KR101833665B1 - Hetero-cyclic compound and organic light emitting device comprising the same - Google Patents

Abstract

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heterocyclic compound of formula (I) and an organic light emitting device including the same.

Description

[0001] HETERO-CYCLIC COMPOUND AND ORGANIC LIGHT EMITTING DEVICE COMPRISING THE SAME [0002]

This specification claims the benefit of Korean Patent Application No. 10-2016-0012932 filed on Feb. 2, 2016, filed with the Korean Intellectual Property Office, the entire contents of which are incorporated herein by reference.

TECHNICAL FIELD The present invention relates to heterocyclic compounds and organic light emitting devices comprising the same.

In general, organic light emission phenomenon refers to a phenomenon in which an organic material is used to convert electric energy into light energy. An organic light emitting device using an organic light emitting phenomenon generally has a structure including an anode, a cathode, and an organic material layer therebetween. Here, in order to increase the efficiency and stability of the organic light emitting device, the organic material layer may have a multi-layer structure composed of different materials and may include a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer. When a voltage is applied between the two electrodes in the structure of such an organic light emitting device, holes are injected in the anode, electrons are injected into the organic layer in the cathode, excitons are formed when injected holes and electrons meet, When it falls back to the ground state, the light comes out.

Development of new materials for such organic light emitting devices has been continuously required.

International Patent Application Publication No. 2003-012890

The present invention provides a heterocyclic compound and an organic light emitting device including the heterocyclic compound.

According to one embodiment of the present invention, there is provided a heterocyclic compound represented by the following formula (1).

[Chemical Formula 1]

In Formula 1,

R1 and R2, R2 and R3, or R3 and R4 in R1 to R13 are connected to the dotted line of the following formula (2) to form a ring, and the rest of them are the same or different and each independently hydrogen; heavy hydrogen; A nitrile group; A nitro group; A hydroxy group; Carbonyl group; An ester group; Imide; Amide group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryloxy group; A substituted or unsubstituted alkylthio group; A substituted or unsubstituted arylthio group; A substituted or unsubstituted alkylsulfoxy group; A substituted or unsubstituted arylsulfoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted amine group; A substituted or unsubstituted arylphosphine group; A substituted or unsubstituted phosphine oxide group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group, or groups adjacent to each other may be bonded to each other to form a substituted or unsubstituted ring,

(2)

In Formula 2,

R14 to R17 and Ar1 are the same or different from each other, and each independently hydrogen; heavy hydrogen; A nitrile group; A nitro group; A hydroxy group; Carbonyl group; An ester group; Imide; Amide group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryloxy group; A substituted or unsubstituted alkylthio group; A substituted or unsubstituted arylthio group; A substituted or unsubstituted alkylsulfoxy group; A substituted or unsubstituted arylsulfoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted amine group; A substituted or unsubstituted arylphosphine group; A substituted or unsubstituted phosphine oxide group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group, or groups adjacent to each other may be bonded to each other to form a substituted or unsubstituted ring,

L1 is a direct bond; A substituted or unsubstituted alkylene group; A substituted or unsubstituted arylene group; Or a substituted or unsubstituted heteroarylene group, or may be bonded to any one of R14 or R1 to R5 to form a substituted or unsubstituted ring.

According to an embodiment of the present invention, there is also provided a plasma display panel comprising: a first electrode; A second electrode facing the first electrode; And at least one organic compound layer disposed between the first electrode and the second electrode, wherein at least one of the organic compound layers comprises a heterocyclic compound represented by Formula 1, to provide.

The organic light emitting device including the heterocyclic compound according to one embodiment of the present invention is excellent in thermal stability, and can improve the efficiency, the driving voltage and / or the lifetime characteristics.

1 shows an organic light emitting device 10 according to an embodiment of the present invention.
2 shows an organic light emitting element 11 according to another embodiment of the present invention.
3 is a graph showing MS data values of the formula 1-e.
4 shows MS data values of the formula 2-ab.
5 shows MS data values of the formula 5-aa.
6 shows MS data values of the formula 5-ac.

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

The present invention provides a heterocyclic compound represented by the above formula (1).

In this specification, when a part is referred to as "including " an element, it is to be understood that it may include other elements as well, without departing from the other elements unless specifically stated otherwise.

In this specification, when a member is located on another member, it includes not only the case where the member is in contact with the other member but also the case where another member exists between the two members.

Examples of substituents in the present specification are described below, but are not limited thereto.

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

As used herein, the term " substituted or unsubstituted " A halogen group; A nitrile group; A nitro group; Imide; Amide group; Carbonyl group; An ester group; A hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryloxy group; A substituted or unsubstituted alkylthio group; A substituted or unsubstituted arylthio group; A substituted or unsubstituted alkylsulfoxy group; A substituted or unsubstituted arylsulfoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted amine group; A substituted or unsubstituted arylphosphine group; A substituted or unsubstituted phosphine oxide group; A substituted or unsubstituted aryl group; And a substituted or unsubstituted heterocyclic group, or that at least two of the substituents exemplified above are substituted with a substituent to which they are linked, or have no substituent. For example, "a substituent to which at least two 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.

는 다른 치환기 또는 결합부에 결합되는 부위를 의미한다.In the present specification,

Quot; refers to a moiety bonded to another substituent or bond.

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

In the present specification, the number of carbon atoms in the imide group is not particularly limited, but is preferably 1 to 30 carbon atoms. Specifically, it may be a compound having the following structure, but is not limited thereto.

In the present specification, the amide group may be substituted with nitrogen of the amide group by hydrogen, a straight chain, branched chain or cyclic alkyl group of 1 to 30 carbon atoms or an aryl group of 6 to 30 carbon atoms. Specifically, it may be a compound of the following structural formula, but is not limited thereto.

In the present specification, the carbon number of the carbonyl group is not particularly limited, but is preferably 1 to 30 carbon atoms. Specifically, it may be a compound having the following structure, but is not limited thereto.

In the present specification, the ester group may be substituted with an ester group oxygen in a straight chain, branched chain or cyclic alkyl group having 1 to 25 carbon atoms or an aryl group having 6 to 30 carbon atoms. Specifically, it may be a compound of the following structural formula, but is not limited thereto.

In the present specification, the alkyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 30. Specific examples include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec- N-pentyl, 3-dimethylbutyl, 2-ethylbutyl, heptyl, n-hexyl, Cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethyl Heptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl and the like.

In the present specification, the cycloalkyl group is not particularly limited, but is preferably a group having 3 to 30 carbon atoms. Specific examples thereof include cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, But are not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, isobutyl, sec-butyl, It is not.

In the present specification, the alkoxy group may be linear, branched or cyclic. The number of carbon atoms of the alkoxy group is not particularly limited, but is preferably 1 to 30 carbon atoms. Specific examples include methoxy, ethoxy, n-propoxy, isopropoxy, i-propyloxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentyloxy, neopentyloxy, N-hexyloxy, n-hexyloxy, 3,3-dimethylbutyloxy, 2-ethylbutyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, benzyloxy, But is not limited thereto.

In this specification, the amine group is -NH ₂ ; An alkylamine group; N-alkylarylamine groups; An arylamine group; An N-arylheteroarylamine group; An N-alkylheteroarylamine group, and a heteroarylamine group, and the number of carbon atoms is not particularly limited, but is preferably 1 to 30. Specific examples of the amine group include methylamine, dimethylamine, ethylamine, diethylamine, phenylamine, naphthylamine, biphenylamine, anthracenylamine, 9-methyl- , Diphenylamine group, N-phenylnaphthylamine group, ditolylamine group, N-phenyltolylamine group and triphenylamine group, but are not limited thereto.

In the present specification, the N-alkylarylamine amine group means an amine group in which N in the amine group is substituted with an alkyl group and an aryl group.

In the present specification, the N-arylheteroarylamine group means an amine group in which N in the amine group is substituted with an aryl group and a heteroaryl group.

