KR102541384B1 - Novel heterocyclic compound and organic light emitting device comprising the same - Google Patents

Abstract

The present invention relates to a novel heterocyclic compound and an organic light emitting device including the same, wherein the heterocyclic compound according to the present invention has dibenzoic acid on both sides centering on 1,4-dihydropentalene. It is a polycyclic heterocyclic compound having a multicyclic skeleton in which dibenzofuran is fused as a mother core and having at least one amino substituent introduced therein, and can be used as a material for an organic material layer of an organic light emitting device.

Description

Novel heterocyclic compound and organic light emitting device containing the same

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

In general, the organic light emitting phenomenon refers to a phenomenon in which electrical energy is converted into light energy using an organic material. An organic electronic device using an organic light emitting phenomenon usually has a structure including an anode, a cathode, and an organic material layer between the anode. Here, the organic material layer is often composed of a multi-layer structure composed of different materials in order to increase the efficiency and stability of the organic electric device, and may include, for example, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer.

Materials used as organic layers in organic electronic devices may be classified into light emitting materials and charge transport materials, such as hole injection materials, hole transport materials, electron transport materials, and electron injection materials, according to their functions. In addition, the light emitting material can be classified into a high molecular weight type and a low molecular weight type according to molecular weight, and can be classified into a fluorescent material derived from a singlet excited state of electrons and a phosphorescent material derived from a triplet excited state of electrons according to a light emitting mechanism. can In addition, light emitting materials may be classified into blue, green, and red light emitting materials and yellow and orange light emitting materials required to realize better natural colors according to the light emitting color.

In particular, several studies are being conducted on organic materials inserted into a hole transport layer or a buffer layer for excellent lifespan characteristics of organic electronic devices. A hole injection layer material having high uniformity and low crystallinity upon formation is required.

It delays penetration and diffusion of metal oxide from the anode electrode (ITO) into the organic layer, which is one of the causes of shortening the lifespan of organic electronic devices, and has stable characteristics against Joule heating generated during device operation, that is, high glass transition temperature. It is necessary to develop a hole injection layer material having In addition, it has been reported that the low glass transition temperature of the material for the hole transport layer greatly affects the lifetime of the device according to the property that the uniformity of the surface of the thin film collapses during device operation. In addition, since the deposition method is the mainstream in the formation of OLED devices, there is a need for a material with strong heat resistance that can withstand such a deposition method for a long time.

On the other hand, when only one material is used as a light emitting material, the maximum emission wavelength moves to a longer wavelength due to intermolecular interactions, and the color purity decreases or the efficiency of the device decreases due to the emission attenuation effect. Therefore, color purity increases and energy transfer A host/dopant system may be used as a light emitting material in order to increase luminous efficiency. The principle is that when a small amount of a dopant having a smaller energy band gap than the host forming the light emitting layer is mixed into the light emitting layer, excitons generated in the light emitting layer are transported to the dopant to emit light with high efficiency. At this time, since the wavelength of the host moves to the wavelength range of the dopant, light of a desired wavelength can be obtained according to the type of dopant used.

In order to fully exhibit the excellent characteristics of the above-mentioned organic electronic device, materials constituting the organic layer in the device, such as hole injection materials, hole transport materials, light emitting materials, electron transport materials, electron injection materials, etc. are supported by stable and efficient materials. Although this should be preceded, stable and efficient organic material layer materials for organic electric devices have not yet been sufficiently developed, and therefore, development of new materials is continuously required.

KR 10-2013-0094171 A (2013.08.23) WO 2018-095940 A1 (2018.05.31)

An object of the present invention is to provide a heterocyclic compound having a novel structure that can be used as a material for an organic layer of an organic light emitting device.

In addition, an object of the present invention is to provide an organic light emitting device including the heterocyclic compound as an organic material layer material.

The present invention relates to a novel heterocyclic compound and an organic light emitting device including the same, wherein the heterocyclic compound according to the present invention has dibenzoic acid on both sides centering on 1,4-dihydropentalene. It is a polycyclic heterocyclic compound having a multicyclic skeleton in which dibenzofuran is fused as a mother core and having at least one amino substituent introduced therein, and can be used as a material for an organic material layer of an organic light emitting device.

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

[Formula 1]

In Formula 1,

R ^a to R ^d are each independently hydrogen, C1-C60 alkyl or C6-C60 aryl;

L ₁ to L ₄ are each independently a single bond, C6-C60 arylene or C3-C60 heteroarylene;

,

또는

이거나, R₁와 R₂, R₃과 R₄, R₅와 R₆ 및 R₇와 R₈은 각각 독립적으로 서로 연결되어 방향족고리가 융합되거나 융합되지 않은 헤테로고리를 형성할 수 있으며;R ₁ to R ₈ are each independently

,

or

Alternatively, R ₁ and R ₂ , R ₃ and R ₄ , R ₅ and R ₆ , and R ₇ and R ₈ may be independently connected to each other to form a fused or unfused aromatic ring heterocycle;

R ₂₁ to R ₂₄ are independently of each other C1-C60 alkyl, haloC1-C60 alkyl, deuterium, halogen, cyano, C3-C60 cycloalkyl, C1-C60 alkoxy, C6-C60 aryl, C6-C60 aryloxy, C6 -C60 arylC1-C60 alkyl, C1-C60 alkylC6-C60 aryl, C3-C60 heteroaryl, -NR ₁₂ R ₁₃ , nitro or hydroxy;

R ₁₂ and R ₁₃ are each independently hydrogen, C1-C60 alkyl, C6-C60 aryl or C3-C60 heteroaryl;

X ₁ is NR ₃₁ , O or S;

R ₃₁ is hydrogen, C1-C60 alkyl, C6-C60 aryl or C3-C60 heteroaryl;

The arylene and heteroarylene of L ₁ to L ₄ and the aryl and heteroaryl of R ₂₁ to R ₂₄ are C1-C60 alkyl, haloC1-C60 alkyl, deuterium, halogen, cyano, C3-C60 cycloalkyl, C1-C60 Alkoxy, C6-C60 Aryl, C6-C60 Aryloxy, C6-C60 ArylC1-C60 Alkyl, C1-C60 AlkylC6-C60 Aryl, C3-C60 Heteroaryl, -NR'R'', nitro and It may be further substituted with one or more selected from the group consisting of hydroxy;

R' and R'' are each independently hydrogen, C1-C60 alkyl, C6-C60 aryl or C3-C60 heteroaryl;

a is an integer from 0 to 5, and when a is an integer of 2 or greater, each R ₂₁ may be the same as or different from each other;

b is an integer from 0 to 7, and when b is an integer of 2 or greater, each R ₂₂ may be the same as or different from each other;

c is an integer from 0 to 3, and when c is an integer of 2 or greater, each R ₂₃ may be the same as or different from each other;

d is an integer from 0 to 4, and when d is an integer of 2 or greater, each R ₂₄ may be the same as or different from each other;

p and q are independently integers from 0 to 4, r and s are independently integers from 0 to 2, provided that p, q, r and s are not 0 at the same time;

The heteroarylene and heteroaryl include one or more heteroatoms selected from N, O, S and Se.

In addition, the present invention 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 at least one layer of the organic material layer includes the heterocyclic compound represented by Chemical Formula 1. to provide.

The heterocyclic compound according to the present invention has a multicyclic skeleton in which dibenzofuran is fused on both sides around 1,4-dihydropentalene as a core, and at least one amino A polycyclic compound having a substituent introduced therein, which can be used as a material for an organic material layer of an organic light emitting device. The heterocyclic compound may serve as a light emitting material, a hole injection material, a hole transport material, a light emitting material, an electron transport material, or an electron injection material in an organic light emitting device.

The heterocyclic compound according to the present invention can be employed as an organic material layer material such as a light emitting material, a hole injection material, a hole transport material, a light emitting material, an electron transport material, and an electron injection material due to its structural specificity, and an organic light emitting device employing the same can be employed It has hole mobility, so it has high efficiency and low driving voltage at the same time, and life characteristics can also be surprisingly improved.

That is, the heterocyclic compound according to the present invention has excellent electron mobility due to its structural specificity, thereby improving the current characteristics of the device and strengthening the driving voltage, thereby inducing an increase in power efficiency to manufacture an organic light emitting device with improved power consumption. there is.

