.316) 21 Comparative Example 7 G 4.51 23.1 (0.684, 0.315) 13 Comparative Example 8 H 4.22 21.3 (0.685, 0.314) 89 Comparative Example 9 I 4.41 23.1 (0.682, 0.317) 41 Comparative Example 10 J 4.19 22.9 (0.682, 0.318) 78 Comparative Example 11 K 3.97 24.1 (0.682, 0.318) 71 Comparative Example 12 L 4.02 24.6 (0.682, 0.318) 59 Comparative Example 13 M 4.11 24.9 (0.681, 0.318) 129 Comparative Example 14 N 3.81 28.7 (0.682, 0.318) 135 Comparative Example 15 O 4.04 26.5 (0.682, 0.317) 122 Comparative Example 16 P 4.32 16.4 (0.687, 0.312) 78 Example 1 G3 3.40 40.2 (0.682, 0.318) 420 Example 2 G4 3.88 36.6 (0.687, 0.312) 480 Example 3 G5 3.92 36.9 (0.687, 0.313) 400 Example 4 G6 3.86 39.8 (0.682, 0.317) 580 Example 5 G8 3.82 38.9 (0.682, 0.317) 640 Example 6 G11 3.42 40.6 (0.682, 0.317) 389 Example 7 G13 3.99 37.5 (0.682, 0.317) 522 Example 8 G16 3.53 42.2 (0.682, 0.317) 369 Example 9 G19 3.49 34.9 (0.682, 0.317) 330 Example 10 G27 3.66 40.9 (0.682, 0.317) 280 Example 11 G31 3.47 39.8 (0.681, 0.318) 377 Example 12 G35 3.67 33.3 (0.682, 0.317) 280 Example 13 G37 4.01 34.2 (0.682, 0.317) 220 Example 14 G44 3.47 42.1 (0.682, 0.317) 226 Example 15 G49 3.65 40.1 (0.682, 0.317) 230 Example 16 G52 3.52 41.2 (0.682, 0.317) 390 Example 17 G53 3.49 41.0 (0.684, 0.315) 422 Example 18 G55 3.52 40.9 (0.682, 0.317) 470 Example 19 G56 3.56 39.8 (0.682, 0.317) 458 Example 20 G66 3.98 44.2 (0.682, 0.317) 199 Example 21 G67 3.99 45.8 (0.682, 0.317) 216 Example 22 G68 4.02 46.1 (0.683, 0.316) 247 Example 23 G69 4.01 43.1 (0.682, 0.318) 199 Example 24 G71 4.22 38.6 (0.682, 0.318) 412 Example 25 G72 3.87 42.8 (0.682, 0.318) 609 Example 26 G74 3.49 33.0 (0.682, 0.318) 216 Example 27 G76 3.59 38.2 (0.682, 0.318) 306 Example 28 G83 4.18 36.6 (0.682, 0.318) 420 Example 29 G88 3.89 35.8 (0.682, 0.318) 599 Example 30 G91 3.76 40.8 (0.682, 0.318) 389 Example 31 G98 4.01 38.9 (0.682, 0.318) 598 Example 32 G102 3.98 38.8 (0.682, 0.318) 412 Example 33 G114 4.02 45.7 (0.682, 0.318) 264 Example 34 G120 4.01 30.9 (0.682, 0.318) 522 Example 35 G122 3.88 34.8 (0.682, 0.318) 587 Example 36 G132 4.11 36.8 (0.682, 0.318) 569 Example 37 G135 4.38 44.1 (0.682, 0.318) 122 Example 38 G147 4.48 30.1 (0.682, 0.318) 98 Example 39 G151 3.36 28.5 (0.683, 0.317) 76 Example 40 G171 3.54 40.2 (0.682, 0.318) 312 Example 41 G174 4.67 33.1 (0.682, 0.318) 69 Example 42 G178 5.24 12.8 (0.681, 0.318) 76 Example 43 G178:G3 (1:3) 4.02 42.8 (0.682, 0.317) 376 Example 44 G179 5.38 14.1 (0.680, 0.319) 55 Example 45 G179:G151 (1:1) 4.56 30.1 (0.680, 0.319) 210 Example 46 G179:G151 (1:3) 4.09 36.9 (0.681, 0.318) 291 Example 47 G184 4.21 41.0 (0.683, 0.317) 558 Example 48 G206 4.18 38.9 (0.681, 0.318) 680 Example 49 G207 4.18 38.2 (0.681, 0.318) 679 Example 50 G210 4.01 44.8 (0.681, 0.318) 620 Example 51 G217 3.82 38.1 (0.682, 0.317) 679 Example 52 G220 3.82 38.0 (0.682, 0.317) 675 Example 53 G225 3.59 42.6 (0.684, 0.315) 444 Example 54 G227 3.59 42.3 (0.684, 0.315) 421

In Table 7, the compounds of Comparative Examples 1 to 16 are the same as Comparative Compounds A to P below.

