KR20160041019A - Hetero-cyclic compound and organic light emitting device using the same - Google Patents

Abstract

The present invention relates to a novel hetero-cyclic compound and an organic light-emitting device using the same. The hetero-cyclic compound is represented by chemical formula 1. The hetero-cyclic compound of the present invention can be used as an organic matter layer material of the organic light-emitting device.

Description

HETERO-CYCLIC COMPOUND AND ORGANIC LIGHT EMITTING DEVICE USING THE SAME [0002]

This application claims the benefit of Korean Patent Application No. 10-2014-0134534 filed on October 6, 2014, filed with the Korean Intellectual Property Office, the entire contents of which are incorporated herein by reference.

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

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

The organic light emitting device has a structure in which an organic thin film is disposed between two electrodes. When a voltage is applied to the organic light emitting device having such a structure, electrons and holes injected from the two electrodes couple to each other in the organic thin film and form a pair, which then extinguishes and emits light. The organic thin film may be composed of a single layer or a multilayer, if necessary.

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

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

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

The present invention provides a novel heterocyclic compound and an organic light emitting device using the same.

One embodiment of the present disclosure provides a heterocyclic compound represented by the following Formula 1:

[Chemical Formula 1]

In Formula 1,

R ₁ and R ₂ are the same or different and each independently represents a substituted or unsubstituted C ₆ to C ₆₀ aryl group; A substituted or unsubstituted C ₂ to C ₆₀ heteroaryl group; And -P (= O) R < ₁₅ > R < ₁₆ &

R ₃ , R ₄ , R ₅ and R ₁₂ are the same or different from each other, and each independently hydrogen; Or deuterium,

R ₆ and R ₇ ; R ₇ and R ₈ ; R ₉ and R ₁₀ ; And at least one pair selected from the group consisting of R ₁₀ and R ₁₁ may combine with each other to form a ring,

R ₁₅ and R ₁₆ are the same or different and each independently hydrogen; heavy hydrogen; A substituted or unsubstituted C ₁ to C ₆₀ alkyl group; A substituted or unsubstituted C ₃ to C ₆₀ cycloalkyl group; A substituted or unsubstituted C ₆ to C ₆₀ aryl group; Or a substituted or unsubstituted C ₂ to C ₆₀ heteroaryl group,

R ₆ to R ₁₁ are the same as or different from each other, and each independently hydrogen or deuterium.

In addition, one embodiment of the present invention is an organic light emitting device including a cathode, a cathode, and at least one organic layer provided between the anode and the cathode, wherein at least one of the organic layers includes the heterocyclic compound Lt; / RTI >

The heterocyclic compound described in this specification can be used as an organic layer material of an organic light emitting device. The heterocyclic compound can be used as an electron transport layer, a hole blocking layer, a light emitting layer, and the like in an organic light emitting device. In particular, the heterocyclic compound represented by Formula 1 may be used as an electron transport layer, a hole blocking layer, or a material of a light emitting layer of an organic light emitting device.

The heterocyclic compound represented by the above formula (1) can be used as a material for a light emitting host.

FIGS. 1 to 3 illustrate the stacking order of electrodes and organic layers of the organic light emitting diode according to the embodiments of the present application.
4 shows a PL measurement graph of Compound 1 at a wavelength of 301 nm.
FIG. 5 shows a graph of LTPL measurement at a wavelength of 380 nm of Compound 1. FIG.

Hereinafter, the present invention will be described in detail.

The heterocyclic compound described in the present specification can be represented by the above formula (1). Specifically, the heterocyclic compound represented by Formula 1 can be used as an organic material layer material of an organic light emitting device according to the structural features of the core structure and the substituent.

As used herein, the term "substituted or unsubstituted"halogen; A C ₁ to C ₆₀ alkyl group; A C ₂ to C ₆₀ alkenyl group; An alkynyl group of C ₂ to C ₆₀ ; A C ₃ to C ₆₀ cycloalkyl group; A C ₂ to C ₆₀ heterocycloalkyl group; A C ₆ to C ₆₀ aryl group; A C ₂ to C ₆₀ heteroaryl group; -SiR ' R "; -P (= O) RR '; C ₁ to C ₂₀ alkylamine groups; C ₆ to C ₆₀ arylamine groups; And a heteroarylamine group of C ₂ to C ₆₀ , or a substituted or unsubstituted aryl group having at least two substituents selected from the substituents exemplified above, substituted or unsubstituted with at least one substituent selected from the group consisting of C ₂ to C ₆₀ heteroarylamine groups, Means that the substituent is substituted or unsubstituted with the substituent to which it is linked. For example, the "substituent group to which two or more substituents are connected" may be a biphenyl group. That is, the biphenyl group may be an aryl group, and may be interpreted as a substituent in which two phenyl groups are connected. The additional substituents may be further substituted.

A substituted or unsubstituted C ₁ to C ₆₀ alkyl group, a substituted or unsubstituted C ₃ to C ₆₀ cycloalkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryl group, Or an unsubstituted C ₆ to C ₆₀ aryl group or a substituted or unsubstituted C ₂ to C ₆₀ heteroaryl group.

According to an exemplary embodiment of the present specification, the "substituted or unsubstituted" of is deuterium, halogen, -SiRR'R ", -P (= O ) RR ', C 6 to C ₆₀ aryl group and C ₂ to C ₆₀ Or heteroaryl of the general formula (I).

Wherein R, R 'and R "are the same or different and each independently represents hydrogen, deuterium, deuterium, halogen, a C ₆ to C ₆₀ aryl group and a C ₂ to C ₆₀ heteroaryl group. Substituted or unsubstituted C ₁ to C ₆₀ alkyl, substituted or unsubstituted with at least one substituent selected from the group consisting of deuterium, halogen, C ₆ to C ₆₀ aryl and C ₂ to C ₆₀ heteroaryl, hwandoen C ₃ to C ₆₀ cycloalkyl group; deuterium, halogen, C ₆ to C ₆₀ aryl group and a C ₂ to C ₆₀ with at least one substituent selected from the heteroaryl group consisting of a substituted or unsubstituted C ₆ to an aryl group of C _60; or heavy hydrogen, halogen, C ₆ to C ₆₀ aryl group and a C ₂ to C substitution ₆₀ heteroaryl group one or more substituents selected from the group consisting of and unsubstituted C ₂ to heteroaryl of C ₆₀ Group-a.

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

In the present specification, the alkyl group includes a straight chain or a branched chain having 1 to 60 carbon atoms, and may be further substituted by another substituent. The alkyl group may have 1 to 60 carbon atoms, specifically 1 to 40 carbon atoms, more particularly 1 to 20 carbon atoms.

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

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

In the present specification, the cycloalkyl group includes monocyclic or polycyclic rings having 3 to 60 carbon atoms, and may be further substituted by other substituents. Here, the polycyclic ring means a group in which cycloalkyl is directly connected to another ring group or condensed. Here, the other ring group may be a cycloalkyl group, but may be another ring group such as a heterocycloalkyl group, an aryl group, a heteroaryl group and the like. The number of carbon atoms of the cycloalkyl group may be 3 to 60, specifically 3 to 40, more particularly 5 to 20.

In the present specification, the heterocycloalkyl group includes O, S, Se, N or Si as a hetero atom, and includes monocyclic or polycyclic rings having 2 to 60 carbon atoms, and may be further substituted by other substituents. Here, the polycyclic ring means a group in which the heterocycloalkyl group is directly connected to another ring group or condensed. Here, the other ring group may be a heterocycloalkyl group, but may be another ring group such as a cycloalkyl group, an aryl group, a heteroaryl group and the like. The number of carbon atoms 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 monocyclic or polycyclic rings having 6 to 60 carbon atoms, and may be further substituted by other substituents. Herein, a polycyclic ring means a group in which an aryl group is directly connected to another ring group or condensed with another ring group. Here, the other ring group may be an aryl group, but may be another kind of ring group such as a cycloalkyl group, a heterocycloalkyl group, a heteroaryl group and the like. The aryl group includes a spiro group. The carbon number of the aryl group may be 6 to 60, specifically 6 to 40, more specifically 6 to 25. Specific examples of the aryl group include phenyl, biphenyl, triphenyl, naphthyl, anthryl, klycenyl, phenanthrenyl, , A tetracenyl group, a pentacenyl group, a fluorenyl group, an indenyl group, an acenaphthylenyl group, a benzofluorenyl group, a spirobifluorenyl group and a 2,3-dihydro-1H-indenyl group, However, the present invention is not limited thereto.

