WO2016175624A1

WO2016175624A1 - Heterocyclic compound and organic light emitting element using same

Info

Publication number: WO2016175624A1
Application number: PCT/KR2016/004567
Authority: WO
Inventors: 라현주; 정원장; 이현주; 이진우; 최진석; 최대혁; 이주동
Original assignee: 희성소재(주)
Priority date: 2015-04-29
Filing date: 2016-04-29
Publication date: 2016-11-03
Also published as: TWI654191B; TW201704236A; CN107548399B; KR101882221B1; CN107548399A; KR20160128941A

Abstract

The present application provides: a heterocyclic compound capable of greatly improving the lifespan, efficiency, electrochemical stability, and thermal stability of an organic light emitting element; and an organic light emitting element having an organic compound layer containing the heterocyclic compound.

Description

Heterocyclic compound and organic light emitting device using the same

This application claims the benefit of Korean Patent Application Nos. 10-2015-0060829 and 10-2015-0060836 filed on April 29, 2015, the contents of which are incorporated herein.

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

The electroluminescent device is a kind of self-luminous display device, and has an advantage of having a wide viewing angle, excellent contrast, and fast response speed.

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

The material of the organic thin film may have a light emitting function as needed. For example, as the organic thin film material, a compound which may itself constitute a light emitting layer may be used, or a compound that may serve as a host or a dopant of a host-dopant-based light emitting layer may be used. In addition, as a material of the organic thin film, a compound capable of performing a role of hole injection, hole transport, electron blocking, hole blocking, electron transport, electron injection, or the like may be used.

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

Compounds having a chemical structure capable of satisfying the conditions required for materials usable in the organic light emitting device, such as appropriate energy level, electrochemical stability and thermal stability, and can play various roles required in the organic light emitting device according to substituents. There is a need for a study on an organic light emitting device comprising a.

An exemplary embodiment of the present application provides a heterocyclic compound represented by Formula 1 below:

[Formula 1]

In Chemical Formula 1,

R1 is hydrogen or deuterium, represented by-(L1) p- (Y1) q,

R2 is hydrogen, deuterium or naphthyl, or is represented by-(L2) r- (Y2) s,

L1 and L2 are each independently a substituted or unsubstituted arylene group; And a substituted or unsubstituted ring or polycyclic heteroarylene group,

Y1 and Y2 are hydrogen; heavy hydrogen; Halogen group; -CN; Substituted or unsubstituted alkyl group; Substituted or unsubstituted alkenyl group; Substituted or unsubstituted alkynyl group; Substituted or unsubstituted alkoxy group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted heterocycloalkyl group; Substituted or unsubstituted aryl group; Substituted or unsubstituted heteroaryl group; -SiRR'R "; -P (= O) RR '; and an alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group substituted or unsubstituted amine group,

p is 0 to 10, q is 1 to 10,

r is 0 to 10, s is 1 to 10,

R3 to R10 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Halogen group; -CN; Substituted or unsubstituted alkyl group; Substituted or unsubstituted alkenyl group; Substituted or unsubstituted alkynyl group; Substituted or unsubstituted alkoxy group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted heterocycloalkyl group; Substituted or unsubstituted aryl group; Substituted or unsubstituted heteroaryl group; -SiRR'R "; -P (= O) RR '; and an alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group substituted or unsubstituted amine group selected from the group or adjacent to each other Two or more groups which are bonded to each other to form a substituted or unsubstituted monocyclic or polycyclic aliphatic or aromatic hydrocarbon ring,

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

In addition, another exemplary embodiment of the present application is an organic light emitting device including an anode, a cathode, and one or more organic material layers provided between the anode and the cathode, wherein one or more layers of the organic material layers include the heterocyclic compound. Provided is an element.

The heterocyclic compound according to the exemplary embodiment of the present application may be used as an organic material layer material of the organic light emitting device. The heterocyclic compound may be used as a material such as a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer in the organic light emitting device. In particular, the heterocyclic compound represented by Formula 1 may be used as a material of an electron transporting layer, a hole transporting layer or a light emitting layer of the organic light emitting device. In addition, when used in the heterocyclic compound organic light emitting device represented by the formula (1) can reduce the drive voltage of the device, improve the light efficiency, and can improve the life characteristics of the device by the thermal stability of the compound.

1 to 4 are diagrams schematically showing a laminated structure of an organic light emitting device according to an exemplary embodiment of the present application.

5 shows a PL measurement graph at 286 nm wavelength of compound 16. FIG.

6 shows a PL measurement graph at 328 nm wavelength of compound 16. FIG.

7 shows a PL measurement graph at 404 nm wavelength of compound 16. FIG.

8 shows a PL measurement graph of 239 nm wavelength of Compound 209.

9 shows a PL measurement graph at 292 nm wavelength of Compound 209.

10 shows a PL measurement graph at 338 nm wavelength of compound 209.

11 shows a PL measurement graph at 408 nm wavelength of Compound 209.

12 shows a PL measurement graph at 280 nm wavelength of compound 44. FIG.

FIG. 13 shows a PL measurement graph at 414 nm wavelength of Compound 44.

100: substrate

200: anode

300: organic material layer

301: hole injection layer

302: hole transport layer

303: light emitting layer

304: hole blocking layer

305: electron transport layer

306: electron injection layer

400: cathode

Hereinafter, the present application will be described in detail.

Heterocyclic compound according to an exemplary embodiment of the present application is characterized in that represented by the formula (1). More specifically, the heterocyclic compound represented by Formula 1 may be used as an organic material layer material of the organic light emitting device by the structural features of the core structure and the substituents as described above.

According to an exemplary embodiment of the present application, Chemical Formula 1 may be represented by any one of the following Chemical Formulas 2 to 7.

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

In Chemical Formulas 2 to 7,

Definitions of R1 to R10 are the same as the definition in Formula 1,

Each R 11 is independently hydrogen; heavy hydrogen; Halogen group; -CN; Substituted or unsubstituted alkyl group; Substituted or unsubstituted alkenyl group; Substituted or unsubstituted alkynyl group; Substituted or unsubstituted alkoxy group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted heterocycloalkyl group; Substituted or unsubstituted aryl group; Substituted or unsubstituted heteroaryl group; -SiRR'R "; -P (= 0) RR '; and an alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group substituted or unsubstituted amine group,

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

m are each independently an integer of 0 to 7, when m is 2 or more, two or more R11 are the same or different from each other,

n is each independently an integer of 0 to 5, and when n is 2 or more, two or more R 11 are the same or different from each other.

In one embodiment of the present application, when R2 of the formula (1) is hydrogen or deuterium, R1 may be represented by-(L1) p- (Y1) q.

In one embodiment of the present application, L1 of Chemical Formula 1 is a substituted or unsubstituted arylene group, Y is hydrogen; heavy hydrogen; Substituted or unsubstituted aryl group; Substituted or unsubstituted heteroaryl group; And -P (= 0) RR '.

In one embodiment of the present application, R 11 of Formulas 2 to 4 are each independently hydrogen; heavy hydrogen; Substituted or unsubstituted aryl group; Substituted or unsubstituted heteroaryl group; And -P (= 0) RR '.

In an exemplary embodiment of the present application, in the case where R1 of Formula 1 is hydrogen or deuterium, R2 may be represented by a naphthyl group or-(L2) r- (Y2) s. R2 may be an unsubstituted naphthyl group.

In one embodiment of the present application, L2 of the general formula (1) is a substituted or unsubstituted arylene group, Y2 is a substituted or unsubstituted aryl group; Substituted or unsubstituted heteroaryl group; And -P (= 0) RR '.

