WO2013100507A1 - Novel compound and organic electroluminescence device including same - Google Patents

Abstract

The present invention relates to a novel compound and an organic electroluminescence device using the same, and particularly, to a compound in which an indole radical is bonded to both ends of tetrahydropyrene or tetrahydrophenanthrene, and an organic electroluminescence device to which the compound is applied. The present invention can provide an organic electroluminescence device having improved efficiency, lifetime, stability, and the like.

Description

New compound and organic electroluminescent device comprising same

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

In the organic electroluminescent device, when a voltage is applied between two electrodes, holes are injected from the anode and electrons are injected into the organic material layer from the cathode. When the injected holes and the electrons meet to form an exciton, the formed excitons fall to the ground state. The light will shine. The material used as the organic material layer may be classified into a light emitting material, a hole injection material, a hole transport material, an electron transport material, an electron injection material and the like according to a function.

The light emitting material may be classified into blue, green, and red light emitting materials and yellow and orange light emitting materials for realizing natural colors according to light emitting colors. In addition, in order to increase luminous efficiency through increasing color purity and energy transfer, a host / dopant system may be used as a light emitting material.

The dopant material may 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 phosphorescent dopants is theoretically able to improve luminous efficiency up to four times as compared to fluorescent dopants, so that not only phosphorescent dopants but also phosphorescent hosts are being studied.

Hole transport layer to date. NPB, BCP, Alq ₃ and the like are used as materials for the hole blocking layer and the electron transport layer, and anthracene derivatives are used as the light emitting material. In addition, metal complex compounds including Ir such as Firpic, Ir (ppy) ₃ , and (acac) Ir (btp) ₂ among the light emitting materials are phosphorescent dopant materials of blue, green, and red, and CBP is used as a phosphorescent host material. have. 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, the conventional luminescent materials have good luminescence properties, but the glass transition temperature is low and the thermal stability is not very good. Thus, the luminescent materials are not satisfactory in terms of the lifespan of the organic EL device. Therefore, there is a demand for development of a light emitting material having excellent performance.

In order to solve the above problems, an object of the present invention is to provide a novel compound and an organic electroluminescent device using the compound which can improve the efficiency, lifespan and stability of the organic electroluminescent device.

In order to achieve the above object, the present invention provides a compound represented by the following formula (1).

[Formula 1]

In Chemical Formula 1,

,

및

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

,

And

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

[Formula 2]

Ar ₁ to Ar ₄ are each independently 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 Is selected from the group consisting of -C ₆₀ heteroaryl group, C ₁ -C ₄₀ alkyloxy group, C ₆ -C ₆₀ aryloxy group, and C ₆ -C ₆₀ 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 aryloxy group and C ₆ ~ C ₆₀ arylamine group,

N and m are each an integer of 0 to 4

Here, the alkyl group, the cycloalkyl group, the heterocycloalkyl group, the aryl group, the heteroaryl group, the alkyloxy group, the aryloxy group and the arylamine group of Ar ₁ to Ar ₄ are each independently hydrogen, an alkyl group of C ₁ to C ₄₀ , aryloxy group of 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 of, C ₁ ~ C ₄₀ alkyloxy group, C ₆ ~ C ₄₀ arylamino group, C ₆ ~ C ₄₀ diarylamino group, C ₆ ~ C ₄₀ arylalkyl group, C ₃ ~ C ₄₀ cycloalkyl group, C ₆ ~ C ₄₀ It may be substituted with one or more substituents selected from the group consisting of an arylsilyl group and a C ₃ to C ₄₀ heterocycloalkyl group.

Alkyl of the present invention means a straight chain 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.

Aryl of the present invention means an aromatic moiety having 6 to 60 carbon atoms combined with a single ring or two or more rings, and two or more rings may be in the form of a simple attachment or condensation with each other.

Heteroaryl of the present invention means a monoheterocyclic or polyheterocyclic aromatic moiety having 5 to 60 nuclear atoms, wherein at least one carbon in the ring, preferably 1 to 3 carbons is N, O, S or Se Mean substituted with a hetero atom such as. Here, the heteroaryl may be in a form in which two or more rings are simply attached or condensed with each other, and a condensed form with an aryl group may also be included.

