KR20160040784A - Organic compound and organic electroluminescent device comprising the same - Google Patents

Abstract

The present invention relates to an organic electroluminescent device, with the improved properties such as light emitting efficiency, driving voltage, durability, and the like, by comprising an organic compound with excellent thermal stability, hole transporting ability, electron blocking ability, light emitting ability, and the like in at least one species of an organic layer. The compound is represented by chemical formula 1.

Description

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

The present invention relates to a novel organic compound and an organic electroluminescent device including the same.

In the organic electroluminescent device, when a voltage is applied between two electrodes, holes are injected into the organic layer and holes are injected into the organic layer, respectively. When the injected holes and electrons meet, an exciton is formed. When the exciton falls to the ground state, light is emitted. At this time, in order to increase the efficiency of the organic electroluminescent device, the organic material layer has a multilayer structure including a hole injection layer, a hole transport layer, a hole blocking layer, an electron transport layer, an electron injection layer, and a light emitting layer.

In order to improve the efficiency of the organic electroluminescent device, it is preferable that the organic material layer has a multilayer structure and a thermally / electrically stable material is applied to the organic material layer. This is because the molecules having low thermal stability are recrystallized due to the heat generated in the organic electroluminescent device to form a nonuniform portion and the electric field is concentrated on the nonuniform portions to cause deterioration and destruction of the organic electroluminescent device.

Considering this point, conventionally, a hole injection layer, a hole transport layer, M-MTDATA, 2-TNATA, TPD, NPB, BCP and Alq ₃ were used for the hole blocking layer, the electron transporting layer and the electron injecting layer and the light emitting layer contained an anthracene derivative as a fluorescent dopant / host material and iridium as a phosphorescent dopant material (For example, Firpic, Ir (ppy) ₃ , (acac) Ir (btp) ₂ ).

However, the m-MTDATA, 2-TNATA, TPD and NPB exhibited low glass transition temperatures (Tg) of 78 ° C, 108 ° C, 60 ° C and 96 ° C, respectively, and the metal complex compounds containing anthracene derivatives and iridium also exhibited low glass transition There is a limitation in obtaining a highly efficient organic electroluminescent device due to a decrease in thermal stability of the organic material layer.

Accordingly, development of an organic electroluminescent device having an organic material layer including a material having a high thermal stability and an excellent hole transporting ability has been developed.

Japanese Patent Application Laid-Open No. 2001-160489

In order to solve the above problems, it is an object of the present invention to provide an organic compound having high thermal stability and being capable of improving hole transporting ability and light emitting ability when applied to an organic material layer.

It is another object of the present invention to provide an organic electroluminescent device including an organic compound layer to which the organic compound is applied, having a low driving voltage, a high luminous efficiency, and an improved lifetime.

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

[Chemical Formula 1]

In Formula 1,

X ₁ to X ₈ are each independently N or C (R ₂ ), wherein at least one is C (R ₂ ) bonded with R ₂ represented by the following formula ( ₂ )

Y ₁ to Y ₈ are each independently N or C (R ₃ )

(2)

In the above Formulas 1 and 2,

* Is the site where the bond with C occurs,

R ₁ , and R ₂ , R ₃ and R ₄ not represented by the above formula (2) are each independently selected from the group consisting of hydrogen, deuterium, a C ₁ to C ₄₀ alkyl group, a C ₆ to C ₆₀ aryl group, A heteroaryl group of C ₆ to C ₆₀ , and an arylamine group of C ₆ to C ₆₀ , or may combine with adjacent groups to form a condensed aromatic ring or condensed heteroaromatic ring,

L ₁ and L ₂ are each independently selected from the group consisting of a single bond, a C ₆ to C ₆₀ arylene group and a heteroarylene group having 5 to 60 nuclear atoms,

Ar ₁ and Ar ₂ are, each independently, C ₁ ~ C ₄₀ alkyl group, C ₆ ~ C ₆₀ aryl group, nuclear atoms, a heteroaryl group of from 5 to 60, and C ₆ ~ from the group consisting of an aryl amine of the C ₆₀ of the Selected,

n and m are each independently an integer of 1 to 3,

a and b are each independently an integer of 0 to 4,

The alkyl, aryl, heteroaryl and arylamine groups of R ₁ to R ₄ , Ar ₁ and Ar ₂ and the arylene group and heteroarylene group of L ₁ and L ₂ are each independently selected from the group consisting of deuterium, , A C ₁ to C ₄₀ alkyl group, a C ₃ to C ₄₀ cycloalkyl group, a heterocycloalkyl group having 3 to 40 nuclear atoms, a C ₆ to C ₆₀ aryl group, a heteroaryl group having 5 to 60 nuclear atoms, C C ₁ to C ₄₀ alkyloxy groups, C ₆ to C ₆₀ aryloxy groups, C ₃ to C ₄₀ alkylsilyl groups, C ₆ to C ₆₀ arylsilyl groups, C ₁ to C ₄₀ alkylboron groups, C with one or more substituents selected from ₆ ~ C ₆₀ aryl boron group, C ₆ ~ C ₆₀ aryl phosphine group, C ₆ ~ C ₆₀ aryl phosphine oxide group, and the group consisting of C ₆ ~ with an aryl amine of the C ₆₀ of the Substituted or unsubstituted. When the substituent is substituted with a plurality of substituents, the plurality of substituents are the same or different from each other.

The present invention also provides an organic electroluminescent device comprising a positive electrode, a negative electrode, and at least one organic material layer interposed between the positive electrode and the negative electrode, wherein at least one of the one or more organic material layers comprises an organic electroluminescent device Lt; / RTI >

The alkyl group 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 groups include methyl, ethyl, propyl, isobutyl, sec-butyl, pentyl, iso-amyl and hexyl.

The aryl group 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. Also, a form in which two or more rings are pendant or condensed with each other may be included. Examples of such an aryl group include a phenyl group, a naphthyl group, a phenanthryl group, and an anthryl group.

The heteroaryl group in the present invention means a monovalent substituent derived from a monoheterocyclic or polyheterocyclic aromatic hydrocarbon having 5 to 60 nuclear atoms. Wherein at least one of the carbons, preferably one to three carbons, is replaced by a heteroatom such as N, O, S or Se. It is also understood that two or more rings may be pendant or fused to each other and further include a condensed form with an aryl group. Examples of such heteroaryl groups include 6-membered monocyclic rings such as pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl and triazinyl groups, phenoxathienyl, indolizinyl, Pyridyl, indolyl, purinyl, quinolyl, benzothiazole, carbosilyl, 2-furanyl, N-imidazolyl, Group, a 2-isoxazolyl group, a 2-pyridinyl group, a 2-pyrimidinyl group and the like.

The arylamine group in the present invention means an amine group substituted with an aryl group having 6 to 60 carbon atoms.

Since the organic electroluminescent device of the present invention includes the compound represented by Formula 1 having excellent thermal stability, hole transporting ability, electron blocking ability, and light emitting ability in the organic layer, aspects of the light emitting performance, driving voltage, And can be effectively applied to a full color display panel and the like.

Hereinafter, the present invention will be described.

1. Organic compounds

The organic compound of the present invention is a compound in which a carbazole group in which an arylamine group is bonded to an aromatic ring and a carbazole group in which an arylamine group is not bonded are asymmetrically bonded,

The compound represented by Formula 1 of the present invention is thermally stable and has excellent hole mobility because an arylamine group having an electron donor (EDG) property is bonded to a carbazole group. It is rich in electrons and has high triplet energies.

Accordingly, when an organic material layer (particularly, a hole transporting layer or a light-emitting auxiliary layer) containing a compound represented by Formula 1 of the present invention is applied to an organic electroluminescent device, an organic electroluminescent device having a low driving voltage, . The compound represented by the formula (1) of the present invention is preferably a compound represented by the following formula (3) or (4) in view of the characteristics of the organic electroluminescent device.