From the results of Table 7, the organic light emitting devices of Comparative Examples 1 to 4 including Comparative Compounds A to D emit excellent light emission in the organic light emitting devices even when the electron transfer functional group (ETU) is changed to the hole propensity of naphthocarbazole. Efficiency and longevity were not shown. In addition, although the organic light emitting device of Comparative Examples 5 to 7 including Comparative Compounds E to G introduced a substituent of naphthocarbazole, it was confirmed that the light emitting efficiency and lifetime of the organic light emitting device were not improved.

The organic light emitting device of Comparative Example 8 including Comparative Compound H uses naphthocarbazole in a bent form with extended conjugation as a hole transfer functional group (HTU), so the driving voltage of the organic light emitting device is improved and the lifetime is increased However, it is expected that the luminous efficiency is not greatly improved because the hole injection/migration tendency of carbazole is still insufficient.

The organic light emitting devices of Comparative Examples 9 and 10 including Comparative Compounds I and J had slightly improved lifespan due to the separation of the electron transfer functional group (ETU) and the hole transfer functional group (HTU), but did not show excellent performance.

The organic light emitting devices of Comparative Examples 11 and 12 including Comparative Compounds K and L, which are cyclic hole transfer functional group (HTU) frameworks capable of enhancing hole injection characteristics with improved stability of the hole transfer functional group (HTU), have hole injection characteristics Although the driving voltage was improved, the lifespan was still not improved.

The organic light emitting devices of Comparative Examples 13 to 16 including Comparative Compounds M to P exhibited an effect of improving driving voltage, but lifespan was not improved.

Accordingly, an organic light emitting device using a heterocyclic compound represented by Formula 1 is a carbazole containing an azulene skeleton in order to control the balance of charges by enhancing hole injection/mobility characteristics in a device having poor hole injection characteristics. A host capable of improving hole transfer characteristics was synthesized by designing a structure introducing a benzofuran ring into the ring. This novel hole transfer functional group (HTU) framework could improve driving voltage, luminous efficiency and lifespan in combination with various electron transfer functional groups (ETU).

From the results of Table 7, it was confirmed that the organic light emitting device using the heterocyclic compound of the present invention had a lower driving voltage and markedly improved light emitting efficiency and lifetime compared to the organic light emitting devices of Comparative Examples 1 to 16. In particular, when triazine, which attracts strong electrons, was used as the electron transport functional group (ETU), the driving voltage could be effectively improved, and when quinazoline derivatives were used as the electron transport functional group (ETU), the lifespan was improved. could As a result, depending on the appropriate electron transfer functional group (ETU) skeleton combination, it showed the effect of exhibiting long lifespan or high efficiency performance. Changes in driving voltage, luminous efficiency, and lifetime performance according to changes in the electron transfer functional group (ETU) framework enable the hole transfer functional group (HTU) framework of the present invention to perform a smooth hole injection role, and have good thin film characteristics, so that various electron transfer functional groups ( ETU) seems to be possible.

Claims (13)

A heterocyclic compound represented by Formula 1 below:
[Formula 1]

In Formula 1,
X and Y are each independently O, S, CR13R14 or a single bond;
W is N or CR6;
R13 and R14 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen; cyano group; A substituted or unsubstituted C1 to C60 alkyl group; A substituted or unsubstituted C6 to C60 aryl group; And it is selected from the group consisting of a substituted or unsubstituted C2 to C60 heteroaryl group,
R1 to R12 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen; cyano group; A substituted or unsubstituted C1 to C60 alkyl group; A substituted or unsubstituted C2 to C60 alkenyl group; A substituted or unsubstituted C2 to C60 alkynyl group; A substituted or unsubstituted C1 to C60 alkoxy group; A substituted or unsubstituted C3 to C60 cycloalkyl group; A substituted or unsubstituted C2 to C60 heterocycloalkyl group; A substituted or unsubstituted C6 to C60 aryl group; A substituted or unsubstituted C2 to C60 heteroaryl group; And a C6 to C60 aromatic hydrocarbon ring selected from the group consisting of a group represented by Formula 1-1, or substituted or unsubstituted by combining two or more groups adjacent to each other; or a substituted or unsubstituted C2 to C60 heterocycle; forming;
L is a single bond, a substituted or unsubstituted C6 to C60 arylene group; Or a substituted or unsubstituted C2 to C60 heteroarylene group;
m is an integer from 0 to 3;
Ar1 is a group represented by Formula 1-1 below,
[Formula 1-1]