In one embodiment of the present application, R 11 of Formulas 5 to 7 are each independently a substituted or unsubstituted aryl group; Substituted or unsubstituted heteroaryl group; And -P (= 0) RR '.

In one embodiment of the present application, p and r of Formula 1 may be each independently 0 to 10, may be 1 to 10.

In one embodiment of the present application, R3 to R10 of Chemical Formula 1 may be each independently hydrogen or deuterium.

In the present application, the substituents of Chemical Formulas 1 to 7 will be described in more detail below.

In the present specification, "substituted or unsubstituted" is deuterium; Halogen group; -CN; C ₁ to C ₆₀ linear or branched alkyl group; C _{2 Through} C ₆₀ A straight or branched alkenyl group; C _{2 Through} C ₆₀ A straight or branched chain alkynyl group; C ₃ to C ₆₀ monocyclic or polycyclic cycloalkyl group; C _{2 Through} C ₆₀ Monocyclic or polycyclic heterocycloalkyl group; C _{6 Through} C ₆₀ Monocyclic or polycyclic aryl group; C _{2 Through} C ₆₀ Monocyclic or polycyclic heteroaryl group; -SiRR'R "; -P (= 0) RR '; C ₁ to C ₂₀ alkylamine group; C _{6 Through} C ₆₀ Monocyclic or polycyclic arylamine group; And it is substituted or unsubstituted with one or more substituents selected from the group consisting of C ₂ to C ₆₀ monocyclic or polycyclic heteroarylamine group, substituted or unsubstituted with a substituent to which two or more of the substituents are bonded, 2 selected from the substituent It means that the above substituent is unsubstituted or substituted with a linked substituent. For example, "a substituent to which two or more substituents are linked" may be a biphenyl group. That is, the biphenyl group may be an aryl group and can be interpreted as a substituent to which two phenyl groups are linked. Said additional substituents may be further substituted further. R, R 'and R "are the same as or different from each other, and each independently hydrogen; deuterium; -CN; substituted or unsubstituted C ₁ to C ₆₀ straight or branched alkyl group; substituted or unsubstituted C ₃ To C ₆₀ monocyclic or polycyclic cycloalkyl group, substituted or unsubstituted C ₆ to C ₆₀ monocyclic or polycyclic aryl group, or substituted or unsubstituted C ₂ to C ₆₀ monocyclic or polycyclic heteroaryl group.

According to an exemplary embodiment of the present application, the "substituted or unsubstituted" is deuterium, a halogen group, -CN, SiRR'R ", P (= O) RR ', C ₁ to C ₂₀ linear or branched alkyl group Substituted or unsubstituted with one or more substituents selected from the group consisting of C ₆ to C ₆₀ monocyclic or polycyclic aryl group, and C ₂ to C ₆₀ monocyclic or polycyclic heteroaryl group,

R, R 'and R "are the same as or different from each other, and each independently hydrogen; deuterium; -CN; deuterium, halogen, -CN, C ₁ to C ₂₀ alkyl group, C ₆ to C ₆₀ aryl group, and C ₂ to C ₆₀ substituted heteroaryl or unsubstituted alkyl group of C ₁ to C _60; an aryl group of deuterium, halogen, -CN, C ₁ to C ₂₀ alkyl group, C ₆ to C ₆₀ a, and C ₂ A C ₃ to C ₆₀ cycloalkyl group unsubstituted or substituted with a C ₆ to C ₆₀ heteroaryl group; deuterium, halogen, —CN, an alkyl group of C ₁ to C ₂₀ , an aryl group of C ₆ to C ₆₀ , and C ₂ to C ₆₀ substituted or unsubstituted group heteroaryl C ₆ to C ₆₀ aryl group; or an alkyl group of deuterium, halogen, -CN, C ₁ to C _20, C ₆ to C ₆₀ aryl, and C ₂ to C ₆₀ Or a C ₂ to C ₆₀ heteroaryl group unsubstituted or substituted with a heteroaryl group.

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

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

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

In the present specification, the alkenyl group includes a straight or branched chain having 2 to 60 carbon atoms, and may be further substituted by another substituent. Carbon number of the alkenyl group may be 2 to 60, specifically 2 to 40, more specifically, 2 to 20. Specific examples thereof include vinyl group, 1-propenyl group, isopropenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, and 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 and the like, but are not limited thereto.

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

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

In the present specification, the heterocycloalkyl group includes O, S, Se, N, or Si as a hetero atom, includes a monocyclic or polycyclic ring having 2 to 60 carbon atoms, and may be further substituted by other substituents. Here, polycyclic 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 be another type of ring group, such as a cycloalkyl group, an aryl group, a heteroaryl group, or the like. Carbon number of the heterocycloalkyl group may be 2 to 60, specifically 2 to 40, more specifically 3 to 20.

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

In the present specification, the spiro group is a group including a spiro structure, and may have 15 to 60 carbon atoms. For example, the spiro group may include a structure in which a 2,3-dihydro-1H-indene group or a cyclohexane group is spiro bonded to a fluorenyl group. Specifically, the following spiro groups may include any of the groups of the following structural formula.

In the present specification, the heteroaryl group includes S, O, 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 another substituent. 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 be another type of ring group, such as a cycloalkyl group, a heterocycloalkyl group, an aryl group, or the like. Carbon number of the heteroaryl group may be 2 to 60, specifically 2 to 40, more specifically 3 to 25. Specific examples of the heteroaryl group include pyridyl, pyrrolyl, pyrimidyl, pyridazinyl, furanyl, thiophene, imidazolyl, pyrazolyl, oxazolyl, isoxazolyl and thiazolyl Group, isothiazolyl group, triazolyl group, furazanyl group, oxdiazolyl group, thiadiazolyl group, dithiazolyl group, tetrazolyl group, pyranyl group, thiopyranyl group, diazinyl group, oxazinyl group , Thiazinyl group, dioxyyl group, triazinyl group, tetragenyl group, quinolyl group, isoquinolyl group, quinazolinyl group, isoquinazolinyl group, quinozolyl group, naphthyridyl group, acridinyl group, phenanthrididi Nyl group, imidazopyridinyl group, diazanaphthalenyl group, triaza indene group, indolyl group, indolinyl group, benzothiazolyl group, benzoxazolyl group, benzimidazolyl group, benzothiophene group, benzofuran group , Dibenzothiophene group, dibenzofuran group, carbazolyl group, benzocarbazolyl group, Dibenzocarbazolyl group, phenazinyl group, dibenzosilol group, spirobi (dibenzosilol), dihydrophenazinyl group, phenoxazinyl group, phenanthridyl group, imidazopyridinyl group, thienyl group, indolo [ 2,3-a] carbazolyl group, indolo [2,3-b] carbazolyl group, indolinyl group, 10,11-dihydro-dibenzo [b, f] azepine group, 9,10-dihydro Acridinyl group, phenanthrazinyl group, phenothiathiazinyl group, phthalazinyl group, naphthyridinyl group, phenanthrolinyl group, benzo [c] [1,2,5] thiadiazolyl group, 5,10-di Hydrodibenzo [b, e] [1,4] azasilinyl, pyrazolo [1,5-c] quinazolinyl group, pyrido [1,2-b] indazolyl group, pyrido [1,2- a] imidazo [1,2-e] indolinyl group, 5,11-dihydroindeno [1,2-b] carbazolyl group, and the like, but are not limited thereto.

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

In the present specification, an arylene group means one having two bonding positions, that is, a divalent group. The description of the aforementioned aryl group can be applied except that they are each divalent. In addition, a heteroarylene group means a thing which has two bonding positions, ie, a bivalent group, in a heteroaryl group. The description of the aforementioned heteroaryl group can be applied except that they are each divalent.