In the present specification, the N-alkylheteroarylamine group means an amine group in which N in the amine group is substituted with an alkyl group and a heteroarylamine group.

In the present specification, the alkyl group in the alkylamine group, the N-arylalkylamine group, the alkylthio group, the alkylsulfoxy group and the N-alkylheteroarylamine group is the same as the alkyl group described above. Specific examples of the alkyloxy group include a methylthio group, an ethylthio group, a tert-butylthio group, a hexylthio group and an octylthio group. Examples of the alkylsulfoxy group include a mesyl group, an ethylsulfoxy group, a propylsulfoxy group, And the like, but the present invention is not limited thereto.

In the present specification, the alkenyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 2 to 30. Specific examples include vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, Butenyl, allyl, 1-phenylvinyl-1-yl, 2-phenylvinyl-1-yl, (Diphenyl-1-yl) vinyl-1-yl, stilbenyl, stilenyl, and the like.

In the present specification, the silyl group specifically includes a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group, a vinyldimethylsilyl group, a propyldimethylsilyl group, a triphenylsilyl group, a diphenylsilyl group, However, the present invention is not limited thereto.

In the present specification, the boron group may be -BR ₁₀₀ R ₁₀₁ , wherein R ₁₀₀ and R ₁₀₁ are the same or different and each independently hydrogen; heavy hydrogen; halogen; A nitrile group; A substituted or unsubstituted monocyclic or polycyclic cycloalkyl group having 3 to 30 carbon atoms; A substituted or unsubstituted, straight or branched chain alkyl group having 1 to 30 carbon atoms; A substituted or unsubstituted monocyclic or polycyclic aryl group having 6 to 30 carbon atoms; And a substituted or unsubstituted monocyclic or polycyclic heteroaryl group having 2 to 30 carbon atoms.

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

In the present specification, the aryl group is not particularly limited, but preferably has 6 to 60 carbon atoms, and the aryl group may be monocyclic or polycyclic.

When the aryl group is a monocyclic aryl group, the number of carbon atoms is not particularly limited, but is preferably 6 to 60 and 6 to 30 carbon atoms. Specific examples of the monocyclic aryl group include a phenyl group, a biphenyl group, a terphenyl group, and the like, but are not limited thereto.

When the aryl group is a polycyclic aryl group, the number of carbon atoms is not particularly limited. Preferably 10 to 60 carbon atoms and 10 to 30 carbon atoms. Specific examples of the polycyclic aryl group include, but are not limited to, a naphthyl group, an anthracenyl group, a phenanthryl group, a triphenyl group, a pyrenyl group, a perylenyl group, a klycenyl group and a fluorenyl group.

In the present specification, the fluorenyl group may be substituted, and adjacent groups may combine with each other to form a ring.

,

,

및

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

,

,

And

And the like. However, the present invention is not limited thereto.

But also the case where a member exists.

As used herein, the term "adjacent" means that the substituent is a substituent substituted on an atom directly connected to the substituted atom, a substituent stereostructically closest to the substituent, or other substituent substituted on the substituted atom . For example, two substituents substituted in the benzene ring to the ortho position and two substituents substituted on the same carbon in the aliphatic ring may be interpreted as "adjacent" groups to each other.

In the present specification, the aryl group in the aryloxy group, the arylthioxy group, the arylsulfoxy group, the N-arylalkylamine group, the N-arylheteroarylamine group and the arylphosphine group is the same as the aforementioned aryl group. Specific examples of the aryloxy group include a phenoxy group, a p-tolyloxy group, a m-tolyloxy group, a 3,5-dimethyl-phenoxy group, a 2,4,6- trimethylphenoxy group, a p- Naphthyloxy group, 4-methyl-1-naphthyloxy group, 5-methyl-2-naphthyloxy group, 1-anthryloxy group , 2-anthryloxy group, 9-anthryloxy group, 1-phenanthryloxy group, 3-phenanthryloxy group and 9-phenanthryloxy group and the arylthioxy group includes phenylthio group, 2- Methylphenylthio group, 4-tert-butylphenylthio group and the like, and examples of the arylsulfoxy group include a benzene sulfoxide group and a p-toluenesulfoxy group. However, the present invention is not limited thereto.

In the present specification, examples of the arylamine group include a substituted or unsubstituted monoarylamine group, a substituted or unsubstituted diarylamine group, or a substituted or unsubstituted triarylamine group. The aryl group in the arylamine group may be a monocyclic aryl group or a polycyclic aryl group. The arylamine group having at least two aryl groups may contain a monocyclic aryl group, a polycyclic aryl group, or a monocyclic aryl group and a polycyclic aryl group at the same time. For example, the aryl group in the arylamine group may be selected from the examples of the aryl group described above.

In the present specification, the heteroaryl group includes at least one non-carbon atom and at least one hetero atom. Specifically, the hetero atom may include one or more atoms selected from the group consisting of O, N, Se and S, and the like. The number of carbon atoms is not particularly limited, but it is preferably 2 to 60 carbon atoms and 2 to 30 carbon atoms, and the heteroaryl group may be monocyclic or polycyclic. Examples of the heterocyclic group include a thiophene group, a furanyl group, a pyrrolyl group, an imidazolyl group, a thiazolyl group, an oxazolyl group, an oxadiazolyl group, a pyridyl group, a bipyridyl group, a pyrimidyl group, A substituted or unsubstituted heterocyclic group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted heterocyclic group, , An isoquinolinyl group, an indolyl group, a carbazolyl group, a benzoxazolyl group, a benzimidazolyl group, a benzofuro pyrimidine group, a benzothieno pyrimidine group, an indenopyrimidine group, A benzothiazolyl group, a benzothiophene group, a dibenzothiophene group, a benzofuranyl group, a phenanthroline group, a thiazolyl group, an isoxazolyl group, an oxadiazole group, A thiadiazolyl group, a benzothiazolyl group, a phenothiazinyl group, Benzo furanoid group, indazolyl group, phthalazine, but the oscillator, etc., and the like.

In the present specification, examples of the heteroarylamine group include a substituted or unsubstituted monoheteroarylamine group, a substituted or unsubstituted diheteroarylamine group, or a substituted or unsubstituted triheteroarylamine group. The heteroarylamine group having two or more heteroaryl groups may include a monocyclic heteroaryl group, a polycyclic heteroaryl group, or a monocyclic heteroaryl group and a polycyclic heteroaryl group at the same time. For example, the heteroaryl group in the heteroarylamine group may be selected from the examples of the above-mentioned heteroaryl group.

In the present specification, examples of the heteroaryl group in the N-arylheteroarylamine group and the N-alkylheteroarylamine group are the same as the examples of the above-mentioned heteroaryl group.

In the present specification, an alkylene group means that the alkyl group has two bonding positions, i.e., divalent. The description of the above-mentioned alkyl groups can be applied, except that they are each 2 groups.

In the present specification, an arylene group means a divalent group having two bonding positions in an aryl group. The description of the aryl group described above can be applied except that each of these is 2 groups.

In the present specification, the heteroarylene group means that the heteroaryl group has two bonding positions, that is, divalent. The description of the above-mentioned heteroaryl groups can be applied, except that they are each 2 groups.

In the present specification, in the substituted or unsubstituted ring formed by bonding adjacent groups to each other, the "ring" means a substituted or unsubstituted hydrocarbon ring; Or a substituted or unsubstituted heterocycle.

In the present specification, the hydrocarbon ring may be an aromatic, aliphatic or aromatic and aliphatic condensed ring, and may be selected from the examples of the cycloalkyl group or the aryl group except the univalent hydrocarbon ring.

In this specification, the aromatic ring may be monocyclic or polycyclic and may be selected from the examples of the aryl group except that it is not monovalent.

In the present specification, the hetero ring includes one or more non-carbon atoms and hetero atoms. Specifically, the hetero atom may include one or more atoms selected from the group consisting of O, N, Se, and S, and the like. The heterocyclic ring may be monocyclic or polycyclic, and may be aromatic, aliphatic or aromatic and aliphatic condensed rings, and may be selected from the examples of the heteroaryl group except that it is not monovalent.

