KR101376874B1 - Novel compounds and organic electro luminescence device using the same - Google Patents

Abstract

The present invention relates to a novel compound and an organic electroluminescent device using the same. Specifically, a compound having an indole group bonded to both ends of tetrahydropyrene or tetrahydrophenanthrene and the compound are applied to the organic electroluminescent device. The present invention can provide an organic electroluminescent device with improved efficiency, lifetime, and stability.

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 as a hole blocking layer and an electron transporting layer, and an anthracene derivative is used as a luminescent 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, Japanese Patent Laid-Open No. 2004-0094842 discloses a technique of using a compound having a nitrogen-containing heterocyclic group bonded to an arylcarbazolyl group or carbazolylalkylene group as a phosphorescent host material.

However, since conventional luminescent materials have good luminescence characteristics, they have low glass transition temperature and are not very satisfactory in terms of the lifetime of the organic electroluminescent devices because of their poor thermal stability, development of luminescent materials 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 general formula (1).

[Formula 1]

In Formula 1,

,

,

로 이루어진 군에서 선택되고, R_a와 R_b 또는 R_b와 R_c 는 하기 화학식 2로 표시된 축합(fused) 고리를 형성하며, R_a와 R_b가 축합고리를 형성할 때, R_c는 수소이고, R_b와 R_c가 축합고리를 형성할 때, R_a는 수소이며,A,

,

,

Selected from the group consisting of R _a and R _b or R _b and R _c form a fused ring represented by the following formula (2), and when R _a and R _b form a condensed ring, R _c is hydrogen When R _b and R _c form a condensed ring, R _a is hydrogen,

(2)

Ar ₁ to Ar ₄ each independently represent a C ₁ to C ₄₀ alkyl group, C ₃ to C ₄₀ cycloalkyl group, C ₃ to C ₄₀ heterocycloalkyl group, C ₆ to C ₆₀ aryl group, C ₅ to C ₆₀ heteroaryl group, C ₁ ~ C ₄₀ Alkyloxy group, C ₆ ~ C ₆₀ An aryloxy group and C ₆ ~ C ₆₀ An arylamine group,

R ₁ to R ₄ are each independently hydrogen, halogen, C ₁ -C ₄₀ alkyl group, C ₃ -C ₄₀ cycloalkyl group, C ₃ -C ₄₀ heterocycloalkyl group, C ₆ -C ₆₀ aryl group , C ₅ ~ C ₆₀ Heteroaryl group, C ₁ ~ C ₄₀ Alkyloxy group, C ₆ ~ C ₆₀ An aryloxy group and C ₆ ~ C ₆₀ An arylamine group,

n and m are integers of 0-4.

Here, Ar ₁ to Ar ₄ is hydrogen, C ₁ ~ C ₄₀ Alkyl group, C ₂ ~ C ₄₀ Alkenyl group, C ₂ ~ C ₄₀ Alkynyl group, C ₆ ~ C ₄₀ Aryl group, C ₅ ~ C ₄₀ heteroaryl group, C ₆ ~ C ₄₀ aryloxy group, C ₁ ~ C ₄₀ alkyloxy group, C ₆ ~ C ₄₀ arylamino group, C ₆ ~ C ₄₀ diarylamino group, C ₆ ~ C ₄₀ It may be substituted with a substituent selected from the group consisting of an arylalkyl group, C ₃ ~ C ₄₀ cycloalkyl group, C ₆ ~ C ₄₀ arylsilyl group, and C ₃ ~ C ₄₀ heterocycloalkyl group.

The term "alkyl" used in the present invention means a linear or branched saturated hydrocarbon having 1 to 40 carbon atoms. Examples thereof include methyl, ethyl, propyl, isobutyl, sec-butyl, pentyl, iso-amyl, . In addition, 'aryl' of the present invention means an aromatic moiety having 6 to 60 carbon atoms in which a single ring or two or more rings are combined, and two or more rings may be in a pendant or fused form with respect to each other. In addition, the term "heteroaryl" of the present invention means a monoheterocyclic or polyheterocyclic aromatic moiety having 5 to 60 nuclear atoms, and at least one carbon in the ring, preferably 1 to 3 carbons is N, O Substituted by a hetero atom, such as S or Se. Here, 'heteroaryl' may be a pendant or fused form of two or more rings to each other, and may include a condensed form with an aryl group. In addition, the 'fused ring' of the present invention means a condensed aliphatic ring, a condensed aromatic ring, a condensed heteroaliphatic ring, a condensed heteroaromatic ring, or a combination thereof.

Meanwhile, the compound represented by Chemical Formula 1 may be selected from the group consisting of compounds represented by the following Chemical Formulas 3 to 6.

(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

In Chemical Formulas 3 to 6,

Ar ₁ to Ar ₄ and R ₁ to R ₄ are the same as defined above.

In addition, the present invention, in the organic electroluminescent device comprising an anode, a cathode, and at least one organic layer interposed between the anode and the cathode, at least one of the organic layer is a compound represented by the formula (1) It provides an organic electroluminescent device comprising an organic material layer comprising.

