KR20170136836A - Organic compounds and organic electro luminescence device comprising the same - Google Patents

Abstract

The present invention relates to a novel compound and an organic electroluminescence device including the same, wherein the compound according to the present invention is used in an organic compound layer of an organic electroluminescence device, preferably a light emitting layer, an electron transporting layer, or an electron transporting supporting layer, thereby improving the luminous efficiency, driving voltage and lifetime of the organic electroluminescence device.

Description

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

The present invention relates to a novel organic compound that can be used as a material for an organic electroluminescence device and an organic electroluminescence device including the same.

The electroluminescent (EL) devices that led to blue electroluminescence using anthracene single crystals in 1965 were followed up with the observation of organic thin film emission from Bernanose in the 1950s. In 1987, Tang The organic light emitting device having a laminated structure in which the hole layer and the functional layer of the light emitting layer are divided. Thereafter, in order to form a high efficiency and high number of organic electroluminescent devices, each organic material layer has been developed into a form in which each organic material layer has been introduced into the device, leading to the development of specialized materials used therefor.

In the organic electroluminescent device, when a voltage is applied between two electrodes, holes are injected into the organic layer in the anode, and electrons are injected into the organic layer in the cathode. When the injected holes and electrons meet, an exciton is formed. When the exciton falls to the ground state, light is emitted. At this time, the material used as the organic material layer can be classified into a light emitting material, a hole injecting material, a hole transporting material, an electron transporting material, an electron injecting material and the like depending on its function.

The luminescent material can be classified into blue, green and red luminescent materials according to luminescent colors and yellow and orange luminescent materials to realize better natural colors. Further, in order to increase the color purity and increase the luminous efficiency through energy transfer, a host / dopant system can be used as a light emitting material.

The dopant material can be divided into a fluorescent dopant using an organic material and a phosphorescent dopant using a metal complex compound containing heavy atoms such as Ir and Pt. At this time, since the development of the phosphorescent material can theoretically improve the luminous efficiency up to 4 times as compared with the fluorescence, the phosphorescent dopant as well as phosphorescent host materials are being studied extensively.

Up to now, hole injecting layer, hole transporting layer. NPB, BCP and Alq ₃ are widely known as electron transporting layer materials and anthracene derivatives as light emitting layer materials. Particularly, metal complex compounds containing Ir such as Firpic, Ir (ppy) ₃ , (acac) Ir (btp) ₂ and the like having advantages in terms of efficiency improvement of the light emitting layer material are blue, green, 4,4-dicarbazolybiphenyl (CBP) is used as a phosphorescent dopant material for red phosphorescent dopants.

However, conventional organic material layers are advantageous from the viewpoint of light emitting properties, but their thermal stability is not very good due to their low glass transition temperature, and thus they are not satisfactory in terms of lifetime of the organic electroluminescent device. Therefore, development of an organic layer material having excellent performance is required.

The present invention has been made to solve the above problems and it is an object of the present invention to provide a novel compound capable of improving the efficiency, lifetime and stability of the organic electroluminescent device and an organic electroluminescent device using the compound.

In order to achieve the above object, the present invention provides a compound represented by the following formula (1): < EMI ID =

[Chemical Formula 1]

In Formula 1,

X is O or N (R < ₁ >);

Each of Z ₁ to Z ₁₂ is independently N or C (R ₂ ), or at least one of Z ₁ to Z ₁₂ is N;

m is an integer from 0 to 4;

Ar ₁ is a substituent represented by the following formula (2), and when a plurality of Ar _{1 s} are present, they are the same or different;

R ₁ is selected from the group consisting of hydrogen, a C ₁ to C ₄₀ alkyl group, a C ₆ to C ₆₀ aryl group, and a heteroaryl group having 5 to 60 ring atoms;

R ₂ is selected from the group consisting of hydrogen, a C ₁ to C ₄₀ alkyl group, a C ₆ to C ₆₀ aryl group and a heteroaryl group having 5 to 60 nuclear atoms, and when a plurality of R _{2 s} are the same or different, ;

The alkyl, aryl and heteroaryl groups of R ₁ and R ₂ are each independently selected from the group consisting of deuterium, C ₁ to C ₄₀ alkyl, C ₂ to C ₄₀ alkenyl, C ₆ to C ₆₀ aryl, To 60 heteroaryl groups and C ₆ to C ₆₀ arylamine groups, and when they are substituted with a plurality of substituents, they are the same as or different from each other;

(2)

In Formula 2,

* Denotes the part where the bond is made;

L ₁ and L ₂ are each independently selected from the group consisting of a single bond, a C ₆ to C ₁₈ arylene group and a heteroarylene group having 5 to 18 nucleus atoms;

R ₃ is selected from the group consisting of hydrogen, a C ₁ to C ₄₀ alkyl group, a C ₆ to C ₆₀ aryl group, and a heteroaryl group having 5 to 60 ring atoms;

Wherein L _1, and arylene group of L ₂ and a heteroarylene group, an alkyl group of said R _3, aryl and heteroaryl groups are each independently a heavy hydrogen, an alkenyl group of C ₁ ~ C ₄₀ alkyl group, C ₂ ~ C ₄₀ of, C substituted with ₆ ~ C over a ₆₀ aryl group, the nuclear atoms of 5 to 60 heteroaryl group, and a C ₆ ~ selected from the aryl group consisting of an amine group in the C ₆₀ 1 more substituents or be unsubstituted, when it is substituted with a plurality of substituents , They are the same or different from each other.

Also, the present invention is an organic electroluminescent device comprising a cathode, a cathode, and at least one organic compound layer interposed between the anode and the cathode, wherein at least one of the organic compound layers of the one or more layers is a compound And an organic electroluminescent device.

"Alkyl" in the present invention is a monovalent substituent derived from a linear or branched saturated hydrocarbon having 1 to 40 carbon atoms, and examples thereof include methyl, ethyl, propyl, isobutyl, sec-butyl, pentyl, iso-amyl, hexyl And the like, but are not limited thereto.

As used herein, the term "alkenyl" is a monovalent substituent derived from a linear or branched unsaturated hydrocarbon having 2 to 40 carbon atoms and having at least one carbon-carbon double bond. Examples thereof include vinyl, But are not limited to, allyl, isopropenyl, 2-butenyl, and the like.

The term "alkynyl" in the present invention is a monovalent substituent derived from a straight or branched chain unsaturated hydrocarbon having 2 to 40 carbon atoms and having at least one carbon-carbon triple bond. Examples thereof include ethynyl, , 2-propynyl, and the like, but are not limited thereto.

"Aryl" in the present invention means a monovalent substituent derived from a C6-C60 aromatic hydrocarbon having a single ring or a combination of two or more rings. In addition, it is also possible that two or more rings are condensed with each other and only carbon atoms are contained as ring-forming atoms (for example, the number of carbon atoms may be from 8 to 60), and the monovalent group having a non-aromacity throughout the molecule Substituents may also be included. Examples of such aryl include, but are not limited to, phenyl, naphthyl, phenanthryl, anthryl, fluorenyl, and the like.

"Heteroaryl" in the present invention means a monovalent substituent derived from a monoheterocyclic or polyheterocyclic aromatic hydrocarbon having 5 to 60 nuclear atoms. Wherein one or more carbons, preferably one to three carbons, of the ring are substituted with a heteroatom selected from N, O, P, S and Se. In addition, it is preferable that two or more rings are pendant or condensed with each other, and include hetero atoms selected from N, O, P, S and Se besides carbon as a ring-forming atom, < / RTI > aromacity). Examples of such heteroaryls include 6-membered monocyclic rings such as pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, and triazinyl; Such as phenoxathienyl, indolizinyl, indolyl, purinyl, quinolyl, benzothiazole, carbazolyl, and the like. ring; Imidazolyl, 2-isoxazolyl, 2-pyridinyl, 2-pyrimidinyl, and the like, but are not limited thereto.

