KR101920101B1 - Novel compounds and organic electro luminescence device using the same - Google Patents

Abstract

The present invention relates to a compound in which a heterocyclic moiety, particularly an indole derivative moiety, is fused to the terminal of benzothienopyridine or benzofuropyridine, and an organic electroluminescent device comprising the same. When the compound of the present invention is used in an organic material layer, an organic electroluminescent device having improved luminous efficiency, driving voltage and lifetime can be provided.

Description

TECHNICAL FIELD [0001] The present invention relates to a novel compound, and an organic electroluminescent device including the same. BACKGROUND OF THE INVENTION [0002]

TECHNICAL FIELD The present invention relates to a novel compound and an organic electroluminescent device including the same and more particularly to a compound used in an organic material layer of an organic electroluminescent device.

A study on the electroluminescent (EL) devices that led to the blue electroluminescence using the anthracene single crystal in 1965 based on the observation of the organic thin film emission of the Bernanose in the 1950s was carried out by Tang in 1987, An organic electroluminescent device having a laminated structure divided by functional layers has been proposed. In order to improve the efficiency and lifetime of the organic electroluminescent device, the organic electroluminescent device has been developed to introduce characteristic organic layers in the device.

In the organic electroluminescent device, when a voltage is applied between the two electrodes, holes are injected from the anode and electrons from the cathode are injected into the organic layer, and the injected holes and electrons meet to form an exciton. When the exciton formed drops to a ground state The light comes out. The material used as the organic material layer may be classified into a light emitting material, a hole injecting material, a hole transporting material, an electron transporting material, and an electron injecting material depending on functions.

The luminescent material can be classified into blue, green and red luminescent materials according to luminescent colors and yellow and orange luminescent materials necessary for realizing better natural colors. Further, in order to increase the color purity and to increase the luminous efficiency through energy transfer, a host / dopant system can be used as a luminescent 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. The development of the phosphorescent dopant can theoretically improve the luminous efficiency up to 4 times as compared with the fluorescent dopant, so that the phosphorescent dopant as well as the phosphorescent host have been studied.

Up to now, the hole transport layer. NPB, BCP, Alq ₃ and the like are widely known as materials used for the hole injecting layer and the electron transporting layer, and anthracene derivatives are used as the light emitting material. In particular, metal complex compounds containing Ir such as Firpic, Ir (ppy) ₃ , (acac) Ir (btp) ₂ and the like having great advantages in terms of efficiency improvement of light emitting materials are blue, green, red phosphorescent dopant materials, CBP is used as a phosphorescent host material. In addition, Korean Patent Publication No. 2010-0108924 discloses a technique of using an azacarbazole derivative as a host material.

However, since the conventional luminescent materials have good luminescent characteristics, they are not satisfactory in terms of the lifetime of the organic electroluminescent devices, and thus it is required to develop luminescent materials having excellent performance.

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 accomplish the above object, the present invention provides a compound represented by the following general formula (1).

[Chemical Formula 1]

Wherein A is O (oxygen) or S (sulfur), X ₁ to X ₄ are each independently CR ₁ or N (nitrogen), Y ₁ and Y ₂ , Y ₂ and Y ₃ , one of Y ₃ and Y ₄ is to form a compound with a fused ring represented by the formula 2, Y ₁ to Y ₄ It is preferable that CR ₂ or N (nitrogen) does not form a condensed ring, and at least one of N (nitrogen)

(2)

In the above formula (2), Z ₁ to Z ₄ are each independently CR ₃ or N (nitrogen)

Wherein R ₁ to R ₃ are, each independently, hydrogen, deuterium, halogen, cyano group, C ₁ ~ C ₄₀ alkyl group, C ₂ ~ C ₄₀ alkenyl group, C ₂ ~ C ₄₀ alkynyl group, C ₆ ~ of for C ₄₀ aryl group, the number of nuclear atoms of 5 to 40 heteroaryl group, C ₆ ~ C ₄₀ aryloxy group, C ₁ ~ C ₄₀ alkyloxy group of, C arylamine group of ₆ ~ C _40, (C ₆ To C ₄₀ aryl) C ₁ to C ₄₀ alkyl, C ₃ to C ₄₀ cycloalkyl, heterocycloalkyl having 3 to 40 nuclear atoms, C ₁ to C ₄₀ alkylsilyl and C ₆ to C ₄₀ An arylsilyl group, and is bonded to adjacent groups to form a fused ring Lt; / RTI >

Wherein Ar ₁ represents hydrogen, a C ₁ to C ₄₀ alkyl group, a C ₂ to C ₄₀ alkenyl group, a C ₂ to C ₄₀ alkynyl group, a C ₆ to C ₄₀ aryl group, a heteroaryl group having 5 to 40 nuclear atoms A C ₆ to C ₄₀ aryloxy group, a C ₁ to C ₄₀ alkyloxy group, a C ₆ to C ₄₀ arylamine group, a (C ₆ to C ₄₀ aryl) C ₁ to C ₄₀ alkyl group, C ₃ ~ C ₄₀ of is selected from cycloalkyl groups, 3 to 40 nuclear atoms heterocycloalkyl group, the group consisting of C ₁ ~ C ₄₀ alkyl silyl group, and a C ₆ ~ C ₄₀ aryl group in the silyl.

Herein, R ₁ to R ₃ may combine with adjacent groups to form a fused ring (a condensed aliphatic ring, a condensed aromatic ring, a condensed heteroaliphatic ring, a condensed heteroaromatic ring, or a combination thereof).