When the compound represented by Chemical Formula 1 of the present invention is used as a light emitting material of an organic light emitting device, the efficiency (luminescence efficiency and power efficiency), lifetime, luminance, driving voltage, etc. of the organic light emitting device are improved compared to the conventional light emitting material. You can. Therefore, the present invention can improve the performance and lifetime of the full color organic EL panel.

Hereinafter, the present invention will be described in detail.

1, a novel compound

The novel compound according to the present invention forms a basic skeleton by binding an indole group to the sock end of tetrahydropyrene or tetrahydrophenanthrene, and is represented by Formula 1 as a compound in which various substituents are bonded. Such, the compound represented by Formula 1 of the present invention is a variety of substituents (R ₁ in Formula ₁ To R ₄ and Ar ₁ to Ar ₄ are combined to regulate the energy level, thereby having a higher molecular weight than conventional organic light emitting device materials (eg, CBP (4,4-dicarbazolybiphenyl)), and having a wide energy bandgap. It is characteristic to show.

In addition, the compound represented by Formula 1 of the present invention having various substituents introduced therein has a significantly increased molecular weight, and thus has an improved glass transition temperature and thus a higher thermal stability than conventional materials.

Therefore, when the compound represented by Formula 1 of the present invention is used as a material for an organic electroluminescent device, not only the phosphorescence characteristics of the device, but also the electron and / or hole transporting ability, luminous efficiency, driving voltage, . In this case, the compound represented by Formula 1 of the present invention may be used as a material of the organic material layer of the organic electroluminescent device, preferably a light emitting layer, a hole transporting layer or an electron transporting layer, more preferably a host material of the light emitting layer.

The compound represented by Chemical Formula 1 of the present invention may be embodied by any one of the following Chemical Formulas 3 to 6, but is not limited thereto.

(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

In Formulas 3 to 6, Ar ₁ to Ar ₄ and R ₁ to R ₄ are the same as those described for Formula 1 above.

Here, Ar ₁ to Ar ₄ of the compounds represented by Chemical Formulas 3 to 6 are hydrogen, an alkyl group of C ₁ to C ₄₀ , C ₆ to C ₆₀ in consideration of the lifespan, luminous efficiency, driving voltage, etc. of the organic EL device. It is preferably selected from the group consisting of an aryl group and a heteroaryl group of C ₅ ~ C ₆₀ , hydrogen, methyl, phenyl, pyridine, pyrimidine, 1,3,5- Triazine (1,3,5-triazine), naphthalene, quinoline, 1,10-phenanthroline, acenaphthylene, biphenyl, flu More preferably, it is selected from the group consisting of fluorine and 9H-carbazole.

In addition, R ₁ to R ₄ of the compounds represented by Formulas 3 to 6 are preferably hydrogen or methyl.

Specific examples of the compound represented by Formula 1 of the present invention include, but are not limited to, the following compounds (C1-C760).

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 an anode, a cathode, and one or more organic material layers interposed between the anode and the cathode, wherein at least one of the one or more organic material layers is represented by Formula 1 above. Compounds represented by, preferably, characterized in that the organic material layer containing a compound represented by the formula (3 to 6). In this case, the compounds represented by Chemical Formulas 3 to 6 may be included alone or in plurality.

The organic material layer including the compound represented by Formula 1 of the present invention may be any one or more of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer. Specifically, the organic material layer is preferably a light emitting layer.

The light emitting layer of the organic electroluminescent device according to the present invention may contain a host material (preferably, a phosphorescent host material), wherein the compound represented by the above formula (1) can be used as a host material. When the light emitting layer contains the compound represented by the above formula (1), the hole transporting ability is increased to increase the bonding force between the hole and the electron in the light emitting layer. Therefore, the organic layer having excellent efficiency (luminous efficiency and power efficiency), lifetime, An electroluminescent element can be provided.

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. 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] TPCA -1 and TPCB Synthesis of -1

<Step 1> 2,7- bis (4,4,5,5- tetramethyl -1,3,2- dioxaborolan -2- yl Synthesis of 4,5,9,10-tetrahydropyrene

23.3 g (0.064 mol) of 2,7-dibromo-4,5,9,10-tetrahydropyrene and 4,4,4 ', 4', 5,5,5 ', 5'-octamethyl-2,2 under nitrogen stream '-bi (1,3,2-dioxaborolane) 48.58g (0.191 mol), Pd (dppf) Cl ₂ 5.2g (5 mol%), KOAc 37.55g (0.383 mol), DMF 900ml was added and stirred for 12h at 130 ℃ After completion of the reaction, the mixture was extracted with ethyl acetate and water was removed with MgSO ₄ . The reaction product from which the solvent was removed was subjected to column chromatography using 2,7-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -4,5,9,10 as a target compound. 11.73 g (yield: 40%) of -tetrahydropyrene were obtained.