According to an exemplary embodiment of the present application, Y1 or Y2 of Formula 1 is

X3 and X4 are substituted or unsubstituted aromatic hydrocarbon rings; Or a substituted or unsubstituted aromatic hetero ring.

remind

May be represented by any one of the following structural formulae, but is not limited thereto.

In the above structural formula, Z _{One To} Z _{3 Are} the same as or different from each other, each independently S or O,

Z ₄ to Z ₉ are the same as or different from each other, and are each independently CR ′ R ″, NR ′, S or O,

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

According to an exemplary embodiment of the present application, Formula 1 may be represented by any one of the compounds of the following [Group 1], but is not limited thereto.

[Group 1]

In addition, according to an exemplary embodiment of the present application, Chemical Formula 1 may be represented by any one of the following Group 2 compounds, but is not limited thereto.

[Group 2]

In addition, by introducing various substituents into the structure of the formula (1) it is possible to synthesize a compound having the intrinsic properties of the introduced substituents. For example, by incorporating a substituent mainly used in the hole injection layer material, the hole transport material, the light emitting layer material, and the electron transport layer material used in the manufacture of the organic light emitting device into the core structure, it is possible to synthesize a material satisfying the requirements of each organic material layer. Can be.

In addition, by introducing a variety of substituents in the structure of the formula (1) it is possible to finely control the energy bandgap, on the other hand to improve the characteristics at the interface between the organic material and to vary the use of the material.

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

The heterocyclic compound according to one embodiment of the present application may be prepared by a multistage chemical reaction. Some intermediate compounds may be prepared first, and compounds of formula 1 may be prepared from the intermediate compounds. More specifically, the heterocyclic compound according to one embodiment of the present application may be prepared based on the preparation examples described below.

Another embodiment of the present application provides an organic light emitting device including the heterocyclic compound represented by Formula 1.

The organic light emitting device according to the exemplary embodiment of the present application may be manufactured by a conventional method and material for manufacturing an organic light emitting device, except that one or more organic material layers are formed using the heterocyclic compound described above.

The heterocyclic compound may be formed as an organic layer by a solution coating method as well as a vacuum deposition method in the manufacture of the organic light emitting device. Here, the solution coating method means spin coating, dip coating, inkjet printing, screen printing, spraying method, roll coating and the like, but is not limited thereto.

Specifically, the organic light emitting device according to the exemplary embodiment of the present application includes an anode, a cathode and at least one organic material layer provided between the anode and the cathode, one or more of the organic material layer is a hetero ring represented by the formula (1) Compound.

1 to 3 illustrate a lamination order of an electrode and an organic material layer of an organic light emitting diode according to an exemplary embodiment of the present application. However, these drawings are not intended to limit the scope of the present application, the structure of the organic light emitting device known in the art can be applied to the present application.

Referring to FIG. 1, an organic light emitting device in which an anode 200, an organic material layer 300, and a cathode 400 are sequentially stacked on a substrate 100 is illustrated. However, the present invention is not limited thereto, and as illustrated 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 a multilayer. The organic light emitting device according to FIG. 3 includes a hole injection layer 301, a hole transport layer 302, a light emitting layer 303, a hole blocking layer 304, an electron transport layer 305, and an electron injection layer 306. However, the scope of the present application is not limited by such a laminated structure, and other layers except for the light emitting layer may be omitted, and other functional layers may be added as needed.

In addition, the organic light emitting device according to the exemplary embodiment of the present application includes an anode, a cathode, and two or more stacks provided between the anode and the cathode, each of the two or more stacks each independently includes a light emitting layer, and the two or more stacks. Between the liver comprises a charge generating layer, the charge generating layer comprises a heterocyclic compound represented by the formula (1).

In addition, an organic light emitting diode according to an exemplary embodiment of the present application includes an anode, a first stack provided on the anode and including a first emission layer, a charge generation layer provided on the first stack, and the charge generation layer. And a second stack provided on the second stack including the second light emitting layer, and a cathode provided on the second stack. In this case, the charge generating layer may include a heterocyclic compound represented by the formula (1). In addition, each of the first stack and the second stack may independently include at least one of the above-described hole injection layer, hole transport layer, hole blocking layer, electron transport layer, electron injection layer, and the like.

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

As an organic light emitting device according to an exemplary embodiment of the present application, an organic light emitting device having a 2-stack tandem structure is schematically illustrated in FIG. 4.

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

The organic light emitting device according to the present specification may be manufactured by materials and methods known in the art, except for including the heterocyclic compound represented by Chemical Formula 1 in at least one layer of the organic material layer.

The heterocyclic compound represented by Chemical Formula 1 may constitute one or more layers of the organic material layer of the organic light emitting device alone. However, if necessary, the organic material layer may be mixed with other materials.

The heterocyclic compound represented by Chemical Formula 1 may be used as an electron transport layer, a hole blocking layer, a light emitting layer, or the like in an organic light emitting device. As an example, the heterocyclic compound represented by Formula 1 may be used as a material of an electron transporting layer, a hole transporting layer, or a light emitting layer of an organic light emitting device.

In addition, the heterocyclic compound represented by Formula 1 may be used as a material of the light emitting layer in the organic light emitting device. As an example, the heterocyclic compound represented by Formula 1 may be used as a material of the phosphorescent host of the light emitting layer in the organic light emitting device.

In the organic light emitting device according to the exemplary embodiment of the present application, materials other than the heterocyclic compound of Chemical Formula 1 are exemplified below, but these are for illustrative purposes only and are not intended to limit the scope of the present application. It may be replaced with materials known in the art.

As the anode material, materials having a relatively large work function may be used, and a transparent conductive oxide, a metal, or a conductive polymer may be used. Specific examples of the positive electrode 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), indium zinc oxide (IZO); A combination of a metal and an oxide such as ZnO: Al or SnO ₂ : Sb; Conductive polymers such as poly (3-methyl compound), poly [3,4- (ethylene-1,2-dioxy) compound] (PEDT), polypyrrole and polyaniline, and the like, but are not limited thereto.

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

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

As the hole transporting material, pyrazoline derivatives, arylamine derivatives, stilbene derivatives, triphenyldiamine derivatives, and the like may be used, and low molecular or polymer materials may be used.

Examples of the electron transporting material include oxadiazole derivatives, anthraquinodimethane and derivatives thereof, benzoquinone and derivatives thereof, naphthoquinone and derivatives thereof, anthraquinone and derivatives thereof, tetracyanoanthhraquinomethane and derivatives thereof, and fluorenone Derivatives, diphenyl dicyanoethylene and derivatives thereof, diphenoquinone derivatives, metal complexes of 8-hydroxyquinoline and derivatives thereof, and the like can be used, as well as high molecular weight materials as well as high molecular materials.

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

As the light emitting material, a red, green or blue light emitting material may be used, and if necessary, two or more light emitting materials may be mixed. In addition, although a fluorescent material can be used as a light emitting material, it can also be used as a phosphorescent material. As the light emitting material, a material which combines holes and electrons injected from the anode and the cathode, respectively, to emit light may be used, but materials in which both the host material and the dopant material are involved in light emission may be used.

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

The heterocyclic compound according to the exemplary embodiment of the present application may act on a principle similar to that applied to organic light emitting devices in organic electronic devices including organic solar cells, organic photoconductors, organic transistors, and the like.

Hereinafter, the present specification will be described in more detail with reference to Examples, but these are merely to illustrate the present application and are not intended to limit the scope of the present application.