In one embodiment of the present invention, the formula (1) is represented by any one of the following formulas (1-1) to (1-6).

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

[Chemical Formula 1-6]

In Formulas 1-1 to 1-6,

The definitions of R 1 to R 13 are the same as those of Formula 1, and the definitions of L 1, Ar 1, and R 14 to R 17 are the same as those of Formula 2.

According to one embodiment of the present disclosure, L1 is a direct bond; A substituted or unsubstituted, linear or branched alkylene group having 1 to 30 carbon atoms; A substituted or unsubstituted monocyclic or polycyclic arylene group having 6 to 30 carbon atoms; Or a substituted or unsubstituted monocyclic or polycyclic heteroarylene group having 2 to 30 carbon atoms.

According to one embodiment of the present disclosure, L1 is a direct bond; A substituted or unsubstituted phenylene group; A substituted or unsubstituted biphenylene group; Or a substituted or unsubstituted naphthylene group.

According to one embodiment of the present disclosure, L1 is a direct bond; A phenylene group; Biphenyllylene groups; Or a naphthylene group.

According to one embodiment of the present disclosure, Ar1 is hydrogen; A nitrile group; A substituted or unsubstituted amine group; A substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group.

According to one embodiment of the present invention, Ar1 is a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group.

According to one embodiment of the present invention, Ar1 is a substituted or unsubstituted aryl group having 6 to 60 carbon atoms or a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms.

According to one embodiment of the present invention, Ar1 is a substituted or unsubstituted aryl group or a heterocyclic compound represented by the following formula (A).

(A)

In formula (A)

Y1 to Y3 are the same or different and are each independently N or CRd,

R201 and Rd are the same or different from each other, and each independently hydrogen; heavy hydrogen; A nitrile group; A nitro group; A hydroxy group; Carbonyl group; An ester group; Imide; Amide group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryloxy group; A substituted or unsubstituted alkylthio group; A substituted or unsubstituted arylthio group; A substituted or unsubstituted alkylsulfoxy group; A substituted or unsubstituted arylsulfoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted amine group; A substituted or unsubstituted arylphosphine group; A substituted or unsubstituted phosphine oxide group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group, or is bonded to an adjacent group to form a substituted or unsubstituted ring.

According to one embodiment of the present disclosure, Ar1 is a substituted or unsubstituted arylamine group; A substituted or unsubstituted phenyl group; A substituted or unsubstituted biphenyl group; A substituted or unsubstituted naphthyl group; Substituted or unsubstituted terphenyl group or represented by the above formula (A).

According to one embodiment of the present invention, Ar1 is according to an embodiment of the present invention, Ar1 is a phenyl group; A biphenyl group; Naphthyl group; A terphenyl group or the above formula (A).

According to one embodiment of the present invention, the formula (A) may be represented by any one of the following formulas (A-1) to (A-4).

[Formula A-1] [Formula A-2]

[Chemical formula A-3] [Chemical formula A-4]

In the above Formulas A-1 to A-4,

R198 to R201 are the same or different from each other and each independently hydrogen; heavy hydrogen; A nitrile group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted aryl group; A substituted or unsubstituted aromatic or aliphatic heterocyclic group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryloxy group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted alkylarylamine group; Or a substituted or unsubstituted heteroarylamine group or is bonded to adjacent substituents to form a ring.

In one embodiment of the present specification, R198 to R201 are the same or different from each other, and each independently hydrogen; heavy hydrogen; A substituted or unsubstituted alkyl group; A substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group.

In one embodiment of the present specification, R198 to R201 are the same or different from each other, and each independently hydrogen; heavy hydrogen; A substituted or unsubstituted alkyl group having 1 to 12 carbon atoms; A substituted or unsubstituted aryl group having 6 to 30 carbon atoms or a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms.

According to one embodiment of the present disclosure, R198 to R201 are the same or different from each other, and each independently hydrogen; heavy hydrogen; A substituted or unsubstituted phenyl group; A substituted or unsubstituted naphthyl group; A substituted or unsubstituted biphenyl group; A substituted or unsubstituted dibenzofuranyl group or a substituted or unsubstituted carbazolyl group.

In one embodiment of the present specification, R198 to R201 are the same or different from each other, and each independently hydrogen; heavy hydrogen; A phenyl group; Naphthyl group; A biphenyl group; A dibenzofuranyl group; A carbazolyl group or a carbazolyl group substituted with a phenyl group.

According to one embodiment of the present invention, the formula (A) is represented by one of the following formulas (A-5) and (A-6).

[A-5]

In the formula (A-5), the definitions of Y1 and Y2 are the same as those of the above formula (A)

Z1 to Z4 are the same or different and each independently N or CRc,

Rc are the same or different and are each independently selected from the group consisting of hydrogen; heavy hydrogen; A nitrile group; A nitro group; A hydroxy group; Carbonyl group; An ester group; Imide; Amide group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryloxy group; A substituted or unsubstituted alkylthio group; A substituted or unsubstituted arylthio group; A substituted or unsubstituted alkylsulfoxy group; A substituted or unsubstituted arylsulfoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted amine group; A substituted or unsubstituted arylphosphine group; A substituted or unsubstituted phosphine oxide group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group, or may be bonded to adjacent groups to form a substituted or unsubstituted ring,

[A-6]

In formula (A-6), Y1 is as defined in formula (A)

X < 1 > is O, S or CR &

A substituted or unsubstituted alkenyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted cycloalkyl group, Or a substituted or unsubstituted aryloxy group, a substituted or unsubstituted aromatic or aliphatic heterocyclic group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkylamine group, A substituted or unsubstituted arylamine group, a substituted or unsubstituted arylamine group, a substituted or unsubstituted arylamine group, a substituted or unsubstituted alkylarylamine group, or a substituted or unsubstituted heteroarylamine group, or is bonded to adjacent substituents to form a ring.

According to one embodiment of the present invention, the formula (A-5) is represented by any one of the following formulas (A-7) to (A-10).

[A-7]

[A-8]

[A-9]

[A-10]

In Formulas A-7 to A-10,

The definitions of Y1 and Y2 are the same as those of the above formula (A)

R202 to R205 are the same or different and each independently hydrogen; heavy hydrogen; A nitrile group; A nitro group; A hydroxy group; Carbonyl group; An ester group; Imide; Amide group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryloxy group; A substituted or unsubstituted alkylthio group; A substituted or unsubstituted arylthio group; A substituted or unsubstituted alkylsulfoxy group; A substituted or unsubstituted arylsulfoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted amine group; A substituted or unsubstituted arylphosphine group; A substituted or unsubstituted phosphine oxide group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group, or is bonded to an adjacent group to form a substituted or unsubstituted ring.

According to one embodiment of the present invention, the formula (A-5) is represented by any one of the following formulas (A-11) to (A-18).

[A-11]

[A-12]

[A-13]

[Chemical formula A-14]

[A-15]

[A-16]

[A-17]

[A-18]

In Formulas A-11 to A-18,

R202 to R209 are the same or different from each other, and each independently hydrogen; heavy hydrogen; A nitrile group; A nitro group; A hydroxy group; Carbonyl group; An ester group; Imide; Amide group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryloxy group; A substituted or unsubstituted alkylthio group; A substituted or unsubstituted arylthio group; A substituted or unsubstituted alkylsulfoxy group; A substituted or unsubstituted arylsulfoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted amine group; A substituted or unsubstituted arylphosphine group; A substituted or unsubstituted phosphine oxide group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group, or is bonded to an adjacent group to form a substituted or unsubstituted ring.

In one embodiment of the present specification, R202 to R209 are the same or different from each other, and each independently hydrogen; heavy hydrogen; A substituted or unsubstituted alkyl group; A substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group.