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

In the present specification, the heteroaryl group includes S, O, Se, N or Si as a hetero atom, and includes monocyclic or polycyclic rings having 2 to 60 carbon atoms, and may be further substituted by other substituents. Herein, the term "polycyclic" means a group in which the heteroaryl group is directly connected to another ring group or condensed therewith. Here, the other ring group may be a heteroaryl group, but may be another ring group such as a cycloalkyl group, a heterocycloalkyl group, an aryl group and the like. The heteroaryl group may have 2 to 60 carbon atoms, specifically 2 to 40 carbon atoms, more particularly 3 to 25 carbon atoms. Specific examples of the heteroaryl group include pyridyl, pyrrolyl, pyrimidyl, pyridazinyl, furanyl, thiophenyl, imidazolyl, pyrazolyl, oxazolyl, isoxazolyl, thiazolyl , A thiazolyl group, a triazolyl group, a furazanyl group, an oxadiazolyl group, a thiadiazolyl group, a dithiazolyl group, a tetrazolyl group, a paranyl group, a thiopyranyl group, a diazinyl group, A thiazolyl group, a dioxinyl group, a triazinyl group, a tetrazinyl group, a quinolyl group, an isoquinolyl group, a quinazolinyl group, an isoquinazolinyl group, a quinolizolyl group, a naphthyridyl group, an acridinyl group, , An imidazopyridinyl group, a diazanaphthalenyl group, a triazinediyl group, an indolyl group, an indolizinyl group, a benzothiazolyl group, a benzoxazolyl group, a benzimidazolyl group, a benzothiophene group, A dibenzothiophene group, a dibenzofuran group, a carbazolyl group, a benzocarbazolyl group, A thienyl group, a thienyl group, a thienyl group, a thiophene group, a thienyl group, a thienyl group, a thienyl group, a thienyl group, Indole [2,3-b] carbazolyl group, indolinyl group, 10,11-dihydro-dibenzo [b, f] azepine group, 9,10-dihydroacrylidinyl group , A phenanthrazinyl group, a phenothiatriazinyl group, a phthalazinyl group, a naphthyridinyl group, a phenanthrolinyl group, a benzo [c] [1,2,5] thiadiazolyl group, a 5,10-dihydrodibenzo [b, e] [1,4] azacyclinyl group, pyrazolo [1,5-c] quinazolinyl group, pyrido [1,2- b] indazolyl group, pyrido [ Diazo [1,2-e] indolinyl group, 5,11-dihydroindeno [1,2-b] carbazolyl group, and condensed rings thereof, but are not limited thereto.

According to one embodiment of the present disclosure,

In Formula 1, at least one of R ₁ and R ₂ is - (L) _p - (Z) _q ,

L is a direct bond; A substituted or unsubstituted C ₆ to C ₆₀ arylene group; A substituted or unsubstituted C ₂ to C ₆₀ heteroarylene group; And -P (= O) R < ₁₇ > -,

p is an integer of 1 to 4,

q is an integer of 1 to 5,

Z is hydrogen; heavy hydrogen; halogen; A substituted or unsubstituted C ₆ to C ₆₀ aryl group; A substituted or unsubstituted C ₂ to C ₆₀ heteroaryl group; And -P (= O) R < ₁₈ > R < ₁₉ &

R ₁₇ to R ₁₉ are the same or different from each other, and each independently hydrogen; heavy hydrogen; A substituted or unsubstituted C ₁ to C ₆₀ alkyl group; A substituted or unsubstituted C ₃ to C ₆₀ cycloalkyl group; A substituted or unsubstituted C ₆ to C ₆₀ aryl group; Or a substituted or unsubstituted C ₂ to C ₆₀ heteroaryl group.

According to one embodiment of the present disclosure,

In Formula 1, at least one of R ₁ and R ₂ is - (L) _p - (Z) _q ,

L is a direct bond; Deuterium, halogen, -SiRR'R ", -P (= O ) RR ', C 6 to C ₆₀ aryl group and a C ₂ to C ₆₀ heteroaryl groups substituted with one or more substituents selected from the group consisting of unsubstituted or A C ₆ to C ₆₀ arylene group selected from the group consisting of deuterium, halogen, -SiRR'R ", -P (= O) RR ', C ₆ to C ₆₀ aryl and C ₂ to C ₆₀ heteroaryl groups A C ₂ to C ₆₀ heteroarylene group substituted or unsubstituted with at least one substituent selected from the group consisting of And -P (= O) R < ₁₇ > -,

p is an integer of 1 to 4,

q is an integer of 1 to 5,

Z is hydrogen; heavy hydrogen; halogen; Deuterium, halogen, -SiRR'R ", -P (= O ) RR ', C 6 to C ₆₀ aryl group and a C ₂ to C ₆₀ heteroaryl groups substituted with one or more substituents selected from the group consisting of unsubstituted or an aryl group of C ₆ to C _60; deuterium, halogen, -SiRR'R ", -P (= O ) RR ', C 6 to an aryl group and a C ₂ to C ₆₀ heteroaryl group consisting of a C ₆₀ A C ₂ to C ₆₀ heteroaryl group substituted or unsubstituted with at least one substituent selected; And -P (= O) R < ₁₈ > R < ₁₉ &

Wherein R, R ', R "and R ₁₇ to R ₁₉ are the same or different and are each independently selected from the group consisting of hydrogen, deuterium, deuterium, halogen, C ₆ to C ₆₀ aryl and C ₂ to C ₆₀ heteroaryl A C ₁ to C ₆₀ alkyl group which is unsubstituted or substituted with at least one substituent selected from the group consisting of a halogen atom, a C ₆ to C ₆₀ aryl group and a C ₂ to C ₆₀ heteroaryl group, A substituted or unsubstituted C ₃ to C ₆₀ cycloalkyl group substituted with at least one substituent selected from the group consisting of deuterium, halogen, C ₆ to C ₆₀ aryl and C ₂ to C ₆₀ heteroaryl, An unsubstituted C ₆ to C ₆₀ aryl group or a substituted or unsubstituted C ₆ to C ₆₀ aryl group which is substituted with at least one substituent selected from the group consisting of deuterium, halogen, C ₆ to C ₆₀ aryl group and C ₂ to C ₆₀ heteroaryl group ₂ my For C ₆₀ heteroaryl group.

According to another embodiment of the present disclosure,

In Formula 1, R ₁ and R ₂ are - (L) _p - (Z) _q ,

L, Z, p and q are the same as described above.

According to another embodiment of the present disclosure,

L is a direct bond; A substituted or unsubstituted C ₆ to C ₆₀ aryl group, and a substituted or unsubstituted C ₂ to C ₆₀ heteroaryl group, each of which is optionally substituted with one or more substituents selected from the group consisting of halogen, halogen, -SiRR'R ", -P (= O) RR ' substituents of the arylene group, a substituted or unsubstituted C ₆ to C ₆₀ of at least; or deuterium, halogen, -SiRR'R ", -P (= O ) RR ', a substituted or unsubstituted C ₆ to C ₆₀ aryl A C ₂ to C ₆₀ heteroarylene group which is substituted or unsubstituted with at least one substituent selected from substituted or unsubstituted C ₂ to C ₆₀ heteroaryl groups; And -P (= O) R < ₁₇ > -,

R, R ', R "and R < ₁₇ > are as described above in the description.

According to another embodiment of the present disclosure,

L is a direct bond; A substituted or unsubstituted C ₆ to C ₆₀ arylene group; A substituted or unsubstituted C ₂ to C ₆₀ heteroarylene group; And -P (= O) R < ₁₇ > -,

The R < ₁₇ > is the same as described hereinabove.

According to another embodiment of the present application,

L is a direct bond; A substituted or unsubstituted phenylene group; A substituted or unsubstituted biphenylene group; A substituted or unsubstituted terphenylene group; A substituted or unsubstituted naphthylene group; A substituted or unsubstituted anthrylene group; A substituted or unsubstituted phenanthrenylene group; A substituted or unsubstituted triphenylene group; A substituted or unsubstituted spirobifluorenylene group; A substituted or unsubstituted pyridyl group; A substituted or unsubstituted pyrimidylene group; A substituted or unsubstituted thiazylene group; A substituted or unsubstituted quinolylene group; A substituted or unsubstituted quinazolinylene group; A substituted or unsubstituted benzothiazolyl group; A substituted or unsubstituted benzoxazolylene group; A substituted or unsubstituted benzimidazolylene group; A substituted or unsubstituted divalent dibenzothiophene group; A substituted or unsubstituted divalent dipheno furan group; A substituted or unsubstituted carbazolylene group; A substituted or unsubstituted indolo [2, 3-a] carbazolylene group; A substituted or unsubstituted naphthylidene group; A substituted or unsubstituted oxadiazolylene group; A substituted or unsubstituted 5,11-dihydroindeno [1,2-b] carbazolylene group; And -P (= O) R < ₁₇ > -,

If the the L-substituted, the substituent is deuterium, halogen, -SiRR'R ", -P (= O ) RR ', substituted or unsubstituted C ₆ to C ₆₀ aryl group and a substituted or unsubstituted C ₂ to the is selected from the group consisting of C ₆₀ heteroaryl is selected from one or more substituents,

R, R ', R "and R < ₁₇ > are the same as described above in this specification.