In addition, the R ₁ to R ₃ and the group of Ar _1, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, an aryloxy group, an alkyloxy group, an arylamine group, an aryl group, a cycloalkyl group, a heterocycloalkyl group, an alkyl The silyl group and the arylsilyl group may be substituted with at least one substituent selected from the group consisting of deuterium, halogen, cyano, C ₁ to C ₄₀ alkyl, C ₂ to C ₄₀ alkenyl, C ₂ to C ₄₀ alkynyl, C ₆ to C ₄₀ aryl, atoms of 5 to 40 heteroaryl group, an aryloxy group of a _{C 6 ~ C 40, C 1} ~ alkyloxy group of C _40, C ₆ ~ C ₄₀ aryl amine, (aryl C ₆ ~ C ₄₀₎ C ₁ ~ C ₄₀ alkyl group, C ₃ ~ C ₄₀ cycloalkyl group, nuclear atoms, 3 to 40 heterocycloalkyl group, C ₁ ~ C ₄₀ alkylsilyl group and a C ₆ ~ C ₄₀ aryl silyl group selected from the group consisting of May be substituted or unsubstituted with one or more substituents, and when plural substituents are present, the respective substituents may be the same or different.

&Quot; Alkyl " in the present invention means a monovalent substituent derived from a linear or branched saturated hydrocarbon having 1 to 40 carbon atoms. Examples of such alkyl include, but are not limited to, methyl, ethyl, propyl, isobutyl, sec-butyl, pentyl, iso-amyl and hexyl.

"Alkenyl" in the present invention means 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 double bond. Examples of such alkenyls include, but are not limited to, vinyl, allyl, isopropenyl, 2-butenyl, and the like.

"Alkynyl" in the present invention means a monovalent substituent derived from a straight-chain or branched-chain unsaturated hydrocarbon having 2 to 40 carbon atoms and having at least one carbon-carbon triple bond. Examples of such alkynyls include, but are not limited to, ethynyl, 2-propynyl, and the like.

&Quot; Aryl " in the present invention means a monovalent substituent derived from an aromatic hydrocarbon having 6 to 60 carbon atoms, in which a single ring or two or more rings are combined, and when two or more rings are pendant or condensed with each other ) ≪ / RTI > Examples of such aryl include, but are not limited to, phenyl, naphthyl, phenanthryl, anthryl and the like.

&Quot; Heteroaryl " in the present invention means a monovalent substituent derived from a monoheterocyclic or polyheterocyclic aromatic hydrocarbon having 5 to 40 nuclear atoms (the number of atoms containing carbon), and at least one of the rings The carbon, preferably 1 to 3 carbons, is substituted with a heteroatom such as N, O, S or Se. Heteroaryl can be attached to two or more rings in a pendant or fused form to each other and can be interpreted to include condensed forms with aryl groups. 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; And 2-furanyl, N-imidazolyl, 2-isoxazolyl, 2-pyridinyl, 2-pyrimidinyl and the like, but are not limited thereto.

In the present invention, "aryloxy" is a monovalent substituent represented by RO-, and R is aryl having 6 to 60 carbon atoms. Examples of such aryloxy include, but are not limited to, phenyloxy, naphthyloxy, diphenyloxy, and the like.

In the present invention, "alkyloxy" means a monovalent substituent group represented by R'O-, wherein R 'represents alkyl having 1 to 40 carbon atoms, and may be linear, branched or cyclic, And the like. Examples of such alkyloxy include, but are not limited to, methoxy, ethoxy, n-propoxy, 1-propoxy, t-butoxy, n-butoxy and pentoxy.

&Quot; 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.

&Quot; 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 carbon, preferably 1 to 3 carbons, of the ring is N, O or S < / RTI > Examples of such heterocycloalkyl include, but are not limited to, morpholine, piperazine, and the like.

&Quot; Alkylsilyl " in the present invention is silyl substituted with alkyl having 1 to 40 carbon atoms, and " arylsilyl " means silyl substituted with aryl having 6 to 40 carbon atoms.

According to another aspect of the present invention, there is provided an organic electroluminescent device comprising a cathode, a cathode, and at least one organic layer sandwiched between the anode and the cathode, wherein at least one of the one or more organic layers includes a compound And an organic electroluminescent device.

Here, the organic material layer including the compound represented by Formula 1 is preferably a light emitting layer. When the compound represented by Formula 1 is used in the light emitting layer, the compound represented by Formula 1 may be used as a blue, green, or red phosphorescent host material.

When the compound represented by the general formula (1) of the present invention is used for an organic material layer (preferably, a light emitting material of a light emitting layer) of an organic electroluminescent device, efficiency (luminous efficiency and messaging efficiency), lifetime, Voltage and the like can be improved. Accordingly, the present invention can provide a full-color organic electroluminescence panel with improved performance and lifetime.

Hereinafter, the present invention will be described in detail.

The present invention has a larger molecular weight than a conventional organic electroluminescent device material (for example, 4,4-dicarbazolybiphenyl (hereinafter referred to as 'CBP')), and has a wide energy band gap, To thereby provide a compound represented by the above formula (1) capable of enhancing the binding force.

Specifically, the compound represented by formula (1) of the present invention is a compound in which a heterocyclic moiety, preferably an indole derivative moiety, is bonded to the terminal of benzothienopyridine or benzofuropyridine Fusion). Since the benzothienopyridine or benzofuropyridine skeleton has a high triplet energy level, when the compound represented by Formula 1 of the present invention is used in an organic electroluminescent device, the phosphorescence property of the device is improved The hole injecting ability, the hole transporting ability, the light emitting efficiency, the driving voltage and the life characteristics can be improved.