In one embodiment of the present specification, R202 to R209 are the same or different from each other, and each independently hydrogen; heavy hydrogen; A substituted or unsubstituted alkyl group having 1 to 12 carbon atoms; A substituted or unsubstituted aryl group having 6 to 30 carbon atoms or a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms.

According to one embodiment of the present disclosure, R202 to R209 are the same or different from each other, and each independently hydrogen; heavy hydrogen; A substituted or unsubstituted phenyl group; A substituted or unsubstituted naphthyl group; A substituted or unsubstituted biphenyl group; A substituted or unsubstituted dibenzofuranyl group or a substituted or unsubstituted carbazolyl group.

In one embodiment of the present specification, R202 to R209 are the same or different from each other, and each independently hydrogen; heavy hydrogen; A phenyl group; Naphthyl group; A biphenyl group; A dibenzofuranyl group; A carbazolyl group or a carbazolyl group substituted with a phenyl group.

In one embodiment of the present specification, R202 and R203 may combine with each other to form a benzene ring.

In one embodiment of the present specification, R204 and R205 may combine with each other to form a benzene ring.

According to one embodiment of the present invention, the formula (A-6) may be represented by one of the following formulas (A-19) to (A-21).

[A-19]

[A-20]

[A-21]

In Formulas A-19 to A-21,

R210 to R213, R 'and R "are the same as defined in A-6,

R230 is hydrogen; Deuterium, or a substituted or unsubstituted aryl group.

In one embodiment of the present specification, R210 to R213 are the same or different from each other, and each independently is hydrogen, deuterium, a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group.

According to one embodiment of the present invention, R210 to R213 are the same or different from each other and each independently hydrogen, deuterium, methyl group or ethyl group.

In another embodiment, R 210 to R 213 are hydrogen.

In one embodiment of the present specification, R230 is hydrogen or a substituted or unsubstituted aryl group.

In another embodiment, R230 is hydrogen.

In another embodiment, R230 is a substituted or unsubstituted phenyl group; A substituted or unsubstituted naphthyl group or a substituted or unsubstituted biphenyl group.

In another embodiment, R230 is selected from the group consisting of a phenyl group; Naphthyl group or biphenyl group.

In one embodiment of the present disclosure, R 'and R "are the same or different from each other, and each independently is hydrogen, deuterium, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group.

According to one embodiment of the present disclosure, R 'and R "are the same or different and are each independently hydrogen or deuterium.

According to another embodiment, R 'and R "are the same or different and each independently an alkyl group having 1 to 12 carbon atoms.

According to another embodiment, R 'and R "are the same or different and are each independently a methyl group or an ethyl group.

According to one embodiment of the present disclosure, Ar1 is hydrogen; A nitrile group; Diphenylamine group; A phenyl group; A biphenyl group; Naphthyl group; A terphenyl group; A phenanthrenyl group; A triazinyl group substituted or unsubstituted with a phenyl group, a biphenyl group or a dibenzofuranyl group; A pyrimidyl group substituted or unsubstituted with a phenyl group or a biphenyl group; Or may be represented by any one of the following structures.

는 화힉식 1 또는 L1에 연결되는 부위이며, 상기 구조는 니트릴기, 메틸기, 페닐포스핀옥사이드기로 치환 또는 비치환된 페닐기, 나프틸기, 바이페닐기, 피리딜기, 페닐기로 치환 또는 비치환된 카바졸릴기, 디벤조퓨라닐기, 디벤조티오펜기, 벤조카바졸릴기, 메틸기로 치환 또는 비치환된 플루오레닐기로 치환 또는 비치환될 수 있다.In the above structure,

Is a moiety connected to a hydrogen atom or a group L1, and the structure is a substituent selected from the group consisting of a phenyl group, a naphthyl group, a biphenyl group, a pyridyl group substituted or unsubstituted with a nitrile group, a methyl group, a phenylphosphine oxide group, A dibenzofuranyl group, a dibenzothiophene group, a benzocarbazolyl group, a substituted or unsubstituted fluorenyl group with a methyl group, and the like.

According to one embodiment of the present disclosure, Formula 1 is selected from the following structures.

According to one embodiment of the present invention, the formula 1 may be represented by any one of the formulas 1-1 to 1-6, and the cores of the formulas 1-1 to 1-6 may be prepared by the method of the following formula .

[Formula 1]

The core of the heterocyclic compound represented by the above formulas 1-1 to 1-6 uses the reaction of Fischer indole synthesis, Ulmann, Buchwald-Hartwig amination, Suzki coupling and Heck coupling as shown in the general formula 1 above.

According to one embodiment of the present disclosure, there is provided a liquid crystal display comprising: a first electrode; A second electrode facing the first electrode; And at least one organic material layer including a light emitting layer provided between the first electrode and the second electrode, wherein at least one of the organic material layers includes the above-described heterocyclic compound, to provide.

According to one embodiment of the present disclosure, the organic material layer of the organic light emitting device may have a single layer structure, but may have a multilayer structure in which two or more organic material layers are stacked. For example, the organic light emitting device of the present invention may have a structure including a hole injecting layer, a hole transporting layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transporting layer, and an electron injecting layer as organic layers. However, the structure of the organic light emitting device is not limited thereto, and may include fewer or more organic layers.

For example, the structure of the organic light emitting device of the present invention may have a structure as shown in FIGS. 1 and 2, but the present invention is not limited thereto.

1 illustrates a structure of an organic light emitting diode 10 in which a first electrode 30, a light emitting layer 40, and a second electrode 50 are sequentially stacked on a substrate 20. 1 is an exemplary structure of an organic light emitting diode according to an embodiment of the present invention, and may further include another organic layer.

2 shows a structure in which a first electrode 30, a hole injection layer 60, a hole transport layer 70, a light emitting layer 40, an electron transport layer 80, an electron injection layer 90 and a second electrode 50) are successively laminated on a substrate. 2 is an exemplary structure according to an embodiment of the present invention, and may further include another organic layer.

According to one embodiment of the present invention, the organic material layer includes a hole transporting layer, and the hole transporting layer includes the heterocyclic compound represented by the general formula (1).

According to one embodiment of the present invention, the light emitting layer includes the heterocyclic compound represented by Formula 1.

According to one embodiment of the present invention, the light emitting layer includes the heterocyclic compound represented by Formula 1 as a host of the light emitting layer.

According to one embodiment of the present invention, the light emitting layer includes the heterocyclic compound represented by Formula 1 as a phosphorescent host or a fluorescent host of the light emitting layer.

According to one embodiment of the present invention, the organic material layer contains the heterocyclic compound represented by the formula (1) as a host of the light emitting layer, and includes another organic compound, metal or metal compound as a dopant.

According to one embodiment of the present disclosure, the dopant may be selected from the following structures, but is not limited thereto.

According to an embodiment of the present invention, the organic material layer may further include 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 organic light emitting device of the present invention is manufactured by materials and methods known in the art except that one or more of the organic layers include the heterocyclic compound of the present specification, that is, the heterocyclic compound represented by the above formula (1) .

When the organic light emitting diode includes a plurality of organic layers, the organic layers may be formed of the same material or different materials.

For example, the organic light emitting device of the present invention can be manufactured by sequentially laminating a first electrode, an organic material layer, and a second electrode on a substrate. At this time, a metal or a metal oxide having conductivity or an alloy thereof is deposited on the substrate using a physical vapor deposition (PVD) method such as sputtering or e-beam evaporation Forming a first electrode, forming an organic material layer including a hole injecting layer, a hole transporting layer, a light emitting layer and an electron transporting layer on the first electrode, and depositing a material usable as a second electrode thereon. In addition to such a method, an organic light emitting device can be formed by sequentially depositing a second electrode material, an organic material layer, and a first electrode material on a substrate. The heterocyclic compound represented by Formula 1 may be formed into an organic layer by a solution coating method as well as a vacuum deposition method in the production of an organic light emitting device. Here, the solution coating method refers to spin coating, dip coating, doctor blading, inkjet printing, screen printing, spraying, roll coating and the like, but is not limited thereto.

