KR20170108894A - Heterocyclic compound and organic light emitting device comprising the same - Google Patents

Abstract

The present invention provides a heterocyclic compound and an organic electroluminescent device comprising the same. The heterocyclic compound is represented by chemical formula 1. The compound according to one embodiment of the present application is used in an organic electroluminescent device to lower the driving voltage of the organic electroluminescent device, improve the light efficiency, and improve the lifetime characteristics of the device by the thermal stability of the compound.

Description

TECHNICAL FIELD [0001] The present invention relates to a heterocyclic compound and an organic electroluminescent device including the heterocyclic compound and an organic electroluminescent device including the same.

The present invention relates to a heterocyclic compound and an organic electroluminescent device including the same. This specification claims the benefit of Korean Patent Application No. 10-2016-0033045, filed on March 18, 2016, to the Korean Intellectual Property Office, the entire contents of which are incorporated herein by reference.

An electroluminescent device is one type of self-luminous display device, and has advantages of wide viewing angle, excellent contrast, and high 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.

Korean Patent Publication No. 2000-0051826

The present invention provides a heterocyclic compound and an organic electroluminescent device including the same.

The present application provides a heterocyclic compound represented by the following formula (1).

[Chemical Formula 1]

In Formula 1, at least two of R 1 to R 8 are -L 1 -Ar 1, and -L 1 -Ar 1 are the same or different from each other,

L 1 are the same or different and are each independently a direct bond; A substituted or unsubstituted arylene group; Or a substituted or unsubstituted heterocyclic group,

Ar 1 is the same or different and is independently selected from the group consisting of a substituted or unsubstituted aryl group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; Or a substituted or unsubstituted heterocyclic group,

The groups other than -L 1 -Ar 1 in R 1 to R 8 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; A halogen group; Cyano; A substituted or unsubstituted alkyl group; A substituted or unsubstituted arylamine group; Or a substituted or unsubstituted heterocyclic group,

Ra to Rc are the same or different from each other, and each independently hydrogen; Or deuterium.

The present application also includes a first electrode; A second electrode facing the first electrode; And at least one organic compound layer provided between the first electrode and the second electrode, wherein at least one of the organic compound layers includes the above-mentioned heterocyclic compound do.

The compound according to one embodiment of the present application is used in an organic electroluminescent device to lower the driving voltage of the organic electroluminescent device, to improve the light efficiency, and to improve the lifetime characteristics of the device by the thermal stability of the compound.

Fig. 1 shows an example of an organic electroluminescent device in which a substrate 1, an anode 2, a light emitting layer 3, and a cathode 4 are sequentially laminated.
2 shows an organic electroluminescent device 1 in which a substrate 1, an anode 2, a hole injecting layer 5, a hole transporting layer 6, a light emitting layer 3, an electron transporting layer 7 and a cathode 4 are sequentially stacked. Fig.
3 is an LC / MS spectrum of Compound 1-1 according to Synthesis Example 1. Fig.
4 is an LC / MS spectrum of Compound 2-1 according to Synthesis Example 2. Fig.
5 is an LC / MS spectrum of Compound 3-1 according to Synthesis Example 3. Fig.
6 is an LC / MS spectrum of Compound 10-1 according to Synthesis Example 4. Fig.
7 is an LC / MS spectrum of Compound 11-1 according to Synthesis Example 5. Fig.
8 is an LC / MS spectrum of Compound 12-1 according to Synthesis Example 6. Fig.

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

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

Examples of substituents herein 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; Cyano; A nitro group; A hydroxy group; An alkyl group; A cycloalkyl group; An alkenyl group; An alkoxy group; A substituted or unsubstituted phosphine oxide group; An aryl group; And a heterocyclic group, or that at least two of the substituents exemplified in the above exemplified substituents are substituted with a connected substituent, 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.

In the present specification, examples of the halogen group include fluorine, chlorine, bromine or iodine.

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 50. 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 preferably has 3 to 60 carbon atoms, and specifically includes cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, But are not limited to, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3,4,5-trimethylcyclohexyl, 4-tert- butylcyclohexyl, cycloheptyl, Do 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 20 carbon atoms. Specific examples include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentyloxy, neopentyloxy, isopentyloxy, n Butyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, benzyloxy, p-methylbenzyloxy and the like. But is not limited thereto.

In the present specification, the alkenyl group may be straight-chain or branched, and the number of carbon atoms is not particularly limited, but is preferably 2 to 40. 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 phosphine oxide group specifically includes a diphenylphosphine oxide group, dinaphthylphosphine oxide, and the like, but is not limited thereto.

In the present specification, when the aryl group is a monocyclic aryl group, the number of carbon atoms is not particularly limited, but is preferably 6 to 25 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. And preferably has 10 to 24 carbon atoms. Specific examples of the polycyclic aryl group include naphthyl, anthracenyl, phenanthryl, pyrenyl, perylenyl, klychenyl, fluorenyl, and the like.

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

,

,

,

,

,

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

,

,

,

,

,

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

), 피리다지닐기, 피라지닐기, 퀴놀리닐기, 퀴나졸리닐기, 퀴녹살리닐기, 프탈라지닐기, 피리도피리미디닐기, 피리도피라지닐기, 피라지노피라지닐기, 이소퀴놀리닐기, 인돌기, 카바졸릴기, 벤즈옥사졸릴기, 벤즈이미다졸릴기, 벤조티아졸릴기, 벤조카바졸릴기, 디벤조카바졸릴기, 벤조티오페닐기, 디벤조티오페닐기, 벤조퓨라닐기, 디벤조퓨라닐기; 벤조실롤기; 디벤조실롤기; 페난트롤리닐기(phenanthrolinyl group), 이소옥사졸릴기, 티아디아졸릴기, 페노티아지닐기, 페노옥사지닐기, 및 이들의 축합구조 등이 있으나, 이들에만 한정되는 것은 아니다. 이외에도 헤테로고리기의 예로서, 술포닐기를 포함하는 헤테로고리 구조, 예컨대,

,

등이 있다.In the present specification, the heterocyclic group includes at least one non-carbon atom or hetero atom, and specifically, the hetero atom may include at least one atom selected from the group consisting of O, N, Se and S, and the like. The number of carbon atoms of the heterocyclic group is not particularly limited, but is preferably 2 to 60 carbon atoms. Examples of the heterocyclic group include thiophenyl group, furanyl group, pyrrolyl group, imidazolyl group, thiazolyl group, oxazolyl group, oxadiazolyl group, triazolyl group, pyridyl group, bipyridyl group, pyrimidyl group, Group, an acridyl group, a hydroacridyl group (e.g.,

), A pyridazinyl group, a pyrazinyl group, a quinolinyl group, a quinazolinyl group, a quinoxalinyl group, a phthalazinyl group, a pyridopyrimidinyl group, a pyridopyranyl group, a pyrazinopyrazinyl group, an isoquinolinyl group , An indole group, a carbazolyl group, a benzoxazolyl group, a benzimidazolyl group, a benzothiazolyl group, a benzocarbazolyl group, a dibenzocarbazolyl group, a benzothiophenyl group, a dibenzothiophenyl group, a benzofuranyl group, A furanyl group; Benzosyl group; Dibenzosilyl groups; A phenanthrolinyl group, an isoxazolyl group, a thiadiazolyl group, a phenothiazinyl group, a phenoxazinyl group, a condensed structure thereof, and the like, but are not limited thereto. In addition, examples of the heterocyclic group include a heterocyclic structure including a sulfonyl group,

,

.

,

,

,

등이 될 수 있으나, 이에 한정되는 것은 아니다.In the present specification, the condensed structure may be a structure in which an aromatic carbon-hydrogen ring is condensed with the substituent. For example, as a condensation ring of benzimidazole

,

,

,

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

In one embodiment of the present specification, the groups other than -L 1 -Ar 1 in R 1 to R 8 are the same or different from each other, and each independently hydrogen; Or deuterium.