<< 실시예Example >>

1. 그룹 1의 화합물의 제조1. Preparation of Compounds of Group 1

<< 제조예Production Example 1> 화합물 1의 제조 1> Preparation of Compound 1

1) 화합물 1-1의 제조1) Preparation of Compound 1-1

2-fluoronitrobenzene (1 eq.) Was dissolved in DMF 600mL, indole (indole, 1 eq.) Was added thereto, cesium carbonate (cesium carbonate, 2.3 eq.) Was added thereto, and the mixture was stirred at room temperature for 18 hours. . After the reaction was completed, cesium carbonate was filtered through a filter paper, and the filtrate was extracted with ethyl acetate and H ₂ O. After extraction, the product was separated and purified through column chromatography, to obtain Compound 1-1.

2) 화합물 1-2의 제조2) Preparation of Compound 1-2

Compound 1-1 (1 eq.) Was dissolved in a ratio of ethanol: H ₂ O = 10: 7, and then ammonium chloride (ammonium chloride, 4 eq.) And iron (iron, 5 eq.) Were sequentially added and heated for 3 hours. . After the reaction was completed, the solvent was concentrated and extracted with ethyl acetate and H ₂ O. After extraction, the residue was purified by column chromatography to obtain Compound 1-2.

3) 화합물 1의 제조3) Preparation of Compound 1

Compound 1-2 (1 eq.) Was dissolved in 500 mL of toluene. 1-naphthalaldehyde (1-naphthaldehyde, 1.1 eq.) And p-toluene sulfonic acid (p-toluene sulfonic acid, 0.1 eq.) Were added thereto, followed by heating for 24 hours. When the reaction was terminated and extracted with dichloromethane and H ₂ O. After extraction, the residue was purified by column chromatography to obtain Compound 1.

<< 제조예Production Example 2> 화합물 2의 제조 2> Preparation of Compound 2

1) 화합물 1-1의 제조1) Preparation of Compound 1-1

It manufactured by the same method as the manufacture of 1-1 in manufacture example 1.

2) 화합물 1-2의 제조2) Preparation of Compound 1-2

It manufactured by the same method as the manufacture of 1-2 in Preparation Example 1.

3) 화합물 2의 제조3) Preparation of Compound 2

Compound 1-2 (1 eq.) Was dissolved in 500 mL of toluene. 2-naphthalaldehyde (2-naphthaldehyde, 1.1 eq.) And p-toluene sulfonic acid (p-toluene sulfonic acid, 0.1 eq.) Were added thereto, followed by heating for 24 hours. When the reaction was terminated and extracted with dichloromethane and H ₂ O. After extraction, the residue was purified by column chromatography to obtain Compound 2.

<< 제조예Production Example 3> 하기 표 1의 치환기를 갖는 화합물의 제조 3> Preparation of Compound Having Substituents of Table 1

1) 화합물 1-1의 제조1) Preparation of Compound 1-1

2) 화합물 1-2의 제조2) Preparation of Compound 1-2

3) 화합물 1-3의 제조3) Preparation of Compound 1-3

Compound 1-2 (1 eq.) Was dissolved in 500 mL of toluene. 4-bromobenzaldehyde (4-bromobenzaldehyde, 1.1 eq.) And p-toluene sulfonic acid (p-toluene sulfonic acid, 0.1 eq.) Were added thereto, followed by heating for 24 hours. When the reaction was terminated and extracted with dichloromethane and H ₂ O. After extraction, the residue was purified by column chromatography to obtain compound 1-3.

4) 화합물 1-4의 제조4) Preparation of Compound 1-4

Compound 1-3 (1 eq.) Was dissolved in 500 mL of 1.4-dioxane. 4,4,4 ', 4', 5,5,5 ', 5'-octamethyl-2,2'-ratio (1,3,2-dioxaborolane) (4,4,4', 4 ', 5,5,5', 5'-octamethyl-2,2'-bi (1,3,2-dioxaborolane), 2 eq.), Potassium acetate (3 eq.), PdCl ₂ ( dppf) (0.05 eq.) and heated for 4 hours.

When the reaction was terminated and extracted with dichloromethane and H ₂ O. After extraction, the residue was separated and purified through column chromatography, obtaining a compound 1-4.

5) 화합물 P3의 제조5) Preparation of Compound P3

Compound 1-4 (2.2 eq.) Was dissolved in a ratio of 1.4-dioxane: H ₂ O = 4: 1, and then Pd (PPh ₃ ) ₄ (0.05 eq.), K ₂ CO ₃ ( 3eq.) And compound S-1 (1eq.) Were added and heated for 4 hours. When the reaction was terminated and extracted with dichloromethane and H ₂ O. After extraction was purified by column chromatography to give the target compound P3 (yield: 42 ~ 75%).

TABLE 1

<< 제조예Production Example 4> 하기 표 2의 치환기를 갖는 화합물의 제조 4> Preparation of Compound Having Substituents of Table 2 below

1) 화합물 1-1의 제조1) Preparation of Compound 1-1

2) 화합물 1-2의 제조2) Preparation of Compound 1-2

3) 화합물 1-3의 제조3) Preparation of Compound 1-3

Compound 1-2 (1 eq.) Was dissolved in 500 mL of toluene. 3-bromobenzaldehyde (3-bromobenzaldehyde, 1.1 eq.) And p-toluene sulfonic acid (p-toluene sulfonic acid, 0.1 eq.) Were added thereto, followed by heating for 24 hours. When the reaction was terminated and extracted with dichloromethane and H ₂ O. After extraction, the residue was purified by column chromatography to obtain compound 1-3.

4) 화합물 1-4의 제조4) Preparation of Compound 1-4

5) 화합물 P4의 제조5) Preparation of Compound P4

Compound 1-4 (2.2 eq.) Was dissolved in a ratio of 1.4-dioxane: H ₂ O = 4: 1, and then Pd (PPh ₃ ) ₄ (0.05 eq.), K ₂ CO ₃ ( 3eq.) And compound S-1 (1eq.) Were added and heated for 4 hours. When the reaction was terminated and extracted with dichloromethane and H ₂ O. After extraction was purified by column chromatography to give the target compound P4 (yield: 43 ~ 78%).

TABLE 2

<< 제조예Production Example 5> 화합물 18의 제조 5> Preparation of Compound 18

1) 화합물 1-1의 제조1) Preparation of Compound 1-1

2) 화합물 1-2의 제조2) Preparation of Compound 1-2

3) 화합물 1-3의 제조3) Preparation of Compound 1-3

It manufactured by the same method as the manufacture of 1-3 in the manufacture example 3.

4) 화합물 18의 제조4) Preparation of Compound 18

Compound 1-3 (1 eq.) Was dissolved in 50 mL of anhydrous THF and cooled to -78 ° C. n-butyllithium (n-butyllithium, 2.5 in hexane, 1 eq.) was slowly added dropwise and stirred for 1 hour. To the solution, chlorodiphenylphosphine (chlorodiphenylphosphine, 1 eq.) Was added dropwise to the solution and stirred at room temperature for 12 hours. The reaction mixture was extracted with MC / H ₂ O and distilled under reduced pressure. The reaction mixture was dissolved in MC (250 ml) and stirred with 20 ml of 30% H ₂ O ₂ aqueous solution at room temperature for 1 hour. After the reaction mixture was extracted with MC / H ₂ O, the concentrated mixture was separated by column chromatography (Column chromatography, SiO ₂ , MC: Methanol = 25: 1) to prepare the target compound 18 in a yield of 22%.

<< 제조예Production Example 6> 화합물 98의 제조 6> Preparation of Compound 98

1) 화합물 1-1의 제조1) Preparation of Compound 1-1

2) 화합물 1-2의 제조2) Preparation of Compound 1-2

3) 화합물 1-3의 제조3) Preparation of Compound 1-3

It manufactured by the same method as the manufacture of 1-3 in the manufacture example 4.