The present invention is detailed below, but unless there is another definition in the technical and scientific terms used at this time, it has the meaning commonly understood by those of ordinary skill in the art to which this invention belongs, and in the following description Descriptions of well-known functions and configurations that may unnecessarily obscure the subject matter of the invention will be omitted.

Throughout this specification, unless the context requires otherwise, the terms "comprise" and "comprising" include a given step or component, or group of steps or components, but any other step or component, or It is to be understood that steps or groups of components are not excluded.

In this specification, “substituent”, “radical”, “group”, “moiety”, and “fragment” may be used interchangeably.

In the present specification, “C _A -C _B ” means “a number of carbon atoms greater than or equal to A and less than or equal to B”.

In the present specification, "alkyl", "alkoxy" and other substituents including "alkyl" moieties include both straight-chain and branched forms.

In the present specification, "alkyl" includes a straight chain or branched chain having 1 to 60 carbon atoms, and may be further substituted by other substituents. Alkyl may have 1 to 60 carbon atoms, specifically 1 to 30, or specifically 1 to 20, preferably 1 to 10.

In the present specification, "alkenyl" includes a straight chain or branched chain having 2 to 60 carbon atoms, and may be further substituted by other substituents. Alkenyl may have 2 to 60 carbon atoms, specifically 2 to 30, or specifically 2 to 20, preferably 2 to 10.

In the present specification, "alkynyl" includes straight or branched chains having 2 to 60 carbon atoms, and may be further substituted by other substituents. The number of carbon atoms of alkynyl may be 2 to 60, specifically 2 to 30, or specifically 2 to 20, preferably 2 to 10.

In the present specification, "cycloalkyl" includes monocyclic or polycyclic groups having 3 to 60 carbon atoms, and may be further substituted with other substituents. Here, polycyclic means a group in which cycloalkyl is directly connected or condensed with another ring group. Here, the other ring group may be cycloalkyl, but other types of ring groups such as heterocycloalkyl, aryl, heterocyclic, etc. may also be used. Cycloalkyl may have 3 to 60 carbon atoms, specifically 3 to 30, or specifically 5 to 20 carbon atoms.

In the present specification, "heterocycloalkyl" includes at least one selected from N, O, S, and Se as a heteroatom, and includes monocyclic or polycyclic groups having 2 to 60 carbon atoms, and may be further substituted by other substituents. can Here, polycyclic means a group in which heterocycloalkyl is directly linked or condensed with another ring group. Here, the other ring group may be heterocycloalkyl, but other types of ring groups such as cycloalkyl, aryl, heterocyclic, etc. may also be used. Heterocycloalkyl may have 2 to 60 carbon atoms, specifically 2 to 30, or specifically 3 to 20 carbon atoms.

In the present specification, "aryl" is an organic radical derived from an aromatic hydrocarbon by removing one hydrogen, and 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 aryl is directly linked or condensed with another ring group. Here, the other ring group may be aryl, but may also be other types of ring groups, such as cycloalkyl, heterocycloalkyl, heterocyclic, and the like. The number of carbon atoms of aryl may be 6 to 60, specifically 6 to 30, specifically 6 to 25, specifically 6 to 20, or specifically 6 to 12. Specific examples of aryl include phenyl, biphenyl, triphenyl, naphthyl, anthryl, chrysenyl, phenanthrenyl, perylenyl, fluoranthenyl, triphenylenyl, phenalenyl, pyrenyl, tetracenyl, pentacenyl, Fluorenyl, indenyl, acenaphthylenyl, fluorenyl, etc., or condensed rings thereof, but are not limited thereto.

In the present specification, "arylene" means a divalent organic radical derived by removing one hydrogen from the aryl, and follows the definition of the aryl.

In the present specification, "heterocyclic group" includes at least one selected from N, O, S, and Se as a hetero atom, and includes a monocyclic or polycyclic group having 2 to 60 carbon atoms, and may be further substituted by another substituent. can Heteroaryl is included in the scope of a heterocyclic group and is a heteroaromatic ring group. Here, the polycyclic means a group in which a heterocyclic group is directly connected or condensed with another cyclic group. Here, the other ring group may be a heterocyclic group, but may also be another type of ring group, such as cycloalkyl, heterocycloalkyl, aryl, and the like. The carbon number of the heterocyclic group may be 2 to 60, specifically 2 to 30, or specifically 3 to 25. Specific examples of the heterocyclic group include pyridyl, pyrrolyl, pyrimidyl, pyridazinyl, furanyl, thienyl, imidazolyl, pyrazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, triazolyl, Furazanil, oxadiazolyl, thiadiazolyl, dithiazolyl, tetrazolyl, pyranil, thiopyranil, diazinyl, oxazinyl, thiazinyl, dioxynyl, triazinyl, tetrazinyl, quinolyl, iso Quinolyl, quinazolinyl, isoquinazolinyl, naphthyridyl, acridinyl, phenanthridinyl, imidazopyridinyl, diazanaphthalenyl, triazinden, indolyl, indolizinyl, benzothiazolyl, Benzoxazolyl, benzoimidazolyl, benzothiophene group, benzofuran group, dibenzothiophene group, dibenzofuran group, carbazolyl, benzocarbazolyl, phenazinyl, etc., or condensed rings thereof, but limited thereto it is not going to be

As used herein, "heteroaryl" refers to an aryl group including at least one heteroatom selected from N, O, S, and Se as an aromatic ring skeletal atom, and the remaining aromatic ring skeletal atoms being carbon. 6-membered monocyclic heteroaryl, and polycyclic heteroaryl condensed with one or more benzene rings, which may be partially saturated. In addition, the heteroaryl in the present invention includes a form in which one or more heteroaryls are connected by a single bond. Specific examples include furyl, thiophenyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, isothiazolyl, isoxazolyl, oxazolyl, triazinyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, etc. Monocyclic heteroaryl of; Benzofuranyl, benzothiophenyl, isobenzofuranyl, benzoimidazolyl, benzothiazolyl, benzoisothiazolyl, benzoisoxazolyl, benzoxazolyl, isoindolyl, indolyl, indazolyl, quinolyl, iso polycyclic heteroaryls such as quinolyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, and benzocarbazolyl; and the like, but are not limited thereto.

In the present specification, "heteroarylene" means a divalent organic radical derived by removing one hydrogen from the heteroaryl, and follows the definition of the heteroaryl.

The present invention relates to a novel heterocyclic compound and an organic light emitting device including the same, and more specifically, the heterocyclic compound according to the present invention may be represented by Formula 1 below:

[Formula 1]

In Formula 1,

R ^a to R ^d are each independently hydrogen, C1-C60 alkyl or C6-C60 aryl;

L ₁ to L ₄ are each independently a single bond, C6-C60 arylene or C3-C60 heteroarylene;

,

또는

이거나, R₁와 R₂, R₃과 R₄, R₅와 R₆ 및 R₇와 R₈은 각각 독립적으로 서로 연결되어 방향족고리가 융합되거나 융합되지 않은 헤테로고리를 형성할 수 있으며;R ₁ to R ₈ are each independently

,

or

Alternatively, R ₁ and R ₂ , R ₃ and R ₄ , R ₅ and R ₆ , and R ₇ and R ₈ may be independently connected to each other to form a fused or unfused aromatic ring heterocycle;

R ₂₁ to R ₂₄ are independently of each other C1-C60 alkyl, haloC1-C60 alkyl, deuterium, halogen, cyano, C3-C60 cycloalkyl, C1-C60 alkoxy, C6-C60 aryl, C6-C60 aryloxy, C6 -C60 arylC1-C60 alkyl, C1-C60 alkylC6-C60 aryl, C3-C60 heteroaryl, -NR ₁₂ R ₁₃ , nitro or hydroxy;

R ₁₂ and R ₁₃ are each independently hydrogen, C1-C60 alkyl, C6-C60 aryl or C3-C60 heteroaryl;

X ₁ is NR ₃₁ , O or S;

R ₃₁ is hydrogen, C1-C60 alkyl, C6-C60 aryl or C3-C60 heteroaryl;