(3)

[Chemical Formula 4]

In the above formulas (3) and (4)

X ₁ to X ₈ , Y ₁ to Y ₈ and R ₁ are as defined above,

R ₅ is either selected from hydrogen, deuterium, C ₁ ~ C ₄₀ alkyl group, C ₆ ~ C ₆₀ aryl group, the number of nuclear atoms of 5 to 60 heteroaryl group, and the group consisting of C ₆ ~ with an aryl amine of the C ₆₀ of, To form a condensed aromatic ring or a condensed heteroaromatic ring by combining with adjacent groups,

c is an integer of 0 to 6,

The alkyl, aryl, heteroaryl and arylamine groups of R ₅ are each independently selected from the group consisting of deuterium, halogen, cyano, C ₁ to C ₄₀ alkyl, C ₃ to C ₄₀ cycloalkyl, A C ₆ to C ₆₀ aryl group, a heteroaryl group having 5 to 60 nuclear atoms, a C ₁ to C ₄₀ alkyloxy group, a C ₆ to C ₆₀ aryloxy group, a C ₃ to C ₄₀ An arylsilyl group of C ₆ to C ₆₀ , a C ₁ to C ₄₀ alkylboron group, a C ₆ to C ₆₀ arylboron group, a C ₆ to C ₆₀ arylphosphine group, a C ₆ to C ₆₀ An aryl phosphine oxide group, and an arylamine group having ₆ to ₆₀ carbon atoms. When the substituent is substituted with a plurality of substituents, the plurality of substituents are the same or different from each other.

In the compound represented by the general formula (1) of the present invention, it is preferable that all of Y ₁ to Y ₈ are C (R ₃ ).

In the compound represented by the formula (1) of the present invention, Ar ₁ and Ar ₂ are each independently preferably a C ₆ to C ₆₀ aryl group or a heteroaryl group having 5 to 60 nuclear atoms.

In the compound represented by formula (1) of the present invention, C (R ₂ ) bonded with R ₂ represented by formula ( ₂ ) means that the substituent (R ₂ ) represented by formula ( ₂ ) it means.

The compound represented by the formula (1) of the present invention may be embodied as the following compounds, but the compound represented by the formula (1) of the present invention is not limited to the following compounds.

The compounds represented by formula (1) of the present invention can be synthesized in various ways with reference to the following Synthesis Examples.

2. Organic electroluminescent device

The present invention provides an organic electroluminescent device to which an organic material layer including the compound represented by the above formula (1), preferably the compound represented by the above formula (3) or (4) is applied.

That is, the organic electroluminescent device of the present invention includes at least one anode, an anode, and at least one organic material layer interposed between the anode and the cathode, 1, preferably a compound represented by the formula (3) or (4). At this time, the compound represented by Formula 1 may be used singly or in combination of two or more.

The one or more organic layers may include at least one of a hole injecting layer, a hole transporting layer, a light emitting auxiliary layer, a light emitting layer, an electron transporting layer, and an electron injecting layer. , Or a light-emission-assisting layer.

In this case, the light-emitting auxiliary layer limits the injection of the triplet exciton into the hole transport layer and has a delta Est (<0.5 eV) characteristic of less than a certain level, so that the triplet exciton flowing into the prime layer And the like. When such a light emitting auxiliary layer is provided, it is possible to reduce the efficiency loss which may occur when the prime layer is not provided, or to increase the efficiency of phosphorescent EML. In addition, when a compound having a high LUMO value is applied, it can also serve as an electron blocking function.

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 auxiliary layer, a light emitting layer, an electron transporting layer and a cathode are sequentially laminated. At this time, an electron injection layer may be further stacked on the electron transport layer. Further, an insulating layer or an adhesive layer may be further inserted between the anode and / or the cathode and the organic material layer.

The substrate used in the fabrication of the organic electroluminescent device of the present invention is not particularly limited, but silicon wafer, quartz, glass plate, metal plate, plastic film and the like can be used.

The material used for the anode is not particularly limited, but may be a metal such as vanadium, chromium, copper, zinc, or gold or an alloy 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 may be used.

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

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

[Preparation Example 1] Synthesis of 3- (4-chlorophenyl) -9H-carbazole

3-bromo-9H-carbazole, 31.77 g (203.17 mmol) of 4-chlorophenyl boronic acid, 84.24 g (84.24 mmol) of K ₂ CO ₃ and 1000 ml / 250 ml / 250 ml of Toluene / H ₂ O / EtOH were added and stirred. 11.74 g (5 mol%) of Pd (PPh ₃ ) ₄ was added at 40 ° C, and the mixture was stirred at 100 ° C for 5 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, 47.97 g (yield: 85%) of 3- (4-chlorophenyl) -9H-carbazole was obtained by column chromatography.

GC-Mass (277.75 g / mol, measured: 277 g / mol)

¹ H-NMR:? 6.52 (d, 1 H), 7.31 (m, 2H), 7.62 (m, 3H)

[Preparation Example 2] Synthesis of 3- (4'-chloro- [1,1'-biphenyl] -4-yl) -9H-carbazole

The same procedure as in Preparation Example 1 was carried out except that 4'-chloro- [1,1'-biphenyl] -4-yl) boronic acid (47.23 g, 203.17 mmol) was used instead of (4-chlorophenyl) boronic acid To obtain 53.92 g (yield: 75%) of 3- (4'-chloro- [1,1'-biphenyl] -4-yl) -9H-carbazole.

GC-Mass (calculated: 353.84 g / mol, measured: 353 g / mol)

¹ H-NMR:? 6.45 (d, IH), 7.28 (d, IH), 7.68 (m, 3H)

[Preparation Example 3] Synthesis of 2- (4-chlorophenyl) -9H-carbazole

To a solution of 50.0 g (203.17 mmol) of 2-bromo-9H-carbazole, 31.77 g (203.17 mmol) of 4-chlorophenyl boronic acid, 84.24 g (84.24 mmol) K ₂ CO ₃ , / 250 ml of Toluene / H ₂ O / EtOH were added and stirred. 11.74 g (5 mol%) of Pd (PPh ₃ ) ₄ was added at 40 ° C, and the mixture was stirred at 100 ° C for 5 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, 47.97 g (yield: 85%) of 2- (4-chlorophenyl) -9H-carbazole was obtained by column chromatography.

GC-Mass (277.75 g / mol, measured: 277 g / mol)

¹ H-NMR:? 6.52 (d, 1 H), 7.31 (m, 2H), 7.62 (m, 3H)

Preparation Example 4 Synthesis of 2- (4'-chloro- [1,1'-biphenyl] -4-yl) -9H-carbazole

The same procedure as in Preparation Example 3 was carried out except that (4'-chloro- [1,1'-biphenyl] -4-yl) boronic acid (47.23 g, 203.17 mmol) was used in place of 4-chlorophenyl boronic acid To obtain 53.92 g (yield: 75%) of 2- (4'-chloro- [1,1'-biphenyl] -4-yl) -9H-carbazole.

GC-Mass (calculated: 353.84 g / mol, measured: 353 g / mol)

¹ H-NMR:? 6.45 (d, IH), 7.28 (d, IH), 7.68 (m, 3H)

[Preparation Example 5] Synthesis of 9- (4'-bromo- [1,1'-biphenyl] -4-yl) -9H-carbazole

To a solution of 50.0 g (187.18 mmol) of 4- (9H-carbazol-9-yl) phenylboronic acid, 47.53 g (187.18 mmol) of 1,4- dibromobenzene, 77.61 g (561.55 mmol) K ₂ CO ₃ , 1000 ml / 250 ml / 250 ml of toluene / H ₂ O / EtOH, and the mixture was stirred. 10.81 g (5 mol%) of Pd (PPh ₃ ) ₄ was added at 40 ° C, and the mixture was stirred at 100 ° C for 5 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, 64.12 g (yield: 86%) of 9- (4'-bromo- [1,1'-biphenyl] -4-yl) -9H-carbazole was obtained using column chromatography Respectively.

GC-Mass (calculated: 398.29 g / mol, measured: 398 g / mol)

¹ H-NMR:? 6.52 (d, 1 H), 7.31 (m, 2H), 7.62 (m, 3H)

Preparation Example 6 Synthesis of 9- (4 '' - bromo- [1,1 ': 4', 1 "-terphenyl] -4-yl) -9H-carbazole

(Yield: 81%) was obtained in the same manner as in Preparation Example 5, except that 4,4'-dibromo-1,1'-biphenyl (58.40 g, 187.18 mmol) was used instead of 1,4-dibromobenzene. (4 '' - bromo- [1,1 ': 4', 1 "-terphenyl] -4-yl) -9H-carbazole.