According to one embodiment of the present invention, the first electrode is an anode and the second electrode is a cathode.

According to another embodiment of the present invention, the first electrode is a cathode and the second electrode is a cathode.

As the anode material, a material having a large work function is preferably used so that hole injection can be smoothly conducted into the organic material layer. Specific examples of the cathode material that can be used in the present invention include metals such as vanadium, chromium, copper, zinc, and gold, or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); ZnO: Al or SNO _2: a combination of a metal and an oxide such as Sb; Conductive polymers such as poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (PEDOT), polypyrrole and polyaniline.

The negative electrode material is preferably a material having a small work function to facilitate electron injection into the organic material layer. Specific examples of the negative electrode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin and lead or alloys thereof; Layer structure materials such as LiF / Al, LiO ₂ / Al, and Mg / Ag, but are not limited thereto.

The hole injecting layer is a layer for injecting holes from the electrode as a hole injecting material and a hole injecting effect for injecting holes in the anode as a hole injecting material and an excellent hole injecting effect for a light emitting layer or a light emitting material , The migration of excitons generated in the light emitting layer to the electron injection layer or the electron injection material, and also the ability to form thin films is preferable. It is preferable that the highest occupied molecular orbital (HOMO) of the hole injecting material be between the work function of the anode material and the HOMO of the surrounding organic layer. Specific examples of the hole injecting material include metal porphyrin, oligothiophene, arylamine-based organic materials, hexanitrile hexaazatriphenylene-based organic materials, quinacridone-based organic materials, and perylene- , Anthraquinone, polyaniline and polythiophene-based conductive polymers, but the present invention is not limited thereto.

The hole transport layer is a layer that transports holes from the hole injection layer to the light emitting layer. The hole transport material is a material capable of transporting holes from the anode or the hole injection layer to the light emitting layer. The material is suitable. Specific examples include arylamine-based organic materials, conductive polymers, and block copolymers having a conjugated portion and a non-conjugated portion together, but are not limited thereto.

The electron blocking layer is a layer which can prevent the holes injected from the hole injection layer from entering the electron injection layer through the light emitting layer to improve the lifetime and efficiency of the device. If necessary, And may be formed in an appropriate portion between the injection layers.

The light emitting material of the light emitting layer is preferably a material capable of emitting light in the visible light region by transporting and receiving holes and electrons from the hole transporting layer and the electron transporting layer, respectively, and having high quantum efficiency for fluorescence or phosphorescence. Specific examples include 8-hydroxy-quinoline aluminum complex (Alq ₃ ); Carbazole-based compounds; Dimerized styryl compounds; BAlq; 10-hydroxybenzoquinoline-metal compounds; Benzoxazole, benzothiazole and benzimidazole compounds; Polymers of poly (p-phenylenevinylene) (PPV) series; Spiro compounds; Polyfluorene, rubrene, and the like, but are not limited thereto.

The light emitting layer may include a host material and a dopant material. The host material may be a condensed aromatic ring derivative or a heterocyclic compound. Specific examples of the condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, and fluoranthene compounds. Examples of the heterocyclic compound include carbazole derivatives, dibenzofuran derivatives, Furan compounds, pyrimidine derivatives, and the like, but are not limited thereto.

Examples of the dopant material include an aromatic amine derivative, a styrylamine compound, a boron complex, a fluoranthene compound, and a metal complex. Specific examples of the aromatic amine derivatives include condensed aromatic ring derivatives having substituted or unsubstituted arylamino groups, and examples thereof include pyrene, anthracene, chrysene, and peripherrhene having an arylamino group. Examples of the styrylamine compound include substituted or unsubstituted Wherein at least one aryl vinyl group is substituted with at least one aryl vinyl group, and at least one substituent selected from the group consisting of an aryl group, a silyl group, an alkyl group, a cycloalkyl group and an arylamino group is substituted or unsubstituted. Specific examples thereof include, but are not limited to, styrylamine, styryldiamine, styryltriamine, styryltetraamine, and the like. Examples of the metal complex include iridium complex, platinum complex, and the like, but are not limited thereto.

The electron transporting material of the electron transporting layer is a layer that transports electrons from the electron injecting layer to the electron transporting layer and transports electrons from the cathode to the light emitting layer. This large material is suitable. Specific examples include an Al complex of 8-hydroxyquinoline; Complexes containing Alq ₃ ; Organic radical compounds; Hydroxyflavone-metal complexes, and the like, but are not limited thereto. The electron transporting layer can be used with any desired cathode material as used according to the prior art. In particular, an example of a suitable cathode material is a conventional material with a low work function followed by an aluminum layer or silver layer. Specifically cesium, barium, calcium, ytterbium and samarium, in each case followed by an aluminum layer or a silver layer.

The electron injection layer is a layer for injecting electrons from the electrode. The electron injection layer has the ability to transport electrons, has an electron injection effect from the cathode, and has an excellent electron injection effect with respect to the light emitting layer or the light emitting material. A compound which prevents migration to a layer and is excellent in a thin film forming ability is preferable. Specific examples thereof include fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preorenylidene methane, A complex compound and a nitrogen-containing five-membered ring derivative, but are not limited thereto.

Examples of the metal complex compound include 8-hydroxyquinolinato lithium, bis (8-hydroxyquinolinato) zinc, bis (8-hydroxyquinolinato) copper, bis (8- Tris (8-hydroxyquinolinato) aluminum, tris (2-methyl-8-hydroxyquinolinato) aluminum, tris (8- hydroxyquinolinato) gallium, bis (10- Quinolinato) beryllium, bis (10-hydroxybenzo [h] quinolinato) zinc, bis (2-methyl-8- quinolinato) chlorogallium, bis (2-methyl-8-quinolinato) (2-naphtholato) gallium, and the like, But is not limited thereto.

The hole blocking layer prevents holes from reaching the cathode, and may be formed under the same conditions as those of the hole injection layer. Specific examples thereof include, but are not limited to, oxadiazole derivatives, triazole derivatives, phenanthroline derivatives, BCP, aluminum complexes and the like.

The organic light emitting device according to the present invention may be of a top emission type, a back emission type, or a both-side emission type, depending on the material used.

In addition, the organic light emitting diode according to the present invention may be an inverted type in which the lower electrode is a cathode, the upper electrode is a cathode, the lower electrode is a cathode, and the upper electrode is an anode.

According to one embodiment of the present invention, the heterocyclic compound represented by Formula 1 may be included in an organic solar cell or an organic transistor in addition to an organic light emitting device.

Hereinafter, the present invention will be described in detail by way of examples with reference to the drawings. However, the embodiments according to the present disclosure can be modified in various other forms, and the scope of the present specification is not construed as being limited to the embodiments described below. Embodiments of the present disclosure are provided to more fully describe the present disclosure to those of ordinary skill in the art.

Specifically, the cores of Formulas 1-1 to 1-12 may be produced by the following Synthesis Examples 1-1 to 1-6 and 2-1 to 2-6.