The arylene and heteroarylene of L ₁ to L ₄ and the aryl and heteroaryl of R ₂₁ to R ₂₄ are C1-C60 alkyl, haloC1-C60 alkyl, deuterium, halogen, cyano, C3-C60 cycloalkyl, C1-C60 Alkoxy, C6-C60 Aryl, C6-C60 Aryloxy, C6-C60 ArylC1-C60 Alkyl, C1-C60 AlkylC6-C60 Aryl, C3-C60 Heteroaryl, -NR'R'', nitro and It may be further substituted with one or more selected from the group consisting of hydroxy;

R' and R'' are each independently hydrogen, C1-C60 alkyl, C6-C60 aryl or C3-C60 heteroaryl;

a is an integer from 0 to 5, and when a is an integer of 2 or greater, each R ₂₁ may be the same as or different from each other;

b is an integer from 0 to 7, and when b is an integer of 2 or greater, each R ₂₂ may be the same as or different from each other;

c is an integer from 0 to 3, and when c is an integer of 2 or greater, each R ₂₃ may be the same as or different from each other;

d is an integer from 0 to 4, and when d is an integer of 2 or greater, each R ₂₄ may be the same as or different from each other;

p and q are independently integers from 0 to 4, r and s are independently integers from 0 to 2, provided that p, q, r and s are not 0 at the same time;

The heteroarylene and heteroaryl include one or more heteroatoms selected from N, O, S and Se.

Specifically, the heterocyclic compound of Formula 1 has a multi-cyclic skeleton in which dibenzofuran is fused on both sides around 1,4-dihydropentalene as a mother core, and at least It is a polycyclic heterocyclic compound in which an amino substituent having a specific structure is introduced, and can be usefully used as an organic material layer material of an organic light emitting device.

The heterocyclic compound of Chemical Formula 1 lowers driving voltage, improves luminous efficiency and color purity, and exhibits surprisingly improved lifespan characteristics when employed as an organic material layer of an organic light emitting device, particularly a hole transport material of an organic light emitting device, due to the above structural characteristics. can

,

또는

이거나, R₁와 R₂, R₃과 R₄, R₅와 R₆ 및 R₇와 R₈은 각각 독립적으로 서로 연결되어 방향족고리가 융합된 헤테로고리를 형성할 수 있으며; R₃₁ 내지 R₃₅는 서로 독립적으로 수소, C1-C60알킬, 중수소, C6-C60아릴, C6-C60아릴C1-C60알킬, C1-C60알킬C6-C60아릴, C3-C60헤테로아릴 또는 -NR₁₂R₁₃이고; R₁₂ 및 R₁₃은 각각 독립적으로 C6-C60아릴 또는 C3-C60헤테로아릴이고; X₁은 O 또는 S이고; 상기 R₃₁ 내지 R₃₅의 아릴 및 헤테로아릴은 C1-C60알킬, 중수소, C6-C60아릴, C6-C60아릴C1-C60알킬, C1-C60알킬C6-C60아릴 및 C3-C60헤테로아릴로 이루어진 군으로부터 선택되는 하나 이상으로 더 치환될 수 있고; p, q, r 및 s는 서로 독립적으로 0 내지 2의 정수이며, 단, 1≤p+q+r+s≤4를 만족할 수 있다.In Formula 1 according to one embodiment, R ^a to R ^d are each independently C1-C60 alkyl or C6-C60 aryl; L ₁ to L ₄ are each independently a single bond, C6-C60 arylene or C3-C60 heteroarylene, and the arylene and heteroarylene of L ₁ to L ₄ are C1-C60 alkyl, C6-C60 aryl and It may be further substituted with one or more selected from the group consisting of -NR'R'';R' and R'' are each independently C6-C60 aryl or C3-C60 heteroaryl; R ₁ to R ₈ are each independently

,

or

Alternatively, R ₁ and R ₂ , R ₃ and R ₄ , R ₅ and R ₆ , and R ₇ and R ₈ may be independently connected to each other to form a heterocyclic ring in which an aromatic ring is fused; R ₃₁ to R ₃₅ are each independently hydrogen, C1-C60 alkyl, deuterium, C6-C60 aryl, C6-C60 arylC1-C60 alkyl, C1-C60 alkyl C6-C60 aryl, C3-C60 heteroaryl or -NR ₁₂ R ₁₃ ; R ₁₂ and R ₁₃ are each independently C6-C60 aryl or C3-C60 heteroaryl; X ₁ is O or S; Aryl and heteroaryl of R ₃₁ to R ₃₅ are a group consisting of C1-C60 alkyl, deuterium, C6-C60 aryl, C6-C60 arylC1-C60 alkyl, C1-C60 alkyl C6-C60 aryl and C3-C60 heteroaryl It may be further substituted with one or more selected from; p, q, r and s are independently integers from 0 to 2, provided that 1≤p+q+r+s≤4 may be satisfied.

In order to realize more improved device characteristics of the heterocyclic compound, p+q+r+s may be an integer of 1 or 2.

In a specific example, p+q+r+s may be an integer of 1.

In a specific example, p+q+r+s may be an integer of 2.

In a specific embodiment, q and s are integers of 0, p and r are independently integers of 0 to 2, and p+r may be an integer of 1 or 2.

In a specific example, p may be an integer of 1, and q, r, and s may be an integer of 0.

In a specific example, p may be an integer of 2, and q, r, and s may be an integer of 0.

In a specific example, r may be an integer of 1, and p, q and s may be an integer of 0.

In a specific example, r may be an integer of 2, and p, q and s may be an integer of 0.

In one embodiment, the heterocyclic compound may be represented by any one of the following formulas 2 or 3:

[Formula 2]

[Formula 3]

In Formulas 2 and 3,

R ^a to R ^d are each independently C1-C30 alkyl;

L ₁ and L ₃ are each independently a single bond, C6-C30 arylene or C3-C30 heteroarylene, and the arylene and heteroarylene of L ₁ and L ₃ are C1-C30 alkyl, C6-C30 aryl and It may be further substituted with one or more selected from the group consisting of -NR'R'';

R' and R'' are each independently C6-C30 aryl or C3-C30 heteroaryl;

,

,

또는

이거나, R₁와 R₂, 및 R₅와 R₆은 각각 독립적으로 서로 연결되어 방향족고리가 융합된 헤테로고리를 형성할 수 있으며; R ₁ , R ₂ , R ₅ and R ₆ are each independently

,

,

or

Alternatively, R ₁ and R ₂ , and R ₅ and R ₆ may be independently connected to each other to form a heterocyclic ring in which an aromatic ring is fused ;

R ₃₁ to R ₃₅ are each independently hydrogen, C1-C30 Alkyl, C6-C30 Aryl, C6-C30 ArylC1-C30 Alkyl, C1-C30 AlkylC6-C30 Aryl, C3-C30 Heteroaryl or -NR ₁₂ R ₁₃ ego;

R ₁₂ and R ₁₃ are each independently C6-C30 aryl or C3-C30 heteroaryl;

Aryl and heteroaryl of R ₃₁ to R ₃₅ are selected from the group consisting of C1-C30 alkyl, C6-C30 aryl, C6-C30 arylC1-C30 alkyl, C1-C30 alkyl C6-C30 aryl and C3-C30 heteroaryl may be further substituted with one or more;

p and r are independently of each other an integer of 1 or 2;

In one embodiment, R ^a to R ^d may each independently be C1-C20 alkyl, preferably C1-C10 alkyl.

In one embodiment, the heterocyclic compound may be represented by any one of Formulas 4 and 5:

[Formula 4]

[Formula 5]

In Formulas 4 and 5,

L ₁ and L ₃ are each independently a single bond, C6-C20 arylene or C3-C20 heteroarylene, and the arylene and heteroarylene of L ₁ and L ₃ are C1-C20 alkyl, C6-C20 aryl and It may be further substituted with one or more selected from the group consisting of -NR'R'';

R' and R'' are each independently C6-C20 aryl or C3-C20 heteroaryl;

,

,

또는

이며;R ₁ , R ₂ , R ₅ and R ₆ are each independently

,

,

or

is;

R ₃₁ to R ₃₅ are each independently hydrogen, C6-C20 aryl, C3-C20 heteroaryl or -NR ₁₂ R ₁₃ ;

R ₁₂ and R ₁₃ are each independently C6-C20 aryl or C3-C20 heteroaryl;

Aryl and heteroaryl of R ₃₁ to R ₃₅ are selected from the group consisting of C1-C20 alkyl, C6-C20 aryl, C6-C20 arylC1-C20 alkyl, C1-C20 alkyl C6-C20 aryl and C3-C20 heteroaryl It may be further substituted with one or more.