In the present invention, "aryloxy" means a monovalent substituent represented by RO-, and R represents aryl having 5 to 60 carbon atoms. Examples of such aryloxy include, but are not limited to, phenyloxy, naphthyloxy, diphenyloxy, and the like.

The term "alkyloxy" in the present invention means a monovalent substituent group represented by R'O-, wherein R 'represents 1 to 40 alkyl, and may be linear, branched or cyclic . ≪ / RTI > Examples of such alkyloxy include, but are not limited to, methoxy, ethoxy, n-propoxy, 1-propoxy, t-butoxy, n-butoxy, pentoxy and the like.

"Arylamine" in the present invention means an amine substituted with aryl having 6 to 60 carbon atoms.

"Cycloalkyl" in the present invention means a monovalent substituent derived from a monocyclic or polycyclic non-aromatic hydrocarbon having 3 to 40 carbon atoms. Examples of such cycloalkyls include, but are not limited to, cyclopropyl, cyclopentyl, cyclohexyl, norbornyl, adamantine, and the like.

"Heterocycloalkyl" in the present invention means a monovalent substituent derived from a non-aromatic hydrocarbon having 3 to 40 nuclear atoms, wherein at least one of the carbons, preferably one to three carbons, S or Se. ≪ / RTI > Examples of such heterocycloalkyls include, but are not limited to, morpholine, piperazine, and the like.

"Alkylsilyl" in the present invention is silyl substituted with alkyl having 1 to 40 carbon atoms, and "arylsilyl" means silyl substituted with aryl having 5 to 60 carbon atoms.

In the present invention, the term "condensed rings" means condensed aliphatic rings, condensed aromatic rings, condensed heteroaliphatic rings, condensed heteroaromatic rings, or a combination thereof.

The compound represented by the general formula (1) of the present invention has excellent thermal stability and luminescent properties and can be used as a material of an organic material layer of an organic electroluminescent device. In particular, when the compound represented by Formula 1 of the present invention is used as a phosphorescent host material, it is possible to produce an organic electroluminescent device having excellent light emitting performance, low driving voltage, high efficiency, and long life time, A full color display panel having improved performance and lifetime can be manufactured.

Hereinafter, the present invention will be described in detail.

1. New organic compounds

The novel compounds of the present invention can be represented by the following formula

[Chemical Formula 1]

In Formula 1,

X is O or N (R < ₁ >);

Each of Z ₁ to Z ₁₂ is independently N or C (R ₂ ), or at least one of Z ₁ to Z ₁₂ is N;

m is an integer from 0 to 4, preferably from 1 to 3;

Ar ₁ is a substituent represented by the following formula (2), and when a plurality of Ar _{1 s} are present, they are the same or different;

R ₁ is selected from the group consisting of hydrogen, a C ₁ to C ₄₀ alkyl group, a C ₆ to C ₆₀ aryl group, and a heteroaryl group having 5 to 60 ring atoms;

R ₂ is selected from the group consisting of hydrogen, a C ₁ to C ₄₀ alkyl group, a C ₆ to C ₆₀ aryl group and a heteroaryl group having 5 to 60 nuclear atoms, and when a plurality of R _{2 s} are the same or different, ;

The alkyl, aryl and heteroaryl groups of R ₁ and R ₂ are each independently selected from the group consisting of deuterium, C ₁ to C ₄₀ alkyl, C ₂ to C ₄₀ alkenyl, C ₆ to C ₆₀ aryl, To 60 heteroaryl groups and C ₆ to C ₆₀ arylamine groups, and when they are substituted with a plurality of substituents, they are the same as or different from each other;

 (2)

In Formula 2,

* Denotes the part where the bond is made;

L ₁ and L ₂ are each independently selected from the group consisting of a single bond, a C ₆ to C ₁₈ arylene group and a heteroarylene group having 5 to 18 nucleus atoms;

R ₃ is selected from the group consisting of hydrogen, a C ₁ to C ₄₀ alkyl group, a C ₆ to C ₆₀ aryl group, and a heteroaryl group having 5 to 60 ring atoms;

Wherein L _1, and arylene group of L ₂ and a heteroarylene group, an alkyl group of said R _3, aryl and heteroaryl groups are each independently a heavy hydrogen, an alkenyl group of C ₁ ~ C ₄₀ alkyl group, C ₂ ~ C ₄₀ of, C substituted with ₆ ~ C over a ₆₀ aryl group, the nuclear atoms of 5 to 60 heteroaryl group, and a C ₆ ~ selected from the aryl group consisting of an amine group in the C ₆₀ 1 more substituents or be unsubstituted, when it is substituted with a plurality of substituents , They are the same or different from each other.

The compound represented by the formula (1) of the present invention is a compound represented by EWG (electron) in a core of spiro [acridine-fluorene] based moiety or spiro [fluorene-xanthene] based core containing at least one hetero atom, -withdrawing group), the electrochemical stability is excellent, and the electron mobility is greatly increased compared with the existing spiro [acridine-fluorene] based moiety or spiro [fluorene-xanthene] based compound Exhibits properties that are particularly excellent, and are excellent in high glass transition temperature and thermal stability, resulting in an increase in blue light emission efficiency.

Accordingly, the compound represented by the general formula (1) of the present invention is excellent in electron transporting ability and light emitting property, and therefore, it is preferable that the compound represented by the general formula (1) It can be used as a material. Preferably an electron transporting auxiliary layer laminated on the light emitting layer, the electron transporting layer and the electron transporting layer, more preferably the material of the electron transporting layer or the electron transporting layer. In addition, since the electron transporting layer has high triplet energy, it can exhibit excellent efficiency due to the triplet-triplet fusion (TTF) effect. In addition, due to physico-chemical properties having a broad band gap due to a low HOMO and a high LUMO energy level, it is possible to prevent the excitons generated in the light emitting layer from diffusing into the electron transporting layer or the hole transporting layer adjacent to the light emitting layer. The number of the excitons contributing to light emission in the light emitting layer can be increased to improve the light emitting efficiency of the device and the durability and stability of the device can be improved and the lifetime of the device can be efficiently increased. Most of the developed materials exhibit physical characteristics that can be driven at low voltage and smooth intermolecular bonding, resulting in excellent amorphous morphology and improved lifetime.

According to one preferred embodiment of the present invention, the compound is a compound represented by any one of the following formulas (3) to (10). Preferably a compound represented by any one of the following Chemical Formulas 3 to 6, 8 and 9, more preferably a compound represented by any one of Chemical Formulas 3 to 5, 8 and 9:

(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

(7)

 [Chemical Formula 8]

[Chemical Formula 9]

[Chemical formula 10]

In the above formulas 3 to 10,

R ₄ to R ₁₄ are each independently selected from the group consisting of hydrogen, a C ₁ to C ₄₀ alkyl group, a C ₆ to C ₆₀ aryl group, and a heteroaryl group having 5 to 60 nuclear atoms;

The alkyl, aryl and heteroaryl groups of R ₄ to R ₁₄ are each independently selected from the group consisting of deuterium, a C ₁ to C ₄₀ alkyl group, a C ₂ to C ₄₀ alkenyl group, a C ₆ to C ₆₀ aryl group, To 60 heteroaryl groups and C ₆ to C ₆₀ arylamine groups, and when they are substituted with a plurality of substituents, they are the same as or different from each other;

Each of R ₁ , Ar ₁ and m is as defined in the above formula (1).

According to a preferred embodiment of the present invention, the compound is a compound represented by the following general formula (11):

(11)

In Formula 11,

X, Z ₁ to Z ₁₂ and Ar ₁ are each as defined in the above formula (1).