Synthesis Example 1-1. Preparation of Formula 1-1

1) Preparation of formula (I-a)

200.0 g (888.5 mmol, 1.0 eq) of 8-bromo-3,4-dihydronaphthalen-1 (2H) -one and 8-bromo-3,4- dihydronaphthalen- 141.3 g (977.4 mmol, 1.1 eq) of phenylhydrazine hydrochloride were dissolved in 2.2 L of ethanol, refluxed and stirred. After 1 hour, the reaction was terminated and the solvent was removed by pressure. This was completely dissolved in ethyl acetate and washed with water. The solvent was removed under reduced pressure to remove 70% of the solvent, and 251.7 g (844.1 mmol, yield 95%) of the compound of the formula 1-a was obtained. [M + H] < + > = 298

2) Preparation of compound of formula 1-b

251.7 g (844.1 mmol, 1.0 eq) of Formula 1-a and 191.6 g (844.1 mmol, 1.0 eq) of DDQ were dissolved in 2.3 L of acetonitrile and stirred. When the reaction is completed after 30 minutes, the solvent is removed by pressure. This was completely dissolved in ethyl acetate and washed with K ₃ PO ₄ aqueous solution. The solvent was then removed under reduced pressure to remove about 80% of the solvent, and 225.0 g (759.7 mmol, yield 90%) of the compound of the formula 1-b was obtained. [M + H] = 295

3) Preparation of formula (1-c)

(759.7 mmol, 1.0 eq), 1-bromo-2-iodobenzene 257.9 g (911.6 mmol, 1.2 eq), copper powder 96.56 g (1519.4 mmol, 2.0 eq), K ₂ 209.9 g (1519.4 mmol, 2.0 eq) of CO _{3 was} placed in 2.0 L of xylene, refluxed and stirred. After the reaction was completed, the mixture was cooled to room temperature and then the copper powder was removed by filtration. The solution in which the product was dissolved was depressurized to remove all of the solvent. The solution was completely dissolved in CHCl ₃ , washed with water, and again decompressed to remove the solvent, which was purified by column chromatography. 246.7 g (546.9 mmol, yield 72%) of the compound of the formula 1-c was obtained. [M] = 448

4) Preparation of formula (1-d)

1-c 246.78 g Pd (dba ) to _{(546.99 mmol, 1.0 eq) 2} 3.14 g (5.46 mmol, 0.01 eq), PCy 3 4.60 g (16.40 mmol, 0.03 eq), K 2 CO 3 151.19 g (1093.98 mmol, 2.0 eq) was placed in 1.4 L of dimethylacetamide, refluxed and stirred. After 3 hours, the reaction mixture was poured into water, and crystals were dropped and filtered. The filtered solid was completely dissolved in CHCl ₃ and washed with water. The solution in which the product was dissolved was concentrated under reduced pressure and purified by column chromatography. 176.19 g (475.88 mmol, yield 87%) of the compound of the formula 1-d was obtained. [M] = 369

5) Preparation of the compound of the formula 1-e

1-d 80.0 g (216.1 mmol , 1.0 eq), 2- chloroaniline 30.2 g (237.7 mmol, 1.1 eq ), K 3 PO 4 91.7 g (432.1 mmol, 2.0 eq), Pd (t-Bu 3 P) 2 0.55 g (1.08 mmol, 0.005 eq) was dissolved in 600 ml of xylene, refluxed and stirred. After completion of the reaction for 2 hours, the solvent was removed by decompression. Thereafter, the reaction mixture was completely dissolved in CHCl ₃ , washed with water, and then decompressed to remove the solvent. The resulting residue was subjected to column chromatography to obtain 75.7 g (181.5 mmol, yield 84%) of the compound of the formula 1-e. [M + H] < + > = 417

3 is a graph showing MS data values of the formula 1-e.

6) Preparation of the compound of the formula 1-f

1-e 75.67 g (181.50 mmol , 1.00 eq) to _{Pd (dba) 2 1.04 g (} 8.32 mmol, 0.01 eq), PCy 3 1.52 g (5.44 mmol, 0.03 eq), K 3 PO 4 77.05 g (363.00 mmol, 2.00 eq) was placed in 2 L of dimethylacetamide, refluxed and stirred. After 3 hours, the reaction mixture was poured into water, and crystals were dropped and filtered. The filtered solid was completely dissolved in ethyl acetate and washed with water. The solution in which the product was dissolved was concentrated under reduced pressure and purified by column chromatography. 53.17 g (139.76 mmol, 77% yield) of the compound of the formula 1-f was obtained. [M + H] < + > = 380

7) Preparation of formula 1-1

(1-1) can be prepared by using L1-Ar1 as a starting material in the same manner as in the production of the above 5) (1-e).

Synthesis Example 1-2. Preparation of Formulas 1-2

1) Preparation of formula (2-a)

A solution of 2.00 g (1.00 eq) of Pd (PPh3) 4, 39.67 g (237.67 mmol, 1.10 eq) of (2-nitrophenyl) boronic acid, 80.00 g (216.07 mmol, 1.00 eq) (2.16 mmol, 0.01 eq) was dissolved in 500 ml of dioxane and stirred. Then, 59.72 g (432.14 mmol, 2.0 eq) of K ₂ CO ₃ was dissolved in 200 ml of water, and the mixture was refluxed and stirred. After 2 hours, when the reaction was completed, the organic layer was separated, and the solvent was removed by decompression. The product was completely dissolved in CHCl ₃ and then washed with water. The solution was concentrated under reduced pressure to about 50%, ethanol was added thereto, and crystals were dropped and filtered. 82.87 g (200.94 mmol, yield 93%) of the compound of the formula 2-a was obtained. [M + H] < + > = 413

2) Preparation of formula 2-b

82.9 g (203.1 mmol, 1.0 eq) of the compound represented by the formula 2-a was dissolved in 400 ml of triethyl phosphite (P (OEt) ₃ ), refluxed and stirred. After 3 hours, when the reaction was completed, the solvent was removed by vacuum decompression to remove about 50% of the solvent and the crystals were dropped. After filtration, the solution was completely dissolved in ethyl acetate and then washed with water. The solution was concentrated under reduced pressure of about 70%, cooled, cooled, and filtered. 70.3 g (184.8 mmol, yield 91%) of the compound of the formula 2-b was obtained. [M] = 380

3) Preparation of Formulas 1-2

(1-2) can be prepared by using L1-Ar1 in the same manner as in the preparation of 5) 5-e of Synthesis Example 1-1, using the compound of Formula 2-b as a starting material.

In Synthesis Examples 1-1 and 1-2, the definitions of L 1 and Ar 1 are the same as those of Formula 2 above.

Synthesis Example 1-3. Preparation of Formulas 1-3

Bromo-3,4-dihydronaphthalen-1 (2H) was obtained as a starting material in the preparation of the compound of Formula 1-2 of Synthesis Example 1-2, except that 8-bromo-3,4-dihydronaphthalen- ) -one in place of 6-bromo-3,4-dihydronaphthalen-1 (2H) -one instead of 6-bromo-3,4-dihydronaphthalen- .

Synthesis Example 1-4. Preparation of Formulas 1-4

Bromo-3,4-dihydronaphthalen-1 (2H) was obtained as a starting material in the preparation of the compound of Formula 1-2 of Synthesis Example 1-2, except that 8-bromo-3,4-dihydronaphthalen- ) -one in place of 7-bromo-3,4-dihydronaphthalen-1 (2H) -one instead of 7-bromo-3,4-dihydronaphthalen- .

Synthesis Example 1-5. Preparation of Formulas 1-5

Bromo-3,4-dihydronaphthalen-1 (2H) was obtained as a starting material in the preparation of the compound of Formula 1-2 of Synthesis Example 1-2, except that 8-bromo-3,4-dihydronaphthalen- ) -one] was used instead of 5-bromo-3,4-dihydronaphthalen-1 (2H) -one instead of 5-bromo- .

Synthesis Example 1-6. Preparation of 1-6

Bromo-3,4-dihydronaphthalen-1 (2H) was obtained as a starting material in the preparation of the compound of Formula 1-1 of Synthesis Example 1-1, except that 8-bromo-3,4-dihydronaphthalen- ) -one] was replaced by 5-bromo-3,4-dihydronaphthalen-1 (2H) -one instead of 5-bromo- .