In particular, the compound represented by the formula (1) of the present invention has a wide band gap (sky blue to red) due to the indole derivative moiety bonded to the end of the benzothiopyridine or benzopyropyridine skeleton, It is possible to exhibit excellent properties as a host material of the light emitting layer, specifically, a blue, green and / or red phosphorescent host material, as compared with the conventional CBP.

In addition, the compound represented by formula (1) of the present invention exhibits a high glass transition temperature because the compound has a significantly increased molecular weight due to various substituents (R ₁ to R ₃ and Ar ₁ ) bonded thereto, And may have thermal stability.

In the compound represented by the general formula (1) of the present invention, Y ₁ to Y ₄ It is preferable that the portion not forming the condensed ring contains at least one of N. It is preferable that all of X ₁ to X ₄ are CR ₁ or N, and that all of Z ₁ to Z ₄ are CR ₃ or N or more.

In the compounds represented by the general formula (1) of the present invention, Ar ₁ substituted on the indole derivative moiety is preferably a C ₆ to C ₄₀ aryl group or a heteroaryl group having 5 to 40 nuclear atoms.

The aryl group, heteroaryl group, arylamine group and arylsilyl group of Ar ₁ may be substituted with a substituent selected from the group consisting of deuterium, halogen, cyano, C ₁ to C ₄₀ alkyl, C ₂ to C ₄₀ alkenyl, C ₂ to C ₄₀ A C ₆ to C ₄₀ aryl group, a heteroaryl group having 5 to 40 nuclear atoms, a C ₆ to C ₄₀ aryloxy group, a C ₁ to C ₄₀ alkyloxy group, a C ₆ to C ₄₀ aryl an amine group, C ₁ ~ C ₄₀ alkyl group, C ₃ ~ C ₄₀ cycloalkyl group, a number of nuclear atoms of 3 to 40 heterocycloalkyl group, C ₁ ~ C ₄₀ alkylsilyl group and a C ₆ ~ C ₄₀ aryl silyl group of the And when there are a plurality of substituents, the respective substituents may be the same or different.

Examples of substituents (functional groups) R ₁ to R ₃ and Ar ₁ of the compound represented by the formula (1) of the invention include the following examples (S1 to S138), but the present invention is not limited thereto.

At this time, Ar ₁ in the substituent of the compound represented by the formula (1) of the present invention is preferably selected from the group consisting of the structures represented by the following S-1 to S-39.

The compound represented by the formula (1) of the present invention is preferably selected from the group consisting of compounds represented by the following formulas (3) to (8), but is not limited thereto.

(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

(7)

[Chemical Formula 8]

In Formulas 3 to 8, A, X ₁ to X ₄ , Y ₁ to Y _{4 ,} Z ₁ to Z _{4 ,} and Ar ₁ are the same as defined in Formula 1.

The compound represented by formula (1) of the present invention is more preferably selected from the group consisting of compounds represented by the following formulas (C1) to (C18), but is not limited thereto.

In the above formulas C1 to C18, A, X ₁ to X _{4 ,} Z ₁ to Z ₄ And Ar ₁ are the same as defined in formula (I). In the compounds represented by the above formulas C1 to C18, A is more preferably S.

Specific examples of the compound represented by the formula (1) of the present invention include, but are not limited to, the following compounds (C-1 to C-578).

The compound represented by formula (1) of the present invention can be synthesized in various ways with reference to the synthesis process of the following examples.

2. Organic Field  Light emitting element

The present invention provides an organic electroluminescent device comprising the compound represented by Formula 1, preferably the compound represented by Formula 3 to 8.

More particularly, the present invention relates to an organic electroluminescent device comprising an anode, a cathode, and at least one organic material layer interposed between the anode and the cathode, wherein at least one of the organic material layers A compound represented by the general formula (1), preferably a compound represented by the general formulas (3) to (8). At this time, the compounds represented by the formulas (3) to (8) may be used singly or in combination of two or more.

The one or more organic layers may be at least one of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer, and may be preferably a hole injection layer, a hole transport layer, a light emitting layer, or an electron transport layer, Emitting layer.

The organic electroluminescent device according to the present invention may include a host material in the light emitting layer. In this case, the compound represented by Formula 1 may be used as the host material. When the compound represented by Formula 1 is used as a phosphorescent host material for blue, green, and red phosphorescent layers of an organic electroluminescent device, preferably a phosphorescent emitting layer, the bonding force between holes and electrons in the phosphorescent emitting layer increases, The efficiency (luminous efficiency and power efficiency), lifetime, luminance, driving voltage and the like of the device can be improved.

The structure of the organic electroluminescent device of the present invention is not particularly limited, but 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. Here, the electron injection layer may be further stacked on the electron transporting layer. In addition, the organic electroluminescent device according to the present invention may have a structure in which an anode, one or more organic layers and an anode are sequentially stacked, and an insulating layer or an adhesive layer is interposed between the electrodes and the organic layer.

Examples of the material usable as the anode included in the organic electroluminescent device according to the present invention include, but are not limited to, 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.

Examples of materials usable as a cathode included in the organic electroluminescent device according to the present invention include, but are not limited to, magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, Tin, or lead, or alloys thereof; And a multilayer structure material such as LiF / Al or LiO ₂ / Al.