The condensed 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.

On the other hand, the present invention, in the organic electroluminescent device comprising an anode, a cathode and one or more organic material layer interposed between the anode and the cathode, at least one of the organic material layer comprises a compound represented by the formula (1) It provides an organic electroluminescent device characterized in that the organic material layer.

Hereinafter, the present invention will be described in detail.

1. New 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 a compound represented by Formula 1 of the present invention is a conventional organic light emitting device material (for example, by adjusting the energy level by combining a variety of substituents (R ₁ to R ₄ and Ar ₁ to Ar ₄ in Formula 1) It has a higher molecular weight than CBP (4,4-dicarbazolybiphenyl)) and is characterized by a wide energy bandgap.

In addition, the compound represented by the formula (1) of the present invention in which various substituents are introduced has a significant increase in molecular weight, thereby improving the glass transition temperature, thereby having a high thermal stability compared to conventional materials.

Therefore, when the compound represented by Chemical Formula 1 of the present invention is used as a material of an organic electroluminescent device, not only phosphorescence properties of the device, but also electron and / or hole transporting ability, luminous efficiency, driving voltage, and lifetime characteristics may be improved. . 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 the formula (1) of the present invention is preferably selected from the group consisting of the compound represented by the following formula (3 to 6).

 [Formula 3]

[Formula 4]

[Formula 5]

[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 Formulas 3 to 6 are each independently hydrogen, an alkyl group of C ₁ to C ₄₀ , C ₆ 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 of ~ C _{60 and} a heteroaryl group of C ₅ ~ C ₆₀ , hydrogen, methyl, phenyl, pyridine, pyrimidine, 1, 3,5-triazine, naphthalene, quinoline, 1,10-phenanthroline, acenaphthylene, biphenyl more preferably selected from the group consisting of biphenyl), fluorine and 9H-carbazole.

In addition, R ₁ to R ₄ of the compounds represented by Formulas 3 to 6 are each independently 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).

Such a 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 electroluminescent device

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 Formulas 3 to 6 may be included alone or two or more.

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 EL device according to the present invention may contain a host material (preferably a phosphorescent host material), in which case, the compound represented by the formula (1) can be used as the host material. As such, when the light emitting layer contains the compound represented by Chemical Formula 1, the hole transporting ability is increased to increase the bonding force between the holes and the electrons in the light emitting layer, so that the organic light emitting layer has excellent efficiency (emission efficiency and power efficiency), lifetime, luminance and driving voltage. An electroluminescent device can be provided.

The structure of the organic electroluminescent device of the present invention is not particularly limited, but may be formed of a structure in which a substrate, an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and a cathode are sequentially stacked. Here, the electron injection layer may be further stacked on the electron transport layer. In addition, the organic electroluminescent device according to the present invention may have a structure in which an anode, one or more organic material layers, and a cathode are sequentially stacked, as well as a structure in which an insulating layer or an adhesive layer is inserted at an interface between the electrode and the organic material layer.

On the other hand, the material that can be used as the anode included in the organic electroluminescent device of the present invention is not particularly limited, but non-limiting examples include metals such as vanadium, chromium, copper, zinc, gold or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO); Combinations of metals and oxides such as ZnO: Al, SnO ₂ : Sb; Conductive polymers such as polythiophene, poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (PEDT), polypyrrole, polyaniline; And carbon black and the like can be used.

In addition, the material that can be used as the cathode included in the organic electroluminescent device of the present invention is not particularly limited, but non-limiting examples include magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin Metals such as lead or alloys thereof; And multilayer structure materials such as LiF / Al, LiO ₂ / Al, and the like.

In addition, the organic material layer included in the organic electroluminescent device of the present invention is in the art, except that the compound represented by Formula 1 is used in any one of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer It may be made of known materials.

The material usable as the substrate included in the organic electroluminescent device of the present invention is not particularly limited, but non-limiting examples may be used a silicon wafer, quartz, glass plate, metal plate, plastic film and sheet.

Such an organic electroluminescent device of the present invention can be produced by a method known in the art. On the other hand, the light emitting layer included in the organic material layer can be produced by a vacuum deposition method or a solution coating method. Here, examples of the solution coating method include, but are not limited to, spin coating, dip coating, doctor blading, inkjet printing, or thermal transfer.