In one embodiment of the present specification, the group other than -L 1 -Ar 1 in R 1 to R 8 is hydrogen.

In one embodiment of the present specification, Ar1 is the same or different and each independently represents a substituted or unsubstituted C6 to C30 aryl; A substituted or unsubstituted arylamine group having 6 to 30 carbon atoms; A substituted or unsubstituted C2 to C30 heteroarylamine group; Or a substituted or unsubstituted heterocyclic group having 2 to 30 carbon atoms.

In one embodiment of the present specification, Ar1 represents a phenyl group which is the same as or different from each other and is independently substituted or unsubstituted; A substituted or unsubstituted naphthyl group; A substituted or unsubstituted biphenyl group; A substituted or unsubstituted terphenyl group; A substituted or unsubstituted phenanthrene group; A substituted or unsubstituted fluorene group; A substituted or unsubstituted triphenylene group; A substituted or unsubstituted diphenylamine group; A substituted or unsubstituted bisbiphenylamine group; A substituted or unsubstituted phenylbiphenylamine group; A substituted or unsubstituted triphenylene dibenzofurane amine group; A substituted or unsubstituted pyridine group; A substituted or unsubstituted pyrimidine group; A substituted or unsubstituted triazine group; A substituted or unsubstituted quinoline group; A substituted or unsubstituted quinazoline group; A substituted or unsubstituted quinoxaline group; A substituted or unsubstituted benzoquinazoline group; A substituted or unsubstituted phthalazine group; Substituted or unsubstituted phenanthrolines; A substituted or unsubstituted dimethylindenopyrimidine group; A substituted or unsubstituted carbazole group; A substituted or unsubstituted benzocarbazole group; A substituted or unsubstituted dibenzothiophene group; A substituted or unsubstituted dibenzofurane group; Or represented by the following formula (A).

(A)

In formula (A), one of U9 and U10 is N and the other is CRg,

L4 is a direct bond; Substituted or unsubstituted arylene; Or substituted or unsubstituted heteroarylene; Rg, R321 and R322 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 adjacent groups to form a substituted or unsubstituted ring, q is an integer of 1 to 5, and when q is 2 or more, structures in parentheses of two or more are the same It is different.

또는

이다. In one embodiment of the present disclosure, the formula (A)

or

to be.

In one embodiment of the present specification, Ar1 and Ar2 are the same or different and each independently represents a substituted or unsubstituted C6 to C30 aryl; Or a substituted or unsubstituted heterocyclic group having 2 to 30 carbon atoms.

In one embodiment of the present specification, Ar1 and Ar2 are the same or different and are each independently a substituted or unsubstituted phenyl group; A substituted or unsubstituted naphthyl group; A substituted or unsubstituted biphenyl group; A substituted or unsubstituted terphenyl group; A substituted or unsubstituted phenanthrene group; A substituted or unsubstituted fluorene group; A substituted or unsubstituted triphenylene group; A substituted or unsubstituted pyridine group; A substituted or unsubstituted pyrimidine group; A substituted or unsubstituted triazine group; A substituted or unsubstituted quinoline group; A substituted or unsubstituted quinazoline group; A substituted or unsubstituted quinoxaline group; A substituted or unsubstituted benzoquinazoline group; A substituted or unsubstituted phthalazine group; Substituted or unsubstituted phenanthrolines; A substituted or unsubstituted dimethylindenopyrimidine group; A substituted or unsubstituted carbazole group; A substituted or unsubstituted benzocarbazole group; A substituted or unsubstituted dibenzothiophene group; A substituted or unsubstituted benzonaphthofuran group; Or a substituted or unsubstituted dibenzofurane group. In one embodiment of the present invention, Ar 1 is a phenyl group which is the same as or different from each other and is independently substituted or unsubstituted; A substituted or unsubstituted naphthyl group; A substituted or unsubstituted biphenyl group; A substituted or unsubstituted terphenyl group; A substituted or unsubstituted phenanthrene group; A substituted or unsubstituted fluorene group; A substituted or unsubstituted triphenylene group; A substituted or unsubstituted pyridine group; A substituted or unsubstituted pyrimidine group; A substituted or unsubstituted triazine group; A substituted or unsubstituted quinoline group; A substituted or unsubstituted quinazoline group; A substituted or unsubstituted quinoxaline group; A substituted or unsubstituted benzoquinazoline group; A substituted or unsubstituted phthalazine group; Substituted or unsubstituted phenanthrolines; A substituted or unsubstituted dimethylindenopyrimidine group; A substituted or unsubstituted carbazole group; A substituted or unsubstituted benzocarbazole group; A substituted or unsubstituted dibenzothiophene group; A substituted or unsubstituted dibenzofurane group; Or a compound represented by the above formula (A), wherein the "substituted or unsubstituted" is a cyano group; An alkyl group; Phosphine oxide groups; An aryl group; Or a heterocyclic group substituted or unsubstituted by at least one of them.

In one embodiment of the present specification, Ar1 represents a phenyl group which is the same as or different from each other and is independently substituted or unsubstituted; A substituted or unsubstituted naphthyl group; A substituted or unsubstituted biphenyl group; A substituted or unsubstituted terphenyl group; A substituted or unsubstituted phenanthrene group; A substituted or unsubstituted fluorene group; A substituted or unsubstituted triphenylene group; A substituted or unsubstituted pyridine group; A substituted or unsubstituted pyrimidine group; A substituted or unsubstituted triazine group; A substituted or unsubstituted quinoline group; A substituted or unsubstituted quinazoline group; A substituted or unsubstituted quinoxaline group; A substituted or unsubstituted benzoquinazoline group; A substituted or unsubstituted phthalazine group; Substituted or unsubstituted phenanthrolines; A substituted or unsubstituted dimethylindenopyrimidine group; A substituted or unsubstituted carbazole group; A substituted or unsubstituted dibenzothiophene group; Or a substituted or unsubstituted dibenzofurane group; the "substituted or unsubstituted" is a methyl group; A phenyl group; Biphenyl group; Naphthyl group; A dibenzothiophene group; Or a dibenzofurane group. The term " substituted or unsubstituted "

In one embodiment of the present specification, Ar1 and Ar2 are the same or different from each other and are each independently a phenyl group; A naphthyl group substituted or unsubstituted with a phenyl group; Biphenyl group; A terphenyl group; Phenanthrene; A methyl group, or a fluorene group substituted or unsubstituted with a phenyl group; Triphenylene group; A phenyl group, a biphenyl group, a naphthyl group, a dibenzothiophene group, or a pyridine group substituted or unsubstituted with a dibenzofurane group; A pyrimidine group substituted or unsubstituted with a phenyl group, a biphenyl group, a naphthyl group, a dibenzothiophene group, or a dibenzofurane group; A triazine group substituted or unsubstituted with a phenyl group, a biphenyl group, a naphthyl group, a dibenzothiophene group, or a dibenzofurane group; A quinolinyl group substituted or unsubstituted with a phenyl group; A quinazoline group substituted or unsubstituted with a phenyl group; A quinoxaline group substituted or unsubstituted with a phenyl group; A benzoquinazoline group substituted or unsubstituted with a phenyl group; A phthalazine group substituted or unsubstituted with a phenyl group; Phenanthroline; A dimethylindenopyrimidine group substituted or unsubstituted with a phenyl group; A carbazole group substituted or unsubstituted with a phenyl group; Benzocarbazole group; A dibenzothiophene group; Or a dibenzofurane group.

L 1 are the same or different and are each independently a direct bond; A substituted or unsubstituted arylene group having 6 to 30 carbon atoms; Or a substituted or unsubstituted divalent heterocyclic group having 2 to 30 carbon atoms.