The organic material layer included in the organic electroluminescent device according to the present invention is not limited to the organic material layer of the organic electroluminescent device according to the present invention except that the compound represented by Chemical Formula 1 is used in any one of the hole injecting layer, the hole transporting layer, the light emitting layer, , ≪ / RTI >

Materials that can be used as the substrate included in the organic electroluminescent device according to the present invention are not particularly limited, but examples thereof include silicon wafers, quartz, glass plates, metal plates, plastic films and sheets.

The organic electroluminescent device of the present invention may be manufactured by a method known in the art, and the luminescent layer included in the organic material layer may be prepared by a vacuum evaporation 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, and thermal transfer.

Hereinafter, the present invention will be described in detail with reference to examples. However, the following examples are for illustrative purposes only and are not intended to limit the scope of the present invention.

[ Preparation Example  One] CORE Synthesis of -1

<Step 1> CORE1 Synthesis of -A

N-nitrophenylboronic acid, 4.8 g (120.4 mmol) of NaOH and 200 ml / 50 ml of THF / H ₂ O were added to 10.6 g (40.13 mmol) of CORE1-A-1 and 8.0 g . At 40 ℃ into the Pd (PPh _{3) 4} of 1.39g (1.2mmol) it was stirred under reflux at 80 ℃ for 12 hours. After completion of the reaction, the reaction mixture was extracted with dichloromethane. The organic layer was dried over MgSO ₄ and filtered under reduced pressure. The filtered organic layer was distilled under reduced pressure, and 6.4 g (yield: 52%) of CORE1-A was obtained by column chromatography.

^& Lt; ¹ &gt; H-NMR: [delta] 7.59 (m, 3H), 8.00 (m,

<Step 2> CORE Synthesis of -1

6.4 g (20.89 mmol) of CORE1-A, 13.7 g (52.22 mmol) of triphenylphosphine and 100 ml of 1,2-dichlorobenzene were placed in a nitrogen stream and stirred for 12 hours. After completion of the reaction, 1,2-dichlorobenzene was removed through distillation and extracted with dichloromethane. The extracted organic layer was dried with MgSO ₄ and filtered under reduced pressure. The filtered organic layer was distilled under reduced pressure and 3.3 g (yield: 57%) of CORE-1 was obtained by column chromatography.

¹ H-NMR:? 7.31 (t, IH), 7.55 (m, 4H), 8.05

[ Preparation Example  2] CORE - 2 of  synthesis

<Step 1> 2,5- dichloro -3- (2- klorophenyl ) pyrazine Synthesis of

Under nitrogen gas stream, 28g (152.65mmol) of 2,3,5-trichloropyrazine, 23.8g (152.65mmol) 2-chlorophenylboronic acid, 63.3g (457.9mmol) of K ₂ CO ₃ and the THF / H ₂ O of 800ml / 200ml of And the mixture was stirred. At 40 ℃ into the Pd (PPh _{3) 4} of 5.3g (4.58mmol) was stirred at 80 ℃ for 12 hours. After completion of the reaction, the reaction mixture was extracted with dichloromethane. The organic layer was dried over MgSO ₄ and filtered under reduced pressure. The filtered organic layer was distilled under reduced pressure, and 12 g (yield: 30%) of 2,5-dichloro-3- (2-chlorophenyl) pyrazine was obtained by column chromatography.

¹ H-NMR:? 7.37 (m, 2H), 7.58 (d, IH), 7.75

<Step 2> ethyl  3- (2- (3,6- dichloropyrazine -2- yl ) 메틸THIO ) propanoate Synthesis of

12.4 g (92.47 mmol) of ethyl 3-mercaptopropanoate, 2.96 g (3.23 mmol) of Pd ₂ dba ₃ , 0.1 g (0.7 mmol) of dpephos and 16 g (115.6 mmol) of K ₂ CO ₃ were placed in 250 ml of toluene, and the mixture was stirred at 110 ° C for 15 hours. After completion of the reaction, the reaction mixture was extracted with dichloromethane. The organic layer was dried over MgSO ₄ and filtered under reduced pressure. The filtered organic layer was distilled under reduced pressure, and 14.7 g (yield: 89%) of ethyl 3- (2- (3,6-dichloropyrazin-2- yl) phenylthio) propanoate was obtained by column chromatography.

^{1 H-NMR: δ 1.27 (} m, 3H), 2.52 (m, 2H), 3.03 (m, 2H), 4.09 (m, 2H), 7.30 (m, 2H), 7.71 (d, 1H), 7.87 ( d, 1 H), 8.69 (s, 1 H)

<Step 3> CORE2 - Of A  synthesis

(Potassium tert-butoxide) of 6.92 g (61.7 mmol) were added to 200 ml of THF under nitrogen atmosphere, and 14.7 g (41.1 mmol) of ethyl 3- (2- (3,6-dichloropyrazin- Lt; / RTI &gt; for 8 hours. After completion of the reaction, the reaction mixture was extracted with dichloromethane. The organic layer was dried over MgSO ₄ and filtered under reduced pressure. The filtered organic layer was distilled under reduced pressure and 6.6 g (yield: 80%) of CORE2-A as a target compound was obtained by column chromatography.

^{1 H-NMR: δ 7.51 (} m, 2H), 8.02 (m, 2H), 8.87 (s, 1H)

<Step 4> CORE2 Synthesis of -B

6 g (yield: 67%) of CORE2-B was obtained by carrying out the same procedure as <Step 1> of Preparation Example 1 except that CORE2-A was used instead of CORE1-A-1.