In one embodiment, the L ₁ to L ₄ are each independently a single bond or a C6-C20 arylene, and the L ₁ to L ₄ arylene is composed of C6-C20 aryl and -NR'R'' may be further substituted with one or more selected from the group; R' and R'' may each independently be C6-C20 aryl or C3-C20 heteroaryl.

,

또는

이고; R₂, R₄, R₆ 및 R₈은 각각 독립적으로

,

또는

이며; R_31a, R_31b, R_31c, R_33a, R_33b, R₃₄ 및 R₃₅은 서로 독립적으로 수소 또는 C6-C20아릴이고; R₁₂ 및 R₁₃은 각각 독립적으로 C6-C20아릴 또는 C3-C20헤테로아릴이고; X₁은 O 또는 S일 수 있다.In one embodiment, the R ₁ , R ₃ , R ₅ and R ₇ are each independently

,

or

ego; R ₂ , R ₄ , R ₆ and R ₈ are each independently

,

or

is; R _31a , R _31b , R _31c , R _33a , R _33b , R ₃₄ and R ₃₅ independently represent hydrogen or C6-C20 aryl; R ₁₂ and R ₁₃ are each independently C6-C20 aryl or C3-C20 heteroaryl; X ₁ may be O or S.

In one embodiment, the L ₁ to L ₄ may each independently be a single bond or may be selected from the following structure, but is not limited thereto:

From above,

R _L1 , R _L2 and R _L3 are each independently hydrogen, C6-C20 aryl or NR'R'';

R' and R'' are each independently C6-C20 aryl or C3-C20 heteroaryl;

Z is CR _Z1 R _Z2 , NR _Z3 , O or S;

R _Z1 and R _Z2 are each independently C1-C20 alkyl or C6-C20 aryl;

R _Z3 is C6-C20 aryl.

,

또는

이며, R_L1 및 R_L2는 각각 독립적으로 수소 또는 NR'R''이고; R' 및 R''는 각각 독립적으로 C6-C12아릴 또는 C3-C12헤테로아릴일 수 있다.In embodiments, the L ₁ to L ₄ are each independently a single bond;

,

or

, and R _L1 and R _L2 are each independently hydrogen or NR'R'';R' and R'' may each independently be C6-C12 aryl or C3-C12 heteroaryl.

,

또는

이고; R₂, R₄, R₆ 및 R₈은 각각 독립적으로

,

,

또는

이며; R₄₁ 내지 R₄₃ 및 R₅₁ 내지 R₅₄은 서로 독립적으로 수소 또는 C6-C12아릴이고; R₁₂ 및 R₁₃은 각각 독립적으로 C6-C12아릴 또는 C3-C12헤테로아릴일 수 있다.In embodiments, R ₁ , R ₃ , R ₅ and R ₇ are each independently

,

or

ego; R ₂ , R ₄ , R ₆ and R ₈ are each independently

,

,

or

is; R ₄₁ to R ₄₃ and R ₅₁ to R ₅₄ independently represent hydrogen or C6-C12 aryl; R ₁₂ and R ₁₃ may each independently be C6-C12 aryl or C3-C12 heteroaryl.

,

또는

이고; R₂ 및 R₆은 각각 독립적으로

,

,

또는

이며; R₄₁ 내지 R₄₃ 및 R₅₁ 내지 R₅₄은 서로 독립적으로 수소 또는 C6-C12아릴이고; R₁₂ 및 R₁₃은 각각 독립적으로 C6-C12아릴 또는 C3-C12헤테로아릴일 수 있다.In one embodiment, in Formula 4 or 5, L ₁ and L ₃ are each independently a single bond or C6-C12 arylene, and the arylene of L ₁ and L ₃ is further selected from the group consisting of C6-C12 aryl and -NR'R'' can be substituted; R' and R'' are each independently C6-C12 aryl or C3-C12 heteroaryl; R ₁ and R ₅ are each independently

,

or

ego; R ₂ and R ₆ are each independently

,

,

or

is; R ₄₁ to R ₄₃ and R ₅₁ to R ₅₄ independently represent hydrogen or C6-C12 aryl; R ₁₂ and R ₁₃ may each independently be C6-C12 aryl or C3-C12 heteroaryl.

In one embodiment, the heterocyclic compound may be selected from the following, but is not limited thereto.

The heterocyclic compound according to an embodiment of the present invention may be used in an organic material layer of an organic light emitting device due to its structural specificity, and may be specifically used as a material for forming a hole transport layer in the organic material layer.

The above-mentioned compounds can be prepared based on Preparation Examples/Examples described below. In Preparation Examples/Examples to be described later, representative examples are described, but, if necessary, substituents may be added or excluded, and the position of the substituent may be changed. In addition, based on techniques known in the art, starting materials, reactants, reaction conditions, and the like can be changed. Changing the type or position of the substituents at the remaining positions, if necessary, can be performed by those skilled in the art using techniques known in the art.

In addition, the present invention provides an organic light emitting device including the heterocyclic compound of Formula 1 above.

Specifically, the organic light emitting device according to the present invention includes an anode, a cathode, and at least one organic material layer provided between the anode and the cathode, and at least one layer of the organic material layer includes the heterocyclic compound represented by Formula 1 above.

However, structures of organic light emitting devices known in the art may also be applied to the present invention. The scope of the present invention is not limited by such a laminated structure.

The organic light emitting device according to the present invention may be manufactured with materials and methods known in the art, except that the heterocyclic compound of Chemical Formula 1 is included in at least one of the organic material layers.

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

The heterocyclic compound of Chemical Formula 1 may be used as a hole injection material, a hole transport material, a light emitting material, an electron transport material, an electron injection material, and the like in an organic light emitting device. The heterocyclic compound may be used as a material for one or more of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer. As an example, the heterocyclic compound may be used as a material for a hole injection and transport layer of an organic light emitting device. As an example, the heterocyclic compound may be used as a material for an electron injection and transport layer of an organic light emitting device. As another example, the heterocyclic compound may be used as a material for a light emitting layer of an organic light emitting device. As another example, the heterocyclic compound may be used as a host material for a phosphorescent emission layer of an organic light emitting device. Preferably, the heterocyclic compound may be used as a material for a hole transport layer of an organic light emitting device.

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

As the anode material, materials having a relatively large work function may be used. Specific examples include metals such as vanadium, chromium, copper, zinc, and gold, or alloys thereof, zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc. Metal oxides such as oxide (IZO), combinations of metals and oxides such as ZnO:Al or SnO2:Sb, poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiol Ofene] (PEDT), conductive polymers such as polypyrrole and polyaniline may be used, but are not limited thereto. In addition, the anode layer may be formed of only one type of the above materials or may be formed of a mixture of a plurality of materials, and a multilayer structure composed of a plurality of layers of the same composition or different compositions may be formed.

Materials with a relatively low work function may be used as the anode material, and specific examples include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead, or alloys thereof , a multi-layer structure material such as LiF/Al or LiO/Al may be used.

As the hole injection material, a known hole injection material may be used. For example, a phthalocyanine compound such as CuPc (copper phthalocyanine) disclosed in U.S. Patent No. 4,356,429 or a document [Advanced Material, 6, p.677 (1994)] , such as TCTA (tris(4-carbazoyl-9-ylphenyl)amine), m-MTDATA (4,4',4"-tris(3-Methylphenylphenylamino)triphenylamine), m- MTDAPB (1,3,5-tris[4-(3-metylphenylphenylamino)phenyl]benzene), soluble conductive polymer Pani/DBSA (Polyaniline/Dodecylbenzenesulfonic acid) or PEDOT:PSS (poly(3,4-ethylenedioxythiophene) -poly(styrnesulfonate)), Pani/CSA (Polyaniline/Camphor sulfonic acid), or PANI/PSS (Polyaniline/Poly(4-styrene-sulfonate)) may be used.