¹ H-NMR: δ 1.24 (s, 24H), 3.14 (m, 8H), 7.27 (m, 4H)

<Step 2> 2,7- bis (2- nitrophenyl ) -4,5,9,10- tetrahydropyrene Synthesis of

8 g (39.6 mmol) of 1-bromo-2-nitrobenzene, 9.07 g (19.8 mmol) of 2,7-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2- under nitrogen stream yl) -4,5,9,10-tetrahydropyrene, 4.75 g (118.8 mmol) of NaOH and 200 ml / 100 ml of THF / H ₂ O were added and stirred. 1.15 g (5 mol%) of Pd (PPh ₃ ) ₄ was added at 40 ° C, and the mixture was stirred at 80 ° C for 12 hours. After completion of the reaction, the reaction mixture was extracted with methylene chloride, and the mixture was filtered with MgSO ₄ . After removing the solvent of the filtered organic layer, 6.13g (yield: 69%) of the target compound, 2,7-bis (2-nitrophenyl) -4,5,9,10-tetrahydropyrene, was obtained by using column chromatography.

¹ H-NMR: δ 3.16 (m, 8H), 7.67 (m, 4H), 7.91 (m. 8H)

<Step 3> TPCA -1 and TPCB Synthesis of -1

Under nitrogen stream, add 4.28 g (9.55 mmol) of 2,7-bis (2-nitrophenyl) -4,5,9,10-tetrahydropyrene, 12.52 g (47.72 mmol) of triphenylphosphine, and 50 ml of 1,2-dichlorobenzene, and then stir for 12 hours. It was. After completion of the reaction, 1,2-dichlorobenzene was removed and extracted with dichloromethane. Water was removed from the extracted organic layer with MgSO ₄ , and TPCA-1 1.58 g (yield: 43%) and TPCB-1 1.50 g (yield: 41%) were obtained by using column chromatography.

¹ H-NMR for TPCA-1: δ 3.10 (m, 8H), 7.48 (m, 2H), 7.62 (m, 2H), 7.67 (m, 2H), 7.91 (m. 4H), 10.42 (s, 2H)

¹ H-NMR for TPCB-1: δ 3.11 (m, 8H), 7.45 (m, 2H), 7.58 (m, 4H), 7.98 (m. 4H), 10.40 (s, 2H)

[ Preparation Example  2] TPCA -2 and TPCB Synthesis of -2

<Step 1> 2,7- bis (5- bromo -2- nitrophenyl ) -4,5,9,10- tetrahydropyrene Synthesis of

Except for using 2,4-dibromo-1-nitrobenzene instead of 1-bromo-2-nitrobenzene was carried out the same procedure as in <Step 2> of Preparation Example 1 to 2,7-bis (5-bromo-2- nitrophenyl) -4,5,9,10-tetrahydropyrene was obtained.

¹ H-NMR: δ 3.16 (m, 8H), 7.67 (m, 6H), 7.91 (m. 2H), 8.12 (m. 2H)

<Step 2> TPCA -2 and TPCB Synthesis of -2

2,7-bis (5-bromo-2-nitrophenyl) -4,5,9,10- of <Step 1> instead of 2,7-bis (2-nitrophenyl) -4,5,9,10-tetrahydropyrene TPCA-2 and TPCB-2 were obtained by the same procedure as <Step 3> of Preparation Example 1, except that tetrahydropyrene was used.

¹ H-NMR for TPCA-2: δ 3.05 (m, 8H), 7.51 (m, 4H), 7.90 (m. 4H), 10.22 (s, 2H)

¹ H-NMR for TPCB-2: δ 3.02 (m, 8H), 7.50 (m, 4H), 7.95 (m. 4H), 10.20 (s, 2H)

[ Preparation Example  3] DPCA -1 and DPCB Synthesis of -1

<Step 1> 2,7- bis (4,4,5,5- tetramethyl -1,3,2- dioxaborolan -2- yl Synthesis of 9,10-dihydrophenanthrene

Except for using 2,7-dibromo-9,10-dihydrophenanthrene instead of 2,7-dibromo-4,5,9,10-tetrahydropyrene, the same procedure as in <Step 1> of Preparation Example 1 was performed. 7-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -9,10-dihydrophenanthrene was obtained.

¹ H-NMR: δ 1.23 (s, 24H), 3.13 (m, 4H), 7.37 (m, 2H), 7.73 (m, 4H)

<Step 2> 2,7- bis (2- nitrophenyl ) -9,10- dihydrophenanthrene Synthesis of

2,7-bis obtained in <Step 1> instead of 2,7-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -4,5,9,10-tetrahydropyrene Perform the same procedure as in <Step 2> of Preparation Example 1, except using bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -9,10-dihydrophenanthrene 2,7-bis (2-nitrophenyl) -9,10-dihydrophenanthrene was obtained.

¹ H-NMR: δ 3.16 (m, 4H), 7.05 (d, 2H), 7.67 (t, 2H), 7.91 (m, 10H)

<Step 3> DPCA -1 and DPCB Synthesis of -1

2,7-2,7-bis (2-nitrophenyl) -9,10-dihydrophenanthrene in <Step 2> instead of 2,7-bis (2-nitrophenyl) -4,5,9,10-tetrahydropyrene Except for this, the same procedure as in <Step 3> of Preparation Example 1 was performed to obtain DPCA-1 and DPCB-1.