According to another embodiment of the present disclosure,

L is a direct bond; A phenylene group; Biphenylene group; A terphenylene group; Naphthylene group; Anthrylene group; Phenanthrenylene group; Triphenylenylene group; A spirobifluorenylene group; A pyridyl group; A pyrimidylene group; Triazinylene group; A quinolylene group; A quinazolinylene group; A benzothiazolyl group; Benzoxazolylene group; Benzimidazolylene group; A divalent dibenzothiophene group; A divalent dipheno furan group; A carbazolylene group; Indolo [2,3-a] carbazolylene group; Naphthylidene group; Oxadiazolylene group; 5, 11-dihydroindeno [1,2-b] carbazolylene group; And -P (= O) R < ₁₇ > -,

The R < ₁₇ > is the same as described hereinabove.

According to another embodiment of the present disclosure,

Z is hydrogen; heavy hydrogen; halogen; A substituted or unsubstituted C ₆ to C ₆₀ aryl group, and a substituted or unsubstituted C ₂ to C ₆₀ heteroaryl group, each of which is optionally substituted with one or more substituents selected from the group consisting of halogen, halogen, -SiRR'R ", -P (= O) RR ' an aryl group, a substituted or unsubstituted C ₆ to C ₆₀ ring by one or more substituents; or deuterium, halogen, -SiRR'R ", -P (= O ) RR ', a substituted or unsubstituted C ₆ to C ₆₀ aryl A C ₂ to C ₆₀ heteroaryl group substituted or unsubstituted with at least one substituent selected from substituted or unsubstituted C ₂ to C ₆₀ heteroaryl groups; And -P (= O) R < ₁₈ > R < ₁₉ &

R, R ', R ", R ₁₈ and R ₁₉ are the same as described above in the specification.

According to another embodiment of the present disclosure,

Z is hydrogen; heavy hydrogen; halogen; A substituted or unsubstituted C ₆ to C ₆₀ aryl group; A substituted or unsubstituted C ₂ to C ₆₀ heteroaryl group; And -P (= O) R < ₁₈ > R < ₁₉ &

R ₁₈ and R ₁₉ are the same as described above in this specification.

According to another embodiment of the present disclosure,

Z is hydrogen; heavy hydrogen; halogen; A substituted or unsubstituted phenyl group; A substituted or unsubstituted biphenyl group; A substituted or unsubstituted terphenyl group; A substituted or unsubstituted naphthyl group; A substituted or unsubstituted anthryl group; A substituted or unsubstituted phenanthrenyl group; A substituted or unsubstituted triphenyl group; A substituted or unsubstituted spirobifluorenyl group; A substituted or unsubstituted pyridyl group; A substituted or unsubstituted pyrimidyl; A substituted or unsubstituted thiazinyl group; A substituted or unsubstituted quinolyl group; A substituted or unsubstituted quinazolinyl group; A substituted or unsubstituted benzothiazolyl group; A substituted or unsubstituted benzoxazolyl group; A substituted or unsubstituted benzimidazolyl group; A substituted or unsubstituted dibenzothiophene group; A substituted or unsubstituted dibenzofuran group; A substituted or unsubstituted carbazolyl group; A substituted or unsubstituted indolo [2, 3-a] carbazolyl group; A substituted or unsubstituted naphthyridyl group; A substituted or unsubstituted oxadiazolyl group; A substituted or unsubstituted 5,11-dihydroindeno [1,2-b] carbazolyl group; And -P (= O) R < ₁₈ > R < ₁₉ &

Case in which the Z-substituted, the substituent is deuterium, halogen, -SiRR'R ", -P (= O ) RR ', substituted or unsubstituted C ₆ to C ₆₀ aryl group and a substituted or unsubstituted C ₂ to the is selected from the group consisting of C ₆₀ heteroaryl is selected from one or more substituents,

R, R ', R ", R ₁₈ and R ₁₉ are the same as described above in this specification.

According to another embodiment of the present disclosure,

Z is hydrogen; heavy hydrogen; halogen; A phenyl group; Biphenyl group; A terphenyl group; A substituted or unsubstituted naphthyl group; Anthryl group; A phenanthrenyl group; A triphenyl group; A spirobifluorenyl group; A pyridyl group; Pyrimidyl; Triazinyl groups; Quinolyl group; A quinazolinyl group; Benzothiazolyl group; Benzoxazolyl group; A benzimidazolyl group; A dibenzothiophene group; A dibenzofuran group; A carbazolyl group; Indolo [2, 3-a] carbazolyl group; Naphthylidyl group; An oxadiazolyl group; 5,11-dihydroindeno [1,2-b] carbazolyl group; And -P (= O) R < ₁₈ > R < ₁₉ &

R ₁₈ and R ₁₉ are the same as described above in this specification.

According to another embodiment of the present disclosure, Z is a substituted or unsubstituted C ₂ to C ₆₀ heteroaryl group,

The heteroaryl group includes at least any one selected from N, O and S as a hetero atom.

이고, 상기 X1 및 X2는 치환 또는 비치환된 C₆ 내지 C₆₀의 단환 또는 다환의 방향족 탄화수소 고리; 또는 치환 또는 비치환된 C₂ 내지 C₆₀의 단환 또는 다환의 방향족 헤테로 고리를 포함한다.According to another embodiment of the present disclosure, Z is

X 1 and X 2 are substituted or unsubstituted C ₆ to C ₆₀ monocyclic or polycyclic aromatic hydrocarbon rings; Or a substituted or unsubstituted C ₂ to C ₆₀ monocyclic or polycyclic aromatic heterocyclic ring.

는 하기 구조식들 중 어느 하나로 표시된다.According to another embodiment of the present disclosure,

Is represented by any one of the following structural formulas.

,

,

,

,

In the above structural formulas, Y ₁ to Y ₄ are the same or different and each independently is S, NY or CYY '

Y and Y 'are the same or different from each other, and each independently hydrogen; A substituted or unsubstituted C ₁ to C ₆₀ alkyl group; Or a substituted or unsubstituted C ₆ to C ₆₀ aryl group.

According to another embodiment of the present disclosure,

Y and Y 'are the same or different from each other, and each independently hydrogen; Methyl group; Or a phenyl group.

According to one embodiment of the present invention, Formula 1 is represented by Formula 2 or 3:

(2)

(3)

In the general formulas (2) and (3), the definitions of R ₁ to R ₁₂ are the same as those defined in the general formula (1)

R ₁₃ and R ₁₄ are the same or different and each independently hydrogen; Or deuterium,

m and n are each an integer of 1 to 4,

If more than the above m is 2, R ₁₄ is the same as or different from each other,

When n is 2 or more, R ₁₃ are the same or different from each other.

According to one embodiment of the present invention, the heterocyclic compound represented by Formula 1 may be selected from the following compounds.

According to one embodiment of the present invention, the above-mentioned compounds can be produced based on the preparation examples described later. Exemplary examples are described below in the preparation examples, but substituents can be added or removed as needed, and the position of the substituent can be changed. In addition, based on techniques known in the art, starting materials, reactants, reaction conditions, and the like can be changed. The type or position of the substituent at the remaining positions may be changed as required by those skilled in the art using techniques known in the art.

Hereinafter, the present application will be described in more detail by way of examples, but these are for the purpose of illustration only and are not intended to limit the scope of the present specification.

For example, the heterocyclic compound represented by Formula 1 may have a core structure as shown in Formula 1 below.

Substituent groups may be attached by methods known in the art, and the substituent position or number of substituent groups may be varied according to techniques known in the art.

[Formula 1]

In Formula 1, E is the same as R ₁ and R ₂ defined in Formula 1, and L is a substituted or unsubstituted phenyl group. The general formula (1) is an example of a reaction for bonding a substituent to the R ₁ and R ₂ positions in the core structure represented by the above formula (1).

Another embodiment of the present invention provides an organic light emitting device comprising a heterocyclic compound represented by Formula 1 described above.

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

FIGS. 1 to 3 illustrate the stacking process of the electrodes and organic layers of the organic light emitting diode according to the embodiments of the present application. However, it is not intended that the scope of the present application be limited by these drawings, and the structure of the organic light emitting device known in the art can be applied to the present application.

1, an organic light emitting device in which an anode 200, an organic layer 300, and a cathode 400 are sequentially stacked on a substrate 100 is shown. However, the present invention is not limited to such a structure, and 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 as shown in FIG.

FIG. 3 illustrates the case where the organic material layer is a multilayer. 3 includes a hole injection layer 301, a hole transport layer 302, a light emitting layer 303, a hole blocking layer 304, an electron transport layer 305, and an electron injection layer 306. However, the scope of the present application is not limited by such a laminated structure, and if necessary, the remaining layers except the light emitting layer may be omitted, and other necessary functional layers may be further added.