In one embodiment of the present specification, L < 1 > is the same as or different from each other, and each independently is a direct bond; A substituted or unsubstituted phenylene group; A substituted or unsubstituted naphthalene group; A substituted or unsubstituted divalent benzofluorene group; A substituted or unsubstituted divalent pyridine group; A substituted or unsubstituted divalent pyrimidine group; A substituted or unsubstituted divalent triazine group; A divalent substituted or unsubstituted divalent carbazole group; A substituted or unsubstituted divalent dibenzocarbazole group; A substituted or unsubstituted divalent quinoline group; A substituted or unsubstituted divalent quinazoline group; Or a divalent formula (A).

In one embodiment of the present specification, L 1 is a phenylene group substituted or unsubstituted with a cyano group or an aryl group; A naphthalene group substituted or unsubstituted with a cyano group or an aryl group; A divalent benzofluorene group substituted or unsubstituted with a cyano group or an aryl group; A divalent pyridine group substituted or unsubstituted with a cyano group or an aryl group; A divalent pyrimidine group substituted or unsubstituted with a cyano group or an aryl group; A divalent triazine group substituted or unsubstituted with a cyano group or an aryl group; A divalent carbazole group substituted or unsubstituted with a cyano group or an aryl group; A divalent dibenzocarbazole group substituted or unsubstituted with a cyano group or an aryl group; A divalent quinoline group substituted or unsubstituted with a cyano group or an aryl group; A divalent quinazoline group substituted or unsubstituted with a cyano group or an aryl group; Or the divalent formula (A).

In one embodiment of the present disclosure, L1 is a phenylene group; A naphthalene group; A divalent benzofluorene group; A divalent pyridine group; A divalent pyrimidine group substituted or unsubstituted with cyano group; A bivalent triazine group; A divalent carbazole group; A divalent dibenzocarbazole group; A divalent quinoline group; Or a divalent quinazoline group; to be.

L1 and L2 are the same or different and are each independently a direct bond; Or a substituted or unsubstituted arylene group having 6 to 30 carbon atoms.

In one embodiment of the present disclosure, L1 and L2 are selected from the group consisting of a phenylene group; Or a naphthalene group.

In one embodiment of the present invention, Formula 1 is represented by the following Formulas 1-1 to 1-16.

The dashed line in Formulas 1-1 to 1-16 represents a position at which the compound bonds with -L1-Ar1 and -L2-Ar2, and L1, L2, Ar1 and Ar2 are as defined in Formula 1 above.

In one embodiment of the present invention, the compound represented by Formula 1 is any one selected from the following structural formulas.

The compounds of the present invention were prepared by using Buchwald-Hartwig coupling reaction, Heck coupling reaction, Suzuki coupling reaction or the like as a typical reaction.

PREPARATION EXAMPLE 1 Preparation of the compound of formula (1A)

1) Preparation of formula (I-a)

70.00 g (1.0 eq) of 2-bromo-9H-carbazole and 52.14 g (1.5 eq) of KOtBu were placed in 1.0 L of DMF (dimethylformamide) and heated and stirred. At the start of the reflux, 80.23 g (1.1 eq) of 1-chloro-3-fluoro-2-iodobenzene was added. After the reaction was completed after 3 hours, the reaction product was poured into water and the crystal was dropped and filtered. The filtered solid was completely dissolved in CHCl ₃ , washed with water, and then decompressed to remove the solvent, which was purified by column chromatography. 107.3 g (yield 78%) of the compound of the formula 1-a was obtained. [M + H] = 482

2) Preparation of compound of formula 1A

Formula 1-a 107.3 g Pd (PPh 3) to _{(1.0 eq) 4 2.58 g (} 0.01 eq), K 2 CO 3 61.72 g (2.0 eq) was stirred under reflux into a 1.1 L dioxane dioxane. 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. 55.1 g (yield 70%) of the formula 1A was obtained. [M + H] < + > = 354

3) The compound of the present invention was synthesized by using Buchwald-Hartwig coupling reaction or Suzuki coupling reaction of the formula (1).

PREPARATION EXAMPLE 2. Preparation of Formula (2A)

2-fluoro-1-iodobenzene was used instead of 1-chloro-3-fluoro-2-iodobenzene to synthesize Formula (2A).

Preparation 3. Preparation of compound (3A)

3-iodobenzene was used instead of 1-chloro-3-fluoro-2-iodobenzene to synthesize Formula (3A).

Production example 4. Preparation of the compound of formula 4A

Bromo-9H-carbazole instead of 2-bromo-9H-carbazole and 1-chloro-2-fluoro-3-iodobenzene instead of 1- (4A) was synthesized in the same manner as in the preparation of compound (1A).

Preparation 5. Preparation of the compound of formula 5A

Fluoro-1-iodobenzene instead of 4-bromo-9H-carbazole and 1-chloro-3-fluoro-2- (5A) was synthesized in the same manner as in the preparation of compound of formula (1A).

Preparation 6. Preparation of the compound of formula 6A

Bromo-9H-carbazole instead of 2-bromo-9H-carbazole and 1-chloro-3-fluoro-2-iodobenzene instead of 1-chloro-3-fluoro-2- (6A) was synthesized in the same manner as in the preparation of compound (1A).

Preparation 7. Preparation of compound 7A

Bromo-9H-carbazole instead of 2-bromo-9H-carbazole and 1-chloro-2-fluoro-3-iodobenzene instead of 1-chloro-3-fluoro-2-iodobenzene (7A) was synthesized in the same manner as in the preparation of compound (1A).

Preparation 8. Preparation of the compound of formula 8A

Fluoro-1-iodobenzene instead of 4-bromo-9H-carbazole and 1-chloro-3-fluoro-2- (8A) was synthesized in the same manner as in the preparation of compound (1A).

Preparation 9. Preparation of 9A

Chloro-3-fluoro-2-iodobenzene instead of 4-bromo-9H-carbazole and 1-chloro-3-fluoro-2-iodobenzene in place of 2-bromo-9H- (9A) was synthesized in the same manner as in the preparation of compound of formula (1A).

Preparation 10. Preparation of Formula 10A

Chloro-3-fluoro-2-iodobenzene, 1-chloro-2-fluoro-3-iodobenzene was used to synthesize the compound of formula (10A).

Preparation 11. Preparation of the compound of formula 11A

Chloro-3-fluoro-2-iodobenzene, 4-chloro-2-fluoro-1-iodobenzene was used instead of 1-chloro-3-

Preparation 12. Preparation of Formula 12A

Bromo-9H-carbazole instead of 2-bromo-9H-carbazole and 1-chloro-2-fluoro-3-iodobenzene instead of 1- (12A) was synthesized in the same manner as in the preparation of compound (1A).

Preparation 13. Preparation of Formula 13A

1) Preparation of the compound of formula 13-a

100.0 g (1.0 eq) of 3-amino-5-chlorophenol and 172.5 g (1.05 eq) of 1,2-dibromobenzene were completely dissolved in 500 ml of toluene in a 1000 ml round-bottomed flask under nitrogen atmosphere and sodium tert-butoxide 7.12 g (0.02 eq) of bis (tri-tert-butylphosphine) palladium (0) was added to 100.4 g (1.5 eq) of sodium tert- And the mixture was heated and stirred for 13 hours. After the temperature was lowered to room temperature and the salt was removed by filtration, the toluene was concentrated under reduced pressure and 177.5 g (yield: 85%) of a compound represented by the formula 13-a was obtained by column chromatography with tetrahydrofuran: hexane = 1: [M + H] < + > = 298

2) Preparation of compound of formula 13-b

Formula 13-a to 177.5 g (1.0 eq) Pd ( PPh 3) 4 6.87 g (0.01 eq), K 2 CO 3 164.3 g (2.0 eq) the mixture was stirred and placed under reflux for 1.7 L DMAC. After 1.5 hours, the reaction mixture was poured into water, and the 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. 99.1 g (yield: 76%) of the compound of the formula 13-b was obtained. [M + H] < + > = 218