¹ H-NMR for DPCA-1: δ 3.00 (m, 4H), 7.30 (t, 2H), 7.51 (m, 6H), 8.09 (m, 4H), 10.20 (s, 2H)

¹ H-NMR for DPCB-1: δ 3.04 (m, 4H), 7.34 (t, 2H), 7.57 (m, 6H), 8.06 (m, 4H), 10.23 (s, 2H)

[ Preparation Example  4] DPCA -2 and DPCB Synthesis of -2

<Step 1> 2,7- bis (5- bromo -2- nitrophenyl ) -9,10- dihydrophenanthrene Synthesis of

Except for using 2,4-dibromo-1-nitrobenzene instead of 1-bromo-2-nitrobenzene was carried out the same procedure as in <Step 2> of Preparation Example 3 to 2,7-bis (5-bromo-2- nitrophenyl) -9,10-dihydrophenanthrene was obtained.

¹ H-NMR: δ 3.06 (m, 4H), 7.07 (d, 2H), 7.81 (m, 8H), 8.10 (d, 2H)

<Step 2> DPCA -2 and DPCB Synthesis of -2

Using 2,7-bis (5-bromo-2-nitrophenyl) -9,10-dihydrophenanthrene in <Step 1> instead of 2,7-bis (2-nitrophenyl) -4,5,9,10-tetrahydropyrene Except for the same procedure as in <Step 3> of Preparation Example 1 to obtain DPCA-2 and DPCB-2.

¹ H-NMR for DPCA-2: δ 3.05 (m, 4H), 7.51 (m, 6H), 8.09 (m, 4H), 10.32 (s, 2H)

¹ H-NMR for DPCB-2: δ 3.02 (m, 4H), 7.50 (m, 6H), 8.05 (m, 4H), 10.30 (s, 2H)

[ Preparation Example  5] mDPCB Synthesis of -1

<Step 1> 2,2 '-(9,10- dimethyl -9,10- dihydrophenanthrene Synthesis of -2,7-diyl) bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolane)

Same as <Step 1> of Preparation Example 1, except that 2,7-dibromo-9,10-dimethyl-9,10-dihydrophenanthrene was used instead of 2,7-dibromo-4,5,9,10-tetrahydropyrene The procedure was followed to obtain 2,2 '-(9,10-dimethyl-9,10-dihydrophenanthrene-2,7-diyl) bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolane) .

¹ H-NMR: δ 1.25 (s, 24H), 1.28 (s, 6H), 3.13 (m, 2H), 7.35 (m, 2H), 7.72 (m, 4H)

<Step 2> 9,10- dimethyl -2,7- bis (2- nitrophenyl ) -9,10- dihydrophenanthrene Synthesis of

2,2 'obtained in <Step 1> instead of 2,7-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -4,5,9,10-tetrahydropyrene Preparation Example 1 except that-(9,10-dimethyl-9,10-dihydrophenanthrene-2,7-diyl) bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolane) was used 9,10-dimethyl-2,7-bis (2-nitrophenyl) -9,10-dihydrophenanthrene was obtained by the same process as in <Step 2>.

¹ H-NMR: δ 1.25 (s, 6H), 3.32 (m, 2H), 7.01 (m, 2H), 7.72 (m, 4H), 8.02 (m, 8H)

<Step 3> mDPCB Synthesis of -1

9,10-dimethyl-2,7-bis (2-nitrophenyl) -9,10-dihydrophenanthrene in <Step 2> instead of 2,7-bis (2-nitrophenyl) -4,5,9,10-tetrahydropyrene Except for using the same procedure as in <Step 3> of Preparation Example 1 to obtain mDPCB-1.

¹ H-NMR: δ 1.24 (s, 6H), 3.36 (m, 2H), 7.31 (m, 2H), 7.72 (m, 6H), 8.12 (m, 4H), 10.33 (s, 2H)

[ Synthetic example  One] SPC Synthesis of -1

TPCA-1 (3.4 g, 8.86 mmol), 1-bromobenzene (4.17 g, 26.56 mmol), Cu powder (0.11 g, 1.77 mmol), K ₂ CO ₃ (2.44 g), which is a compound prepared in Preparation Example 1, under nitrogen stream. , 17.71 mmol), Na ₂ SO ₄ (2.52 g, 17.71 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 was purified by column chromatography to give the title compound SPC-1 (3.28g, 69% yield).

GC-Mass (Theoretical value: 536.66 g / mol, Measured value: 536 g / mol)

[ Synthetic example  2] SPC Synthesis of -2

Except for using 2-bromopyridine instead of 1-bromobenzene was carried out the same procedure as in Synthesis Example 1 to obtain the target compound SPC-2 (3.09 g, yield 65%).

GC-Mass (Theoretical value: 538.64 g / mol, Measured value: 538 g / mol)

[ Synthetic example  3] SPC Synthesis of -3

Except for using 3-bromopyridine instead of 1-bromobenzene was carried out the same procedure as in Synthesis Example 1 to obtain the target compound SPC-3 (2.85 g, yield 60%).