According to a preferred embodiment of the present invention, each of L ₁ and L ₂ is independently selected from the group consisting of a phenylene group, a biphenylene group, a naphthalenyl group, a fluorenyl group and a carbazolyl group,

Wherein L ₁ and the phenyl group, a biphenyl of the L ₂ group, a naphthyl Frontale group, a fluorenyl group and carbazolyl groups are each independently a heavy hydrogen, an alkenyl group of C ₁ ~ C ₄₀ alkyl group, C ₂ ~ C ₄₀ of, C ₆ ~ If C ₆₀ aryl group, the nuclear atoms of 5 to 60 heteroaryl group, and a C ₆ ~ substituted by one substituent at least one selected from the group consisting of an aryl amine of the C ₆₀ or is unsubstituted, substituted by a plurality of substituents, these are They are the same or different.

According to a preferred embodiment of the present invention, Ar ₁ may be a substituent represented by any of the following formulas 12 to 14:

[Chemical Formula 12]

[Chemical Formula 13]

[Chemical Formula 14]

In the above Formulas 12 to 14,

* Denotes the part where the bond is made;

R ₃ is as defined in the above formula (2).

According to a preferred embodiment of the present invention, R ₃ is preferably a heteroaryl group having 5 to 60 nuclear atoms, more preferably 5 to 60 heteroaryl groups containing at least 2 N atoms .

According to one more preferred embodiment of the present invention, R ₃ is selected from the group consisting of pyrimidine, pyrazine, triazine, imidazole, benzimidazole, phenanthroidimidazole, imidazopyridine, quinazoline and triazolopyridine And,

The pyrimidine, pyrazine, triazine, imidazole, benzimidazole, phenanthroidimidazole, imidazopyridine, quinazoline and triazolopyridine of R ₃ are each independently selected from deuterium, a C ₁ to C ₄₀ alkyl group, C ₂ ~ C ₄₀ alkenyl group, C ₆ ~ C ₆₀ aryl group, nuclear atoms of 5 to 60 heteroaryl group, and a C ₆ ~ C is substituted by at least at ₆₀ the group consisting of an aryl amine of the selected one more substituents or being unsubstituted , When they are substituted with a plurality of substituents, they may be the same or different.

According to one more preferred embodiment of the present invention, R ₃ may be a substituent represented by any one of the following Al to A13:

In the above-mentioned A1 to A13,

* Denotes the part where the bond is made;

p is an integer from 0 to 3;

q is an integer from 0 to 2;

R ₁₅ is selected from the group consisting of C ₁ ~ C ₄₀ alkyl group, C ₆ ~ C ₆₀ aryl group, the number of nuclear atoms of 5 to 60 heteroaryl group, and a C ₆ ~ with an aryl amine of the C ₆₀ of the R ₁₅ is When plural are the same or different from each other;

R ₁₆ is selected from the group consisting of hydrogen, a C ₁ to C ₄₀ alkyl group, a C ₆ to C ₆₀ aryl group, a heteroaryl group having 5 to 60 nuclear atoms and an arylamine group having a C ₆ to C ₆₀ ;

The alkyl, aryl, heteroaryl and arylamine groups of R ₁₅ and R ₁₆ are each independently selected from the group consisting of deuterium, a C ₁ to C ₄₀ alkyl group, a C ₂ to C ₄₀ alkenyl group, a C ₆ to C ₆₀ aryl group, A heteroaryl group having 5 to 60 nuclear atoms and an arylamine group having ₆ to ₆₀ carbon atoms, and when they are substituted with a plurality of substituents, they are the same as or different from each other.

According to a preferred embodiment of the present invention, R ₁₅ may be selected from the group consisting of a C ₁ to C ₄₀ alkyl group, a C ₆ to C ₆₀ aryl group and a heteroaryl group having 5 to 60 nuclear atoms, Preferably a C ₆ to C ₆₀ aryl group.

According to a preferred embodiment of the present invention, R ₁₆ may be selected from the group consisting of hydrogen, a C ₁ to C ₄₀ alkyl group, a C ₆ to C ₆₀ aryl group and a heteroaryl group having 5 to 60 nuclear atoms , More preferably a C ₆ to C ₆₀ aryl group.

The compounds represented by formula (1) of the present invention can be represented by the following compounds, but are not limited thereto:

In the present invention, the compound represented by Formula 1 may be synthesized according to a general synthetic method (Chem. Rev., 60: 313 (1960), J. Chem. SOC. 4482 (1955) 2457 (1995)). Detailed synthesis of the compound of the present invention will be described in detail in Synthesis Examples to be described later.

2. Organic Field  Light emitting element

Another aspect of the present invention relates to an organic electroluminescent device (organic EL device) comprising the compound represented by the general formula (1) according to the present invention described above.

Specifically, the present invention is an organic electroluminescent device comprising an anode, a cathode, and one or more organic layers sandwiched between the anode and the cathode, wherein at least one of the one or more organic layers includes Include compounds represented by the above formula (1). At this time, the compounds may be used singly or in combination of two or more.

The at least one organic material layer may be at least one of a hole injecting layer, a hole transporting layer, a light emitting layer, a light emitting auxiliary layer, a life improving layer, an electron transporting layer, an electron transporting auxiliary layer and an electron injecting layer, 1 < / RTI >

In the present invention, the spiropyroxenic acid or the spiroacridine fluorene moiety of the compound represented by the above formula (1) is basically excellent in electrochemical stability, has a high glass transition temperature and carrier transporting ability, The mobility is also excellent and the blue luminescence efficiency is enhanced. The materials represented by Formula 1 are structurally characteristic to be bonded with core core and EWG (electron withdrawing group), and have excellent electron mobility and excellent high glass transition temperature and thermal stability. Therefore, it is preferable that the organic material layer containing the compound represented by Formula 1 is a light emitting layer, an electron transporting layer, or an electron transporting supporting layer.

According to an embodiment of the present invention, the light emitting layer of the organic electroluminescent device may include a host material, which may include a compound represented by the above formula (1) as a host material. Thus, when the compound represented by Formula 1 is incorporated as a light emitting layer material of an organic electroluminescent device, preferably a green phosphorescent host, the bonding strength between holes and electrons in the light emitting layer increases, Efficiency and power efficiency), lifetime, luminance and driving voltage, etc., can be improved.

The structure of the organic electroluminescent device according to the present invention is not particularly limited and may be a structure in which a substrate, an anode, a hole injecting layer, a hole transporting layer, a light emitting layer, an electron transporting layer, and a cathode are sequentially stacked. At this time, an electron transporting auxiliary layer may be further laminated between the light emitting layer and the electron transporting layer, and an electron injection layer may further be laminated on the electron transporting layer. In the present invention, at least one of the hole injecting layer, the hole transporting layer, the light emitting layer, the electron transporting layer, the electron transporting auxiliary layer, and the electron injecting layer may include the compound represented by the above Formula 1, And the transporting auxiliary layer may include the compound represented by the above formula (1).

In addition, the structure of the organic electroluminescent device of the present invention may be a structure in which not only an anode, one or more organic compound layers and a cathode are sequentially laminated but also an insulating layer or an adhesive layer is inserted into the interface between the electrode and the organic compound layer.

The organic electroluminescent device of the present invention can be formed by using a material known in the art (for example, an electron transport layer or an electron transporting auxiliary layer) such that at least one or more of the organic material layers And forming other organic layers and electrodes using the method.

The organic material layer may be formed by a vacuum deposition method or a solution coating method. Examples of the solution coating method include, but are not limited to, spin coating, dip coating, doctor blading, inkjet printing, or thermal transfer.

The substrate usable in the present invention is not particularly limited, and a silicon wafer, quartz, a glass plate, a metal plate, a plastic film and a sheet can be used.