3) Preparation of the compound of formula 13-c

99.1 g (1.0 eq) of the compound represented by the formula 13-b and 83.47 g (1.5 eq) of KOtBu were added to 1.0 L of DMF (dimethylformamide) and the mixture was heated and stirred. At the beginning of the reflux, 121.30 g (1.2 eq) of 1-fluoro-2-iodobenzene was added. After the reaction was completed after 5 hours, the reaction product was poured into water and the crystals were dropped and filtered. The filtered solid was completely dissolved in CHCl ₃ , washed with water, and then decompressed to remove the solvent, which was purified by column chromatography. 136.6 g (71% yield) of the compound represented by the formula 13-c was obtained. [M + H] < + > = 420

4) Preparation of the compound of formula 13-d

Formula 13-c 136.6 g Pd (PPh 3) to _{(1.0 eq) 4 3.76 g (} 0.01 eq), K 2 CO 3 89.98 g (2.0 eq) was stirred under reflux into a 1.3 L dioxane dioxane. 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. 64.9 g (yield 68%) of the compound of the formula 13-d was obtained. [M + H] < / RTI > = 292

5) Preparation of compound of formula 13A

To 64.9 g (1.0 eq) of the compound of the formula 13-d was dissolved 400 ml of acetonitrile and K ₂ CO ₃ After dissolving 50.77 g (1.5 eq) in 250 ml of water, 44.05 ml (1.1 eq) of nonafluorobutanesulfonyl fluoride is slowly added dropwise at 0 for 30 minutes. Thereafter, the mixture was stirred at room temperature for 3 hours. After the reaction was completed, the solution was completely dissolved in dichloromethane, washed with water, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, recrystallized using ethanol, and dried to obtain 90.9 g of a compound of Formula 13A (yield 71%). [M + H] < + > = 574

6) The compound of the present invention was synthesized by using Buchwald-Hartwig coupling reaction or Suzuki coupling reaction.

Preparation 14. Preparation of Formula 14A

5-bromo-1-chloro-3-fluoro-2-iodobenzene was used instead of 9H-carbazole and 1-chloro-3-fluoro-2-iodobenzene in place of 2-bromo-9H- (14A) was synthesized in the same manner as in the preparation of compound (1A).

Preparation 15. Preparation of compound of formula 15A

Bromo-4-chloro-2-fluoro-3-iodobenzene instead of 9H-carbazole, l-chloro-3-fluoro- (15A) was synthesized in the same manner as in the preparation of compound (1A).

Preparation 16. Preparation of Formula 16A

Bromo-2-chloro-3-fluoro-4-iodobenzene instead of 9H-carbazole, l-chloro-3- fluoro- (16A) was synthesized in the same manner as in the preparation of compound (1A).

The present invention also provides an organic electroluminescent device comprising the aforementioned compound.

In one embodiment of the present application, the first electrode; A second electrode facing the first electrode; And at least one organic material layer provided between the first electrode and the second electrode, wherein at least one of the organic material layers includes the heterocyclic compound .

When a member is referred to herein as being "on " another member, it includes not only a member in contact with another member but also another member between the two members.

Whenever a component is referred to as "comprising ", it is to be understood that the component may include other components as well, without departing from the scope of the present invention.

The organic material layer of the organic electroluminescent device of the present application may have a single-layer structure, but may have a multilayer structure in which two or more organic material layers are stacked. For example, as a representative example of the organic electroluminescent device of the present invention, the organic electroluminescent device may have a structure including a hole injecting layer, a hole transporting layer, a light emitting layer, an electron transporting layer, an electron injecting layer, etc. as an organic material layer. However, the structure of the organic electroluminescent device is not limited thereto and may include a smaller number of organic layers.

In one embodiment of the present application, the organic layer includes a light emitting layer, and the light emitting layer includes the heterocyclic compound.

In one embodiment of the present application, the thickness of the organic material layer is 1 ANGSTROM to 1000 ANGSTROM, more preferably 1 ANGSTROM to 500 ANGSTROM.

In one embodiment of the present application, the organic layer includes a light emitting layer, and the light emitting layer includes the heterocyclic compound as a host material.

In one embodiment of the present application, the organic layer includes a light emitting layer, and the light emitting layer includes the heterocyclic compound as a host material, and further includes another host material.

In one embodiment of the present application, the organic layer includes a light emitting layer, the light emitting layer includes the heterocyclic compound as a host material, and further includes another host material, 9 to 9: 1.

In one embodiment of the present application, the organic layer includes a light emitting layer, the light emitting layer includes the heterocyclic compound as a host material, and further includes another host material, 5 < / RTI >

In one embodiment of the present application, the other host material is a material comprising a carbazole.

In one embodiment of the present application, the other host material may be represented by the following formula (B).

[Chemical Formula B]

In the formula (B), R200 and 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 heterocyclic group.

In one embodiment of the present application, R200 and R201 are the same or different and each independently a substituted or unsubstituted aryl group.

In one embodiment of the present application, R200 and R201 are the same or different and each independently represents 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 triphenylene group; A substituted or unsubstituted phenanthrene group; Or a substituted or unsubstituted fluorene group.

In one embodiment of the present application, R200 and R201 are the same or different and each independently represents 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 triphenylene group; A substituted or unsubstituted phenanthrene group; Or a substituted or unsubstituted fluorene group, and the "substituted or unsubstituted" substituent is substituted or unsubstituted with a cyano group, a halogen group, an alkyl group, an alkoxy group, or an aryl group.

In one embodiment of the present application, R200 and R201 are the same or different and each independently represents 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 triphenylene group; A substituted or unsubstituted phenanthrene group; Or a substituted or unsubstituted fluorene group means that the substituent of the "substituted or unsubstituted" is substituted or unsubstituted with cyano group, F, methyl group, methoxy group, phenyl group, naphthyl group or phenanthrene group.

In one embodiment of the present application, R200 and R201 are the same or different and each independently represents a substituted or unsubstituted phenyl group; A substituted or unsubstituted biphenyl group; Or a substituted or unsubstituted naphthyl group.

In one embodiment of the present application, R200 and R201 are the same or different and each independently represents a substituted or unsubstituted phenyl group; Or a substituted or unsubstituted biphenyl group.

In one embodiment of the present application, R200 and R201 are the same or different and are each independently a phenyl group; Or a biphenyl group.

In one embodiment of the present application, R200 is a phenyl group, and R201 is a biphenyl group.

In one embodiment of the present application, the compound of formula (B) is a compound selected from the following structural formulas.

In one embodiment of the present application, the organic layer includes a light emitting layer, the light emitting layer includes the heterocyclic compound, and further includes a dopant compound.

In one embodiment of the present application, the organic layer includes a light emitting layer, and the light emitting layer contains the heterocyclic compound and the dopant compound in a ratio of 100: 1 to 5: 5.

In one embodiment of the present application, the dopant compound can be selected from the following structural formulas, but is not limited thereto.

In one embodiment of the present application, the organic material layer includes a hole injecting layer or a hole transporting layer, and the hole injecting layer or the hole transporting layer includes the heterocyclic compound.

In one embodiment of the present application, the organic layer includes an electron transporting layer or an electron injecting layer, and the electron transporting layer or the electron injecting layer includes the heterocyclic compound.

In one embodiment of the present application, the organic layer includes an electron blocking layer or a hole blocking layer, and the electron blocking layer or the hole blocking layer includes the heterocyclic compound.

In one embodiment of the present application, the organic electroluminescent device includes a first electrode; A second electrode facing the first electrode; And a light emitting layer provided between the first electrode and the second electrode; And two or more organic layers disposed between the light emitting layer and the first electrode or between the light emitting layer and the second electrode, and at least one of the two or more organic layers includes the heterocyclic compound.