¹ H-NMR:? 7.61 (m, 3H), 8.02 (m, 4H), 8.18

<Step 5> CORE - 2 of  synthesis

3.2 g (yield: 54%) of CORE-2 was obtained by carrying out the same procedure as <Step 2> of Preparation Example 1 except that CORE2-B was used instead of CORE1-A.

¹ H-NMR: [delta] 7.27 (t, IH), 7.59 (m, 4H), 8.07 (m, 3H)

[ Preparation Example  3] CORE - 3 of  synthesis

<Step 1> 2,5- dichloro -3- (2- klorophenyl ) 피리딘 Synthesis of

The procedure of Step 1 of Preparation Example 2 was repeated except that 2,3,5-trichloropyridine was used instead of 2,3,5-trichloropyrazine to obtain 2,5-dichloro-3- (2-chlorophenyl) pyridine 13 g (yield: 46%).

^{1 H-NMR: δ 7.38 (} m, 2H), 7.75 (m, 2H), 8.81 (s, 1H)

< Step 2 > ethyl  3- (2- (2,5- dichloropyridine -3- yl ) 메틸THIO ) propanoate Synthesis of

Step 2 of Preparation Example 2 was carried out except that 2,5-dichloro-3- (2-chlorophenyl) pyridine was used instead of 2,5-dichloro-3- (2-chlorophenyl) pyrazine 15.3 g (yield: 85%) of ethyl 3- (2- (2,5-dichloropyridin-3-yl) phenylthio) propanoate.

^{1 H-NMR: δ 1.28 (} m, 3H), 2.56 (m, 2H), 3.32 (m, 2H), 4.19 (m, 2H), 7.39 (m, 2H), 7.64 (m, 2H), 8.44 ( s, 1 H), 8.67 (s, 1 H)

< Step 3 > CORE3 Synthesis of -A

except that ethyl 3- (2- (2,5-dichloropyridin-3-yl) phenylthio) propanoate was used in place of ethyl 3- (3- (6,6-dichloropyrazin- (Yield: 78%) of CORE3-A was obtained by performing the same procedure as in <Step 3>.

¹ H-NMR:? 7.48 (m, 2H), 7.96 (m, 2H), 8.49

< Step 4 > CORE3 Synthesis of -B

6.2 g (yield: 60%) of CORE3-B was obtained by carrying out the same procedure as <Step 1> of Preparation Example 1 except that CORE3-A was used instead of CORE1-A-1.

¹ H-NMR:? 7.49 (m, 2H), 7.66 (t, IH), 8.01 (m, 4H), 8.19 (d,

< Step 5 > CORE Synthesis of -3A and 3B

(Yield: 32%) CORE-3B (yield: 36%) was performed in the same manner as <Step 2> of Preparation Example 1 except that CORE3-B was used instead of CORE1- &Lt; / RTI &gt;

^{CORE-3A 1 H-NMR:} δ 7.32 (t, 1H), 7.49 (m, 3H), 7.81 (s, 1H), 8.05 (m, 2H), 8.49 (d, 1H), 10.35 (s, 1H)

^{CORE-3B 1 H-NMR:} δ 7.31 (t, 1H), 7.51 (m, 3H), 7.83 (d, 1H), 8.02 (d, 1H), 8.15 (d, 1H), 8.47 (d, 1H) , 9.55 (s, 1 H)

[Preparation Example 4] Synthesis of CORE-4

&Lt; Step 1 > 3- (2- nitrophenyl ) benzofuro [2,3-b] 피리딘 Synthesis of

Except that 3-chlorobenzofuro [2,3-b] pyridine was used in place of CORE1-A-1 to prepare 3- (2-nitrophenyl) benzofuro [2,3 -b] pyridine (yield: 56%).

¹ H-NMR:? 7.34 (m, 2H), 7.66 (m, 2H), 7.95

<Step 2> CORE Synthesis of -4A and 4B

The procedure of Step 2 of Preparation Example 1 was repeated except that 3- (2-nitrophenyl) benzofuro [2,3-b] pyridine was used in place of CORE1-A to yield 2.8 g (yield: 32 %) And 3.0 g (yield: 35%) of CORE-4B.

^{CORE-4A 1 H-NMR:} δ 7.34 (m, 3H), 7.50 (t, 1H), 7.65 (m, 2H), 7.80 (s, 1H), 7.92 (d, 1H), 8.15 (d, 1H) , 10.45 (s, 1 H)

^{CORE-4B 1 H-NMR:} δ 7.32 (m, 3H), 7.49 (t, 1H), 7.64 (m, 2H), 7.89 (d, 1H), 8.13 (d, 1H), 9.53 (s, 1H) , 10.42 (s, 1 H)

[ Synthetic example  One] Mat Synthesis of -1

(3.28 g, 12.00 mmol), 1-bromo-3,5-diphenylbenzene (7.39 g, 24.00 mmol), Cu powder (0.09 g, 1.30 mmol), K ₂ CO ₃ (3.58 g, 26.00 mmol), Na ₂ SO ₄ (3.70 g, 26.00 mmol) and nitrobenzene (100 ml) were mixed and stirred at 190 ° C for 12 hours.

After the reaction was completed, the nitrobenzene was removed, the organic layer was separated with methylene chloride, and water was removed using MgSO ₄ . After removing the solvent of the organic layer, the residue was purified by column chromatography to obtain 4.22 g (yield 70%) of the object compound Mat-1.