Examples of the positive electrode material include metals such as vanadium, chromium, copper, zinc, and gold, or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), 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 polythiophene, poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (PEDT), polypyrrole or polyaniline; And carbon black, but are not limited thereto.

The negative electrode material may be a metal such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin or lead or an alloy thereof; And multi-layer structure materials such as LiF / Al or LiO ₂ / Al, but are not limited thereto.

Hereinafter, the present invention will be described in detail with reference to examples. However, the following examples are illustrative of the present invention, and the present invention is not limited by the following examples.

[ Preparation Example  1] Synthesis of Core 1

7- Bromo spiro [indeno [2,1-b] Synthesis of pyridine-9,9'-xanthene]

30 mL (0.46 mol) of methanesulfonic acid was added to 30 g (0.12 mol) of 7-bromo-9H-indeno [2,1- b] pyridin-9-one and 108.6 g (1.15 mol) of phenol. The mixture was heated to 120 DEG C for 12 hours under reflux. The reaction mixture was cooled to room temperature and the reaction was terminated with 300 mL of purified water. The mixture was extracted with 1.0 L of CH ₂ Cl ₂ , and the separated organic layer was neutralized with 500 mL of saturated calcium carbonate and washed with distilled water. The obtained organic layer was dried over anhydrous MgSO ₄ , distilled under reduced pressure, and purified by silica gel column chromatography to obtain 31.4 g (yield 66%) of the desired compound.

_{^{1 H-NMR (in CDCl 3}} ): δ 8.35 (d, 1H), 7.83 (d, 1H), 7.60 (d, 1H), 7.40 (t, 1H), 7.29 (d, 1H), 7.25 (m, 4H), 7.15 (d, IH), 6.77 (t, 2H), 6.40 (d, 2H)

[LCMS]: 412

[ Preparation Example  2] 7- (4,4,5,5- Tetramethyl -1,3,2- Dioxaborolane Yl) spiro [ It is Ylo [2,1-b] pyridine-9,9'-xanthene]

31.0 g (75.2 mmol) of 7-bromospiro [indeno [2,1-b] pyridine-9,9'-xanthene] synthesized in Preparation Example 1 and 4,4,4 ' Dioxane was added to 22.9 g (90.2 mmol) of 5,5,5 ', 5'-octamethyl-2,2' -bis (1,3,2-dioxaborolane). Then 3.1 g (3.8 mmol) of Pd (dppf) Cl ₂ and 22.1 g (226 mmol) of KOAc were added and the mixture was heated to reflux at 130 for 3 hours. Then, the reaction solution was cooled to room temperature and 500 mL of ammonium chloride aqueous solution was added to the reaction solution to terminate the reaction. The reaction solution was extracted with 1.0 L of EA and washed with distilled water. Thereafter, the obtained organic layer was dried over anhydrous MgSO ₄ , distilled under reduced pressure, and then purified by silica gel column chromatography to obtain 26.9 g (yield 78%) of the desired compound.

[LCMS]: 459

[ Preparation Example  3] Synthesis of Core 2

7- Bromo-spiro [indeno [1,2-b] Pyridine-5,9'-xanthene]

The same procedure as in [Preparation Example 1] was conducted to obtain 32.3 g (68%) of the target compound corresponding to the structural isomer of Core 2.

[LCMS]: 412

[ Preparation Example  4] 7- (4,4,5,5- Tetramethyl -1,3,2- Dioxaborolane Yl) spiro [ Indeno [l, 2-b] pyridine -5,9'-xanthene]

The procedure of Preparation Example 2 was repeated to obtain 18.7 g (76%) of the target compound corresponding to the structural isomer of Preparation Example 2.

[LCMS]: 459

[ Preparation Example  5] Synthesis of Core 3

<Step 1> 7- Bromo -9- (2- ( Diphenylamino ) Phenyl) -9H- Indeno [2,1-b] pyridine -9-ol

To 30 g (92.5 mmol) of 2-bromo-N, N-diphenyl aniline was added 500 mL of THF. The temperature of the reaction solution was lowered to -78 ° C, and 42.1 mL (105 mmol) of a 2.5M solution of n-BuLi was slowly added dropwise over 1 hour. Then 25.1 g (102 mmol) of 7-bromo-9H-indeno [2,1-b] pyridin-9-one was dissolved in 500 mL of THF and slowly added to the reaction solution. And further stirred at room temperature for 24 hours. Then, 500 mL of purified water was added to the reaction solution to terminate the reaction, and the mixture was extracted with 1.5 L of EA and washed with distilled water. Thereafter, the obtained organic layer was dried over anhydrous MgSO ₄ , distilled under reduced pressure, and then purified by silica gel column chromatography to obtain 33.2 g (yield 75%) of the target compound.

[LCMS]: 505

&Lt; Step 2 > Bromo -10-phenyl-10H-spiro [acridine-9,9'- Indeno [2,1-b] pyridine ] Synthesis of

To 33.0 g (65.3 mmol) of 7-bromo-9- (2- (diphenylamino) phenyl) -9H-indeno [2,1- b] pyridin-9- ol were added 330 mL of AcOH and 3 drops Were added. The reaction solution was heated to reflux at 100 ° C for 2 hours. After the reaction mixture was cooled to room temperature, 500 mL of purified water was added to the reaction mixture to terminate the reaction. The resultant solid was filtered under reduced pressure and dried under a humid atmosphere to obtain the desired compound (28.6 g, yield 90%).

[LCMS]: 487

[ Preparation Example  6] 10-phenyl-7 '- (4,4,5,5- Tetramethyl -1,3,2- Dioxaborolane Yl) -10H-spiro [acridine-9,9'-indeno [2,1-b] pyridine]

Bromo-10-phenyl-10H-spiro [acridine-9,9 ' -methanol instead of 7-bromospiro [indeno [2,1- - indeno [2,1-b] pyridine] was used in place of [N, N-dimethylformamide] in the same manner as in [Preparation Example 2] to obtain 22.1 g (yield 72%) of the desired compound.

[LCMS]: 534

[ Preparation Example  7] Synthesis of Core 4

<Step 1> 7- Bromo -5- (2- ( Diphenylamino ) Phenyl) -5H- Indeno [l, 2-b] pyridine Synthesis of 5-ol

The procedure of Step 1 of [Preparation Example 5] was repeated to obtain 20.5 g (72%) of the target compound corresponding to the structural isomer of Preparation Example 5. [

[LCMS]: 505

&Lt; Step 2 > Bromo -10-phenyl-10H-spiro [acridine-9,5'- Indeno [l, 2-b] pyridine ] Synthesis of

The procedure of Step 2 of [Preparation Example 5] was repeated to obtain 20.5 g (72%) of the target compound corresponding to the structural isomer of Preparation Example 5. [

[LCMS]: 487

[ Preparation Example  8] 10-phenyl-7 '- (4,4,5,5- Tetramethyl -1,3,2- Dioxaborolane Yl) -10H-spiro [acridine-9,9'-indeno [2,1-b] pyridine]

Bromo-10-phenyl-10H-spiro [acridine-9,5 '] pyridine-9,9'-xanthene was used instead of 7-bromospiro [indeno [ - indeno [1, 2-b] pyridine] was used in place of 2-bromoaniline to give the title compound (14.5 g, yield 65%).

[LCMS]: 534

[ Preparation Example  9] Core 5 of  synthesis

2- Bromospyro [fluorene-9,10'-pyrano [3,2- c: 5 , 6-c '] Dipyridine ] Synthesis of

The procedure of Preparation Example 1 was repeated except that 4-hydroxypyridine was used instead of phenol to obtain 13.5 g (yield: 48%) of the desired compound.