In one embodiment of the present application, the two or more organic layers may be selected from the group consisting of an electron transport layer, an electron injection layer, a layer that simultaneously transports electrons and electrons, and a hole blocking layer.

In one embodiment of the present application, the organic material layer includes two or more electron transporting layers, and at least one of the two or more electron transporting layers includes the heterocyclic compound. Specifically, in one embodiment of the present specification, the heterocyclic compound may be contained in one of the two or more electron transporting layers, and may be included in each of two or more electron transporting layers.

In the embodiment of the present application, when the compound is contained in each of the two or more electron transporting layers, the materials other than the above compounds may be the same or different from each other.

In one embodiment of the present application, the organic layer further includes a hole injection layer or a hole transport layer containing a compound having an arylamino group, a carbazolyl group or a benzocarbazolyl group in addition to the organic compound layer containing the heterocyclic compound.

In another embodiment, the organic electroluminescent device may be a normal type organic electroluminescent device in which an anode, at least one organic material layer, and a cathode are sequentially stacked on a substrate.

 In another embodiment, the organic electroluminescent device may be an inverted type organic electroluminescent device in which a cathode, at least one organic material layer, and an anode are sequentially stacked on a substrate.

For example, the structure of an organic electroluminescent device according to one embodiment of the present application is illustrated in Figs. 1 and 2. Fig.

1 shows a structure of an organic electroluminescent device in which a substrate 1, an anode 2, a light emitting layer 3, and a cathode 4 are sequentially laminated. In such a structure, the heterocyclic compound may be included in the light emitting layer (3).

2 shows an organic electroluminescent device 1 in which a substrate 1, an anode 2, a hole injecting layer 5, a hole transporting layer 6, a light emitting layer 3, an electron transporting layer 7 and a cathode 4 are sequentially stacked. Are illustrated. In such a structure, the heterocyclic compound may be contained in at least one of the hole injection layer 5, the hole transport layer 6, the light emitting layer 3, and the electron transport layer 7.

In such a structure, the heterocyclic compound may be contained in at least one of the hole injecting layer, the hole transporting layer, the light emitting layer, and the electron transporting layer.

The organic electroluminescent device of the present application can be produced by materials and methods known in the art, except that at least one of the organic layers includes the heterocyclic compound of the present invention, i.e., the heterocyclic compound.

When the organic electroluminescent device includes a plurality of organic layers, the organic layers may be formed of the same material or different materials.

 The organic electroluminescent device of the present application can be produced by materials and methods known in the art, except that one or more of the organic layers include the above compound, that is, the compound represented by the above formula (1).

For example, the organic electroluminescent device of the present application can be manufactured by sequentially laminating a first electrode, an organic material layer, and a second electrode on a substrate. At this time, by using a PVD (physical vapor deposition) method such as a sputtering method or an e-beam evaporation method, a metal or a metal oxide having conductivity or an alloy thereof is deposited on the substrate to form a positive electrode Forming an organic material layer including a hole injecting layer, a hole transporting layer, a light emitting layer and an electron transporting layer thereon, and depositing a material usable as a cathode thereon. In addition to such a method, an organic electroluminescent device can be manufactured by sequentially depositing a cathode material, an organic material layer, and a cathode material on a substrate.

In addition, the heterocyclic compound of 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 electroluminescent 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.

In addition to such a method, an organic electroluminescent device can also be fabricated by sequentially depositing an organic material layer and a cathode material on a substrate from a cathode material (International Patent Application Publication No. 2003/012890). However, the manufacturing method is not limited thereto.

In one embodiment of the present application, the first electrode is an anode and the second electrode is a cathode.

In another embodiment, 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 or LiO ₂ / Al, but are not limited thereto.

The hole injecting material is a layer for injecting holes from the electrode. The hole injecting material has a hole injecting effect, a hole injecting effect in the anode, and an excellent hole injecting effect in the light emitting layer or the light emitting material. A compound which prevents the exciton from migrating to the electron injection layer or the electron injection material and is also excellent in the thin film forming ability 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 light emitting material 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 good 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; Compounds of the benzoxazole, benzothiazole and benzimidazole series; 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 is 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 heterocycle-containing compounds include dibenzofuran derivatives, ladder furan compounds, And derivatives thereof, but are not limited thereto.

The electron transporting material is a layer that receives electrons from the electron injecting layer and transports electrons to the light emitting layer. The electron transporting material is a material capable of transferring electrons from the cathode well to the light emitting layer. 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 having a low work function followed by an aluminum layer or a 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 injecting layer. Specific examples thereof include, but are not limited to, oxadiazole derivatives, triazole derivatives, phenanthroline derivatives, BCP, aluminum complexes and the like.

The organic electroluminescent device according to the present invention may be a front emission type, a back emission type, or a both-sided emission type, depending on the material used.

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 application is not construed as being limited to the embodiments described below. The embodiments of the present application are provided to enable those skilled in the art to more fully understand the present invention.

Synthetic example

Synthesis Example 1. Compound 1-1

(A) Preparation of intermediate 1a

Formula 1A 20.00 g (9- phenyl -9H- carbazol-3-yl) Boro Nick acid 17.81 g (1.1 eq), the _{Pd (PPh 3) 4 0.65 g} (0.01 eq), dissolved in water in (1.0 eq) 23.38 g (3.0 eq) of K ₂ CO ₃ was added to 200 ml of THF, and the mixture was refluxed and stirred. After 6 hours, the aqueous layer was removed and the solution was concentrated under reduced pressure. This was dissolved in CHCl ₃ and completely washed with water. The solution in which the product was dissolved was further concentrated under reduced pressure and purified by column chromatography to obtain 22.6 g (yield 77%) of Intermediate 1a as a white solid. [M + H] < + > = 517

(B) Preparation of intermediate 1b

6.40 g (1.2 eq) of bis (pinacolato) diboron, 0.75 g (0.03 eq) of Pd (dba) ₂ , 0.74 g (0.06 eq) of PCy ₃ and 12.87 g (3.0 eq) of KOAc were added to 22.6 g eq) was added to 250 mL of dioxane, refluxed, and stirred for 3 hours. After completion of the reaction was confirmed by TLC, the salt was removed by filtration, and the solution was concentrated under reduced pressure. This was dissolved in CHCl ₃ and completely washed with water. The solution in which the product was dissolved was concentrated under reduced pressure, recrystallized using ethanol, and dried to obtain 20.8 g (yield 78%) of Intermediate 1b. [M + H] = 609

(C) Preparation of formula 1-1

2-chloro-4,6-diphenyl-1,3,5-triazine 9.61 g (1.05 eq), Pd (PPh 3) 4 0.79 g (0.02 eq), water in the intermediate 1b 20.8 g (1.0 eq) 14.17 g (3.0 eq) of dissolved K ₂ CO ₃ was added to 200 mL of THF, and the mixture was refluxed and stirred. After 12 hours, the aqueous layer was removed and the solution was concentrated under reduced pressure. This was dissolved in CHCl ₃ and completely washed with water. The solution in which the product was dissolved was further concentrated under reduced pressure, and tetrahydrofuran and ethyl acetate were recrystallized using a mixed solution to obtain 17.6 g (yield 72%) of Compound 1-1. [M + H] = 714

The LC / MS spectrum of the compound 1-1 is shown in FIG.