4) 화합물 98의 제조4) Preparation of Compound 98

Compound 1-3 (1 eq.) Was dissolved in 50 mL of anhydrous THF and cooled to -78 ° C. n-butyllithium (n-butyllithium, 2.5 in hexane, 1 eq.) was slowly added dropwise and stirred for 1 hour. To the solution, chlorodiphenylphosphine (chlorodiphenylphosphine, 1 eq.) Was added dropwise to the solution and stirred at room temperature for 12 hours. The reaction mixture was extracted with MC / H ₂ O and distilled under reduced pressure. The reaction mixture was dissolved in MC (250 ml) and stirred with 20 ml of 30% H ₂ O ₂ aqueous solution at room temperature for 1 hour. After the reaction mixture was extracted with MC / H ₂ O, the concentrated mixture was separated by column chromatography (column chromatography, SiO ₂ , MC: Methanol = 25: 1) to prepare the target compound 98 in a yield of 22%.

<< 제조예Production Example 7> 화합물 146의 제조 7> Preparation of Compound 146

1) 화합물 A-1의 제조1) Preparation of Compound A-1

In one neck rbf, (9,9-dimethyl-9H-fluoren-2-yl) boronic acid ((9,9-dimethyl-9H-fluoren-2-yl) boronic acid, 2 eq. ), 1-bromo-2-nitrobenzene (1 eq.), Pd (PPh ₃ ) ₄ (0.05 eq.), TH _{2 in} K ₂ CO ₃ (2 eq.) ) / H ₂ O (50 ml) was stirred under reflux for 24 hours. After removing the water layer, the organic layer was dried over MgSO ₄ . After concentration was separated by column chromatography (column chromatography, SiO ₂ , Hexane: MC = 2: 1) to give a yellow solid Compound A-1.

2) 화합물 A-2의 제조2) Preparation of Compound A-2

A nitrogen mixture of A-1 (1 eq.) And PPh ₃ (3 eq.) Of o-DCB (300 ml) was stirred under reflux for 18 hours in a one neck rbf flask under nitrogen. o-DCB was removed by vacuum distillation, followed by column chromatography (Column chromatography, SiO ₂ , Hexane: MC = 3: 1) to obtain a white solid compound A-2.

3) 화합물 1-1의 제조3) Preparation of Compound 1-1

4) 화합물 1-2의 제조4) Preparation of Compound 1-2

5) 화합물 1-3의 제조5) Preparation of Compound 1-3

6) 화합물 P7의 제조6) Preparation of Compound P7

In a one neck round bottom flask under nitrogen, 1-3 (1 eq.), A-2 (2 eq.), Cu (0.05 eq.) 18-crown-6-ether, 0.05 eq.) And a mixture of o-DCB (80 ml) of K ₂ CO ₃ (2 eq.) Were refluxed for 12 hours. o-DCB was removed by vacuum distillation, followed by column chromatography (Column chromatography, SiO ₂ , Hexane: MC = 4: 1) to prepare the target compound P7 with a yield of 54%.

<< 제조예Production Example 8> 화합물 165의 제조 8> Preparation of Compound 165

1) 화합물 B-1의 제조1) Preparation of Compound B-1

1,000 ml of ethanol (1,2-Dicyclohexanone, 1 eq.), Phenylhydrazine hydrochloride (2 eq.) In a one neck round bottom flask under nitrogen. ) Sulphonic acid (Sulfuric acid, 1 eq.) Was slowly added dropwise to the mixture and stirred for 4 hours at 60 ℃. The solution cooled to room temperature was filtered to give a tan solid.

In a one neck rbf flask, trifluoroacetic acid (2 eq.) Was added to a mixture of solid (68.9 g, 0.25 mol) and acetic acid (acetic acid, 700 ml) and stirred at 100 ° C. for 15 hours. It was. The solution cooled to room temperature was washed with acetic acid and hexane and filtered to obtain an ivory-colored solid B-1.

2) 화합물 B-2의 제조2) Preparation of Compound B-2

In a two neck rbf under nitrogen, B-1 (1 eq.), Iodobenzene, 1.5 eq., Cu (0.05 eq.), 18-crown-6-ether (18-Crown) O-DCB (20 ml) mixture of -6-ether, 0.05 eq.), K ₂ CO ₃ (2 eq.) Was refluxed for 16 hours. The solution cooled to room temperature was extracted with MC / H ₂ O, concentrated and separated by column chromatography (column chromatography, SiO ₂ , Hexane: Ethyl acetate = 10: 1) to obtain a white solid compound B-2.

3) 화합물 1-1의 제조3) Preparation of Compound 1-1

4) 화합물 1-2의 제조4) Preparation of Compound 1-2

5) 화합물 1-3의 제조5) Preparation of Compound 1-3

6) 화합물 165의 제조6) Preparation of Compound 165

In a one neck rbf under nitrogen, 1-3 (1 eq.), A-2 (2 eq.), Cu (0.05 eq.) 18-crown-6-ether, 0.05 eq.) And a mixture of o-DCB (80 ml) of K ₂ CO ₃ (2 eq.) Were refluxed for 12 hours. o-DCB was removed by vacuum distillation, followed by column chromatography (Column chromatography, SiO ₂ , Hexane: MC = 4: 1) to prepare the target compound 165 with a yield of 51%.

Compounds were prepared in the same manner as in Preparation Examples, and the results of the synthesis confirmation are shown in the table. Table 3 shows measured values of FD-MS (Field Desorption Mass Spectrometry), and Table 4 shows NMR values.

TABLE 3

TABLE 4

5 shows a PL measurement graph at 286 nm wavelength of compound 16. FIG.

6 shows a PL measurement graph at 328 nm wavelength of compound 16. FIG.

7 shows a PL measurement graph at 404 nm wavelength of compound 16. FIG.

8 shows a PL measurement graph of 239 nm wavelength of Compound 209.

9 shows a PL measurement graph at 292 nm wavelength of Compound 209.

10 shows a PL measurement graph at 338 nm wavelength of compound 209.

11 shows a PL measurement graph at 408 nm wavelength of Compound 209.

12 shows a PL measurement graph at 280 nm wavelength of compound 44. FIG.

FIG. 13 shows a PL measurement graph at 414 nm wavelength of Compound 44.

2. 그룹 2의 화합물의 제조2. Preparation of Compounds of Group 2

<< 제조예Production Example 9> 하기 표 5의 치환기를 갖는 화합물의 제조 9> Preparation of Compound Having Substituents of Table 5

1) 화합물 1-1의 제조1) Preparation of Compound 1-1

Indole (1 eq.) Was added, (4-bromophenyl) hydrazine ((4-bromophenyl) hydrazine, 1.2 eq.) Was dissolved in 500 mL of PhCl, and then Pd (OAc) ₂ (0.01 eq.), F ₃ CCO ₂ H (1 eq.) And 10-phenanthroline (10-Phenanthroline, 0.5 eq.) Were added and heated for 5 hours. After the reaction was completed, the mixture was extracted with ethyl acetate and H ₂ O. After extraction, the residue was purified by column chromatography to obtain Compound 1-1.

2) 화합물 1-2의 제조2) Preparation of Compound 1-2

After 2-fluoronitrobenzene (1 eq.) Was dissolved in 600 mL of DMF, 1-1 (1 eq.) Was added thereto, followed by stirring at room temperature for 18 hours after adding calcium carbonate (2.3 eq.). . After the reaction was completed, the calcium carbonate was filtered through a filter paper, and the filtrate was extracted with ethyl acetate and H ₂ O. After extraction, the residue was purified by column chromatography to obtain Compound 1-2.