[LCMS]: 413

[ Preparation Example  10] 2- (4,4,5,5- Tetramethyl -1,3,2- Dioxaborolane Yl) spiro [ Fluorene -9,10'-pyrano [3,2-c: 5,6-c '] dipyridine]

Bromopyrrolo [9,10'-pyrano [3,2-c] pyridine-9,9'-xanthene was used instead of 7-bromospiro [indeno [2,1- : 5,6-c '] dipyridine] was used in place of [N, N-dimethylformamide], to obtain 9.8 g (yield 52%) of the desired compound.

[LCMS]: 460

[ Synthetic example  1] Synthesis of Compound 1

To 5.0 g (12.1 mmol) of Core 1 of Preparation Example 1 and 4.9 g (18.2 mmol) of 2-chloro-4,6-diphenyl-1,3,5-triazine were added 100 mL of DMF. 0.97 g (24.3 mmol) of 60% NaH was added to the reaction solution. After stirring at room temperature for 12 hours, 100 mL of purified water was added to terminate the reaction. The mixture was extracted with 300 mL of EA and washed twice with distilled water. The obtained organic layer was dried over anhydrous MgSO ₄ , distilled under reduced pressure and purified by silica gel column chromatography to obtain 4.2 g (yield 62%) of the target compound.

[LCMS]: 564

[ Synthetic example  2] Synthesis of Compound 6

Preparation of 2- (4,4,5,5-tetramethyl-1,3,2-dioxabororen-2-yl) spiro [indeno [2,1- b] pyridin- 9'- xanthene] was added 7.0 g (15.2 mmol) and 2-chloro-4-phenyl-quinazoline 4.8 g of dioxane, 200 mL, H ₂ O 50 mL in (19.8 mmol). _{Pd (PPh 3) 4 0.88 g} (0.8 mmol), K 2 CO 3 6.3 g After the addition of (45.7 mmol) was heated to reflux at 120 ℃ 6 hours. The reaction solution was cooled to room temperature and the reaction was terminated with 500 mL of purified water. The mixture was extracted with 1.0 L of EA, and then washed with distilled water. The obtained organic layer was dried over anhydrous MgSO ₄ , distilled under reduced pressure, and purified by silica gel column chromatography to obtain the desired compound (4.3 g, yield 52%).

[LCMS]: 537

[ Synthetic example  3] Synthesis of Compound 7

Preparation of 2- (4,4,5,5-tetramethyl-1,3,2-dioxabororen-2-yl) spiro [indeno [2,1- b] pyridin- The same procedure as in [Synthesis Example 2] was repeated except for using 2-bromo-6-methyl-9'-xanthene and 2-bromo-6,8-diphenyl- [1,2,4] triazolo [ To obtain 3.8 g of the desired compound (yield: 45%).

[LCMS]: 602

[ Synthetic example  4] Synthesis of Compound 15

Preparation of 2- (4,4,5,5-tetramethyl-1,3,2-dioxabororen-2-yl) spiro [indeno [2,1- b] pyridin- (3-bromophenyl) -2-phenylpyrimidine was used instead of 4 - ([1,1'-biphenyl] ] To obtain the objective compound (2.9 g, yield 53%).

[LCMS]: 715

[ Synthetic example  5] Synthesis of Compound 17

Preparation of 2- (4,4,5,5-tetramethyl-1,3,2-dioxabororen-2-yl) spiro [indeno [2,1- b] pyridin- (4-bromophenyl) -2-phenylpyrimidine was used instead of 4 - ([1,1'-biphenyl] ], 3.5 g (yield 40%) of the desired compound was obtained.

[LCMS]: 715

[ Synthetic example  6] Synthesis of Compound 21

Preparation Example 2 Of [7- (4,4,5,5-tetramethyl-1,3,2-dioxabororan-2-yl) spiro [indeno [2,1- b] pyridine- Xanthine] and 2- (4-chlorophenyl) -6,8-diphenyl- [1,2,4] triazolo [1,5- a] pyridine were used in place of [ (Yield: 34%) of the target compound.

[LCMS]: 678

[ Synthetic example  7] Synthesis of Compound 22

Preparation Example 2 Of [7- (4,4,5,5-tetramethyl-1,3,2-dioxabororan-2-yl) spiro [indeno [2,1- b] pyridine- Xanthene] and 2- (3'-chloro- [1,1'-biphenyl] -3-yl) -4,6-diphenyl-1,3,5- Example 2] to obtain 4.4 g of the desired compound (yield: 54%).

[LCMS]: 716

[ Synthetic example  8] Synthesis of Compound 24

Preparation Example 2 Of [7- (4,4,5,5-tetramethyl-1,3,2-dioxabororan-2-yl) spiro [indeno [2,1- b] pyridine- Xanthene] and 2- (3'-chloro- [1,1'-biphenyl] -4-yl) -4,6-diphenyl-1,3,5-triazine was used Example 2] to obtain the object compound (4.2 g, yield: 48%).

[LCMS]: 716

[ Synthetic example  9] Synthesis of Compound 28

Preparation Example 2 Of [7- (4,4,5,5-tetramethyl-1,3,2-dioxabororan-2-yl) spiro [indeno [2,1- b] pyridine- Xanthan] and 4- (3'-chloro- [1,1'-biphenyl] -3-yl) -2,6-diphenylpyrimidine were used in place of [ To obtain 6.0 g of the desired compound (yield: 45%).

[LCMS]: 715

[ Synthetic example  10] Synthesis of Compound 32

Preparation of 2- (4,4,5,5-tetramethyl-1,3,2-dioxabororen-2-yl) spiro [indeno [2,1- b] pyridin- (4'-chloro-1,1'-biphenyl-3-yl) -6- Phenyl-1,3,5-triazine was used, 3.1 g (yield 54%) of the title compound was obtained by carrying out the same procedure as in [Synthesis Example 2].

[LCMS]: 792

[ Synthetic example  11] Synthesis of Compound 39

Preparation Example 2 Of [7- (4,4,5,5-tetramethyl-1,3,2-dioxabororan-2-yl) spiro [indeno [2,1- b] pyridine- [1,1'-biphenyl] -3-yl) -6,8-diphenyl- [1,2,4] triazolo [1,5- a] Pyridine, the procedure of Synthesis Example 2 was repeated to obtain the desired compound (4.0 g, yield 52%).

[LCMS]: 754

[ Synthetic example  12] Synthesis of Compound 44

Biphenyl-5,9'-xanthene] and 2 - ([1,1'-biphenyl] -4-yl) -4 -Chloro-6-phenyl-1,3,5-triazine was used in place of 2-chloro-6-phenyl-1,3,5-triazine in the same manner as in [Synthesis Example 1] to obtain the desired compound (5.8 g, yield 43%).

[LCMS]: 640

[ Synthetic example  13] Synthesis of Compound 53

Preparation of 4- (4,4,5,5-tetramethyl-1,3,2-dioxabororan-2-yl) spiro [indeno [1,2- b] pyridin- 3.3 g (yield: 49%) of the desired compound was obtained by carrying out the same processes as in [Synthesis Example 2] except that 4- (4-bromophenyl) ).

[LCMS]: 639

[ Synthetic example  14] Synthesis of Compound 58

Preparation of 4- (4,4,5,5-tetramethyl-1,3,2-dioxabororan-2-yl) spiro [indeno [1,2- b] pyridin- (40%) was obtained by carrying out the same processes as in [Synthesis Example 2] except that 2- (3-chlorophenyl) -4'-xanthene and 2- (3-chlorophenyl) -4-phenylquinazoline were used.

[LCMS]: 613

[ Synthetic example  15] Synthesis of Compound 67

Preparation of 4- (4,4,5,5-tetramethyl-1,3,2-dioxabororan-2-yl) spiro [indeno [1,2- b] pyridin- Synthesis Example 2] was repeated except that 9'-xanthene and 2- (3'-chloro- [1,1'-biphenyl] -4-yl) -4,6-diphenylpyrimidine were used. The same procedure was followed to obtain 7.2 g of the title compound (yield: 60%).