Synthesis Example 2. Synthesis of Compound 2-1

(A) Preparation of intermediate 2a

12.89 g (1.2 eq) of bis (pinacolato) diboron and 0.31 g (0.01 eq) of Pd (dppf) Cl ₂ were added to 15.0 g (1.0 eq) of the formula 2A and 12.45 g (3.0 eq) of KOAc were added to 150 mL of dioxane Refluxed and stirred for 9 hours. After completion of the reaction was confirmed by TLC, the salt was removed by filtration, and the solution was concentrated under reduced pressure. This was dissolved in CHCl ₃ and completely washed with water. The solution in which the product was dissolved was concentrated under reduced pressure, recrystallized using ethanol, and dried to obtain 13.9 g (yield 82%) of intermediate 2a. [M + H] = 402

(B) Preparation of intermediate 2b

For intermediate 2a 13.9 g (1.0 eq) 2- chloro-4,6-diphenyl-1,3,5-triazine 9.73 g (1.05 eq), Pd (PPh 3) 4 0.40 g (0.01 eq), in water 14.35 g (3.0 eq) of dissolved K ₂ CO ₃ was added to 140 mL of THF, and the mixture was refluxed and stirred. After 6 hours, the aqueous layer was removed and the solution was concentrated under reduced pressure. This was dissolved in CHCl ₃ and completely washed with water. The solution in which the product was dissolved was further concentrated under reduced pressure, and CHCl ₃ and ethyl acetate were recrystallized using a mixed solution to obtain 12.1 g (yield 69%) of intermediate 2b. [M + H] < + > = 507

(C) Preparation of Formula 2-1

Intermediate 2b 12.1 g (1.0 eq) in triphenylene-2-yl Boro Nick acid 7.10 g (1.1 eq), Pd (t-Bu 3 P) 2 0.36 g (0.03 eq), dissolved in water, K ₃ PO ₄ 10.1 g (2.00 eq) was added to 150 mL of dioxane, and the mixture was refluxed and stirred. After 5 hours, the aqueous layer was removed and the solution was concentrated under reduced pressure. This CHCl ₃ Dissolve and wash thoroughly with water to remove salts. Tetrahydrofuran and ethyl acetate were recrystallized using a mixed solution to obtain 11.8 g (yield 71%) of the compound 2-1. [M + H] = 699

The LC / MS spectrum of the compound 2-1 is shown in Fig.

Synthesis Example 3. Synthesis of Compound 3-1

(A) Preparation of intermediate 3a

Intermediate 3a was prepared in the same manner as Intermediate 2a except for using Compound (3) instead of Compound (2).

(B) Preparation of intermediate 3b

(Dibenzo [b, d] furan-l-yl) -6-phenyl (2-chloro-phenyl) -1,3,5-triazine, the intermediate 3b was prepared in the same manner as the intermediate 2b.

(C) Preparation of Formula 3-1

2-ylboronic acid instead of [1,1'-biphenyl] -4-ylboronic acid in place of Intermediate 3b, Intermediate 3b was obtained in the same manner as in the method for preparing Compound (2) (3-1).

The LC / MS spectrum of the compound 3-1 is shown in Fig.

Synthesis Example 4. Compound 10-1

(A) Preparation of intermediate 10a

Intermediate 1a was prepared except that (9-phenyl-9H-carbazol-2-yl) boronic acid was used instead of (10-A) The intermediate 10a was prepared in the same manner as the intermediate 10a.

(B) Preparation of intermediate 10b

Intermediate 10b was prepared in the same manner as Intermediate 1b except that Intermediate 10a was used instead of Intermediate 1a.

(C) Preparation of formula (10-1)

(10-1) was prepared in the same manner as in the preparation of the compound of formula (1-1), except that Intermediate 10b was used instead of Intermediate 1b.

The LC / MS spectrum of the compound 10-1 is shown in Fig.

Synthesis Example 5: Synthesis of Compound 11-1

(A) Preparation of intermediate 11a

Intermediate 1a was prepared except that dibenzo [b, d] thiophen-3-ylboronic acid was used instead of the compound of formula (11A), (9-phenyl-9H-carbazol- The intermediate 11a was prepared.

(B) Preparation of intermediate 11b

Intermediate 11b was prepared in the same manner as Intermediate 11b except for using Intermediate 11a instead of Intermediate 1a.

(C) Preparation of Formula 11-1

(11-1) was prepared in the same manner as in the preparation of compound (1-1) except that intermediate (11b) was used instead of intermediate (1b).

The LC / MS spectrum of the compound 11-1 is shown in Fig.

Synthesis Example 6. Synthesis of Compound 12-1

(A) Preparation of intermediate 12a

Except that dibenzo [b, d] furan-1-ylboronic acid was used instead of (9-phenyl-9H-carbazol-3-yl) , The intermediate 12a was prepared.

(B) Preparation of (12-1)

Intermediate 12a was obtained in the place of Intermediate 2b, and 2,4-diphenyl-6- (4- (4,4,5,5,5-tetramethyl-1,3,2-dioxabor 2-yl) phenyl) -1,3,5-triazine was used in place of the compound of the formula (1).

The LC / MS spectrum of the compound 12-1 is shown in FIG.

< Comparative Example  1>

A thin glass substrate coated with ITO (indium tin oxide) at a thickness of 1,300 Å was immersed in distilled water containing detergent and washed with ultrasonic waves. At this time, a Fischer Co. product was used as a detergent, and distilled water, which was filtered with a filter of Millipore Co., was used as distilled water. The ITO was washed for 30 minutes and then washed twice with distilled water and ultrasonically cleaned for 10 minutes. After the distilled water was washed, it was ultrasonically washed with a solvent of isopropyl alcohol, acetone, and methanol, dried, and then transported to a plasma cleaner. Further, the substrate was cleaned using oxygen plasma for 5 minutes, and then the substrate was transported by a vacuum evaporator.

The following HI-1 compound was thermally vacuum deposited on the ITO transparent electrode prepared above to a thickness of 50 Å to form a hole injection layer.

The HT-1 compound was thermally vacuum-deposited on the hole injection layer to a thickness of 250 Å to form a hole transport layer, and an HT-2 compound was vacuum deposited on the HT-1 deposition layer to a thickness of 50 Å to form an electron blocking layer.

Then, Compound H-1 and phosphorescent dopant Dp-25 were co-deposited on the HT-2 deposited film at a weight ratio of 12-20% to form a 400Å thick light emitting layer.

An ET-1 material was vacuum deposited on the light emitting layer to a thickness of 250 ANGSTROM and an ET-2 material was vacuum deposited on the ETQ material to a thickness of 100 ANGSTROM to a 2% weight ratio of LiQ to form an electron transport layer and an electron injection layer. Aluminum was deposited on the electron injecting layer to a thickness of 1000 to form a cathode.

In the above process, the deposition rate of the organic material was maintained at 0.4 to 0.7 Å / sec, the deposition rate of aluminum was maintained at 2 Å / sec, and the vacuum degree during deposition was maintained at 1 × 10 ^-7 to 5 × 10 ^-8 torr Respectively.

< Experimental Example  1>

An organic electroluminescent device was fabricated in the same manner as in Comparative Example 1, except that Compound 1-1 was used in place of Compound H-1 in Comparative Example 1.

< Experimental Example  2>

An organic electroluminescent device was fabricated in the same manner as in Comparative Example 1, except that Compound 2-1 was used instead of Compound H-1 in Comparative Example 1.

< Experimental Example  3>

An organic electroluminescent device was fabricated in the same manner as in Comparative Example 1, except that Compound 3-1 was used instead of Compound H-1 in Comparative Example 1.

< Experimental Example  4>

An organic electroluminescent device was fabricated in the same manner as in Comparative Example 1, except that Compound 10-1 was used in place of Compound H-1 in Comparative Example 1.

< Experimental Example  5>

An organic electroluminescent device was fabricated in the same manner as in Comparative Example 1, except that Compound 11-1 was used instead of Compound H-1 in Comparative Example 1.

< Experimental Example  6>

An organic electroluminescent device was fabricated in the same manner as in Comparative Example 1, except that Compound 12-1 was used instead of Compound H-1 in Comparative Example 1.

< Comparative Example  2>

An organic electroluminescent device was fabricated in the same manner as in Comparative Example 1, except that Compound H-1 and H-2 were used in a ratio of 50:50 instead of Compound H-1 in Comparative Example 1.