GC-Mass (Theoretical value: 538.64 g / mol, Measured value: 538 g / mol)

[ Synthetic example  4] SPC Synthesis of -4

Except for using 4-bromopyridine instead of 1-bromobenzene was carried out the same procedure as in Synthesis Example 1 to obtain the target compound SPC-4 (3.10 g, yield 65%).

GC-Mass (Theoretical value: 538.64 g / mol, Measured value: 538 g / mol)

[ Synthetic example  5] SPC Synthesis of -5

Except for using 2-bromo-4,6-diphenylpyridine instead of 1-bromobenzene was carried out the same procedure as in Synthesis Example 1 to obtain the target compound SPC-5 (4.67 g, 55% yield).

GC-Mass (Theoretical value: 843.02 g / mol, Measured value: 842 g / mol)

[ Synthetic example  6] SPC Synthesis of -6

Except for using 2-bromo-4,6-diphenylpyrimidine instead of 1-bromobenzene was carried out the same procedure as in Synthesis Example 1 to obtain the target compound SPC-6 (4.60 g, yield 54%).

GC-Mass (Theoretical value: 845.00 g / mol, Measured value: 844 g / mol)

[ Synthetic example  7] SPC Synthesis of -7

Except for using 2-bromo-4,6-diphenyl-1,3,5-triazine instead of 1-bromobenzene, the same procedure as in Synthesis Example 1 was carried out to obtain the target compound SPC-6 (4.80 g, yield 57% )

GC-Mass (Theoretical value: 846.98 g / mol, Measured value: 846 g / mol)

[ Synthetic example  8] SPC Synthesis of -8

Except for using another compound TPCB-1 prepared in Preparation Example 1 instead of TPCA-1 to the same procedure as in Synthesis Example 1 to obtain the target compound SPC-8 (3.27 g, yield 69%).

GC-Mass (Theoretical value: 536.66 g / mol, Measured value: 536 g / mol)

[ Synthetic example  9] SPC Synthesis of -9

Except for using 2-bromopyridine instead of 1-bromobenzene was carried out the same procedure as in Synthesis Example 8 to obtain the target compound SPC-9 (2.86 g, yield 60%).

GC-Mass (Theoretical value: 538.64 g / mol, Measured value: 538 g / mol)

[ Synthetic example  10] SPC Synthesis of -10

Except for using 3-bromopyridine instead of 1-bromobenzene was carried out the same procedure as in Synthesis Example 8 to obtain the target compound SPC-10 (2.83 g, 59% yield).

GC-Mass (Theoretical value: 538.64 g / mol, Measured value: 538 g / mol)

[ Synthetic example  11] SPC Synthesis of -11

Except for using 4-bromopyridine instead of 1-bromobenzene was carried out the same procedure as in Synthesis Example 8 to obtain the target compound SPC-11 (2.80 g, yield 58%).

GC-Mass (Theoretical value: 538.64 g / mol, Measured value: 538 g / mol)

[ Synthetic example  12] SPC Synthesis of -12

Except for using DPCA-1 prepared in Preparation Example 3 instead of TPCA-1 to obtain the target compound SPC-12 (3.77 g, yield 71%) was carried out in the same manner as in Synthesis Example 1.

GC-Mass (calculated: 510.63 g / mol, measured: 510 g / mol)

[ Synthetic example  13] SPC Synthesis of -13

Except for using 2-bromopyridine instead of 1-bromobenzene was carried out in the same manner as in Synthesis Example 12 to obtain the target compound SPC-13 (3.58 g, yield 68%).

GC-Mass (calculated: 512.60 g / mol, measured: 512 g / mol)

[ Synthetic example  14] SPC Synthesis of -14

Except for using 2-bromo-4,6-diphenylpyridine instead of 1-bromobenzene was carried out in the same manner as in Synthesis Example 12 to obtain the target compound SPC-14 (4.96 g, yield 70%).

GC-Mass (Theoretical value: 816.99 g / mol, Measured value: 816 g / mol)

[ Synthetic example  15] SPC Synthesis of -15

Except for using 2-bromo-4,6-diphenylpyrimidine instead of 1-bromobenzene was carried out in the same manner as in Synthesis Example 12 to obtain the target compound SPC-15 (4.90 g, 69% yield).

GC-Mass (theory: 818.96 g / mol, measurement: 818 g / mol)

[ Synthetic example  16] SPC Synthesis of -16

Except for using 2-bromo-4,6-diphenyl-1,3,5-triazine instead of 1-bromobenzene, the same procedure as in Synthesis Example 1 was carried out to obtain the target compound SPC-16 (4.05 g, yield 57% )

GC-Mass (calculated: 820.94 g / mol, measured: 820 g / mol)

[ Synthetic example  17] SPC Synthesis of -17

Except for using another compound DPCB-1 prepared in Preparation Example 3 instead of TPCA-1 to the same procedure as in Synthesis Example 1 to obtain the target compound SPC-17 (3.00 g, yield 68%).