The organic light emitting device according to the present invention can be manufactured by materials and methods known in the art, except that at least one of the organic material layers contains the heterocyclic compound represented by the formula (1).

The heterocyclic compound represented by the formula (1) 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 represented by Formula 1 may be used as an electron transport layer, a hole blocking layer, a material for a light emitting layer, and the like in an organic light emitting device. As one example, the heterocyclic compound represented by the above formula (1) can be used as a material for an electron transport layer of an organic light emitting device.

Since the heterocyclic compound represented by the above formula (1) contains two N (nitrogen) atoms capable of attracting electrons, electron transfer is easy.

The heterocyclic compound represented by the formula (1) has a high planarity and has a structural form capable of being laminated between molecules when fabricating an organic light emitting device, so that the cell mobility is high.

In the organic light emitting device according to the present invention, materials other than the heterocyclic compound represented by the formula (1) are illustrated below, but these are for illustrative purposes only and are not intended to limit the scope of the present application. ≪ / RTI >

As the cathode material, materials having a relatively large work function can be used, and a transparent conductive oxide, a metal, or a conductive polymer can be used.

As the cathode material, materials having relatively low work functions can be used, and metals, metal oxides, conductive polymers, and the like can be used.

As the hole injecting material, a known hole injecting material may be used. For example, a phthalocyanine compound such as copper phthalocyanine disclosed in U.S. Patent No. 4,356,429 or a compound described in Advanced Material, 6, p. 677 (1994) Star burst type amine derivatives such as tris (4-carbamoyl-9-phenyl) amine (TCTA), 4,4 ', 4 "-tri [phenyl (m- tolyl) amino] triphenylamine MTDAPA), polyaniline / dodecylbenzenesulfonic acid (poly (vinylidene fluoride)) or poly (vinylidene fluoride), which is a soluble conductive polymer, such as 1,3,5-tris [4- (3,4-ethylenedioxythiophene) / poly (4-styrenesulfonate), polyaniline / camphor sulfonic acid or polyaniline / Poly (4-styrene-sulfonate) and the like can be used.

As the hole transporting material, a pyrazoline derivative, an arylamine derivative, a stilbene derivative, a triphenyldiamine derivative, or the like may be used, and a low molecular weight or a high molecular weight material 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, tetracyanoanthraquinodimethane and derivatives thereof, Derivatives thereof, diphenyldicyanoethylene and derivatives thereof, diphenoquinone derivatives, metal complexes of 8-hydroxyquinoline and derivatives thereof, and the like may be used as well as low molecular weight materials and high molecular weight materials.

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

As the light emitting material, red, green or blue light emitting materials may be used, and if necessary, two or more light emitting materials may be mixed and used. Further, a fluorescent material may be used as a light emitting material, but it may be used as a phosphorescent material. As the light emitting material, a material which emits light by coupling holes and electrons respectively injected from the anode and the cathode may be used. However, materials in which both the host material and the dopant material participate in light emission may also be used.

Hereinafter, the present invention will be described in more detail by way of examples, but these are for the purpose of illustrating the present specification and are not intended to limit the scope of the present specification.

< Manufacturing example  1> Preparation of compound 1

Preparation of Compound 1-1

1,5-dichloro-2,4-dinitrobenzene (60 g, 253 mmol), phenylboronic acid (67.7 g, 556 mmol) _{, Pd (PPh 3) 4 (} 29.2g, 25.3 mmol), K 2 CO 3 (39g, 1012 mmol), tetrahydrofuran (tetrahydrofuran) (600ml) / ethanol (ethanol) (120ml) / water (H ₂ O) (50 ml) was refluxed at 110 &lt; 0 &gt; C for 24 hours. The mixture was extracted with ethyl acetate and the organic layer was dried over MgSO ₄ . After concentration, the mixture was separated by column chromatography (SiO ₂ , hexane: dichloromethane = 3: 1), precipitated with hexane / dichloromethane and dissolved in ethyl acetate / re-crystallization with hexane (hexane) to obtain the compound 1-1. (40 g, 50%).

Preparation of Compound 1-2

(33.1 g, 593 mmol) was added to a mixture of Compound 1-1 (38 g, 118 mmol) and ethanol (1000 ml) under nitrogen, followed by stirring for 10 minutes. Acetic acid (228 ml) was added thereto, and the mixture was refluxed at 80 ° C for 24 hours. After neutralization with NaHCO ₃ at 0 ° C, the extracted organic layer was dried over MgSO ₄ with ethyl acetate. After concentration was purified by column chromatography (column chromatography) (SiO _2, hexane: dichloromethane (Hexane: Dichloromethane) = 3: 1) to give a yellow solid separated as a compound 1-2. (29 g, 94%).

Preparation of compounds 1-3

Triethyl amine (20 ml, 161 mmol) was added to a mixture of Compound 1-2 (7 g, 26.88 mmol) and tetrahydrofuran (200 ml) under nitrogen, followed by stirring for 10 minutes. A mixture of benzoyl chloride (7.5 ml, 64.53 mmol) in tetrahydrofuran (40 ml) was added and stirred for 3 h. The reaction was filtered and washed with tetrahydrofuran. The white solid compound was added to tetrahydrofuran / water (H ₂ O) and refluxed for 1 hour. After filtration, the reaction mixture was washed with water (H ₂ O), methanol (methanol) and hexane (Hexane) to obtain white solid compound 1-3 . (10.67 g, 84%)

Preparation of Compound (1)

POCl ₃ (0.789 ml, 8.4 mmol) was added to a mixture of Compound 1-3 (9.8 g, 21 mmol) and Nitrobenzene (100 ml) under nitrogen charging and the mixture was stirred at 150 ° C for 1 hour. SnCl 4 (5.87 ml, 63 mmol) was added thereto, followed by stirring at 150 ° C for 2 hours. The reaction mixture was cooled, dichloromethane / H ₂ O was added, and the mixture was stirred for 1 hour. The mixture was filtered and washed with H ₂ O, cold dichloromethane, methanol, and hexane to obtain a brown compound 1 . (8 g, 88%).

< Manufacturing example  2> Preparation of Compound 22

Preparation of Compound 22-1

Triethyl amine (20 ml, 161 mmol) was added to a mixture of Compound 1-2 (7 g, 26.88 mmol) and tetrahydrofuran (200 ml) under nitrogen, followed by stirring for 10 minutes. A mixture of 4-bromo Benzoyl chloride (14.1 g, 64.53 mmol) in tetrahydrofuran (40 ml) was added thereto, followed by stirring for 3 hours. The reaction was filtered and washed with tetrahydrofuran. The white solid compound was added to tetrahydrofuran / water (H ₂ O) and refluxed for 1 hour. Filtered, washed with water (H ₂ O), methanol (methanol), and hexane (Hexane) to obtain a white solid compound 22-1 . (13.2 g, 92%).

Preparation of Compound 22-2

POCl ₃ (0.788 ml, 8.4 mmol) was added to a mixture of Compound 22-1 (13.2 g, 21 mmol) and Nitrobenzene (120 ml) under nitrogen charging, followed by stirring at 150 ° C for 1 hour. SnCl ₄ (7.3 ml, 63 mmol) was added thereto, followed by stirring at 150 ° C for 12 hours. The reaction mixture was cooled, dichloromethane / H ₂ O was added, and the mixture was stirred for 1 hour. The mixture was filtered H ₂ O, cold dichloromethane (Dichloromethane), methanol (Methanol), washed with hexane to give (Hexane) to obtain the compound 22-2. (6.5 g, 64%)

Preparation of Compound 22

Compound 22-2 (7 g, 11.85 mmol) was dissolved in anhydrous tetrahydrofuran (100 ml) under nitrogen and then cooled to -78 ° C. n-butyllithium (2.5 M in hexane) (11.37 ml, 28.44 mmol) was slowly added dropwise thereto, followed by stirring for 1 hour. Chlorodiphenylphosphine (5.2 ml, 28.44 mmol) was added dropwise to the solution, and the mixture was stirred at room temperature for 12 hours. The reaction mixture was extracted with dichloromethane / H ₂ O and then distilled under reduced pressure. The reaction mixture was dissolved in dichloromethane (200 ml) and stirred with 30% aqueous H ₂ O ₂ (7 ml) at room temperature for 1 hour. The reaction mixture was extracted with dichloromethane / H ₂ O and the concentrated mixture was separated by column chromatography (SiO ₂ , Dichloromethane: Methanol = 40: 1) Compound 22 was obtained. (8.2 g, 64%).