< Experimental Example  7>

An organic electroluminescent device was fabricated in the same manner as in Comparative Example 1, except that Compound 1-1 and H-2 were used in a ratio of 50:50 instead of Compound H-1 in Comparative Example 1.

< Experimental Example  8>

An organic electroluminescent device was fabricated in the same manner as in Comparative Example 1, except that Compound 2-1 and H-2 were used in a ratio of 50:50 instead of Compound H-1 in Comparative Example 1.

< Experimental Example  9>

An organic electroluminescent device was fabricated in the same manner as in Comparative Example 1, except that Compound 3-1 and H-2 were used in a ratio of 50:50 instead of Compound H-1 in Comparative Example 1.

< Experimental Example  10>

An organic electroluminescent device was fabricated in the same manner as in Comparative Example 1, except that Compound 11-1 and H-2 were used in a ratio of 50:50 instead of Compound H-1 in Comparative Example 1.

< Experimental Example  11>

An organic electroluminescent device was fabricated in the same manner as in Comparative Example 1, except that Compound 12-1 and H-2 were used in a ratio of 50:50 instead of Compound H-1 in Comparative Example 1.

< Comparative Example  3>

An organic electroluminescent device was fabricated in the same manner as in Comparative Example 1 except that the compound C-1 was used instead of the compound H-1 in the above Comparative Example 1.

< Comparative Example  4>

An organic luminescent device was prepared in the same manner as in Comparative Example 1, except that the compound C-2 was used instead of the compound H-1 in the above Comparative Example 1.

< Comparative Example  5>

An organic electroluminescent device was fabricated in the same manner as in Comparative Example 1 except that the compound C-3 was used instead of the compound H-1 in the above Comparative Example 1.

< Comparative Example  6>

An organic electroluminescent device was fabricated in the same manner as in Comparative Example 1, except that the compound C-1 and the compound H-2 were used in a ratio of 50:50 instead of the compound H-1.

< Comparative Example  7>

An organic electroluminescent device was fabricated in the same manner as in Comparative Example 1, except that Compound C-2 and H-2 were used in a ratio of 50:50 instead of Compound H-1 in Comparative Example 1.

compound Voltage V
(@ 10 mA / cm ² ) Efficiency cd / A
(@ 10 mA / cm ² ) Luminous color T95
(@ 20 mA / cm ² ) Comparative Example 1 H-1 3.01 60 green 40 Experimental Example 1 Compound 1-1 2.73 64.8 green 69 Experimental Example 2 Compound 2-1 2.69 63.7 green 65 Experimental Example 3 Compound 3-1 2.80 63.3 green 57 Experimental Example 4 Compound 10-1 2.75 66.2 green 62 Experimental Example 5 Compound 11-1 2.84 62.0 green 60 Experimental Example 6 Compound 12-1 2.77 65.1 green 64 Comparative Example 2 H-1, H-2 3.52 67 green 140 Experimental Example 7 Compound 1-1, H-2 3.29 73.5 green 186 Experimental Example 8 Compound 2-1, H-2 3.26 75.7 green 183 Experimental Example 9 Compound 3-1, H-2 3.32 68.3 green 167 Experimental Example 10 Compound 11-1, H-2 3.29 70.8 green 170 Experimental Example 11 Compound 12-1, H-2 3.27 72.2 green 173 Comparative Example 3 C-1 2.85 61.5 green 44 Comparative Example 4 C-2 2.88 61.1 green 43 Comparative Example 5 C-3 3.19 58.7 green 37 Comparative Example 6 C-1, H-2 3.70 69.0 green 144 Comparative Example 7 C-2, H-2 3.72 69.5 green 141

< Comparative Example 8 >

A thin glass substrate coated with ITO (indium tin oxide) at a thickness of 1,300 Å was immersed in distilled water containing detergent and washed with ultrasonic waves. At this time, a Fischer Co. product was used as a detergent, and distilled water, which was filtered with a filter of Millipore Co., was used as distilled water. The ITO was washed for 30 minutes and then washed twice with distilled water and ultrasonically cleaned for 10 minutes. After the distilled water was washed, it was ultrasonically washed with a solvent of isopropyl alcohol, acetone, and methanol, dried, and then transported to a plasma cleaner. Further, the substrate was cleaned using oxygen plasma for 5 minutes, and then the substrate was transported by a vacuum evaporator.

The following HI-1 compound was thermally vacuum-deposited on the ITO transparent electrode to a thickness of 500 Å to form a hole injection layer.

The HT-1 compound was thermally vacuum deposited on the hole injection layer to a thickness of 800 Å, and HT-3 compound was vacuum deposited thereon to a thickness of 500 Å to form a hole transport layer.

Subsequently, compound H-1 was co-deposited with a phosphorescent dopant DP-30 at a weight ratio of 10% on the hole transport layer to form a 400Å thick light emitting layer.

An ET-3 material was vacuum deposited on the light emitting layer to form a hole blocking layer, and an ET-4 material and LiQ were vacuum deposited on the hole blocking layer at a weight ratio of 1: 1 to form an electron transporting layer of 250 ANGSTROM . Lithium fulleride (LiF) was sequentially deposited on the electron transporting layer to a thickness of 10 Å, and aluminum was deposited thereon to a thickness of 1000 Å to form a cathode.

The deposition rate of the organic material was maintained at 0.4 to 0.7 Å / sec, the lithium fluoride at the cathode was maintained at a deposition rate of 0.3 Å / sec, and the deposition rate of aluminum was maintained at 2 Å / sec. ^-7 to 5 x 10 &lt; ^-8 &gt; torr.

< Experimental Example  12>

An organic electroluminescent device was prepared in the same manner as in Comparative Example 8, except that the compound 1-1 was used instead of the compound H-1 in the above Comparative Example 8.

< Experimental Example  13>

An organic electroluminescent device was fabricated in the same manner as in Comparative Example 8, except that Compound 2-1 was used instead of Compound H-1 in Comparative Example 8.

< Experimental Example  14>

An organic electroluminescent device was fabricated in the same manner as in Comparative Example 8, except that Compound 3-1 was used instead of Compound H-1 in Comparative Example 8.

< Experimental Example  15>

An organic electroluminescent device was fabricated in the same manner as in Comparative Example 8, except that Compound 12-1 was used instead of Compound H-1 in Comparative Example 8.

< Comparative Example  9>

An organic electroluminescent device was fabricated in the same manner as in Comparative Example 8, except that Compound H-1 and H-3 were used in a ratio of 50:50 instead of Compound H-1 in Comparative Example 8.

< Experimental Example  16>

An organic electroluminescent device was fabricated in the same manner as in Comparative Example 8 except that Compound 1-1 and H-3 were used in a ratio of 50:50 instead of Compound H-1 in Comparative Example 8.

< Experimental Example  17>

An organic electroluminescent device was prepared in the same manner as in Comparative Example 8, except that Compound 2-1 and H-3 were used in a ratio of 50:50 instead of Compound H-1 in Comparative Example 8.

< Experimental Example  18>

An organic electroluminescent device was fabricated in the same manner as in Comparative Example 8, except that Compound 3-1 and H-3 were used in a ratio of 50:50 instead of Compound H-1 in Comparative Example 8.

< Experimental Example  19>

An organic electroluminescent device was fabricated in the same manner as in Comparative Example 8 except that Compound 10-1 and H-3 were used in a ratio of 50:50 instead of Compound H-1 in Comparative Example 8.

< Experimental Example  20>

An organic electroluminescent device was fabricated in the same manner as in Comparative Example 8, except that Compound 11-1 and H-3 were used in a ratio of 50:50 instead of Compound H-1 in Comparative Example 8.

< Experimental Example  21>

An organic electroluminescent device was fabricated in the same manner as in Comparative Example 8, except that Compound 12-1 and H-3 were used in a ratio of 50:50 instead of Compound H-1 in Comparative Example 8.