GC-Mass (calculated: 474.39 g / mol, measured: 474 g / mol)

¹ H-NMR:? 6.45 (d, IH), 7.28 (d, IH), 7.68 (m, 3H)

Preparation Example 7 Synthesis of 9- (3'-bromo- [1,1'-biphenyl] -4-yl) -9H-carbazole

(Yield: 75%) of 9- (3'-bromo (3-bromo-4-methoxyphenyl) propanoate was obtained by carrying out the same procedure as described in Preparation Example 5, except that 1,3-dibromobenzene (58.40 g, 187.18 mmol) - [1,1'-biphenyl] -4-yl) -9H-carbazole.

GC-Mass (calculated: 398.29 g / mol, measured: 398 g / mol)

¹ H-NMR:? 6.45 (d, IH), 7.28 (d, IH), 7.68 (m, 3H)

Preparation Example 8 Synthesis of 9- (4'-bromo- [1,1'-biphenyl] -3-yl) -9H-carbazole

50.0 g (187.18 mmol) of (3- (9H-carbazol-9 -yl) phenyl) boronic acid, 47.53 g (187.18 mmol) 1,4-dibromobenzene, 77.61 g K 2 CO a (561.55 mmol) of a nitrogen stream ₃ , 1000 ml / 250 ml / 250 ml of toluene / H ₂ O / EtOH, and the mixture was stirred. 10.81 g (5 mol%) of Pd (PPh ₃ ) ₄ was added at 40 ° C, and the mixture was stirred at 100 ° C for 5 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, 57.41 g (yield: 77%) of 9- (4'-bromo- [1,1'-biphenyl] -3-yl) -9H-carbazole was obtained using column chromatography Respectively.

GC-Mass (calculated: 398.29 g / mol, measured: 398 g / mol)

¹ H-NMR:? 6.52 (d, 1 H), 7.31 (m, 2H), 7.62 (m, 3H)

[Preparation Example 9] Synthesis of 9- (3'-bromo- [1,1'-biphenyl] -3-yl) -9H-carbazole

(Yield: 75%) of 9- (3'-bromo (3-bromo-4-methoxyphenyl) boronic acid) was obtained by following the same procedure as described in Preparation Example 8, except that 1,3-dibromobenzene (58.40 g, 187.18 mmol) - [1,1'-biphenyl] -3-yl) -9H-carbazole.

GC-Mass (calculated: 398.29 g / mol, measured: 398 g / mol)

¹ H-NMR:? 6.45 (d, IH), 7.28 (d, IH), 7.68 (m, 3H)

[Preparation Example 10] Synthesis of intermediate-1

(4'-bromo- [1,1'-biphenyl] -4-yl) carbamate (10 g, 36.00 mmol) -9H-carbazole, 0.99 g (1.08 mmol) of _{Pd 2 (dba) 3, 0.73} g (3.60 mmol) of _{P (t-bu) 3,} NaO (t-bu) , and toluene 1000 of 8.55 g (90.01 mmol) ml were mixed and stirred at 110 ° C for 5 hours. After completion of the reaction, the reaction mixture was extracted with dichloromethane, and the mixture was filtered through MgSO ₄ . After removing the solvent of the filtered organic layer, 17.36 g (yield: 81%) of intermediate-1 was obtained by column chromatography.

GC-Mass (calculated: 595.13 g / mol, measured: 595 g / mol)

2H), 7.54 (m, 7H), 7.66 (d, 2H), 7.50 (d,

[Preparation Example 11] Synthesis of intermediate-2

Bromo- [1,1 ': 4', 1 &quot; -terphenyl] -9H-carbazole instead of 9- (4'-bromo- [1,1'- -4-yl) -9H-carbazole (17.08 g, 36.00 mmol) was used in the same manner as in Preparation Example 10 to obtain 18.13 g (yield: 75%) of Intermediate-2.

GC-Mass (calculated: 671.23 g / mol, measured: 671 g / mol)

¹ H-NMR:? 6.45 (d, IH), 7.28 (d, IH), 7.68 (m, 3H)

[Preparation Example 12] Synthesis of intermediate-3

9- (4'-bromo- [1,1'-biphenyl] -3-yl) -9H-carbazole instead of 9- (4'- (yield: 71%) of Intermediate-3 was obtained by following the same procedure as described in Preparation Example 10, except that carbazole (14.34 g, 36.00 mmol) was used.

GC-Mass (calculated: 595.13 g / mol, measured: 595 g / mol)

¹ H-NMR:? 6.45 (d, IH), 7.28 (d, IH), 7.68 (m, 3H)

[Preparation Example 13] Synthesis of intermediate-4

9- (3'-bromo- [1,1'-biphenyl] -4-yl) -9H-carbazole instead of 9- (4'- (yield: 75%) of Intermediate-4 was obtained by following the same procedure as described in Preparation Example 10 except that carbazole (14.34 g, 36.00 mmol) was used.

GC-Mass (calculated: 595.13 g / mol, measured: 595 g / mol)

¹ H-NMR:? 6.45 (d, IH), 7.28 (d, IH), 7.68 (m, 3H)

[Preparation Example 14] Synthesis of intermediate-5

9- (3'-bromo- [1,1'-biphenyl] -3-yl) -9H-carbazole instead of 9- (4'- (yield: 70%) of Intermediate-5 was obtained by following the same procedure as described in Preparation Example 10, except that carbazole (14.34 g, 36.00 mmol) was used.

GC-Mass (calculated: 595.13 g / mol, measured: 595 g / mol)

¹ H-NMR:? 6.45 (d, IH), 7.28 (d, IH), 7.68 (m, 3H)

[Preparation Example 15] Synthesis of intermediate-6

(4'-bromo- [1,1'-biphenyl] -4-yl) carbamate (14.34 g, 36.00 mmol) -9H-carbazole, 0.99 g (1.08 mmol) of _{Pd 2 (dba) 3, 0.73} g (3.60 mmol) of _{P (t-bu) 3,} NaO (t-bu) , and toluene 1000 of 8.55 g (90.01 mmol) ml were mixed and stirred at 110 ° C for 5 hours. After completion of the reaction, the reaction mixture was extracted with dichloromethane, and the mixture was filtered through MgSO ₄ . After removing the solvent of the filtered organic layer, 17.36 g (yield: 81%) of intermediate-6 was obtained by column chromatography.

GC-Mass (calculated: 595.13 g / mol, measured: 595 g / mol)

^{1 H-NMR: δ 4.0 (} s, 1H), 6.50 (d, 2H), 7.30 (d, 2H), 7.54 (m, 7H), 7.66 (d, 2H)

[Preparation Example 16] Synthesis of intermediate-7

(4'-chloro- [1,1'-biphenyl] -4-yl) -9H-carbazole and 11.26 g (28.26 mmol) of 9- (4'-bromo - [1,1'-biphenyl] -4- yl) -9H-carbazole, 0.78 Pd 2 (dba of _{g (0.85 mmol)) 3,} 0.57 g (2.83 mmol) of _{P (t-bu) 3,} 6.79 g (70.65 mmol) of NaO (t-bu) and 500 ml of toluene were mixed and stirred at 110 ° C for 5 hours. After completion of the reaction, the reaction mixture was extracted with dichloromethane, and the mixture was filtered through MgSO ₄ . After removing the solvent of the filtered organic layer, 14.42 g (yield: 76%) of intermediate-7 was obtained by column chromatography.