< Manufacturing example  3> Preparation of Compound 37

Preparation of Compound A-1

(9,9-dimethyl-9H-fluoren-2-yl) boronic acid (25.9 g, 0.108 mol), 1- bromo -2 nitro benzene (1-bromo-2-nitrobenzene ) (20g, 0.099mol), Pd (PPh 3) 4 (5.7g, 4.95mmol), K 2 CO 3 (27.3 g, 0.198 mol) and tetrahydrofuran (250 ml) / H ₂ O (50 ml) was refluxed for 24 hours. After the water layer was removed, the organic layer was dried with MgSO ₄ . Concentrated and then subjected to column chromatography (SiO ₂ , hexane: dichloromethane = 2: 1) to obtain yellow solid compound A-1 . (21 g, 61%).

Preparation of Compound A-2

Compound A-1 (20 g, 0.0634 mmol), PPh ₃ (49.8 g, 0.190 mol) in o -dichlorobenzene ( o- DCB) (300 ml) was refluxed for 18 hours. The o -dichlorobenzene ( o- DCB) was removed by vacuum distillation and then separated by column chromatography (SiO ₂ , Hexane: Dichloromethane = 3: 1) Compound A- 2 was obtained. (6.6 g, 36%).

Preparation of Compound 37

A nitrogen compound 22-2 (14g, 15.72 mmol), compound A-2 (8.9g, 31.44 mmol ), Cu (2g, 31.44 mol) 18- crown-6-ether (18-crown-6-ether ) (1g , 3.14 mmol) and o -dichlorobenzene ( o- DCB) (200 ml) of K ₂ CO ₃ (8.86 g, 62.88 mmol) was refluxed for 12 hours. The o -dichlorobenzene ( o- DCB) was removed by vacuum distillation and then separated by column chromatography (SiO ₂ , Hexane: Dichloromethane = 1: 5) 37 was obtained. (11 g, 70%).

< Manufacturing example  4> Preparation of Compound 39

Preparation of Compound B-1

To a mixture of 1,2-Dicyclohexanone (30.0 g, 0.374 mol) and phenylhydrazine hydrochloride (77.37 g, 0.749 mol) in ethanol (1000 ml) under nitrogen was added Sulfuric acid (1.4 mL, 0.0374 mol) was slowly added dropwise, followed by stirring at 60 ° C for 4 hours. The solution cooled to room temperature was filtered to give a tan solid. (69 g, 93%).

Trifluoroacetic acid (46.5 mL, 0.6 mol) was added to a mixture of the above solid (68.9 g, 0.25 mol) and acetic acid (700 mL) and the mixture was stirred at 100 ° C for 15 hours. The solution cooled to room temperature was washed with acetic acid and hexane and filtered to obtain an ivory solid compound B-1 . (27.3 g, 42%).

Preparation of compound B-2

A nitrogen compound B- 1 (2.1g, 0.0082mol), iodo-benzene (Iodobenzene) (2.5g, 0.013mol) , Cu (0.312g, 0.0049), 18- crown-6-ether (18-crown-6- A mixture of o -dichlorobenzene ( o- DCB) (20 ml) and K ₂ CO ₃ (3.397 g, 0.0246 mol) was stirred at reflux for 16 hours. The solution cooled to room temperature was extracted with dichloromethane / H ₂ O, concentrated and separated by column chromatography (SiO ₂ , hexane: ethyl acetate = 10: 1) To obtain a solid compound B-2 . (1.76 g, 64%)

Preparation of Compound 39

A nitrogen compound 22-2 (14g, 15.72 mmol), compound B-2 (10.45g, 31.44 mmol ), Cu (2g, 31.44 mol) 18- crown-6-ether (18-crown-6-ether ) (1g , 3.14 mmol) and o -dichlorobenzene ( o- DCB) (200 ml) of K ₂ CO ₃ (8.86 g, 62.88 mmol) was refluxed for 12 hours. The o -dichlorobenzene ( o- DCB) was removed by vacuum distillation and then separated by column chromatography (SiO ₂ , Dichloromethane) to obtain a solid compound 39 . (10.2 g, 59%).

< Manufacturing example  5> Preparation of Compound 93

Preparation of Compound C-1

Naphthalen-2-ylboronic acid (10 g, 58.1 mmol), 6-bromonaphthalen-2-ol (10.8 g, 48.4 mmol) _{, K 2 CO 3 (16g,} 116.2 mmol) Pd (PPh 3) 4 (1.12g, 2mol%) in tetrahydrofuran (tetrahydrofuran) / water _{(H 2 O) (100ml /} 100ml) stirring the mixed solution was refluxed for 5 hours in the Respectively. The temperature was lowered to room temperature, and the water layer was removed and dried with MgSO ₄ . The concentrate was precipitated with hexane / dichloromethane and then hot filtered with hexane to obtain filtered compound C-1 . (8.5 g, 65%).

Preparation of Compound C-2

Compound C-1 (7.2 g, 26.7 mmol) was dissolved in dichloromethane under nitrogen, triethylamine (7.47 ml, 53.6 mmol) was added dropwise and the mixture was stirred for 10 minutes. (CF ₃ SO ₂ ) ₂ O (6.76 ml, 40.2 mmol) was added slowly at 0 ° C, and the mixture was stirred at room temperature for 1 hour. After completion of the reaction with saturated NaHCO ₃ solution, the water layer was removed and dried with MgSO ₄ . The concentrate was recrystallized with hexane to obtain Compound C-2 . (8.69 g, 81%).

Preparation of Compound 93-1

1,5-dichloro-2,4-dinitrobenzene (60 g, 253 mmol), naphthalen-1-yl boronic acid acid) (95.62g, 556 mmol) , Pd (PPh 3) 4 (29.2g, 25.3 mmol), K 2 CO 3 A mixture of tetrahydrofuran (600 ml) / ethanol (120 ml) / H ₂ O (50 ml) was refluxed at 110 ° C for 24 hours. The mixture was extracted with ethyl acetate and the organic layer was dried over MgSO ₄ . After concentration was purified by column chromatography (column chromatography) (SiO _2, hexane: dichloromethane (Hexane: Dichloromethane) = 3: 1) to obtain the compound 93-1 as a separation. (72.4 g, 68%).

Preparation of Compound 93-2

Under nitrogen, compound 93-1 (40 g, 95.1 mmol), ethanol (Ethanol) (1000 ml) was added Fe (26.55 g, 475 mmol), followed by stirring for 10 minutes. Acetic acid (230 ml) was added thereto, and the mixture was refluxed at 80 ° C for 24 hours. After neutralization with NaHCO ₃ at 0 ° C, the extracted organic layer was dried over MgSO ₄ with ethyl acetate. After concentration was purified by column chromatography (column chromatography) (SiO _2, hexane: dichloromethane (Hexane: Dichloromethane) = 3: 1) to give a yellow solid separated as compound 93-2. (29 g, 94%).

Preparation of compound 93-3

Triethyl amine (23 ml, 166.4 mmol) was added to a mixture of compound 93-2 (10 g, 27.74 mmol) and tetrahydrofuran (200 ml) under nitrogen, followed by stirring for 10 minutes. A mixture of 3-bromo Benzoyl chloride (14.6 g, 66.57 mmol) in tetrahydrofuran (40 ml) was added thereto, followed by stirring for 3 hours. The reaction was filtered and washed with tetrahydrofuran. The white solid compound was added to tetrahydrofuran / water (H ₂ O) and refluxed for 1 hour. After filtration, the reaction mixture was washed with H ₂ O, methanol and hexane to obtain a white solid compound 93-3 . (18.2 g, 90%).

Preparation of compound 93-4

POCl ₃ (0.565 ml, 6.05 mmol) was added to a mixture of compound 93-3 (11 g, 15.14 mmol) and Nitrobenzene (100 ml) under nitrogen charging, followed by stirring at 150 ° C for 1 hour. SnCl ₄ (5.3 ml, 45.4 mmol) was added thereto, followed by stirring at 150 ° C for 12 hours. The reaction mixture was cooled, dichloromethane / H ₂ O was added, and the mixture was stirred for 1 hour. The mixture was filtered to obtain the compound 93-4. (6.5 g, 62%).

Preparation of Compound (93)

A nitrogen compound 93-4 (6.5g, 9.41 mmol), compound C-2 (7.57g, 18.82 mmol ), K 2 CO 3 (5.2g, 37.64 mmol), Pd (PPh 3) 4 (1g, 0.94 mmol) (150 ml / 30 ml) of tetrahydrofuran / water (H ₂ O) was refluxed for 6 hours. The hot reactant was hot-filtered and washed with hot 1,4-dioxane, H ₂ O, methanol and then dried to obtain Compound 93 . (8.2 g, 84%)

< Manufacturing example  6> Preparation of Compound 105

Preparation of Compound 105-1

1,5-dichloro-2,4-dinitrobenzene (30 g, 126.58 mmol), naphthalen-2-ylboronic acid (47.89g, 278.4 mmol), Pd (PPh 3) 4 (14.5g, 12.6 mmol), K 2 CO 3 A mixture of tetrahydrofuran (300 ml) / ethanol (70 ml) / H ₂ O (70 ml) was refluxed at 110 ° C for 24 hours. The mixture was extracted with ethyl acetate acetate) and the organic layer was dried over MgSO ₄ . After concentration was purified by column chromatography (column chromatography) (SiO _2, hexane: dichloromethane (Hexane: Dichloromethane) = 3: 1) to obtain the title compound separated as 105-1. (32 g, 60%).