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

Preparation Example 1 Synthesis of TPCA-1 and TPCB-1

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

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 stirred at 80 ° C. for 12 hours. After completion of the reaction, the mixture was extracted with methylene chloride, MgSO ₄ was added and filtered. 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 Synthesis of TPCA-1 and TPCB-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 the reaction was completed, 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 Synthesis of TPCA-2 and TPCB-2

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

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 Synthesis of TPCA-2 and TPCB-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 Synthesis of DPCA-1 and DPCB-1

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

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 To 2,7-bis (2-nitrophenyl) -9,10-dihydrophenanthrene.

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

Step 3 Synthesis of DPCA-1 and DPCB-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 Synthesis of DPCA-2 and DPCB-2

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

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 Synthesis of DPCA-2 and DPCB-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 Synthesis of mDPCB-1

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

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 Synthesis of mDPCB-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)

Synthesis Example 1 Synthesis of SPC-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, 17.71) prepared in Preparation Example 1 under nitrogen stream. 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 completion of the reaction, 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)

Synthesis Example 2 Synthesis of SPC-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)

Synthesis Example 3 Synthesis of SPC-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)

Synthesis Example 4 Synthesis of SPC-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)

Synthesis Example 5 Synthesis of SPC-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)

Synthesis Example 6 Synthesis of SPC-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)

Synthesis Example 7 Synthesis of SPC-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-7 (4.80 g, yield 57% )

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

Synthesis Example 8 Synthesis of SPC-8

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

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

Synthesis Example 9 Synthesis of SPC-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)

Synthesis Example 10 Synthesis of SPC-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)

Synthesis Example 11 Synthesis of SPC-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)

Synthesis Example 12 Synthesis of SPC-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 (Theoretical value: 510.63 g / mol, Measured value: 510 g / mol)

Synthesis Example 13 Synthesis of SPC-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 (Theoretical value: 512.60 g / mol, Measured value: 512 g / mol)

Synthesis Example 14 Synthesis of SPC-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)

Synthesis Example 15 Synthesis of SPC-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 (Theoretical value: 818.96 g / mol, Measured value: 818 g / mol)

Synthesis Example 16 Synthesis of SPC-16

Except for using 2-bromo-4,6-diphenyl-1,3,5-triazine instead of 1-bromobenzene, the same procedure as in Synthesis Example 12 was carried out to obtain the target compound SPC-16 (4.05 g, yield 57% )

GC-Mass (Theoretical value: 820.94 g / mol, Measured value: 820 g / mol)

Synthesis Example 17 Synthesis of SPC-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 (Theoretical value: 510.63 g / mol, Measured value: 510 g / mol)

Synthesis Example 18 Synthesis of SPC-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 (Theoretical value: 512.60 g / mol, Measured value: 512 g / mol)

Synthesis Example 19 Synthesis of SPC-19

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 (Theoretical value: 512.60 g / mol, Measured value: 512 g / mol)

Synthesis Example 20 Synthesis of SPC-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 (Theoretical value: 512.60 g / mol, Measured value: 512 g / mol)

Synthesis Example 21 Synthesis of SPC-21

Except for using mDPCB-1 prepared in Preparation Example 5 instead of TPCA-1 was carried out in the same manner 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)

Synthesis Example 22 Synthesis of SPC-22

Except for using 2-bromopyridine instead of 1-bromobenzene was carried out in the same manner 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)

Synthesis Example 23 Synthesis of SPC-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 mmol) prepared in Preparation Example 2 under a nitrogen stream. , Na ₂ SO ₄ (1.97 g, 13.84 mmol) and nitrobenzene (80 ml) were mixed and stirred at 190 ° C. for 12 hours. After completion of the reaction, 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 terminated and extracted with methylene chloride, MgSO ₄ was added 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)

Synthesis Example 24 Synthesis of SPC-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)

Synthesis Example 25 Synthesis of SPC-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)

Synthesis Example 26 Synthesis of SPC-26

The same procedure as in Synthesis Example 23 was performed, but SPC-26 (2.56 g, yield 77%) was obtained using TPCB-2 prepared in Preparation Example 2 instead of TPCA-2.