In Formula 1-1,
X1 is N or CRa;
X2 is N or CRb;
X3 is N or CRc;
X4 is N or CRd;
X5 is N or CRe;
Ra to Re are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen; cyano group; A substituted or unsubstituted C1 to C60 alkyl group; A substituted or unsubstituted C2 to C60 alkenyl group; A substituted or unsubstituted C2 to C60 alkynyl group; or a substituted or unsubstituted C1 to C60 alkoxy group; A substituted or unsubstituted C6 to C60 aryl group; and a substituted or unsubstituted C2 to C60 heteroaryl group, or a substituted or unsubstituted C6 to C60 aromatic hydrocarbon ring by combining two or more groups adjacent to each other; Or a substituted or unsubstituted C2 to C60 heterocycle; to form. According to claim 1,
The compound represented by Formula 1 is any one of the following Formulas 1-a and 1-b, a heterocyclic compound:
[Formula 1-a]

[Formula 1-b]

In Formulas 1-a and 1-b,
Z is O, S or CR13R14;
W is N or CR6;
R13 and R14 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen; cyano group; A substituted or unsubstituted C1 to C60 alkyl group; And a substituted or unsubstituted C6 to C60 aryl group; selected from the group consisting of
R1 to R12, Ar1, L and m are as defined in Formula 1 above. According to claim 1,
In the group represented by Formula 1-1,
At least one of X1 to X5 is N, or X1 to X5 are each independently CRa to CRe, a heterocyclic compound. According to claim 1,
A heterocyclic compound wherein the group represented by Formula 1-1 is any one of Formulas 1-1-a to 1-1-h:
[Formula 1-1-a]

[Formula 1-1-b]

[Formula 1-1-c]

[Formula 1-1-d]

[Formula 1-1-e]

[Formula 1-1-f]

[Formula 1-1-g]

[Formula 1-1-h]

In Formulas 1-1-a to 1-1-h,
Ra to Re are as defined in Formula 1-1 above. According to claim 1,
R1 to R12 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; A substituted or unsubstituted C6 to C60 aryl group; A substituted or unsubstituted C2 to C60 heteroaryl group; And a C6 to C60 aromatic hydrocarbon ring selected from the group consisting of a group represented by Formula 1-1, or substituted or unsubstituted by combining two or more groups adjacent to each other; Or a substituted or unsubstituted C2 to C60 heterocycle; to form a heterocyclic compound. According to claim 1,
Of the heterocyclic compound represented by Formula 1, the content of deuterium based on the total number of hydrogen atoms and deuterium atoms is 1% to 100%, or a heterocyclic compound that does not contain deuterium. According to claim 1,
The heterocyclic compound represented by Formula 1 is any one selected from the group consisting of the following compounds, the heterocyclic compound:

. a first electrode;
a second electrode provided to face the first electrode; and
An organic light emitting device comprising one or more organic material layers provided between the first electrode and the second electrode,
At least one layer of the organic material layer will include the heterocyclic compound according to any one of claims 1 to 7, an organic light emitting device. According to claim 8,
The organic material layer includes a light emitting layer or an auxiliary light emitting layer, wherein the light emitting layer or the auxiliary light emitting layer includes the heterocyclic compound, the organic light emitting device. According to claim 8,
The organic material layer includes a light emitting layer or an auxiliary light emitting layer, wherein the light emitting layer or the auxiliary light emitting layer includes a host material, and the host material includes the heterocyclic compound. According to claim 8,
The organic light emitting device further comprises one or two or more layers selected from the group consisting of a light emitting layer, a light emitting auxiliary layer, a hole injection layer, a hole transport layer, an electron injection layer, an electron transport layer, a battery blocking layer, and a hole blocking layer. , organic light emitting device. A composition for an organic layer of an organic light emitting device, comprising two or more heterocyclic compounds represented by Formula 1 according to any one of claims 1 to 7. According to claim 12,
The heterocyclic compound represented by Formula 1 may include a first compound and a second compound, and the weight ratio of the first compound and the second compound is 1:10 to 10:1, an organic layer of an organic light emitting device. composition for.

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