GC-Mass (calculated: 510.63 g / mol, measured: 510 g / mol)

[ Synthetic example  18] SPC Synthesis of -18

Except for using 2-bromopyridine instead of 1-bromobenzene was carried out the same procedure as in Synthesis Example 17 to obtain the target compound SPC-18 (2.66 g, 61% yield).

GC-Mass (calculated: 512.60 g / mol, measured: 512 g / mol)

[ Synthetic example  19] SPC -19 Synthesis

Except for using 3-bromopyridine instead of 1-bromobenzene was carried out the same procedure as in Synthesis Example 17 to obtain the target compound SPC-19 (2.64 g, yield 60%).

GC-Mass (calculated: 512.60 g / mol, measured: 512 g / mol)

[ Synthetic example  20] SPC Synthesis of -20

Except for using 4-bromopyridine instead of 1-bromobenzene was carried out the same procedure as in Synthesis Example 17 to obtain the target compound SPC-20 (2.65 g, yield 60%).

GC-Mass (calculated: 512.60 g / mol, measured: 512 g / mol)

[ Synthetic example  21] SPC Synthesis of -21

Except for using another compound mDPCB-1 prepared in Preparation Example 5 instead of TPCA-1 to the same procedure as in Synthesis Example 1 to obtain the target compound SPC-21 (3.26 g, yield 70%).

GC-Mass (Theoretical value: 538.68 g / mol, Measured value: 538 g / mol)

[ Synthetic example  22] SPC Synthesis of -22

Except for using 2-bromopyridine instead of 1-bromobenzene was carried out the same procedure as in Synthesis Example 21 to obtain the target compound SPC-22 (2.85 g, 61% yield).

GC-Mass (Theoretical value: 540.66 g / mol, Measured value: 540 g / mol)

[ Synthetic example  23] SPC Synthesis of -23

TPCA-2 (3.75 g, 6.92 mmol), iodobenzene (4.24 g, 20.76 mmol), Cu powder (0.09 g, 1.38 mmol), K ₂ CO ₃ (1.91 g, 13.84), a compound prepared in Preparation Example 2 under a nitrogen stream. mmol), Na ₂ SO ₄ (1.97 g, 13.84 mmol) and nitrobenzene (80 ml) were mixed and stirred at 190 ° C. for 12 h. 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 was purified by column chromatography to give the intermediate compound TPCA-2-Ph (2.74 g, yield 57%).

Under nitrogen stream, the obtained intermediate compound TPCA-2-Ph (2.74 g, 3.94 mmol), pyridin-2-ylboronic acid (1.16 g, 9.47 mmol), NaOH (0.95 g, 23.67 mmol) and THF / H ₂ O (100 ml / 50 ml) was mixed and stirred, and 0.46 g (5 mol%) of Pd (PPh ₃ ) ₄ was added at 40 ° C. and stirred at 80 ° C. for 12 hours. After the reaction was completed, the reaction mixture was extracted with methylene chloride, added with MgSO ₄ and filtered. The solvent of the obtained organic layer was removed, and then purified by column chromatography to obtain SPC-23 (2.27 g, yield 83%) as a target compound.

GC-Mass (Theoretical value: 690.83 g / mol, Measured value: 690 g / mol)

[ Synthetic example  24] SPC Synthesis of -24

The same procedure as in Synthesis Example 23 was performed, but SPC-24 (2.53 g, yield 76%) was obtained using 2,3'-bipyridin-6-ylboronic acid instead of pyridin-2-ylboronic acid.

GC-Mass (Theoretical value: 845.00 g / mol, Measured value: 844 g / mol)

[ Synthetic example  25] SPC Synthesis of -25

The same procedure as in Synthesis Example 23 was performed, but phenylboronic acid was used instead of pyridin-2-ylboronic acid to obtain the target compound SPC-25 (2.37 g, 71% yield).

GC-Mass (Theoretical value: 688.86 g / mol, Measured value: 688 g / mol)

[ Synthetic example  26] SPC Synthesis of -26

Performing the same process as in Synthesis Example 23, using TPCB-2 prepared in Preparation Example 2 instead of TPCA-2 to obtain the intermediate compound TPCB-2-Ph, the same process was performed on the obtained TPCB-2-Ph SPC-26 (2.56 g, yield 77%) was obtained.

GC-Mass (Theoretical value: 690.83 g / mol, Measured value: 690 g / mol)

[ Synthetic example  27] SPC -27

The same procedure as in Synthesis Example 25 was carried out, using TPCB-2 prepared in Preparation Example 2 instead of TPCA-2 to obtain TPCB-2-Ph as an intermediate compound, and the same procedure was performed on the obtained TPCB-2-Ph as desired. SPC-27 (2.33 g, yield 70%) was obtained.

GC-Mass (Theoretical value: 688.86 g / mol, Measured value: 688 g / mol)

[ Synthetic example  28] SPC -28 Synthesis

The same procedure as in Synthesis Example 25 was performed, but SPC-28 (2.50 g, yield 75%) was obtained using 2,3'-bipyridin-6-ylboronic acid instead of pyridin-2-ylboronic acid.