Exact Mass: 502.15 g / mol

Elemental Analysis: C, 83.64; H, 4.41; N, 5.57; S, 6.38

[ Synthetic example  2] Mat Synthesis of -2

Mat-2 (4.04 g, yield 67%) was obtained in the same manner as in Synthesis Example 1, except that 2-bromo-4,6-diphenylpyridine was used in place of 1-bromo-3,5-diphenylbenzene .

Exact Mass: 503.15 g / mol

Elemental Analysis: C, 81.09; H, 4.20; N, 8.34; S, 6.37

[ Synthetic example  3] Mat Synthesis of -3

(3.28 g, 12.00 mmol), 2-chloro-4,6-diphenylpyrimidine (6.38 g, 24.00 mmol), NaH (3.45 g, 14.40 mmol) and DMF 80 ml) were mixed and stirred at room temperature for 3 hours. After completion of the reaction, water was added thereto, and the solid compound was filtered and purified by column chromatography to obtain 4.79 g (yield: 81%) of the target compound Mat-3.

Exact Mass: 504.14 g / mol

Elemental Analysis: C, 78.55; H, 3.99; N, 11.10; S, 6.35

[ Synthetic example  4] Mat Synthesis of -4

The procedure of Synthesis Example 3 was repeated except that 2-chloro-4,6-diphenyl-1,3,5-triazine was used instead of 2-chloro-4,6-diphenylpyrimidine to obtain the target compound Mat- g, yield: 80%).

Exact Mass: 505 g / mol

Elemental Analysis: C, 76.02; H, 3.79; N, 13.85; S, 6.34

[ Synthetic example  5] Mat Synthesis of -5

The procedure of Synthesis Example 3 was repeated except that 2,4-di (biphenyl-3-yl) -6-chloro-1,3,5-triazine was used in place of 2-chloro-4,6-diphenylpyrimidine Mat-5 (5.99 g, yield 76%) as a target compound was obtained.

Exact Mass: 657.20 g / mol

Elemental Analysis: C, 80.34; H, 4.14; N, 10.65; S, 4.87

[ Synthetic example  6] Mat Synthesis of -6

Mat-6 (4.38 g, yield 71%) was obtained in the same manner as in Synthesis Example 1, except that 3-bromo-9-phenyl-9H-carbazole was used instead of 1-bromo-3,5- ).

Exact Mass: 515.15 g / mol

Elemental Analysis: C, 81.53; H, 4.11; N, 8.15; S, 6.22

[ Synthetic example  7] Mat Synthesis of -7

Mat-7 (3.48 g, yield 68%) was obtained in the same manner as in Synthesis Example 1, except that 2-bromo-5-phenylpyridine was used instead of 1-bromo-3,5-diphenylbenzene.

Exact Mass: 427.11 g / mol

Elemental Analysis: C, 78.66; H, 4.01; N, 9.83; S, 7.50

[ Synthetic example  8] Mat Synthesis of -8

Mat-8 (4.22 g, yield 70%) was obtained by carrying out the same procedure as in Synthesis Example 1, except that CORE-2 was used instead of CORE-1.

Exact Mass: 503.15 g / mol

Elemental Analysis: C, 81.09; H, 4.20; N, 8.34; S, 6.37

[ Synthetic example  9] Mat Synthesis of -9

Mat-9 (3.93 g, yield 65%) was obtained by carrying out the same procedure as in Synthesis Example 2 except that CORE-2 was used instead of CORE-1.

Exact Mass: 504.14 g / mol

Elemental Analysis: C, 78.55; H, 3.99; N, 11.10; S, 6.35

[ Synthetic example  10] Mat Synthesis of -10

Mat-10 (4.48 g, yield 74%) was obtained by carrying out the same procedure as in Synthesis Example 3 except that CORE-2 was used instead of CORE-1.

Exact Mass: 505.14 g / mol

Elemental Analysis: C, 76.02; H, 3.79; N, 13.85; S, 6.34

[ Synthetic example  11] Mat Synthesis of -11

Mat-11 (4.31 g, yield 71%) was obtained by carrying out the same procedure as in Synthesis Example 4, except that CORE-2 was used instead of CORE-1.

Exact Mass: 506.13 g / mol

Elemental Analysis: C, 73.50; H, 3.58; N, 16.59; S, 6.33

[ Synthetic example  12] Mat Synthesis of -12

Mat-12 (5.92 g, yield 75%) was obtained by carrying out the same procedure as in Synthesis Example 5 except that CORE-2 was used instead of CORE-1.

Exact Mass: 658.19 g / mol

Elemental Analysis: C, 78.40; H, 3.98; N, 12.76; S, 4.87

[ Synthetic example  13] Mat Synthesis of -13

Mat-13 (4.08 g, yield 66%) was obtained by carrying out the same procedure as in Synthesis Example 6 except that CORE-2 was used instead of CORE-1.

Exact Mass: 516.14 g / mol

Elemental Analysis: C, 79.05; H, 3.90; N, 10.84; S, 6.21

[ Synthetic example  14] Mat Synthesis of -14

Mat-14 (3.23 g, yield 63%) was obtained by carrying out the same procedure as in Synthesis Example 7, except that CORE-2 was used instead of CORE-1.

Exact Mass: 428.11 g / mol

Elemental Analysis: C, 75.68; H, 3.76; N, 13.07; S, 7.48

[ Synthetic example  15] Mat Synthesis of -15

Mat-15 (4.21 g, yield 70%) was obtained in the same manner as in Synthesis Example 1 except that CORE-3A was used instead of CORE-1.