[LCMS]: 715

[ Synthetic example  16] Synthesis of Compound 71

Preparation of 4- (4,4,5,5-tetramethyl-1,3,2-dioxabororan-2-yl) spiro [indeno [1,2- b] pyridin- Biphenyl-3-yl) -6- (4-methylpiperidin-1-yl) Phenyl-1,3,5-triazine was used in place of the compound obtained in Synthesis Example 1 to obtain 5.6 g (yield: 42%) of the desired compound.

[LCMS]: 792

[ Synthetic example  17] Synthesis of Compound 74

Preparation of 4- (4,4,5,5-tetramethyl-1,3,2-dioxabororan-2-yl) spiro [indeno [1,2- b] pyridin- 4'-yl) -6- (3'-chloro- [1,1'-biphenyl] -3-yl) -2- Phenylpyrimidine, the procedure of Synthesis Example 2 was repeated to obtain the desired compound (4.9 g, yield 50%).

[LCMS]: 791

[ Synthetic example  18] Synthesis of Compound 78

Preparation of 4- (4,4,5,5-tetramethyl-1,3,2-dioxabororan-2-yl) spiro [indeno [1,2- b] pyridin- The same procedure as in [Synthesis Example 2] was carried out except that 9'-xanthene was used and 2- (4'-chloro - [1,1'-biphenyl] -3-yl) -4-phenylquinazoline was used To obtain 3.0 g of the objective compound (yield: 59%).

[LCMS]: 689

[ Synthetic example  19] Synthesis of Compound 81

Synthesis of 7'-bromo-10-phenyl-10H-spiro [acridine-9,9'-indeno [2,1-b] pyridine] of Preparation Example 5 and 2-chloro-4,6- -1,3,5-triazine was used in place of 2-chloro-4-methylpyridine, the target compound (2.6 g, yield: 41%) was obtained in the same manner as in [Synthesis Example 1].

[LCMS]: 639

[ Synthetic example  20] Synthesis of Compound 91

Preparation of 10-phenyl-7 '- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -10H-spiro [acridine- , 9'-indeno [2,1-b] pyridine] and 2- (4-bromophenyl) -4,6-diphenylpyrimidine were used in place of [ To obtain 5.5 g of the desired compound (yield: 44%).

[LCMS]: 714

[ Synthetic example  21] Synthesis of Compound 94

Preparation of 10-phenyl-7 '- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -10H-spiro [acridine- (3-bromophenyl) -6-phenyl-1, 9'-indeno [2,1-b] pyridine] and 2- The same procedure as in [Synthesis Example 2] was conducted except that 3,5-triazine was used to obtain the desired compound (4.0 g, yield 52%).

[LCMS]: 791

[ Synthetic example  22] Synthesis of compound 99

Preparation of 10-phenyl-7 '- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -10H-spiro [acridine- The procedure was the same as in [Synthesis Example 2], except that 2-bromo-2-methylpyridine, 9'-indeno [2,1- g (yield: 65%).

[LCMS]: 688

[ Synthetic example  23] Synthesis of Compound 102

Preparation of 10-phenyl-7 '- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -10H-spiro [acridine- , 9'-indeno [2,1-b] pyridine] and 2- (3'-chloro- [1,1'- biphenyl] The procedure of Synthesis Example 2 was repeated except that 5-triazine was used to obtain 5.3 g of the desired compound (yield: 40%).

[LCMS]: 791

[ Synthetic example  24] Synthesis of compound 110

Preparation of 10-phenyl-7 '- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -10H-spiro [acridine- , 9'-indeno [2,1-b] pyridine] and 4- (3'-chloro- [1,1'- biphenyl] -4-yl) -2,6-diphenylpyrimidine , The same procedure as in [Synthesis Example 2] was carried out to obtain 4.2 g of the desired compound (yield: 35%).

[LCMS]: 790

[ Synthetic example  25] Synthesis of Compound 116

Preparation of 10-phenyl-7 '- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -10H-spiro [acridine- , 9'-indeno [2,1- b] pyridine] and 4 - ([1,1'-biphenyl] -4-yl) -6- (3'-chloro- [ ] -4-yl) -2-phenylpyrimidine, the procedure of Synthesis Example 2 was repeated to obtain the desired compound (5.2 g, yield: 46%).

[LCMS]: 867

[ Synthetic example  26] Synthesis of Compound 120

Preparation of 10-phenyl-7 '- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -10H-spiro [acridine- , 9'-indeno [2,1- b] pyridine] and 2- (3'-chloro- [1,1'- biphenyl] -4- yl) -6,8- , 4] triazolo [l, 5-a] pyridine was used in place of 2-pyridylmethylaniline to obtain 5.2 g (yield 46%) of the desired compound.

[LCMS]: 830

[ Synthetic example  27] Synthesis of Compound 121

Synthesis of 7'-bromo-10-phenyl-10H-spiro [acridine-9,5'-indeno [1,2- b] pyridine] of Preparation Example 7 and 2-chloro-4,6- -1,3,5-triazine was used in place of 1,3,5-triazine, the procedure of Synthesis Example 1 was repeated to obtain 3.7 g of the desired compound (yield: 45%).

[LCMS]: 639

[ Synthetic example  28] Synthesis of Compound 130

Preparation of 10-phenyl-7 '- (4,4,5,5-tetramethyl-1,3,2-dioxabororane-2-yl) -10H-spiro [acridine-9 , 5'-indeno [1,2-b] pyridine] and 2- (3-bromophenyl) -4,6-diphenylpyrimidine were used in place of [ To obtain 5.2 g of the desired compound (yield: 46%).

[LCMS]: 714

[ Synthetic example  29] Synthesis of Compound 151

Preparation of 10-phenyl-7 '- (4,4,5,5-tetramethyl-1,3,2-dioxabororane-2-yl) -10H-spiro [acridine-9 , 5'-indeno [1,2-b] pyridine] and 2- (4-chlorophenyl) -6,8-diphenyl- [1,2,4] triazolo [ The same procedure as in [Synthesis Example 2] was repeated to obtain the desired compound (4.7 g, yield: 54%).

[LCMS]: 753

[ Synthetic example  30] Synthesis of compound 152

Preparation of 10-phenyl-7 '- (4,4,5,5-tetramethyl-1,3,2-dioxabororane-2-yl) -10H-spiro [acridine-9 , 5'-indeno [1,2-b] pyridine] and 2- (3'-chloro- [1,1'-biphenyl] The procedure of Synthesis Example 2 was repeated except that 5-triazine was used to obtain 3.3 g of the desired compound (yield 49%).

[LCMS]: 791

[ Synthetic example  31] Synthesis of Compound 160

Preparation of 10-phenyl-7 '- (4,4,5,5-tetramethyl-1,3,2-dioxabororane-2-yl) -10H-spiro [acridine-9 , 5'-indeno [1,2-b] pyridine] and 4- (3'-chloro- [1,1'-biphenyl] -4-yl) -2,6-diphenylpyrimidine , The same procedure as in [Synthesis Example 2] was conducted to obtain 5.2 g of the desired compound (yield: 41%).

[LCMS]: 790

[ Synthetic example  32] Synthesis of Compound 166

Preparation of 2- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) spiro [fluorene-9,10'-pyrano [ 2-c: 5,6-c '] dipyridine] and 4- (4-bromophenyl) -2,6-diphenylpyrimidine were used in place of [ 7.7 g (yield 67%) of the desired compound was obtained.