GC-Mass (Theoretical value: 845.00 g / mol, Measured value: 844 g / mol)

[ Synthetic example  29] SPC Synthesis of -29

Perform the same procedure as in Synthesis Example 23, using DPCB-2 prepared in Preparation Example 4 instead of TPCA-2, and using 2-bromo-4,6-diphenyl-1,3,5-triazine instead of iodobenzene Compound TPCB-2-Taz was obtained, and the same procedure was performed on the obtained TPCB-2-Taz to obtain SPC-29 (2.25 g, yield 66%) as a target compound.

GC-Mass (Theoretical value: 975.11 g / mol, Measured value: 974 g / mol)

[ Synthetic example  30] SPC Synthesis of -30

The same procedure as in Synthesis Example 29 was performed, but phenylboronic acid was used instead of pyridin-2-ylboronic acid to obtain the target compound SPC-30 (2.20 g, 64% yield).

GC-Mass (Theoretical value: 973.13 g / mol, Measured value: 972 g / mol)

[ Example  1 ~ 30] Green organic Field  Fabrication of light emitting device

Compounds SPC-1 to SPC-30 synthesized in Synthesis Example 1-30 were subjected to high purity sublimation purification by a method known in the art, and then a green organic electroluminescent device was manufactured according to the following procedure.

First, a glass substrate coated with ITO (Indium tin oxide) having a thickness of 1500 A was washed with distilled water ultrasonic waves. After the distilled water was washed, the substrate was ultrasonically washed with a solvent such as isopropyl alcohol, acetone, or methanol, dried and transferred to a UV OZONE cleaner (Power Sonic 405, Hoshin Tech), the substrate was cleaned using UV for 5 minutes, The substrate was transferred.

M-MTDATA (60 nm) / TCTA (80 nm) / Compound SPC-1 to SPC-30 were applied on the prepared ITO transparent electrode, respectively + 10% Ir (ppy) ₃ (300 nm) / BCP (10 nm) / Alq ₃ (30 nm) / LiF (1 nm) / Al (200 nm) were stacked to fabricate an organic EL device.

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

[ Comparative Example  One]

An organic electroluminescent device was manufactured in the same manner as in Example 1 except for using the following CBP instead of the compound SPC-1 as a light emitting host material when forming the light emitting layer.

[ Evaluation example ]

For each organic electroluminescent device produced in Example 1-30 and Comparative Example 1, the driving voltage, current efficiency and emission peak at a current density of 10 mA / cm 2 were measured, and the results are shown in Table 1 below.

device Host The driving voltage (V) Emission peak (nm) Current efficiency (cd / A) Example 1 SPC-1 6.78 515 42.4 Example 2 SPC-2 6.81 518 41.1 Example 3 SPC-3 6.83 517 40.8 Example 4 SPC-4 6.81 515 41.0 Example 5 SPC-5 6.81 518 41.3 Example 6 SPC-6 6.77 516 39.4 Example 7 SPC-7 6.78 518 41.1 Example 8 SPC-8 6.80 515 41.1 Example 9 SPC-9 6.79 518 40.8 Example 10 SPC-10 6.85 516 41.0 Example 11 SPC-11 6.77 515 42.0 Example 12 SPC-12 6.79 518 41.3 Example 13 SPC-13 6.82 517 41.1 Example 14 SPC-14 6.83 518 40.8 Example 15 SPC-15 6.81 516 41.0 Example 16 SPC-16 6.79 516 41.3 Example 17 SPC-17 6.87 517 39.4 Example 18 SPC-18 6.86 515 41.1 Example 19 SPC-19 6.89 518 40.8 Example 20 SPC-20 6.85 517 41.3 Example 21 SPC-21 6.82 518 39.4 Example 22 SPC-22 6.83 518 41.1 Example 23 SPC-23 6.84 516 39.2 Example 24 SPC-24 6.84 516 39.1 Example 25 SPC-25 6.85 517 39.2 Example 26 SPC-26 6.88 515 39.3 Example 27 SPC-27 6.87 517 38.9 Example 28 SPC-28 6.67 515 39.1 Example 29 SPC-29 6.80 517 38.9 Example 30 SPC-30 6.79 516 39.2 Comparative Example 1 CBP 6.93 516 38.2

As shown in Table 1 above, when the compounds (SPC-1 to SPC-30) according to the present invention were used as the light emitting layer of the green organic electroluminescent device (Examples 1 to 30), the green organic electroluminescent device using the conventional CBP (Comparative Example 1) and the light emission wavelength were similar, it was confirmed that the better performance in terms of efficiency and driving voltage.

[ Example  31-40] Blue Organic Field  Fabrication of light emitting device

Compounds SPC-21 to SPC-30 synthesized in Synthesis Example 21-30 were subjected to high purity sublimation purification by a method known in the art, and then a blue organic EL device was manufactured according to the following procedure.