Exact Mass: 502.15 g / mol

Elemental Analysis: C, 83.64; H, 4.41; N, 5.57; S, 6.38

[ Synthetic example  16] Mat Synthesis of -16

Mat-16 (3.62 g, yield 60%) was obtained by carrying out the same procedure as in Synthesis Example 2 except that CORE-3A was used instead of CORE-1.

Exact Mass: 503.15 g / mol

Elemental Analysis: C, 81.09; H, 4.20; N, 8.34; S, 6.37

[ Synthetic example  17] Mat Synthesis of -17

Mat-17 (4.53 g, yield 75%) was obtained by carrying out the same procedure as in Synthesis Example 3 except that CORE-3A was used instead of CORE-1.

Exact Mass: 504.14 g / mol

Elemental Analysis: C, 78.55; H, 3.99; N, 11.10; S, 6.35

[ Synthetic example  18] Mat Synthesis of -18

Mat-18 (4.36 g, yield 72%) was obtained by carrying out the same procedure as in Synthesis Example 4 except that CORE-3A was used instead of CORE-1.

Exact Mass: 505.14 g / mol

Elemental Analysis: C, 76.02; H, 3.79; N, 13.85; S, 6.34

[ Synthetic example  19] Mat -19 Synthesis

Mat-19 (5.51 g, yield 70%) was obtained by carrying out the same procedure as in Synthesis Example 5, except that CORE-3A was used instead of CORE-1.

Exact Mass: 657.20 g / mol

Elemental Analysis: C, 80.34; H, 4.14; N, 10.65; S, 4.87

[ Synthetic example  20] Mat Synthesis of -20

Mat-20 (3.98 g, yield 63%) was obtained by carrying out the same procedure as in Synthesis Example 6 except that CORE-3A was used instead of CORE-1.

Exact Mass: 515.15 g / mol

Elemental Analysis: C, 81.53; H, 4.11; N, 8.15; S, 6.22

[ Synthetic example  21] Mat Synthesis of -21

Mat-21 (3.33 g, yield 65%) was obtained by carrying out the same procedure as in Synthesis Example 7, except that CORE-3A was used instead of CORE-1.

Exact Mass: 427.11 g / mol

Elemental Analysis: C, 78.66; H, 4.01; N, 9.83; S, 7.50

[ Synthetic example  22] Mat Synthesis of -22

Mat-22 (4.33 g, yield 72%) was obtained by carrying out the same procedure as in Synthesis Example 1 except that CORE-3B was used instead of CORE-1.

Exact Mass: 502.15 g / mol

Elemental Analysis: C, 83.64; H, 4.41; N, 5.57; S, 6.38

[ Synthetic example  23] Mat Synthesis of -23

Mat-23 (3.92 g, yield 65%) was obtained by carrying out the same procedure as in Synthesis Example 2 except that CORE-3B was used instead of CORE-1.

Exact Mass: 503.15 g / mol

Elemental Analysis: C, 81.09; H, 4.20; N, 8.34; S, 6.37

[ Synthetic example  24] Mat Synthesis of -24

Mat-24 (4.23 g, yield 70%) was obtained by carrying out the same procedure as in Synthesis Example 3 except that CORE-3B was used instead of CORE-1.

Exact Mass: 504.14 g / mol

Elemental Analysis: C, 78.55; H, 3.99; N, 11.10; S, 6.35

[ Synthetic example  25] Mat Synthesis of -25

Mat-25 (4.24 g, yield 70%) was obtained by carrying out the same procedure as in Synthesis Example 4, except that CORE-3B was used instead of CORE-1.

Exact Mass: 505.14 g / mol

Elemental Analysis: C, 76.02; H, 3.79; N, 13.85; S, 6.34

[ Synthetic example  26] Mat Synthesis of -26

Mat-26 (5.36 g, yield 68%) was obtained by carrying out the same procedure as in Synthesis Example 5, except that CORE-3B was used instead of CORE-1.

Exact Mass: 657.20 g / mol

Elemental Analysis: C, 80.34; H, 4.14; N, 10.65; S, 4.87

[ Synthetic example  27] Mat -27

Mat-27 (4.02 g, yield 65%) was obtained by carrying out the same procedure as in Synthesis Example 6, except that CORE-3B was used instead of CORE-1.

Exact Mass: 515.15 g / mol

Elemental Analysis: C, 81.53; H, 4.11; N, 8.15; S, 6.22

[ Synthetic example  28] Mat -28 Synthesis

Mat-28 (3.12 g, yield 61%) was obtained by carrying out the same procedure as in Synthesis Example 7, except that CORE-3B was used instead of CORE-1.

Exact Mass: 427.11 g / mol

Elemental Analysis: C, 78.66; H, 4.01; N, 9.83; S, 7.50

[ Synthetic example  29] Mat Synthesis of -29

Mat-29 (4.24 g, yield 70%) was obtained by carrying out the same procedure as in Synthesis Example 4 except that CORE-4A was used instead of CORE-1.

Exact Mass: 489.16 g / mol

Elemental Analysis: C, 78.51; H, 3.91; N, 14.31; O, 3.27

[ Synthetic example  30] Mat Synthesis of -30

Mat-30 (5.00 g, yield 65%) was obtained by carrying out the same procedure as in Synthesis Example 5, except that CORE-4A was used instead of CORE-1.

Exact Mass: 641.22 g / mol

Elemental Analysis: C, 82.35; H, 4.24; N, 10.91; O, 2.49

[ Synthetic example  31] Mat Synthesis of -31

Mat-31 (3.77 g, yield 63%) was obtained by carrying out the same procedure as in Synthesis Example 6 except that CORE-4A was used instead of CORE-1.