As the hole transport material, the heterocyclic compound according to an embodiment of the present invention may be used alone or in combination with known hole transport materials.

Specifically, the hole transport material includes a heterocyclic compound according to an embodiment of the present invention, but may be used together with pyrazoline derivatives, arylamine derivatives, stilbene derivatives, triphenyldiamine derivatives, etc., and low molecular or high molecular materials may be used As a specific example, NPB (N, N'-bis (naphthalen-1-yl) -N, N'-bis (phenyl) -benzidine), NPD (N, N'-bis (naphthalen-1-yl) -N, N'-bis(phenyl)-2,2'-dimethylbenzidine), mCP (1,3-Bis(N-carbazolyl)benzene), TPD (N,N'-Bis(3-methylphenyl)-N,N'- diphenylbenzidine), TTB (N,N,N',N'-tetrakis(4-methylphenyl)-(1,1'-biphenyl)-4,4-diamine), TTP (N1,N4-diphenyl-N1,N4- dim-tolylbenzene-1,4-diamine), ETPD (N,N'-bis(4-methylphenyl)-N,N'-bis(4-ethylphenyl)-[1,1'-(3,3'-dimethyl )biphenyl]-4,4'-diamine), VNPB (N4,N4'-di(naphthalen-1-yl)-N4,N4'-bis(4-vinylphenyl)biphenyl-4,4'-diamine), ONPB (N4,N4'-bis(4-(6-((3-ethyloxetan-3-yl)methoxy)hexyl)phenyl)-N4,N4'-diphenylbiphenyl-4,4'-diamine), OTPD (N4,N4 small molecule hole transporters such as '-bis(4-(6-((3-ethyloxetan-3-yl)methoxy)hexyl)phenyl)-N4,N4'-diphenylbiphenyl-4,4'-diamine); There are polymer hole transport materials such as PVK (poly-N-vinylcarbazole), polyaniline, and (phenylmenyl) polysilane.

Examples of the electron transport material 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. Metal complexes of derivatives, diphenyldicyanoethylene and its derivatives, diphenoquinone derivatives, 8-hydroxyquinoline and its derivatives, etc. may be used, and high molecular materials as well as low molecular materials may be used. As specific examples, TSPO1 (diphenyl[4-(triphenylsilyl)phenyl]phosphine oxide), TPBI (1,3,5-tris(N-phenylbenzimidazol-2-yl)benzene); Alq ₃ (tris(8-hydroxyquinolinato)aluminum); BCP (2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline); PBD (2-(4-biphenyl)-5-(4-tert-butyl-phenyl)-1,3,4-oxadizole), TAZ (3-(4-biphenyl)-4-phenyl-5-(4- tert-butyl-phenyl)-1,2,4-triazole), OXD-7 (1,3-bis[2-(4-tert-butylphenyl)-1,3,4-oxadiazo-5-yl]benzene) azole compounds such as; tris(phenylquinoxaline) (TPQ); TmPyPB (3,3'-[5'-[3-(3-Pyridinyl)phenyl][1,1':3',1''-terphenyl]-3,3''-diyl]bispyridine) etc. may, but is not limited thereto.

As an electron injection material, for example, LIF or Liq (lithium quinolate) is typically used in the art, but is not limited thereto.

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

The light emitting layer may be formed by a method such as a vacuum deposition method, a spin coating method, a cast method, an LB method, etc. of a light emitting material. In general, it can be selected from almost the same range of conditions as the formation of the hole injection layer. In addition, a known compound can be used as a host or dopant for the light emitting layer material.

Also, for example, as a material for the light emitting layer, as a fluorescent dopant, IDE102 or IDE105 from Idemitsu, BD-331 or BD-142 (N ⁶ ,N ¹² -bis(3,4-dimethylphenyl)-N ⁶ ,N ¹² -Dimesityl trisene-6,12-diamine) can be used, and as a phosphorescent dopant, green phosphorescent dopant Ir(ppy) ₃ (tris(2-phenylpyridine)iridium), blue dot F2Irpic (iridium(III) bis[ 4,6-difluorophenyl)-pyridinato-N,C2']picolinate), UDC's red phosphorescent dopant RD61, etc. may be co-evaporated (doped).

The phosphorescent dopant is a compound capable of emitting light from triplet excitons, and is not particularly limited as long as it emits light from triplet excitons. A specific example may be a metal complex including one or more metals selected from the group consisting of Ir, Ru, Pd, Pt, Os, and Re, and may be a porphyrin metal complex or an ortho metallized metal complex.

The porphyrin metal complex may be specifically a porphyrin platinum complex.

The ortho metallized metal complex is a 2-phenylpyridine (ppy) derivative, a 7,8-benzoquinoline derivative, a 2-(2-thienyl)pyridine (2-(2-thienyl)pyridine, tp) derivative , 2-(1-naphthyl)pyridine (2-(1-naphthyl)pyridine, npy) derivatives, 2-phenylquinoline (2-phenylquinoline, pq) derivatives, etc. may be included as a ligand. These derivatives may have substituents as needed. As an auxiliary ligand, it may further have ligands other than the above ligands, such as acetylacetonato (acac) and picric acid. Specific examples include bisthienylpyridine acetylacetonate iridium, bis(2-benzo[b]thiophen-2-yl-pyridine)(acetylacetonato)iridium(III) (bis(2- benzo[b]thiophen-2-yl-pyridine)(acetylacetonato)iridium(III), Ir(btp) ₂ (acac)), bis(2-phenylbenzothiazole)(acetylacetonato)iridium(III) ( bis(2-phenylbenzothiazole)(acetylacetonato)iridium(III), Ir(bt) ₂ (acac)), bis(1-phenylisoquinoline)(acetylacetonato)iridium(III) (bis(1-phenylisoquinoline)( acetylacetonato)Iridium(III), Ir(piq) ₂ (acac)), tris(1-phenylisoquinoline)iridium(III) (tris(1-phenylisoquinoline)iridium(III), Ir(piq) ₃ ), tris( 2-phenylpyridine) iridium (III) (tris (2-phenylpyridine) iridium (III), Ir (ppy) ₃ ), tris (2-biphenylpyridine) iridium (tris (2-biphenylpyridine) iridium), tris (3 - Biphenylpyridine) iridium (tris (3-biphenylpyridine) iridium), tris (4-biphenylpyridine) iridium (tris (4-biphenylpyridine) iridium), and the like, but are not limited thereto.

In addition, when used with a phosphorescent dopant in the light emitting layer, a hole blocking material (HBL) may be additionally laminated by vacuum deposition or spin coating to prevent diffusion of triplet excitons or holes into the electron transport layer. The hole blocking material that can be used at this time is not particularly limited, but can be selected and used arbitrarily from known ones used as hole blocking materials. For example, it may be an oxadiazole derivative or a triazole derivative or a phenanthroline derivative, specifically Balq (bis(8-hydroxy-2-methylquinolinato)-aluminum biphenoxide), phenanthrolines based compounds (: BCP (vasocuproin) from UDC), etc. can be used.

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

[Example 1] Preparation of compounds P1 and P2

Preparation of compound P-8

10 g (57.14 mmol) of 1-bromo-4-iodobenzene in 290 mL of DMF (dimethylformamide), 2-methylbur-3-yne -2-ol) 5.77 g (68.57 mmol), palladium (II) acetate (Pd (OAc) ₂ ) 0.64 g (2.86 mmol), copper (I) Iodide, CuI) 1.63 g ( 8.57mmol), triphenylphosphine (PPh ₃ ) 2.29g (8.57mmol), and diethylamine (diethylamine, Et ₂ NH) 12mL (114.28mmol) were added and then stirred at 30° C. for 10 minutes under a nitrogen atmosphere. Then, the reaction solution was stirred under reflux. After the reaction was completed, extraction was performed using an aqueous solution of ethylenediamine and methylene chloride (MC), and magnesium sulfate was added to the MC layer to retain moisture, followed by filtering. After removing the solvent, 8.86 g (87%) of the target compound P-8 was obtained by column chromatography purification using EA (ethyl acetate) and Hex (hexane).