First, a glass substrate coated with ITO (Indium tin oxide) having a thickness of 1500 A was washed with distilled water ultrasonic waves. After washing the distilled water, ultrasonic cleaning with a solvent such as isopropyl alcohol, acetone, methanol, etc., dried and transferred to a UV OZONE cleaner (Power sonic 405), the substrate is cleaned using UV for 5 minutes and the substrate is vacuum-deposited. Transferred.

CuPc (10 nm) / TPAC (30 nm) / Compound SPC-21 ~ SPC-30 were applied on the prepared ITO transparent electrode, respectively + 7% Flrpic (30 nm) / Alq ₃ (30 nm) / LiF (0.2 nm) / Al (150 nm) were stacked in order to fabricate an organic EL device.

The structures of CuPc, TPAC, and Flrpic used are as follows.

[ Comparative Example  2]

A blue organic electroluminescent device was manufactured in the same manner as in Example 31, except for using the CBP instead of the compound SPC-21 as a light emitting host material when forming the light emitting layer.

[ Evaluation example ]

For each of the blue organic EL devices produced in Examples 31-40 and Comparative Example 2, the driving voltage, current efficiency, and emission peak at a current density of 10 mA / cm 2 were measured, and the results are shown in Table 2 below.

device Host The driving voltage (V) Emission peak (nm) Current efficiency (cd / A) Example 31 SPC-21 7.55 471 5.99 Example 32 SPC-22 7.67 472 5.85 Example 33 SPC-23 7.22 472 6.34 Example 34 SPC-24 7.12 473 6.90 Example 35 SPC-25 7.00 474 6.34 Example 36 SPC-26 7.29 475 6.55 Example 37 SPC-27 7.30 471 6.94 Example 38 SPC-28 7.24 472 6.25 Example 39 SPC-29 7.15 473 6.47 Example 40 SPC-30 7.23 473 6.94 Comparative Example 2 CBP 7.80 474 5.80

As shown in Table 2, when the compound (SPC-21 ~ SPC-30) according to the present invention is used as the light emitting layer of the blue organic electroluminescent device (Examples 31 to 40) Blue organic electroluminescent device using a conventional CBP From Comparative Example 2, it was confirmed that the device exhibited better performance in terms of current efficiency and driving voltage.

Claims (8)

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

In Formula 1,
A,

,

,

Selected from the group consisting of R _a and R _b or R _b and R _c form a fused ring represented by the following formula (2), and when R _a and R _b form a condensed ring, R _c is hydrogen When R _b and R _c form a condensed ring, R _a is hydrogen,
(2)

Ar ₁ to Ar ₄ each independently represent a C ₁ to C ₄₀ alkyl group, C ₃ to C ₄₀ cycloalkyl group, C ₃ to C ₄₀ heterocycloalkyl group, C ₆ to C ₆₀ aryl group, C ₅ to C ₆₀ heteroaryl group, C ₁ ~ C ₄₀ Alkyloxy group, C ₆ ~ C ₆₀ An aryloxy group and C ₆ ~ C ₆₀ An arylamine group,
R ₁ to R ₄ are each independently hydrogen, halogen, C ₁ -C ₄₀ alkyl group, C ₃ -C ₄₀ cycloalkyl group, C ₃ -C ₄₀ heterocycloalkyl group, C ₆ -C ₆₀ aryl group , C ₅ ~ C ₆₀ Heteroaryl group, C ₁ ~ C ₄₀ Alkyloxy group, C ₆ ~ C ₆₀ An aryloxy group and C ₆ ~ C ₆₀ An arylamine group,
n and m are integers of 0-4. The method of claim 1,
Compound represented by Formula 1 is selected from the group consisting of compounds represented by the following formulas 3 to 6:
(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

In Chemical Formulas 3 to 6,
Ar ₁ to Ar ₄ and R ₁ to R ₄ are the same as defined in claim 1. 3. The method of claim 2,
Ar ₁ to Ar ₄ is hydrogen, C ₁ ~ C ₄₀ Alkyl group, C ₆ ~ C _{60 It} is selected from the group consisting of aryl group and C ₅ ~ C ₆₀ heteroaryl group. 3. The method of claim 2,
Ar ₁ to Ar ₄ is hydrogen, methyl (phenyl), phenyl (phenyl), pyridine, pyrimidine, 1,3,5-triazine (1,3,5- triazine), naphthalene ( naphthalene, quinoline, 1,10-phenanthroline, 1,10-phenanthroline, acenaphthylene, biphenyl, fluorine and 9H-carbazole Compounds, characterized in that selected from the group consisting of. 3. The method of claim 2,
The R ₁ To R ₄ is hydrogen or methyl. 1. An organic electroluminescent device comprising an anode, a cathode, and at least one organic material layer interposed between the anode and the cathode,
At least one of the organic material layer is an organic electroluminescent device, characterized in that the organic material layer comprising a compound according to any one of claims 1 to 5. The method according to claim 6,
Wherein the organic compound layer containing the compound is a light emitting layer. The method according to claim 6,
The organic material layer containing the compound is an organic electroluminescent device, characterized in that the phosphorescent layer.