PREPARATION EXAMPLE 1. Preparation of Formulas 2-a-a

4-bromophenyl) -4, 6-diphenyl-l, 3,5-triazine [0157] 10.0 g (26.2 mmol, 1.0 eq) of 2- 11.5 g (52.5 mmol, 2.0 eq) of Pd (t-Bu ₃ P) _2, 0.07 g (0.13 mmol) of 11.2 g (28.9 mmol, 1.1 eq) of K ₃ PO ₄ , 0.005 eq) was dissolved in 60 ml of xylene, refluxed and stirred. After 1 hour, the reaction was terminated and the solvent was removed under reduced pressure. After that, it was completely dissolved in CHCl ₃ , washed with water and decompressed again to remove about 50% of the solvent. Ethyl acetate was added in the refluxing state, and the crystals were dropped, cooled and filtered. This was subjected to column chromatography to obtain 14.5 g (21.0 mmol, yield 80%) of a compound represented by the formula 2-aa. [M] = 687

PREPARATION EXAMPLE 2 Preparation of Formulas 2-a-b

2-chloro-4- (naphthalen-2-yl) quinazoline] 8.40 g (28.9 mmol) was added to 10.0 g (26.2 mmol, 1.0 eq) _{, 1.1 eq), K 3 PO} 4 11.15 g (52.5 mmol, 2.0 eq), Pd (t-Bu 3 P) 2 0.07 g (0.13 mmol, 0.005 eq) with a stirrer to reflux and dissolved in 60 ml of xylene (xylene) did. When the reaction was completed after 3 hours, the solvent was removed by decompression. After that, it was completely dissolved in CHCl ₃ , washed with water and decompressed again to remove about 50% of the solvent. Ethyl acetate was added in the refluxing state, and the crystals were dropped, cooled and filtered. This was subjected to column chromatography to obtain 13.8 g (21.8 mmol, yield 83%) of the compound represented by the formula 2-ab. [M + H] < + > = 635

4 is a graph showing the MS data value of the formula (2-a-b).

Preparation Example 3. Preparation of the compound of formula 4-a-a

10.0 g (26.2 mmol, 1.0 eq) of the core molecule of the formula 1-4 prepared according to Synthesis Example 1-4, 6.9 g (28.9 mmol, 1 eq) of 4-chloro-2-phenylquinazoline, 0.075 g (0.13 mmol, 0.005 eq) of Pd (t-Bu ₃ P) ₂ were dissolved in 60 ml of xylene and refluxed with stirring to obtain 11.15 g (52.5 mmol, 2.0 eq) of K ₃ PO ₄ . When the reaction was completed after 3 hours, the solvent was removed by decompression. After that, it was completely dissolved in CHCl ₃ , washed with water and decompressed again to remove about 50% of the solvent. Ethyl acetate was added in the refluxing state, and the crystals were dropped, cooled and filtered. This was subjected to column chromatography to obtain 12.4 g (21.2 mmol, yield 81%) of the compound represented by the formula 4-aa. [M] = 584

Production Example 4. Preparation of the compound of the formula 5-a-a

10.0 g (26.2 mmol, 1.0 eq) of the core molecule of the formula 1-5 prepared according to Synthesis Example 1-5, 2 - ([1,1'- biphenyl] -4-yl) -4-chloroquinazoline { A solution of 9.1 g (28.9 mmol, 1.1 eq) of K ₂ PO ₄ 11.15 g (52.5 mmol, 2.0 eq), Pd (t-Bu) 2 - ([1,1'-biphenyl] -4- ₃ P) ₂ (0.03 g, 0.13 mmol, 0.005 eq) was dissolved in 60 ml of xylene and refluxed and stirred. When the reaction was completed after 3 hours, the solvent was removed by decompression. After that, it was completely dissolved in CHCl ₃ , washed with water and decompressed again to remove about 50% of the solvent. Ethyl acetate was added in a refluxing state, and the crystals were dropped, cooled and filtered. This was subjected to column chromatography to obtain 15.9 g (21.5 mmol, yield 82%) of the compound represented by the formula 5-aa. [M + H] = 661

5 shows MS data values of the formula 5-a-a.

Preparation Example 5. Preparation of the compound of the formula 5-a-b

10.0 g (26.2 mmol, 1.0 eq) of the core molecule of the formula 1-5 prepared according to Synthesis Example 1-5, 9- (2-chloroquinazolin-4-yl) -4-yl) -9H-carbazole] 9.5 g (28.9 mmol, 1.1 eq), K 3 PO 4 11.15 g (52.5 mmol, 2.0 eq), Pd (t-Bu 3 P) 2 0.07 g (0.13 mmol, 0.005 eq) was dissolved in 60 ml of xylene, refluxed and stirred. When the reaction was completed after 3 hours, the solvent was removed by decompression. After that, it was completely dissolved in CHCl ₃ , washed with water and decompressed again to remove about 50% of the solvent. Ethyl acetate was added in the refluxing state, and the crystals were dropped, cooled and filtered. This was subjected to column chromatography to obtain 14.8 g (22.0 mmol, yield 84%) of the compound represented by the formula 5-ab. [M + H] < + > = 674

Preparation Example 6. Preparation of the compound of the formula 5-a-c

10.0 g (26.2 mmol, 1.0 eq) of the core molecule of the formula 1-5 prepared according to Synthesis Example 1-5, 6.9 g (28.9 mmol) of 2-chloro-4-phenylquinazoline _{, 1.1 eq), K 3 PO} 4 11.15 g (52.5 mmol, 2.0 eq), Pd (t-Bu 3 P) 2 0.07 g (0.13 mmol, 0.005 eq) with a stirrer to reflux and dissolved in 60 ml of xylene (xylene) did. When the reaction was completed after 3 hours, the solvent was removed by decompression. After that, it was completely dissolved in CHCl ₃ , washed with water and decompressed again to remove about 50% of the solvent. Ethyl acetate was added in a refluxing state, and the crystals were dropped, cooled and filtered. This was subjected to column chromatography to obtain 13.4 g (22.8 mmol, yield 87%) of the compound represented by the formula 5-ac. [M + H] = 585

FIG. 6 is a graph showing MS data values of the formula 5-a-c.

PREPARATION EXAMPLE 7 Preparation of Formulas 5-a-d

10.0 g (26.2 mmol, 1.0 eq) of the core molecule of the formula 1-5 prepared according to Synthesis Example 1-5, 2- (4-bromophenyl) -4,6-diphenyl-1,3,5-tri 11.25 g (28.9 mmol, 1.1 eq) of K ₂ PO _4, 11.15 g (52.5 mmol, 2.0 eq) of K ₃ PO ₄ , Pd t-Bu ₃ P) ₂ (0.07 g, 0.13 mmol, 0.005 eq) was dissolved in 60 ml of xylene and refluxed and stirred. When the reaction was completed after 3 hours, the solvent was removed by decompression. After that, it was completely dissolved in CHCl ₃ , washed with water and decompressed again to remove about 50% of the solvent. Ethyl acetate was added in the refluxing state, and the crystals were dropped, cooled and filtered. This was subjected to column chromatography to obtain 18.97 g (23.9 mmol, yield 91%) of the compound 5-ad. [M + H] < + > = 687

Preparation Example 8. Preparation of the formula 6-a-a

10.0 g (26.2 mmol, 1.0 eq) of the core molecule of Formula 1-6 prepared in Synthesis Example 1-6, 6.9 g (28.9 mmol, 2-chloro-4-phenylquinazoline) 0.075 g (0.13 mmol, 0.005 eq) of Pd (t-Bu ₃ P) ₂ were dissolved in 60 ml of xylene and refluxed with stirring to obtain 11.15 g (52.5 mmol, 2.0 eq) of K ₃ PO ₄ . When the reaction was completed after 3 hours, the solvent was removed by decompression. After that, it was completely dissolved in CHCl ₃ , washed with water and decompressed again to remove about 50% of the solvent. Ethyl acetate was added in a refluxing state, and the crystals were dropped, cooled and filtered. This was subjected to column chromatography to obtain 13.7 g (22.3 mmol, yield 89%) of the compound represented by the formula 6-aa. [M + H] = 584

Example .

Example 1.