Exact Mass: 499.17 g / mol

Elemental Analysis: C, 84.15; H, 4.24; N, 8.41; , 3.20

[ Synthetic example  32] Mat Synthesis of -32

Mat-32 (4.34 g, yield 74%) was obtained by carrying out the same procedure as in Synthesis Example 4 except that CORE-4B was used instead of CORE-1.

Exact Mass: 489.16 g / mol

Elemental Analysis: C, 78.51; H, 3.91; N, 14.31; O, 3.27

[ Synthetic example  33] Mat Synthesis of -33

Mat-33 (5.38 g, yield 70%) was obtained by carrying out the same procedure as in Synthesis Example 5 except that CORE-4B was used instead of CORE-1.

Exact Mass: 641.22 g / mol

Elemental Analysis: C, 82.35; H, 4.24; N, 10.91; O, 2.49

[ Synthetic example  34] Mat Synthesis of -34

Mat-34 (4.07 g, yield 68%) was obtained by carrying out the same procedure as in Synthesis Example 6, except that CORE-4B was used instead of CORE-1.

Exact Mass: 499.17 g / mol

Elemental Analysis: C, 84.15; H, 4.24; N, 8.41; , 3.20

[ Example  1] Green organic Field  Fabrication of light emitting device

Compound Mat-1 synthesized in Synthesis Example 1 was subjected to high-purity sublimation purification by a conventionally known method, and then a green organic electroluminescent device was produced as follows.

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

M-MTDATA (60 nm) / TCTA (80 nm) / Compound Mat-1 + 10% Ir (ppy) ₃ (80 nm) was formed on the ITO transparent electrode prepared above using the compound Mat- (300 nm) / BCP (10 nm) / Alq ₃ (30 nm) / LiF (1 nm) / Al (200 nm) were stacked in this order to prepare a green organic electroluminescent device.

The structures of m-MTDATA, TCTA, Ir (ppy) ₃ and BCP used are as follows.

[ Example  2 ~ 34]

Mat-2 to Mat-34 each synthesized in Synthesis Examples 2 to 34 were used instead of the compound Mat-1 used as a light emitting host material in the formation of the light emitting layer in Example 1, Thereby preparing a green organic electroluminescent device.

[ Comparative Example  One]

A green organic electroluminescent device was fabricated in the same manner as in Example 1, except that CBP was used in place of the compound Mat-1 used as a luminescent host material in the light emitting layer formation in Example 1. The structure of CBP used is as follows.

[ Experimental Example ]

The driving voltage, current efficiency and emission peak at a current density of 10 mA / cm 2 were measured for the green organic electroluminescent devices prepared in Examples 1 to 34 and Comparative Example 1, respectively, and the results are shown in Table 1 below.

Sample Host Driving voltage
(V) Emission peak
(nm) Current efficiency
(cd / A) Example 1 Mat-1 6.50 520 41.0 Example 2 Mat-2 6.61 523 41.2 Example 3 Mat-3 6.60 523 40.8 Example 4 Mat-4 6.58 523 41.1 Example 5 Mat-5 6.70 522 41.8 Example 6 Mat-6 6.70 520 41.3 Example 7 Mat-7 6.51 521 41.4 Example 8 Mat-8 6.66 520 40.9 Example 9 Mat-9 6.50 520 41.0 Example 10 Mat-10 6.45 519 41.5 Example 11 Mat-11 6.60 521 41.3 Example 12 Mat-12 6.55 518 41.1 Example 13 Mat-13 6.70 520 41.2 Example 14 Mat-14 6.50 523 41.3 Example 15 Mat-15 6.64 520 41.1 Example 16 Mat-16 6.60 522 41.5 Example 17 Mat-17 6.62 522 40.9 Example 18 Mat-18 6.70 520 41.4 Example 19 Mat-19 6.64 520 41.0 Example 20 Mat-20 6.50 521 41.6 Example 21 Mat-21 6.70 520 41.5 Example 22 Mat-22 6.63 521 41.0 Example 23 Mat-23 6.70 522 40.9 Example 24 Mat-24 6.55 520 41.8 Example 25 Mat-25 6.65 519 40.9 Example 26 Mat-26 6.60 521 41.1 Example 27 Mat-27 6.65 520 41.5 Example 28 Mat-28 6.52 521 41.4 Example 29 Mat-29 6.79 520 39.8 Example 30 Mat-30 6.75 519 39.5 Example 31 Mat-31 6.70 520 39.0 Example 32 Mat-32 6.81 521 39.2 Example 33 Mat-33 6.75 521 39.5 Example 34 Mat-34 6.80 520 39.7 Comparative Example 1 CBP 6.93 516 38.2

As shown in Table 1, the green organic electroluminescent devices prepared in Examples 1 to 34 using the compounds (Mat-1 to Mat-34) represented by the formula 1 of the present invention as host materials for the light emitting layer, It was confirmed that the green organic electroluminescent device of Comparative Example 1 used had better current efficiency and excellent driving voltage.

Claims (7)

The following compounds are selected from the group consisting of Mat-8 to Mat-21, and Mat-29 to Mat-31:

. delete delete delete delete 1. An organic electroluminescent device comprising an anode, a cathode, and at least one organic material layer interposed between the anode and the cathode,
Wherein at least one of the one or more organic layers includes the compound according to claim 1. The method according to claim 6,
Wherein the organic compound layer containing the compound is a light emitting layer.