Preparation of compound P-7

After dissolving 10 g (56.11 mmol) of Compound P-8 in 170 mL of MC, 17.09 g (67.33 mmol) of iodine (I ₂ ) was added and stirred at room temperature. After the reaction was completed, the organic layer was collected by extraction with an aqueous solution of sodium thiosulfate. After removing the solvent from the organic layer, 17.66 g (76%) of target compound P-7 was obtained by column chromatography purification using EA and Hex.

Preparation of compound P-6

Under an argon atmosphere, the temperature was lowered to -78°C while stirring 10 g (24.15 mmol) of compound P-7 in 120 mL of diethyl ether. At this temperature, 19mL (28.98mmol) of butyllithium (n-butyllithium/1.6M solution in hex.) was slowly added thereto while stirring. After 1 hour, 2.3mL (31.40mmol) of acetone was added at the same temperature and stirred for 1 hour under an argon atmosphere. Thereafter, the mixture was stirred while slowly raising the temperature to room temperature for 24 hours. When the reaction was completed, the reaction was terminated with 1N HCl aqueous solution, and the organic layer was collected by extraction with MC. After removing the solvent from the organic layer, 5.18g (62%) of the target compound P-6 was obtained by column chromatography purification using EA and Hex.

Preparation of compound P-5

10 g (28.89 mmol) of compound P-6 in toluene/ethanol/water (volume ratio 4:1:1, 110 mL), 2-(4-fluorophenyl)-4,4,5,5-tetramethyl-1,3 ,2-dioxaborolane (2-(4-fluorophenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane) 7.70g (34.66mmol), potassium carbonate (K ₂ CO ₃ ) After adding 7.99g (57.78mmol), the mixture was stirred at 30°C for 10 minutes under a nitrogen atmosphere. Thereafter, 1.67 g (1.45 mmol) of tetrakis(triphenylphosphine)palladium (Pd(PPh ₃ ) ₄ ) was added and refluxed at 120°C. When the reaction was completed, the mixture was filtered using celite and florisil, and then washed with MC. 7.56 g (85%) of target compound P-5 was obtained by column chromatography purification using MC and Hex.

Preparation of compound P-4

10 g (31.81 mmol) of compound P-5 was added to 160 mL of MC and stirred while lowering the temperature to 0°C. 4.7 mL (38.17 mmol) of boron trifluoride diethyl etherate (BF ₃ OEt ₂ ) was added thereto, and the mixture was stirred at 0° C. for 1 hour. Thereafter, the mixture was stirred for 24 hours while slowly raising the temperature to room temperature. After the reaction was completed, extraction was performed using EA and H ₂ O, the solvent was removed, and 6.98 g (74%) of target compound P-4 was obtained by column chromatography purification using Hex and EA.

Preparation of compound P-3

10 g (33.74 mmol) of compound P-4 was added to 170 mL of NMP (N-methyl-2-pyrrolidone) and stirred under an argon atmosphere. After adding 4.30 mL (40.49 mmol) of 2-bromophenol and 5.60 g (40.49 mmol) of K ₂ CO ₃ thereto, the mixture was stirred at 30° C. for 10 minutes under a nitrogen atmosphere. Then, it was stirred at 80° C. for 24 hours. When the reaction was completed, the mixture was filtered using celite and florisil, and then washed with MC. 11.52 g (76%) of target compound P-3 was obtained by column chromatography purification using MC and Hex.

Preparation of compound P-2

10 g (33.74 mmol) of compound P-3 was added to 170 mL of NMP and stirred under an argon atmosphere. After adding 8.40 g (40.49 mmol) of 2-bromo-6-chlorophenol and 5.60 g (40.49 mmol) of K ₂ CO ₃ thereto, the mixture was stirred at 30 ° C. for 10 minutes under a nitrogen atmosphere. . Then, it was stirred at 140° C. for 24 hours. When the reaction was completed, the mixture was filtered using celite and florisil, and then washed with MC. 13.97g (65%) of target compound P-2 was obtained by column chromatography purification using MC and Hex.

Preparation of Compound P-1

10 g (15.70 mmol) of Compound P-2 was added to 80 mL of DMF, and dissolved by stirring at room temperature under an argon atmosphere. 0.53g (2.36mmol) of Pd(OAc) ₂ and 4.34g (31.4mmol) of K ₂ CO ₃ were added thereto, and the mixture was refluxed and stirred at 150°C for 24 hours. When the reaction was completed, water was added to terminate the reaction. The resulting solid was filtered and washed several times with Hex. 4.55 g (61%) of target compound P-1 was obtained by column chromatography purification using MC and Hex.

Preparation of compound P1

A target compound P1 was obtained through a Suzuki coupling reaction using compound P-1, a boron compound, and a palladium catalyst.

Compound P-1 (1eq.), substituted boronic acid or boronic ester compound (1,2eq.), Pd(PPh ₃ ) ₄ (0.05eq.) in toluene/ethanol/water (volume ratio 4:1:1, 100mL) .), and K ₂ CO ₃ (2eq.) were added thereto, and the mixture was refluxed and stirred at 120° C. under a nitrogen atmosphere. After the reaction was completed, the mixture was filtered using celite and florisil, and then washed with MC. The target compound P1 was obtained by recrystallization and purification using EA and Hex.

Preparation of compound P2

A target compound P2 was obtained through palladium amination using compound P-1, a secondary amine compound, and a palladium catalyst.

Toluene compound P-1 (1eq.), secondary amine compound (1,2eq.), tris (dibenzylideneacetone) dipalladium (Pd ₂ (dba) ₃ ) (0.05eq.), tri After putting (tert-butyl)phosphine (P(t-Bu) ₃ ) (0.15eq.) and sodium tert-butoxide (NaOt-Bu) (2eq.), reflux stirring at 120°C under an argon atmosphere. made it When the reaction was completed, the mixture was filtered using celite and florisil, and then washed with MC. The target compound P2 was obtained by recrystallization and purification using EA and Hex.

The structures of the substituted boronic acids, boronic esters, and secondary amine compounds as reactants, and the structures and yields of the prepared compounds P1 and P2 are shown in Table 1 below. However, the structure of the reactant boron compound and the secondary amine compound is not limited to the following.

Compound No. reactant Product (P1, P2) transference number COM 4-1

81% COM 4-2

82% COM 4-3

74% COM 4-4

89% Com 4-5

78% Com 4-6

70% Com 4-7

65% Com 4-8

63% Com 4-9

66% Com 4-10

75%

[Example 2] Preparation of compounds P3 and P4

Preparation of compound Q-3

10 g (33.74 mmol) of compound P-4 was added to 170 mL of NMP and stirred under an argon atmosphere. After adding 7.52mL (70.85mmol) of 2-bromophenol and 13.99g (101.22mmol) of K ₂ CO ₃ thereto, the mixture was stirred at 30°C for 10 minutes under a nitrogen atmosphere. Then, it was stirred at 150 °C for 24 hours. When the reaction was completed, the mixture was filtered using celite and florisil, and then washed with MC. 12.40 g (61%) of target compound Q-3 was obtained by column chromatography purification using MC and Hex.

Preparation of compound Q-2

10 g (16.60 mmol) of target compound Q-3 was added to 80 mL of DMF, and dissolved by stirring at room temperature under an argon atmosphere. 0.56 g (2.49 mmol) of Pd(OAc) ₂ and 5.74 g (41.5 mmol) of K ₂ CO ₃ were added thereto, and the mixture was refluxed and stirred at 150° C. for 24 hours. When the reaction was completed, water was added to terminate the reaction. The resulting solid was filtered and washed several times with Hex. 4.55 g (61%) of target compound Q-2 was obtained by column chromatography purification using MC and Hex.

Preparation of compound Q-1

10 g (22.70 mmol) of compound Q-2 was added to 80 mL of tetrachloromethane (CCl ₄ ), and dissolved by stirring at room temperature under an argon atmosphere. 4.56g (20.43mmol) of copper (II) bromide (CuBr ₂ ) and 4.64g (45.40mmol) of aluminum oxide (Al ₂ O ₃ ) were added to this, and the mixture was heated at 40°C for 24 hours. stirred for an hour. When the reaction was completed, the reaction was terminated with water. The resulting solid was filtered and washed several times with Hex. 6.25 g (53%) of target compound Q-1 was obtained by column chromatography purification using MC and Hex.

Preparation of compound P3

Target compound P3 was obtained through a Suzuki coupling reaction using compound Q-1, a boron compound, and a palladium catalyst.