A glass substrate (corning 7059 glass) coated with ITO (indium tin oxide) at a thickness of 1,000 Å was immersed in distilled water containing a dispersing agent and washed with ultrasonic waves. The detergent was a product of Fischer Co. The distilled water was supplied by Millipore Co. Distilled water, which was secondly filtered with a filter of the product, was used. After the ITO was washed for 30 minutes, ultrasonic washing was repeated 10 times with distilled water twice. After the distilled water was washed, ultrasonic washing was performed in the order of isopropyl alcohol, acetone, and methanol solvent, followed by drying. Hexanitrile hexaazatriphenylene (HAT-CN) was thermally vacuum deposited on the prepared ITO transparent electrode to a thickness of 50 Å to form a hole injection layer. HT1 (700 Å) for transporting holes was vacuum deposited thereon, followed by HT2 (200 Å) deposition. A compound of Formula 2-a-a and dopant Dp-7 was vacuum-deposited as a host to a thickness of 300 Å. The amount of the dopant was 3 wt% based on the total amount of the host and the dopant. Then, an E1 compound (300 ANGSTROM) was sequentially vacuum-deposited by electron injection and transport layer. Lithium fluoride (LiF) having a thickness of 12 Å and aluminum having a thickness of 2,000 Å were sequentially deposited on the electron transporting layer to form a cathode, thereby preparing an organic light emitting device. In the above process, the deposition rate of the organic material was maintained at 1 Å / sec, the deposition rate of LiF was 0.2 Å / sec, and the deposition rate of aluminum was 3 Å / sec to 7 Å / sec.

≪ Example 2 >

An organic light emitting device was fabricated in the same manner as in Example 1, except that the compound of the formula 2-a-b was used instead of the compound of the formula 2-a-a.

≪ Example 3 >

An organic light emitting device was fabricated in the same manner as in Example 1, except that the compound of Formula 4-a-a was used instead of the compound of Formula 2-a-a in Example 1,

<Example 4>

An organic light emitting device was fabricated in the same manner as in Example 1 except that the compound represented by the formula 5-a-a was used instead of the compound represented by the formula 2-a-a.

&Lt; Example 5 >

An organic light emitting device was fabricated in the same manner as in Example 1, except that the compound represented by the formula 5-a-b was used instead of the compound represented by the formula 2-a-a.

&Lt; Example 6 >

An organic light emitting device was fabricated in the same manner as in Example 1 except that the compound represented by the formula 5-a-c was used instead of the compound represented by the formula 2-a-a in Example 1.

&Lt; Example 7 >

An organic light emitting device was fabricated in the same manner as in Example 1 except that the compound represented by the formula 5-a-d was used instead of the compound represented by the formula 2-a-a in Example 1

&Lt; Example 8 >

An organic light emitting device was fabricated in the same manner as in Example 1 except that the compound represented by the formula 6-a-a was used instead of the compound represented by the formula 2-a-a in Example 1

&Lt; Comparative Example 1 &

An organic light-emitting device was fabricated in the same manner as in Example 1, except that H-1 was used instead of the compound of Formula 2-a-a in Example 1.

&Lt; Comparative Example 2 &

An organic light emitting device was fabricated in the same manner as in Example 1, except that H-2 was used instead of the compound of Formula 2-a-a.

Table 1 shows the results of the organic luminescent devices fabricated by Examples 1 to 8 and Comparative Examples 1 and 2. Voltage, efficiency, and emission color are data at 5000 nit brightness. The lifetime is 100% of the initial photocurrent value, and the time of 98% is indicated.

division matter The driving voltage (V) Efficiency (cd / A) Life span T98 (hr) Luminous color Example 1 2-a-a 4.0 30.7 37 Red Example 2 2-a-b 4.4 28.5 37 Red Example 3 4-a-a 4.3 29.0 31 Red Example 4 5-a-a 4.3 29.7 30 Red Example 5 5-a-b 4.5 28.2 53 Red Example 6 5-a-c 4.5 27.9 50 Red Example 7 5-a-d 4.1 30.2 33 Red Example 8 6-a-a 4.6 27.5 45 Red Comparative Example 1 H-1 4.6 24.6 21 Red Comparative Example 2 H-2 4.9 26.1 16 Red

As can be seen from the results of Table 1, the organic light emitting device using the compound of the present invention exhibited improved luminescence efficiency while lowering the driving voltage and all emitted red light. The efficiency of the H-1 and H-2 compared to the comparative examples was improved by up to 80%, and the overall driving voltage was advantageous. Comparative Example 1 showed an advantage of driving voltage, but its lifetime was half of that of Example 5, and Comparative Example 2 showed an advantage in terms of efficiency. However, the driving voltage increased and the lifetime was less than half of Example 5. Therefore, the compound of the present invention can be considered to have the advantages of high efficiency, low driving voltage and long life in an organic light emitting device.

10, 11: Organic light emitting device
20: substrate
30: first electrode
40: light emitting layer
50: second electrode
60: Hole injection layer
70: hole transport layer
80: electron transport layer
90: electron injection layer

Claims (11)

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

In Formula 1,
R 1 and R 2, R 2 and R 3 or R 3 and R 4 in R 1 to R 13 are connected to a dotted line of the following formula (2) to form a ring,
(2)

In Formula 2,
R14 to R17 are hydrogen,
L1 is a direct bond; Or a monocyclic or polycyclic arylene group having 6 to 30 carbon atoms,
Ar &lt; 1 &gt; is represented by the following formula (A)
(A)

In the above formula (A)
Y1 to Y3 are the same or different and are each independently N or CRd,
R201 and Rd are the same or different from each other, and each independently hydrogen; An aryl group having 6 to 30 carbon atoms; Or a heteroaryl group having 2 to 30 carbon atoms, or is bonded to adjacent groups to form a ring. The heterocyclic compound according to claim 1, wherein the formula (1) is represented by any one of the following formulas (1-1) to (1-6)
[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

[Chemical Formula 1-6]

In Formulas 1-1 to 1-6,
The definitions of R 1 to R 13 are the same as those of Formula 1, and the definitions of L 1, Ar 1, and R 14 to R 17 are the same as those of Formula 2. delete delete The heterocyclic compound according to claim 1, wherein the formula (A) is represented by one of the following formulas (A-5) and (A-6)
[A-5]

In the formula (A-5), the definitions of Y1 and Y2 are the same as those of the above formula (A)
Z1 to Z4 are the same or different and each independently N or CRc,
Rc is hydrogen, or combines with adjacent groups to form a ring,
[A-6]

In formula (A-6), Y1 is as defined in formula (A)
X &lt; 1 &gt; is O, S or CR &
R210 to R213, R &apos; and R "are the same or different from each other, and are each independently hydrogen or combine with adjacent substituents to form a ring. The heterocyclic compound according to claim 5, wherein the formula (A-5) is represented by one of the following formulas (A-7) to (A-10).
[A-7]

[A-8]

[A-9]

[A-10]

In Formulas A-7 to A-10,
The definitions of Y1 and Y2 are the same as those of the above formula (A)
R202 to R205 are hydrogen, or combine with adjacent groups to form a ring. The heterocyclic compound according to claim 5, wherein the formula (A-5) is represented by one of the following formulas (A-11) to (A-18)
[A-11]

[A-12]

[A-13]

[Chemical formula A-14]

[A-15]

[A-16]

[A-17]

[A-18]

In Formulas A-11 to A-18,
R202 to R205 are hydrogen or combine with adjacent groups to form a ring,
R206 to R209 are the same or different and each independently hydrogen; An aryl group having 6 to 30 carbon atoms; Or a heteroaryl group having 2 to 30 carbon atoms. The heterocyclic compound according to claim 1, wherein the formula (1) is selected from the following structures:

A first electrode; A second electrode facing the first electrode; And at least one organic material layer including a light-emitting layer provided between the first electrode and the second electrode, wherein at least one of the organic material layers is formed of a material according to any one of claims 1, 2, and 5 to 8 And a heterocyclic compound. [Claim 11] The organic light emitting device according to claim 9, wherein the light emitting layer comprises the heterocyclic compound. [Claim 11] The organic light emitting device according to claim 9, wherein the organic material layer includes a hole transporting layer, and the hole transporting layer comprises the heterocyclic compound.

Images