3) 화합물 1-3의 제조3) Preparation of Compound 1-3

Compound 1-2 (1 eq.) Was dissolved in a ratio of ethanol: H ₂ O = 10: 7, and then ammonium chloride (ammonium chloride, 4 eq.) And iron (iron, 5 eq.) Were sequentially added and heated for 3 hours. . After the reaction was completed, the solvent was concentrated and extracted with ethyl acetate and H ₂ O. After extraction, the residue was purified by column chromatography to obtain Compound 1-3.

4) 화합물 1-4의 제조4) Preparation of Compound 1-4

Compound 1-3 (1 eq.) Was dissolved in 500 mL of toluene. Formaldehyde (formaldehyde, 1.1 eq.) And p-toluene sulfonic acid (p-toluene sulfonic acid, 0.1 eq.) Were added and then heated for 24 hours. When the reaction was terminated and extracted with dichloromethane and H ₂ O. After extraction, the residue was separated and purified through column chromatography, obtaining a compound 1-4.

5) 화합물 1-5의 제조5) Preparation of Compound 1-5

Compound 1-4 (1 eq.) Was dissolved in 500 mL of 1.4-dioxane. 4,4,4 ', 4', 5,5,5 ', 5'-octamethyl-2,2'-ratio (1,3,2-dioxaborolane) (4,4,4', 4 ', 5,5,5', 5'-octamethyl-2,2'-bi (1,3,2-dioxaborolane), 2 eq.), Potassium acetate (3 eq.), PdCl ₂ ( dppf) (0.05 eq.) and heated for 4 hours.

When the reaction was terminated and extracted with dichloromethane and H ₂ O. After extraction, the residue was purified by column chromatography to obtain compound 1-5.

6) 화합물 P8의 제조6) Preparation of Compound P8

Compound 1-5 (2.2 eq.) Was dissolved in a ratio of 1.4-dioxane: H ₂ O = 4: 1, and then Pd (PPh ₃ ) ₄ (0.05 eq.), K ₂ CO ₃ ( 3eq.) And compound S-1 (1eq.) Were added and heated for 4 hours. When the reaction was terminated and extracted with dichloromethane and H ₂ O. After extraction was purified by column chromatography to give the target compound P8 (yield: 43 ~ 82%).

TABLE 5

<< 제조예Production Example 10> 하기 표 6의 치환기를 갖는 화합물의 제조 10> Preparation of Compound Having Substituents of Table 6

1) 화합물 1-1의 제조1) Preparation of Compound 1-1

Add indole (Indole, 1 eq.) And dissolve (3-bromophenyl) hydrazine ((3-bromophenyl) hydrazine, 1.2 eq.) In 500 mL of PhCl, then Pd (OAc) ₂ (0.01 eq.), F ₃ CCO ₂ H (1 eq.) And 10-phenanthroline (10-Phenanthroline, 0.5 eq.) Were added and heated for 5 hours. After the reaction was completed, the mixture was extracted with ethyl acetate and H ₂ O. After extraction, the residue was purified by column chromatography to obtain Compound 1-1.

2) 화합물 1-2의 제조2) Preparation of Compound 1-2

3) 화합물 1-3의 제조3) Preparation of Compound 1-3

It manufactured by the same method as the manufacture of 1-3 in the manufacture example 1.

4) 화합물 1-4의 제조4) Preparation of Compound 1-4

It manufactured by the same method as the manufacture of 1-4 in Preparation Example 1.

5) 화합물 1-5의 제조5) Preparation of Compound 1-5

It manufactured by the same method as the manufacture of 1-5 in manufacture example 1.

6) 화합물 P9의 제조6) Preparation of Compound P9

Compound 1-5 (2.2 eq.) Was dissolved in a ratio of 1.4-dioxane: H ₂ O = 4: 1, and then Pd (PPh ₃ ) ₄ (0.05 eq.), K ₂ CO ₃ ( 3eq.) And compound S-1 (1eq.) Were added and heated for 4 hours. When the reaction was terminated and extracted with dichloromethane and H ₂ O. After extraction was purified by column chromatography to give the target compound P9 (yield: 43 ~ 78%).

TABLE 6

<< 제조예Production Example 11> 화합물 237의 제조 11> Preparation of Compound 237

1) 화합물 1-1의 제조1) Preparation of Compound 1-1

It manufactured by the same method as the manufacture of 1-1 in the manufacture example 9.

2) 화합물 1-2의 제조2) Preparation of Compound 1-2

It manufactured by the same method as the manufacture of 1-2 in the manufacture example 9.

3) 화합물 1-3의 제조3) Preparation of Compound 1-3

It manufactured by the same method as the manufacture of 1-3 in the manufacture example 9.

4) 화합물 1-4의 제조4) Preparation of Compound 1-4

It manufactured by the same method as the manufacture of 1-4 in manufacture example 9.

5) 화합물 237의 제조5) Preparation of Compound 237

Compound 1-4 (1 eq.) Was dissolved in 50 mL of anhydrous THF and cooled to -78 ° C. n-butyllithium (n-butyllithium, 2.5 in hexane, 1 eq.) was slowly added dropwise and stirred for 1 hour. To the solution, chlorodiphenylphosphine (chlorodiphenylphosphine, 1 eq.) Was added dropwise to the solution and stirred at room temperature for 12 hours. The reaction mixture was extracted with MC / H ₂ O and distilled under reduced pressure. The reaction mixture was dissolved in MC (250ml) and stirred with 20ml of 30% H ₂ O ₂ aqueous solution at room temperature for 1 hour. After the reaction mixture was extracted with MC / H ₂ O, the concentrated mixture was separated by column chromatography (column chromatography, SiO ₂ , MC: Methanol = 25: 1) to prepare the target compound 237 (yield: 58%).

<< 제조예Production Example 12> 화합물 317의 제조 12> Preparation of Compound 317

1) 화합물 1-1의 제조1) Preparation of Compound 1-1

It manufactured by the same method as the manufacture of 1-1 in manufacture example 10.

2) 화합물 1-2의 제조2) Preparation of Compound 1-2

It manufactured by the same method as the manufacture of 1-2 in the preparation example 10.

3) 화합물 1-3의 제조3) Preparation of Compound 1-3

It manufactured by the same method as the manufacture of 1-3 in the preparation example 10.

4) 화합물 1-4의 제조4) Preparation of Compound 1-4

It manufactured by the same method as the manufacture of 1-4 in manufacture example 10.

5) 화합물 317의 제조5) Preparation of Compound 317

Compound 1-4 (1 eq.) Was dissolved in 50 mL of dry THF and cooled to -78 ° C. n-butyllithium (n-butyllithium, 2.5 in hexane, 1 eq.) was slowly added dropwise and stirred for 1 hour. To the solution, chlorodiphenylphosphine (chlorodiphenylphosphine, 1 eq.) Was added dropwise to the solution and stirred at room temperature for 12 hours. The reaction mixture was extracted with MC / H ₂ O and distilled under reduced pressure. The reaction mixture was dissolved in MC (250 ml) and stirred with 20 ml of 30% H ₂ O ₂ aqueous solution at room temperature for 1 hour. After the reaction mixture was extracted with MC / H ₂ O, the concentrated mixture was separated by column chromatography (column chromatography, SiO ₂ , MC: Methanol = 25: 1) to prepare the target compound 317 (yield: 62%).

Compounds were prepared in the same manner as in Preparation Examples, and the results of the synthesis are shown in the following table. Table 7 shows the measured values of the field desorption mass spectrometry (FD-MS), and Table 8 shows the NMR values.