Compound Q-1 (1eq.), substituted boronic acid or boronic ester compound (1,2eq.), Pd(PPh ₃ ) ₄ (0.05eq.) in toluene/ethanol/water (volume ratio 4:1:1, 100mL) .), and K ₂ CO ₃ (2eq.) were added thereto, and the mixture was refluxed and stirred at 120° C. under a nitrogen atmosphere. After the reaction was completed, the mixture was filtered using celite and florisil, and then washed with MC. The target compound P3 was obtained by recrystallization and purification using EA and Hex.

Preparation of compound P4

A target compound P4 was obtained through palladium amination using compound Q-1, a secondary amine compound, and a palladium catalyst.

Compound Q-1 in toluene (1eq.), secondary amine compound (1,2eq.), Pd ₂ (dba) ₃ (0.05eq.), P(t-Bu) ₃ (0.15eq.), and NaOt-Bu (2eq.) were added thereto, followed by reflux stirring at 120°C under an argon atmosphere. When the reaction was completed, the mixture was filtered using celite and florisil, and then washed with MC. The target compound P4 was obtained by recrystallization and purification using EA and Hex.

The structures of the substituted boronic acids, boronic esters and secondary amine compounds as reactants, and the structures and yields of the prepared compounds P3 and P4 are shown in Table 2 below. However, the structure of the reactant boron compound and the secondary amine compound is not limited to the following.

Compound No. reactant Products (P3, P4) transference number Com 5-1

80% COM 5-2

78% Com 5-3

76% COM 5-4

78% Com 5-5

74% Com 5-6

72% Com 5-7

67% Com 5-8

60% Com 5-9

63% Com 5-10

70%

¹ H NMR and MS values of the compounds prepared in the above examples are shown in Table 3 below.

Compound No. ¹ H NMR MS found calculated Com. 4-1 δ = 8.08(1H, d), 8.02(1H, d), 7.98(1H, d), 7.70(1H, d), 7.56-7.54(4H, m), 7.51(1H, t), 7.45(1H, d), 7.39-7.31(5H, m), 7.24(4H, t), 7.08(4H, d), 7.00(2H, t), 1.46(12H, s) 683.85 683.28 Com. 4-2 δ = 8.08(1H, d), 8.02(1H, d), 7.98(1H, d), 7.78(1H, d), 7.70(2H, d), 7.56-7.31(15H, m), 7.24(2H, t), 7.11-7.08 (3H, m), 7.00 (1H, t), 1.46 (12H, s) 733.91 733.30 Com. 4-3 δ = 8.08(1H, d), 8.02(1H, d), 7.98(1H, d), 7.78(2H, d), 7.71-7.70(3H, m), 7.56-7.51(7H, m), 7.45- 7.31(12H, m), 7.11(2H, s), 1.46(12H, s) 783.97 783.31 Com. 4-4 δ = 8.08(1H, d), 8.02(1H, d), 7.98(1H, d), 7.75(2H, d), 7.70(1H, d), 7.56-7.51(7H, m), 7.49-7.24( 13H, m), 7.08(2H, d), 7.00(1H, t), 1.46(12H, s) 759.95 759.31 Com. 4-5 δ = 8.08(1H, d), 8.02(1H, d), 7.98(2H, d), 7.75(2H, d), 7.70(1H, d), 7.64(1H, d), 7.56-7.28(22H, m), 6.97 (1H, d), 1.46 (12H, s) 850.03 849.32 Com. 4-6 δ = 7.98(1H, d), 7.75(2H, d), 7.70(1H, d), 7.64(2H, d), 7.56-7.54(5H, m), 7.49-7.24(18H, m), 7.08( 2H, d), 7.00 (1H, t), 6.97 (1H, d), 6.83 (1H, s), 6.74 (2H, d), 1.46 (12H, s) 941.14 940.37 Com. 4-7 δ = 8.10(1H, d), 8.08(1H, d), 8.02(1H, d), 7.98(2H, d), 7.70(1H, d), 7.64(1H, d), 7.56-7.28(20H, m), 7.14-7.08 (3H, m), 6.97 (1H, d), 1.46 (12H, s) 850.03 849.32 Com. 4-8 δ = 8.08(1H, d), 8.02(1H, d), 7.98(2H, d), 7.75(2H, d), 7.70(1H, d), 7.64(1H, d), 7.56-7.24(23H, m), 7.08(4H, d), 7.00(2H, t), 6.93(3H, s), 1.46(12H, s) 1017.24 1016.40 Com. 4-9 δ = 8.08(1H, d), 8.02(1H, d), 7.98(2H, d), 7.75(2H, d), 7.70(1H, d), 7.64(1H, d), 7.56-7.24(23H, m), 7.08(4H, d), 7.00(2H, t), 6.93(3H, s), 1.46(12H, s) 1017.24 1016.40 Com. 4-10 δ = 7.98(1H, d), 7.75(4H, d), 7.70(1H, d), 7.64(1H, d), 7.56-7.54(4H, m), 7.49(4H, t), 7.45-7.24( 13H, m), 7.08(4H, d), 7.00(2H, t), 6.97(1H, d), 6.93(3H, s), 1.46(12H, s) 927.16 926.39 Com. 5-1 δ = 7.98(2H, d), 7.70(1H, d), 7.69(1H, s), 7.56-7.54(5H, m), 7.39-7.31(6H, m), 7.24(4H, t), 7.08( 4H, d), 7.00 (2H, t), 1.46 (12H, s) 683.85 683.28 Com. 5-2 δ = 7.98(2H, d), 7.78(1H, d), 7.71(1H, d), 7.70(1H, d), 7.69(1H, s), 7.56-7.54(6H, m), 7.45-7.24( 11H, m), 7.11-7.08 (3H, m), 7.00 (1H, t), 1.46 (12H, s) 733.91 733.30 Com. 5-3 δ = 7.98(2H, d), 7.78(2H, d), 7.71(3H, d), 7.69(1H, s), 7.56-7.54(7H, m), 7.45-7.31(12H, m), 7.11( 2H, s), 1.46 (12H, s) 783.97 783.31 Com. 5-4 δ = 7.98(2H, d), 7.75(2H, d), 7.70(1H, d), 7.69(1H, s), 7.56-7.54(7H, m), 7.49(2H, t), 7.41-7.31( 9H, m), 7.24 (2H, t), 7.08 (2H, d), 7.00 (1H, t), 1.46 (12H, s) 759.95 759.31 Com. 5-5 δ = 7.98(3H, d), 7.75(2H, d), 7.70(1H, d), 7.69(1H, s), 7.64(1H, d), 7.56-7.28(22H, m), 6.97(1H, d), 1.46 (12H, s) 850.03 849.32 Com. 5-6 δ = 7.98(3H, d), 7.75(2H, d), 7.70(1H, d), 7.64(1H, d), 7.56-7.54(6H, m), 7.49-7.24(15H, m), 7.13( 1H, s), 7.08(2H, d), 7.00(1H, t), 6.97(1H, d), 6.83(1H, s), 6.74(2H, d), 1.46(12H, s) 941.14 940.37 Com. 5-7 δ = 8.10 (1H, d), 7.98 (3H, d), 7.70 (1H, d), 7.69 (1H, s), 7.64 (1H, d), 7.56-7.54 (5H, m), 7.43-7.28 ( 14H, m), 7.14(1H, t), 7.08(2H, d), 7.00(1H, t), 6.97(1H, d), 1.46(12H, s) 850.03 849.32 Com. 5-8 δ = 7.98(3H, d), 7.75(2H, d), 7.70(1H, d), 7.69(1H, s), 7.64(1H, d), 7.56-7.54(6H, m), 7.49-7.24( 16H, m), 7.08(4H, d), 7.00(2H, t), 6.97(1H, d), 6.93(3H, s), 1.46(12H, s) 1017.24 1016.40 Com. 5-9 δ = 7.98(3H, d), 7.75(4H, d), 7.70(1H, d), 7.64(1H, d), 7.56-7.24(23H, m), 7.13(1H, s), 7.08(2H, d), 7.00(1H, t), 6.97(1H, d), 6.93(3H, s), 1.46(12H, s) 1017.24 1016.40 Com. 5-10 δ = 7.98(2H, d), 7.75(4H, d), 7.70(1H, d), 7.56-7.24(21H, m), 7.13(1H, s), 7.08(4H, d), 7.00(2H, t), 6.93(3H, s), 1.46(12H, s) 927.16 926.39

[Example 3] Preparation and evaluation of organic light emitting device

An organic light emitting diode was fabricated according to a conventional method using the compounds obtained in Examples as a hole transport layer, respectively.