GC-Mass (calculated: 671.23 g / mol, measured: 671 g / mol)

^{1 H-NMR: δ 4.0 (} s, 1H), 6.50 (d, 2H), 7.30 (d, 2H), 7.54 (m, 7H), 7.66 (d, 2H)

[Preparation Example 17] Synthesis of intermediate-8

(4'-chloro- [1,1'-biphenyl] -4-yl) -9H-carbazole and 14.34 g (36.00 mmol) of 9- (4'-bromo - [1,1'-biphenyl] -4- yl) -9H-carbazole, 0.78 Pd 2 (dba of _{g (0.85 mmol)) 3,} 0.57 g (2.83 mmol) of _{P (t-bu) 3,} 6.79 g (70.65 mmol) of NaO (t-bu) and 500 ml of toluene were mixed and stirred at 110 ° C for 5 hours. After completion of the reaction, the reaction mixture was extracted with dichloromethane, and the mixture was filtered through MgSO ₄ . After removing the solvent of the filtered organic layer, 13.47 g (yield: 71%) of intermediate-8 was obtained by column chromatography.

GC-Mass (calculated: 671.23 g / mol, measured: 671 g / mol)

^{1 H-NMR: δ 4.0 (} s, 1H), 6.50 (d, 2H), 7.30 (d, 2H), 7.54 (m, 7H), 7.66 (d, 2H)

[Synthesis Example 1] Synthesis of A-1

To a solution of 10 g (16.80 mmol) of Intermediate-1, 3.18 g (16.80 mmol) diphenylamine, 0.46 g (0.50 mmol) Pd ₂ (dba) _3, 0.34 g (1.68 mmol) P _3, 4.04 g (42.01 mmol) of NaO (t-bu) and 500 ml of toluene were mixed and stirred at 110 ° C for 5 hours. After completion of the reaction, the reaction mixture was extracted with dichloromethane, and the mixture was filtered through MgSO ₄ . After removing the solvent of the filtered organic layer, 8.68 g (yield: 71%) of A-1 was obtained by column chromatography.

GC-Mass (calculated: 727.89 g / mol, measured: 727 g / mol)

[Synthesis Example 2] Synthesis of A-2

8.64 g (yield: 68%) of A-2 was obtained by following the same procedure as in Synthesis Example 1 except that di-p-tolylamine (3.31 g, 16.80 mmol) was used instead of diphenylamine.

GC-Mass (calculated: 755.94 g / mol, measured: 755 g / mol)

[Synthesis Example 3] Synthesis of A-3

(yield: 65%) of di ((1,1'-biphenyl) -4-yl) amine (5.40 g, 16.80 mmol) was used in place of diphenylamine A-3 was obtained.

GC-Mass (calculated: 880.08 g / mol, measured: 880 g / mol)

[Synthesis Example 4] Synthesis of A-4

except that N - ([1,1'-biphenyl] -4-yl) -9,9-dimethyl-9H-fluoren-2-amine (6.07 g, 16.80 mmol) was used in place of diphenylamine. The same procedure was followed to obtain 10.36 g (yield: 67%) of A-4.

GC-Mass (calculated: 920.15 g / mol, measured: 920 g / mol)

[Synthesis Example 5] Synthesis of A-5

(yield: 75%) of A-5 was obtained by following the same procedure as in Synthesis Example 1, except that N-phenylnaphthalen-1-amine (3.68 g, 16.80 mmol) was used instead of diphenylamine.

GC-Mass (calculated: 777.95 g / mol, measured: 777 g / mol)

[Synthesis Example 6] Synthesis of A-6

10.43 g (yield: 75%) of A-6 was obtained in the same manner as in Synthesis Example 1 except that di (naphthalen-1-yl) amine (4.53 g, 16.80 mmol) was used instead of diphenylamine.

GC-Mass (theory: 828.01 g / mol, measured: 828 g / mol)

[Synthesis Example 7] Synthesis of A-7

13.07 g (yield: 71%) of A-7 was obtained in the same manner as in Synthesis Example 1 except that N-phenylnaphthalen-2-amine (3.68 g, 16.80 mmol) was used instead of diphenylamine.

GC-Mass (calculated: 777.95 g / mol, measured: 777 g / mol)

[Synthesis Example 8] Synthesis of A-8

10.43 g (yield: 75%) of A-8 was obtained in the same manner as in Synthesis Example 1 except that di (naphthalen-2-yl) amine (4.53 g, 16.80 mmol) was used instead of diphenylamine.

GC-Mass (theory: 828.01 g / mol, measured: 828 g / mol)

[Synthesis Example 9] Synthesis of A-14

(yield: 75%) of A-14 was obtained by following the same procedure as in Synthesis Example 1, except that N-phenyldibenzo [b, d] furan-4-amine (4.36 g, 16.80 mmol) .

GC-Mass (calculated: 817.97 g / mol, measured: 817 g / mol)

[Synthesis Example 10] Synthesis of A-15

(yield: 68%) of A-15 was obtained by following the same procedure as in Synthesis Example 1 except that N-phenyldibenzo [b, d] thiophen-2-amine (4.63 g, 16.80 mmol) .

GC-Mass (theory: 834.04 g / mol, measurement: 834 g / mol)

[Synthesis Example 11] Synthesis of A-17

To a solution of 10 g (14.90 mmol) of Intermediate 7, 2.82 g (14.90 mmol) diphenylamine, 0.41 g (0.45 mmol) Pd ₂ (dba) _{3 and} 0.30 g (1.49 mmol) P _3, 3.58 g (37.25 mmol) of NaO (t-bu) and 500 ml of toluene were mixed and stirred at 110 ° C for 5 hours. After completion of the reaction, the reaction mixture was extracted with dichloromethane, and the mixture was filtered through MgSO ₄ . After removing the solvent of the filtered organic layer, 8.98 g (yield: 75%) of A-17 was obtained by column chromatography.

GC-Mass (theory: 803.99 g / mol, measurement: 803 g / mol)

[Synthesis Example 12] Synthesis of A-18

8.80 g (yield: 71%) of A-18 was obtained in the same manner as in Synthetic Example 11 except that di-p-tolylamine (2.94 g, 14.90 mmol) was used instead of diphenylamine.

GC-Mass (calculated: 832.04 g / mol, measured: 832 g / mol)

[Synthesis Example 13] Synthesis of A-19

9 (yield: 76%) of A-19 was obtained by following the same procedure as in Synthesis Example 11, except that N-phenylnaphthalen-1 -amine (3.27 g, 14.90 mmol) was used instead of diphenylamine.

GC-Mass (calculated: 854.05 g / mol, measured: 854 g / mol)

[Synthesis Example 14] Synthesis of A-23

(yield: 71%) of A-23 was obtained by following the same procedure as in Synthesis Example 11, except that N-phenylnaphthalen-2-amine (3.27 g, 14.90 mmol) was used instead of diphenylamine.

GC-Mass (calculated: 854.05 g / mol, measured: 854 g / mol)

[Synthesis Example 15] Synthesis of B-1

To a solution of 10 g (16.80 mmol) of Intermediate-6, 3.18 g (16.80 mmol) diphenylamine, 0.46 g (0.50 mmol) Pd ₂ (dba) _3, 0.34 g (1.68 mmol) P _3, 4.04 g (42.01 mmol) of NaO (t-bu) and 500 ml of toluene were mixed and stirred at 110 ° C for 5 hours. After completion of the reaction, the reaction mixture was extracted with dichloromethane, and the mixture was filtered through MgSO ₄ . After removing the solvent of the filtered organic layer, 8.68 g (yield: 71%) of B-1 was obtained by column chromatography.

GC-Mass (calculated: 727.89 g / mol, measured: 727 g / mol)

[Synthesis Example 16] Synthesis of B-2

(yield: 71%) of B-2 was obtained by following the same procedure as in Synthesis Example 15, except that di-p-tolylamine (3.31 g, 16.80 mmol) was used instead of diphenylamine.

GC-Mass (calculated: 755.94 g / mol, measured: 755 g / mol)

[Synthesis Example 17] Synthesis of B-3

(yield: 66%) of di ((1,1'-biphenyl) -4-yl) amine (5.40 g, 16.80 mmol) was used in place of diphenylamine B-3 was obtained.

GC-Mass (calculated: 880.08 g / mol, measured: 880 g / mol)

[Synthesis Example 18] Synthesis of B-4

except that N - ([1,1'-biphenyl] -4-yl) -9,9-dimethyl-9H-fluoren-2-amine (6.07 g, 16.80 mmol) was used in place of diphenylamine. The same procedure was followed to obtain 11.43 g (yield: 74%) of B-4.