TABLE 7

TABLE 8

<< 실험예Experimental Example 1> 그룹 1의 화합물을 이용한 유기 발광 소자 1> organic light emitting device using the compound of Group 1

1) 유기 발광 소자의 제작1) Fabrication of organic light emitting device

The glass substrate coated with the thin film of ITO to a thickness of 1500 kPa was washed by distilled water ultrasonically. After washing the distilled water, ultrasonic cleaning with a solvent such as acetone, methanol, isopropyl alcohol and the like was dried and then treated with UVO for 5 minutes using UV in a UV cleaner. Subsequently, the substrate was transferred to a plasma cleaner (PT), and then plasma-treated to remove ITO work function and residual film in a vacuum state, and then transferred to a thermal deposition apparatus for organic deposition.

An organic material was formed on the ITO transparent electrode (anode) in a 2 stack WOLED (White Orgainc Light Device) structure. The first stack was first vacuum-deposited TAPC to a thickness of 300 kPa to form a hole transport layer. After the hole transport layer was formed, the light emitting layer was thermally vacuum deposited on it as follows. The light emitting layer was deposited to 300 하여 by dope 8% of FIrpic with blue phosphor dopant on the host TCz1. The electron transporting layer was formed using 400mW using TmPyPB, and then, 100% by Cs ₂ CO ₃ doped to 20% of the compound shown in Table 7 as a charge generating layer.

In the second stack, MoO ₃ was thermally vacuum deposited to a thickness of 50 kPa to form a hole injection layer. Common layer is then in the hole transport layer is doped with the MoO ₃ 20% in TAPC 100Å formed, the TAPC was formed by depositing 300Å, the over light-emitting layer and the green phosphorescent topeon open Ir (ppy) ₃ in the host TCz1 doped with 8% After 300 mW deposition, 600 mW was formed using TmPyPB as the electron transport layer. Finally, lithium fluoride (LiF) is deposited on the electron transport layer to form a electron injecting layer by depositing 10 Å thick. Then, an aluminum (Al) cathode is deposited to a thickness of 1,200 위에 on the electron injecting layer to form a cathode. A light emitting device was manufactured.

On the other hand, all of the organic compounds required for the OLED device fabrication is 10 ^-6 to 10 respectively, for each material ^- and vacuum sublimation purification under 8torr was used in OLED production.

2) 유기 발광 소자의 구동 전압 및 발광 효율2) Driving voltage and luminous efficiency of organic light emitting device

The electroluminescence (EL) characteristics of the organic light emitting device manufactured as described above were measured by Maxiers M7000, and the reference luminance was 3,500 cd / m using the life measurement equipment (M6000) manufactured by McScience Inc. with the measurement result. When m ² , T ₉₅ was measured. The driving voltage, the luminous efficiency, the external quantum efficiency, and the color coordinates (CIE) of the white organic light emitting diodes manufactured according to the present invention were measured as shown in Table 9.

TABLE 9

As can be seen from the results of Table 9, the organic light emitting device using the charge generating layer material of the two-stack white organic light emitting device of the present invention has a lower driving voltage and improved luminous efficiency than Comparative Example 1.

The reason for this result is that the compound of the present invention used as an N-type charge generating layer composed of an invented backbone having appropriate length, strength and flat properties and a suitable heterocompound capable of binding to a metal is selected from alkali or alkaline earth metals. It is assumed that a gap state is formed in the N-type charge generation layer, and electrons generated from the P-type charge generation layer may be easily injected into the electron transport layer through the gap state generated in the N-type charge generation layer. Judging. Therefore, the P-type charge generating layer can perform electron injection and electron transfer well to the N-type charge generating layer. Therefore, the driving voltage of the organic light emitting device is lowered, and the efficiency and lifetime are considered to be improved.

<< 실험예Experimental Example 2> 그룹 1의 화합물을 이용한 유기 발광 소자 2> organic light emitting device using the compound of Group 1

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

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

Subsequently, after evacuating the chamber until the vacuum reached 10 ⁻⁶ torr, a current was applied to the cell to evaporate 2-TNATA to deposit a 600 kW hole injection layer on the ITO substrate.

N, N'-bis (α-naphthyl) -N, N'-diphenyl-4,4'-diamine (N, N'-bis (α-naphthyl) -N, N'-diphenyl-4,4'-diamine: NPB) was added thereto, and a 300 Å thick hole transport layer was deposited on the hole injection layer by evaporation by applying a current to the cell.

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

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

Lithium fluoride (LiF) was deposited to an electron injecting layer with a thickness of 10 mW and an OLED was fabricated with an Al cathode having a thickness of 1000 mW.

On the other hand, all of the organic compounds required for the OLED device fabrication is 10 ^-6 to 10 respectively, for each material ^were purified by vacuum sublimation under 8 torr used in OLED production

The electroluminescence (EL) characteristics of the organic electroluminescent device manufactured as described above were measured with M7000's M7000, and the reference luminance was 700 cd through the life measurement equipment (M6000) manufactured by McScience Inc. with the measurement results. T ₉₅ was measured at / m ² . The driving voltage, the luminous efficiency, the external quantum efficiency, and the color coordinate (CIE) of the organic electroluminescent device manufactured according to the present invention were measured as shown in Table 10.

TABLE 10

As can be seen from the results of Table 10, the organic light emitting device using the electron transporting layer material of the blue organic light emitting device of the present invention has a lower driving voltage and significantly improved luminous efficiency and lifespan compared to Comparative Example 2.

The reason for this result is that when the invented compound having the proper length, strength and flat properties is used as the electron transporting layer, the compound is in the excited state by receiving electrons under certain conditions, and in particular, the excited state of the heteroskeletal site of the compound. Is formed, the excited heteroskeleton site will be moved to a stable state before the other reaction, and the relatively stabilized compound is considered to be able to transfer electrons efficiently without causing decomposition or destruction of the compound. For reference, those that have a stable state are considered to be aryl or acene compounds or polycyclic hetero compounds. Therefore, it is considered that the compound of the present invention has improved in terms of driving, efficiency, and lifespan by improving the improved electron-transporting property or improved stability.

<실험예 3> 그룹 2의 화합물을 이용한 유기 발광 소자Experimental Example 3 Organic Light-Emitting Device Using Compound of Group 2

An organic material was formed on the ITO transparent electrode (anode) in a 2 stack WOLED (White Orgainc Light Device) structure. The first stack was first vacuum-deposited TAPC to a thickness of 300 kPa to form a hole transport layer. After the hole transport layer was formed, the light emitting layer was thermally vacuum deposited on it as follows. The light emitting layer was deposited at 300 하여 by dope 8% of FIrpic with blue phosphorescent dopant on TCz1. The electron transporting layer was formed using 400mW using TmPyPB, and then, 100% of the charge generating layer was formed by doping 20% of Cs ₂ CO ₃ to the compound shown in Table 5 below.

The electroluminescence (EL) characteristics of the organic light emitting device manufactured as described above were measured by Maxiers M7000, and the reference luminance was 3,500 cd / m using the life measurement equipment (M6000) manufactured by McScience Inc. with the measurement result. When m ² , T ₉₅ was measured. The driving voltage, the luminous efficiency, the external quantum efficiency, and the color coordinates (CIE) of the white organic light emitting diodes manufactured according to the present invention were measured.

TABLE 11

As can be seen from the results of Table 11, the organic light emitting device using the charge generating layer material of the two-stack white organic light emitting device of the present invention has a lower driving voltage and improved luminous efficiency than Comparative Example 3. The reason for this result is that the compound of the present invention used as an N-type charge generating layer composed of an invented backbone having appropriate length, strength and flat properties and a suitable heterocompound capable of binding to a metal is selected from alkali or alkaline earth metals. It is presumed that a gap state was formed in the N-type charge generation layer, and electrons generated from the P-type charge generation layer were easily injected into the electron transport layer through the gap state generated in the N-type charge generation layer. It seems to be. Therefore, the P-type charge generating layer can perform electron injection and electron transfer well to the N-type charge generating layer. Therefore, the driving voltage of the organic light emitting device is lowered, and the efficiency and lifetime are considered to be improved.