Preparation of Compound 105-2

Under nitrogen, compound 105-1 (15 g, 35.67 mmol), ethanol (Ethanol) (300 ml) was added Fe (9.93 g, 178 mmol), followed by stirring for 10 minutes. Acetic acid (100 ml) was added thereto, and the mixture was refluxed at 80 ° C for 12 hours. After neutralization with NaHCO ₃ at 0 ° C, the extracted organic layer was dried over MgSO ₄ with ethyl acetate. After concentration was purified by column chromatography (column chromatography) (SiO _2, hexane: dichloromethane (Hexane: Dichloromethane) = 4: 1) to give a yellow solid separated as a compound 105-2. (10 g, 77%)

Preparation of Compound 105-3

Triethyl amine (23 ml, 166 mmol) was added to a mixture of compound 105-2 (10 g, 27.77 mmol) and tetrahydrofuran (200 ml) under nitrogen, followed by stirring for 10 minutes. A mixture of 2-naphthoyl chloride (12.7 g, 66.6 mmol) in tetrahydrofuran (40 ml) was added and stirred for 3 hours. The reaction was filtered and washed with tetrahydrofuran. The white solid compound was added to tetrahydrofuran / water (H ₂ O) and refluxed for 1 hour. Filtered, washed with H ₂ O, methanol and hexane to obtain a white solid compound 105-3 . (17 g, 91%).

Preparation of Compound 105

POCl ₃ (0.950 ml, 10.16 mmol) was added to a mixture of compound 105-3 (17 g, 25.41 mmol) and Nitrobenzene (150 ml) under nitrogen charging and the mixture was stirred at 150 ° C for 1 hour. SnCl ₄ (8.9 ml, 76.2 mmol) was added thereto, followed by stirring at 150 ° C for 2 hours. The reaction mixture was cooled, dichloromethane / H ₂ O was added, and the mixture was stirred for 1 hour. The mixture was filtered and washed with H ₂ O, cold dichloromethane, methanol, and hexane to obtain yellow light 105. (10.2 g, 62%).

< Manufacturing example  7> Preparation of Compound 31

To a one neck round bottom flask (One neck rbf) was added compound 22-2 (10 g, 16.9 mmol), 1-phenyl-2- (4- (4,4,5,5,5- tetramethyl- 2-yl) phenyl) -1H-benzo [d] imidazole was prepared by the same procedure as described for the synthesis of 4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan- yl) phenyl) -1H-benzo [ d] imidazole, 14g, 16.67mmol), Pd (PPh 3) 4 (1.9 g, 1.69 mmol) and K ₂ CO ₃ (9.3 g, 67.6 mmol) in 1,4-dioxane (400 ml) / H ₂ O (100 ml) was stirred at 110 ° C for 5 h. After extracting the reaction with MC by concentration was purified by column chromatography _{(column chromatography, SiO 2, MeOH} : Dichloromethane = 1: 20) and separated by gave Compound 31 (10.2g, 62%).

< Manufacturing example  8> Preparation of Compound 32

Dibenzo [b, d] furan-2-ylboronic acid was used instead of 2-chloro-4,6-diphenylpyridine pyrimidine) was used in place of the compound 31 to obtain the desired compound 32 (11.1 g, 73%).

< Manufacturing example  9> Preparation of Compound 43

Compound 9H-carbazole was used instead of 11,11-dimethyl-5,11-dihydroindeno [l, 2-b] carbazole (11,11-dimethyl-5,11- dihydroindeno [ (9H-carbazole), the target compound 43 was obtained (8.6 g, 67%) in the same manner as in the preparation of the compound 37 in Preparation Example 3.

< Manufacturing example  10> Preparation of Compound 45

Preparation of Compound 45-1

Triethylamine (20 ml, 161 mmol) was added to a mixture of Compound 1-2 (7 g, 26.88 mmol) and tetrahydrofuran (200 ml) under nitrogen, followed by stirring for 10 minutes. A mixture of 3-bromo Benzoyl chloride (14.1 g, 64.53 mmol) in tetrahydrofuran (40 ml) was added thereto, followed by stirring for 3 hours. The reaction was filtered and washed with tetrahydrofuran. The white solid compound was added to tetrahydrofuran / water (H ₂ O) and refluxed for 1 hour. After filtration, the reaction mixture was washed with water (H ₂ O), methanol (methanol), and hexane (Hexane) to obtain a white solid compound 45-1 (10.4 g, 72%).

Preparation of Compound 45-2

POCl ₃ (0.788 ml, 8.4 mmol) was added to a mixture of compound 45-1 (13.2 g, 21 mmol) and Nitrobenzene (120 ml) under nitrogen charging and the mixture was stirred at 150 ° C for 1 hour. SnCl ₄ (7.3 ml, 63 mmol) was added thereto, followed by stirring at 150 ° C for 12 hours. The reaction mixture was cooled, dichloromethane / H ₂ O was added, and the mixture was stirred for 1 hour. The mixture was filtered H ₂ O, cold dichloromethane (Dichloromethane), washed with methanol to give (Methanol), hexane (Hexane) to give the compound 45- 2 (7.3g, 71%) .

Preparation of Compound 45

Phenyl) -1H-benzo [d] imidazole (prepared according to the procedure of 1 phenyl-1H-benzo [d] imidazole) instead of Compound 22-2, Compound Naphthalene (Compound No. 22-2) 1-ylboronic acid, compound 45-2 was used in place of the compound 45-2 to obtain the desired compound 45 (7.3 g, 63%) in the same manner as in the preparation of the compound 31 in Preparation Example 7, except that naphthalen- %).

< Manufacturing example  11> Preparation of Compound 52

(12.7 g, 77%) was prepared in the same manner as in the preparation of Compound 31 in Production Example 7, except that Compound 45-2 was used instead of Compound 22-2.

< Manufacturing example  12> Preparation of Compound 61

Was prepared in the same manner as in the preparation of Compound 1 in Production Example 1 except that the compound naphthalen-1-ylboronic acid was used in place of phenylboronic acid to obtain the desired Compound 61 (7.4 g, 65%).

< Manufacturing example  13> Preparation of Compound 75

3-bromobenzoyl chloride, 4-bromobenzoyl chloride, dibenzo [b, d] thiophene-4-ylboronic acid (dibenzo [b, ] thiophen-4-ylboronic acid was used in place of the compound obtained in Preparation Example 5, the target compound 75 was obtained (8.3 g, 63%).

< Manufacturing example  14> Preparation of Compound 76

3-bromobenzoyl chloride, 4-bromobenzoyl chloride instead of C-2, 1-phenyl-2- (4- (4,4,5,5,5-tetra Methyl-1,3,2-dioxaborolan-2-yl) phenyl) -1H-benzo [d] imidazole (1-phenyl- 2- (4- (4,4,5,5- 1,3,2-dioxaborolan-2-yl) phenyl) -1H-benzo [d] imidazole) was used in place of the compound (11.3 g, 72%).

< Manufacturing example  15> Preparation of Compound 95

Except that the compound dibenzo [b, d] thiophen-4-ylboronic acid (dibenzo [b, d] The target compound 95 was obtained (11.3 g, 72%).

< Manufacturing example  16> Preparation of Compound 123

Preparation of Compound 123-1

Triethylamine (23 ml, 166.4 mmol) was added to a mixture of compound 105-2 (10 g, 27.74 mmol) and tetrahydrofuran (200 ml) under nitrogen, followed by stirring for 10 minutes. A mixture of 3-bromo Benzoyl chloride (14.6 g, 66.57 mmol) in tetrahydrofuran (40 ml) was added thereto, followed by stirring for 3 hours. The reaction was filtered and washed with tetrahydrofuran. The white solid compound was added to tetrahydrofuran / water (H ₂ O) and refluxed for 1 hour. After filtration, it was washed with H ₂ O, methanol and hexane to obtain a white solid compound 123-1 (16.3 g, 80%).