GC-Mass (calculated: 920.15 g / mol, measured: 920 g / mol)

[Synthesis Example 19] Synthesis of B-5

(yield: 75%) of B-5 was obtained by following the same procedure as in Synthesis Example 15, except that N-phenylnaphthalen-1-amine (3.68 g, 16.80 mmol) was used instead of diphenylamine.

GC-Mass (calculated: 777.95 g / mol, measured: 777 g / mol)

[Synthesis Example 20] Synthesis of B-6

10.01 g (yield: 75%) of B-6 was obtained in the same manner as in Synthesis Example 15 except that di (naphthalen-1-yl) amine (4.53 g, 16.80 mmol) was used instead of diphenylamine.

GC-Mass (theory: 828.01 g / mol, measured: 828 g / mol)

[Synthesis Example 21] Synthesis of B-7

8.49 g (yield: 65%) of B-7 was obtained by following the same procedure as in Synthesis Example 15, except that N-phenylnaphthalen-2-amine (3.68 g, 16.80 mmol) was used instead of diphenylamine.

GC-Mass (calculated: 777.95 g / mol, measured: 777 g / mol)

[Synthesis Example 22] Synthesis of B-8

11.54 g (yield: 75%) of B-8 was obtained in the same manner as in Synthesis Example 15 except that di (naphthalen-2-yl) amine (4.53 g, 16.80 mmol) was used instead of diphenylamine.

GC-Mass (theory: 828.01 g / mol, measured: 828 g / mol)

[Synthesis Example 23] Synthesis of B-14

(yield: 75%) of B-14 was obtained by following the same procedure as in Synthesis Example 15 except that N-phenyldibenzo [b, d] furan-4-amine (4.36 g, 16.80 mmol) .

GC-Mass (calculated: 817.97 g / mol, measured: 817 g / mol)

[Synthesis Example 24] Synthesis of B-15

(yield: 70%) of B-5 was obtained by following the same procedure as in Synthesis 15 except that N-phenyldibenzo [b, d] thiophen-2-amine (4.63 g, 16.80 mmol) .

GC-Mass (theory: 834.04 g / mol, measurement: 834 g / mol)

[Synthesis Example 25] Synthesis of B-17

To a solution of 10 g (14.90 mmol) of Intermediate-8, 2.82 g (14.90 mmol) diphenylamine, 0.41 g (0.45 mmol) Pd ₂ (dba) _3, 0.30 g (1.49 mmol) _3, 3.58 g (37.25 mmol) of NaO (t-bu) and 500 ml of toluene were mixed and stirred at 110 ° C for 5 hours. After completion of the reaction, the reaction mixture was extracted with dichloromethane, and the mixture was filtered through MgSO ₄ . After removing the solvent of the filtered organic layer, 7.78 g (yield: 65%) of B-17 was obtained by column chromatography.

GC-Mass (theory: 803.99 g / mol, measurement: 803 g / mol)

[Synthesis Example 26] Synthesis of B-18

(yield: 65%) of B-18 was obtained by following the same procedure as in Synthesis Example 25 except that di-p-tolylamine (2.94 g, 14.90 mmol) was used instead of diphenylamine.

GC-Mass (calculated: 832.04 g / mol, measured: 832 g / mol)

[Synthesis Example 27] Synthesis of B-19

(yield: 76%) of B-19 was obtained by following the same procedure as in Synthesis Example 25, except that N-phenylnaphthalen-1 -amine (3.27 g, 14.90 mmol) was used instead of diphenylamine.

GC-Mass (calculated: 854.05 g / mol, measured: 854 g / mol)

[Synthesis Example 28] Synthesis of B-23

9.54 g (yield: 75%) of B-23 was obtained by following the same procedure as in Synthesis Example 25 except that N-phenylnaphthalen-2-amine (3.27 g, 14.90 mmol) was used instead of diphenylamine.

GC-Mass (calculated: 854.05 g / mol, measured: 854 g / mol)

[Synthesis Example 29] Synthesis of C-1

To a solution of 10 g (16.80 mmol) of intermediate 3, 2.84 g (16.80 mmol) diphenylamine, 0.46 g (0.50 mmol) Pd ₂ (dba) _{3 and} 0.34 g (1.68 mmol) P _3, 4.04 g (42.01 mmol) of NaO (t-bu) and 500 ml of toluene were mixed and stirred at 110 ° C for 5 hours. After completion of the reaction, the reaction mixture was extracted with dichloromethane, and the mixture was filtered through MgSO ₄ . After removing the solvent of the filtered organic layer, 8.83 g (yield: 73%) of C-1 was obtained by column chromatography.

GC-Mass (calculated: 727.89 g / mol, measured: 727 g / mol)

[Synthesis Example 30] Synthesis of C-2

9.52 g (yield: 75%) of C-2 was obtained in the same manner as in Synthesis Example 29 except that di-p-tolylamine (3.31 g, 16.80 mmol) was used instead of diphenylamine.

GC-Mass (calculated: 755.94 g / mol, measured: 755 g / mol)

[Synthesis Example 31] Synthesis of C-3

(yield: 66%) was obtained by following the same procedure as in Synthesis Example 29, except that di ([1,1'-biphenyl] -4-yl) amine (5.40 g, 16.80 mmol) C-3 was obtained.

GC-Mass (calculated: 880.08 g / mol, measured: 880 g / mol)

[Synthesis Example 32] Synthesis of C-5

(yield: 75%) of C-5 was obtained by following the same procedure as in Synthesis Example 29, except that N-phenylnaphthalen-1-amine (3.68 g, 16.80 mmol) was used instead of diphenylamine.

GC-Mass (calculated: 777.95 g / mol, measured: 777 g / mol)

[Synthesis Example 33] Synthesis of C-6

10.01 g (yield: 75%) of C-6 was obtained in the same manner as in Synthesis Example 29 except that di (naphthalen-1-yl) amine (4.53 g, 16.80 mmol) was used instead of diphenylamine.

GC-Mass (theory: 828.01 g / mol, measured: 828 g / mol)

[Synthesis Example 34] Synthesis of C-11

To a solution of 10 g (16.80 mmol) of Intermediate -4, 2.84 g (16.80 mmol) diphenylamine, 0.46 g (0.50 mmol) Pd ₂ (dba) _{3 and} 0.34 g (1.68 mmol) P _3, 4.04 g (42.01 mmol) of NaO (t-bu) and 500 ml of toluene were mixed and stirred at 110 ° C for 5 hours. After completion of the reaction, the reaction mixture was extracted with dichloromethane, and the mixture was filtered through MgSO ₄ . After removing the solvent of the filtered organic layer, 8.83 g (yield: 73%) of C-11 was obtained by column chromatography.

GC-Mass (calculated: 727.89 g / mol, measured: 727 g / mol)

[Synthesis Example 35] Synthesis of C-12

9.52 g (yield: 75%) of C-12 was obtained in the same manner as in Synthetic Example 34 except that di-p-tolylamine (3.31 g, 16.80 mmol) was used instead of diphenylamine.

GC-Mass (calculated: 755.94 g / mol, measured: 755 g / mol)

[Synthesis Example 36] Synthesis of C-13

(yield: 70%) of di ((1,1'-biphenyl) -4-yl) amine (5.40 g, 16.80 mmol) was used in place of diphenylamine C-13 was obtained.

GC-Mass (calculated: 880.08 g / mol, measured: 880 g / mol)

[Synthesis Example 37] Synthesis of C-15

8.36 g (yield: 64%) of C-15 was obtained in the same manner as in Synthetic Example 34 except that N-phenylnaphthalen-1-amine (3.68 g, 16.80 mmol) was used instead of diphenylamine.

GC-Mass (calculated: 777.95 g / mol, measured: 777 g / mol)

[Synthesis Example 38] Synthesis of C-16

16.80 g (yield: 79%) of C-16 was obtained in the same manner as in Synthetic Example 34 except that di (naphthalen-1-yl) amine (4.53 g, 16.80 mmol) was used instead of diphenylamine.