[LCMS]: 640

[ Synthetic example  33] Synthesis of Compound 173

Preparation of 2- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) spiro [fluorene-9,10'-pyrano [ 2-c] 5,6-c '] dipyridine and 2- (3-chlorophenyl) -6,8-diphenyl- [l, 2,4] triazolo [ The procedure of Synthesis Example 2 was followed except that 5.4 g (yield 49%) of the desired compound was obtained.

[LCMS]: 679

[ Synthetic example  34] Synthesis of Compound 175

Preparation of 2- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) spiro [fluorene-9,10'-pyrano [ 2-c: 5,6-c '] dipyridine] and 2- (3'-chloro- [1,1'-biphenyl] -Triazine was used, 3.1 g (yield: 59%) of the desired compound was obtained by carrying out the same procedure as in [Synthesis Example 2].

[LCMS]: 717

[ Synthetic example  35] Synthesis of compound 183

Preparation of 2- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) spiro [fluorene-9,10'-pyrano [ 2-c: 5,6-c '] dipyridine] and 4- (3'-chloro- [1,1'-biphenyl] -4-yl) -2,6-diphenylpyrimidine , The same procedure as in [Synthesis Example 2] was repeated to obtain 2.7 g of the desired compound (yield: 55%).

[LCMS]: 716

[ Example  1 to 15] blue organic Field  Fabrication of light emitting device

Compounds 1, 7, 17, 21, 24, 44, 53, 78, 81, 91, 99, 121, 151, 166 and 183 synthesized in Synthesis Example were subjected to high purity sublimation purification by a conventionally known method, A blue organic electroluminescent device was prepared.

first. Glass substrate coated with ITO (Indium tin oxide) thin film with thickness of 1500 Å was washed with distilled water ultrasonic wave. After the distilled water was washed, the substrate was ultrasonically washed with a solvent such as isopropyl alcohol, acetone, and methanol, and dried. Then, the substrate was transferred to a UV OZONE cleaner (Power sonic 405, Hoshin Tech), and the substrate was cleaned using UV for 5 minutes The substrate was transferred to a vacuum evaporator.

NPN (15 nm) / ADN + 5% DS-405 (Doosan Electronics, 30 nm) / Compound 1, 7, 17 and 21 (30 nm) / LiF (1 nm) / Al (200 nm) were stacked in this order to form an organic electroluminescent device, Respectively.

[ Comparative Example  1] Blue organic Field  Fabrication of light emitting device

A blue organic electroluminescent device was fabricated in the same manner as in Example 1 except that Alq ₃ was used instead of Compound 1 as the electron transport layer material.

[ Comparative Example  2] Blue organic Field  Fabrication of light emitting device

A blue organic electroluminescent device was fabricated in the same manner as in Example 1 except that Compound 1 was not used as the electron transport layer material.

The structures of NPB, AND and Alq3 used in Examples 1 to 15 and Comparative Examples 1 and 2 are as follows.

[ Evaluation example  One]

The driving voltage, current efficiency and emission wavelength at the current density of 10 mA / cm 2 were measured for the blue organic electroluminescent devices fabricated in Examples 1 to 15 and Comparative Examples 1 and 2, Respectively.

Sample Electron transport layer The driving voltage (V) Emission peak (nm) Current efficiency (cd / A) Example 1 Compound 1 4.0 452 7.8 Example 2 Compound 7 3.8 452 8.5 Example 3 Compound 17 3.3 453 8.8 Example 4 Compound 21 3.4 452 8.5 Example 5 Compound 24 4.2 453 7.9 Example 6 Compound 44 4.0 452 8.2 Example 7 Compound 53 3.6 455 8.4 Example 8 Compound 78 3.5 450 8.0 Example 9 Compound 81 3.6 452 8.1 Example 10 Compound 91 3.4 453 8.5 Example 11 Compound 99 3.6 450 8.3 Example 12 Compound 121 4.1 454 7.9 Example 13 Compound 151 3.3 452 8.8 Example 14 Compound 166 3.6 455 8.5 Example 15 Compound 183 3.9 455 8.6 Comparative Example 1 Alq ₃ 5.4 458 5.8 Comparative Example 2 - 5.2 458 6.2

As shown in Table 1 above, the blue organic electroluminescent devices (Examples 1 to 13) using the compound of the present invention as the electron transporting layer (Comparative Examples 1 and 2) using conventional Alq ₃ as the electron transporting layer and the blue organic electroluminescent devices Emitting layer and the blue organic electroluminescent device without the electron transport layer (Comparative Example 2).

[ Example  16 to 34] Blue organic Field  Fabrication of light emitting device

The compound 6, 15, 22, 28, 32, 39, 58, 67, 71, 74, 94, 102, 110, 116, 130, 152, 160, 173, 175 synthesized in Synthesis Example was subjected to high purity After sublimation purification, a blue organic electroluminescent device was fabricated according to the following procedure.

First, glass substrate coated with ITO (Indium tin oxide) thin film of 1500 Å thickness was cleaned with distilled water ultrasonic wave. After the distilled water was washed, the substrate was ultrasonically washed with a solvent such as isopropyl alcohol, acetone, or methanol, and dried. Then, the substrate was transferred to a UV OZONE cleaner (Power sonic 405, Hoshin Tech) And the substrate was transferred to a vacuum evaporator.

NPN (15 nm) / ADN + 5% DS-405 (Doosan Electronics, 30 nm) / Compound 6, 15, 22, 28 (5 nm) / Alq ₃ (25 nm) / LiF (1 nm) / Al (2 nm), 32, 39, 58, 67, 71, 74, 94, 102, 200 nm) were stacked in this order to fabricate an organic electroluminescent device.

[ Comparative Example  3] Blue organic Field  Manufacturing of light emitting device

A blue organic electroluminescent device was fabricated in the same manner as in Example 16 except that Compound 6 was not used as an electron transporting auxiliary layer material and Alq ₃ , which is an electron transporting layer material, was deposited at 30 nm instead of 25 nm .

[ Evaluation example  2]

The driving voltage, light emission wavelength and current efficiency at the current density of 10 mA / cm 2 were measured for the organic electroluminescent devices manufactured in Examples 16 to 34 and Comparative Example 3, respectively, and the results are shown in Table 2 below.

Sample Electron transporting auxiliary layer The driving voltage (V) Emission peak (nm) Current efficiency (cd / A) Example 16 Compound 6 4.2 455 7.8 Example 17 Compound 15 3.4 452 8.2 Example 18 Compound 22 3.3 450 8.9 Example 19 Compound 28 3.2 452 8.5 Example 20 Compound 32 3.5 455 8.3 Example 21 Compound 39 3.3 452 8.6 Example 22 Compound 58 3.8 451 8.2 Example 23 Compound 67 3.7 452 8.4 Example 24 Compound 71 3.8 453 8.0 Example 25 Compound 74 3.5 451 8.6 Example 26 Compound 94 3.6 452 8.3 Example 27 Compound 102 3.2 451 8.8 Example 28 Compound 110 3.4 452 8.4 Example 29 Compound 116 3.7 453 8.1 Example 30 Compound 130 3.6 452 8.3 Example 31 Compound 152 3.3 450 8.7 Example 32 Compound 160 3.5 453 8.4 Example 33 Compound 173 3.4 452 8.7 Example 34 Compound 175 3.5 451 8.9 Comparative Example 3 - 4.8 458 6.0

As shown in Table 2, the blue organic electroluminescent devices (Examples 16 to 34) using the compound of the present invention as the electron transporting auxiliary layer (Examples 16 to 34) were superior to the blue organic electroluminescent devices without the electron transporting auxiliary layer Current efficiency, emission peak, and driving voltage.