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

Synthesis Example 27 Synthesis of SPC-27

The same procedure as in Synthesis Example 25 was carried out, but SPC-27 (2.33 g, yield 70%) was obtained using TPCB-2 prepared in Preparation Example 2 instead of TPCA-2.

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

Synthesis Example 28 Synthesis of SPC-28

The same procedure as in Synthesis Example 24 was performed, but SPC-28 (2.50 g, yield 75%) was obtained using TPCB-2 prepared in Preparation Example 2 instead of TPCA-2.

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

Synthesis Example 29 Synthesis of SPC-29

Perform the same process 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 SPC-29 (2.25 g, yield 66%) was obtained.

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

Synthesis Example 30 Synthesis of SPC-30

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

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

Examples 1 to 30 Fabrication of Green Organic Electroluminescent Devices

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

First, an ITO (Indium tin oxide) was ultrasonically cleaned with distilled water to a glass substrate coated with a thin film of 1500Å thickness. 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, Hwasin Tech), the substrate is cleaned by UV for 5 minutes and vacuum evaporator The substrate was transferred to.

M-MTDATA (60 nm) / TCTA (80 nm) / Compound SPC-1 to SPC-30 applied on the ITO transparent electrode thus prepared + 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 1

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 1]

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.

Table 1 device Host Drive 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 It was confirmed that (Comparative Example 1) and the light emission wavelength were similar, and showed better performance in terms of efficiency and driving voltage.

Examples 31 to 40 Fabrication of Blue Organic Electroluminescent Devices

The compound synthesized in Synthesis Example 21-30 was 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, an ITO (Indium tin oxide) was ultrasonically cleaned with distilled water to a glass substrate coated with a thin film of 1500Å thickness. 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 respectively applied on the prepared ITO transparent electrode + 7% Flrpic (30 nm) / Alq ₃ (30 nm) / LiF (0.2 nm) / Al (150 nm) were laminated in order to produce 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 that CBP used in Comparative Example 1 was used instead of Compound SPC-21 as a light emitting host material when forming the emission layer.

[Evaluation Example 2]

For each of the blue organic electroluminescent devices fabricated 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.

TABLE 2 device Host Drive 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 a 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.

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 (light emitting 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 lifespan of a full color organic electroluminescent panel.

Claims (8)

Compound represented by the following formula (1): [Formula 1]

In Chemical Formula 1, A is

,

And

Selected from the group consisting of, R _a and R _b or R _b and R _c form a condensed ring represented by the following formula (2), and when R _a and R _b form a condensed ring, R _c is hydrogen and R _{When b} and R _c form a condensed ring, R _a is hydrogen, [Formula 2]

Ar ₁ to Ar ₄ are each independently 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 Is selected from the group consisting of -C ₆₀ heteroaryl group, C ₁ -C ₄₀ alkyloxy group, C ₆ -C ₆₀ aryloxy group, and C ₆ -C ₆₀ 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 aryloxy group and C ₆ ~ C ₆₀ arylamine group, N and m are each an integer of 0 to 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: [Formula 3]

[Formula 4]

[Formula 5]

[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. The method of claim 2, Ar ₁ to Ar ₄ are each independently selected from the group consisting of hydrogen, C ₁ ~ C ₄₀ alkyl group, C ₆ ~ C ₆₀ aryl group and C ₅ ~ C ₆₀ heteroaryl group. The method of claim 2, Ar ₁ to Ar ₄ are each independently hydrogen, methyl, phenyl, pyridine, pyrimidine, 1,3,5-triazine (1,3,5-triazine) ), Naphthalene, quinoline, 1,10-phenanthroline, 1,10-phenanthroline, acenaphthylene, biphenyl, fluorine and 9H-carbazole ( 9H-carbazole). The method of claim 2, R ₁ to R ₄ are each independently hydrogen or methyl. In an 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 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 of claim 6, The organic material layer containing the compound is an organic electroluminescent device, characterized in that the light emitting layer. The method of claim 6, The organic material layer containing the compound is an organic electroluminescent device, characterized in that the phosphorescent light emitting layer.