GC-Mass (theory: 828.01 g / mol, measured: 828 g / mol)

[Synthesis Example 39] Synthesis of C-21

To a solution of 10 g (16.80 mmol) of Intermediate -5, 2.84 g (16.80 mmol) diphenylamine, 0.46 g (0.50 mmol) Pd ₂ (dba) _3, 0.34 g (1.68 mmol) P _3, 4.04 g (42.01 mmol) of NaO (t-bu) and 500 ml of toluene were mixed and stirred at 110 ° C for 5 hours. After completion of the reaction, the reaction mixture was extracted with dichloromethane, and the mixture was filtered through MgSO ₄ . After removing the solvent of the filtered organic layer, 8.68 g (yield: 71%) of C-21 was obtained by column chromatography.

GC-Mass (calculated: 727.89 g / mol, measured: 727 g / mol)

[Synthesis Example 40] Synthesis of C-22

(yield: 67%) of C-22 was obtained by following the same procedure as Synthesis Example 39, except that di-p-tolylamine (3.31 g, 16.80 mmol) was used instead of diphenylamine.

GC-Mass (calculated: 755.94 g / mol, measured: 755 g / mol)

[Synthesis Example 41] Synthesis of C-23

(yield: 66%) of di ((1,1'-biphenyl) -4-yl) amine (5.40 g, 16.80 mmol) was used in place of diphenylamine C-23 was obtained.

GC-Mass (calculated: 880.08 g / mol, measured: 880 g / mol)

[Synthesis Example 42] Synthesis of C-25

(yield: 76%) of C-25 was obtained by following the same procedure as Synthesis Example 39, except that N-phenylnaphthalen-1-amine (3.68 g, 16.80 mmol) was used instead of diphenylamine.

GC-Mass (calculated: 777.95 g / mol, measured: 777 g / mol)

[Synthesis Example 43] Synthesis of C-26

9.32 g (yield: 67%) of C-26 was obtained in the same manner as in Synthesis Example 39 except that di (naphthalen-1-yl) amine (4.53 g, 16.80 mmol) was used instead of diphenylamine.

GC-Mass (theory: 828.01 g / mol, measured: 828 g / mol)

[Synthesis Example 44] Synthesis of D-1

To a solution of 10 g (14.90 mmol) of Intermediate-2, 2.52 g (14.90 mmol) diphenylamine, 0.41 g (0.45 mmol) Pd ₂ (dba) _{3 and} 0.30 g (1.49 mmol) P _3, 3.58 g (37.25 mmol) of NaO (t-bu) and 500 ml of toluene were mixed and stirred at 110 ° C for 5 hours. After completion of the reaction, the reaction mixture was extracted with dichloromethane, and the mixture was filtered through MgSO ₄ . After removing the solvent of the filtered organic layer, 8.74 g (yield: 73%) of D-1 was obtained by column chromatography.

GC-Mass (theory: 803.99 g / mol, measurement: 803 g / mol)

[Synthesis Example 45] Synthesis of D-2

8.68 g (yield: 70%) of D-2 was obtained in the same manner as in Synthesis Example 44 except that di-p-tolylamine (2.94 g, 14.90 mmol) was used instead of diphenylamine.

GC-Mass (calculated: 832.04 g / mol, measured: 832 g / mol)

[Synthesis Example 46] Synthesis of D-6

D-6 of 8.65 g (yield: 68%) was obtained by following the same procedure as Synthesis Example 44 except that N-phenylnaphthalen-1-amine (3.27 g, 14.90 mmol) was used instead of diphenylamine.

GC-Mass (calculated: 854.05 g / mol, measured: 854 g / mol)

[Synthesis Example 47] Synthesis of D-9

9.42 g (yield: 74%) of D-9 was obtained in the same manner as in Synthesis Example 44 except that N-phenylnaphthalen-2-amine (3.27 g, 14.90 mmol) was used instead of diphenylamine.

GC-Mass (calculated: 854.05 g / mol, measured: 854 g / mol)

[Example 1] Production of organic electroluminescent device

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

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

M-MTDATA (60 nm) / Compound A-1 (80 nm) / DS-H522 + 5% DS-501 (30 nm) / BCP (10 nm) / Alq3 (60 nm) of Synthesis Example 1 was formed on the ITO transparent substrate 30 nm) / LiF (1 nm) / Al (200 nm) in this order to fabricate an organic electroluminescent device.

The DS-H522 and DS-501 used are the products of Doosan Electronics Co., Ltd., and the structures of the m-MTDATA and BCP are as follows.

[Examples 2 to 47] Preparation of Organic Electroluminescent Device

An organic electroluminescent device was prepared in the same manner as in Example 1, except that the compounds synthesized in Synthesis Examples 2 to 47 were used in place of the compound A-1 used as a hole transporting layer material in Example 1.

[Comparative Example 1] Production of organic electroluminescent device

An organic electroluminescent device was prepared in the same manner as in Example 1, except that NPB was used instead of the compound A-1 used as a hole transporting layer material in Example 1.

The structure of the NPB is as follows.

[Experimental Example 1]

The driving voltage and the current efficiency at a current density of 10 mA / cm 2 were measured for the organic electroluminescent devices manufactured in Examples 1 to 47 and Comparative Example 1, respectively, and the results are shown in Table 1 below.

Sample Hole transport layer The driving voltage (V) Current efficiency (cd / A) Example 1 Compound A-1 4.1 22.2 Example 2 Compound A-2 4.3 20.1 Example 3 Compound A-3 4.4 21.3 Example 4 Compound A-4 4.0 22.6 Example 5 Compound A-5 4.5 19.5 Example 6 Compound A-6 4.7 20.1 Example 7 Compound A-7 4.3 21.6 Example 8 Compound A-8 4.5 20.5 Example 9 Compound A-14 4.7 20.6 Example 10 Compound A-15 4.4 21.6 Example 11 Compound A-17 5.0 20.1 Example 12 Compound A-18 5.1 18.6 Example 13 Compound A-19 4.3 22.0 Example 14 Compound A-23 4.6 21.2 Example 15 Compound B-1 4.5 21.2 Example 16 Compound B-2 4.4 22.3 Example 17 Compound B-3 5.1 18.3 Example 18 Compound B-4 5 18.9 Example 19 Compound B-5 4.5 21.7 Example 20 Compound B-6 4.7 21.2 Example 21 Compound B-7 4.8 20.8 Example 22 Compound B-8 4.5 21.4 Example 23 Compound B-14 5.1 18.2 Example 24 Compound B-15 5.1 18.5 Example 25 Compound B-17 4.3 22.3 Example 26 Compound B-18 4.6 21.4 Example 27 Compound B-19 4.8 21.6 Example 28 Compound B-23 4.2 22.5 Example 29 Compound C-1 4.7 20.6 Example 30 Compound C-2 4.6 20.2 Example 31 Compound C-3 4.2 22.1 Example 32 Compound C-5 4.6 21.2 Example 33 Compound C-6 4.8 20.0 Example 34 Compound C-11 4.2 22.3 Example 35 Compound C-12 4.8 21.8 Example 36 Compound C-13 5.0 19.2 Example 37 Compound C-15 4.5 20.3 Example 38 Compound C-16 5.1 18.5 Example 39 Compound C-21 4.9 20.3 Example 40 Compound C-22 4.8 20.8 Example 41 Compound C-23 4.2 21.4 Example 42 Compound C-25 4.7 18.2 Example 43 Compound C-26 4.6 18.5 Example 44 Compound D-1 4.2 22.3 Example 45 Compound D-2 4.6 21.4 Example 46 Compound D-6 4.8 21.6 Example 47 Compound D-9 4.2 22.5 Comparative Example 1 NPB 5.2 18.1

As shown in Table 1, the organic electroluminescent devices (Examples 1 to 47) using the compound according to the present invention in the organic material layer are superior in current efficiency and driving efficiency compared to the organic electroluminescent device (Comparative Example 1) It can be confirmed that the voltage is excellent.

[Example 48] Production of green organic electroluminescent device

Compound A-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.

The glass substrate coated with ITO (Indium tin oxide) thin film with thickness of 1500 Å was ultrasonically cleaned with distilled water. After the distilled water was cleaned, the substrate 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 for 5 minutes And the substrate was transferred to a vacuum evaporator.