< Comparative Example  10>

An organic electroluminescent device was fabricated in the same manner as in Comparative Example 8 except that the compound C-1 was used instead of the compound H-1 in the above Comparative Example 8.

< Comparative Example  11>

An organic electroluminescent device was fabricated in the same manner as in Comparative Example 8 except that the compound C-2 was used instead of the compound H-1 in the above Comparative Example 8.

< Comparative Example  12>

An organic electroluminescent device was fabricated in the same manner as in Comparative Example 8 except that the compound C-3 was used instead of the compound H-1 in the above Comparative Example 8.

< Comparative Example  13>

An organic electroluminescent device was fabricated in the same manner as in Comparative Example 8 except that the compound C-4 was used in place of the compound H-1 in the above Comparative Example 8.

< Comparative Example  14>

An organic electroluminescent device was fabricated in the same manner as in Comparative Example 8, except that the compound C-2 and the compound H-3 were used in a ratio of 50:50 instead of the compound H-1.

< Comparative Example  15>

An organic electroluminescent device was fabricated in the same manner as in Comparative Example 8, except that the compound C-3 and the compound H-3 were used in a ratio of 50:50 instead of the compound H-1.

< Comparative Example  16>

An organic electroluminescent device was fabricated in the same manner as in Comparative Example 8 except that the compound C-4 and the compound H-3 were used in a ratio of 50:50 instead of the compound H-1 in the Comparative Example 8

compound Voltage V
(@ 10 mA / cm ² ) Efficiency cd / A
(@ 10 mA / cm ² ) Luminous color T95
(@ 20 mA / cm ² ) Comparative Example 8 H-1 4.03 50.0 green 47 Experimental Example 12 Compound 1-1 3.76 57.3 green 70 Experimental Example 13 Compound 2-1 3.79 53.6 green 64 Experimental Example 14 Compound 3-1 3.86 54.1 green 68 Experimental Example 15 Compound 12-1 3.72 55.5 green 70 Comparative Example 9 H-1, H-3 4.33 58.0 green 121 Experimental Example 16 Compound 1-1, H-3 3.96 63.5 green 152 Experimental Example 17 Compound 2-1, H-3 3.92 63.9 green 170 Experimental Example 18 Compound 3-1, H-3 4.17 63.5 green 136 Experimental Example 19 Compound 10-1, H-3 3.95 67.5 green 149 Experimental Example 20 Compound 11-1, H-3 4.07 63.4 green 130 Experimental Example 21 Compound 12-1, H-3 4.01 64.8 green 134 Comparative Example 10 C-1 3.83 52.5 green 51 Comparative Example 11 C-2 3.87 52.0 green 53 Comparative Example 12 C-3 4.2 48.3 green 40 Comparative Example 13 C-4 3.98 50.7 green 49 Comparative Example 14 C-2, H-3 4.17 60.3 green 121 Comparative Example 15 C-3, H-3 4.50 52.0 green 108 Comparative Example 16 C-4, H-3 4.28 58.1 green 117

The results of Tables 1 and 2 show that the compounds of the present invention have the advantages of low driving voltage, high efficiency, and long life, compared with Compound H-1, which is a conventional green luminescent host material. In addition, it can be confirmed that the two-component host shows better performance in terms of driving voltage and lifetime. Compared with the compounds C-1 to C-4 of the comparative examples, the present invention in which the number of substituent groups in the para-direction of nitrogen in the indolo [3,2,1-jk]

1: substrate
2: anode
3: light emitting layer
4: cathode
5: Hole injection layer
6: hole transport layer
7: Electron transport layer

Claims (11)

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

In Formula 1, at least two of R 1 to R 8 are -L 1 -Ar 1, and -L 1 -Ar 1 are the same or different from each other,
L 1 are the same or different and each independently a direct bond; A substituted or unsubstituted arylene group; Or a substituted or unsubstituted divalent heterocyclic group,
Ar 1 is the same or different and is independently selected from the group consisting of a substituted or unsubstituted aryl group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; Or a substituted or unsubstituted heterocyclic group,
The groups other than -L 1 -Ar 1 in R 1 to R 8 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; A halogen group; Cyano; A substituted or unsubstituted alkyl group; A substituted or unsubstituted arylamine group; Or a substituted or unsubstituted heterocyclic group,
Ra to Rc are the same or different from each other, and each independently hydrogen; Or deuterium. The compound according to claim 1, wherein the groups other than -L 1 -Ar 1 in R 1 to R 8 are the same or different and each independently hydrogen; Or a heterocyclic compound which is deuterium. 2. The compound according to claim 1, wherein Ar1 and Ar2 are the same or different and are each independently a substituted or unsubstituted phenyl group; A substituted or unsubstituted naphthyl group; A substituted or unsubstituted biphenyl group; A substituted or unsubstituted terphenyl group; A substituted or unsubstituted phenanthrene group; A substituted or unsubstituted fluorene group; A substituted or unsubstituted triphenylene group; A substituted or unsubstituted diphenylamine group; A substituted or unsubstituted bisbiphenylamine group; A substituted or unsubstituted phenylbiphenylamine group; A substituted or unsubstituted triphenylene dibenzofurane amine group; A substituted or unsubstituted pyridine group; A substituted or unsubstituted pyrimidine group; A substituted or unsubstituted triazine group; A substituted or unsubstituted quinoline group; A substituted or unsubstituted quinazoline group; A substituted or unsubstituted quinoxaline group; A substituted or unsubstituted benzoquinazoline group; A substituted or unsubstituted phthalazine group; Substituted or unsubstituted phenanthrolines; A substituted or unsubstituted dimethylindenopyrimidine group; A substituted or unsubstituted carbazole group; A substituted or unsubstituted benzocarbazole group; A substituted or unsubstituted dibenzothiophene group; A substituted or unsubstituted benzonaphthofuran group; Or a substituted or unsubstituted dibenzofurane group. [3] The compound according to claim 1, wherein L1 and L2 are the same or different from each other and each independently is a direct bond; A substituted or unsubstituted phenylene group; A substituted or unsubstituted naphthalene group; A substituted or unsubstituted divalent pyridine group; A substituted or unsubstituted divalent pyrimidine group; A substituted or unsubstituted divalent triazine group; A substituted or unsubstituted divalent carbazole group; A substituted or unsubstituted divalent dibenzocarbazole group; A substituted or unsubstituted divalent quinoline group; Or a substituted or unsubstituted divalent quinazoline group. 2. The heterocyclic compound according to claim 1, wherein the formula 1 is selected from the formulas shown by any one of the following formulas 1-1 to 1-16:

In the above formulas 1-1 to 1-15, the dotted line represents a position at which they are bonded to -L 1 -Ar 1, and L 1 and Ar 1 have the same meanings as defined in Formula 1. The heterocyclic compound according to claim 1, wherein the compound of formula (1) is selected from the following structural formulas:

A first electrode; A second electrode facing the first electrode; And at least one organic material layer provided between the first electrode and the second electrode, wherein at least one of the organic material layers includes a heterocyclic compound according to any one of claims 1 to 6 Organic electroluminescent device. The organic electroluminescent device according to claim 7, wherein the organic layer includes a light emitting layer, and the light emitting layer includes the heterocyclic compound. The organic electroluminescent device according to claim 7, wherein the organic material layer includes an electron injection layer, an electron transport layer, or an electron injection and transport layer, and the electron injection layer, the electron transport layer, or the electron injection and transport layer includes the heterocyclic compound. [Claim 7] The organic electroluminescent device according to claim 7, wherein the organic compound layer includes a hole injection layer, a hole transport layer or a hole injection and transport layer, and the hole injection layer, the hole transport layer or the hole injection and transport layer includes the heterocyclic compound. [Claim 7] The organic electroluminescent device according to claim 7, wherein the organic layer includes a light emitting layer, and the light emitting layer comprises the heterocyclic compound as a host material.

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