First, an ITO substrate is installed in the substrate folder of the vacuum deposition equipment, and 2-TNATA (4,4',4"-Tris[2-naphthyl(phenyl)amino]triphenylamine) is applied on the ITO layer (anode) formed on the glass substrate. was vacuum deposited to form a hole injection layer having a thickness of 10 nm, and then a hole transport layer having a thickness of 20 nm was formed by vacuum depositing the heterocyclic compound prepared in Example of the present invention.

Subsequently, BD-331 (Idemitsu Co.) was used as a light emitting dopant, AND (9,10-Bis(2-naphthyl)anthracene) was used as a host material, and the doping concentration was fixed at 4% to form a layer on the hole transport layer. A light emitting layer was deposited with a thickness of 30 nm.

Subsequently, Alq3 (tris-(8-hydroxyquinoline)aluminum) was vacuum deposited to a thickness of 40 nm as an electron transport layer on the light emitting layer. Thereafter, LiF, an alkali metal halide, was deposited to a thickness of 0.2 nm, followed by Al to a thickness of 150 nm, and Al/LiF was used as a cathode to fabricate an organic light emitting device.

[Comparative Examples 1 to 3]

An organic light emitting device was manufactured in the same manner as in Example 3, except that Comparative Compound A, Comparative Compound B, or Comparative Compound C was used instead of the heterocyclic compound of the present invention as a hole transport material.

A forward bias DC voltage was applied to each organic light emitting device manufactured by Example 3 and Comparative Examples 1 to 3 of the present invention, and electroluminescence (EL) characteristics were measured with PR-650 of Photoresearch, 300 cd / m ² At the standard luminance, T95 life was measured through life measurement equipment manufactured by McScience. The measurement results are shown in Table 4 below. T95 means the time taken for the luminance of the light emitting device to reach 95% of the initial luminance.

hole transport material Driving voltage (V)
@300 cd/m ² Current (mA/cm ² )
@300 cd/m ² Efficiency (Cd/A)
@300 cd/m ² life characteristics Compound No. T95 (hr) Example Com. 4-1 5.3 5.4 5.4 124 Com. 4-2 5.1 6.8 5.0 105 Com. 4-3 5.0 6.2 4.8 110 Com. 4-4 5.0 7.0 4.9 112 Com. 4-5 5.0 6.3 5.2 110 Com. 4-6 4.9 5.4 6.0 118 Com. 4-7 5.0 5.4 5.7 109 Com. 4-8 5.1 5.6 5.8 105 Com. 4-9 4.6 5.1 6.4 129 Com. 4-10 5.1 7.8 4.3 108 Com. 5-1 5.1 6.5 5.0 122 Com. 5-2 4.9 5.4 5.9 109 Com. 5-3 4.8 6.3 5.0 107 Com. 5-4 5.0 6.9 4.9 100 Com. 5-5 5.0 6.3 4.9 115 Com. 5-6 4.7 5,3 6.3 127 Com. 5-7 5.0 6.5 5.2 112 Com. 5-8 4.9 5.4 5.4 117 Com. 5-9 4.9 5.9 5.4 101 Com. 5-10 4.7 6.8 5.7 111 Comparative Example 1 Comparative Compound A 5.4 9.6 3.1 62 Comparative Example 2 Comparative Compound B 5.5 9.5 3.2 72 Comparative Example 3 Comparative Compound C 5.4 8.0 3.7 64

From Table 4, it can be seen that the heterocyclic compounds developed in the present invention, as hole transport materials, can improve power consumption by inducing an increase in power efficiency by lowering the driving voltage along with better light emission characteristics than conventional hole transport materials. It can also be seen that there is a significant increase in life characteristics.

Therefore, the heterocyclic compound of the present invention can be used as a material for forming an organic layer such as a hole transport material to produce an organic light emitting device exhibiting low driving voltage, excellent color purity, high luminous efficiency and long lifespan. In addition, it is obvious that the same effect can be obtained even when the compounds of the present invention are used in other organic material layers of an organic light emitting device, for example, a light emitting layer, a hole injection layer, an electron injection layer, and an electron transport layer.

Claims (9)

delete delete A heterocyclic compound represented by Formula 2 or Formula 3:
[Formula 2]

[Formula 3]

In Formulas 2 and 3,
R ^a to R ^d are each independently C1-C30 alkyl;
L ₁ and L ₃ are each independently a single bond, C6-C30 arylene or C3-C30 heteroarylene, and the arylene and heteroarylene of L ₁ and L ₃ are C1-C30 alkyl, C6-C30 aryl and It may be further substituted with one or more selected from the group consisting of -NR'R'';
R' and R'' are each independently C6-C30 aryl or C3-C30 heteroaryl;
R ₁ , R ₂ , R ₅ and R ₆ are each independently

,

,

or

is;
R ₃₁ to R ₃₅ are each independently hydrogen, C1-C30 alkyl, C6-C30 aryl, C6-C30 arylC1-C30 alkyl, C1-C30 alkyl C6-C30 aryl, C3-C30 heteroaryl or -NR ₁₂ R ₁₃ ego;
R ₁₂ and R ₁₃ are each independently C6-C30 aryl or C3-C30 heteroaryl;
Aryl and heteroaryl of R ₃₁ to R ₃₅ are selected from the group consisting of C1-C30 alkyl, C6-C30 aryl, C6-C30 arylC1-C30 alkyl, C1-C30 alkyl C6-C30 aryl and C3-C30 heteroaryl may be further substituted with one or more;
p and r are independently of each other an integer of 1; According to claim 3,
The heterocyclic compound is a heterocyclic compound represented by any one of Formulas 4 and 5 below:
[Formula 4]

[Formula 5]

In Formulas 4 and 5,
L ₁ and L ₃ are each independently a single bond, C6-C20 arylene or C3-C20 heteroarylene, and the arylene and heteroarylene of L ₁ and L ₃ are C1-C20 alkyl, C6-C20 aryl and It may be further substituted with one or more selected from the group consisting of -NR'R'';
R' and R'' are each independently C6-C20 aryl or C3-C20 heteroaryl;
R ₁ , R ₂ , R ₅ and R ₆ are each independently

,

,

or

is;
R ₃₁ to R ₃₅ are each independently hydrogen, C6-C20 aryl, C3-C20 heteroaryl or -NR ₁₂ R ₁₃ ;
R ₁₂ and R ₁₃ are each independently C6-C20 aryl or C3-C20 heteroaryl;
Aryl and heteroaryl of R ₃₁ to R ₃₅ are selected from the group consisting of C1-C20 alkyl, C6-C20 aryl, C6-C20 arylC1-C20 alkyl, C1-C20 alkyl C6-C20 aryl and C3-C20 heteroaryl It may be further substituted with one or more. delete According to claim 4,
Wherein L ₁ and L ₃ are each independently a single bond or C6-C12 arylene, and the arylene of L ₁ and L ₃ is at least one selected from the group consisting of C6-C12 aryl and -NR'R'' may be further substituted;
R' and R'' are each independently C6-C12 aryl or C3-C12 heteroaryl;
R ₁ and R ₅ are each independently

,

or

ego;
R ₂ and R ₆ are each independently

,

,

or

is;
R ₄₁ to R ₄₃ and R ₅₁ to R ₅₄ independently represent hydrogen or C6-C12 aryl;
R ₁₂ and R ₁₃ are each independently C6-C12 aryl or C3-C12 heteroaryl, a heterocyclic compound. According to claim 3,
The heterocyclic compound is selected from the following, the heterocyclic compound:

It includes an anode, a cathode, and one or more organic material layers provided between the anode and the cathode, wherein the organic material layer comprises a heterocyclic compound according to any one of claims 3, 4, 6, and 7. An organic light emitting device comprising a hole transport layer comprising:
delete