(60 nm) / TCTA (80 nm) / Compound A-1 (40 nm) / CBP + 10% Ir (ppy) 3 (30 nm) / BCP (10 nm) on the ITO transparent substrate nm) / Alq3 (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.

[Examples 49 to 94] Preparation of green organic electroluminescent device

A green organic electroluminescent device was fabricated in the same manner as in Example 48 except that the compounds synthesized in Synthesis Examples 2 to 47 were used in place of the compound A-1 used as the hole transport layer material in Example 48.

[Comparative Example 2] Production of green organic electroluminescent device

A green organic electroluminescent device was prepared in the same manner as in Example 48 except that the compound A-1 used as the hole transport layer material in Example 48 was not used.

[Experimental Example 2]

The driving voltage and the current efficiency at a current density of 10 mA / cm 2 were measured for the organic electroluminescent devices manufactured in Examples 48 to 94 and Comparative Example 2, respectively, and the results are shown in Table 2 below.

Sample Hole transport layer The driving voltage (V) Current efficiency (cd / A) Example 48 Compound A-1 6.7 41.9 Example 49 Compound A-2 6.85 42.1 Example 50 Compound A-3 6.8 44.8 Example 51 Compound A-4 6.8 47.5 Example 52 Compound A-5 6.85 41.5 Example 53 Compound A-6 6.9 41.9 Example 54 Compound A-7 6.9 42.4 Example 55 Compound A-8 6.8 42.3 Example 56 Compound A-14 6.9 45.2 Example 57 Compound A-15 6.8 44.6 Example 58 Compound A-17 6.7 44.1 Example 59 Compound A-18 6.65 43.6 Example 60 Compound A-19 6.7 42.6 Example 61 Compound A-23 6.9 44.1 Example 62 Compound B-1 6.8 42.8 Example 63 Compound B-2 6.7 41.4 Example 64 Compound B-3 6.7 41.8 Example 65 Compound B-4 6.65 45.3 Example 66 Compound B-5 6.7 45.1 Example 67 Compound B-6 6.65 42.6 Example 68 Compound B-7 6.6 41.3 Example 69 Compound B-8 6.6 42.1 Example 70 Compound B-14 6.7 41.9 Example 71 Compound B-15 6.9 42.1 Example 72 Compound B-17 6.8 44.8 Example 73 Compound B-18 6.8 47.5 Example 74 Compound B-19 6.85 41.5 Example 75 Compound B-23 6.85 41.9 Example 76 Compound C-1 6.65 42.4 Example 77 Compound C-2 6.6 42.3 Example 78 Compound C-3 6.7 45.2 Example 79 Compound C-5 6.85 44.6 Example 80 Compound C-6 6.7 44.1 Example 81 Compound C-11 6.8 43.6 Example 82 Compound C-12 6.75 42.6 Example 83 Compound C-13 6.8 44.1 Example 84 Compound C-15 6.8 42.8 Example 85 Compound C-16 6.85 41.4 Example 86 Compound C-21 6.9 41.8 Example 87 Compound C-22 6.7 45.3 Example 88 Compound C-23 6.7 45.1 Example 89 Compound C-25 6.65 42.6 Example 90 Compound C-26 6.7 41.3 Example 91 Compound D-1 6.65 42.1 Example 92 Compound D-2 6.6 41.9 Example 93 Compound D-6 6.6 42.1 Example 94 Compound D-9 6.7 44.8 Comparative Example 2 - 6.93 38.2

As shown in the above Table 2, the green organic electroluminescent devices (Examples 48 to 94) using the compound according to the present invention in the organic material layer (Comparative Examples 2 to 4), compared to the green organic electroluminescent device It can be confirmed that the efficiency and the driving voltage are excellent.

[Example 95] Production of red organic electroluminescent device

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

The glass substrate coated with ITO (Indium tin oxide) thin film with thickness of 1500 Å was ultrasonically cleaned with distilled water. After the distilled water was washed, the substrate was ultrasonically cleaned with a solvent such as isopropyl alcohol, acetone, and 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.

(60 nm) / TCTA (80 nm) / Compound A-1 (40 nm) / CBP + 10% (piq) 2 Ir (acac) (30 nm) / BCP on the ITO transparent substrate (10 nm) / Alq3 (30 nm) / LiF (1 nm) / Al (200 nm) were laminated in this order to prepare a red organic electroluminescent device.

The structures of m-MTDATA, TCTA and BCP used are as described above, and the structure of (piq) 2Ir (acac) is as follows.

[Examples 96 to 141] Preparation of red organic electroluminescent device

A red organic electroluminescent device was prepared in the same manner as in Example 95 except that the compounds synthesized in Synthesis Examples 2 to 47 were used instead of the compound A-1 used as a hole transporting material in Example 95.

[Comparative Example 3] Production of red organic electroluminescent device

A red organic electroluminescent device was prepared in the same manner as in Example 95 except that the compound A-1 used as the hole transport layer material in Example 95 was not used.

[Experimental Example 3]

The driving voltage and the current efficiency at a current density of 10 mA / cm 2 were measured for the organic electroluminescent devices manufactured in Examples 95 to 141 and Comparative Example 3, respectively, and the results are shown in Table 3 below.

Sample Hole transport layer The driving voltage (V) Current efficiency (cd / A) Example 95 Compound A-1 4.9 11.9 Example 96 Compound A-2 5.1 12.1 Example 97 Compound A-3 5.0 14.8 Example 98 Compound A-4 5.0 17.5 Example 99 Compound A-5 5.1 11.5 Example 100 Compound A-6 5.1 11.9 Example 101 Compound A-7 5.2 12.4 Example 102 Compound A-8 5.0 12.3 Example 103 Compound A-14 5.1 15.2 Example 104 Compound A-15 5.0 14.6 Example 105 Compound A-17 4.9 14.1 Example 106 Compound A-18 4.9 13.6 Example 107 Compound A-19 4.9 12.6 Example 108 Compound A-23 5.1 14.1 Example 109 Compound B-1 5.0 12.8 Example 110 Compound B-2 4.9 11.4 Example 111 Compound B-3 4.9 11.8 Example 112 Compound B-4 4.9 15.3 Example 113 Synthesis of Compound B-5 4.9 15.1 Example 114 Compound B-6 4.9 12.6 Example 115 Compound B-7 4.8 11.3 Example 116 Compound B-8 4.8 12.1 Example 117 Compound B-14 4.9 11.9 Example 118 Compound B-15 5.1 12.1 Example 119 Compound B-17 5.0 14.8 Example 120 Compound B-18 5.0 17.5 Example 121 Compound B-19 5.1 11.5 Example 122 Compound B-23 5.1 11.9 Example 123 Compound C-1 4.9 12.4 Example 124 Compound C-2 4.8 12.3 Example 125 Compound C-3 4.9 15.2 Example 126 Compound C-5 5.1 14.6 Example 127 Compound C-6 4.9 14.1 Example 128 Compound C-11 5.0 13.6 Example 129 Compound C-12 5.0 12.6 Example 130 Compound C-13 5.0 14.1 Example 131 Compound C-15 5.0 12.8 Example 132 Compound C-16 5.1 11.4 Example 133 Compound C-21 5.1 11.8 Example 134 Compound C-22 4.3 15.3 Example 135 Compound C-23 4.9 15.1 Example 136 Compound C-25 4.7 12.6 Example 137 Compound C-26 4.5 11.3 Example 138 Compound D-1 4.9 12.1 Example 139 Compound D-2 4.8 11.9 Example 140 Compound D-6 4.8 12.1 Example 141 Compound D-9 4.9 14.8 Comparative Example 3 - 5.2 8.2

As shown in Table 3, the red organic electroluminescent devices (Examples 95 to 141) using the compound according to the present invention as an organic material layer (Comparative Examples 3 to 6) And the driving voltage is excellent.

[Example 142] Production of blue organic electroluminescent device

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

The glass substrate coated with ITO (Indium tin oxide) thin film with thickness of 1500 Å was ultrasonically cleaned with distilled water. After the distilled water was washed, the substrate was ultrasonically cleaned with a solvent such as isopropyl alcohol, acetone, and 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.