Preparation of Compound 123-2

POCl ₃ (0.565 ml, 6.05 mmol) was added to a mixture of compound 123-1 (11 g, 15.14 mmol), and Nitrobenzene (100 ml) under nitrogen charging, followed by stirring at 150 ° C for 1 hour. SnCl ₄ (5.3 ml, 45.4 mmol) was added thereto, followed by stirring at 150 ° C for 12 hours. The reaction mixture was cooled, dichloromethane / H ₂ O was added, and the mixture was stirred for 1 hour. The mixture was filtered to obtain a compound 123- 2 (7.4g, 70%) .

Preparation of Compound 123

Except that dibenzo [b, d] thiophen-4-ylboronic acid, 123-2 was used instead of the compound dibenzo [b, d] thiophen-4-ylboronic acid The compound 123 was obtained in the same manner as in the preparation of the compound 93 in Example 5 (9.8 g, 75%).

< Manufacturing example  17> Preparation of Compound 128

Dibenzo [b, d] thiophen-4-ylboronic acid instead of 2-chloro-4,6-diphenylpyrimidine -diphenyl pyrimidine) was used in place of the compound 123 in Production Example 16, the target compound 128 was obtained (10.3 g, 71%).

< Manufacturing example  18> Preparation of Compound 141

Bromobenzoyl chloride instead of 4-bromobenzoyl chloride and dibenzo [b, d] thiophen-4-ylboronic acid in place of dibenzo [b, 3-bromobenzoyl chloride, 4 - ([1,1'-biphenyl] -4-yl) -6- -6-chloro-2-phenylpyrimidine) was used in place of the compound 123 in Production Example 16 to obtain the desired compound 141 (11.8 g, 71%).

The compounds were prepared in the same manner as in the above Preparation Examples, and the results of the confirmation of the synthesis were shown in Tables 1 and 2. Table 1 shows the measured values of ¹ H NMR (CDCl ₃ , 200 Mz) and Table 2 shows the measured values of FD-MS (field desorption mass spectrometry).

[Table 1]

[Table 2]

4 and 5 are graphs showing PL absorption spectra measured by PL (Photoluminescence) or LTPL (Low Temperature Photoluminescence) in a specific UV wavelength region. PL was measured at room temperature using a model LS55 spectrophotometer of Perkin Elmer, and LTPL was measured at -196 ° C (77K) using liquid nitrogen at a temperature of -196 ° C (77K) using a HITACHI model F7000 instrument.

4 shows a PL measurement graph of Compound 1 at a wavelength of 301 nm.

FIG. 5 shows a graph of LTPL measurement at a wavelength of 380 nm of Compound 1. FIG.

Fabrication of organic light emitting device

< Comparative Example  1>

The transparent electrode ITO thin film obtained from the glass for OLED (manufactured by Samsung Corning) was ultrasonically cleaned for 5 minutes each using trichlorethylene, acetone, ethanol and distilled water sequentially, and stored in isopropanol before use. Next, ITO The substrate was placed in a vacuum deposition apparatus. Then, in a vacuum chamber, 4,4 ', 4 "-tris (N, N- (2-naphthyl) -phenylamino) triphenylamine (4,4' N, N- (2-naphthyl) -phenylamino) triphenyl amine: 2-TNATA) was vacuum deposited to a thickness of 600 Å to form a hole injection layer . Thereafter, an N, N'-bis (α-naphthyl) -N, N'-diphenyl-4,4'-diamine , N'-diphenyl-4,4'-diamine: NPB) was vacuum-deposited to a thickness of 300 Å to form a hole transport layer . A blue light emitting host material H1 and a blue light emitting dopant material D1 were mixed in a ratio of 95: 5 on the hole transport layer to form a 200 Å thick light emitting layer .

Then, a compound of the following structural formula E1 was deposited on the light emitting layer to a thickness of 300 Å to form an electron transporting layer .

Thereafter, lithium fluoride, an electron injection layer on the electron transport layer: a (lithium fluoride LiF) was deposited to a thickness of 10Å, to form a negative electrode to the Al on the electron injection layer to a thickness of 1,000Å to manufacture an OLED device Respectively. On the other hand, all organic compounds required for OLED device fabrication were vacuum sublimated and refined under 10 ^-6 ~ 10 ^{- 8} torr to be used for OLED

< Example  1 to 44>

An organic light emitting device was fabricated in the same manner as in Comparative Example 1, except that the compound according to the present invention was used instead of E1 used in forming the electron transport layer in Comparative Example 1.

< Experimental Example > Evaluation of Organic Light Emitting Device

The driving voltage, efficiency, color coordinate and lifetime of the organic luminescent device fabricated in each of Comparative Example 1 and Examples 1 to 44 were measured and evaluated at an emission luminance of 700 cd / m ² . same. At this time, the lifetime was measured using M6000PMX manufactured by Mac Science.

[Table 3]

As shown in Table 3, the organic light emitting devices of Examples 1 to 44 of the present invention had lower driving voltage and higher light emitting efficiency than organic light emitting devices using E1 electron transport layer materials of Comparative Examples. In addition, it was found that the device durability, that is, the life characteristics was superior to the comparative example.

100 substrate
200 anode
300 organic layer
301 hole injection layer
302 hole transport layer
303 luminous layer
304 hole stop layer
305 electron transport layer
306 electron injection layer
400 cathode

Claims (14)