Claims (11)

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

In Formula 1,
X is O or N (R &lt; ₁ &gt;);
Each of Z ₁ to Z ₁₂ is independently N or C (R ₂ ), or at least one of Z ₁ to Z ₁₂ is N;
m is an integer from 0 to 4;
Ar ₁ is a substituent represented by the following formula (2), and when a plurality of Ar _{1 s} are present, they are the same or different;
R ₁ is selected from the group consisting of hydrogen, a C ₁ to C ₄₀ alkyl group, a C ₆ to C ₆₀ aryl group, and a heteroaryl group having 5 to 60 ring atoms;
R ₂ is selected from the group consisting of hydrogen, a C ₁ to C ₄₀ alkyl group, a C ₆ to C ₆₀ aryl group and a heteroaryl group having 5 to 60 nuclear atoms, and when a plurality of R _{2 s} are the same or different, ;
The alkyl, aryl and heteroaryl groups of R ₁ and R ₂ are each independently selected from the group consisting of deuterium, C ₁ to C ₄₀ alkyl, C ₂ to C ₄₀ alkenyl, C ₆ to C ₆₀ aryl, To 60 heteroaryl groups and C ₆ to C ₆₀ arylamine groups, and when they are substituted with a plurality of substituents, they are the same as or different from each other;
(2)

In Formula 2,
* Denotes the part where the bond is made;
L ₁ and L ₂ are each independently selected from the group consisting of a single bond, a C ₆ to C ₁₈ arylene group and a heteroarylene group having 5 to 18 nucleus atoms;
R ₃ is selected from the group consisting of hydrogen, a C ₁ to C ₄₀ alkyl group, a C ₆ to C ₆₀ aryl group, and a heteroaryl group having 5 to 60 ring atoms;
Wherein L _1, and arylene group of L ₂ and a heteroarylene group, an alkyl group of said R _3, aryl and heteroaryl groups are each independently a heavy hydrogen, an alkenyl group of C ₁ ~ C ₄₀ alkyl group, C ₂ ~ C ₄₀ of, C substituted with ₆ ~ C over a ₆₀ aryl group, the nuclear atoms of 5 to 60 heteroaryl group, and a C ₆ ~ selected from the aryl group consisting of an amine group in the C ₆₀ 1 more substituents or be unsubstituted, when it is substituted with a plurality of substituents , They are the same or different from each other. The method according to claim 1,
Wherein said compound is represented by any one of the following formulas (3) to (10):
(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

(7)

[Chemical Formula 8]

[Chemical Formula 9]

[Chemical formula 10]

In the above formulas 3 to 10,
R ₄ to R ₁₄ are each independently selected from the group consisting of hydrogen, a C ₁ to C ₄₀ alkyl group, a C ₆ to C ₆₀ aryl group, and a heteroaryl group having 5 to 60 nuclear atoms;
The alkyl, aryl and heteroaryl groups of R ₄ to R ₁₄ are each independently selected from the group consisting of deuterium, a C ₁ to C ₄₀ alkyl group, a C ₂ to C ₄₀ alkenyl group, a C ₆ to C ₆₀ aryl group, To 60 heteroaryl groups and C ₆ to C ₆₀ arylamine groups, and when they are substituted with a plurality of substituents, they are the same as or different from each other;
Each of R &_lt; ₁ &gt;, Ar &_lt; ₁ &gt; and m is as defined in claim ₁ . The method according to claim 1,
Wherein said compound is represented by the following formula (11):
(11)

In Formula 11,
X, Z ₁ to Z ₁₂ and Ar ₁ are each as defined in claim ₁ . The method according to claim 1,
Each of L ₁ and L ₂ is independently selected from the group consisting of a phenylene group, a biphenylene group, a naphthalenyl group, a fluorenyl group and a carbazolyl group,
Wherein L ₁ and the phenyl group, a biphenyl of the L ₂ group, a naphthyl Frontale group, a fluorenyl group and carbazolyl groups are each independently a heavy hydrogen, an alkenyl group of C ₁ ~ C ₄₀ alkyl group, C ₂ ~ C ₄₀ of, C ₆ ~ If C ₆₀ aryl group, the nuclear atoms of 5 to 60 heteroaryl group, and a C ₆ ~ substituted by one substituent at least one selected from the group consisting of an aryl amine of the C ₆₀ or is unsubstituted, substituted by a plurality of substituents, these are Are the same or different. The method according to claim 1,
Wherein Ar &lt; ₁ &gt; is a substituent represented by any one of the following formulas (12) to (14):
[Chemical Formula 12]

[Chemical Formula 13]

[Chemical Formula 14]

In the above Formulas 12 to 14,
* Denotes the part where the bond is made;
R &lt; ₃ &gt; is as defined in claim 1. The method according to claim 1,
Wherein R ₃ is selected from the group consisting of pyrimidine, pyrazine, triazine, imidazole, benzimidazole, phenanthroidimidazole, imidazopyridine, quinazoline and triazolopyridine,
The pyrimidine, pyrazine, triazine, imidazole, benzimidazole, phenanthroidimidazole, imidazopyridine, quinazoline and triazolopyridine of R ₃ are each independently selected from deuterium, a C ₁ to C ₄₀ alkyl group, C ₂ ~ C ₄₀ alkenyl group, C ₆ ~ C ₆₀ aryl group, nuclear atoms of 5 to 60 heteroaryl group, and a C ₆ ~ C is substituted by at least at ₆₀ the group consisting of an aryl amine of the selected one more substituents or being unsubstituted , When they are substituted with a plurality of substituents, they are the same as or different from each other. The method according to claim 1,
Wherein R &lt; ₃ &gt; is a substituent represented by any one of the following Al to A13:

In the above-mentioned A1 to A13,
* Denotes the part where the bond is made;
p is an integer from 0 to 3;
q is an integer from 0 to 2;
R ₁₅ is selected from the group consisting of C ₁ ~ C ₄₀ alkyl group, C ₆ ~ C ₆₀ aryl group, the number of nuclear atoms of 5 to 60 heteroaryl group, and a C ₆ ~ with an aryl amine of the C ₆₀ of the R ₁₅ is When plural are the same or different from each other;
R ₁₆ is selected from the group consisting of hydrogen, a C ₁ to C ₄₀ alkyl group, a C ₆ to C ₆₀ aryl group, a heteroaryl group having 5 to 60 nuclear atoms and an arylamine group having a C ₆ to C ₆₀ ;
The alkyl, aryl, heteroaryl and arylamine groups of R ₁₅ and R ₁₆ are each independently selected from the group consisting of deuterium, a C ₁ to C ₄₀ alkyl group, a C ₂ to C ₄₀ alkenyl group, a C ₆ to C ₆₀ aryl group, A heteroaryl group having 5 to 60 nuclear atoms and an arylamine group having ₆ to ₆₀ carbon atoms, and when they are substituted with a plurality of substituents, they are the same as or different from each other. 8. The method of claim 7,
Wherein R ₁₅ is C ₁ ~ C ₄₀ alkyl group, C ₆ ~ C ₆₀ aryl group and a nuclear atoms selected from 5 to 60 heteroaryl group the group consisting of, wherein R ₁₆ is hydrogen, C alkyl group of ₁ ~ C ₄₀ , An aryl group having ₆ to ₆₀ carbon atoms, and a heteroaryl group having 5 to 60 nuclear atoms. The method according to claim 1,
Wherein the compound represented by Formula 1 is selected from the group consisting of the following compounds:

1. An organic electroluminescent device comprising: (i) an anode, (ii) a cathode, and (iii) one or more organic layers sandwiched between the anode and the cathode,
Wherein at least one of the one or more organic layers includes a compound represented by the general formula (1). 11. The method of claim 10,
Wherein the organic compound layer containing the compound is selected from the group consisting of a hole injecting layer, a hole transporting layer, an electron transporting layer, an electron transporting auxiliary layer, an electron injecting layer, a lifetime improving layer, a light emitting layer and a light emitting auxiliary layer.