NPN (15 nm) / Compound A-1 (15 nm) / ADN + 5% DS-405 (Doosan) (30 nm) / The blue organic electroluminescent device was fabricated by laminating BCP (10 nm) / Alq3 (30 nm) / LiF (1 nm) / Al (200 nm) in this order.

The structures of BCP and NPB used are as described above, and the structure of ADN is as follows.

[Examples 143 to 188] Manufacture of blue organic electroluminescent device

A blue organic electroluminescent device was prepared in the same manner as in Example 142 except that the compounds synthesized in Synthesis Examples 2 to 47 were used instead of the compound A-1 used as the hole transporting material in Example 142. [

[Comparative Example 4] Production of blue organic electroluminescent device

A blue organic electroluminescent device was prepared in the same manner as in Example 142 except that A-1 was not used as the hole transport layer material in Example 142. [

[Experimental Example 4]

The driving voltage and the current efficiency at the current density of 10 mA / cm 2 were measured for each of the organic electroluminescent devices manufactured in Examples 142 to 188 and Comparative Example 4, and the results are shown in Table 4 below.

Sample Hole transport layer The driving voltage (V) Current efficiency (cd / A) Example 142 [ Compound A-1 4.3 9.2 Example 143 Compound A-2 4.5 7.1 Example 144 Compound A-3 4.6 8.3 Example 145 Compound A-4 4.2 9.6 Example 146 Compound A-5 4.7 6.5 Example 147 Compound A-6 4.9 7.1 Example 148 Compound A-7 4.5 8.6 Example 149 Compound A-8 4.7 7.5 Example 150 Compound A-14 4.9 7.6 Example 151 Compound A-15 4.6 8.6 Example 152 Compound A-17 5.2 7.1 Example 153 Compound A-18 5.3 5.6 Example 154 Compound A-19 4.5 9.0 Example 155 Compound A-23 4.8 8.2 Example 156 Compound B-1 4.7 8.2 Example 157 Compound B-2 4.6 9.3 Example 158 Compound B-3 5.3 5.3 Example 159 Compound B-4 5.2 5.9 Example 160 Compound B-5 4.7 8.7 Example 161 Compound B-6 4.9 8.2 Example 162 Compound B-7 5.0 7.8 Example 163 Compound B-8 4.7 8.4 Example 164 Compound B-14 5.3 5.2 Example 165 Compound B-15 5.3 5.5 Example 166 Compound B-17 4.5 9.3 Example 167 Compound B-18 4.8 8.4 Example 168 Compound B-19 5.0 8.6 Example 169 Compound B-23 4.4 9.5 Example 170 Compound C-1 4.9 7.6 Example 171 Compound C-2 4.8 7.2 Example 172 Compound C-3 4.4 9.1 Example 173 Compound C-5 4.8 8.2 Example 174 Compound C-6 5.0 7.0 Example 175 Compound C-11 4.4 9.3 Example 176 Compound C-12 5.0 8.8 Example 177 Compound C-13 5.2 6.2 Example 178 Compound C-15 4.7 7.3 Example 179 Compound C-16 5.3 5.5 Example 180 Compound C-21 5.1 7.3 Example 181 Compound C-22 5.0 7.8 Example 182 Compound C-23 4.4 8.4 Example 183 Compound C-25 4.9 5.2 Example 184 Compound C-26 4.8 5.5 Example 185 Compound D-1 4.4 9.3 Example 186 Compound D-2 4.8 8.4 Example 187 Compound D-6 5.0 8.6 Example 188 Compound D-9 4.4 9.5 Comparative Example 4 - 5.6 4.8

As shown in Table 4, the blue organic electroluminescent devices (Examples 142 to 188) using the compound according to the present invention in the organic material layer had higher current efficiency and driving voltage than the conventional blue organic electroluminescent device (Comparative Example 4) I can confirm that it is excellent.

Claims (5)

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

In Formula 1,
X ₁ to X ₈ are each independently N or C (R ₂ ), wherein at least one is C (R ₂ ) bonded with R ₂ represented by the following formula ( ₂ )
Y ₁ to Y ₈ are each independently N or C (R ₃ )
(2)

In the above Formulas 1 and 2,
* Is the binding site,
R ₁ to R ₄ are each independently selected from the group consisting of hydrogen, deuterium, a C ₁ to C ₄₀ alkyl group, a C ₆ to C ₆₀ aryl group, a heteroaryl group having 5 to 60 nuclear atoms, and a C ₆ to C ₆₀ arylamine Or a group selected from the group consisting of a hydrogen atom or a group to form a condensed aromatic ring or a condensed heteroaromatic ring,
L ₁ and L ₂ are each independently selected from the group consisting of a single bond, a C ₆ to C ₆₀ arylene group and a heteroarylene group having 5 to 60 nuclear atoms,
Ar ₁ and Ar ₂ are, each independently, C ₁ ~ C ₄₀ alkyl group, C ₆ ~ C ₆₀ aryl group, nuclear atoms, a heteroaryl group of from 5 to 60, and C ₆ ~ from the group consisting of an aryl amine of the C ₆₀ of the Selected,
n and m are each independently an integer of 1 to 3,
a and b are each independently an integer of 0 to 4,
The alkyl, aryl, heteroaryl and arylamine groups of R ₁ to R ₄ , Ar ₁ and Ar ₂ and the arylene group and heteroarylene group of L ₁ and L ₂ are each independently selected from the group consisting of deuterium, , A C ₁ to C ₄₀ alkyl group, a C ₃ to C ₄₀ cycloalkyl group, a heterocycloalkyl group having 3 to 40 nuclear atoms, a C ₆ to C ₆₀ aryl group, a heteroaryl group having 5 to 60 nuclear atoms, C C ₁ to C ₄₀ alkyloxy groups, C ₆ to C ₆₀ aryloxy groups, C ₃ to C ₄₀ alkylsilyl groups, C ₆ to C ₆₀ arylsilyl groups, C ₁ to C ₄₀ alkylboron groups, C substituted with at least one element selected from ₆ ~ C ₆₀ aryl boron group, C ₆ ~ C ₆₀ aryl phosphine group, C ₆ ~ C ₆₀ aryl phosphine oxide group, and the group consisting of C ₆ ~ with an aryl amine of the C ₆₀ of the Or is unsubstituted. The method according to claim 1,
Wherein the compound represented by Formula 1 is a compound represented by Formula 3 or Formula 4 below.
(3)

[Chemical Formula 4]

In the above formulas (3) and (4)
X ₁ to X ₈ , Y ₁ to Y ₈ and R ₁ are the same as defined in claim 1,
R ₅ is either selected from hydrogen, deuterium, C ₁ ~ C ₄₀ alkyl group, C ₆ ~ C ₆₀ aryl group, the number of nuclear atoms of 5 to 60 heteroaryl group, and the group consisting of C ₆ ~ with an aryl amine of the C ₆₀ of, To form a condensed aromatic ring or a condensed heteroaromatic ring by combining with adjacent groups,
c is an integer of 0 to 6,
The alkyl, aryl, heteroaryl and arylamine groups of R ₅ are each independently selected from the group consisting of deuterium, halogen, cyano, C ₁ to C ₄₀ alkyl, C ₃ to C ₄₀ cycloalkyl, A C ₆ to C ₆₀ aryl group, a heteroaryl group having 5 to 60 nuclear atoms, a C ₁ to C ₄₀ alkyloxy group, a C ₆ to C ₆₀ aryloxy group, a C ₃ to C ₄₀ An arylsilyl group of C ₆ to C ₆₀ , a C ₁ to C ₄₀ alkylboron group, a C ₆ to C ₆₀ arylboron group, a C ₆ to C ₆₀ arylphosphine group, a C ₆ to C ₆₀ An aryl phosphine oxide group and an arylamine group having ₆ to ₆₀ carbon atoms. The method according to claim 1,
Wherein each of Y ₁ to Y ₈ is C (R ₃ ). The method according to claim 1,
Ar ₁ and Ar ₂ are each independently a C ₆ to C ₆₀ aryl group or a heteroaryl group having 5 to 60 nuclear atoms. 1. An organic electroluminescent device comprising an anode, 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 the compound according to any one of claims 1 to 4.