<실험예 4> 그룹 2의 화합물을 이용한 유기 발광 소자Experimental Example 4 Organic Light-Emitting Device Using Compound of Group 2

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

The electroluminescence (EL) characteristics of the organic electroluminescent device manufactured as described above were measured with M7000's M7000, and the reference luminance was 700 cd through the life measurement equipment (M6000) manufactured by McScience Inc. with the measurement results. T ₉₅ was measured at / m ² . The driving voltage, the luminous efficiency, the external quantum efficiency, and the color coordinate (CIE) of the organic light emitting device manufactured according to the present invention were measured as shown in Table 12.

TABLE 12

As can be seen from the results in Table 12, the organic electroluminescent device using the electron transporting layer material of the blue organic light emitting device of the present invention has a lower driving voltage, and significantly improved luminous efficiency and lifetime compared to Comparative Example 4.

The reason for this result is that when the invented compound having proper length, strength and flat characteristics is used as the electron transporting layer, the compound is in the excited state by receiving electrons under certain conditions, and in particular, the excited state of the heteroskeletal site of the compound. Is formed, the excited heteroskeleton site will be moved to a stable state before the other reaction, and the relatively stabilized compound is considered to be able to transfer electrons efficiently without causing decomposition or destruction of the compound. For reference, those that have a stable state are considered to be aryl or acene compounds or polycyclic hetero compounds. Therefore, it is considered that the compound of the present invention has improved in terms of driving, efficiency, and lifespan by improving the improved electron-transporting property or improved stability.

Claims

Heterocyclic compounds represented by the formula (1):

[Formula 1]

In Chemical Formula 1,

R1 is hydrogen or deuterium, represented by-(L1) p- (Y1) q,

R2 is hydrogen, deuterium or naphthyl, or is represented by-(L2) r- (Y2) s,

L1 and L2 are each independently a substituted or unsubstituted arylene group; And a substituted or unsubstituted ring or polycyclic heteroarylene group,

Y1 and Y2 are hydrogen; heavy hydrogen; Halogen group; -CN; Substituted or unsubstituted alkyl group; Substituted or unsubstituted alkenyl group; Substituted or unsubstituted alkynyl group; Substituted or unsubstituted alkoxy group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted heterocycloalkyl group; Substituted or unsubstituted aryl group; Substituted or unsubstituted heteroaryl group; -SiRR'R "; -P (= O) RR '; and an alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group substituted or unsubstituted amine group,

p is 0 to 10, q is 1 to 10,

r is 0 to 10, s is 1 to 10,

R3 to R10 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Halogen group; -CN; Substituted or unsubstituted alkyl group; Substituted or unsubstituted alkenyl group; Substituted or unsubstituted alkynyl group; Substituted or unsubstituted alkoxy group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted heterocycloalkyl group; Substituted or unsubstituted aryl group; Substituted or unsubstituted heteroaryl group; -SiRR'R "; -P (= O) RR '; and an alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group substituted or unsubstituted amine group selected from the group or adjacent to each other Two or more groups which are bonded to each other to form a substituted or unsubstituted monocyclic or polycyclic aliphatic or aromatic hydrocarbon ring,

R, R 'and R "are the same as or different from each other, and each independently hydrogen; deuterium; -CN; substituted or unsubstituted alkyl group; substituted or unsubstituted cycloalkyl group; substituted or unsubstituted aryl group; or substituted or It is an unsubstituted heteroaryl group.
The heterocyclic compound according to claim 1, wherein when R2 of Formula 1 is hydrogen or deuterium, R1 is represented by-(L1) p- (Y1) q.
The heterocyclic compound according to claim 1, wherein when R1 of Formula 1 is hydrogen or deuterium, R2 is represented by a naphthyl group or-(L2) r- (Y2) s.
The heterocyclic compound according to claim 1, wherein Chemical Formula 1 is represented by any one of the following Chemical Formulas 2 to 7.

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

In Chemical Formulas 2 to 7,

Definitions of R1 to R10 are the same as the definition in Formula 1,

Each R 11 is independently hydrogen; heavy hydrogen; Halogen group; -CN; Substituted or unsubstituted alkyl group; Substituted or unsubstituted alkenyl group; Substituted or unsubstituted alkynyl group; Substituted or unsubstituted alkoxy group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted heterocycloalkyl group; Substituted or unsubstituted aryl group; Substituted or unsubstituted heteroaryl group; -SiRR'R "; -P (= 0) RR '; and an alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group substituted or unsubstituted amine group,

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

m are each independently an integer of 0 to 7, when m is 2 or more, two or more R11 are the same or different from each other,

n is each independently an integer of 0 to 5, and when n is 2 or more, two or more R 11 are the same or different from each other.
The method according to claim 1, L1 and L2 of Formula 1 are each independently a substituted or unsubstituted arylene group,

Y1 and Y2 are each independently hydrogen; heavy hydrogen; Substituted or unsubstituted aryl group; Substituted or unsubstituted heteroaryl group; And -P (= 0) RR '.
The heterocyclic compound according to claim 1, wherein R 3 to R 10 in Formula 1 are each independently hydrogen or deuterium.
The method according to claim 2, R 11 of Formula 2 to 7 are each independently hydrogen; heavy hydrogen; Substituted or unsubstituted aryl group; Substituted or unsubstituted heteroaryl group; And -P (= 0) RR '.
The method according to claim 1, wherein Y1 or Y2 is
X3 and X4 are substituted or unsubstituted aromatic hydrocarbon rings; Or a substituted or unsubstituted aromatic hetero ring.
The method according to claim 8, wherein
Is a heterocyclic compound represented by any one of the following structural formulas:

In the above structural formula, Z One To Z 3 Are the same as or different from each other, each independently S or O,

Z 4 to Z 9 are the same as or different from each other, and are each independently CR ′ R ″, NR ′, S or O,

R 'and R "are the same as or different from each other, and each independently hydrogen; a substituted or unsubstituted alkyl group; or a substituted or unsubstituted aryl group.
The heterocyclic compound according to claim 1, wherein Formula 1 is represented by any one of the following Group 1 compounds:

[Group 1]
The heterocyclic compound according to claim 1, wherein Formula 1 is represented by any one of the following Group 2 compounds:

[Group 2]
An organic light emitting device comprising an anode, a cathode and at least one organic layer provided between the anode and the cathode, at least one layer of the organic layer comprises a heterocyclic compound according to any one of claims 1 to 11.
The method according to claim 12, wherein the organic material layer comprises at least one of a hole blocking layer, an electron injection layer and an electron transport layer, wherein at least one of the hole blocking layer, electron injection layer and the electron transport layer comprises the heterocyclic compound An organic light emitting device characterized in that.
The organic light emitting device of claim 12, wherein the organic material layer comprises a light emitting layer, and the light emitting layer comprises the heterocyclic compound.
The method according to claim 12, wherein the organic layer comprises a hole injection layer, a hole transport layer, and at least one layer of the hole injection and hole transport at the same time, wherein one of the layers comprises the heterocyclic compound An organic light emitting element.
The organic light emitting device of claim 12, wherein the organic material layer comprises a charge generating layer, and the charge generating layer comprises the heterocyclic compound.
The method according to claim 16, wherein the organic light emitting device, an anode, a first stack provided on the anode and including a first light emitting layer, a charge generating layer provided on the first stack, the charge generating layer is provided on the 2. An organic light emitting device comprising: a second stack including a light emitting layer; and a cathode provided on the second stack.