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

In Formula 1,
R ₁ and R ₂ are the same or different and each independently represents a substituted or unsubstituted C ₆ to C ₆₀ aryl group; A substituted or unsubstituted C ₂ to C ₆₀ heteroaryl group; And -P (= O) R &lt; ₁₅ &gt; R &lt; ₁₆ &
R ₃ , R ₄ , R ₅ and R ₁₂ are the same or different from each other, and each independently hydrogen; Or deuterium,
R ₆ and R ₇ ; R ₇ and R ₈ ; R ₉ and R ₁₀ ; And at least one pair selected from the group consisting of R ₁₀ and R ₁₁ may combine with each other to form a ring,
R ₁₅ and R ₁₆ are the same or different and are each independently a C ₁ to C ₆₀ alkyl group; A substituted or unsubstituted C ₃ to C ₆₀ cycloalkyl group; A substituted or unsubstituted C ₆ to C ₆₀ aryl group; Or a substituted or unsubstituted C ₂ to C ₆₀ heteroaryl group,
R ₆ to R ₁₁ are the same as or different from each other, and each independently hydrogen or deuterium. The method according to claim 1,
The term "substituted or unsubstituted"halogen; A C ₁ to C ₆₀ alkyl group; A C ₂ to C ₆₀ alkenyl group; An alkynyl group of C ₂ to C ₆₀ ; A C ₃ to C ₆₀ cycloalkyl group; A C ₂ to C ₆₀ heterocycloalkyl group; A C ₆ to C ₆₀ aryl group; A C ₂ to C ₆₀ heteroaryl group; -SiR ' R &quot;; -P (= O) RR '; C ₁ to C ₂₀ alkylamine groups; C ₆ to C ₆₀ arylamine groups; And a heteroarylamine group having from ₂ to ₆₀ carbon atoms,
Wherein R, R 'and R "are the same or different and each independently represents hydrogen, deuterium, deuterium, halogen, C ₆ to C ₆₀ aryl groups and C ₂ to C ₆₀ heteroaryl groups, alkyl group of ₁ to C _60; heavy hydrogen, halogen, C ₆ to C ₆₀ aryl group and a C ₂ to a substituted or unsubstituted group heteroaryl of C ₆₀ C ₃ to C ₆₀ cycloalkyl group; deuterium, halogen, C ₆ to an aryl group of C ₆₀ aryl group and a C ₂ to C ₆₀ heteroaryl group unsubstituted or substituted C ₆ to C ₆₀ a; or deuterium, halogen, heteroaryl, a C ₆ to C ₆₀ aryl group and C ₂ to C ₆₀ of And is a C ₂ to C ₆₀ heteroaryl group substituted or unsubstituted with an aryl group. The method according to claim 1,
At least one of R ₁ and R ₂ is - (L) _p - (Z) _q ,
L is a direct bond; Substituted or unsubstituted C ₆ to C ₆₀ arylene; A substituted or unsubstituted C ₂ to C ₆₀ heteroarylene group; And substituted or unsubstituted -P (= O) R &lt; ₁₇ &gt; -,
p is an integer of 1 to 4,
q is an integer of 1 to 15,
Z is hydrogen; heavy hydrogen; halogen; A substituted or unsubstituted C ₆ to C ₆₀ aryl group; A substituted or unsubstituted C ₂ to C ₆₀ heteroaryl group; And -P (= O) R &lt; ₁₈ &gt; R &lt; ₁₉ &
R ₁₇ to R ₁₉ are the same or different from each other, and each independently hydrogen; heavy hydrogen; A substituted or unsubstituted C ₁ to C ₆₀ alkyl group; A substituted or unsubstituted C ₃ to C ₆₀ cycloalkyl group; A substituted or unsubstituted C ₆ to C ₆₀ aryl group; Or a substituted or unsubstituted C ₂ to C ₆₀ heteroaryl group. The method according to claim 1,
At least one of R ₁ and R ₂ is - (L) _p - (Z) _q ,
L is a direct bond; Deuterium, halogen, -SiRR'R ", -P (= O ) RR ', C 6 to C ₆₀ aryl group and a C ₂ to C ₆₀ heteroaryl groups substituted with one or more substituents selected from the group consisting of unsubstituted or a C ₆ to C ₆₀ aryl group; deuterium, halogen, -SiRR'R ", -P (= O ) RR ', C 6 to an aryl group and a C ₂ to C ₆₀ heteroaryl group the group consisting of the C ₆₀ from A C ₂ to C ₆₀ heteroarylene group substituted or unsubstituted with at least one substituent selected; And -P (= O) R &lt; ₁₇ &gt; -,
p is an integer of 1 to 4,
q is an integer of 1 to 5,
Z is hydrogen; heavy hydrogen; halogen; Deuterium, halogen, -SiRR'R ", -P (O =) RR ', C ₆ to C ₆₀ aryl group and a C ₂ to C ₆₀ heteroaryl groups substituted with one or more substituents selected from the group consisting of unsubstituted or an aryl group of C ₆ to C _60; deuterium, halogen, -SiRR'R ", -P (= O ) RR ', from the group consisting of a heteroaryl group of C ₆ to C ₆₀ aryl group and C ₂ to C ₆₀ of A C ₂ to C ₆₀ heteroaryl group substituted or unsubstituted with at least one substituent selected; And -P (= O) R &lt; ₁₈ &gt; R &lt; ₁₉ &
Wherein R, R 'and R "and R ₁₇ to R ₁₉ are the same or different and each independently represents hydrogen, deuterium, deuterium, halogen, C ₆ to C ₆₀ aryl and C ₂ to C ₆₀ heteroaryl A C ₁ to C ₆₀ alkyl group which is unsubstituted or substituted with at least one substituent selected from the group consisting of a halogen atom, a C ₆ to C ₆₀ aryl group and a C ₂ to C ₆₀ heteroaryl group, A substituted or unsubstituted C ₃ to C ₆₀ cycloalkyl group substituted with at least one substituent selected from the group consisting of deuterium, halogen, C ₆ to C ₆₀ aryl and C ₂ to C ₆₀ heteroaryl, An unsubstituted C ₆ to C ₆₀ aryl group or a substituted or unsubstituted C ₆ to C ₆₀ aryl group which is substituted with at least one substituent selected from the group consisting of deuterium, halogen, C ₆ to C ₆₀ aryl group and C ₂ to C ₆₀ heteroaryl group ₂ A heterocyclic compound group of the heteroaryl will not C _60. The method of claim 3,
L is a direct bond; A substituted or unsubstituted phenylene group; A substituted or unsubstituted biphenylene group; A substituted or unsubstituted terphenylene group; A substituted or unsubstituted naphthylene group; A substituted or unsubstituted anthrylene group; A substituted or unsubstituted phenanthrenylene group; A substituted or unsubstituted triphenylene group; A substituted or unsubstituted spirobifluorenylene group; A substituted or unsubstituted pyridyl group; A substituted or unsubstituted pyrimidylene group; A substituted or unsubstituted thiazylene group; A substituted or unsubstituted quinolylene group; A substituted or unsubstituted quinazolinylene group; A substituted or unsubstituted benzothiazolyl group; A substituted or unsubstituted benzoxazolylene group; A substituted or unsubstituted benzimidazolylene group; A substituted or unsubstituted divalent dibenzothiophene group; A substituted or unsubstituted divalent dipheno furan group; A substituted or unsubstituted carbazolylene group; A substituted or unsubstituted indolo [2, 3-a] carbazolylene group; A substituted or unsubstituted naphthylidene group; A substituted or unsubstituted oxadiazolylene group; A substituted or unsubstituted 5,11-dihydroindeno [1,2-b] carbazolylene group; And substituted or unsubstituted-P (= O) R &lt; ₁₇ &gt; -,
If the the L-substituted, the substituent is deuterium, halogen, -SiRR'R ", -P (= O ) RR ', substituted or unsubstituted C ₆ to C ₆₀ aryl group and a substituted or unsubstituted C ₂ to the is selected from the group consisting of C ₆₀ heteroaryl is selected from one or more substituents,
Wherein R, R ', R "and R ₁₇ are the same as or different from each other, each independently represent hydrogen, heavy hydrogen; substituted or unsubstituted C ₁ to alkyl groups of C _60; a substituted or unsubstituted C ₃ to C ₆₀ cycloalkyl alkyl group; a substituted or unsubstituted C ₆ to C ₆₀ aryl group; or a substituted or unsubstituted C ₂ to the heteroaryl group to the heterocyclic compound of C _60. The method of claim 3,
Z is hydrogen; heavy hydrogen; A halogen group; A substituted or unsubstituted phenyl group; A substituted or unsubstituted biphenyl group; A substituted or unsubstituted terphenyl group; A substituted or unsubstituted naphthyl group; A substituted or unsubstituted anthryl group; A substituted or unsubstituted phenanthrenyl group; A substituted or unsubstituted triphenyl group; A substituted or unsubstituted spirobifluorenyl group; A substituted or unsubstituted pyridyl group; A substituted or unsubstituted pyrimidyl; A substituted or unsubstituted thiazinyl group; A substituted or unsubstituted quinolyl group; A substituted or unsubstituted quinazolinyl group; A substituted or unsubstituted benzothiazolyl group; A substituted or unsubstituted benzoxazolyl group; A substituted or unsubstituted benzimidazolyl group; A substituted or unsubstituted dibenzothiophene group; A substituted or unsubstituted dibenzofuran group; A substituted or unsubstituted carbazolyl group; A substituted or unsubstituted indolo [2, 3-a] carbazolyl group; A substituted or unsubstituted naphthyridyl group; A substituted or unsubstituted oxadiazolyl group; A substituted or unsubstituted 5,11-dihydroindeno [1,2-b] carbazolyl group; And substituted or unsubstituted-P (= O) R &lt; ₁₈ &gt; R &lt; ₁₉ &
Case in which the Z-substituted, the substituent is deuterium, halogen, -SiRR'R ", -P (= O ) RR ', substituted or unsubstituted C ₆ to C ₆₀ aryl group and a substituted or unsubstituted C ₂ to the is selected from the group consisting of C ₆₀ heteroaryl is selected from one or more substituents,
Wherein R, R ', R ", R ₁₈ and R ₁₉ are the same or different and each is independently of the others hydrogen; heavy hydrogen; substituted or unsubstituted C ₁ to alkyl groups of C _60; a substituted or unsubstituted C ₃ to C ₆₀ cycloalkyl group; a substituted or unsubstituted C ₆ to C ₆₀ aryl group; or a substituted or unsubstituted C ₂ to the heteroaryl group to the heterocyclic compound of C _60. The method of claim 3,
Z is a substituted or unsubstituted C ₂ to C ₆₀ heteroaryl group, and the heteroaryl group contains at least any one selected from N, O and S as a hetero atom. The method of claim 3,
Z is

, X 1 and X 2 are substituted or unsubstituted C ₆ to C ₆₀ aromatic hydrocarbon rings; Or a substituted or unsubstituted C ₂ to C ₆₀ aromatic heterocycle. The method of claim 8,
remind

Is a heterocyclic compound represented by any one of the following structural formulas:

,

,

In the above structural formulas, Y ₁ to Y ₄ are the same or different and each independently is S, NY or CYY '
Y and Y 'are the same or different from each other, and each independently hydrogen; A substituted or unsubstituted C ₁ to C ₆₀ alkyl group; Or a substituted or unsubstituted C ₆ to C ₆₀ aryl group. The method according to claim 1,
Wherein the formula 1 is a heterocyclic compound represented by the following formula 2 or 3:
(2)

(3)

In the general formulas (2) and (3), the definitions of R ₁ to R ₁₂ are the same as those defined in the general formula (1)
R ₁₃ and R ₁₄ are the same or different and each independently hydrogen; Or deuterium,
m and n are each an integer of 1 to 4,
If more than the above m is 2, R ₁₄ is the same as or different from each other,
When n is 2 or more, R ₁₃ are the same or different from each other. The method according to claim 1,
The heterocyclic compound represented by Formula 1 is selected from the following compounds:

An organic light emitting device comprising a cathode, an anode, and at least one organic layer provided between the anode and the cathode, wherein at least one of the organic layers includes the heterocyclic compound according to any one of claims 1 to 11. The method of claim 12,
Wherein the organic compound layer containing the heterocyclic compound is at least one layer selected from the group consisting of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer. The method of claim 12,
Wherein the organic material layer including the heterocyclic compound represented by Formula 1 is an electron transport layer.

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